{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,17]],"date-time":"2026-04-17T07:46:29Z","timestamp":1776411989115,"version":"3.51.2"},"reference-count":75,"publisher":"MDPI AG","issue":"22","license":[{"start":{"date-parts":[[2022,11,15]],"date-time":"2022-11-15T00:00:00Z","timestamp":1668470400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Romanian Ministry of Education and Research, CNCS-UEFISCDI","award":["PN-III-P1-1.1-TE-2019-1767"],"award-info":[{"award-number":["PN-III-P1-1.1-TE-2019-1767"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Materials"],"abstract":"<jats:p>Iron phosphate materials have attracted a lot of attention due to their potential as cathode materials for lithium-ion rechargeable batteries. It has been shown that lithium insertion or extraction depends on the Fe mixed valence and reduction or oxidation of the Fe ions\u2019 valences. In this paper, we report a new synthesis method for the Fe3(PO3OH)4(H2O)4 mixed valence iron phosphate. In addition, we perform temperature-dependent measurements of structural and physical properties in order to obtain an understanding of electronic\u2013structural interplay in this compound. Scanning electron microscope images show needle-like single crystals of 50 \u03bcm to 200 \u03bcm length which are stable up to approximately 200 \u00b0C, as revealed by thermogravimetric analysis. The crystal structure of Fe3(PO3OH)4(H2O)4 single crystals has been determined in the temperature range of 90 K to 470 K. A monoclinic isostructural phase transition was found at ~213 K, with unit cell volume doubling in the low temperature phase. While the local environment of the Fe2+ ions does not change significantly across the structural phase transition, small antiphase rotations occur for the Fe3+ octahedra, implying some kind of electronic order. These results are corroborated by first principle calculations within density functional theory, which also point to ordering of the electronic degrees of freedom across the transition. The structural phase transition is confirmed by specific heat measurements. Moreover, hints of 3D antiferromagnetic ordering appear below ~11 K in the magnetic susceptibility measurements. Room temperature visible light absorption is consistent with the Fe2+\/Fe3+ mixed valence.<\/jats:p>","DOI":"10.3390\/ma15228059","type":"journal-article","created":{"date-parts":[[2022,11,16]],"date-time":"2022-11-16T02:36:36Z","timestamp":1668566196000},"page":"8059","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Phase Transitions and Physical Properties of the Mixed Valence Iron Phosphate Fe3(PO3OH)4(H2O)4"],"prefix":"10.3390","volume":"15","author":[{"given":"Maria","family":"Poienar","sequence":"first","affiliation":[{"name":"National Institute for Research and Development in Electrochemistry and Condensed Matter, Str. Dr. Aurel P\u0103unescu Podeanu Nr. 144, 300569 Timisoara, Romania"},{"name":"MANSiD Research Center and Faculty of Forestry, Stefan Cel Mare University, 720229 Suceava, Romania"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Matthias Josef","family":"Gutmann","sequence":"additional","affiliation":[{"name":"Rutherford Appleton Laboratory, ISIS Facility, Chilton Didcot, Oxfordshire OX11 0QX, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5699-2470","authenticated-orcid":false,"given":"Gheorghe Lucian","family":"Pascut","sequence":"additional","affiliation":[{"name":"MANSiD Research Center and Faculty of Forestry, Stefan Cel Mare University, 720229 Suceava, Romania"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"V\u00e1clav","family":"Pet\u0159\u00ed\u010dek","sequence":"additional","affiliation":[{"name":"Institute of Physics, Academy of Sciences of the Czech Republic, 182 21 Prague 8, Czech Republic"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Gavin","family":"Stenning","sequence":"additional","affiliation":[{"name":"Rutherford Appleton Laboratory, ISIS Facility, Chilton Didcot, Oxfordshire OX11 0QX, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Paulina","family":"Vlazan","sequence":"additional","affiliation":[{"name":"National Institute for Research and Development in Electrochemistry and Condensed Matter, Str. Dr. Aurel P\u0103unescu Podeanu Nr. 144, 300569 Timisoara, Romania"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Paula","family":"Sfirloaga","sequence":"additional","affiliation":[{"name":"National Institute for Research and Development in Electrochemistry and Condensed Matter, Str. Dr. Aurel P\u0103unescu Podeanu Nr. 144, 300569 Timisoara, Romania"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Carsten","family":"Paulmann","sequence":"additional","affiliation":[{"name":"Mineralogisch-Petrographisches Institute, Universit\u00e4t Hamburg, 20146 Hamburg, Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Martin","family":"Tolkiehn","sequence":"additional","affiliation":[{"name":"Deutsches Elektronensynchrotron DESY, Notkestrasse 85, 22603 Hamburg, Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Pascal","family":"Manuel","sequence":"additional","affiliation":[{"name":"Rutherford Appleton Laboratory, ISIS Facility, Chilton Didcot, Oxfordshire OX11 0QX, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0204-1266","authenticated-orcid":false,"given":"Philippe","family":"Veber","sequence":"additional","affiliation":[{"name":"Institut Lumi\u00e8re Mati\u00e8re, Universit\u00e9 Claude Bernard Lyon 1, University of Lyon, CNRS, F-69622 Villeurbanne, France"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2022,11,15]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1623","DOI":"10.1021\/acs.chemrev.0c00767","article-title":"Promises and Challenges of Next-Generation \u201cBeyond Li-ion\u201d Batteries for Electric Vehicles and Grid Decarbonization","volume":"121","author":"Tian","year":"2021","journal-title":"Chem. 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