锂离子电池正极材料Li1.2Mn0.54-xNi0.13Co0.13ZrxO2的制备及电化学性能

引用本文: 任祥忠, 刘涛, 孙灵娜, 张培新. 锂离子电池正极材料Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂的制备及电化学性能[J]. 物理化学学报, 2014, 30(9): 1641-1649. doi: 10.3866/PKU.WHXB201406172 shu

Citation: REN Xiang-Zhong, SUN Ling-Na, ZHANG Pei-Xin, Preparation and Electrochemical Performances of Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂ Cathode Materials for Lithium-Ion Batteries[J]. Acta Physico-Chimica Sinica, 2014, 30(9): 1641-1649. doi: 10.3866/PKU.WHXB201406172 shu

锂离子电池正极材料Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂的制备及电化学性能

通讯作者: 张培新,

基金项目:
国家自然科学基金（21000174)

深圳市战略新兴产业发展基金（JCYJ20120613163733279，JCYJ20130329113849606）资助项目

摘要:

为了改善富锂锰基正极材料Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ 的循环性能，采用燃烧法合成了正极材料Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂（x=0.00，0.01，0.02，0.03，0.06）. 通过X射线衍射（XRD）和扫描电镜（SEM）对其结构与形貌进行了表征，利用恒电流充放电测试，循环伏安（CV）及电化学交流阻抗谱（EIS）技术对其电化学性能进行测试. 结果表明，Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂（x=0.00，0.01，0.02，0.03，0.06）正极材料均具有α-NaFeO₂型层状结构；在室温，2.0-4.8 V电压范围，以0.1C和1.0C（充放电电流以1.0C=180 mA·g^-1计算）倍率充放电进行测试，样品Li_1.2Mn_0.52Ni_0.13Co_0.13Zr_0.02O₂的首次放电比容量分别为280.3 和206.4 mAh·g^-1. 其中，在1.0C倍率下，100次循环后容量保持率由原来的73.2%提高到88.9%；以5.0C倍率充放电进行测试，经50次循环后，掺杂正极材料的放电比容量为76.5 mAh·g^-1，而未掺杂材料仅有15.0 mAh·g^-1. 在50、25 和-10 ℃，2.0C倍率条件下，掺杂正极材料的电化学性能均得到有效改善，其中，在- 10℃ 经过50 次循环后正极材料Li_1.2Mn_0.52Ni_0.13Co_0.13Zr_0.02O₂比未掺杂的正极材料相比，其放电比容量提高了61.1%.

关键词:

English

Preparation and Electrochemical Performances of Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂ Cathode Materials for Lithium-Ion Batteries

1.
College of Chemistry and Chemical Engineering, Shenzhen University, Shenzhen 518060, Guangdong Province, P. R. China

Corresponding author: ,

Received Date: 18 April 2014
Available Online: 29 August 2014
Fund Project:
国家自然科学基金（21000174)

深圳市战略新兴产业发展基金（JCYJ20120613163733279，JCYJ20130329113849606）资助项目

Abstract:

To improve the cycling performance of lithium-rich cathode materials, Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ and Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂ (x=0.00, 0.01, 0.02, 0.03, and 0.06) were synthesized by a combustion method. The structure and morphology were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical performances were examined by cyclic voltammetry (CV), electrochemical AC impedance spectroscopy, and galvanostatic charge-discharge cycling. The results indicate that all of the doped samples have a layer of α-NaFeO₂. When charged and discharged at 0.1C and 1.0C (1.0C=180 mA·g^-1) in the voltage range of 2.0-4.8 V, the initial discharge capacities of Li_1.2Mn_0.52Ni_0.13Co_0.13Zr_0.02O₂ were 280.3 and 206.4 mAh·g^-1, respectively. Moreover, the capacity retention after 50 cycles improved from 73.2% to 88.9% at 1.0C at room temperature. Meanwhile, this system delivered a higher discharge capacity of 76.5 mAh·g^-1 than that of the bare materials (15 mAh·g^-1) at 5.0C after 50 cycles. Electrochemical performances of the doped samples were improved at a 2.0C rate at different temperatures (50, 25, and -10 ℃). Furthermore, compared with the undoped material, the specific discharge capacity increased by 61.1% at -10 ℃ after 50 cycles.

Key words:

1. [1]
  
  (1) Gao, M.; Liu, N.;Wang,W.; Li, C.; Zhang, H.; Chen, Y.; Yu, Z.; Huang, Y. Solid State Ionics 2014, 258, 8. doi: 10.1016/j.ssi.2014.01.041
  (1) Gao, M.; Liu, N.;Wang,W.; Li, C.; Zhang, H.; Chen, Y.; Yu, Z.; Huang, Y. Solid State Ionics 2014, 258, 8. doi: 10.1016/j.ssi.2014.01.041
2. [2]
  (2) Wang, Z.;Wu, F.; Su, Y. F.; Bao, L. Y.; Chen, L.; Li, N.; Chen, S. Acta Phys. -Chim. Sin. 2012, 28, 823. [王昭, 吴锋, 苏岳锋, 包丽颖, 陈来, 李宁, 陈实. 物理化学学报, 2012, 28, 823.] doi: 10.3866/PKU.WHXB201202102(2) Wang, Z.;Wu, F.; Su, Y. F.; Bao, L. Y.; Chen, L.; Li, N.; Chen, S. Acta Phys. -Chim. Sin. 2012, 28, 823. [王昭, 吴锋, 苏岳锋, 包丽颖, 陈来, 李宁, 陈实. 物理化学学报, 2012, 28, 823.] doi: 10.3866/PKU.WHXB201202102
3. [3]
  (3) Cao, Y. B.; Duan, J. G.; Jiang, F.; Hu, Y. R.; Peng, Z. D.; Du, K. Acta Phys. -Chim. Sin. 2012, 28, 1183. [曹雁冰, 段建国, 姜锋, 胡园荣, 彭忠东, 杜柯. 物理化学学报, 2012, 28, 1183.] doi: 10.3866/PKU.WHXB201202221(3) Cao, Y. B.; Duan, J. G.; Jiang, F.; Hu, Y. R.; Peng, Z. D.; Du, K. Acta Phys. -Chim. Sin. 2012, 28, 1183. [曹雁冰, 段建国, 姜锋, 胡园荣, 彭忠东, 杜柯. 物理化学学报, 2012, 28, 1183.] doi: 10.3866/PKU.WHXB201202221
4. [4]
  (4) Ohzuku, T.; Ueda, A. J. Electrochem. Soc. 1994, 141, 2972. doi: 10.1149/1.2059267(4) Ohzuku, T.; Ueda, A. J. Electrochem. Soc. 1994, 141, 2972. doi: 10.1149/1.2059267
5. [5]
  (5) Hosono, E.; Kudo, T.; Honma, I.; Matsuda, H.; Zhou, H. Nano Lett. 2009, 9, 1045. doi: 10.1021/nl803394v(5) Hosono, E.; Kudo, T.; Honma, I.; Matsuda, H.; Zhou, H. Nano Lett. 2009, 9, 1045. doi: 10.1021/nl803394v
6. [6]
  (6) Padhi, A. K.; Nanjundaswamy, K. S.; odenough, J. B. J. Electrochem. Soc. 1997, 144, 1188. doi: 10.1149/1.1837571(6) Padhi, A. K.; Nanjundaswamy, K. S.; odenough, J. B. J. Electrochem. Soc. 1997, 144, 1188. doi: 10.1149/1.1837571
7. [7]
  (7) Wang, Z.; Liu, E.; He, C.; Shi, C.; Li, J.; Zhao, N. J. Power Sources 2013, 236, 25. doi: 10.1016/j.jpowsour.2013.02.022(7) Wang, Z.; Liu, E.; He, C.; Shi, C.; Li, J.; Zhao, N. J. Power Sources 2013, 236, 25. doi: 10.1016/j.jpowsour.2013.02.022
8. [8]
  (8) Nie,W. B.; Xiao, Q. C.;Wang, J. L.; Lei, G. T.; Xiao, Q. Z.; Li, C. H. J. Inorg. Mater. 2014, 29, 258. [聂文波, 肖其昌, 王京亮, 雷钢铁, 肖启振, 李朝晖. 无机材料学报, 2014, 29, 258.](8) Nie,W. B.; Xiao, Q. C.;Wang, J. L.; Lei, G. T.; Xiao, Q. Z.; Li, C. H. J. Inorg. Mater. 2014, 29, 258. [聂文波, 肖其昌, 王京亮, 雷钢铁, 肖启振, 李朝晖. 无机材料学报, 2014, 29, 258.]
9. [9]
  (9) Song, B.; Lai, M. O.; Lu, L. Electrochim. Acta 2012, 80, 187. doi: 10.1016/j.electacta.2012.06.118(9) Song, B.; Lai, M. O.; Lu, L. Electrochim. Acta 2012, 80, 187. doi: 10.1016/j.electacta.2012.06.118
10. [10]
  (10) Jafta, C. J.; Ozoemena, K. I.; Mathe, M. K.; Roos,W. D. Electrochim. Acta 2012, 85, 411. doi: 10.1016/j.electacta.2012.08.074(10) Jafta, C. J.; Ozoemena, K. I.; Mathe, M. K.; Roos,W. D. Electrochim. Acta 2012, 85, 411. doi: 10.1016/j.electacta.2012.08.074
11. [11]
  (11) Ren, X. Z.; Hu, S. M.; Shi, C.; Zhang, P. X.; Yuan, Q. H.; Liu, J. H. J. Solid State Electrochem. 2012, 16, 2135. doi: 10.1007/s10008-011-1630-2(11) Ren, X. Z.; Hu, S. M.; Shi, C.; Zhang, P. X.; Yuan, Q. H.; Liu, J. H. J. Solid State Electrochem. 2012, 16, 2135. doi: 10.1007/s10008-011-1630-2
12. [12]
  (12) Ding, C. X.; Bai, Y. C.; Feng, X. Y.; Chen, C. H. Solid State Ionics 2011, 189, 69. doi: 10.1016/j.ssi.2011.02.015(12) Ding, C. X.; Bai, Y. C.; Feng, X. Y.; Chen, C. H. Solid State Ionics 2011, 189, 69. doi: 10.1016/j.ssi.2011.02.015
13. [13]
  (13) Zhang, K. K.; Jia, M. K.; Tang, H.; Guo, G. H. Wu Han Univ. Technol., Nat. Sci. 2002, 48, 409. [张克立, 贾漫珂, 汤昊,郭光辉. 武汉大学学报: 理学版, 2002, 48, 409.](13) Zhang, K. K.; Jia, M. K.; Tang, H.; Guo, G. H. Wu Han Univ. Technol., Nat. Sci. 2002, 48, 409. [张克立, 贾漫珂, 汤昊,郭光辉. 武汉大学学报: 理学版, 2002, 48, 409.]
14. [14]
  (14) Dai, K. H.; Zhang, Y.; Jin, Q. J.; Zhai, Y. C. J. Power Sources 2013, 37, 1111. [代克化, 张莹, 金秋瑾, 翟玉春. 电源技术, 2013, 37, 1111.](14) Dai, K. H.; Zhang, Y.; Jin, Q. J.; Zhai, Y. C. J. Power Sources 2013, 37, 1111. [代克化, 张莹, 金秋瑾, 翟玉春. 电源技术, 2013, 37, 1111.]
15. [15]
  (15) Yamada, A.; Chung, S. C.; Hinokuma, K. J. J. Electrochem. Soc. 2001, 148, 224. doi: 10.1149/1.1348257(15) Yamada, A.; Chung, S. C.; Hinokuma, K. J. J. Electrochem. Soc. 2001, 148, 224. doi: 10.1149/1.1348257
16. [16]
  (16) Prosini, P. P.; Carewska, M.; Scaccia, S.;Wisniewski, P.; Passerini, S.; Pasquali, M. J. Electrochem. Soc. 2002, 149, A886.(16) Prosini, P. P.; Carewska, M.; Scaccia, S.;Wisniewski, P.; Passerini, S.; Pasquali, M. J. Electrochem. Soc. 2002, 149, A886.
17. [17]
  (17) Yoon,W. S.; Iannopollo, S.; Grey, C. P.; Carlier, D.; rman, J.; Reed, J.; Ceder, G. Electrochem. Solid-State Lett. 2004, 7, A167.(17) Yoon,W. S.; Iannopollo, S.; Grey, C. P.; Carlier, D.; rman, J.; Reed, J.; Ceder, G. Electrochem. Solid-State Lett. 2004, 7, A167.
18. [18]
  (18) Cheng, C. X.; Tan, L.; Liu, H.W.; Huang, X. T. Mater. Res. Bull. 2011, 46, 2032. doi: 10.1016/j.materresbull.2011.07.004(18) Cheng, C. X.; Tan, L.; Liu, H.W.; Huang, X. T. Mater. Res. Bull. 2011, 46, 2032. doi: 10.1016/j.materresbull.2011.07.004
19. [19]
  (19) ng, Z. L.; Liu, H. S.; Guo, X. J.; Zhang, Z. R.; Yong, Y. J. Power Sources 2004, 136, 139. doi: 10.1016/j.jpowsour.2004.05.022(19) ng, Z. L.; Liu, H. S.; Guo, X. J.; Zhang, Z. R.; Yong, Y. J. Power Sources 2004, 136, 139. doi: 10.1016/j.jpowsour.2004.05.022
20. [20]
  (20) Oh, S. H.; Lee, S, M.; Cho,W. I. Electrochim. Acta 2006, 51, 3637. doi: 10.1016/j.electacta.2005.10.023(20) Oh, S. H.; Lee, S, M.; Cho,W. I. Electrochim. Acta 2006, 51, 3637. doi: 10.1016/j.electacta.2005.10.023
21. [21]
  (21) Johnson, C. S.; Li, N.; Lefief, C.; Thackeray, M. M. Electrochem. Commun. 2007, 9, 787. doi: 10.1016/j.elecom.2006.11.006(21) Johnson, C. S.; Li, N.; Lefief, C.; Thackeray, M. M. Electrochem. Commun. 2007, 9, 787. doi: 10.1016/j.elecom.2006.11.006
22. [22]
  (22) Wu, Y.; Manthiram, A. Solid State Ionics 2009, 180, 50. doi: 10.1016/j.ssi.2008.11.002(22) Wu, Y.; Manthiram, A. Solid State Ionics 2009, 180, 50. doi: 10.1016/j.ssi.2008.11.002
23. [23]
  (23) Xiong, X. D.; Li, X. Q.; Li,W. S. J. Power Sources 2013, 230, 89.(23) Xiong, X. D.; Li, X. Q.; Li,W. S. J. Power Sources 2013, 230, 89.
24. [24]
  (24) Park, S. H.; Kang, S. H.; Johnson, C.; Amine, K.; Thackeray, M. Electrochem. Commun. 2007, 9, 262. doi: 10.1016/j.elecom.2006.09.014(24) Park, S. H.; Kang, S. H.; Johnson, C.; Amine, K.; Thackeray, M. Electrochem. Commun. 2007, 9, 262. doi: 10.1016/j.elecom.2006.09.014
25. [25]
  (25) Riley, L. A.; Atta, A. V.; Cavanagh, A. S.; Yan, Y. F.; George, S. M.; Liu, P.; Dillon, A. C.; Lee, S. H. J. Power Sources 2011, 196, 3317. doi: 10.1016/j.jpowsour.2010.11.124(25) Riley, L. A.; Atta, A. V.; Cavanagh, A. S.; Yan, Y. F.; George, S. M.; Liu, P.; Dillon, A. C.; Lee, S. H. J. Power Sources 2011, 196, 3317. doi: 10.1016/j.jpowsour.2010.11.124
26. [26]
  (26) Huang, Y. Y.; Chen, J. T.; Ni, J. F.; Zhou, H. H.; Zhang, X. X. J. Power Sources 2009, 188, 538. doi: 10.1016/j.jpowsour.2008.12.037(26) Huang, Y. Y.; Chen, J. T.; Ni, J. F.; Zhou, H. H.; Zhang, X. X. J. Power Sources 2009, 188, 538. doi: 10.1016/j.jpowsour.2008.12.037
27. [27]
  (27) Jiang, Z. Q.; Jiang, Z. G. J. Alloy. Compd. 2012, 537, 308.
  (27) Jiang, Z. Q.; Jiang, Z. G. J. Alloy. Compd. 2012, 537, 308.

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

锂离子电池正极材料Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂的制备及电化学性能

通讯作者: 张培新,

English

Preparation and Electrochemical Performances of Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂ Cathode Materials for Lithium-Ion Batteries

Corresponding author: ,

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