Cargando…
Surface modification of garnet fillers with a polymeric sacrificial agent enables compatible interfaces of composite solid-state electrolytes
The poly (vinylidene fluoride) (PVDF)-based composite solid-state electrolyte (CSE) has garnered attention due to its excellent comprehensive performance. However, challenges persist in the structural design and preparation process of the ceramic-filled CSE, as the PVDF-based matrix is susceptible t...
Autores principales: | , , , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2023
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10664466/ https://www.ncbi.nlm.nih.gov/pubmed/38023503 http://dx.doi.org/10.1039/d3sc04710e |
_version_ | 1785138622804000768 |
---|---|
author | Luo, Bin Wu, Jintian Zhang, Ming Zhang, Zhihao Zhang, Xingwei Fang, Zixuan Xu, Ziqiang Wu, Mengqiang |
author_facet | Luo, Bin Wu, Jintian Zhang, Ming Zhang, Zhihao Zhang, Xingwei Fang, Zixuan Xu, Ziqiang Wu, Mengqiang |
author_sort | Luo, Bin |
collection | PubMed |
description | The poly (vinylidene fluoride) (PVDF)-based composite solid-state electrolyte (CSE) has garnered attention due to its excellent comprehensive performance. However, challenges persist in the structural design and preparation process of the ceramic-filled CSE, as the PVDF-based matrix is susceptible to alkaline conditions and dehydrofluorination, leading to its incompatibility with ceramic fillers and hindering the preparation of solid-state electrolytes. In this study, the mechanism of dehydrofluorination failure of a PVDF-based polymer in the presence of Li(2)CO(3) on the surface of Li(6.4)La(3)Zr(1.4)Ta(0.6)O(12) (LLZTO) is analyzed, and an effective strategy is proposed to inhibit the dehydrofluorination failure on the basis of density functional theory (DFT). We introduce a molecule with a small LUMO–HOMO gap as a sacrificial agent, which is able to remove the Li(2)CO(3) impurities. Therefore, the approach of polyacrylic acid (PAA) as a sacrificial agent reduces the degree of dehydrofluorination in the PVDF-based polymer and ensures slurry fluidity, promoting the homogeneous distribution of ceramic fillers in the electrolyte membrane and enhancing compatibility with the polymer. Consequently, the prepared electrolyte membranes exhibit good electrochemical and mechanical properties. The assembled Li-symmetric cell can cycle at 0.1 mA cm(−2) for 3500 h. The LiFePO(4)‖Li cell maintains 91.45% of its initial capacity after 650 cycles at 1C, and the LiCoO(2)‖Li cell maintains 84.9% of its initial capacity after 160 cycles, demonstrating promising high-voltage performance. This facile modification strategy can effectively improve compatibility issues between the polymer and fillers, which paves the way for the mass production of solid-state electrolytes. |
format | Online Article Text |
id | pubmed-10664466 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-106644662023-10-27 Surface modification of garnet fillers with a polymeric sacrificial agent enables compatible interfaces of composite solid-state electrolytes Luo, Bin Wu, Jintian Zhang, Ming Zhang, Zhihao Zhang, Xingwei Fang, Zixuan Xu, Ziqiang Wu, Mengqiang Chem Sci Chemistry The poly (vinylidene fluoride) (PVDF)-based composite solid-state electrolyte (CSE) has garnered attention due to its excellent comprehensive performance. However, challenges persist in the structural design and preparation process of the ceramic-filled CSE, as the PVDF-based matrix is susceptible to alkaline conditions and dehydrofluorination, leading to its incompatibility with ceramic fillers and hindering the preparation of solid-state electrolytes. In this study, the mechanism of dehydrofluorination failure of a PVDF-based polymer in the presence of Li(2)CO(3) on the surface of Li(6.4)La(3)Zr(1.4)Ta(0.6)O(12) (LLZTO) is analyzed, and an effective strategy is proposed to inhibit the dehydrofluorination failure on the basis of density functional theory (DFT). We introduce a molecule with a small LUMO–HOMO gap as a sacrificial agent, which is able to remove the Li(2)CO(3) impurities. Therefore, the approach of polyacrylic acid (PAA) as a sacrificial agent reduces the degree of dehydrofluorination in the PVDF-based polymer and ensures slurry fluidity, promoting the homogeneous distribution of ceramic fillers in the electrolyte membrane and enhancing compatibility with the polymer. Consequently, the prepared electrolyte membranes exhibit good electrochemical and mechanical properties. The assembled Li-symmetric cell can cycle at 0.1 mA cm(−2) for 3500 h. The LiFePO(4)‖Li cell maintains 91.45% of its initial capacity after 650 cycles at 1C, and the LiCoO(2)‖Li cell maintains 84.9% of its initial capacity after 160 cycles, demonstrating promising high-voltage performance. This facile modification strategy can effectively improve compatibility issues between the polymer and fillers, which paves the way for the mass production of solid-state electrolytes. The Royal Society of Chemistry 2023-10-27 /pmc/articles/PMC10664466/ /pubmed/38023503 http://dx.doi.org/10.1039/d3sc04710e Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Luo, Bin Wu, Jintian Zhang, Ming Zhang, Zhihao Zhang, Xingwei Fang, Zixuan Xu, Ziqiang Wu, Mengqiang Surface modification of garnet fillers with a polymeric sacrificial agent enables compatible interfaces of composite solid-state electrolytes |
title | Surface modification of garnet fillers with a polymeric sacrificial agent enables compatible interfaces of composite solid-state electrolytes |
title_full | Surface modification of garnet fillers with a polymeric sacrificial agent enables compatible interfaces of composite solid-state electrolytes |
title_fullStr | Surface modification of garnet fillers with a polymeric sacrificial agent enables compatible interfaces of composite solid-state electrolytes |
title_full_unstemmed | Surface modification of garnet fillers with a polymeric sacrificial agent enables compatible interfaces of composite solid-state electrolytes |
title_short | Surface modification of garnet fillers with a polymeric sacrificial agent enables compatible interfaces of composite solid-state electrolytes |
title_sort | surface modification of garnet fillers with a polymeric sacrificial agent enables compatible interfaces of composite solid-state electrolytes |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10664466/ https://www.ncbi.nlm.nih.gov/pubmed/38023503 http://dx.doi.org/10.1039/d3sc04710e |
work_keys_str_mv | AT luobin surfacemodificationofgarnetfillerswithapolymericsacrificialagentenablescompatibleinterfacesofcompositesolidstateelectrolytes AT wujintian surfacemodificationofgarnetfillerswithapolymericsacrificialagentenablescompatibleinterfacesofcompositesolidstateelectrolytes AT zhangming surfacemodificationofgarnetfillerswithapolymericsacrificialagentenablescompatibleinterfacesofcompositesolidstateelectrolytes AT zhangzhihao surfacemodificationofgarnetfillerswithapolymericsacrificialagentenablescompatibleinterfacesofcompositesolidstateelectrolytes AT zhangxingwei surfacemodificationofgarnetfillerswithapolymericsacrificialagentenablescompatibleinterfacesofcompositesolidstateelectrolytes AT fangzixuan surfacemodificationofgarnetfillerswithapolymericsacrificialagentenablescompatibleinterfacesofcompositesolidstateelectrolytes AT xuziqiang surfacemodificationofgarnetfillerswithapolymericsacrificialagentenablescompatibleinterfacesofcompositesolidstateelectrolytes AT wumengqiang surfacemodificationofgarnetfillerswithapolymericsacrificialagentenablescompatibleinterfacesofcompositesolidstateelectrolytes |