High-Entropy NASICON Phosphates (Na3M2(PO4)3 and NaMPO4Ox, M = Ti, V, Mn, Cr, and Zr) for Sodium Electrochemistry
- Bing Wu*Bing Wu*E-mail: [email protected]Department of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech RepublicMore by Bing Wu
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- Guorong HouGuorong HouDepartment of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech RepublicMore by Guorong Hou
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- Evgeniya KovalskaEvgeniya KovalskaDepartment of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech RepublicMore by Evgeniya Kovalska
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- Vlastimil MazanekVlastimil MazanekDepartment of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech RepublicMore by Vlastimil Mazanek
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- Petr MarvanPetr MarvanDepartment of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech RepublicMore by Petr Marvan
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- Liping LiaoLiping LiaoDepartment of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech RepublicMore by Liping Liao
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- Lukas DekanovskyLukas DekanovskyDepartment of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech RepublicMore by Lukas Dekanovsky
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- David SedmidubskyDavid SedmidubskyDepartment of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech RepublicMore by David Sedmidubsky
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- Ivo MarekIvo MarekCentral Laboratories, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech RepublicMore by Ivo Marek
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- Charles HervochesCharles HervochesNuclear Physics Institute, Czech Academy of Sciences, 250 68 Řež, Czech RepublicMore by Charles Hervoches
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- Zdenek Sofer*Zdenek Sofer*E-mail: [email protected]Department of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech RepublicMore by Zdenek Sofer
Abstract
High-entropy materials, with complex compositions and unique cocktail characteristics, have recently drawn significant attention. Additionally, a family of sodium super ion conductors (NASICONs)-structured phosphates in energy storage areas shows a comprehensive application for traditional alkaline ion batteries and, in particular, solid-state electrolytes. However, there is no precedent in fabricating this kind of NASICON-type high-entropy phase. Here, we report the successful fabrication of two well-crystallized high-entropy phosphates, namely, Na3(Ti0.2V0.2Mn0.2Cr0.2Zr0.2)2(PO4)3 (HE-N3M2P3) and Na(Ti0.2V0.2Mn0.2Cr0.2Zr0.2)2PO4Ox (HE-NMP). The prepared materials in which the transition metals (TMs) of Ti, V, Mn, Cr, and Zr occupy the same 12c Wykoff position can form a structure analogous to R3̅c Na3V2(PO4)3 that is carefully determined by X-ray diffraction, neutron diffraction, and transmission electron microscopy. Further, their performance for sodium ion batteries and sodium-based solid-state electrolytes was evaluated. The HE-N3M2P3 might exhibit a promising electrochemical performance for sodium storage in terms of its structure resembling that of Na3V2(PO4)3. Meanwhile, the HE-NMP shows considerable electrochemical activity with numerous broad redox ranges during extraction and insertion of Na+, related to the coexistence of several TM elements. The evaluated temperature-dependent ionic conductivity for HE-NMP solid electrolyte varies from 10–6 to 10–5 S cm–1 from room temperature to 398.15 K, offering high potential for energy storage applications as a new high-entropy system.
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