Mg、Ti离子复合掺杂改性磷酸铁锂正极材料及其电池性能

doi:10.3866/PKU.WHXB201207043

物理化学学报 >> 2012, Vol. 28 >> Issue (09): 2084-2090.doi: 10.3866/PKU.WHXB201207043

Mg、Ti离子复合掺杂改性磷酸铁锂正极材料及其电池性能

王震坡¹, 刘文², 王悦³, 赵春松⁴, 张淑萍⁴, 陈继涛², 周恒辉², 张新祥²

1. 北京理工大学电动车辆国家工程实验室, 北京 100081;
2. 北京大学化学与分子工程学院, 北京分子科学国家实验室,北京 100871;
3. 中国人民解放军防化学院, 北京 102205;
4. 北大先行科技产业有限公司, 北京 102200

收稿日期:2012-04-20 修回日期:2012-07-04 发布日期:2012-08-02
通讯作者: 王震坡, 陈继涛 E-mail:wangzhenpo@bit.edu.cn; chenjitao@pku.edu.cn
基金资助:
国家自然科学基金(61004092)和国家高技术研究发展计划项目(863) (2009AA035200)资助

Synthesis and Characterization of Mg and Ti Ions Co-Doped Lithium Iron Phosphate and Its Lithium-Ion Batteries

WANG Zhen-Po¹, LIU Wen², WANG Yue³, ZHAO Chun-Song⁴, ZHANG Shu-Ping⁴, CHEN Ji-Tao², ZHOU Heng-Hui², ZHANG Xin-Xiang²

1. National Engineering Laboratory for Electric Vehicles, Beijing Institute of Technology, Beijing 100081, P. R. China;
2. Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China;
3. Institute of Chemical Defense of PLA, Beijing 102205, P. R. China;
4. Pulead Technology Industry Co., LTD., Beijing 102200, P. R. China

Received:2012-04-20 Revised:2012-07-04 Published:2012-08-02
Supported by:
The project was supported by the National Natural Science Foundation of China (61004092) and National High-Tech Research and Development Program of China (863) (2009AA035200).

摘要/Abstract

摘要：

在氮气气氛下采用高温固相方法, 合成了Mg、Ti 离子复合掺杂改性的锂离子电池正极材料(Li_0.98Mg_0.01)(Fe_0.98Ti_0.01)PO₄/C, 并通过粉末X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和充放电循环对材料进行性能表征. 测试结果表明, 复合离子掺杂可显著改善材料的电化学性能, 模拟电池在0.2C和1C倍率下的放电比容量分别为154.7 和146.9 mAh·g^-1. 以此复合掺杂样品为正极材料组装60 Ah动力电池, 其3C倍率放电容量仍保持为1C倍率放电容量的100%; 低温0 和-20 °C测试条件下, 动力电池放电容量分别保持为常温初始放电容量的89.7%和63.1%; 在常温1C/1C充放电条件下, 经过2000次循环后, 电池容量依然保持为初始放电容量的89%, 显示出优良的倍率放电性能和循环性能. 研究结果表明, Mg、Ti 离子复合掺杂改性的磷酸铁锂正极材料及其电池具有优良的放电性能和循环稳定性, 可广泛应用于电动(或混合动力)汽车和储能电池系统.

关键词: 磷酸铁锂, 复合掺杂, 倍率性能, 动力电池, 储能电池

Abstract:

Mg and Ti ions co-doped (Li_0.98Mg_0.01)(Fe_0.98Ti_0.01)PO₄/C cathode material for lithium-ion batteries was prepared by a solid-state method under N₂ atmosphere. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and galvanostatic charge-discharge test. Results indicated that Mg and Ti ions co-doping remarkably improved the electrochemical performance of LiFePO₄, including rate capacity, temperature behavior, and cycling stability. Discharge capacities of 154.7 and 146.9 mAh·g^-1 were obtained at the rates of 0.2C and 1C for half-cell tests, respectively. For 60 Ah full-cell tests, 100% of 1C capacity was maintained even at 3C rate, 89.7% and 63.1% of initial capacity at room temperature were retained at 0 and -20 °C, respectively. 89% capacity retention remained after 2000 cycles at room temperature, presenting excellent cycle stability. This investigation suggests that the present co-doping material and the resulting battery possess large discharge capacity and excellent cycling performance, making it applicable in electric vehicle (EV)/hybrid electric vehicle (HEV) and energy storage systems on a large scale.

Key words: Lithium iron phosphate, Co-doping, Rate capacity, Power battery, Energy storage battery

王震坡, 刘文, 王悦, 赵春松, 张淑萍, 陈继涛, 周恒辉, 张新祥. Mg、Ti离子复合掺杂改性磷酸铁锂正极材料及其电池性能[J]. 物理化学学报, 2012, 28(09): 2084-2090.

WANG Zhen-Po, LIU Wen, WANG Yue, ZHAO Chun-Song, ZHANG Shu-Ping, CHEN Ji-Tao, ZHOU Heng-Hui, ZHANG Xin-Xiang. Synthesis and Characterization of Mg and Ti Ions Co-Doped Lithium Iron Phosphate and Its Lithium-Ion Batteries[J]. Acta Phys. -Chim. Sin., 2012, 28(09): 2084-2090.

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201207043

https://www.whxb.pku.edu.cn/CN/Y2012/V28/I09/2084

参考文献

(1) Padhi, A. K.; Nanjundaswamy, K. S.; Goodenough, J. B.J. Electrochem. Soc. 1997, 144, 1188. doi: 10.1149/1.1837571
(2) Tarascon, J. M.; Armand, M. Nature 2001, 414, 359. doi: 10.1038/35104644
(3) Yuan, L. X.;Wang, Z. H.; Zhang,W. X.; Hu, X. L.; Chen, J. T.;Huang, Y. H.; Goodenough, J. B. Energy & Environmental Science 2011, 4, 269. doi: 10.1039/c0ee00029a
(4) Zhou, H.; Upreti, S.; Chernova, N. A.; Hautier, G.; Ceder, G.;Whittingham, M. S. Chem. Mater. 2011, 23, 293. doi: 10.1021/cm102922q
(5) Wang, Y. G.; He, P.; Zhou, H. S. Energy & Environmental Science 2011, 4, 805. doi: 10.1039/c0ee00176g
(6) Andersson, A. S.; Thomas, J. O. Journal of Power Sources2001, 97-98, 498.
(7) Okada, S.; Sawa, S.; Egashira, M.; Yamaki, J.; Tabuchi, M.;Kageyama, H.; Konishi, T.; Yoshino, A. Journal of Power Sources 2001, 97, 430. doi: 10.1016/S0378-7753(01)00631-0
(8) Prosini, P. P.; Lisi, M.; Zane, D.; Pasquali, M. Solid State Ionics2002, 148, 45. doi: 10.1016/S0167-2738(02)00134-0
(9) Ouyang, C. Y.; Shi, S. Q.;Wang, Z. X.; Huang, X. J.; Chen, L.Q. Physical Review B 2004, 69, 104303. doi: 10.1103/PhysRevB.69.104303
(10) Morgan, D.; Van der Ven, A.; Ceder, G. Electrochem. Solid-State Lett. 2004, 7, A30.
(11) Wang, Y.;Wang, Y.; Hosono, E.;Wang, K.; Zhou, H. Angew. Chem. Int. Edit. 2008, 47, 7461. doi: 10.1002/anie.200802539
(12) Arnold, G.; Garche, J.; Hemmer, R.; Strobele, S.; Vogler, C.;Wohlfahrt-Mehrens, A. Journal of Power Sources 2003, 119,247. doi: 10.1016/S0378-7753(03)00241-6
(13) Franger, S.; Le Cras, F.; Bourbon, C.; Rouault, H. Journal of Power Sources 2003, 119, 252. doi: 10.1016/S0378-7753(03)00242-8
(14) Huang, H.; Yin, S. C.; Nazar, L. F. Electrochem. Solid-State Lett. 2001, 4, A170.
(15) Prosini, P. P.; Zane, D.; Pasquali, M. Electrochim. Acta 2001,46, 3517. doi: 10.1016/S0013-4686(01)00631-4
(16) Chen, Z. H.; Dahn, J. R. J. Electrochem. Soc. 2002, 149, A1184
(17) Chung, S. Y.; Bloking, J. T.; Chiang, Y. M. Nat. Mater. 2002, 1,123. doi: 10.1038/nmat732
(18) Ni, J. F.; Zhou, H. H.; Chen, J. T.; Zhang, X. X. Mater. Lett.2005, 59, 2361. doi: 10.1016/j.matlet.2005.02.080
(19) Islam, M. S.; Driscoll, D. J.; Fisher, C. A. J.; Slater, P. R. Chem. Mater. 2005, 17, 5085. doi: 10.1021/cm050999v
(20) Ni, J. F.; Zhou, H. H.; Chen, J. T.; Su, G. Y. Acta Phys. -Chim. Sin. 2004, 20, 582. [倪江锋, 周恒辉, 陈继涛, 苏光耀. 物理化学学报, 2004, 20, 582.] doi: 10.3866/PKU.WHXB20040606
(21) Wen, Y. X.; Zheng, M. P.; Tong, Z. F.; Su, H. F.; Xue, M. H.J. Inorg. Mater. 2006, 21, 115. [文衍宣, 郑绵平, 童张法,粟海锋, 薛敏华. 无机材料学报, 2006, 21, 115.]
(22) Zhuang, D. G.; Zhao, X. B.; Xie, J.; Tu, J.; Zhu, T. J.; Cao, G. S.Acta Phys. -Chim. Sin. 2006, 22, 840. [庄大高, 赵新兵,些健, 涂健, 朱铁军, 曹高劭. 物理化学学报, 2006, 22,840.] doi: 10.1016/S1872-1508(06)60037-5
(23) Wu, S. H.; Chen, M. S.; Chien, C. J.; Fu, Y. P. Journal of Power Sources 2009, 189, 440. doi: 10.1016/j.jpowsour.2009.01.015
(24) Lu, J. B.; Tang, Z. L.; Zhang, Z. T.; Jin, Y. Z. Acta Phys. -Chim. Sin. 2005, 21, 319. [卢俊彪, 唐子龙, 张中太, 金永柱. 物理化学学报, 2005, 21, 319.] doi: 10.3866/PKU.WHXB20050319
(25) Wang, D. Y.; Li, H.; Shi, S. Q.; Huang, X. J.; Chen, L. Q.Electrochim. Acta 2005, 50, 2955. doi: 10.1016/j.electacta.2004.11.045
(26) Ou, X. Q.; Liang, G. C.;Wang, L.; Xu, S. Z.; Zhao, X. Journal of Power Sources 2008, 184, 543. doi: 10.1016/j.jpowsour.2008.02.077
(27) Huang, Y. Y.; Zhou, H. H.; Chen, J. T.; Gao, D. S.; Su, G. Y.Acta Phys. -Chim. Sin. 2005, 21, 725. [黄友元, 周恒辉, 陈继涛, 高德淑, 苏光耀. 物理化学学报, 2005, 21, 725.] doi: 10.3866/PKU.WHXB20050706
(28) Wang, Z. H.; Yuan, L. X.;Wu, M.; Sun, D.; Huang, Y. H.Electrochim. Acta 2011, 56, 8477. doi: 10.1016/j.electacta.2011.07.018
(29) Roberts, M. R.; Vitins, G.; Owen, J. R. Journal of Power Sources 2008, 179, 754. doi: 10.1016/j.jpowsour.2008.01.034
(30) Meethong, N.; Kao, Y. H.; Speakman, S. A.; Chiang, Y. M. Adv. Funct. Mater. 2009, 19, 1060. doi: 10.1002/adfm.200801617
(31) Zhang, P. X.;Wang, Y. Y.; Lin, M. C.; Zhang, D. Y.; Ren, X. Z.;Yuan, Q. H. Journal of the Electrochemical Society 2012, 159,A402.
(32) Li, J.; Yuan, C. F.; Guo, Z. H.; Zhang, Z. A.; Lai, Y. Q.; Liu, J. Electrochim. Acta 2012, 59, 69. doi: 10.1016/j.electacta.2011.10.041

[1]	薛国勇, 李静, 陈俊超, 陈代前, 胡晨吉, 唐凌飞, 陈博文, 易若玮, 沈炎宾, 陈立桅. 单离子聚合物快离子导体[J]. 物理化学学报, 2023, 39(8): 2205012 -0 .
[2]	潘雯丽,关文浩,姜银珠. 聚阴离子型钠离子电池正极材料的研究进展[J]. 物理化学学报, 2020, 36(5): 1905017 - .
[3]	魏风,毕宏晖,焦帅,何孝军. 超级电容器用相互连接的类石墨烯纳米片[J]. 物理化学学报, 2020, 36(2): 1903043 - .
[4]	胡江涛, 郑家新, 潘锋. 锂电池磷酸铁锂正极材料的结构与性能相关性的研究进展[J]. 物理化学学报, 2019, 35(4): 361 -370 .
[5]	何磊.,徐俊敏.,王永建.,张昌锦.. LiFePO₄包覆的Li_1.2Mn_0.54Ni_0.13Co_0.13O₂锂离子电池正极材料:增强的库伦效率和循环性能[J]. 物理化学学报, 2017, 33(8): 1605 -1613 .
[6]	张继斌, 滑纬博, 郑卓, 刘文元, 郭孝东, 钟本和. 高倍率性能锂离子电池Li[Ni_1/3Co_1/3Mn_1/3]O₂正极材料的制备及其电化学性能[J]. 物理化学学报, 2015, 31(5): 905 -912 .
[7]	张远航, 王志远, 师春生, 刘恩佐, 何春年, 赵乃勤. 均匀负载氧化镍纳米颗粒多孔硬碳球的制备及其高性能锂离子电池负极材料应用[J]. 物理化学学报, 2015, 31(2): 268 -276 .
[8]	张传香, 张晓雪, 陶海军. 花瓣状微球MoS₂/石墨烯复合材料的制备及其电化学性能[J]. 物理化学学报, 2014, 30(10): 1963 -1969 .
[9]	孙孝飞, 徐友龙, 刘养浩, 李璐. 微米橄榄石型LiFePO₄的水热合成优化[J]. 物理化学学报, 2012, 28(12): 2885 -2892 .
[10]	朱福良, 赵景新, 程永亮, 李海宝, 阎兴斌. 静电纺丝法制备的钴酸镍微米带的磁性以及电化学性能[J]. 物理化学学报, 2012, 28(12): 2874 -2878 .
[11]	毛景, 代克化, 翟玉春. 凝胶燃烧法合成Li_1.07Mn_1.93O₄纳米片及其高倍率放电和循环稳定性[J]. 物理化学学报, 2012, 28(02): 349 -354 .
[12]	高平, 谭卓, 成富圈, 周恒辉, 谭松庭. 钛离子掺杂对LiFe_0.6Mn_0.4PO₄/C 电化学性能的影响[J]. 物理化学学报, 2012, 28(02): 338 -342 .
[13]	赵浩川, 宋杨, 郭孝东, 钟本和, 董静, 刘恒. 前驱体配料温度对水热法制备LiFePO₄的影响[J]. 物理化学学报, 2011, 27(10): 2347 -2352 .
[14]	贺勇, 唐子龙, 张中太. 负载Cr₂O₃的H₂Ti₂O₅·H₂O纳米管的制备及其作为锂离子电池正极材料的电化学性能[J]. 物理化学学报, 2010, 26(11): 2962 -2966 .
[15]	熊利芝, 何则强. 一种新的流变相法制备锂离子电池纳米-LiVOPO₄正极材料[J]. 物理化学学报, 2010, 26(03): 573 -577 .

Mg、Ti离子复合掺杂改性磷酸铁锂正极材料及其电池性能

Synthesis and Characterization of Mg and Ti Ions Co-Doped Lithium Iron Phosphate and Its Lithium-Ion Batteries

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

推荐阅读 0