Poly(ethylene oxide)(PEO)and Li_(6.75)La_(3)Zr_(1.75)Ta_(0.25)O_(12)(LLZTO)-based composite polymer electrolytes(CPEs)are considered one of the most promising solid electrolyte systems.However,agglomeration of LLZTO w...Poly(ethylene oxide)(PEO)and Li_(6.75)La_(3)Zr_(1.75)Ta_(0.25)O_(12)(LLZTO)-based composite polymer electrolytes(CPEs)are considered one of the most promising solid electrolyte systems.However,agglomeration of LLZTO within PEO and lack of Li^(+)channels result in poor electrochemical properties.Herein,a functional supramolecular combination(CD-TFSI)consisting of activeβ-cyclodextrin(CD)supramolecular with self-assembled LiTFSI salt is selected as an interface modifier to coat LLZTO fillers.Benefiting from vast H-bonds formed betweenβ-CD and PEO matrix and/or LLZTO,homogeneous dispersion and tight interface contact are obtained.Moreover,^(6)Li NMR spectra confirm a new Li^(+)transmission pathway from PEO matrix to LLZTO ceramic then to PEO matrix in the as-prepared PEO/LLZTO@CD-TFSI CPEs due to the typical cavity structure ofβ-CD.As a proof,the conductivity is increased from 5.3×10^(-4)S cm^(-1)to 8.7×10^(-4)S cm^(-1)at 60℃,the Li^(+)transference number is enhanced from 0.38 to 0.48,and the electrochemical stability window is extended to 5.1 V versus Li/Li^(+).Li‖LiFePO_(4)CR2032 coin full cells and pouch cells prove the practical application of the as-prepared PEO/LLZTO@CD-TFSI CPEs.This work offers a new strategy of interface modifying LLZTO fillers with functional supramolecular combination to optimize PEO/LLZTO CPEs for solid lithium batteries.展开更多
基金the financial support of the National Natural Science Foundation of China(Nos.21773167,51972220)the National Key Research and Development Program of China(No.2021YFE0107200)+1 种基金the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.20KJA480003)the Key R&D Project funded by Department of Science and Technology of Jiangsu Province(No.BE2020003)
文摘Poly(ethylene oxide)(PEO)and Li_(6.75)La_(3)Zr_(1.75)Ta_(0.25)O_(12)(LLZTO)-based composite polymer electrolytes(CPEs)are considered one of the most promising solid electrolyte systems.However,agglomeration of LLZTO within PEO and lack of Li^(+)channels result in poor electrochemical properties.Herein,a functional supramolecular combination(CD-TFSI)consisting of activeβ-cyclodextrin(CD)supramolecular with self-assembled LiTFSI salt is selected as an interface modifier to coat LLZTO fillers.Benefiting from vast H-bonds formed betweenβ-CD and PEO matrix and/or LLZTO,homogeneous dispersion and tight interface contact are obtained.Moreover,^(6)Li NMR spectra confirm a new Li^(+)transmission pathway from PEO matrix to LLZTO ceramic then to PEO matrix in the as-prepared PEO/LLZTO@CD-TFSI CPEs due to the typical cavity structure ofβ-CD.As a proof,the conductivity is increased from 5.3×10^(-4)S cm^(-1)to 8.7×10^(-4)S cm^(-1)at 60℃,the Li^(+)transference number is enhanced from 0.38 to 0.48,and the electrochemical stability window is extended to 5.1 V versus Li/Li^(+).Li‖LiFePO_(4)CR2032 coin full cells and pouch cells prove the practical application of the as-prepared PEO/LLZTO@CD-TFSI CPEs.This work offers a new strategy of interface modifying LLZTO fillers with functional supramolecular combination to optimize PEO/LLZTO CPEs for solid lithium batteries.
