Deciphering the morphology of transition metal carbonate cathode precursors

Barai, Pallab; Wang, Xiaoping; Wolfman, Mark; Chen, Jiajun; Gutierrez, Arturo; Garcia, Juan C.; Wen, Jianguo; Kinnibrugh, Tiffany; Fister, Timothy T.; Iddir, Hakim H.; Srinivasan, Venkat

doi:10.1039/d3ta08095a

Deciphering the morphology of transition metal carbonate cathode precursors

Journal Article · Tue Mar 26 00:00:00 EDT 2024 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d3ta08095a· OSTI ID:2467337

^[1]; Wang, Xiaoping ^[1]; Wolfman, Mark ^[2]; Chen, Jiajun ^[1]; Gutierrez, Arturo ^[1]; Garcia, Juan C. ^[1]; ^[3]; Kinnibrugh, Tiffany ^[1]; ^[1]; ^[1]; Srinivasan, Venkat ^[1]

Argonne National Laboratory (ANL), Argonne, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)

The performance and life of Li-ion battery cathode materials are determined by both the composition (crystal structure and transition metal ratio) and the morphology (particle size, size distribution, and surface area). Careful control of these two aspects is the key to long lasting, high-energy batteries that can undergo fast charge. Developing such cathodes requires manipulation of the synthesis conditions, namely the coprecipitation process to develop the precursor and a calcination step to lithiate and convert it to a transition metal oxide. In this paper, we utilize a combination of controlled synthesis, microscopic and spectroscopic characterization, and multi-scale mathematical modeling to shed light on the synthesis of cathode precursors. The complex interplay between the various chemical reactions in the co-precipitation process is studied to provide experimentalists with guidance on achieving composition control during synthesis. Further, the formation of a variety of morphologies of the primary particles and the driving force for agglomeration is mathematically described, for the first time, based on an energy minimization approach. Results suggest that the presence of Ni and/or Co significantly lowers the reaction rate constant compared to Mn, resulting in agglomerated growth in the former and single crystal growth in the latter. Modeling studies are used to provide a phase map describing the synthesis conditions needed to control the secondary particle size and corresponding size distribution. Finally, this paper represents an important step in developing a computationally guided approach to the synthesis of battery cathode materials.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2467337

Alternate ID(s):: OSTI ID: 2345953

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 21 Vol. 12; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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