硅酸盐学报

锗基锂离子电池负极材料研究进展

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刘饶 ¹ , 高标 ¹ , 汤和扬 ¹ , 郭鑫博 ¹ , 罗实 ¹ , 沙磊 ¹ , 张徽 ¹ , 刘宇 ¹ , 张桥保 ²

硅酸盐学报 | 综合评述 2026,54(7): 2481-2507

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硅酸盐学报 |综合评述 2026 , 54 (7) : 2481 -2507

锗基锂离子电池负极材料研究进展

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刘饶¹, 高标¹, 汤和扬¹, 郭鑫博¹, 罗实¹, 沙磊¹, 张徽¹, 刘宇¹, 张桥保²

作者信息

^1．武汉科技大学冶金与能源学院，武汉 430081

^2．厦门大学材料学院，福建厦门 361005

通讯作者:

张桥保（1983—），男，博士，教授；

高标（1986—），男，博士，教授。

作者简介:

刘饶（2000—），男，硕士研究生；

高标（1986—），男，博士，教授。

Progress on Germanium-based Anode Materials for Lithium-ion Batteries

Rao LIU¹, Biao GAO¹, Heyang TANG¹, Xinbo GUO¹, Shi LUO¹, Lei SHA¹, Hui ZHANG¹, Yu LIU¹, Qiaobao ZHANG²

Affiliations

^1.School of Metallurgy and Energy, Wuhan University of Science and Technology, Wuhan 430081, China

^2.College of Materials, Xiamen University, Xiamen 361005, Fujian, China

Corresponding Author:

ZHANG Qiaobao (1983-), male, Ph.D., Professor. E-mail: zhangqiaobao@xmu.edu.cn;

GAO Biao (1986-), male, Ph.D., Professor. gaobiao@wust.edu.cn

LIU Rao (2000-), male, Master candidate; E-mail: 3041204412@qq.com;

GAO Biao (1986-), male, Ph.D., Professor. gaobiao@wust.edu.cn

出版时间: 2026-04-07 doi: 10.14062/j.issn.0454-5648.20250435

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摘要

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锗因其高理论比容量（1624 mA·h·g^-1）、快速的离子/电子传输速率等特性，在锂离子电池领域的应用引起了广泛关注。然而，锗在循环中的大幅体积膨胀（完全锂化时达370%）会产生剧烈内应力，造成电极材料开裂和集流体剥离，同时，固体电解质界面（SEI）的反复破裂/再生过程会持续消耗电解液中的锂离子，共同引发容量快速衰减。此外，较高的应用成本阻碍了锗基锂离子电池的发展。近年来，以锗纳米化、锗基复合化、锗合金化为主的锗基负极材料改性策略的研究取得一定突破，在锂离子电池领域中的应用方面取得了良好进展。本文首先介绍了锗基负极的特点和失效机制，接着梳理了锗基负极材料的研究和应用进展，最后展望了锗基材料在锂离子电池领域的发展趋势。

关键词

锂离子电池 / 负极材料 / 锗 / 纳米结构设计 / 复合材料 / 锗合金

Abstract

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Germanium (Ge) anode materials emerge as promising candidates for high-power, high-energy-density lithium-ion batteries due to their high theoretical specific capacity (i.e., 1600 mA·h·g^-1) and exceptional electrical conductivity (i.e., >10³ times higher than silicon). However, their practical implementation faces critical challenges, i.e., the substantial volume expansion (up to 370%) during lithiation/delithiation generates extreme internal stress, causing electrode pulverization. The concurrent volume fluctuations induce repeated rupture/reformation of the solid electrolyte interphase (SEI) layer, continuously depleting active lithium ions from the electrolyte and accelerating capacity fading. Also, commercialization is hindered due to the germanium scarcity and high purification costs.

To address the core challenge of volume expansion, the existing research focuses on material structural design and compositional optimization. Nanostructuring strategies (e.g., nanoparticles, nanowires/nanotubes, and porous frameworks) effectively shorten ion transport pathways and alleviate stress concentration (nano-sized Ge demonstrates the superior anti-pulverization properties). Compositing approaches integrate small-sized Ge (i.e., nanoparticles or quantum dots) with carbon-based matrices or metal oxide frameworks, leveraging buffering networks and conductive scaffolds to maintain structural integrity, suppress particle fragmentation, minimize side reactions, and stabilize the SEI. Alloying tactics (e.g., forming alloys with Cu/Sn/Si or developing Ge-based high-entropy alloys) utilize a multi-component synergy to distribute stress, enhance mechanical stability and conductivity. Furthermore, employing germanium oxide precursors or multi-phase composites offers viable routes to reduce costs.

This review systematically represents recent advances about Ge-based anode materials. First, this review comprehensively analyzes their intrinsic properties, lithiation mechanisms, and failure modes. Subsequently, this review classifies key modification strategies, i.e., ranging from low-dimensional nanostructures (particles, wires) to nano-/micro-sized composite architectures, from Ge/carbon, Ge/transition metal oxide composites to multi-element alloys and emerging high-entropy alloy systems. Stress-buffering mechanisms are elucidated in conjunction with synthesis methodologies, with particular attention to structural evolution during cycling. Finally, this review outlines future research directions, emphasizing the need to synergistically resolve volume expansion, interfacial instability, and cost constraints through structural engineering and low-cost processes, thereby paving an effective way for their practical deployment in high-performance lithium-ion batteries.

Summary and Prospects

Germanium-based anode materials have achieved significant progress in lithium-ion batteries, primarily in cost reduction, structural optimization, and interface engineering. High material costs restrict large-scale application, thus prompting the development of diverse Ge sources (e.g., GeO₂, organic precursors), Ge/metal and Ge/metalloid composites, and Ge-based high-entropy alloys. Ge combined with conductive metals like Cu or Ni improves electrical conductivity and structural stability, while pairing with active elements like Si or Sn mitigates volume expansion. In high-entropy systems, Ge can regulate lithiation behavior, effectively controlling volume change.

To address severe volume expansion during cycling that leads to material pulverization and capacity decay, various nanostructural materials including Ge nanoparticles, nanowires, and porous frameworks are designed. Nanoparticles have low expansion and fast kinetics, requiring artificial SEI layers and conductive matrices for stability. Ge nanowires exhibit radial resilience and axial flexibility, especially when directly grown on current collectors, offering a practical potential. Porous Ge integrates nanoscale activity with a high tap density, improving energy density, while avoiding particle agglomeration.

Interface instability and poor conductivity at a high current are also challenges for Ge-based anodes. The reactive surface of Ge can form unstable SEI layers, limiting performance. To address this, some engineered artificial SEI coatings such as N-doped carbon, heterojunction-carbon, and TiO₂ are developed to enhance ion/electron transport and mechanical integrity. In addition, a uniform dispersion of nanoscale Ge within conductive networks also improves fast-charging capabilities and cycling stability. Integrating structure and composition design through high-throughput element screening, one-step synthesis, and precise structural tuning is a key to reducing Ge dependency and enhancing performance. Further advancement requires in-situ characterization and multiscale simulations to uncover lithiation-induced phase transitions and stress evolution, facilitating the transition of Ge-based anodes from lab-scale research to industrial application.

The market adoption of germanium-based anodes is expected to follow a trajectory starting from high-end applications and gradually expanding to broader markets. In the short term, their use focuses on niche sectors with extreme requirements for energy density and fast charging but low sensitivity to cost, such as aerospace, military equipment, advanced medical devices, and long endurance drones. In the medium to long term, as manufacturing costs decrease and processing techniques become mature, germanium is expected to serve as a dopant or an alloying modifier for mainstream anode materials like silicon and tin, enhancing their kinetics and structural stability, and thereby indirectly improving the range and fast-charging performance of electric vehicle batteries. China has a unique strategic advantage in the global germanium supply chain. China develops a complete technological system covering refining, purification, and deep processing, enabling efficient production of high-purity precursors such as GeO₂ and GeCl₄. In parallel, the extensive recycling of germanium-containing by-products from industries like optical fibers, infrared optics, and solar cells creates a sustainable "resource-product-recycling" loop. These advantages significantly lower the marginal cost of use and ensure resource security, offering a practical and competitive environment to overcome cost barriers and scale up applications.

Key words

lithium-ion batteries / anode materials / germanium / nanostructure design / composite material / germanium alloys

引用本文

刘饶, 高标, 汤和扬, 郭鑫博, 罗实, 沙磊, 张徽, 刘宇, 张桥保. 锗基锂离子电池负极材料研究进展. 硅酸盐学报, 2026 , 54 (7) : 2481 -2507 . DOI: 10.14062/j.issn.0454-5648.20250435

Rao LIU, Biao GAO, Heyang TANG, Xinbo GUO, Shi LUO, Lei SHA, Hui ZHANG, Yu LIU, Qiaobao ZHANG. Progress on Germanium-based Anode Materials for Lithium-ion Batteries[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (7) : 2481 -2507 . DOI: 10.14062/j.issn.0454-5648.20250435

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国家自然科学基金重大研究计划培育项目(92575110)

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2026年第54卷第7期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250435

接收时间：2025-06-05
首发时间：2026-10-22
出版时间：2026-04-07

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出版历史

收稿日期：2025-06-05
修回日期：2025-08-30

基金

国家自然科学基金重大研究计划培育项目(92575110)

作者信息

^1．武汉科技大学冶金与能源学院，武汉 430081

^2．厦门大学材料学院，福建厦门 361005

通讯作者:

张桥保（1983—），男，博士，教授；

高标（1986—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250435

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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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