硅酸盐学报

废旧磷酸铁锂正极材料循环再生研究现状及展望

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张胜东 ¹ , 王云峰 ¹ , 张文杰 ² , 华中宝 ² , 宋强 ³ , 谢贤 ³ , 童雄 ³

硅酸盐学报 | 综合评述 2026,54(7): 2534-2544

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硅酸盐学报 |综合评述 2026 , 54 (7) : 2534 -2544

废旧磷酸铁锂正极材料循环再生研究现状及展望

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张胜东¹, 王云峰¹, 张文杰², 华中宝², 宋强³, 谢贤³, 童雄³

作者信息

^1．云南师范大学能源与环境科学学院，昆明 650500

^2．昆明冶金研究院有限公司，昆明 650031

^3．昆明理工大学国土资源工程学院，昆明 650093

通讯作者:

王云峰（1984—），男，博士，教授。

作者简介:

张胜东（1992—），男，博士，讲师；

Research Status and Prospects of Recycling and Regeneration of Spent Lithium Iron Phosphate Cathode Materials

Shengdong ZHANG¹, Yunfeng WANG¹, Wenjie ZHANG², Zhongbao HUA², Qiang SONG³, Xian XIE³, Xiong TONG³

Affiliations

^1.School of Energy and Environmental Science, Yunnan Normal University, Kunming 650500, China

^2.Kunming Metallurgical Research Institute Co., Ltd., Kunming 650031, China

^3.School of Land Resources Engineering, Kunming University of Science and Technology, Kunming 650093, China

Corresponding Author:

{WANG} Yunfeng (1984-), male, Ph.D., Professor. E-mail: 1752092604@qq.com

ZHANG Shengdong (1992-), male, Ph.D., Lecturer. E-mail: 18088266534@163.com

出版时间: 2026-06-01 doi: 10.14062/j.issn.0454-5648.20250838

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摘要

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随着新能源汽车的快速崛起，对锂离子电池的需求与日俱增，其中磷酸铁锂电池凭借稳定安全、成本低、循环利用率高等优势，占据新能源汽车锂电池的大部分市场。随着使用年限的增长，磷酸铁锂（LFP）电池报废量剧增，对其有效利用不仅能增加金属利用率，还能降低对环境的危害。本文详细综述废旧LFP正极材料直接修复再生和有价金属回收再利用的研究现状，重点介绍了固相烧结法、水热合成法、电化学法等工艺的作用原理和应用存在的优劣势。在此基础上，总结了废旧LFP正极材料全回收工艺中酸浸、碱浸、微生物浸出和火法等工艺的应用现状和作用机理，对比了有价金属的回收效果，同时揭示了回收中存在的瓶颈，从多角度展望未来行业发展的方向，为高效利用LFP材料提供借鉴。

关键词

磷酸铁锂 / 正极材料 / 修复再生 / 浸出 / 回收利用

Abstract

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The rapid proliferation of new energy vehicles (NEVs) leads to an unprecedented surge in the demand for lithium-ion batteries (LIBs). Among various LIBs, lithium iron phosphate (LFP) batteries have a significant market due to their inherent advantages, including superior thermal and chemical stability, low manufacturing cost, long cycle life (i.e., 2000-6000 cycles), and environmental friendliness. However, the service life of LFP batteries in NEVs is normally 6-10 years. These batteries are retired after decaying their capacity to below 80% of the initial value. The massive and growing volume of spent LFP batteries presents both a critical environmental challenge and a waste of valuable metal resources. Improper disposal can lead to the release of toxic substances from the electrolyte and heavy metals. Conversely, the spent cathodes contain abundant lithium (Li) and iron (Fe) that hold a significant economic value for recovery. Therefore, developing green, efficient, and economically viable recycling technologies is crucial for closing the material loop, ensuring resource security, and mitigating environmental hazards. This review represents the existing research status of two primary routes for managing spent LFP cathode materials, i.e., direct regeneration and hydrometallurgical/pyrometallurgical recycling. The underlying mechanisms, advantages, limitations, and key technological bottlenecks of each method are critically analyzed. Furthermore, future perspectives for the sustainable and efficient utilization of spent LFP materials are proposed to guide both academic research and industrial application.

This review systematically analyzes and compares the principal technologies for processing spent LFP cathode materials based on their structural integrity. For LFP materials that the olivine crystal structure remains largely intact despite Li⁺ loss, some direct regeneration methods are applicable. These motheds include (1) solid-state sintering, which involves supplementing missing Li, Fe, or P sources and calcining at high temperatures (i.e., typically 600-800 ℃) under an inert atmosphere to restore stoichiometry and repair defects; (2) hydrothermal synthesis, which uses aqueous lithium salts (e.g., LiOH, Li₂SO₄) and reducing agents (e.g., organic acids) at lower temperatures (i.e., 80-220 ℃) to re-lithiate the material and reduce Fe³⁺ back to Fe²⁺; and (3) electrochemical re-lithiation, where an external electric field drives Li⁺ insertion into the degraded cathode, potentially without dismantling the battery cell. For severely degraded LFP with an irreversibly damaged structure, full recycling methods are employed to extract valuable metals. These are primarily based on hydrometallurgy, i.e., acid leaching (using inorganic acids like H₂SO₄, H₃PO₄ or organic acids like oxalic, citric, formic acid), alkaline leaching (using NaOH for selective Li extraction), and bioleaching (using microbial metabolites). Pyrometallurgical processes that are often assisted by some additives like Na₂CO₃ or NaOH are also reviewed for their ability to convert LFP into separable metal compounds at high temperatures.

Direct regeneration is advantageous due to its short process flow, low cost, and high resource efficiency, making it a preferred industrial approach when applicable. Solid-state sintering offers high throughput and excellent recovery of electrochemical performance (discharge specific capacity up to ~147 mA·h·g^-1), but suffers from high energy consumption and potential impurity introduction. Hydrothermal synthesis operates under milder conditions (as low as 80 ℃), yielding repaired LFP with performance comparable to virgin material (>145 mA·h·g^-1), though it requires a strict control of pH value and a specialized autoclave equipment. Electrochemical methods avoid disassembly but face some challenges in scaling up due to the low repair efficiency. For full recycling, acid leaching achieves the maximum metal extraction rates (i.e., Li > 98%), but generates large volumes of acidic waste and introduces impurities. Organic acids offer a greener alternative but are costly and often less effective for Fe/P recovery. Selective Li leaching with oxalic acid or formic acid shows a promising potential via leaving Fe as a solid residue. Alkaline leaching is highly selective, but requires harsh conditions. Bioleaching is environmentally friendly, but suffers from slow kinetics and low efficiency. Pyrometallurgy is robust and feedstock-flexible, effectively converting LFP into soluble Li salts and magnetic Fe compounds, with Li recovery of exceeding 99% with Na₂CO₃ as an additive. However, it is energy-intensive and can emit toxic gases like HF and P₂O₅ from fluorinated binders and electrolytes, necessitating costly gas treatment. A key bottleneck across all the methods is a pretreatment step (i.e., discharging, disassembly, separation of cathode material from Al foil), which is often labor-intensive and inconsistent. Furthermore, the presence of impurities like Al, Cu, and residual carbon significantly affects the purity and performance of regenerated or recovered products. Most novel technologies remain in a lab-scale, with some challenges in industrial scalability, economic viability, and secondary waste management.

Summary and Perspects

The recycling and regeneration of spent LFP cathodes are essential for environmental protection and resource sustainability. Direct regeneration is the most economically and environmentally favorable route for cathodes with intact crystal structures. Among these methods, hydrothermal synthesis presents a promising balance between energy consumption and product quality. For severely degraded materials, full recycling via acid leaching is currently the most mature process, but it must be optimized to reduce waste and improve selectivity. Pyrometallurgy offers a robust alternative, but requires better gas cleaning and energy integration. Future research and industrial efforts should focus on, (1) developing intelligent, automated disassembly systems (e.g., robotic sorting and dismantling based on AI and 3D vision) to improve the purity and consistency of recovered black mass; (2) advancing novel, selective, and reusable leaching agents (e.g., deep eutectic solvents, functionalized ionic liquids) and integrating them with efficient electrochemical or membrane-based recovery systems; (3) enhancing the performance of regenerated materials through targeted doping (e.g., with Mn, N, B) and advanced coating technologies; (4) implementing holistic recovery processes that valorize all battery components, including the anode (graphite), electrolyte, and separator; and (5) designing future LFP batteries with greater structural modularity, standardized formats, and materials optimized for end-of-life repairability and recyclability. Addressing these challenges will pave an effective way for a truly circular and sustainable lithium-ion battery economy.

Key words

lithium iron phosphate / cathode materials / repair and regeneration / leaching / recycling

引用本文

张胜东, 王云峰, 张文杰, 华中宝, 宋强, 谢贤, 童雄. 废旧磷酸铁锂正极材料循环再生研究现状及展望. 硅酸盐学报, 2026 , 54 (7) : 2534 -2544 . DOI: 10.14062/j.issn.0454-5648.20250838

Shengdong ZHANG, Yunfeng WANG, Wenjie ZHANG, Zhongbao HUA, Qiang SONG, Xian XIE, Xiong TONG. Research Status and Prospects of Recycling and Regeneration of Spent Lithium Iron Phosphate Cathode Materials[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (7) : 2534 -2544 . DOI: 10.14062/j.issn.0454-5648.20250838

基金

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云南省基础研究专项青年项目(202301AU070151)
云南师范大学博士科研启动项目(2021ZB029)

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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.0454-5648.20250838

接收时间：2025-11-14
首发时间：2026-10-22
出版时间：2026-06-01

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收稿日期：2025-11-14
修回日期：2025-11-26

基金

云南省基础研究专项青年项目(202301AU070151)

云南师范大学博士科研启动项目(2021ZB029)

作者信息

^1．云南师范大学能源与环境科学学院，昆明 650500

^2．昆明冶金研究院有限公司，昆明 650031

^3．昆明理工大学国土资源工程学院，昆明 650093

通讯作者:

王云峰（1984—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250838

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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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