退役锂电池回收废液制备磷酸锂工艺研究

摘要鉴于锂电池报废量大、锂含量高,探讨从退役锂电池回收废液中利用锂资源。根据溶液高钠含锂、碱含量高的特性,采用磷酸钠沉淀法回收锂,系统研究了反应过程中各工艺参数对磷酸锂回收率、纯度及粒度的影响。结果表明反应温度为102 ℃,磷酸钠1.1倍理论用量,磷酸钠浓度350 g·L^-1,加料速率5 mL·min^-1,搅拌速率500 r·min^-1,冷水洗1 L时,磷酸锂收率能达到92.63%,纯度(质量分数,下同)达到98.81%,产品达到彩色荧光粉用磷酸锂行业标准二级要求。该工艺能广泛应用于各种高钠含锂溶液,特别是从锂浓度较低的溶液中回收锂资源,不仅解决了退役锂电池废液排放问题,还为锂资源提取提供了新途径。

	Service

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	Email Alert
	RSS
	作者相关文章
	姚晓燕
	王宇璇
	徐萌娜
	孙淑英

关键词：高钠含锂溶液退役锂电池磷酸锂化学沉淀

Abstract： Consindering the large amount of discarded lithium batteries and the high content of lithium, lithium resources from the waste liquid of retired lithium batteries were studied. According to the characteristics of high sodium content and high alkali content in the solution, lithium was recovered by sodium phosphate precipitation method. The effects of various process parameters on the recovery yield, purity and particle size of lithium phosphate were systematically studied. The optimized process conditions were as follows: reaction temperature was 102 ℃, dosage of sodium phosphate was 1.1 of the theoretical amount, concentration of sodium phosphate was 350 g·L^-1, feeding rate was 5 mL·min^-1, stirring rate was 500 r·min^-1, the cold water washing is 1 L. Under the optimized conditions, the precipitation yield of lithium phosphate was 92.63%, the purity of lithium phosphate was 98.81%. The products meet the industry standard of lithium phosphate for color phosphor. This process can be widely used in various high-sodium lithium-containing solutions, especially in the recovery of lithium resources from solutions with low lithium concentration, which not only solves the problem of waste liquid discharge of retired lithium batteries, but also provides a new way for lithium resource extraction.

Keywords： high sodium lithium solution spent lithium ion battery lithium phosphate chemical precipitation

Received 2023-02-08;

Fund:国家自然科学基金区域创新发展联合基金—盐湖领域(U20A20142)。

Corresponding Authors: 孙淑英,教授,E-mail:shysun@ecust.edu.cn。 Email: shysun@ecust.edu.cn

About author: 姚晓燕(1998-),女,硕士研究生,主要从事退役锂电池有价元素回收与再利用。

引用本文:

姚晓燕, 王宇璇, 徐萌娜, 孙淑英.退役锂电池回收废液制备磷酸锂工艺研究[J]. 化学工业与工程, 2024,41(3): 179-190

YAO Xiaoyan, WANG Yuxuan, XU Mengna, SUN Shuying.Preparation of lithium phosphate from waste liquid of retired lithium batteries[J]. Chemcial Industry and Engineering, 2024,41(3): 179-190

[1] 左世全. 解读《新能源汽车产业发展规划(2021-2035)》 [J]. 智能网联汽车, 2020(6): 21-23 ZUO Shiquan. Interpretation of the "New Energy Vehicle Industry Development Plan (2021-2035)"[J]. Intelligent Connected Vehicles, 2020(6): 21-23
[2] 钱海峰, 王尧峰. 中国汽车行业争议解决年度观察(2022)[J]. 北京仲裁, 2022(2): 77-114 QIAN Haifeng, Wang Yaofeng. An annual look at dispute resolution in China’s automotive industry[J]. Beijing Arbitration, 2022(2): 77-114(in Chinese)
[3] CHEN Y, DOU A, ZHANG Y. A review of recycling status of decommissioned lithium batteries[J]. Frontiers in Materials, 2021, 8: 12
[4] 王万航. 新型杂多酸类共萃剂用于盐湖卤水萃取提锂的应用基础研究 [D]. 北京: 北京化工大学, 2023 WANG Wanhang. Application fundamental research on lithium extraction from salt lake brines with novel heteropoly acid co-extraction agent [D]. Beijing: Beijing University of Chemical Technology, 2023 (in Chinese)
[5] 王浩, 黄根红, 陈瑞英, 等. 全球锂资源供需展望及锂产品价格预测[J]. 中国有色冶金, 2022, 51(6): 1-11 WANG Hao, HUANG Genhong, CHEN Ruiying, et al. Supply and demand outlook of lithium resources and price forecast of lithium products[J]. China Nonferrous Metallurgy, 2022, 51(6): 1-11(in Chinese)
[6] 亓树茂. 锂离子筛纳米纤维毡的制备及其盐湖提锂性能研究 [D]. 西宁:青海师范大学, 2024 QI Shumao. Preparation of lithium ion-sieve nanofiber mats and property research of lithium extraction from salt-lake [D]. Xining: Qinghai Normal University, 2024(in Chinese)
[7] ZOU H, GRATZ E, APELIAN D, et al. A novel method to recycle mixed cathode materials for lithium ion batteries[J]. Green Chemistry, 2013, 15(5): 1183-1191
[8] 李培岭, 李转玲. 退役动力锂电池正极有价金属的浸出与纯化研究进展[J]. 当代化工研究, 2022(22): 80-82 LI Peiling, LI Zhuanling. Leaching and purification of valuable metals in cathode of decommissioned power lithium batteries[J]. Modern Chemical Research, 2022(22): 80-82(in Chinese)
[9] 何艳君. 废旧锂离子电池三元正极材料的回收利用综述[J]. 新疆有色金属, 2022, 45(6): 56-57 HE Yanjun. Review on recycling of ternary cathode materials for waste lithium ion batteries[J]. Xinjiang Nonferrous Metals, 2022, 45(6): 56-57(in Chinese)
[10] ÇELEBI E E, ÖNCEL M S, KOBYA M, et al. Extraction of lithium from wastewaters using a synergistic solvent extraction system consisting of Mextral EOL and Cyanex 923[J]. Hydrometallurgy, 2019, 185: 46-54
[11] SONG Y, ZHAO Z. Recovery of lithium from spent lithium-ion batteries using precipitation and electrodialysis techniques[J]. Separation and Purification Technology, 2018, 206: 335-342
[12] 熊福军, 陈星宇, 张许, 等. 钛系锂离子筛在沉锂母液锂回收上的连续离子交换工艺研究[J]. 广东化工, 2022, 49(3): 8-11 XIONG Fujun, CHEN Xingyu, ZHANG Xu, et al. Study on continuous ion exchange process of titanium lithium ion sieve for lithium recovery from mother liquor of lithium precipitation[J]. Guangdong Chemical Industry, 2022, 49(3): 8-11(in Chinese)
[13] 杨事成. 离子液体基萃取体系用于沉锂母液提锂的基础研究[D]. 北京: 北京化工大学, 2019 YANG Shicheng. Research on the mechanism of ionic liquid-based system for lithium extraction from lithium deposition mother liquor[D].Beijing: Beijing University of Chemical Technology, 2019 (in Chinese)
[14] 蓝碧波, 黄怀国, 陈华标,et al. 从沉锂母液中回收锂的方法:CN114853037A [P]. 2022-08-05 LAN Bibo, HUANG Huaiguo, CHEN Huabiao, et al. Recovery method of lithium from mother liquor: CN, 114853037A [P].2022-08-05 (in Chinese)
[15] 李汝杰. 从盐湖卤水与沉锂母液选择性萃取提锂新工艺的开发与研究[D]. 北京: 北京化工大学, 2022 LI Rujie. Development and research on new technologies for selective extraction of lithium from salt lake brines and lithium precipitation mother liquor[D].Beijing: Beijing University of Chemical Technology, 2022 (in Chinese)
[16] 何永平, 刘发贵, 景海德, et al. 一种沉锂母液处理的方法和装置:CN111268704A [P]. 2020-06-12 HE Yongping, LIU Fagui, JING Haide, et al. Method and device for treating lithium mother liquor: CN, 111268704A [P]. 2020-06-12. (in Chinese)
[17] 孙建之. 单分散微米磷酸锂的制备[J]. 化工矿物与加工, 2008, 37(8): 4-5 SUN Jianzhi. Preparation of monodisperse micron lithium phosphate[J]. Industrial Minerals & Processing, 2008, 37(8): 4-5(in Chinese)
[18] ZHANG L, LI L J, SHI D, et al. Recovery of lithium from alkaline brine by solvent extraction with β-diketone[J]. Hydrometallurgy, 2018, 175: 35-42
[19] 李岁党, 燕护道, 余佳, 等. 一种用于沉锂母液中锂回收的方法: CN112717468A[P]. 2021-04-30 LI Suidang, YAN Hudao, YU Jia, et al. Method for recycling lithium in lithium precipitation mother liquor: CN112717468A[P]. 2021-04-30 (in Chinese)
[20] 李丽君, 刘程琳, 宋兴福, 等. 碱性溶液体系制备磷酸锂结晶过程优化[J]. 华东理工大学学报(自然科学版), 2020, 46(5): 598-607 LI Lijun, LIU Chenglin, SONG Xingfu, et al. Optimization of crystallization process for preparation of lithium phosphate in alkaline solution system[J]. Journal of East China University of Science and Technology, 2020, 46(5): 598-607(in Chinese)
[21] 石钰川. 赣锋锂业新能源电池企业价值评估[D]. 山东青岛: 青岛科技大学, 2023 SHI Yuchuan. Enterprise value evaluation of ganfeng lithium new energy lithiumbattery[D]. Shandong Qingdao: Qingdao University of Science and Technology, 2023 (in Chinese)
[22] 张小霞. 低浓度含锂废液生产磷酸锂的工艺研究[J]. 无机盐工业, 2020, 52(5): 68-70 ZHANG Xiaoxia. Study on process of producing lithium phosphate by low-concentration lithium-containing waste liquid[J]. Inorganic Chemicals Industry, 2020, 52(5): 68-70(in Chinese)
[23] 伍德佑, 潘湛昌, 刘志强. 从废旧锂离子电池中回收制备磷酸锂的工艺研究[J]. 材料研究与应用, 2020, 14(4): 312-316, 343 WU Deyou, PAN Zhanchang, LIU Zhiqiang. Study on the process for recycling lithium phosphate from spent Li-ion batteries[J]. Materials Research and Application, 2020, 14(4): 312-316, 343(in Chinese)