WO2023160101A1 - 掺铝型针状四氧化三钴及其制备方法 - Google Patents

掺铝型针状四氧化三钴及其制备方法 Download PDF

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WO2023160101A1
WO2023160101A1 PCT/CN2022/135944 CN2022135944W WO2023160101A1 WO 2023160101 A1 WO2023160101 A1 WO 2023160101A1 CN 2022135944 W CN2022135944 W CN 2022135944W WO 2023160101 A1 WO2023160101 A1 WO 2023160101A1
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aluminum
cobalt
acid solution
preparation
doped
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PCT/CN2022/135944
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French (fr)
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余海军
李爱霞
谢英豪
李波
李长东
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
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Priority to DE112022002314.7T priority Critical patent/DE112022002314T5/de
Priority to GB2313796.1A priority patent/GB2619445A/en
Publication of WO2023160101A1 publication Critical patent/WO2023160101A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the application belongs to the technical field of lithium ion batteries, and in particular relates to an aluminum-doped acicular tricobalt tetroxide and a preparation method thereof.
  • waste lithium-ion battery recycling strategies mainly include wet and fire recycling. Among them, wet recycling is more widely used. It is used because of its high recovery rate, normal temperature reaction, and suitability for industrialization.
  • the popular hydrometallurgical methods include pretreatment, leaching and regeneration processes. Generally speaking, pretreatment is the basic process of the above process, and the effective separation of waste materials and aluminum foil in waste electrode plates is the key to pretreatment.
  • the commonly used separation methods can be divided into organic solvent dissolution, thermal decomposition, alkali leaching and acid leaching.
  • the organic solvent dissolution method can realize polyvinylidene fluoride (PVDF) dissolution with a short operating time, but there are disadvantages such as organic toxicity, easy volatility, and high price. And this method is used to dissolve the aluminum foil to separate the cathode material, which is also easy to damage the equipment.
  • the thermal decomposition method can be used for PVDF decomposition, but it has high energy consumption, low cost and harmful gas release.
  • Alkaline leaching to dissolve aluminum generally has the problems of incomplete removal of aluminum, loss of cobalt, cumbersome recovery steps, and easy residues in the solution.
  • Inorganic acid leaching dissolves aluminum, there are few selectively dissolved substances, and both the positive electrode active material and aluminum will be dissolved, and aluminum needs to be further recovered.
  • wet recovery requires steps such as precipitation and impurity removal, extraction, back-extraction, and crystallization to recover cobalt.
  • the recovery process is long, and there are many types of chemical reagents used at the same time.
  • the subsequent treatment of the solution is troublesome. Therefore, a clean and efficient recovery method has been developed. It is of great significance to recover aluminum and prepare doped tricobalt tetroxide.
  • the present application aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the application proposes an aluminum-doped acicular cobalt tetroxide and a preparation method thereof.
  • the preparation method not only effectively recycles the aluminum in waste batteries, but in the case of adding a templating agent and adjusting the pH, heat treatment is carried out to utilize Cobalt is wrapped in carbon and aluminum produced by heat treatment, which eases the coupling between the template agent and cobalt ions in the further agglomeration and encapsulation process, and obtains acicular cobalt tetroxide with better shape.
  • a method for preparing aluminum-doped acicular cobalt tetroxide comprising the following steps:
  • the waste battery powder is divided into monomers by the waste lithium cobaltate power battery pack, and then the monomers are discharged, sent to the rotary kiln for pyrolysis, cooling, crushing, and screening, that is Get used battery powder.
  • the discharge process of the cell is to put the cell on a metal frame for resistance discharge until the voltage of the cell is ⁇ 2.0V.
  • the pyrolysis temperature in the rotary kiln is 400-800° C.
  • the pyrolysis time is 4-24 hours
  • the pyrolysis atmosphere is nitrogen.
  • the amino acid is glycine; the solid-to-liquid ratio of the waste battery powder and the amino acid solution is 10-60 g/L.
  • the concentration of the amino acid solution is 5-20wt%.
  • the alkali used in the pH adjustment process is one of lithium hydroxide, sodium hydroxide and potassium hydroxide.
  • adjusting the pH to alkaline is adjusting the pH to 9.5-12.
  • the temperature of the acid solution is ⁇ 10°C.
  • the acid solution is sulfuric acid.
  • the concentration of the sulfuric acid is 0.01-0.05mol/L.
  • the solid-to-liquid ratio of the aluminum-removing battery powder and the acid solution is 10-150 g/L.
  • step (3) adding water to the cobalt-containing acid solution to dilute to obtain a cobalt-containing acid solution with a cobalt concentration of 0.01-0.05 mol/L.
  • the molar amount of the templating agent added dropwise to the cobalt-containing acid solution is 1-5 times that of the cobalt in the cobalt-containing acid solution.
  • the first solution in step (1) is also added during the dropwise addition of the templating agent to the cobalt acid-containing solution, and the amount of the first solution added is 0.001-0.01 volume of the cobalt acid-containing solution.
  • the templating agent is one of aminosalicylic acid and hydroxybenzoic acid.
  • the synthesis steps of Co(OH)(C 7 H 6 NO 3 ) are:
  • Co(OH)(C 7 H 6 NO 3 ) is synthesized by carboxyl dehydrogenation and alkali delithiation combined with cobalt ions.
  • the pH adjustment by adding alkali is to adjust the pH to 6.5-7.2.
  • the temperature of the heat treatment is 550-750°C, and the time of heat treatment is 1-6h.
  • the atmosphere of the heat treatment is air.
  • Heat treatment is a process of pyrolysis of Co(OH)(C 7 H 6 NO 3 ) for dehydration, deoxidation and decarburization.
  • An aluminum-doped acicular cobalt tetroxide is prepared by the above preparation method, the chemical formula of the aluminum-doped acicular cobalt tetroxide is Co 3 O 4 @C/Al 2 O 3 ; the ratio of the aluminum-doped acicular cobalt tetroxide Surface area 3.4-3.6m 2 /g.
  • the present application also provides the application of the above-mentioned aluminum-doped acicular cobalt tetroxide in the preparation of catalysts, positive electrode materials or capacitors.
  • This application uses amino acids to effectively recycle aluminum in waste batteries.
  • heat treatment is performed, and the carbon and aluminum produced by heat treatment are used to wrap cobalt to ease further agglomeration and packaging
  • the template agent in the process is coupled with cobalt ions to obtain aluminum-doped acicular cobalt tetroxide with better morphology.
  • the battery powder and amino acid (glycerin) are mixed, and the pH is adjusted to alkaline, and the protons on the carboxyl groups of the amino acid (glycerin) are removed to form glycine anions.
  • Aluminum reacts to form metaaluminate ions, which can prevent the formation of aluminum hydroxide precipitation at weakly alkaline pH values.
  • Metaaluminate ions react with aminoacetic acid to form Al(OOC-CH 2 -NH 2 ) 3 chelates.
  • amino Acetic acid reacts with alumina and aluminum to form Al(OOC-CH 2 -NH 2 ) 3 chelate, which effectively combines Al 3+ under weak acidic and alkaline conditions, with stronger stability and prevents Formation of aluminum hydroxide precipitate.
  • Co(OH)(C 7 H 6 NO 3 ) ⁇ Al(OOC-CH 2 -NH 2 ) 3 was synthesized by introducing template aminosalicylic acid and cobalt ions, and after heat treatment, Co(OH)(C 7 H 6 NO 3 ) dehydration, deoxidation, and decarburization at the same time, Co(OH) + interlayer C 7 H 6 NO 3 - , Al(OOC-CH 2 -NH 2 ) 3 carbonization generated carbon, aluminum, etc. wrapped cobalt , to alleviate further agglomeration and nano-coupling in the encapsulation process, and to obtain acicular cobalt tetroxide with better morphology.
  • Fig. 1 is the SEM picture of the acicular cobalt tetroxide prepared in Example 1 of the present application;
  • FIG. 2 is a TEM image of the needle-shaped cobalt tetroxide prepared in Example 1 of the present application.
  • Fig. 1 is the SEM image of the acicular cobalt tetroxide prepared in Example 1 of the present application
  • Fig. 2 is the TEM image of the acicular cobalt tetroxide prepared in Example 1 of the present application
  • the prepared aluminum-doped Acicular tricobalt tetroxide (Co 3 O 4 @C/Al 2 O 3 ) is long needle-shaped with a diameter of about 0.3 ⁇ m, and has good shape consistency and dispersion.
  • Embodiment 1-4 analyzes:
  • Example 1 91.9% 1.5% 6.1% 0.5%
  • Example 2 92.7% 2.8% 3.8% 0.7%
  • Example 3 94.9% 2.5% 2.4% 0.2%
  • Example 4 93.8% 0.3% 3.6% 0.4%
  • the aluminum content of the first filtrate accounts for 85.7%, 89.8%, 94.5%, and 92.3% of the total aluminum (the total aluminum content is the battery powder containing impurities, the first filtrate, containing The sum of copper slag and cobalt-containing acid solution), the aluminum content in the miscellaneous battery powder accounts for 7.1%, 5.0%, 2.8%, and 3.9% of the total aluminum, while the cobalt content in the miscellaneous battery powder accounts for 91.9% and 92.7% of the total cobalt , 94.9%, and 93.8%, indicating that the selective removal of aluminum by aminoacetic acid and alkali is good, most of the aluminum in the battery powder containing impurities is removed and the cobalt is retained in the copper-containing slag, and the aluminum is recovered cleanly and efficiently, and Table 3
  • the aluminum-doped acicular cobalt tetroxide prepared in Examples 1-4 has relatively concentrated specific surface area, D max
  • Table 3 The specific surface area and particle size of aluminum-doped acicular cobalt tetroxide prepared in Examples 1-4

Abstract

本申请属于电池材料技术领域，公开了一种掺铝型针状四氧化三钴及其制备方法，该制备方法包括以下步骤：将废旧电池粉和氨基酸混合，调pH至碱性，固液分离，得到除铝电池粉和第一滤液；将除铝电池粉加酸混合，固液分离，得到含钴酸溶液和含铜渣；向含钴酸溶液中滴加模板剂，再加碱调pH，离心，热处理，得到掺铝型针状四氧化三钴。本申请利用氨基酸有效的回收了废旧电池中的铝，在加入模板剂的情况下，并调pH后，进行热处理，利用热处理产生的碳、铝等包裹了钴，缓解进一步的团聚和封装过程中的模板剂与钴离子的耦合，得到形貌较好的针状四氧化三钴。

Description

掺铝型针状四氧化三钴及其制备方法 技术领域
本申请属于锂离子电池技术领域，具体涉及掺铝型针状四氧化三钴及其制备方法。
背景技术
现有的废锂离子电池回收策略主要包括湿法、火法回收。其中以湿法回收更为广泛。因其回收率高，常温反应，适合工业化而被使用。目前，流行的湿法冶金方法包括预处理、浸出和再生过程。一般来说，预处理是以上过程的基本过程，而有效分离废材料和废电极板中的铝箔是预处理的关键。
常用的分离方法可分为有机溶剂法溶解、热分解、碱浸和酸浸。有机溶剂溶解法可以实现聚偏二氟乙烯(PVDF)溶解操作时间短，但存在有机毒性、易挥发、价格高等缺点。而且该方法用于溶解铝箔以分离阴极材料，这也容易损坏设备。热分解方法可用于PVDF分解，但能耗高，成本低，有害气体释放。碱浸溶解铝，一般存在铝脱除不彻底、损失钴、而且回收步骤繁琐，容易残留于溶液中的问题。无机酸浸溶解铝，存在选择性溶解的物质较少，对正极活性材料、铝均会溶解，需要进一步回收铝。另外，湿法回收中需要沉淀除杂、萃取、反萃、结晶等工序回收钴，回收过程长，同时使用的化学试剂种类多，对溶液后续的处理麻烦，因此开发一种清洁高效的回收方法用于回收铝并可制备出掺杂型四氧化三钴，具有非常重要的意义。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请旨在至少解决上述现有技术中存在的技术问题之一。为此，本申请提出一种掺铝型针状四氧化三钴及其制备方法，该制备方法既有效的回收了废旧 电池中的铝，在加入模板剂的情况下，并调pH后，进行热处理，利用热处理产生的碳、铝等包裹了钴，缓解进一步的团聚和封装过程中的模板剂与钴离子的耦合，得到形貌较好的针状四氧化三钴。
为实现上述目的，本申请采用以下技术方案：
一种掺铝型针状四氧化三钴的制备方法，包括以下步骤：
(1)将废旧电池粉和氨基酸溶液混合，调pH至碱性，固液分离，得到除铝电池粉和第一滤液；
(2)将所述除铝电池粉加入酸液中混合，固液分离，得到含钴酸溶液和含铜渣；
(3)向所述含钴酸溶液中滴加模板剂，再加碱调pH，离心，热处理，得到掺铝型针状四氧化三钴。
优选地，步骤(1)中，所述废旧电池粉是由废旧钴酸锂动力电池包拆分成单体，再将单体放电，送至回转窑炉热解、降温、破碎、筛选，即得废旧电池粉。
进一步优选地，所述单体放电过程为将单体放至金属架上电阻放电，直至单体电压<2.0V。
进一步优选地，所述回转窑炉热解的温度为400-800℃，热解的时间为4-24h，热解的气氛为氮气。
优选地，步骤(1)中，所述氨基酸为氨基乙酸；所述废旧电池粉和氨基酸溶液的固液比为10-60g/L。
进一步优选地，所述氨基酸溶液的浓度为5-20wt％。
优选地，步骤(1)和步骤(3)中，所述调pH过程中使用的碱为氢氧化锂、氢氧化钠、氢氧化钾中的一种。
优选地，步骤(1)中，所述调pH至碱性是将pH调为9.5-12。
优选地，步骤(2)中，所述酸液的温度<10℃。
优选地，步骤(2)中，所述酸液为硫酸。
进一步优选地，所述硫酸的浓度为0.01-0.05mol/L。
优选地，步骤(2)中，所述除铝电池粉和酸液的固液比为10-150g/L。
优选地，步骤(3)中，还包括向所述含钴酸溶液加水稀释，得到钴浓度在0.01-0.05mol/L的含钴酸溶液。
优选地，步骤(3)中，向所述含钴酸溶液中滴加模板剂的摩尔量为所述含钴酸溶液中钴的1-5倍。
进一步优选地，在向所述含钴酸溶液滴加模板剂期间还加入步骤(1)所述第一溶液，所述第一溶液的加入量为含钴酸溶液体积的0.001-0.01。
优选地，步骤(3)中，所述模板剂为氨基水杨酸、含羟基苯甲酸中的一种。
优选地，所述Co(OH)(C 7H 6NO 3)合成步骤为：
Co 2++C 7H 7NO 3+LiOH+Al(OOC-CH 2-NH 2) 3+Al(OOC-CH 2-NH 2) 3→
Co(OH)(C 7H 6NO 3)·Al(OOC-CH 2-NH 2) 3+H 2O+Li +。
羧基脱氢、碱脱锂结合钴离子合成Co(OH)(C 7H 6NO 3)。
优选地，步骤(3)中，所述加碱调pH是将pH调为6.5-7.2。
优选地，步骤(3)中，所述热处理的温度为550-750℃，热处理的时间为1-6h。
优选地，步骤(3)中，所述热处理的气氛为空气。
热处理为高温分解Co(OH)(C 7H 6NO 3)脱水、脱氧、脱碳的过程。
制备掺铝型针状四氧化三钴的反应方程式：
HOOC-CH 2-NH 2+LiOH→Li-OOC-CH 2-NH 2+H 2O；
Al 2O 3+LiOH→LiAlO 2+H 2O；
2Al+2LiOH+2H 2O→2LiAlO 2+3H 2；
6HOOC-CH 2-NH 2+Al 2O 3→2Al(OOC-CH 2-NH 2) 3+3H 2O；
6HOOC-CH 2-NH 2+2Al→2Al(OOC-CH 2-NH 2) 3+3H 2；
LiAlO 2+4HOOC-CH 2-NH 2+H 2O→Al(OOC-CH 2-NH 2) 3+LiOOC-CH 2-NH 2+2H 2O；
Co 2++C 7H 7NO 3+LiOH+Al(OOC-CH 2-NH 2) 3→
Co(OH)(C 7H 6NO 3)·Al(OOC-CH 2-NH 2) 3+H 2O+Li +。
一种掺铝型针状四氧化三钴，是由上述制备方法制得，所述掺铝型针状四氧化三钴的化学式为Co 3O 4@C/Al 2O 3；所述掺铝型针状四氧化三钴的比表面积3.4-3.6m 2/g。
本申请还提供上述的掺铝型针状四氧化三钴在制备催化剂、正极材料或电容器中的应用。
相对于现有技术，本申请的有益效果如下：
1、本申请利用氨基酸有效的回收了废旧电池中的铝，在加入模板剂的情况下，并调pH后，进行热处理，利用热处理产生的碳、铝等包裹了钴，缓解进一步的团聚和封装过程中的模板剂与钴离子的耦合，得到形貌较好的掺铝型针状四氧化三钴。
2、本申请将电池粉、氨基酸(氨基乙酸)混合，调pH至碱性，氨基酸(氨基乙酸)上的羧基上的质子被移除，形成氨基乙酸阴离子，一方面，过量碱与氧化铝、铝反应生成偏铝酸根离子，能防止弱碱性pH值下形成氢氧化铝沉淀，偏铝酸根离子与氨基乙酸反应生成Al(OOC-CH 2-NH 2) 3螯合物，另一方面氨基乙酸与氧化铝、铝反应生成Al(OOC-CH 2-NH 2) 3螯合物，在弱酸性和碱性条件下有效结合Al 3+，稳定性更强，并防止在弱碱性pH下氢氧化铝沉淀的形成。再通过引入模板剂氨基水杨酸与钴离子，合成Co(OH)(C 7H 6NO 3)·Al(OOC-CH 2-NH 2) 3，再通过热处理，Co(OH)(C 7H 6NO 3)脱水、脱氧、脱碳的同时，Co(OH) +层间C 7H 6NO 3 -、Al(OOC-CH 2-NH 2) 3碳化产生的碳、铝等包裹了钴，缓解进一步的团聚和封装过程中的纳米耦合，得到形貌较好的针状四氧化三钴。
附图说明
图1为本申请实施例1制备得到的针状四氧化三钴的SEM图；
图2为本申请实施例1制备得到的针状四氧化三钴的TEM图。
具体实施方式
以下将结合实施例对本申请的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本申请的目的、特征和效果。显然，所描述的实施例只是本申请的一部分实施例，而不是全部实施例，基于本申请的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本申请保护的范围。
实施例1
本实施例的掺铝型针状四氧化三钴的制备方法，包括以下步骤：
(1)将废旧钴酸锂动力电池包拆分成单体，将单体放至金属架上电阻放电，直至单体电压<2.0V，再送至回转窑炉400℃下通氮气下热解6h、降温、破碎、筛选除去铜铝箔、隔膜，得到废旧电池粉；
(2)将废旧电池粉和15.3wt％的氨基乙酸溶液按固液比为15g/L进行混合，加入氢氧化锂至溶液pH＝10.3，固液分离得到除铝电池粉和第一滤液；
(3)将除铝电池粉加入温度<10℃的0.0147mol/L的硫酸混合(固液比35g/L)，固液分离，得到含钴酸溶液和含铜渣；
(4)测定含钴酸溶液中钴量为3.47g/L，取150mL含钴酸溶液，加水稀释含钴酸溶液中钴浓度为0.029g/L，再向含钴酸溶液中滴加氨基水杨酸至浓度为0.057mol/L，并加入0.3mL第一滤液(铝含量为0.23g/L)，加入氢氧化锂调含钴酸溶液的pH至6.8，静置约1.5h、离心、洗涤得到第三固体Co(OH)(C 7H 6NO 3)；
(5)将第三固体Co(OH)(C 7H 6NO 3)，送至加热设备中565℃加热，保温约3h，得到掺铝型针状四氧化三钴(Co 3O 4@C/Al 2O 3)。
图1为本申请实施例1制备得到的针状四氧化三钴的SEM图；图2为本申请实施例1制备得到的针状四氧化三钴的TEM图；从图1-2可得，制备得到的掺铝型针状四氧化三钴(Co 3O 4@C/Al 2O 3)为长针状，直径大小为0.3μm左右， 形貌一致性、分散性均较好。
实施例2
本实施例的掺铝型针状四氧化三钴的制备方法，包括以下步骤：
(1)将废旧钴酸锂动力电池包拆分成单体，将单体放至金属架上电阻放电，直至单体电压<2.0V，再送至回转窑炉400℃下通氮气下热解6h、降温、破碎、筛选除去铜铝箔、隔膜，得到废旧电池粉；
(2)将废旧电池粉和15.3wt％氨基乙酸溶液按固液比为18g/L进行混合，加氢氧化锂至溶液pH＝10.1，固液分离，得到除铝电池粉和第一滤液；
(3)将除铝电池粉加入温度<10℃的0.0147mol/L的硫酸混合(固液比42g/L)，固液分离，得到含钴酸溶液和含铜渣；
(4)测定含钴酸溶液中钴量为4.22g/L，取150mL含钴酸溶液，加水稀释含钴酸溶液中钴浓度为0.034g/L，再向含钴酸溶液中滴加氨基水杨酸至浓度为0.063mol/L，并加入0.5mL第一滤液(铝含量为0.25g/L)，加入氢氧化锂调含钴酸溶液的pH至6.3，静置约1.5h、离心、洗涤，得到第三固体Co(OH)(C 7H 6NO 3)；
(5)将第三固体Co(OH)(C 7H 6NO 3)，送至加热设备中615℃加热，保温约3h，得到掺铝型针状四氧化三钴(Co 3O 4@C/Al 2O 3)。
实施例3
本实施例的掺铝型针状四氧化三钴的制备方法，包括以下步骤：
(1)将废旧钴酸锂动力电池包拆分成单体，将单体放至金属架上电阻放电，直至单体电压<2.0V，再送至回转窑炉400℃下通氮气下热解6h、降温、破碎、筛选除去铜铝箔、隔膜，得到废旧电池粉；
(2)将废旧电池粉和12.5wt％氨基乙酸溶液按固液比为34g/L进行混合，加氢氧化锂至溶液pH＝10.2，固液分离得到除铝电池粉和第一滤液；
(3)将除铝电池粉加入温度<10℃的0.0147mol/L的硫酸混合(固液比味66g/L)，固液分离，得到含钴酸溶液和含铜渣；
(4)测定含钴酸溶液中钴量为6.49g/L，取150mL含钴酸溶液，加水稀释含钴酸溶液中钴浓度为0.027g/L，再向含钴酸溶液中滴加氨基水杨酸至浓度为0.077mol/L，并加入0.5mL第一滤液(铝含量为0.27g/L)，加入氢氧化锂调含钴酸溶液的pH至7.0，静置约1.5h、离心、洗涤得到第三固体Co(OH)(C 7H 6NO 3)；
(5)将第三固体Co(OH)(C 7H 6NO 3)，送至加热设备中565℃加热，保温约3h，得到掺铝型针状四氧化三钴(Co 3O 4@C/Al 2O 3)。
实施例4
本实施例的掺铝型针状四氧化三钴的制备方法，包括以下步骤：
(1)将废旧钴酸锂动力电池包拆分成单体，将单体放至金属架上电阻放电，直至单体电压<2.0V，再送至回转窑炉400℃下通氮气下热解6h、降温、破碎、筛选除去铜铝箔、隔膜，得到废旧电池粉；
(2)将废旧电池粉和12.5wt％氨基乙酸溶液按固液比为34g/L进行混合，加氢氧化锂至溶液pH＝10.3，固液分离得到除铝电池粉和第一滤液；
(3)将除铝电池粉加入温度<10℃的0.0147mol/L的硫酸混合(固液比为66g/L)，固液分离，得到含钴酸溶液和含铜渣；
(4)测定含钴酸溶液中钴量为6.49g/L，取150mL含钴酸溶液，加水稀释含钴酸溶液中钴浓度为0.027g/L，再向含钴酸溶液中滴加氨基水杨酸至浓度为0.077mol/L，并加入0.5mL第一滤液(铝含量为0.27g/L)，加入氢氧化锂调含钴酸溶液的pH至7.0，静置约1.5h、离心、洗涤得到第三固体Co(OH)(C 7H 6NO 3)；
(5)将第三固体Co(OH)(C 7H 6NO 3)，送至加热设备中565℃加热，保温约3h，得到掺铝型针状四氧化三钴(Co 3O 4@C/Al 2O 3)。
实施例1-4分析：
表1实施例1-4中各组分中铝含量/总铝比例
Figure PCTCN2022135944-appb-000001
Figure PCTCN2022135944-appb-000002
表2实施例1-4中各组分中钴含量/总钴比例
项目 含杂电池粉 第一滤液 含铜渣 含钴酸溶液
实施例1 91.9％ 1.5％ 6.1％ 0.5％
实施例2 92.7％ 2.8％ 3.8％ 0.7％
实施例3 94.9％ 2.5％ 2.4％ 0.2％
实施例4 93.8％ 0.3％ 3.6％ 0.4％
从表1-3可得，实施例1-4中，第一滤液铝含量占总铝的85.7％、89.8％、94.5％、92.3％(总铝量为含杂电池粉、第一滤液、含铜渣、含钴酸溶液总和)，含杂电池粉中铝含量占总铝的7.1％、5.0％、2.8％、3.9％，而含杂电池粉中钴含量占总钴的91.9％、92.7％、94.9％、93.8％，说明利用氨基乙酸加碱选择性除铝效果好，大部分含杂电池粉中的铝除掉而钴保留至含铜渣中，清洁高效的回收了铝，并且表3实施例1-4制备得到掺铝型针状四氧化三钴比表面以及D max、D min数值比较集中，侧面说明制备方法得到的掺铝型针状四氧化三钴的形貌一致性较高。
表3实施例1-4制备得到掺铝型针状四氧化三钴比表面积以及粒径值
Figure PCTCN2022135944-appb-000003
上面结合附图对本申请实施例作了详细说明，但是本申请不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本申请宗旨的前提下作出各种变化。此外，在不冲突的情况下，本申请的实施例及实施例中的特征可以相互组合。

Claims (10)

  1. 一种掺铝型针状四氧化三钴的制备方法，其中，包括以下步骤：
    (1)将废旧电池粉和氨基酸溶液混合，调pH至碱性，固液分离，得到除铝电池粉和第一滤液；
    (2)将所述除铝电池粉加入酸液中混合，固液分离，得到含钴酸溶液和含铜渣；
    (3)向所述含钴酸溶液中滴加模板剂，再加碱调pH，离心，热处理，得到所述掺铝型针状四氧化三钴。
  2. 根据权利要求1所述的制备方法，其中，步骤(1)中，所述废旧电池粉是由废旧钴酸锂动力电池包拆分成单体，经过放电，送至回转窑炉热解、降温、破碎、筛选后得到的。
  3. 根据权利要求1所述的制备方法，其中，步骤(1)中，所述氨基酸为氨基乙酸，所述氨基酸溶液的浓度为5-20wt％；所述废旧电池粉和氨基酸溶液的固液比为10-60g/L。
  4. 根据权利要求1所述的制备方法，其中，步骤(1)和步骤(3)中，所述调pH过程中使用的碱为氢氧化锂、氢氧化钠、氢氧化钾中的一种。
  5. 根据权利要求1所述的制备方法，其中，步骤(3)中，向所述含钴酸溶液中滴加模板剂的摩尔量为所述含钴酸溶液中钴的1-5倍。
  6. 根据权利要求1所述的制备方法，其中，步骤(3)中，在向所述含钴酸溶液滴加模板剂期间还加入步骤(1)所述第一滤液，所述第一滤液加入量为含钴酸溶液体积的0.001-0.01。
  7. 根据权利要求1所述的制备方法，其中，步骤(3)中，所述模板剂为氨基水杨酸、含羟基苯甲酸中的一种。
  8. 根据权利要求1所述的制备方法，其中，步骤(3)中，所述热处理的温度为550-750℃，热处理的时间为1-6h；所述热处理的气氛为空气。
  9. 一种掺铝型针状四氧化三钴，是由权利要求1-8任一项所述的制备方法制得，所述掺铝型针状四氧化三钴的化学式为Co 3O 4@C/Al 2O 3；所述掺铝型针状四氧化三钴的比表面积3.4-3.6m 2/g。
  10. 权利要求9所述的掺铝型针状四氧化三钴在制备催化剂、正极材料或电容器中的应用。
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CN115092970A (zh) * 2022-02-22 2022-09-23 广东邦普循环科技有限公司 掺铝型针状四氧化三钴及其制备方法

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