基于LLZTO电解质的固态锂金属电池负极界面调控

doi:10.15541/jim20240492

无机材料学报 ›› 2025, Vol. 40 ›› Issue (9): 1013-1021.DOI: 10.15541/jim20240492

基于LLZTO电解质的固态锂金属电池负极界面调控

文伸豪¹^,²(), 彭德招¹^,², 林喆与¹^,², 郭霞¹^,², 黄培鑫¹^,², 章志珍¹^,²()

1.中山大学材料学院, 广州 510006
2.中山大学·深圳材料学院深圳 518107

收稿日期:2024-11-22 修回日期:2025-03-04 出版日期:2025-09-20 网络出版日期:2025-03-19
通讯作者: 章志珍, 副教授. E-mail: zhangzhzh28@mail.sysu.edu.cn
作者简介:文伸豪(2002-), 博士研究生. E-mail: wenshh9@mail2.sysu.edu.cn
基金资助:
广东省科技计划项目(2023B0909060004);深圳市优秀科技创新人才培养项目(RCYX20221008092929074);深圳市面上项目(JCYJ20220530150200001);广东省“珠江人才计划”青年拔尖人才项目(2021QN02L210)

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

WEN Shenhao¹^,²(), PENG Dezhao¹^,², LIN Zheyu¹^,², GUO Xia¹^,², HUANG Peixin¹^,², ZHANG Zhizhen¹^,²()

1. School of Materials, Sun Yat-sen University, Guangzhou 510006, China
2. School of Materials, Shenzhen Campus of Sun Yat-sen University, Shenzhen 518107, China

Received:2024-11-22 Revised:2025-03-04 Published:2025-09-20 Online:2025-03-19
Contact: ZHANG Zhizhen, associate professor. E-mail: zhangzhzh28@mail.sysu.edu.cn
About author:WEN Shenhao (2002-), PhD candidate. E-mail: wenshh9@mail2.sysu.edu.cn
Supported by:
Guangdong S&T Program(2023B0909060004);Shenzhen Science and Technology Program(RCYX20221008092929074);Shenzhen Fundamental Research Program(JCYJ20220530150200001);Zhujiang Talent Program of Guangdong Province(2021QN02L210)

摘要/Abstract

摘要：

石榴石型固态电解质(LLZTO)具有高离子电导率、宽电化学稳定窗口等优点, 近年来受到了广泛关注。但LLZTO存在与金属锂负极浸润性差、循环过程中锂枝晶生长严重等问题, 限制了其大规模应用。本研究通过熔融金属Li和AlF₃, 制备了含氟化物(LiF、AlF₃)和Li-Al合金的复合负极(LAF)。元素分布分析表明LAF复合负极与LLZTO电解质接触后, 在界面处形成氟化物。与金属Li相比, 该复合负极能与LLZTO形成较小的界面接触角, 使得界面浸润性显著提升。改性后的LAF3复合负极(Li与AlF₃质量比3 : 1)与LLZTO的界面电阻仅为3.9 Ω/cm², 远小于金属Li负极与LLZTO的界面电阻(138.6 Ω/cm²); 同时, 临界电流密度从0.2 mA/cm²提升至0.8 mA/cm²。组装的LAF3|LLZTO|LAF3对称电池在0.2 mA/cm²电流密度下能稳定沉积/剥离3500 h, 表明LLZTO|LAF3界面处具有稳定的锂离子沉积/剥离过程。LiFePO₄|LLZTO|LAF3准固态电池在0.1C(1C=170 mA/g)电流密度下实现了151.1 mAh/g的放电比容量, 且在1C电流密度下循环240圈后, 容量保持率高达96.5%。本研究提出的LAF复合负极有效降低了LLZTO|负极的界面电阻, 并显著提升了锂离子在界面处的沉积/剥离稳定性, 为高性能LLZTO基金属锂电池提供了新的设计思路。

关键词: 锂离子电池, 固态电解质, LLZTO, 负极界面

Abstract:

Garnet-type solid electrolytes (LLZTO) have attracted tremendous attention in the past few years, owing to their high ionic conductivity and wide electrochemical stability window. However, the poor wettability with lithium metal and severe lithium dendrite formation during cycling greatly hindered their 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 formed a significantly smaller interface contact angle with LLZTO, notably improving the interfacial wettability. As a result, the modified LAF3|LLZTO interface (a mass ratio of Li to AlF3 is 3 : 1) exhibits an ultralow interfacial resistance of 3.9 Ω/cm², which is 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 increases 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 151.1 mAh/g at 0.1C rate (1C=170 mA/g) and retains 96.5% of its initial capacity after 240 cycles at 1C rate. 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

中图分类号:

TM912

文伸豪, 彭德招, 林喆与, 郭霞, 黄培鑫, 章志珍. 基于LLZTO电解质的固态锂金属电池负极界面调控[J]. 无机材料学报, 2025, 40(9): 1013-1021.

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, 2025, 40(9): 1013-1021.

图/表 8

图1 LLZTO电解质片表征

Fig. 1 Characterization of LLZTO electrolyte (a) EIS spectra; (b) XRD pattern; (c-e) Cross-sectional SEM images; (f) Cross-sectional SEM image and EDS mappings

表1 LLZTO电解质片的截面元素比例

Table 1 Proportion of cross-sectional elements in LLZTO electrolyte

Element	Mass ratio/%	Molar ratio/%
La	46.3	14.0
Zr	13.2	6.0
Ta	10.9	2.5
O	29.6	77.4

图2 LAF3复合负极的XRD图谱

Fig. 2 XRD pattern of LAF3 composite anode

图3 LLZTO复合负极表征

图4 LAF3|LLZTO的界面形貌和元素分布

Fig. 4 Morphology and element distribution of LAF3|LLZTO interface (a) SEM image of the interface; (b-d) EDS spectra across the interface displaying (b) F, (c) Zr, and (d) La element distributions

参考文献 35

[1]	徐学笛. 化学电源的发展及展望. 化学工程与装备, 2008(2): 95.
[2]	XIE J, LU Y C. A retrospective on lithium-ion batteries. Nature Communications, 2020, 11: 2499.
[3]	赵光金, 李晶晶, 胡玉霞, 等. 锂离子电池储能电站安全风险及应对策略. 电源技术, 2024, 48(12): 2343. DOI
[4]	徐琛. 固态锂电池复合固态电解质研究进展. 中外能源, 2023, 28(9): 18.
[5]	KIM A, WOO S, KANG M, et al. Research progresses of garnet-type solid electrolytes for developing all-solid-state Li batteries. Frontiers in Chemistry, 2020, 8: 468.
[6]	WU J, CHEN L, SONG T, et al. A review on structural characteristics, lithium ion diffusion behavior and temperature dependence of conductivity in perovskite-type solid electrolyte Li_3-_xLa_2/3-_xTiO₃. Functional Materials Letters, 2017, 10(3): 1730002.
[7]	LI C, LI R, LIU K, et al. NaSICON: a promising solid electrolyte for solid-state sodium batteries. Interdisciplinary Materials, 2022, 1(3): 396.
[8]	ZHAO Y, DAEMEN L L. Superionic conductivity in lithium- rich anti-perovskites. Journal of the American Chemical Society, 2012, 134(36): 15042.
[9]	AIMI A, ONODERA H, SHIMONISHI Y, et al. High Li-ion conductivity in pyrochlore-type solid electrolyte Li_2-_xLa₍₁₊_x_)/3M₂O₆F (M=Nb, Ta). Chemistry of Materials, 2024, 36(8): 3717.
[10]	WANG C, FU K, KAMMAMPATA S P, et al. Garnet-type solid-state electrolytes: materials, interfaces, and batteries. Chemical reviews, 2020, 120(10): 4257. DOI PMID
[11]	MURUGAN R, THANGADURAI V, WEPPNER W. Fast lithium ion conduction in garnet-type Li₇La₃Zr₂O₁₂. Angewandte Chemie International Edition, 2007, 46(41): 7778.
[12]	CHEN R, NOLAN A M, LU J, et al. The thermal stability of lithium solid electrolytes with metallic lithium. Joule, 2020, 4(4): 812.
[13]	CHENG E J, DUAN H, WANG M J, et al. Li-stuffed garnet solid electrolytes: current status, challenges, and perspectives for practical. Energy Storage Materials, 2024, 75: 103970.
[14]	张念, 任国玺, 章辉, 等. 石榴石型固态电解质表界面问题及优化的研究进展. 物理学报, 2020, 69(22): 224.
[15]	HAN X, GONG Y, FU K, et al. Negating interfacial impedance in garnet-based solid-state Li metal batteries. Nature Materials, 2017, 16(5): 572. DOI PMID
[16]	PORZ L, SWAMY T, SHELDON B W, et al. Mechanism of lithium metal penetration through inorganic solid electrolytes. Advanced Energy Materials, 2017, 7(20): 1701003.
[17]	SHARAFI A, KAZYAK E, DAVIS A L, et al. Surface chemistry mechanism of ultra-low interfacial resistance in the solid-state electrolyte Li₇La₃Zr₂O₁₂. Chemistry of Materials, 2017, 29(18): 7961.
[18]	DUAN H, CHEN W P, FAN M, et al. Building an air stable and lithium deposition regulable garnet interface from moderate- temperature conversion chemistry. Angewandte Chemie International Edition, 2020, 132(29): 12167.
[19]	BI Z, SUN Q, JIA M, et al. Molten salt driven conversion reaction enabling lithiophilic and air-stable garnet surface for solid-state lithium batteries. Advanced Functional Materials, 2022, 32(52): 2208751.
[20]	RUAN Y, LU Y, LI Y, et al. A 3D cross-linking lithiophilic and electronically insulating interfacial engineering for garnet-type solid-state lithium batteries. Advanced Functional Materials, 2021, 31(5): 2007815.
[21]	LEE S, LEE K S, KIM S, et al. Design of a lithiophilic and electron-blocking interlayer for dendrite-free lithium-metal solid-state batteries. Science Advances, 2022, 8(30): eabq0153.
[22]	BI Z, HUANG W, MU S, et al. Dual-interface reinforced flexible solid garnet batteries enabled by in-situ solidified gel polymer electrolytes. Nano Energy, 2021, 90: 106498.
[23]	BI Z, SHI R, LIU X, et al. In situ conversion reaction triggered alloy@antiperovskite hybrid layers for lithiophilic and robust lithium/garnet interfaces. Advanced Functional Materials, 2023, 33(43): 2307701.
[24]	ALEXANDER G V, SHI C, O’NEILL J, et al. Extreme lithium- metal cycling enabled by a mixed ion-and electron-conducting garnet three-dimensional architecture. Nature Materials, 2023, 22(9): 1136.
[25]	FENG W, DONG X, LI P, et al. Interfacial modification of Li/garnet electrolyte by a lithiophilic and breathing interlayer. Journal of Power Sources, 2019, 419: 91.
[26]	LI Z, ZHENG W, LU G, et al. Superionic conductor enabled composite lithium with high ionic conductivity and interfacial wettability for solid-state lithium batteries. Advanced Functional Materials, 2024, 34(12): 2309751.
[27]	HU X, YU J, WANG Y, et al. A lithium intrusion-blocking interfacial shield for wide-pressure-range solid-state lithium metal batteries. Advanced Materials, 2024, 36(7): 2308275.
[28]	CHEN B, ZHANG J, ZHANG T, et al. Directly using Li₂CO₃ as a lithiophobic interlayer to inhibit Li dendrites for high- performance solid-state batteries. ACS Energy Letters, 2023, 8(5): 2221.
[29]	SHI K, WAN Z, YANG L, et al. In situ construction of an ultra-stable conductive composite interface for high-voltage all-solid-state lithium metal batteries. Angewandte Chemie International Edition, 2020, 59(29): 11784.
[30]	LU Y, HUANG X, RUAN Y, et al. An in situ element permeation constructed high endurance Li-LLZO interface at high current densities. Journal of Materials Chemistry A, 2018, 6(39): 18853.
[31]	MA C, JIANG W, DUAN Q, et al. Superdense lithium deposition via mixed ionic/electronic conductive interfaces implanted in vivo/vitro for stable lithium metal batteries. Advanced Energy Materials, 2024, 14(25): 2400202.
[32]	LI Y, LI J, XIAO H, et al. A novel 3D Li/Li₉Al₄/Li-Mg alloy anode for superior lithium metal batteries. Advanced Functional Materials, 2023, 33(14): 2213905.
[33]	PENG Z, REN F, YANG S, et al. A highly stable host for lithium metal anode enabled by Li₉Al₄-Li₃N-AlN structure. Nano Energy, 2019, 59: 110.
[34]	SHI X, PANG Y, WANG B, et al. In situ forming LiF nanodecorated electrolyte/electrode interfaces for stable all- solid-state batteries. Materials Today Nano, 2020, 10: 100079.
[35]	CHEN Y, OUYANG C, SONG L, et al. Electrical and lithium ion dynamics in three main components of solid electrolyte interphase from density functional theory study. The Journal of Physical Chemistry C, 2011, 115(14): 7044.

基于LLZTO电解质的固态锂金属电池负极界面调控

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

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