Mitigating Jahn–Teller effects by fast electrode kinetics inducing charge redistribution
Manganese hexacyanomanganates have attracted significant attention as promising cathode materials for sodium-ion batteries owing to the high theoretical capacity and low cost of Mn resources. Because of the strong Jahn–Teller effect, causing unstable local phase transition and distortion, the redox...
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sg-ntu-dr.10356-1632892022-11-30T05:28:22Z Mitigating Jahn–Teller effects by fast electrode kinetics inducing charge redistribution Choi, Ahreum Kim, Taewon Kim, Min-Ho Lee, Seok Woo Jung, Young Hwa Lee, Hyun-Wook School of Electrical and Electronic Engineering Engineering::Electrical and electronic engineering Charge Redistribution Jahn-Teller Effect Manganese hexacyanomanganates have attracted significant attention as promising cathode materials for sodium-ion batteries owing to the high theoretical capacity and low cost of Mn resources. Because of the strong Jahn–Teller effect, causing unstable local phase transition and distortion, the redox reactions of the high-spin state of Mn(III) are considered to be a conundrum. Herein, it is reported that the charge-redistribution mechanism of low-spin MnIII + high-spin MnIII → low-spin MnII + high-spin MnIV in manganese hexacyanomanganates can decrease unstable high-spin MnIII, leading to the mitigation of Jahn–Teller distortion. X-ray absorption near-edge spectroscopy and X-ray photoelectron spectroscopy suggest that the fast reaction rate activates charge redistribution. Moreover, different crystal structures, reported using post-mortem synchrotron X-ray diffraction analysis, confirm a large orthorhombic structure, thus verifying the presence of charge redistribution based on the superexchange rule. These results demonstrate that manganese hexacyanomanganate in an aqueous electrolyte can achieve long-term cyclability, thus paving the way for high-performance batteries. Ministry of Education (MOE) A.C. and T.K. contributed equally to this work. This work was supported by the 2021 Research Fund (Grant No. 1.210033.01) of UNIST, Individual Basic Science & Engineering Research Program (Program No. 2019R1C1C1009324), and the Technology Development Program to Solve Climate Changes (Program No. 2021M1A2A2038148) through the National Research Foundation of Korea funded by the Ministry of Science and ICT (MSIT). A.C. and H.-W.L. acknowledge support from the Ministry of Trade, Industry & Energy/Korea Institute of Energy Technology Evaluation and Planning (MOTIE/KETEP) (Grant No. 20194010000100). S.W.L. acknowledges the support by Academic Research Fund Tier 2 from Ministry of Education, Singapore under ref. no. MOE2019-T2-1-122. 2022-11-30T05:28:21Z 2022-11-30T05:28:21Z 2022 Journal Article Choi, A., Kim, T., Kim, M., Lee, S. W., Jung, Y. H. & Lee, H. (2022). Mitigating Jahn–Teller effects by fast electrode kinetics inducing charge redistribution. Advanced Functional Materials, 32(19), 2111901-. https://dx.doi.org/10.1002/adfm.202111901 1616-301X https://hdl.handle.net/10356/163289 10.1002/adfm.202111901 2-s2.0-85122638647 19 32 2111901 en MOE2019-T2-1-12 Advanced Functional Materials © 2022 Wiley-VCH GmbH. All rights reserved. |
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Engineering::Electrical and electronic engineering Charge Redistribution Jahn-Teller Effect Choi, Ahreum Kim, Taewon Kim, Min-Ho Lee, Seok Woo Jung, Young Hwa Lee, Hyun-Wook Mitigating Jahn–Teller effects by fast electrode kinetics inducing charge redistribution |
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Manganese hexacyanomanganates have attracted significant attention as promising cathode materials for sodium-ion batteries owing to the high theoretical capacity and low cost of Mn resources. Because of the strong Jahn–Teller effect, causing unstable local phase transition and distortion, the redox reactions of the high-spin state of Mn(III) are considered to be a conundrum. Herein, it is reported that the charge-redistribution mechanism of low-spin MnIII + high-spin MnIII → low-spin MnII + high-spin MnIV in manganese hexacyanomanganates can decrease unstable high-spin MnIII, leading to the mitigation of Jahn–Teller distortion. X-ray absorption near-edge spectroscopy and X-ray photoelectron spectroscopy suggest that the fast reaction rate activates charge redistribution. Moreover, different crystal structures, reported using post-mortem synchrotron X-ray diffraction analysis, confirm a large orthorhombic structure, thus verifying the presence of charge redistribution based on the superexchange rule. These results demonstrate that manganese hexacyanomanganate in an aqueous electrolyte can achieve long-term cyclability, thus paving the way for high-performance batteries. |
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School of Electrical and Electronic Engineering |
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School of Electrical and Electronic Engineering Choi, Ahreum Kim, Taewon Kim, Min-Ho Lee, Seok Woo Jung, Young Hwa Lee, Hyun-Wook |
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Article |
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Choi, Ahreum Kim, Taewon Kim, Min-Ho Lee, Seok Woo Jung, Young Hwa Lee, Hyun-Wook |
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Choi, Ahreum |
title |
Mitigating Jahn–Teller effects by fast electrode kinetics inducing charge redistribution |
title_short |
Mitigating Jahn–Teller effects by fast electrode kinetics inducing charge redistribution |
title_full |
Mitigating Jahn–Teller effects by fast electrode kinetics inducing charge redistribution |
title_fullStr |
Mitigating Jahn–Teller effects by fast electrode kinetics inducing charge redistribution |
title_full_unstemmed |
Mitigating Jahn–Teller effects by fast electrode kinetics inducing charge redistribution |
title_sort |
mitigating jahn–teller effects by fast electrode kinetics inducing charge redistribution |
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2022 |
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https://hdl.handle.net/10356/163289 |
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1751548499612139520 |