电解液类型对双离子电池阴阳离子储存行为的影响

doi:10.11949/0438-1157.20230015

摘要/Abstract

摘要：

双离子电池是一种阴阳离子同时参与能量储存过程的新型电池，具有工作电压高、成本低、环境友好等优点。但正极高电压特性会引起电解液氧化分解。通过调节电解液浓度和溶剂组成系统地考察了电解液类型对 $P F 6 -$ 嵌入行为的影响规律以及溶剂组成与负极稳定性之间的相容性关系。链状碳酸甲乙酯（EMC）溶剂促进 $P F 6 -$ 在正极的嵌入过程，环状碳酸乙烯酯（EC）溶剂有利于负极稳定性。具有链状EMC和环状EC混合溶剂的1 mol·L^-1 LiPF₆-EC/EMC（3∶7，体积比）电解液更适用于双离子电池，以此作为电解液组装的石墨//软炭-双离子电池在580 W·kg^-1的功率密度下可提供98 W·h·kg^-1的能量密度，且在1 A·g^-1电流密度下经1000圈循环后容量保持率为86.9%。

关键词: 电化学, 反应动力学, 双离子电池, 电解质, 阴离子嵌入, 碳酸甲乙酯, 碳酸乙烯酯

Abstract:

Dual-ion batteries (DIBs) have attracted extensive attention due to the virtues of high working voltage, low cost and environmental friendliness. However, the high voltage characteristics of the positive electrode will cause the electrolyte to oxidize and decompose. Since the electrolyte acts as the only source of active charge carriers, the electrochemical performance is limited by long-term decomposition and gas production of the electrolyte. We herein systematically investigate the effects of electrolyte concentration and types on the $P F 6 -$ intercalation behaviors and the compatibility between solvent composition and anodes by adjusting electrolyte concentration and solvent composition. The linear ethyl methyl carbonate (EMC) solvent is more favorable for the $P F 6 -$ to insert into the graphene layers than cyclic ethylene carbonate (EC) solvent. Moreover, EC solvent is the key component for the stability of anode. The mixed electrolyte of 1 mol·L^-1 LiPF₆-EC/EMC (3∶7, volume ratio) with the combination of linear EMC and cyclic EC is more applicable for DIBs, and the graphite//soft carbon DIB configuration assembled by the above electrolyte can provide an energy density of 98 W·h·kg^-1 at a power density of 580 W·kg^-1 with a capacity retention rate of 86.9% after 1000 cycles at 1 A·g^-1.

Key words: electrochemistry, reaction kinetics, dual-ion batteries, electrolytes, anion intercalation, ethyl methyl carbonate, ethylene carbonate

中图分类号:

TQ 152

张蒙蒙, 颜冬, 沈永峰, 李文翠. 电解液类型对双离子电池阴阳离子储存行为的影响[J]. 化工学报, 2023, 74(7): 3116-3126.

Mengmeng ZHANG, Dong YAN, Yongfeng SHEN, Wencui LI. Effect of electrolyte types on the storage behaviors of anions and cations for dual-ion batteries[J]. CIESC Journal, 2023, 74(7): 3116-3126.

图/表 12

图1 NG和PSC的XRD谱图和拉曼光谱

Fig.1 XRD patterns and Raman spectra of NG and PSC samples

表1 NG和PSC样品的石墨微晶参数和比表面积

Table 1 Graphite microcrystalline parameters and specific surface area of NG and SC samples

样品	d₀₀₂/nm	L_a /nm	L_c /nm	A_G/A_D	S_BET/(m²·g^-¹)
NG	0.336	27.22	36.56	4.46	5.88
PSC	0.346	4.50	5.98	0.63	8.80

图2 4 mol·L-1 LiPF6-EMC、1 mol·L-1 LiPF6-EMC和1 mol·L-1 LiPF6-EC/EMC(3∶7)三种电解液中NG和PSC正极在0.2 A·g-1电流密度下的恒流充放电曲线

Fig.2 GCD curves at 0.2 A·g-1 of NG and PSC cathodes in 4 mol·L-1 LiPF6-EMC, 1 mol·L-1 LiPF6-EMC and 1 mol·L-1 LiPF6-EC/EMC(3∶7) electrolytes

图3 4 mol·L-1 LiPF6-EMC、1 mol·L-1 LiPF6-EMC和1 mol·L-1 LiPF6-EC/EMC(3∶7)三种电解液中NG和PSC正极的倍率性能

Fig.3 Rate performance of NG and PSC cathodes in 4 mol·L-1 LiPF6-EMC, 1 mol·L-1 LiPF6-EMC and 1 mol·L-1 LiPF6-EC/EMC(3∶7) electrolytes

图4 NG正极在不同电解液中的电化学性能

Fig.4 Electrochemical performances of NG cathode in different electrolytes

图5 NG正极在不同电解液中的电化学性能

Fig.5 Electrochemical performances of NG cathode in different electrolytes

表2 NG正极在不同电解液中的电化学阻抗谱拟合结果

Table 2 The fitting results of Nyquist plots for NG cathode in different electrolytes

电解液	R_s/Ω	R_ct/Ω	W_o/Ω
4mol·L^-1LiPF₆-EMC	22.70	364.2	358.4
1mol·L^-1LiPF₆-EMC	10.07	123.7	61.93
1mol·L^-1LiPF₆-EC/EMC(3∶7)	6.79	145.8	332.1

图6 4 mol·L-1 LiPF6-EMC、1 mol·L-1 LiPF6-EMC和1 mol·L-1 LiPF6-EC/EMC(3∶7)三种电解液中NG和PSC负极在0.2 A·g-1电流密度下的恒流充放电曲线

Fig.6 GCD curves at 0.2 A·g-1 of NG and PSC anodes in 4 mol·L-1 LiPF6-EMC, 1 mol·L-1 LiPF6-EMC and 1 mol·L-1 LiPF6-EC/EMC(3∶7) electrolytes

图7 4 mol·L-1 LiPF6-EMC、1 mol·L-1 LiPF6-EMC和1 mol·L-1 LiPF6-EC/EMC(3∶7)三种电解液中NG和PSC负极的倍率性能

Fig.7 Rate performance of NG and PSC anodes in 4 mol·L-1 LiPF6-EMC, 1 mol·L-1 LiPF6-EMC and 1 mol·L-1 LiPF6-EC/EMC(3∶7) electrolytes

图8 PSC负极在不同电解液中的电化学性能

Fig.8 Electrochemical performances of PSC anode in different electrolytes

图9 NG//PSC构型双离子电池的电化学性能

Fig.9 Electrochemical performances of the DIBs of NG//PSC

图10 NG//PSC双离子电池的Ragone图及与文献值的比较

Fig.10 Ragone plot for the DIBs of NG//PSC and comparison with other previously reported DIBs

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