双功能电解液添加剂对钴酸锂高电压锂离子电池性能的影响

doi:10.19799/j.cnki.2095-4239.2025.0119

摘要/Abstract

摘要：

钴酸锂(LCO)具有长循环、能量密度高和记忆效应小等优点，被广泛应用在穿戴类数码产品中。通过提升充电截止电压能快速有效地提升电池的能量密度，但随之而来的电解液氧化分解和钴离子溶出会导致电池性能下降。本研究通过引入双功能添加剂氰甲基对苯磺酸酯(cyanomethyl p-toluenesulfonate, CMPTS)，有效参与负极表面固态电解质界面(solid electrolyte interphase, SEI)和正极表面固态电解质界面(cathode electrolyte interphase, CEI)的形成，抑制碳酸酯溶剂和六氟磷酸锂(LiPF₆)进一步的氧化还原反应及LCO材料中钴离子的溶出，促进锂离子(Li⁺)在固体钝化膜的嵌入和脱出。将CMPTS作为AG/LCO软包电池的电解液添加剂，以0.5C在3.0~4.55 V条件下充放电测试，电解液中含有质量分数1% CMPTS的电池室温循环500周次后容量保持率90.4%，空白组电池容量保持率只有80.8%，高温(45 ℃)循环350周次后，CMPTS和空白组电池容量保持率分别为83.2%和78.1%。实验及后续表征结果表明，双功能添加剂CMPTS能够显著改善锂离子电池的电化学性能。

关键词: 钴酸锂, 电解液添加剂, 高电压

Abstract:

Lithium cobalt oxide (LCO) offers advantages such as long cycle life, high energy density, and no memory effect, making it widely used in wearable digital products. Increasing the charging cut-off voltage can effectively enhance the battery's energy density; however, it also induces adverse effects, including electrolyte oxidation and decomposition and cobalt ion dissolution, resulting in performance degradation. In this study, a bifunctional additive, cyanomethyl p-toluenesulfonate (CMPTS), was introduced to improve battery performance. CMPTS participates in the formation of the solid electrolyte interphase (SEI) on the anode and the cathode electrolyte interphase (CEI) on the cathode, suppressing further redox reactions of carbonate solvents and lithium hexafluorophosphate (LiPF₆), and preventing cobalt ion dissolution from LCO. This promotes the insertion and extraction of lithium ions (Li⁺) through the solid passivation film. Using CMPTS as an electrolyte additive in AG/LCO full cells, charge-discharge tests were conducted at 0.5 C within 3.0—4.55 V. The cell containing 1% CMPTS exhibited a capacity retention of 90.4% after 500 cycles at room temperature, compared to 80.8% for the baseline cell. At 45 ℃, after 350 cycles, the capacity retention rates of the CMPTS-containing and baseline cells were 83.2% and 78.1%, respectively. These results demonstrate that CMPTS significantly enhances the electrochemical performance of lithium-ion batteries.

Key words: lithium cobalt oxide, electrolyte additive, high voltage

中图分类号:

TM 911

潘立宁, 汪海滨, 方翔, 施萍灏, 谭飞, 赵俊华. 双功能电解液添加剂对钴酸锂高电压锂离子电池性能的影响[J]. 储能科学与技术, 2025, 14(9): 3279-3289.

Lining PAN, Haibin WANG, Xiang FANG, Pinghao SHI, Fei TAN, Junhua ZHAO. The effect of bifunctional electrolyte additive (cyanomethyl p-toluenesulfonate) on the performance of lithium cobalt oxide high-voltage lithium-ion batteries[J]. Energy Storage Science and Technology, 2025, 14(9): 3279-3289.

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参考文献 23

[1]	XU K. Electrolytes and interphases in Li-ion batteries and beyond[J]. Chemical Reviews, 2014, 114(23): 11503-11618. DOI: 10.1021/cr500003w.
[2]	KIM T, SONG W T, SON D Y, et al. Lithium-ion batteries: Outlook on present, future, and hybridized technologies[J]. Journal of Materials Chemistry A, 2019, 7(7): 2942-2964. DOI: 10.1039/C8TA10513H.
[3]	CHEN S, HUANG L L, WEN X Y, et al. Formation mechanism and regulation of LiF in a solid electrolyte interphase on graphite anodes in carbonate electrolytes[J]. The Journal of Physical Chemistry C, 2023, 127(24): 11462-11471. DOI: 10.1021/acs.jpcc.3c02731.
[4]	SUN Z Y, ZHOU H B, LUO X H, et al. Design of a novel electrolyte additive for high voltage LiCoO₂ cathode lithium-ion batteries: Lithium 4-benzonitrile trimethyl borate[J]. Journal of Power Sources, 2021, 503: 230033. DOI: 10.1016/j.jpowsour. 2021.230033.
[5]	WANG K, WAN J J, XIANG Y X, et al. Recent advances and historical developments of high voltage lithium cobalt oxide materials for rechargeable Li-ion batteries[J]. Journal of Power Sources, 2020, 460: 228062. DOI: 10.1016/j.jpowsour.2020. 228062.
[6]	WANG L L, CHEN B B, MA J, et al. Reviving lithium cobalt oxide-based lithium secondary batteries-toward a higher energy density[J]. Chemical Society Reviews, 2018, 47(17): 6505-6602. DOI: 10.1039/C8CS00322J.
[7]	HU Z M, WANG K, CHE Y X, et al. A novel electrolyte additive enables high-voltage operation of nickel-rich oxide/graphite cells[J]. The Journal of Physical Chemistry Letters, 2021, 12(18): 4327-4338. DOI: 10.1021/acs.jpclett.1c00803.
[8]	TANG C, CHEN Y W, ZHANG Z F, et al. Stable cycling of practical high-voltage LiCoO₂ pouch cell via electrolyte modification[J]. Nano Research, 2023, 16(3): 3864-3871. DOI: 10.1007/s12274-022-4955-5.
[9]	SHAO L, ZHOU L, YANG L S, et al. Enhanced 4.5 V/55  ℃ cycling performance of LiCoO₂ cathode via LiAlO₂ LiCo_1- xAlxO₂ double-layer coatings[J]. Electrochimica Acta, 2019, 297: 742-748. DOI: 10.1016/j.electacta.2018.12.044.
[10]	KONG W J, ZHANG J C, WONG D, et al. Tailoring Co3d and O2p band centers to inhibit oxygen escape for stable 4.6 V LiCoO₂ cathodes[J]. Angewandte Chemie International Edition, 2021, 60(52): 27102-27112. DOI: 10.1002/anie.202112508.
[11]	SUN L W, ZHANG Z S, HU X F, et al. Realization of Ti doping by electrostatic assembly to improve the stability of LiCoO₂ cycled to 4.5 V[J]. Journal of the Electrochemical Society, 2019, 166(10): A1793-A1798. DOI: 10.1149/2.0421910jes.
[12]	LI G J, LIAO Y H, LI Z F, et al. Constructing a low-impedance interface on a high-voltage LiNi_0.8Co_0.1Mn_0.1O₂ cathode with 2, 4, 6-triphenyl boroxine as a film-forming electrolyte additive for Li-ion batteries[J]. ACS Applied Materials & Interfaces, 2020, 12(33): 37013-37026. DOI: 10.1021/acsami.0c05623.
[13]	LI G J, FENG Y, ZHU J Y, et al. Achieving a highly stable electrode/electrolyte interface for a nickel-rich cathode via an additive-containing gel polymer electrolyte[J]. ACS Applied Materials & Interfaces, 2022, 14(32): 36656-36667. DOI: 10.1021/acsami.2c09103.
[14]	LI T T, LIN J L, XING L D, et al. Insight into the contribution of nitriles as electrolyte additives to the improved performances of the LiCoO₂ cathode[J]. The Journal of Physical Chemistry Letters, 2022, 13(37): 8801-8807. DOI: 10.1021/acs.jpclett.2c02032.
[15]	LI C L, ZONG F F, HUANG J, et al. Inhibition of silicon-based anode interfacial volume expansion behavior by 1, 3, 6-hexane trinitrile additive via induced interfacial solvation effect[J]. Journal of Power Sources, 2024, 613: 234922. DOI: 10.1016/j.jpowsour. 2024.234922.
[16]	LIU W, SHI Y L, ZHUANG Q C, et al. Ethylene glycol bis(propionitrile) ether as an additive for SEI film formation in lithium-ion batteries[J]. International Journal of Electrochemical Science, 2020, 15(5): 4722-4738. DOI: 10.20964/2020.05.13.
[17]	XIA J, SINHA N N, CHEN L P, et al. Study of methylene methanedisulfonate as an additive for Li-ion cells[J]. Journal of the Electrochemical Society, 2014, 161(1): A84-A88. DOI: 10. 1149/2.034401jes.
[18]	ZHANG Z, LIU F Y, HUANG Z Y, et al. Enhancing the electrochemical performance of a high-voltage LiCoO₂ cathode with a bifunctional electrolyte additive[J]. ACS Applied Energy Materials, 2021, 4(11): 12954-12964. DOI: 10.1021/acsaem.1c02593.
[19]	ZUO X X, DENG X, MA X D, et al. 3-(Phenylsulfonyl)propionitrile as a higher voltage bifunctional electrolyte additive to improve the performance of lithium-ion batteries[J]. Journal of Materials Chemistry A, 2018, 6(30): 14725-14733. DOI: 10.1039/C8TA04558E.
[20]	ZOU Y, CHENG Y, LIN J D, et al. Boosting high voltage cycling of LiCoO₂ cathode via triisopropanolamine cyclic borate electrolyte additive[J]. Journal of Power Sources, 2022, 532: 231372. DOI: 10.1016/j.jpowsour.2022.231372.
[21]	CHEN S, WEN X Y, CHEN Y L, et al. Distinctive interphasial properties and high structural reversibility endowed by B-/ CN–electrolyte additive and its superior electrochemical performance for graphite/LiCoO₂ pouch cells[J]. Chemical Engineering Journal, 2024, 479: 147813. DOI: 10.1016/j.cej.2023.147813.
[22]	XU K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries[J]. Chemical Reviews, 2004, 104(10): 4303-4418. DOI: 10.1021/cr030203g.
[23]	ZHAO W M, ZHENG B Z, LIU H D, et al. Toward a durable solid electrolyte film on the electrodes for Li-ion batteries with high performance[J]. Nano Energy, 2019, 63: 103815. DOI: 10.1016/j.nanoen.2019.06.011.