{"title":"原位转化氟化镁反应以提高硫化物电解质 Li6PS5Cl 在全固态金属锂电池中的性能","authors":"Yuzhe Zhang, Haolong Chang, Xiaohu Hu, Shijie Xu, Xinyu Wang, Shunjin Yang, Yujiang Sun, Xiao Sun, Dehang Ren, Xing Chen, Fangyi Cheng and Yongan Yang","doi":"10.1039/D4QI02717E","DOIUrl":null,"url":null,"abstract":"<p >Among the solid electrolytes of all-solid-state lithium metal batteries being pursued globally, Li<small><sub>6</sub></small>PS<small><sub>5</sub></small>Cl is one of the most promising candidates owing to its high ionic conductivity and easy processibility. However, Li<small><sub>6</sub></small>PS<small><sub>5</sub></small>Cl is vulnerable to the lithium anode because lithium can not only reduce Li<small><sub>6</sub></small>PS<small><sub>5</sub></small>Cl to generate passive interfaces but can also lead to the growth of lithium dendrites, which could penetrate the Li<small><sub>6</sub></small>PS<small><sub>5</sub></small>Cl bulk and eventually short-circuit the battery. Herein, we report that the electrochemical performance of Li<small><sub>6</sub></small>PS<small><sub>5</sub></small>Cl could be greatly enhanced by compositing it with MgF<small><sub>2</sub></small>, which was the most effective metal fluoride among five studied materials. Specifically, critical current density was increased by 4.7 times, cycling durability in Li|electrolyte|Li symmetric cells was extended by 19 times, capacity retention in Li|electrolyte|LiNi<small><sub>0.7</sub></small>Co<small><sub>0.2</sub></small>Mn<small><sub>0.1</sub></small>O<small><sub>2</sub></small> full cells was enhanced from 76% to 86%, and rate capability was boosted from 0.2C to 1C. Combination studies involving experimental characterizations and theoretical computations revealed that the performance-improving mechanism involved a sustained-release effect of capsule medicines, meaning during the charging/discharging cycles, MgF<small><sub>2</sub></small> could timely scavenge lithium dendrites to generate Li<small><sub><em>x</em></sub></small>Mg alloy and LiF, wherein Li<small><sub><em>x</em></sub></small>Mg could reversibly release/uptake Li and LiF could suppress the nucleation of lithium dendrites.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 3","pages":" 1010-1020"},"PeriodicalIF":6.1000,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"In situ conversion reaction of magnesium fluoride to boost the performance of the sulfide-based electrolyte Li6PS5Cl for all-solid-state lithium metal batteries†\",\"authors\":\"Yuzhe Zhang, Haolong Chang, Xiaohu Hu, Shijie Xu, Xinyu Wang, Shunjin Yang, Yujiang Sun, Xiao Sun, Dehang Ren, Xing Chen, Fangyi Cheng and Yongan Yang\",\"doi\":\"10.1039/D4QI02717E\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Among the solid electrolytes of all-solid-state lithium metal batteries being pursued globally, Li<small><sub>6</sub></small>PS<small><sub>5</sub></small>Cl is one of the most promising candidates owing to its high ionic conductivity and easy processibility. However, Li<small><sub>6</sub></small>PS<small><sub>5</sub></small>Cl is vulnerable to the lithium anode because lithium can not only reduce Li<small><sub>6</sub></small>PS<small><sub>5</sub></small>Cl to generate passive interfaces but can also lead to the growth of lithium dendrites, which could penetrate the Li<small><sub>6</sub></small>PS<small><sub>5</sub></small>Cl bulk and eventually short-circuit the battery. Herein, we report that the electrochemical performance of Li<small><sub>6</sub></small>PS<small><sub>5</sub></small>Cl could be greatly enhanced by compositing it with MgF<small><sub>2</sub></small>, which was the most effective metal fluoride among five studied materials. Specifically, critical current density was increased by 4.7 times, cycling durability in Li|electrolyte|Li symmetric cells was extended by 19 times, capacity retention in Li|electrolyte|LiNi<small><sub>0.7</sub></small>Co<small><sub>0.2</sub></small>Mn<small><sub>0.1</sub></small>O<small><sub>2</sub></small> full cells was enhanced from 76% to 86%, and rate capability was boosted from 0.2C to 1C. Combination studies involving experimental characterizations and theoretical computations revealed that the performance-improving mechanism involved a sustained-release effect of capsule medicines, meaning during the charging/discharging cycles, MgF<small><sub>2</sub></small> could timely scavenge lithium dendrites to generate Li<small><sub><em>x</em></sub></small>Mg alloy and LiF, wherein Li<small><sub><em>x</em></sub></small>Mg could reversibly release/uptake Li and LiF could suppress the nucleation of lithium dendrites.</p>\",\"PeriodicalId\":79,\"journal\":{\"name\":\"Inorganic Chemistry Frontiers\",\"volume\":\" 3\",\"pages\":\" 1010-1020\"},\"PeriodicalIF\":6.1000,\"publicationDate\":\"2024-12-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry Frontiers\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/qi/d4qi02717e\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/qi/d4qi02717e","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
In situ conversion reaction of magnesium fluoride to boost the performance of the sulfide-based electrolyte Li6PS5Cl for all-solid-state lithium metal batteries†
Among the solid electrolytes of all-solid-state lithium metal batteries being pursued globally, Li6PS5Cl is one of the most promising candidates owing to its high ionic conductivity and easy processibility. However, Li6PS5Cl is vulnerable to the lithium anode because lithium can not only reduce Li6PS5Cl to generate passive interfaces but can also lead to the growth of lithium dendrites, which could penetrate the Li6PS5Cl bulk and eventually short-circuit the battery. Herein, we report that the electrochemical performance of Li6PS5Cl could be greatly enhanced by compositing it with MgF2, which was the most effective metal fluoride among five studied materials. Specifically, critical current density was increased by 4.7 times, cycling durability in Li|electrolyte|Li symmetric cells was extended by 19 times, capacity retention in Li|electrolyte|LiNi0.7Co0.2Mn0.1O2 full cells was enhanced from 76% to 86%, and rate capability was boosted from 0.2C to 1C. Combination studies involving experimental characterizations and theoretical computations revealed that the performance-improving mechanism involved a sustained-release effect of capsule medicines, meaning during the charging/discharging cycles, MgF2 could timely scavenge lithium dendrites to generate LixMg alloy and LiF, wherein LixMg could reversibly release/uptake Li and LiF could suppress the nucleation of lithium dendrites.