硫系电解液添加剂对镍钴锰酸锂//石墨锂离子电池性能的影响

doi:10.19799/j.cnki.2095-4239.2023.0250

摘要/Abstract

摘要：

本工作系统研究了6种添加剂[碳酸亚乙烯酯(VC)、亚硫酸乙烯酯(ES)、硫酸乙烯酯(DTD)、1，3-丙二醇环硫酸酯(PCS)、1，3-丙烷磺酸内酯(PS)、1，3-丙烯磺酸内酯(PST)]对镍钴锰酸锂(NCM111)//石墨体系锂离子电池电化学性能的影响，通过对比首次充放电效率、放电容量、倍率特性、低温放电能力、高温存储性能以及循环寿命等发现：VC在各方面性能比较均衡，碳碳双键(C＝C)能够改善成膜特性，循环性能优异，可独立使用；ES在化成、循环和存储过程中因电解液持续分解而胀气，无法单独使用；硫酸酯添加剂(DTD和PCS)能够明显降低阻抗并提升低温性能，但高温性能稍差；磺酸内酯添加剂(PS和PST)对抑制高温胀气效果突出，含有双功能基团的PST循环性能及抑制电压衰减的能力优于PS，但低温阻抗较高。综合对比发现，单组分硫系添加剂在某些性能方面有自己的特色，但也存在显而易见的缺陷，无法独立使用。通过与VC进行等比例复配，硫系添加剂循环性能差的问题得以解决，而高首效、低内阻、大倍率和高温稳定性等特色功能得以保持，二元联用后的综合性能显著优于单组分添加剂，采用添加剂联用方式来改善电池综合性能是较佳选择。

关键词: 电解液, 添加剂, 硫系, 锂离子, 镍钴锰酸锂

Abstract:

The effects of six electrolyte additives: vinylene carbonate (VC), ethylene sulfite (ES), ethylene sulfate (DTD), 1,3-propanediol cyclo-sulfate (PCS), 1,3-propylene sultone (PS), 1,3-propylene sultone (PST) on the electrochemical performance of lithium nickel cobalt manganese oxide (NCM111)//graphite lithium-ion batteries were investigated herein. Some conclusions were obtained by comparing the results of the first charging-discharging efficiency, discharged capacity, rate characteristics, low-temperature discharging capability, high-temperature storage performance and cycle life, etc. C＝C double bond can improve the film-forming property and promote the cycle life, making VC possess a relatively balanced performance in all aspects and can be used independently. The continuous gas production for ES in the formation, cycle, and storage processes can be observed because of the unstoppable decomposition of the electrolyte, making it impossible to use. Sulphate Additives (DTD and PCS) can significantly reduce the DCR and improve the low-temperature performance; however, their high-temperature performance is slightly restricted. Sulfonate additives (PS and PST) have outstanding effects in inhibiting high-temperature flatulence. Especially, PST with dual functional groups has better cycle performance and capability to suppress the voltage decay in high-temperature environments than PS but has higher impedance in low-temperature environments than other additives. A comprehensive comparison shows that the single-component sulfur-containing additive is equipped with unique characteristics in some properties but also has obvious defects, making it lonely and impossible. The problem of poor cycling performance of sulfur-containing additives can be solved by proportionally compounding them with VC, while their characteristics such as high initial coulombic efficiency, low internal resistance, excellent rate performance and high-temperature stability can be maintained. The comprehensive performance of binary combination is better than that of the single-component additive, making it a better choice for additive combination to improve the battery performance.

Key words: electrolyte, additive, sulfur-containing, Li-ion, lithium nickel cobalt manganese oxide

中图分类号:

TM 911.3

夏恒恒, 梁鹏程, 安仲勋. 硫系电解液添加剂对镍钴锰酸锂//石墨锂离子电池性能的影响[J]. 储能科学与技术, 2023, 12(8): 2390-2400.

Hengheng XIA, Pengcheng LIANG, Zhongxun AN. Effects of sulfur-containing electrolyte additives on the performance of lithium nickel cobalt manganese oxide//graphite Li-ion batteries[J]. Energy Storage Science and Technology, 2023, 12(8): 2390-2400.

图/表 6

图1

表1

图2

图3

图4

图5

参考文献 40

1	索鎏敏, 李泓. 锂离子电池过往与未来[J]. 物理, 2020, 49(1): 17-23.
	SUO L M, LI H. The past, present and future of lithium ion batteries[J]. Physics, 2020, 49(1): 17-23.
2	封迈, 陈楠, 陈人杰. 锂离子电池低温电解液的研究进展[J]. 储能科学与技术, 2023, 12(3): 792-807.
	FENG M, CHEN N, CHEN R J. Research progress of low-temperature electrolyte for lithium-ion battery[J]. Energy Storage Science and Technology, 2023, 12(3): 792-807.
3	倪江锋, 周恒辉, 陈继涛, 等. 锂离子电池中固体电解质界面膜(SEI)研究进展[J]. 化学进展, 2004, 16(3): 335-342.
	NI J F, ZHOU H H, CHEN J T, et al. Progress in solid electrolyte interface in lithium ion batteries[J]. Progress in Chemistry, 2004, 16(3): 335-342.
4	ZHAO D N, WANG P, CUI X L, et al. Robust and sulfur-containing ingredient surface film to improve the electrochemical performance of LiDFOB-based high-voltage electrolyte[J]. Electrochimica Acta, 2018, 260: 536-548.
5	XU M Q, LI W S, ZUO X X, et al. Performance improvement of lithium ion battery using PC as a solvent component and BS as an SEI forming additive[J]. Journal of Power Sources, 2007, 174(2): 705-710.
6	ZHANG S S. A review on electrolyte additives for lithium-ion batteries[J]. Journal of Power Sources, 2006, 162(2): 1379-1394.
7	BURNS J C, PETIBON R, NELSON K J, et al. Studies of the effect of varying vinylene carbonate (VC) content in lithium ion cells on cycling performance and cell impedance[J]. Journal of the Electrochemical Society, 2013, 160(10): A1668-A1674.
8	BURNS J C, SINHA N N, COYLE D J, et al. The impact of varying the concentration of vinylene carbonate electrolyte additive in wound Li-ion cells[J]. Journal of the Electrochemical Society, 2011, 159(2): A85-A90.
9	WU Z L, LI S G, ZHENG Y Z, et al. The roles of sulfur-containing additives and their working mechanism on the temperature-dependent performances of Li-ion batteries[J]. Journal of the Electrochemical Society, 2018, 165(11): A2792-A2800.
10	周丹, 梁风, 姚耀春. 锂离子电池电解液负极成膜添加剂的研究进展[J]. 化工进展, 2016, 35(5): 1477-1483.
	ZHOU D, LIANG F, YAO Y C. Research progress of negative film-forming additives in electrolyte for Li-ion batteries[J]. Chemical Industry and Engineering Progress, 2016, 35(5): 1477-1483.
11	张晓妍, 任宇飞, 高洁, 等. 动力电池电解液用添加剂的研究进展[J]. 储能科学与技术, 2018, 7(3): 404-417.
	ZHANG X Y, REN Y F, GAO J, et al. Progress of electrolyte additives for high-capacity power lithium ion batteries[J]. Energy Storage Science and Technology, 2018, 7(3): 404-417.
12	XIA J, AIKEN C P, MA L, et al. Combinations of ethylene sulfite (ES) and vinylene carbonate (VC) as electrolyte additives in Li(Ni_1/3Mn_1/3Co_1/3)O₂/graphite pouch cells[J]. Journal of the Electrochemical Society, 2014, 161(6): A1149-A1157.
13	邓邦为, 孙大明, 万琦, 等. 锂离子电池三元正极材料电解液添加剂的研究进展[J]. 化学学报, 2018, 76(4): 259-277.
	DENG B W, SUN D M, WAN Q, et al. Review of electrolyte additives for ternary cathode lithium-ion battery[J]. Acta Chimica Sinica, 2018, 76(4): 259-277.
14	REN F C, ZUO W H, YANG X R, et al. Comprehensive understanding of reduction mechanisms of ethylene sulfite in EC-based lithium-ion batteries[J]. The Journal of Physical Chemistry C, 2019, 123(10): 5871-5880.
15	PARK G, NAKAMURA H, LEE Y, et al. The important role of additives for improved lithium ion battery safety[J]. Journal of Power Sources, 2009, 189(1): 602-606.
16	WRODNIGG G H, BESENHARD J O, WINTER M. Cyclic and acyclic sulfites: New solvents and electrolyte additives for lithium ion batteries with graphitic anodes?[J]. Journal of Power Sources, 2001, 97: 592-594.
17	陈高明, 胡立新, 王超. 锂离子电池电解液添加剂的研究进展[J]. 能源研究与管理, 2011(2): 57-61.
	CHEN G M, HU L X, WANG C. Research progress of additives for Li-ion battery electrolytes[J]. Energy Research and Management, 2011(2): 57-61.
18	周密, 王希敏, 袁银男, 等. 电解液添加剂对高镍锂离子电池性能的影响[J]. 电池, 2022, 52(3): 237-242.
	ZHOU M, WANG X M, YUAN Y N, et al. Effect of electrolyte additives on the performance of high nickel Li-ion battery[J]. Battery Bimonthly, 2022, 52(3): 237-242.
19	SELF J, HALL D S, MADEC L, et al. The role of prop-1-ene-1,3-sultone as an additive in lithium-ion cells[J]. Journal of Power Sources, 2015, 298: 369-378.
20	XU G J, PANG C G, CHEN B B, et al. Batteries: Prescribing functional additives for treating the poor performances of high-voltage (5 V-class) LiNi_0.5Mn_1.5O₄/MCMB Li-ion batteries[J]. Advanced Energy Materials, 2018, 8(9): 1870038.
21	FUJIMOTO M, SHOUJI Y, NOHMA T, et al. Charge-discharge characteristics of natural graphite electrode in some cyclic carbonates[J]. Denki Kagaku Oyobi Kogyo Butsuri Kagaku, 1997, 65(11): 949-953.
22	MOSALLANEJAD B. Phthalimide derivatives: New promising additives for functional electrolyte in lithium-ion batteries[J]. Chemical Methodologies, 2019, doi: 10.22034/chemm.2018. 155768.1109.
23	XING L D, LI W S, XU M Q, et al. The reductive mechanism of ethylene sulfite as solid electrolyte interphase film-forming additive for lithium ion battery[J]. Journal of Power Sources, 2011, 196(16): 7044-7047.
24	LI X C, YIN Z L, LI X H, et al. Ethylene sulfate as film formation additive to improve the compatibility of graphite electrode for lithium-ion battery[J]. Ionics, 2014, 20(6): 795-801.
25	FELIX, CHENG J H, HY S, et al. Mechanistic basis of enhanced capacity retention found with novel sulfate-based additive in high-voltage Li-ion batteries[J]. The Journal of Physical Chemistry C, 2013, 117(44): 22619-22626.
26	JANKOWSKI P, LINDAHL N, WEIDOW J, et al. Impact of sulfur-containing additives on lithium-ion battery performance: From computational predictions to full-cell assessments[J]. ACS Applied Energy Materials, 2018, 1(6): 2582-2591.
27	杜强, 张一鸣, 田爽, 等. 锂离子电池SEI膜形成机理及化成工艺影响[J]. 电源技术, 2018, 42(12): 1922-1926.
	DU Q, ZHANG Y M, TIAN S, et al. Formation mechanism of solid electrolyte interphase (SEI) and effect of formation process on it in lithium ion batteries[J]. Chinese Journal of Power Sources, 2018, 42(12): 1922-1926.
28	XU Y B, WU H P, HE Y, et al. Atomic to nanoscale origin of vinylene carbonate enhanced cycling stability of lithium metal anode revealed by cryo-transmission electron microscopy[J]. Nano Letters, 2020, 20(1): 418-425.
29	ITAGAKI M, YOTSUDA S, KOBARI N, et al. Electrochemical impedance of electrolyte/electrode interfaces of lithium-ion rechargeable batteries: Effects of additives to the electrolyte on negative electrode[J]. Electrochimica Acta, 2006, 51(8/9): 1629-1635.
30	周邵云, 洪坤光, 余乐, 等. 1-丙烯-1,3-磺酸内酯对高电压锂离子电池的影响[J]. 电池, 2016, 46(4): 189-192.
	ZHOU S Y, HONG K G, YU L, et al. Effect of 1-propenyl-1,3-sultones on high-voltage Li-ion battery[J]. Battery Bimonthly, 2016, 46(4): 189-192.
31	TONG B, SONG Z Y, WAN H H, et al. Sulfur-containing compounds as electrolyte additives for lithium-ion batteries[J]. InfoMat, 2021, 3(12): 1364-1392.
32	MADEC L, PETIBON R, XIA J, et al. Understanding the role of prop-1-ene-1,3-sultone and vinylene carbonate in LiNi_1/3Mn_1/3Co_1/3O₂/graphite pouch cells: Electrochemical, GC-MS and XPS analysis[J]. Journal of the Electrochemical Society, 2015, 162(14): A2635-A2645.
33	ZHANG B, METZGER M, SOLCHENBACH S, et al. Role of 1, 3-propane sultone and vinylene carbonate in solid electrolyte interface formation and gas generation[J]. The Journal of Physical Chemistry C, 2015, 119(21): 11337-11348.
34	LIU Y L, HAMAM I, DAHN J R. A study of vinylene carbonate and prop-1-ene-1,3 sultone electrolyte additives using polycrystalline Li[Ni_0.6Mn_0.2Co_0.2]O₂ in positive/positive symmetric cells[J]. Journal of the Electrochemical Society, 2020, 167(11): 110527.
35	JANSSEN P, SCHMITZ R, MÜLLER R, et al. 1,3,2-Dioxathiolane-2,2-dioxide as film-forming agent for propylene carbonate based electrolytes for lithium-ion batteries[J]. Electrochimica Acta, 2014, 125: 101-106.
36	LEE H, CHOI S, CHOI S, et al. SEI layer-forming additives for LiNi_0.5Mn_1.5O₄/graphite 5 V Li-ion batteries[J]. Electrochemistry Communications, 2007, 9(4): 801-806.
37	KOREPP C, SANTNER H J, FUJII T, et al. 2-Cyanofuran—A novel vinylene electrolyte additive for PC-based electrolytes in lithium-ion batteries[J]. Journal of Power Sources, 2006, 158(1): 578-582.
38	PRITZL D, SOLCHENBACH S, WETJEN M, et al. Analysis of vinylene carbonate (VC) as additive in graphite/LiNi_0.5Mn_1.5O₄ cells[J]. Journal of the Electrochemical Society, 2017, 164(12): A2625-A2635.
39	CHENG H R, SUN Q J, LI L L, et al. Emerging era of electrolyte solvation structure and interfacial model in batteries[J]. ACS Energy Letters, 2022, 7(1): 490-513.
40	XIA J, HARLOW J E, PETIBON R, et al. Comparative study on methylene methyl disulfonate (MMDS) and 1,3-propane sultone (PS) as electrolyte additives for Li-ion batteries[J]. Journal of the Electrochemical Society, 2014, 161(4): A547-A553.

电解液添加剂	还原电位(vs. Li/Li⁺)/V	LUMO/eV	熔点/℃
碳酸亚乙烯酯(VC)	0.9 (1.0 mol/L LiPF₆-VC/DEC)^[21]	-0.01^[22]	22
亚硫酸乙烯酯(ES)	1.7 (1.0 mol/L LiPF₆-EC/DMC)^[4]	-1.25^[23]	-17
硫酸乙烯酯(DTD)	1.25 (1.0 mol/L LiPF₆-EC/DMC/EMC)^[24]	0.11^[24]	99
1,3-丙二醇环硫酸酯(PCS)	1.8 (1.0 mol/L LiPF₆-EC/DEC)^[25]	-0.34^[9]	60
1,3-丙烷磺酸内酯(PS)	0.74 (1.0 mol/L LiPF₆-EC/DMC)^[26]	0.03^[26]	30
1,3-丙烯磺酸内酯(PST)	1.12 (1.0 mol/L LiPF₆-EC/DMC)^[26]	-0.27^[26]	83

[1]	黄永浩, 臧国景, 朱霨亚, 廖友好, 李伟善. LiF添加剂改善含锂陶瓷隔膜与4.35 V LiNi_0.8Co_0.1Mn_0.1O₂ 正极的界面稳定性[J]. 储能科学与技术, 2023, 12(8): 2361-2369.
[2]	杨佳兴, 张恒运, 徐屹东. 基于电化学-热耦合模型的锂离子电池组件产热分析[J]. 储能科学与技术, 2023, 12(8): 2615-2625.
[3]	张吉禄, 董育辰, 宋强, 袁思鸣, 郭孝东. 多晶及单晶高镍三元材料LiNi_0.9Co_0.05Mn_0.05O₂ 的可控制备及其电化学储锂特性[J]. 储能科学与技术, 2023, 12(8): 2382-2389.
[4]	郭煜, 王亦伟, 钟隽, 杜进桥, 田杰, 李艳, 蒋方明. 基于增量容量曲线的锂离子电池微内短路故障诊断方法[J]. 储能科学与技术, 2023, 12(8): 2536-2546.
[5]	刘志浩, 杜童, 李瑞瑞, 邓涛. 宽温域、高电压、安全无EC电解液研究进展[J]. 储能科学与技术, 2023, 12(8): 2504-2525.
[6]	左安昊, 方儒卿, 李哲. 锂离子电池单颗粒动力学表征方法综述[J]. 储能科学与技术, 2023, 12(8): 2457-2481.
[7]	陈满, 程志翔, 赵春朋, 彭鹏, 雷旗开, 金凯强, 王青松. 锂离子电池储能集装箱爆炸危害数值模拟[J]. 储能科学与技术, 2023, 12(8): 2594-2605.
[8]	李聪, 王桃, 任延杰, 周立波, 陈荐, 陈维. 熔融碳酸盐燃料电池阴极溶解与防护[J]. 储能科学与技术, 2023, 12(8): 2444-2456.
[9]	唐程波, 锁要红, 何昭坤. 基于正弦函数的液冷板上流体流向对锂离子电池散热性能的影响[J]. 储能科学与技术, 2023, 12(8): 2547-2555.
[10]	陈智伟, 张维戈, 张珺玮, 张言茹. 基于视觉特征的动力电池组综合健康评估及分筛方法[J]. 储能科学与技术, 2023, 12(7): 2211-2219.
[11]	张宇波, 王有元, 黄洞宁, 王子懿, 陈伟根. 面向变工况条件的锂离子电池寿命退化预测方法[J]. 储能科学与技术, 2023, 12(7): 2238-2245.
[12]	陈育新, 杨家沐, 练成, 刘洪来. 基于相场模型的锂电池电极浆料稳定涂布窗口分析[J]. 储能科学与技术, 2023, 12(7): 2185-2193.
[13]	张贵萍, 闫筱炎, 王兵, 姚培新, 胡昌杰, 刘奕哲, 李纾黎, 薛建军. 长寿命循环的磷酸铁锂电池及材料、工艺[J]. 储能科学与技术, 2023, 12(7): 2134-2140.
[14]	杲齐新, 赵景腾, 李国兴. 锂离子电池快速充电研究进展[J]. 储能科学与技术, 2023, 12(7): 2166-2184.
[15]	范茂松, 耿萌萌, 赵光金, 杨凯, 王放放, 刘皓. 基于多频点阻抗的梯次利用电池分选技术研究[J]. 储能科学与技术, 2023, 12(7): 2202-2210.