{"title":"Elucidating interfacial behaviors of Li-ion argyrodites through μ-cavity electrode analysis","authors":"Orynbassar Mukhan , Yuvaraj Subramanian , Sharon Mugobera , Sung-Soo Kim , Kwang-Sun Ryu","doi":"10.1016/j.progsolidstchem.2025.100518","DOIUrl":null,"url":null,"abstract":"<div><div>In the current scenario, All-Solid-State Batteries (ASSBs) are one of the inevitable energy storage systems due to their high energy density and safety aspects. Nonetheless, they have some limitations in their implementation for high performance solid-state lithium batteries. Notably, the reactions at the electrode and electrolyte interface, which negatively affects the Li-ion transport. From this perspective, we prepared the renowned high ionic conductive solid electrolytes (Li<sub>6</sub>PS<sub>5</sub>Cl, Li<sub>6.2</sub>P<sub>0.8</sub>Si<sub>0.2</sub>S<sub>5</sub>Cl<sub>0.5</sub>Br<sub>0.5</sub>, Li<sub>5.3</sub>PS<sub>4.3</sub>Cl<sub>1.7</sub> and Li<sub>5.3</sub>PS<sub>4.3</sub>ClBr<sub>0.7</sub>) using a ball milling process subsequent to calcination at appropriate temperatures. The prepared electrolytes exhibited ionic conductivity values of 4.5, 5.3, 9.0 and 15.9 mS cm<sup>−1</sup>, respectively. Importantly, the electrode and electrolyte interface processes are examined through microcavity electrode system using our prepared electrolyte and LiNi<sub>0.5</sub>Co<sub>0.2</sub>Mn<sub>0.3</sub>O<sub>2</sub> (NCM523) cathode. In this case, a single particle confined in a micro cavity electrode system, NCM523-Li<sub>6.2</sub>P<sub>0.8</sub>Si<sub>0.2</sub>S<sub>5</sub>Cl<sub>0.5</sub>Br<sub>0.5</sub> exhibits the highest initial discharge capacity value of 5.27 nAh, and an even higher initial Coulombic efficiency of 87.9 % surpassing other micro electrode systems. This and the electrochemical kinetic parameters evaluated through the Tafel plot analysis confirm that Si substitution minimizes chemical side reactions at the interface. The electrochemical kinetic parameters reveal that Li<sub>6.2</sub>P<sub>0.8</sub>Si<sub>0.2</sub>S<sub>5</sub>Cl<sub>0.5</sub>Br<sub>0.5</sub> electrolyte has high exchange current, low charge transfer resistance and high lithium diffusion coefficient values. This proves that a favorable interface was formed between the NCM523 and the SE, thereby resulting in high rate of lithium-ion exchange between the NCM523 and the SE. The comparative study confirms the electrochemical kinetics improved by the bromine and silicon incorporation in the Li-argyrodite structure and offers flexible Li-ion pathways for better electrochemical performances.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"78 ","pages":"Article 100518"},"PeriodicalIF":9.1000,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Progress in Solid State Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0079678625000111","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
In the current scenario, All-Solid-State Batteries (ASSBs) are one of the inevitable energy storage systems due to their high energy density and safety aspects. Nonetheless, they have some limitations in their implementation for high performance solid-state lithium batteries. Notably, the reactions at the electrode and electrolyte interface, which negatively affects the Li-ion transport. From this perspective, we prepared the renowned high ionic conductive solid electrolytes (Li6PS5Cl, Li6.2P0.8Si0.2S5Cl0.5Br0.5, Li5.3PS4.3Cl1.7 and Li5.3PS4.3ClBr0.7) using a ball milling process subsequent to calcination at appropriate temperatures. The prepared electrolytes exhibited ionic conductivity values of 4.5, 5.3, 9.0 and 15.9 mS cm−1, respectively. Importantly, the electrode and electrolyte interface processes are examined through microcavity electrode system using our prepared electrolyte and LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode. In this case, a single particle confined in a micro cavity electrode system, NCM523-Li6.2P0.8Si0.2S5Cl0.5Br0.5 exhibits the highest initial discharge capacity value of 5.27 nAh, and an even higher initial Coulombic efficiency of 87.9 % surpassing other micro electrode systems. This and the electrochemical kinetic parameters evaluated through the Tafel plot analysis confirm that Si substitution minimizes chemical side reactions at the interface. The electrochemical kinetic parameters reveal that Li6.2P0.8Si0.2S5Cl0.5Br0.5 electrolyte has high exchange current, low charge transfer resistance and high lithium diffusion coefficient values. This proves that a favorable interface was formed between the NCM523 and the SE, thereby resulting in high rate of lithium-ion exchange between the NCM523 and the SE. The comparative study confirms the electrochemical kinetics improved by the bromine and silicon incorporation in the Li-argyrodite structure and offers flexible Li-ion pathways for better electrochemical performances.
期刊介绍:
Progress in Solid State Chemistry offers critical reviews and specialized articles written by leading experts in the field, providing a comprehensive view of solid-state chemistry. It addresses the challenge of dispersed literature by offering up-to-date assessments of research progress and recent developments. Emphasis is placed on the relationship between physical properties and structural chemistry, particularly imperfections like vacancies and dislocations. The reviews published in Progress in Solid State Chemistry emphasize critical evaluation of the field, along with indications of current problems and future directions. Papers are not intended to be bibliographic in nature but rather to inform a broad range of readers in an inherently multidisciplinary field by providing expert treatises oriented both towards specialists in different areas of the solid state and towards nonspecialists. The authorship is international, and the subject matter will be of interest to chemists, materials scientists, physicists, metallurgists, crystallographers, ceramists, and engineers interested in the solid state.