正负极混合宏量回收废旧磷酸铁锂电池的探索

doi:10.19799/j.cnki.2095-4239.2022.0420

摘要/Abstract

摘要：

为模拟实际工业生产中废旧LiFePO₄电池回收及其综合应用，本文设计了在酸性条件下对废旧LiFePO₄电池正负混合极片中有价金属Li、Cu、Fe的选择性浸出及其产物回收再利用。电池拆解后，将正负混合极片机械粉碎后过筛，得到Cu、Al高含量杂质的正负极混合粉，700 ℃高温焙烧后，除碳率和除氟率分别为99.03%和99.93%，后对其进行Li、Cu的选择性浸出实验。研究结果表明，浸Li段在H⁺/Li⁺的物质的量之比为0.7、浸出温度90 ℃、浸出时间3 h、液固比为3∶1时，金属元素Li、Fe、Cu、Al的浸出率分别为：91.88 %、0.0024%、4.71%、0.11%，实现对Li的有效分离。对浸出液引入饱和Na₂CO₃作为沉淀剂后，成功回收合成电池级碳酸锂。另一方面，对浸出渣进行450 ℃焙烧后，滴加浓硫酸控制pH为1.5、浸出温度90 ℃、浸出时间3 h、液固比5∶1，金属元素Fe、Cu浸出率为：0.11%和92.54%，实现了有价金属Cu的选择性浸出。将处理后的浸铜渣进行酸溶，滴加氨水调节pH至1.8，形成二水磷酸铁，沉淀率可达到95%。焙烧除去二水磷酸铁中的结晶水，得到电池级磷酸铁，纯度为99.48%。

关键词: 废旧LiFePO₄电池, 正负极混合回收, 锂浸出回收, 铜浸出回收, 再生磷酸铁

Abstract:

This study explored the selective leaching of valuable metals Li, Cu, and Fe in the mixed positive and negative electrodes of spent LiFePO₄ batteries under acidic conditions to simulate the recycling and comprehensive application of spent LiFePO₄ batteries in industrial production. The positive and negative electrodes are mechanically crushed and sieved to obtain the mixed powder, which contains high contents of Cu and Al impurities. The carbon and fluorine removal rates are 99.03% and 99.93% after calcination at 700 ℃. When the H⁺/Li⁺ molar ratio equals 0.7, the leaching temperature is 90 ℃, the leaching time is 3 h, and the liquid-solid ratio is 3∶1. Additionally, the leaching rates distribution of Li, Fe, Cu, and Al are 91.88%, 0.0024%, 4.71%, 0.11%, respectively, indicating the satisfactory separation of Li. Saturated Na₂CO₃ successfully recovered the battery-grade lithium carbonate as a precipitant. However, the leaching cinder was calcinated at 450 ℃ to convert Cu into CuO. The metal elements Fe and Cu leaching rates are 0.11% and 92.54%, respectively, under a pH of 1.5, 90 ℃ leaching temperature, 3 h leaching time, and the liquid-solid ratio of 5∶1. Finally, the copper leaching residue was completely dissolved in sulfuric acid. The precipitation rate of ferric phosphate dihydrate reached approximately 95% under adjusting pH to 1.8 by ammonia. The battery-grade ferric phosphate with a purity of 99.48% (weight fraction) was obtained by calcining crystal water.

Key words: spent LiFePO₄ battery, mixed recovery of positive and negative electrodes, lithium leaching and recovery, copper leaching and recovery, regenerated iron phosphate

中图分类号:

TM 912

姚健, 刘朝阳, 王海, 王佳东, 高宣雯, 李建中, 刘朝孟, 翟玉春, 骆文彬. 正负极混合宏量回收废旧磷酸铁锂电池的探索[J]. 储能科学与技术, 2022, 11(12): 3759-3767.

Jian YAO, Zhaoyang LIU, Hai WANG, Jiadong WANG, Xuanwen GAO, Jianzhong LI, Zhaomeng LIU, Yuchun ZHAI, Wenbin LUO. Exploration of mixed positive and negative electrodes of spent lithium iron phosphate batteries[J]. Energy Storage Science and Technology, 2022, 11(12): 3759-3767.

图/表 11

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