低温磷酸铁锂电池用全醚高熵电解液的设计研究

doi:10.19799/j.cnki.2095-4239.2024.0338

储能科学与技术 ›› 2024, Vol. 13 ›› Issue (7): 2131-2140.doi: 10.19799/j.cnki.2095-4239.2024.0338

低温磷酸铁锂电池用全醚高熵电解液的设计研究

王美龙¹(), 薛煜瑞¹, 胡文茜¹, 杜可遇¹, 孙瑞涛¹, 张彬³(), 尤雅¹^,²()

^1.武汉理工大学材料复合新技术国家重点实验室
^2.武汉理工大学材料科学与工程国际化示范学院，湖北武汉 430070
^3.宜宾锂宝新材料有限公司，四川宜宾 644000

收稿日期:2024-04-17 修回日期:2024-05-16 出版日期:2024-07-28 发布日期:2024-07-23
通讯作者: 张彬,尤雅 E-mail:wangmeilong@whut.edu.cn;10062904@libode.com.cn;yayou@whut.edu.cn
作者简介:王美龙（1996—），男，博士研究生，研究方向为极端条件二次电池电解液的设计研究，E-mail：wangmeilong@whut.edu.cn；
基金资助:
国家重点研发计划(2022YFB3803400);宜宾市揭榜挂帅项目(2022JB003)

Design and research of all-ether high-entropy electrolyte for low-temperature lithium iron phosphate batteries

Meilong WANG¹(), Yurui XUE¹, Wenxi HU¹, Keyu DU¹, Ruitao SUN¹, Bin ZHANG³(), Ya YOU¹^,²()

^1.State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology
^2.International School of Materials Science and Engineering, School of Materials Science and Microelectronics, Wuhan University of Technology, Wuhan 430070, Hubei, China
^3.Yibin Libode New Materals Co. , Ltd, Yibin 644000, Sichuan, China

Received:2024-04-17 Revised:2024-05-16 Online:2024-07-28 Published:2024-07-23
Contact: Bin ZHANG, Ya YOU E-mail:wangmeilong@whut.edu.cn;10062904@libode.com.cn;yayou@whut.edu.cn

摘要/Abstract

摘要：

磷酸铁锂材料在常温下展现出优异的循环稳定性和能量密度，但低温性能受到了其低离子电导率和缓慢动力学的严重限制。本文利用具有不同溶剂化能力的醚类溶剂设计了一种新型的全醚高熵电解液，以提高磷酸铁锂电池在低温条件下的电化学性能。实验结果表明，该策略可有效提高电解液在低温环境下的离子导电率和改善动力学稳定性，从而提高磷酸铁锂电池的低温放电容量和循环寿命。在低温(-20 ℃)环境下，本工作所设计的电解液展现出了出色的充放电稳定性。经过150次循环测试后，其容量保持率高达99.7%，且在低温下仍可保持室温容量的81.1%，并具有效性和普适性。这一新的策略提升了磷酸铁锂电池的低温性能和应用范围。

关键词: 锂离子电池, 磷酸铁锂正极, 低温性能, 醚类溶剂, 高熵电解液

Abstract:

Lithium iron phosphate (LFP) materials are known for their outstanding cycle stability and energy density at room temperature (RT, 25 ℃); however, their performance at low temperatures (LT, -20 ℃) is hindered owing to poor ionic conductivity and sluggish kinetics. This study introduces a novel all-ether high-entropy electrolyte, formulated by integrating ethers of varying solvating powers, to enhance the electrochemical performance of LFP batteries at LT. Experimental results confirm that this approach considerably enhances the ionic conductivity and kinetic stability of the electrolyte at LT, thereby substantially improving the low-temperature discharge capacity and cycle lifespan of LFP batteries. The mix-7 electrolyte variant, in particular, demonstrates exceptional charge-discharge stability at LT. After 150 cycles, it retains a high capacity retention rate of 99.7% and maintains 81.1% of its initial capacity at RT. This strategy proves effective and versatile, markedly enhancing the low-temperature performance and broadening the application spectrum of LFP batteries.

Key words: lithium-ion batteries, lithium iron phosphate cathode, low-temperature performance, ether solvents, high-entropy electrolyte

中图分类号:

TM 911

王美龙, 薛煜瑞, 胡文茜, 杜可遇, 孙瑞涛, 张彬, 尤雅. 低温磷酸铁锂电池用全醚高熵电解液的设计研究[J]. 储能科学与技术, 2024, 13(7): 2131-2140.

Meilong WANG, Yurui XUE, Wenxi HU, Keyu DU, Ruitao SUN, Bin ZHANG, Ya YOU. Design and research of all-ether high-entropy electrolyte for low-temperature lithium iron phosphate batteries[J]. Energy Storage Science and Technology, 2024, 13(7): 2131-2140.

图/表 5

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参考文献 35

1	YUAN L X, WANG Z H, ZHANG W X, et al. Development and challenges of LiFePO₄ cathode material for lithium-ion batteries[J]. Energy & Environmental Science, 2011, 4(2): 269-284.
2	YANG L, DENG W T, XU W, et al. Olivine LiMnxFe_1- xPO₄ cathode materials for lithium ion batteries: Restricted factors of rate performances[J]. Journal of Materials Chemistry A, 2021, 9(25): 14214-14232.
3	SAIFULLAH M, MOSTAFIZUR R, MD K, et al. Recent advances in lithium-ion battery materials for improved electrochemical performance: A review[J]. Results in Engineering, 2022, 15: 100472.
4	CHEN X L, GONG Y D, LI X, et al. Perspective on low-temperature electrolytes for LiFePO₄-based lithium-ion batteries[J]. International Journal of Minerals, Metallurgy and Materials, 2023, 30(1): 1-13.
5	李淼, 于永利, 吴剑扬, 等. 高能量密度磷酸铁锂正极设计[J]. 储能科学与技术, 2023, 12(7): 2045-2058.
	LI M, YU Y L, WU J Y, et al. Design of high-energy-density LiFePO₄ cathode materials[J]. Energy Storage Science and Technology, 2023, 12(7): 2045-2058.
6	KE X, XIAO R, LIAO X F, et al. LiFePO₄/C cathode material prepared with sphere mesoporous-FePO₄ as precursors for lithium-ion batteries[J]. Journal of Electroanalytical Chemistry, 2018, 820: 18-23.
7	LI B K, XIAO J Q, ZHU X Y, et al. Enabling high-performance lithium iron phosphate cathodes through an interconnected carbon network for practical and high-energy lithium-ion batteries[J]. Journal of Colloid and Interface Science, 2024, 653: 942-948.
8	HSIEH C T, CHEN I L, CHEN W Y, et al. Synthesis of iron phosphate powders by chemical precipitation route for high-power lithium iron phosphate cathodes[J]. Electrochimica Acta, 2012, 83: 202-208.
9	SCANLAN K, MANTHIRAM A. Revealing the electrochemical kinetics of electrolytes in nanosized LiFePO₄ electrodes[J]. Journal of the Electrochemical Society, 2023, 170(10): 100515.
10	APACHITEI G, HEYMER R, LAIN M, et al. Scale-up of lithium iron phosphate cathodes with high active materials contents for lithium ion cells[J]. Batteries, 2023, 9(10): 518-.
11	GAO X S, ZHENG C Y, SHAO Y Q, et al. Lithium iron phosphate enhances the performance of high-areal-capacity sulfur composite cathodes[J]. ACS Applied Materials & Interfaces, 2023, 15(15): 19011-19020.
12	HU Q, HE Y F, REN D S, et al. Targeted masking enables stable cycling of LiNi_0.6Co_0.2Mn_0.2O₂ at 4.6V[J]. Nano Energy, 2022, 96: 107123.
13	RUI X, JIN Y J, FENG X Y, et al. A comparative study on the low-temperature performance of LiFePO₄/C and Li₃V₂(PO₄)₃/C cathodes for lithium-ion batteries[J]. Journal of Power Sources, 2011, 196(4): 2109-2114.
14	YANG S C, HE R, ZHANG Z J, et al. CHAIN: Cyber hierarchy and interactional network enabling digital solution for battery full-lifespan management[J]. Matter, 2020, 3(1): 27-41.
15	SONG Y N, ZAVALIJ P Y, CHERNOVA N A, et al. Synthesis, crystal structure, and electrochemical and magnetic study of new iron (III) hydroxyl-phosphates, isostructural with lipscombite[J]. Chemistry of Materials, 2005, 17(5): 1139-1147.
16	HUBBLE D, BROWN D E, ZHAO Y Z, et al. Liquid electrolyte development for low-temperature lithium-ion batteries[J]. Energy & Environmental Science, 2022, 15(2): 550-578.
17	THENUWARA A C, SHETTY P P, KONDEKAR N, et al. Efficient low-temperature cycling of lithium metal anodes by tailoring the solid electrolyte interphase[J]. ACS Energy Letters, 2020, 5(7): 2411-2420.
18	WANG Z C, HAN R, HUANG D, et al. Co-intercalation-free ether-based weakly solvating electrolytes enable fast-charging and wide-temperature lithium-ion batteries[J]. ACS Nano, 2023, 17(18): 18103-18113.
19	LIU J X, NGUYEN D, WANG J Q, et al. Reevaluate low-concentration ether-based electrolytes for lithium metal batteries[J]. Nano Energy, 2024, 124: 109492.
20	LIU J, IHUAENYI S, KUPHAL R, et al. A Comparison of carbonate-based and ether-based electrolyte systems for lithium metal batteries[J]. Journal of The Electrochemical Society, 2023, 170(1): 010535.
21	JIANG Z, YANG T, LI C, et al. Synergistic additives enabling stable cycling of ether electrolyte in 4.4 V Ni-rich/Li metal batteries[J]. Advanced Functional Materials, 2023, 33(51): 2306868.
22	YIN L M, WANG M L, XIE C, et al. High-voltage cyclic ether-based electrolytes for low-temperature sodium-ion batteries[J]. ACS Applied Materials & Interfaces, 2023: 15(7): 9517-9523.
23	LI A M, BORODIN O, POLLARD T P, et al. Methylation enables the use of fluorine-free ether electrolytes in high-voltage lithium metal batteries[J]. Nature Chemistry, 2024.
24	ZHANG G Z, CHANG J, WANG L G, et al. A monofluoride ether-based electrolyte solution for fast-charging and low-temperature non-aqueous lithium metal batteries[J]. Nature Communications, 2023, 14: 1081.
25	FAN X L, CHEN L, JI X, et al. Highly fluorinated interphases enable high-voltage Li-metal batteries[J]. Chem, 2018, 4(1): 174-185.
26	PAL U, RAKOV D, LU B Y, et al. Interphase control for high performance lithium metal batteries using ether aided ionic liquid electrolyte[J]. Energy & Environmental Science, 2022, 15(5): 1907-1919.
27	李萌, 邱景义, 张松通, 等. 新型锂盐氟代磺酰亚胺锂电解液对锂离子电池性能的影响[J]. 储能科学与技术, 2017, 6(1): 101-107.
	LI M, QIU J Y, ZHANG S T, et al. The effect of lithium bis(fluorosulfonyl)imide salt on the performance of Li-ion battery[J]. Energy Storage Science and Technology, 2017, 6(1): 101-107.
28	HEHRE W J, DITCHFIELD R, POPLE J A. Self—Consistent molecular orbital methods. XII. further extensions of Gaussian—Type basis sets for use in molecular orbital studies of organic molecules[J]. Journal of Chemical Physics, 1972, 56(5): 2257-2261.
29	DITCHFIELD R, HEHRE W J, POPLE J A. Self-consistent molecular-orbital methods. IX. an extended gaussian-type basis for molecular-orbital studies of organic molecules[J]. The Journal of Chemical Physics, 1971, 54(2): 724-728.
30	LI Y, WU F, LI Y, et al. Ether-based electrolytes for sodium ion batteries[J]. Chemical Society Reviews, 2022, 51(11): 4484-4536.
31	SEO D M, BORODIN O, HAN S, et al. Electrolyte solvation and ionic association II. acetonitrile-lithium salt mixtures: Highly dissociated salts[J]. Journal of The Electrochemical Society, 2012, 159(9): A1489.
32	KIM S C, WANG J Y, XU R, et al. High-entropy electrolytes for practical lithium metal batteries[J]. Nature Energy, 2023, 8: 814-826.
33	JIANG L L, YAN C, YAO Y X, et al. Inhibiting solvent co-intercalation in a graphite anode by a localized high-concentration electrolyte in fast-charging batteries[J]. Angewandte Chemie (International Ed in English), 2021, 60(7): 3402-3406.
34	LI Y, LIU M, WANG K, et al. Single-solvent-based electrolyte enabling a high-voltage lithium-metal battery with long cycle life[J]. Advanced Energy Materials, 2023, 13(30): 2300918.
35	YIN Y C, YANG J T, LUO J D, et al. A LaCl₃-based lithium superionic conductor compatible with lithium metal[J]. Nature, 2023, 616: 77-83.

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低温磷酸铁锂电池用全醚高熵电解液的设计研究

Design and research of all-ether high-entropy electrolyte for low-temperature lithium iron phosphate batteries

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