Citation: Zu-Wei YIN, Jun-Tao LI, Ling HUANG, Feng PAN, Shi-Gang SUN. High-capacity Li-rich Mn-based Cathodes for Lithium-ion Batteries[J]. Chinese Journal of Structural Chemistry, ;2020, 39(1): 20-25. doi: 10.14102/j.cnki.0254-5861.2011-2718 shu

High-capacity Li-rich Mn-based Cathodes for Lithium-ion Batteries

Zu-Wei YIN ^{a, c} ,
Jun-Tao LI ^a ,
Ling HUANG ^b ,
Feng PAN ^c,, ,
Shi-Gang SUN ^{a, b,,}

a.
College of Energy, Xiamen University, Xiamen 361005, China
b.
State Key Lab of Physical Chemistry of Solid Surface, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
c.
School of Advanced Materials, Peking University, Shenzhen Graduate School, Shenzhen 518055, China

Corresponding author: Feng PAN, panfeng@puesz.edu.cn Shi-Gang SUN, sgsun@xmu.edu.cn
Received Date: 25 December 2019
Accepted Date: 26 December 2019

Fund Project: NSFC 21621091National Key Research and Development of China 2016YFB0100202Natural Science Foundation of Fujian Province 2015J01063National Materials Genome Project 2016YFB0700600National Key R & D Program of China 2016YFB0700600the Guangdong Innovation Team Project 2013N080Shenzhen Science and Technology Research JCYJ20151015162256516Shenzhen Science and Technology Research JCYJ20150729111733470Shenzhen Science and Technology Research JCYJ20160226105838578

Figures(2)

Layered Li-rich Mn-based oxides are promising cathode materials for Li-ion batteries due to their high capacity and high operation voltage. However, their commercial applications are hindered by irreversible capacity loss in the first charge-discharge process, voltage decay during cycling, inefficient cyclability and rate capability. Many attempts have been performed to solve such issues, including the mechanism study and strategies to improve the electrochemical performance. This article provides a brief review and future perspective on the main challenges of the high-capacity Li-rich Mn-based cathodes for Li-ion batteries.
- Li-ion batteries,
- Li-rich Mn-based cathodes,
- the first charge-discharge process,
- voltage decay,
- cyclability,
- rate capability
1. [1]
  Mohanty, D.; Li, J.; Abraham, D. P.; Huq, A.; Payzant, E. A.; Wood III, D. L.; Daniel, C. Unraveling the voltage-fade mechanism in high-energy-density lithium-ion batteries: origin of the tetrahedral cations for spinel conversion. Chem. Mater. 2014, 26, 6272–6280. doi: 10.1021/cm5031415
2. [2]
  Liu, C.; Neale, Z. G.; Cao, G. Understanding electrochemical potentials of cathode materials in rechargeable batteries. Mater. Today 2016, 19, 109–123. doi: 10.1016/j.mattod.2015.10.009
3. [3]
  Shunmugasundaram, R.; Senthil Arumugam, R.; Dahn, J. R. High capacity Li-rich positive electrode materials with reduced first-cycle irreversible capacity loss. Chem. Mater. 2015, 27, 757–767. doi: 10.1021/cm504583y
4. [4]
  Gu, M.; Belharouak, I.; Zheng, J.; Wu, H.; Xiao, J.; Genc, A.; Amine, A.; Thevuthasan, S.; Baer, D.; Zhang, J.; Browning, N. D.; Liu, J.; Wang, C. (2012). Formation of the spinel phase in the layered composite cathode used in Li-ion batteries. ACS Nano 2013, 7, 760–767. doi: 10.1021/nn305065u
5. [5]
  Liu, W.; Oh, P.; Liu, X.; Myeong, S.; Cho, W., Cho, J. Countering voltage decay and capacity fading of lithium-rich cathode material at 60 ℃ by hybrid surface protection layers. Adv. Energy Mater. 2015, 5, 1500274. doi: 10.1002/aenm.201500274
6. [6]
  Yu, X.; Lyu, Y.; Gu, L.; Wu, H.; Bak, S. M.; Zhou, Y.; Amine, K.; Ehrlich, S.; Li, H.; Nam, K.; Yang, X. Q. Understanding the rate capability of high-energy-density Li-rich layered Li_1.2Ni_0.15Co_0.1Mn_0.55O₂ cathode materials. Adv. Energy Mater. 2014, 4, 1300950. doi: 10.1002/aenm.201300950
7. [7]
  Seo, D. H.; Lee, J.; Urban, A.; Malik, R.; Kang, S.; Ceder, G. The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials. Nat. Chem. 2016, 8, 692–697. doi: 10.1038/nchem.2524
8. [8]
  Gent, W. E.; Lim, K.; Liang, Y.; Li, Q.; Barnes, T.; Ahn, S. J.; Chueh, W. Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides. Nat. Commun. 2017, 8, 2091. doi: 10.1038/s41467-017-02041-x
9. [9]
  Hy, S.; Felix, F.; Rick, J.; Su, W. N.; Hwang, B. J. Direct in situ observation of Li₂O evolution on Li-rich high-capacity cathode material, Li[Ni_xLi_(1-2x)/3Mn_(2-x)/3]O₂ (0≤x≤0.5). J. Am. Chem. Soc. 2014, 136, 999–1007. doi: 10.1021/ja410137s
10. [10]
  Li, X.; Qiao, Y.; Guo, S.; Xu, Z.; Zhu, H.; Zhang, X.; Yuan, Y.; He, P.; Ishida, M.; Zhou, H. Direct visualization of the reversible O²⁻/O⁻ redox process in Li-rich cathode materials. Adv. Mater. 2018, 30, 1705197. doi: 10.1002/adma.201705197
11. [11]
  Shen, C. H.; Wang, Q.; Fu, F.; Huang, L.; Lin, Z.; Shen, S. Y.; Su, H.; Zheng, X.; Xu, B.; Li, J. T.; Sun, S. G. Facile synthesis of the Li-rich layered oxide Li_1.23Ni_0.09Co_0.12Mn_0.56O₂ with superior lithium storage performance and new insights into structural transformation of the layered oxide material during charge–discharge cycle: in situ XRD characterization. ACS Appl. Mater. Inter. 2014, 6, 5516–5524. doi: 10.1021/am405844b
12. [12]
  Yin, Z. W.; Peng, X. X.; Li, J. T.; Shen, C. H.; Deng, Y. P.; Wu, Z. G.; Zhang, T.; Zhang, Q.; Mo, Y.; Wang, K.; Huang, L.; Zheng, H.; Sun, S. G. Revealing of the activation pathway and cathode electrolyte interphase evolution of Li-Rich 0.5Li₂MnO₃·0.5LiNi_0.3Co_0.3Mn_0.4O₂ cathode by in situ electrochemical quartz crystal microbalance. ACS Appl. Mater. Inter. 2019, 11, 16214–16222. doi: 10.1021/acsami.9b02236
13. [13]
  Shen, C. H.; Shen, S. Y.; Fu, F.; Shi, C. G.; Zhang, H. Y.; Pierre, M. J.; Su, H.; Wang, Q.; Xu, B.; Huang, L.; Li, J. T.; Sun. S. G. New insight into structural transformation in Li-rich layered oxide during the initial charging. J. Mater. Chem. A 2015, 3, 12220–12229. doi: 10.1039/C5TA01849H
14. [14]
  Shen, S.; Hong, Y.; Zhu, F.; Cao, Z.; Li, Y.; Ke, F.; Fan, J.; Zhou, L.; Wu, L.; Dai, P.; Cai, M.; Huang, L.; Zhou, Z.; Li, J.; Wu, Q.; Sun. S. G. Tuning electrochemical properties of Li-rich layered oxide cathodes by adjusting Co/Ni ratios and mechanism investigation using in situ X-ray diffraction and online continuous flow differential electrochemical mass spectrometry. ACS Appl. Mater. Inter. 2018, 10, 12666–12677. doi: 10.1021/acsami.8b00919
15. [15]
  Nayak, P. K.; Grinblat, J.; Levi, M.; Levi, E.; Kim, S.; Choi, J. W.; Aurbach, D. Al doping for mitigating the capacity fading and voltage decay of layered Li and Mn-rich cathodes for Li-Ion batteries. Adv. Energy Mater. 2016, 6, 1502398. doi: 10.1002/aenm.201502398
16. [16]
  Zheng, J.; Gu, M.; Genc, A.; Xiao, J.; Xu, P.; Chen, X.; Zhu, Z.; Zhao, W.; Pullan, L.; Wang, C.; Zhang, J. G. Mitigating voltage fade in cathode materials by improving the atomic level uniformity of elemental distribution. Nano Lett. 2014, 14, 2628–2635 doi: 10.1021/nl500486y
17. [17]
  Bloom, I.; Trahey, L.; Abouimrane, A.; Belharouak, I.; Zhang, X.; Wu, Q.; Lu, W.; Abraham, D.; Bettge, M.; Elam, J.; Meng, X.; Burrell, A.; Ban, C.; Tenent, R.; Nanda, J.; Dudney, N. Effect of interface modifications on voltage fade in 0.5Li₂MnO₃·0.5LiNi_0.375Mn_0.375Co_0.25O₂ cathode materials. J. Power Sources 2014, 249, 509–514. doi: 10.1016/j.jpowsour.2013.10.035
18. [18]
  Zheng, F.; Yang, C.; Xiong, X.; Xiong, J.; Hu, R.; Chen, Y.; Liu, M. Nanoscale surface modification of lithium-rich layered-oxide composite cathodes for suppressing voltage fade. Angew. Chem. Int. Edit. 2015, 54, 13058–13062. doi: 10.1002/anie.201506408
19. [19]
  Zhang, T.; Li, J. T.; Liu, J.; Deng, Y. P.; Wu, Z. G.; Yin, Z. W.; Guo, D.; Huang, L.; Sun, S. G. Suppressing the voltage-fading of layered lithium-rich cathode materials via an aqueous binder for Li-ion batteries. Chem. Commun. 2016, 52, 4683–4686. doi: 10.1039/C5CC10534J
20. [20]
  Hu, S.; Pillai, A. S.; Liang, G.; Pang, W. K.; Wang, H.; Li, Q.; Guo, Z. Li-rich layered oxides and their practical challenges: recent progress and perspectives. Electrochem. Energy Rev. 2019, 1–35.
21. [21]
  Wei, G. Z.; Lu, X.; Ke, F. S.; Huang, L.; Li, J. T.; Wang, Z. X.; Zhou, Z. Y.; Sun, S. G. Crystal habit-tuned nanoplate material of Li[Li_1/3-2x/3Ni_xMn_2/3-x/3]O₂ for high-rate performance lithium-ion batteries. Adv. Mater. 2010, 22, 4364–4367. doi: 10.1002/adma.201001578
22. [22]
  Fu, F.; Deng, Y. P.; Shen, C. H.; Xu, G. L.; Peng, X. X.; Wang, Q.; Xu, Y.; Fang, J.; Huang, L.; Sun, S. G. A hierarchical micro/nanostructured 0.5Li₂MnO₃·0.5LiMn_0.4Ni_0.3Co_0.3O₂ material synthesized by solvothermal route as high rate cathode of lithium ion battery. Electrochem. Commun. 2014, 44, 54–58. doi: 10.1016/j.elecom.2014.04.013
23. [23]
  Fu, F.; Yao, Y.; Wang, H.; Xu, G. L.; Amine, K.; Sun, S. G.; Shao, M. Structure dependent electrochemical performance of Li-rich layered oxides in lithium-ion batteries. Nano Energy 2017, 35, 370–378. doi: 10.1016/j.nanoen.2017.04.005
24. [24]
  Deng, Y. P.; Fu, F.; Wu, Z. G.; Yin, Z. W.; Zhang, T.; Li, J. T.; Huang, L.; Sun, S. G.; Layered/spinel heterostructured Li-rich materials synthesized by a one-step solvothermal strategy with enhanced electrochemical performance for Li-ion batteries. J. Mater. Chem. A 2016, 4, 257–263. doi: 10.1039/C5TA06945A
25. [25]
  Yin, Z. W.; Wu, Z. G.; Deng, Y. P.; Zhang, T.; Su, H.; Fang, J. C.; Xu, B.; Wang, J.; Li, J. T.; Huang, L.; Zhou, X.; Sun, S. G. A synergistic effect in a composite cathode consisting of spinel and layered structures to increase the electrochemical performance for Li-ion batteries. J. Phys. Chem. C 2016, 120, 25647–25656. doi: 10.1021/acs.jpcc.6b07169
26. [26]
  Huang, W.; Xing, L.; Wang, Y.; Xu, M.; Li, W.; Xie, F.; Xia, S. 4-(Trifluoromethyl)-benzonitrile: a novel electrolyte additive for lithium nickel manganese oxide cathode of high voltage lithium ion battery. J. Power Sources 2014, 267, 560–565. doi: 10.1016/j.jpowsour.2014.05.124
27. [27]
  Li, J.; Zhang, L.; Yu, L.; Fan, W.; Wang, Z.; Yang, X.; Lin, Y.; Xing, L.; Xu, M.; Li, W. Understanding interfacial properties between Li-rich layered oxide and electrolyte containing triethyl borate. J. Phys. Chem. C 2016, 120, 26899–26907. doi: 10.1021/acs.jpcc.6b09097
28. [28]
  Kong, D.; Hu, J.; Chen, Z.; Song, K.; Li, C.; Weng, M.; Li, M.; Wang, R.; Liu, T.; Liu, J.; Zhang, M.; Xiao, Y.; Pan, F. Ti-Gradient doping to stabilize layered surface structure for high performance high-Ni oxide cathode of Li-ion battery. Adv. Energy Mater. 2019, 1901756.
29. [29]
  Zheng, J.; Ye, Y.; Liu, T.; Xiao, Y.; Wang, C.; Wang, F.; Pan, F. Ni/Li disordering in layered transition metal oxide: electrochemical impact, origin, and control. Accounts Chem. Res. 2019, 52, 2201–2209. doi: 10.1021/acs.accounts.9b00033
30. [30]
  Luo, K.; Roberts, M. R.; Hao, R.; Guerrini, N.; Pickup, D. M.; Liu, Y. S.; Edstrom, K.; Guo, J.; Chadwick, A. V.; Duda, L. C.; Bruce, P. G. Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen. Nat. Chem. 2016, 8, 684–691. doi: 10.1038/nchem.2471
31. [31]
  Armstrong, A. R.; Holzapfel, M.; Novák, P.; Johnson, C. S.; Kang, S. H.; Thackeray, M. M.; Bruce, P. G. Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni_0.2Li_0.2Mn_0.6]O₂. J. Am. Chem. Soc. 2006, 128, 8694–8698. doi: 10.1021/ja062027+
1. [1]
  Yue Wang , Caixia Xu , Xingtao Tian , Siyu Wang , Yan Zhao . Challenges and Modification Strategies of High-Voltage Cathode Materials for Li-ion Batteries. Chinese Journal of Structural Chemistry, 2023, 42(10): 100167-100167. doi: 10.1016/j.cjsc.2023.100167
2. [2]
  Xinpin Pan , Yongjian Cui , Zhe Wang , Bowen Li , Hailong Wang , Jian Hao , Feng Li , Jing Li . Robust chemo-mechanical stability of additives-free SiO₂ anode realized by honeycomb nanolattice for high performance Li-ion batteries. Chinese Chemical Letters, 2024, 35(10): 109567-. doi: 10.1016/j.cclet.2024.109567
3. [3]
  Yaping Wang , Pengcheng Yuan , Zeyuan Xu , Xiong-Xiong Liu , Shengfa Feng , Mufan Cao , Chen Cao , Xiaoqiang Wang , Long Pan , Zheng-Ming Sun . Ti₃C₂T_x MXene in-situ transformed Li₂TiO₃ interface layer enabling 4.5 V-LiCoO₂/sulfide all-solid-state lithium batteries with superior rate capability and cyclability. Chinese Chemical Letters, 2024, 35(6): 108776-. doi: 10.1016/j.cclet.2023.108776
4. [4]
  Yongjian Li , Xinyu Zhu , Chenxi Wei , Youyou Fang , Xinyu Wang , Yizhi Zhai , Wenlong Kang , Lai Chen , Duanyun Cao , Meng Wang , Yun Lu , Qing Huang , Yuefeng Su , Hong Yuan , Ning Li , Feng Wu . Unraveling the chemical and structural evolution of novel Li-rich layered/rocksalt intergrown cathode for Li-ion batteries. Chinese Chemical Letters, 2024, 35(12): 109536-. doi: 10.1016/j.cclet.2024.109536
5. [5]
  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
6. [6]
  Yue Zheng , Tianpeng Huang , Pengxian Han , Jun Ma , Guanglei Cui . Cathodal Li-ion interfacial transport in sulfide-based all-solid-state batteries: Challenges and improvement strategies. Chinese Journal of Structural Chemistry, 2024, 43(10): 100390-100390. doi: 10.1016/j.cjsc.2024.100390
7. [7]
  Yue Qian , Zhoujia Liu , Haixin Song , Ruize Yin , Hanni Yang , Siyang Li , Weiwei Xiong , Saisai Yuan , Junhao Zhang , Huan Pang . Imide-based covalent organic framework with excellent cyclability as an anode material for lithium-ion battery. Chinese Chemical Letters, 2024, 35(6): 108785-. doi: 10.1016/j.cclet.2023.108785
8. [8]
  Long Li , Kang Yang , Chenpeng Xi , Mengchao Li , Borong Li , Gui Xu , Yuanbin Xiao , Xiancai Cui , Zhiliang Liu , Lingyun Li , Yan Yu , Chengkai Yang . Highly-chlorinated inert and robust interphase without mineralization of oxide enhancing high-rate Li metal batteries. Chinese Chemical Letters, 2024, 35(6): 108814-. doi: 10.1016/j.cclet.2023.108814
9. [9]
  Hengyi ZHU , Liyun JU , Haoyue ZHANG , Jiaxin DU , Yutong XIE , Li SONG , Yachao JIN , Mingdao ZHANG . Efficient regeneration of waste LiNi_0.5Co_0.2Mn_0.3O₂ cathode toward high-performance Li-ion battery. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 625-638. doi: 10.11862/CJIC.20240358
10. [10]
  Bin Feng , Tao Long , Ruotong Li , Yuan-Li Ding . Rationally constructing metallic Sn-ZnO heterostructure via in-situ Mn doping for high-rate Na-ion batteries. Chinese Chemical Letters, 2025, 36(2): 110273-. doi: 10.1016/j.cclet.2024.110273
11. [11]
  Shengyu Zhao , Xuan Yu , Yufeng Zhao . A water-stable high-voltage P3-type cathode for sodium-ion batteries. Chinese Chemical Letters, 2024, 35(9): 109933-. doi: 10.1016/j.cclet.2024.109933
12. [12]
  Lingjiang Kou , Yong Wang , Jiajia Song , Taotao Ai , Wenhu Li , Mohammad Yeganeh Ghotbi , Panya Wattanapaphawong , Koji Kajiyoshi . Mini review: Strategies for enhancing stability of high-voltage cathode materials in aqueous zinc-ion batteries. Chinese Chemical Letters, 2025, 36(1): 110368-. doi: 10.1016/j.cclet.2024.110368
13. [13]
  Xi Tang , Chunlei Zhu , Yulu Yang , Shihan Qi , Mengqiu Cai , Abdullah N. Alodhayb , Jianmin Ma . Additive regulating Li⁺ solvation structure to construct dual LiF−rich electrode electrolyte interphases for sustaining 4.6 V Li||LiCoO₂ batteries. Chinese Chemical Letters, 2024, 35(12): 110014-. doi: 10.1016/j.cclet.2024.110014
14. [14]
  Mei-Chen Liu , Qing-Song Liu , Yi-Zhou Quan , Jia-Ling Yu , Gang Wu , Xiu-Li Wang , Yu-Zhong Wang . Phosphorus-silicon-integrated electrolyte additive boosts cycling performance and safety of high-voltage lithium-ion batteries. Chinese Chemical Letters, 2024, 35(8): 109123-. doi: 10.1016/j.cclet.2023.109123
15. [15]
  Xuejie Gao , Xinyang Chen , Ming Jiang , Hanyan Wu , Wenfeng Ren , Xiaofei Yang , Runcang Sun . Long-lifespan thin Li anode achieved by dead Li rejuvenation and Li dendrite suppression for all-solid-state lithium batteries. Chinese Chemical Letters, 2024, 35(10): 109448-. doi: 10.1016/j.cclet.2023.109448
16. [16]
  Renshu Huang , Jinli Chen , Xingfa Chen , Tianqi Yu , Huyi Yu , Kaien Li , Bin Li , Shibin Yin . Synergized oxygen vacancies with Mn2O3@CeO2 heterojunction as high current density catalysts for Li–O2 batteries. Chinese Journal of Structural Chemistry, 2023, 42(11): 100171-100171. doi: 10.1016/j.cjsc.2023.100171
17. [17]
  Tianyi Hou , Yunhui Huang , Henghui Xu . Interfacial engineering for advanced solid-state Li-metal batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100313-100313. doi: 10.1016/j.cjsc.2024.100313
18. [18]
  Benjian Xin , Rui Wang , Lili Liu , Zhiqiang Niu . Metal-organic framework derived MnO@C/CNTs composite for high-rate lithium-based semi-solid flow batteries. Chinese Journal of Structural Chemistry, 2023, 42(11): 100116-100116. doi: 10.1016/j.cjsc.2023.100116
19. [19]
  Tao Long , Peng Chen , Bin Feng , Caili Yang , Kairong Wang , Yulei Wang , Can Chen , Yaping Wang , Ruotong Li , Meng Wu , Minhuan Lan , Wei Kong Pang , Jian-Fang Wu , Yuan-Li Ding . Reinforced concrete-like Na_3.5V_1.5Mn_0.5(PO₄)₃@graphene hybrids with hierarchical porosity as durable and high-rate sodium-ion battery cathode. Chinese Chemical Letters, 2024, 35(4): 109267-. doi: 10.1016/j.cclet.2023.109267
20. [20]
  Zhenqiang Guo , Huicong Yang , Qian Wei , Shengjun Xu , Guangjian Hu , Shuo Bai , Feng Li . Dual-additives enable stable electrode-electrolyte interfaces for long life Li-SPAN batteries. Chinese Chemical Letters, 2024, 35(5): 108622-. doi: 10.1016/j.cclet.2023.108622

Get Citation

PDF

XML

Metrics

PDF Downloads(15)
Abstract views(734)
HTML views(98)

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