调控LiPF6 基电解液溶剂化结构稳定富锂锰基正极界面

doi:10.19799/j.cnki.2095-4239.2023.0072

摘要/Abstract

摘要：

富锂锰基正极材料具有高比容量和低成本的优势，有望成为下一代高能量密度金属锂电池的正极材料。然而在实际应用中，其相对于金属锂高达4.8 V的充电截止电压，会引发电解液氧化分解失效，导致正极与电解液的界面恶化使得电池难以稳定循环。为此本文开发了以1，1，2，2-四氟乙基-2，2，3，3-四氟丙基醚(TTE)充当促配位溶剂的六氟磷酸锂(LiPF₆)基新型高电压电解液。实验与表征结果说明，适量TTE引入后具有更多锂盐阴离子参与锂离子配位的溶剂化结构的电解液，能够在正极表面形成5 nm厚且富含氟元素的正极电解液中间相(CEI)，稳定正极界面并抑制正极层状结构的退化。使用新型电解液的富锂锰基正极对金属锂扣式电池，以99.8%的平均效率循环400次后，仍有83.9%的容量保持率(0.5 C)。组装1.25 Ah的富锂锰基正极对金属锂软包电池，在0.04 C下能够提供370 Wh/kg的质量能量密度，在0.08 C下循环45次后，仍有80%的容量保持率，表现出良好的应用前景。本研究有助于推动富锂锰基正极的应用，为高能量密度金属锂电池的研发提供实验依据。

关键词: 富锂锰基正极, 高电压, 电解液, 正极-电解液中间相, 层状结构, 金属锂软包电池

Abstract:

Li-rich Mn-based cathode has the advantages of high specific capacity and low cost, which is expected to be the cathode material for the next generation of high-energy density Li-metal batteries. However, in practical applications, its charging cutoff voltage is 4.8 V versus Li, leading to the failure of electrolyte oxygenation decompositions, thereby deteriorating the interface between the cathode and electrolyte, making stable battery cycling challenging. A novel high-voltage electrolyte based on LiPF₆ is developed, in which 1, 1, 2, 2-tetrafluoroethyl-2, 2, 3, 3-tetrafluoropropylether (TTE) is used as a solvent to promote coordination. The experimental and characterization results show that many Li anions participate in the solvated structure of Li⁺ coordination after introducing appropriate TTE in the electrolyte, which can form a 5-nm-thick fluorine-rich cathode electrolyte interphase (CEI) on the surface of the cathode, stabilizing its interface and inhibiting the degradation of the cathode layer structure. The Li-rich Mn-based cathode Li-metal battery with the new electrolyte has an 83.9% capacity retention rate after 400 cycles with an average efficiency of 99.8% (0.5 C). The 1.25-Ah Li-rich Mn-based cathode Li-metal battery pouch cell can provide 370 Wh/kg mass-energy density at 0.04 C and still has an 80% capacity retention rate after 45 cycles at 0.08 C, showing a good application prospect. This study is helpful to promote the application of Li-rich Mn-based cathode and provide an experimental basis for the research and development of high energy density Li-metal batteries.

Key words: lithium-rich manganese-based cathode, high voltage, electrolyte solvent, cathode-electrolyte interphase, layered structure, lithium metal pouch cell

中图分类号:

TM 911

胡川, 胡志伟, 李振东, 李帅, 王豪, 王丽平. 调控LiPF₆ 基电解液溶剂化结构稳定富锂锰基正极界面[J]. 储能科学与技术, 2023, 12(5): 1604-1615.

Chuan HU, Zhiwei HU, Zhendong LI, Shuai LI, Hao WANG, Liping WANG. Tailoring LiPF₆-base electrolyte solvation structure toward a stable Lithium-rich manganese-based cathode interface[J]. Energy Storage Science and Technology, 2023, 12(5): 1604-1615.

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组成	特征/单位	参数
正极	正极材料	Li_1.2Mn_0.54Ni_0.13Co_0.13O₂
	放电比容量/(mAh/g)	300
	双面涂布厚度/(Al箔6 μm)(μm)	200
	尺寸/mm³	65.0×45.0×0.2
	面载量/(mAh/cm²)	4.0
	正极片层数	5
负极	负极材料	金属锂
	厚度/μm	120
	负极片层数	6
隔膜电解液	20 μm PP隔膜
	1 mol/L LiPF₆FEC/DMC/TTE+1% LiDFOB
	电解液用量/g	3.0
电池	尺寸/mm³	85.0×50.0×2.4
	质量/g	11.7
	N/P	3.0
	容量/Ah	1.25
	充放电电压区间/V	2.0～4.8
	能量密度/(Wh/kg)	370

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调控LiPF₆ 基电解液溶剂化结构稳定富锂锰基正极界面

Tailoring LiPF₆-base electrolyte solvation structure toward a stable Lithium-rich manganese-based cathode interface

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