Structures, Thermodynamics, and Li+ Mobility of Li10GeP2S12: A First-Principles Analysis

被引：56

作者：

Du, Fuming ^{[1
]}

Ren, Xiaodong ^{[1
]}

Yang, Jiong ^{[2
]}

Liu, Jianjun ^{[1
]}

Zhang, Wenqing ^{[1
,3
,4
]}

机构：

[1] Chinese Acad Sci, Shanghai Inst Ceram, State Key Lab High Performance Ceram & Superfine, Shanghai 200050, Peoples R China

[2] Univ Washington, Dept Mat Sci & Engn, Seattle, WA 98195 USA

[3] Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Jiangsu, Peoples R China

[4] Nanjing Univ, State Key Lab Coordinat Chem, Nanjing 210093, Jiangsu, Peoples R China

来源：

JOURNAL OF PHYSICAL CHEMISTRY C | 2014年 / 118卷 / 20期

关键词：

TOTAL-ENERGY CALCULATIONS; CONDUCTIVITY; ELECTROLYTE; STABILITY;

D O I：

10.1021/jp5000039

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 first-principles and thermodynamic calculations were performed to study structural stability, thermodynamic properties, and Li+ migration mechanism of the superionic conductor Li10GeP2S12 (LGPS). Our calculations show that the zigzag and parallel arrangements of GeS44- and P(1)S-4(3-) units form three types of stable structures. Among them, zigzag-type structures with 2-4 Li+ occupied in the Li4 position were found to be the most stable. Our thermodynamic calculations show that LGPS may be stable at >276 K when configuration and vibration entropies are considered based on disordered arrangement of GeS44- and P(1)S-4(3-) units, and partially occupied Li+. Based on the calculation for minimum energy paths, we found that Li+ migration along the c axis may be more favorable than that in the ab plane, indicating a very weak anisotropy for Li+ migration of LGPS. These structural and mechanistic studies are helpful to design a novel superionic conductor with high performance.

引用

页码：10590 / 10595

页数：6

共 25 条

[1] Structural requirements for fast lithium ion migration in Li10GeP2S12 [J].

Adams, Stefan ;

Rao, R. Prasada .

JOURNAL OF MATERIALS CHEMISTRY, 2012, 22 (16) :7687-7691

[2] Li10SnP2S12: An Affordable Lithium Superionic Conductor [J].

Bron, Philipp ;

Johansson, Sebastian ;

Zick, Klaus ;

auf der Guenne, Joern Schmedt ;

Dehnen, Stefanie ;

Roling, Bernhard .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (42) :15694-15697

[3] Challenges for Rechargeable Li Batteries [J].

Goodenough, John B. ;

Kim, Youngsik .

CHEMISTRY OF MATERIALS, 2010, 22 (03) :587-603

[4] A structural, spectroscopic and electrochemical study of a lithium ion conducting Li10GeP2S12 solid electrolyte [J].

Hassoun, Jusef ;

Verrelli, Roberta ;

Reale, Priscilla ;

Panero, Stefania ;

Mariotto, Gino ;

Greenbaum, Steven ;

Scrosati, Bruno .

JOURNAL OF POWER SOURCES, 2013, 229 :117-122

[5] A climbing image nudged elastic band method for finding saddle points and minimum energy paths [J].

Henkelman, G ;

Uberuaga, BP ;

Jónsson, H .

JOURNAL OF CHEMICAL PHYSICS, 2000, 113 (22) :9901-9904

[6] Insights into structural stability and Li superionic conductivity of Li10GeP2S12 from first-principles calculations [J].

Hu, C. H. ;

Wang, Z. Q. ;

Sun, Z. Y. ;

Ouyang, C. Y. .

CHEMICAL PHYSICS LETTERS, 2014, 591 :16-20

[7]

Kamaya N, 2011, NAT MATER, V10, P682, DOI [10.1038/nmat3066, 10.1038/NMAT3066]

[8] Discharge Performance of All-Solid-State Battery Using a Lithium Superionic Conductor Li10GeP2S12 [J].

Kato, Yuki ;

Kawamoto, Koji ;

Kanno, Ryoji ;

Hirayama, Masaaki .

ELECTROCHEMISTRY, 2012, 80 (10) :749-751

[9] Interfacial reactions at electrode/electrolyte boundary in all solid-state lithium battery using inorganic solid electrolyte, thio-LISICON [J].

Kobayashi, Takeshi ;

Yamada, Atsuo ;

Kanno, Ryoji .

ELECTROCHIMICA ACTA, 2008, 53 (15) :5045-5050

[10] Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set [J].

Kresse, G ;

Furthmuller, J .

PHYSICAL REVIEW B, 1996, 54 (16) :11169-11186

← 1 2 3 →