More Like this

1. Structural Control of Electrodeposited Sb Anodes through Solution Additives and Their Influence on Electrochemical Performance in Na-Ion Batteries

   https://doi.org/10.1021/acs.jpcc.3c01086  

   Nieto, Kelly; Windsor, Daniel S; Kale, Amanda R; Gallawa, Jessica R; Medina, Dylan A; Prieto, Amy L (July 2023, The Journal of Physical Chemistry C)

   Alloy-based materials such as antimony (Sb) are of interest for both Li/Na-ion batteries due to their high theoretical capacity and electronic conductivity. Of the various ways to fabricate Sb films (slurry casting, sputtering, etc.) one promising route is through electrodeposition. Electrodeposition is an industrially relevant synthetic technique that allows for the use of solution additives to control different characteristics such as film uniformity, morphology, and electrical conductivity. Solution additives such as cetyltrimethylammonium bromide (CTAB) and bis(3-sulfopropyl) disulfide (SPS) have been used to control different characteristics such as particle morphology and electrical conductivity in various electrodeposits but have not been applied to the electrodeposition of Sb for battery applications. In this study, Sb films were electrodeposited with varied concentrations of CTAB and SPS and the structure, morphology, composition, and electrochemical performance in Na-ion batteries were compared. We report that CTAB and SPS additives can significantly influence electrodeposited Sb films by altering the morphology and reduce the crystallinity, affecting the electrochemical performance. These studies provide valuable insight into the tunability of alloy-based films through electrodeposition and solution additives for battery applications. 

   more » « less
2. The Role of FEC-Electrolyte Additive on the Chemo-Mechanical Stability of NaCrO ₂ Cathodes in Na-Ion Batteries

   https://doi.org/10.1149/MA2025-013319mtgabs  

   Teklie, Debash; Wable, Minal; Capraz, Omer Özgür (July 2025, ECS Meeting Abstracts)

   Na-ion batteries have taken more interest in recent years as an alternative battery chemistry to Li-ion batteries because of material abundance, cost, and sufficient volumetric energy density for large-scale energy storage applications. However, Na-ion batteries suffer from rapid capacity fade associated with chemo-mechanical instabilities such as the formation of resistive solid-electrolyte / cathode-electrolyte interphase (SEI/CEI) layers, irreversible phase formations, and particle fracture. The cathode materials are fragile, especially metal oxides, therefore Na-ion cathodes are more prone to mechanical deformations upon larger volumetric expansions/reductions during Na-ion intercalation. Electrolyte additives have been utilized to improve the electrochemical performance of Li-ion and Na-ion batteries by modifying the chemistry of the SEI layers. In situ stress measurements on Si anode in Li-ion batteries demonstrated the generation of less mechanical deformations in the electrode when cycled in the presence of FEC additives.¹However, there is not much known about the impact of electrolyte additives on the chemo-mechanical properties of CEI layers in Na-ion battery cathodes. Furthermore, the question still stands about how the electrolyte additives may impact the mechanical stability of the Na-ion cathodes. To address this gap, we systematically investigated the role of FEC additives on the electrochemical performance and associated chemo-mechanical instabilities in NaCrO2 cathodes. Experiments were performed in organic electrolytes with/without FEC additives. First, the talk will start with presenting the impact of FEC additives on the capacity retention and cyclic voltammeter profiles of NaCrO2 cathodes. Then, digital image correlation and multi-beam optical stress sensor techniques were employed to probe electrochemical strain and stress generation in the composite NaCrO2 cathodes during electrochemical cycling in organic electrolytes with/without FEC additives. Surface chemistry of the NaCrO2 cathodes after cycling was investigated with the FT-IR measurements. In summary, the talk will present contrast differences in the electrochemical and chemo-mechanical properties of NaCrO2 cathodes when cycled in the presence of the FEC additives. Acknowledgement: This work is supported by National Science Foundation (award number 2321405). Reference: 1) Tripathi et al 2023 J. Electrochem. Soc. 170 090544 

   more » « less
3. The early-stage growth and reversibility of Li electrodeposition in Br-rich electrolytes

   https://doi.org/10.1073/pnas.2012071118  

   Biswal, Prayag; Kludze, Atsu; Rodrigues, Joshua; Deng, Yue; Moon, Taylor; Stalin, Sanjuna; Zhao, Qing; Yin, Jiefu; Kourkoutis, Lena F.; Archer, Lynden A. (December 2020, Proceedings of the National Academy of Sciences)

   The physiochemical nature of reactive metal electrodeposits during the early stages of electrodeposition is rarely studied but known to play an important role in determining the electrochemical stability and reversibility of electrochemical cells that utilize reactive metals as anodes. We investigated the early-stage growth dynamics and reversibility of electrodeposited lithium in liquid electrolytes infused with brominated additives. On the basis of equilibrium theories, we hypothesize that by regulating the surface energetics and surface ion/adatom transport characteristics of the interphases formed on Li, Br-rich electrolytes alter the morphology of early-stage Li electrodeposits; enabling late-stage control of growth and high electrode reversibility. A combination of scanning electron microscopy (SEM), image analysis, X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS), and contact angle goniometry are employed to evaluate this hypothesis by examining the physical–chemical features of the material phases formed on Li. We report that it is possible to achieve fine control of the early-stage Li electrodeposit morphology through tuning of surface energetic and ion diffusion properties of interphases formed on Li. This control is shown further to translate to better control of Li electrodeposit morphology and high electrochemical reversibility during deep cycling of the Li metal anode. Our results show that understanding and eliminating morphological and chemical instabilities in the initial stages of Li electroplating via deliberately modifying energetics of the solid electrolyte interphase (SEI) is a feasible approach in realization of deeply cyclable reactive metal batteries. 

   more » « less
4. Electrodeposition of Tin and Antimony-Based Anode Materials for Sodium-Ion Batteries

   https://doi.org/10.1149/1945-7111/ad3854  

   Gallawa, Jessica R; Ma, Jeffrey; Prieto, Amy L (April 2024, Journal of The Electrochemical Society)

   Tin antimonide (SnSb) is a promising alloying anode for sodium-ion batteries due to its high theoretical capacity and relative stability. The material is popular in the battery field, but, to our knowledge, few studies have been conducted on the influence of altering Sn and Sb stoichiometry on anode capacity retention and efficiency over time. Here, Sn-Sb electrodes were synthesized with compositional control by optimizing electrodeposition parameters and stoichiometry in solution and the alloys were cycled in sodium-ion half-cells to investigate the effects of stoichiometry on both performance and electrochemical phenomena. Higher concentrations of antimony deposited into the films were found to best maintain specific capacity over 270 cycles in the tin-antimony alloys, with each cell showing a slow, gradual decrease in capacity. We identified that a 1:3 ratio of Sn:Sb retained a specific capacity of 486 mAh g⁻¹after 270 cycles, highlighting a need to explore this material further. These results demonstrate how control over stoichiometry in Sn-Sb electrodes is a viable method for tuning performance. 

   more » « less
5. Electrodeposition vs Slurry Casting: How Fabrication Affects Electrochemical Reactions of Sb Electrodes in Sodium-Ion Batteries

   https://doi.org/10.1149/1945-7111/ac6b5e  

   Nieto, Kelly; Gimble, Nathan J; Rudolph, Layton J; Kale, Amanda R; Prieto, Amy L (May 2022, Journal of The Electrochemical Society)

   Antimony (Sb) electrodes are an ideal anode material for sodium-ion batteries, which are an attractive energy storage system to support grid-level energy storage. These anodes have high thermal stability, good rate performance, and good electronic conductivity, but there are limitations on the fundamental understanding of phases present as the material is sodiated and desodiated. Therefore, detailed investigations of the impact of the structure-property relationships on the performance of Sb electrodes are crucial for understanding how the degradation mechanisms of these electrodes can be controlled. Although significant work has gone into understanding the sodiation/desodiation mechanism of Sb-based anodes, the fabrication method, electrode composition and experimental parameters vary tremendously and there are discrepancies in the reported sodiation/desodiation reactions. Here we report the use of electrodeposition and slurry casting to fabricate Sb composite films to investigate how different fabrication techniques influence observed sodiation/desodiation reactions. We report that electrode fabrication techniques can dramatically impact the sodiation/desodiation reaction mechanism due to mechanical stability, morphology, and composition of the film. Electrodeposition has been shown to be a viable fabrication technique to process anode materials and to study reaction mechanisms at longer lengths scales without the convolution of binders and additives. 

   more » « less