journal article·2023-01-13

Fluorine Substitution at the O-Site Imparts Enhanced Chemical Stability for Garnet-Structured Electrolytes

Jingyu Shi, Ge Sun, Liping Li, Yuanhua Xia, Fei Du, Xiaojuan Liu, Hongwei Hou, Xiangyan Hou, Beining Zheng, Xiaofeng Wu, Keke Huang, Shouhua Feng

ACS Energy Letters· Volume 8· Issue 1
Publisher page

Abstract

Garnet-based superionic conductors hold great promise in next-generation lithium-ion batteries (LIBs) because of their favorable ionic conductivity and unique stability against Li-metal anodes; however, they still face the challenge of air stability for mass production/practical application. Herein, we identify their structural features and tailor the functional elements to enhance the chemical stability via synergistic control of doping and non-stoichiometry. The optimal composition of Li6.25Ga0.2La3Zr2O11.85F0.15 (LGLZO-0.15F) garnet exhibits great air durability without noticeable impurity accumulation, even during continuous air exposure for 60 days, owing to the high affinity of the fluorine dopant for lithium occupying the octahedral site. Meanwhile, LGLZO-0.15F possesses an appreciable Li-ion conductivity of 8.4 × 10–4 S cm–1 with an activation energy of 0.29 eV. Benefiting from these properties, hybrid and all-solid-state lithium batteries constructed with LGLZO-0.15F electrolytes demonstrate low overpotential, high Coulombic efficiency, and stable cycling performance.
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Research context

OpenAlex topics: Advanced Battery Materials and Technologies · Advancements in Battery Materials · Thermal Expansion and Ionic Conductivity

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Affiliations

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Qianjin Street 2699, Changchun 130012, P. R. China

Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Qianjin Street 2699, Changchun 130012, P. R. China

Key Laboratory of Neutron Physics and Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, Sichuan 621999, P. R. China

State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China

College of Physics, Jilin University, Qianjin Street 2699, Changchun 130012, P. R. China

Funding

Ministry of Science and Technology of the People's Republic of China · Department of Science and Technology of Jilin Province · National Natural Science Foundation of China · Chinese Academy of Sciences

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