Monitoring the Formation of Nickel-Poor and Nickel-Rich Oxide Cathode Materials for Lithium-Ion Batteries with Synchrotron Radiation

Bixian Ying; Jack R Fitzpatrick; Zhenjie Teng; Tianxiang Chen; Tsz Woon Benedict Lo; Vassilios Siozios; Claire A Murray; Helen E A Brand; Sarah Day; Chiu C Tang; Robert S Weatherup; Michael Merz; Peter Nagel; Stefan Schuppler; Martin Winter; Karin Kleiner

doi:10.1021/acs.chemmater.2c02639

Monitoring the Formation of Nickel-Poor and Nickel-Rich Oxide Cathode Materials for Lithium-Ion Batteries with Synchrotron Radiation

Chem Mater. 2023 Jan 31;35(4):1514-1526. doi: 10.1021/acs.chemmater.2c02639. eCollection 2023 Feb 28.

Authors

Bixian Ying¹, Jack R Fitzpatrick², Zhenjie Teng¹, Tianxiang Chen³, Tsz Woon Benedict Lo³, Vassilios Siozios¹, Claire A Murray⁴, Helen E A Brand⁵, Sarah Day⁴, Chiu C Tang⁴, Robert S Weatherup⁶, Michael Merz^{7

8}, Peter Nagel^{7

8}, Stefan Schuppler^{7

8}, Martin Winter^{1

9}, Karin Kleiner¹

Affiliations

¹ MEET, Battery Research Center, University of Muenster, Corrensstr. 46, 48149Münster, Germany.
² Department of Chemistry, Molecular Sciences Research Hub, Imperial College London, White City Campus, 82 Wood Lane, W12 0BZLondon, U.K.
³ Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hunghom, 999077Kowloon, Hong Kong, China.
⁴ Diamond Light Source Ltd, Harwell Science & Innovation Campus, Didcot, OX11 0DEOxfordshire, U.K.
⁵ Australian Synchrotron ANSTO, 800 Blackburn Rd., Clayton, 3168Victoria, Australia.
⁶ Department of Materials, University of Oxford, Parks Road, OX1 3PHOxford, U.K.
⁷ Institute for Quantum Materials and Technologies, Karlsruhe Institute of Technology, 76021Karlsruhe, Germany.
⁸ Karlsruhe Nano Micro Facility (KNMFi), Karlsruhe Institute of Technology (KIT), 76344Eggenstein-Leopoldshafen, Germany.
⁹ Helmholtz-Institute Münster, Forschungszentrum Jülich GmbH, 48149Muenster, Germany.

Abstract

The syntheses of Ni-poor (NCM111, LiNi_1/3Co_1/3Mn_1/3O₂) and Ni-rich (NCM811 LiNi_0.8Co_0.1Mn_0.1O₂) lithium transition-metal oxides (space group R3̅m) from hydroxide precursors (Ni_1/3Co_1/3Mn_1/3(OH)₂, Ni_0.8Co_0.1Mn_0.1(OH)₂) are investigated using in situ synchrotron powder diffraction and near-edge X-ray absorption fine structure spectroscopy. The development of the layered structure of these two cathode materials proceeds via two utterly different reaction mechanisms. While the synthesis of NCM811 involves a rock salt-type intermediate phase, NCM111 reveals a layered structure throughout the entire synthesis. Moreover, the necessity and the impact of a preannealing step and a high-temperature holding step are discussed.