Wu Bing, Hou Guorong, Kovalska Evgeniya, Mazanek Vlastimil, Marvan Petr, Liao Liping, Dekanovsky Lukas, Sedmidubsky David, Marek Ivo, Hervoches Charles, Sofer Zdenek
Department of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic.
Central Laboratories, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic.
Inorg Chem. 2022 Mar 7;61(9):4092-4101. doi: 10.1021/acs.inorgchem.1c03861. Epub 2022 Feb 22.
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, Na(TiVMnCrZr)(PO) (HE-NMP) and Na(TiVMnCrZr)POO (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 3̅ NaV(PO) 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-NMP might exhibit a promising electrochemical performance for sodium storage in terms of its structure resembling that of NaV(PO). 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 to 10 S cm from room temperature to 398.15 K, offering high potential for energy storage applications as a new high-entropy system.
具有复杂成分和独特混合特性的高熵材料最近引起了广泛关注。此外，储能领域中的一族钠超离子导体（NASICONs）结构的磷酸盐在传统碱性离子电池，特别是固态电解质方面显示出广泛的应用。然而，制造这种NASICON型高熵相尚无先例。在此，我们报告成功制备了两种结晶良好的高熵磷酸盐，即Na(TiVMnCrZr)(PO)（HE-NMP）和Na(TiVMnCrZr)POO（HE-NMP）。通过X射线衍射、中子衍射和透射电子显微镜仔细确定，所制备的材料中Ti、V、Mn、Cr和Zr的过渡金属（TMs）占据相同的12c Wyckoff位置，可形成类似于3̅ NaV(PO)的结构。此外，还评估了它们在钠离子电池和钠基固态电解质方面的性能。HE-NMP因其结构类似于NaV(PO)，在钠存储方面可能表现出有前景的电化学性能。同时，HE-NMP在Na的脱出和嵌入过程中表现出相当大的电化学活性，具有多个宽的氧化还原范围，这与几种TM元素的共存有关。评估的HE-NMP固体电解质的温度依赖性离子电导率在室温至398.15 K范围内从10到10 S cm变化，作为一种新的高熵体系，在储能应用方面具有很高的潜力。
