基于铁法工艺制备电池级磷酸铁技术的研究

doi:10.19964/j.issn.1006-4990.2024-0450

Abstract

Abstract:

In order to obtain the industrial production technology conditions for ferric phosphate by using pure iron，Yunnan Yuntianhua Co.，Ltd.，R&D Center after completing the small-scale exploratory experiment and model verification experiment，built a 1 000 t/a pilot plant for ferric phosphate production.The process used high-purity iron ingots（99.9%），purified phosphoric acid（85.0%），and 27.5% hydrogen peroxide as raw materials to produce ferric phosphate by the process of phosphoric acid dissolving iron，hydrogen peroxide oxidizing and precipitating dihydrogen phosphate.The process required the phosphate dihydrogen phosphate solution Fe²⁺mass fraction to be controlled as the target during the phosphoric acid dissolving process，and the optimized process conditions were as follows：phosphoric acid mass fraction of 26%~27%，dissolving temperature of 88~90 ℃，and dissolving time of 13~15 h.Suggestions were also given for the storage of phosphate dihydrogen phosphate solution.When the mass fraction of the phosphate dihydrogen phosphate Fe²⁺ was controlled at 44~46 g/L and the n（P）∶n（Fe） ratio was（2.65~2.75）∶1，the optimized oxidation precipitation process conditions for producing products with specific surface area as the target were as follows：the initial oxidation temperature of 62~64 ℃，and the hydrogen peroxide feeding time of 50~60 min.The final ferric phosphate product had a P mass fraction of 20.40%~20.70%，Fe mass fraction of 36.18%~36.58%，n（Fe）∶n（P） of （0.970~0.985）∶1，particle size D₅₀ of 3~5 μm，specific surface area of 6~9 m²/g，bulk density greater than 0.60 g/cm³，magnetic impurities controlled below 0.5 mg/kg，and all the indicators met the requirements for battery-grade ferric phosphate.

Key words: iron ingots, phosphate soluble iron, storage of ferrous dihydrogen phosphate solution, oxidation precipitation, battery grade ferric phosphate

CLC Number:

TQ138.1

NI Shuanglin, MA Hang, XUE He′nan, WAN Banglong, YAN Yinxian, ZHANG Jinyuan, CHEN Zhanghong, WEI Xing, CHEN Yunjian, DU Jianbo, DAI Jinfeng. Study on iron-based process for preparing battery-grade ferric phosphate[J]. Inorganic Chemicals Industry, 2025, 57(9): 73-81.

Figures/Tables 13

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Table 1

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References 13

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指标项	w（Fe）/ %	w（P）/ %	n（Fe）/n（P）	振实密度/ （g·cm^-3）		比表面积/ （m²·g^-1）		粒度（D₅₀）/μm		w（磁性物）/%		w（H₂O）/ %	w（Ca）/ %	w（Mg）/ %
HG/T 4701—2021（Ⅰ）	35.7~36.7	20.0~21.1	0.96~1.0	≥0.6		3~16		1~9		≤0.000 25		≤0.5	≤0.01	≤0.06
自制（铁法工艺）	36.18~36.58	20.40~20.70	0.970~0.985	0.60~0.85		6~9		3~5		≤0.000 05		≤0.24	≤0.002 7	≤0.000 2
铵法两步法工艺	36.32	20.93	0.962	0.82		8.71		4.57		≤0.000 02		≤0.33	≤0.001 6	≤0.001 2
指标项	w（Na）/ %	w（K）/ %	w（Cu）/ %	w（Mn）/ %	w（Al）/ %		w（Ti）/ %		w（Co）/ %		w（Pb）/ %		w（Cr）/ %	w（S）/ %
HG/T 4701—2021（Ⅰ）	≤0.02	≤0.02	≤0.003	≤0.1	≤0.05		≤0.18		—		—		—	≤0.03
自制（铁法工艺）	≤0.001 1	≤0.000 98	≤0.000 4	≤0.001 2	≤0.005 6		≤0.000 05		≤0.000 19		≤0.000 89		≤0.002 6	≤0.000 3
铵法两步法工艺	≤0.000 5	≤0.000 39	≤0.000 2	≤0.002 5	≤0.000 3		≤0.000 26		≤0.000 14		≤0.000 86		≤0.000 9	≤0.004 6

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Study on iron-based process for preparing battery-grade ferric phosphate

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