Improvement of Li1.5Al0.5Ge1.5(PO4)3 (LAGP) superionic conductivity via antimony doping

IF 2.4 4区化学 Q3 CHEMISTRY, PHYSICAL

Ionics Pub Date : 2024-12-04 DOI:10.1007/s11581-024-05941-3

Maria Lebedeva, Viktor Markov, Artem Kim, Vladislav Chernyavsky, Denis Olkhovskii, Pavel Vishniakov, Maxim Maximov

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引用次数: 0

Abstract

Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) solid electrolytes are promising for solid-state batteries (SSBs) because of their electrochemical and air stability. However, to improve the power characteristics of SSBs, increasing the ionic conductivity of the solid electrolyte is necessary. To improve the conductive properties of a superionic glass–ceramic electrolyte of the composition Li_1.5+xAl_0.5Sb_xGe_1.5-x(PO₄)₃, Sb was added. It employs the melt quenching technique, which includes a pre-synthesis stage that decreases the time and temperature of synthesis. An increase in the conductivity of the glass ceramic to 7.7⋅10⁻⁴ S⋅cm⁻¹ by antimony doping was discovered via impedance spectroscopy analysis. The introduction of antimony was discovered to improve the diffusion of lithium ions both in the bulk and at the grain boundaries. The influence of antimony on the grain boundary conductivity was explained by the change in the microstructure of the samples which consists of reducing the average crystallite size and improving contact between them. X-ray data were used to refine the structure parameters and atomic coordinates via the Rietveld method, which revealed a small increase in diffusion channels upon antimony introduction. Using a jump diffusion model, the thermodynamic assumptions for the increase in ionic conductivity were evaluated. The growth of the grain bulk conductivity is determined by increase in the pre-exponential factor.

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锑掺杂提高Li1.5Al0.5Ge1.5(PO4)3 （LAGP）超离子电导率

Li1.5Al0.5Ge1.5(PO4)3 （LAGP）固体电解质由于其电化学稳定性和空气稳定性而在固态电池（ssb）中具有广阔的应用前景。然而，为了改善固态电池的功率特性，必须提高固体电解质的离子电导率。为了提高Li1.5+xAl0.5SbxGe1.5-x(PO4)3组成的超离子玻璃陶瓷电解质的导电性能，添加Sb。它采用熔体淬火技术，其中包括一个预合成阶段，减少了合成的时间和温度。通过阻抗谱分析发现，锑掺杂使玻璃陶瓷的电导率提高到7.7⋅10−4 S⋅cm−1。发现锑的引入可以改善锂离子在体和晶界的扩散。锑对晶界电导率的影响可以通过试样微观结构的改变来解释，微观结构的改变主要表现为晶粒平均尺寸的减小和晶粒间接触的增加。利用x射线数据通过Rietveld方法对结构参数和原子坐标进行了细化，发现引入锑后扩散通道有小幅增加。利用跳跃扩散模型，对离子电导率增加的热力学假设进行了评估。晶粒体积电导率的增长是由指前因子的增加决定的。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Ionics 化学-电化学

CiteScore

5.30

自引率

7.10%

发文量

427

审稿时长

2.2 months

期刊介绍： Ionics is publishing original results in the fields of science and technology of ionic motion. This includes theoretical, experimental and practical work on electrolytes, electrode, ionic/electronic interfaces, ionic transport aspects of corrosion, galvanic cells, e.g. for thermodynamic and kinetic studies, batteries, fuel cells, sensors and electrochromics. Fast solid ionic conductors are presently providing new opportunities in view of several advantages, in addition to conventional liquid electrolytes.