亲锂电解液在LiNi0.6Mn0.2Co0.2O2／Li二次锂金属电池中的电化学性能

doi:10.19894/j.issn.1000-0518.210090

摘要/Abstract

摘要：

金属锂电池被认为是具有良好前景的下一代高能量密度电池。然而，传统的碳酸酯类电解液与锂的亲和性差，在循环过程中由于锂枝晶的生长和固体电解质膜（SEI）的不稳定导致金属锂电池性能快速衰减。采用1.2 mol／L六氟磷酸锂（LiPF₆）／二氟草酸硼酸锂（LiDFOB）／氟代碳酸乙烯酯（FEC）／碳酸二乙酯（DEC），并添加了双三氟甲磺酰亚胺锂（LiTFSI）作为电解液，对其在LiNi_0.6Mn_0.2Co_0.2O₂／40 μm-Li（单位面积上负／正极材料的实际容量的比N／P＝2.85）电池中的电化学性能进行了研究。LiNi_0.6Mn_0.2Co_0.2O₂／40 μm-Li电池表现出优异的循环稳定性（循环120圈后，容量保持率>93%）和倍率性能（3C倍率下放电比容量为110 mA·h／g）。良好的电化学性能主要归因于该电解液可以在金属锂表面形成致密且稳定的SEI，并抑制锂枝晶的产生。

关键词: 金属锂电池, 双三氟甲磺酰亚胺锂, LiNi_0.6Mn_0.2Co_0.2O₂, 薄锂

Abstract:

Lithium metal batteries are considered to be the next generation high-energy-density batteries with good prospects. However, the traditional carbonate-based electrolyte has poor compatibility with lithium, and the lithium metal battery has fast capacity decay due to the growth of lithium dendrites and the instability of the solid electrolyte interface (SEI) during cycling. Using 1.2 mol/L lithium hexafluorophosphate (LiPF₆) /lithium difluorooxalate (LiDFOB) /fluoroethylene carbonate (FEC) /diethylcarbonate (DEC), and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) added as an electrolyte, the electrochemical performance of LiNi_0.6Mn_0.2Co_0.2O₂/40 μm-Li battery (ratio of negative to positive capacity per unit area N/P=2.85) was studied. The LiNi_0.6Mn_0.2Co_0.2O₂/40 μm-Li battery exhibits excellent cycle stability (after 120 cycles, the capacity retention>93%) and rate performance (the specific discharge capacity is 110 mA·h/g at 3 C). The good electrochemical performance is mainly due to the fact that the electrolyte can form a dense and stable SEI on the surface of metal lithium and inhibit the generation of lithium dendrites.

Key words: Lithium metal battery, Lithium bis (trifluoromethanesulfonyl) imide, LiNi_0.6Mn_0.2Co_0.2O₂, Thin lithium

中图分类号:

O646.5

黄杜斌, 王培民, 邬金龙. 亲锂电解液在LiNi_0.6Mn_0.2Co_0.2O₂／Li二次锂金属电池中的电化学性能[J]. 应用化学, 2022, 39(02): 298-306.

Du-Bin HUANG, Pei-Min WANG, Jin-Long WU. Electrochemical Performance of Lithiophilic Electrolyte in LiNi_0.6Mn_0.2Co_0.2O₂/Li Rechargeable Lithium Metal Battery[J]. Chinese Journal of Applied Chemistry, 2022, 39(02): 298-306.

图/表 8

图1 不同电解液在－20～60℃下的电导率（A）；不同电解液的Li／Li对称电池（B）

Fig.1 Conductivity of different electrolytes at－20～60℃（A）；Li／Li symmetric cells with different electrolytes（B）

图2 不同电解液在NCM622／Li电池中的循环性能（A）；E-0电解液（B）、E-1电解液（C）、E-2电解液（D）、E-3电解液（E）和CE电解液（F）在NCM622／Li电池中的充放电曲线图

Fig.2 Cycling performance of NCM622／Li cells in different electrolytes（A）and voltage profiles of NCM622／Li cell in E-0（B），E-1（C），E-2（D），E-3（E）and CE（F）electrolytes

图3 NCM622／Li电池在不同电解液下的倍率性能（A）；E-0电解液（B）、E-1电解液（C）、E-2电解液（D）、E-3电解液（E）和CE电解液（F）在NCM622／Li电池不同倍率下的充放电曲线图

Fig.3 Rate capability of NCM622／Li cells in different electrolytes（A）and rate voltage profiles of NCM622／Li cell in E-0（B），E-1（C），E-2（D），E-3（E）and CE（F）electrolytes

图4 NCM622／Li电池在不同电解液下循环5圈（A）和循环30圈或50圈（B）的交流阻抗图和等效电路图

Fig.4 The AC impedance diagram and equivalent circuit diagram of NCM622／Li full cells in different electrolytes at the 5th cycle（A）and 30th or 50th cycle（B）

表1 NCM622／Li电池电阻分析

Table 1 Resistance analysis of NCM622／Li cells

电解液	圈数	欧姆内阻	电荷转移内阻	扩散内阻	扩散系数
Electrolyte	Cycles	Ohmic resistance R₁／（Ω·cm²）	Charge transfer resistance R₂／（Ω·cm²）	Diffusion resistance／（Ω·cm²）	Diffusion coefficient／（cm²·S^－1）
E-0	5th	9	25	37	2.8×10^－9
?	50th	13	28	48.5	2.3×10^－9
E-1	5th	4	28	32.7	2.6×10^－9
?	50th	5	24	44.7	2.5×10^－9
E-2	5th	5	7	23.4	3.3×10^－9
?	50th	3	8	24.6	3.2×10^－9
E-3	5th	4	23	54.6	2.5×10^－9
?	50th	4.8	28	37.9	2.4×10^－9
CE	5th	8	143	299.2	1.7×10^－9
?	30th	10	150	304.6	1.5×10^－9

图5 循环后NCM622／Li电池金属锂负极表面扫描电镜图. E-0电解液（A）；E-1电解液（B）；E-2电解液（C）；E-3电解液（D）和CE电解液（E）

Fig.5 The scanning electron micrographs of cycled lithium anodes in NCM622／Li full cells with E-0（A），E-1（B），E-2（C），E-3（D）and CE（E）electrolytes

图6 循环后NCM622／Li电池金属锂负极表面XPS图谱. E-2（A－D）；E-3（E－H）；CE电解液（I－L）

Fig.6 XPS spectra of cycled lithium anodes in NCM622／Li full cells with E-2（A－D），E-3（E－H）and CE（I－L）electrolytes

图7 E-2和E-3电解液在NCM622／Li电池循环后的金属锂负极表面S2p XPS图谱

Fig.7 S2p XPS spectra on the surface of cycled lithium anode in NCM622／Li full cells with E-2 and E-3 electrolytes

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亲锂电解液在LiNi_0.6Mn_0.2Co_0.2O₂／Li二次锂金属电池中的电化学性能

Electrochemical Performance of Lithiophilic Electrolyte in LiNi_0.6Mn_0.2Co_0.2O₂/Li Rechargeable Lithium Metal Battery

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