Entropy‐Mediated Stable Structural Evolution of Prussian White Cathodes for Long‐Life Na‐Ion Batteries
Angewandte Chemie, vol. 136
Abstract
Abstract The high‐entropy approach is applied to monoclinic Prussian White (PW) Na‐ion cathodes to address the issue of unfavorable multilevel phase transitions upon electrochemical cycling, leading to poor stability and capacity decay. A series of Mn‐based samples with up to six metal species sharing the N‐coordinated positions was synthesized. The material of composition Na1.65Mn0.4Fe0.12Ni0.12Cu0.12Co0.12Cd0.12[Fe(CN)6]0.92□0.08 ⋅ 1.09H2O was found to exhibit superior cyclability over medium/low‐entropy and conventional single‐metal PWs. We also report, to our knowledge for the first time, that a high‐symmetry crystal structure may be advantageous for high‐entropy PWs during battery operation. Computational comparisons of the formation enthalpy demonstrate that the compositionally less complex materials are prone to phase transitions, which negatively affect cycling performance. Based on data from complementary characterization techniques, an intrinsic mechanism for the stability improvement of the disordered PW structure upon Na+ insertion/extraction is proposed, namely the dual effect of suppression of phase transitions and mitigation of gas evolution.
Authors 15
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Karlsruhe Institute of Technology
Affiliation as printed
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
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Karlsruhe Institute of Technology
Affiliation as printed
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
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Yin‐Ying Ting Aachen Chair of Theory and Computation of Energy Materials Faculty of Georesources and Materials Engineering
Forschungszentrum Jülich · RWTH Aachen University
Affiliation as printed
Chair of Theory and Computation of Energy Materials Faculty of Georesources and Materials Engineering RWTH Aachen University 52062 Aachen Germany
Institute of Energy and Climate Research (IEK-13) Forschungszentrum Jülich GmbH Wilhelm-Johnen-Str. 52428 Jülich Germany
Institute of Energy and Climate Research (IEK-13) Forschungszentrum Jülich GmbH Wilhelm-Johnen-Str. 52428 Jülich Germany
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Yuan Ma corresponding
Karlsruhe Institute of Technology · Nanjing Normal University
Affiliation as printed
Current address: School of Energy and Mechanical Engineering Jiangsu Key Laboratory of New Power Batteries Nanjing Normal University Nanjing 210023 China
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
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Karlsruhe Institute of Technology · Umicore (Belgium) · Helmholtz-Institute Ulm
Affiliation as printed
Helmholtz Institute Ulm (HIU) for Electrochemical Energy Storage Helmholtzstr. 11 89081 Ulm Germany
Current address: Corporate Research and Development, Umicore Watertorenstraat 33 2250 Olen Belgium
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
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Karlsruhe Institute of Technology · Umicore (Belgium)
Affiliation as printed
Current address: Corporate Research and Development, Umicore Watertorenstraat 33 2250 Olen Belgium
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
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Karlsruhe Institute of Technology · Helmholtz-Institute Ulm
Affiliation as printed
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
Helmholtz Institute Ulm (HIU) for Electrochemical Energy Storage Helmholtzstr. 11 89081 Ulm Germany
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Karlsruhe Institute of Technology · Helmholtz-Institute Ulm
Affiliation as printed
Helmholtz Institute Ulm (HIU) for Electrochemical Energy Storage Helmholtzstr. 11 89081 Ulm Germany
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
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Bei Zhou Aachen Chair of Theory and Computation of Energy Materials Faculty of Georesources and Materials Engineering
Karlsruhe Institute of Technology · Universitätsklinikum Aachen · Jülich Aachen Research Alliance · RWTH Aachen University
Affiliation as printed
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
Jülich Aachen Research Alliance JARA Energy & Center for Simulation and Data Science (CSD) 52425 Jülich Germany
Uniklinik RWTH Aachen: Universitatsklinikum Aachen, Chair of Theory and Computation of Energy Materials, Faculty of Georesources and Materials Engineering, GERMANY
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Piotr M. Kowalski Aachen Chair of Theory and Computation of Energy Materials Faculty of Georesources and Materials Engineering
Helmholtz-Institute Ulm · Jülich Aachen Research Alliance · RWTH Aachen University
Affiliation as printed
Chair of Theory and Computation of Energy Materials Faculty of Georesources and Materials Engineering RWTH Aachen University 52062 Aachen Germany
Jülich Aachen Research Alliance JARA Energy & Center for Simulation and Data Science (CSD) 52425 Jülich Germany
Helmholtz Institute Ulm (HIU) for Electrochemical Energy Storage Helmholtzstr. 11 89081 Ulm Germany
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Karlsruhe Institute of Technology · Helmholtz-Institute Ulm · University of Oklahoma
Affiliation as printed
Helmholtz Institute Ulm (HIU) for Electrochemical Energy Storage Helmholtzstr. 11 89081 Ulm Germany
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
School of Chemical Biological and Materials Engineering The University of Oklahoma Norman OK, 73019 USA
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Karlsruhe Institute of Technology · University of Oklahoma
Affiliation as printed
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
School of Chemical Biological and Materials Engineering The University of Oklahoma Norman OK, 73019 USA
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
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Karlsruhe Institute of Technology
Affiliation as printed
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
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Karlsruhe Institute of Technology
Affiliation as printed
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
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Karlsruhe Institute of Technology · Nanjing Normal University
Affiliation as printed
Institute of Nanotechnology Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany
Current address: School of Energy and Mechanical Engineering Jiangsu Key Laboratory of New Power Batteries Nanjing Normal University Nanjing 210023 China
Karlsruhe Institute of Technology: Karlsruher Institut fur Technologie, Institute of Nanotechnology, Hermann-von-Helmholtz Platz 1, 76344 Eggenstein-Leopoldshafen, GERMANY
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