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废旧LiFePO4
Processes · 2025 ·Vol. 13 ·期 5 ·1478 · IF 2.8

Spent LiFePO4 to High-Value LiF: Enhanced Mechanical Chlorination Coupled with a Fluorination Reaction Mechanism

Chao Liang,Nengwu Zhu,Fei Li,Pengfei Zhang,Pingxiao Wu,Yaxi Hu

LiFePO4(LFP) batteries are among the earliest commercialized and most discarded lithium-ion batteries. Although existing recovery technologies focus on the conversion of LiFePO4to Li2CO3, challenges associated with achieving near-full recovery and high-value products remain. This study proposes a strategy for the conversion of spent LiFePO4to LiF by mechanical chlorination coupled with a fluorination reaction. The optimum conditions were determined to be a ball-to-powder ratio (BPR) = 15, NH4Cl:LFP = 3, H2O2= 2.0 mL, rotation speed = 600 rpm, and grinding time = 12 h. Results showed that 97.14% Li was converted into LiCl by H2O2–NH4Cl mechanical chlorination. When chlorinated intermediates were immersed in water, FePO4could be harvested, and 96.79% Li could be recovered as LiF with a purity of 99.50% after adding NH4F. When Cl-functionalized renewable resin was used to exchange 99.89% F−, 0.63 g NH4Cl per litre of LiF conversion residual liquid was derived. The favourable results were attributed to the1O2generated by H2O2, which had a strong electron affinity to break Li–O bonds and provided superior conditions for the combination of Li and Cl. During fluorination, the formation of LiF reduced the ion concentration, and the entropy decreased, contributing to the spontaneous reaction. Therefore, the proposed method paves the way for near-full recovery and high-value products of spent LiFePO4.

CAS / MDL: 12125-02-9 7722-84-1
研究领域: 材料科学 · 环境工程 · 化学工程
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Materials Today Energy · 2025 · IF 8.6

Cost-effective and efficient preparation of FePO4 electrodes from spent LiFePO4 batteries for enhanced lithium extraction from salt lakes

Yawen Gao,Luxiang Ma,Shuaifei Zhao,Chunxi Hai,Tiandong Chen,Junyi Zhang,Yan Zhao,Yanxia Sun,Shengde Dong,Xin He,Qi Xu,Xiaowang Wu,Caixiong Quan,Hongli Su,Yuan Zhou

Cost-effective and efficient lithium extraction technology is vital to foster the growth of lithium industry. This paper proposed a novel approach for the high value utilization of spent LiFePO 4 (S-LiFePO 4 ) in the field of lithium extraction from salt lakes was proposed using spent LiFePO 4 (S-LiFePO 4 ) as raw material. The anode, made from spent LiFePO 4 , is prepared via a sintering process, while FePO 4 , obtained through chemical oxidation, is used as the cathode. Compared with commercial LiFePO 4 , this system not only reduces the cost but also greatly shortens the preparation time of FePO 4 (only about 10min is required). And the electrochemical extraction system had a favorable lithium extraction capacity (29.25 mg/g) from actual brine, reducing the Mg/Li ratio from 61.4 to 0.8. This study not only achieved the low-cost preparation of electrode materials and facilitated the large-scale implementation of this process, but also proposed a high-value comprehensive utilization strategy for lithium-ion batteries recycling.

CAS / MDL: 872-50-4
研究领域: 材料科学 · 环境工程 · 能源技术
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ADVANCED MATERIALS · 2022 ·Vol. 35 ·期 5 ·2208034 · IF 32.086

Long-Life Regenerated LiFePO4 from Spent Cathode by Elevating the d-Band Center of Fe

Kai Jia,Jun Ma,Junxiong Wang,Zheng Liang,Guanjun Ji,Zhihong Piao,Runhua Gao,Yanfei Zhu,Zhaofeng Zhuang,Guangmin Zhou,Hui-Ming Cheng

A large amount of spent LiFePO 4 (LFP) has been produced in recent years because it is one of the most widely used cathode materials for electric vehicles. The traditional hydrometallurgical and pyrometallurgical recycling methods are doubted because of the economic and environmental benefits; the direct regeneration method is considered a promising way to recycle spent LFP. However, the performance of regenerated LFP by direct recycling is not ideal due to the migration of Fe ions during cycling and irreversible phase transition caused by sluggish Li + diffusion. The key to addressing the challenge is to immobilize Fe atoms in the lattice and improve the Li + migration capability during cycling. In this work, spent LFP is regenerated by using environmentally friendly ethanol, and its cycling stability is promoted by elevating the d-band center of Fe atoms via construction of a heterogeneous interface between LFP and nitrogen-doped carbon. The Fe  O bonding is strengthened and the migration of Fe ions during cycling is suppressed due to the elevated d-band center. The Li + diffusion kinetics in the regenerated LFP are improved, leading to an excellent reversibility of the phase transition. Therefore,  the regenerated LFP exhibits an ultrastable cycling performance at a high rate of 10 C with ≈80% capacity retention after 1000 cycles.

研究领域: 材料科学 · 环境科学
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Selective lithium recovery from spent LiFePO4 battery cathode materials using a green oxidizing reagent

Hao Yang,Nianke Zheng,Liping Dong,Yongxiao Song,Wenze Li,Xin Zhou,Zhongqi Ren,Zhiyong Zhou

The green and efficient recovery of Li + from spent LiFePO 4 (S-LFP) batteries and subsequent preparation of high-purity lithium products hold significant industrial importance. It can be applied in various fields such as electronic products, energy storage, and healthcare. A green and non-toxic potassium monopersulfate triple salt (PMTS) was used for the first time as a dual-functional reagent serving as both leaching reagent and oxidant, enabling highly in-situ selective leaching of Li + from S-LFP. Furthermore, a novel extraction system employing dibenzoylmethane (DBM) and triisobutyl phosphate (TIBP) was innovatively applied to selectively recover Li + from the leachate, ultimately yielding battery-grade lithium carbonate. Under optimized conditions, the leaching efficiency of Li + reached up to 99.40 % with nearly negligible iron dissolution (0.01 %). The DBM-TIBP system achieved selective extraction of Li + from the leachate with a single-stage extraction efficiency exceeding 94 %. A comprehensive purification process involving washing with NH 4 Cl/LiCl solution, three-stage cross-flow stripping with NH 4 HCO 3 solution, and high-temperature crystallization was implemented. This protocol achieved remarkable impurity removal efficiencies of 99.05 % for K + and 98.10 % for Na + while maintaining complete Li + retention. The stripping efficiency of Li + reached up to 99.36 %, leading to producing battery-grade lithium carbonate with 99.9 % purity. Additionally, potassium sulfate with 98.30 % purity was recovered from the residual leachate via fractional crystallization. This cost-effective and environmentally benign strategy provided a new perspective for industrial-scale green recycling of S-LFP battery cathode materials.

CAS / MDL: 1066-33-7
研究领域: 环境工程 · 材料科学 · 化学工程 · 可持续技术 · 冶金学
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Energy Storage Materials · 2024 · IF 18.9

Potential regulation strategy enables ferrocene as p-type redox mediator for direct regeneration of spent LiFePO4 cathode

Mingli Xu,Chen Wu,Fengxue Zhang,Yanhui Zhang,Jiaxin Ren,Chengyi Zhang,Xuanze Wang,Li Xiao,Olivier Fontaine,Jiangfeng Qian

Conventional metallurgical technologies for recycling cathode materials from retired Li-ion batteries go against carbon neutrality owing to massive material input and energy consumption. Although featuring with simplified process, direct regeneration technology still fails to bypass high-temperature driving forces for Li + compensation of degraded cathodes. Herein, chemical re-lithiation strategy mediated by ferrocene is proposed to directly regenerate the Li-deficient spent cathodes. Ferrocene and its derivatives, the so-called p-type redox mediators, can be oxidized spontaneously from neutral molecules to stable cations under ambient conditions, allowing them to function as electron donors . Meanwhile, lithium salts serve as Li + donors to ensure charge neutrality of the cathode lattice. The effects of solvation and substituent are thoroughly investigated to precisely regulate the potential of a series of ferrocene-based reductants. Chemical re-lithiation is driven thermodynamically by the intrinsic potential gap between ferrocene and degraded cathodes, thus fundamentally realizing a rapid lithiation reaction (taking less than 20 min at 25 °C), while avoiding the involvement of high-temperature operation. Diverse characterizations have been performed to explore the Li + -electron concerted re-lithiation mechanism. The regenerated LiFePO 4 cathode demonstrated comparable Li + storage capability to commercial cathode. Life-cycle analysis verifies the economical and environmental superiority of our chemical re-lithiation strategy to metallurgy in practical industry. The thermodynamically spontaneous chemical re-lithiation provides competitive options for greener recycling of retired batteries in the future.

研究领域: 材料科学 · 化学 · 能源存储 · 可持续性 · 电池回收
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JOURNAL OF HAZARDOUS MATERIALS · 2022 · IF 14.224

Hydroxylamine mediated Fenton-like interfacial reaction dynamics on sea urchin-like catalyst derived from spent LiFePO4 battery

Wensong Zou,Jing Li,Ranhao Wang,Jingyi Ma,Zhijie Chen,Lele Duan,Hongwei Mi,Hong Chen

Herein, we converted spent LiFePO 4 battery to the sea urchin-like material (SULM) with a highly efficient and environment-friendly method, which can contribute to building a zero-waste city. With SULM as a Fenton-like catalyst, a highly-efficient degradation process was realized for organic pollutants with interface and solution synergistic effect. In our SULM+NH 2 OH+H 2 O 2 Fenton-like system, NH 2 OH can effectively promote the interface iron ( Fe(Ⅲ)/ Fe(Ⅱ)) and solution iron (Fe(Ⅲ)/Fe(Ⅱ)) redox cycle, thus promoting the generation of reactive oxygen species (ROS). However, the ROS generation process and organic pollutants degradation pathway with the presence of NH 2 OH remains a puzzle. Here the detailed ROS generation mechanism and pollutants degradation pathway have been illustrated carefully based on experimental exploration and characterization. Therein, hydroxyl radicals (·OH) and singlet oxygen ( 1 O 2 ) are the main ROS for oxidizing and degrading organic pollutants. Notably, 1 O 2 can be converted from superoxide radicals (·O 2 ) in SULM+NH 2 OH+H 2 O 2 system. This study not only demonstrates the strategy of "trash-to-treasure" and "waste-to-control-waste" to simultaneously reduce the hazardous release from industrial solid waste and organic wastewater, it also provides new mechanistic insights for NH 2 OH mediated Fenton-like redox system.

研究领域: 环境科学 · 材料科学 · 化学工程 · 废物管理
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