原位电势表征揭示聚合物固态锂电池界面降解机理

doi:10.6023/A24090267

摘要/Abstract

聚合物固态锂金属电池具有较高的能量密度和安全性, 十分具有发展前景. 然而, 该电池在高电压体系下的循环稳定性较差, 了解高电压体系下电池性能衰减的机理至关重要. 本工作使用扫描开尔文探针力显微镜对LiFePO₄/LiNi_0.6Co_0.2Mn_0.2O₂ (NCM)正极与聚离子液体基聚合物电解质的界面电势变化进行原位表征分析. 结果表明高电压的NCM正极-电解质界面能级差由–0.1 eV上升到1.0 eV, 容易导致电解质优先失去电子而发生界面降解副反应, 从而引起正极-电解质界面结构性质变化, 增大了界面阻抗, 使电池循环性能显著下降. 因此, 该原位表征技术有助于提升电解质的高电压稳定性, 为发展性能优异的高电压聚合物固态锂电池提供指导帮助.

关键词: 固态锂电池, 聚合物电解质, 原位表征, 扫描探针显微镜, 电解质降解

Solid-state polymer electrolyte lithium metal batteries (SPE-LIBs) with high energy density and safety have been widely considered as the next generation of lithium batteries. In recent years, the ion transport mechanism of SPE has been extensively studied, resulting in a significant increase in its ionic conductivity and lithium transference number. However, SPE has poor cycling stability when used with high-voltage cathodes, limiting its further development. Therefore, it is important to understand the mechanism of battery performance degradation in high-voltage systems. In this work, first, the SPE was prepared by photopolymerization using 1-butyl-3-vinylimidazolium bis(trifluoromethylsulfonyl) imide, vinylethylene carbonate and poly(ethylene glycol) diacrylate. The LiFePO₄(LFP)||SPE||Li battery was prepared by the in-situ polymerization method. This battery has an initial discharge specific capacity of 159.6 mAh•g^-1 at room temperature, and the capacity retention rate reaches 95% after 145 cycles, indicating that the cell has a low interface impedance and the electrolyte has a high ionic conductivity. Then, in-situ Scanning Kelvin Probe Force Microscopy was used to characterize the interfacial potential of the cross-sections of batteries with two different cathodes, which were prepared by argon ion beam polishing, during charging. Compared with the LFP cathode, the LiNi_0.6Co_0.2Mn_0.2O₂ (NCM) cathode with higher electrochemical reaction potential has a greater potential difference between the cathode and the electrolyte after charging. As a result, it indicates that the energy level of high-voltage cathode materials changes greatly during the charging process, which makes the electrolyte materials more susceptible to losing electrons preferentially and cause degradation side reactions. Combined with electrochemical impedance spectroscopy and laser confocal Raman spectroscopy to characterize the interfacial structure of the SPE-LIB. It found that side reactions would destroy the structure of the cathode electrolyte interphase, resulting in a significant increase in the interfacial impedance and the attenuation of the battery capacity. The electrolyte degradation mechanism of SPE-LIBs under high-voltage systems was revealed through in-situ characterization, which provided guidance for improving the cycling stability with high-voltage cathodes.

Key words: solid-state lithium battery, solid-state polymer electrolyte, in-situ characterization, scanning probe microscopy, electrolyte degradation

引用此文

陈博文, 徐克, 陈琪, 陈立桅. 原位电势表征揭示聚合物固态锂电池界面降解机理[J]. 化学学报, 2024, 82(12): 1209-1215.

Bowen Chen, Ke Xu, Qi Chen, Liwei Chen. In-situ Potential Characterization Reveals the Interface Degradation Mechanism of Solid-state Polymer Lithium Batteries[J]. Acta Chimica Sinica, 2024, 82(12): 1209-1215.

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图/表 4

图1. 聚合物固态锂电池的制备与电化学性能: (a)电池制备流程示意图; (b)不同正极锂电池的循环性能对比图; (c) LFP||Li电池不同循环圈数的电压-容量曲线; (d) NCM||Li电池不同循环圈数的电压-容量曲线

Figure 1. Preparation and electrochemical properties of solid-state polymer lithium batteries: (a) schematic diagram of battery preparation process; (b) comparison of the batteries cycling performance of different cathode lithium; (c) voltage-capacity curves of different cycles of LFP||Li battery; (d) voltage- capacity curves of different cycles of NCM||Li battery

图2. 聚合物固态锂电池横截面电势原位表征: (a)原位SKPM表征示意图; (b)电池在原位表征过程中的充放电曲线; (c)充电前和(d)充电后LFP||Li电池横截面的电势分布图像; (e) LFP-SPE界面电势变化曲线; (f)充电前和(g)充电后NCM||Li电池横截面的电势分布图像; (h) NCM-SPE界面电势变化曲线

Figure 2. In-situ characterization of cross-sectional potential of solid-state polymer lithium batteries: (a) schematic diagram of in-situ SKPM characterization; (b) charge-discharge curves of the battery during in-situ characterization; image of the potential distribution of the LFP||Li cell cross-section (c) before charging and (d) after charging; (e) LFP-SPE interface potential curve; image of the potential distribution of the NCM||Li cell cross-section (f) before charging and (g) after charging; (h) NCM-SPE interface potential curve

图3. 正极-电解质充电过程中的能级变化示意图: (a)充电过程中LFP正极与SPE之间的能级变化图; (b)充电过程中NCM正极与SPE之间的能级变化图

Figure 3. Schematic diagram of the energy level change during the cathode-electrolyte charging process: (a) the energy level change between the LFP cathode and the SPE during the charging process; (b) the energy level change between the NCM cathode and the SPE during the charging process

图4. NCM||Li电池正极-电解质界面结构表征: (a, b)充放电过程中正极表面的原位拉曼光谱图, (a)充电过程, (b)放电过程; (c, d)充放电过程中原位EIS表征结果, (c)电池充放电曲线, (d)不同电压下的Nyquist图; (e, f)循环前后正极表面XPS表征谱图, (e) C 1s谱图, (f) F 1s谱图

Figure 4. Characterization of the cathode-electrolyte interface structure of NCM||Li battery: (a, b) in-situ Raman spectra of the cathode surface during charging and discharging, (a) charging process, (b) discharging process; (c, d) in-situ EIS characterization during charging and discharging, (c) charge-discharge curves of batteries, (d) Nyquist plots at different voltages; (e, f) XPS spectra of the cathode surface before and after cycle, (e) C 1s spectra, (f) F 1s spectra

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