In Situ Insights into Cathode Calcination for Predictive Synthesis: Kinetic Crystallization of LiNiO 2 from Hydroxides

Tayal, Akhil; Barai, Pallab; Zhong, Hui; Kahvecioglu, Ozgenur; Wang, Xiaoping; Pupek, Krzysztof Z.; Ma, Lu; Ehrlich, Steven N.; Srinivasan, Venkat; Qu, Xiaohui; Bai, Jianming; Wang, Feng

doi:10.1002/adma.202312027

Title: In Situ Insights into Cathode Calcination for Predictive Synthesis: Kinetic Crystallization of LiNiO ₂ from Hydroxides

Journal Article · Mon Feb 26 00:00:00 EST 2024 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202312027· OSTI ID:2311937

^[1]; Barai, Pallab ^[2]; Zhong, Hui ^[3]; Kahvecioglu, Ozgenur ^[2]; Wang, Xiaoping ^[2]; Pupek, Krzysztof Z. ^[2]; Ma, Lu ^[1]; Ehrlich, Steven N. ^[1]; Srinivasan, Venkat ^[2];

^[1]; Bai, Jianming ^[1];

^[2]

National Synchrotron Light Source II Brookhaven National Laboratory Upton NY 11973 USA
Argonne National Laboratory Lemont IL 60439 USA
Joint Photon Sciences Institute Stony Brook University Stony Brook NY 11794 USA

Abstract Calcination is a solid‐state synthesis process widely deployed in battery cathode manufacturing. However, its inherent complexity associated with elusive intermediates hinders the predictive synthesis of high‐performance cathode materials. Here, correlative in situ X‐ray absorption/scattering spectroscopy is used to investigate the calcination of nickel‐based cathodes, focusing specifically on the archetypal LiNiO ₂ from Ni(OH) ₂ . Combining in situ observation with data‐driven analysis reveals concurrent lithiation and dehydration of Ni(OH) ₂ and consequently, the low‐temperature crystallization of layered LiNiO ₂ alongside lithiated rocksalts. Following early nucleation, LiNiO ₂ undergoes sluggish crystallization and structural ordering while depleting rocksalts; ultimately, it turns into a structurally‐ordered layered phase upon full lithiation but remains small in size. Subsequent high‐temperature sintering induces rapid crystal growth, accompanied by undesired delithiation and structural degradation. These observations are further corroborated by mesoscale modeling, emphasizing that, even though calcination is thermally driven and favors transformation towards thermodynamically equilibrium phases, the actual phase propagation and crystallization can be kinetically tuned via lithiation, providing freedom for structural and morphological control during cathode calcination.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: SC0012704; AC02-06CH11357

OSTI ID:: 2311937

Alternate ID(s):: OSTI ID: 2333670

Report Number(s):: BNL-225453-2024-JAAM; 2312027

Journal Information:: Advanced Materials, Journal Name: Advanced Materials; ISSN 0935-9648

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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correlative in situ X‐ray absorption/scattering spectroscopy
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Title: In Situ Insights into Cathode Calcination for Predictive Synthesis: Kinetic Crystallization of LiNiO 2 from Hydroxides

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Title: In Situ Insights into Cathode Calcination for Predictive Synthesis: Kinetic Crystallization of LiNiO ₂ from Hydroxides