{"title":"由含锂盐的聚丙烯腈纳米纤维组成的聚合物复合电解质膜:改善离子导电特性和全固态电池性能","authors":"Yu Matsuda, Shun Nakazawa, Manabu Tanaka, Hiroyoshi Kawakami","doi":"10.1002/macp.202400196","DOIUrl":null,"url":null,"abstract":"Polymer electrolyte membranes with superior lithium‐ion (Li<jats:sup>+</jats:sup>) conductivity and sufficient electrochemical stability are desired for all‐solid‐state lithium‐ion batteries (ASS‐LIBs). This paper reports novel polymer composite membranes consisting of polyacrylonitrile (PAN) nanofibers (Nfs) containing lithium salts. It is first revealed that the lithium salt addition increases polar surface groups on the PAN nanofibers. Subsequently, the lithium salts‐containing PAN nanofiber (PAN/Li Nf) composite membrane affects the matrix poly(ethylene oxide) (PEO)/lithium bis(trifluoromethyl sulfonylimide) (LiTFSI) electrolyte to increase the numbers of Li<jats:sup>+</jats:sup> with high mobility. Consequently, the PAN/Li Nf composite membrane shows relatively good ion conductivity (<jats:italic>σ</jats:italic> = 9.0 × 10<jats:sup>−5</jats:sup> S cm<jats:sup>−1</jats:sup>) and a considerably large Li<jats:sup>+</jats:sup> transference number (<jats:italic>t</jats:italic><jats:sub>Li+</jats:sub> = 0.41) at 60 °C, compared to the PEO/LiTFSI membrane without nanofibers. The <jats:sup>6</jats:sup>Li solid‐state NMR study supports that the PAN/Li Nf bearing abundant polar nitrile groups at their surface enhances Li<jats:sup>+</jats:sup> diffusion in the PEO‐based electrolyte membranes. The galvanostatic constant current cycling tests reveal that the PAN/Li Nf composite membrane possesses good electrochemical and mechanical stabilities. The ASS‐LIB consisting of the PAN/Li Nf composite membrane shows significantly improved charge and discharge cycling performances, promising future all‐solid‐state batteries.","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Polymer Composite Electrolytes Membrane Consisted of Polyacrylonitrile Nanofibers Containing Lithium Salts: Improved Ion Conductive Characteristics and All‐Solid‐State Battery Performance\",\"authors\":\"Yu Matsuda, Shun Nakazawa, Manabu Tanaka, Hiroyoshi Kawakami\",\"doi\":\"10.1002/macp.202400196\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Polymer electrolyte membranes with superior lithium‐ion (Li<jats:sup>+</jats:sup>) conductivity and sufficient electrochemical stability are desired for all‐solid‐state lithium‐ion batteries (ASS‐LIBs). This paper reports novel polymer composite membranes consisting of polyacrylonitrile (PAN) nanofibers (Nfs) containing lithium salts. It is first revealed that the lithium salt addition increases polar surface groups on the PAN nanofibers. Subsequently, the lithium salts‐containing PAN nanofiber (PAN/Li Nf) composite membrane affects the matrix poly(ethylene oxide) (PEO)/lithium bis(trifluoromethyl sulfonylimide) (LiTFSI) electrolyte to increase the numbers of Li<jats:sup>+</jats:sup> with high mobility. Consequently, the PAN/Li Nf composite membrane shows relatively good ion conductivity (<jats:italic>σ</jats:italic> = 9.0 × 10<jats:sup>−5</jats:sup> S cm<jats:sup>−1</jats:sup>) and a considerably large Li<jats:sup>+</jats:sup> transference number (<jats:italic>t</jats:italic><jats:sub>Li+</jats:sub> = 0.41) at 60 °C, compared to the PEO/LiTFSI membrane without nanofibers. The <jats:sup>6</jats:sup>Li solid‐state NMR study supports that the PAN/Li Nf bearing abundant polar nitrile groups at their surface enhances Li<jats:sup>+</jats:sup> diffusion in the PEO‐based electrolyte membranes. The galvanostatic constant current cycling tests reveal that the PAN/Li Nf composite membrane possesses good electrochemical and mechanical stabilities. 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引用次数: 0
摘要
全固态锂离子电池(ASS-LIB)需要具有卓越锂离子(Li+)传导性和足够电化学稳定性的聚合物电解质膜。本文报道了由含有锂盐的聚丙烯腈(PAN)纳米纤维(Nfs)组成的新型聚合物复合膜。研究首先发现,锂盐的添加增加了 PAN 纳米纤维上的极性表面基团。随后,含锂盐的 PAN 纳米纤维(PAN/Li Nf)复合膜影响了基质聚环氧乙烷(PEO)/双(三氟甲基磺酰亚胺)锂(LiTFSI)电解质,增加了具有高迁移率的 Li+ 数量。因此,与不含纳米纤维的 PEO/LiTFSI 膜相比,PAN/Li Nf 复合膜在 60 °C 时显示出相对较好的离子传导性(σ = 9.0 × 10-5 S cm-1)和相当大的 Li+ 转移数(tLi+ = 0.41)。6Li 固态核磁共振研究证明,表面含有大量极性腈基的 PAN/Li Nf 增强了 Li+ 在 PEO 基电解质膜中的扩散。电静态恒流循环测试表明,PAN/Li Nf 复合膜具有良好的电化学和机械稳定性。由 PAN/Li Nf 复合膜组成的 ASS-LIB 显著改善了充放电循环性能,有望成为未来的全固态电池。
Polymer Composite Electrolytes Membrane Consisted of Polyacrylonitrile Nanofibers Containing Lithium Salts: Improved Ion Conductive Characteristics and All‐Solid‐State Battery Performance
Polymer electrolyte membranes with superior lithium‐ion (Li+) conductivity and sufficient electrochemical stability are desired for all‐solid‐state lithium‐ion batteries (ASS‐LIBs). This paper reports novel polymer composite membranes consisting of polyacrylonitrile (PAN) nanofibers (Nfs) containing lithium salts. It is first revealed that the lithium salt addition increases polar surface groups on the PAN nanofibers. Subsequently, the lithium salts‐containing PAN nanofiber (PAN/Li Nf) composite membrane affects the matrix poly(ethylene oxide) (PEO)/lithium bis(trifluoromethyl sulfonylimide) (LiTFSI) electrolyte to increase the numbers of Li+ with high mobility. Consequently, the PAN/Li Nf composite membrane shows relatively good ion conductivity (σ = 9.0 × 10−5 S cm−1) and a considerably large Li+ transference number (tLi+ = 0.41) at 60 °C, compared to the PEO/LiTFSI membrane without nanofibers. The 6Li solid‐state NMR study supports that the PAN/Li Nf bearing abundant polar nitrile groups at their surface enhances Li+ diffusion in the PEO‐based electrolyte membranes. The galvanostatic constant current cycling tests reveal that the PAN/Li Nf composite membrane possesses good electrochemical and mechanical stabilities. The ASS‐LIB consisting of the PAN/Li Nf composite membrane shows significantly improved charge and discharge cycling performances, promising future all‐solid‐state batteries.
期刊介绍:
Macromolecular Chemistry and Physics publishes in all areas of polymer science - from chemistry, physical chemistry, and physics of polymers to polymers in materials science. Beside an attractive mixture of high-quality Full Papers, Trends, and Highlights, the journal offers a unique article type dedicated to young scientists – Talent.