Probing thermally-induced structural evolution during the synthesis of layered Li-, Na-, or K-containing 3<i>d</i> transition-metal oxides

Hua Weibo; Yang Xiaoxia; Casati Nicola P.M.; Liu Laijun; Wang Suning; Baran Volodymyr; Knapp Michael; Ehrenberg Helmut; Indris Sylvio

doi:10.1016/j.esci.2022.02.007

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Hua Weibo, Yang Xiaoxia, Casati Nicola P.M., Liu Laijun, Wang Suning, Baran Volodymyr, Knapp Michael, Ehrenberg Helmut, Indris Sylvio. Probing thermally-induced structural evolution during the synthesis of layered Li-, Na-, or K-containing 3d transition-metal oxides[J]. eScience, 2022, 2(2): 183-191. doi: 10.1016/j.esci.2022.02.007

Citation:

Hua Weibo, Yang Xiaoxia, Casati Nicola P.M., Liu Laijun, Wang Suning, Baran Volodymyr, Knapp Michael, Ehrenberg Helmut, Indris Sylvio. Probing thermally-induced structural evolution during the synthesis of layered Li-, Na-, or K-containing 3d transition-metal oxides[J]. eScience, 2022, 2(2): 183-191. doi: 10.1016/j.esci.2022.02.007

Citation:

Hua Weibo, Yang Xiaoxia, Casati Nicola P.M., Liu Laijun, Wang Suning, Baran Volodymyr, Knapp Michael, Ehrenberg Helmut, Indris Sylvio. Probing thermally-induced structural evolution during the synthesis of layered Li-, Na-, or K-containing 3d transition-metal oxides[J]. eScience, 2022, 2(2): 183-191. doi: 10.1016/j.esci.2022.02.007

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Probing thermally-induced structural evolution during the synthesis of layered Li-, Na-, or K-containing 3d transition-metal oxides

doi: 10.1016/j.esci.2022.02.007

a.
School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an, Shaanxi, 710049, China
b.
Institute for Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, D-76344, Eggenstein-Leopoldshafen, Germany
c.
College of Materials Science and Engineering, Guilin University of Technology, Guilin, 541004, China
d.
Paul Scherrer Institut (PSI), WLGA/229, 5232, Villigen PSI, Switzerland
e.
Deutsches Elektronen-Synchrotron (DESY), Notkestr. 85, Hamburg, 22607, Germany

More Information

Corresponding author: Weibo Hua weibo.hua@xjtu.edu.cn; Suning Wang suning.wang@xjtu.edu.cn; Sylvio Indris sylvio.indris@kit.edu
Received Date: 2021-12-13
Revised Date: 2022-01-16
Accepted Date: 2022-02-22

Available Online: 2022-03-07

Abstract

Abstract

Layered alkali-containing 3d transition-metal oxides are of the utmost importance in the use of electrode materials for advanced energy storage applications such as Li-, Na-, or K-ion batteries. A significant challenge in the field of materials chemistry is understanding the dynamics of the chemical reactions between alkali-free precursors and alkali species during the synthesis of these compounds. In this study, in situ high-resolution synchrotron-based X-ray diffraction was applied to reveal the Li/Na/K-ion insertion-induced structural transformation mechanism during high-temperature solid-state reaction. The in situ diffraction results demonstrate that the chemical reaction pathway strongly depends on the alkali-free precursor type, which is a structural matrix enabling phase transitions. Quantitative phase analysis identifies for the first time the decomposition of lithium sources as the most critical factor for the formation of metastable intermediates or impurities during the entire process of Li-rich layered Li[Li_0.2Ni_0.2Mn_0.6]O₂ formation. Since the alkali ions have different ionic radii, Na/K ions tend to be located on prismatic sites in the defective layered structure (Na[Ni_0.25Mn_0.75]O₂ or K[Ni_0.25Mn_0.75]O₂) during calcination, whereas the Li ions prefer to be localized on the tetrahedral and/or octahedral sites, forming O-type structures.
- In situ sXRD,
- Structural evolution,
- 3d transition-metal oxides,
- Layered structure,
- High-temperature solid-state reaction

● In situ high-resolution HT-sXRD techniques was used to unveil the Li/Na/K-ion insertion induced structural evolution during heating.
● High-temperature lithiation reaction pathway strongly depends on the alkali-free precursor type.
● The dynamics of chemical reaction between alkali-free precursor and alkali species upon calcination were systematically investigated.
● Site preferences of Li/Na/K-ion leads to the formation of various types of layered structures.

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