Electric-field-reinforced affinitive electrolytes for highly reversible aqueous zinc metal batteries

Domain: chemistry
Published: 2026-03-06
Editorial outcome: major_revision

Abstract
Aqueous Zn metal batteries offer a safe, low-cost route to grid-scale energy storage yet suffer from dendrite growth and corrosion issues. Conventional electrolyte designs largely overlook electric-field-driven interfacial dynamics such as solvation structure evolution and component redistribution during operation. Here, we propose an affinitive additive strategy featuring high donor number and dipole moment, exemplified by N,N-dimethylurea (DMU), to dynamically modulate Zn2+ solvation and the structure of the electric double layer under operational electric fields. Guided by physically grounded molecular descriptors, we identify additives capable of electric-field-induced interfacial enrichment, during which strong dipole-field coupling promotes their incorporation into the Zn2+ solvation shell and promotes more uniform Zn deposition. As a result, the optimized electrolyte achieves a coulombic efficiency of ~99.9% for Zn plating/stripping with only 2 wt% additive. It also sustains stable operation for 700 h at 60% depth of discharge, outperforming the baseline electrolyte. Descriptor-guided screening further reveals that other candidates follow the same pattern, suggesting broader applicability of this approach. Practical Zn||ZnI2 full cells with high areal capacity (~3 mAh cm-2) and low N/P ratio (~1.8) achieve 750 stable cycles at 0.15 A g-1 with 84.5% capacity retention.

Introduction
Aqueous batteries, with their intrinsic safety, low cost, and environmental compatibility, have emerged as viable alternatives for large-scale electrical energy storage1–3. In particular, Zn metal batteries (ZMBs) combine low redox potential, high theoretical capacity, and the use of abundant raw materials, making them attractive candidates for grid-scale storage4. Nevertheless, the thermodynamic instability of Zn in aqueous electrolytes promotes persistent parasitic hydrogen evolution reactions (HER) and corrosion during plating/stripping cycles. As a result, these irreversible side reactions degrade coulombic efficiency (CE) and severely undermine the cycle life essential for practical applications5,6. Besides, Zn negative electrodes also suffer from dendritic growth, a common issue with metal negative electrodes. Consequently, addressing the fundamental negative-electrode-related challenges in ZMBs remains a critical hurdle for commercialization.

Electrolyte engineering has emerged as a powerful strategy for mitigating the interfacial irreversibility of Zn metal negative electrodes7–9, particularly in aqueous systems where dendrite growth, hydrogen evolution, and parasitic corrosion are prevalent. By modulating Zn2+ coordination environments and interfacial ion distributions, solvation structure tailoring10–14 and electric double layer (EDL) engineering15,16 have enabled notable improvements in reversibility and cycling stability. However, these advances remain constrained by inherent trade-offs. Dilute electrolytes offer insufficient interfacial regulation due to excessive water activity, while highly concentrated systems introduce challenges including elevated viscosity, sluggish ion transport, and increased cost17,18. In parallel, many formulations rely on high loadings of organic co-solvents (>10 wt%)19, which compromise safety margins and scale-up viability. These limitations reflect a broader conceptual gap: most existing strategies assume static solvation and interfacial behavior and depend on empirical additive screening without accounting for the dynamic electric field environment that governs real-time interfacial processes during operation. A critical yet often overlooked factor underlying these limitations is the dynamic nature of the electrode-electrolyte interface. In practical operation, intense interfacial electric fields, ranging from 105 to 107 V cm-120,21, continuously modulate the spatial distribution of ions and solvent molecules, dynamically reshaping Zn2+ solvation shells and interfacial composition. These field-driven perturbations profoundly impact nucleation behavior, surface reactivity, and additive functionality, yet remain largely unaddressed in conventional electrolyte design. Incorporating this dynamic perspective could provide a foundation for rational additive selection, particularly for systems engineered to respond to operational electric fields in situ.

In this work, we report an affinitive additive design for improved reversibility in aqueous ZMBs. Specifically, these affinitive additives combine high donor number (DN) and dipole moment (μ), enabling dual functionality: high‑DN molecules engage in stronger coordination interactions with Zn2+, while high-μ imparts strong electric-field-responsiveness. Unlike prior cosolvent engineering strategies, our framework explicitly treats the electrode’s interfacial electric field as an active driver of additive migration and adsorption, rather than a passive environment. A combination of experimental and computational methods revealed that under operational polarization, these additives dynamically redistribute to the electric double layer, modulating Zn2+ solvation environments. We further establish DN and μ as practical molecular-level descriptors that predict field-responsive enrichment, providing a generalizable selection rule. Building on this descriptor framework, we performed a high-throughput computational-experimental screening to identify additional molecules that satisfy DN-μ criterion, further supporting the broader applicability of this design approach. When incorporated into a ZnSO4 electrolyte (BE), this electric-field-reinforced affinitive electrolyte (ERAE) exhibits rapid interfacial accumulation of additives, modulating the Zn2+ solvation shell and markedly extending negative electrode lifespan. ERAE(DMU) achieves a Zn plating/stripping CE of 99.9% and demonstrates high compatibility with diverse positive electrode materials such as V6O13 and ZnI2, enabling stable full-cell cycling at high mass loadings.

Results
Design principles of additives
Achieving effective interfacial regulation at low additive concentrations relies on a clear mechanistic understanding of Zn2+ solvation and its interplay with interfacial electric fields. To this end, we begin by examining how Zn2+ interacts with its surrounding environment, as the solvation structure strongly influences ion transport and deposition behavior13. In aqueous ZMBs, Zn2+ functions as a Lewis acid that coordinates with solvent molecules or additives containing lone-pair electrons. Molecules with high DN donate electron density more efficiently to Zn2+,22,23 forming stable coordination complexes that enable co-migration under an applied electric field24,25. Meanwhile, species with larger μ exhibit strong dipole-field interactions, allowing them to align under electric fields and lower interfacial free energy, which enhances their adsorption26. Guided by this dual-parameter principle, we constructed a molecular library spanning a wide range of DN and μ values, and evaluated each candidate’s interfacial behavior under realistic field conditions. As shown in Figure 1a, we identified three types of additive response: electric-field-weakened shielding electrolytes (EWSE) with low μ cannot compete with water for interfacial adsorption; electric-field-weakened inert electrolytes (EWIE) with low DN lack coordination ability and fail to migrate; ERAE with both high DN and μ tend to exhibit strong co‑migration and sustained interfacial retention.

To systematically assess the effectiveness of additive-induced interfacial regulation, we screened 12 additives spanning a broad range of DN, μ, the adiabatic ionization energies (AIEs) and adiabatic electron affinities (AEAs), each introduced at a fixed loading of 2 wt% (Figures S1, S2 and Table S1). Electrochemical Zn plating/stripping tests were conducted using Zn‖Zn symmetric cells under harsh conditions (60 μL electrolyte, 60% depth of discharge (DOD); Figure S3), which ensured that observed performance differences could be primarily attributed to interfacial effects. We found that Zn plating/stripping duration correlated strongly and reproducibly with the combined DN-μ descriptor, supporting the predictive value of our design approach (Figures S4-S6). Interestingly, neither DN nor μ alone showed clear correlation with stability, nor did other common properties (Figure S7). This observation reinforces the importance of jointly considering both DN and μ when selecting affinitive additives. We further refined our analysis by employing a machine learning approach to identify the optimal feature pair (Figure 1b and Table S2). Twelve features, including dipole moment, dielectric constant, donor number, ET, and total polar surface area, were selected to generate 66 unique feature pairs. Utilizing Leave-One-Out Cross-Validation (LOOCV) with Ridge regression, we assessed each pair’s performance. The DN-μ combination yielded the lowest root mean square error, identifying it as a robust descriptor pair for predicting additive efficacy.

As shown in Figure 1c, the Zn plating/stripping duration achieved at 60 % DOD is plotted against each additive’s DN and μ, with bubble size representing performance. Additives located in the upper-right quadrant, combining both high DN and high μ, generally achieved lifetimes exceeding 200 hours, reflecting strong interfacial enrichment and stabilization even at low concentration. In contrast, additives with low μ are displaced by water at the interface, while those with low DN lacked the coordination ability needed for co-migration with Zn2+. As a result, neither class improved negative electrode lifetime relative to the BE, and in several cases, even reduced it. Conversely, ERAE showed clear improvements in Zn plating/stripping duration. This overall trend, mapped against molecular descriptors, highlights the utility of the DN-μ design framework. Based on these results, ERAE(DMU) and ERAE(MF) emerged as the potential candidates (Figure S8), both extending the Zn plating/stripping duration (Figure S5). Among them, DMU was selected as the principal focus for subsequent studies because it combines strong electrochemical performance with practical advantages in terms of safety and sustainability.

Electric-field-induced EDL reconfiguration
To gain deeper insights into the reconfiguration of the electric double layer (EDL) under applied electric fields, we conducted a comprehensive analysis using in situ electrochemical quartz crystal microbalance (eQCM) coupled with cyclic voltammetry (CV). This technique enables real-time monitoring of additive adsorption and desorption dynamics at the electrode-electrolyte interface27. Three different types of electrolytes were evaluated in 2 m ZnSO4. Electrode mass changes were detected via quartz-crystal frequency shifts following the Sauerbrey relation28. When paired with CV, this setup enables continuous tracking of interfacial mass variations29. Importantly, additives in the ERAE region undergo clear field-driven adsorption/desorption (Figure 2a), as revealed by the combined Pearson-amplitude ratio (AR) analysis in Figures 2b, S9. The Pearson coefficient captures the directional consistency between potential and mass variation, while the AR, extracted from the fundamental oscillation of the mass response, quantifies the strength of electric-field-induced adsorption/desorption. ERAE additives show large negative Pearson values together with high AR, consistent with strong electro-responsiveness. By contrast, EWIE, EWSE, and BE additives exhibit weak correlation and minimal AR values, indicating negligible mass modulation under the applied field. Control QCM measurements on Zn-coated QCM sensors suggest that the observed mass changes are not due to specific chemical adsorption (Figures S10-S12). Based on these observations, we infer that high-DN, high-μ additives accumulate at the Zn surface under field, leading to the formation of an organic-rich EDL. This is evidenced by a pronounced decrease in electric double‑layer capacitance (EDLC) and Mott-Schottky analysis (Figures S13, S14), which reflects the field-driven enrichment of additives. This conclusion is further supported by the reduced Arrhenius activation energy under an applied electric field (Figure S46) To assess the protective effect of this organic‑rich EDL, differential electrochemical mass spectrometry (DEMS) was used to monitor H2 evolution during cycling. Results show that the BE produces consistently higher H2 levels with intermittent bubble-detachment spikes19. In contrast, the ERAE(DMU) substantially reduces gas evolution (Figure 2c). Because the HER is strongly suppressed in ERAE(DMU), fewer byproducts are generated, as confirmed by XRD (Figure S15), and the interfacial passivation layer is correspondingly much thinner, as revealed by XPS depth profiling (Figure S16) and TEM imaging (Figure S17). These results suggest that affinitive additives enrich the EDL and suppress parasitic H2 evolution.

To further elucidate the electric-field-induced reconfiguration of the EDL at the Zn electrode interface, we performed constant-potential molecular dynamics (MD) simulations with and without applied bias (Figures 2d, 2e and S18-S20). When an external electric field is applied, DMU molecules accumulate strongly at the interface, demonstrating clear field responsiveness. By contrast, EWIE(SL) shows no field-induced enhancement, with its interfacial distribution remaining nearly unchanged under bias. Quantitative analysis (Figure 2f) further reveals that the surface coverage of ERAE increases markedly under bias, positioning them above the diagonal line, while EWSE and EWIE lie below the line, reflecting their depleted interfacial populations. This field-responsive enrichment suggests that affinitive additives can dynamically reorganize the interfacial environment under electric field, which is associated with reduced parasitic reactions and improved Zn negative electrode stability.

Interfacial dynamics of Zn2+ solvation shells
The interfacial dynamics of Zn2+ solvation are also important for efficient additive design. To further elucidate the dynamic modulation of the Zn2+ solvation shells by ERAE(DMU) under operational electric fields, in situ attenuated-total-reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy was conducted in combination with chronoamperometry to record the time evolution of absolute absorbance, [A(t)] (Figures S21, S22). In addition, surface-enhanced infrared absorption spectroscopy (SEIRAS) was employed to selectively probe interfacial species with higher sensitivity (Figures S23, S24), thereby complementing the ATR-FTIR analysis. This technique enables real-time monitoring of interfacial chemical environments, providing insights into solvation dynamics during Zn plating and stripping processes30. Relative absorbance changes, [A(t)-A(t0)], were calculated by subtracting the initial spectrum recorded at t0. We then analyzed [A(t)-A(t0)] over the plating (t0-t900) and stripping (t900-t1800) intervals. Notably, the relative absorbance variations closely track the current response, particularly for the O-H stretching vibration [ν(H2O)] and asymmetric S-O stretching [ν(SO42-)]. The ν(H2O) includes contributions from both weak (W-H) and strong (S-H) hydrogen bonds. Consistent with previous studies31, in the BE, ν(SO42-) absorbance decreases during plating, indicating that SO42- moves away from the interface. During stripping, ν(SO42-) absorbance increases, suggesting that SO42- returns toward the interface. Additionally, hydrogen bonding (HB) in water weakens during plating and strengthens during stripping (Figure 3a). In stark contrast, in the ERAE(DMU), changes in ν(H2O) and ν(SO42-) are markedly suppressed (Figure 3b). SEIRAS demonstrates that ERAE(DMU) undergoes potential-dependent dynamic adsorption and desorption and adsorption at the electrode surface. This finding indicates that the variations of SO42- and H2O observed by in situ ATR-FTIR are instead induced by the interfacial adsorption of ERAE(DMU), highlighting its role in regulating the interfacial environment. These findings suggest that affinitive additives partially exclude both H2O and SO42- from the Zn2+ solvation shell at the interface. These observations are schematically illustrated in Figure 3c, where the dynamic reorganization of Zn2+ solvation shells under an applied field is depicted.

Subsequently, the interfacial Zn2+ hydration in ERAE(DMU) and BE was quantified in real time using in situ eQCM during the negative polarization process with carbon black-coated quartz crystals, which allows solvated Zn species to diffuse into the pore structure (Figure S25). The measured Δm-ΔQ relations were compared with the dotted and dashed theoretical mass, charge slopes corresponding to bare Zn2+ and fully hydrated Zn2+·6H2O, respectively. In the BE electrolyte, the Δm-ΔQ plot closely follows the theoretical behavior of the fully hydrated species, and the fitted slope corresponds to an apparent molar mass of 179 g mol-1 (details of the slope calculation and molar-mass extraction are provided in the Supporting Information). In contrast, the ERAE(DMU) electrolyte exhibits markedly larger mass changes per unit charge, yielding an apparent molar mass of 202 g mol-1. These heavier, less-hydrated interfacial Zn complexes suggest that the associative additive may participate in modifying the interfacial solvation environment by partially displacing water molecules from the primary solvation shell of Zn2+.

To quantitatively assess the electric-field-responsiveness of molecules in relation to their coordination with Zn2+, the binding energy (Eb) between each additive and Zn2+ was calculated as a measure of coordination strength. Electric-field-responsiveness was then evaluated for a series of molecules (Figure 3g). A strong positive correlation between Eb and field-responsiveness is observed for ERAE(DMAC, DMSO, DMU, DMF, NMP) indicating both high Zn2+ affinity and pronounced field sensitivity. By contrast, EWSE(MeOH), EWIE(ACN) and H2O exhibit weak Zn2+ binding and low field-responsiveness, indicating limited interfacial affinity. As the field strength increases from 0 to 0.2 ×10-3 V Å-1, Eb decreases markedly for EWIE(ACN), H2O, and EWSE(MeOH) (Figure S26). Among them, H2O shows the steepest decline, indicating facile stripping of water ligands under field. In contrast, ERAE(DMAC, DMU, DMF, NMP) exhibit slight increases in Eb, indicating their resistance to field-induced dissociation and further reinforcement of Zn2+ coordination. This behavior is consistent with field-driven enrichment and stabilization of Zn2+ solvation at the interface.

Furthermore, MD simulations were conducted to compare Zn2+ solvation structures under field-free (bulk) and applied-field (interfacial) conditions (Figure 3h). In the absence of bias, Zn2+ solvation is dominated by water molecules, and most additives show negligible participation in the primary solvation shell. Under an applied field, however, ERAE(DMAC, DMF, DMU, DMSO, NMP) partially replace water ligands and become incorporated into the Zn2+ solvation shell, reflecting their strong electric-field responsiveness. By contrast, EWIE (ACN, SL) and EWSE (TAA, TBA) remain largely excluded, indicating little contribution to field-driven solvation restructuring. These results highlight a dual-parameter design principle: additives that combine high Zn2+ binding affinity with strong dipolar response are more likely to accumulate at the interface and actively reorganize Zn2+ solvation under operating conditions.

To rule out bulk effects, ex situ ATR-FTIR, X-ray absorption fine structure (XAFS) and ionic conductivity measurements were performed on both BE and ERAE(DMU). These techniques probe coordination environment, local structure, and transport properties, respectively. ATR-FTIR spectra for BE and ERAE(DMU) (Figure S27) indicates similar Zn2+ coordination environments. Similarly, XANES data (Figure S28) show that the Zn K-edge absorption energies are virtually the same for BE and ERAE(DMU). FT-EXAFS fitting in R space confirms that the first-shell Zn-O coordination is preserved (Figure S29). Wavelet transform analyses (Figures S30, S31) likewise indicate that the local solvation sheath experiences only minimal perturbation. Together, these results indicate that at 2 wt% additive loading, ERAE(DMU) does not substantially infiltrate bulk Zn2+ solvation clusters despite their high DN. Moreover, BE and ERAE(DMU) display comparable ionic conductivities (Figure S32), confirming that bulk transport properties remain effectively constant. Therefore, the performance enhancements arise predominantly from interfacial, rather than bulk, additive effects.

Morphology of deposited Zn
Generally, interfacial Zn2+ solvation structure plays an important role in governing nucleation behavior32, so we next investigated its impact on deposition uniformity. Since electric‑field inhomogeneity at the metal-electrolyte interface is known to drive dendritic growth33, scanning electrochemical microscopy (SECM) was employed to map the local electric-field distributions across Zn deposit (Figure 4a). Ferrocene methanol (FcMeOH) served as a redox mediator, and its tip current was monitored to report field strength. SECM imaging revealed highly uniform current signals in the ERAE(DMU) (Figure 4b), whereas the BE exhibited distinct inhomogeneity with a depressed region in the center (Figure 4c). This field distortion is associated with uneven Zn2+ flux, which may promote preferential growth at the electrode edges and symmetry breaking in the nucleation pattern34. To observe the dynamic evolution of Zn plating, in situ optical microscopy was performed. The BE system showed increasing surface roughness and visible gas evolution over time, while the ERAE(DMU) exhibited a more compact and uniform deposition front (Figure 4d). Confocal laser scanning microscopy (CLSM) further confirmed these trends, with the BE showing a rougher and more disordered surface compared to the smoother morphology under the ERAE(DMU) (Figure 4e). High-resolution SEM images revealed dense, layered Zn deposits in the ERAE(DMU), in contrast to the porous and irregular structure observed in the BE (Figure 4f). Given that the electro-crystallization rate depends on overpotential and is reflected in current transients, potentiostatic experiments were performed. These measurements were used to probe Zn nucleation and growth kinetics. The resulting i-t curves (Figure S33) were normalized using the peak current (im) and corresponding time (tm), and compared with two classical models: the Scharifker-Hills (SH) model35 describing 3D diffusion-controlled hemispherical growth (3DI, 3DP), and the Bewick-Fleischmann-Thirsk (BFT) model36 describing 2D lateral cylindrical growth (2DI, 2DP) (Figure 4g). In the BE, Zn nucleation follows a mixed 2D/3D growth mode. Consequently, 3D growth produces rough, porous deposits that disrupt the uniformity of the Zn plating layer37. By contrast, in the ERAE(DMU), Zn deposition is consistent with a predominantly 2DP mode, leading to a smoother, homogeneous layer without pronounced agglomeration.

Electrochemical performance
Building on the observed interfacial behavior, the electrochemical performance of half cells was further evaluated. The Zn plating/stripping stability of Zn||Zn symmetric cells was assessed at DOD of 30%, 60%, 70%, and 80% using the ERAE(DMU). At 30 % DOD, ERAE(DMU) exhibited a Zn plating/stripping duration of 1625 h; at 60 % DOD, Zn plating/stripping duration was 700 h; at 70 % DOD, 455 h; and at 80 % DOD, 315 h (BE < 100h) (Figure 5a). Furthermore, under a stepwise high-DOD protocol (30%, 60%, 80%, 60%, 30%), the ERAE(DMU) maintained prolonged Zn plating/stripping stability (Figure 5b). Using Aurbach’s protocol38,39 at 60% DOD, Zn CE reached 99.92% in the ERAE(DMU) versus 97.82% in the BE (Figures 5c). CE measurements across all electrolytes (Figures S34-S37) show that ERAE consistently maintains the higher Coulombic efficiency during long-term cycling, indicating enhanced reversibility of Zn plating/stripping behavior. In contrast, EWIE and EWSE display lower reversibility and shorter lifetimes. These results suggest that affinitive additives enhance both Zn negative electrode stability and reversibility, with the improved performance arising from interfacial enrichment that modulates Zn2+ solvation clusters and promotes a water-deficient EDL. Considering DOD, cumulative plating capacity (CPC), and electrolyte cost, the Zn negative electrode metrics reported here achieve competitive performance (Figure 5d).

Furthermore, positive electrodes compatibility and full-cell performance under harsh conditions were explored. Zn||V6O13 (intercalation-type) full cells were assembled using the ERAE(DMU) to evaluate long-term stability and reversibility. The galvanostatic charge-discharge (GCD) profiles of the ERAE-based Zn||V6O13 cell at 0.3 A g-1 (Figure S38) closely match the characteristic V6O13 GCD profiles40. The N/P ratio was set to approximately 3. After 900 cycles, the ERAE-based Zn||V6O13 cell retained 87.5% capacity, with an average CE of 98.8% (Figure 6a). In comparison, the BE-based cell retained only 55% of capacity after just 200 cycles and then gradually faded to near zero, without short circuiting. This indicates that parasitic side reactions41, rather than dendrite‑induced failure, are the dominant cause of capacity loss. These findings suggest that ERAE(DMU) effectively suppresses parasitic reactions and improved Zn negative electrode durability in full cells.

Moreover, Zn||ZnI2 (conversion-type) full cells were also assembled under high mass loading conditions. GCD profiles at 1 C (0.15 A g-1) and 4 C exhibit typical ZnI2 positive electrode characteristics (Figure S39). Under harsh conditions (E/C ~ 16 µL mAh-1, N/P ~ 1.8), the ERAE(DMU) completed 750 cycles at 1 C, retaining 84.5% capacity with an average CE of 99% (Figure 6b). At 4 C rate, the cell sustained 1,000 cycles with 91.5% retention, indicating stable cycling performance and high-rate capability (Figure S40), as well as improved CE. In contrast, the BE showed large CE fluctuations and experienced short circuiting after 130 cycles. This failure is attributed to polyiodide shuttling, which accelerates parasitic reactions at the Zn negative electrode42 and leads to rapid Zn depletion and dendritic formation. Open-circuit voltage decay tests of fully charged Zn||ZnI2 cells after 24 h storage show 92.9% capacity retention in the ERAE(DMU), indicating effective suppression of polyiodide shuttling (Figure S41). The ERAE(DMU) also delivers high cumulative discharge capacity (CDC) at low electrolyte cost (Table S6). These results highlight the ability of ERAE(DMU) to stabilize Zn negative electrodes and enable durable, high-performance operation with conversion-type positive electrodes. To assess scale‑up feasibility, a Zn||ZnI2 pouch cell was fabricated using ERAE a 30 mg cm-2 ZnI2 positive electrode, a separator, and a 20 µm Zn negative electrode. This configuration yielded an areal capacity of 4 mAh cm-2, with an N/P ratio of approximately 3, and a total discharge capacity of 100 mAh for the 25 cm2 pouch cell. The cell exhibited stable polarization throughout cycling, with only a slight increase compared to the coin cell (Figure 6c). As a result, a long-term cycling stability of 200 cycles with 99.2% capacity retention was achieved (Figure 6d). Even when paired with MnO2 positive electrodes, ERAE(DMU) still exhibits enhanced cycling stability and higher CE compared with the BE, demonstrating its broad compatibility with different cathode chemistries (Figures S44, S45). Overall, the electric-field responsiveness of ERAE(DMU) enables stable and efficient cycling performance under demanding full-cell conditions.

High-throughput screening workflow
To explore the applicability of the DN-μ design principle beyond the additives experimentally examined in this work, we further developed a high-throughput computational screening pipeline (Figure 7a). Beginning with ~569,000 organic molecules downloaded from PubChem, we applied a sequence of filters based on toxicity, chemical stability, and pH compatibility, narrowing the pool to ~223,000 candidates. Additional constraints related to synthetic accessibility and commercial availability reduced this set to ~20,000 molecules. Efficient xTB calculations were then performed to evaluate three molecular-level criteria informed by our mechanistic understanding: (1) electrochemical stability (AIE > 10.4 eV and AEA < 6.4 eV), (2) high dipole moment (> 5.0 D), and (3) strong Zn-ion binding affinity (0.18 Hartree higher than Zn2+-H2O interaction).

Application of these criteria yielded ~300 promising candidates (Supplementary Data 1), which were subsequently filtered by cost and commercial accessibility, arriving at ~30 final molecules with DN-μ characteristics aligned with our design framework. To experimentally interrogate the predictive power of this screening strategy, we selected two inexpensive and commercially accessible additives (piracetam (PIR) and 1-(2-Hydroxyethyl)-2-pyrrolidone (HEP)) from this set and incorporated them into Zn||Zn symmetric cells. As shown in Figure 7b, both additives led to extended Zn plating/stripping duration: ERAE(HEP) achieved a lifetime of 270 h at 60% DOD, while the ERAE(PIR) achieved 615 h under the same conditions. These results provide experimental support for the applicability of our computational design logic.

Methods
Chemical reagents
N,N-Dimethylurea (DMU, 98% purity), tert-Butanol (TBA, ≥ 99% purity), tert-Amyl alcohol (TAA, 99% purity), Methanol (MeOH, 99.5% purity), 1-Methyl-2-pyrrolidinone (NMP, > 99.5% purity), N,N-Dimethylacetamide (DMAC, 99% purity), N-Methylformamide (MF, 99% purity), Triethyl phosphate (TEP, > 99.5% purity), Piracetam (PIR, > 98% purity), 1-(2-Hydroxyethyl)-2-pyrrolidone (HEP, > 99.5%), Ferrocene methanol (FcMeOH, 98% purity) and vanadium pentoxide (V2O5, 99% purity) were purchased from Macklin Biochemical Technology Co. Dimethyl sulfoxide (DMSO, > 99.8% purity), N,N-Dimethylformamide (DMF, > 99.9% purity) and Sulfolane (SL, 99% purity), Ethylene glycol (EG, > 99.5% purity) were purchased from Energy Chemical Co. Zinc sulfate heptahydrate (ZnSO4·7H2O) was purchased from Sinopharm Chemical Reagent Co. Trimethyl phosphate (TMP, 98% purity), Zinc Iodide (ZnI2, 99% purity) were purchased from Shanghai Adamas Reagent Co, the gold plating solution was purchased from Shanghai Yuanfang Technology Co., Ltd, The commercial nanoscale α-MnO2 was purchased from Shanghai Yunfu Nano Technology Co., Ltd. Acetylene black (Kappa 100), CNT-3213, PTFE aqueous dispersion (60 wt%), Ketjen black (EC-600JD) and PVDF 5130 were purchased from Guangdong Canrd New Technology Co.

Electrolyte preparation
Deionized water was used as the solvent to prepare the aqueous electrolytes. BE (2m ZnSO4) was prepared by dissolving 0.02 mol ZnSO4·7H2O in 7.48g of H2O. The 2 wt% additive content was calculated based on the total mass of the mixed electrolyte.

Electrode preparation and cell assembly
V6O13 was prepared as follows43 (Figure S42, S43). Briefly, 0.9 g of vanadium pentoxide (V2O5) was dissolved in a mixture of 10 mL of ethanol and 30 mL of DI. After continuously stirring for 1 h, the solution was transferred to a 50 mL Teflon autoclave and heated at 180°C for 12 h. It was then washed several times with ethanol and dried overnight at 60°C in a vacuum atmosphere to obtain V6O13. For V6O13 free standing positive electrodes, a mixture of active material V6O13, acetylene black, CNTs and PTFE binder were pressed in a weight ratio of 7:1:1:1. For ZnI2 free standing positive electrodes, a mixture of active material ZnI2, activated carbon (YEC-8A, Fuzhou Yihuan Carbon Co., Ltd.), and PTFE binder was pressed in a weight ratio of 6:3:1. For α-MnO2 positive electrodes, a slurry was prepared by mixing α-MnO2, Ketjen black, and PVDF binder in a weight ratio of 7:2:1. The slurry was uniformly coated onto 39BB carbon paper (Toray) using a doctor blade, followed by drying overnight at 80 °C. Electrodes were cut into circular disks using a precision puncher. CR2032 coin cells (Guangdong Canrd New Technology Co.) were assembled for electrochemical measurements, maintained at 25°C in a temperature-controlled chamber (Shenzhen Neware Technology Co.). Zn||Cu cells were assembled by using Zn foil (thickness: 200 μm, diameter: 14 mm) as negative electrode and Cu foil (thickness: 20 μm, diameter: 19 mm) as positive electrode. Symmetrical cells were assembled by using two Zn foils (thickness: 10 μm, diameter: 12 mm). Full cells, including Zn||ZnI2, Zn||V6O13 were assembled by using thin Zn foil (thickness: 10 μm, diameter: 12 mm) as negative electrode and high-loading self-standing positive electrode (diameter: 12mm). Zn||ZnI2 pouch cell was assembled by using thin Zn foil (thickness: 20 μm, 25 cm2) as negative electrode and ZnI2 self-standing positive electrode (25 cm2) and were cycled under a fixed external mechanical pressure applied using a commercial clamping fixture (Guangdong Canrd New Technology Co.). No additional surface treatment was applied to the current collectors prior to electrode fabrication. A commercial glass fiber membrane (Whatman GF/D, pore size: 0.7 μm, thickness: 420 μm) was used as the separator for all the cells.

Electrochemical analyses
Galvanostatic charge/discharge tests of Zn||Cu, Zn||Zn, Zn||ZnI2, Zn||V6O13 Zn||MnO2 coin cells and Zn||ZnI2 pouch cell were performed using the Landt battery test system (Wuhan LAND Electronic Co.) and NEWARE battery test system (Shenzhen Neware Technology Co.). The Zn plating/stripping CE was measured in Zn||Cu cells by the Aurbach’s method and cycle method38,39. The processes of Aurbach’s method were as follows: First, the plating was deposited, cycled, and formed at 5 mA cm-2 and 10 mAh cm-2; then, the former plating was cycled again at 5 mA cm-2 and 6 mAh cm-2. Finally, the remaining Zn was stripped at 5 mA cm-2 until the cutoff voltage of 0.5 V was reached. Electrochemical measurements were performed on a Gamry workstation. Chronoamperometry measurements of Zn||Zn cells were conducted by holding cells at 0.07 V for 0.005 s. Electrochemical impedance spectroscopy (EIS) measurements were carried out in a potentiostatic mode with an AC perturbation amplitude of 10 mV over the frequency range of 100 kHz to 0.01 Hz, using 10 data points per decade. Prior to EIS measurements, the cells were rested at open-circuit voltage (OCV) for 2 h to ensure a quasi-stationary state. During data analysis, obvious outlier points were excluded from the fitting process. The cyclic voltammetry curves of Zn||Zn cells were tested at a scan rate of (2, 6, 10, 14 mV s-1), and the EDLC was calculated using Cc = i v-1, where Cc is the capacitance, i is the electric double layer current, v is the scan rate. The capacitance can be obtained from the slope of the i versus v. Here, i was defined as half the difference between current during the forward and reverse scans at 0 V, that is (i0v+ - i0v-)/244.

The mathematical expressions for classical nucleation models are provided below:
3DI: I/Im = (1.9542/tm) [1-exp(-1.2564t/tm)]^0.5 (1)
3DP: I/Im = (1.2254/tm) [1-exp(-2.3367t/tm)]^0.5 (2)
2DI: I/Im = exp{-(t/tm)} [1-exp(t/tm)] (3)
2DP: I/Im = (t/tm) exp{-(t/tm)} (4)

Characterizations
In situ eQCM was measured through the eQCM system (15M and Interface 1010E, Gamry) with Au-sputtered 5 MHz quartz substrates (diameter: 14 mm) to monitor the resonance frequency changes of the electrodes. The mass change of the QCM electrode (Δm) was determined from the resonance frequency shift (Δf) using the Sauerbrey equation. In the eQCM tests, 2 m ZnSO4 served as the BE, and the quartz crystal resonator functioned as the working electrode. Platinum wire and Ag/AgCl electrodes were used as the counter and reference electrodes, respectively. The cyclic voltammetry curves were recorded at a scan rate of 50 mV s-1, ranging from 0 V to 0.6 V. The QCM test was conducted in three steps: first, a frequency balance was established using a continuously flowing 2 m ZnSO4 electrolyte; second, the original solution was replaced with various additive electrolytes; and finally, the baseline electrolyte was reintroduced to monitor the frequency change and determine the formation of an adsorption layer. The electrolytes were delivered to the test chamber via a peristaltic pump at a flow rate of 1 mL min-1. In the Zn2+ hydration number test, porous carbon materials (Vulcan XC-72R, Cabot) and PVDF were mixed with NMP at a weight ratio of 9:1. The resulting mixture was uniformly coated onto quartz substrates and dried in a vacuum oven at 80 °C. The coated quartz crystal resonator served as the working electrode, while platinum wire and Ag/AgCl electrodes functioned as the counter and reference electrodes, respectively. CV tests were then performed starting from the open-circuit voltage in the negative direction at a scan rate of 10 mV s-1 ranging from 0 V to -0.5 V. During cyclic voltammetry, the charge stored or released on the electrode surface can be determined by integrating the current over time (the CV curve). The eQCM data were presented as the relationship between the electrode mass change (Δm) and the charge passed (ΔQ) during the negative polarization process45 (red and blue lines in Figures 3d,e).

To establish the theoretical reference for interpreting the eQCM results, the mass-charge responses of bare Zn2+ and fully hydrated Zn2+·6H2O were calculated according to Faraday’s law (dot and dashed lines in Figures 3d,e). These curves provide the expected Δm-ΔQ slopes for ions carrying either no hydration water or a full primary hydration shell. By comparing these theoretical slopes with the experimental Δm-ΔQ relations, the apparent molecular weight (Mw') of the interfacial species can be extracted using equation (5) 46. A deviation of the experimental slope toward higher apparent molecular weight than either theoretical limit suggests that the interfacial Zn species carry additional coordinated components beyond water.

MW' = (nF∙Δm)/Q (5)

Where n is the valence state of Zn2+, F is the Faraday constant (96485 C mol−1), Q is the charge amount transferred through the electrode at presumptive 100% coulomb efficiency.

In situ FTIR spectra were acquired using a battery test system (Shenzhen Neware Technology Co.) coupled with a Thermo Fisher Scientific Nicolet iS20 spectrometer. In situ differential electrochemical mass spectrometry was performed using a commercial mass spectrometer (QMS 200 Atmospheric Sampling System, Stanford Research Systems, Inc., USA) connected to a sealed EL-CELL. Prior to testing, the system was purged with pure Ar at 1 mL min-1 for 12 hours; subsequently, the evolved gas was analyzed during charging and discharging at 5 mA cm-2 and 5 mAh cm-2, respectively. The entire cell setup was maintained in a temperature-controlled environment at 25 ℃.

In situ SEIRAS measurements were carried out using a Si ATR prism coated with a chemically deposited Au nanofilm. The prism was pretreated by immersion in HCl:HNO3 solution (3:1 v/v, 30 min), polishing with 50 nm alumina slurry (10 min), ultrasonic cleaning, oxidation in H2SO4:H2O2 solution (3:1 v/v, 20 min), and etching in 40 wt% NH4F (1 min). For Au deposition, 15 mL of Au plating solution was preheated to 55 °C, mixed with 3 mL of 2% HF, and the treated prism was immersed for 20 min, then rinsed thoroughly with deionized water. The SEIRAS cell employed the Au-coated Si prism as the working electrode and Zn foil as the counter electrode, and spectra were collected in situ during electrochemical cycling.

The interfacial electrochemical behavior of the Zn negative electrode was probed using scanning electrochemical microscopy (SECM, CHI920D). In the SECM experiment, a Cu foil with deposited Zn served as the substrate electrode, while a Pt ultramicroelectrode (UME) with a 10 μm radius functioned as the working electrode. All SECM measurements were performed in a 2 m ZnSO4 aqueous solution containing 1 mM FcMeOH as the mediator. In SECM feedback imaging, the process involves scanning an ultramicroelectrode at a constant height above the substrate interface, variations in probe current reflect differences in surface topography and electron-transfer activity.

X-ray diffraction patterns (XRD) were recorded on Bruker D2, with Cu Kα radiation. Scanning electron microscopy (SEM) images were taken by Thermo Fisher Apero 2s. X-ray photoelectron spectroscopy (XPS) data were required using an A PHI-5702 instrument with Mg Kα X-ray source, with a standard binding energy of 284.8 eV for C 1s. Transmission electron microscopy (TEM) images were taken by Talos F200X. XAFS measurements were performed on the RapidSXAFS in Anhui Absorption Spectroscopy Analysis Instrument Co, Ltd. The Athena and Artemis modules of the Demeter software package were used to process the extended XAFS (EXAFS) data according to the standard procedures47. Wavelet transform was also conducted to analyze EXAFS data48.

Machine learning selection
A machine learning approach was adopted for feature selection to identify the most predictive combination of features for our regression model, with Coulombic efficiency designated as the target value. Our dataset encompassed a variety of chemical properties, including dipole moment, dielectric constant, donor number, molecular weight, and others (Table S1). Ridge regression was selected as the base model owing to its effectiveness in mitigating overfitting through L2 regularization. Polynomial features of degree two were generated to capture potential non-linear relationships between features. An exhaustive search across all possible pairs of these features was performed to evaluate their predictive performance, utilizing Leave-One-Out Cross-Validation (LOOCV). The Root Mean Square Error (RMSE) served as the evaluation metric for assessing the predictive accuracy of each feature pair.

Calculation methods
The constant-potential molecular dynamics simulations were executed using LAMMPS software49, complemented with the ELECTRODE package. Initial configurations for the electrode-electrolyte systems were generated utilizing PACKMOL50 and Moltemplate (http://www.moltemplate.org/). The characteristics of H2O were depicted using the SPC/E model. For the force-fields parameters of the Zn2+ and SO42-, a combination of previous publications51–53 and RESP2 charges54,55 was employed. Similarly, the OPLS force field combined with RESP2 charges was utilized for the additives. To address electronic polarization, an electronic continuum correction method was applied with scaled charges (0.75). The simulation protocol began with Langevin dynamics at 500 K for 1 ns to facilitate salt dissociation. Following this, an NVT ensemble run at 500 K for another 1 ns was conducted to further promote salt dissociation. Subsequently, the system underwent an NVT run at 298 K for 5 ns to reach equilibrium without the application of a constant potential. Finally, to simulate the EDL structure under an electric field, an NVT run with a constant potential of 2 V was carried out for 5 ns. The binding energies were determined utilizing the ORCA software package56. Geometry optimizations of clusters were conducted at B97-3c level. Single-point energy calculations were then executed at the B3LYP/def2-TZVP level. To adequately address long-range dispersion interactions, Grimme's D3 dispersion correction was applied. Visualization of the EDL structures was accomplished using VESTA57 and VMD58.

Peer review rounds
[{"round": 1, "reviewer_comments": {"reviewer_1": "This manuscript reports an affinitive additive strategy for aqueous Zn metal batteries (ZMBs) that leverages high donor number and dipole moment molecules to enable electric-field-induced interfacial enrichment. Through a combination of in situ spectroscopy (eQCM, ATR-FTIR), molecular dynamics simulations, and electrochemical testing, the authors demonstrate that such additives can dynamically modulate Zn²⁺ solvation and guide uniform Zn deposition, resulting in a Coulombic efficiency of 99.9% and stable full-cell cycling even at high areal capacities. The work presents a novel angle for electrolyte design that emphasizes interfacial field responsiveness—a dimension often neglected in previous studies. However, some specific points should be addressed before the manuscript can be accepted for publication.\nQ1. Why was the dielectric constant not chosen as a descriptor, given that it directly reflects a molecule’s ability to resist or respond to external electric field strength?\nQ2. Although Zn deposition is excluded during eQCM measurements to isolate ion distribution effects, the difference in charge between Na⁺ and Zn²⁺ results in distinct interfacial electric field distributions. Would it be more informative to examine interfacial mass changes within the non-deposition voltage window of Zn²⁺ itself?\nQ3. This paper also focuses on interfacial structural changes induced by organic additives. Could the authors more clearly differentiate their interpretation of interfacial dynamic evolution from those previously reported, especially in relation to the cited work: “Deciphering multi-dimensional interfacial mechanisms via organic cosolvent engineering for sustainable zinc metal batteries”?\nQ4. Should the dynamic interfacial behavior of the electrolyte also account for changes after SEI formation? Wouldn’t this also fall within the scope of “dynamic interfacial structure” as discussed?\nQ5. In Figure 2c, the baseline signals of the two electrolytes in the DEMS measurements are inconsistent. Could the authors explain this discrepancy?\nQ6. In Figure 2d, please indicate the thickness of the highlighted interfacial region (distance from the electrode surface). Additionally, it would be helpful to plot the MD results for the no-bias case alongside for a direct comparison of interfacial structure under different field conditions.\nQ7. In Figure 2f, a diagonal separation line could help clarify the classification of additive types. However, since both SL and ACN are considered shielding additives, how should their placement and distinction be interpreted?\nQ8. In Figure 1b, the affinitive additives show significantly different effectiveness. What other factors besides donor number and dipole moment may influence their performance?\nQ9. In Figure 5, only one electrolyte from a Nature-sister journal is used for comparison. Please include additional state-of-the-art electrolyte systems for benchmarking and better contextualization of the current work.\nQ10. The activation step shown in Figure 5c involves a large number of cycles. Could similar Coulombic efficiency (~99.9%) be achieved using the standard 10-cycle activation protocol?\nQ11. The authors attribute deposition behavior to solvation structure effects, yet the bulk electrolyte composition remains unchanged. Would it be more accurate to describe this as an effect of interfacial rather than bulk solvation structure?\nQ12. Throughout the manuscript, terms like “affinitive additives,” “ERAE,” and “charge-reinforced” are used somewhat interchangeably. Please standardize this terminology to avoid confusion for non-specialist readers.\nQ13. The color schemes used in Figures S17 and S18 are different, but the captions for both state \"varying from yellow in plating to purple in stripping,\" which may cause confusion.\nQ14. In the Figure 3 c schematic illustrations, organic additives are consistently shown occupying the first solvation sheath of Zn²⁺, which may lead to the misconception that all additives fully displace water. Please consider revising or reducing the number of such diagrams to avoid overgeneralization.\nQ15. The Figure 3d-f suggests that affinitive additives can effectively replace water molecules in the Zn²⁺ solvation shell and that their large molecular size limits their access to carbon pores. In such cases, are the remaining coordination sites of Zn²⁺ left unsolvated (“naked”)?\nQ16. While the current in-situ FTIR setup provides valuable information, it lacks surface enhancement, which limits its ability to directly resolve interfacial structural changes. Would the authors consider employing surface-enhanced techniques to strengthen this aspect of the work?", "reviewer_2": "In this work, the author used affinitive additive with high donor number and dipole moment to modulate Zn2+ solvation and the structure of the electric double layer under operational electric fields and to promote the stability of anode in zinc-ion batteries.\nAlthough the electric-field-induced interfacial enrichment facilitates uniform Zn deposition and long-term cycling life of batteries, this work still followed traditional electrolytes papers in zinc battery filed, illustrating additive with different donor number or dipole moment. The novelty or performance are not significant and satisfactory. In addition, the overall quality of this manuscript cannot meet the standards of this journal as well. The reviewers don't recommend further consideration of this work. Some detailed comments are as follows.\n1. In abstract and introduction, the author still hasn’t mentioned DMU molecule. And the full name of all molecules should be given.\n2. In figure 1c, author should list the colored balls represented elements.\n3. For eQCM, the sensor is gold sensor or author put zinc electrode on the sensor? If author want to claim the good adsorption of DMU on zinc, it would be better to attach the zinc foil on the sensor.\n4. In figure 2f, why for the inert molecules, the number of them without E field is much higher than them with E field. They are inert molecules, not shielding.\n5. What does this mean in figure s17, s18, “ with the color of the spectra varying from yellow in plating to purple in stripping”\n6. Why for DMF, DMSO, the number of additive molecules in the Zn2+ solvation shell without E field are higher than them with E field. The calculation should be double checked.\n7. Relevant XRD results of cycled zinc electrode should be tested.\n8. Self-discharge analysis of bare electrolyte should also be provided.\nWe would like to point it out that, the overall electrochemical measurements and analyses are not sufficient and quite routine, hardly generating sufficient data and results for deep analysis of the mechanisms. Besides, there are not sufficient direct and solid evidence to support the authors' claims on the mechanisms.", "reviewer_3": "I co-reviewed this manuscript with one of the reviewers who provided the listed reports. This is part of the Nature Communications initiative to facilitate training in peer review and to provide appropriate recognition for Early Career Researchers who co-review manuscripts.", "reviewer_4": "The authors herein developed an electric‑field‑reinforced affinitive additive strategy for aqueous Zn metal batteries, leveraging high DN and μ to create an electrolyte that dynamically responds to applied fields. The use of descriptors and MD theory calculations to develop electrolyte additive strategies has scientific significance. The mechanism of double-layer and solvation, as well as the description of morphology and electrochemical performance, are complete and clear, but the electrochemical performance is not outstanding enough, and there is relatively little chemical analysis of the microstructure of the anode and cathode surface. I would suggest a major revision based on the following comments:\n1. The author screened 12 additives, covering a wide range of DN and μ, with each additive introduced at a fixed concentration of 2 wt%. Why is the concentration 2 wt%? Do other concentrations also follow the general pattern of DN and μ?\n2. According to this paper, affinity additives need to balance DN and μ, but \"DMU and MF emerged as the promising candidates (Figure 1c)\" mentions that using MF and DMU as candidates. Figure 1c tells MF seem to be not as good as DMSO. Why does the author take MF and DMU as the two promising candidates? In addition, MF was not used in the characterization of the double layer and solvation structure, while DMSO and DMU were used to evaluate adsorption and desorption. Why?\n3. This work believes that ideal additives have high zinc ion binding affinity and strong electric field responsiveness, which can accumulate at the interface and actively recombine zinc ion solvation under on-site conditions. The author should provide HOMO and LOMO for the three categories of additives (affinity additives, shielding additives, and inert additives), as well as the binding energy between additive molecules and zinc ions, to verify the advantages of ideal additives with high zinc ion binding affinity and strong electric field responsiveness from the perspectives of molecular reactivity and binding energy.\n4. What are the effects of affinity additives, shielding additives, and inert additives on the composition and morphology of negative SEI and positive CEI? It is recommended that the author provide characterizations, such as XPS and TEM tests, for illustration.\n5. 2m ZnSO4/H2O electrolyte can maintain an average coulombic efficiency of 98%. According to this work, the average coulombic efficiency of affinitive additives can reach 99.8%. What is the average coulombic efficiency of shielding and inert additives? It is recommended to provide long-cycle coulombic efficiency data to demonstrate how other additives affect the capacity degradation of anode electrodes during long-term cycling.\n6. To enhance the generality of the proposed affinity additives, the authors are encouraged to evaluate manganese-based cathodes (e.g., MnO₂) in full-cell configurations. This would validate the additives' efficacy across different cathode chemistries.\n7. Please provide the calculation method for mass molar concentration. The author mentioned “BE (2m ZnSO4) was prepared by dissolving 0.02 mol ZnSO4 in 7.48g of H2O”. The mass molar concentration of ZnSO4 seems to be 2.67 m.\n8. The inner Helmholtz plane is inherently defined for ionic species at the interface, making it conceptually inappropriate to use this term for describing the localization of uncharged additives.\n9. The author mentioned “For BE and ERAE, the local solvation sheath remains largely unaltered”. It is quite difficult to understand that the additive does not change the solvation structure of zinc ion in the bulk, but can co-migrate with zinc ion at the interface. The author is suggested to clarify it.\n10. While high-donor-number additives effectively exclude water from the Zn²⁺ solvation sheath, their strong coordination may impede timely desolvation and charge transfer during Zn²⁺ deposition. The author is suggested to provide further investigation into the desolvation kinetics of such additives.\n11. In Figure 1a, the schematic representation of solvent molecules is not labeled.\n12. On page 7, lines 7–11, “Five representative additives from shielding (MeOH), inert (ACN) and affinitive (DMSO, DMU) categories were evaluated at 2 wt% in 0.2 m Na2SO4, and 0.2 m Na2SO4 aqueous solution was adopted as the control electrolyte to eliminate the disturbance of Zn deposition/dissolution in ZnSO4 electrolyte.” The author only present four additives in this description. The author appears to take NSO (an abbreviation not defined in the manuscript) as one of the five additives according to Figure 2a and b, which is confusing. Dipole moment and donor number information of NSO cannot be found in Table S1. The author should check it.\n13. The authors proposed that high-DN and high-μ additives cover the electrode surface, leading to a decrease in electrode capacitance. Figure S15 provides the CV curves of a Zn/Zn symmetric battery. However, the CV curves do not exhibit capacitive behavior; instead, they resemble resistive behavior.\n14. According to the description in the main text, the authors proposed that high-DN and high-μ additives can respond to the electric field, undergoing adsorption and desorption on the electrode under its influence. How were the numerical values of mass change in Figure 2b obtained? The data presented in Figure 2a and Figure 2b, Figure S8-10 appear to show some inconsistencies in their numerical values. The authors are suggested to provide a Table to show the data clearly. The SI provides EQCM data for DMSO, MeOH, and ACN, but please supplement the measurement results for other additives. Furthermore, the authors indicate that the adsorption/desorption of additive molecules is the cause of mass change. Since these molecules have significantly different molecular weights, it is recommended to use the molar amount of adsorption/desorption—rather than the mass change, for comparison.\n15. Equation S5 is not clearly described. For the entire manuscript, it is suggested to use ERAE(X) (e.g., ERAE(DMSO)) to denote specific samples instead of the generic term \"ERAE\". This notation will enhance clarity and avoid ambiguity when referencing different samples."}, "author_response": "We thank the reviewers for their insightful and constructive comments, which have greatly helped us enhance the quality of our manuscript. We have done our utmost to address all concerns raised. For ease of reference, the reviewers’ comments are shown in blue, our responses are given in black.\nResponses to Reviewers:\nTo Reviewer #1: .........................................................................................................................................2-21\nTo Reviewer #2: ...................................................................................................................................... 22-43\nTo Reviewer #3: ............................................................................................................................................. 44\nTo Reviewer #4: ...................................................................................................................................... 45-68\nGeneral Comment: This manuscript reports an affinitive additive strategy for aqueous\nZn metal batteries (ZMBs) that leverages high donor number and dipole moment\nmolecules to enable electric-field-induced interfacial enrichment. Through a\ncombination of in situ spectroscopy (eQCM, ATR-FTIR), molecular dynamics\nsimulations, and electrochemical testing, the authors demonstrate that such additives\ncan dynamically modulate Zn²⁺ solvation and guide uniform Zn deposition, resulting in\na Coulombic efficiency of 99.9% and stable full-cell cycling even at high areal\ncapacities. The work presents a novel angle for electrolyte design that emphasizes\ninterfacial field responsiveness—a dimension often neglected in previous studies.\nHowever, some specific points should be addressed before the manuscript can be\naccepted for publication.\nResponse to Comment: We appreciate your positive assessment of our strategy and\nthe recognition that electric-field responsiveness provides a novel design dimension for\nZn metal batteries. In this revision we substantially expanded both electrochemical and\nmechanistic evidence. Long-term Coulombic efficiency measurements were added for\nall electrolytes, confirming that only electric-field-reinforced affinitive electrolytes\n(ERAE) sustain both high efficiency and long lifetimes. We also re-measured eQCM\nfor all electrolytes in 2 m ZnSO and complemented these with Zn-coated QCM\n4\nexperiments, directly probing adsorption and desorption dynamics at the Zn interface.\nTo strengthen the spectroscopic evidence, we supplemented in-situ ATR-FTIR with\nsurface-enhanced infrared absorption spectroscopy (SEIRAS), which resolves\npotential-dependent vibrational shifts that were not visible before. Finally, we\nincorporated machine-learning validation showing that donor number and dipole\nmoment are the most robust predictors of additive performance under lean loading.\nTogether, these additions establish both the generality and the mechanistic foundation\nof our field-responsive additive strategy.\nComment 1-1: Why was the dielectric constant not chosen as a descriptor, given that\n2\nit directly reflects a molecule’s ability to resist or respond to external electric field\nstrength?\nResponse to Comment 1-1: Thank you for this insightful question. The dielectric\nconstant indeed reflects how a medium responds to an external electric field, largely\ndue to cooperative reorientation among solvent molecules. However, its applicability\nin interfacial systems, such as the electrode-electrolyte double layer, is inherently\nlimited by its dependence on collective solvent behavior and environmental factors. For\ninstance, ε reflects the averaged reorientation of many solvent molecules, which may\nnot directly translate to the local electrostatic interactions occurring at the nanoscale\nelectrode interface. Recent studies have highlighted this discrepancy, showing that ε\ncan vary significantly under confined conditions, such as in double layers (doi:\n10.1016/j.jcis.2023.04.169). In contrast, the dipole moment serves as an intrinsic\nmolecular descriptor that directly quantifies how individual additives interact with\napplied electric fields. Given our objective to assess the responsiveness of additives at\nhighly localized electrode interfaces, μ provides a more suitable primary metric for\nscreening purposes. That said, ε and μ can correlate approximately (Figure R1) and ε\nmay still serve as a complementary parameter; combining μ with selected bulk or\naggregate properties can improve predictive power when screening additives for\npractical electrolytes.\nFigure R1 (for discussion). Dielectric constant vs. dipole moment.\nComment 1-2: Although Zn deposition is excluded during eQCM measurements to\n3\nisolate ion distribution effects, the difference in charge between Na⁺ and Zn²⁺ results in\ndistinct interfacial electric field distributions. Would it be more informative to examine\ninterfacial mass changes within the non-deposition voltage window of Zn²⁺ itself?\nResponse to Comment 1-2: Thank you for this important and constructive suggestion.\nTo address the concern that using Na+ may not fully represent the interfacial field\nproduced by Zn2+, we re-ran the eQCM experiments within the non-deposition voltage\nwindow of Zn2+, as suggested by the reviewer. Using the same electrolyte concentration\nemployed in our performance tests, i.e., BE (2 m ZnSO ), with additives at 2 wt%. All\n4\nmeasurements used the same working electrode and cell geometry as in the main study\nand the CV scan rate was identical to our prior eQCM runs to ensure comparability.\nKey points and findings are summarized below:\n(1) eQCM traces were recorded concurrently with CV and the mass transients were\nanalyzed in the same way as in the original experiments. Each additive class was\ntested in five replicates to ensure reproducibility; the quantitative mass changes and\nstatistical metrics are provided in Table S3 and mass change in Figures 2a and 2b.\n(2) Additives classified as ERAE show pronounced, reversible mass changes that are\nsynchronous with CV potential swings. These mass transients are significantly\nabove baseline noise and show clear field-direction dependence, consistent with\nelectric-field-induced interfacial enrichment. By contrast, inert and shielding\nadditives display only small, near-noise mass variations under the same conditions,\nindicating limited field responsiveness in the presence of Zn2+. The full set of traces\nand averaged mass changes are reported in Figure S9.\n(3) The Zn2+ eQCM findings agree with our SEIRAS, ATR-FTIR and constant-\npotential MD results, all of which indicate field-responsive enrichment and\ninterfacial solvation restructuring for ERAE additives. Overall, these orthogonal\ntechniques provide strong evidence for the mechanistic link between additive\nmolecular properties, field-driven enrichment, and altered interfacial solvation.\nChange list:\nSupplementary Information: Figure S9 and Table S3 have been added.\nFigure 2a (revised). eQCM-measured dynamic mass variation with applied potential\non an Au QCM electrode in 2 m ZnSO and the ERAE(DMU).\nelectrolytes.\nComment 1-3: This paper also focuses on interfacial structural changes induced by\norganic additives. Could the authors more clearly differentiate their interpretation of\ninterfacial dynamic evolution from those previously reported, especially in relation to\nthe cited work: “Deciphering multi-dimensional interfacial mechanisms via organic\ncosolvent engineering for sustainable zinc metal batteries”?\nResponse to Comment 1-3: Thank you for raising this important point. Most previous\nstudies have primarily focused on static interfacial modifications, often requiring high\nadditive or cosolvent loadings to achieve noticeable effects. The cited work\n“Deciphering multi-dimensional interfacial mechanisms via organic cosolvent\nengineering for sustainable zinc metal batteries” advanced this by emphasizing the\ndynamic evolution of interfacial species under cycling. Our work further extends this\nunderstanding by uncovering the driving force behind such interfacial dynamics:\nelectric-field-induced enrichment of additives. By identifying donor number and dipole\nmoment as predictive descriptors, and validating them with machine-learning analysis\nand operando probes, we show that efficient interfacial regulation can be achieved\neven at low additive loadings, offering a more general and scalable electrolyte design\nframework.\nComment 1-4: Should the dynamic interfacial behavior of the electrolyte also account\n6\nfor changes after SEI formation? Wouldn’t this also fall within the scope of “dynamic\ninterfacial structure” as discussed?\nResponse to Comment 1-4: Thank you for this important point. Our results show that\nthe interfacial changes we describe also include the evolution of the surface passivation\nlayer. XPS depth profiling and TEM (Figures S16, S17) reveal that this layer is much\nthinner in ERAE(DMU) than in BE, and XRD (Figure S15) confirms fewer crystalline\nbyproducts. These findings indicate that ERAE(DMU), through field-driven interfacial\nenrichment, effectively suppresses water decomposition and parasitic reactions. Thus,\nthe dynamic interfacial structure in ERAE(DMU) reflects both reversible additive\nadsorption and the restrained formation of Zn2+-rich passivation products, together\nstabilizing Zn deposition.\nChange List:\nMain text: Revised description of “dynamic interfacial structure” to include\nsuppression of parasitic reactions and restrained passivation evolution.\nSupplementary Information: Added Figures S15-S17 (XRD, XPS, TEM).\nFigure S15 (added). XRD of Zn electrodes after 10 cycles.\nERAE(DMU), (b) BE, (c) EWSE(MeOH), and (d) EWIE(SL), each shown at the\nsurface and after 60 nm etching.\nFigure S17 (added). (a) HRTEM image of Zn deposited surface in ERAE(DMU). (b)\nHRTEM image of Zn deposited surface in BE.\nComment 1-5: In Figure 2c, the baseline signals of the two electrolytes in the DEMS\nmeasurements are inconsistent. Could the authors explain this discrepancy?\nResponse to Comment 1-5: Thank you for noting the baseline offset. We found that\nthe original 6 h rest allowed ongoing corrosion in BE to produce continuous H\n2\nevolution, which contributed to an elevated baseline signal. To remove this procedural\nartifact, we first purged the gas lines with carrier gas to displace ambient air, then\n8\nshortened the rest period to 1 h and increased the carrier flow from 1 SCCM to 2 SCCM\nto accelerate purging and minimize residual H . In the revised DEMS traces (Figure\n2\n2c) the H baselines for BE and ERAE(DMU) became nearly identical; the small\n2\nremaining offset is attributable to the greater initial H release from BE during the first\n2\nplating pulse. These results confirm that the original baseline difference arose from\ntesting procedures rather than an intrinsic electrolyte difference.\nChange list:\nMain text: Figure 2c has been updated.\nFigure 2c (revised). H evolution during Zn plating/stripping in a Zn||Cu asymmetric\n2\ncell using the ERAE(DMU) and the BE.\nComment 1-6: In Figure 2d, please indicate the thickness of the highlighted interfacial\nregion (distance from the electrode surface). Additionally, it would be helpful to plot\nthe MD results for the no-bias case alongside for a direct comparison of interfacial\nstructure under different field conditions.\nResponse to Comment 1-6: We thank the reviewer for this helpful suggestion. In the\nrevised manuscript, we have (1) indicated the thickness of the interfacial region in\nFigures 2d, e (5 Å from the electrode surface), and (2) added MD results under no-bias\nconditions for direct comparison (Figures S19, 20). These results show that\nERAE(DMU) molecules exhibit pronounced interfacial enrichment when bias is\n9\napplied, confirming their strong field-responsive behavior. In contrast, EWIE(SL) does\nnot display any noticeable field-induced enhancement, indicating the absence of\nelectrostatic reinforcement. This comparison highlights the essential role of field-\nresponsive interfacial regulation in ERAE, which is not shared by EWIE.\nChange list:\nMain text: Figures 2d, 2e have been revised.\nSupplementary Information: Figures S19, S20 have been added.\nFigure 2(d), (e) MD simulation snapshots of ERAE(DMU) and EWIE(SL) in the EDL\nstructure at the Zn interface with applied bias, respectively.\nFigure S19. MD simulation snapshots of ERAE(DMU) in the EDL structure at the Zn\ninterface without applied bias.\ninterface without applied bias.\nComment 1-7: In Figure 2f, a diagonal separation line could help clarify the\nclassification of additive types. However, since both SL and ACN are considered\nshielding additives, how should their placement and distinction be interpreted?\nResponse to Comment 1-7: We appreciate your suggestion to add a diagonal guideline.\nAfter including the diagonal guideline n (with E-field) = n (without E-field),\nAdditive Additive\nthe pattern becomes clear: the ERAE additives plot above the diagonal, indicating\ngenuine field-driven accumulation, while the majority of inert and shielding additives\nfall at or below the diagonal, indicating no net enrichment under the applied field.\nEWSE(TAA) falls essentially on the diagonal, reflecting its mixed behavior: its high\nDN can promote transient co-migration with Zn2+, but its low μ makes it susceptible to\ndisplacement by interfacial water, so it does not produce sustained enrichment. For this\nreason, we retain TAA’s classification as a shielding-type additive. Regarding SL and\nACN, both are consistently classified as shielding additives since they exhibit no field-\ndriven accumulation; their slightly different placements simply reflect their distinct\nintrinsic DN and μ values, which influence their baseline distributions but not their\nclassification.\nChange list:\nMain text: Figure 2f has been revised.\nMD simulations, with and without an applied electric field.\nComment 1-8: In Figure 1b, the affinitive additives show significantly different\neffectiveness. What other factors besides donor number and dipole moment may\ninfluence their performance?\nResponse to Comment 1-8: This is an insightful question. DN and μ are our primary\ndescriptors, but additive performance can also be influenced by polarity (Dimroth and\nReichardt ET), dielectric constant, molecular size and shape, hydrogen-bonding\npropensity, and bulk self-association. Our data support two mechanistic requirements\nfor interfacial enrichment at low loading: sufficient Zn2+ coordination to enable co-\nmigration from the bulk to the interface, and adequate field responsiveness after\ndesolvation to compete with water in the EDL. DN and μ capture these complementary\nneeds, while orthogonal descriptors help screen edge cases, for example ET for\naggregation tendency, size for steric accessibility, and dielectric measures for collective\nfield response. We updated the parameter set using the latest compilation by Stenutz\nand incorporated ET analysis; ERAE additives fall in an intermediate ET window that\navoids aggregation without imposing excessive desolvation barriers. To further test\ndescriptor importance, we evaluated 12 molecular features with leave-one-out cross-\nvalidation (Figure 1b) (LOOCV); DN plus μ yielded the lowest prediction error,\nsupporting their primacy under lean loading.\nMain text: Added a machine learning analysis (Figure 1b) showing DN & μ as the\noptimal predictor pair; clarified the two mechanistic requirements and the role of\nsecondary descriptors.\nSupplementary Information: Figure S7 has been revised, showing no properties\nalone exhibited clear correlation with stability at 2 wt% additive loading.\nFigure 1b (added). (b) Heatmap of LOOCV RMSE for predicting feature pairs using\nRidge Regression. Each cell in the heatmap represents the prediction error between two\nfeatures. Full names of the abbreviated features are provided in Table S2.\n(c) dielectric constant, (d) Dimorth and Reichardt ET.\nComment 1-9: In Figure 5, only one electrolyte from a Nature-sister journal is used for\ncomparison. Please include additional state-of-the-art electrolyte systems for\nbenchmarking and better contextualization of the current work.\nResponse to Comment 1-9: To address this issue, we expanded Figure 5d and Table\nS6 to benchmark against multiple representative state-of-the-art electrolyte systems.\nThis broader comparison highlights the advantages of our low-dosage, field-responsive\nregulation strategy in achieving efficient interfacial control, low cost, and high\nperformance.\nSpecifically, we incorporated five new benchmark references and included their\nperformance data in Figure 5d and Table S6:\n(Ref. 32) Zhao, R. et al. Lanthanum nitrate as aqueous electrolyte additive for\nfavourable zinc metal electrodeposition. Nat. Commun. 13, 3252 (2022).\n(Ref. 33) Song, Y. et al. Bilateral in-situ functionalization towards ah-scale aqueous\nzinc metal batteries. Nat. Commun. 16, (2025).\n(Ref. 34) Dong, D., Wang, T., Sun, Y., Fan, J. & Lu, Y.-C. Hydrotropic solubilization\nof zinc acetates for sustainable aqueous battery electrolytes. Nat. Sustain. 6, 1474–1484\n(2023).\n(Ref. 35) Zhao, M. et al. Ordered zinc electrodeposition from single-crystal units to\n14\npolycrystalline stacking within solid-electrolyte interphase in battery anodes. Nat.\nCommun. 16, 2843 (2025).\n(Ref. 36) Zhao, X. et al. A self-phase separated electrolyte toward durable and rollover-\nstable zinc metal batteries. J. Am. Chem. Soc. 147, 2714–2725 (2025).\nWe also corrected a previous exchange-rate conversion error. The revised values,\nrecalculated using the new exchange rate, are now presented in the updated Tables S4-\nS7. This correction does not affect the overall conclusions of our study.\nFigure 5d (revised). DOD, CPC and normalized electrolyte cost with previous studies,\nestimated using simplified post hoc calculations.\nComment 1-10: The activation step shown in Figure 5c involves a large number of\ncycles. Could similar Coulombic efficiency (~99.9%) be achieved using the standard\n10-cycle activation protocol?\nResponse to Comment 1-10: According to your suggestion, we repeated the CE\nmeasurement using the standard 10-cycle activation protocol. Under identical\nconditions, ERAE(DMU) delivers an average CE of 99.92% over the 10-cycle window,\nwhereas BE yields 97.82%. This verifies that the ~99.9% CE of ERAE(DMU) is\nintrinsic and reproducible, not an artifact of extended activation.\nChange list:\nMain text: Figure 5c has been revised to show CE measured with the standard 10-\ncycle activation protocol.\nAurbach’s method.\nComment 1-11: The authors attribute deposition behavior to solvation structure effects,\nyet the bulk electrolyte composition remains unchanged. Would it be more accurate to\ndescribe this as an effect of interfacial rather than bulk solvation structure?\nResponse to Comment 1-11: We agree that the deposition behavior is governed\nprimarily by interfacial rather than bulk solvation effects, and this distinction is central\nto our design philosophy. To isolate interfacial phenomena, we intentionally maintained\nthe additive concentration at 2 wt%—a level sufficiently low to minimize perturbation\nof the bulk electrolyte structure and properties. To directly probe these interfacial\nprocesses, we employed a suite of surface-sensitive techniques: in-situ eQCM/QCM to\ntrack interfacial mass changes, in-situ ATR-FTIR and SEIRAS to follow potential-\ndependent vibrational signatures in the EDL, and constant-potential MD to show bias-\ninduced migration and solvation-shell rearrangement. In contrast, bulk diagnostics\n(XANES, ATR-FTIR, ionic conductivity) show only minor changes, confirming that\nthe additive acts predominantly at the interface, the region that directly governs Zn\nnucleation and deposition.\nChange list:\nMain text (page 13, line 9): “interfacial Zn2+ solvation structure plays a critical role\n16\nin governing nucleation behavior, so we next investigated its impact on deposition\nuniformity.”.\nComment 1-12: Throughout the manuscript, terms like “affinitive additives,” “ERAE,”\nand “charge-reinforced” are used somewhat interchangeably. Please standardize this\nterminology to avoid confusion for non-specialist readers.\nResponse to Comment 1-12: Thank you for highlighting this inconsistency. We have\nstandardized terminology across the manuscript to ensure clarity: ERAE (electric-field-\nreinforced affinitive electrolyte), EWIE (electric-field-weakened inert electrolyte), and\nEWSE (electric-field-weakened shielding electrolyte). Specific systems are written as\nERAE(X), EWIE(X), or EWSE(X), for example ERAE(DMU).\nChange list:\nMain text: Terminology unified throughout the main text, figure captions, and\nSupplementary Information; full chemical names and abbreviations consolidated in\nMethods and summarized in Table S1.\nComment 1-13: The color schemes used in Figures S17 and S18 are different, but the\ncaptions for both state \"varying from yellow in plating to purple in stripping,\"\nwhich may cause confusion.\nResponse to Comment 1-13: Thank you for pointing out the caption inconsistency. We\ncorrected the captions so that the color-scale description matches the plotted data and\nthe plating-to-stripping sequence. The revised wording states that lighter shades\ncorrespond to plating and darker shades to stripping, in both ERAE(DMU) and BE.\nChange list:\nSupplementary Information (page 17, line 8): “In-situ FTIR spectra and absolute\nabsorbance collected during the initial Zn-plating/stripping in the ERAE(DMU) with\nthe color scale varies from light shades during plating to dark shades during\nstripping. … in the BE with the color scale varies from light shades during plating to\n17\ndark shades during stripping.”.\nComment 1-14: In the Figure 3 c schematic illustrations, organic additives are\nconsistently shown occupying the first solvation sheath of Zn²⁺, which may lead to the\nmisconception that all additives fully displace water. Please consider revising or\nreducing the number of such diagrams to avoid overgeneralization.\nResponse to Comment 1-14: This is a very helpful point. We revised Figure 3c to\ndepict partial, not complete, occupation of the Zn2+ first solvation shell by organic\nadditives and to emphasize competitive adsorption with water. We also streamlined the\nschematic to avoid redundancy. This presentation aligns with our in-situ FTIR and\nSEIRAS results, which indicate that additives restructure the interfacial solvation\nenvironment without fully displacing water.\nChange list:\nMain text: Figure 3c has been revised and the accompanying text updated to clarify\npartial occupation and additive-water competition in the interfacial solvation shell.\nFigure 3c (revised). Schematic of ERAE regulation mechanism for organic-rich\ninterface.\nComment 1-15: The Figure 3d-f suggests that affinitive additives can effectively\nreplace water molecules in the Zn²⁺ solvation shell and that their large molecular size\nlimits their access to carbon pores. In such cases, are the remaining coordination sites\nof Zn²⁺ left unsolvated (“naked”)?\nResponse to Comment 1-15: This is a very good question. Zn2+ remains fully\n18\ncoordinated in both electrolytes; the difference lies in the ligand composition of the first\nshell. In BE, Zn2+ is coordinated by about six H O molecules. In ERAE(DMU), the\n2\naverage hydration number decreases to roughly 2.5, indicating partial replacement of\nwater by DMU. All coordination sites remain occupied by water or additive, and no\nnaked Zn2+ is present.\nFigure 3f. Solvated Zn2+ ions show organic exclusion in ERAE and water penetration\nin BE within mesoporous carbon.\nComment 1-16: While the current in-situ FTIR setup provides valuable information, it\nlacks surface enhancement, which limits its ability to directly resolve interfacial\nstructural changes. Would the authors consider employing surface-enhanced techniques\nto strengthen this aspect of the work?\nResponse to Comment 1-16: Thank you for your valuable suggestion. To enhance the\nsensitivity of our in-situ vibrational measurements to interfacial species, we have\ncomplemented ATR-FTIR data with surface-enhanced infrared absorption spectroscopy\n(SEIRAS) using a gold-coated ATR. SEIRAS resolves potential-dependent shifts and\nintensity changes in the DMU ν(C=O) and δ(N-H) modes that were barely discernible\nin ATR-FTIR, providing direct evidence for electric-field-responsive adsorption at the\ninterface. Together with ATR-FTIR tracking of H O and SO 2-, these results show that\n2 4\nthe spectral changes arise from field-driven DMU adsorption and interfacial solvation\nreorganization.\nMain text: Added SEIRAS results and interpretation to the Results.\nSupplementary Information: Added Figures S23, S24, updated Methods to describe\nthe SEIRAS setup and protocol.\nFigure R2 (for discussion). Optical photograph of a gold coated silicon crystal\nsubstrate used for surface enhanced infrared measurements.\nFigure S23 (added). Schematic of surface-enhanced Fourier transform infrared\nspectroscopy (SEIRAS).\nERAE(DMU) in the range of 1550-1510 cm-1.\nGeneral Comment: In this work, the author used affinitive additive with high donor\nnumber and dipole moment to modulate Zn2+ solvation and the structure of the electric\ndouble layer under operational electric fields and to promote the stability of anode in\nzinc-ion batteries.\nAlthough the electric-field-induced interfacial enrichment facilitates uniform Zn\ndeposition and long-term cycling life of batteries, this work still followed traditional\nelectrolytes papers in zinc battery filed, illustrating additive with different donor\nnumber or dipole moment. The novelty or performance are not significant and\nsatisfactory. In addition, the overall quality of this manuscript cannot meet the standards\nof this journal as well. The reviewers don't recommend further consideration of this\nwork. Some detailed comments are as follows.\nResponse to Comment: We appreciate the concerns raised regarding the novelty,\nperformance, and overall impact of our study. In response, we have undertaken a\ncomprehensive revision—expanding both the conceptual framework and the\nexperimental foundation—to more clearly articulate the paradigm shift our work\nrepresents in electrolyte design for aqueous zinc metal batteries.\nWe fully acknowledge that many prior studies have explored additives based on donor\nnumber (DN) or dipole moment (μ). However, the core novelty of this work lies not\nmerely in the use of such parameters, but in establishing a field-driven, dynamic\ninterfacial regulation principles that fundamentally rethink how electrolyte additives\nfunction under operational conditions. Below, we outline the key advances that\ndistinguish our approach from conventional additive-based strategies.\n(1) Conceptual advance: field-responsive, low-loading interfacial regulation.\nTraditional electrolyte engineering typically relies on static strategies—e.g., high-\nconcentration salts or organic cosolvents—to suppress water activity. In contrast, our\nwork introduces electric-field-reinforced affinitive electrolyte (ERAE), which exploit\n22\nthe in situ electric field as an active driving force to enable reversible, potential-\ndependent interfacial enrichment of functional additives at ultra-low loadings (2\nwt%). This represents a conceptual advance:\n(1) Instead of relying on static adsorption, ERAEs enable on-demand, field-driven\nadsorption and desorption.\n(2) Interfacial control is decoupled from bulk composition, minimizing side effects\non ionic conductivity and cost.\n(3) The process is inherently dynamic and responsive to operational conditions—\naligning with real-world battery cycling.\n(2) Predictive, validated selection rule.\nWe introduce a dual-parameter descriptor (DN and μ) that captures the two\nmechanistic requirements at lean loading: sufficient Zn2+ coordination to co-migrate to\nthe interface and adequate field responsiveness to compete with water in the EDL.\nUniversality is supported by long-term CE screening of all additives at 2 wt% and\nsymmetric-cell lifetimes at 1 and 3 wt%. To validate the generality and robustness of\nthis descriptor, we conducted a machine learning-guided leave-one-out cross-\nvalidation (LOOCV) across 12 molecular features (including ET, polar surface area,\ndielectric constant, etc.). The DN–μ pair achieved the lowest prediction error,\nconfirming its primacy in forecasting additive performance (Figure 1b, Table S2).\n(3) Direct operando proof under realistic conditions with competitive performance.\nIn-situ surface-enhanced infrared absorption spectroscopy (SEIRAS) resolves\npotential-dependent DMU bands at the interface; eQCM in 2 m ZnSO and Zn-coated\nPractically, ERAE(DMU) delivers near-unity CE with the standard 10-cycle activation,\nlong symmetric-cell lifetimes at 60% DOD, demonstrating both mechanistic novelty\nand performance significance.\nPerformance clarification:\nTo address the performance concern, we added standardized, head-to-head benchmarks.\nsustains 700 h Zn||Zn operation at 60% DOD, and enables stable full-cell cycling with\nV O and ZnI at low N/P. We further benchmarked against representative electrolytes\n6 13 2\nusing comparable metrics: for symmetric cells, we compared depth of discharge,\nelectrolyte price, and cumulative plating capacity (CPC) (Table S6); ERAE(DMU)\nachieves higher CPC at higer DOD while maintaining a lower electrolyte cost. For full\ncells, we compared electrolyte price and cumulative discharge capacity (CDC)\n(Table S7); ERAE(DMU) delivers higher CDC per electrolyte cost, indicating superior\nprice-normalized energy throughput.\nMajor experimental additions:\nMachine-learning cross-check (Figure 1b): Leave-one-out analysis over 12 features\nidentifies DN plus μ as the most predictive pair, validating the selection rule.\nInterfacial mass probes under realistic Zn2+ conditions (Figures 2a, 2b and S9-S12):\neQCM in 2 m ZnSO and QCM on Zn-coated sensors, completed for all electrolytes,\n4\nshowing reversible, field-driven interfacial adsorption for ERAE.\nSEIRAS at the interface (Figures S23, S24): Directly resolves potential-dependent\nν(C=O) and δ(N–H) of DMU, giving operando proof of field-responsive adsorption.\nElectrochemical benchmarks under standard protocols (Figures 5c, S5, S6, S33-\nS36): Near-unity CE for ERAE(DMU) with the 10-cycle activation protocol,\nsymmetric-cell lifetimes at 60% DOD across 1, 2, and 3 wt% additive loadings, and\nlong-term CE screening of all additives.\nFar from following a conventional additive-screening approach, this work establishes a\nnew framework for electrolyte design: dynamic, field-responsive, low-loading\ninterfacial regulation guided by mechanistic descriptors. We believe the\nstrengthened manuscript—now supported by direct operando evidence, predictive\nmodeling, and rigorous performance benchmarks—demonstrates clear novelty,\nscientific depth, and broad relevance that meet the standards of Nature\nFigure 1a (revised). Schematic illustration of the interfacial behavior of shielding, inert\nand affinitive additives at the Zn interface under an applied electric field.\nFigure 1b (added). LOOCV heatmap of pairwise descriptor root mean square error\n(RMSE).\nstate-of-the-art reported aqueous electrolytes for AZBs.\nCPC\nNormalized electrolyte price DOD\n(mAh Ref.\n(USD$ kg-1) (%)\ncm-2)\n3.77 30 1418 this work\n3.77 60 1235 this work\n3.77 70 935 this work\n3.77 80 734 this work\n167.21 26 250 10.1002/ange.202218452\n274.25 8.5 225 10.1002/anie.202410210\n10.1038/s41467-023-\n164.16 8.2 1000\n38460-2\n113.32 20 939 10.1002/adma.202405889\n25.8 0.2 750 10.1002/ange.202316499\n10.1038/s41893-023-\n196 17.1 1000\n01092-x\n5.54 30 500 10.1021/jacs.2c00551\n10.1038/s41467-022-\n22.83 80 225\n30939-8\n10.1038/s41467-025-\n29.46 80 100\n58153-2\n10.1038/s41893-023-\n13.24 0.8 300\n01172-y\n10.1038/s41467-025-\n211.56 85 200\n58063-3\n1048.36 0.3 250 10.1021/jacs.4c15132\ndischarge capacity in this work and state-of-the-art reported aqueous electrolytes for\nAZBs.\nNormalized electrolyte price CDC (mAh\nRef.\n(USD$ kg-1) cm-2)\n3.77 2625 this work\n274.25 57 10.1002/anie.202410210\n10.1038/s41467-023-\n164.16 1000\n38460-2\n113.32 480 10.1002/adma.202405889\n25.8 1260 10.1002/ange.202316499\n10.1038/s41893-023-\n196 1320\n01092-x\n5.54 80 10.1021/jacs.2c00551\n10.1038/s41467-022-\n22.83 1330\n30939-8\n10.1038/s41467-025-\n29.46 900\n58153-2\n176.3 270 10.1021/jacs.4c16880\n13.22 280 10.1002/anie.202400337\nmolecule. And the full name of all molecules should be given.\nResponse to Comment 2-1: Thank you for this careful observation. We have now\nexplicitly added N,N-dimethylurea (DMU) in the Abstract and Introduction as the\nrepresentative high-donor-number, high-dipole-moment additive that exemplifies our\nelectric-field-reinforced affinitive electrolyte (ERAE) design. In addition, we\nstandardized terminology throughout the manuscript as ERAE (electric-field-\nreinforced affinitive electrolyte), EWIE (electric-field-weakened inert electrolyte), and\nEWSE (electric-field-weakened shielding electrolyte), ensuring that the full names\nappear at first mention. Full chemical names and abbreviations for all additives are also\nprovided in the Methods section and summarized in Table S1. These revisions improve\nclarity and consistency while addressing your concern.\nChange List:\nMain text: Added N,N-dimethylurea (DMU) to the Abstract and Introduction as the\nrepresentative ERAE additive. Standardized terminology with full names at first\nmention (ERAE, EWIE, EWSE) and updated corresponding captions/text passages.\nSupplementary Information: Provided full chemical names and abbreviations for all\nadditives in the Methods section and summarized them in Table S1.\nComment 2-2: In figure 1c, author should list the colored balls represented elements.\nResponse to Comment 2-2: Thank you for pointing this out. In the revised version, we\nadded element symbols of Figure 1c (revised as Figure S8) directly in the caption for\nclarity (O, red; C, brown; N, blue; H, white). To avoid ambiguity elsewhere, we also\nchecked all other schematics to ensure atom types are consistently labeled.\nChange list:\nMain text: Figure 1c has been revised as Figure S8.\nSupplementary Information: The caption of Figure S8 has been updated to explicitly\nlist the element symbols (O, red; C, brown; N, blue; H, white).\nbrown; N, blue; H, white).\nComment 2-3: For eQCM, the sensor is gold sensor or author put zinc electrode on the\nsensor? If author want to claim the good adsorption of DMU on zinc, it would be better\nto attach the zinc foil on the sensor.\nResponse to Comment 2-3: We sincerely thank you for this insightful suggestion. The\ninterfacial behavior of additives on Au may not fully represent their adsorption on Zn.\nDirect Zn plating onto QCM sensors, however, introduces significant challenges: Zn\ndissolution and hydrogen evolution (HER) in aqueous electrolytes generate large, non-\nfaradaic mass fluctuations that can obscure the subtle, reversible mass changes\nassociated with molecular adsorption. To address this, we revised our approach in two\nways. First, we repeated the eQCM measurements in 2 m ZnSO within a non-\n4\ndeposition potential window (0-0.6 V vs. Ag/AgCl), which avoids Zn plating/stripping\nand HER while preserving realistic interfacial fields. Second, following your\nrecommendation, we prepared Au sensors with a thin sputtered Zn coating and repeated\nthe QCM tests. Overall, these results confirm that the reversible mass changes observed\nin eQCM mainly reflect dynamic, field-driven adsorption/desorption rather than stable\nfilm formation.\nChange list:\nMain text: Figures 2a and 2b were replotted with new eQCM data collected in 2 m\n4\npicture of adsorption/desorption behavior.\nSupplementary Information: The eQCM methodology section was revised to clarify\nthat Figures 2b and S9 reflects measurements in the non-deposition potential window.\nAdditional Zn-coated QCM (Figure R3) results have been added as Figures S10-S12.\nFigure 2a (revised). eQCM-measured dynamic mass variation with applied potential\non an Au QCM electrode in 2 m ZnSO and the ERAE.\nelectrolytes.\nFigure R3 (for discussion). Optical photograph of QCM sensors. Top, bare Au sensor;\nbottom, Zn-coated sensor prepared by magnetron sputtering.\nDMAC, NMP, MF).\nFigure S11 (added). QCM mass transients for EWSE additives (TAA, TBA, MeOH,\nTEP, TMP, EG).\nFigure S12 (added). QCM mass transients for EWIE additives (ACN, SL).\nComment 2-4: In figure 2f, why for the inert molecules, the number of them without\nE field is much higher than them with E field. They are inert molecules, not shielding.\nResponse to Comment 2-4: Thank you for raising this point. The apparent higher\n32\ncounts of inert molecules without bias arose from the asymmetric axis range used in the\noriginal plot. We corrected this in the revised version of Figure 2f and added a diagonal\nreference line n (with E-field) = n (without E-field) to guide interpretation.\nAdditive Additive\nWith these adjustments, the trends are clear: ERAE lie well above the diagonal,\nindicating field-driven enrichment, while EWIE and EWSE fall on or below it due to\ninsufficient DN and μ.\nChange list:\nMain text: Figure 2f was revised with corrected axis scaling and a diagonal reference\nline, and the corresponding discussion was updated for clarity.\nFigure 2f (revised). Quantification of additive distributions within the EDL based on\nMD simulations, with and without an applied electric field.\nComment 2-5: What does this mean in figure s17, s18, “ with the color of the spectra\nvarying from yellow in plating to purple in stripping”\nResponse to Comment 2-5: Thank you for pointing this out. The original captions for\nFigures S17 and S18 (revised as Figures S21, S22) were inconsistent with the actual\ncolor scales used. We have corrected this in the revised version: the spectra now vary\nfrom lighter shades during plating to darker shades during stripping. All figure legends\nand the caption list have been checked to ensure consistency.\nChange list:\nS21 and S22) corrected to accurately describe the color scale.\nComment 2-6: Why for DMF, DMSO, the number of additive molecules in the Zn2+\nsolvation shell without E field are higher than them with E field. The calculation should\nbe double checked.\nResponse to Comment 2-6: Thank you for this insightful question. After rechecking\nthe analysis, we identified the origin of this behavior: poor statistical sampling in the\nfield-free (zero-bias) condition, not an error in calculation. In the absence of an electric\nfield, the local Zn2+ density near the electrode is very low (Figure R4), resulting in a\nsmall number of interfacial ion events. This leads to high relative uncertainty in the\ncomputed coordination numbers for additives like DMF and DMSO, which are present\nat only 2 wt% loading. In contrast, under an applied electric field, the Zn2+ ions are\ndriven toward the interface, significantly increasing their interfacial concentration and\nthe number of sampled events. This yields much more reliable statistics and reveals the\ntrue trend: field-enhanced accumulation of affinitive additives (e.g., DMU) in the EDL\nand their partial displacement of H O in the Zn2+ solvation shell.\nanalysis in the manuscript to compare: bulk solvation structure (no field)—well-\nsampled, volume-averaged coordination numbers, and EDL solvation structure (with\nfield)—interfacial coordination under operational conditions. This approach avoids the\npitfalls of comparing poorly converged interfacial counts in low-density regimes. With\nthis correction, the results clearly show that only ERAE additives participate in the\ninterfacial Zn2+ solvation under an electric field, displacing water and modifying\nsolvation structure—while non-ERAE additives remain excluded.\nChange List:\nMain text: Figure 3h has been revised to report bulk (no field) versus EDL (with field)\nsolvation numbers, and the accompanying text has been updated accordingly.\nand without applied field.\nFigure 3h (revised). Number of additive molecules in the Zn2+ solvation shell from\nMD simulations under field-free and electric field conditions.\nComment 2-7: Relevant XRD results of cycled zinc electrode should be tested.\nResponse to Comment 2-7: We appreciate this helpful suggestion. We have now\ncarried out XRD characterization of cycled Zn electrodes (Figure S15). The results\nshow clearly fewer byproducts in ERAE(DMU) compared with BE, indicating\nsuppressed parasitic reactions. This is further supported by XPS depth profiling (Figure\nS16), which reveals a thinner Zn2+-rich surface layer in ERAE(DMU), and by TEM\nobservations (Figure S17), where only a negligible amorphous interfacial layer is\n35\nobserved in ERAE(DMU) versus a thicker (~3.2 nm) layer in BE. Taken together, XRD,\nXPS, and TEM consistently demonstrate that ERAE(DMU) effectively suppresses side\nreactions, leading to fewer crystalline byproducts and a much thinner passivation layer.\nChange List:\nMain text: Added discussion of cycled-electrode characterizations, highlighting\nsuppressed parasitic reactions and thinner passivation in ERAE(DMU).\nSupplementary Information: Added new XRD results of cycled Zn electrodes\n(Figure S15). Added interpretation of Figures S16, S17 to emphasize the consistency\nof evidence for reduced byproduct formation and passivation thickness in\nERAE(DMU).\nFigure S15 (added). XRD of Zn electrodes after 20 cycles.\nERAE(DMU), (b) BE, (c) EWSE(MeOH), and (d) EWIE(SL), each shown at the\nsurface and after 60 nm etching.\nFigure S17 (added). (a) HRTEM image of Zn deposited surface in ERAE(DMU). (b)\nHRTEM image of Zn deposited surface in BE.\nResponse to Comment 2-8: According to your suggestion, we have carried out self-\ndischarge tests on the baseline electrolyte (BE) for direct comparison with\nERAE(DMU). In these experiments, cells were charged to 1.6 V, held under open-\ncircuit conditions for 24 h, and then discharged. The BE cell retained only 56.4% of its\ncharge after 24 h, while the ERAE(DMU) cell retained 92.9%. These results confirm\n37\nthat ERAE(DMU) substantially suppresses self-discharge relative to BE.\nChange List:\nSupplementary Information: Added new self-discharge data in Figure S40 and\ncorresponding description.\nFigure S40 (revised). Self-discharge analysis of the cells in the ERAE(DMU) and BE.\nGeneral Comment: We would like to point it out that, the overall electrochemical\nmeasurements and analyses are not sufficient and quite routine, hardly generating\nsufficient data and results for deep analysis of the mechanisms. Besides, there are not\nsufficient direct and solid evidence to support the authors' claims on the mechanisms.\nResponse to Comment: Thank you for raising this important point. In this revision,\nwe have significantly expanded both the electrochemical dataset and the mechanistic\nvalidation to ensure that our conclusions are supported by rigorous and non-routine\nevidence. Below, we outline the key enhancements that collectively address the\nconcerns regarding data depth and mechanistic rigor.\n(1) Expanded Electrochemical Measurements and Analyses.\nWe added long-term Coulombic efficiency traces across all electrolytes (Figures S33-\n36) and performed symmetric-cell cycling at different additive concentrations (1 wt%\nand 3 wt%) (Figures S5, S6). These systematic results confirm that the ERAE strategy\ndelivers reproducible improvements in Zn reversibility and stability under diverse\n38\ntesting conditions, going beyond standard electrochemical characterization.\n(2) Direct and Solid Mechanistic Evidence.\nTo strengthen mechanistic understanding, we complemented the original ATR-FTIR\nwith additional surface-sensitive and field-aware probes. In-situ surface-enhanced\ninfrared absorption spectroscopy (SEIRAS) (Figures S23, S24, R2) provides direct\nvibrational evidence of field-responsive DMU adsorption. We also extended eQCM\ntests to all electrolytes (Figures 2b and S9), now using 2 m ZnSO as the baseline\n4\nelectrolyte to more closely mimic realistic conditions. Furthermore, QCM\nmeasurements (Figures S10-S12) with Zn-coated Au sensors (Figure R3) were carried\nout to better approximate the real Zn surface. These experiments consistently\ndemonstrate that affinitive additives undergo field-driven adsorption/desorption at the\ninterface, validating the mechanistic framework.\nThe revised manuscript no longer relies on routine electrochemical tests or indirect\ncorrelations. Instead, it integrates systematic performance benchmarks, operando\nspectroscopic validation, and interfacial mass sensing on Zn-relevant surfaces to\nbuild a mechanistically grounded, experimentally rich narrative. We believe these\nsubstantial additions fully address your concerns and elevate the work to meet the\nstandards of mechanistic depth expected in Nature Communications.\nDMF, DMAC, DMU) at 1 mA cm−2 and 1 mAh cm−2.\nFigure S34 (added). Zn plating/stripping CE for EWSE additives (TAA, TBA, TEP,\nTMP, EG, MeOH) at 1 mA cm−2 and 1 mAh cm−2.\nFigure S35 (added). Zn plating/stripping CE for EWIE additives (ACN, SL) at\n1 mA cm−2 and 1 mAh cm−2.\nelectrolytes.\nFigure S5 (revised). Symmetric cell cycling performance of Zn||Zn cells in electrolytes\ncontaining 1 wt% and 3 wt% additives: (a) ERAE, (b) EWSE, and (c) EWIE.\nmoment for 14 additives at the concentration of (a) 1 wt%, (b) 3 wt%.\nFigure R2 (for discussion). Optical photograph of a gold coated silicon crystal\nsubstrate used for surface enhanced infrared measurements.\nFigure S23 (added). Schematic of surface-enhanced Fourier transform infrared\nspectroscopy (SEIRAS).\nERAE(DMU) in the range of 1550-1510 cm-1.\nGeneral Comment: I co-reviewed this manuscript with one of the reviewers who\nprovided the listed reports. This is part of the Nature Communications initiative to\nfacilitate training in peer review and to provide appropriate recognition for Early Career\nResearchers who co-review manuscripts.\nResponse to Comment: Thank you very much for your time and effort in assisting\nwith the review. We note that you did not provide specific scientific comments, but we\ntruly appreciate your contribution to the peer-review process. For your reference, the\nmajor revisions we implemented are summarized below:\n(1) Extended validation of the DN–μ selection rule:\nWe expanded CE and symmetric-cell tests (including 1 wt% and 3 wt% concentrations)\nand complemented these with machine-learning analysis of 12 molecular descriptors,\nwhich rigorously confirmed DN and μ as the optimal pair.\n(2) Direct interfacial evidence:\nWe added in-situ surface-enhanced infrared spectroscopy (SEIRAS) spectra resolving\nfield-driven DMU adsorption, and extended eQCM/QCM tests in 2 m ZnSO and Zn-\n4\ncoated electrodes to better mimic real interfacial conditions.\n(3) Improved clarity:\nWe standardized terminology and refined figures and captions to enhance readability\nand emphasize interfacial versus bulk effects.\nThese revisions collectively enhance both the scientific breadth and mechanistic rigor\nof the study, ensuring that our conclusions are supported by systematic data and direct\nevidence.\nGeneral Comment: The authors herein developed an electric-field-reinforced\naffinitive additive strategy for aqueous Zn metal batteries, leveraging high DN and μ to\ncreate an electrolyte that dynamically responds to applied fields. The use of descriptors\nand MD theory calculations to develop electrolyte additive strategies has scientific\nsignificance. The mechanism of double-layer and solvation, as well as the description\nof morphology and electrochemical performance, are complete and clear, but the\nelectrochemical performance is not outstanding enough, and there is relatively little\nchemical analysis of the microstructure of the anode and cathode surface. I would\nsuggest a major revision based on the following comments:\nResponse to Comment: We sincerely thank you for your thoughtful evaluation and for\nrecognizing the scientific significance of our electric-field–reinforced affinitive\nelectrolyte (ERAE) strategy, particularly the rational use of donor number (DN) and\ndipole moment (μ) as molecular design descriptors, the integration of MD simulations,\nand the mechanistic clarity regarding double-layer restructuring and solvation\ndynamics.\nWe fully agree with your assessment that the initial submission could be strengthened\nby more robust electrochemical benchmarks and deeper chemical analysis of\nelectrode interfaces. In this revised manuscript, we have comprehensively addressed\nthese points through a series of targeted experiments and analyses that significantly\nenhance both the practical relevance and mechanistic foundation of our work. On the\nelectrochemical side, we have added long-term Coulombic efficiency data across all\nelectrolytes and extended symmetric-cell cycling to 1 wt%, 2 wt%, and 3 wt%\nconcentrations. In addition, we introduced machine learning analysis across 12\nmolecular descriptors, which rigorously validated DN and μ as the optimal feature pair\nfor predicting additive effectiveness, further supporting the design principle. Full-cell\nstudies were also expanded to establish practical relevance. To strengthen mechanistic\nevidence, we incorporated in-situ surface-enhanced infrared absorption spectroscopy\n(SEIRAS), which provides direct vibrational proof of field-driven DMU adsorption,\n45\nand broadened the QCM dataset by re-running eQCM in 2 m ZnSO and performing\ndetailed surface analyses of cycled electrodes, including XPS, TEM, and XRD,\nshowing that ERAE(DMU) produces fewer byproducts and suppresses side reactions,\nconsistent with its improved reversibility.\nThese substantial additions provide comprehensive electrochemical validation,\nmechanistic reinforcement from spectroscopy and QCM, robust statistical support from\nmachine learning, and direct surface chemical evidence, substantially strengthening\nboth the performance and novelty of our strategy.\nFigure 1b (added). LOOCV heatmap of pairwise descriptor root mean square error\n(RMSE).\nFigure R2 (for discussion). Optical photograph of a gold coated silicon crystal\nsubstrate used for surface enhanced infrared measurements.\nspectroscopy (SEIRAS).\nFigure S24 (added). In situ ATR-SEIRAS spectra under various potentials for the\nERAE(DMU) in the range of 1550-1510 cm-1.\nwith each additive introduced at a fixed concentration of 2 wt%. Why is the\nconcentration 2 wt%? Do other concentrations also follow the general pattern of DN\nand μ?\nResponse to Comment 4-1: Thank you for raising this point. We chose 2 wt% as a\npractical compromise: it is low enough to minimize bulk perturbation while still\nproviding clear interfacial signatures. At this concentration, ERAE(DMU) achieves\noptimal performance without altering bulk electrolyte properties.\nTo address your concern on concentration dependence, we repeated the screening at 1\nwt% and 3 wt%. The results show that the DN-μ correlation is robust across this\nconcentration window: additives with both high DN and high μ consistently promote\ninterfacial enrichment and extend cycle life, whereas low-DN or low-μ additives remain\nineffective. These findings confirm that the descriptor-guided design principle does not\nrely on a single optimized loading but applies generally under lean additive conditions.\nChange list:\nSupplementary Information: Added Figures S5 showing symmetric-cell lifetimes for\nall additives at 1 wt% and 3 wt%, and updated DN-μ correlation plots in Figure S6 to\ninclude these datasets.\nFigure S5 (revised). Symmetric cell cycling performance of Zn||Zn cells in electrolytes\n48\ncontaining 1 wt% and 3 wt% additives: (a) ERAE, (b) EWSE, and (c) EWIE.\nFigure S6 (revised). Cycle life at 60% DOD plotted against donor number and dipole\nmoment for 14 additives at the concentration of (a) 1 wt%, (b) 3 wt%.\nComment 4-2: According to this paper, affinity additives need to balance DN and μ,\nbut \"DMU and MF emerged as the promising candidates (Figure 1c)\" mentions that\nusing MF and DMU as candidates. Figure 1c tells MF seem to be not as good as DMSO.\nWhy does the author take MF and DMU as the two promising candidates? In addition,\nMF was not used in the characterization of the double layer and solvation structure,\nwhile DMSO and DMU were used to evaluate adsorption and desorption. Why?\nResponse to Comment 4-2: Thank you for this careful question. DMU and MF were\ninitially highlighted because both satisfy the DN-μ criterion and thus represent the\nERAE class. However, subsequent evaluation considered more than just descriptor\nvalues. DMU combined favorable DN-μ characteristics with good electrochemical\nperformance in our initial screening, and it is also relatively benign to handle, which\nmade it the most appropriate candidate for detailed interfacial and spectroscopic studies.\nMF, although meeting the DN-μ threshold, showed weaker practical performance and\npresents toxicity and handling issues, so it was not selected for deeper analysis.\nDMSO was included because it is a widely studied coordinating additive for Zn systems,\nproviding a useful benchmark that links our results to the broader literature. In this\nrevision, we also repeated eQCM experiments for all additives in 2 m ZnSO baseline\n4\nelectrolyte. These results confirm that ERAE exhibit clear field-responsive interfacial\nadsorption, whereas EWIE and EWSE show negligible or unstable adsorption, thereby\n49\nsupporting our mechanistic conclusions.\nChange list:\nMain text: Updated with new eQCM data collected in 2 m ZnSO BE, covering all\n4\nadditives. Figures 2a and 2b were revised accordingly.\nSupplementary Information: Added detailed eQCM datasets for all additives (Figure\nS9, Table S3).\nFigure 2a (revised). eQCM-measured dynamic mass variation with applied potential\non an Au QCM electrode in 2 m ZnSO and the ERAE(DMU).\n50\nelectrolytes.\nFigure S9 (revised). eQCM mass transients for (a) ERAE, (b) EWSE and (c) EWIE.\nComment 4-3: This work believes that ideal additives have high zinc ion binding\naffinity and strong electric field responsiveness, which can accumulate at the interface\nand actively recombine zinc ion solvation under on-site conditions. The author should\nprovide HOMO and LOMO for the three categories of additives (affinity additives,\nshielding additives, and inert additives), as well as the binding energy between additive\nmolecules and zinc ions, to verify the advantages of ideal additives with high zinc ion\nbinding affinity and strong electric field responsiveness from the perspectives of\nmolecular reactivity and binding energy.\nResponse to Comment 4-3: We sincerely thank the reviewer for this valuable\nsuggestion, we have added frontier orbital analyses (HOMO/LUMO isosurfaces and\nenergies) and calculated Zn2+-additive binding energies for all three categories of\nadditives. These results provide molecular-level evidence supporting our design\nprinciple. ERAE additives show higher LUMO energies than H O, indicating reduced\n2\nsusceptibility to cathodic reduction at the Zn anode. In addition, ERAE additives exhibit\nstronger Zn2+ binding energies than EWIE, EWSE, or H O, consistent with their higher\n2\ndonor numbers and confirming their ability to participate in interfacial solvation.\nThese results demonstrate that high DN and high μ not only promote field-driven\nenrichment but also correlate with electronic stability and stronger Zn2+ coordination.\nSupplementary Information: Added Figures S1-S3 presenting HOMO/LUMO\nisosurfaces, orbital energy levels, and Zn2+-additive binding energies.\nFigure S1 (added). HOMO isosurfaces for 14 representative additives.\nFigure S2 (added). LUMO isosurfaces for 14 representative additives.\nFigure R5 (for discussion). Computed Zn2+-additive binding energies (Eb).\nComment 4-4: What are the effects of affinity additives, shielding additives, and inert\nadditives on the composition and morphology of negative SEI and positive CEI?\nIt is recommended that the author provide characterizations, such as XPS and TEM tests,\nfor illustration.\nResponse to Comment 4-4: Thank you for this insightful suggestion. To address it, we\nadded systematic ex situ characterizations of both anode and cathode interfaces.\n(1) Zn anode. Depth-profiled Zn 2p XPS spectra (Figure S16) reveal that the Zn2+/Zn0\n53\nratio at the surface is much lower in ERAE(DMU) compared with BE, confirming\nfewer oxidized by-products. High-resolution TEM (Figure S17) further shows that\nBE develops a heterogeneous passivation layer of ~3.2 nm, whereas ERAE(DMU)\nmaintains a much cleaner and more uniform surface without a continuous insulating\nfilm. Complementary XRD analysis (Figure S15) also indicates markedly fewer\ncrystalline by-products in ERAE(DMU).\n(2) Cathode. XPS of cycled MnO electrodes (Figure S43) demonstrates weaker Zn\n2\n2p and Zn 2p signals in ERAE(DMU) compared with BE, suggesting reduced\n3/2 1/2\nZn-containing by-product deposition and more reversible Zn2+ intercalation.\nOverall, these results confirm that the interfacial stabilization arises from suppressed\nparasitic reactions rather than conventional SEI/CEI formation, with ERAE(DMU)\nproducing far fewer inorganic by-products and thinner passivation layers than BE.\nChange List:\nMain text: Revised discussion to include systematic interfacial characterization,\nhighlighting that ERAE(DMU) suppresses by-product formation and maintains cleaner\nelectrode surfaces.\nSupplementary Information: Added Figure S14-16, S44 to provide a comprehensive\ncomparison of interfacial composition and morphology.\nFigure S15 (added). XRD of Zn electrodes after 10 cycles.\nERAE(DMU), (b) BE, (c) EWSE(MeOH), and (d) EWIE(SL), each shown at the\nsurface and after 60 nm etching.\nFigure S17 (added). (a) HRTEM image of Zn deposited surface in ERAE(DMU). (b)\nHRTEM image of Zn deposited surface in BE.\nComment 4-5: 2m ZnSO4/H2O electrolyte can maintain an average coulombic\nefficiency of 98%. According to this work, the average coulombic efficiency of\naffinitive additives can reach 99.8%. What is the average coulombic efficiency of\nshielding and inert additives? It is recommended to provide long-cycle coulombic\nefficiency data to demonstrate how other additives affect the capacity degradation of\nanode electrodes during long-term cycling.\nResponse to Comment 4-5: Thank you for raising this important point. We added long-\nterm Coulombic efficiency (CE) measurements for all electrolytes. The results show\nthat ERAE sustain both high CE and long lifetimes, whereas other additives exhibit\nlower CE and much shorter lifetimes. These data confirm that the superior reversibility\nof ERAE originates from their field-driven interfacial regulation.\nChange List:\nMain text: Added a statement that long-term CE measurements demonstrate ERAE\nmaintain both high CE and long lifetimes, while other additives do not.\nSupplementary Information: Added long-term CE traces for all electrolytes (Figures\nS33-S36), confirming the superior performance of ERAE relative to others.\nDMF, DMAC, DMU) at 1 mA cm−2 and 1 mAh cm−2\n.\nFigure S34 (added). Zn plating/stripping CE for EWSE additives (TAA, TBA, TEP,\nTMP, EG, MeOH) at 1 mA cm−2 and 1 mAh cm−2\n.\n1 mA cm−2 and 1 mAh cm−2\n.\nFigure S36 (added). Comparison of Zn plating/stripping CE across different\nelectrolytes.\nComment 4-6: To enhance the generality of the proposed affinity additives, the authors\nare encouraged to evaluate manganese-based cathodes (e.g., MnO₂) in full-cell\nconfigurations. This would validate the additives' efficacy across different cathode\nchemistries.\nResponse to Comment 4-6: As suggested, we have evaluated MnO cathodes in full-\n2\ncell configurations to test the generality of our additive strategy. Zn|| MnO cells with\nidentical conditions. These results demonstrate that the interfacial solvation-\nengineering effect of ERAE(DMU) extends beyond ZnI /V O cathodes and is\n2 6 13\napplicable to MnO as well.\n2\nSupplementary Information: Added Zn|| MnO full-cell cycling data (Figure S43),\n2\nconfirming that ERAE(DMU) improves both capacity retention and CE compared with\nBE.\nFigure S43 (added). Cycling performance of Zn||MnO full cells at C/4.\nThe author mentioned “BE (2m ZnSO4) was prepared by dissolving 0.02 mol ZnSO4\nin 7.48g of H2O”. The mass molar concentration of ZnSO4 seems to be 2.67 m.\nResponse to Comment 4-7: You are right that the original description was ambiguous.\nThe baseline electrolyte was prepared from ZnSO ·7H O, and in calculating the\n4 2\nmolality the crystallization water is treated as part of the solvent mass. When this\ncontribution is included, the resulting concentration is indeed 2 m rather than 2.67 m.\nWe have clarified this point in the revised text to avoid confusion. The additive content\n(2 wt%) is consistently defined relative to the total mass of the mixed electrolyte.\nChange List:\nSupplementary Information: Electrolyte preparation section revised to explicitly\nstate that the solvent mass includes both the added deionized water and the\ncrystallization water in ZnSO ·7H O, yielding a correct 2 m solution.\n4 2\nComment 4-8: The inner Helmholtz plane is inherently defined for ionic species at the\n59\ninterface, making it conceptually inappropriate to use this term for describing the\nlocalization of uncharged additives.\nResponse to Comment 4-8: Thank you for this important clarification. You are correct\nthat the term “inner Helmholtz plane (IHP)” is conceptually inappropriate for neutral\nadditives. Our additives remain uncharged under the electrolyte conditions used here,\nand our operando probes (SEIRAS and eQCM) as well as MD simulations resolve their\nnear-surface enrichment within the broader electric double layer (EDL), but cannot\nassign them to the IHP specifically. We have therefore revised the wording to emphasize\nfield-induced enrichment in the EDL rather than localization in the IHP.\nChange List:\nMain text: Wording updated (page 2, line 7) to: “… to dynamically modulate Zn2+\nsolvation and the structure of the electric double layer under operational electric fields.\nThese additives undergo electric-field-induced interfacial enrichment during\nplating. …”.\nComment 4-9: The author mentioned “For BE and ERAE, the local solvation sheath\nremains largely unaltered”. It is quite difficult to understand that the additive does not\nchange the solvation structure of zinc ion in the bulk, but can co-migrate with zinc ion\nat the interface. The author is suggested to clarify it.\nResponse to Comment 4-9: Thank you for this helpful clarification. At the low loading\nused here, affinitive additives exert only a modest influence on bulk Zn2+ solvation.\nTheir donor ability allows them to co-migrate with Zn2+ under bias, but they remain too\ndilute to significantly perturb the bulk solvation sheath. In other words, they act\nprimarily at the interface, where the electric field selectively enriches them, while\nleaving bulk solvation largely unchanged.\nChange List:\nMain text: Revised wording (page 12, line 9) to: “Together, these results demonstrate\nthat at 2 wt% additive loading, affinitive additives do not substantially infiltrate bulk\nat the interface.”.\nComment 4-10: While high-donor-number additives effectively exclude water from\nthe Zn²⁺ solvation sheath, their strong coordination may impede timely desolvation and\ncharge transfer during Zn²⁺ deposition. The author is suggested to provide further\ninvestigation into the desolvation kinetics of such additives.\nResponse to Comment 4-10: You raise an important point about whether strong donor\ncoordination could hinder Zn2+ desolvation and slow charge transfer. To address this,\nwe performed temperature-dependent EIS and extracted charge-transfer activation\nenergies. Arrhenius analysis shows E = 46.8 kJ mol-1 for BE and E = 43.4 kJ mol-1 for\na a\nERAE(DMU), values within experimental uncertainty. This indicates that DMU does\nnot impose any kinetic penalty on desolvation.\nThis can be understood mechanistically: (1) the interfacial electric field aligns DMU’s\ndipole, effectively lowering the energy barrier for desolvation, and (2) DMU reduces\nthe compactness of the solvation shell and enhances its polarization, thereby\naccelerating charge transfer by lowering the reorganization energy (doi:\n10.1126/science.abg3954). These effects explain why ERAE(DMU) excludes water\nfrom the solvation sheath yet preserves fast charge-transfer kinetics.\nChange List:\nSupplementary Information: Added temperature-dependent EIS and Arrhenius\nanalysis (Figure S45) to compare charge-transfer activation energies in BE and\nERAE(DMU).\ncells of BE and ERAE(DMU). (c) Arrhenius curves of activation energies tested with\nsymmetric cells.\nComment 4-11: In Figure 1a, the schematic representation of solvent molecules is not\nlabeled.\nResponse to Comment 4-11: Thank you for pointing this out. We have revised the\nfigure so that all solvent molecules are now explicitly labeled. In addition, element\nsymbols have been added to Figure 1c (revised as Figure S8) to identify each sphere,\nand we carefully reviewed all other schematics to ensure that molecular components\nare consistently and clearly annotated. These updates make the schematics fully self-\nexplanatory and improve readability.\nChange List:\nMain text: Revised Figure 1a to include labels for all solvent molecules; revised\nFigure 1c (revised as Figure S8) to include element symbols on colored spheres.\nand affinitive additives at the Zn interface under an applied electric field.\nFigure S8 (revised). ESP maps of the promising candidates DMU and MF (O, red; C,\nbrown; N, blue; H, white).\nComment 4-12: On page 7, lines 7–11, “Five representative additives from shielding\n(MeOH), inert (ACN) and affinitive (DMSO, DMU) categories were evaluated at 2 wt%\nin 0.2 m Na2SO4, and 0.2 m Na2SO4 aqueous solution was adopted as the control\nelectrolyte to eliminate the disturbance of Zn deposition/dissolution in ZnSO4\nelectrolyte.” The author only present four additives in this description. The author\nappears to take NSO (an abbreviation not defined in the manuscript) as one of the five\nadditives according to Figure 2a and b, which is confusing. Dipole moment and donor\nnumber information of NSO cannot be found in Table S1. The author should check it.\n“NSO” was a mistaken shorthand for the Na SO control electrolyte and was not an\n2 4\nactual additive. To resolve this issue, we re-ran all eQCM experiments using the\nbaseline electrolyte (2 m ZnSO ) to match the conditions of the electrochemical tests.\nperformance. All 14 additives were re-evaluated under this protocol, and the per-cycle\nΔm values are now summarized in Table S3 and shown in the revised Figure 2b.\nChange List:\nMain text: eQCM data updated to use 2 m ZnSO as the baseline electrolyte, ensuring\n4\nconsistency with electrochemical tests; Figure 2a and 2b revised accordingly.\nSupplementary Information: Added Figure S9 showing eQCM traces for all 14\nadditives and Table S3 summarizing their per-cycle Δm values.\nTable S3 (added). Summary of eQCM Δm across five CV cycles for BE (2 m ZnSO )\n4\nΔm (cyc1) Δm (cyc2) Δm (cyc3) Δm (cyc4) Δm (cyc5) Δm (avg)\nBE 60.89627 58.46777 54.40071 52.60743 57.88265 56.85097\nERAE(DMU) 72.06107 87.43551 81.03176 81.19877 72.55332 78.85609\nERAE(DMAC) 89.15352 76.55582 78.3978 91.52589 101.9787 87.52234\nERAE(DMF) 53.57824 93.53456 92.80458 106.1377 86.95831 86.60267\nERAE(DMSO) 82.30647 76.82156 95.39396 89.10498 90.65441 86.85628\nERAE(MF) 83.49767 99.25794 103.337 94.0264 83.04937 92.63368\nERAE(NMP) 75.26986 73.83803 88.76677 84.84137 91.59512 82.86223\nEWSE(TAA) 44.48176 46.5418 47.98485 49.83717 55.96404 48.96192\nEWSE(TBA) 65.82562 53.01279 68.00778 68.20843 61.08166 63.22726\nEWSE(TEP) 46.07557 43.43653 46.47151 47.03224 68.0692 50.21701\nEWSE(TMP) 48.02918 65.79967 64.25901 74.01703 71.51366 64.72371\nEWSE(EG) 66.44559 63.64664 70.67291 59.15249 71.45841 66.27521\nEWSE(MEOH) 56.34004 68.14055 61.1169 57.78606 55.22082 59.72087\nEWIE(SL) 53.24996 57.35159 66.79794 66.79794 66.52701 62.14489\nEWIE(ACN) 46.22577 55.57641 54.4393 54.4393 52.2728 52.59072\nelectrode surface, leading to a decrease in electrode capacitance. Figure S15 provides\nthe CV curves of a Zn/Zn symmetric battery. However, the CV curves do not exhibit\ncapacitive behavior; instead, they resemble resistive behavior.\nResponse to Comment 4-13: Thank you for this insightful observation. The CV curves\nof Zn||Zn symmetric cells in the original Figure S15 (revised as Figure S13) do not\nexhibit a typical rectangular capacitive shape, but instead show nearly linear current-\nvoltage (I-V) profiles resembling resistive behavior. This is because they were collected\nin a very narrow non-faradaic potential window (10 mV around OCP), where the\ncurrent is dominated by very small double-layer charging contributions. In such a range,\nthe I-V profiles appear nearly linear, and this effect has also been noted in prior studies\n(doi: 10.1021/acsenergylett.3c00859).\nTo make the capacitive behavior more explicit, we added complementary EIS-derived\ncapacitance-potential plots. These measurements directly quantify the double-layer\ncapacitance and confirm that ERAE(DMU) consistently yields lower capacitance than\nBE, supporting stronger surface adsorption of DMU. This provides a clearer picture of\nthe interfacial response.\nChange List:\nSupplementary Information: Added EIS-derived capacitance-potential plots (Figure\nS14) to complement Zn||Zn CV curves (Figure S13).\nFigure S14 (added). Capacitance-potential profiles of ERAE(DMU) and BE.\nthat high-DN and high-μ additives can respond to the electric field, undergoing\nadsorption and desorption on the electrode under its influence. How were the numerical\nvalues of mass change in Figure 2b obtained? The data presented in Figure 2a and\nFigure 2b, Figure S8-10 appear to show some inconsistencies in their numerical values.\nThe authors are suggested to provide a Table to show the data clearly. The SI provides\nEQCM data for DMSO, MeOH, and ACN, but please supplement the measurement\nresults for other additives. Furthermore, the authors indicate that the\nadsorption/desorption of additive molecules is the cause of mass change. Since these\nmolecules have significantly different molecular weights, it is recommended to use the\nmolar amount of adsorption/desorption—rather than the mass change, for comparison.\nResponse to Comment 4-14: All eQCM traces were converted from frequency change\n(Δf) to mass change (Δm) using the Sauerbrey relation, as described in the Methods.\nTo make the dataset complete and transparent, we re-measured all 14 additives under\nconsistent conditions in 2 m ZnSO , replacing the earlier Na SO baseline. The full per-\n4 2 4\ncycle Δm values (cycles 1–5) are now provided in Table S3, which directly underlies\nFigure 2b and resolves the apparent inconsistencies. The corresponding eQCM traces\nfor all additives are now included in Figure S9.\nRegarding the reviewer’s suggestion to present molar rather than mass adsorption: the\nobserved Δm reflects the net interfacial mass change, which may include contributions\nnot only from additive molecules but also from solvent, anions, and Zn2+ complexes;\nwe report Δm rather than Δn to ensure reproducibility and comparability across\nelectrolytes. The much larger and more reversible Δm observed for ERAE confirms\ntheir ability to undergo field-driven adsorption/desorption, while EWSE and EWIE\nshow weaker or negligible responses.\nChange List:\nMain text: Figures 2a and 2b were updated with newly acquired eQCM data collected\nin 2 m ZnSO , ensuring consistent and realistic testing conditions for all electrolytes.\n4\n(Figure S9) and summarized per-cycle Δm values in Table S3, resolving\ninconsistencies and enhancing transparency.\nComment 4-15: Equation S5 is not clearly described. For the entire manuscript, it is\nsuggested to use ERAE(X) (e.g., ERAE(DMSO)) to denote specific samples instead of\nthe generic term \"ERAE\". This notation will enhance clarity and avoid ambiguity when\nreferencing different samples.\nResponse to Comment 4-15: We sincerely thank you for this particularly valuable\nsuggestion. To improve clarity, we have standardized the terminology throughout the\nmanuscript so that each electrolyte is now explicitly denoted by its full category name\nwith abbreviation: electric-field-reinforced affinitive electrolytes (ERAE), electric-\nfield-weakened inert electrolytes (EWIE), and electric-field-weakened shielding\nelectrolytes (EWSE). Specific cases are written as ERAE(DMU), EWIE(SL), etc.,\ninstead of using the generic “ERAE”. This uniform notation avoids ambiguity and\nmakes references to individual systems precise.\nIn addition, the description of Equation (5) has been rewritten for clarity. During cyclic\nvoltammetry, the charge stored or released on the electrode is obtained by integrating\nthe current, while the corresponding electrochemical quartz crystal microbalance\n(eQCM) data provide electrode mass change (Δm) versus charge (ΔQ). Assuming a\ndominant ionic species, the slope of the Δm-ΔQ plot yields the apparent molecular\nweight (Mw’) interacting with the electrode. Reference lines in Figures 3d, 3e\nrepresent Zn2+ species with different hydration states, and Equation (5) directly relates\nthe slope to the experimentally derived Mw’.\nChange List:\nMain text: Standardized terminology to “electric-field-reinforced affinitive\nelectrolytes (ERAE), electric-field-weakened inert electrolytes (EWIE), and electric-field-weakened shielding electrolytes (EWSE)” throughout. Specific systems are now\nwritten as ERAE(X), EWIE(X), EWSE(X).\nexplain how Δm-ΔQ analysis is used to obtain the apparent molecular weight of Zn2+\nspecies.\nTitle: “Electric-Field-Reinforced Affinitive Electrolytes for Highly Reversible Aqueous\nZinc Metal Batteries”\nWe thank the reviewers for their insightful and constructive comments, which have\ngreatly helped us enhance the quality of our manuscript. We have done our utmost to\naddress all concerns raised. For ease of reference, the reviewers’ comments are shown\nin blue, our responses are given in black.\nResponses to Reviewers:\nTo Reviewer #1: ................................................................................................................................................2\nTo Reviewer #2: ............................................................................................................................................ 3-9\nTo Reviewer #3: ..............................................................................................................................................10\nTo Reviewer #4: ........................................................................................................................................ 11-23\nGeneral Comment: I think this revision looks good and can be published.\nResponse to Comment: Thank you very much for your recognition and\nrecommendation. We sincerely appreciate your time and constructive feedback.\nGeneral Comment: The reviewer acknowledges that the authors have put great efforts\nin improving the work presented in the manuscript, and that most questions from the\nreviewer have been responded. However, the overall novelty is still quite questionable.\nThe emphasized \"new mechanism\" or \"advances\" seem more like a contrived or\nstrained explanation. The story actually still talks about a normal electrolyte\nengineering based on additives when looking into the electrochemical behaviours\nevolution. The authors provide a significant account of more characterizations\nincluding operando/in situ operations, but these still cannot be considered as direct\nevidence and could be explained by normal ways.\nOverall, this manuscript presents a good research work, but the reviewer still feels that\nthe quality and significance are below the expected of Nature Communications.\nResponse to Comment: We sincerely appreciate your continued engagement with our\nmanuscript and your recognition of the substantial revisions we have made. While we\nunderstand your remaining concerns regarding novelty, we would like to respectfully\nemphasize that this work goes beyond incremental electrolyte engineering. It presents\na mechanism-driven framework for interfacial molecular selection in aqueous\nbatteries, rooted in a clear scientific narrative, distinct from recent approaches in the\nliterature, and validated through a closed-loop computational-experimental pipeline.\nWe outline three key aspects below:\n1. The scientific story: From an unresolved contradiction to a predictive\ninterfacial principle.\nOur research did not begin with screening additives followed by post hoc mechanistic\nrationalization. Instead, it originated from a fundamental hypothesis about polarity and\nZn2+ desolvation. As illustrated in Figure S7a-c, we initially expected a volcano-type\nrelationship between polarity of organic additives and cycling stability. High-polarity\nadditives strongly coordinate water molecules, remain solvated in the bulk, and fail to\naccumulate at the interface. By contrast, low-polarity additives lack sufficient\n3\ninteraction with Zn2+ and tend to self-aggregate, also losing interfacial access. However,\nnone of the conventional polarity descriptors (DN, μ, ε) captured this trend in our low-\nconcentration regime. Intriguingly, even the recently reported ET(30)-based volcano\ncorrelation1, while successful in high-concentration systems, showed inconsistencies in\nour data: several additives within the optimal ET(30) window performed poorly. This\ndiscrepancy led us to a pivotal realization: at trace concentrations, bulk-phase\ndescriptors are insufficient because they ignore whether an additive can actually\nenrich at the electrode under operating conditions. This motivated our central\nquestion: What molecular traits enable a uniformly dispersed additive to actively\nmigrate to, and persist at, the interface during polarization?\nThrough systematic analysis of physicochemical parameters (Figure R1), we identified\nthat only two properties govern the sequential steps of interfacial delivery: (1) donor\nnumber (DN) enables Zn2+-additive co-migration; (2) dipole moment (μ) drives field-\nresponsive adsorption at the charged interface. Only when DN and μ are considered\njointly does a robust performance boundary emerge, resolving prior contradictions and\noffering a predictive, mechanism-based descriptor, rather than an empirical\ncorrelation. Guided by this DN-μ framework, we designed a suite of interface-focused\nexperiments, including measurements of surface affinity, desolvation kinetics, and\nfield-induced solvation reorganization. All consistently corroborated the model’s\npredictions. Critically, our conclusions arise not from fitting data to a specific additive,\nbut from a descriptor-first, mechanism-predicted, and experiment-verified\nworkflow.\nparameters influence additive behavior.\n2. Distinctiveness from recent advances: A dynamic, field-responsive interfacial\npathway\nAs summarized in Table R1, many recent strategies toward Zn anode stabilization have\nemployed high-concentration additives, artificial SEI layers, or bulk electrolyte\nrestructuring. In contrast, our approach operates efficiently at just 2 wt% additive\nloading and relies on an operationally activated, concentration-efficient mechanism:\nadditives with high DN and μ are selectively enriched at the interface during cycling\nthrough the synergistic effects of Zn2+ coordination and electric-field alignment. This\nresults in a field-responsive associative solvation structure that dynamically modulates\nZn2+ desolvation and deposition, without perturbing the bulk electrolyte composition.\nUnlike static shielding or thermodynamically driven passivation strategies, our\nmechanism in inherently dynamic and electrochemically gated. It offers a new\nperspective on how molecular design can harness operando electrostatic forces or\ninterfacial control, a concept potentially generalizable to other multivalent or aqueous\nbattery chemistries.\nyears.\nElectrolyte Mechanism Universality Reference\nElectric-field-\n2 m ZnSO + 2% DMU high-DN-μ\n4\nenhanced phase this work\n(w) additives\ndecoupling\nPhase\n4 2\nchemistry/Water-\n(1:1 v/v) systems Energy (2025)2\nsolvent interaction\nMnSO + 1 mM Liquid crystal\n4 systems Energy (2024)3\nsurfactant\n0.83 m Zn(TFSI) + Nature\nH O/TFEA/TTE (1:1.8:2 specific Nanotechnology (20\n2\nhydrophobic solvation\nv/v/v) 25)4\nNature\nZnSO + Zn(ClO ) (2:8\n4 4 2\nAnion decoupling specific Sustainability (2025\nmol/mol)\n)5\nNature\npolysorbate (w)\n(2025)6\n(Cl-/Br-/I-) halogen specific Communications\nsolvation\nanions (2025)7\nNature\n4\nspecific Communications\nHTFSI layer\n(2024)8\nH-\nNature\n4\nspecific Communications\nDMSO/AN (v) rption/passivation/char\n(2025)9\nge-transfer\nmol/mol) + 5% ACN (v) Society (2025) 10\nJournal of the\nACN/SL\nSociety (2025)11\nJournal of the\nBmBr synergy/SEI based IL\nSociety (2025)12\nMedium\nJournal of the\n2 m Zn(BF ) in dielectric\n4 2\nIon-pair interaction American Chemical\nAN:H O (7:3 v/v) constant\nsolvents\n6\n0.5 M Zn(OTf) + Advanced Materials\nTHF:H O (3:7 v/v) (2024)14\n2\nsaponin + 0.03% specific\nbond (2025)15\nanisaldehyde (w)\n1 m Zn(BF ) + 0.2 m\n4 2\nZn(Ac) + Advanced Materials\nH O:TEGDME (40:1 (2024)16\n2\nmol/mol)\n2\nspecific\ncyclodextrin interaction (2024)17\n1 m Zn(OTf) + Angewandte\nDGDE:H O (6:4 v/v) Chemie (2025)18\n7.5 m ZnCl + 6 g L-1 SF Adsorption specific\n2 m Zn(ClO ) in Angewandte\n4 2\nSolvation/H-bond specific\nH O:BDO (73:27 v/v) Chemie (2025)20\n7\n3. Newly added high-throughput validation: Demonstrating generality and\npractical utility\nTo directly address the need for broader validation and real-world applicability, we have\nnewly incorporated a high-throughput computational screening workflow (Figure\n7). Since direct computation of DN is expensive, we used the binding energy with Zn2+\nas a practical surrogate. Starting from ~569,000 organic molecules in PubChem, we\napplied successive filters for stability, safety, cost, and critically, our dual-descriptor\ncriteria:\n(1) Electrochemical stability: adiabatic ionization energies > 10.4 eV and adiabatic\nionization affinities < 6.4 eV.\n(2) High dipole moment: > 5.0 D.\n(3) Strong Zn2+ binding: 0.18 Hartree higher than the Zn2+-H O interaction.\nreduced to ~30 molecules after considering price and availability. From these, two\ninexpensive and commercially accessible additives (piracetam (PIR) and 1-(2-\nHydroxyethyl)-2-pyrrolidone (HEP)) were experimentally evaluated in Zn||Zn\nsymmetric cells. As shown in Figure 7b, both additives significantly extended cycling\nstability: the ERAE(HEP) achieved a lifetime of 270 h at 60% DOD, while the\nERAE(PIR) had already surpassed 465 h under the same conditions without failure and\nwas still undergoing testing at the time of writing. This result directly demonstrates that\nour descriptor predicts functional interfacial behavior, not just theoretical affinity. This\nnewly added end-to-end pipeline, from mechanistic insight to molecular design rule,\nlarge-scale screening, and experimental realization, provides strong evidence that our\nframework is not limited to a few hand-picked examples, but constitutes a scalable,\nrational strategy for electrolyte design.\nConcluding remark\nAlthough our system employs electrolyte additives, the core advance lies in uncovering\na general physical principle governing molecular selection at electrified interfaces\nunder dilute conditions. The newly added high-throughput validation further\n8\nunderscores the robustness and transferability of this principle. We believe this\nconceptual shift—from empirical trial-and-error to field-aware, descriptor-guided\ndesign—offers timely and broadly relevant insights for the energy materials community,\naligning well with Nature Communications’ mission to publish interdisciplinary work\nof high scientific and technological impact.\n[Figure Redacted]\nGeneral Comment: I co-reviewed this manuscript with one of the reviewers who\nprovided the listed reports. This is part of the Nature Communications initiative to\nfacilitate training in peer review and to provide appropriate recognition for Early Career\nResearchers who co-review manuscripts.\nResponse to Comment: Thanks for participating in the evaluation of our work, we\nappreciate your time and effort contributed to the co-review process. We value the\nconstructive feedback provided through this collaborative review framework.\nGeneral Comment: The authors have provided satisfactory responses to most of my\nquestions. However, further clarification is still required regarding the following issues:\nResponse to Comment: Thanks for your constructive comments. We noticed that the\nrevised manuscript indeed had some unclear points, and we have made further\nimprovements following your suggestions.\nComment 4-1: The donor numbers and dipole moments of the additives involved in\nthis study serve as the crucial basis for the discussion. However, significant changes in\nthe DN and μ values of several additives (EG & MeOH, TAA & TBA) were observed\nbetween the initial submission and the revised manuscript. The authors did not declare\nthese changes in their response to the reviewer comments, which raises concerns.\nResponse to Comment 4-1: Your concerns are entirely reasonable. As noted in our\nprevious response (Previous response to comment 1-8), the parameter set was updated\nusing tabulated solvent properties compiled by Roland Stenutz (stenutz.eu/chem). In\naddition, in our initial submission, the DN-μ values for TAA and TBA were\ninadvertently interchanged. This mistake was corrected in the revised manuscript, but\nwe regret that it was not explicitly mentioned in our previous response. Importantly,\nthis correction does not affect any of the analyses, descriptor correlations, or\nconclusions of the study, as the corrected values remain fully consistent with the overall\nDN-μ trends.\nComment 4-2: Regarding \"Response to Comment 4-2\": As shown in Table S1, DMSO\noutperforms MF in both donor number and dipole moment. Meanwhile, Figure S5\n(revised) indicates that the lifespan performance of MF and DMSO as additives is very\nsimilar. Given this, what is the authors' rationale for classifying MF as a \"promising\ncandidate\" (in Figure 1c) with a higher ranking than DMSO? It seems unnecessary to\nmake such a clear distinction between MF and DMSO.\nResponse to Comment 4-2: Thank you for your careful observation. In our work, we\ninitially screened and evaluated twelve widely studied additives at low concentrations\n11\nto establish a dual-descriptor criterion based on DN and μ. This criterion was developed\nto identify electric-field-reinforced affinitive additives that could enhance Zn2+\ndesolvation and deposition efficiency. To demonstrate the generality and practical\nutility of this selection principle, we selected two potential candidates, MF and DMU,\nthat meet the ERAE descriptor requirements and have received limited attention in the\ncontext of zinc metal batteries.\nOur subsequent tests confirmed that both MF and DMU exhibited durable\nelectrochemical performance, consistent with the predictions made by the DN-μ\ncriterion. Specifically, DMU possesses simultaneously higher μ and DN within our\nadditive library, indicating its stronger potential for both Zn2+ co-migration and field-\nresponsive interfacial adsorption. MF, while slightly lower in the parameters compared\nto DMSO, still satisfies the DN-μ selection criteria and demonstrated comparable cycle\nlife performance in our experiments (Figure S3).\nThe reason for classifying MF as a “promising candidate” (now revised to “potential\ncandidate”) is twofold:\n(1) Satisfaction with selection criteria: MF meets the DN-μ threshold, making it a\nviable candidate according to our established framework.\n(2) Additional practical advantages: While MF and DMSO exhibit broadly comparable\nelectrochemical performance in our tests, DMSO has already been extensively\nreported in prior Zn-electrolyte studies and was therefore included primarily as a\nreference compound for validating the DN-μ screening criterion. In contrast, MF\nemerged directly from our descriptor-guided selection and remains largely\nunexplored in the context of Zn metal batteries. For this reason, we chose MF as a\n“promising candidate” to exemplify the ability of the proposed DN-μ framework to\nidentify new and previously overlooked additives.\nWe acknowledge that the initial phrasing of “promising candidate” might have caused\nsome confusion. To address this, we have revised the manuscript to use “potential\ncandidate” instead, which more accurately reflects the intended meaning.\nMoreover, we emphasize that our primary goal is to identify additives that satisfy the\nacross all metrics. The observed similarities in lifespan performance between MF and\nDMSO support the robustness of our framework, showing that multiple candidates can\nfulfill the necessary conditions for effective interface stabilization. In conclusion, the\nclassification of MF as a potential candidate is justified by its adherence to the DN-μ\ncriterion and its practical benefits. Our revised terminology aims to better convey the\nnuances of our selection process.\nChange list:\nMain text: The description of DMU and MF as “promising candidates” has been\nrevised to “potential candidates”.\nFigure 1c (revised). Plot of donor number versus dipole moment for 12 additives,\ndelineating EWSE (I), EWIE (II) and ERAE (III) regions. The area of each circle\nrepresents the Zn||Zn symmetric cell life span at 60% DOD, and stars indicate potential\ncandidates.\nComment 4-3: The authors used the size sieving effect of mesoporous carbon to\ncharacterize the influence of additives on the hydration number of Zn²⁺ at the interface.\nHowever, the pore size information of the mesoporous carbon is not provided.\nAdditionally, it is recommended to use carbon materials with larger pore sizes as\ncontrols to enhance the persuasiveness of the results.\nResponse to Comment 4-3: Following your suggestion, we have replaced the original\nmesoporous carbon with a larger-pore carbon material (XC-72R), and its pore-size\ninformation obtained from BET analysis has been added to Figure S25. Using this\ncarbon black, we re-measured the mass-charge (Δm-ΔQ) response to further verify the\n13\neffect of DMU on the interfacial hydration structure. As shown in Figures 3d,e, the\nmass change on the carbon surface varies linearly with charge. The dotted and dashed\nlines represent the theoretical mass-charge relations of bare Zn2+ and fully hydrated\n[Zn(H O) ]2+, respectively. In the BE, both the experimental mass change and the fitted\n2 6\nslope closely follow the theoretical behavior of [Zn(H O) ]2+. In contrast, in\n2 6\nERAE(DMU), the observed mass change is substantially higher, and the slopes\ncorrespond to molar masses of approximately 179 and 202 g mol-1, indicating that the\nheavier and less-hydrated interfacial Zn species may result from additive-assisted\nmodification of the local solvation structure. These results obtained using a larger-pore\ncarbon material provide additional support for our conclusion that DMU decreases the\ninterfacial hydration number of Zn2+.\nChange list:\nMain text: Revised Figures 3d-f and updated the corresponding conclusions in the\nmain text.\nSupplementary information: The hydration-number calculation has been replaced by\na molar-mass-based comparison, and the experimental and methodological descriptions\nhave been updated accordingly, with the pore-size information of the mesoporous\ncarbon added (Figures S25).\nFigure S25 (added) Differential pore size distribution of Vulcan XC-72R.\nCoordinated species determined from Δm-ΔQ analysis for ERAE(DMU) (d), and the\nBE (e).\nFigure 3f (revised) Solvated Zn2+ show organic exclusion in ERAE(DMU) and water\npenetration in BE within carbon black.\nComment 4-4: In the eQCM measurements, the authors did not specify the potential\nrange corresponding to the mass change (Δm). The description indicates that the Δm\nvalues are derived from Figure S9; however, there appears to be inconsistency between\nthe two datasets. For example, in Figure S9, the electrode mass exhibits a significant\npotential-dependent change in the electrolyte with TEP additive, which is notably larger\nthan that in the electrolyte with EG additive, but this is not reflected in Figure 2b.\nThe authors should provide a more detailed explanation of the value extraction process.\nResponse to Comment 4-4: We sincerely appreciate your insightful comment. In our\nprevious revision, we quantified the mass variation during potential cycling in ZnSO\n4\nelectrolytes containing different additives using a peak-to-peak (P2P) approach.\nSpecifically, for each additive, the mass change (Δm) was determined by calculating\nthe difference between the maximum and minimum values (Figure R2) within each of\nfive consecutive cycles, and the average P2P value was used as an indicator of electric-\nfield responsiveness. However, because the absolute mass change during each\n15\nvoltametric cycle was extremely small, this P2P method was highly susceptible to\nbaseline drift and high-frequency noise. In several cases, the noise amplitude was\ncomparable to or even larger than the true voltage-induced adsorption/desorption\nresponse, which caused artificial inflation of Δm or Δm . This susceptibility\nmax min\nexplains the discrepancy you noted, for example, that the mass variation in the EG-\ncontaining electrolyte appeared larger than that in the TEP-containing electrolyte,\ndespite their actual electrochemical behaviors.\nAs correctly pointed out, the direct comparison of Δm alone does not capture the\npotential-dependent nature of the adsorption/desorption process, and this metric cannot\nquantitatively reflect the amount of additive adsorption. Our initial P2P treatment,\ndefined as the difference between maximum and minimum mass within each cycle, was\nhighly susceptible to baseline drift and high-frequency noise, which can exceed the true\nvoltage-driven mass variation and lead to misleading trends.\nOur intention in these measurements was to elucidate the adsorption/desorption\nbehavior of additives under a periodically varying electric field. In this revision, we\nrecognized that the applied potential follows a triangular waveform, and that the\nadditive response is strongly synchronized with this periodic modulation. To more\nrigorously quantify this relationship, we introduced two complementary descriptors:\n1. Pearson correlation coefficient (r), which captures the overall linear correlation\nbetween potential and mass variation, thereby translating qualitative graphical\ntrends into a quantitative measure of trend consistency.\n2. Amplitude Ratio (AR), obtained by extracting the fundamental-frequency\namplitude of both potential and mass signals via Fourier analysis. AR represents the\nmagnitude of mass modulation per unit potential amplitude (ng V-1), providing a\nrobust measure of the true electric-field-driven adsorption/desorption strength\nindependent of noise.\nAccordingly, Figure 2b has been comprehensively revised using the combined\nPearson-AR framework. Additives located in the ERAE region exhibit pronounced\nnegative Pearson coefficients together with large AR values, indicating strong and\n16\ncoherent electric-field-driven adsorption/desorption behavior. The full mathematical\nprocedure, including Fourier decomposition and AR calculation, is provided in the\nSupplementary Information.\nChange list:\nMain text: Revised Figure 2b using a Pearson-AR analysis instead of peak-to-peak\nΔm, and updated the corresponding description in the main text to reflect the improved\nquantification of electric-field-driven adsorption/desorption.\nSupplementary information: Added a detailed description of the Pearson correlation\nand amplitude ratio analysis used to quantify the potential-mass relationship and\nremoved Table S3.\nFigure R2 (for discussion). Illustration of the peak-to-peak method previously used to\nestimate mass variation during one voltametric cycle.\nFigure 2b (revised). Correlation between electrode mass variation and potential in 15\n17\nelectrolytes. The BE point (H O) serves as the reference electrolyte for evaluating field‐\n2\nresponsive behavior.\nComment 4-5: Regarding \"Response to Comment 4-3\": The calculated values of\nHOMO and LUMO show a significant deviation from the typical value range,\nparticularly for the LUMO values.\nResponse to Comment 4-5: Thank you for this insightful observation. The apparent\ndeviation in the previously reported HOMO/LUMO energies indeed arose from the\ninclusion of the SMD implicit solvation model in our calculations. As you correctly\nnote, gas-phase orbital energies are not directly comparable to solvated values,\nespecially for the LUMO, which is particularly sensitive to solvent polarization effects.\nTo address this concern, we have now recomputed all frontier molecular orbitals in the\ngas phase at the same level of theory. As shown in the revised Figure S1, the gas-phase\nLUMO energies across the molecular series are indeed much more consistent with\ntypical literature ranges, and the relative energy differences between molecules are\nmodest, as expected. More importantly, to provide a physically meaningful and\nquantitative assessment of redox stability beyond orbital energies, we have performed\nadditional calculations using the xTB method to evaluate the adiabatic ionization\nenergies (AIEs) and adiabatic electron affinities (AEAs) for all candidate molecules\n(Figure S2). These thermodynamic descriptors are directly related to electrochemical\noxidation and reduction potentials. Notably, our results show that DMU exhibits a lower\nAEA compared to water, indicating that it is thermodynamically more difficult to reduce\nthan water under electrochemical conditions. This implies an expanded cathodic\nstability window for the ERAE. We have incorporated these AIE/AEA-based analyses\ninto our high-throughput screening protocol and updated the manuscript accordingly.\nIn parallel, we expanded our study by adding a new high-throughput screening\nworkflow to explore a broader chemical space of potential additives. Because direct\ncomputation of donor numbers is prohibitively expensive for large-scale screening, the\nworkflow instead incorporates a set of physically meaningful and computationally\naccessible descriptors. Specifically, we now evaluate each molecule using (1) xTB-\nlevel AIE and AEA as indicators of intrinsic electrochemical stability, (2) dipole\nmoment to reflect field responsiveness, and (3) Zn2+ binding energy as a practical\nsurrogate for donor strength. Molecules are retained only if they simultaneously satisfy\nall three criteria: high oxidative stability (AIE > 10.4 eV), low reducibility (AEA < 6.4\neV), sufficiently large dipole moment (> 5.0 D) and sufficiently strong Zn-binding\naffinity (0.18 Hartree higher than Zn2+-H O interaction). This newly included workflow\n2\nis presented in Figure 7a. Two inexpensive and commercially accessible representative\nadditives (piracetam (PIR) and 1-(2-Hydroxyethyl)-2-pyrrolidone (HEP)) that passed\nall criteria were further tested in symmetric Zn cells (Figure 7b), the ERAE(HEP)\nachieved a lifetime of 270 h at 60% DOD, while the ERAE(PIR) had already surpassed\n465 h under the same conditions without failure and was still undergoing testing at the\ntime of writing, demonstrating the practical relevance and predictive power of the\nscreening pipeline.\nChange list:\nMain text: Added a new section describing the high-throughput screening workflow,\ntogether with the corresponding results presented in Figure 7.\nSupplementary Information: Figure S1 was updated with revised HOMO/LUMO\ndata, and Figure S2 was newly added to present adiabatic ionization energies and\nelectron affinities.\nFigure S1 (revised). Gas-phase HOMO and LUMO energies for water and various\norganic solvents.\naffinity using.\n[Figure Redacted]\nComment 4-6: As indicated in Figure S5 (revised), the effect of DMU additive on\nlifespan is highly sensitive to additive concentration. The authors should discuss this\nconcentration-dependent behavior.\nwe first examined the charge-transfer resistance (Figure S7). The R increases\nct\nmonotonically with additive concentration, indicating increasingly hindered Zn2+\ndesolvation at higher concentrations. At the same time, higher additive concentration\nenhances the interfacial regulation effect, as more DMU becomes available to\nparticipate in Zn2+ solvation restructuring and interfacial stabilization.\nThese two opposing trends are summarized in Figure R3. Although the regulation\neffect improves with concentration, the penalty from the rising R also becomes more\nct\nsignificant. Their intersection defines an optimal concentration window, within which\nthe interfacial benefits outweigh the increased desolvation resistance, which explains\nwhy the 2 wt% electrolyte exhibits the best cycling performance among the three\nconditions tested.\nChange list:\nSupplementary information: Figure S7 has been added.\n1800\n1 wt% DMU\n2 wt% DMU\n3 wt% DMU\n1200\n)m\nh\no\n(\n''Z\n-\n600\n0\n0 600 1200 1800\nZ' (ohm)\nFigure S7 (added). Nyquist plot for Zn||Zn symmetric cells in electrolytes containing\nfrom 1 wt% and 3 wt% additives.\nregulation and R , identifying the optimal concentration.\nct\nComment 4-7: In Figure 1c, the authors intend to indicate lifespan length by dot size.\nHowever, it is inappropriate to use pentagrams (which have no size meaning) for the\nmost performant DMU and MF, while using size-indicative dots for other samples.\nResponse to Comment 4-7: We appreciate your insightful comment. In Figure 1c, MF\nand DMU are presented as potential candidates identified from the first 12 additives\nbased on our screening criteria, rather than as part of the screened set itself. In the\nprevious version, labeling them as promising candidates may have caused confusion,\nas their actual performance was characterized in subsequent sections. In the revised\nfigure, we have clarified this distinction by re-designating MF and DMU as potential\ncandidates, which resolves the inconsistency between symbol meaning and data\nrepresentation. Their detailed electrochemical results are provided in the later part of\nthe manuscript.\nComment 4-8: In LOOCV, the RMSE caused by dielectric constant is excessively large,\nmaking it difficult to distinguish the colors of other cells. Using color to indicate values\nactually impairs reading efficiency; it is recommended to remove the color intensity\nindicator.\nResponse to Comment 4-8: Thanks for your suggestion regarding the removal of the\ncolor intensity indicator to improve the readability of Figure 1b. In the revised Figure\n1b, we have adjusted the colormap such that all RMSE values greater than 2.3 are\ndisplayed in white. This modification prevents the excessively large RMSE of the\n22\ndielectric constant from dominating the color scale and allows the remaining cells to\nexhibit meaningful color contrast while still displaying their numerical values. We\nbelieve this updated visualization significantly improves readability and comparison\nacross descriptors.\nChange list:\nMain text: Revised Figure 1b by setting RMSE > 2.3 to white to improve readability.\nFigure 1b (revised). RMSE matrix from LOOCV analysis of Ridge Regression-based\nfeature-pair prediction. Each cell shows the prediction error between two descriptors.\nValues greater than 2.3 are displayed in white to prevent extreme entries from\ndominating the color scale. Full descriptor names are listed in Table S2.\nReferences\n1. Heo, J., Dong, D., Wang, Z., Chen, F. & Wang, C. Electrolyte design for aqueous Zn\nbatteries. Joule 9, 101844 (2025).\n2. Zhao, C.-X., Li, Z., Chen, B., Chen, F. & Wang, C. Self-adaptive electrolytes for\nfast-charging batteries. Nat. Energy 10, 904–913 (2025).\n3. Li, Y. et al. In situ formation of liquid crystal interphase in electrolytes with soft\ntemplating effects for aqueous dual-electrode-free batteries. Nat. Energy 9, 1350–\n1359 (2024).\n4. Zheng, X. et al. Nanoengineered aqueous-hydrotrope hybrid liquid electrolyte\nsolutions for efficient zinc batteries across a wide temperature range. Nat.\n5. Li, G. et al. Decoupled dual-salt electrolyte for practical aqueous zinc batteries. Nat.\nSustain. 8, 1349–1359 (2025).\n6. Peng, Z. et al. Water-shielding electric double layer and stable interphase\nengineering for durable aqueous zinc-ion batteries. Nat. Commun. 16, 4490 (2025).\n7. Chang, L. et al. High-entropy solvation chemistry towards affordable and practical\nah-level zinc metal battery. Nat. Commun. 16, 6134 (2025).\n8. Nian, Q. et al. Highly reversible zinc metal anode enabled by strong Brønsted acid\nand hydrophobic interfacial chemistry. Nat. Commun. 15, 4303 (2024).\n9. Yu, X. et al. Deciphering multi-dimensional interfacial mechanisms via organic\ncosolvent engineering for sustainable zinc metal batteries. Nat. Commun. 16, 3820\n(2025).\n10. Zhang, X. et al. Hydrogen bond reconstruction maneuver in eutectic electrolyte\nenables ultralong-lifespan zinc-ion batteries. J. Am. Chem. Soc. 147, 39440–39451\n(2025).\n11. Li, C. et al. Well-aligned liquid crystal interface and expanded solvation sheath\naccelerate Zn2+ desolvation kinetics for stable zinc batteries. J. Am. Chem. Soc. 147,\n27640–27650 (2025).\n12. Lv, Y. et al. Synergistic anion–cation chemistry enables highly stable Zn metal\nanodes. J. Am. Chem. Soc. 147, 8523–8533 (2025).\n13. Zha, Z. et al. Electrolyte Design via Cation–Anion Association Regulation for\nHigh-Rate and Dendrite-Free Zinc Metal Batteries at Low Temperature. J. Am. Chem.\n14. You, S. et al. Achieving Highly Stable Zn Metal Anodes at Low Temperature via\nRegulating Electrolyte Solvation Structure. Adv. Mater. 36, 2402245 (2024).\n15. Liu, K. et al. Binary Electrolyte Additive‐Reinforced Interfacial Molecule\nAdsorption Layer for Ultra‐Stable Zinc Metal Anodes. Adv. Mater. 37, 2420079\n(2025).\n16. Guan, K. et al. A dual salt/dual solvent electrolyte enables ultrahigh utilization of\nzinc metal anode for aqueous batteries. Adv. Mater. 36, 2405889 (2024).\n17. Zhang, G. et al. Hofmeister Effects in Supramolecular Chemistry for Anion‐\nModulation to Stabilize Zn Anode. Adv. Mater. 36, 2405949 (2024).\n18. Chen, J. et al. Electrostatic potential‐dominated weak solvation chemistry for\nsynergistic optimization of V O cathode and Zn anode. Angew. Chem. Int. Ed. 64,\n2 5\ne202510638 (2025).\n19. Zhang, L. et al. Aqueous Zinc‐Ion Batteries with Boosted Stability and Kinetics\nunder a Wide Temperature Range. Angew. Chem. Int. Ed. 64, e202500434 (2025).\n20. Liu, Y. et al. Balancing tetrahedral and cation entropies for long‐lifespan low‐\ntemperature Zn‐ion batteries. Angew. Chem. Int. Ed. 64, e202506010 (2025).\n21. Wang, P. et al. Targeted Docking of Localized Hydrogen Bond for Efficient and\nReversible Zinc‐Ion Batteries. Angew. Chem. Int. Ed. 64, e202422547 (2025).\n25"}, {"round": 2, "reviewer_comments": {"reviewer_1": "I think this revision looks good and can be published.", "reviewer_2": "The reviewer acknowledges that the authors have put great efforts in improving the work presented in the manuscript, and that most questions from the reviewer have been responded. However, the overall novelty is still quite questionable. The emphasized \"new mechanism\" or \"advances\" seem more like a contrived or strained explanation. The story actually still talks about a normal electrolyte engineering based on additives when looking into the electrochemical behaviours evolution. The authors provide a significant account of more characterizations including operando/in situ operations, but these still cannot be considered as direct evidence and could be explained by normal ways.\nOverall, this manuscript presents a good research work, but the reviewer still feels that the quality and significance are below the expected of Nature Communications.", "reviewer_3": "I co-reviewed this manuscript with one of the reviewers who provided the listed reports. This is part of the Nature Communications initiative to facilitate training in peer review and to provide appropriate recognition for Early Career Researchers who co-review manuscripts.", "reviewer_4": "The authors have provided satisfactory responses to most of my questions. However, further clarification is still required regarding the following issues:\n1. The donor numbers and dipole moments of the additives involved in this study serve as the crucial basis for the discussion. However, significant changes in the DN and μ values of several additives (EG & MeOH, TAA & TBA) were observed between the initial submission and the revised manuscript. The authors did not declare these changes in their response to the reviewer comments, which raises concerns.\n2. Regarding \"Response to Comment 4-2\": As shown in Table S1, DMSO outperforms MF in both donor number and dipole moment. Meanwhile, Figure S5 (revised) indicates that the lifespan performance of MF and DMSO as additives is very similar. Given this, what is the authors' rationale for classifying MF as a \"promising candidate\" (in Figure 1c) with a higher ranking than DMSO? It seems unnecessary to make such a clear distinction between MF and DMSO.\n3. The authors used the size sieving effect of mesoporous carbon to characterize the influence of additives on the hydration number of Zn²⁺ at the interface. However, the pore size information of the mesoporous carbon is not provided. Additionally, it is recommended to use carbon materials with larger pore sizes as controls to enhance the persuasiveness of the results.\n4. In the eQCM measurements, the authors did not specify the potential range corresponding to the mass change (Δm). The description indicates that the Δm values are derived from Figure S9; however, there appears to be inconsistency between the two datasets. For example, in Figure S9, the electrode mass exhibits a significant potential-dependent change in the electrolyte with TEP additive, which is notably larger than that in the electrolyte with EG additive, but this is not reflected in Figure 2b. The authors should provide a more detailed explanation of the value extraction process.\n5. Regarding \"Response to Comment 4-3\": The calculated values of HOMO and LUMO show a significant deviation from the typical value range, particularly for the LUMO values.\n6. As indicated in Figure S5 (revised), the effect of DMU additive on lifespan is highly sensitive to additive concentration. The authors should discuss this concentration-dependent behavior.\n7. In Figure 1c, the authors intend to indicate lifespan length by dot size. However, it is inappropriate to use pentagrams (which have no size meaning) for the most performant DMU and MF, while using size-indicative dots for other samples.\n8. In LOOCV, the RMSE caused by dielectric constant is excessively large, making it difficult to distinguish the colors of other cells. Using color to indicate values actually impairs reading efficiency; it is recommended to remove the color intensity indicator."}, "author_response": "Nature communications (Manuscript number: NCOMMS-25-36287B)\nTitle: “Electric-Field-Reinforced Affinitive Electrolytes for Highly Reversible Aqueous\nZinc Metal Batteries”\nWe thank the reviewers for their insightful and constructive comments, which have\ngreatly helped us enhance the quality of our manuscript. We have done our utmost to\naddress all concerns raised. For ease of reference, the reviewers’ comments are shown\nin blue, our responses are given in black.\nResponses to Reviewers:\nTo Reviewer #1: ................................................................................................................................................2\nTo Reviewer #2: ............................................................................................................................................ 3-9\nTo Reviewer #3: ..............................................................................................................................................10\nTo Reviewer #4: ........................................................................................................................................ 11-23\nGeneral Comment: I think this revision looks good and can be published.\nResponse to Comment: Thank you very much for your recognition and\nrecommendation. We sincerely appreciate your time and constructive feedback.\nGeneral Comment: The reviewer acknowledges that the authors have put great efforts\nin improving the work presented in the manuscript, and that most questions from the\nreviewer have been responded. However, the overall novelty is still quite questionable.\nThe emphasized \"new mechanism\" or \"advances\" seem more like a contrived or\nstrained explanation. The story actually still talks about a normal electrolyte\nengineering based on additives when looking into the electrochemical behaviours\nevolution. The authors provide a significant account of more characterizations\nincluding operando/in situ operations, but these still cannot be considered as direct\nevidence and could be explained by normal ways.\nOverall, this manuscript presents a good research work, but the reviewer still feels that\nthe quality and significance are below the expected of Nature Communications.\nResponse to Comment: We sincerely appreciate your continued engagement with our\nmanuscript and your recognition of the substantial revisions we have made. While we\nunderstand your remaining concerns regarding novelty, we would like to respectfully\nemphasize that this work goes beyond incremental electrolyte engineering. It presents\na mechanism-driven framework for interfacial molecular selection in aqueous\nbatteries, rooted in a clear scientific narrative, distinct from recent approaches in the\nliterature, and validated through a closed-loop computational-experimental pipeline.\nWe outline three key aspects below:\n1. The scientific story: From an unresolved contradiction to a predictive\ninterfacial principle.\nOur research did not begin with screening additives followed by post hoc mechanistic\nrationalization. Instead, it originated from a fundamental hypothesis about polarity and\nZn2+ desolvation. As illustrated in Figure S7a-c, we initially expected a volcano-type\nrelationship between polarity of organic additives and cycling stability. High-polarity\nadditives strongly coordinate water molecules, remain solvated in the bulk, and fail to\naccumulate at the interface. By contrast, low-polarity additives lack sufficient\n3\ninteraction with Zn2+ and tend to self-aggregate, also losing interfacial access. However,\nnone of the conventional polarity descriptors (DN, μ, ε) captured this trend in our low-\nconcentration regime. Intriguingly, even the recently reported ET(30)-based volcano\ncorrelation1, while successful in high-concentration systems, showed inconsistencies in\nour data: several additives within the optimal ET(30) window performed poorly. This\ndiscrepancy led us to a pivotal realization: at trace concentrations, bulk-phase\ndescriptors are insufficient because they ignore whether an additive can actually\nenrich at the electrode under operating conditions. This motivated our central\nquestion: What molecular traits enable a uniformly dispersed additive to actively\nmigrate to, and persist at, the interface during polarization?\nThrough systematic analysis of physicochemical parameters (Figure R1), we identified\nthat only two properties govern the sequential steps of interfacial delivery: (1) donor\nnumber (DN) enables Zn2+-additive co-migration; (2) dipole moment (μ) drives field-\nresponsive adsorption at the charged interface. Only when DN and μ are considered\njointly does a robust performance boundary emerge, resolving prior contradictions and\noffering a predictive, mechanism-based descriptor, rather than an empirical\ncorrelation. Guided by this DN-μ framework, we designed a suite of interface-focused\nexperiments, including measurements of surface affinity, desolvation kinetics, and\nfield-induced solvation reorganization. All consistently corroborated the model’s\npredictions. Critically, our conclusions arise not from fitting data to a specific additive,\nbut from a descriptor-first, mechanism-predicted, and experiment-verified\nworkflow.\nparameters influence additive behavior.\n2. Distinctiveness from recent advances: A dynamic, field-responsive interfacial\npathway\nAs summarized in Table R1, many recent strategies toward Zn anode stabilization have\nemployed high-concentration additives, artificial SEI layers, or bulk electrolyte\nrestructuring. In contrast, our approach operates efficiently at just 2 wt% additive\nloading and relies on an operationally activated, concentration-efficient mechanism:\nadditives with high DN and μ are selectively enriched at the interface during cycling\nthrough the synergistic effects of Zn2+ coordination and electric-field alignment. This\nresults in a field-responsive associative solvation structure that dynamically modulates\nZn2+ desolvation and deposition, without perturbing the bulk electrolyte composition.\nUnlike static shielding or thermodynamically driven passivation strategies, our\nmechanism in inherently dynamic and electrochemically gated. It offers a new\nperspective on how molecular design can harness operando electrostatic forces or\ninterfacial control, a concept potentially generalizable to other multivalent or aqueous\nbattery chemistries.\nyears.\nElectrolyte Mechanism Universality Reference\nElectric-field-\n2 m ZnSO + 2% DMU high-DN-μ\n4\nenhanced phase this work\n(w) additives\ndecoupling\nPhase\n4 2\nchemistry/Water-\n(1:1 v/v) systems Energy (2025)2\nsolvent interaction\nMnSO + 1 mM Liquid crystal\n4 systems Energy (2024)3\nsurfactant\n0.83 m Zn(TFSI) + Nature\nH O/TFEA/TTE (1:1.8:2 specific Nanotechnology (20\n2\nhydrophobic solvation\nv/v/v) 25)4\nNature\nZnSO + Zn(ClO ) (2:8\n4 4 2\nAnion decoupling specific Sustainability (2025\nmol/mol)\n)5\nNature\npolysorbate (w)\n(2025)6\n(Cl-/Br-/I-) halogen specific Communications\nsolvation\nanions (2025)7\nNature\n4\nspecific Communications\nHTFSI layer\n(2024)8\nH-\nNature\n4\nspecific Communications\nDMSO/AN (v) rption/passivation/char\n(2025)9\nge-transfer\nmol/mol) + 5% ACN (v) Society (2025) 10\nJournal of the\nACN/SL\nSociety (2025)11\nJournal of the\nBmBr synergy/SEI based IL\nSociety (2025)12\nMedium\nJournal of the\n2 m Zn(BF ) in dielectric\n4 2\nIon-pair interaction American Chemical\nAN:H O (7:3 v/v) constant\nsolvents\n6\n0.5 M Zn(OTf) + Advanced Materials\nTHF:H O (3:7 v/v) (2024)14\n2\nsaponin + 0.03% specific\nbond (2025)15\nanisaldehyde (w)\n1 m Zn(BF ) + 0.2 m\n4 2\nZn(Ac) + Advanced Materials\nH O:TEGDME (40:1 (2024)16\n2\nmol/mol)\n2\nspecific\ncyclodextrin interaction (2024)17\n1 m Zn(OTf) + Angewandte\nDGDE:H O (6:4 v/v) Chemie (2025)18\n7.5 m ZnCl + 6 g L-1 SF Adsorption specific\n2 m Zn(ClO ) in Angewandte\n4 2\nSolvation/H-bond specific\nH O:BDO (73:27 v/v) Chemie (2025)20\n7\n3. Newly added high-throughput validation: Demonstrating generality and\npractical utility\nTo directly address the need for broader validation and real-world applicability, we have\nnewly incorporated a high-throughput computational screening workflow (Figure\n7). Since direct computation of DN is expensive, we used the binding energy with Zn2+\nas a practical surrogate. Starting from ~569,000 organic molecules in PubChem, we\napplied successive filters for stability, safety, cost, and critically, our dual-descriptor\ncriteria:\n(1) Electrochemical stability: adiabatic ionization energies > 10.4 eV and adiabatic\nionization affinities < 6.4 eV.\n(2) High dipole moment: > 5.0 D.\n(3) Strong Zn2+ binding: 0.18 Hartree higher than the Zn2+-H O interaction.\nreduced to ~30 molecules after considering price and availability. From these, two\ninexpensive and commercially accessible additives (piracetam (PIR) and 1-(2-\nHydroxyethyl)-2-pyrrolidone (HEP)) were experimentally evaluated in Zn||Zn\nsymmetric cells. As shown in Figure 7b, both additives significantly extended cycling\nstability: the ERAE(HEP) achieved a lifetime of 270 h at 60% DOD, while the\nERAE(PIR) had already surpassed 465 h under the same conditions without failure and\nwas still undergoing testing at the time of writing. This result directly demonstrates that\nour descriptor predicts functional interfacial behavior, not just theoretical affinity. This\nnewly added end-to-end pipeline, from mechanistic insight to molecular design rule,\nlarge-scale screening, and experimental realization, provides strong evidence that our\nframework is not limited to a few hand-picked examples, but constitutes a scalable,\nrational strategy for electrolyte design.\nConcluding remark\nAlthough our system employs electrolyte additives, the core advance lies in uncovering\na general physical principle governing molecular selection at electrified interfaces\nunder dilute conditions. The newly added high-throughput validation further\n8\nunderscores the robustness and transferability of this principle. We believe this\nconceptual shift—from empirical trial-and-error to field-aware, descriptor-guided\ndesign—offers timely and broadly relevant insights for the energy materials community,\naligning well with Nature Communications’ mission to publish interdisciplinary work\nof high scientific and technological impact.\n[Figure Redacted]\nGeneral Comment: I co-reviewed this manuscript with one of the reviewers who\nprovided the listed reports. This is part of the Nature Communications initiative to\nfacilitate training in peer review and to provide appropriate recognition for Early Career\nResearchers who co-review manuscripts.\nResponse to Comment: Thanks for participating in the evaluation of our work, we\nappreciate your time and effort contributed to the co-review process. We value the\nconstructive feedback provided through this collaborative review framework.\nGeneral Comment: The authors have provided satisfactory responses to most of my\nquestions. However, further clarification is still required regarding the following issues:\nResponse to Comment: Thanks for your constructive comments. We noticed that the\nrevised manuscript indeed had some unclear points, and we have made further\nimprovements following your suggestions.\nComment 4-1: The donor numbers and dipole moments of the additives involved in\nthis study serve as the crucial basis for the discussion. However, significant changes in\nthe DN and μ values of several additives (EG & MeOH, TAA & TBA) were observed\nbetween the initial submission and the revised manuscript. The authors did not declare\nthese changes in their response to the reviewer comments, which raises concerns.\nResponse to Comment 4-1: Your concerns are entirely reasonable. As noted in our\nprevious response (Previous response to comment 1-8), the parameter set was updated\nusing tabulated solvent properties compiled by Roland Stenutz (stenutz.eu/chem). In\naddition, in our initial submission, the DN-μ values for TAA and TBA were\ninadvertently interchanged. This mistake was corrected in the revised manuscript, but\nwe regret that it was not explicitly mentioned in our previous response. Importantly,\nthis correction does not affect any of the analyses, descriptor correlations, or\nconclusions of the study, as the corrected values remain fully consistent with the overall\nDN-μ trends.\nComment 4-2: Regarding \"Response to Comment 4-2\": As shown in Table S1, DMSO\noutperforms MF in both donor number and dipole moment. Meanwhile, Figure S5\n(revised) indicates that the lifespan performance of MF and DMSO as additives is very\nsimilar. Given this, what is the authors' rationale for classifying MF as a \"promising\ncandidate\" (in Figure 1c) with a higher ranking than DMSO? It seems unnecessary to\nmake such a clear distinction between MF and DMSO.\nResponse to Comment 4-2: Thank you for your careful observation. In our work, we\ninitially screened and evaluated twelve widely studied additives at low concentrations\n11\nto establish a dual-descriptor criterion based on DN and μ. This criterion was developed\nto identify electric-field-reinforced affinitive additives that could enhance Zn2+\ndesolvation and deposition efficiency. To demonstrate the generality and practical\nutility of this selection principle, we selected two potential candidates, MF and DMU,\nthat meet the ERAE descriptor requirements and have received limited attention in the\ncontext of zinc metal batteries.\nOur subsequent tests confirmed that both MF and DMU exhibited durable\nelectrochemical performance, consistent with the predictions made by the DN-μ\ncriterion. Specifically, DMU possesses simultaneously higher μ and DN within our\nadditive library, indicating its stronger potential for both Zn2+ co-migration and field-\nresponsive interfacial adsorption. MF, while slightly lower in the parameters compared\nto DMSO, still satisfies the DN-μ selection criteria and demonstrated comparable cycle\nlife performance in our experiments (Figure S3).\nThe reason for classifying MF as a “promising candidate” (now revised to “potential\ncandidate”) is twofold:\n(1) Satisfaction with selection criteria: MF meets the DN-μ threshold, making it a\nviable candidate according to our established framework.\n(2) Additional practical advantages: While MF and DMSO exhibit broadly comparable\nelectrochemical performance in our tests, DMSO has already been extensively\nreported in prior Zn-electrolyte studies and was therefore included primarily as a\nreference compound for validating the DN-μ screening criterion. In contrast, MF\nemerged directly from our descriptor-guided selection and remains largely\nunexplored in the context of Zn metal batteries. For this reason, we chose MF as a\n“promising candidate” to exemplify the ability of the proposed DN-μ framework to\nidentify new and previously overlooked additives.\nWe acknowledge that the initial phrasing of “promising candidate” might have caused\nsome confusion. To address this, we have revised the manuscript to use “potential\ncandidate” instead, which more accurately reflects the intended meaning.\nMoreover, we emphasize that our primary goal is to identify additives that satisfy the\nacross all metrics. The observed similarities in lifespan performance between MF and\nDMSO support the robustness of our framework, showing that multiple candidates can\nfulfill the necessary conditions for effective interface stabilization. In conclusion, the\nclassification of MF as a potential candidate is justified by its adherence to the DN-μ\ncriterion and its practical benefits. Our revised terminology aims to better convey the\nnuances of our selection process.\nChange list:\nMain text: The description of DMU and MF as “promising candidates” has been\nrevised to “potential candidates”.\nFigure 1c (revised). Plot of donor number versus dipole moment for 12 additives,\ndelineating EWSE (I), EWIE (II) and ERAE (III) regions. The area of each circle\nrepresents the Zn||Zn symmetric cell life span at 60% DOD, and stars indicate potential\ncandidates.\nComment 4-3: The authors used the size sieving effect of mesoporous carbon to\ncharacterize the influence of additives on the hydration number of Zn²⁺ at the interface.\nHowever, the pore size information of the mesoporous carbon is not provided.\nAdditionally, it is recommended to use carbon materials with larger pore sizes as\ncontrols to enhance the persuasiveness of the results.\nResponse to Comment 4-3: Following your suggestion, we have replaced the original\nmesoporous carbon with a larger-pore carbon material (XC-72R), and its pore-size\ninformation obtained from BET analysis has been added to Figure S25. Using this\ncarbon black, we re-measured the mass-charge (Δm-ΔQ) response to further verify the\n13\neffect of DMU on the interfacial hydration structure. As shown in Figures 3d,e, the\nmass change on the carbon surface varies linearly with charge. The dotted and dashed\nlines represent the theoretical mass-charge relations of bare Zn2+ and fully hydrated\n[Zn(H O) ]2+, respectively. In the BE, both the experimental mass change and the fitted\n2 6\nslope closely follow the theoretical behavior of [Zn(H O) ]2+. In contrast, in\n2 6\nERAE(DMU), the observed mass change is substantially higher, and the slopes\ncorrespond to molar masses of approximately 179 and 202 g mol-1, indicating that the\nheavier and less-hydrated interfacial Zn species may result from additive-assisted\nmodification of the local solvation structure. These results obtained using a larger-pore\ncarbon material provide additional support for our conclusion that DMU decreases the\ninterfacial hydration number of Zn2+.\nChange list:\nMain text: Revised Figures 3d-f and updated the corresponding conclusions in the\nmain text.\nSupplementary information: The hydration-number calculation has been replaced by\na molar-mass-based comparison, and the experimental and methodological descriptions\nhave been updated accordingly, with the pore-size information of the mesoporous\ncarbon added (Figures S25).\nFigure S25 (added) Differential pore size distribution of Vulcan XC-72R.\nCoordinated species determined from Δm-ΔQ analysis for ERAE(DMU) (d), and the\nBE (e).\nFigure 3f (revised) Solvated Zn2+ show organic exclusion in ERAE(DMU) and water\npenetration in BE within carbon black.\nComment 4-4: In the eQCM measurements, the authors did not specify the potential\nrange corresponding to the mass change (Δm). The description indicates that the Δm\nvalues are derived from Figure S9; however, there appears to be inconsistency between\nthe two datasets. For example, in Figure S9, the electrode mass exhibits a significant\npotential-dependent change in the electrolyte with TEP additive, which is notably larger\nthan that in the electrolyte with EG additive, but this is not reflected in Figure 2b.\nThe authors should provide a more detailed explanation of the value extraction process.\nResponse to Comment 4-4: We sincerely appreciate your insightful comment. In our\nprevious revision, we quantified the mass variation during potential cycling in ZnSO\n4\nelectrolytes containing different additives using a peak-to-peak (P2P) approach.\nSpecifically, for each additive, the mass change (Δm) was determined by calculating\nthe difference between the maximum and minimum values (Figure R2) within each of\nfive consecutive cycles, and the average P2P value was used as an indicator of electric-\nfield responsiveness. However, because the absolute mass change during each\n15\nvoltametric cycle was extremely small, this P2P method was highly susceptible to\nbaseline drift and high-frequency noise. In several cases, the noise amplitude was\ncomparable to or even larger than the true voltage-induced adsorption/desorption\nresponse, which caused artificial inflation of Δm or Δm . This susceptibility\nmax min\nexplains the discrepancy you noted, for example, that the mass variation in the EG-\ncontaining electrolyte appeared larger than that in the TEP-containing electrolyte,\ndespite their actual electrochemical behaviors.\nAs correctly pointed out, the direct comparison of Δm alone does not capture the\npotential-dependent nature of the adsorption/desorption process, and this metric cannot\nquantitatively reflect the amount of additive adsorption. Our initial P2P treatment,\ndefined as the difference between maximum and minimum mass within each cycle, was\nhighly susceptible to baseline drift and high-frequency noise, which can exceed the true\nvoltage-driven mass variation and lead to misleading trends.\nOur intention in these measurements was to elucidate the adsorption/desorption\nbehavior of additives under a periodically varying electric field. In this revision, we\nrecognized that the applied potential follows a triangular waveform, and that the\nadditive response is strongly synchronized with this periodic modulation. To more\nrigorously quantify this relationship, we introduced two complementary descriptors:\n1. Pearson correlation coefficient (r), which captures the overall linear correlation\nbetween potential and mass variation, thereby translating qualitative graphical\ntrends into a quantitative measure of trend consistency.\n2. Amplitude Ratio (AR), obtained by extracting the fundamental-frequency\namplitude of both potential and mass signals via Fourier analysis. AR represents the\nmagnitude of mass modulation per unit potential amplitude (ng V-1), providing a\nrobust measure of the true electric-field-driven adsorption/desorption strength\nindependent of noise.\nAccordingly, Figure 2b has been comprehensively revised using the combined\nPearson-AR framework. Additives located in the ERAE region exhibit pronounced\nnegative Pearson coefficients together with large AR values, indicating strong and\n16\ncoherent electric-field-driven adsorption/desorption behavior. The full mathematical\nprocedure, including Fourier decomposition and AR calculation, is provided in the\nSupplementary Information.\nChange list:\nMain text: Revised Figure 2b using a Pearson-AR analysis instead of peak-to-peak\nΔm, and updated the corresponding description in the main text to reflect the improved\nquantification of electric-field-driven adsorption/desorption.\nSupplementary information: Added a detailed description of the Pearson correlation\nand amplitude ratio analysis used to quantify the potential-mass relationship and\nremoved Table S3.\nFigure R2 (for discussion). Illustration of the peak-to-peak method previously used to\nestimate mass variation during one voltametric cycle.\nFigure 2b (revised). Correlation between electrode mass variation and potential in 15\n17\nelectrolytes. The BE point (H O) serves as the reference electrolyte for evaluating field‐\n2\nresponsive behavior.\nComment 4-5: Regarding \"Response to Comment 4-3\": The calculated values of\nHOMO and LUMO show a significant deviation from the typical value range,\nparticularly for the LUMO values.\nResponse to Comment 4-5: Thank you for this insightful observation. The apparent\ndeviation in the previously reported HOMO/LUMO energies indeed arose from the\ninclusion of the SMD implicit solvation model in our calculations. As you correctly\nnote, gas-phase orbital energies are not directly comparable to solvated values,\nespecially for the LUMO, which is particularly sensitive to solvent polarization effects.\nTo address this concern, we have now recomputed all frontier molecular orbitals in the\ngas phase at the same level of theory. As shown in the revised Figure S1, the gas-phase\nLUMO energies across the molecular series are indeed much more consistent with\ntypical literature ranges, and the relative energy differences between molecules are\nmodest, as expected. More importantly, to provide a physically meaningful and\nquantitative assessment of redox stability beyond orbital energies, we have performed\nadditional calculations using the xTB method to evaluate the adiabatic ionization\nenergies (AIEs) and adiabatic electron affinities (AEAs) for all candidate molecules\n(Figure S2). These thermodynamic descriptors are directly related to electrochemical\noxidation and reduction potentials. Notably, our results show that DMU exhibits a lower\nAEA compared to water, indicating that it is thermodynamically more difficult to reduce\nthan water under electrochemical conditions. This implies an expanded cathodic\nstability window for the ERAE. We have incorporated these AIE/AEA-based analyses\ninto our high-throughput screening protocol and updated the manuscript accordingly.\nIn parallel, we expanded our study by adding a new high-throughput screening\nworkflow to explore a broader chemical space of potential additives. Because direct\ncomputation of donor numbers is prohibitively expensive for large-scale screening, the\nworkflow instead incorporates a set of physically meaningful and computationally\naccessible descriptors. Specifically, we now evaluate each molecule using (1) xTB-\nlevel AIE and AEA as indicators of intrinsic electrochemical stability, (2) dipole\nmoment to reflect field responsiveness, and (3) Zn2+ binding energy as a practical\nsurrogate for donor strength. Molecules are retained only if they simultaneously satisfy\nall three criteria: high oxidative stability (AIE > 10.4 eV), low reducibility (AEA < 6.4\neV), sufficiently large dipole moment (> 5.0 D) and sufficiently strong Zn-binding\naffinity (0.18 Hartree higher than Zn2+-H O interaction). This newly included workflow\n2\nis presented in Figure 7a. Two inexpensive and commercially accessible representative\nadditives (piracetam (PIR) and 1-(2-Hydroxyethyl)-2-pyrrolidone (HEP)) that passed\nall criteria were further tested in symmetric Zn cells (Figure 7b), the ERAE(HEP)\nachieved a lifetime of 270 h at 60% DOD, while the ERAE(PIR) had already surpassed\n465 h under the same conditions without failure and was still undergoing testing at the\ntime of writing, demonstrating the practical relevance and predictive power of the\nscreening pipeline.\nChange list:\nMain text: Added a new section describing the high-throughput screening workflow,\ntogether with the corresponding results presented in Figure 7.\nSupplementary Information: Figure S1 was updated with revised HOMO/LUMO\ndata, and Figure S2 was newly added to present adiabatic ionization energies and\nelectron affinities.\nFigure S1 (revised). Gas-phase HOMO and LUMO energies for water and various\norganic solvents.\naffinity using.\n[Figure Redacted]\nComment 4-6: As indicated in Figure S5 (revised), the effect of DMU additive on\nlifespan is highly sensitive to additive concentration. The authors should discuss this\nconcentration-dependent behavior.\nwe first examined the charge-transfer resistance (Figure S7). The R increases\nct\nmonotonically with additive concentration, indicating increasingly hindered Zn2+\ndesolvation at higher concentrations. At the same time, higher additive concentration\nenhances the interfacial regulation effect, as more DMU becomes available to\nparticipate in Zn2+ solvation restructuring and interfacial stabilization.\nThese two opposing trends are summarized in Figure R3. Although the regulation\neffect improves with concentration, the penalty from the rising R also becomes more\nct\nsignificant. Their intersection defines an optimal concentration window, within which\nthe interfacial benefits outweigh the increased desolvation resistance, which explains\nwhy the 2 wt% electrolyte exhibits the best cycling performance among the three\nconditions tested.\nChange list:\nSupplementary information: Figure S7 has been added.\n1800\n1 wt% DMU\n2 wt% DMU\n3 wt% DMU\n1200\n)m\nh\no\n(\n''Z\n-\n600\n0\n0 600 1200 1800\nZ' (ohm)\nFigure S7 (added). Nyquist plot for Zn||Zn symmetric cells in electrolytes containing\nfrom 1 wt% and 3 wt% additives.\nregulation and R , identifying the optimal concentration.\nct\nComment 4-7: In Figure 1c, the authors intend to indicate lifespan length by dot size.\nHowever, it is inappropriate to use pentagrams (which have no size meaning) for the\nmost performant DMU and MF, while using size-indicative dots for other samples.\nResponse to Comment 4-7: We appreciate your insightful comment. In Figure 1c, MF\nand DMU are presented as potential candidates identified from the first 12 additives\nbased on our screening criteria, rather than as part of the screened set itself. In the\nprevious version, labeling them as promising candidates may have caused confusion,\nas their actual performance was characterized in subsequent sections. In the revised\nfigure, we have clarified this distinction by re-designating MF and DMU as potential\ncandidates, which resolves the inconsistency between symbol meaning and data\nrepresentation. Their detailed electrochemical results are provided in the later part of\nthe manuscript.\nComment 4-8: In LOOCV, the RMSE caused by dielectric constant is excessively large,\nmaking it difficult to distinguish the colors of other cells. Using color to indicate values\nactually impairs reading efficiency; it is recommended to remove the color intensity\nindicator.\nResponse to Comment 4-8: Thanks for your suggestion regarding the removal of the\ncolor intensity indicator to improve the readability of Figure 1b. In the revised Figure\n1b, we have adjusted the colormap such that all RMSE values greater than 2.3 are\ndisplayed in white. This modification prevents the excessively large RMSE of the\n22\ndielectric constant from dominating the color scale and allows the remaining cells to\nexhibit meaningful color contrast while still displaying their numerical values. We\nbelieve this updated visualization significantly improves readability and comparison\nacross descriptors.\nChange list:\nMain text: Revised Figure 1b by setting RMSE > 2.3 to white to improve readability.\nFigure 1b (revised). RMSE matrix from LOOCV analysis of Ridge Regression-based\nfeature-pair prediction. Each cell shows the prediction error between two descriptors.\nValues greater than 2.3 are displayed in white to prevent extreme entries from\ndominating the color scale. Full descriptor names are listed in Table S2.\nReferences\n1. Heo, J., Dong, D., Wang, Z., Chen, F. & Wang, C. Electrolyte design for aqueous Zn\nbatteries. Joule 9, 101844 (2025).\n2. Zhao, C.-X., Li, Z., Chen, B., Chen, F. & Wang, C. Self-adaptive electrolytes for\nfast-charging batteries. Nat. Energy 10, 904–913 (2025).\n3. Li, Y. et al. In situ formation of liquid crystal interphase in electrolytes with soft\ntemplating effects for aqueous dual-electrode-free batteries. Nat. Energy 9, 1350–\n1359 (2024).\n4. Zheng, X. et al. Nanoengineered aqueous-hydrotrope hybrid liquid electrolyte\nsolutions for efficient zinc batteries across a wide temperature range. Nat.\n5. Li, G. et al. Decoupled dual-salt electrolyte for practical aqueous zinc batteries. Nat.\nSustain. 8, 1349–1359 (2025).\n6. Peng, Z. et al. Water-shielding electric double layer and stable interphase\nengineering for durable aqueous zinc-ion batteries. Nat. Commun. 16, 4490 (2025).\n7. Chang, L. et al. High-entropy solvation chemistry towards affordable and practical\nah-level zinc metal battery. Nat. Commun. 16, 6134 (2025).\n8. Nian, Q. et al. Highly reversible zinc metal anode enabled by strong Brønsted acid\nand hydrophobic interfacial chemistry. Nat. Commun. 15, 4303 (2024).\n9. Yu, X. et al. Deciphering multi-dimensional interfacial mechanisms via organic\ncosolvent engineering for sustainable zinc metal batteries. Nat. Commun. 16, 3820\n(2025).\n10. Zhang, X. et al. Hydrogen bond reconstruction maneuver in eutectic electrolyte\nenables ultralong-lifespan zinc-ion batteries. J. Am. Chem. Soc. 147, 39440–39451\n(2025).\n11. Li, C. et al. Well-aligned liquid crystal interface and expanded solvation sheath\naccelerate Zn2+ desolvation kinetics for stable zinc batteries. J. Am. Chem. Soc. 147,\n27640–27650 (2025).\n12. Lv, Y. et al. Synergistic anion–cation chemistry enables highly stable Zn metal\nanodes. J. Am. Chem. Soc. 147, 8523–8533 (2025).\n13. Zha, Z. et al. Electrolyte Design via Cation–Anion Association Regulation for\nHigh-Rate and Dendrite-Free Zinc Metal Batteries at Low Temperature. J. Am. Chem.\n14. You, S. et al. Achieving Highly Stable Zn Metal Anodes at Low Temperature via\nRegulating Electrolyte Solvation Structure. Adv. Mater. 36, 2402245 (2024).\n15. Liu, K. et al. Binary Electrolyte Additive‐Reinforced Interfacial Molecule\nAdsorption Layer for Ultra‐Stable Zinc Metal Anodes. Adv. Mater. 37, 2420079\n(2025).\n16. Guan, K. et al. A dual salt/dual solvent electrolyte enables ultrahigh utilization of\nzinc metal anode for aqueous batteries. Adv. Mater. 36, 2405889 (2024).\n17. Zhang, G. et al. Hofmeister Effects in Supramolecular Chemistry for Anion‐\nModulation to Stabilize Zn Anode. Adv. Mater. 36, 2405949 (2024).\n18. Chen, J. et al. Electrostatic potential‐dominated weak solvation chemistry for\nsynergistic optimization of V O cathode and Zn anode. Angew. Chem. Int. Ed. 64,\n2 5\ne202510638 (2025).\n19. Zhang, L. et al. Aqueous Zinc‐Ion Batteries with Boosted Stability and Kinetics\nunder a Wide Temperature Range. Angew. Chem. Int. Ed. 64, e202500434 (2025).\n20. Liu, Y. et al. Balancing tetrahedral and cation entropies for long‐lifespan low‐\ntemperature Zn‐ion batteries. Angew. Chem. Int. Ed. 64, e202506010 (2025).\n21. Wang, P. et al. Targeted Docking of Localized Hydrogen Bond for Efficient and\nReversible Zinc‐Ion Batteries. Angew. Chem. Int. Ed. 64, e202422547 (2025).\n25"}, {"round": 3, "reviewer_comments": {"reviewer_4": "The authors have adequately addressed all of my concerns in this revision."}, "author_response": ""}]

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