Effects of Sulfate Modification of Stoichiometric and Lithium-Rich LiNiO2 Cathode Materials

Bo Dong; Andrey Poletayev; Jonathon Cottom; Javier Castells-Gil; Ben F Spencer; Cheng Li; Pengcheng Zhu; Yongxiu Chen; Jaime-Marie Price; Laura Driscoll; Phoebe Allan; Emma Kendrick; M. Saiful Islam; Peter Slater

doi:10.1039/D4TA00284A

Effects of Sulfate Modification of Stoichiometric and Lithium-Rich LiNiO2 Cathode Materials

Bo Dong^*, Andrey Poletayev, Jonathon Cottom, Javier Castells-Gil, Ben F Spencer, Cheng Li, Pengcheng Zhu, Yongxiu Chen, Jaime-Marie Price, Laura Driscoll, Phoebe Allan, Emma Kendrick, M. Saiful Islam^*, Peter Slater^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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Abstract

Lithium nickel oxide, LiNiO2, has attracted considerable interest as a high energy cathode for next generation lithium-ion batteries. Nevertheless, shortcomings such as significant cycling capacity decay and low stability in ambient atmosphere have hindered its practical application, and consequently most work has focused on the more stable Mn and Co doped analogues Li(Ni,Mn,Co)O2. Here, we report an investigation of an alternative strategy, sulfate modification, in the LiNiO2 system. We show that improved performance can be achieved, attributed to the dual effect of a low level of bulk doping and the presence of a self-passivation Li2SO4 layer formed beyond the solid solution limit. Ab initio simulations suggest that the behavior is similar to that of other high valent dopants such as W and Mo. These dual effects contribute to the improved air stability and enhanced electrochemical performance for the sulfate modified lithium-rich LiNiO2, leading to high initial capacities (∼245 mA h g−1 at 25 mA g−1, and ∼205 mA h g−1 at 100 mA g−1) and better capacity retention. Overall, the results show that polyanion modification represents an excellent alternative low-cost strategy to improve the performance of lithium nickel oxide cathode materials.

Original language	English
Pages (from-to)	11390-11402
Journal	Journal of Materials Chemistry A
Volume	12
Issue number	19
Early online date	4 Apr 2024
DOIs	https://doi.org/10.1039/D4TA00284A
Publication status	Published - 21 May 2024

Bibliographical note

Acknowledgment: We would like to thank the Faraday Institution CATMAT (FIRG016, EP/S003053/1) and NEXTRODE (FIRG015) projects for funding. We would like to thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. The XPS/HAXPES work was supported by the Henry Royce Institute, funded through EPSRC grants EP/R00661X/1, EP/P025021/1 and EP/P025498/1. We are also grateful to the HEC Materials Chemistry Consortium (EP/R029431) for the use of Archer2 high-performance computing (HPC) facilities, and for the Faraday Institution’s Michael HPC resource. A portion of this research used resources at the Spallation Neutron Source, as appropriate, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.

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10.1039/D4TA00284ALicence: Creative Commons: Attribution (CC BY)

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Next Generation Electrodes (via Oxford, Faraday)
Simmons, M. (Co-Investigator), Kendrick, E. (Principal Investigator) & Slater, P. (Co-Investigator)
TECHNOLOGY STRATEGY BOARD
1/09/19 → 30/09/23
Project: Other Government Departments

Research data supporting the publication ''Effects of Sulfate Modification of Stoichiometric and Lithium-Rich LiNiO2 Cathode Materials''
Dong, B. (Creator), Poletayev, A. (Creator), Cottom, J. (Creator), Castells-Gil, J. (Creator), Spencer, B. (Creator), Li, C. (Creator), Zhu, P. (Creator), Chen, Y. (Creator), Price, J.-M. (Creator), Driscoll, L. (Creator), Allan, P. (Creator), Kendrick, E. (Creator), Islam, M. S. (Creator) & Slater, P. (Creator), University of Birmingham, 8 Apr 2024
DOI: 10.25500/edata.bham.00001084
Dataset

Cite this

@article{02092fee769043018a4fa4d5b3910ddf,

title = "Effects of Sulfate Modification of Stoichiometric and Lithium-Rich LiNiO2 Cathode Materials",

abstract = "Lithium nickel oxide, LiNiO2, has attracted considerable interest as a high energy cathode for next generation lithium-ion batteries. Nevertheless, shortcomings such as significant cycling capacity decay and low stability in ambient atmosphere have hindered its practical application, and consequently most work has focused on the more stable Mn and Co doped analogues Li(Ni,Mn,Co)O2. Here, we report an investigation of an alternative strategy, sulfate modification, in the LiNiO2 system. We show that improved performance can be achieved, attributed to the dual effect of a low level of bulk doping and the presence of a self-passivation Li2SO4 layer formed beyond the solid solution limit. Ab initio simulations suggest that the behavior is similar to that of other high valent dopants such as W and Mo. These dual effects contribute to the improved air stability and enhanced electrochemical performance for the sulfate modified lithium-rich LiNiO2, leading to high initial capacities (∼245 mA h g−1 at 25 mA g−1, and ∼205 mA h g−1 at 100 mA g−1) and better capacity retention. Overall, the results show that polyanion modification represents an excellent alternative low-cost strategy to improve the performance of lithium nickel oxide cathode materials.",

author = "Bo Dong and Andrey Poletayev and Jonathon Cottom and Javier Castells-Gil and Spencer, {Ben F} and Cheng Li and Pengcheng Zhu and Yongxiu Chen and Jaime-Marie Price and Laura Driscoll and Phoebe Allan and Emma Kendrick and Islam, {M. Saiful} and Peter Slater",

note = "Acknowledgment: We would like to thank the Faraday Institution CATMAT (FIRG016, EP/S003053/1) and NEXTRODE (FIRG015) projects for funding. We would like to thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. The XPS/HAXPES work was supported by the Henry Royce Institute, funded through EPSRC grants EP/R00661X/1, EP/P025021/1 and EP/P025498/1. We are also grateful to the HEC Materials Chemistry Consortium (EP/R029431) for the use of Archer2 high-performance computing (HPC) facilities, and for the Faraday Institution{\textquoteright}s Michael HPC resource. A portion of this research used resources at the Spallation Neutron Source, as appropriate, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.",

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language = "English",

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T1 - Effects of Sulfate Modification of Stoichiometric and Lithium-Rich LiNiO2 Cathode Materials

AU - Dong, Bo

AU - Poletayev, Andrey

AU - Cottom, Jonathon

AU - Castells-Gil, Javier

AU - Spencer, Ben F

AU - Li, Cheng

AU - Zhu, Pengcheng

AU - Chen, Yongxiu

AU - Price, Jaime-Marie

AU - Driscoll, Laura

AU - Allan, Phoebe

AU - Kendrick, Emma

AU - Islam, M. Saiful

AU - Slater, Peter

N1 - Acknowledgment: We would like to thank the Faraday Institution CATMAT (FIRG016, EP/S003053/1) and NEXTRODE (FIRG015) projects for funding. We would like to thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. The XPS/HAXPES work was supported by the Henry Royce Institute, funded through EPSRC grants EP/R00661X/1, EP/P025021/1 and EP/P025498/1. We are also grateful to the HEC Materials Chemistry Consortium (EP/R029431) for the use of Archer2 high-performance computing (HPC) facilities, and for the Faraday Institution’s Michael HPC resource. A portion of this research used resources at the Spallation Neutron Source, as appropriate, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.

PY - 2024/5/21

Y1 - 2024/5/21

N2 - Lithium nickel oxide, LiNiO2, has attracted considerable interest as a high energy cathode for next generation lithium-ion batteries. Nevertheless, shortcomings such as significant cycling capacity decay and low stability in ambient atmosphere have hindered its practical application, and consequently most work has focused on the more stable Mn and Co doped analogues Li(Ni,Mn,Co)O2. Here, we report an investigation of an alternative strategy, sulfate modification, in the LiNiO2 system. We show that improved performance can be achieved, attributed to the dual effect of a low level of bulk doping and the presence of a self-passivation Li2SO4 layer formed beyond the solid solution limit. Ab initio simulations suggest that the behavior is similar to that of other high valent dopants such as W and Mo. These dual effects contribute to the improved air stability and enhanced electrochemical performance for the sulfate modified lithium-rich LiNiO2, leading to high initial capacities (∼245 mA h g−1 at 25 mA g−1, and ∼205 mA h g−1 at 100 mA g−1) and better capacity retention. Overall, the results show that polyanion modification represents an excellent alternative low-cost strategy to improve the performance of lithium nickel oxide cathode materials.

AB - Lithium nickel oxide, LiNiO2, has attracted considerable interest as a high energy cathode for next generation lithium-ion batteries. Nevertheless, shortcomings such as significant cycling capacity decay and low stability in ambient atmosphere have hindered its practical application, and consequently most work has focused on the more stable Mn and Co doped analogues Li(Ni,Mn,Co)O2. Here, we report an investigation of an alternative strategy, sulfate modification, in the LiNiO2 system. We show that improved performance can be achieved, attributed to the dual effect of a low level of bulk doping and the presence of a self-passivation Li2SO4 layer formed beyond the solid solution limit. Ab initio simulations suggest that the behavior is similar to that of other high valent dopants such as W and Mo. These dual effects contribute to the improved air stability and enhanced electrochemical performance for the sulfate modified lithium-rich LiNiO2, leading to high initial capacities (∼245 mA h g−1 at 25 mA g−1, and ∼205 mA h g−1 at 100 mA g−1) and better capacity retention. Overall, the results show that polyanion modification represents an excellent alternative low-cost strategy to improve the performance of lithium nickel oxide cathode materials.

U2 - 10.1039/D4TA00284A

DO - 10.1039/D4TA00284A

M3 - Article

SN - 2050-7488

VL - 12

SP - 11390

EP - 11402

JO - Journal of Materials Chemistry A

JF - Journal of Materials Chemistry A

IS - 19

ER -

Effects of Sulfate Modification of Stoichiometric and Lithium-Rich LiNiO2 Cathode Materials

Abstract

Bibliographical note

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Research data supporting the publication ''Effects of Sulfate Modification of Stoichiometric and Lithium-Rich LiNiO2 Cathode Materials''

Cite this