硅酸盐学报

Sc、O共掺杂制备Li₁₀GeP₂S₁₂基固态电解质及其电化学性能

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肖星月 ¹^,² , 张霓 ¹ , 刘高瞻 ¹ , 姚霞银 ¹^,²

硅酸盐学报 | 全固态电池发展专刊—研究论文 2025,53(6): 1405-1413

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硅酸盐学报 |全固态电池发展专刊—研究论文 2025 , 53 (6) : 1405 -1413

Sc、O共掺杂制备Li₁₀GeP₂S₁₂基固态电解质及其电化学性能

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肖星月¹^,², 张霓¹, 刘高瞻¹, 姚霞银¹^,²

作者信息

^1．中国科学院宁波材料技术与工程研究所，浙江宁波 315201

^2．中国科学院大学材料与光电研究中心，北京 100049

通讯作者:

姚霞银（1982—），男，博士，研究员。

作者简介:

肖星月（2000—），女，硕士研究生。

Sc and O Co-Doped Li₁₀GeP₂S₁₂-Based Solid Electrolytes and Their Electrochemical Properties in All-Solid-State Lithium Batteries

Xingyue XLAO¹^,², Ni ZHANG¹, Gaozhan LIU¹, Xiayin YAO¹^,²

Affiliations

^1.Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China

^2.Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding Author:

YAO Xiayin (1982-), male, Ph.D., Professor. E-mail: yaoxy@nimte.ac.cn

XIAO Xingyue (2000-), female, Mater candidate. E-mail: xiaoxingyue@nimte.ac.cn

出版时间: 2025-06-20 doi: 10.14062/j.issn.0454-5648.20240824

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摘要

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Li₁₀GeP₂S₁₂硫化物固态电解质凭借其超高的锂离子电导率及低晶界电阻等特点，被视为是一种极具应用潜力的电解质材料。然而，Li₁₀GeP₂S₁₂对湿空气敏感且与锂金属不相容的特性阻碍了其在全固态锂电池中的应用。本工作通过Sc、O共掺杂制备出一种室温离子电导率达5.85 mS·cm^-1的Li_10.04Ge_0.92Sc_0.08P₂S_11.88O_0.12固态电解质，其中硬碱O对S的取代，使其表现出高的湿空气耐受性。基于Li_10.04Ge_0.92Sc_0.08P₂S_11.88O_0.12的对称锂电池的极限电流密度由1.0 mA·cm^-2提升至2.4 mA·cm^-2。LiCoO₂ | Li_10.04Ge_0.92Sc_0.08P₂S_11.88O_0.12 | Li全固态锂电池在1 C条件下表现出95.98 mA·h·g^-1的初始放电比容量，循环500次后容量保持率为81.7%。

关键词

锂锗磷硫 / 硫化物固态电解质 / 湿空气稳定性 / 全固态锂电池

Abstract

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Introduction

Li₁₀GeP₂S₁₂ solid electrolyte is regarded as a promising candidate for all-solid-state lithium batteries due to its ultra-high ionic conductivity and low grain boundary resistance. However, its instability against moisture and incompatibility with lithium metal impede its application. Elemental substitution or doping is commonly employed to improve the overall properties of solid electrolytes. Based on hard-soft acid-base theory, partially substituting S with O can form a more stable structure, thereby inhibiting hydrolysis and structural damage upon exposure to moist air. However, excessive O doping causes a reduction of ionic conductivity. The introduction of rare-earth elements, such as scandium (Sc) with larger ionic radius, can enlarge the lattice volume and mitigate the adverse effects of O doping. Meanwhile, Sc-containing compounds generated in the interface between solid electrolyte and lithium metal is beneficial to suppress the interfacial side reactions. In this work, Sc and O co-doped Li₁₀GeP₂S₁₂-based electrolytes were synthesized. The moisture stability, interface between the electrolyte and lithium metal and electrochemical performances of all-solid-state lithium batteries were significantly improved.

Methods

Li_10+0.5_xGe_1-_xSc_xP₂S_12-1.5_xO_1.5_x(x=0, 4%, 8%, 12%, 16%, in mole) solid electrolytes were prepared by ball-milling and subsequent high-temperature sintering. The structure of obtained solid electrolytes was analyzed by a model AXS D8 Advance X-ray diffractometer (Bruker Co., Germany) with Cu K_α radiation in the angular range of 10°-80°. The Raman spectra were recorded by a model inVia-reflex Raman spectrophotometer (Renishaw Co., UK) with an excitation wavelength of 532 nm. The morphology and elemental distribution of the solid electrolyte particles were determined by a model Regulus-8230 scanning electron microscope (SEM, Hitachi Co., Japan) with an energy-dispersive X-ray spectroscope. The ionic conductivity of the solid electrolytes was measured by an electrochemical impedance spectroscope and the electronic conductivity was tested through direct current polarization at 0.5 V by a model 1470E electrochemical workstation (Solartron Co., UK). The air stability of the solid electrolytes was evaluated through the amount of H₂S gas released in a confined environment with approximately 40% relative humidity by a model GX-2009 H₂S gas sensor (Riken Keiki Co., Ltd., Japan).

Symmetric batteries were fabricated with two lithium foils attached to both sides of the pelletized solid electrolytes. The critical current density was conducted through galvanostatic cycling at step-increased current densities using a model Land-CT2001A battery test system (Wuhan Rambo Testing Equipment Co., Ltd., China). To assemble LiCoO₂ ⊥ solid electrolyte/Li all-solid state lithium batteries, composite cathode was prepared by mixing LiCoO₂ and the electrolyte powder in a mass ratio of 70∶30. The composite cathode was spread on to one side of the solid electrolyte tablet uniformly and pressed at 360 MPa. The lithium foil was placed on the another side of solid electrolyte to serve as an anode. The charge and discharge measurements of all-solid-state batteries were conducted at room temperature in a voltage range of 3.0-4.2 V using a model Land-CT2001A battery test system.

Results and discussion

Sc and O co-doped Li₁₀GeP₂S₁₂ solid electrolytes are synthesized through ball-milling and subsequent high-temperature sintering at 620 ℃. The XRD patterns and Raman spectra indicate that the optimal doping concentration is 8%, at which the lattice volume is enlarged and no heterogeneous phase is detected. The ionic conductivity of optimized Li_10.04Ge_0.92Sc_0.08P₂S_11.88O_0.12 solid electrolytes sintered at 620 ℃ has a high ionic conductivity of 5.85 mS∙cm^-1. In addition, it also exhibits a decreased electronic conductivity from 2.93×10^-8 S∙cm^-1 to 1.65×10^-8 S∙cm^-1 with a low activation energy of 0.20 eV. After 120-min exposure in a confined environment with a relative humidity of approximately 40%, Li₁₀GeP₂S₁₂ undergoes irreversible hydrolysis and releases 0.59 cm³∙g^-1 of H₂S gas. In contrast, Li_10.04Ge_0.92Sc_0.08P₂S_11.88O_0.12 produces only 0.24 cm³∙g^-1 of H₂S gas under the same conditions and retains an ionic conductivity of 1.21 mS∙cm^-1, which is one order of magnitude greater than that of Li₁₀GeP₂S₁₂. Annealing can restore up to 70.77% of its original ionic conductivity, which is attributed to Sc and O doping that forms a more stable structure, thereby inhibiting the hydrolysis reaction.

Li_10.04Ge_0.92Sc_0.08P₂S_11.88O_0.12-based symmetric cell achieves a significant increase in critical current density from 1.0 mA∙cm^-2 to 2.4　mA∙cm^-2. After undergoing constant-current cycling for 800 h at a current density of 0.1 mA∙cm^-2, the polarization voltage of Li\Li_10.04Ge_0.92Sc_0.08P₂S_11.88O_0.12\Li maintains at ±0.5 V, demonstrating an effective suppression of the side reaction between electrolyte and lithium metal. LiCoO₂\Li_10.04Ge_0.92Sc_0.08P₂S_11.88O_0.12 \Li all-solid-state lithium battery exhibits superior cycling stability and rate performance, with an initial discharge capacity of 128.45 mA∙h∙g^-1 and a capacity retention of 87.5% after 100 cycles at 0.1 C. Furthermore, the capacity retention remains at 81.7% after 500 cycles at 1 C.

Conclusions

Sc and O co-doped Li_10.04Ge_0.92Sc_0.08P₂S_11.88O_0.12 solid electrolyte sintered at 620 ℃ had an optimal ionic conductivity of 5.85 mS∙cm^-1. The humid air stability was improved after partially substituting S with hard base O. LiCoO₂ | Li all-solid-state lithium battery assembled with Li_10.04Ge_0.92Sc_0.08P₂S_11.88O_0.12 exhibited enhanced long-term cyclic performance and rate capability. This work demonstrated a significant potential of Sc and O co-doping in enhancing both the structural stability and electrochemical performance of Li₁₀GeP₂S₁₂-based solid electrolytes, making them promising candidates for all-solid-state lithium batteries.

Key words

lithium germanium phosphorus sulfide / sulfide electrolytes / humid air stability / all-solid-state lithium batteries

引用本文

肖星月, 张霓, 刘高瞻, 姚霞银. Sc、O共掺杂制备Li₁₀GeP₂S₁₂基固态电解质及其电化学性能. 硅酸盐学报, 2025 , 53 (6) : 1405 -1413 . DOI: 10.14062/j.issn.0454-5648.20240824

Xingyue XLAO, Ni ZHANG, Gaozhan LIU, Xiayin YAO. Sc and O Co-Doped Li₁₀GeP₂S₁₂-Based Solid Electrolytes and Their Electrochemical Properties in All-Solid-State Lithium Batteries[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (6) : 1405 -1413 . DOI: 10.14062/j.issn.0454-5648.20240824

基金

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国家重点研发计划(2022YFB3807700)
国家自然科学基金(22309194; 52372244)
中国科学院青年创新促进会项目(Y2021080)

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2025年第53卷第6期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240824

接收时间：2024-12-25
首发时间：2026-10-22
出版时间：2025-06-20

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收稿日期：2024-12-25
修回日期：2025-02-22

基金

国家重点研发计划(2022YFB3807700)

国家自然科学基金(22309194; 52372244)

中国科学院青年创新促进会项目(Y2021080)

作者信息

^1．中国科学院宁波材料技术与工程研究所，浙江宁波 315201

^2．中国科学院大学材料与光电研究中心，北京 100049

通讯作者:

姚霞银（1982—），男，博士，研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240824

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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