WO2024016469A1 - 一种锰掺杂四氧化三钴及其制备方法与应用 - Google Patents

一种锰掺杂四氧化三钴及其制备方法与应用 Download PDF

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WO2024016469A1
WO2024016469A1 PCT/CN2022/120644 CN2022120644W WO2024016469A1 WO 2024016469 A1 WO2024016469 A1 WO 2024016469A1 CN 2022120644 W CN2022120644 W CN 2022120644W WO 2024016469 A1 WO2024016469 A1 WO 2024016469A1
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manganese
cobalt
doped
doped cobalt
preparation
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French (fr)
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卢星华
李长东
阮丁山
刘更好
周思源
胡海涵
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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
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Priority to GBGB2309832.0A priority Critical patent/GB202309832D0/en
Priority to DE112022000865.2T priority patent/DE112022000865T5/de
Publication of WO2024016469A1 publication Critical patent/WO2024016469A1/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
    • 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
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • C01P2004/61—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
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of battery materials, and in particular to a manganese-doped cobalt tetraoxide and its preparation method and application.
  • Lithium cobalt oxide cathode material is mainly used in the 3C field due to its high energy density.
  • the existing technology often uses the method of doping other metal elements to replace part of the cobalt to improve the performance of lithium cobalt oxide-based lithium-ion batteries.
  • the spinel-type lithium manganate is also a layered structure compound that can intercalate and deintercalate lithium ions. Therefore, at this stage, manganese-doped cobalt acid
  • This product can significantly increase the capacity of lithium-ion batteries.
  • manganese doping can enhance the ordering of cations and suppress cation mixing, it can also improve the cycle performance of the battery.
  • Lithium cobalt oxide doping with manganese is generally carried out in the precursor stage.
  • Cobalt tetroxide as the precursor of lithium cobalt oxide cathode material, is generally produced by thermal decomposition of cobalt carbonate.
  • the raw material for manganese doping is generally manganese carbonate.
  • solubility product of manganese carbonate is smaller than that of cobalt carbonate, if wet co-precipitation is used for doping, agglomeration will easily occur, resulting in a wide particle size distribution of the precursor; at the same time, divalent manganese is easily oxidized into trivalent or tetravalent manganese.
  • the purpose of the present invention is to provide a method for preparing manganese-doped cobalt tetraoxide.
  • This method uses specific processes and a composite surfactant to dope manganese element into cobalt carbonate, and then sinters it at high temperature.
  • Manganese-doped cobalt tetroxide particle products with uniform particle size, dispersed and fine can be obtained.
  • the doped manganese has a high proportion of low-valence manganese, and the crystal form of the product obtained by sintering is complete; the preparation method has simple operation steps and can be industrialized. Mass production.
  • a method for preparing manganese-doped cobalt tetroxide including the following steps:
  • the mixed metal solution and precipitant will continue to be introduced to keep the volume ratio of the mixed solution in the reaction vessel stable; when the particle size obtained by concentration and precipitation reaches 4 ⁇ 6 ⁇ m, stop the reaction to obtain manganese-doped cobalt carbonate particle slurry; the mixed metal solution includes cobalt salt, divalent manganese salt, crown ether surfactant and nonionic surfactant, and the crown ether surface
  • the mass ratio of manganese in the active agent, nonionic surfactant and divalent manganese salt is (0.02 ⁇ 0.08): (0.02 ⁇ 0.08): 1;
  • the protective atmosphere is nitrogen.
  • the protective atmosphere environment is maintained during the preparation of the bottom liquid and the mixing of the reaction liquid, and the pressure in the reaction vessel is controlled at the same time, which can avoid the divalent manganese element in the mixed metal solution. Oxidation can also increase the reactivity of each reactant, accelerate the rate of Brownian motion of solute molecules, and control the uniform and complete precipitation of metallic cobalt. If the pressure of the reaction vessel is not properly controlled, it will not only easily cause oxidation of divalent manganese, but may even cause safety issues.
  • the present invention also introduces two specific ratios of surfactants for matching.
  • the crown ether surfactant has a cavity structure formed by macrocyclic ligands. , can effectively form complexes with metal ions, thereby slowing down the precipitation rate of metal ions and helping the steady progress of the concentration and precipitation reaction.
  • this surfactant easily interacts with protective atmospheres such as nitrogen during the reaction to generate a large number of bubbles, this is not only It will make it difficult to control the liquid level and volume of the reaction vessel during the reaction. It will also affect the precipitation rate and morphological quality of the local reaction precipitation particles, and a large number of small crystal nuclei will be generated.
  • Non-ionic surfactants have a certain defoaming effect. When used together with crown ether surfactants, they can effectively eliminate the bubble effect and greatly increase the amount of precipitates that can be replaced by the two surfactants during the concentration and precipitation reaction stage. The amount of moisture adsorbed on the particle surface reduces the capillary force generated by particle agglomeration. At the same time, the hydroxyl groups adsorbed on the particle surface are replaced by organic molecular groups, which increases the steric hindrance between particles.
  • the present invention effectively alleviates the agglomeration between particles and reduces the generation of coarse particles through the dual effects of reducing capillary force and increasing steric hindrance. However, it is difficult to achieve the same effect with other types of surfactants. In addition, if the ratio of the two surfactants is inappropriate, it will cause the particles of the final product to agglomerate or have different morphologies.
  • the present invention also uses an antioxidant solution to wash the precipitated manganese-doped cobalt carbonate particles.
  • This step can effectively reduce the oxidation probability of divalent manganese elements, thereby avoiding the risk of high-valent manganese elements in the sintering precursor.
  • the content is too high, which makes it difficult for the primary grains to grow and connect during the sintering process, and the secondary ball structure is loose.
  • the final sintered manganese-doped cobalt tetroxide secondary particle balls have poor particle quality and the morphology is easily destroyed.
  • the molar concentration of cobalt salt in the mixed metal solution is 1.5-2 mol/L, and the mass ratio of manganese element to cobalt element is (0.005-0.012):1.
  • the cobalt salt is at least one of cobalt chloride, cobalt sulfate, and cobalt nitrate;
  • the divalent manganese salt is at least one of manganese chloride, manganese sulfate, and manganese nitrate.
  • the crown ether surfactant is at least one of 15-crown-5, 18-crown-6, and dibenzo-18-crown-6;
  • the nonionic surfactant is HL-610 Nonionic surfactants.
  • crown ether surfactants can effectively complex metal ions during the reaction process, avoid segregation of manganese ions, and improve the uniform dispersion of the obtained manganese-doped cobalt tetroxide. If other types of surfactants are used, the particle sizes of the final product will be different; and the use of crown ether defoaming agents needs to be combined with non-ionic surfactants such as HL-610 to maintain the stability of the reaction system. Avoid broadening the product particle size distribution.
  • the precipitating agent is an ammonium bicarbonate solution with a molar concentration of 2 to 3 mol/L.
  • the molar concentration of the bottom liquid in step (1) is 1.3-1.8 mol/L, and the temperature is 30-35°C.
  • the stirring rate during mixing in step (2) is 450-600 rpm, and the flow rate of the mixed metal solution when added to the reaction vessel is 2-3L/h.
  • the production efficiency of the product in the preparation process can be higher and the reaction can be more uniform.
  • the mass concentration of the antioxidant solution in step (3) is 8wt% to 12wt%
  • the antioxidant is a water-soluble antioxidant, more preferably ascorbic acid, disodium ethylenediaminetetraacetate, hydrated At least one of hydrazine.
  • Another object of the present invention is to provide manganese-doped cobalt tetroxide prepared by the method for preparing manganese-doped cobalt tetroxide.
  • the preparation method of the present invention obtains manganese-doped cobalt tetraoxide with narrow particle size distribution, uniform morphology and small size.
  • the mass proportion of low-valent manganese in the manganese element is relatively high, and the mass proportion of divalent manganese can basically reach about 50wt%.
  • Product quality is high.
  • Another object of the present invention is to provide the application of the manganese-doped cobalt tetroxide in preparing doped lithium cobalt oxide cathode materials.
  • the manganese-doped cobalt tetroxide of the present invention has uniform particle size and high dispersion, and the doped manganese element has high low-valence components. Whether it is further directly prepared into a doped lithium cobalt oxide cathode material, or further modified before preparation. All have good use effects and high commercial value.
  • the beneficial effect of the present invention is that the present invention provides a method for preparing manganese-doped cobalt tetroxide.
  • This method uses specific processes and cooperates with a composite surfactant to dope manganese element into cobalt carbonate. After high-temperature sintering, uniform particle size can be obtained. , dispersed and fine manganese-doped cobalt tetraoxide particle products, the doped manganese has a high proportion of low-valent manganese, and the crystal form of the product obtained by sintering is complete; the preparation method has simple operation steps and can realize industrial large-scale production.
  • Figure 1 is a scanning electron microscope image of manganese-doped cobalt tetroxide obtained in Example 1 of the present invention
  • Figure 2 is a scanning electron microscope image of manganese-doped cobalt tetroxide obtained in Example 2 of the present invention
  • Figure 3 is a scanning electron microscope image of manganese-doped cobalt tetroxide obtained in Example 3 of the present invention.
  • Figure 4 is a scanning electron microscope image of manganese-doped cobalt tetroxide obtained in Comparative Example 1 of the present invention.
  • Figure 5 is a scanning electron microscope image of manganese-doped cobalt tetroxide obtained in Comparative Example 2 of the present invention.
  • Figure 6 is a scanning electron microscope image of manganese-doped cobalt tetroxide obtained in Comparative Example 3 of the present invention.
  • Figure 7 is a scanning electron microscope image of manganese-doped cobalt tetroxide obtained in Comparative Example 4 of the present invention.
  • Figure 8 is a scanning electron microscope image of manganese-doped cobalt tetroxide obtained in Comparative Example 5 of the present invention.
  • Figure 9 is a scanning electron microscope image of manganese-doped cobalt tetroxide obtained in Comparative Example 6 of the present invention.
  • Figure 10 is a scanning electron microscope image of manganese-doped cobalt tetroxide obtained in Comparative Example 7 of the present invention.
  • the reaction is stopped to obtain a manganese-doped cobalt carbonate particle slurry;
  • the mixed metal solution is cobalt chloride, manganese chloride, 15-Crown-5 and HL-610
  • a mixed aqueous solution of nonionic surfactants the cobalt ion concentration in the mixed metal solution is 2mol/L
  • the mass ratio of manganese element to cobalt element is 0.005:1, 15-Crown-5, HL-610 nonionic surfactants
  • the mass ratio to manganese element is 0.02:0.02:1
  • the precipitant is 3 mol/L ammonium bicarbonate aqueous solution;
  • the reaction is stopped to obtain a manganese-doped cobalt carbonate particle slurry;
  • the mixed metal solution is cobalt nitrate, manganese nitrate, 18-Crown-6 and HL-610 nonionic surfactant
  • the mixed aqueous solution, the cobalt ion concentration in the mixed metal solution is 1.8mol/L, the mass ratio of manganese element to cobalt element is 0.008:1, the ratio of 18-Crown-6, HL-610 nonionic surfactant and manganese element
  • the mass ratio is 0.04:0.04:1;
  • the precipitant is 2.5 mol/L ammonium bicarbonate aqueous solution;
  • the reaction is stopped to obtain a manganese-doped cobalt carbonate particle slurry;
  • the mixed metal solution is cobalt sulfate, manganese sulfate, dibenzo-18-crown-6 and HL- 610
  • a mixed aqueous solution of nonionic surfactants the cobalt ion concentration in the mixed metal solution is 1.5 mol/L
  • the mass ratio of manganese element to cobalt element is 0.012:1, dibenzo-18-crown-6, HL-
  • the mass ratio of 610 nonionic surfactant to manganese element is 0.06:0.06:1
  • the precipitant is 2 mol/L ammonium bicarbonate aqueous solution;
  • the reaction is stopped to obtain a manganese-doped cobalt carbonate particle slurry;
  • the mixed metal solution is cobalt nitrate, manganese nitrate, 18-Crown-6 and HL-610 non-ionic surface activity
  • a mixed aqueous solution of agent, the cobalt ion concentration in the mixed metal solution is 1.8mol/L, the mass ratio of manganese element to cobalt element is 0.008:1, 18-Crown-6, HL-610 nonionic surfactant and manganese element The mass ratio is 0.04:0.04:1;
  • the precipitant is 2.5 mol/L ammonium bicarbonate aqueous solution;
  • the reaction is stopped to obtain a manganese-doped cobalt carbonate particle slurry;
  • the mixed metal solution is a mixed aqueous solution of cobalt nitrate and manganese nitrate, and the cobalt ion concentration in the mixed metal solution is 1.8mol/L, the mass ratio of manganese element to cobalt element is 0.008:1; the precipitant is 2.5mol/L ammonium bicarbonate aqueous solution;
  • Example 1 The only difference between this comparative example and Example 1 is that the 15-crown-5 is replaced with the same amount of dedecyltrimethylammonium chloride.
  • Example 1 The only difference between this comparative example and Example 1 is that the HL-610 nonionic surfactant was replaced with the same amount of triethanolamine oleate.
  • Example 1 The only difference between this comparative example and Example 1 is that the mass ratio of 15-Crown-5 to HL-610 nonionic surfactant is 1:2, and the mass ratio of 15-Crown-5 to HL-610 nonionic surfactant is 1:2.
  • the total dosage of the agent is consistent with Example 1.
  • Example 1 The only difference between this comparative example and Example 1 is that the mass ratio of 15-Crown-5 to HL-610 nonionic surfactant is 2:1, and the mass ratio of 15-Crown-5 to HL-610 nonionic surfactant is 2:1.
  • the total dosage of the agent is consistent with Example 1.
  • Example 3 The only difference between this comparative example and Example 3 is that the pressure of the reaction kettle in step (1) is 0.05MPa.
  • Example 1 The only difference between this comparative example and Example 1 is that the pH decrease rate of the mixed solution obtained in step (2) is 0.05/h.
  • each product was subjected to particle size statistics and element content statistics.
  • the valence state of the manganese element in the product was fitted through XPS analysis and statistics were performed. The results are as follows: As shown in Table 1.
  • the content of high-valent manganese in the manganese element was relatively high, and the product particles obtained by sintering were crushed. phenomenon, the crystal form is incomplete; no surfactant was introduced during the preparation process of the product of Comparative Example 2, the dispersion of the product was poor, and agglomeration occurred; the crown ether surfactant was replaced in the steps of the preparation method described in Comparative Example 3 It has become other types of conventional surfactants, which are difficult to perform good metal ion complexing during the precursor synthesis process, causing the manganese element to segregate, resulting in uneven sizes and wide particle size distribution of the final sintered product; for In the preparation method step described in Proportion 4, the HL-610 nonionic surfactant is replaced with triethylamine oleate, which cannot effectively suppress the bubble effect caused by the crown ether surfactant, and the liquid level fluctuates during the reaction in the reactor.
  • the product particles with more components of tetravalent manganese are incomplete, and it can also be clearly seen from Figure 10 that the product particles are damaged; in the preparation method described in Comparative Example 8, the pH change rate is too large during the reaction process of the mixed solution, which will directly accelerate the crystallization.
  • the agglomeration phenomenon between the cores causes uneven particle size, causing the Span value of the product to be too large under the same particle size; and the pH change rate in the preparation method described in Comparative Example 9 is too small, and when the reactor liquid level reaches the concentrated liquid level , the ammonium bicarbonate in the bottom liquid is not completely consumed, and there will be a large amount of manganese ammonia complex.
  • the clear liquid produced by concentration is discharged from the reaction system, the manganese content in the final product will be lower than the theoretical value.

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Abstract

一种锰掺杂四氧化三钴及其制备方法与应用，其制备方法以特定的工序并配合复合表面活性剂将锰元素掺杂至碳酸钴中，经高温烧结可以得到粒度均匀、分散且细小的锰掺杂四氧化三钴颗粒产品，掺杂锰中低价态锰占比高，烧结得到的产品晶型完整；制备方法操作步骤简单，可实现工业化大规模生产。

Description

一种锰掺杂四氧化三钴及其制备方法与应用 技术领域
本发明涉及电池材料技术领域，具体涉及一种锰掺杂四氧化三钴及其制备方法与应用。
背景技术
钴酸锂正极材料由于其能量密度高的优点，主要应用在3C领域。为了提高电池充放电寿命，现有技术常用其它金属元素掺杂取代部分钴的方法来改善钴酸锂系锂离子电池的性能。其中，由于我国锰矿储量大，且锰的价格相对较低，毒性更低，而且尖晶石型锰酸锂也是层状结构化合物，能够嵌入和脱嵌锂离子，因此现阶段锰掺杂钴酸锂的技术研究非常多，该产品能够显著提升锂离子电池的容量；同时，由于锰掺杂可增强阳离子的有序度，抑制阳离子混排，也可以提高电池的循环性能。
钴酸锂掺杂锰一般在前驱体阶段进行，四氧化三钴作为钴酸锂正极材料的前驱体，一般由碳酸钴热分解制得，而锰掺杂的原料一般采用的是碳酸锰。但由于碳酸锰的溶度积小于碳酸钴，若采用湿法共沉淀进行掺杂，会极易发生团聚，造成前驱体粒度分布较宽；同时，二价锰极易氧化成三价或四价，而四价锰的烧结活性低，导致一次晶粒难以生长，抑制了晶粒间的融合生长，不利于制备出完整晶型的锰掺杂四氧化三钴。
发明内容
基于现有技术存在的缺陷，本发明的目的在于提供了一种锰掺杂四氧化三钴的制备方法，该方法以特定的工序并配合复合表面活性剂将锰元素掺杂至碳酸钴中，经高温烧结可以得到粒度均匀、分散且细小的锰掺杂四氧化三钴颗粒产品，所述的掺杂锰中低价态锰占比高，烧结得到的产品晶型完整；所述制备方法操作步骤简单，可实现工业化大规模生产。
为了达到上述目的，本发明采取的技术方案为：
一种锰掺杂四氧化三钴的制备方法，包括以下步骤：
(1)在保护气氛、0.1～0.5MPa压力的反应容器中配制碳酸氢铵溶液作为底液，所述底液在反应容器中的体积占比为40％～50％，pH＝8～8.5；
(2)在稳压状态下向反应容器中加入混合金属溶液和沉淀剂混合，控制所得混合液的pH以0.08～0.12/h的速率下降至7.3～7.6进行反应，直至混合液在反应容器中的体积占比达到70％～80％，开始浓缩沉淀，浓缩沉淀期间继续通入混合金属溶液和沉淀剂，以保持混合液在反应容器中的体积占比稳定；当浓缩沉淀所得颗粒粒度至4～6μm时，停止反应，得锰掺杂碳酸钴颗粒浆料；所述混合金属溶液包括钴盐、二价锰盐、冠醚类表面活性剂和非离子表面活性剂，所述冠醚类表面活性剂、非离子表面活性剂与二价锰盐中锰的质量之比为(0.02～0.08)：(0.02～0.08)：1；
(3)将锰掺杂碳酸钴颗粒浆料过滤后，采用抗氧剂溶液洗涤10～30min，再经烘干、过筛，得锰掺杂碳酸钴前驱体；
(4)将锰掺杂碳酸钴前驱体在650～680℃下烧结3～5h，即得所述锰掺杂四氧化三钴。
优选地，所述保护气氛为氮气。
在本发明所述锰掺杂四氧化三钴的制备方法过程中，在底液配制以及反应液混合期间均保持保护气氛环境，同时控制反应容器中的压力，既可以避免混合金属溶液中的二价锰元素发生氧化，还可以增加各反应物的反应活性，加速溶质分子布朗运动的速率，控制金属钴均匀完全地沉淀。如果反应容器的压力控制不当，不仅容易造成二价锰元素的氧化，甚至会造成安全性问题。另一方面，当反应过程中反应容器中的体积占比过小，会降低反应容器的利用率，但如果体积占比过大，则存在安全隐患。反应容器中酸碱度的变化速率对于反应产物晶核形貌及沉淀速率有一定影响，因此需要维持在特定的范围内。
另一方面，在反应过程中，除了基本的反应物质外，本发明还引入了两种特定配比的表面活性剂进行搭配，其中冠醚类表面活性剂具有大环配体形成的空腔结构，能够有效与金属离子生成配合物，从而减缓金属离子的沉淀速率，有助于浓缩沉淀反应的稳步进行，但由于该表面活性剂在反应期间容易与氮气等保护气氛作用生成大量气泡，这不仅会造成反应期间反应容器的液位体积难以控制，还会影响局部反应沉淀颗粒的沉淀速率及形貌质量，会生成多量小晶 核。而非离子表面活性剂具有一定的消泡作用，将其与冠醚类表面活性剂搭配使用时，可以有效消除气泡效应，还可大大增加两种表面活性剂在浓缩沉淀反应阶段可置换的沉淀颗粒表面吸附的水分的量，从而降低颗粒聚结所产生的毛细管力，同时颗粒表面吸附的羟基基团被有机分子基团取代，增大了颗粒间的空间位阻。本发明通过毛细管力的降低和空间位阻的增大的双重作用使颗粒间的团聚得到有效的缓解，减小粗颗粒的生成，而其他种类的表面活性剂配合难以达到相同的效果。此外，若两种表面活性剂的搭配比例不当，将会造成最终产品颗粒团聚或形貌不一的现象。
最后，在烧结前，本发明还采用抗氧剂溶液对沉淀所得的锰掺杂碳酸钴颗粒进行洗涤，该步骤可有效降低二价锰元素的氧化概率，进而避免因烧结前驱体中高价锰元素含量过高，导致其在烧结的过程中一次晶粒难以长大、连结，二次球结构松散，最终烧结后的锰掺杂四氧化三钴二次颗粒球颗粒质量差，形貌容易被破坏。
优选地，所述混合金属溶液中钴盐的摩尔浓度为1.5～2mol/L，锰元素与钴元素的质量之比为(0.005～0.012)：1。
更优选地，所述钴盐为氯化钴、硫酸钴、硝酸钴中的至少一种；二价锰盐为氯化锰、硫酸锰、硝酸锰中的至少一种。
优选地，所述冠醚类表面活性剂为15-冠-5、18-冠-6、二苯并-18-冠-6中的至少一种；所述非离子表面活性剂为HL-610非离子表面活性剂。
经过筛选，上述种类的冠醚类表面活性剂均可有效在反应过程中络合金属离子，避免锰离子发生偏析，提升所得锰掺杂四氧化三钴的均匀分散程度。如果采用其他种类的表面活性剂，会导致最终得到的产品颗粒大小不一；而冠醚类消泡剂的使用需要同时搭配HL-610这类非离子表面活性剂才能维持反应体系的稳定性，避免产品粒度分布变宽。
优选地，所述沉淀剂为摩尔浓度2～3mol/L的碳酸氢铵溶液。
优选地，所述步骤(1)中底液的摩尔浓度为1.3～1.8mol/L，温度为30～35℃。
优选地，所述步骤(2)中混合时的搅拌速率为450～600rpm，混合金属溶液在加入反应容器时的流量为2～3L/h。
所述反应条件下可使得所述产品在制备过程中的生产效率更高，反应更加 均匀。
优选地，所述步骤(3)中抗氧剂溶液的质量浓度为8wt％～12wt％，所述抗氧剂为水溶性抗氧剂，更优选为抗坏血酸、乙二胺四乙酸二钠、水合肼中的至少一种。
本发明的另一目的在于提供所述锰掺杂四氧化三钴的制备方法制备得到的锰掺杂四氧化三钴。
本发明所述制备方法得到锰掺杂四氧化三钴粒度分布窄，形貌均匀且尺寸较小，锰元素中低价锰的质量占比较高，其中二价锰的质量占比基本可达到50wt％左右，产品质量高。
本发明的再一目的在于提供所述锰掺杂四氧化三钴在制备掺杂钴酸锂正极材料中的应用。
本发明所述锰掺杂四氧化三钴粒度均匀且分散性高，掺杂锰元素低价态成分高，无论是进一步直接制备成掺杂钴酸锂正极材料，亦或是在制备前进行进一步的改性均具有很好的使用效果，商业价值高。
本发明的有益效果在于，本发明提供了一种锰掺杂四氧化三钴的制备方法，该方法以特定的工序并配合复合表面活性剂将锰元素掺杂至碳酸钴中，经高温烧结可以得到粒度均匀、分散且细小的锰掺杂四氧化三钴颗粒产品，所掺杂的锰中低价态锰含量占比高，烧结得到的产品晶型完整；所述制备方法操作步骤简单，可实现工业化大规模生产。
附图说明
图1为本发明实施例1所得锰掺杂四氧化三钴的扫描电镜图；
图2为本发明实施例2所得锰掺杂四氧化三钴的扫描电镜图；
图3为本发明实施例3所得锰掺杂四氧化三钴的扫描电镜图；
图4为本发明对比例1所得锰掺杂四氧化三钴的扫描电镜图；
图5为本发明对比例2所得锰掺杂四氧化三钴的扫描电镜图；
图6为本发明对比例3所得锰掺杂四氧化三钴的扫描电镜图；
图7为本发明对比例4所得锰掺杂四氧化三钴的扫描电镜图；
图8为本发明对比例5所得锰掺杂四氧化三钴的扫描电镜图；
图9为本发明对比例6所得锰掺杂四氧化三钴的扫描电镜图；
图10为本发明对比例7所得锰掺杂四氧化三钴的扫描电镜图。
具体实施方式
为了更好地说明本发明的目的、技术方案和优点，下面将结合具体实施例及对比例对本发明作进一步说明，其目的在于详细地理解本发明的内容，而不是对本发明的限制。本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明的保护范围。本发明实施、对比例所设计的实验试剂、原料及仪器，除非特别说明，均为常用的普通试剂、原料及仪器。
实施例1
本发明所述锰掺杂四氧化三钴及其制备方法与应用的一种实施例，包括以下步骤：
(1)在氮气气氛、0.5MPa压力的反应釜中配制浓度为1.3mol/L的碳酸氢铵水溶液作为底液，所述底液在反应釜中的体积占比为40％，pH＝8，温度为30℃，待温度稳定后持续稳压通氮气30min；
(2)在稳压状态下向反应釜中分别以2.5L/h的流量加入混合金属溶液和沉淀剂，以500rpm速率混合，通过PLC系统控制所得混合液的pH以0.1/h的速率下降至7.3并稳定进行反应，直至混合液在反应釜中的体积占比达到70％～80％，开始浓缩沉淀，浓缩沉淀期间混合金属溶液和沉淀剂继续通入以保持混合液在反应釜中的体积占比稳定，当浓缩沉淀所得颗粒粒度至4.1μm，停止反应，得锰掺杂碳酸钴颗粒浆料；所述混合金属溶液为氯化钴、氯化锰、15-冠-5及HL-610非离子表面活性剂的混合水溶液，所述混合金属溶液中钴离子浓度为2mol/L，锰元素与钴元素的质量比为0.005:1，15-冠-5、HL-610非离子表面活性剂与锰元素的质量比为0.02:0.02:1；所述沉淀剂为3mol/L的碳酸氢铵水溶液；
(3)将锰掺杂碳酸钴颗粒浆料过滤后，采用10wt％抗坏血酸水溶液洗涤20min，再经烘干、过筛，得锰掺杂碳酸钴前驱体；
(4)将锰掺杂碳酸钴前驱体在箱式炉中加热至650℃烧结3h，即得所述锰掺杂四氧化三钴。
实施例2
本发明所述锰掺杂四氧化三钴及其制备方法与应用的一种实施例，包括以 下步骤：
(1)在氮气气氛、0.3MPa压力的反应釜中配制浓度为1.5mol/L的碳酸氢铵水溶液作为底液，所述底液在反应釜中的体积占比为45％，pH＝8.2，温度为32℃，待温度稳定后持续稳压通氮气20min；
(2)在稳压状态下向反应釜中分别以3L/h的流量加入混合金属溶液和沉淀剂，以520rpm速率混合，通过PLC系统控制所得混合液的pH以0.1/h的速率下降至7.4并稳定进行反应，直至混合液在反应釜中的体积占比达到70～80％，开始浓缩沉淀，浓缩沉淀期间混合金属溶液和沉淀剂继续通入以保持混合液在反应釜中的体积占比稳定，当浓缩沉淀所得颗粒粒度至5μm，停止反应，得锰掺杂碳酸钴颗粒浆料；所述混合金属溶液为硝酸钴、硝酸锰、18-冠-6及HL-610非离子表面活性剂的混合水溶液，所述混合金属溶液中钴离子浓度为1.8mol/L，锰元素与钴元素的质量比为0.008:1，18-冠-6、HL-610非离子表面活性剂与锰元素的质量比为0.04:0.04:1；所述沉淀剂为2.5mol/L的碳酸氢铵水溶液；
(3)将锰掺杂碳酸钴颗粒浆料过滤后，采用10wt％乙二胺四乙酸二钠水溶液洗涤20min，再经烘干、过筛，得锰掺杂碳酸钴前驱体；
(4)将锰掺杂碳酸钴前驱体在箱式炉中加热至665℃烧结4h，即得所述锰掺杂四氧化三钴。
实施例3
本发明所述锰掺杂四氧化三钴及其制备方法与应用的一种实施例，包括以下步骤：
(1)在氮气气氛、0.1MPa压力的反应釜中配制浓度为1.8mol/L的碳酸氢铵水溶液作为底液，所述底液在反应釜中的体积占比为50％，pH＝8.4，温度为35℃，待温度稳定后持续稳压通氮气15min；
(2)在稳压状态下向反应釜中分别以2L/h的流量加入混合金属溶液和沉淀剂，以600rpm速率混合，通过PLC系统控制所得混合液的pH以0.1/h的速率下降至7.6并稳定进行反应，直至混合液在反应釜中的体积占比达到70％～80％，开始浓缩沉淀，浓缩沉淀期间混合金属溶液和沉淀剂继续通入以保持混合液在反应釜中的体积占比稳定，当浓缩沉淀所得颗粒粒度至5.8μm，停止反应，得锰掺杂碳酸钴颗粒浆料；所述混合金属溶液为硫酸钴、硫酸锰、二苯并-18-冠-6及 HL-610非离子表面活性剂的混合水溶液，所述混合金属溶液中钴离子浓度为1.5mol/L，锰元素与钴元素的质量比为0.012:1，二苯并-18-冠-6、HL-610非离子表面活性剂与锰元素的质量比为0.06:0.06:1；所述沉淀剂为2mol/L的碳酸氢铵水溶液；
(3)将锰掺杂碳酸钴颗粒浆料过滤后，采用10wt％水合肼溶液洗涤20min，再经烘干、过筛，得锰掺杂碳酸钴前驱体；
(4)将锰掺杂碳酸钴前驱体在箱式炉中加热至665℃烧结4h，即得所述锰掺杂四氧化三钴。
对比例1
本对比例与实施例2的差别仅在于，所述产品的制备方法包括以下步骤：
(1)在0.3MPa压力的空气气氛下的反应釜中配制浓度为1.5mol/L的碳酸氢铵水溶液作为底液，所述底液在反应釜中的体积占比为45％，pH＝8.2，温度为32℃，待温度稳定后持续稳压通氮气20min；
(2)在稳压状态下向反应釜中分别以3L/h的流量加入混合金属溶液和沉淀剂，以520rpm速率混合，通过PLC系统控制所得混合液的pH以0.1/h的速率下降至7.4并稳定进行反应，直至混合液在反应釜中的体积占比达到70％～80％，开始浓缩沉淀，浓缩沉淀期间混合金属溶液和沉淀剂继续通入以保持混合液在反应釜中的体积占比稳定，当浓缩沉淀所得颗粒粒度至5μm，停止反应，得锰掺杂碳酸钴颗粒浆料；所述混合金属溶液为硝酸钴、硝酸锰、18-冠-6及HL-610非离子表面活性剂的混合水溶液，所述混合金属溶液中钴离子浓度为1.8mol/L，锰元素与钴元素的质量比为0.008:1，18-冠-6、HL-610非离子表面活性剂与锰元素的质量比为0.04:0.04:1；所述沉淀剂为2.5mol/L的碳酸氢铵水溶液；
(3)将锰掺杂碳酸钴颗粒浆料过滤后，采用去离子水洗涤20min，再经烘干、过筛，得锰掺杂碳酸钴前驱体；
(4)将锰掺杂碳酸钴前驱体在箱式炉中加热至665℃烧结4h，即得所述锰掺杂四氧化三钴。
对比例2
本对比例与实施例2的差别仅在于，所述产品的制备方法包括以下步骤：
(1)在氮气气氛、0.3MPa压力的反应釜中配制浓度为1.5mol/L的碳酸氢铵水溶液作为底液，所述底液在反应釜中的体积占比为45％，pH＝8.2，温度为32℃，待温度稳定后持续稳压通氮气20min；
(2)在稳压状态下向反应釜中分别以3L/h的流量加入混合金属溶液和沉淀剂，以520rpm速率混合，通过PLC系统控制所得混合液的pH以0.1/h的速率下降至7.4并稳定进行反应，直至混合液在反应釜中的体积占比达到70％～80％，开始浓缩沉淀，浓缩沉淀期间混合金属溶液和沉淀剂继续通入以保持混合液在反应釜中的体积占比稳定，当浓缩沉淀所得颗粒粒度至5μm，停止反应，得锰掺杂碳酸钴颗粒浆料；所述混合金属溶液为硝酸钴、硝酸锰的混合水溶液，所述混合金属溶液中钴离子浓度为1.8mol/L，锰元素与钴元素的质量比为0.008:1；所述沉淀剂为2.5mol/L的碳酸氢铵水溶液；
(3)将锰掺杂碳酸钴颗粒浆料过滤后，采用10wt％乙二胺四乙酸二钠水溶液洗涤20min，再经烘干、过筛，得锰掺杂碳酸钴前驱体；
(4)将锰掺杂碳酸钴前驱体在箱式炉中加热至665℃烧结4h，即得所述锰掺杂四氧化三钴。
对比例3
本对比例与实施例1的差别仅在于，所述15-冠-5替换为同等添加量的十烷基三甲基氯化铵。
对比例4
本对比例与实施例1的差别仅在于，所述HL-610非离子表面活性剂替换为同等添加量的油酸三乙醇胺。
对比例5
本对比例与实施例1的差别仅在于，所述15-冠-5与HL-610非离子表面活性剂的质量之比为1:2，15-冠-5与HL-610非离子表面活性剂的总用量与实施例1一致。
对比例6
本对比例与实施例1的差别仅在于，所述15-冠-5与HL-610非离子表面活 性剂的质量之比为2:1，15-冠-5与HL-610非离子表面活性剂的总用量与实施例1一致。
对比例7
本对比例与实施例3的差别仅在于，所述步骤(1)中反应釜的压力为0.05MPa。
对比例8
本对比例与实施例1的差别仅在于，所述步骤(2)中所得混合液的pH下降速率为0.15/h。
对比例9
本对比例与实施例1的差别仅在于，所述步骤(2)中所得混合液的pH下降速率为0.05/h。
效果例1
为了验证本发明所述锰掺杂四氧化三钴的制备方法制备产品的品质，将各产品进行粒径尺寸统计、元素含量统计，同时通过XPS分析拟合产品中锰元素的价态并进行统计，结果如表1所示。
表1
Figure PCTCN2022120644-appb-000001
同时，将各实施例/对比例产品进行扫描电镜观察，结果如图1～10所示。结合表1数据及各扫描电镜图可以看出，各实施例产品制备的锰掺杂四氧化三钴 产品颗粒均匀完整，分散性高，没有明显的粉碎现象，锰元素掺杂量可控且锰元素中二价锰的占比较高，最高可达到55wt％。相比之下，对比例1所述方法中未采用保护气氛及抗氧剂溶液洗涤以确保二价锰的稳定性，锰元素中高价态锰的含量占比较高，烧结得到的产品颗粒出现粉碎现象，晶型不完整；对比例2产品在制备过程中未引入表面活性剂，产品的分散性不佳，出现了团聚现象；对比例3所述制备方法步骤中冠醚类表面活性剂被替换成了其他种类的常规表面活性剂，其在前驱体合成过程中难以起到良好的金属离子络合作用，使得锰元素发生偏析，导致最终烧结的产品大小不均，粒径分布较宽；对比例4所述制备方法步骤中将HL-610非离子表面活性剂替换成了油酸三乙胺醇，无法有效抑制冠醚类表面活性剂造成的气泡效应，在反应釜反应过程中液位波动过大，稳定性较差，导致锰掺杂碳酸钴颗粒在合成过程中持续生成新的小晶核，最终产品的颗粒大小不均。从对比例5和6产品性能结果可知，当同时采用冠醚类表面活性剂和非离子表面活性剂复配时，任一种过多或过少均会导致产品的颗粒生长效果变差，分散性和尺寸均匀性均会受到影响；对比例7所述制备方法将恒压压力控制较低，所述压力环境将会减弱分子间布朗运动，同时会导致氮气量不足，最终产品中仍会出现较多成分的四价锰，产品颗粒不完整，从图10也可明显看出产品颗粒出现破损现象；对比例8所述制备方法在混合液反应过程中pH变化速率过大，将直接加速晶核之间的团聚现象，造成颗粒大小不均匀，相同粒径下造成产品的Span值偏大；而对比例9所述制备方法中pH变化速率过小，当反应釜液位达到浓缩液位时，底液中碳酸氢铵未完全消耗，会存在大量锰氨络合物，随着浓缩产生的清液排出反应体系，进而导致最终产品中锰元素含量低于理论值。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

  1. 一种锰掺杂四氧化三钴的制备方法，其特征在于，包括以下步骤：
    (1)在保护气氛、0.1～0.5MPa压力的反应容器中配制碳酸氢铵溶液作为底液，所述底液在反应容器中的体积占比为40％～50％，pH＝8～8.5；
    (2)在稳压状态下向反应容器中加入混合金属溶液和沉淀剂混合，控制所得混合液的pH以0.08～0.12/h的速率下降至7.3～7.6进行反应，直至混合液在反应容器中的体积占比达到70％～80％，开始浓缩沉淀；浓缩沉淀期间继续通入混合金属溶液和沉淀剂，以保持混合液在反应容器中的体积占比稳定；当浓缩沉淀所得颗粒粒度至4～6μm时，停止反应，得锰掺杂碳酸钴颗粒浆料；所述混合金属溶液包括钴盐、二价锰盐、冠醚类表面活性剂和非离子表面活性剂，所述冠醚类表面活性剂、非离子表面活性剂与二价锰盐中锰的质量之比为(0.02～0.08)：(0.02～0.08)：1；
    (3)将锰掺杂碳酸钴颗粒浆料过滤后，采用抗氧剂溶液洗涤10～30min，再经烘干、过筛，得锰掺杂碳酸钴前驱体；
    (4)将锰掺杂碳酸钴前驱体在650～680℃下烧结3～5h，即得所述锰掺杂四氧化三钴。
  2. 如权利要求1所述锰掺杂四氧化三钴的制备方法，其特征在于，所述混合金属溶液中钴盐的摩尔浓度为1.5～2mol/L，锰元素与钴元素的质量之比为(0.005～0.012)：1。
  3. 如权利要求1所述锰掺杂四氧化三钴的制备方法，其特征在于，所述钴盐为氯化钴、硫酸钴、硝酸钴中的至少一种；二价锰盐为氯化锰、硫酸锰、硝酸锰中的至少一种。
  4. 如权利要求1所述锰掺杂四氧化三钴的制备方法，其特征在于，所述冠醚类表面活性剂为15-冠-5、18-冠-6、二苯并-18-冠-6中的至少一种；所述非离子表面活性剂为HL-610非离子表面活性剂。
  5. 如权利要求1所述锰掺杂四氧化三钴的制备方法，其特征在于，所述沉淀剂为摩尔浓度2～3mol/L的碳酸氢铵溶液。
  6. 如权利要求1所述锰掺杂四氧化三钴的制备方法，其特征在于，所述步骤(1)中底液的摩尔浓度为1.3～1.8mol/L，温度为30～35℃；所述保护气氛为氮气。
  7. 如权利要求1所述锰掺杂四氧化三钴的制备方法，其特征在于，所述步骤(2)中混合时的搅拌速率为450～600rpm，混合金属溶液在加入反应容器时的流量为2～3L/h。
  8. 如权利要求1所述锰掺杂四氧化三钴的制备方法，其特征在于，所述步骤(3)中抗氧剂溶液的质量浓度为8wt％～12wt％，所述抗氧剂为水溶性抗氧剂。
  9. 如权利要求1～8任一项所述锰掺杂四氧化三钴的制备方法制备得到的锰掺杂四氧化三钴。
  10. 如权利要求9所述的锰掺杂四氧化三钴在制备钴酸锂正极材料中的应用。
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