All-solid-state Li-ion batteries(ASSLIBs)have been widely studied to achieve Li-ion batteries(LIBs)with high safety and energy density.Recent reviews and experimental papers have focused on methods that improve the io...All-solid-state Li-ion batteries(ASSLIBs)have been widely studied to achieve Li-ion batteries(LIBs)with high safety and energy density.Recent reviews and experimental papers have focused on methods that improve the ionic conductivity,stabilize the electrochemical performance,and enhance the electrolyte/electrode interfacial compatibility of several solid-state electrolytes(SSEs),including oxides,sulfides,composite and gel electrolytes,and so on.Garnet-structured Li_(7)La_(3)Zr_(2)O_(12)(LLZO)is highly regarded an SSE with excellent application potential.However,this type of electrolyte also possesses a number of disadvantages,such as low ionic conductivity,unstable cubic phase,and poor interfacial compatibility with anodes/cathodes.The benefits of LLZO have urged many researchers to explore effective solutions to overcome its inherent limitations.Herein,we review recent developments on garnet-structured LLZO and provide comprehensive insights to guide the development of garnet-structured LLZO-type electrolytes.We not only systematically and comprehensively discuss the preparation,element doping,structure,stability,and interfacial improvement of LLZOs but also provide future perspectives for these materials.This review expands the current understanding on advanced solid garnet electrolytes and provides meaningful guidance for the commercialization of ASSLIBs.展开更多
Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storag...Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storage systems.Among the numerous types of SSEs,inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12(LLZO)crystallized with the cubic Iaˉ3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity,wide electrochemical voltage window,high shear modulus,and excellent chemical stability with electrodes.However,no SSEs possess all the properties necessary for SSLBs,thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement.Hence,this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration,Li vacancy concentration,Li carrier concentration and mobility,Li occupancy at available sites,lattice constant,triangle bottleneck size,oxygen vacancy defects,and Li-O bonding interactions.Furthermore,the general illustration of structures and fundamental features being crucial to chemical stability is examined,including Li concentration,Li-site occupation behavior,and Li-O bonding interactions.Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures,revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions.We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors,thus assisting in promoting the rapid development of alternative green and sustainable technologies.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.21701083 and 51801078)the Zhenjiang Key Laboratory of Marine Power Equipment Performance(No.SS2018006)+1 种基金the Postgraduate Research&Practice Innovation Program of Jiangsu Province,China(Nos.SJCX19_0612 and KYCX20_3137)the Project of Jiangsu University(High-Tech Ship)Collaborative Innovation Center(No.2019,1174871801-11).
文摘All-solid-state Li-ion batteries(ASSLIBs)have been widely studied to achieve Li-ion batteries(LIBs)with high safety and energy density.Recent reviews and experimental papers have focused on methods that improve the ionic conductivity,stabilize the electrochemical performance,and enhance the electrolyte/electrode interfacial compatibility of several solid-state electrolytes(SSEs),including oxides,sulfides,composite and gel electrolytes,and so on.Garnet-structured Li_(7)La_(3)Zr_(2)O_(12)(LLZO)is highly regarded an SSE with excellent application potential.However,this type of electrolyte also possesses a number of disadvantages,such as low ionic conductivity,unstable cubic phase,and poor interfacial compatibility with anodes/cathodes.The benefits of LLZO have urged many researchers to explore effective solutions to overcome its inherent limitations.Herein,we review recent developments on garnet-structured LLZO and provide comprehensive insights to guide the development of garnet-structured LLZO-type electrolytes.We not only systematically and comprehensively discuss the preparation,element doping,structure,stability,and interfacial improvement of LLZOs but also provide future perspectives for these materials.This review expands the current understanding on advanced solid garnet electrolytes and provides meaningful guidance for the commercialization of ASSLIBs.
基金supported by the National Natural Science Foundation of China(Nos.22171102 and 22090044)the National Key R&D Program of China(Nos.2021YFF0500502 and 2023YFA1506304)+2 种基金the Jilin Province Science and Technology Development Plan(No.20230101024JC)the"Medicine+X"crossinnovation team of Bethune Medical Department of Jilin University"Leading the Charge with Open Competition"construction project(No.2022JBGS04)the Jilin University Graduate Training Office(Nos.2021JGZ08 and 2022YJSJIP20).
文摘Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storage systems.Among the numerous types of SSEs,inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12(LLZO)crystallized with the cubic Iaˉ3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity,wide electrochemical voltage window,high shear modulus,and excellent chemical stability with electrodes.However,no SSEs possess all the properties necessary for SSLBs,thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement.Hence,this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration,Li vacancy concentration,Li carrier concentration and mobility,Li occupancy at available sites,lattice constant,triangle bottleneck size,oxygen vacancy defects,and Li-O bonding interactions.Furthermore,the general illustration of structures and fundamental features being crucial to chemical stability is examined,including Li concentration,Li-site occupation behavior,and Li-O bonding interactions.Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures,revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions.We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors,thus assisting in promoting the rapid development of alternative green and sustainable technologies.
