Glass-ceramics in Li1+xAlxGe2-x(PO4)3 system: The effect of Al2O3 addition on microstructure, structure and electrical properties

被引：38

作者：

Pershina, S. V. ^{[1
]}

Antonov, B. D. ^{[1
]}

Farlenkov, A. S. ^{[1
]}

Vovkotrub, E. G. ^{[1
]}

机构：

[1] RAS, Inst High Temp Electrochem, Ural Branch, 20 Akad Skaya St, Ekaterinburg 620990, Russia

来源：

JOURNAL OF ALLOYS AND COMPOUNDS | 2020年 / 835卷

基金：

俄罗斯科学基金会;

关键词：

All-solid-state lithium batteries; Solid electrolytes; Glass-ceramics; Synthesis design; Li+ conductivity; NASICON-Type structure; Raman spectroscopy; IONIC-CONDUCTIVITY; RAMAN-SPECTRA; SOLID ELECTROLYTES; PHASE-COMPOSITION; LI1.5AL0.5GE1.5(PO4)(3); TEMPERATURE; CRYSTALLIZATION; CONDUCTORS; TRANSPORT; TITANIUM;

D O I：

10.1016/j.jallcom.2020.155281

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：

Glass-ceramics of the Li1+xAlxGe2-x(PO4)3 series (0 <= x <= 0.65) was obtained by glass crystallization under the same conditions of heat treatment. The influence of the heating rate (1, 3 and 8 degrees C min(-1)) and the different heat treatment times (2, 8 and 12 h) on the lithium-ion conductivity of glass-ceramics were studied. The impact of Al2O3 addition on the phase composition, microstructure, transport properties and molecular structure of lithium germanophosphate was investigated by XRD, SEM, impedance spectroscopy and Raman spectroscopy, respectively. The obtained electrolytes have the NASICON-type structure with space group R-3c. Glass-ceramics is single-phase when 0.3 <= x <= 0.5, but impurity phases Li4P2O7, AlPO4, and GeO2 appear at x = 0.65. An increase in Al2O3 content leads to the formation of larger crystallites. A significant improvement in ionic conductivity was observed in Al-doped samples. The conductivity of undoped LiGe2(PO4)3 was found to be 4 orders of magnitude lower compared to the Al-doped solid electrolytes. Among the Li1+xAlxGe2-x(PO4)3 glass-ceramics, the composition of Li1.5Al0.5Ge1.5(PO4)3 (x = 0.5) has the highest lithium-ion conductivity, which is 5.03 x 10-4 S cm(-1) at 25 degrees C. The electron conductivity of solid electrolyte at x = 0.5 is 4 x 10(-9) S cm(-1) at 25 degrees C. Ionic transference number was found to be close to 0.99. (C) 2020 Elsevier B.V. All rights reserved.

引用

页数：9

共 50 条

[31] Temperature dependence of Raman spectra of the quartz- and rutile-types of GeO2 [J].

Mernagh, TP ;

Liu, LG .

PHYSICS AND CHEMISTRY OF MINERALS, 1997, 24 (01) :7-16

[32] Structure and lithium ion conductivity of bismuth containing lithium garnets Li5La3Bi2O12 and Li6SrLa2Bi2O12 [J].

Murugan, Ramaswamy ;

Weppner, Werner ;

Schmid-Beurmann, Peter ;

Thangadurai, Venkataraman .

MATERIALS SCIENCE AND ENGINEERING B-SOLID STATE MATERIALS FOR ADVANCED TECHNOLOGY, 2007, 143 (1-3) :14-20

[33] Effect of Li2O-Al2O3-GeO2-P2O5 glass crystallization on stability versus molten lithium [J].

Pershina, S. V. ;

Il'ina, E. A. ;

Druzhinin, K. V. ;

Farlenkov, A. S. .

JOURNAL OF NON-CRYSTALLINE SOLIDS, 2020, 527

[34] Promising high-conductivity Li1.5Al0.5Ge1.5(PO4)3 solid electrolytes: the effect of crystallization temperature on the microstructure and transport properties [J].

Pershina, S. V. ;

Pankratov, A. A. ;

Vovkotrub, E. G. ;

Antonov, B. D. .

IONICS, 2019, 25 (10) :4713-4725

[35] Extreme behavior of Li-ion conductivity in the Li2O-Al2O3-P2O5 glass system [J].

Pershina, S. V. ;

Raskovalov, A. A. ;

Antonov, B. D. ;

Yaroslavtseva, T. V. ;

Reznitskikh, O. G. ;

Baklanova, Ya. V. ;

Pletneva, E. D. .

JOURNAL OF NON-CRYSTALLINE SOLIDS, 2015, 430 :64-72

[36] Phase Composition, Density, and Ionic Conductivity of the Li7La3Zr2O12-Based Composites with LiPO3 Glass Addition [J].

Pershina, Svetlana V. ;

Il'ina, Eugenia A. ;

Reznitskikh, Olga G. .

INORGANIC CHEMISTRY, 2017, 56 (16) :9880-9891

[37] Structural evolution of NASICON-type Li1+xAlxGe2-x(PO4)3 using in situ synchrotron X-ray powder diffraction [J].

Safanama, Dorsasadat ;

Sharma, Neeraj ;

Rao, Rayavarapu Prasada ;

Brand, Helen E. A. ;

Adams, Stefan .

JOURNAL OF MATERIALS CHEMISTRY A, 2016, 4 (20) :7718-7726

[38] Local structure of sodium aluminum metaphosphate glasses [J].

Schneider, J ;

Oliveira, SL ;

Nunes, LAO ;

Panepucci, H .

JOURNAL OF THE AMERICAN CERAMIC SOCIETY, 2003, 86 (02) :317-324

[39] RAMAN SPECTRA OF GEO2 [J].

SCOTT, JF .

PHYSICAL REVIEW B, 1970, 1 (08) :3488-&

[40] Recent advances in all-solid-state rechargeable lithium batteries [J].

Sun, Chunwen ;

Liu, Jin ;

Gong, Yudong ;

Wilkinson, David P. ;

Zhang, Jiujun .

NANO ENERGY, 2017, 33 :363-386

← 1 2 3 4 5 →