Lithium Salt Association-Mediated Interfacial Charge Exchange for Low-Temperature Lithium-Metal Batteries: Beyond Lithium De-Solvation Manner

Fairly assessing energy barrier that shifts coordinated lithium (Li) to naked Li on the interface, as well as deeply exploring interfacial descriptors that can interpret rapid interfacial redox kinetics with anion-dominated electrolyte species, has been long-standing fundamentals to design well-perf...

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Main Authors: Fei Zhao, Jin-Hao Zhang, Jin-Xiu Chen, Zhi-Yuan Gu, Xiao-Zhong Fan, Lin Zhu, Hui-Ling Na, Ming-Xia Dong, Cao Guan, Long Kong
Format: Article
Language:English
Published: American Association for the Advancement of Science (AAAS) 2025-01-01
Series:Research
Online Access:https://spj.science.org/doi/10.34133/research.0802
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author Fei Zhao
Jin-Hao Zhang
Jin-Xiu Chen
Zhi-Yuan Gu
Xiao-Zhong Fan
Lin Zhu
Hui-Ling Na
Ming-Xia Dong
Cao Guan
Long Kong
author_facet Fei Zhao
Jin-Hao Zhang
Jin-Xiu Chen
Zhi-Yuan Gu
Xiao-Zhong Fan
Lin Zhu
Hui-Ling Na
Ming-Xia Dong
Cao Guan
Long Kong
author_sort Fei Zhao
collection DOAJ
description Fairly assessing energy barrier that shifts coordinated lithium (Li) to naked Li on the interface, as well as deeply exploring interfacial descriptors that can interpret rapid interfacial redox kinetics with anion-dominated electrolyte species, has been long-standing fundamentals to design well-performing electrolytes for low-temperature Li metal batteries. The Li de-solvation concept is merely a picture that can describe the transformation of coordinated Li to naked Li. This work highlights the importance of Li de-coordination instead of Li de-solvation to illustrate such Li transformation behavior, since it considers entire Li de-sheath events (both solvent and anion). Theoretical calculations inform that anions entering into the first Li solvation sheath (mimic to the weak solvation electrolyte) unavoidably elevate the Li de-coordination energy due to the intrinsically greater ion–ion than ion–dipole interactions in the bulk electrolyte. The subsequent interfacial model suggests that interfacial charge exchange is a more effective descriptor to mediate interfacial redox kinetics and interpret experimental results that anion-rich Li species exhibit better battery performances. This work underscores anion effects on the Li de-coordination in the bulk electrolyte and charge exchange in the interface, hoping to unveil the fundamental causes why anion-prevailed Li species work well in low-temperature Li metal batteries.
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spelling doaj-art-ffd29351a451490a9761afc92d45f5aa2025-08-20T03:22:12ZengAmerican Association for the Advancement of Science (AAAS)Research2639-52742025-01-01810.34133/research.0802Lithium Salt Association-Mediated Interfacial Charge Exchange for Low-Temperature Lithium-Metal Batteries: Beyond Lithium De-Solvation MannerFei Zhao0Jin-Hao Zhang1Jin-Xiu Chen2Zhi-Yuan Gu3Xiao-Zhong Fan4Lin Zhu5Hui-Ling Na6Ming-Xia Dong7Cao Guan8Long Kong9Institute of Flexible Electronics, Northwestern Polytechnical University, Xi’an 710129, China.Institute of Flexible Electronics, Northwestern Polytechnical University, Xi’an 710129, China.Institute of Flexible Electronics, Northwestern Polytechnical University, Xi’an 710129, China.Institute of Flexible Electronics, Northwestern Polytechnical University, Xi’an 710129, China.Institute of Flexible Electronics, Northwestern Polytechnical University, Xi’an 710129, China.Air Defense and Antimissile School, Air Force Engineering University, Xi’an 710100, China.CNPC Research Institute of Safety & Environment Technology, Beijing 102206, China.BASF Shanshan Battery Materials Co. Ltd., Changsha 410205, China.Institute of Flexible Electronics, Northwestern Polytechnical University, Xi’an 710129, China.Institute of Flexible Electronics, Northwestern Polytechnical University, Xi’an 710129, China.Fairly assessing energy barrier that shifts coordinated lithium (Li) to naked Li on the interface, as well as deeply exploring interfacial descriptors that can interpret rapid interfacial redox kinetics with anion-dominated electrolyte species, has been long-standing fundamentals to design well-performing electrolytes for low-temperature Li metal batteries. The Li de-solvation concept is merely a picture that can describe the transformation of coordinated Li to naked Li. This work highlights the importance of Li de-coordination instead of Li de-solvation to illustrate such Li transformation behavior, since it considers entire Li de-sheath events (both solvent and anion). Theoretical calculations inform that anions entering into the first Li solvation sheath (mimic to the weak solvation electrolyte) unavoidably elevate the Li de-coordination energy due to the intrinsically greater ion–ion than ion–dipole interactions in the bulk electrolyte. The subsequent interfacial model suggests that interfacial charge exchange is a more effective descriptor to mediate interfacial redox kinetics and interpret experimental results that anion-rich Li species exhibit better battery performances. This work underscores anion effects on the Li de-coordination in the bulk electrolyte and charge exchange in the interface, hoping to unveil the fundamental causes why anion-prevailed Li species work well in low-temperature Li metal batteries.https://spj.science.org/doi/10.34133/research.0802
spellingShingle Fei Zhao
Jin-Hao Zhang
Jin-Xiu Chen
Zhi-Yuan Gu
Xiao-Zhong Fan
Lin Zhu
Hui-Ling Na
Ming-Xia Dong
Cao Guan
Long Kong
Lithium Salt Association-Mediated Interfacial Charge Exchange for Low-Temperature Lithium-Metal Batteries: Beyond Lithium De-Solvation Manner
Research
title Lithium Salt Association-Mediated Interfacial Charge Exchange for Low-Temperature Lithium-Metal Batteries: Beyond Lithium De-Solvation Manner
title_full Lithium Salt Association-Mediated Interfacial Charge Exchange for Low-Temperature Lithium-Metal Batteries: Beyond Lithium De-Solvation Manner
title_fullStr Lithium Salt Association-Mediated Interfacial Charge Exchange for Low-Temperature Lithium-Metal Batteries: Beyond Lithium De-Solvation Manner
title_full_unstemmed Lithium Salt Association-Mediated Interfacial Charge Exchange for Low-Temperature Lithium-Metal Batteries: Beyond Lithium De-Solvation Manner
title_short Lithium Salt Association-Mediated Interfacial Charge Exchange for Low-Temperature Lithium-Metal Batteries: Beyond Lithium De-Solvation Manner
title_sort lithium salt association mediated interfacial charge exchange for low temperature lithium metal batteries beyond lithium de solvation manner
url https://spj.science.org/doi/10.34133/research.0802
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