WO2023202186A1 - Method for coating lithium cobalt oxide positive electrode material by spraying and application thereof - Google Patents

Method for coating lithium cobalt oxide positive electrode material by spraying and application thereof Download PDF

Info

Publication number
WO2023202186A1
WO2023202186A1 PCT/CN2023/074948 CN2023074948W WO2023202186A1 WO 2023202186 A1 WO2023202186 A1 WO 2023202186A1 CN 2023074948 W CN2023074948 W CN 2023074948W WO 2023202186 A1 WO2023202186 A1 WO 2023202186A1
Authority
WO
WIPO (PCT)
Prior art keywords
cobalt oxide
lithium cobalt
combustion
lithium
mixed
Prior art date
Application number
PCT/CN2023/074948
Other languages
French (fr)
Chinese (zh)
Inventor
余海军
谢英豪
李爱霞
张学梅
李长东
Original Assignee
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 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 filed Critical 广东邦普循环科技有限公司
Publication of WO2023202186A1 publication Critical patent/WO2023202186A1/en

Links

Classifications

    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 belongs to the technical field of lithium ion battery cathode materials, and specifically relates to a method of spray coating lithium cobalt oxide cathode materials and its application.
  • lithium cobalt oxide is widely used due to its high operating voltage and energy density, easy synthesis, and rapid charge and discharge.
  • higher requirements have been put forward for the energy density of battery output.
  • the application of conventional lithium cobalt oxide at high voltage still has many problems and challenges, especially Problems such as structural phase change at the interface with the electrolyte, transition metal dissolution, oxygen precipitation, and continuous oxidation and decomposition of the electrolyte severely limit its application in high-energy-density lithium batteries.
  • the structural properties and electrochemical properties of the particles can be optimized by forming a coating layer on the surface of the material, improving the corrosion resistance of the material, and reducing side reactions between the material and the electrolyte.
  • lithium cobalt oxide is mainly prepared by high-temperature solid phase method.
  • Solid lithium sources such as LiOH and Li 2 CO 3 are easily volatile at high temperatures, so when the raw materials are mixed, an excess of lithium source will be added to compensate for the lithium loss during the high temperature process.
  • the amount of lithium volatilized during the sintering process is difficult to control, so excess lithium source will inevitably remain on the surface of the material after the high-temperature solid-state reaction is completed.
  • Excess lithium source generally exists in the form of Li 2 O.
  • Li 2 O can easily combine with H 2 O and CO 2 in the air to form LiOH and Li 2 CO 3 attached to the surface of the material, resulting in high alkalinity of the material, making the slurry easily forms a "jelly" form, causing difficulty in slurry mixing.
  • the cathode material is very sensitive to water and can easily undergo a chemical delithiation reaction in water, causing the lithium ions in the crystal lattice to dissolve into the water in the form of LiOH, destroying the structure and electrochemical performance of the material.
  • the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art.
  • the present invention proposes a method for spray coating lithium cobalt oxide cathode material and its application. This method involves mixing the lithium cobalt oxide cathode material and organic silicon liquid. After combining, a spray combustion reaction is performed to remove residual lithium and obtain a silica-coated lithium cobalt oxide material.
  • a method for spray coating lithium cobalt oxide cathode material including the following steps:
  • the organic silicon is hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane or dodecamethylcyclosiloxane. At least one of hexasiloxanes.
  • the surfactant is at least one of laureth polyoxyethylene ether or nonylphenol polyoxyethylene ether.
  • the combustion accelerant is at least one of alkyl nitroanisole, nitrophenylhydrazine, alkoxynitroaniline or nitrobenzophenone.
  • step S1 the ratio of the silicone, diethyl ether, surfactant and combustion accelerator is (1.0-10.0) mL: (100-300) mL: (0.5-1.0) g :(1.0-2.0)g.
  • step S2 the mass ratio of the lithium cobalt oxide to the volume ratio of the mixed solution (solid-liquid ratio) is 1 g: (1.0-3.0) mL.
  • step S3 the nozzle aperture of the spray combustion device is 30-50 ⁇ m, and the spray pressure is 0.8-1.5 MPa.
  • the carrier gas flow is air or oxygen, and the carrier gas flow rate is 100-150L/h.
  • step S3 the temperature of the combustion chamber is 750-1000°C.
  • the invention also provides the application of the method in preparing lithium-ion batteries.
  • the present invention uses flammable organic silicon as the coating source, and after the ether and lithium cobalt oxide cathode material are evenly mixed, In the spray combustion device, it is ignited to generate a silicon dioxide coating layer, which is coated on the surface of the lithium cobalt oxide cathode material. And at high temperatures, silicon dioxide further reacts with the remaining lithium on the surface of lithium cobalt oxide to generate lithium silicate, which reduces the alkalinity of the material surface and avoids the problem of lithium precipitation in the crystal lattice caused by the removal of residual lithium by water washing. It not only achieves silica coating on the surface of lithium cobalt oxide, but also further eliminates the slurrying problem caused by residual lithium, killing two birds with one stone.
  • the reaction equation is as follows: xLi 2 O+ySiO 2 ⁇ xLi 2 O ⁇ ySiO 2 .
  • Figure 1 is an SEM image of silica-coated lithium cobalt oxide prepared in Example 1 of the present invention.
  • a method of spray coating lithium cobalt oxide cathode material, the specific process is:
  • Step 2 Add the sintered lithium cobalt oxide positive electrode material to the mixed solution in step 1 according to the solid-liquid ratio of 1g:2.0mL to obtain a mixed material;
  • Step 3 Add the mixed material obtained in Step 2 to the spray combustion device, set the nozzle aperture to 40 ⁇ m, and the spray pressure to 1.2MPa. Under constant stirring, oxygen is used as the carrier gas flow, and the flow rate is set to 120L/h. The airflow enters the combustion chamber for combustion, and the temperature of the combustion chamber is controlled to 900°C;
  • Step 4 After the reaction is completed, collect the solid material in the combustion chamber to obtain spray-coated silica-coated lithium cobalt oxide.
  • a method of spray coating lithium cobalt oxide cathode material, the specific process is:
  • Step 2 Add the sintered lithium cobalt oxide positive electrode material to the mixed solution in step 1 according to the solid-liquid ratio of 1g:1.0mL to obtain a mixed material;
  • Step 3 Add the mixed material obtained in Step 2 to the spray combustion device, set the nozzle aperture to 30 ⁇ m, and the spray pressure to 0.8MPa. Under constant stirring, use air as the carrier gas flow, and set the flow rate to 100L/h. The airflow enters the combustion chamber for combustion, and the temperature of the combustion chamber is controlled to 1000°C;
  • Step 4 After the reaction is completed, collect the solid materials in the combustion chamber to obtain the spray-coated lithium cobalt oxide cathode material.
  • a method of spray coating lithium cobalt oxide cathode material, the specific process is:
  • Step 2 Add the sintered lithium cobalt oxide positive electrode material to the mixed solution in step 1 according to a solid-liquid ratio of 1g:3.0mL to obtain a mixed material;
  • Step 3 Add the mixed material obtained in Step 2 to the spray combustion device, set the nozzle aperture to 50 ⁇ m, and the spray pressure to 1.5MPa. Under constant stirring, oxygen is used as the carrier gas flow, and the flow rate is set to 150L/h. The airflow enters the combustion chamber for combustion, and the temperature of the combustion chamber is controlled to 750°C;
  • Step 4 After the reaction is completed, collect the solid materials in the combustion chamber to obtain the spray-coated lithium cobalt oxide cathode material.
  • the preparation of the sintered lithium cobalt oxide cathode material used in step 2 of Example 1-3 is as follows: batch cobalt tetroxide and lithium carbonate, control the molar ratio of Li:Co to 1.06, and place it in a push plate kiln for high-temperature solid phase sintering. , the sintering temperature was 1000°C, the sintering time was 12 hours, and the sintered lithium cobalt oxide cathode material was obtained, and the sintered lithium cobalt oxide cathode material was used as Comparative Example 1.
  • the coated lithium cobalt oxide material obtained in the examples and the lithium cobalt oxide of the comparative example were used as raw materials, acetylene black was used as the conductive agent, and PVDF was used as the binder.
  • the active material, conductive agent, and The binder is added with a certain amount of organic solvent NMP, stirred and then coated on aluminum foil to make a positive electrode sheet.
  • the negative electrode is made of metal lithium sheet, and a CR2430 button battery is made in a glove box filled with argon.
  • Conduct electrical performance testing on the CT2001A blue battery testing system. Test conditions: 3.0-4.48V, current density 1C 180mAh/g, test temperature 25 ⁇ 1°C. The test results are shown in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Disclosed are a method for coating a lithium cobalt oxide positive electrode material by spraying and an application thereof. The method comprises: preparing an organic silicon-based ethyl ether solution, adding a surfactant and a combustion improver to obtain a mixed solution; adding lithium cobalt oxide into the mixed solution to obtain a mixed material; adding the mixed material into a spraying combustion device, enabling, by means a carrier gas flow, the mixed material to enter a combustion chamber for combustion, and collecting a solid material after a reaction is finished, so as to obtain silicon dioxide-coated lithium cobalt oxide. According to the present invention, flammable organic silicon is used as a coating source, diethyl ether and a lithium cobalt oxide positive electrode material are uniformly mixed and then ignited in a spraying combustion device to generate a silicon dioxide coating layer which coats the surface of the lithium cobalt oxide positive electrode material, and lithium silicate is further generated at high temperature, so that the alkalinity of the surface of the material is reduced.

Description

喷雾包覆钴酸锂正极材料的方法及其应用Method and application of spray coating lithium cobalt oxide cathode material 技术领域Technical field
本发明属于锂离子电池正极材料技术领域，具体涉及一种喷雾包覆钴酸锂正极材料的方法及其应用。The invention belongs to the technical field of lithium ion battery cathode materials, and specifically relates to a method of spray coating lithium cobalt oxide cathode materials and its application.
背景技术Background technique
在锂离子正极材料中，钴酸锂由于具有较高的工作电压和能量密度、易合成且可快速充放电，因此被广泛应用。近年来，随着电子产品的进一步小型化和多功能化，对电池输出的能量密度提出了更高的要求，常规的钴酸锂在高电压下的应用还具有较多问题与挑战，尤其是与电解液界面处的结构相变、过渡金属溶解、氧析出、电解液持续氧化分解等问题，严重地限制着其在高能量密度锂电池中的应用。Among lithium-ion cathode materials, lithium cobalt oxide is widely used due to its high operating voltage and energy density, easy synthesis, and rapid charge and discharge. In recent years, with the further miniaturization and multi-function of electronic products, higher requirements have been put forward for the energy density of battery output. The application of conventional lithium cobalt oxide at high voltage still has many problems and challenges, especially Problems such as structural phase change at the interface with the electrolyte, transition metal dissolution, oxygen precipitation, and continuous oxidation and decomposition of the electrolyte severely limit its application in high-energy-density lithium batteries.
针对以上的问题，现有技术中可以通过在材料表面形成包覆层来优化颗粒的结构性能和电化学性能，提高材料的抗腐蚀能力、降低材料与电解液之间的副反应。In response to the above problems, in the existing technology, the structural properties and electrochemical properties of the particles can be optimized by forming a coating layer on the surface of the material, improving the corrosion resistance of the material, and reducing side reactions between the material and the electrolyte.
另一方面，钴酸锂在制备时主要是采用高温固相法。采用LiOH和Li2CO3等固体锂源在高温下易挥发，因此在原料混合的时候会加入过量的锂源以补偿高温过程中的锂损失。但是，烧结过程中锂的挥发量难以控制，因此高温固相反应完成后的材料表面难免会残留过量锂源。过量的锂源一般以Li2O的形式存在，Li2O很容易与空气中的H2O和CO2结合形成LiOH和Li2CO3附着在材料表面，导致材料碱度偏高，使得在电极制作的调浆过程中浆料容易形成“果冻”形态，造成调浆困难。On the other hand, lithium cobalt oxide is mainly prepared by high-temperature solid phase method. Solid lithium sources such as LiOH and Li 2 CO 3 are easily volatile at high temperatures, so when the raw materials are mixed, an excess of lithium source will be added to compensate for the lithium loss during the high temperature process. However, the amount of lithium volatilized during the sintering process is difficult to control, so excess lithium source will inevitably remain on the surface of the material after the high-temperature solid-state reaction is completed. Excess lithium source generally exists in the form of Li 2 O. Li 2 O can easily combine with H 2 O and CO 2 in the air to form LiOH and Li 2 CO 3 attached to the surface of the material, resulting in high alkalinity of the material, making the During the slurry mixing process of electrode production, the slurry easily forms a "jelly" form, causing difficulty in slurry mixing.
为了除去材料表面的多余Li2O，研究者做了大量的工作。其中最简单有效的方法就是水洗。然而，正极材料对水非常敏感，其在水中很容易发生化学脱锂反应，使得晶格中的锂离子以LiOH的形式溶入水中，破坏材料的结构和电化学性能。In order to remove excess Li 2 O on the surface of the material, researchers have done a lot of work. The simplest and most effective method is washing with water. However, the cathode material is very sensitive to water and can easily undergo a chemical delithiation reaction in water, causing the lithium ions in the crystal lattice to dissolve into the water in the form of LiOH, destroying the structure and electrochemical performance of the material.
发明内容Contents of the invention
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种喷雾包覆钴酸锂正极材料的方法及其应用，该方法通过将钴酸锂正极材料与有机硅液混 合后，进行喷雾燃烧反应，去除残锂的同时，得到包覆二氧化硅的钴酸锂材料。The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a method for spray coating lithium cobalt oxide cathode material and its application. This method involves mixing the lithium cobalt oxide cathode material and organic silicon liquid. After combining, a spray combustion reaction is performed to remove residual lithium and obtain a silica-coated lithium cobalt oxide material.
根据本发明的一个方面，提出了一种喷雾包覆钴酸锂正极材料的方法，包括以下步骤：According to one aspect of the present invention, a method for spray coating lithium cobalt oxide cathode material is proposed, including the following steps:
S1：配制有机硅的乙醚溶液，并加入表面活性剂和助燃剂，得到混合液；S1: Prepare an ether solution of silicone, and add surfactant and combustion accelerator to obtain a mixed solution;
S2：将钴酸锂加入到所述混合液中，得到混合物料；S2: Add lithium cobalt oxide to the mixed solution to obtain a mixed material;
S3：将所述混合物料加入到喷雾燃烧装置中，所述混合物料经载气气流进入燃烧室燃烧，反应结束后，收集燃烧室内的固体料，即得包覆二氧化硅的钴酸锂。S3: Add the mixed material into the spray combustion device, and the mixed material enters the combustion chamber through the carrier gas flow for combustion. After the reaction is completed, collect the solid materials in the combustion chamber to obtain lithium cobalt oxide coated with silicon dioxide.
在本发明的一些实施方式中，步骤S1中，所述有机硅为六甲基环三硅氧烷、八甲基环四硅氧烷、十甲基环五硅氧烷或十二甲基环六硅氧烷中的至少一种。In some embodiments of the present invention, in step S1, the organic silicon is hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane or dodecamethylcyclosiloxane. At least one of hexasiloxanes.
在本发明的一些实施方式中，步骤S1中，所述表面活性剂为月桂醇聚氧乙烯醚或壬基酚聚氧乙烯醚中的至少一种。In some embodiments of the present invention, in step S1, the surfactant is at least one of laureth polyoxyethylene ether or nonylphenol polyoxyethylene ether.
在本发明的一些实施方式中，步骤S1中，所述助燃剂为烷基硝基茴香醚、硝基苯肼、烷氧基硝基苯胺或硝基二苯甲酮中的至少一种。In some embodiments of the present invention, in step S1, the combustion accelerant is at least one of alkyl nitroanisole, nitrophenylhydrazine, alkoxynitroaniline or nitrobenzophenone.
在本发明的一些实施方式中，步骤S1中，所述有机硅、乙醚、表面活性剂和助燃剂的配比为(1.0-10.0)mL：(100-300)mL：(0.5-1.0)g：(1.0-2.0)g。In some embodiments of the present invention, in step S1, the ratio of the silicone, diethyl ether, surfactant and combustion accelerator is (1.0-10.0) mL: (100-300) mL: (0.5-1.0) g :(1.0-2.0)g.
在本发明的一些实施方式中，步骤S2中，所述钴酸锂的质量与混合液的体积比(固液比)为1g：(1.0-3.0)mL。In some embodiments of the present invention, in step S2, the mass ratio of the lithium cobalt oxide to the volume ratio of the mixed solution (solid-liquid ratio) is 1 g: (1.0-3.0) mL.
在本发明的一些实施方式中，步骤S3中，所述喷雾燃烧装置的喷头孔径为30-50μm，喷雾压力为0.8-1.5MPa。In some embodiments of the present invention, in step S3, the nozzle aperture of the spray combustion device is 30-50 μm, and the spray pressure is 0.8-1.5 MPa.
在本发明的一些实施方式中，步骤S3中，所述载气气流为空气或氧气，载气流量为100-150L/h。In some embodiments of the present invention, in step S3, the carrier gas flow is air or oxygen, and the carrier gas flow rate is 100-150L/h.
在本发明的一些实施方式中，步骤S3中，所述燃烧室的温度为750-1000℃。In some embodiments of the present invention, in step S3, the temperature of the combustion chamber is 750-1000°C.
本发明还提供所述的方法在制备锂离子电池中的应用。The invention also provides the application of the method in preparing lithium-ion batteries.
根据本发明的一种优选的实施方式，至少具有以下有益效果：According to a preferred embodiment of the present invention, it has at least the following beneficial effects:
1、本发明以可燃性的有机硅为包覆源，通过乙醚与钴酸锂正极材料混合均匀后， 在喷雾燃烧装置中，引燃，生成二氧化硅包覆层，包覆在钴酸锂正极材料表面。并且在高温下，二氧化硅与钴酸锂表面残留的锂进一步反应，生成硅酸锂，降低了材料表面的碱性，避免水洗去除残锂导致晶格锂析出的问题。不但实现了钴酸锂表面二氧化硅的包覆，而且进一步去除了残锂带来的调浆问题，一举两得。反应方程式如下：
xLi2O+ySiO2→xLi2O·ySiO2。1. The present invention uses flammable organic silicon as the coating source, and after the ether and lithium cobalt oxide cathode material are evenly mixed, In the spray combustion device, it is ignited to generate a silicon dioxide coating layer, which is coated on the surface of the lithium cobalt oxide cathode material. And at high temperatures, silicon dioxide further reacts with the remaining lithium on the surface of lithium cobalt oxide to generate lithium silicate, which reduces the alkalinity of the material surface and avoids the problem of lithium precipitation in the crystal lattice caused by the removal of residual lithium by water washing. It not only achieves silica coating on the surface of lithium cobalt oxide, but also further eliminates the slurrying problem caused by residual lithium, killing two birds with one stone. The reaction equation is as follows:
xLi 2 O+ySiO 2 →xLi 2 O·ySiO 2 .
2、在喷雾热解过程中，利用有机硅的可燃性，采用乙醚作为溶剂，进行火法包覆，避免了水热包覆等湿法带来的晶格锂析出问题；同时，为降低喷雾过程产生的液滴粘性，加入有机类的表面活性剂，提高喷雾的分散性，使钴酸锂颗粒与液体同时喷出时，不会产生黏连，提高燃烧及包覆的效果；为避免不完全燃烧带来的钴还原问题，通过加入硝基类的助燃剂，使所有液体均能充分燃烧，保证了钴酸锂材料的稳定性。2. During the spray pyrolysis process, the flammability of silicone is utilized and diethyl ether is used as the solvent for fire coating, which avoids the precipitation problem of lattice lithium caused by wet methods such as hydrothermal coating; at the same time, in order to reduce the spray Due to the viscosity of the droplets generated during the process, organic surfactants are added to improve the dispersion of the spray, so that when the lithium cobalt oxide particles and the liquid are sprayed out at the same time, they will not stick to each other and improve the combustion and coating effects; in order to avoid inconveniences. To solve the cobalt reduction problem caused by complete combustion, by adding nitro-based combustion accelerant, all liquids can be fully burned, ensuring the stability of the lithium cobalt oxide material.
附图说明Description of the drawings
下面结合附图和实施例对本发明做进一步的说明，其中：The present invention will be further described below in conjunction with the accompanying drawings and examples, wherein:
图1为本发明实施例1制备的包覆二氧化硅的钴酸锂的SEM图。Figure 1 is an SEM image of silica-coated lithium cobalt oxide prepared in Example 1 of the present invention.
具体实施方式Detailed ways
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，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，均属于本发明保护的范围。The concept of the present invention and the technical effects produced will be clearly and completely described below with reference to the embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without exerting creative efforts are all protection scope of the present invention.
实施例1Example 1
一种喷雾包覆钴酸锂正极材料的方法，具体过程为：A method of spray coating lithium cobalt oxide cathode material, the specific process is:
步骤1，配制六甲基环三硅氧烷的乙醚溶液，并加入月桂醇聚氧乙烯醚作为表面活性剂、硝基苯肼为助燃剂，混合均匀，得到混合液，其中，各物料配比为：有机硅：乙醚：表面活性剂：助燃剂＝5mL:200mL:0.8g:1.5g；Step 1: Prepare an ether solution of hexamethylcyclotrisiloxane, add laureth polyoxyethylene ether as surfactant and nitrophenylhydrazine as combustion accelerator, mix evenly to obtain a mixed liquid, in which the proportion of each material It is: silicone: ether: surfactant: combustion accelerant = 5mL: 200mL: 0.8g: 1.5g;
步骤2，按照固液比为1g:2.0mL，将烧结好的钴酸锂正极材料加入到步骤1中的混合液中，得到混合物料； Step 2: Add the sintered lithium cobalt oxide positive electrode material to the mixed solution in step 1 according to the solid-liquid ratio of 1g:2.0mL to obtain a mixed material;
步骤3，将步骤2所得混合物料加入到喷雾燃烧装置中，设置喷头孔径为40μm，喷雾压力为1.2MPa，在不断搅拌下，以氧气为载气气流，设置流量为120L/h，经载气气流进入燃烧室燃烧，控制燃烧室温度为900℃；Step 3: Add the mixed material obtained in Step 2 to the spray combustion device, set the nozzle aperture to 40 μm, and the spray pressure to 1.2MPa. Under constant stirring, oxygen is used as the carrier gas flow, and the flow rate is set to 120L/h. The airflow enters the combustion chamber for combustion, and the temperature of the combustion chamber is controlled to 900°C;
步骤4，反应结束后，收集燃烧室内的固体料即得到喷雾包覆二氧化硅的钴酸锂。Step 4: After the reaction is completed, collect the solid material in the combustion chamber to obtain spray-coated silica-coated lithium cobalt oxide.
实施例2Example 2
一种喷雾包覆钴酸锂正极材料的方法，具体过程为：A method of spray coating lithium cobalt oxide cathode material, the specific process is:
步骤1，配制八甲基环四硅氧烷的乙醚溶液，并加入壬基酚聚氧乙烯醚作为表面活性剂、烷氧基硝基苯胺为助燃剂，混合均匀，得到混合液，其中，各物料配比为：乙醚：表面活性剂：助燃剂＝1mL:100mL:0.5g:1.0g，；Step 1: Prepare an ether solution of octamethylcyclotetrasiloxane, add nonylphenol polyoxyethylene ether as surfactant and alkoxynitroaniline as combustion accelerator, mix evenly to obtain a mixed liquid, wherein each The material ratio is: ether: surfactant: combustion accelerant = 1mL: 100mL: 0.5g: 1.0g;
步骤2，按照固液比为1g:1.0mL，将烧结好的钴酸锂正极材料加入到步骤1中的混合液中，得到混合物料；Step 2: Add the sintered lithium cobalt oxide positive electrode material to the mixed solution in step 1 according to the solid-liquid ratio of 1g:1.0mL to obtain a mixed material;
步骤3，将步骤2所得混合物料加入到喷雾燃烧装置中，设置喷头孔径为30μm，喷雾压力为0.8MPa，在不断搅拌下，以空气为载气气流，设置流量为100L/h，经载气气流进入燃烧室燃烧，控制燃烧室温度为1000℃；Step 3: Add the mixed material obtained in Step 2 to the spray combustion device, set the nozzle aperture to 30 μm, and the spray pressure to 0.8MPa. Under constant stirring, use air as the carrier gas flow, and set the flow rate to 100L/h. The airflow enters the combustion chamber for combustion, and the temperature of the combustion chamber is controlled to 1000°C;
步骤4，反应结束后，收集燃烧室内的固体料即得到喷雾包覆的钴酸锂正极材料。Step 4: After the reaction is completed, collect the solid materials in the combustion chamber to obtain the spray-coated lithium cobalt oxide cathode material.
实施例3Example 3
一种喷雾包覆钴酸锂正极材料的方法，具体过程为：A method of spray coating lithium cobalt oxide cathode material, the specific process is:
步骤1，配制十甲基环五硅氧烷的乙醚溶液，并加入月桂醇聚氧乙烯醚作为表面活性剂、硝基二苯甲酮为助燃剂，混合均匀，得到混合液，其中，各物料配比为：有机硅：乙醚：表面活性剂：助燃剂＝10mL:300mL:1.0g:2.0g；Step 1: Prepare an ether solution of decamethylcyclopentasiloxane, add laureth polyoxyethylene ether as surfactant and nitrobenzophenone as combustion accelerator, mix evenly to obtain a mixed liquid, in which each material The ratio is: silicone: ether: surfactant: combustion accelerant = 10mL: 300mL: 1.0g: 2.0g;
步骤2，按照固液比为1g:3.0mL，将烧结好的钴酸锂正极材料加入到步骤1中的混合液中，得到混合物料；Step 2: Add the sintered lithium cobalt oxide positive electrode material to the mixed solution in step 1 according to a solid-liquid ratio of 1g:3.0mL to obtain a mixed material;
步骤3，将步骤2所得混合物料加入到喷雾燃烧装置中，设置喷头孔径为50μm，喷雾压力为1.5MPa，在不断搅拌下，以氧气为载气气流，设置流量为150L/h，经载气气流进入燃烧室燃烧，控制燃烧室温度为750℃； Step 3: Add the mixed material obtained in Step 2 to the spray combustion device, set the nozzle aperture to 50 μm, and the spray pressure to 1.5MPa. Under constant stirring, oxygen is used as the carrier gas flow, and the flow rate is set to 150L/h. The airflow enters the combustion chamber for combustion, and the temperature of the combustion chamber is controlled to 750°C;
步骤4，反应结束后，收集燃烧室内的固体料即得到喷雾包覆的钴酸锂正极材料。Step 4: After the reaction is completed, collect the solid materials in the combustion chamber to obtain the spray-coated lithium cobalt oxide cathode material.
实施例1-3中步骤2所用烧结好的钴酸锂正极材料的制备如下：将四氧化三钴与碳酸锂进行配料，控制Li:Co的摩尔比为1.06，置于推板窑中进行高温固相烧结，烧结温度为1000℃，烧结时间为12h，得到烧结好的钴酸锂正极材料，并以此烧结好的钴酸锂正极材料作为对比例1。The preparation of the sintered lithium cobalt oxide cathode material used in step 2 of Example 1-3 is as follows: batch cobalt tetroxide and lithium carbonate, control the molar ratio of Li:Co to 1.06, and place it in a push plate kiln for high-temperature solid phase sintering. , the sintering temperature was 1000°C, the sintering time was 12 hours, and the sintered lithium cobalt oxide cathode material was obtained, and the sintered lithium cobalt oxide cathode material was used as Comparative Example 1.
取500ml去离子水，搅拌的条件下，维持水温在30℃，将500g烧结好的钴酸锂正极材料(对比例1)加入去离子水中，搅拌速度为400r/min，经过10min，采用抽滤分离物料和水分，在120℃的条件下烘干物料10h，得到水洗烘干的钴酸锂正极材料，作为对比例2。Take 500ml of deionized water and maintain the water temperature at 30°C while stirring. Add 500g of sintered lithium cobalt oxide cathode material (Comparative Example 1) into the deionized water. The stirring speed is 400r/min. After 10min, use suction filtration. Separate the material and moisture, and dry the material at 120°C for 10 hours to obtain a washed and dried lithium cobalt oxide cathode material as Comparative Example 2.
试验例Test example
对实施例得到的包覆钴酸锂材料和对比例的钴酸锂中的残锂进行检测。The residual lithium in the coated lithium cobalt oxide material obtained in the examples and the lithium cobalt oxide in the comparative example was detected.
以实施例得到的包覆的钴酸锂材料、对比例的钴酸锂为原料，乙炔黑为导电剂，PVDF为粘结剂，以92:4:4的比例称取活性材料、导电剂、粘结剂，并加入一定量的有机溶剂NMP，搅拌后涂覆于铝箔上制成正极片，负极采用金属锂片，在充满氩气的手套箱内制成CR2430型纽扣电池。在CT2001A型蓝电测试系统进行电性能测试。测试条件：3.0-4.48V，电流密度1C＝180mAh/g，测试温度为25±1℃。测试结果如表1所示。The coated lithium cobalt oxide material obtained in the examples and the lithium cobalt oxide of the comparative example were used as raw materials, acetylene black was used as the conductive agent, and PVDF was used as the binder. The active material, conductive agent, and The binder is added with a certain amount of organic solvent NMP, stirred and then coated on aluminum foil to make a positive electrode sheet. The negative electrode is made of metal lithium sheet, and a CR2430 button battery is made in a glove box filled with argon. Conduct electrical performance testing on the CT2001A blue battery testing system. Test conditions: 3.0-4.48V, current density 1C=180mAh/g, test temperature 25±1℃. The test results are shown in Table 1.
表1
Table 1
由表1可见，实施例中经过喷雾包覆处理的钴酸锂的残锂量明显低于对比例1，残 锂的去除量与普通水洗法的对比例2相当，但对比例2材料的放电容量和循环性能明显不如实施例，这是由于在对比例2的水洗过程中，材料在水中发生化学脱锂反应，使得晶格中的锂离子以LiOH的形式溶入水中，破坏了材料的结构，导致电化学性能降低。It can be seen from Table 1 that the residual lithium amount of the lithium cobalt oxide treated by spray coating in the embodiment is significantly lower than that of Comparative Example 1. The removal amount of lithium is equivalent to that of Comparative Example 2 of the ordinary water washing method, but the discharge capacity and cycle performance of the material of Comparative Example 2 are obviously not as good as those of the Example. This is due to the chemical delithiation reaction of the material in the water during the water washing process of Comparative Example 2. , causing the lithium ions in the crystal lattice to dissolve into water in the form of LiOH, destroying the structure of the material, resulting in reduced electrochemical performance.
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。 The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those of ordinary skill in the art, various modifications can be made without departing from the purpose of the present invention. Variety. In addition, the embodiments of the present invention and the features in the embodiments may be combined with each other without conflict.

Claims (10)

  1. 一种喷雾包覆钴酸锂正极材料的方法，其特征在于，包括以下步骤：A method of spray coating lithium cobalt oxide cathode material, which is characterized by including the following steps:
    S1：配制有机硅的乙醚溶液，并加入表面活性剂和助燃剂，得到混合液；S1: Prepare an ether solution of silicone, and add surfactant and combustion accelerator to obtain a mixed solution;
    S2：将钴酸锂加入到所述混合液中，得到混合物料；S2: Add lithium cobalt oxide to the mixed solution to obtain a mixed material;
    S3：将所述混合物料加入到喷雾燃烧装置中，所述混合物料经载气气流进入燃烧室燃烧，反应结束后，收集燃烧室内的固体料，即得包覆二氧化硅的钴酸锂。S3: Add the mixed material into the spray combustion device, and the mixed material enters the combustion chamber through the carrier gas flow for combustion. After the reaction is completed, collect the solid materials in the combustion chamber to obtain lithium cobalt oxide coated with silicon dioxide.
  2. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述有机硅为六甲基环三硅氧烷、八甲基环四硅氧烷、十甲基环五硅氧烷或十二甲基环六硅氧烷中的至少一种。The method according to claim 1, characterized in that in step S1, the organic silicon is hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane or decamethylcyclopentasiloxane. At least one kind of dimethylcyclohexasiloxane.
  3. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述表面活性剂为月桂醇聚氧乙烯醚或壬基酚聚氧乙烯醚中的至少一种。The method according to claim 1, characterized in that in step S1, the surfactant is at least one of laureth polyoxyethylene ether or nonylphenol polyoxyethylene ether.
  4. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述助燃剂为烷基硝基茴香醚、硝基苯肼、烷氧基硝基苯胺或硝基二苯甲酮中的至少一种。The method according to claim 1, characterized in that in step S1, the combustion accelerant is at least one of alkyl nitroanisole, nitrophenylhydrazine, alkoxynitroaniline or nitrobenzophenone. A sort of.
  5. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述有机硅、乙醚、表面活性剂和助燃剂的配比为(1.0-10.0)mL：(100-300)mL：(0.5-1.0)g：(1.0-2.0)g。The method according to claim 1, characterized in that in step S1, the ratio of the silicone, ether, surfactant and combustion accelerant is (1.0-10.0) mL: (100-300) mL: (0.5 -1.0)g: (1.0-2.0)g.
  6. 根据权利要求1所述的方法，其特征在于，步骤S2中，所述钴酸锂的质量与混合液的体积比为1g：(1.0-3.0)mL。The method according to claim 1, characterized in that, in step S2, the mass ratio of the lithium cobalt oxide to the volume of the mixed solution is 1g: (1.0-3.0) mL.
  7. 根据权利要求1所述的方法，其特征在于，步骤S3中，所述喷雾燃烧装置的喷头孔径为30-50μm，喷雾压力为0.8-1.5MPa。The method according to claim 1, characterized in that in step S3, the aperture of the nozzle of the spray combustion device is 30-50 μm, and the spray pressure is 0.8-1.5 MPa.
  8. 根据权利要求1所述的方法，其特征在于，步骤S3中，所述载气气流为空气或氧气，载气流量为100-150L/h。The method according to claim 1, characterized in that in step S3, the carrier gas flow is air or oxygen, and the carrier gas flow rate is 100-150L/h.
  9. 根据权利要求1所述的方法，其特征在于，步骤S3中，所述燃烧室的温度为750-1000℃。The method according to claim 1, characterized in that in step S3, the temperature of the combustion chamber is 750-1000°C.
  10. 如权利要求1-9任一项所述的方法在制备锂离子电池中的应用。 Application of the method according to any one of claims 1 to 9 in the preparation of lithium ion batteries.
PCT/CN2023/074948 2022-04-22 2023-02-08 Method for coating lithium cobalt oxide positive electrode material by spraying and application thereof WO2023202186A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210428372.9A CN114744142A (en) 2022-04-22 2022-04-22 Method for coating lithium cobaltate cathode material by spraying and application thereof
CN202210428372.9 2022-04-22

Publications (1)

Publication Number Publication Date
WO2023202186A1 true WO2023202186A1 (en) 2023-10-26

Family

ID=82283893

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/074948 WO2023202186A1 (en) 2022-04-22 2023-02-08 Method for coating lithium cobalt oxide positive electrode material by spraying and application thereof

Country Status (2)

Country Link
CN (1) CN114744142A (en)
WO (1) WO2023202186A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114744142A (en) * 2022-04-22 2022-07-12 广东邦普循环科技有限公司 Method for coating lithium cobaltate cathode material by spraying and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105161700A (en) * 2015-08-05 2015-12-16 华东理工大学 Molybdenum trioxide coated molybdenum doped titanium dioxide nano composite particle and preparation method and application thereof
CN109994711A (en) * 2017-12-29 2019-07-09 格林美（无锡）能源材料有限公司 A kind of preparation method of doping and the lithium cobaltate cathode material coated
CN111483994A (en) * 2019-07-09 2020-08-04 艾姆新能源(江苏)有限公司 Clean production process for recycling lithium iron phosphate cathode material by spray roasting method
CN113299915A (en) * 2021-04-12 2021-08-24 深圳大学 Lithium cobaltate composite material coated by lithium orthosilicate and carbon, preparation method and application
CN114014380A (en) * 2021-10-28 2022-02-08 蜂巢能源科技有限公司 Lithium nickel manganese oxide, preparation method and application thereof
CN114744142A (en) * 2022-04-22 2022-07-12 广东邦普循环科技有限公司 Method for coating lithium cobaltate cathode material by spraying and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105161700A (en) * 2015-08-05 2015-12-16 华东理工大学 Molybdenum trioxide coated molybdenum doped titanium dioxide nano composite particle and preparation method and application thereof
CN109994711A (en) * 2017-12-29 2019-07-09 格林美（无锡）能源材料有限公司 A kind of preparation method of doping and the lithium cobaltate cathode material coated
CN111483994A (en) * 2019-07-09 2020-08-04 艾姆新能源(江苏)有限公司 Clean production process for recycling lithium iron phosphate cathode material by spray roasting method
CN113299915A (en) * 2021-04-12 2021-08-24 深圳大学 Lithium cobaltate composite material coated by lithium orthosilicate and carbon, preparation method and application
CN114014380A (en) * 2021-10-28 2022-02-08 蜂巢能源科技有限公司 Lithium nickel manganese oxide, preparation method and application thereof
CN114744142A (en) * 2022-04-22 2022-07-12 广东邦普循环科技有限公司 Method for coating lithium cobaltate cathode material by spraying and application thereof

Also Published As

Publication number Publication date
CN114744142A (en) 2022-07-12

Similar Documents

Publication Publication Date Title
WO2020147671A1 (en) Method for modifying surface of high nickel ternary positive electrode material
CN106848264A (en) A kind of porous silicon oxide lithium ion battery negative material and preparation method thereof
CN106058228A (en) Core-shell structure silicon-carbon composite material as well as preparation method and application thereof
CN107623116A (en) A kind of composite cathode material of lithium ion battery and preparation method thereof
CN112768688B (en) Lithium iron phosphate material, preparation method thereof and lithium ion battery
WO2023202186A1 (en) Method for coating lithium cobalt oxide positive electrode material by spraying and application thereof
CN109037602A (en) A kind of double oxide cladding tertiary cathode material and preparation method thereof
CN109473658A (en) A kind of its lithium ion battery of the preparation method and application of lithium ion battery negative material
CN105576221B (en) A kind of lithium ion battery anode active material presoma and lithium ion battery anode active material and preparation method thereof
WO2023020460A1 (en) Negative electrode composite material, and preparation method therefor and application thereof
CN114843482B (en) Core-shell type silicon-carbon composite material and preparation method and application thereof
CN106207128A (en) A kind of Zr (OH)4the preparation method of cladding nickel cobalt aluminum tertiary cathode material
CN109192961B (en) Preparation method of positive electrode material
CN113193181B (en) Pre-lithiated silica-oxygen composite material, precursor, preparation method and application thereof
CN113991084A (en) SnS-SnO2-GO @ C heterostructure composite material and preparation method and application thereof
CN117673340A (en) High-nickel ternary positive electrode material, preparation method thereof and battery
CN106099227A (en) Battery with a battery cell
JP2020061338A (en) Production method of cathode active material for all-solid-state lithium ion battery, and manufacturing method of all-solid-state lithium ion battery
CN103855406B (en) A kind of lithium-air battery positive pole and Synthesis and applications thereof
WO2023226556A1 (en) Preparation method for and use of lithium iron phosphate
CN112349902A (en) Ternary cathode material of lithium ion battery, preparation method of ternary cathode material, cathode and lithium ion battery
CN108565410B (en) Tin dioxide/graphene composite negative electrode material of lithium ion battery and preparation method thereof
WO2024000814A1 (en) Preparation method for positive electrode active material and use thereof
CN114843483B (en) Hard carbon composite material and preparation method and application thereof
CN115566264A (en) Hollow nano-sphere-based composite solid electrolyte of lithium battery and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23790850

Country of ref document: EP

Kind code of ref document: A1