Citation: Feng Wu, Qing Li, Lai Chen, Zirun Wang, Gang Chen, Liying Bao, Yun Lu, Shi Chen, Yuefeng Su. An Optimized Synthetic Process for the Substitution of Cobalt in Nickel-Rich Cathode Materials[J]. Acta Physico-Chimica Sinica, ;2022, 38(5): 200701. doi: 10.3866/PKU.WHXB202007017 shu

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: Lai Chen, chenlai144@sina.com Yuefeng Su, suyuefeng@bit.edu.cn

^†

Received Date: 6 July 2020
Revised Date: 7 August 2020
Accepted Date: 18 August 2020
Available Online: 24 August 2020
Fund Project: the National Key R & D Program of China 2016YFB0100301the National Natural Science Foundation of China 21875022the National Natural Science Foundation of China 51802020the National Natural Science Foundation of China U1664255the Science and Technology Innovation Foundation of Beijing Institute of Technology Chongqing Innovation Center 2020CX5100006the Beijing Institute of Technology Research Fund Program for Young Scholars, and the Young Elite Scientists Sponsorship Program by CAST 2018QNRC001

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%.
- Lithium ion battery,
- Nickle-rich cathode material,
- Cobalt free,
- Cycling stability
1. [1]
  Wang, 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 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 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 doi: 10.1002/smll.201805389
5. [5]
  Chen, 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 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 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 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 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 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 doi: 10.1002/anie.201409262
13. [13]
  Kou, 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 doi: 10.1039/C3EE42398K
15. [15]
  Wu, 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 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 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 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 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 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 doi: 10.1021/acs.jpclett.7b02498
22. [22]
  Whittingham, M. S. Chem. Rev. 2004, 104, 4271. doi: 10.1021/cr020731c 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 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 doi: 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 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 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 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 doi: 10.1016/j.jallcom.2018.11.189
29. [29]
  Cui, 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.
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 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 doi: 10.1016/j.electacta.2017.12.034
1. [1]
  Siyu Zhang , Kunhong Gu , Bing'an Lu , Junwei Han , Jiang Zhou . Hydrometallurgical Processes on Recycling of Spent Lithium-lon Battery Cathode: Advances and Applications in Sustainable Technologies. Acta Physico-Chimica Sinica, 2024, 40(10): 2309028-. doi: 10.3866/PKU.WHXB202309028
2. [2]
  Qi Li , Pingan Li , Zetong Liu , Jiahui Zhang , Hao Zhang , Weilai Yu , Xianluo Hu . Fabricating Micro/Nanostructured Separators and Electrode Materials by Coaxial Electrospinning for Lithium-Ion Batteries: From Fundamentals to Applications. Acta Physico-Chimica Sinica, 2024, 40(10): 2311030-. doi: 10.3866/PKU.WHXB202311030
3. [3]
  Qingtang ZHANG , Xiaoyu WU , Zheng WANG , Xiaomei WANG . Performance of nano Li₂FeSiO₄/C cathode material co-doped by potassium and chlorine ions. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1689-1696. doi: 10.11862/CJIC.20240115
4. [4]
  Hongyi LI , Aimin WU , Liuyang ZHAO , Xinpeng LIU , Fengqin CHEN , Aikui LI , Hao HUANG . Effect of Y(PO₃)₃ double-coating modification on the electrochemical properties of Li[Ni_0.8Co_0.15Al_0.05]O₂. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1320-1328. doi: 10.11862/CJIC.20230480
5. [5]
  Xinpeng LIU , Liuyang ZHAO , Hongyi LI , Yatu CHEN , Aimin WU , Aikui LI , Hao HUANG . Ga₂O₃ coated modification and electrochemical performance of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode material. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1105-1113. doi: 10.11862/CJIC.20230488
6. [6]
  Yuanchao LI , Weifeng HUANG , Pengchao LIANG , Zifang ZHAO , Baoyan XING , Dongliang YAN , Li YANG , Songlin WANG . Effect of heterogeneous dual carbon sources on electrochemical properties of LiMn_0.8Fe_0.2PO₄/C composites. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 751-760. doi: 10.11862/CJIC.20230252
7. [7]
  Yifeng Xu , Jiquan Liu , Bin Cui , Yan Li , Gang Xie , Ying Yang . “Xiao Li’s School Adventures: The Working Principles and Safety Risks of Lithium-ion Batteries”. University Chemistry, 2024, 39(9): 259-265. doi: 10.12461/PKU.DXHX202404009
8. [8]
  Junke LIU , Kungui ZHENG , Wenjing SUN , Gaoyang BAI , Guodong BAI , Zuwei YIN , Yao ZHOU , Juntao LI . Preparation of modified high-nickel layered cathode with LiAlO₂/cyclopolyacrylonitrile dual-functional coating. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1461-1473. doi: 10.11862/CJIC.20240189
9. [9]
  Zhihuan XU , Qing KANG , Yuzhen LONG , Qian YUAN , Cidong LIU , Xin LI , Genghuai TANG , Yuqing LIAO . Effect of graphene oxide concentration on the electrochemical properties of reduced graphene oxide/ZnS. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1329-1336. doi: 10.11862/CJIC.20230447
10. [10]
  Zhenming Xu , Mingbo Zheng , Zhenhui Liu , Duo Chen , Qingsheng Liu . Experimental Design of Project-Driven Teaching in Computational Materials Science: First-Principles Calculations of the LiFePO₄ Cathode Material for Lithium-Ion Batteries. University Chemistry, 2024, 39(4): 140-148. doi: 10.3866/PKU.DXHX202307022
11. [11]
  Doudou Qin , Junyang Ding , Chu Liang , Qian Liu , Ligang Feng , Yang Luo , Guangzhi Hu , Jun Luo , Xijun Liu . Addressing Challenges and Enhancing Performance of Manganese-based Cathode Materials in Aqueous Zinc-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(10): 2310034-. doi: 10.3866/PKU.WHXB202310034
12. [12]
  Guang Huang , Lei Li , Dingyi Zhang , Xingze Wang , Yugai Huang , Wenhui Liang , Zhifen Guo , Wenmei Jiao . Cobalt’s Valor, Nickel’s Foe: A Comprehensive Chemical Experiment Utilizing a Cobalt-based Imidazolate Framework for Nickel Ion Removal. University Chemistry, 2024, 39(8): 174-183. doi: 10.3866/PKU.DXHX202311051
13. [13]
  Jianbao Mei , Bei Li , Shu Zhang , Dongdong Xiao , Pu Hu , Geng Zhang . Enhanced Performance of Ternary NASICON-Type Na_3.5-xMn_0.5V_1.5-xZr_x(PO₄)₃/C Cathodes for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(12): 2407023-. doi: 10.3866/PKU.WHXB202407023
14. [14]
  Zhihong LUO , Yan SHI , Jinyu AN , Deyi ZHENG , Long LI , Quansheng OUYANG , Bin SHI , Jiaojing SHAO . Two-dimensional silica-modified polyethylene oxide solid polymer electrolyte to enhance the performance of lithium-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 1005-1014. doi: 10.11862/CJIC.20230444
15. [15]
  Qingyan JIANG , Yanyong SHA , Chen CHEN , Xiaojuan CHEN , Wenlong LIU , Hao HUANG , Hongjiang LIU , Qi LIU . Constructing a one-dimensional Cu-coordination polymer-based cathode material for Li-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 657-668. doi: 10.11862/CJIC.20240004
16. [16]
  Jie XIE , Hongnan XU , Jianfeng LIAO , Ruoyu CHEN , Lin SUN , Zhong JIN . Nitrogen-doped 3D graphene-carbon nanotube network for efficient lithium storage. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1840-1849. doi: 10.11862/CJIC.20240216
17. [17]
  Jiahong ZHENG , Jiajun SHEN , Xin BAI . Preparation and electrochemical properties of nickel foam loaded NiMoO₄/NiMoS₄ composites. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 581-590. doi: 10.11862/CJIC.20230253
18. [18]
  Qin ZHU , Jiao MA , Zhihui QIAN , Yuxu LUO , Yujiao GUO , Mingwu XIANG , Xiaofang LIU , Ping NING , Junming GUO . Morphological evolution and electrochemical properties of cathode material LiAl_0.08Mn_1.92O₄ single crystal particles. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1549-1562. doi: 10.11862/CJIC.20240022
19. [19]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
20. [20]
  Haihua Yang , Minjie Zhou , Binhong He , Wenyuan Xu , Bing Chen , Enxiang Liang . Synthesis and Electrocatalytic Performance of Iron Phosphide@Carbon Nanotubes as Cathode Material for Zinc-Air Battery: a Comprehensive Undergraduate Chemical Experiment. University Chemistry, 2024, 39(10): 426-432. doi: 10.12461/PKU.DXHX202405100

Get Citation

PDF

XML

Metrics

PDF Downloads(21)
Abstract views(1393)
HTML views(339)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142