{"title":"人工合成 NH4HCO3 可抑制氟聚合物/石榴石的界面反应,使其达到 1mS cm-1 和 5V 级复合固体电解质的水平","authors":"Yaping Wang, Pengcheng Yuan, Xiong Xiong Liu, Shengfa Feng, Mufan Cao, Jianxiang Ding, Jiacheng Liu, Song‐Zhu Kure‐Chu, Takehiko Hihara, Long Pan, Zhengming Sun","doi":"10.1002/adfm.202405060","DOIUrl":null,"url":null,"abstract":"Composite solid electrolytes (CSEs) integrate the fast ion conductivity of inorganic electrolytes and the excellent interfacial compatibility of polymer electrolytes. Typically, fluoropolymers and garnets are promising individuals to formulate cutting‐edge CSEs owing to their unique properties. However, the alkaline garnets can induce the dehydrofluorination of fluoropolymers, deteriorating their CSEs performance. Here, for the first time, NH4HCO3 is proposed as a sacrificial inhibitor to effectively prevent the garnet‐induced dehydrofluorination, using Li6.4La3Zr1.4Ta0.6O12 (LLZTO) and poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVH) as symbolic garnets and fluoropolymers, respectively. Various findings demonstrate that NH4HCO3 can buffer the alkalinity of LLZTO, thereby inhibiting the dehydrofluorination of PVH. In addition, NH4HCO3 can completely decompose to volatiles upon drying without compromising the properties of LLZTO and PVH. Additionally, a polymer‐in‐salt strategy is further introduced by adding high‐concentration LiTFSI salt to the above system, resulting in the PVH/LiTFSI/LLZTO (PLL) CSEs. Benefiting from the synergetic coupling of the sacrificial inhibitor and polymer‐in‐salt strategies, the PLL exhibits an exceptionally high ionic conductivity of 1.2 mS cm−1 at 25 °C and stable voltage of 5.09 V, outperforming other reported CSEs. Consequently, the PLL delivers impressive high‐rate cyclability in solid‐state lithium‐metal batteries with an outstanding capacity retention of 95.4% after 240 cycles at 1 C (25 °C).","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":18.5000,"publicationDate":"2024-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Sacrificial NH4HCO3 Inhibits Fluoropolymer/Garnet Interfacial Reactions Toward 1mS cm−1 and 5V‐Level Composite Solid Electrolyte\",\"authors\":\"Yaping Wang, Pengcheng Yuan, Xiong Xiong Liu, Shengfa Feng, Mufan Cao, Jianxiang Ding, Jiacheng Liu, Song‐Zhu Kure‐Chu, Takehiko Hihara, Long Pan, Zhengming Sun\",\"doi\":\"10.1002/adfm.202405060\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Composite solid electrolytes (CSEs) integrate the fast ion conductivity of inorganic electrolytes and the excellent interfacial compatibility of polymer electrolytes. Typically, fluoropolymers and garnets are promising individuals to formulate cutting‐edge CSEs owing to their unique properties. However, the alkaline garnets can induce the dehydrofluorination of fluoropolymers, deteriorating their CSEs performance. Here, for the first time, NH4HCO3 is proposed as a sacrificial inhibitor to effectively prevent the garnet‐induced dehydrofluorination, using Li6.4La3Zr1.4Ta0.6O12 (LLZTO) and poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVH) as symbolic garnets and fluoropolymers, respectively. Various findings demonstrate that NH4HCO3 can buffer the alkalinity of LLZTO, thereby inhibiting the dehydrofluorination of PVH. In addition, NH4HCO3 can completely decompose to volatiles upon drying without compromising the properties of LLZTO and PVH. Additionally, a polymer‐in‐salt strategy is further introduced by adding high‐concentration LiTFSI salt to the above system, resulting in the PVH/LiTFSI/LLZTO (PLL) CSEs. Benefiting from the synergetic coupling of the sacrificial inhibitor and polymer‐in‐salt strategies, the PLL exhibits an exceptionally high ionic conductivity of 1.2 mS cm−1 at 25 °C and stable voltage of 5.09 V, outperforming other reported CSEs. Consequently, the PLL delivers impressive high‐rate cyclability in solid‐state lithium‐metal batteries with an outstanding capacity retention of 95.4% after 240 cycles at 1 C (25 °C).\",\"PeriodicalId\":112,\"journal\":{\"name\":\"Advanced Functional Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":18.5000,\"publicationDate\":\"2024-06-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Advanced Functional Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1002/adfm.202405060\",\"RegionNum\":1,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Functional Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1002/adfm.202405060","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Composite solid electrolytes (CSEs) integrate the fast ion conductivity of inorganic electrolytes and the excellent interfacial compatibility of polymer electrolytes. Typically, fluoropolymers and garnets are promising individuals to formulate cutting‐edge CSEs owing to their unique properties. However, the alkaline garnets can induce the dehydrofluorination of fluoropolymers, deteriorating their CSEs performance. Here, for the first time, NH4HCO3 is proposed as a sacrificial inhibitor to effectively prevent the garnet‐induced dehydrofluorination, using Li6.4La3Zr1.4Ta0.6O12 (LLZTO) and poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVH) as symbolic garnets and fluoropolymers, respectively. Various findings demonstrate that NH4HCO3 can buffer the alkalinity of LLZTO, thereby inhibiting the dehydrofluorination of PVH. In addition, NH4HCO3 can completely decompose to volatiles upon drying without compromising the properties of LLZTO and PVH. Additionally, a polymer‐in‐salt strategy is further introduced by adding high‐concentration LiTFSI salt to the above system, resulting in the PVH/LiTFSI/LLZTO (PLL) CSEs. Benefiting from the synergetic coupling of the sacrificial inhibitor and polymer‐in‐salt strategies, the PLL exhibits an exceptionally high ionic conductivity of 1.2 mS cm−1 at 25 °C and stable voltage of 5.09 V, outperforming other reported CSEs. Consequently, the PLL delivers impressive high‐rate cyclability in solid‐state lithium‐metal batteries with an outstanding capacity retention of 95.4% after 240 cycles at 1 C (25 °C).
期刊介绍:
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