双功能电解液添加剂对锂离子电池高温高电压性能的影响

doi:10.15541/jim20210653

无机材料学报 ›› 2022, Vol. 37 ›› Issue (7): 710-716.DOI: 10.15541/jim20210653

双功能电解液添加剂对锂离子电池高温高电压性能的影响

江依义¹(), 沈旻¹, 宋半夏¹, 李南¹, 丁祥欢¹, 郭乐毅², 马国强¹^,²()

1.浙江省化工研究院有限公司锂电材料重点实验室, 杭州 310012
2.中国计量大学光电材料与器件研究院, 杭州 310018

收稿日期:2021-10-22 修回日期:2022-01-19 出版日期:2022-07-20 网络出版日期:2022-03-18
通讯作者: 马国强, 高级工程师. E-mail: erguo87@163.com; maguoqiang@sinochem.com
作者简介:江依义(1988-), 女, 硕士. E-mail: jiangyiyi@sinochem.com
基金资助:
科技厅省属科研院所扶持专项(330000210130304027003-03);国家自然科学基金(51802300);国家重点研发计划(2019YFE0100200)

Effect of Dual-functional Electrolyte Additive on High Temperature and High Voltage Performance of Li-ion Battery

JIANG Yiyi¹(), SHEN Min¹, SONG Banxia¹, LI Nan¹, DING Xianghuan¹, GUO Leyi², MA Guoqiang¹^,²()

1. Key Laboratory of Lithium-ion Battery Materials, Zhejiang Research Institute of Chemical Industry Co., Ltd., Hangzhou 310012, China
2. Institute of Optoelectronic Materials and Devices, China Jiliang University, Hangzhou 310018, China

Received:2021-10-22 Revised:2022-01-19 Published:2022-07-20 Online:2022-03-18
Contact: MA Guoqiang, senior engineer. E-mail: erguo87@163.com; maguoqiang@sinochem.com
About author:JIANG Yiyi(1988-), female, Master. E-mail: jiangyiyi@sinochem.com
Supported by:
Zhejiang Provincial Department of Science and Technology(330000210130304027003-03);National Natural Science Foundation of China(51802300);National Key Research and Development Program of China(2019YFE0100200)

摘要/Abstract

摘要：

三元锂离子动力电池的开发和应用受制于高温高电压条件下的容量衰减和电池产气鼓胀等技术难题。解决这些问题一方面要注重电极材料改性和电池设计, 另一方面还依赖于电解液的技术进步。本研究报道了四乙烯基硅烷(Tetravinylsilane, TVS)作为LiNi_0.6Co_0.2Mn_0.2O₂(NCM622)/石墨软包电池的电解液添加剂, 可以显著改善电池的高温(45~60 ℃) 高电压(4.4 V)性能, 包括存储和循环性能。结果表明, 电解液中含有质量分数0.5% TVS的电池在2.8~4.4 V区间, 1C (1C=1.1 Ah)倍率下循环400次后的容量保持率达到92%, 而电解液中未添加TVS的软包电池仅为82%。进一步研究表明, 一方面TVS高电压下优先被氧化, 可以在NCM622颗粒表面形成耐高温的CEI膜, 有效抑制NCM622颗粒内部裂纹和过渡金属离子溶出; 另一方面, TVS在低电位下还可以优先被还原, 在石墨负极表面聚合形成稳定的SEI膜, 抑制电解液与负极之间的副反应。

关键词: 高温, 软包锂离子电池, 电解液添加剂, 循环稳定性, 过渡金属离子溶出

Abstract:

Development and application of power lithium-ion batteries are strictly restricted by their high temperature and high voltage performance, such as capacity degradation and gas swelling, which are related to not only the modified electrode material and battery design but also the electrolyte. Herein, tetravinylsilane (TVS) was applied as electrolyte additive to improve storage and cycling performances of LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622)/graphite pouch cell at high cutoff voltage (4.4 V) and high temperature (45-60 ℃). The capacity retention rate of the cell after 400 cycles (2.8-4.4 V) at 1C (1C=1.1 Ah) with mass fraction 0.5% TVS in the electrolyte is as high as 92%, compared with 82% for its counterpart without TVS. On the one hand, TVS is preferentially oxidized under high voltage, contributing to the formation of a high-temperature resistant CEI (cathode electrolyte interphase) film on the surface of NCM622 particles, which effectively inhibits generation of internal cracks in NCM622 particles and dissolution of transition metal ions. On the other hand, TVS can also be preferentially reduced and polymerized, thus forming a stable SEI film on the surface of graphite anode, which inhibits the side reaction between the electrolyte and the negative electrode.

Key words: high temperature, lithium-ion pouch cell, electrolyte additive, cycle stability, transition metal dissolution

中图分类号:

TM911

江依义, 沈旻, 宋半夏, 李南, 丁祥欢, 郭乐毅, 马国强. 双功能电解液添加剂对锂离子电池高温高电压性能的影响[J]. 无机材料学报, 2022, 37(7): 710-716.

JIANG Yiyi, SHEN Min, SONG Banxia, LI Nan, DING Xianghuan, GUO Leyi, MA Guoqiang. Effect of Dual-functional Electrolyte Additive on High Temperature and High Voltage Performance of Li-ion Battery[J]. Journal of Inorganic Materials, 2022, 37(7): 710-716.

图/表 12

图1 对称电池组装流程图

Fig. 1 Schematic procedure for preparing the symmetric cell

图2 对照组和实验组电解液的LSV(a)氧化和(b)还原曲线

Fig. 2 LSV curves of (a) oxidation and (b) reduction of electrolytes with and without TVS

图S1 对照组和实验组电解液以NCM622为工作电极的CV曲线

Fig. S1 CV curves of NMC622 electrodes with and without TVS in electrolytes (a) 1st cycle; (b) 2nd cycle

图3 对照组和实验组电池经60 ℃存储14 d后的(a)体积和内阻变化率、(b)自放电率和容量恢复率以及(c)充放电曲线

Fig. 3 (a) Gas swelling rates and ACR change rates, (b) K values and capacity recovery rates, (c) charge and discharge curves of pouch cells with and without TVS in electrolytes after storage at 60 ℃ for 14 d

表1 对照组和实验组电池经4.4 V、60 ℃存储14 d后负极上沉积的过渡金属离子含量(质量分数)

Table 1 Uess fractions of Ni, Co and Mn ions deposited on anodes from pouch cell with and without TVS in electrolyte stored at cutoff potential of 4.4 V and temperature of 60 ℃ for 14 d

Sample	Ni/(×10^-4, %)	Co/(×10^-4, %)	Mn/(×10^-4, %)
Base	90	21	130
TVS	35	4	69

表S1 实验组和对照组电池经4.4 V、60 ℃存储14 d后的气体成分及含量

Table S1 Gas composition and contents of pouch cells with and without TVS in electrolytes stored at cutoff potential of 4.4 V and temperature of 60 ℃ for 14 d

Sample	CO/µL	CH₄/µL	CO₂/µL	C₂H₄/µL	H₂/µL
Base	393.3	253.2	209.3	67.0	17.6
TVS	9.2	4.8	2.2	1.1	0.2

图4 对照组和实验组电池在45 ℃的循环性能

Fig. 4 Cycling performance of pouch cells with and without TVS in electrolytes at 45 ℃ (a) Discharge capacity and (b) ΔV vs cycle number; EIS plots of (c) pouch full cells, (d) graphite/graphite symmetric cells and (e) NCM622/NCM622 symmetric cells before and after 100 cycles

图S2 对照组和实验组电池在45 ℃的循环性能

Fig. S2 Cycling performance of pouch cells with and without TVS in electrolytes at 45 ℃ (a) Differential capacity (dQ/dV) versus potential of Base; (b) Differential capacity (dQ/dV) versus potential of TVS

表S2 对照组和实验组电池循环100周前后及相应的对称电池的EIS拟合参数

Table S2 Fitted EIS results before and after 100 cycles of pouch full cells and corresponding symmetric cells with and without TVS in electrolytes

Sample	Full cell			Anode symmetric cell			Cathode symmetric cell
Sample	R_s/mΩ	R_sei/mΩ	R_ct/mΩ	R_s/mΩ	R_sei/mΩ	R_ct/mΩ	R_s/mΩ	R_sei/mΩ	R_ct/mΩ
Base-before cycle	16.2	7.5	14.2	3.4	4.7	23.2	2.6	116.1	21.2
Base-after cycle	46.7	9.1	19.3	4.2	17.1	26.5	2.7	144.3	26.7
TVS-before cycle	16.4	8.9	25.8	4.5	20.5	43.3	2.1	86.1	18.2
TVS-after cycle	38.5	10.2	25.4	4.8	22.6	43.8	2.2	100.4	18.1

图5 (a)对照组和(b)实验组电池循环100周后正极SEM照片, (c)对照组和实验组电池循环10周后正极表面XPS分谱

Fig. 5 SEM images of cathodes from pouch cells (a) without and (b) with TVS in electrolytes after 100 cycles; (c) XPS spectra of cathodes from pouch cells without and with TVS in electrolytes after 10 cycles

图S3 (a)对照组和(b)实验组电池循环100周后负极SEM照片; (c)实验组电池循环10周后负极表面Si2p XPS分谱

Fig. S3 SEM images of anodes from pouch cells (a) without and (b) with TVS in electrolytes after 100 cycles; (c) Si2p XPS spectra of anode from pouch cell with TVS in electrolyte after 10 cycles

图S4 TVS 添加剂在NCM622/石墨软包电池正负极界面的工作机理

Fig. S4 Working mechanism of TVS additive on cathode and anode of NCM622/graphite pouch cell

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双功能电解液添加剂对锂离子电池高温高电压性能的影响

Effect of Dual-functional Electrolyte Additive on High Temperature and High Voltage Performance of Li-ion Battery

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