高压锂电池正极电解质界面研究进展

doi:10.3866/PKU.WHXB202308048

物理化学学报 >> 2025, Vol. 41 >> Issue (2): 100011.doi: 10.3866/PKU.WHXB202308048

高压锂电池正极电解质界面研究进展

刘建东¹^,², 张志佳³, MikhailKamenskii⁴, FilippVolkov⁴, SvetlanaEliseeva⁴, 马建民¹^,*

¹ 天津工业大学化学学院, 天津 300387
² 湖南大学物理与微电子科学学院, 长沙 410022
³ 天津工业大学材料科学与工程学院, 天津 300387
⁴ Institute of Chemistry, Saint Petersburg State University, Saint Petersburg 199034, Russia

收稿日期:2023-08-30 修回日期:2023-10-06 录用日期:2023-10-30 发布日期:2023-12-20
通讯作者: Email: nanoelechem@hnu.edu.cn (马建民)
基金资助:
国家自然科学基金(U21A20311)

Research Progress on Cathode Electrolyte Interphase in High-Voltage Lithium Batteries

Jiandong Liu¹^,², Zhijia Zhang³, Kamenskii Mikhail⁴, Volkov Filipp⁴, Eliseeva Svetlana⁴, Jianmin Ma¹^,*

¹ School of Chemistry, Tiangong University, Tianjin 300387, China
² School of Physics and Electronics, Hunan University, Changsha 410022, China
³ School of Material Science and Engineering, Tiangong University, Tianjin 300387, China
⁴ Institute of Chemistry, Saint Petersburg State University, Saint Petersburg 199034, Russia

Received:2023-08-30 Revised:2023-10-06 Accepted:2023-10-30 Published:2023-12-20
Contact: Email: nanoelechem@hnu.edu.cn (Jianmin Ma)
Supported by:
the National Natural Science Foundation of China(U21A20311)

摘要/Abstract

摘要：

提高电池的截止电压上限可以显著提升锂电池的能量密度。然而，高截止电压也会导致正极材料在高压下发生不可逆相变和副反应，从而损害电池性能。为了解决这一问题，建立一个稳定的正极电解质界面(CEI)在提高电池性能方面起到了关键作用。本文探讨了CEI的形成机制，并概述了构建CEI的方法，包括人工构建CEI和原位生成CEI。此外，从电解质的角度出发，我们还展望了构建高压正极CEI的设计思路。

关键词: 高压正极, 正极电解质界面, 电解质工程, 电解质添加剂, 锂电池

Abstract:

Achieving high energy density batteries is currently a key focus in the field of energy storage. Lithium batteries, due to their high energy density, have garnered significant attention in research. Increasing the upper limit of the battery's cut-off voltage can boost the energy density of lithium batteries. However, high-voltage conditions can lead to irreversible phase transitions and side reactions in cathode materials, which can degrade battery performance and even result in safety risks, including explosions. The electrolyte can also decompose, causing capacity loss and releasing flammable gases when subjected to high voltage, which can lead to battery swelling and potential combustion and explosions. Designing an ideal cathode electrolyte interphase (CEI) on the cathode's surface to regulate the electrode-electrolyte interface reaction can effectively enhance the cycling stability of the battery, reduce irreversible phase transitions in the cathode, and improve the oxidation stability of the electrolyte. The ideal CEI should possess high ion conductivity, high thermal stability, and should minimize interface side reactions to ensure optimal battery performance. Understanding the formation and development of CEI is crucial for enhancing battery performance under high voltage. Apart from creating artificial CEI, modifying electrolytes has gained significant attention. By altering the electrolyte recipe, an ideal CEI can be achieved. Electrolyte engineering is considered an effective strategy for attaining an ideal CEI and enhancing the stability of high nickel positive electrodes. This approach is simple, cost-effective, and holds great promise for achieving higher energy density in lithium batteries. To provide a better understanding of CEI in lithium ion batteries (LIBs), this article reviews the latest advancements in CEI, including the formation mechanism of CEI, the key factors influencing CEI, methods for modifying CEI, and techniques for characterizing CEI. Additionally, it summarizes the current status of artificial CEI development and in situ CEI generation through electrolyte design. The aim is to offer fundamental guidance for future research and the design of high-voltage battery CEI. Finally, the article outlines the opportunities and challenges in electrolyte engineering for modified CEI, pointing towards the future direction of constructing an ideal CEI.

Key words: High-voltage cathode, Cathode electrolyte interphase, Electrolyte engineering, Electrolyte additive, Lithium battery

刘建东, 张志佳, MikhailKamenskii, FilippVolkov, SvetlanaEliseeva, 马建民. 高压锂电池正极电解质界面研究进展[J]. 物理化学学报, 2025, 41(2), 100011. doi: 10.3866/PKU.WHXB202308048

Jiandong Liu, Zhijia Zhang, Kamenskii Mikhail, Volkov Filipp, Eliseeva Svetlana, Jianmin Ma. Research Progress on Cathode Electrolyte Interphase in High-Voltage Lithium Batteries[J]. Acta Phys. -Chim. Sin. 2025, 41(2), 100011. doi: 10.3866/PKU.WHXB202308048

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202308048

https://www.whxb.pku.edu.cn/CN/Y2025/V41/I2/100011

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Methods	Advantage	Disadvantage
XPS	Provides the content of elements on the surface/ analyze the valence states of elements/ better quantitative ability	Not easy to focus/ the large irradiation area/ the detection limit
SEM	Simple to prepare samples/ dynamically observed/ high resolution	The lower resolution/ vacuum environment limits the type of sample/ only the surface morphology observed/ no height direction information/ not liquid samples
TEM	High resolution/ observing the crystal lattice on the crystal surface	Certain destructive effects on the sample/ high material requirements/ small observation range
Cryo-EM	Close to the living state/ observing microstructure of different split surfaces/ withstanding electron beam bombardment and long-term preservation	Artificial damage to samples/ Limitations of observation area selection
XRD	High analysis speed/ no extra changes in the chemical state/ measured repeatedly with good reproducibility/ simple sample preparation	Poor absolute analysis/ quantitative analysis needs standard samples/ less sensitive to light elements/ easily affected by mutual element interference and superposition peaks
AFM	True three-dimensional surface map/ not require any special treatment of the sample/ work well at atmospheric pressure	Small imaging range/ slow speed/ great influence of the probe
XAS	More accurate atomic structure identification/ the coordination environment and the chemical state/ low sample requirements/ nondestructive	Only the planar average structure and no three-dimensional information
ToF-SIMS	High resolution/ high sensitivity/ accurate mass measurement/ three-dimensional manner	Little damage to the sample/ mainly solid at present

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高压锂电池正极电解质界面研究进展

Research Progress on Cathode Electrolyte Interphase in High-Voltage Lithium Batteries

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