Full
LIU Rao (2000-), male, Master candidate; E-mail: 3041204412@qq.com;
GAO Biao (1986-), male, Ph.D., Professor. gaobiao@wust.edu.cn
Outline
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.
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.
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| 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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