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，在三种方式最优条件下，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%（质量分数）。X射线衍射和X射线光电子能谱分析浸出机理，结果表明，在机械化学固相氧化过程中，机械力不仅诱导了LiFePO₄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:

K₂S₂O₈ was used as an oxidant to treat the cathode powder of spent lithium iron phosphate (LiFePO₄) batteries by three methods: oxidation leaching, mechanical activation combined oxidation leaching, and mechanical solid-phase oxidation combined water leaching. The results showed that under the optimal conditions of the three methods, the Li leaching rate of the oxidation leaching method was 89.03%(mass), and the Li leaching rate of the mechanical activation combined oxidation leaching method was 92.36%(mass). The mechanical solid-phase oxidation combined with water leaching method had the best effect, with a Li leaching rate of 98.26%(mass). 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%(mass). The leaching mechanism was analyzed by 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:

TF 803.21

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, 2024, 75(10): 3775-3782.

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, 2024, 75(10): 3775-3782.

图/表 11

图1 选择性提取回收锂的流程图

Fig.1 Flow chart of selective extraction and recovery of lithium

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

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谱图

Fig.6 XRD patterns of vacuum filtration residue

图7 化学沉淀产物的XRD谱图

Fig.7 XRD patterns of chemical precipitation products

图8 化学沉淀产物的SEM图

Fig.8 SEM image of chemical precipitation products

图9 混合原料的XRD谱图

Fig.9 XRD patterns 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

Fig. 11 Mechanism of mechanochemical solid-phase oxidation reaction

参考文献 35

1	Xu Z R, Gao L B, Liu Y J, et al. Review—recent developments in the doped LiFePO₄ cathode materials for power lithium ion batteries[J]. Journal of the Electrochemical Society, 2016, 163(13): A2600-A2610.
2	Wei G L, Liu Y X, Jiao B L, et al. Direct recycling of spent Li-ion batteries: challenges and opportunities toward practical applications[J]. iScience, 2023, 26(9): 107676.
3	Lebedeva N P, Boon-Brett L. Considerations on the chemical toxicity of contemporary Li-ion battery electrolytes and their components[J]. Journal of the Electrochemical Society, 2016, 163(6): A821-A830.
4	Ruan J Q, Tong Y C, Ran J Y, et al. Simplifying and optimizing Li₄SiO₄ preparation from spent LiFePO₄ batteries with enhanced CO₂ adsorption[J]. ACS Sustainable Chemistry & Engineering, 2023, 11(38): 14158-14166.
5	Saju D, Ebenezer J, Chandran N, et al. Recycling of lithium iron phosphate cathode materials from spent lithium-ion batteries: a mini-review[J]. Industrial & Engineering Chemistry Research, 2023, 62(30): 11768-11783.
6	Shangguan E B, Fu S Q, Wu S Q, et al. Evolution of spent LiFePO₄ powders into LiFePO₄/C/FeS composites: a facile and smart approach to make sustainable anodes for alkaline Ni-Fe secondary batteries[J]. Journal of Power Sources, 2018, 403: 38-48.
7	Wu J, MacKenzie A, Sharma N. Recycling lithium-ion batteries: adding value with multiple lives[J]. Green Chemistry, 2020, 22(7): 2244-2254.
8	Lin J, Li L, Fan E S, et al. Conversion mechanisms of selective extraction of lithium from spent lithium-ion batteries by sulfation roasting[J]. ACS Applied Materials & Interfaces, 2020, 12(16): 18482-18489.
9	Hu G R, Gong Y F, Peng Z D, et al. Direct recycling strategy for spent lithium iron phosphate powder: an efficient and wastewater-free process[J]. ACS Sustainable Chemistry & Engineering, 2022, 10(35): 11606-11616.
10	Chen J P, Li Q W, Song J S, et al. Environmentally friendly recycling and effective repairing of cathode powders from spent LiFePO₄ batteries[J]. Green Chemistry, 2016, 18(8): 2500-2506.
11	Song X, Hu T, Liang C, et al. Direct regeneration of cathode materials from spent lithium iron phosphate batteries using a solid phase sintering method[J]. RSC Advances, 2017, 7(8): 4783-4790.
12	Li X L, Zhang J, Song D W, et al. Direct regeneration of recycled cathode material mixture from scrapped LiFePO₄ batteries[J]. Journal of Power Sources, 2017, 345: 78-84.
13	Zhang X X, Xue Q, Li L, et al. Sustainable recycling and regeneration of cathode scraps from industrial production of lithium-ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(12): 7041-7049.
14	Liu Y, Lv W G, Zheng X H, et al. Near-to-stoichiometric acidic recovery of spent lithium-ion batteries through induced crystallization[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(8): 3183-3194.
15	Meshram P, Mishra A, Abhilash, et al. Environmental impact of spent lithium ion batteries and green recycling perspectives by organic acids-A review[J]. Chemosphere, 2020, 242: 125291.
16	Yao Y L, Zhu M Y, Zhao Z, et al. Hydrometallurgical processes for recycling spent lithium-ion batteries: a critical review[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(11): 13611-13627.
17	Chagnes A, Pospiech B. A brief review on hydrometallurgical technologies for recycling spent lithium-ion batteries[J]. Journal of Chemical Technology & Biotechnology, 2013, 88(7): 1191-1199.
18	Li H, Xing S Z, Liu Y, et al. Recovery of lithium, iron, and phosphorus from spent LiFePO₄ batteries using stoichiometric sulfuric acid leaching system[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(9): 8017-8024.
19	Shangguan E B, Wang Q, Wu C K, et al. Novel application of repaired LiFePO₄ as a candidate anode material for advanced alkaline rechargeable batteries[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(10): 13312-13323.
20	Xiao J F, Li J, Xu Z M. Challenges to future development of spent lithium ion batteries recovery from environmental and technological perspectives[J]. Environmental Science & Technology, 2020, 54(1): 9-25.
21	Dai Y, Xu Z D, Hua D, et al. Theoretical-molar Fe³⁺ recovering lithium from spent LiFePO₄ batteries: an acid-free, efficient, and selective process[J]. Journal of Hazardous Materials, 2020, 396: 122707.
22	Zheng R J, Zhao L, Wang W H, et al. Optimized Li and Fe recovery from spent lithium-ion batteries via a solution-precipitation method[J]. RSC Advances, 2016, 6(49): 43613-43625.
23	Zhang J L, Hu J T, Liu Y B, et al. Sustainable and facile method for the selective recovery of lithium from cathode scrap of spent LiFePO₄ batteries[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(6): 5626-5631.
24	Shiga T, Kondo H, Kato Y, et al. Mediator catalyst for lithium fluoride decomposition for lithium recovery[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(5): 2260-2266.
25	马伊, 曹世伟, 王家骏, 等. 低共熔溶剂回收废旧锂离子电池正极材料的研究进展[J]. 化工进展, 2023, 42(S1): 219-232.
	Ma Y, Cao S W, Wang J J, et al. Research progress of recycling cathode materials for waste lithium ion batteries in deep eutectic solvents[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 219-232.
26	Howard J L, Cao Q, Browne D L. Mechanochemistry as an emerging tool for molecular synthesis: what can it offer?[J]. Chemical Science, 2018, 9(12): 3080-3094.
27	Wang M M, Tan Q Y, Huang Q F, et al. Converting spent lithium cobalt oxide battery cathode materials into high-value products via a mechanochemical extraction and thermal reduction route[J]. Journal of Hazardous Materials, 2021, 413: 125222.
28	Liu K, Yang J K, Hou H J, et al. Facile and cost-effective approach for copper recovery from waste printed circuit boards via a sequential mechanochemical/leaching/recrystallization process[J]. Environmental Science & Technology, 2019, 53(5): 2748-2757.
29	Yin X F, Wu Y F, Tian X M, et al. Green recovery of rare earths from waste cathode ray tube phosphors: oxidative leaching and kinetic aspects[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(12): 7080-7089.
30	Wang M M, Tan Q Y, Li J H. Unveiling the role and mechanism of mechanochemical activation on lithium cobalt oxide powders from spent lithium-ion batteries[J]. Environmental Science & Technology, 2018, 52(22): 13136-13143.
31	Shentu H J, Xiang B, Cheng Y J, et al. A fast and efficient method for selective extraction of lithium from spent lithium iron phosphate battery[J]. Environmental Technology & Innovation, 2021, 23: 101569.
32	Dedryvère R, Maccario M, Croguennec L, et al. X-ray photoelectron spectroscopy investigations of carbon-coated Li _x FePO₄ materials[J]. Chemistry of Materials, 2008, 20(22): 7164-7170.
33	Castro L, Dedryvère R, El Khalifi M, et al. The spin-polarized electronic structure of LiFePO₄ and FePO₄ evidenced by in-lab XPS[J]. The Journal of Physical Chemistry C, 2010, 114(41): 17995-18000.
34	Zhou F, Kang K, Maxisch T, et al. The electronic structure and band gap of LiFePO₄ and LiMnPO₄ [J]. Solid State Communications, 2004, 132(3/4): 181-186.
35	Mahmud S, Rahman M, Kamruzzaman M, et al. Recent advances in lithium-ion battery materials for improved electrochemical performance: a review[J]. Results in Engineering, 2022, 15: 100472.

编辑推荐 0

Metrics

阅读次数

全文

108

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
2	0	10	31	0	65

来源	本网站	其他网站

次数	65	43
比例	60%	40%

摘要

200

最新录用	在线预览	正式出版

91	0	109

来源	本网站	其他网站

次数	58	142
比例	29%	71%

[1]	唐宇昊, 张迎迎, 赵智伟, 鲁梦悦, 张飞飞, 王小青, 杨江峰. 弱极性超微孔Sc/In-CPM-66A用于CH₄/N₂吸附分离性能[J]. 化工学报, 2024, 75(9): 3210-3220.
[2]	郑晓园, 蔡炎嶙, 应芝, 王波, 豆斌林. 污水污泥磷形态亚临界水热转化研究[J]. 化工学报, 2024, 75(8): 2970-2982.
[3]	吴哲明, 张碧云, 郑仁朝. 腈水解酶立体选择性改造及其合成布瓦西坦[J]. 化工学报, 2024, 75(7): 2633-2643.
[4]	秦晓巧, 谭宏博, 温娜. 储能式低温空分系统热力学与经济性分析[J]. 化工学报, 2024, 75(7): 2409-2421.
[5]	周文轩, 刘珍, 张福建, 张忠强. 高通量-高截留率时间维度膜法水处理机理研究[J]. 化工学报, 2024, 75(7): 2583-2593.
[6]	王涛虹, 王超, 李政, 刘莹, 田歌, 常刚刚, 阳晓宇, 鲍宗必. 固载Cu（Ⅰ）的π络合MOF吸附剂用于乙烷/乙烯的选择性分离[J]. 化工学报, 2024, 75(7): 2565-2573.
[7]	吕田田, 原敏, 王江, 高美珍, 杨佳辉, 徐红, 董晋湘, 石琪. ZTIF基疏水微介孔碳的制备及5-羟甲基糠醛吸附分离性能[J]. 化工学报, 2024, 75(4): 1642-1654.
[8]	孟园, 倪善, 刘亚锋, 王文杰, 赵越, 朱育丹, 杨良嵘. 功能化多孔氮化碳材料对铀的吸附性能研究[J]. 化工学报, 2024, 75(4): 1616-1629.
[9]	张凯博, 沈佳新, 李玉霞, 谈朋, 刘晓勤, 孙林兵. Y沸石中Cu（Ⅰ）的可控构筑及其乙烯/乙烷吸附分离性能研究[J]. 化工学报, 2024, 75(4): 1607-1615.
[10]	张天永, 张晶怡, 姜爽, 李彬, 吕东军, 陈都民, 陈雪. 弱酸性蓝AS染料排放的废盐制碳基吸附剂及利用[J]. 化工学报, 2024, 75(3): 890-899.
[11]	王灵洁, 高海龙, 靳继鹏, 王志浩, 李见波. 海水中的污染物对逆电渗析电堆性能的影响[J]. 化工学报, 2024, 75(2): 695-705.
[12]	李泓宇, 刘祥坤, 施尧, 曹约强, 钱刚, 段学志. 颗粒分辨的乙炔选择性加氢固定床反应器数值模拟[J]. 化工学报, 2024, 75(10): 3610-3622.
[13]	刘琦, 陈子康, 朴宇, 肖鹏, 葛亚粉, 巩雁军. 烃类催化裂解高选择性制低碳烯烃的分子筛催化剂[J]. 化工学报, 2024, 75(1): 120-137.
[14]	黄琮琪, 吴一梅, 陈建业, 邵双全. 碱性电解水制氢装置热管理系统仿真研究[J]. 化工学报, 2023, 74(S1): 320-328.
[15]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.