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...
| Autores: | , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2023 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/341689 |
| Acceso en línea: | http://hdl.handle.net/10261/341689 https://api.elsevier.com/content/abstract/scopus_id/85177747889 |
| Access Level: | acceso abierto |
| Palabra clave: | Prussian blue analogues Density functional theory Magnesium batteries Operando XRD |
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Prussian Blue Analogues as Positive Electrodes for Mg Batteries: Insights into Mg2+ IntercalationTrócoli, RafaelHoudeville, RaphaëlleFrontera, CarlosVincent, SmobinGarcia Lastra, Juan MariaPalacín, M. RosaPrussian blue analoguesDensity functional theoryMagnesium batteriesOperando XRDPotassium 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.The authors are grateful to Ashley Black (ICMAB-CSIC) and Jean-Frederic Martin (CEA) for helpful discussions and to François Fauth (ALBA synchrotron beamline scientist) for assistance during SXRD measurements (beamtime awarded under proposal 2021075225). ICMAB-CSIC authors are grateful to the Spanish Agencia Estatal de Investigación for Severo Ochoa FUNFUTURE (CEX2019-000917-S) distinction. Funding through the European Union's Horizon 2020 research and innovation programme under grant agreement No 824066 (E-MAGIC), Junta de Andalucía (EMERGIA_00153, ProyExcel_00330 PAIDI 2020), and project TED2021-129314A-100 funded by MCIN/AEI/10.13039/501100011033 and European Union NextGenerationEU/PRTR is gratefully acknowledged. Authors acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI).With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).Peer reviewedWiley-VCHAgencia Estatal de Investigación (España)European CommissionJunta de AndalucíaMinisterio de Ciencia e Innovación (España)CSIC - Unidad de Recursos de Información Científica para la Investigación (URICI)Trócoli, Rafael [0000-0001-8071-6882]Houdeville, Raphaëlle [0000-0002-6100-1432]Frontera, Carlos [0000-0002-0091-4756]Vincent, Smobin [0000-0002-6147-4360]Garcia Lastra, Juan Maria [0000-0001-5311-3656]Palacín, M. Rosa [0000-0001-7351-2005]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202420242023info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/341689https://api.elsevier.com/content/abstract/scopus_id/85177747889reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de investigación Científica y Técnica y de Innovación 2017-2020/CEX2019-000917-Sinfo:eu-repo/grantAgreement/EC/H2020/824066info:eu-repo/grantAgreement/AEI//TED2021-129314A-100ChemSusChemhttp://doi.org/10.1002/cssc.202301224Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3416892026-05-22T06:33:51Z |
| dc.title.none.fl_str_mv |
Prussian Blue Analogues as Positive Electrodes for Mg Batteries: Insights into Mg2+ Intercalation |
| title |
Prussian Blue Analogues as Positive Electrodes for Mg Batteries: Insights into Mg2+ Intercalation |
| spellingShingle |
Prussian Blue Analogues as Positive Electrodes for Mg Batteries: Insights into Mg2+ Intercalation Trócoli, Rafael Prussian blue analogues Density functional theory Magnesium batteries Operando XRD |
| title_short |
Prussian Blue Analogues as Positive Electrodes for Mg Batteries: Insights into Mg2+ Intercalation |
| title_full |
Prussian Blue Analogues as Positive Electrodes for Mg Batteries: Insights into Mg2+ Intercalation |
| title_fullStr |
Prussian Blue Analogues as Positive Electrodes for Mg Batteries: Insights into Mg2+ Intercalation |
| title_full_unstemmed |
Prussian Blue Analogues as Positive Electrodes for Mg Batteries: Insights into Mg2+ Intercalation |
| title_sort |
Prussian Blue Analogues as Positive Electrodes for Mg Batteries: Insights into Mg2+ Intercalation |
| dc.creator.none.fl_str_mv |
Trócoli, Rafael Houdeville, Raphaëlle Frontera, Carlos Vincent, Smobin Garcia Lastra, Juan Maria Palacín, M. Rosa |
| author |
Trócoli, Rafael |
| author_facet |
Trócoli, Rafael Houdeville, Raphaëlle Frontera, Carlos Vincent, Smobin Garcia Lastra, Juan Maria Palacín, M. Rosa |
| author_role |
author |
| author2 |
Houdeville, Raphaëlle Frontera, Carlos Vincent, Smobin Garcia Lastra, Juan Maria Palacín, M. Rosa |
| author2_role |
author author author author author |
| dc.contributor.none.fl_str_mv |
Agencia Estatal de Investigación (España) European Commission Junta de Andalucía Ministerio de Ciencia e Innovación (España) CSIC - Unidad de Recursos de Información Científica para la Investigación (URICI) Trócoli, Rafael [0000-0001-8071-6882] Houdeville, Raphaëlle [0000-0002-6100-1432] Frontera, Carlos [0000-0002-0091-4756] Vincent, Smobin [0000-0002-6147-4360] Garcia Lastra, Juan Maria [0000-0001-5311-3656] Palacín, M. Rosa [0000-0001-7351-2005] Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72] |
| dc.subject.none.fl_str_mv |
Prussian blue analogues Density functional theory Magnesium batteries Operando XRD |
| topic |
Prussian blue analogues Density functional theory Magnesium batteries Operando XRD |
| description |
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. |
| publishDate |
2023 |
| dc.date.none.fl_str_mv |
2023 2024 2024 |
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info:eu-repo/semantics/article http://purl.org/coar/resource_type/c_6501 Publisher's version info:eu-repo/semantics/publishedVersion |
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article |
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publishedVersion |
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http://hdl.handle.net/10261/341689 https://api.elsevier.com/content/abstract/scopus_id/85177747889 |
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http://hdl.handle.net/10261/341689 https://api.elsevier.com/content/abstract/scopus_id/85177747889 |
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Inglés |
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Inglés |
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#PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# info:eu-repo/grantAgreement/AEI/Plan Estatal de investigación Científica y Técnica y de Innovación 2017-2020/CEX2019-000917-S info:eu-repo/grantAgreement/EC/H2020/824066 info:eu-repo/grantAgreement/AEI//TED2021-129314A-100 ChemSusChem http://doi.org/10.1002/cssc.202301224 Sí |
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Wiley-VCH |
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