Structural Evolution and Li Dynamics in Nanophase Li3PS4 by Solid-State and Pulsed-Field Gradient NMR

被引:72
作者
Gobet, Mallory [1 ]
Greenbaum, Steve [1 ]
Sahu, Gayatri [2 ]
Liang, Chengdu [2 ]
机构
[1] CUNY Hunter Coll, Dept Phys & Astron, New York, NY 10065 USA
[2] Oak Ridge Natl Lab, Ctr Nanophase Mat Sci, Oak Ridge, TN 37830 USA
关键词
LITHIUM-SULFUR BATTERIES; CONDUCTOR; GLASSES; SPECTRA; SULFIDE; P-31;
D O I
10.1021/cm5012058
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
The ceramic lithium ion conductor beta-Li3PS4 has a disordered and nanoporous structure that leads to an enhancement in ionic conductivity by some 3 orders of magnitude compared to the crystalline gamma phase. The beta phase is prepared by thermal treatment of an inorganic-organic complex based on Li3PS4 and THF. Multinuclear (H-1, Li-6,Li-7, P-31) solid-state NMR spectroscopy is used to characterize the structural phase evolution of the starting material at various steps in the thermal treatment. The beta phase formed after high temperature treatment is recognized as spectroscopically distinct from the bulk gamma-Li3PS4 compound. Also formed is an amorphous lithium thiophosphate phase that is metastable as verified by annealing over an extended period. Lithium ion self-diffusion coefficients are measurable by standard pulsed-field gradient NMR methods at 100 degrees C and with values consistent with the high ionic conductivity previously reported for this material.
引用
收藏
页码:3558 / 3564
页数:7
相关论文
共 11 条
[1]   Dendrite-Free Lithium Deposition via Self-Healing Electrostatic Shield Mechanism [J].
Ding, Fei ;
Xu, Wu ;
Graff, Gordon L. ;
Zhang, Jian ;
Sushko, Maria L. ;
Chen, Xilin ;
Shao, Yuyan ;
Engelhard, Mark H. ;
Nie, Zimin ;
Xiao, Jie ;
Liu, Xingjiang ;
Sushko, Peter V. ;
Liu, Jun ;
Zhang, Ji-Guang .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (11) :4450-4456
[2]   STRUCTURAL TRANSFORMATION OF NONOXIDE CHALCOGENIDE GLASSES - THE SHORT-RANGE ORDER OF LI2S-P2S5 GLASSES STUDIED BY QUANTITATIVE P-31 AND LI-6,7 HIGH-RESOLUTION SOLID-STATE NMR [J].
ECKERT, H ;
ZHANG, ZM ;
KENNEDY, JH .
CHEMISTRY OF MATERIALS, 1990, 2 (03) :273-279
[3]   Lithium ion diffusion in solid electrolyte (Li2S)7(P2S5)3 measured by pulsed-gradient spin-echo 7Li NMR spectroscopy [J].
Hayamizu, Kikuko ;
Aihara, Yuichi .
SOLID STATE IONICS, 2013, 238 :7-14
[4]   Si-29 and P-31 MAS-NMR spectra of Li2S-SiS3-Li3PO4 rapidly quenched glasses [J].
Hirai, K ;
Tatsumisago, M ;
Takahashi, M ;
Minami, T .
JOURNAL OF THE AMERICAN CERAMIC SOCIETY, 1996, 79 (02) :349-352
[5]   Crystal structure and phase transitions of the lithium ionic conductor Li3PS4 [J].
Homma, Kenji ;
Yonemura, Masao ;
Kobayashi, Takeshi ;
Nagao, Miki ;
Hirayama, Masaaki ;
Kanno, Ryoji .
SOLID STATE IONICS, 2011, 182 (01) :53-58
[6]  
Kamaya N, 2011, NAT MATER, V10, P682, DOI [10.1038/nmat3066, 10.1038/NMAT3066]
[7]   Lithium Polysulfidophosphates: A Family of Lithium-Conducting Sulfur-Rich Compounds for Lithium-Sulfur Batteries [J].
Lin, Zhan ;
Liu, Zengcai ;
Fu, Wujun ;
Dudney, Nancy J. ;
Liang, Chengdu .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (29) :7460-7463
[8]   Lithium Superionic Sulfide Cathode for All-Solid Lithium-Sulfur Batteries [J].
Lin, Zhan ;
Liu, Zengcai ;
Dudney, Nancy J. ;
Liang, Chengdu .
ACS NANO, 2013, 7 (03) :2829-2833
[9]   Anomalous High Ionic Conductivity of Nanoporous β-Li3PS4 [J].
Liu, Zengcai ;
Fu, Wujun ;
Payzant, E. Andrew ;
Yu, Xiang ;
Wu, Zili ;
Dudney, Nancy J. ;
Kiggans, Jim ;
Hong, Kunlun ;
Rondinone, Adam J. ;
Liang, Chengdu .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (03) :975-978
[10]   Modelling one- and two-dimensional solid-state NMR spectra [J].
Massiot, D ;
Fayon, F ;
Capron, M ;
King, I ;
Le Calvé, S ;
Alonso, B ;
Durand, JO ;
Bujoli, B ;
Gan, ZH ;
Hoatson, G .
MAGNETIC RESONANCE IN CHEMISTRY, 2002, 40 (01) :70-76