Insight into Multiple Intermolecular Coordination of Composite Solid Electrolytes via Cryo-Electron Microscopy for High-Voltage All-Solid-State Lithium Metal Batteries

Wang, Qingrong1; Xu, Hongli1; Fan, Yanchen1; Chi, Shang-Sen1; Han, Bing1; Ke, Ruohong1; Wang, Ruo1; Wang, Jun1; Wang, Chaoyang2; Xu, Xiaoxiong1; Zheng, Zijian3; Deng, Yonghong1; Chang, Jian1,4

2024-06-01

10.1002/adma.202314063

ADVANCED MATERIALS   影响因子和分区

0935-9648

1521-4095

["Polymer/ceramic-based composite solid electrolytes (CSE) are promising candidates for all-solid-state lithium metal batteries (SLBs), benefiting from the combined mechanical robustness of polymeric electrolytes and the high ionic conductivity of ceramic electrolytes. However, the interfacial instability and poorly understood interphases of CSE hinder their application in high-voltage SLBs. Herein, a simple but effective CSE that stabilizes high-voltage SLBs by forming multiple intermolecular coordination interactions between polyester and ceramic electrolytes is discovered. The multiple coordination between the carbonyl groups in poly(epsilon-caprolactone) and the fluorosulfonyl groups in anions with Li6.5La3Zr1.5Ta0.5O12 nanoparticles is directly visualized by cryogenic transmission electron microscopy and further confirmed by theoretical calculation. Importantly, the multiple coordination in CSE not only prevents the continuous decomposition of polymer skeleton by shielding the vulnerable carbonyl sites but also establishes stable inorganic-rich interphases through preferential decomposition of anions. The stable CSE and its inorganic-rich interphases enable Li||Li symmetric cells with an exceptional lifespan of over 4800 h without dendritic shorting at 0.1 mA cm-2. Moreover, the high-voltage SLB with LiNi0.5Co0.2Mn0.3O2 cathode displays excellent cycling stability over 1100 cycles at a 1C charge/discharge rate. This work reveals the underlying mechanism behind the excellent stability of coordinating composite electrolytes and interfaces in high-voltage SLBs.","In this work, a simple and effective composite solid electrolyte with multiple coordination to stabilize high-voltage lithium metal batteries is discovered, and the interface formation mechanism is visualized using cryogenic transmission electron microscopy. The multiple coordination prevents the continuous decomposition of the polymer skeleton by shielding the vulnerable carbonyl sites and establishing stable inorganic-rich interphases through the preferential decomposition of anions, thereby ensuring the long-term cycling stability of high-voltage solid-state lithium metal batteries. image"]

composite solid electrolyte cryo-TEM intermolecular coordination lithium metal batteries solid electrolyte interphase and cathode electrolyte interphase

SCI ; EI

英语

第一 ; 通讯

Guangdong Basic and Applied Basic Research Foundation["2022A1515011005","2021A1515010206"] ; Shenzhen Science and Technology Program["JCYJ20220818100407016","JCYJ20220818100218040"] ; Guangdong Provincial Key Laboratory of Energy Materials for Electric Power[2018B030322001] ; null[22109066] ; null[22371116] ; null[22078144]

Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics

Chemistry, Multidisciplinary ; Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary ; Physics, Applied ; Physics, Condensed Matter

WOS:001183886800001

WILEY-V C H VERLAG GMBH

MATERIALS SCIENCE

Web of Science

1.Southern Univ Sci & Technol, Sch Innovat & Entrepreneurship, Dept Mat Sci & Engn, Guangdong Prov Key Lab Energy Mat Elect Power, Shenzhen 518055, Peoples R China
2.South China Univ Technol, Res Inst Mat Sci, Guangzhou 510640, Peoples R China
3.Hong Kong Polytech Univ, Dept Appl Biol & Chem Technol, Kowloon, Hong Kong, Peoples R China
4.Great Bay Univ, Sch Phys Sci, Dongguan Key Lab Interdisciplinary Sci Adv Mat & L, Dongguan 523000, Peoples R China

Wang, Qingrong,Xu, Hongli,Fan, Yanchen,et al. Insight into Multiple Intermolecular Coordination of Composite Solid Electrolytes via Cryo-Electron Microscopy for High-Voltage All-Solid-State Lithium Metal Batteries[J]. ADVANCED MATERIALS,2024,36(23).

Wang, Qingrong.,Xu, Hongli.,Fan, Yanchen.,Chi, Shang-Sen.,Han, Bing.,...&Chang, Jian.(2024).Insight into Multiple Intermolecular Coordination of Composite Solid Electrolytes via Cryo-Electron Microscopy for High-Voltage All-Solid-State Lithium Metal Batteries.ADVANCED MATERIALS,36(23).

Wang, Qingrong,et al."Insight into Multiple Intermolecular Coordination of Composite Solid Electrolytes via Cryo-Electron Microscopy for High-Voltage All-Solid-State Lithium Metal Batteries".ADVANCED MATERIALS 36.23(2024).