Interface Engineering for the Anode in Solid-state Lithium Batteries Based on LLZTO Electrolyte

doi:10.15541/jim20240492

Abstract

Abstract: Garnet-type solid electrolytes (LLZTO) have attracted tremendous attention in the past few years, owing to its high ionic conductivity and wide electrochemical stability window. However, its poor wettability with lithium metal and severe lithium dendrite formation during cycling greatly hindered its application in large-scale devices. In this study, a composite anode (LAF) was prepared by melting Li metal and AlF₃, which eventually formed fluorides (LiF, AlF₃) and Li-Al alloys. Elemental distribution analysis revealed that a fluoride layer was formed at LLZTO|LAF interface upon contact with LLZTO. Compared to metallic lithium, the composite anode forms a significantly smaller interface contact angle with LLZTO, notably improving the interfacial wettability. As a result, the modified LAF|LLZTO interface exhibits an ultralow interfacial resistance of 3.9 Ω/cm², being much lower than that of the lithium anode with LLZTO (138.6 Ω/cm²). Meanwhile, the critical current density of the composite anode with LLZTO increased from 0.2 mA/cm² to 0.8 mA/cm². LAF|LLZTO|LAF symmetric cells demonstrate stable plating/stripping for 3500 h under a current density of 0.2 mA/cm², illustrating the good stability of lithium-ion plating/stripping process. LiFePO₄|LLZTO|LAF quasi-solid-state battery delivers a high discharge capacity of 148.7 mAh/g at 0.1C rate (1C=170 mA/g) and retain 96.5% of its initial capacity after 240 cycles at a current rate of 1C. The LAF composite anode demonstrated in this study effectively decreases the interfacial resistance between LLZTO and anode, and stabilizes lithium-ion plating/stripping process, offering a promising approach for designing high-performance LLZTO-based lithium metal batteries.

Key words: Lithium-ion battery, solid Electrolyte, LLZTO, anode interface

CLC Number:

TM912

WEN Shenhao, PENG Dezhao, LIN Zheyu, GUO Xia, HUANG Peixin, ZHANG Zhizhen. Interface Engineering for the Anode in Solid-state Lithium Batteries Based on LLZTO Electrolyte[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20240492.

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