Inhibiting Formation and Reduction of Li2CO3 to LiCx at Grain Boundaries in Garnet Electrolytes to Prevent Li Penetration

Biao, Jie1,2; Han, Bing3; Cao, Yidan1; Li, Qidong1; Zhong, Guiming4; Ma, Jiabin1,2; Chen, Likun1,2; Yang, Ke1,2; Mi, Jinshuo1,2; Deng, Yonghong3; Liu, Ming1; Lv, Wei1; Kang, Feiyu1,2; He, Yan-Bing1

2023-02-01

10.1002/adma.202208951

ADVANCED MATERIALS   Impact Factor & Quartile

0935-9648

1521-4095

Poor ion and high electron transport at the grain boundaries (GBs) of ceramic electrolytes are the primary reasons for lithium filament infiltration and short-circuiting of all-solid-state lithium metal batteries (ASLMBs). Herein, it is discovered that Li2CO3 at the GBs of Li7La3Zr2O12 (LLZO) sheets is reduced to highly electron-conductive LiCx during cycling, resulting in lithium penetration of LLZO. The ionic and electronic conductivity of the GBs within LLZO can be simultaneously tuned using sintered Li3AlF6. The generated LiAlO2 (LAO) infusion and F-doping at the GBs of LLZO (LAO-LLZOF) significantly reduce the Li2CO3 content and broaden the energy bandgap of LLZO, which decreases the electronic conductivity of LAO-LLZOF. LAO forms a 3D continuous ion transport network at the GB that significantly improves the total ionic conductivity. Lithium penetration within LLZO is suppressed and an all-solid-state LiFePO4/LAO-LLZOF/Li battery stably cycled for 5500 cycles at 3 C. This work reveals the chemistry of Li2CO3 at the LLZO GBs during cycling, presents a novel lithium penetration mechanism within garnet electrolytes, and provides an innovative method to simultaneously regulate the ion and electron transport at the GBs in garnet electrodes for advanced ASLMBs.

ion electron transport Li2CO3 Lithium penetration mechanism LLZO grain boundary

SCI

English

NI Journal Papers ; NI论文

Others

National Key Research and Development Program of China[2021YFF0500600] ; National Natural Science Foundation of China[U2001220] ; Key-Area Research and Development Program of Guangdong Province[2020B090919001] ; Local Innovative Research Teams Project of Guangdong Pearl River Talents Program[2017BT01N111] ; Shenzhen Technical Plan Project["JCYJ20220818101003007","JCYJ20220818101003008","XMHT20200203006"] ; null[RCJC20200714114436091]

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

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

WOS:000929505600001

WILEY-V C H VERLAG GMBH

MATERIALS SCIENCE

Web of Science

1.Tsinghua Univ, Inst Mat Res IMR, Shenzhen Geim Graphene Ctr, Tsinghua Shenzhen Int Grad Sch, Shenzhen 518055, Peoples R China
2.Tsinghua Univ, Sch Mat Sci & Engn, Lab Adv Mat, Beijing 100084, Peoples R China
3.Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen 518055, Peoples R China
4.Chinese Acad Sci, Dalian Inst Chem Phys, Lab Adv Spectro Electrochem & Lithium Ion Batterie, Dalian Natl Lab Clean Energy, Dalian 116023, Peoples R China

Biao, Jie,Han, Bing,Cao, Yidan,et al. Inhibiting Formation and Reduction of Li2CO3 to LiCx at Grain Boundaries in Garnet Electrolytes to Prevent Li Penetration[J]. ADVANCED MATERIALS,2023.

Biao, Jie.,Han, Bing.,Cao, Yidan.,Li, Qidong.,Zhong, Guiming.,...&He, Yan-Bing.(2023).Inhibiting Formation and Reduction of Li2CO3 to LiCx at Grain Boundaries in Garnet Electrolytes to Prevent Li Penetration.ADVANCED MATERIALS.

Biao, Jie,et al."Inhibiting Formation and Reduction of Li2CO3 to LiCx at Grain Boundaries in Garnet Electrolytes to Prevent Li Penetration".ADVANCED MATERIALS (2023).