硅酸盐学报

废LiFePO₄含锂浸出液低碳深度除杂技术及机理

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章小明 ¹^,² , 陈建安 ¹ , 邓莘彦 ¹ , 徐振华 ¹ , 王馨 ¹^,² , 黄国勇 ¹

硅酸盐学报 | 支撑碳中和目标的新能源材料与器件循环利用专题—研究论文 2025,53(8): 2088-2099

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硅酸盐学报 |支撑碳中和目标的新能源材料与器件循环利用专题—研究论文 2025 , 53 (8) : 2088 -2099

废LiFePO₄含锂浸出液低碳深度除杂技术及机理

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章小明¹^,², 陈建安¹, 邓莘彦¹, 徐振华¹, 王馨¹^,², 黄国勇¹

作者信息

^1．中国石油大学（北京）新能源与材料学院，重质油全国重点实验室，北京 102249

^2．江西赣锋锂业集团股份有限公司，江西新余 338000

通讯作者:

王馨（1997—），女，博士研究生；

黄国勇（1983—），男，博士，教授。

作者简介:

章小明（1984—），男，博士研究生。

Spent LiFePO₄ Lithium Leach Solution Low Carbon Deep Decontamination Technology and Mechanism

Xiaoming ZHANG¹^,², Jianan CHEN¹, Xinyan DENG¹, Zhenhua XU¹, Xin WANG¹^,², Guoyong HUANG¹

Affiliations

^1.State Key Laboratory of Heavy Oil, College of New Energy and Materials, China University of Petroleum-Beijing, Beijing 102249, China

^2.Lithium Group Co., Ltd., Xinyu 338000, Jiangxi, China

Corresponding Author:

WANG Xin (1997-), female, Doctoral Candidate. E-mail: WX841780383@163.com;

HUANG Guoyong (1983-), male, Ph.D., Professor. huanggy@cup.edu.cn

ZHANG Xiaoming (1984-), male, Doctoral Candidate. E-mail: Zxm998866@163.com

出版时间: 2025-08-20 doi: 10.14062/j.issn.0454-5648.20240857

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摘要

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退役LiFePO₄电池拆解得到的正极粉一般通过酸浸进行回收，但酸浸后还含有大量杂质，需再次进行除杂才能回收利用。本工作采用废LiFePO₄含锂浸出液，通过还原除铜、中和除铁铝磷、碱化除镍钴锰、树脂除钙和吸附除氟，进行杂质的去除，得到可进行沉锂的净化液。结果表明：铁粉加入量为理论量的1.1倍，铜回收率达到99.95%。在最优实验条件下，用Ca（OH）₂可将Fe、Al、P大部分除去，去除率分别为86.11%、70.75%和99.27%。同时，贵重金属Ni、Co、Mn损失低于5%。采用纯碱除杂，Ni、Co、Mn、Cu和Al等金属几乎沉淀完全，沉淀率均达99.5%以上，可以除到5 mg/L以下。50 ℃下HP4040树脂对Ca的单级吸附达91.6%以上。以廉价的β锂辉石为原料，制备的MgO修饰β锂辉石可进行除氟，对F的单次吸附率可达85.8%以上，为开发低成本深度除氟材料提供一条路径。

关键词

分离与提纯 / 吸附分离 / 回收率 / 吸附动力学 / 吸附热力学

Abstract

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Introduction

The complexity of lithium iron phosphate waste sources dictates the intricate composition of the solution after acid leaching. Particularly during the pretreatment process, lithium iron phosphate waste can become mixed with anode materials and may contain trace amounts of nickel, cobalt, and manganese. Therefore, in addition to the characteristic impurities of lithium iron phosphate, such as iron, aluminum, and phosphate, the acid leach solution obtained from lithium iron phosphate waste through high-pressure oxidation leaching is typically accompanied by small amounts of copper, nickel, cobalt, manganese, fluorine, and other impurity elements. On one hand, regarding product purity, if these impurity elements are not adequately removed, they may lead to the deterioration of lithium carbonate quality, adversely affecting subsequent processing. On the other hand, considering recycling value, metals like copper, nickel, and cobalt have significant market value, necessitating their recovery to improve the economic viability of the entire process.

Methods

Remove Cu, Fe, Al, P, Ni, Co, Mn and other impurities by chemical method. Removal of calcium impurities by HP4040 resin. The adsorption process of Ca²⁺ was correlated using kinetic equations, confirming that the adsorption process of HP4040 resin for calcium removal aligns more closely with a pseudo-second-order kinetic model. This indicates that the adsorption reaction between calcium ions and the resin is predominantly governed by chemical adsorption. Thermodynamic analysis revealed that the adsorption process of calcium ions on the resin conforms to the Langmuir isotherm model. Removal of fluorine impurities by modification of MgO-modified β-spodumene, both pseudo-first-order and pseudo-second-order kinetic equations were employed to describe the adsorption of fluoride ions onto the adsorbent. The fitting results suggest that the fluoride adsorption process largely adheres to the pseudo-second-order kinetic model. Thermodynamic analysis further indicated that the adsorption of fluoride by the defluorination agent aligns better with the Langmuir model, suggesting a preference for monolayer adsorption.

Results and discussion

The main conclusions of this study are summarized as follows. This research systematically investigates the purification and decontamination processes of waste LiFePO₄ lithium-containing leach solutions, focusing on the reduction and removal of copper, neutralization of iron, aluminum, and phosphorus, alkalization for nickel, cobalt, and manganese removal, resin-based calcium removal, and adsorption for fluoride removal. The distribution of impurity ions in the acid leach solution, including Fe, Al, Cu, Ni, Co, Mn, Ca, and F, has been analyzed throughout the decontamination process, and the entire flow of acid leach solution decontamination has been experimentally validated. The findings are as follows: To effectively reduce and remove copper, the optimal addition of iron powder is 1.1 times the theoretical amount, achieving a recovery rate of 99.95% and a copper sponge purity of 95.02%. For neutralization to remove iron, aluminum, and phosphorus, the optimal reaction conditions are a temperature of 30 ℃, an endpoint pH value of 4, and a reaction time of 30 min. Under these conditions, the impurity elements Fe, Al, and P are predominantly removed, while the loss of valuable metals like Ni, Co, and Mn is minimal. In the alkalization process for removing Ni, Co, and Mn, precipitation occurs at pH 12, with precipitation rates exceeding 99.5% for all target metals. The resin-based calcium removal process studies and compares the advantages of three commercially available calcium removal resins, ultimately selecting HP4040 resin, which demonstrates a maximum adsorption capacity of 35.28 mg/g for calcium, achieving over 91.6% single-stage calcium adsorption. Meanwhile, the synthesized MgO-modified β- spodumene adsorbent material achieves a single-stage adsorption rate of over 85.8% for fluoride, providing a pathway for developing low-cost deep fluoride removal materials.

Conclusions

This study systematically investigates the purification and decontamination process for waste LiFePO₄ lithium leach solutions. After the reduction to remove copper, neutralization to eliminate iron, aluminum, and phosphorus, alkalization for nickel, cobalt, manganese removal, resin-based calcium removal, and adsorption for fluoride removal, the purification of the liquid obtained allows for lithium carbonate recovery.

Key words

separation and purification / adsorption separation / recovery rate / adsorption kinetics / adsorption thermodynamics

引用本文

章小明, 陈建安, 邓莘彦, 徐振华, 王馨, 黄国勇. 废LiFePO₄含锂浸出液低碳深度除杂技术及机理. 硅酸盐学报, 2025 , 53 (8) : 2088 -2099 . DOI: 10.14062/j.issn.0454-5648.20240857

Xiaoming ZHANG, Jianan CHEN, Xinyan DENG, Zhenhua XU, Xin WANG, Guoyong HUANG. Spent LiFePO₄ Lithium Leach Solution Low Carbon Deep Decontamination Technology and Mechanism[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (8) : 2088 -2099 . DOI: 10.14062/j.issn.0454-5648.20240857

基金

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国家自然科学基金项目(52274307)
国家重点研发计划(2021YFC2901100)
中国石油大学科学基金(2462021QNX2010)
重质油全国重点实验室(HON-KFKT2022-10)

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2025年第53卷第8期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240857

接收时间：2024-12-31
首发时间：2026-10-21
出版时间：2025-08-20

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出版历史

收稿日期：2024-12-31
修回日期：2025-01-31

基金

国家自然科学基金项目(52274307)

国家重点研发计划(2021YFC2901100)

中国石油大学科学基金(2462021QNX2010)

重质油全国重点实验室(HON-KFKT2022-10)

作者信息

^1．中国石油大学（北京）新能源与材料学院，重质油全国重点实验室，北京 102249

^2．江西赣锋锂业集团股份有限公司，江西新余 338000

通讯作者:

王馨（1997—），女，博士研究生；

黄国勇（1983—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240857

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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