Theory-Guided Regulation of FeN4 Spin State by Neighboring Cu Atoms for Enhanced Oxygen Reduction Electrocatalysis in Flexible Metal-Air Batteries

Ting He; Yang Chen; Qiming Liu; Bingzhang Lu; Xianwen Song; Hongtao Liu; Min Liu; You-Nian Liu; Yi Zhang; Xiaoping Ouyang; Shaowei Chen

doi:10.1002/anie.202201007

Theory-Guided Regulation of FeN₄ Spin State by Neighboring Cu Atoms for Enhanced Oxygen Reduction Electrocatalysis in Flexible Metal-Air Batteries

Angew Chem Int Ed Engl. 2022 Jul 4;61(27):e202201007. doi: 10.1002/anie.202201007. Epub 2022 May 5.

Authors

Ting He^{1

2}, Yang Chen¹, Qiming Liu³, Bingzhang Lu³, Xianwen Song¹, Hongtao Liu¹, Min Liu⁴, You-Nian Liu¹, Yi Zhang^{1

5}, Xiaoping Ouyang², Shaowei Chen³

Affiliations

¹ Hunan Provincial Key Laboratory of Micro & Nano Materials Interface Science, College of Chemistry and Chemical Engineering, Central South University, 932 Lushan South Road, Changsha, Hunan, 410083, China.
² School of Materials Science and Engineering, Xiangtan University Yuhu District, Xiangtan, Hunan, 411105, China.
³ Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, CA 95064, USA.
⁴ School of Physics and Electronics, Central South University, Changsha, Hunan, 410083, China.
⁵ Key Laboratory of Materials Processing and Mold, Ministry of Education, Zhengzhou University, Zhengzhou, Henan, 450002, China.

PMID: 35468253
DOI: 10.1002/anie.202201007

Abstract

Iron, nitrogen-codoped carbon (Fe-N-C) nanocomposites have emerged as viable electrocatalysts for the oxygen reduction reaction (ORR) due to the formation of FeN_x C_y coordination moieties. In this study, results from first-principles calculations show a nearly linear correlation of the energy barriers of key reaction steps with the Fe magnetic moment. Experimentally, when single Cu sites are incorporated into Fe-N-C aerogels (denoted as NCAG/Fe-Cu), the Fe centers exhibit a reduced magnetic moment and markedly enhanced ORR activity within a wide pH range of 0-14. With the NCAG/Fe-Cu nanocomposites used as the cathode catalyst in a neutral/quasi-solid aluminum-air and alkaline/quasi-solid zinc-air battery, both achieve a remarkable performance with an ultrahigh open-circuit voltage of 2.00 and 1.51 V, large power density of 130 and 186 mW cm^-2 , and good mechanical flexibility, all markedly better than those with commercial Pt/C or Pt/C-RuO₂ catalysts at the cathode.

Keywords: Electron Spin State; Heteronuclear Site; Magnetic Moment; Metal-Air Battery; Oxygen Reduction Reaction.

Abstract

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