两步固相法合成LiFe1-xNbxPO4/C复合正极材料及其电化学性能

doi:10.3866/PKU.WHXB201304231

物理化学学报 >> 2013, Vol. 29 >> Issue (07): 1507-1514.doi: 10.3866/PKU.WHXB201304231

两步固相法合成LiFe_1-xNb_xPO₄/C复合正极材料及其电化学性能

曹雁冰^1,2, 罗亮¹, 杜柯¹, 彭忠东¹, 胡国荣¹, 姜锋²

1 中南大学冶金科学与工程学院, 长沙 410083;
2 中南大学材料科学与工程学院, 长沙 410083

收稿日期:2013-01-18 修回日期:2013-04-19 发布日期:2013-06-14
通讯作者: 彭忠东 E-mail:cybcsu@csu.edu.cn
基金资助:
国家科技支撑计划(2007BAE12B01); 中央高校基本科研业务费(2012QNZT018); 中国博士后科学基金(2012M521546)和中南大学博士后基金资助项目

Synthesis and Electrochemical Properties of LiFe_1-xNb_xPO₄/C Composite Cathode Material by Two-Step Synthesis Route

CAO Yan-Bing^1,2, LUO Liang¹, DU Ke¹, PENG Zhong-Dong¹, HU Guo-Rong¹, JIANG Feng²

1 School of Metallurgical Science and Engineering, Central South University, Changsha 410083;
2 School of Materials Science and Engineering, Central South University, Changsha 410083

Received:2013-01-18 Revised:2013-04-19 Published:2013-06-14
Contact: PENG Zhong-Dong E-mail:cybcsu@csu.edu.cn
Supported by:
The project was supported by the National Key Technology R&D Program of China (2007BAE12B01), Fundamental Research Funds for the Central Universities, China (2012QNZT018), China Postdoctoral Science Foundation (2012M521546), and Postdoctoral Science Foundation of Central South University, China.

摘要/Abstract

摘要：

以LiH₂PO₄和FeC₂O₄·2H₂O为原料, 采用分步添加聚乙烯醇和葡萄糖两种碳源的方式, 通过两步固相法合成了碳包覆的LiFePO₄材料. 700℃下处理的产物结晶良好, 颗粒分布均匀, 具有良好的电化学性能, 0.1C和1C倍率下放电比容量分别为157.3 和138.3 mAh·g^-1. 在碳包覆的基础上, 选择高价Nb⁵⁺进行铁位取代获得了复合改性的LiFe_1-xNb_xPO₄/C (x=0.005, 0.01, 0.015, 0.02)材料. 优化的LiFe_0.99Nb_0.01PO₄/C 材料显示了良好的倍率充放电能力和循环稳定性, 0.1C和5C倍率下放电比容量分别为160.5 和136.0 mAh·g^-1, 5C倍率下循环50 次后比容量保持在134.8 mAh·g^-1, 容量保持率为99.1%. 循环伏安测试结果表明, Nb⁵⁺离子掺杂减少了锂离子扩散阻力, 降低了充放电过程中的动力学限制, 提高了电极的可逆性.

关键词: 聚阴离子型正极材料, LiFePO₄, 两步固相法合成, Nb掺杂

Abstract:

LiFePO₄/C composite was prepared by two-step synthesis route, with LiH₂PO₄ and FeC₂O₄· 2H₂O as starting materials. In the process, the carbon sources polyvinyl alcohol (PVA) and glucose were added in a stepwise fashion. The well-crystallized LiFePO₄/C composite with homogeneous small particles was obtained after reacting at 700℃ for 4 h. This composite had a discharge specific capacity of 157.3 mAh·g^-1 at 0.1C rate and 138.4 mAh·g^-1 at 1C rate. On the basis of carbon coating modification, Nb-ion-doped LiFe_1-xNb_xPO₄/C (x=0.005, 0.01, 0.015, 0.02) composites were prepared. The optimized LiFe_0.99Nb_0.01PO₄/C cathode displayed a discharge specific capacity 160.5 mAh·g^-1 at 0.1C discharge rate, 136.0 mAh·g^-1 at 5C and maintained 134.8 mAh·g^-1 after 50 cycles, showing good rate properties and cycling stability. Cyclic voltammetry (CV) measurements indicated that aliovalent dopant substituting on the Fe sites can reduce the resistance of Li ion diffusion in the electrode process, increase phase transformation kinetics during cycling, and enhance the reversibility of LiFePO₄ electrodes.

Key words: Polyanion cathode material, LiFePO₄, Two-step synthesis, Nb doping

MSC2000:

O646

曹雁冰, 罗亮, 杜柯, 彭忠东, 胡国荣, 姜锋. 两步固相法合成LiFe_1-xNb_xPO₄/C复合正极材料及其电化学性能[J]. 物理化学学报, 2013, 29(07): 1507-1514.

CAO Yan-Bing, LUO Liang, DU Ke, PENG Zhong-Dong, HU Guo-Rong, JIANG Feng. Synthesis and Electrochemical Properties of LiFe_1-xNb_xPO₄/C Composite Cathode Material by Two-Step Synthesis Route[J]. Acta Phys. -Chim. Sin., 2013, 29(07): 1507-1514.

参考文献

(1) Padhi, A. K.; Nanjundaswamy, K. S.; Goodenough, J. B.J. Eletrochem. Soc. 1997, 144, 1188. doi: 10.1149/1.1837571
(2) Padhi, A. K.; Nanjundaswamy, K. S.; Masquelier, C.; Okada, S.;Goodenough, J. B. J. Electrochem. Soc. 1997, 144, 1609.
(3) Goodenough, J. B.; Kim, Y. Chem. Mater. 2010, 22, 587. doi: 10.1021/cm901452z
(4) Yamada, A.; Chung, S. C.; Hinokuma, K. J. J. Electrochem. Soc.2001, 148, A224.
(5) Morgan, D.; Van der Ven, A.; Ceder, G. Electrochem. Solid- State Lett. 2004, 7, A30.
(6) Fisher, C. A. J.; Hart Prieto, V. M.; Islam, M. S. Chem. Mater.2008, 20, 5907.
(7) Delacourt, C.; Poizot, P.; Levasseur, S.; Masquelier, C.Electrochem. Solid-State Lett. 2006, 9, A352.
(8) Lim, S. Y.; Yoon, C. S.; Cho, J. P. Chem. Mater. 2008, 20, 4560.doi: 10.1021/cm8006364
(9) Wang, Y. G.;Wang, Y. R.; Hosono, E.;Wang, K. X.; Zhou, H. S.Angew. Chem. Int. Edit. 2008, 47, 7461. doi: 10.1002/anie.v47:39
(10) Kang, B.; Ceder, G. Nature 2009, 458, 190.
(11) Chung, S. Y.; Bloking, J. T.; Chiang, Y. M. Nat. Mater. 2002, 1,123.
(12) Chen, Y.;Wang, Z. L.; Yu, C. Y.; Xia, D. G.;Wu, Z. Y. Acta Phys. -Chim. Sin. 2008, 24, 1498. [陈宇, 王忠丽, 于春洋,夏定国, 吴自玉. 物理化学学报, 2008, 24, 1498.] doi: 10.3866/PKU.WHXB20080829
(13) Zhang,W. J. J. Electrochem. Soc. 2010, 157, A1040.
(14) Dominko, R.; Gaberš?ek, M.; Drofenik, J.; Bele, M.; Pejovnik,S.; Jamnik, J. J. Power Sources 2003, 119 -121, 770.
(15) Yu, H. M.; Zheng,W.; Cao, G. S.; Zhao, X. B. Acta Phys. -Chim. Sin. 2009, 25, 2186. [余红明, 郑威, 曹高劭,赵新兵. 物理化学学报, 2009, 25, 2186.] doi: 10.3866/PKU.WHXB20091113
(16) Wang, Z. P.; Liu,W.;Wang, Y.; Zhao, C. S.; Zhang, S. P.; Chen,J.T.; Zhou, H. H.; Zhang, X. X. Acta Phys. -Chim. Sin. 2012, 28,2084. [王震坡, 刘文, 王悦, 赵春松, 张淑萍, 陈继涛, 周恒辉, 张新祥. 物理化学学报, 2012, 28, 2084.] doi: 10.3866/PKU.WHXB201207043
(17) 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
(18) Wang, G. X.; Bewlay, S.; Needham, S.; Liu, H. K.; Liu, R. S.;Drozd, V. A.; Lee, J. F.; Chen, J. M. J. Electrochem. Soc. 2006,153, A25
(19) Maier, J.; Amin, R. J. Electrochem. Soc. 2008, 155, A339.
(20) Ning, L. J.;Wu, Y. P.; Fang, S. B.; Rahm, E.; Holze, R. J. Power Sources 2004, 133, 229. doi: 10.1016/j.jpowsour.2004.01.048
(21) Ong, C.W.; Lin, Y. K.; Chen, J. S. J. Electrochem. Soc. 2007,154, A527
(22) Zhang, P. X.;Wang, Y. Y.; Lin, M. C.; Zhang, D. Y.; Ren, X. Z.;Yuan, Q. H. J. Electrochem. Soc. 2012, 159, A402.
(23) Wang, J. J.; Sun, X. L. Energy Environ. Sci. 2012, 5, 5163. doi: 10.1039/c1ee01263k
(24) Nonglak, M.; Yu, H. K.; Scott, A. S.; Chiang, Y. M. Adv. Funct. Mater. 2009, 19, 1060. doi: 10.1002/adfm.v19:7
(25) Sun, C. S.; Zhou, Z.; Xu, Z. G.;Wang, D. G.;Wei, J. P.; Bian,X. K.; Yan, J. J. Power Sources 2009, 193, 841. doi: 10.1016/j.jpowsour.2009.03.061
(26) Yang, M. R.; Ke,W. H. J. Electrochem. Soc. 2008, 155, A729.
(27) Ma, J.; Li, B. H.; Du, H. D.; Xu, C. J.; Kang, F. Y.J. Electrochem. Soc. 2011, 158, A26.

[1]	张英杰,朱子翼,董鹏,邱振平,梁慧新,李雪. LiFePO₄电化学反应机理、制备及改性研究新进展[J]. 物理化学学报, 2017, 33(6): 1085 -1107 .
[2]	任建新, 胡有坤, 郭孝东, 唐艳, 钟本和, 刘恒. 真空辅助法合成Fe₃（PO₄）₂·8H₂O及对LiFePO₄/C结构、形貌和电化学性能的影响[J]. 物理化学学报, 2014, 30(5): 866 -872 .
[3]	胡有坤, 任建新, 魏巧玲, 郭孝东, 唐艳, 钟本和, 刘恒. 多元醇法合成具有不同长径比的棒状LiFePO₄/C材料[J]. 物理化学学报, 2014, 30(1): 75 -82 .
[4]	孙超, 严六明, 岳宝华. 石墨烯和硼氮类石墨烯对LiFePO₄表面结构的改进及其电导的促进作用[J]. 物理化学学报, 2013, 29(08): 1666 -1672 .
[5]	曹雁冰, 段建国, 姜锋, 胡国荣, 彭忠东, 杜柯. 机械活化辅助多元醇法合成锂离子正极材料LiFePO₄[J]. 物理化学学报, 2012, 28(05): 1183 -1188 .
[6]	徐科, 申来法, 米常焕, 张校刚. 石墨烯掺杂LiFePO₄电极材料的合成及其电化学性能[J]. 物理化学学报, 2012, 28(01): 105 -110 .
[7]	苏畅, 陆国强, 徐立环, 张诚, 马淳安. 纺锤体形LiFePO₄锂离子电池正极材料的制备与性能[J]. 物理化学学报, 2011, 27(03): 609 -614 .
[8]	庄大高;赵新兵;谢健;涂健;朱铁军;曹高劭. Nb 掺杂LiFePO₄/C 的一步固相合成及电化学性能[J]. 物理化学学报, 2006, 22(07): 840 -844 .
[9]	薛明喆;傅正文. 脉冲激光沉积LiFePO₄阴极薄膜材料及其电化学性能[J]. 物理化学学报, 2005, 21(07): 707 -710 .
[10]	卢俊彪;唐子龙;张中太;金永拄. 镁离子掺杂对LiFePO₄/C材料电池性能的影响[J]. 物理化学学报, 2005, 21(03): 319 -323 .

两步固相法合成LiFe_1-xNb_xPO₄/C复合正极材料及其电化学性能

Synthesis and Electrochemical Properties of LiFe_1-xNb_xPO₄/C Composite Cathode Material by Two-Step Synthesis Route

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 10

Metrics

推荐阅读 0