(Invited) Solvation Control in Deep Eutectic Solvent Electrolytes for Stable Plating/Stripping of Zn in Battery Applications
Authors: Bozzini Benedetto , Emanuele Elisa , Mele Claudio , Strada Jacopo 
Published: February 2024

Within the field of battery applications, deep eutectic solvents (DESs) have emerged as innovative electrolytes for rechargeable Zinc-ion batteries (ZIBs) . ZIBs traditionally employ neutral or weakly acidic aqueous electrolytes, which are susceptible to the standard anode drawback such as dendrite formation and passivation. DES-based electrolytes can facilitate the reversible plating and stripping of Zn, mitigating also dendrite growth . One notable benefit of DES solvents over their aqueous counterparts is that the concentration of electroactive species controls the shape evolution of electrodes during electroplating. For this reason, the coordination chemistry and metal complex formed between the Lewis acid of the metal and the Lewis base of the DES play a central role. Moreover, water can be added to the eutectic mixtures to increase the diffusion coefficient of the electroactive species and lower the electrolyte viscosity without destroying the eutectic nature if the concentration is kept under 40%.
Regarding metal plating/stripping processes, DESs offer a notable advantage due to their high capacity to dissolve metal salts, oxides, and hydroxides, inhibiting the formation of insoluble oxides and hydroxides . Moreover, the unique coordination properties of Zn2+ in DESs lead to an atypical voltammetric behavior, characterized by a cathodic peak in the cathodic branch of the anodic-going scan. The mechanistic studies of Zn electrodeposition onto glassy carbon (GC) from DESs have concluded that the metal is formed by the reduction of an intermediate Zn-containing species. Finally, the reactivity of choline chloride and ethylene glycol can impact coordination in that these species can be dehydrogenated at negative potential forming RO¯, which can replace one or more chloride ligands in [ZnCl4]2− . The correlation between the chemistry of Zn2+ solutions and DESs is elucidated, and the peculiarities of Zn electrochemistry can be rationalized in terms of the DES–electrode interface structure. Although few studies on hydrated DESs have been conducted, the literature remains scant.
Shi et al. conducted a study on DES composed of ZnCl2 and acetamide with different concentration of water. The authors employed various spectroscopic techniques, including FT-IR, Raman, and 17O NMR, to investigate the effect of water on the coordination geometry of Zn2+ and its consequent impact on Zn plating. Interestingly, the authors observed that the addition of small amounts of water, below the threshold for direct water-water interaction, resulted in significant alterations of the Zn2+ coordination geometry. In fact, based on the accepted view that Zn electrodeposition is a process that involves desolvation and charge-transfer steps, [ZnCl(acetamide)2(H2O)]+ was shown to undergo successive deamidation and dehydration, yielding [ZnCl(acetamide)]+ from which the metal center is finally reduced. Although [ZnCl(acetamide)3]+ is the most stable species, the energy barrier for dehydration is significantly lower than that for deamidation. Therefore, [ZnCl(acetamide)2(H2O)]+ with lower dissociation energy is the actual electroactive species . The solvation of Zn also affects the nucleation overpotential, as Zn2+ in hydrated DES exhibits faster desolvation kinetics, resulting in a lower nucleation overpotential. In addition, Zhao et al. investigated the properties of a “water-in-DES” electrolyte (~30 mol.% H2O) based on the urea/LiTFSI/Zn(TFSI)2 mixture and discovered that the preferential interaction between water and metal cations promotes interfacial charge transfer. Notwithstanding the important contribution of these papers, the mechanism of Zn electrodeposition in DES has not been conclusively assessed. To address this knowledge gap, our research aims to investigate Zn electrodeposition from two distinct, hydrated DESs: ChU and ChEG with approximately 30% H2O content. To gain control of the impact of the cathode material, we carried out our electrochemical tests by employing GC, Zn, Pt and Au electrodes. Furthermore, to evaluate the performance of these electrolytes under realistic device conditions, electrochemical cycling tests were conducted on symmetric CR2023 coin cells.
In this study, we have demonstrated the beneficial effect of water addition on reducing the electrolyte viscosity, which consequently resulted in lower anodic and cathodic overpotentials and improved charge/discharge cyclability. Specifically, the electrolytes ChEG and ChU failed due to passivation and short circuits, respectively. The ChU electrolyte showed regular chronopotentiometric transients until cell failure, and this was supported by multiple cyclic voltammetry (CV) measurements, which showed reversible Zn plating/stripping in this system. Notably, our cell cycling tests were performed at higher current densities and exhibited longer lifetimes compared to previous literature reports. The unusual CV patterns observed with gold and glassy carbon (GC) electrodes, featuring cathodic peaks on both forward and backward scans, were elucidated using complementary electrochemical and in situ Raman spectroscopy measurements.

Figure 1