LiF添加剂改善含锂陶瓷隔膜与4.35 V LiNi0.8Co0.1Mn0.1O2 正极的界面稳定性

doi:10.19799/j.cnki.2095-4239.2023.0128

储能科学与技术 ›› 2023, Vol. 12 ›› Issue (8): 2361-2369.doi: 10.19799/j.cnki.2095-4239.2023.0128

LiF添加剂改善含锂陶瓷隔膜与4.35 V LiNi_0.8Co_0.1Mn_0.1O₂ 正极的界面稳定性

黄永浩¹^,²(), 臧国景², 朱霨亚¹, 廖友好¹^,²(), 李伟善¹^,²()

^1.潮州三环（集团）股份有限公司，广东潮州 515646
^2.华南师范大学化学学院，广东广州 510006

收稿日期:2023-03-15 修回日期:2023-04-07 出版日期:2023-08-05 发布日期:2023-08-23
通讯作者: 廖友好,李伟善 E-mail:731581530@qq.com;liaoyh@scnu.edu.cn;liwsh@scnu.edu.cn
作者简介:黄永浩（1998—），男，硕士研究生，研究方向为电池固体电解质材料，E-mail：731581530@qq.com；
基金资助:
“潮州市陶瓷产业人才振兴计划”创新创业团队引进项目(2021YJ01)

Enhancing interfacial stability between lithium-containing ceramic separator and 4.35 V LiNi_0.8Co_0.1Mn_0.1O₂ cathode through LiF additives

Yonghao HUANG¹^,²(), Guojing ZANG², Weiya ZHU¹, Youhao LIAO¹^,²(), Weishan LI¹^,²()

^1.Chaozhou Three-circle (Group) Co. Ltd, Chaozhou 515646, Guangdong, China
^2.School of Chemistry, South China Normal University, Guangzhou 510006, Guangdong, China

Received:2023-03-15 Revised:2023-04-07 Online:2023-08-05 Published:2023-08-23
Contact: Youhao LIAO, Weishan LI E-mail:731581530@qq.com;liaoyh@scnu.edu.cn;liwsh@scnu.edu.cn

摘要/Abstract

摘要：

锂离子电池用LiNi_0.8Co_0.1Mn_0.1O₂（NCM811）正极，具有较高比容量和较低成本的优点，但是其在高电压长循环时正极界面极不稳定、安全性能亟待提高。虽然锂快离子导体Li_1.2Ca_0.1Zr_1.9（PO₄）₃制备的陶瓷隔膜在很大程度上可以解决电池的安全性问题，但是与NCM811正极界面稳定性差。本工作通过在陶瓷隔膜中添加具有稳定界面功能的氟化锂（LiF）的方法来解决此问题。采用扫描电子显微镜（SEM）、热重分析（TGA）、差示扫描量热法（DSC）、机械拉伸强度、热收缩、吸液率、电化学阻抗谱（EIS）、线性扫描伏安法（LSV）和充放电测试等方法进行表征。结果表明，当LiF占涂覆无机陶瓷颗粒总质量的10%时，得到的陶瓷隔膜性能最佳：具有良好的离子传输性能（室温离子电导率提高至9.5×10^-4 S/cm）和最佳的界面稳定性。隔膜组装的Li||LiNi_0.8Co_0.1Ni_0.1O₂扣式电池在3.0～4.35 V的高电压范围以0.3 C倍率循环400次后，放电比容量从195.2 mAh/g减少到119.9 mAh/g，保持初始容量的61.4%，而没有添加LiF的陶瓷隔膜电池仅为32.7%。含LiF的陶瓷隔膜提升电池循环稳定性的原因是形成了高质量的高压正极/电解质界面膜，稳定了正极与陶瓷隔膜的界面，使正极材料在高电压下仍能保持结构的稳定。因此，本工作制备的陶瓷隔膜为NCM811正极在高电压锂离子电池中的商业化应用提供了一种便捷方法。

关键词: 含锂陶瓷隔膜, 氟化锂, LiNi_0.8Co_0.1Mn_0.1O₂正极, 电极/隔膜界面, 高电压, 锂离子电池

Abstract:

LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) cathodes in lithium-ion batteries have the advantages of high specific capacity and relatively low cost. However, long-term cycling at high voltage poses challenges to the cathode interface, leading to instability and a need for improved safety performance. Although the lithium fast ion conductor Li_1.2Ca_0.1Zr_1.9(PO₄)₃ ceramic separator can considerably enhance battery safety, it exhibits poor interface stability when paired with NCM811 cathode. Herein, a lithium fluoride (LiF) additive with a stable interface function is added to the ceramic separator to solve this problem. The LiF-modified ceramic separator was characterized using scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, mechanical tensile strength, thermal shrinkage, electrolyte uptake ability, electrochemical impedance spectroscopy, linear sweep voltammetry, and charge-discharge testing. The results show that the ceramic separator performs best when LiF accounts for 10% of the total mass of coated inorganic ceramic particles. It exhibits improved ionic transport properties, with room temperature ionic conductivity of 9.5×10^-4 S/cm and excellent interfacial stability. In a Li||LiNi_0.8Co_0.1Ni_0.1O₂ coin cell operating in the high-voltage range of 3.0—4.35 V, the discharge-specific capacity decreases from 195.2 to 119.9 mAh/g at a 0.3 C rate after 400 cycles, while maintaining 61.4% of the initial capacity when using LiF-contained ceramic separator. In contrast, the capacity retention of the cell without LiF is only 32.7%. The enhanced cycling stability of the battery using a LiF-contained ceramic separator can be ascribed to the formation of a high-quality, high-voltage cathode-electrolyte interface film, stabilizing the interface between the cathode and separator, thereby preserving the structural stability of the cathode material under high voltages. Therefore, the developed ceramic separator in this study provides a convenient method for commercializing NCM811 cathodes in high-voltage lithium-ion batteries by enhancing interfacial stability and cycling performance.

Key words: lithium-containing ceramic separator, lithium fluoride, LiNi_0.8Co_0.1Mn_0.1O₂ cathode, electrode/separator interface, high-voltage, lithium-ion batteries

中图分类号:

TM 912

黄永浩, 臧国景, 朱霨亚, 廖友好, 李伟善. LiF添加剂改善含锂陶瓷隔膜与4.35 V LiNi_0.8Co_0.1Mn_0.1O₂ 正极的界面稳定性[J]. 储能科学与技术, 2023, 12(8): 2361-2369.

Yonghao HUANG, Guojing ZANG, Weiya ZHU, Youhao LIAO, Weishan LI. Enhancing interfacial stability between lithium-containing ceramic separator and 4.35 V LiNi_0.8Co_0.1Mn_0.1O₂ cathode through LiF additives[J]. Energy Storage Science and Technology, 2023, 12(8): 2361-2369.

图/表 6

图1

图2

图3

图4

图5

图6

参考文献 21

1	张言, 王海, 刘朝孟, 等. 锂离子电池富镍三元正极材料NCM的研究进展[J]. 储能科学与技术, 2022, 11(6): 1693-1705.
	ZHANG Y, WANG H, LIU Z M, et al. Research progress of nickel-rich ternary cathode material ncm for lithium-ion batteries[J]. Energy Storage Science and Technology, 2022, 11(6): 1693-1705.
2	栗志展, 秦金磊, 梁嘉宁, 等. 高镍三元层状锂离子电池正极材料: 研究进展、挑战及改善策略[J]. 储能科学与技术, 2022, 11(9): 2900-2920.
	LI Z Z, QIN J L, LIANG J N, et al. High-nickel ternary layered cathode materials for lithium-ion batteries: Research progress, challenges and improvement strategies[J]. Energy Storage Science and Technology, 2022, 11(9): 2900-2920.
3	QIU R Y, WU Z C. Artificial cathode-electrolyte interphases on Ni-rich LiNi_0.8Co_0.1Mn_0.1O₂ by carbon nanotubes modified LiF for enhanced cycleability[J]. Electrochemistry, 2021, 89(3): 296-302.
4	LEI T X, XUE L L, LI Y J, et al. Enhanced electrochemical performances via introducing LiF electrolyte additive for lithium ion batteries[J]. Ceramics International, 2019, 45(14): 18106-18110.
5	LIU W, OH P, LIU X E, et al. Nickel-rich layered lithium transition-metal oxide for high-energy lithium-ion batteries[J]. Angewandte Chemie (International Ed in English), 2015, 54(15): 4440-4457.
6	LAI Y Q, SUN Z, JIANG L X, et al. Rapid sintering of ceramic solid electrolytes LiZr₂(PO₄)₃ and Li_1.2Ca_0.1Zr_1.9(PO₄)₃ using a microwave sintering process at low temperatures[J]. Ceramics International, 2019, 45(8): 11068-11072.
7	LI G J, FENG Y, ZHU J Y, et al. Achieving a highly stable electrode/electrolyte interface for a nickel-rich cathode via an additive-containing gel polymer electrolyte[J]. ACS Applied Materials & Interfaces, 2022, 14(32): 36656-36667.
8	ZHANG B, SHEN J, WANG Q, et al. Boosting high-voltage and ultralong-cycling performance of single-crystal LiNi_0.5Co_0.2Mn_0.3O₂ cathode materials via three-in-one modification[J]. Energy & Environmental Materials, 2023, 6(1): e12270.
9	PAN R J, CUI Z H, YI M, et al. Ethylene carbonate-free electrolytes for stable, safer high-nickel lithium-ion batteries[J]. Advanced Energy Materials, 2022, 12(19): 2103806.
10	THAPALIYA B P, MISRA S, YANG S Z, et al. Enhancing cycling stability and capacity retention of NMC811 cathodes by reengineering interfaces via electrochemical fluorination[J]. Advanced Materials Interfaces, 2022, 9(18): 2200035.
11	TAN J, MATZ J, DONG P, et al. A growing appreciation for the role of LiF in the solid electrolyte interphase[J]. Advanced Energy Materials, 2021, 11(16): 2100046.
12	LI L G, WANG M C, WANG J A, et al. Asymmetric gel polymer electrolyte with high lithium ion conductivity for dendrite-free lithium metal batteries[J]. Journal of Materials Chemistry A, 2020, 8(16): 8033-8040.
13	DONG N X, WANG J E, CHEN N J, et al. In situ reinforcing: ZrO₂-armored hybrid polyimide separators for advanced and safe lithium-ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(18): 6250-6257.
14	ZANG G J, HE M, LIAO Y H, et al. Electrochemical improvement in high-voltage Li-ion batteries by electrospinning a small amount of nano-Al₂O₃ in P(MVE-MA)/P(VdF-HFP)-blended gel electrolyte[J]. Ionics, 2022, 28(2): 767-777.
15	GAO T T, WANG B, GAO J L, et al. Lithium fluoride additive for inorganic LiAlCl₄ ·3SO₂ electrolyte toward stable lithium metal anode[J]. Electrochimica Acta, 2020, 345: 136193.
16	HUANG J H, HONG M Y, LI G J, et al. Application of terpolymer encapsulated flame-retardant separator in Ni-rich and high-voltage lithium-ion batteries[J]. Journal of the Electrochemical Society, 2022, 169(2): 020513.
17	TAN J A, MATZ J, DONG P, et al. A growing appreciation for the role of LiF in the solid electrolyte interphase[J]. Advanced Energy Materials, 2021, 11(16): 2100046.
18	LU Y Y, TU Z Y, ARCHER L A. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes[J]. Nature Materials, 2014, 13(10): 961-969.
19	JIANG J L, OU Y H, LU S Y, et al. In-situ construction of Li-Mg/LiF conductive layer to achieve an intimate lithium-garnet interface for all-solid-state Li metal battery[J]. Energy Storage Materials, 2022, 50: 810-818.
20	LI G J, LIAO Y H, LI Z F, et al. Constructing a low-impedance interface on a high-voltage LiNi_0.8Co_0.1Mn_0.1O₂ cathode with 2, 4, 6-triphenyl boroxine as a film-forming electrolyte additive for Li-ion batteries[J]. ACS Applied Materials & Interfaces, 2020, 12(33): 37013-37026.
21	SHI J L, XIA Y G, HAN S J, et al. Lithium ion conductive Li_1.5Al_0.5Ge_1.5(PO₄)₃ based inorganic-organic composite separator with enhanced thermal stability and excellent electrochemical performances in 5 V lithium ion batteries[J]. Journal of Power Sources, 2015, 273: 389-395.

[1]	杨佳兴, 张恒运, 徐屹东. 基于电化学-热耦合模型的锂离子电池组件产热分析[J]. 储能科学与技术, 2023, 12(8): 2615-2625.
[2]	张吉禄, 董育辰, 宋强, 袁思鸣, 郭孝东. 多晶及单晶高镍三元材料LiNi_0.9Co_0.05Mn_0.05O₂ 的可控制备及其电化学储锂特性[J]. 储能科学与技术, 2023, 12(8): 2382-2389.
[3]	郭煜, 王亦伟, 钟隽, 杜进桥, 田杰, 李艳, 蒋方明. 基于增量容量曲线的锂离子电池微内短路故障诊断方法[J]. 储能科学与技术, 2023, 12(8): 2536-2546.
[4]	刘志浩, 杜童, 李瑞瑞, 邓涛. 宽温域、高电压、安全无EC电解液研究进展[J]. 储能科学与技术, 2023, 12(8): 2504-2525.
[5]	左安昊, 方儒卿, 李哲. 锂离子电池单颗粒动力学表征方法综述[J]. 储能科学与技术, 2023, 12(8): 2457-2481.
[6]	陈满, 程志翔, 赵春朋, 彭鹏, 雷旗开, 金凯强, 王青松. 锂离子电池储能集装箱爆炸危害数值模拟[J]. 储能科学与技术, 2023, 12(8): 2594-2605.
[7]	唐程波, 锁要红, 何昭坤. 基于正弦函数的液冷板上流体流向对锂离子电池散热性能的影响[J]. 储能科学与技术, 2023, 12(8): 2547-2555.
[8]	张青松, 包防卫, 牛江昊. 环境压力对锂电池热失控产气及爆炸风险的影响[J]. 储能科学与技术, 2023, 12(7): 2263-2270.
[9]	陈育新, 杨家沐, 练成, 刘洪来. 基于相场模型的锂电池电极浆料稳定涂布窗口分析[J]. 储能科学与技术, 2023, 12(7): 2185-2193.
[10]	杲齐新, 赵景腾, 李国兴. 锂离子电池快速充电研究进展[J]. 储能科学与技术, 2023, 12(7): 2166-2184.
[11]	范茂松, 耿萌萌, 赵光金, 杨凯, 王放放, 刘皓. 基于多频点阻抗的梯次利用电池分选技术研究[J]. 储能科学与技术, 2023, 12(7): 2202-2210.
[12]	李晋, 王青松, 孔得朋, 王晓冬, 俞振华, 乐艳飞, 黄鑫炎, 胡振恺, 吴候福, 方华斌, 曹伟, 张少禹, 卓萍, 陈晔, 李紫婷, 梅文昕, 张越, 赵丽香, 唐亮, 黄宗侯, 陈篪, 刘彦辉, 储玉喜, 许晓元, 张晋, 李贻恺, 冯蓉, 杨标, 户波, 杨晓滢. 锂离子电池储能安全评价研究进展[J]. 储能科学与技术, 2023, 12(7): 2282-2301.
[13]	张佳怡, 翁素婷, 王兆翔, 王雪锋. 石墨负极界面SEI膜与锂离子电池热失控[J]. 储能科学与技术, 2023, 12(7): 2105-2118.
[14]	徐冲, 徐宁, 蒋志敏, 李中凯, 胡洋, 严红, 马国强. 锂离子电池产气机制及基于电解液的抑制策略[J]. 储能科学与技术, 2023, 12(7): 2119-2133.
[15]	陈钦佩, 王学辉, 米文忠. 电动汽车锂离子电池系统热失控气体毒害及爆炸特性研究[J]. 储能科学与技术, 2023, 12(7): 2256-2262.

LiF添加剂改善含锂陶瓷隔膜与4.35 V LiNi_0.8Co_0.1Mn_0.1O₂ 正极的界面稳定性

Enhancing interfacial stability between lithium-containing ceramic separator and 4.35 V LiNi_0.8Co_0.1Mn_0.1O₂ cathode through LiF additives

RichHTML

PDF