无负极锂金属电池在局部高浓度电解液中的产气研究

doi:10.6023/A24050167

化学学报 ›› 2024, Vol. 82 ›› Issue (9): 919-924.DOI: 10.6023/A24050167 上一篇下一篇

研究通讯

无负极锂金属电池在局部高浓度电解液中的产气研究

郭姿珠^a, 张睿^a^,^*(), 孙旦^a, 王海燕^a, 黄小兵^b, 唐有根^a^,^*()

a 中南大学化学化工学院长沙 410083
b 湖南文理学院化学与材料工程学院常德 415000

投稿日期:2024-08-27 发布日期:2024-09-05
基金资助:
国家自然科学基金(22272205); 国家资助博士后研究人员计划(GZC20233152); 湖南省普通高等学校科技创新团队支持项目资助.

Gas Generation in Anode-Free Li-Metal Batteries with Localized High-Concentration Electrolytes

Zizhu Guo^a, Rui Zhang^a,*(), Dan Sun^a, Haiyan Wang^a, Xiaobing Huang^b, Yougen Tang^a,*()

a College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
b School of Chemistry and Materials Engineering, Hunan University of Arts and Science, Changde 415000, China

Received:2024-08-27 Published:2024-09-05
Contact: *E-mail: csuzr606@csu.edu.cn, ygtang@csu.edu.cn; Tel.: 15243665341, 13607315350
Supported by:
National Natural Science Foundation of China(22272205); Postdoctoral Fellowship Program of China Postdoctoral Science Foudation(GZC20233152); Aid Program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province, China.

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摘要/Abstract

引入局部高浓电解液(LHCE)是提升金属锂负极循环稳定性的重要方法之一. 虽然该类电解液在提高无负极锂金属电池(AF-LMB)循环寿命方面已有报道, 但是较少有研究关注电解液的分解反应和产气情况. 本工作组装了软包全电池Cu||NCM712, 研究了LHCE电解液浓度、工作温度以及充电截止电压对AF-LMB体系产气情况的影响. 结合气相色谱、Raman光谱以及电化学测试, 发现锂盐浓度是影响循环寿命和产气量的显著因子, 提高锂盐浓度可以减少LHCE中自由溶剂分子的数量, 抑制电解液的氧化分解和电池产气.

关键词: 无负极锂金属电池, 局部高浓电解液, 产气分析, 溶剂化结构

The introduction of localized high-concentration electrolyte (LHCE), which inherits the advanced properties of concentrated electrolytes and exhibits lower viscosity and cost, is one of the important methods to improve the cycling stability of lithium metal anode. Although the similar strategy also has been proposed to extend the durable life of anode-free lithium metal batteries (AF-LMBs), few studies have focused on the electrolyte decomposition reaction and gas production. In this work, a typical LHCE system consisting of lithium bis(fluorosulfonyl)imide (LiFSI) salt, 1,2-dimethoxyethane (DME) solvent and tetrafluoroethyl tetrafluoropropyl ether (HFE) diluter were chosen, and Cu||NCM712 pouch cells were assembled to investigate the effects of LHCE concentration (0.7, 1.2, 1.7 and 2.3 mol/L), working temperature (25 and 45 ℃) and charging cutoff voltage (3.8 and 4.3 V) on the gas production of AF-LMB systems. Combined with gas chromatography, Raman spectroscopy and electrochemical tests, it is found that the concentration of lithium salt is a significant factor affecting the cycle life and gas production volume. The solvation structure gradually evolves and the number of free solvent molecules in LHCE reduces as the concentration of lithium salt increases, inhibiting the oxidation decomposition of electrolyte and gas production of battery. Moreover, the electrolyte decomposition is also dependent with the variety of cathode material. In contrast with lithium iron phosphate (LiFePO₄) cathode, NCM712 cathode results in faster capacity decay of the full-cell and higher gas volume, which might be ascribed to the transition metal elements with the catalytic effect. Meanwhile, scanning electron microscope images indicate uniform and dense lithium deposition on the Cu foil, and X-ray photoelectron spectroscopy tests also reveal that more inorganic solid electrolyte interface (SEI) components are formed on the surface of lithium metal, which serves as the excellent protective layer and is beneficial to suppressing the side reaction. This work is expected to provide guidance for the gas production research of other ether-based LHCE systems.

Key words: anode-free lithium metal battery, localized high-concentration electrolyte, gas generation analysis, solvation structure

引用此文

郭姿珠, 张睿, 孙旦, 王海燕, 黄小兵, 唐有根. 无负极锂金属电池在局部高浓度电解液中的产气研究[J]. 化学学报, 2024, 82(9): 919-924.

Zizhu Guo, Rui Zhang, Dan Sun, Haiyan Wang, Xiaobing Huang, Yougen Tang. Gas Generation in Anode-Free Li-Metal Batteries with Localized High-Concentration Electrolytes[J]. Acta Chimica Sinica, 2024, 82(9): 919-924.

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图/表 8

图1. Cu||NCM712全电池在不同运行温度、充电截止电压和锂盐浓度下的循环性能

Figure 1. Cycling performance of Cu||NCM712 full-cell with different operation temperatures, charging cutoff voltages and lithium salt concentrations (a) 25 ℃, 3.6~3.8 V; (b) 45 ℃, 3.6~4.3 V; (c) 25 ℃, 3.6~4.3 V; (d) 45 ℃, 3.6~3.8 V

锂盐浓度/ (mol•L⁻¹)	运行温度/℃	充电截止电压/V	循环寿命/圈	产气量/ (mL•Ah⁻¹)	产气成分及占比
1.2	25	3.8	49	8.32	CH₄ (98%)
2.3	25	3.8	320	0.14	CH₄ (98%)
0.7	25	4.3	7	21.9	CH₄ (98%)
1.7	25	4.3	120	0.21	CH₄ (98%)
1.2	45	4.3	10	19.38	CH₄ (98%)
2.3	45	4.3	81	1.1	CH₄ (98%)
0.7	45	3.8	5	50.6	CH₄ (98%)
1.7	45	3.8	200	0.71	CH₄ (98%)

表1. Cu||NCM712全电池在不同运行温度、充电截止电压和锂盐浓度下的循环性能和产气情况对比

Table 1. Cycling performance and gas generation analysis of Cu||NCM712 full-cell with different operation temperatures, charging cutoff voltages and lithium salt concentrations

图2. Cu||LFP和Cu||NCM712全电池的(a)循环性能和(b)产气量对比

Figure 2. (a) Cycling performances and (b) gas generation volumes of Cu||LFP and Cu||NCM712

图3. 不同浓度电解液的LSV曲线

Figure 3. LSV curves of electrolytes with different concentrations

图4. 不同浓度电解液在(a) 800~900 cm?1和(b) 680~800 cm?1处的Raman光谱

Figure 4. Raman spectra of different electrolytes at (a) 800~900 cm?1 and (b) 680~800 cm?1

图5. 不同浓度电解液溶剂化结构分布

Figure 5. Solvation structure distribution of electrolyte with different concentrations

图6. 负极金属锂在(a) 0.7 mol?L?1, (b) 1.2 mol?L?1, (c) 1.7 mol?L?1和(d) 2.3 mol?L?1 LiFSI/DME/HFE电解液中的沉积形貌

Figure 6. SEM images of lithium metal anode deposited in (a) 0.7 mol? L?1, (b) 1.2 mol?L?1, (c) 1.7 mol?L?1 and (d) 2.3 mol?L?1 LiFSI/DME/HFE

图7. 高分辨(a) C1s和(b) F1s XPS谱

Figure 7. High-resolution (a) C 1s and (b) F 1s XPS spectra

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无负极锂金属电池在局部高浓度电解液中的产气研究

Gas Generation in Anode-Free Li-Metal Batteries with Localized High-Concentration Electrolytes

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