锂离子电池正极材料磷酸钒锂制备方法研究进展

doi:10.19964/j.issn.1006-4990.2021-0337

摘要/Abstract

摘要：

单斜结构的磷酸钒锂[Li₃V₂（PO₄）₃]材料与其他锂离子电池正极材料相比具有较高的工作电压（3.0~4.8 V）、良好的离子迁移率和优良的热稳定性,是一种具有竞争优势和发展前景的大功率锂离子电池正极材料,成为了近年来研究的热点。综述了锂离子电池正极材料磷酸钒锂的结构特点及其充放电机理。磷酸钒锂的常用合成方法有碳热还原法、水热法、溶胶-凝胶法及流变相法等,着重阐述了磷酸钒锂的不同合成方法对所制备样品的形貌和电化学性能的影响。分析总结了不同合成方法的改进方法,以改善磷酸钒锂正极材料电子导电性和锂离子扩散系数较低的问题。最后,针对磷酸钒锂正极材料在锂离子电池的应用中所存在的问题展望了该材料未来可能的发展方向和研究热点。指出需要优化材料的制备方法以改善材料的颗粒形貌、提高电子导电率和扩散系数等,进而改善材料的循环性能、倍率性能和充放电性能等;需要改进制备流程、提高实验的安全性、简化反应流程和减少制备成本等,以实现磷酸钒锂正极材料的工业化应用。

关键词: 锂离子电池, 磷酸钒锂, 合成方法, 电化学性能

Abstract:

Compared with other lithium-ion battery cathode material,lithium vanadium phosphate[Li₃V₂（PO₄）₃] material with monoclinic structure has higher working voltage（3.0~4.8 V）,good ion mobility and excellent thermal stability.It is a high-power lithium-ion battery cathode material with competitive advantages and development prospects,and has become a research hotspot in recent years.The structural characteristics of lithium vanadium phosphate and its charging and discharging mechanism were reviewed.The common synthesis methods of lithium vanadium phosphate included carbothermic reduction,hydrothermal method,sol-gel method and fluidization method,and the influence of different synthesis methods and processes of lithium vanadium phosphate on the different morphologies and electrochemical properties of the prepared samples was emphasized.The improvement methods of different synthesis methods are analyzed and summarized to improve the shortco-mings and defects of low electronic conductivity and lithium ion diffusion coefficient of lithium vanadium phosphate cathode materials.Finally,In view of the problems existing in the application of vanadium lithium phosphate cathode material in lithium ion battery,the possible development direction and research focus of this material in the future were prospected.It was pointed out that the preparation method of materials needed to be optimized to improve the particle morphology,electronic conductivity and diffusion coefficient of materials,so as to improve the cycle performance,rate performance and charge/dis-charge performance of materials.It was necessary to improve the preparation process,improve the safety of the experiment,simplify the reaction process and reduce the preparation cost in order to realize the industrial application of lithium vanadium phosphate cathode materials.

Key words: lithium-ion battery, Li₃V₂（PO₄）₃, synthesis methods, electrochemical performance

中图分类号:

TQ131.11

张鑫意,狄玉丽,董琦,陈星宇,张正冬. 锂离子电池正极材料磷酸钒锂制备方法研究进展[J]. 无机盐工业, 2022, 54(3): 38-44.

ZHANG Xinyi,DI Yuli,DONG Qi,CHEN Xingyu,ZHANG Zhengdong. Research progress on preparation of Li₃V₂（PO₄）₃ cathode material for lithium-ion batteries[J]. Inorganic Chemicals Industry, 2022, 54(3): 38-44.

图/表 14

图1

图2

图3

图4

图5

图6

图7

图8

图9

图10

图11

图12

图13

图14

参考文献 46

[1]	LEE H S, RAMAR V, KUPPAN S, et al. Key design considerations for synjournal of mesoporous α-Li₃V₂(PO₄)₃/C for high power lithium batteries[J]. Electrochimica Acta, 2021, 372.Doi: 10.1016/j.electacta.2021.137831.
[2]	QI N, MA Y Y, REN B, et al. Comparison of the La-doped and Gd-doped Li₃V₂(PO₄)₃/C via electrochemical tests and first-principle calculations for lithium-ion batteries[J]. Journal of Physics and Che-mistry of Solids, 2021, 150.Doi: 10.1016/j.jpcs.2020.109889.
[3]	WANG X, ZHAO X, WANG J, et al. Electrospun Li₃V₂(PO₄)₃ nano-belts:Synjournal and electrochemical properties as cathode materials of lithium-ion batteries[J]. Journal of the Chinese Chemical Society, 2017, 64(7):557-564.
[4]	CHEN Y, CHEN H, XIAO L, et al. Preparation for honeycombed Li₃V₂(PO₄)₃/C composites via vacuum-assisted immersion method and their high-rates performance in lithium-ion batteries[J]. Vacu-um, 2020, 172.Doi: 10.1016/j.vacuum.2019.108926.
[5]	GUO Y, HUANG Y, JIA D, et al. Preparation and electrochemical properties of high-capacity LiFePO₄-Li₃V₂(PO₄)₃/C composite for li-thium-ion batteries[J]. Journal of Power Sources, 2014, 246:912-917.
[6]	SØRENSEN D R, MATHIESEN J K, RAVNSBÆK D B, et al. Dyna-mic charge-discharge phase transitions in Li₃V₂(PO₄)₃ cathodes[J]. Journal of Power Sources, 2018, 396:437-443.
[7]	ZHANG X, GUO H, LI X, et al. High tap-density Li₃V₂(PO₄)₃/C co-mposite material synthesized by sol spray-drying and post-calcining method[J]. Electrochimica Acta, 2012, 64:65-70.
[8]	LI L, FAN C, HUANG X, et al. The influence of different carbon so-urces on Li₃V₂(PO₄)₃/C synthesized by a hybrid sol-gel method as cathode for lithium-ion batteries[J]. Energy Technology, 2015, 3(9):955-960.
[9]	XIA Y, YU L, LU C, et al. Passion fruit-like structure endows Li₃V₂(PO₄)₃@C/CNT composite with superior cyclic stability and rate performance[J]. Journal of Alloys and Compounds, 2021, 859.Doi: 10.1016/j.jallcom.2020.157806.
[10]	刘艺培. 磷酸钒锂正极材料的制备及电化学性能研究[D]. 马鞍山:安徽工业大学, 2018.
[11]	邓玲, 陈善华, 吴骏, 等. 聚阴离子型锂离子电池正极材料Li₃V₂(PO₄)₃的研究进展[J]. 应用化工, 2014, 43(3):522-526.
[12]	GUO S, BAI Y, GENG Z, et al. Facile synjournal of Li₃V₂(PO₄)₃/C cathode material for lithium-ion battery via freeze-drying[J]. Jour-nal of Energy Chemistry, 2019, 32:159-165.
[13]	LEE S, PARK S S. Atomistic simulation study of monoclinic Li₃V₂(PO₄)₃ as a cathode material for lithium ion battery:Structure, defect chemistry,lithium ion transport pathway,and dynamics[J]. Journal of Physical Chemistry C, 2012, 116(48):25190-25197.
[14]	KUGANATHAN N, CHRONEOS A. Defects and dopant properties of Li₃V₂(PO₄)₃[J]. Scientific Reports, 2019, 9(1).Doi: 10.1038/s41598-018-36398-w.
[15]	RAI A K, THI T V, GIM J, et al. Li₃V₂(PO₄)₃/graphene nanocompo-site as a high performance cathode material for lithium ion ba-ttery[J]. Ceramics International, 2015, 41(1):389-396.
[16]	LUO Y, SHUI M, SHU J. Understanding the lithium transport me-chanism in monoclinic Li₃V₂(PO₄)₃ cathode material by atomistic simulation[J]. Results in Physics, 2019, 14.Doi: 10.1016/j.rinp.2019.102490.
[17]	DING M, CHENG C, WEI Q, et al. Carbon decorated Li₃V₂(PO₄)₃ for high-rate lithium-ion batteries:Electrochemical performance and charge compensation mechanism[J]. Journal of Energy Che-mistry, 2020, 53:124-131.
[18]	LIN X, SHEN Z, HAN T, et al. Hydrogel assisted synjournal of Li₃V₂(PO₄)₃ composite as high energy density and low-tempera-ture stable secondary battery cathode[J]. Journal of Alloys and Co-mpounds, 2018, 739:837-847.
[19]	QIAO Y Q, TU J P, XIANG J Y, et al. Effects of synthetic route on structure and electrochemical performance of Li₃V₂(PO₄)₃/C catho-de materials[J]. Electrochimica Acta, 2011, 56(11):4139-4145.
[20]	LI Y, XIN L, JIE Y. Study on synjournal routes and their influences on chemical and electrochemical performances of Li₃V₂(PO₄)₃/car-bon[J]. Electrochimica Acta, 2007, 53(2):474-479.
[21]	HUANG H, FAULKNER T, BARKER J, et al. Lithium metal pho-sphates,power and automotive applications[J]. Journal of Power Sources, 2009, 189(1):748-751.
[22]	BARKER J, SAIDI M Y, SWOYER J L. Lithium iron(Ⅱ) phospho-olivines prepared by a novel carbothermal reduction method[J]. Electrochemical and Solid-State Letters, 2003, 6(3):53-55.
[23]	姜霖琳, 田彦文, 刘丽英. 碳热还原法制备锂离子电池正极材料Li₃V₂(PO₄)₃的研究[J]. 材料与冶金学报, 2006, 5(2):115-118.
[24]	李娜丽, 同艳维, 崔旭梅, 等. 烧结工艺对锂离子电池正极材料磷酸钒锂结构和电化学性能的影响[J]. 钢铁钒钛, 2018, 39(6):59-64.
[25]	SECCHIAROLI M, NOBILI F, TOSSICI R, et al. Synjournal and elec-trochemical characterization of high rate capability Li₃V₂(PO₄)₃/C prepared by using poly(acrylic acid) and d-(+)-glucose as carbon sources[J]. Journal of Power Sources, 2015, 275:792-798.
[26]	SAÏDI M Y, BARKER J, HUANG H, et al. Performance character-istics of lithium vanadium phosphate as a cathode material for lithi-um-ion batteries[J]. Journal of Power Sources, 2003, 119-121(6):266-272.
[27]	LIU L, XIAO W, CHEN M, et al. Improved rate and cycle perfor-mance of nano-sized 5LiFePO₄·Li₃V₂(PO₄)₃/C via high-energy ball milling assisted carbothermal reduction[J]. Journal of Alloys and Compounds, 2017, 719(30):281-287.
[28]	HUANG B, FAN X, ZHENG X, et al. Synjournal and rate performa-nce of lithium vanadium phosphate as cathode material for Li-ion batteries[J]. Journal of Alloys and Compounds, 2011, 509(14):4765-4768.
[29]	DUAN W, HU Z, ZHANG K, et al. Li₃V₂(PO₄)₃@C core-shell nano-composite as a superior cathode material for lithium-ion batteri-es[J]. Nanoscale, 2013, 5(14):6485-6490.
[30]	CHANG C, XIANG J, SHI X, et al. Hydrothermal synjournal of car-bon-coated lithium vanadium phosphate[J]. Electrochimica Acta, 2009, 54(2):623-627.
[31]	REN M, ZHEN Z, LI Y, et al. Preparation and electrochemical stu-dies of Fe-doped Li₃V₂(PO₄)₃ cathode materials for lithium-ion ba-tteries[J]. Journal of Power Sources, 2006, 162(2):1357-1362.
[32]	TENG F, HU Z H, MA X H, et al. Hydrothermal synjournal of plate-like carbon-coated Li₃V₂(PO₄)₃ and its low temperature performa-nce for high power lithium ion batteries[J]. Electrochimica Acta, 2013, 91:43-49.
[33]	LIU H, CHENG C, HUANG X, et al. Hydrothermal synjournal and rate capacity studies of Li₃V₂(PO₄)₃ nanorods as cathode material for lithium-ion batteries[J]. Electrochimica Acta, 2010, 55(28):8461-8465.
[34]	REN M M, ZHOU Z, GAO X P, et al. Core-Shell Li₃V₂(PO₄)₃@C composites as cathode materials for lithium-ion batteries[J]. The Journal of Physical Chemistry C, 2008, 112(14):5689-5693.
[35]	MOSHURCHAK L M, BUHRMESTER C, WANG R L, et al. Com-parative studies of three redox shuttle molecule classes for over-charge protection of LiFePO₄-based Li-ion cells[J]. Electrochimi-ca Acta, 2007, 52(11):3779-3784.
[36]	DOEFF M M, HU Yaoqin, MCLARNON F, et al. Effect of surface carbon structure on the electrochemical performance of LiFePO₄[J]. Office of Scientific & Technical Information Technical Reports, 2003, 3(3):311-313.
[37]	ZHUANG B, GUO Z, CHU W, et al. Mesoporous carbon film inlaid with Li₃V₂(PO₄)₃ nanoclusters through delaying sol-gel method for high performance lithium-ion hybrid supercapacitors[J]. Electro-chimica Acta, 2018, 283:1589-1599.
[38]	LI Y, ZHEN Z, REN M, et al. Electrochemical performance of nano-crystalline Li₃V₂(PO₄)₃/carbon composite material synthesized by a novel sol-gel method[J]. Electrochimica Acta, 2006, 51(28):6498-6502.
[39]	ZHANG Q, LI Y H, ZHONG S K, et al. Synjournal and electrochemi-cal performance of Li₃V₂(PO₄)₃ by optimized sol-gel synjournal rou-tine[J]. Transactions of Nonferrous Metals Society of China, 2010, 20(8):1545-1549.
[40]	RUI X H, LI C, LIU J, et al. The Li₃V₂(PO₄)₃/C composites with high-rate capability prepared by a maltose-based sol-gel route[J]. Electrochimica Acta, 2010, 55(22):6761-6767.
[41]	CAO X, ZHAN H, XIE J. Synjournal of Ag₂V₄O₁₁ as a cathode mate-rial for lithium battery via a rheological phase method[J]. Materi-als Letters, 2006, 60(4):435-438.
[42]	XIE L, CAO X, LIU C, et al. Rheological phase synjournal and cha-racterization of micro-sized Li₄Ti₅O₁₂[J]. Journal of the Chilean Chemical Society, 2010, 55(3):343-346.
[43]	XIE L L, XU Y D, ZHANG J J, et al. Rheological phase synjournal of Er-doped LiV₃O₈ as electroactive material for a cathode of sec-ondary lithium storage[J]. Electronic Materials Letters, 2013, 9(4):549-553.
[44]	CHANG C, XIANG J, SHI X, et al. Rheological phase reaction synjournal and electrochemical performance of Li₃V₂(PO₄)₃/carbon cathode for lithium ion batteries[J]. Electrochimica Acta, 2008, 53(5):2232-2237.
[45]	李丽, 李国华, 王石泉, 等. 磷酸钒锂正极材料的合成与性能研究[J]. 无机化学学报, 2010, 26(1):126-131.
[46]	CAO X, ZHANG J. Rheological phase synjournal and characteriza-tion of Li₃V₂(PO₄)₃/C composites as cathode materials for lithium ion batteries[J]. Electrochimica Acta, 2014, 129:305-311.

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会