Compositionally Complex Spinel Oxides as Conversion Anodes for Lithium-Ion Batteries

Nam, Ki-Hun [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0009000320536179); Wang, Zhongling [Stony Brook Univ., NY (United States)] (ORCID:0000000331266189); Luo, Jessica [Stony Brook Univ., NY (United States)]; Ahn, Juhyeon [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)]; Mansley, Zachary R. [Brookhaven National Laboratory (BNL), Upton, NY (United States)] (ORCID:0000000212846316); Kim, Seungkyu [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; University of California, Berkeley, CA (United States); Korea Institute of Energy Technology (KENTECH) (Korea, Republic of)]; Oh, Myoung Hwan [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; Korea Institute of Energy Technology (KENTECH) (Korea, Republic of)]; Scott, Mary C. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; University of California, Berkeley, CA (United States)]; Rodriguez-Campos, Armando [Stony Brook Univ., NY (United States)]; Huang, Cynthia [Stony Brook Univ., NY (United States)] (ORCID:0000000267613317); Millares, Marie F. [Stony Brook Univ., NY (United States)]; Pace, Alexis [Stony Brook Univ., NY (United States)] (ORCID:0009000800956834); Ma, Lu [Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)]; Ehrlich, Steven [Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)]; Bai, Jianming [Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)] (ORCID:0000000205752987); Zhu, Yimei [Stony Brook Univ., NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)] (ORCID:0000000216387217); Takeuchi, Esther S. [Stony Brook Univ., NY (United States)] (ORCID:0000000185181047); Marschilok, Amy C. [Stony Brook Univ., NY (United States)] (ORCID:0000000191740474); Yan, Shan [Stony Brook Univ., NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)] (ORCID:0000000297159100); Takeuchi, Kenneth J. [Stony Brook Univ., NY (United States)] (ORCID:000000018129444X); Doeff, Marca M. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000221488047)

doi:10.1021/acsami.4c21332

DOE OSTI · 2560701

Compositionally Complex Spinel Oxides as Conversion Anodes for Lithium-Ion Batteries

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Abstract

Four different compositionally complex multicomponent M 3 O 4 spinels containing 5–8 distinct metals were prepared by a rapid combustion synthesis method or solvothermal synthesis. High resolution synchrotron X-ray diffraction patterns show that the materials consist primarily of spinel phases with small amounts of rock salt impurities, and, in several samples, a minor amount of contracted spinel phase. Materials were investigated as conversion anodes in lithium half-cells and delivered significantly higher capacities than two-component MgFe 2 O 4 made by combustion synthesis. X-ray absorption near-edge structure (XANES) was used to estimate the oxidation states of the metals in the pristine, lithiated (discharged) and delithiated (charged) materials to better understand the redox processes in half cells that led to the improvement. Co, Ni, and Zn are reduced to low oxidation states during lithiation (cell discharge) but are only partially oxidized. The presence of a conductive metallic network that forms after lithiation is thought to account for the improved electrochemical characteristics. Interestingly, in most of the samples, iron is not fully reduced during initial lithiation unlike what happens with a set of related high entropy spinel ferrites studied previously. Finally, the improved electrochemical properties of these materials illustrates both the advantages of complexity and the difficulties in predicting their behavior.

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Nam, Ki-Hun [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0009000320536179), Wang, Zhongling [Stony Brook Univ., NY (United States)] (ORCID:0000000331266189), Luo, Jessica [Stony Brook Univ., NY (United States)], Ahn, Juhyeon [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)], Mansley, Zachary R. [Brookhaven National Laboratory (BNL), Upton, NY (United States)] (ORCID:0000000212846316), Kim, Seungkyu [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; University of California, Berkeley, CA (United States); Korea Institute of Energy Technology (KENTECH) (Korea, Republic of)], Oh, Myoung Hwan [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; Korea Institute of Energy Technology (KENTECH) (Korea, Republic of)], Scott, Mary C. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; University of California, Berkeley, CA (United States)], Rodriguez-Campos, Armando [Stony Brook Univ., NY (United States)], Huang, Cynthia [Stony Brook Univ., NY (United States)] (ORCID:0000000267613317), Millares, Marie F. [Stony Brook Univ., NY (United States)], Pace, Alexis [Stony Brook Univ., NY (United States)] (ORCID:0009000800956834), Ma, Lu [Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)], Ehrlich, Steven [Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)], Bai, Jianming [Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)] (ORCID:0000000205752987), Zhu, Yimei [Stony Brook Univ., NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)] (ORCID:0000000216387217), Takeuchi, Esther S. [Stony Brook Univ., NY (United States)] (ORCID:0000000185181047), Marschilok, Amy C. [Stony Brook Univ., NY (United States)] (ORCID:0000000191740474), Yan, Shan [Stony Brook Univ., NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)] (ORCID:0000000297159100), Takeuchi, Kenneth J. [Stony Brook Univ., NY (United States)] (ORCID:000000018129444X), Doeff, Marca M. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000221488047). 2025-04-07. Compositionally Complex Spinel Oxides as Conversion Anodes for Lithium-Ion Batteries. https://doi.org/10.1021/acsami.4c21332

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