废旧磷酸铁锂电池机械化学固相氧化回收锂机理

doi:10.11949/0438-1157.20240557

摘要/Abstract

摘要：

采用K₂S₂O₈作为氧化剂，分别通过氧化浸出、机械活化联合氧化浸出、机械固相氧化联合水浸等三种方法对废旧磷酸铁锂（LiFePO₄）电池正极粉末进行处理。结果表明，在三种方式最佳条件下，氧化浸出方式的Li浸出率为89.03%（质量分数）、机械活化联合氧化浸出方式的Li浸出率为92.36%（质量分数），机械固相氧化联合水浸方式的效果最佳，Li浸出率为98.26%（质量分数）。此时，Fe化合物也与Li完全分离，选择性较高。通过添加K₃PO₄将浸出的锂离子以Li₃PO₄沉淀的形式提取回收，经电感耦合等离子体质谱仪检测，纯度可达98.67%。采用X射线衍射仪和X射线光电子能谱仪对浸出机理进行分析，结果表明，在机械化学固相氧化过程中，机械力不仅诱导了粒度的减小，还作为氧化反应的驱动力，使得Li⁺迁出，Fe（Ⅱ）被氧化为Fe（Ⅲ），为之后的水浸过程提供了良好条件，实现了Li和Fe的选择性分离。

关键词: 废旧磷酸铁锂电池, 回收, 机械固相氧化, 浸取, 选择性, 过硫酸钾

Abstract:

This study used K₂S₂O₈ as an oxidant and employe d three methods: oxidation leaching, mechanical activation combined with oxidation leaching, and mechanical solid-phase oxidation combined with water leaching to treat waste lithium iron phosphate (LiFePO₄) battery cathode powder. The results showed that under the optimal conditions of the three methods, the Li leaching rate of the oxidation leaching method was 89.03%, and the Li leaching rate of the mechanical activation combined oxidation leaching method was 92.36%. The mechanical solid-phase oxidation combined with water leaching method had the best effect, with a Li leaching rate of 98.26%. At this point, Fe compounds can also be completely separated from Li, improving selectivity. The leached lithium ions were extracted and recovered in the form of Li₃PO₄ precipitation by adding K₃PO₄. After detection by inductively coupled plasma mass spectrometry, the purity can reach 98.67%. The leaching mechanism was analyzed using X-ray diffraction and X-ray photoelectron spectroscopy. The results showed that in the process of mechanochemical solid-phase oxidation, mechanical force not only induced a decrease in particle size, but also acted as a driving force for the oxidation reaction, causing Li⁺to migrate out and Fe (Ⅱ) to be oxidized to Fe (Ⅲ), providing good conditions for the subsequent water leaching process and achieving selective separation of Li and Fe.

Key words: spent lithium iron phosphate batteries, recovery, mechanical solid-phase oxidation, leaching, selectivity, potassium persulfate

中图分类号:

TF803.21

刘家稳, 夏文成, 武锋, 彭耀丽, 谢广元. 废旧磷酸铁锂电池机械化学固相氧化回收锂机理[J]. 化工学报, DOI: 10.11949/0438-1157.20240557.

Jiawen LIU, Wencheng XIA, Feng WU, Yaoli PENG, Guangyuan XIE. Mechanism study on mechanochemical solid-phase oxidation recovery of spent LiFePO₄ batteries[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240557.

图/表 11

图1 基于机械化学法选择性提取回收锂的流程图

Fig. 1 Flow chart of selective extraction and recovery of lithium based on mechanochemical method

图2 三种不同处理方式下Li的浸出率

Fig. 2 Leaching rate of Li under three different treatment methods

图3 研磨前后正极粉末样品的粒径分布情况

Fig.3 Particle size distribution of positive electrode powder samples before and after grinding

图4 K2S2O8/正极LiFePO4粉末质量比对金属回收率的影响

Fig. 4 Effect of mass ratio of K2S2O8/positive electrode LiFePO4 powder on metal recovery rate

图5 球磨时间对Li、Fe浸出率的影响

Fig. 5 Effect of ball milling time on the leaching rate of Li and Fe

图6 真空过滤滤渣的XRD图谱

Fig. 6 XRD pattern of vacuum filtration residue

图7 化学沉淀产物的XRD图谱

Fig.7 XRD pattern of chemical precipitation products

图8 化学沉淀产物的形貌SEM图

Fig. 8 SEM image of chemical precipitation products

图9 混合原料的XRD图谱

Fig. 9 XRD pattern of mixed raw materials

图10 混合原料发生机械化学反应前后的Fe 2p的XPS谱图，

Fig. 10 XPS spectra of Fe 2p before and after mechanochemical reaction of the mixed raw materials

图11 机械化学固相氧化反应机理图

Fig. 11 Mechanism diagram of mechanochemical solid-phase oxidation reaction

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