锂离子电池正极材料Li3V2-2x/3Mnx(PO4)3的溶胶-凝胶法合成和电化学性能

doi:10.3724/SP.J.1077.2012.11735

无机材料学报 ›› 2012, Vol. 27 ›› Issue (10): 1017-1022.DOI: 10.3724/SP.J.1077.2012.11735 CSTR: 32189.14.SP.J.1077.2012.11735

锂离子电池正极材料Li₃V_2-2x/3Mn_x(PO₄)₃的溶胶-凝胶法合成和电化学性能

刘国聪^1,2, 刘又年¹, 刘素琴¹, 董辉²

(1. 中南大学化学化工学院, 长沙 410083; 2. 惠州学院化学工程系, 惠州 516007)

收稿日期:2011-11-24 修回日期:2012-01-13 出版日期:2012-10-20 网络出版日期:2012-09-17
基金资助:
国家自然科学基金(51162026); 中国博士后基金(20100480949, 201104509); 中南大学博士后基金

Sol-Gel Synthesis and Electrochemical Performance of Li₃V_2-2x/3Mnx(PO₄)₃ Cathode Material for Lithium-ion Batteries

LIU Guo-Cong^1,2, LIU You-Nian¹, LIU Su-Qing¹, DONG Hui²

(1. College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China; 2. Department of Chemical Engineering, Huizhou University, Huizhou 516007, China)

Received:2011-11-24 Revised:2012-01-13 Published:2012-10-20 Online:2012-09-17
Supported by:
National Natural Science Foundation of China (51162026); Projects of China Postdoctoral Science Foundation (20100480949, 201104509 ); Postdoctoral Science Foundation of Central South University

摘要/Abstract

摘要： 以CH₃COOLi·2H₂O、V₂O₅、Mn(CH₃COO)₂·4H₂O、(NH₄)₂HPO₄和蔗糖为原料, 采用溶胶–凝胶法合成了掺锰磷酸钒锂/碳(Li₃V_2-2x/3Mn_x(PO₄)₃/C)复合正极材料, 用XRD、XPS、SEM、电化学性能对样品进行了表征. 测试结果表明, 少量锰的掺杂并未改变Li₃V₂(PO₄)₃/C的单斜结构, Li₃V_1.94Mn_0.09(PO₄)₃中的Mn和V分别以+2和+3价存在, 其颗粒类似球形, 直径比较均匀且小于200 nm, 并表现出良好的电化学性能. 在0.1C倍率和3.0~4.8 V电压内, 该样品的首次充、放电容量分别为182.1和168.8 mAh/g, 放电效率高达92.69%, 而且100次循环后, 其放电比容量仍是首次放电容量的77.4%.

关键词: 正极材料, 锂离子电池, Li₃V_2-2x/3Mn_x(PO₄)₃, 溶胶-凝胶法

Abstract: Novel cathode material Li₃V_2-2x/3Mnx(PO₄)₃/C was successfully synthesized by Sol-Gel method using CH₃COOLi·2H₂O, V₂O₅, Mn(CH₃COO)₂·4H₂O, (NH₄)₂HPO₄ and sucrose as raw materials. The as-prepared products were characterized by XRD, XPS, SEM.The results show that a small amount of Mn2+doping do not alter the structure of Li₃V₂(PO₄)₃ materials with a monoclinic structure (space group P21/n), and the valence states of V and Mn in Li₃V_1.94Mn_0.09(PO₄)₃/C are +3 and +2, respectively. The Li₃V_1.94Mn_0.09(PO₄)₃ particle with uniform shape of sphere and diameter less than 200 nm, shows the best cyclic stability and rate performance. Controlling the charge and discharge voltage range from 3.0 to 4.8 V at the rate of 0.1C, the first charge and discharge capacity of Li₃V_1.94Mn_0.09(PO₄)₃ are up to 182.1 and 168.8 mAh/g, respectively, and its discharge efficiency is up to 92.69%. After 100 cycles, its discharge capacity can also retain 77.4% of the first one.

Key words: cathodic materials, lithiumion batteries, Li₃V_2-2x/3Mn_x(PO₄)₃, Sol-Gel method

中图分类号:

TM912

刘国聪, 刘又年, 刘素琴, 董辉. 锂离子电池正极材料Li₃V_2-2x/3Mn_x(PO₄)₃的溶胶-凝胶法合成和电化学性能[J]. 无机材料学报, 2012, 27(10): 1017-1022.

LIU Guo-Cong, LIU You-Nian, LIU Su-Qing, DONG Hui. Sol-Gel Synthesis and Electrochemical Performance of Li₃V_2-2x/3Mnx(PO₄)₃ Cathode Material for Lithium-ion Batteries[J]. Journal of Inorganic Materials, 2012, 27(10): 1017-1022.

参考文献

[1] 刘素琴, 李世彩, 唐联兴, 等(LIU Su-Qing, et al)．Li3V2(PO4)3的溶胶–凝胶法合成及其性能研究．无机化学学报(Chinese Journal of Inorganic Chemistry), 2006, 22(4): 645-650．

[2] Zhai J, ZHAO M S, Wang D D.Effect of Mn-doping on performance of Li3V2(PO4)3/C cathode material for lithium ion batteries. Trans. Nonferrous Met. Soc. China, 2011, 21(3): 523-528.

[3] Xia Y, Zhang W K, Huang H, et al. Synthesis and electrochemical properties of Nb-doped Li3V2(PO4)3/C cathode materials for lithium-ion batteries. Mater. Sci. Eng. B, 2011, 176(8): 633-639.

[4] Liu H D, Gao P, Fang J H, et al. Li3V2(PO4)3/graphene nanocomposites as cathode material for lithium ion batteries. Chem. Commun., 2011, 47: 9110-9112.

[5] Yin S C, Grondey H, Strobel P, et al. Electrochemical property: structure relationships in monoclinic Li3-yV2(PO4)3. J. Am. Chem. Soc., 2003, 125(34): 10402-10411.

[6] Tarascon J M, Armand M. Issues and challenges facing rechargeable lithium batteries. Nature, 2001, 415(15): 359-367.

[7] Kuo H T, Bagkar N C, Liu R S, et al. Structure Transformation of LiVOPO4 to Li3V2(PO4)3 with enhanced capacity. J. Phys. Chem. B, 2008, 112(36): 11250-11257.

[8] Huang H, Faulkner T, Barker J, et al. Lithium metal phosphate, power and automotive application. J. Power Sources, 2009, 189(1): 748-751.

[9] Rui X H, Ding N, Liu J, et al. Analysis of the chemical diffusion coefficient of lithium ions in Li3V2(PO4)3 cathode material. Electrochim. Acta, 2010, 55(7): 2384-2390.

[10] Armand M, Tarascon J M. Building better batteries. Nature, 2008, 451(7): 652-657.

[11] Davis L J M, Heinmaa I, Groward G R. Study of lithium dynamics in monoclinic Li3Fe2(PO4)3 using LiVT and 2D exchange MAS NMR spectroscopy. Chem.Mater., 2010, 22(3): 769-775.

[12] Qiao Y Q, Tu J P, Mai Y J, et al. Enhanced electrochemical performances of multi-walled carbon nanotubes modified Li3V2(PO4)3/C cathode material for lithium-ion batteries. J. Alloys Compd., 2011, 509(25): 7181-7185.

[13] 唐安平, 王先友, 伍文, 等. 不同碳源对Li3V2(PO4)3正极材料性能的影响. 中国有色金属学报, 2008, 18(12): 2218-2223.

[14] 钟胜奎, 尹周澜, 刘洁群, 等(ZHONG Sheng-Kui, et al). 低温碳热还原法合成Li3V2(PO4)3及其电化学性能. 稀有金属材料与工程(Rare Metal Mat. Eng.), 2008, 37(9): 1652-1655.

[15] YU Feng, ZHANG Jing-Jie, YANG Yan-Feng, et al. Synthesis and performance of cathode material Li3V2(PO4)3/C by spray drying and carbothermal method (SDATM). Journal of Inorganic Materials, 2009, 24(2): 349-352.

[16] Zhong S K, Liu L T, Jiang J Q, et al. Preparation and electrochemical properties of Y-doped Li3V2(PO4)3 cathode materials for lithium batteries. J. Rare Earths, 2009, 27(1): 134-137.

[17] Marcella B, Stefania F, Doretta C, et al. Mn influence on the electrochemical behaviour of Li3V2(PO4)3 cathode material. Electrochim. Acta, 2011, 56(6): 2648-2655.

[18] Ren M M, Zhou Z, Li Y Z, et al. Preparation and electrochemical studies of Fe-doped Li3V2(PO4)3 cathode materials for lithium-ion batteries. J.Power Sources, 2006, 162(2): 1357-1362.

[19] Kuang Q, Zhao Y M, An X N, et al. Synthesis and electrochemical properties of Co-doped Li3V2(PO4)3 cathode materials for lithium- ion batteries. Electrochim. Acta, 2010, 55(5): 1575-1581.

[20] Chen Y H, Zhao Y M, An X M, et al. Preparation and electrochemical performance studies on Cr-doped Li3V2(PO4)3 as cathode materials for lithium-ion batteries. Electrochim. Acta, 2009, 54(24): 5844-5850.

[21] 钟胜奎, 尹周澜, 王志兴, 等(ZHONG Shen-Kui, et al). 低温固相反应合成正极材料及其性能. 无机化学学报(Chinese Journal of inorganic Chemistry), 2006, 22(10): 1843-1846.

[22] Fu P, Zhao Y M, Dong Y Z, et al. Synthesis of Li3V2(PO4)3 with high performance by optimized solid-state synthesis routine. J. Power Sources, 2006, 162(1): 651-657.

[23] Zhou X H, Liu Y M, Guo Y L. Effect of reduction agent on the performance of Li3V2(PO4)3/C positive material by one-step solid-state reaction. Electrochim. Acta, 2009, 54(8): 2253-2258.

[24] 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. 材料与冶金学报, 2006, 5(2): 115-118.

[25] 任慢慢, 李宇展, 周震, 等. 微波法合成正极材料Li3V2(PO4)3. 电池, 2006, 31(6): 13-14.

[26] Liu L Y, Jiang L L, Wu H Q, et al. One-Step synthesis of Li3V2(PO4)3 for Li-ion battery by microwave irradiation. Rare Metal Mat. Eng., 2010, 39(suppl.1): 364-368.

[27] Sun C W, Rajasekhara S, Dong Y Z, et al. Hydrothermal synthesis and electrochemical properties of Li3V2(PO4)3/C-based composites for lithium-ion batteries. Appl. Mater. Interfaces, 2011, 3(9): 3772-3776.

[28] Yang G, Ji H M, Liu H D, et al. Crystal structure and electrochemical performance of Li3V2(PO4)3 synthesized by optimized microwave solid-state synthesis route. Electrochim. Acta, 2010, 55(11): 3669-3680.

[29] 师秀萍, 唐致远, 刘东. Sol-gel 法合成Li3V2(PO4)3及其性能研究. 电池工业, 2010, 15(2): 103-107.

[30] 翟静, 赵敏寿, 沙鸥, 等(ZHAI Jing, et al). 锂离子电池正极材料Li3V2(PO4)3的研究进展. 稀有金属材料与工程(Rare Metal Mat.Eng.), 2010, 39(7): 1310-1315.

锂离子电池正极材料Li₃V_2-2x/3Mn_x(PO₄)₃的溶胶-凝胶法合成和电化学性能

Sol-Gel Synthesis and Electrochemical Performance of Li₃V_2-2x/3Mnx(PO₄)₃ Cathode Material for Lithium-ion Batteries

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	刘鹏东, 王桢, 刘永锋, 温广武. 硅泥在锂离子电池中的应用研究进展[J]. 无机材料学报, 2024, 39(9): 992-1004.
[2]	程节, 周月, 罗薪涛, 高美婷, 骆思妃, 蔡丹敏, 吴雪垠, 朱立才, 袁中直. 蛋黄壳结构FeF₃·0.33H₂O@N掺杂碳纳米笼正极材料的构筑及其电化学性能[J]. 无机材料学报, 2024, 39(3): 299-305.
[3]	戴乐, 刘洋, 高轩, 王书豪, 宋雅婷, 唐明猛, 刘丽莎, 汪尧进. 浓度梯度掺杂实现BiFeO₃薄膜自极化[J]. 无机材料学报, 2024, 39(1): 99-106.
[4]	胡梦菲, 黄丽萍, 李贺, 张国军, 吴厚政. 锂/钠离子电池硬碳负极材料的研究进展[J]. 无机材料学报, 2024, 39(1): 32-44.
[5]	苏楠, 邱介山, 王治宇. 高容量氟掺杂碳包覆纳米硅负极材料: 气相氟化法制备及其储锂性能[J]. 无机材料学报, 2023, 38(8): 947-953.
[6]	孔国强, 冷明哲, 周战荣, 夏池, 沈晓芳. Sb掺杂O3型Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂钠离子电池正极材料[J]. 无机材料学报, 2023, 38(6): 656-662.
[7]	杨卓, 卢勇, 赵庆, 陈军. X射线衍射Rietveld精修及其在锂离子电池正极材料中的应用[J]. 无机材料学报, 2023, 38(6): 589-605.
[8]	贾玉娜, 曹旭, 焦秀玲, 陈代荣. 无机酸铝体系氧化铝连续纤维的制备技术研究[J]. 无机材料学报, 2023, 38(11): 1257-1264.
[9]	李涛, 曹鹏飞, 胡力涛, 夏勇, 陈一, 刘跃军, 孙翱魁. NH₄⁺扩层MoS₂的制备及其储锌性能研究[J]. 无机材料学报, 2023, 38(1): 79-86.
[10]	宿拿拿, 韩静茹, 郭印毫, 王晨宇, 石文华, 吴亮, 胡执一, 刘婧, 李昱, 苏宝连. 基于ZIF-8的三维网络硅碳复合材料锂离子电池性能研究[J]. 无机材料学报, 2022, 37(9): 1016-1022.
[11]	王洋, 范广新, 刘培, 尹金佩, 刘宝忠, 朱林剑, 罗成果. 钾离子掺杂提高锂离子电池正极锰酸锂性能的微观机制[J]. 无机材料学报, 2022, 37(9): 1023-1029.
[12]	朱河圳, 王选朋, 韩康, 杨晨, 万睿哲, 吴黎明, 麦立强. 超高镍LiNi_0.91Co_0.06Al_0.03O₂@Ca₃(PO₄)₂正极材料的储锂稳定性的提升机制[J]. 无机材料学报, 2022, 37(9): 1030-1036.
[13]	冯锟, 朱勇, 张凯强, 陈长, 刘宇, 高彦峰. 勃姆石纳米片增强锂离子电池隔膜性能研究[J]. 无机材料学报, 2022, 37(9): 1009-1015.
[14]	陈莹, 栾伟玲, 陈浩峰, 朱轩辰. 基于应力场的锂离子电池正极多尺度失效研究[J]. 无机材料学报, 2022, 37(8): 918-924.
[15]	江依义, 沈旻, 宋半夏, 李南, 丁祥欢, 郭乐毅, 马国强. 双功能电解液添加剂对锂离子电池高温高电压性能的影响[J]. 无机材料学报, 2022, 37(7): 710-716.