Insights into the Rich Polymorphism of the Na+ Ion Conductor Na3PS4 from the Perspective of Variable-Temperature Diffraction and Spectroscopy

被引：44

作者：

Famprikis, Theodosios ^{[10
,12
,14
,15
,16
]}

Bouyanfif, Houssny ^{[1
]}

Canepa, Pieremanuele ^{[2
,3
]}

Zbiri, Mohamed ^{[4
]}

Dawson, James A. ^{[5
,6
]}

Suard, Emmanuelle ^{[4
]}

Fauth, Francois ^{[7
]}

Playford, Helen Y. ^{[8
]}

Dambournet, Damien ^{[9
,10
]}

Borkiewicz, Olaf J. ^{[11
]}

Courty, Matthieu ^{[10
,12
]}

Clemens, Oliver ^{[13
]}

Chotard, Jean-Noel ^{[10
,12
]}

Islam, M. Saiful ^{[14
,15
]}

Masquelier, Christian ^{[10
,12
,15
]}

机构：

[1] Univ Picardie Jules Verne, UR 2081, Lab Phys Matiere Condensee LPMC, F-80039 Amiens, France

[2] Natl Univ Singapore, Dept Mat Sci & Engn, Singapore 117576, Singapore

[3] Natl Univ Singapore, Dept Chem & Biomol Engn, Singapore 117585, Singapore

[4] Inst Laue Langevin ILL, F-38042 Grenoble, France

[5] Newcastle Univ, Chem Sch Nat & Environm Sci, Newcastle Upon Tyne NE1 7RU, Tyne & Wear, England

[6] Newcastle Univ, Ctr Energy, Newcastle Upon Tyne NE1 7RU, Tyne & Wear, England

[7] ILL, CELLS ALBA Synchrotron, Barcelona 08290, Spain

[8] Rutherford Appleton Lab, ISIS Facil, Didcot OX11 0QX, Oxon, England

[9] Sorbonne Univ, Phys Chim Electrolytes & Nanosyst Interfaciaux PH, CNRS, UMR 8234, F-75005 Paris, France

[10] CNRS FR 3459, Reseau Stockage Electrochim Energie RS2E, F-80039 Amiens, France

[11] Argonne Natl Lab, Xray Sci Div, Adv Photon Source, Argonne, IL 60439 USA

[12] Univ Picardie Jules Verne, Lab Reactivite & Chim Solides LRCS, CNRS, UMR 7314, F-80039 Amiens, France

[13] Univ Stuttgart, Inst Mat Sci, Mat Synth Grp, D-70569 Stuttgart, Germany

[14] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England

[15] CNRS FR 3104, ALISTORE European Res Inst, F-80039 Amiens, France

[16] Delft Univ Technol, Dept Radiat Sci & Technol, Storage Electrochem Energy, Delft, Netherlands

来源：

CHEMISTRY OF MATERIALS | 2021年 / 33卷 / 14期

基金：

英国工程与自然科学研究理事会; 新加坡国家研究基金会;

关键词：

SUPERIONIC CONDUCTOR; CRYSTAL-STRUCTURE; LATTICE-DYNAMICS; FDDD PHASE; NA3SBS4; ELECTROLYTES; STABILITY; TRANSPORT; NETWORK; TRANSITIONS;

D O I：

10.1021/acs.chemmater.1c01113

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Solid electrolytes are crucial for next-generation solid-state batteries, and Na3PS4 is one of the most promising Na+ conductors for such applications, despite outstanding questions regarding its structural polymorphs. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 over a wide temperature range 30 < T < 600 degrees C through combined experimental-computational analysis. Although Bragg diffraction experiments indicate a second-order phase transition from the tetragonal ground state (a, P (4) over bar2(1)c) to the cubic polymorph (beta, I (4) over bar 3m) above similar to 250 degrees C, pair distribution function analysis in real space and Raman spectroscopy indicate remnants of a tetragonal character in the range 250 < T < 500 degrees C, which we attribute to dynamic local tetragonal distortions. The first-order phase transition to the mesophasic high-temperature polymorph (gamma, Fddd) is associated with a sharp volume increase and the onset of liquid-like dynamics for sodium-cations (translational) and thiophosphate-polyanions (rotational) evident by inelastic neutron and Raman spectroscopies, as well as pair-distribution function and molecular dynamics analyses. These results shed light on the rich polymorphism of Na3PS4 and are relevant for a range host of high-performance materials deriving from the Na3PS4 structural archetype.

引用

页码：5652 / 5667

页数：16