磷铁渣高温活化浸出-沉淀法制备电池级FePO4的工艺及应用

doi:10.16085/j.issn.1000-6613.2023-1067

化工进展 ›› 2024, Vol. 43 ›› Issue (8): 4726-4737.DOI: 10.16085/j.issn.1000-6613.2023-1067

• 资源与环境化工 • 上一篇

磷铁渣高温活化浸出-沉淀法制备电池级FePO₄的工艺及应用

袁明哲¹^,²(), 秦安瑞¹^,², 周桂民¹^,², 陈秋霖¹^,², 袁亚杰¹^,², 姚耀春¹^,²(), 李银¹^,²()

^1.昆明理工大学冶金与能源工程学院，云南昆明 650093
^2.昆明理工大学真空冶金国家工程研究中心，云南昆明 650093

收稿日期:2023-06-27 修回日期:2023-08-23 出版日期:2024-08-15 发布日期:2024-09-02
通讯作者: 姚耀春,李银
作者简介:袁明哲（1998—），男，硕士研究生，研究方向为新能源电池材料。E-mail：845419721@qq.com。
基金资助:
国家自然科学基金(52064031);云南省基础研究发展项目(202301AU070055);昆明理工大学分析测试基金(2022T20210167)

Process and application study on the preparation of battery-grade FePO₄ by high-temperature activated leaching-precipitation of iron phosphate slag

YUAN Mingzhe¹^,²(), QIN Anrui¹^,², ZHOU Guimin¹^,², CHEN Qiulin¹^,², YUAN Yajie¹^,², YAO Yaochun¹^,²(), LI Yin¹^,²()

^1.School of Metallurgy and Energy Engineering, Kunming University of Technology, Kunming 650093, Yunnan, China
^2.National Engineering Laboratory of Vacuum Metallurgy, Kunming University of Technology, Kunming 650093, Yunnan, China

Received:2023-06-27 Revised:2023-08-23 Online:2024-08-15 Published:2024-09-02
Contact: YAO Yaochun, LI Yin

摘要/Abstract

摘要：

磷铁渣是黄磷生产的副产物之一，化学性质稳定，常作为固体废物处理，不仅污染环境，也消耗了大量人力物力。如何合理利用磷铁渣中铁（Fe）、磷（P）元素是磷化工企业必须解决的问题。以磷铁渣制备磷酸铁（FePO₄）的传统技术存在能耗大、副产物安全隐患大、难以实现工业化生产等缺点。有鉴于此，本文采用磷铁渣、磷酸、盐酸、氨水为原料，通过高温活化浸出-沉淀法制备了电池级FePO₄。在高温活化浸出阶段，探究了浸出时间、浸出温度、盐酸浓度、液固比与磷铁渣浸出率的关联规律。并研究了反应温度、时间、pH、投料比等条件对制备FePO₄性能的影响。对浸出液中Fe、P元素浓度和FePO₄晶体结构、形貌和粒度进行了分析。实验结果表明，磷铁渣浸出的最佳条件是：浸出时间3h、浸出温度90℃、盐酸浓度5.5mol/L、液固比20mL/g，在此浸出条件下Fe元素浸出率可达93.55%，P元素浸出率可达82.21%，固体渣浸出率可达90.06%。沉淀反应过程的最佳条件为：反应温度70℃、反应时间2h、反应pH=1.2、Fe/P投料比为1，此条件制备的磷酸铁（FePO₄）材料结晶度高，形貌均匀，分散性好，一次粒径为100~200nm，铁磷比为0.97，杂质含量完全符合行业标准。以此合成的磷酸铁锂（LiFePO₄）正极材料电化学性能较好，在1C倍率下，放电比容量可达到151.62mA·h/g，表明所制备的FePO₄完全满足LiFePO₄正极材料前体的要求。

关键词: 磷铁渣, 活化, 浸出, 沉淀法, 电池级磷酸铁

Abstract:

Phosphorus iron slag is one of the by-products of the production of yellow phosphorus. It is often treated as solid waste due to its chemically stable, which not only pollutes the environment but also consumes a lot of manpower and material resources. How to rationally utilize the iron (Fe) and phosphorus (P) elements in iron phosphate slag is a problem that must be solved by phosphorus chemical enterprises. The traditional technology of preparing iron phosphate (FePO₄) from iron phosphate slag has the disadvantages of high energy consumption, large safety hazards of by-products and difficulty in industrialized production. Thus, this paper adopted iron phosphate slag, phosphoric acid, hydrochloric acid and ammonia as raw materials, and prepared battery-grade FePO₄ by a combination of high-temperature activated leaching-precipitation method. In the stage of high-temperature activated leaching, the correlation law between the leaching time, the leaching temperature, the concentration of hydrochloric acid, the liquid-solid ratio and the leaching ratio of iron phosphate slag was explored. The effects of reaction temperature, time, pH and feeding ratio on the performance of prepared FePO₄ were also investigated. The concentrations of Fe and P elements in the leaching solution and the crystal structure, morphology and particle size of FePO₄ were analyzed. The experimental results showed that the optimal conditions for the leaching of ferrophosphorus slag were: leaching time of 3h, leaching temperature of 90℃, hydrochloric acid concentration of 5.5mol/L and liquid-solid ratio of 20mL/g, under which the leaching rate of elemental Fe could be up to 93.55%, the rate of elemental P could be up to 82.21%, and the rate of solid slag leaching could be up to 90.06%. The optimal conditions of the precipitation reaction process were: reaction temperature 70℃, reaction time 2h, reaction pH=1.2 and Fe/P feeding ratio of 1. This condition of the preparation of iron phosphate (FePO₄) materials with high crystallinity, uniform morphology, good dispersion, a particle size of 100—200nm, iron and phosphorus ratio of 0.97 and the content of impurities was in full compliance with the industry standards. The lithium iron phosphate (LiFePO₄) cathode material synthesized in this way had good electrochemical performance, and the discharge specific capacity can reach 151.62mA·h/g at 1C multiplicity, indicating that the prepared FePO₄ fully met the requirements of the precursor of LiFePO₄ cathode material.

Key words: iron phosphate slag, activation, leach, precipitation method, battery-grade iron phosphate

中图分类号:

袁明哲, 秦安瑞, 周桂民, 陈秋霖, 袁亚杰, 姚耀春, 李银. 磷铁渣高温活化浸出-沉淀法制备电池级FePO₄的工艺及应用[J]. 化工进展, 2024, 43(8): 4726-4737.

YUAN Mingzhe, QIN Anrui, ZHOU Guimin, CHEN Qiulin, YUAN Yajie, YAO Yaochun, LI Yin. Process and application study on the preparation of battery-grade FePO₄ by high-temperature activated leaching-precipitation of iron phosphate slag[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4726-4737.

图/表 23

表1 活化后磷铁渣成分分析

元素	质量分数/%
Fe	65.85
P	25.79
Co	0.26
Mn	3.09
Ni	0.13
Ti	0.66
V	0.24

图1 磷铁渣活化前后XRD图

图2 磷铁渣活化前后SEM图

图3 浸出条件对磷铁渣浸出率及溶液中Fe、P元素浓度的影响

图4 Fe/P投料比对磷酸铁中Fe、P元素质量分数及铁磷比的影响

图5 不同Fe/P投料比条件下制备磷酸铁的XRD谱图

图6 Fe/P投料比对磷酸铁粒度的影响

图7 反应时间对磷酸铁中Fe、P元素含量及铁磷比的影响

图8 不同反应时间条件下制备磷酸铁的XRD谱图

图9 反应时间对磷酸铁颗粒粒径的影响

图10 反应温度对磷酸铁中Fe、P元素质量分数及铁磷比的影响

图11 不同反应温度条件下制备磷酸铁的XRD谱图

图12 反应温度对磷酸铁颗粒粒径的影响

图13 反应pH对磷酸铁中Fe、P元素质量分数及铁磷比的影响

图14 不同反应pH条件下制备磷酸铁的XRD谱图

图15 反应pH对磷酸铁颗粒粒径的影响

表2 最佳条件制备的磷酸铁的化学成分分析（质量分数）

元素	样品/%	行业标准/%
Ni	未检出	≤0.005
Mn	0.0015	≤0.1
Co	未检出	≤0
Ti	0.01	≤0.18
V	0.047	≤0.18
K	未检出	≤0.02
Na	0.0069	≤0.02
Ca	未检出	≤0.01
Mg	未检出	≤0.005
Cu	0.0009	≤0.003
Zn	未检出	≤0.015

图16 最佳条件下制备的磷酸铁不同放大倍数下SEM图

图17 以最佳条件下制备的磷酸铁前体合成LiFePO4的XRD谱图

图18 以最佳条件下制备的磷酸铁前体合成LiFePO4的SEM图

图19 以最佳条件下制备的磷酸铁前体合成LiFePO4/C的电化学性能

图20 以最佳条件下制备的磷酸铁前体合成LiFePO4/C的BET图

图21 以最佳条件下制备的磷酸铁前体合成LiFePO4/C的粒度分布

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磷铁渣高温活化浸出-沉淀法制备电池级FePO₄的工艺及应用

Process and application study on the preparation of battery-grade FePO₄ by high-temperature activated leaching-precipitation of iron phosphate slag

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