bluuebunny/crossref_metadata_2025_split huggingface dataset:
Explaining the Voltage Hysteresis and Slow Relaxation of Silicon Nanoparticles with a Chemo-Mechanical Particle-SEI Model
Authors: Köbbing Lukas , Latz Arnulf , Horstmann Birger 
Published: December 2024

Silicon is widely considered to be a promising next-generation anode material, primarily due to its remarkably high theoretical capacity. Furthermore, silicon is an abundant, cheap, and widely spread material. However, a major challenge for the commercialization of silicon anodes is the significant voltage hysteresis reducing efficiency and leading to detrimental heat generation during fast-charging. Additionally, the hysteresis causes an unclear state-of-charge (SOC) to voltage relation impeding precise SOC estimation.
The voltage hysteresis behavior of silicon anodes is addressed in literature with three different arguments: phase transformations, plastic flow of silicon, and slow diffusion. These approaches can interpret the voltage hysteresis of crystalline silicon, thin films, and large anode particles, respectively. Nevertheless, we show that they cannot explain the hysteresis observed for silicon anodes consisting of amorphous nanoparticles, the relevant material for next-generation lithium-ion batteries.
Our investigation highlights the chemo-mechanical interplay between the silicon nanoparticle and the covering Solid-Electrolyte Interphase (SEI) as the underlying cause for the significant voltage hysteresis. The SEI, a thin passivating layer, forms on negative electrode particles due to electrolyte decomposition [1]. In the case of silicon particles, the volume changes during lithiation and delithiation result in massive strains and plastic deformation occurring within the SEI [2]. Our chemo-mechanical particle-SEI description successfully replicates the observed open-circuit voltage hysteresis in experiments and aligns with the Plett model [3]. Moreover, our visco-elastoplastic SEI model reproduces the voltage difference between slow cycling and the relaxed open-circuit voltage. In our recent work, we show that a sophisticated mechanical model explains the slow voltage relaxation observed for silicon nanoparticles as well as the observed C rate dependence [4].
To conclude, we explain the voltage hysteresis and the slow voltage relaxation of silicon nanoparticles with a visco-elastoplastic particle-SEI model and discuss options to mitigate the size of the voltage hysteresis. This detailed physical understanding can improve the performance of all-silicon anodes and contribute to their commercialization.
[1] Köbbing, L.; Latz, A.; Horstmann, B. J. Power Sources
2023, DOI: 10.1016/j.jpowsour.2023.232651.
[2] Kolzenberg, L.; Latz, A.; Horstmann, B. Batter.
Supercaps
2022, DOI: 10.1002/batt.202100216.
[3] Köbbing, L.; Latz, A.; Horstmann, B. Adv. Funct. Mater. 2024, DOI: 10.1002/adfm.202308818.
[4] Köbbing, L.; Latz, A.; Horstmann, B. (in preparation).

Figure 1
(Battery Division Postdoctoral Associate Research Award Sponsored by MTI Corporation and the Jiang Family Foundation) Silicon SEI Instability and its Effect on Calendar Aging
Authors: McBrayer Josey D, , Schorr Noah B. , Harrison Katharine L. , Allcorn Eric , Lam Mila Nhu , Meyerson Melissa L , Minteer Shelley 
Published: December 2024

Poor calendar aging has been identified as a major hurdle for commercialization of high-loading silicon anodes. Here, we will discuss a series of efforts identifying and defining the problem of silicon calendar aging and hypotheses for why aging is worse in silicon than in graphite. Some of these hypotheses were tested through a specially designed variable open circuit (OCV) protocol modified from the USABC’s calendar aging protocol to determine contributions from mechanical and chemical degradation. Microcalorimetry and scanning electrochemical microscopy (SECM) were performed to study changes in the solid electrolyte interphase (SEI) on silicon with time. From SECM, the passivation of silicon thin films was found to decrease with increasing time and potential relative to Li/Li+. The overall failure mode of the SEI with time appeared to be global suggesting possible SEI dissolution. X-ray photoelectron spectroscopy supported that there was a loss of SEI species with time. In further support for chemical degradation during calendar aging, when the frequency of reference performance tests (RPTs) was varied, capacity fade was minimally affected. This suggests that time since assembly, rather than cycling, dominated the capacity fade in the calendar aging tests. Microcalorimetry demonstrated changes in heat during the rest as well as after an RPT, highlighting the complexity of silicon aging and setting the stage for our next efforts of in situ quantification of electrolyte degradation products.
This research was supported by the U.S. Department of Energy’s Vehicle Technologies Office under the Silicon Consortium Project, directed by Brian Cunningham, and managed by Anthony Burrell. This work was conducted in part by the Alliance for Sustainable Energy, LLC, the manager and operator of the National Renewable Energy Laboratory for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Sandia National Laboratories is a multimission Laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.
Maximizing Battery Performance: Unveiling the Potential of Ion Pair-Based Electrolytes
Authors: Ko Seongjae , Yamada Atsuo 
Published: December 2024

Developing next-generation rechargeable batteries with high energy density, low cost, high scalability, and long-term cycleability is of utmost importance for realizing a carbon-neutral society amidst the increasing adoption of renewable energies. In this context, high-voltage Li-ion batteries, high-capacity Li-metal batteries, and cobalt-free Li-ion batteries have been proposed. These batteries offer substantially high energy density while maintaining compatibility with current battery production processes and reducing heavy reliance on rare metals. However, significant challenges such as extreme reaction potentials of the cathode and anode that lie outside the electrochemical potential window of the electrolyte, damage/crack of the solid electrolyte interface (SEI) due to the huge volume change of the anode, corrosion of the Al cathode current collector, transition metals disslution from the cathode, and degradation of cathode carbon additives lead to severe electrolyte decomposition, a large consumption of Li+ sources, and an increase in battery resistance, thus hindering their practical utilization.
In this presentation, strategies to overcome these side reactions based on electrolyte design with aggressive ion-pair formation will be discussed. Specifically, the importance of i) kinetic hindrance of anion intercalation into the cathode carbon additives (S. Ko et al., and A. Yamada, Joule 5, 998–1009, 2021), ii) the thermodynamic upshift of electrode potential (S. Ko et al., A. Yamada, and Y. Yamada, Nature Energy, 7, 1217–1224, 2022), and iii) optimization of the overall potential diagram of full cells and electrolytes (S.Ko et al., and A. Yamada, Nature Sustainability, 6, 1705–1714, 2023) will be presented in detail.
Enabling 5V Solid-State Lithium Metal Batteries Using Catholyte for LiNi0.5Mn1.5O4 Spinel
Authors: Yim Chae-Ho , Karkar Zouina , Houache Mohamed S.E. , Kim Daeil , Jang Boyun , Abu-Lebdeh Yaser 
Published: December 2024

Solid-state lithium metal batteries, SSLMBs, are widely sought after as the next generation battery technology due to their potential intrinsic safety and higher energy density. However, several challenges need to be addressed to achieve this goal. Previous studies have identified various challenges with the cathode electrode, including interphases, low active material contents, and limited overall ionic and electronic conductivity for high power density. [1] Additionally, there are different types of cathode materials that are currently under R&D for SSBs such as layered oxides, olivine phosphates, and spinel oxides. Among these, the spinel oxide LiNi0.5Mn1.5O4 (LNMO) has the highest voltage compared to other cathode materials, making it an attractive candidate for maximizing the energy density of active materials in solid-state batteries.
However, most solid-state batteries require a catholyte,[2] solid electrolyte in the cathode electrode, to provide bulk ionic conductivity, but this, in turn, reduces energy density due to the addition of inactive materials.[3] Therefore, utilizing LNMO, a high energy density cathode, is a promising solution for solid-state batteries to compensate for this energy density loss.
To ensure high voltage stability, it is crucial to have a well-designed catholyte composition that minimizes the use of solid electrolyte while ensuring excellent electronic and ionic conductivity to the cathode. In this work, we introduce a catholyte formulation that can effectively utilize LNMO and demonstrate promising cycling results with a Garnet-based solid electrolyte, having cycled over 100 times. This research opens up new possibilities for enhancing the performance of 5V solid-state lithium batteries using catholyte for the LMNO spinel cathode while maintaining high energy densities.

Liang, Y., et al., Challenges, interface engineering, and processing strategies toward practical sulfide‐based all‐solid‐state lithium batteries. InfoMat, 2022. 4(5): p. e12292.

Al-Salih, H., Houache, M.S.E., Baranova, E.A. and Abu-Lebdeh, Y. (2022), Composite Cathodes for Solid-State Lithium Batteries: “Catholytes” the Underrated Giants. Adv. Energy Sustainability Res., 3: 2200032.

Yim, C.-H., et al., Understanding key limiting factors for the development of all-solid-state-batteries. Chemical Engineering Journal Advances, 2023. 13: p. 100436.
Enhancing Performance of Li-Metal Batteries through Optimization of Their Overall Potential Diagram
Authors: Fang Zhong , Ko Seongjae , Yamada Atsuo 
Published: December 2024

Various electrolyte strategies have been explored to improve the cycling stability of Li-metal batteries. Specifically, high-concentration electrolytes and localized high-concentration electrolytes, which facilitate the formation of an anion-derived solid electrolyte interphase on the Li metal surface, thereby kinetically preventing electrolyte reduction, have been extensively studied. However, the issue of drastic capacity decay still persists, indicating the presence of overlooked issues in the development of Li-metal batteries.
Recently, our group has discovered that the electrode potentials of both the cathode and anode shift substantially, by over 0.6 V, governed by the electrostatic potential (Liquid Madelung potential) of Li+ ions in the electrolyte.1-4 This large shift occurs identically at both the cathode and anode, maintaining the overall battery voltage but often resulting in a significant imbalance between the potential diagram of full cells and the potential window of electrolytes.
In this study, we systematically investigated the essential relationship between electrode potential shifts and battery performance using LiNi0.8Mn0.1Co0.1O2 | Li and LiFePO4 | Li batteries with diverse localized high-concentration electrolytes. Our findings underscore important insights for designing batteries and electrolytes:

Optimizing the overall potential diagram of full cells alongside electrolytes substantially improves battery performance.

An excessive upward shift in the Li/Li+ redox potential leads to cycling decay in LiNi0.8Mn0.1Co0.1O2 | Li batteries by accelerating electrolyte oxidation at the cathode surface.

The mild-potential LiFePO4 cathode enables the use of electrolytes that largely upshift the Li/Li+ redox potential, thus maximizing the battery performance.

References

S.Ko, T. Obukata, et al., and A. Yamada, Y. Yamada, Nature Energy, 7, 1217-1224 (2022)

S.Ko, N.Takenaka, A.Kitada, and A.Yamada, Next Energy, 1 (2), 100014 (2023)

S.Ko et al., and A. Yamada, Nature Sustainability, 6, 1705-1714 (2023)

N.Takenaka, S.Ko, A.Kitada, and A. Yamada, Nature Communications, 15, 1319 (2024)
Advancing Electrolyte Stability in Lithium Metal Batteries: A Strategy to Suppress Ionic Liquid Decomposition through Lithium Solvation Power Optimization
Authors: Eom Sewon , Park Minhee , Lee Hongkyung , Lee Wonbo , Lee Hochun 
Published: December 2024

Non-flammable and electrochemically stable ionic liquid electrolytes (ILEs) have emerged as promising candidates for thermally stable high-voltage lithium metal batteries (LMBs). To mitigate the high viscosity of ILEs and improve their applicability, research has increasingly focused on incorporating non-solvating co-solvents (NSCs) that dilute ILEs without altering the local Li+ solvation structure. However, NSC with ILEs often undergo extensive reductive decomposition.
Herein, we investigated the reductive behavior of NSC with ILEs and proposed highly stable hybrid electrolyte systems that integrate ILEs with weakly solvating co-solvents (WSCs). Our comparative analysis of various co-solvents, based on their solvation power, elucidates that the interaction between the n-propyl-n-methylpyrrolidinium cation (Pyr13+) and the co-solvents is governed by the co-solvents’ solvation power, which triggers the reductive decomposition of the electrolytes. The incorporation of strongly solvating co-solvents (SSCs) into ILEs, shifts the preferential interaction towards Li+ rather than Pyr13+, thereby minimizing Pyr13+ interaction and reducing reductive decomposition. Furthermore, replacing SSCs with WSCs in ILs results in a reduction in free solvent species, which improves chemical stability and compatibility with Li metal anode. As a result, a novel finding of our study is the effectiveness of an WSC with ILEs system in inhibiting electrolyte decomposition. Specifically, Employing the 1,2-diethoxyethane (DEE) with ILEs system, which incorporates DEE as a representative WSC, we assembled characterized by a high-nickel layered oxide cathode (3.0 mAh cm-2) and thin lithium foil (20 μm). This configuration enables us to achieve an impressive initial battery-level energy density exceeding 380 Wh kg-1 and the capacity retention was 95% for 180 cycles. On the other hand, when TTE, non-solvating co-solvent was added to ILEs, the capacity retention was only 51% for 50 cycles. This research not only advances our understanding of co-solvents with ILE systems but also paves the way for the development of ILs for LMBs with improved performance and stability.

Figure 1
Enhancing Stability of Glass Fiber Separators in Lithium-Ion Batteries through Sol-Gel Hybrid Coatings
Authors: Kang Taewook , Park Young Ji , Kim Jin Ho , Kim Sun Woog , Lee Mi Jai 
Published: December 2024

Lithium ion batteries are largely divided into an anode, a cathode, and a separator impregnated with an electrolyte. It is well known that the battery separator is an important element in all batteries, as it physically separates the anode and cathode to prevent the direct flow of electrons, and allows the flow of charge through the movement of ions. Polyolefin-based separators, which are widely used in existing batteries, are vulnerable to rapid environmental changes, drastically reducing battery performance. Additionally, the thermal contraction and expansion that leads to a short circuit significantly reduces the stability of the battery. To overcome stability in such extreme environments, glass fiber separators are emerging as an alternative. To overcome stability in such extreme environments, glass fiber separators are emerging as an alternative. Glass fiber has excellent mechanical properties, electrical insulation, heat resistance, and chemical resistance, so it can drastically improve the stability of the battery. It can also improve electrolyte impregnation by controlling porosity to improve battery performance.
In this study, a sol-gel hybrid coating solution was synthesized and coated on a glass fiber separator to enhance the ionic conductivity and stability. The coating on glass fiber was performed using a dip coating method. The optimization of the hybrid solution and coating conditions led to a reduction in the porosity and enhancement of the flexibility of the glass fiber separators. The adhesion of the coating was evaluated by measuring the hardness of the coating using pencil hardness, and the results showed that the tensile strength of the coated glass fiber separator was improved by about two times compared to before coating. Finally, as a result of evaluating the electrical performance according to the coating, the battery performance was similar at room temperature. On the other hand, it was confirmed that the operating voltage and discharge time at low temperatures were increased by the sol-gel hybrid coating. These results suggest that the coated glass fiber separators are promising candidates for overcoming the stability of battery operation in extreme environments.
Revealing Morphological and Chemical Changes of Nickel-Rich Oxide Cathodes in Sulfide-Based All-Solid-State Batteries
Authors: Zheng Xueli , Cho Yukio , Yang Guang , Nanda Jagjit 
Published: December 2024

Solid-state batteries have emerged as a transformative technology with the potential to revolutionize energy storage systems. Unlike conventional lithium-ion batteries, which rely on liquid electrolytes, solid-state batteries utilize solid electrolytes, offering numerous advantages including enhanced safety, higher energy density, and wider operating temperature ranges. Particularly, sulfide solid electrolytes represent a significant component of solid-state batteries due to their high ionic conductivity. However, key challenges in sulfide solid electrolytes including issues related to interfacial stability and mechanical instability has hindered their commercialization.
Herein, we investigated the capacity loss in LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes when using argyrodite sulfide solid electrolytes, Li6PS5Cl (LPSCl). Specifically, we explored the changes in chemical phase, oxidation state, and morphology of NMC811 cathode and LPSCl solid state electrolyte using synchrotron X-ray absorption spectroscopy and microscopy. Transmission X-ray microscopy images show a clear distinction between charged and charged-discharged NMC811 cathode. Visible microstructural cracking (pulverization) and degradation was observed after discharging the NMC811 cathode. To suppress the cracking formation during battery cycling, we coated NMC811 with lithium niobium oxide (LNO). The LixIn|LPSCl Film|NMC811@LNO full cell exhibited much improved capacity and cycling stability than that of the full cell with the bare NMC811 cathode. Using full-field transmission X-ray microscopy combined with X-ray absorption near edge structure, and sulfur K-edge X-ray absorption spectroscopy, we revealed the interface between NMC811 and argyrodite sulfide solid electrolytes. Our work illuminates the immense potential of solid-state batteries in shaping the future of energy storage, paving the way for safer, more efficient, and sustainable battery technologies.
How Reproducible Is the Performance of All-Solid-State Battery Cells? Α Round Robin Study
Authors: Puls Sebastian , Vargas-Barbosa Nella Marie 
Published: December 2024

As the field of all-solid-state battery (ASSB) cells rapidly develops, both from the perspective of new materials as well as processing and cell assembly methods, the necessity for standardized benchmarking protocols that enable interlaboratory comparability increases. At an academic level there are no well-established nor unified protocols for quantifying ASSB cell performance. The latter is in larger part due to the lack of standardized cell setups, processing and cycling parameters among the groups, sometimes limited by accessibility to similar equipment.
To evaluate the interlaboratory reproducibility of ASSB cell performance, we coordinated and report on a Round Robin study that involves 21 experienced groups* across Asia, Europe, and North America. We provided state-of-the-art, commercially-sourced battery materials, namely single crystal LiNi0.6Mn0.2Co0.2O2, (NMC-622) positive electroactive material (CAM), a thiophosphate-based (Li6PS5Cl) solid electrolyte (SE), and indium foil for the preparation of an In/(InLi)
x
alloy negative electrode. All groups were asked to assemble three ASSB cells with the provided materials at specified CAM- and SE-loadings as well as to use the same electrochemical cycling procedure. Moreover, all groups were asked to provide detailed information on their cell assembly protocols and results, including (but not limited to) applied pressures to prepare the battery electrodes, cell dimensions, weighed amounts of materials, and raw electrochemical data.
Massive differences were observed in the specific discharge capacities, which initially ranged from 23.7 to 143.1 mAh⋅g-1, and showed large variabilities in capacity retention (ranging from 0 to 107%). This result is not surprising considering that each group reports its own materials’ processing and cell assembly protocol in which different uniaxial pressures, compression times and cycling (stack) pressures are applied. Although challenging to correlate differences in cycling performance to a single parameter, we identified the initial open circuit voltage, the initial polarization and the cycling pressure as main contributors. We report that 43% of the attempted cells failed. This was mainly due to issues during cell assembly but also due to errors during cycling, suggesting that lab scale ASSB research is challenging and error prone. These problems may have a negative impact on reproducibility if they are not detected during assembly. Considering all the obtained results, we emphasize that triplicate cell data should always be reported by all groups. Due to the large available dataset, we identify important parameters that, if reported, would help improve the interlaboratory reproducibility and comparability of ASSB cell cycling data.
*The total number of researchers involved in this study is 108, representing 26 institutions and will be duly acknowledged in the presentation. Due to space limitations, they are not included in the abstract.