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Nano Research 2022, 15(10): 9038-9046 https://doi.org/10.1007/s12274-022-4889-0
Research Article | Issue | Published: 19 August 2022

Unveiling the impact of residual Li conversion and cation ordering on electrochemical performance of Co-free Ni-rich cathodes

Show Author's Information Chu Wang1,  Lei Tan2,  Hongling Yi1,  Zixiang Zhao1,  Xiaoli Yi3,  Youyuan Zhou4,  Junchao Zheng3,  Jiexi Wang3,  Lingjun Li1( )
School of Materials Science and Engineering, Changsha University of Science and Technology, Changsha 410114, China
School of Energy and Power Engineering, Changsha University of Science and Technology, Changsha 410114, China
School of Metallurgy and Environment, Central South University, Changsha 410083, China
Hunan Changyuan Lico Co., Ltd., Changsha 410205, China
Keywords:
Li-ion batteries, Co-free Ni-rich cathodes, residual Li conversion, cation ordering
Topics:
Lithium batteries
Cite this article:
Wang C, Tan L, Yi H, et al. Unveiling the impact of residual Li conversion and cation ordering on electrochemical performance of Co-free Ni-rich cathodes. Nano Research, 2022, 15(10): 9038-9046. https://doi.org/10.1007/s12274-022-4889-0
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Abstract Full text Electronic supplementary material About this article

The residual Li and Li+/Ni2+ cation mixing play essential roles in the electrochemical properties of Ni-rich cathodes. However, a general relationship between the residual Li conversion, cation mixing, and their effects on the Li+ kinetics and structural stability has yet to be established, due to the presence of cobalt in the cathode. Here, we explore the synergistic impact of the residual Li conversion and cation ordering on a Co-free Ni-rich cathode (i.e., LiNi0.95Mn0.05O2). It discloses that the rate capability is mainly affected by residual Li contents and operating voltage. Specifically, residual Li can be electrochemically converted to cathode electrolyte interphase (CEI) below 4.3 V, thus inducing high interphase resistance, and decomposes to produce CO2-dominated gas at 4.5 V, causing temporary enhancement of Li+ diffusivity but severe surface degradation during cycling. Moreover, the cycling performance of Co-free Ni-rich cathode is not only determined by Li+/Ni2+ cation-ordered superlattice, which enhances the structural stability as it functions as the pillar to impede lattice collapse at a highly charged state, but also by the robust CEI layers which protect the bulk from electrolyte attack under 4.3 V. These findings promote an in-depth understanding of residual Li conversion and Li+/Ni2+ cation ordering on Co-free Ni-rich cathode.


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Electronic supplementary material
About this article

Unveiling the impact of residual Li conversion and cation ordering on electrochemical performance of Co-free Ni-rich cathodes

Show Author's information Chu Wang1, Lei Tan2, Hongling Yi1, Zixiang Zhao1, Xiaoli Yi3, Youyuan Zhou4, Junchao Zheng3, Jiexi Wang3, Lingjun Li1( )
School of Materials Science and Engineering, Changsha University of Science and Technology, Changsha 410114, China
School of Energy and Power Engineering, Changsha University of Science and Technology, Changsha 410114, China
School of Metallurgy and Environment, Central South University, Changsha 410083, China
Hunan Changyuan Lico Co., Ltd., Changsha 410205, China

Abstract

The residual Li and Li+/Ni2+ cation mixing play essential roles in the electrochemical properties of Ni-rich cathodes. However, a general relationship between the residual Li conversion, cation mixing, and their effects on the Li+ kinetics and structural stability has yet to be established, due to the presence of cobalt in the cathode. Here, we explore the synergistic impact of the residual Li conversion and cation ordering on a Co-free Ni-rich cathode (i.e., LiNi0.95Mn0.05O2). It discloses that the rate capability is mainly affected by residual Li contents and operating voltage. Specifically, residual Li can be electrochemically converted to cathode electrolyte interphase (CEI) below 4.3 V, thus inducing high interphase resistance, and decomposes to produce CO2-dominated gas at 4.5 V, causing temporary enhancement of Li+ diffusivity but severe surface degradation during cycling. Moreover, the cycling performance of Co-free Ni-rich cathode is not only determined by Li+/Ni2+ cation-ordered superlattice, which enhances the structural stability as it functions as the pillar to impede lattice collapse at a highly charged state, but also by the robust CEI layers which protect the bulk from electrolyte attack under 4.3 V. These findings promote an in-depth understanding of residual Li conversion and Li+/Ni2+ cation ordering on Co-free Ni-rich cathode.

Keywords: Li-ion batteries, Co-free Ni-rich cathodes, residual Li conversion, cation ordering

References(39)

1

Luo, D.; Fan, J. M.; Yao, Z.; Xie, H. X.; Cui, J. X.; Yang, Y. J.; Ding, X. K.; Ji, J. P.; Wu, S. X.; Ling, M. et al. An almost full reversible lithium-rich cathode: Revealing the mechanism of high initial coulombic efficiency. J. Energy Chem. 2021, 62, 120–126.
DOI Google Scholar
2

Zou, Y. G.; Mao, H. C.; Meng, X. H.; Du, Y. H.; Sheng, H.; Yu, X. Q.; Shi, J. L.; Guo, Y. G. Mitigating the kinetic hindrance of single-crystalline Ni-rich cathode via surface gradient penetration of tantalum. Angew. Chem., Int. Ed. 2021, 60, 26535–26539.
DOI Google Scholar
3

Liu, Y. C.; Chen, Y. F.; Wang, J.; Wang, W.; Ding, Z. Y.; Li, L. Y.; Zhang, Y.; Deng, Y. D.; Wu, J. W.; Chen, Y. N. Hierarchical yolk–shell structured Li-rich cathode boosting cycling and voltage stabled LIBs. Nano Res. 2022, 15, 3178–3186.
DOI Google Scholar
4

Nam, G. W.; Park, N. Y.; Park, K. J.; Yang, J. H.; Liu, J.; Yoon, C. S.; Sun, Y. K. Capacity fading of Ni-rich NCA cathodes: Effect of microcracking extent. ACS Energy Lett. 2019, 4, 2995–3001.
DOI Google Scholar
5

You, B. Z.; Wang, Z. X.; Shen, F.; Chang, Y. J.; Peng, W. J.; Li, X. H.; Guo, H. J.; Hu, Q. Y.; Deng, C. W.; Yang, S. et al. Research progress of single-crystal nickel-rich cathode materials for lithium ion batteries. Small Methods 2021, 5, 2100234.
DOI Google Scholar
6

Du, Y. H.; Sheng, H.; Meng, X. H.; Zhang, X. D.; Zou, Y. G.; Liang, J. Y.; Fan, M.; Wang, F. Y.; Tang, J. L.; Cao, F. F. et al. Chemically converting residual lithium to a composite coating layer to enhance the rate capability and stability of single-crystalline Ni-rich cathodes. Nano Energy 2022, 94, 106901.
DOI Google Scholar
7

Wu, F.; Liu, N.; Chen, L.; Li, N.; Dong, J. Y.; Lu, Y.; Tan, G. Q.; Xu, M. Z.; Cao, D. Y.; Liu, Y. F. et al. The nature of irreversible phase transformation propagation in nickel-rich layered cathode for lithium-ion batteries. J. Energy Chem. 2021, 62, 351–358.
DOI Google Scholar
8

Zou, Y. H.; Yang, X. F.; Lv, C. X.; Liu, T. C.; Xia, Y. Z.; Shang, L.; Waterhouse, G. I. N.; Yang, D. J.; Zhang, T. R. Multishelled Ni-rich Li(NixCoyMnz)O2 hollow fibers with low cation mixing as high-performance cathode materials for Li-ion batteries. Adv. Sci. 2017, 4, 1600262.
DOI Google Scholar
9

Liu, W.; Oh, P.; Liu, X. E.; Lee, M. J.; Cho, W.; Chae, S.; Kim, Y.; Cho, J. Nickel-rich layered lithium transition-metal oxide for high-energy lithium-ion batteries. Angew. Chem., Int. Ed. 2015, 54, 4440–4457.
DOI Google Scholar
10

Kim, U. H.; Park, G. T.; Son, B. K.; Nam, G. W.; Liu, J.; Kuo, L. Y.; Kaghazchi, P.; Yoon, C. S.; Sun, Y. K. Heuristic solution for achieving long-term cycle stability for Ni-rich layered cathodes at full depth of discharge. Nat. Energy 2020, 5, 860–869.
DOI Google Scholar
11

Li, M.; Lu, J. Cobalt in lithium-ion batteries: Replacements are sought for cobalt, a costly element used in lithium-ion battery cathodes. Science 2020, 367, 979–980.
DOI Google Scholar
12

Choi, J. U.; Voronina, N.; Sun, Y. K.; Myung, S. T. Recent progress and perspective of advanced high-energy Co-less Ni-rich cathodes for Li-ion batteries: Yesterday, today, and tomorrow. Adv. Energy Mater. 2020, 10, 2002027.
DOI Google Scholar
13

Liu, T. C.; Yu, L.; Liu, J. J.; Lu, J.; Bi, X. X.; Dai, A.; Li, M.; Li, M. F.; Hu, Z. X.; Ma, L. et al. Understanding Co roles towards developing Co-free Ni-rich cathodes for rechargeable batteries. Nat. Energy 2021, 6, 277–286.
DOI Google Scholar
14

Cho, D. H.; Jo, C. H.; Cho, W.; Kim, Y. J.; Yashiro, H.; Sun, Y. K.; Myung, S. T. Effect of residual lithium compounds on layer Ni-rich Li[Ni0.7Mn0.3]O2. J. Electrochem. Soc. 2014, 161, A920–A926.
DOI Google Scholar
15

Zhang, S. S. Problems and their origins of Ni-rich layered oxide cathode materials. Energy Storage Mater. 2020, 24, 247–254.
DOI Google Scholar
16

Seong, W. M.; Cho, K. H.; Park, J. W.; Park, H.; Eum, D.; Lee, M. H.; Kim, I. S. S.; Lim, J.; Kang, K. Controlling residual lithium in high-nickel (> 90 %) lithium layered oxides for cathodes in lithium-ion batteries. Angew. Chem., Int. Ed. 2020, 59, 18662–18669.
DOI Google Scholar
17

Xu, G. L.; Liu, X.; Daali, A.; Amine, R.; Chen, Z. H.; Amine, K. Challenges and strategies to advance high-energy nickel-rich layered lithium transition metal oxide cathodes for harsh operation. Adv. Funct. Mater. 2020, 30, 2004748.
DOI Google Scholar
18

Zhang, J. T.; Tan, X. H.; Guo, L. M.; Jiang, Y.; Liu, S. N.; Wang, H. F.; Kang, X. H.; Chu, W. G. Controllable formation of lithium carbonate surface phase during synthesis of nickel-rich LiNi0.9Mn0.1O2 in air and its protection role in electrochemical reaction. J. Alloys Compd. 2019, 771, 42–50.
DOI Google Scholar
19

Li, L. J.; Chen, J. X.; Huang, H.; Tan, L.; Song, L. B.; Wu, H. H.; Wang, C.; Zhao, Z. X.; Yi, H. L.; Duan, J. F. et al. Role of residual Li and oxygen vacancies in Ni-rich cathode materials. ACS Appl. Mater. Interfaces 2021, 13, 42554–42563.
DOI Google Scholar
20

Li, L. J.; Fu, L. Z.; Li, M.; Wang, C.; Zhao, Z. X.; Xie, S. C.; Lin, H. C.; Wu, X. W.; Liu, H. D.; Zhang, L. et al. B-doped and La4NiLiO8-coated Ni-rich cathode with enhanced structural and interfacial stability for lithium-ion batteries. J. Energy Chem. 2022, 71, 588–594.
DOI Google Scholar
21

Ryu, H. H.; Park, N. Y.; Yoon, D. R.; Kim, U. H.; Yoon, C. S.; Sun, Y. K. New class of Ni-rich cathode materials Li[NixCoyB1−x−y]O2 for next lithium batteries. Adv. Energy Mater. 2020, 10, 2000495.
DOI Google Scholar
22

Wang, D. W.; Kou, R. H.; Ren, Y.; Sun, C. J.; Zhao, H.; Zhang, M. J.; Li, Y.; Huq, A.; Ko, J. Y. P.; Pan, F. et al. Synthetic control of kinetic reaction pathway and cationic ordering in high-Ni layered oxide cathodes. Adv. Mater. 2017, 29, 1606715.
DOI Google Scholar
23

Wang, S. N.; Hua, W. B.; Missyul, A.; Darma, M. S. D.; Tayal, A.; Indris, S.; Ehrenberg, H.; Liu, L. J.; Knapp, M. Kinetic control of long-range cationic ordering in the synthesis of layered Ni-rich oxides. Adv. Funct. Mater. 2021, 31, 2009949.
DOI Google Scholar
24

Seong, W. M.; Kim, Y.; Manthiram, A. Impact of residual lithium on the adoption of high-nickel layered oxide cathodes for lithium-ion batteries. Chem. Mater. 2020, 32, 9479–9489.
DOI Google Scholar
25

Kim, Y.; Park, H.; Warner, J. H.; Manthiram, A. Unraveling the intricacies of residual lithium in high-Ni cathodes for lithium-ion batteries. ACS Energy Lett. 2021, 6, 941–948.
DOI Google Scholar
26

Yang, H. P.; Wu, H. H.; Ge, M. Y.; Li, L. J.; Yuan, Y. F.; Yao, Q.; Chen, J.; Xia, L. F.; Zheng, J. M.; Chen, Z. Y. et al. Simultaneously dual modification of Ni-rich layered oxide cathode for high-energy lithium-ion batteries. Adv. Funct. Mater. 2019, 29, 1808825.
DOI Google Scholar
27

Ke, C. Z.; Liu, F.; Zheng, Z. M.; Zhang, H. H.; Cai, M. T.; Li, M.; Yan, Q. Z.; Chen, H. X.; Zhang, Q. B. Boosting lithium storage performance of Si nanoparticles via thin carbon and nitrogen/phosphorus co-doped two-dimensional carbon sheet dual encapsulation. Rare Met. 2021, 40, 1347–1356.
DOI Google Scholar
28

Liu, Y.; Tang, L. B.; Wei, H. X.; Zhang, X. H.; He, Z. J.; Li, Y. J.; Zheng, J. C. Enhancement on structural stability of Ni-rich cathode materials by in-situ fabricating dual-modified layer for lithium-ion batteries. Nano Energy 2019, 65, 104043.
DOI Google Scholar
29

Fan, X. M.; Ou, X.; Zhao, W. G.; Liu, Y.; Zhang, B.; Zhang, J. F.; Zou, L. F.; Seidl, L.; Li, Y. Z.; Hu, G. R. et al. In situ inorganic conductive network formation in high-voltage single-crystal Ni-rich cathodes. Nat. Commun. 2021, 12, 5320.
DOI Google Scholar
30

Feng, X. Y.; Wu, H. H.; Gao, B.; Świętosławski, M.; He, X.; Zhang, Q. B. Lithiophilic N-doped carbon bowls induced Li deposition in layered graphene film for advanced lithium metal batteries. Nano Res. 2022, 15, 352–360.
DOI Google Scholar
31

Cai, M. T.; Zhang, H. H.; Zhang, Y. G.; Xiao, B. S.; Wang, L.; Li, M.; Wu, Y.; Sa, B. S.; Liao, H. G.; Zhang, L. et al. Boosting the potassium-ion storage performance enabled by engineering of hierarchical MoSSe nanosheets modified with carbon on porous carbon sphere. Sci. Bull. 2022, 67, 933–945.
DOI Google Scholar
32

Sheng, H.; Meng, X. H.; Xiao, D. D.; Fan, M.; Chen, W. P.; Wan, J.; Tang, J. L.; Zou, Y. G.; Wang, F. Y.; Wen, R. et al. An air-stable high-nickel cathode with reinforced electrochemical performance enabled by convertible amorphous Li2CO3 modification. Adv. Mater. 2022, 34, 2108947.
DOI Google Scholar
33

Liu, W.; Li, J. X.; Li, W. T.; Xu, H. Y.; Zhang, C.; Qiu, X. P. Inhibition of transition metals dissolution in cobalt-free cathode with ultrathin robust interphase in concentrated electrolyte. Nat. Commun. 2020, 11, 3629.
DOI Google Scholar
34

Heenan, T. M. M.; Wade, A.; Tan, C.; Parker, J. E.; Matras, D.; Leach, A. S.; Robinson, J. B.; Llewellyn, A.; Dimitrijevic, A.; Jervis, R. et al. Identifying the origins of microstructural defects such as cracking within Ni-rich NMC811 cathode particles for lithium-ion batteries. Adv. Energy Mater. 2020, 10, 2002655.
DOI Google Scholar
35

Sun, H. H.; Manthiram, A. Impact of microcrack generation and surface degradation on a nickel-rich layered Li[Ni0.9Co0. 05Mn0.05]O2 cathode for lithium-ion batteries. Chem. Mater. 2017, 29, 8486–8493.
DOI Google Scholar
36

Li, H. Y.; Liu, A.; Zhang, N.; Wang, Y. Q.; Yin, S.; Wu, H. H.; Dahn, J. R. An unavoidable challenge for Ni-rich positive electrode materials for lithium-ion batteries. Chem. Mater. 2019, 31, 7574–7583.
DOI Google Scholar
37

Aishova, A.; Park, G. T.; Yoon, C. S.; Sun, Y. K. Cobalt-free high-capacity Ni-rich layered Li[Ni0.9Mn0.1]O2 cathode. Adv. Energy Mater. 2020, 10, 1903179.
DOI Google Scholar
38

Kim, U. H.; Park, G. T.; Conlin, P.; Ashburn, N.; Cho, K.; Yu, Y. S.; Shapiro, D. A.; Maglia, F.; Kim, S. J.; Lamp, P. et al. Cation ordered Ni-rich layered cathode for ultra-long battery life. Energy Environ. Sci. 2021, 14, 1573–1583.
DOI Google Scholar
39

Yoon, C. S.; Choi, M. J.; Jun, D. W.; Zhang, Q.; Kaghazchi, P.; Kim, K. H.; Sun, Y. K. Cation ordering of Zr-doped LiNiO2 cathode for lithium-ion batteries. Chem. Mater. 2018, 30, 1808–1814.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 02 May 2022
Revised: 03 July 2022
Accepted: 09 August 2022
Published: 19 August 2022
Issue date: October 2022

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgement

This work was financially supported by the National Natural Science Foundation of China (No. 51774051), the Science and Technology Planning Project of Hunan Province (No. 2019RS2034), the Hunan High-tech Industry Science and Technology Innovation Leading Plan (No. 2020GK2072), and the Changsha City Fund for Distinguished and Innovative Young Scholars (No. KQ1707014).

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