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Nano Research 2023, 16(5): 6771-6779 https://doi.org/10.1007/s12274-022-4768-6
Research Article | Issue | Published: 20 August 2022

In-situ construction of a thermodynamically stabilized interface on the surface of single crystalline Ni-rich cathode materials via a one-step molten-salt route

Show Author's Information Huiya Yang,  Xiangbang Kong,  Jiyang Li,  Pengpeng Dai,  Jing Zeng,  Yang Yang( ),  Jinbao Zhao( )
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Centre of Chemistry for Energy Materials, State-Province Joint Engineering Laboratory of Power Source Technology for New Energy Vehicle, Engineering Research Center of Electrochemical Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
Keywords:
lithium-ion battery, cathode, single crystalline, LiNixCoyMn1−x−yO2, polycrystalline
Topics:
Lithium batteries
Cite this article:
Yang H, Kong X, Li J, et al. In-situ construction of a thermodynamically stabilized interface on the surface of single crystalline Ni-rich cathode materials via a one-step molten-salt route. Nano Research, 2023, 16(5): 6771-6779. https://doi.org/10.1007/s12274-022-4768-6
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Abstract Full text Electronic supplementary material About this article

Nickel rich LiNixCoyMn1−x−yO2 cathode materials have been studied extensively to increase the energy density of lithium-ion batteries (LIBs) due to their advantages of high capacity and low cost. However, the anisotropic crystal expansion and contraction inside the secondary particles would cause detrimental micro-cracks and severe parasitic reactions at the electrode/electrolyte interface during cycling, which severely decreases the stability of crystalline structure and cathode-electrolyte interphase and ultimately affects the calendar life of batteries. Herein, a thermodynamically stabilized interface is constructed on the surface of single-crystalline Ni-rich cathode materials (SC811@RS) via a facile molten-salt route to suppress the generation of microcracks and interfacial parasitic side reactions simultaneously. Density functional theory calculations show that the formation energy of interface layer (−1.958 eV) is more negative than that of bulk layered structure (−1.421 eV). Such a thermodynamically stable protective layer can not only prevent the direct contact between highly reactive LiNixCoyMn1−x−yO2 and electrolyte, but also mitigate deformation of structure caused by stress thus strengthening the mechanical properties. Raman spectra further confirm the excellent structural reversibility and reaction homogeneity of SC811@RS at particle, electrode, and time scales. Consequently, SC811@RS cathode material delivers significantly improved cycling stability (high capacity retention of 92% after 200 cycles at 0.5 C) compared with polycrystalline LiNi0.8Co0.1Mn0.1O2 (82%).


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About this article

In-situ construction of a thermodynamically stabilized interface on the surface of single crystalline Ni-rich cathode materials via a one-step molten-salt route

Show Author's information Huiya Yang, Xiangbang Kong, Jiyang Li, Pengpeng Dai, Jing Zeng, Yang Yang( ), Jinbao Zhao( )
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Centre of Chemistry for Energy Materials, State-Province Joint Engineering Laboratory of Power Source Technology for New Energy Vehicle, Engineering Research Center of Electrochemical Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China

Abstract

Nickel rich LiNixCoyMn1−x−yO2 cathode materials have been studied extensively to increase the energy density of lithium-ion batteries (LIBs) due to their advantages of high capacity and low cost. However, the anisotropic crystal expansion and contraction inside the secondary particles would cause detrimental micro-cracks and severe parasitic reactions at the electrode/electrolyte interface during cycling, which severely decreases the stability of crystalline structure and cathode-electrolyte interphase and ultimately affects the calendar life of batteries. Herein, a thermodynamically stabilized interface is constructed on the surface of single-crystalline Ni-rich cathode materials (SC811@RS) via a facile molten-salt route to suppress the generation of microcracks and interfacial parasitic side reactions simultaneously. Density functional theory calculations show that the formation energy of interface layer (−1.958 eV) is more negative than that of bulk layered structure (−1.421 eV). Such a thermodynamically stable protective layer can not only prevent the direct contact between highly reactive LiNixCoyMn1−x−yO2 and electrolyte, but also mitigate deformation of structure caused by stress thus strengthening the mechanical properties. Raman spectra further confirm the excellent structural reversibility and reaction homogeneity of SC811@RS at particle, electrode, and time scales. Consequently, SC811@RS cathode material delivers significantly improved cycling stability (high capacity retention of 92% after 200 cycles at 0.5 C) compared with polycrystalline LiNi0.8Co0.1Mn0.1O2 (82%).

Keywords: lithium-ion battery, cathode, single crystalline, LiNixCoyMn1−x−yO2, polycrystalline

References(52)

[1]

Mizushima, K.; Jones, P. C.; Wiseman, P. J.; Goodenough, J. B. LixCoO2 (0 < x < −1): A new cathode material for batteries of high energy density. Mater. Res. Bull. 1980, 15, 783–789.
DOI Google Scholar
[2]

Megahed, S.; Scrosati, B. Lithium-ion rechargeable batteries. J. Power Sources 1994, 51, 79–104.
DOI Google Scholar
[3]

Manthiram, A. An outlook on lithium ion battery technology. ACS Cent. Sci. 2017, 3, 1063–1069.
DOI Google Scholar
[4]

Li, W. D.; Erickson, E. M.; Manthiram, A. High-nickel layered oxide cathodes for lithium-based automotive batteries. Nat. Energy 2020, 5, 26–34.
DOI Google Scholar
[5]

Kempton, W. Electric vehicles: Driving range. Nat. Commun. 2016, 1, 16131.
DOI Google Scholar
[6]

Schmuch, R.; Wagner, R.; Hörpel, G.; Placke, T.; Winter, M. Performance and cost of materials for lithium-based rechargeable automotive batteries. Nat. Commun. 2018, 3, 267–278.
DOI Google Scholar
[7]

Su, X.; Wu, Q. L.; Li, J. C.; Xiao, X. C.; Lott, A.; Lu, W. Q.; Sheldon, B. W.; Wu, J. Silicon-based nanomaterials for lithium-ion batteries: A review. Adv. Energy Mater. 2014, 4, 1300882.
DOI Google Scholar
[8]

Yin, S. Y.; Deng, W. T.; Chen, J.; Gao, X.; Zou, G. Q.; Hou, H. S.; Ji, X. B. Fundamental and solutions of microcrack in Ni-rich layered oxide cathode materials of lithium-ion batteries. Nano Energy 2021, 83, 105854.
DOI Google Scholar
[9]

Manthiram, A.; Song, B. H.; Li, W. D. A perspective on nickel-rich layered oxide cathodes for lithium-ion batteries. Energy Storage Mater. 2017, 6, 125–139.
DOI Google Scholar
[10]

Chen, R. S.; Li, Q. H.; Yu, X. Q.; Chen, L. Q.; Li, H. Approaching practically accessible solid-state batteries: Stability issues related to solid electrolytes and interfaces. Chem. Rev. 2020, 120, 6820–6877.
DOI Google Scholar
[11]

Noh, H. J.; Youn, S.; Yoon, C. S.; Sun, Y. K. Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2 (x = 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries. J. Power Sources 2013, 233, 121–130.
DOI Google Scholar
[12]

Zou, L. F.; Zhao, W. G.; Jia, H. P.; Zheng, J. M.; Li, L. Z.; Abraham, D. P.; Chen, G. Y.; Croy, J. R.; Zhang, J. G.; Wang, C. M. The role of secondary particle structures in surface phase transitions of Ni-rich cathodes. Chem. Mater. 2020, 32, 2884–2892.
DOI Google Scholar
[13]

Zhang, S.; Ma, J.; Hu, Z. L.; Cui, G. L.; Chen, L. Q. Identifying and addressing critical challenges of high-voltage layered ternary oxide cathode materials. Chem. Mater. 2019, 31, 6033–6065.
DOI Google Scholar
[14]

Xie, Q.; Li, W. D.; Manthiram, A. A Mg-doped high-nickel layered oxide cathode enabling safer, high-energy-density Li-ion batteries. Chem. Mater. 2019, 31, 938–946.
DOI Google Scholar
[15]

Han, B. H.; Key, B.; Lapidus, S. H.; Garcia, J. C.; Iddir, H.; Vaughey, J. T.; Dogan, F. From coating to dopant: How the transition metal composition affects alumina coatings on Ni-rich cathodes. ACS Appl. Mater. Interfaces 2017, 9, 41291–41302.
DOI Google Scholar
[16]

Bianchini, M.; Roca-Ayats, M.; Hartmann, P.; Brezesinski, T.; Janek, J. There and back again-the journey of LiNiO2 as a cathode active material. Angew. Chem., Int. Ed. 2019, 58, 10434–10458.
DOI Google Scholar
[17]

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
[18]

Gao, S.; Zhan, X. W.; Cheng, Y. T. Structural, electrochemical and Li-ion transport properties of Zr-modified LiNi0.8Co0.1Mn0.1O2 positive electrode materials for Li-ion batteries. J. Power Sources 2019, 410–411, 45–52.
DOI Google Scholar
[19]

Liu, W.; Li, X. F.; Hao, Y. C.; Xiong, D. B.; Shan, H.; Wang, J. J.; Xiao, W.; Yang, H. J.; Yang, H.; Kou, L. et al. Functional passivation interface of LiNi0.8Co0.1Mn0.1O2 toward superior lithium storage. Adv. Funct. Mater. 2021, 31, 2008301.
DOI Google Scholar
[20]

Zhang, C. F.; Zhao, W. G.; Zheng, S. Y.; Li, Y. X.; Gong, Z. L.; Zhang, Z. R.; Yang, Y. Research progresses in Ni-Co-Mn/Al ternary concentration gradient cathode materials for Li-ion batteries. J. Electrochem. 2020, 26, 73–83.
DOI Google Scholar
[21]

Kim, J.; Lee, H.; Cha, H.; Yoon, M.; Park, M.; Cho, J. Prospect and reality of Ni-rich cathode for commercialization. Adv. Energy Mater. 2018, 8, 1702028.
DOI Google Scholar
[22]

Li, J.; Li, H. Y.; Stone, W.; Weber, R.; Hy, S.; Dahn, J. R. Synthesis of single crystal LiNi0.5Mn0.3Co0.2O2 for lithium ion batteries. J. Electrochem. Soc. 2017, 164, A3529–A3537.
DOI Google Scholar
[23]

Langdon, J.; Manthiram, A. A perspective on single-crystal layered oxide cathodes for lithium-ion batteries. Energy Storage Mater. 2021, 37, 143–160.
DOI Google Scholar
[24]

Kim, Y. Lithium nickel cobalt manganese oxide synthesized using alkali chloride flux: Morphology and performance As a cathode material for lithium ion batteries. ACS Appl. Mater. Interfaces 2012, 4, 2329–2333.
DOI Google Scholar
[25]

Tu, W. Q.; Wang, X. S.; Tian, W. Y.; Zhou, Y. N.; Han, C. P.; Li, C.; Kang, F. Y.; Li, B. H. A green water-induced spinel heterostructure interface enabling high performance lithium and manganese rich oxides. J. Mater. Chem. A 2021, 9, 20576–20584.
DOI Google Scholar
[26]

Zhang, Q. Q.; Liu, K.; Li, C.; Li, L.; Liu, X. J.; Li, W.; Zhang, J. L. In situ induced surface reconstruction of single-crystal lithium-ion cathode toward effective interface compatibility. ACS Appl. Mater. Interfaces 2021, 13, 13771–13780.
DOI Google Scholar
[27]

Wu, F.; Li, N.; Su, Y. F.; Shou, H. F.; Bao, L. Y.; Yang, W.; Zhang, L. J.; An, R.; Chen, S. Spinel/layered heterostructured cathode material for high-capacity and high-rate Li-ion batteries. Adv. Mater. 2013, 25, 3722–3726.
DOI Google Scholar
[28]

Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169–11186.
DOI Google Scholar
[29]

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
DOI Google Scholar
[30]

Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758–1775.
DOI Google Scholar
[31]

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953–17979.
DOI Google Scholar
[32]

Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010, 132, 154104.
DOI Google Scholar
[33]
LiOH-Li2SO4 Phase Diagram [Online]. https://www.crct.polymtl.ca/fact/phase_diagram.php?file=LiOH-Li2SO4.jpg&dir=FTsalt (accessed Aug 7, 2021).
[34]

Park, J. H.; Choi, B.; Kang, Y. S.; Park, S. Y.; Yun, D. J.; Park, I.; Shim, J. H.; Park, J. H.; Han, H. N.; Park, K. Effect of residual lithium rearrangement on Ni-rich layered oxide cathodes for lithium-ion batteries. Energy Technol. 2018, 6, 1361–1369.
DOI Google Scholar
[35]

Sharifi-Asl, S.; Lu, J.; Amine, K.; Shahbazian-Yassar, R. Oxygen release degradation in Li-ion battery cathode materials: Mechanisms and mitigating approaches. Adv. Energy Mater. 2019, 9, 1900551.
DOI Google Scholar
[36]

Min, K.; Cho, E. Intrinsic origin of intra-granular cracking in Ni-rich layered oxide cathode materials. Phys. Chem. Chem. Phys. 2018, 20, 9045–9052.
DOI Google Scholar
[37]

Li, J. Y.; Huang, J. X.; Li, H. Y.; Kong, X. B.; Li, X.; Zhao, J. B. Insight into the redox reaction heterogeneity within secondary particles of nickel-rich layered cathode materials. ACS Appl. Mater. Interfaces 2021, 13, 27074–27084.
DOI Google Scholar
[38]

Ryu, H. H.; Namkoong, B.; Kim, J. H.; Belharouak, I.; Yoon, C. S.; Sun, Y. K. Capacity fading mechanisms in Ni-rich single-crystal NCM cathodes. ACS Energy Lett. 2021, 6, 2726–2734.
DOI Google Scholar
[39]

Fan, X. M.; Hu, G. R.; Zhang, B.; Ou, X.; Zhang, J. F.; Zhao, W. G.; Jia, H. P.; Zou, L. F.; Li, P.; Yang, Y. Crack-free single-crystalline Ni-rich layered NCM cathode enable superior cycling performance of lithium-ion batteries. Nano Energy 2020, 70, 104450.
DOI Google Scholar
[40]

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
[41]

Zhu, J.; Zheng, J. C.; Cao, G. L.; Li, Y. J.; Zhou, Y.; Deng, S. Y.; Hai, C. X. Flux-free synthesis of single-crystal LiNi0.8Co0.1Mn0.1O2 boosts its electrochemical performance in lithium batteries. J. Power Sources 2020, 464, 228207.
DOI Google Scholar
[42]

Kong, X. B.; Zhang, Y. G.; Peng, S. Y.; Zeng, J.; Zhao, J. B. Superiority of single-crystal to polycrystalline LiNixCoyMn1−x−yO2 cathode materials in storage behaviors for lithium-ion batteries. ACS Sustainable Chem. Eng. 2020, 8, 14938–14948.
DOI Google Scholar
[43]

Bi, Y. J.; Tao, J. H.; Wu, Y. Q.; Li, L. Z.; Xu, Y. B.; Hu, E. Y.; Wu, B. B.; Hu, J. T.; Wang, C. M.; Zhang, J. G. et al. Reversible planar gliding and microcracking in a single-crystalline Ni-rich cathode. Science 2020, 370, 1313–1317.
DOI Google Scholar
[44]

Kong, X. B.; Peng, S. Y.; Li, J. Y.; Chen, Z. J.; Chen, Z. Q.; Wang, J.; Zhao, J. B. Pre-blended conductive agent to effectively improve the storage properties of LiNi0.6Co0.2Mn0.2O2 cathode materials. J. Power Sources 2020, 448, 227445.
DOI Google Scholar
[45]

Li, W. D.; Song, B. H.; Manthiram, A. High-voltage positive electrode materials for lithium-ion batteries. Chem. Soc. Rev. 2017, 46, 3006–3059.
DOI Google Scholar
[46]

Lin, R. Q.; Bak, S. M.; Shin, Y.; Zhang, R.; Wang, C. Y.; Kisslinger, K.; Ge, M. Y.; Huang, X. J.; Shadike, Z.; Pattammattel, A. et al. Hierarchical nickel valence gradient stabilizes high-nickel content layered cathode materials. Nat. Commun. 2021, 12, 2350.
DOI Google Scholar
[47]

Chen, Z.; Wang, J.; Chao, D. L.; Baikie, T.; Bai, L. Y.; Chen, S.; Zhao, Y. L.; Sum, T. C.; Lin, J. Y.; Shen, Z. X. Hierarchical porous LiNi1/3Co1/3Mn1/3O2 nano-/micro spherical cathode material: Minimized cation mixing and improved Li+ mobility for enhanced electrochemical performance. Sci. Rep. 2016, 6, 25771.
DOI Google Scholar
[48]

Li, J. Y.; Huang, J. X.; Kong, X. B.; Zeng, J.; Zhao, J. B. The apparent capacity decay by kinetic degradation of LiNi0.5Co0.2Mn0.3O2 during cycling under the high upper-limit charging potential. J. Power Sources 2021, 496, 229856.
DOI Google Scholar
[49]

Li, J. Y.; Hua, H. M.; Kong, X. B.; Yang, H. Y.; Dai, P. P.; Zeng, J.; Zhao, J. B. In-situ probing the near-surface structural thermal stability of high-nickel layered cathode materials. Adv. Energy Mater. 2022, 46, 90–99.
DOI Google Scholar
[50]

Kasnatscheew, J.; Evertz, M.; Streipert, B.; Wagner, R.; Klöpsch, R.; Vortmann, B.; Hahn, H.; Nowak, S.; Amereller, M.; Gentschev, A. C. et al. The truth about the 1st cycle coulombic efficiency of LiNi1/3Co1/3Mn1/3O2 (NCM) cathodes. Phys. Chem. Chem. Phys. 2016, 18, 3956–3965.
DOI Google Scholar
[51]

Ghanty, C.; Markovsky, B.; Erickson, E. M.; Talianker, M.; Haik, O.; Tal-Yossef, Y.; Mor, A.; Aurbach, D.; Lampert, J.; Volkov, A. et al. Li+-ion extraction/insertion of Ni-rich Li1+x(NiyCozMnz)wO2 (0.005 < x < 0.03; y:z = 8:1, w ≈ 1) electrodes: In situ XRD and Raman spectroscopy study. ChemElectroChem 2015, 2, 1479–1486.
DOI Google Scholar
[52]

Cha, H.; Kim, J.; Lee, H.; Kim, N.; Hwang, J.; Sung, J.; Yoon, M.; Kim, K.; Cho, J. Boosting reaction homogeneity in high-energy lithium-ion battery cathode materials. Adv. Mater. 2020, 32, 2003040.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 10 May 2022
Revised: 15 June 2022
Accepted: 13 July 2022
Published: 20 August 2022
Issue date: May 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

We gratefully acknowledge the financial support of the Key Project of Science and Technology of Xiamen (No. 3502Z20201013) and the National Natural Science Foundation of China (Nos. 21875198, 21875195, and 22021001). We also acknowledge the help of Tan Kah Kee Innovation Laboratory on the scientific tests.

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