菱锰矿酸浸液直接制备电池级四氧化三锰的研究
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作者单位:

1.阿克陶科邦锰业制造有限公司, 新疆 阿克陶 845550 ;2.东华理工大学 地下水污染与成因江西省重点实验室, 江西 南昌 330013 ;3.东华理工大学 水资源与环境工程学院, 江西 南昌 330013 1

作者简介:

马晓磊(1987—),甘肃山丹人,学士,高级工程师,主要研究方向为有色金属冶金。

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中图分类号:

TF792;TF803.2

基金项目:

“天山英才”培养计划项目(2022TSYCJC0014;2023TSYCJC0013);新疆维吾尔自治区重点研发计划项目(2023A03003-2);江西省科技对口支援项目(20240BDB29003;20250BFA99001)


Study on the direct preparation of battery-grade manganese tetroxidefrom the acid leaching solution of rhodochrosite
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Affiliation:

1.Aketao Kebang Manganese Manufacturing Co., Ltd., Aketao 845550 , China ;2.Key Laboratory of Groundwater Pollution and Causes of Jiangxi Province, East China University of Technology,Nanchang 330013 , China ;3.School of Water Resources and Environmental Engineering, East China University of Technology, Nanchang 330013 , China

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    摘要:

    电池级四氧化三锰作为制备锂离子电池正极材料锰酸锂的关键前驱体,凭借其独特的晶体结构和电化学性能,在新能源电池行业中占据重要的位置,但传统制备方法存在生产成本高的缺点。本文以科邦锰业的菱锰矿酸浸液为原料,采用初步除杂-深度除杂-氧化沉淀工艺制备了电池级四氧化三锰,深度研究了菱锰矿酸浸液的净化工艺,并详细考察了锰净化液氧化沉淀工艺过程中各因素对电池级四氧化三锰制备的影响,结果表明,初步除杂时加入碳酸氢铵-硫酸溶液进行Mn、Mg的沉淀再溶解,Mn浓度富集至122.5g/L,Mg降低至91.5mg/L,Cl、Na、K和Si的浓度分别显著降至6.2mg/L、16.8mg/L、2.3mg/L和9.8mg/L;深度除杂工序中加入1.0g/L BaS和4.2g/L MnF2脱除重金属以及Ca、Mg后,溶液中Mg、Ca浓度降低至21.3mg/L和11.6mg/L,重金属Pb降低至1.3mg/L,Zn、Ni、Cd和Cu均降至<1mg/L;直接氧化法制备电池级四氧化三锰的工艺条件为,在Mn浓度为1mol/L、氧气作为氧化剂、2%氨水作为中和剂、反应温度为70℃的条件下反应时间12h,采用2%氨水对产物进行洗涤后干燥,获得Mn含量为71%、比表面积为0.813m2/g、振实密度为2.53g/cm3、中值粒径为12.5μm、杂质含量低于国家标准的类球形电池级四氧化三锰。

    Abstract:

    As a key precursor for preparing lithium manganate, a cathode material for lithium-ion batteries, battery-grade manganese dioxide holds an important position in the new energy battery industry due to its unique crystal structure and electrochemical performance. However, traditional preparation methods have the drawback of high production costs. In this study, using the acid leaching solution of rhodochrosite from Kebang Manganese Industry as the raw material, battery-grade manganese dioxide was prepared through a process of preliminary impurity removal-deep impurity removal-oxidation precipitation. The purification process of the rhodochrosite acid leaching solution was deeply studied, and the effects of various factors in the oxidation precipitation process of the manganese purification solution on the preparation of battery-grade manganese dioxide were investigated in detail. The results showed that during the preliminary impurity removal, the addition of ammonium bicarbonate-sulfuric acid solution for the precipitation and redissolution of Mn and Mg enriched the Mn concentration to 122.5g/L and reduced the Mg concentration to 91.5mg/L. The concentrations of Cl, Na, K, and Si were significantly reduced to 6.2mg/L, 16.8mg/L, 2.3mg/L, and 9.8mg/L, respectively. In the deep impurity removal process, the addition of 1.0g/L BaS and 4.2g/L MnF2 to remove heavy metals and Ca, Mg reduced the concentrations of Mg and Ca to 21.3mg/L and 11.6mg/L, respectively. The concentration of Pb was reduced to 1.3mg/L, and the concentrations of Zn, Ni, Cd, and Cu were all reduced to less than 1mg/L. The process conditions for preparing battery-grade manganese dioxide by direct oxidation were as follows: at a Mn concentration of 1mol/L, with oxygen as the oxidant, 2% ammonia water as the neutralizer, and a reaction temperature of 70℃, the reaction time was 12hours. After washing the product with 2% ammonia water and drying, spherical battery-grade manganese dioxide with a Mn content of 71%, a specific surface area of 0.813m2/g, a tap density of 2.53g/cm3, and a median particle size of 12.5μm, and with impurity content lower than the national standard was obtained.

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马晓磊,柯平超,万凌云,周义朋,万廷勇.菱锰矿酸浸液直接制备电池级四氧化三锰的研究[J].中国有色冶金,2025,54(3):104-114

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  • 收稿日期:2024-12-20
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