Prussian Blue Analogues as Positive Electrodes for Mg Batteries: Insights into Mg2+ Intercalation

Potassium manganese hexacianoferrate has been prepared by co-precipitation from manganese (II) chloride and potassium citrate, with chemical analysis yielding the formula K1.72 Mn[Fe(CN)6 ]0.92 □0.08  ⋅ 1.1H2 O (KMnHCF). Its X-ray diffraction pattern is consistent with a monoclinic structure (space...

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Detalhes bibliográficos
Autores: Trócoli, Rafael, Houdeville, Raphaëlle, Frontera, Carlos, Vincent, Smobin, Garcia Lastra, Juan Maria, Palacín, M. Rosa
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/341689
Acesso em linha:http://hdl.handle.net/10261/341689
https://api.elsevier.com/content/abstract/scopus_id/85177747889
Access Level:acceso abierto
Palavra-chave:Prussian blue analogues
Density functional theory
Magnesium batteries
Operando XRD
Descrição
Resumo:Potassium manganese hexacianoferrate has been prepared by co-precipitation from manganese (II) chloride and potassium citrate, with chemical analysis yielding the formula K1.72 Mn[Fe(CN)6 ]0.92 □0.08  ⋅ 1.1H2 O (KMnHCF). Its X-ray diffraction pattern is consistent with a monoclinic structure (space group P 21 /n, no. 14) with cell parameters a=10.1202(6)Å, b=7.2890(5)Å, c=7.0193(4)Å, and β=89.90(1)°. Its redox behavior has been studied in magnesium containing electrolytes. Both K+ ions deintercalated from the structure upon oxidation and contamination with Na+ ions coming from the separator were found to interfere in the electrochemical response. In the absence of alkaline ions, pre-oxidized manganese hexacianoferrate showed reversible magnesium intercalation, and the process has been studied by operando synchrotron X-ray diffraction. The location of Mg2+ ions in the crystal structure was not possible with the available experimental data. Still, density functional theory simulations indicated that the most favorable position for Mg2+ intercalation is at 32f sites (considering a pseudo cubic F m-3m phase), which are located between 8c and Mn sites.