Realizing continuous cation order-to-disorder tuning in a class of high-energy spinel-type Li-ion cathodes

Zijian Cai; Huiwen Ji; Yang Ha; Jue Liu; Deok Hwang Kwon; Yaqian Zhang; Alexander Urban; Emily E. Foley; Raynald Giovine; Hyunchul Kim; Zhengyan Lun; Tzu Yang Huang; Guobo Zeng; Yu Chen; Jingyang Wang; Bryan D. McCloskey; Mahalingam Balasubramanian; Raphaële J. Clément; Wanli Yang; Gerbrand Ceder

doi:10.1016/j.matt.2021.10.013

Realizing continuous cation order-to-disorder tuning in a class of high-energy spinel-type Li-ion cathodes

Zijian Cai, Huiwen Ji, Yang Ha, Jue Liu, Deok Hwang Kwon, Yaqian Zhang, Alexander Urban, Emily E. Foley, Raynald Giovine, Hyunchul Kim, Zhengyan Lun, Tzu Yang Huang, Guobo Zeng, Yu Chen, Jingyang Wang, Bryan D. McCloskey, Mahalingam Balasubramanian, Raphaële J. Clément, Wanli Yang, Gerbrand Ceder

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Abstract

Conventional Li-ion cathode materials are dominated by well-ordered structures, in which Li and transition metals occupy distinct crystallographic sites. We show in this paper that profoundly new degrees of freedom for the optimization of electrochemical properties may be accessed if controllable cation disorder is introduced. In a class of high-capacity spinel-type cathode materials, we identify cation to anion ratio in synthesis as a key parameter for tuning the structure continuously from a well-ordered spinel, through a partially ordered spinel, to rocksalt. We find that the varying degree of cation disorder modifies the voltage profile, rate capability, and charge-compensation mechanism in a rational and predictable way. Our results indicate that spinel-type order is most beneficial for achieving high-rate performance as long as the cooperative 8a to 16c phase transition is suppressed, while more rocksalt-like disorder facilitates O redox, which can increase capacity. Our findings reveal an important tuning handle for achieving high energy and power in the vast space of partially ordered cathode materials.

Original language	English
Pages (from-to)	3897-3916
Number of pages	20
Journal	Matter
Volume	4
Issue number	12
DOIs	https://doi.org/10.1016/j.matt.2021.10.013
State	Published - Dec 1 2021

Funding

This work is supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office , under the Applied Battery Materials Program, of the US Department of Energy (DOE ) under contract no. DE-AC02-05CH11231 and by Umicore Specialty Oxides and Chemicals. Work at the Advanced Light Source is supported by the Director, Office of Science , Office of Basic Energy Sciences , of the US DOE under contract no. DE-AC02-05CH11231 . Research conducted at the Nanoscale Ordered Materials Diffractometer Beamline at Oak Ridge National Laboratory's Spallation Neutron Source is sponsored by the Scientific User Facilities Division, Office of Basic Sciences of the US DOE . Work at the Molecular Foundry at Lawrence Berkeley National Laboratory is supported by the Office of Science , Office of Basic Energy Sciences of the US DOE under contract no. DE-AC02-05CH11231 . This research used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US DOE Office of Science by Argonne National Laboratory , and is supported by the US DOE under contract no. DE-AC02-06CH11357 . The NMR experimental work reported here made use of the shared facilities of the UCSB MRSEC ( NSF DMR 1720256 ), a member of the Material Research Facilities Network. E. E.E.F. was supported by the NSF Graduate Research Fellowship Program under Grant No. DGE 1650114 . T.-Y.H. was supported collectively by both Ministry of Education in Taiwan and UC Berkeley College of Chemistry through Taiwan Fellowship Program. The computational analysis was performed using computational resources sponsored by the US DOE Office of Energy Efficiency and Renewable Energy and located at the National Renewable Energy Laboratory, and computational resources were provided by Extreme Science and Engineering Discovery Environment (XSEDE), which was supported by National Science Foundation grant no. ACI1053575 , as well as the National Energy Research Scientific Computing Center (NERSC) , a DOE Office of Science User Facility supported by the Office of Science and the US DOE under contract no. DE-AC02-05CH11231. The authors thank Bin Ouyang and Han-Ming Hau for helpful discussions. This work is supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, under the Applied Battery Materials Program, of the US Department of Energy (DOE) under contract no. DE-AC02-05CH11231 and by Umicore Specialty Oxides and Chemicals. Work at the Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US DOE under contract no. DE-AC02-05CH11231. Research conducted at the Nanoscale Ordered Materials Diffractometer Beamline at Oak Ridge National Laboratory's Spallation Neutron Source is sponsored by the Scientific User Facilities Division, Office of Basic Sciences of the US DOE. Work at the Molecular Foundry at Lawrence Berkeley National Laboratory is supported by the Office of Science, Office of Basic Energy Sciences of the US DOE under contract no. DE-AC02-05CH11231. This research used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US DOE Office of Science by Argonne National Laboratory, and is supported by the US DOE under contract no. DE-AC02-06CH11357. The NMR experimental work reported here made use of the shared facilities of the UCSB MRSEC (NSF DMR 1720256), a member of the Material Research Facilities Network. E. E.E.F. was supported by the NSF Graduate Research Fellowship Program under Grant No. DGE 1650114. T.-Y.H. was supported collectively by both Ministry of Education in Taiwan and UC Berkeley College of Chemistry through Taiwan Fellowship Program. The computational analysis was performed using computational resources sponsored by the US DOE Office of Energy Efficiency and Renewable Energy and located at the National Renewable Energy Laboratory, and computational resources were provided by Extreme Science and Engineering Discovery Environment (XSEDE), which was supported by National Science Foundation grant no. ACI1053575, as well as the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science and the US DOE under contract no. DE-AC02-05CH11231. The authors thank Bin Ouyang and Han-Ming Hau for helpful discussions. Z.C. planned the project with G.C. and H.J; Z.C. and H.J. designed, synthesized, characterized, and electrochemically tested the proposed compounds with help from Z.L. Y.C. and J.W.; Y.H. acquired and analyzed the mRIXS data with input from W.Y.; J.L. acquired and analyzed the sXRD and neutron diffraction data; D.-H.K. and Y.Z. acquired and analyzed the TEM data; A.U. performed Monte Carlo and DFT calculations and analyzed the data; E.E.F and R.G. acquired and analyzed the NMR data with input from R.J.C.; Z.C. and H.K. acquired and analyzed the XAS data with help from M.B. and Z.L.; T.-Y.H. acquired and analyzed the DEMS data with input from B.D.M; G.Z. performed SEM. The manuscript was written by Z.C. and H.J. and was revised by R.J.C. and G.C. with help from the other authors. All authors contributed to discussions. The authors declare no competing interests.

Funders	Funder number
Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office
Office of Basic Energy Sciences of the US DOE
UCSB MRSEC	NSF DMR 1720256
Umicore Specialty Oxides and Chemicals
National Science Foundation	DGE 1650114, ACI1053575
U.S. Department of Energy	DE-AC02-05CH11231
Office of Science
Office of Energy Efficiency and Renewable Energy
Basic Energy Sciences
Argonne National Laboratory	DE-AC02-06CH11357
Oak Ridge National Laboratory

Keywords

Li-ion batteries
MAP3: Understanding
cathode materials
fast-charging
spinel structure

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1016/j.matt.2021.10.013

Cite this

Cai, Z., Ji, H., Ha, Y., Liu, J., Kwon, D. H., Zhang, Y., Urban, A., Foley, E. E., Giovine, R., Kim, H., Lun, Z., Huang, T. Y., Zeng, G., Chen, Y., Wang, J., McCloskey, B. D., Balasubramanian, M., Clément, R. J., Yang, W., & Ceder, G. (2021). Realizing continuous cation order-to-disorder tuning in a class of high-energy spinel-type Li-ion cathodes. Matter, 4(12), 3897-3916. https://doi.org/10.1016/j.matt.2021.10.013

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abstract = "Conventional Li-ion cathode materials are dominated by well-ordered structures, in which Li and transition metals occupy distinct crystallographic sites. We show in this paper that profoundly new degrees of freedom for the optimization of electrochemical properties may be accessed if controllable cation disorder is introduced. In a class of high-capacity spinel-type cathode materials, we identify cation to anion ratio in synthesis as a key parameter for tuning the structure continuously from a well-ordered spinel, through a partially ordered spinel, to rocksalt. We find that the varying degree of cation disorder modifies the voltage profile, rate capability, and charge-compensation mechanism in a rational and predictable way. Our results indicate that spinel-type order is most beneficial for achieving high-rate performance as long as the cooperative 8a to 16c phase transition is suppressed, while more rocksalt-like disorder facilitates O redox, which can increase capacity. Our findings reveal an important tuning handle for achieving high energy and power in the vast space of partially ordered cathode materials.",

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author = "Zijian Cai and Huiwen Ji and Yang Ha and Jue Liu and Kwon, {Deok Hwang} and Yaqian Zhang and Alexander Urban and Foley, {Emily E.} and Raynald Giovine and Hyunchul Kim and Zhengyan Lun and Huang, {Tzu Yang} and Guobo Zeng and Yu Chen and Jingyang Wang and McCloskey, {Bryan D.} and Mahalingam Balasubramanian and Cl{\'e}ment, {Rapha{\"e}le J.} and Wanli Yang and Gerbrand Ceder",

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doi = "10.1016/j.matt.2021.10.013",

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Cai, Z, Ji, H, Ha, Y, Liu, J, Kwon, DH, Zhang, Y, Urban, A, Foley, EE, Giovine, R, Kim, H, Lun, Z, Huang, TY, Zeng, G, Chen, Y, Wang, J, McCloskey, BD, Balasubramanian, M, Clément, RJ, Yang, W & Ceder, G 2021, 'Realizing continuous cation order-to-disorder tuning in a class of high-energy spinel-type Li-ion cathodes', Matter, vol. 4, no. 12, pp. 3897-3916. https://doi.org/10.1016/j.matt.2021.10.013

TY - JOUR

T1 - Realizing continuous cation order-to-disorder tuning in a class of high-energy spinel-type Li-ion cathodes

AU - Cai, Zijian

AU - Ji, Huiwen

AU - Ha, Yang

AU - Liu, Jue

AU - Kwon, Deok Hwang

AU - Zhang, Yaqian

AU - Urban, Alexander

AU - Foley, Emily E.

AU - Giovine, Raynald

AU - Kim, Hyunchul

AU - Lun, Zhengyan

AU - Huang, Tzu Yang

AU - Zeng, Guobo

AU - Chen, Yu

AU - Wang, Jingyang

AU - McCloskey, Bryan D.

AU - Balasubramanian, Mahalingam

AU - Clément, Raphaële J.

AU - Yang, Wanli

AU - Ceder, Gerbrand

PY - 2021/12/1

Y1 - 2021/12/1

N2 - Conventional Li-ion cathode materials are dominated by well-ordered structures, in which Li and transition metals occupy distinct crystallographic sites. We show in this paper that profoundly new degrees of freedom for the optimization of electrochemical properties may be accessed if controllable cation disorder is introduced. In a class of high-capacity spinel-type cathode materials, we identify cation to anion ratio in synthesis as a key parameter for tuning the structure continuously from a well-ordered spinel, through a partially ordered spinel, to rocksalt. We find that the varying degree of cation disorder modifies the voltage profile, rate capability, and charge-compensation mechanism in a rational and predictable way. Our results indicate that spinel-type order is most beneficial for achieving high-rate performance as long as the cooperative 8a to 16c phase transition is suppressed, while more rocksalt-like disorder facilitates O redox, which can increase capacity. Our findings reveal an important tuning handle for achieving high energy and power in the vast space of partially ordered cathode materials.

AB - Conventional Li-ion cathode materials are dominated by well-ordered structures, in which Li and transition metals occupy distinct crystallographic sites. We show in this paper that profoundly new degrees of freedom for the optimization of electrochemical properties may be accessed if controllable cation disorder is introduced. In a class of high-capacity spinel-type cathode materials, we identify cation to anion ratio in synthesis as a key parameter for tuning the structure continuously from a well-ordered spinel, through a partially ordered spinel, to rocksalt. We find that the varying degree of cation disorder modifies the voltage profile, rate capability, and charge-compensation mechanism in a rational and predictable way. Our results indicate that spinel-type order is most beneficial for achieving high-rate performance as long as the cooperative 8a to 16c phase transition is suppressed, while more rocksalt-like disorder facilitates O redox, which can increase capacity. Our findings reveal an important tuning handle for achieving high energy and power in the vast space of partially ordered cathode materials.

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KW - MAP3: Understanding

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KW - fast-charging

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AN - SCOPUS:85120941019

SN - 2590-2393

VL - 4

SP - 3897

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JO - Matter

JF - Matter

IS - 12

ER -

Realizing continuous cation order-to-disorder tuning in a class of high-energy spinel-type Li-ion cathodes

Abstract

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Keywords

UN SDGs

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