English

An Optimized Synthetic Process for the Substitution of Cobalt in Nickel-Rich Cathode Materials

• Feng Wu ^{1, 2, †,} ,
• Qing Li ^{1, 2, 3, †,} ,
• Lai Chen ^{1, 2, ,} ,
• Zirun Wang ^1, ,
• Gang Chen ^{1, 2,} ,
• Liying Bao ^1, ,
• Yun Lu ^{1, 2,} ,
• Shi Chen ^1, ,
• Yuefeng Su ^{1, 2, ,}

• 1.

  School of Materials Science and Engineering, Beijing Key Laboratory of Environmental Science and Engineering, Beijing Institute of Technology, Beijing 100081, China

• 2.

  Beijing Institute of Technology Chongqing Innovation Center, Chongqing 401120, China

• 3.

  Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA

Corresponding author: Email: chenlai144@sina.com (L.C.); Email: suyuefeng@bit.edu.cn (Y.S.)

• Received Date: 06 July 2020
  Accepted Date: 18 August 2020
  Revised Date: 07 August 2020
  Available Online: 15 May 2022
• Fund Project:

  the National Key R & D Program of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the Science and Technology Innovation Foundation of Beijing Institute of Technology Chongqing Innovation Center 

  the Beijing Institute of Technology Research Fund Program for Young Scholars, and the Young Elite Scientists Sponsorship Program by CAST 

• ^† These authors contribute equally to this work.

Abstract: High-performance rechargeable lithium ion batteries have been widely applied in electrochemical energy storage fields, such as, energy storage grids, portable electronic devices, and electric vehicles (EVs). However, the energy density of lithium ion batteries needs to be increased, and the cost of battery materials could be further reduced for wider commercial applications. An Ni-rich cathode, LiNi_xMn_yCo_1-x-yO₂ (x > 0.8), with high specific capacity is the most promising material for next-generation Li-ion batteries. LiNi_xMn_yCo_1-x-yO₂ (x > 0.8) contains three transition metal elements, Ni, Mn, and Co, respectively. The role of Ni²⁺ is to provide high capacity for recharge The role of Mn⁴⁺ is to stabilize the lattice structure during charging-discharging cycling. Crucially, the role of Co³⁺ in Ni-rich materials is to improve the electrical conductivity and inhibit cation disorder in the lattice during electrochemical cycling. However, Co is both in shortage and expensive, which limits its worldwide commercial application. This work investigates substituting Co with other abundant and cheap transition metals. Transition metal ions Cr³⁺, Cd²⁺, and Zr⁴⁺ can replace Co³⁺ in Ni-rich cathode materials. LiNi_0.8Cr_0.1Mn_0.1O₂, LiNi_0.8Cd_0.1Mn_0.1O₂, and LiNi_0.8Zr_0.1Mn_0.1O₂ were synthesized by a co-precipitation method. Zr was found to be the best candidate for replacing Co in Ni-rich cathode materials. This study investigated Zr⁴⁺-doped Co-free Ni-rich materials. Initially, a carbonate co-precipitation process was used to synthesize Ni_0.8Zr_0.1Mn_0.1CO₃. This is due to that Zr³⁺/Zr⁴⁺ ions are not precipitated in the strong alkali solution, and the pH during hydroxide co-precipitation and carbonate co-precipitation processes are approximately 11 and 8, respectively. Therefore, the carbonate co-precipitation synthesis method was chosen. Ni_0.8Zr_0.1Mn_0.1CO₃ was synthesized by carbonate co-precipitation at pH = 7.6, 7.8, 8.0, and 8.2. After electrochemical analysis, pH = 7.8 was identified as the optimal value. The next stage of the research involved completing an electrochemical performance comparison on two lithium sources. The following lithium sources were added to the precursor; LiOH·₂O, and a 1:1 mixture of LiOH·₂O and Li₂CO₃. The lithium source with the 1:1 mixture, exhibited better performance for the Ni-rich cathode, LiNi_0.8Zr_0.1Mn_0.1O₂. In this study, the ideal doping amount of Zr in Ni-rich materials was 0.05. In conclusion, by careful control of co-precipitation pH and Li source, the Zr doped cobalt free Ni-rich cathode LiNi_0.85Mn_0.1Zr_0.05O₂ delivered a discharge capacity of 179.9 mAh·g^-1 at 0.2C. This was achieved between the voltage range of 2.75-4.3 V, with an 80 cycle capacity retention of 96.52%.

Key words:
• Lithium ion battery
•  /  Nickle-rich cathode material
•  /  Cobalt free
•  /  Cycling stability

• 1. [1]

     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.WHXB201202102Wang, Z.; Wu, F.; Su, Y.; Bao, L.; Chen, L.; Li, N.; Chen, S. Acta Phys. -Chim. Sin. 2012, 28, 823. doi: 10.3866/PKU.WHXB201202102

  2. [2]

     Tarascon, J. M.; Aamand, M. Nature 2001, 414, 359. doi: 10.1038/35104644

  3. [3]

     Wu, F.; Li, Q.; Chen, L.; Zhang, Q.; Wang, Z.; Lu, Y.; Bao, L.; Chen, S.; Su, Y. ACS Appl. Mater. Interfaces 2019, 11, 36751. doi: 10.1021/acsami.9b12595

  4. [4]

     Zhu, G. -L.; Zhao, C. -Z.; Huang, J. -Q.; He, C.; Zhang, J.; Chen, S.; Xu, L.; Yuan, H.; Zhang, Q. Small 2019, 15, 1805389. doi: 10.1002/smll.201805389

  5. [5]

     陈来, 陈实, 胡道中, 苏岳锋, 李维康, 王昭, 包丽颖, 吴锋. 物理化学学报, 2014, 30, 467. doi: 10.3866/PKU.WHXB201312252Chen, L.; Chen, S.; Hu, D.; Su, Y.; Li, W.; Wang, Z.; Bao, L.; Wu, F. Acta Phys. -Chim. Sin. 2014, 30, 467. doi: 10.3866/PKU.WHXB201312252

  6. [6]

     Li, M.; Lu, J.; Chen, Z. Adv. Mater. 2018, 30, 1800561. doi: 10.1002/adma.201800561

  7. [7]

     Sakti, A.; Michalek, J. J.; Fuchs, E. R. H.; Whitacre, J. F. J. Power Sources 2015, 273, 966. 10.1016/j.jpowsour.2014.09.078 doi: 10.1016/j.jpowsour.2014.09.078

  8. [8]

     Kim, J.; Lee, H.; Cha, H.; Yoon, M.; Park, M.; Cho, J. Adv. Energy Mater. 2017, 8, 1702028. doi: 10.1002/aenm.201702028

  9. [9]

     Bessette, S.; Paolella, A.; Kim, C.; Zhu, W.; Hovington, P.; Gauvin, R.; Zaghib, K. Sci. Rep. 2018, 8, 17575. doi: 10.1038/s41598-018-33608-3

  10. [10]

      Myung, S. -T.; Maglia, F.; Park, K. -J.; Yoon, C. S.; Lamp, P.; Kim, S. J.; Sun, Y. -K. ACS Energy Lett. 2017, 2, 196. doi: 10.1021/acsenergylett.6b00594

  11. [11]

      Jiang, L.; Luo, Z.; Wu, T.; Shao, L.; Sun, J.; Liu, C.; Li, G.; Cao, K.; Wang, Q. J. Electrochem. Soc. 2019, 166, A1055. doi: 10.1149/2.0661906jes

  12. [12]

      Liu, W.; Oh, P.; Liu, X.; Lee, M. -J.; Cho, W.; Chae, S.; Kim, Y.; Cho, J. Angew. Chem. Int. Ed. 2015, 54, 4440. doi: 10.1002/anie.201409262

  13. [13]

      寇建文, 王昭, 包丽颖, 苏岳锋, 胡宇, 陈来, 徐少禹, 陈芬, 陈人杰, 孙逢春. 物理化学学报, 2016, 32, 717. doi: 10.3866/PKU.WHXB201512301Kou, J.; Wang, Z.; Bao, L.; Su, Y.; Hu, Y.; Chen, L.; Xu, S.; Chen, F.; Chen, R.; Sun, F. Acta Phys. -Chim. Sin. 2016, 32, 717. doi: 10.3866/PKU.WHXB201512301

  14. [14]

      Yu, H.; Qian, Y.; Otani, M.; Tang, D.; Guo, S.; Zhu, Y.; Zhou, H. Energy Environ. Sci. 2014, 7, 1068. doi: 10.1039/C3EE42398K

  15. [15]

      吴锋, 王萌, 苏岳锋, 陈实. 物理化学学报, 2009, 25, 629. doi: 10.3866/PKU.WHXB20090411Wu, F.; Wang, M.; Su, Y.; Chen, S. Acta Phys. -Chim. Sin. 2009, 25, 629. doi: 10.3866/PKU.WHXB20090411

  16. [16]

      Wu, F.; Li, Q.; Chen, L.; Lu, Y.; Su, Y.; Bao, L.; Chen, R.; Chen, S. ChemSusChem 2019, 12, 935. doi: 10.1002/cssc.201802304

  17. [17]

      Kong, F.; Liang, C.; Wang, L.; Zheng, Y.; Perananthan, S.; Longo, R. C.; Ferraris, J. P.; Kim, M.; Cho, K. Adv. Energy Mater. 2018, 9, 1802586. doi: 10.1002/aenm.201802586

  18. [18]

      Kim, J. -H.; Park, K. -J.; Kim, S. J.; Yoon, C. S.; Sun, Y. -K. J. Mater. Chem. A 2019, 7, 2694. doi: 10.1039/C8TA10438G

  19. [19]

      Kim, D.; Lim, J. -M.; Lim, Y. -G.; Yu, J. -S.; Park, M. -S.; Cho, M.; Cho, K. Chem. Mater. 2015, 27, 6450. doi: 10.1021/acs.chemmater.5b02697

  20. [20]

      Wu, Z.; Ji, S.; Hu, Z.; Zheng, J.; Xiao, S.; Lin, Y.; Xu, K.; Amine, K.; Pan, F. ACS Appl. Mater. Interfaces 2016, 8, 15361. doi: 10.1021/acsami.6b0373

  21. [21]

      Zheng, J.; Teng, G.; Xin, C.; Zhou, Z.; Liu, J.; Li, Q.; Hu, Z.; Xu, M.; Yan, S.; Yang, W.; et al. Phys. Chem. Lett. 2017, 8, 5537. doi: 10.1021/acs.jpclett.7b02498

  22. [22]

      Whittingham, M. S. Chem. Rev. 2004, 104, 4271. doi: 10.1021/cr020731c

  23. [23]

      Jian, L. F.; Zhang, M.; Yuan, H. T.; Zhao, M.; Guo, J.; Wang, W.; Zhou, X. D.; Wang, Y. M. J. Power Sources 2007, 167, 178. doi: 10.1016/j.jpowsour.2007.01.070

  24. [24]

      Kim, Y. Int. J. Quantum Chem. 2019, 119, e26028. doi: org/ 10.1002/qua.26028

  25. [25]

      He, T.; Lu, Y.; Su, Y.; Bao, L.; Tan, J.; Chen, L.; Zhang, Q.; Li, W.; Chen, S.; Wu, F. ChemSusChem 2018, 11, 1639. doi: 10.1002/cssc.201702451

  26. [26]

      Han, B.; Xu, S.; Zhao, S.; Lin, G.; Feng, Y.; Chen, L.; Ivey, D. G.; Wang, P.; Wei, W. ACS Appl. Mater. Interfaces 2018, 10, 39599. doi: 10.1021/acsami.8b11112

  27. [27]

      Deng, S.; Lin, Z.; Li, Y.; Xue, L.; Li, H.; Chen, Y.; Lei, T.; Zhu, J.; Li, J.; Zhang, J. Int. J. Mater. Res. 2018, 109, 1043. doi: 10.3139/146.111701

  28. [28]

      Ma, Y.; Li, L.; Wang, L.; Luo, R.; Xu, S.; Wu, F.; Chen, R. J. Alloys Compd. 2019, 778, 643. doi: 10.1016/j.jallcom.2018.11.189

  29. [29]

      崔永福, 崔金龙, 满建宗, 程付鹏, 张鹏超, 李嵩, 文钟晟, 孙俊才. 稀有金属材料与工程, 2019, 48, 587. https://www.cnki.com.cn/Article/CJFDTOTAL-JFJY202001002.htmCui, Y. F.; Cui, J. L.; Man, J. Z.; Cheng, F. P.; Zhang, P. C.; Li, S.; Wen, Z. H.; Sun, J. C. Rare Metal Mat. Eng. 2019, 48, 587. https://www.cnki.com.cn/Article/CJFDTOTAL-JFJY202001002.htm

  30. [30]

      Wang, D.; Belharouak, I.; Koenig, G. M., Jr.; Zhou, G.; Amine, K. J. Mater. Chem. C 2011, 21, 9290. doi: 10.1039/C1JM11077B

  31. [31]

      Wu, F.; Li, Q.; Bao, L.; Zheng, Y.; Lu, Y.; Su, Y.; Wang, J.; Chen, S.; Chen, R.; Tian, J. Electrochim. Acta 2018, 260, 986. doi: 10.1016/j.electacta.2017.12.034

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