梯度包覆镍酸锂材料Li[Ni0.92Co0.04Mn0.04]O2的合成与研究

引用本文: 杜柯, 黄金龙, 胡国荣, 彭忠东, 曹雁冰, 潭潮溥, 王伟刚. 梯度包覆镍酸锂材料Li[Ni_0.92Co_0.04Mn_0.04]O₂的合成与研究[J]. 无机化学学报, 2013, 29(5): 1031-1036. doi: 10.3969/j.issn.1001-4861.2013.00.142 shu

Citation: DU Ke, HUANG Jin-Long, HU Guo-Rong, PENG Zhong-Dong, CAO Yan-Bing, TANG Cao-Pu, WANG Wei-Gang. Research on Synthesis and Performance of Composite Cathode Material Li[Ni_0.92Co_0.04Mn_0.04]O₂ with Gradient-Coating Layer as Lithium Ion Battery[J]. Chinese Journal of Inorganic Chemistry, 2013, 29(5): 1031-1036. doi: 10.3969/j.issn.1001-4861.2013.00.142 shu

梯度包覆镍酸锂材料Li[Ni_0.92Co_0.04Mn_0.04]O₂的合成与研究

通讯作者: 杜柯,E-mail:Duke22@csu.edu.cn

基金项目:
中央高校基本科研业务费(No.2012QNZT018)资助项目。 (No.2012QNZT018)

摘要: 采用浓度梯度加料的方式，首先沉淀制备了核为Ni(OH)₂、壳为镍钴锰氢氧化物浓度梯度包覆的复合前驱体，然后配锂高温焙烧，合成了梯度包覆的镍酸锂复合正极材料Li[Ni_0.92Co_0.04Mn_0.04]O₂。采用X射线衍射(XRD)、扫描电镜(SEM)、恒电流充放电测试等方法对材料的结构、表观形貌及电化学性能进行了表征。结果表明，该材料具有良好的六方单相层状α-NaFeO₂结构，呈类球型状。切面元素线扫描显示该材料的包覆壳层中主要金属元素呈梯度变化。同时该新型梯度包覆的镍酸锂复合正极材料表现出了优越的电化学性能:在25 ℃下，2.8～4.3 V充放电范围，0.1C首次放电比容量可达198.3 mAh·g^-1，循环40次容量保持96.8%;1C和2C倍率下放电比容量可达175 mAh·g^-1和165.1 mAh·g^-1。55 ℃下，该材料首次放电比容量可达236.1 mAh·g^-1，循环40次容量仍能保持77.5%。

关键词:

锂离子电池;镍酸锂;梯度包覆;过渡金属氧化物

English

Research on Synthesis and Performance of Composite Cathode Material Li[Ni_0.92Co_0.04Mn_0.04]O₂ with Gradient-Coating Layer as Lithium Ion Battery

1.
School of Metallurgical Science and Engineering, Central South University, Changsha 410083, China

Corresponding author: 杜柯,E-mail:Duke22@csu.edu.cn

Received Date: 02 November 2012
Fund Project:
中央高校基本科研业务费(No.2012QNZT018)资助项目。

Abstract: A new core-shell structure precursor were prepared by a co-precipitation method. A gradient concentration of Ni-Co-Mn shell layer was co-precipitated on the Ni(OH)₂ core which was used as the precursor. Then, the well-ordered spherical LiNi_0.92Co_0.04Mn_0.04O₂ was synthesized by sintering the mixture of as-prepared precursor and LiOH·H₂O in O₂. The prepared samples were characterized by X-ray diffractometry, SEM and galvanostatic charge-discharge test. The results show that, the product has a layered hexagonal α-NaFeO₂ structure and a spherical morphology. The line scan test of elements on the cross section area of coating shell show that the main elements of the materials change gradiently. The initial discharge capacity is 193.8 mAh·g^-1 at 0.1C rate between 2.8 and 4.3 V and retains 96.8% after 40 cycles at 25 ℃. The capacity at 1C and 2C is 175 mAh·g^-1 and 165.1 mAh·g^-1. When cycled at 55 ℃, the initial discharge capacity is 236.1 mAh·g^-1 and retains 77.5% after 40 cycles, indicating good electrochemical capacity and cycling stability.

Key words:

Li-ion battery;lithium nickel oxide;gradient coating;transition metal oxide

1. [1] Liu W M, Hu G R, Peng Z D, et al. Chin. Chem. Lett., 2011,22:1099-1102[1] Liu W M, Hu G R, Peng Z D, et al. Chin. Chem. Lett., 2011,22:1099-1102
2. [2] Park B C, Kim H B, Bang H J, et al. Chem. Res., 2008,47: 3876-3882[2] Park B C, Kim H B, Bang H J, et al. Chem. Res., 2008,47: 3876-3882
3. [3] Arai H, Tsuda M, Saito K, et al. J. Electrochem. Soc., 2002, 149:A401-A406[3] Arai H, Tsuda M, Saito K, et al. J. Electrochem. Soc., 2002, 149:A401-A406
4. [4] Ju J H, Ryu K S. J. Alloys Compd., 2011,509:7985-7992[4] Ju J H, Ryu K S. J. Alloys Compd., 2011,509:7985-7992
5. [5] Sun Y K, Kim D H, Yoon C S, et al. Adv. Funct. Mater., 2010,20:485-491[5] Sun Y K, Kim D H, Yoon C S, et al. Adv. Funct. Mater., 2010,20:485-491
6. [6] Ohzuku T, Ueda A, Nagayama M, et al. Electrochim. Acta, 1993,38(9):1159-1167[6] Ohzuku T, Ueda A, Nagayama M, et al. Electrochim. Acta, 1993,38(9):1159-1167
7. [7] Delmas C, Saadoune I. Solid State Ionics, 1992,53-56(1): 370-375[7] Delmas C, Saadoune I. Solid State Ionics, 1992,53-56(1): 370-375
8. [8] Rougier A, Saadouane I, P Gravereau, et al. Solid State Ionics, 1996,90(1-4):83-90[8] Rougier A, Saadouane I, P Gravereau, et al. Solid State Ionics, 1996,90(1-4):83-90
9. [9] Saadouane I, Delmas C. Mater. Chem., 1996,6(2):193-199[9] Saadouane I, Delmas C. Mater. Chem., 1996,6(2):193-199
10. [10] Saadouane I, Ménétrier M, Delmas C, et al. Mater. Chem., 1997,7(12):2505-2511[10] Saadouane I, Ménétrier M, Delmas C, et al. Mater. Chem., 1997,7(12):2505-2511
11. [11] Zhecheva E, Stoyanova R. Solid State Ionics, 1993,66(1-2): 143-149[11] Zhecheva E, Stoyanova R. Solid State Ionics, 1993,66(1-2): 143-149
12. [12] Weaving J S, Coowar F, Teagel D A. J. Power Sources., 2001,97(98):733-735[12] Weaving J S, Coowar F, Teagel D A. J. Power Sources., 2001,97(98):733-735
13. [13] Lee D J, Bruno S, Sun Y K, et al. J. Power Sources, 2011, 196:7742-7746[13] Lee D J, Bruno S, Sun Y K, et al. J. Power Sources, 2011, 196:7742-7746
14. [14] SunY K, Myung S T, Park B C, et al. Chem. Mater., 2006, 18:5159-5163[14] SunY K, Myung S T, Park B C, et al. Chem. Mater., 2006, 18:5159-5163
15. [15] Seinoa Y, Ota T, Takada K, et al. J. Power Sources, 2011, 196:64886492[15] Seinoa Y, Ota T, Takada K, et al. J. Power Sources, 2011, 196:64886492
16. [16] Cho Y, Cho J. J. Electrochem. Soc., 2010,157(6):A625- A629[16] Cho Y, Cho J. J. Electrochem. Soc., 2010,157(6):A625- A629
17. [17] SunY K, Myung S T, Kim M H. J. Am. Chem. Soc., 2005,9 (38):13418-13422[17] SunY K, Myung S T, Kim M H. J. Am. Chem. Soc., 2005,9 (38):13418-13422
18. [18] Sun Y K, Myung S T, Shin H S J, et al. Phys. Chem., 2006, 110:6810-6815[18] Sun Y K, Myung S T, Shin H S J, et al. Phys. Chem., 2006, 110:6810-6815
19. [19] SunY K, Myung S T, Park B C, et al. Chem. Mater., 2006, 18:5159-5163[19] SunY K, Myung S T, Park B C, et al. Chem. Mater., 2006, 18:5159-5163
20. [20] SunY K, Myung S T, Park B C, et al. Nature Mater., 2009, 8:320-324[20] SunY K, Myung S T, Park B C, et al. Nature Mater., 2009, 8:320-324
21. [21] Sun Y K, Kima D H, Junga H G, et al. Electrochim. Acta, 2010,55:8621-8627[21] Sun Y K, Kima D H, Junga H G, et al. Electrochim. Acta, 2010,55:8621-8627
22. [22] Koenig G M, Belharouak I, Deng H X, et al. Chem. Mater., 2011,23:1954-1963[22] Koenig G M, Belharouak I, Deng H X, et al. Chem. Mater., 2011,23:1954-1963
23. [23] Sun Y K, Noh H J, Yoon C S, et al. J. Electrochem. Soc., 2012,159(1):A1-A5[23] Sun Y K, Noh H J, Yoon C S, et al. J. Electrochem. Soc., 2012,159(1):A1-A5
24. [24] Sun Y K, Lee Bo-Ram, Hyung J Noh, J. Mater. Chem., 2011,21:10108-10112[24] Sun Y K, Lee Bo-Ram, Hyung J Noh, J. Mater. Chem., 2011,21:10108-10112
25. [25] Lee H J, Kim Y J. J. Electrochem. Soc., 2006,153(4):A781- 786[25] Lee H J, Kim Y J. J. Electrochem. Soc., 2006,153(4):A781- 786
26. [26] Hwang B J, Santhanam R. J. Power Sources, 2003,114:244- 252[26] Hwang B J, Santhanam R. J. Power Sources, 2003,114:244- 252
27. [27] Delmas C. Electrochim. Acta, 1999,45;243-253[27] Delmas C. Electrochim. Acta, 1999,45;243-253
28. [28] Lee M H, Kang Y J, Myung S T, et al. Electrochim. Acta, 2004,50:939-948[28] Lee M H, Kang Y J, Myung S T, et al. Electrochim. Acta, 2004,50:939-948
29. [29] Ohzuku T, Makimura Y. Chem. Lett., 2001:744-745[29] Ohzuku T, Makimura Y. Chem. Lett., 2001:744-745
30. [30] ZHANG Jun(张军), YANG Qing-He(杨清河), SONG Qing- Mei(宋庆梅), et al. Chin. J. Electrochem.(Dianhuaxue), 2002,8(3):306-314[30] ZHANG Jun(张军), YANG Qing-He(杨清河), SONG Qing- Mei(宋庆梅), et al. Chin. J. Electrochem.(Dianhuaxue), 2002,8(3):306-314

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

梯度包覆镍酸锂材料Li[Ni_0.92Co_0.04Mn_0.04]O₂的合成与研究

通讯作者: 杜柯,E-mail:Duke22@csu.edu.cn

English

Research on Synthesis and Performance of Composite Cathode Material Li[Ni_0.92Co_0.04Mn_0.04]O₂ with Gradient-Coating Layer as Lithium Ion Battery

Corresponding author: 杜柯,E-mail:Duke22@csu.edu.cn

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