WO2022193784A1 - Method for modifying lithium battery negative electrode material graphite, and modified graphite - Google Patents

Method for modifying lithium battery negative electrode material graphite, and modified graphite Download PDF

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WO2022193784A1
WO2022193784A1 PCT/CN2021/142807 CN2021142807W WO2022193784A1 WO 2022193784 A1 WO2022193784 A1 WO 2022193784A1 CN 2021142807 W CN2021142807 W CN 2021142807W WO 2022193784 A1 WO2022193784 A1 WO 2022193784A1
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graphite
negative electrode
modified
electrode material
reaction
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PCT/CN2021/142807
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French (fr)
Chinese (zh)
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余海军
谢英豪
李长东
张学梅
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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 HU2200280A priority Critical patent/HUP2200280A1/en
Publication of WO2022193784A1 publication Critical patent/WO2022193784A1/en

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/027—Negative 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 battery materials, and in particular relates to a method for modifying graphite as a negative electrode material for lithium batteries and modified graphite.
  • Graphite material has many advantages such as low electrode potential, high specific capacity, abundant reserves, low price, and low environmental pollution, so it has also developed into an ideal choice for negative electrode materials for lithium-ion batteries.
  • negative electrode materials for lithium-ion batteries.
  • there are shortcomings such as poor cycle performance and low capacity retention. This is mainly because it is difficult for lithium ions to diffuse between the graphite layers, and there are many active points on the graphite surface. The existence of these active points also makes the surface of the graphite extremely prone to side reactions, resulting in the peeling off of the graphite sheets, resulting in a decrease in its reversible capacity and cycling. Performance drops.
  • 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 modifying graphite of a lithium battery negative electrode material and modified graphite.
  • the modification method adopts a chemical modification method to modify the graphite negative electrode material, and has the advantages that the modified film layer is stable and not easy to fall off. .
  • the electrochemical properties of the anode can be improved from the material properties, thereby improving the performance and stability of the overall battery.
  • the present invention adopts the following technical solutions:
  • a method for modifying lithium battery anode material graphite comprising the following steps:
  • step (3) mixing the pre-modified graphite material and modifier, heating to react, adding the reaction product into hot water to dissolve and stir, and then performing suction filtration to obtain modified graphite; in step (3), the described
  • the modifier is o-phenylenediamine.
  • the mass ratio of the graphite negative electrode material and phthalic anhydride is (1-2): (1-2).
  • the temperature of the heating reaction is 100°C-200°C, and the time of the heating reaction is 20-40 hours.
  • the heating reaction is carried out under anhydrous and oxygen-free conditions.
  • the liquid-solid ratio of the alcohol to phthalic anhydride is (1-5): 1L/kg.
  • the alcohol is one of ethanol, methanol, propanol or butanol.
  • the reaction time is 10-30 min.
  • the mass ratio of the o-phenylenediamine to phthalic anhydride is (1-1.2):1.
  • the mixed reaction modification of phthalic anhydride and the negative electrode material is by inserting phthalic anhydride into the graphite layer, so that the phthalic anhydride and the negative electrode material are closely combined.
  • the negative electrode material modified by phthalic anhydride reacts with o-phenylenediamine to form polyimide on the surface of the negative electrode material, and a uniform and thin modified film layer is formed to coat the surface of the negative electrode material. Because the polyimide material has high and low temperature resistance, excellent mechanical properties, oxidation resistance, and small thermal expansion coefficient, by chemically modifying the graphite anode material itself, the electrochemical properties of the anode can be improved from the material characteristics, thereby Improve overall battery performance and stability.
  • the heating temperature is 50°C-100°C, and the heating time is 10-30 hours.
  • the temperature of the hot water is 60°C-100°C.
  • a modified graphite is prepared by the above method, the modified graphite comprises graphite and a modified film layer formed on the surface thereof, the thickness of the modified film layer is 2-20 nm; the ratio of the modified graphite is 2-20 nm.
  • the surface area is 1.0-1.8 m 2 ⁇ g -1 .
  • the treatment process adopted in the present invention is simple, and phthalic anhydride is used to modify the graphite.
  • the treatment steps are few, the reaction raw materials are cheap and easy to obtain, and the modification treatment of the negative electrode graphite material has important application value. It meets the needs of industrial applications in the actual production process and is suitable for large-scale production applications.
  • the present invention adopts the chemical modification method to modify the graphite negative electrode material, and has the advantage that the modified film layer is stable and not easy to fall off.
  • the mixed reaction modification of phthalic anhydride and the negative electrode material is made by inserting phthalic anhydride into the graphite layers, so that phthalic anhydride and the negative electrode material are modified.
  • the negative electrode material modified by phthalic anhydride reacts with o-phenylenediamine to form polyimide on the surface of the negative electrode material, forming a uniform and thin modified film layer covering the surface of the negative electrode material,
  • the electrochemical properties of the negative electrode can be improved from the material properties, thereby improving the performance and stability of the overall battery.
  • the modification method adopted in the present invention can form a uniform and thin modified film layer on the surface of the graphite negative electrode. greater impact.
  • FIG. 1 is a SEM image of the modified graphite of Example 1 of the present invention.
  • step (2) adding ethanol to the mixture in step (1) to remove unreacted organic raw materials, and then performing suction filtration to separate solid-liquid to prepare a pre-modified graphite material;
  • step (3) (4) adding the reaction product of step (3) into hot water at 75° C., fully dissolving and stirring, and then performing suction filtration. After solid-liquid separation, remove the unreacted organic raw materials in step (3) to obtain modified graphite negative electrode material.
  • FIG. 1 is an SEM image of the modified graphite in Example 1 of the present invention. It can be seen from FIG. 1 that the modification method adopted in the present invention can form a uniform and thin modified film layer on the surface of the graphite negative electrode.
  • step (2) ethanol is added to the mixture of step (1) to remove unreacted organic raw materials, and suction filtration is performed to separate solid-liquid to obtain pre-modified graphite material;
  • step (3) (4) adding the reaction product of step (3) into hot water at 70° C., fully dissolving and stirring, and then performing suction filtration. After solid-liquid separation, remove the unreacted organic raw materials in step (3) to obtain modified graphite negative electrode material.
  • step (2) adding ethanol to the mixture in step (1) to remove unreacted organic raw materials, and performing suction filtration to separate solid-liquid to prepare a pre-modified graphite material;
  • step (3) (4) adding the reaction product of step (3) into hot water at 100° C., fully dissolving and stirring, and then performing suction filtration. After solid-liquid separation, remove the unreacted organic raw materials in step (3) to obtain modified graphite negative electrode material.
  • the method of PVA physical coating modified graphite negative electrode material of this comparative example comprises the following steps:
  • the modification method of the lithium battery anode material graphite of this comparative example includes the following specific steps:
  • step (2) adding ethanol to the mixture in step (1) to remove unreacted organic raw materials, and then performing suction filtration to separate solid-liquid to prepare a pre-modified graphite material;
  • step (3) (4) adding the reaction product of step (3) into hot water at 75° C., fully dissolving and stirring, and then performing suction filtration. After solid-liquid separation, remove the unreacted organic raw materials in step (3) to obtain modified graphite negative electrode material.
  • Table 1 shows that the modified graphite anode materials prepared in Examples 1, 2, 3 and Comparative Example 1 are applied to lithium ion batteries, and the electrochemical performance parameters of the batteries are obtained by testing. The specific data are tested by equipment such as electrochemical workstations. get. It can be seen from Table 1 that when the graphite anode material prepared in the example is used in a battery, the electrochemical performance of the battery is obviously better than that of the comparative example 1, especially the example 2.

Abstract

Provided is a method for modifying lithium battery negative electrode material graphite, the method comprising the following steps: taking a graphite negative electrode material and phthalic anhydride, and mixing and heating same for a reaction to obtain a mixture; adding an alcohol to the mixture for a reaction, and performing suction filtration to obtain a pre-modified graphite material; and mixing the pre-modified graphite material with a modifier, then heating same for a reaction, adding hot water, dissolving and stirring same, and performing suction filtration to obtain the modified graphite, wherein the modifier is o-phenylenediamine. The modification treatment of graphite using phthalic anhydride has few treatment steps, the reaction raw materials are cheap and readily available, and the modification treatment on the negative electrode graphite material has important application value. The present invention is more suitable for industrial application requirements in practical production processes and suitable for large-scale production applications.

Description

一种锂电池负极材料石墨的改性方法及改性石墨A kind of modification method of lithium battery anode material graphite and modified graphite 技术领域technical field
本发明属于锂电池材料技术领域，具体涉及一种锂电池负极材料石墨的改性方法及改性石墨。The invention belongs to the technical field of lithium battery materials, and in particular relates to a method for modifying graphite as a negative electrode material for lithium batteries and modified graphite.
背景技术Background technique
石墨材料具有电极电势低、比容量高、储量丰富、价格低廉、环境污染小等诸多优势，因此也发展成为锂离子电池用负极材料的理想选择。但是，天然石墨用作电池负极材料时，存在循环性能差、容量保持率低等短板。这主要是由于锂离子难以在石墨层间扩散，且石墨表面有许多活性点，这些活性点的存在也导致石墨表面极易发生副反应，从而导致石墨片层脱落，导致其可逆容量降低，循环性能下降。Graphite material has many advantages such as low electrode potential, high specific capacity, abundant reserves, low price, and low environmental pollution, so it has also developed into an ideal choice for negative electrode materials for lithium-ion batteries. However, when natural graphite is used as a negative electrode material for batteries, there are shortcomings such as poor cycle performance and low capacity retention. This is mainly because it is difficult for lithium ions to diffuse between the graphite layers, and there are many active points on the graphite surface. The existence of these active points also makes the surface of the graphite extremely prone to side reactions, resulting in the peeling off of the graphite sheets, resulting in a decrease in its reversible capacity and cycling. Performance drops.
研究发现，对负极材料进行改性处理可以显著改善提高锂离子电池的电化学性能，同时能够增强电池稳定性，通过一些物理或化学的方法对负极石墨材料进行改性或包覆是一种行之有效的策略。The study found that the modification of the negative electrode material can significantly improve the electrochemical performance of lithium-ion batteries, and at the same time can enhance the battery stability. an effective strategy.
截止目前，已经有相当多对负极石墨材料进行改性或包覆从而提高电池可逆容量、增强容量保持率、提升电池稳定性的方案被提出并采纳。但目前的改性剂一是价格昂贵，二是并没有完全从材料特性上改良负极的电化学性质，导致整体电池的性能及稳定性提升不高。Up to now, quite a number of schemes for modifying or coating anode graphite materials to improve battery reversible capacity, enhance capacity retention rate, and improve battery stability have been proposed and adopted. However, the current modifier is expensive, and the electrochemical properties of the negative electrode are not completely improved from the material properties, resulting in a low improvement in the performance and stability of the overall battery.
发明内容SUMMARY 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，本发明提出一种锂电池负极材料石墨的改性方法及改性石墨，该改性方法采用化学改性法对石墨负极材料进行改性处理，具有改性膜层稳定不易脱落的优点。同时，由于对石墨负极材料本身进行了化学改性，可以从材料特性上改良负极的电化学性质，从而提升整体电池的性能及稳定性。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 modifying graphite of a lithium battery negative electrode material and modified graphite. The modification method adopts a chemical modification method to modify the graphite negative electrode material, and has the advantages that the modified film layer is stable and not easy to fall off. . At the same time, due to the chemical modification of the graphite anode material itself, the electrochemical properties of the anode can be improved from the material properties, thereby improving the performance and stability of the overall battery.
为实现上述目的，本发明采用以下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种锂电池负极材料石墨的改性方法，包括以下步骤：A method for modifying lithium battery anode material graphite, comprising the following steps:
(1)取石墨负极材料和邻苯二甲酸酐混合，加热反应，得到混合物；(1) get graphite negative electrode material and phthalic anhydride and mix, heating reaction, obtain mixture;
(2)将醇加入所述混合物中反应，并进行抽滤，得到预改性石墨材料；(2) adding alcohol to the mixture to react, and performing suction filtration to obtain a pre-modified graphite material;
(3)将所述预改性石墨材料与改性剂混合，加热进行反应，反应的产物加入热水中溶解搅拌，再进行抽滤，即得改性石墨；步骤(3)中，所述改性剂为邻苯二胺。(3) mixing the pre-modified graphite material and modifier, heating to react, adding the reaction product into hot water to dissolve and stir, and then performing suction filtration to obtain modified graphite; in step (3), the described The modifier is o-phenylenediamine.
优选地，步骤(1)中，所述石墨负极材料和邻苯二甲酸酐的质量比为(1-2)：(1-2)。Preferably, in step (1), the mass ratio of the graphite negative electrode material and phthalic anhydride is (1-2): (1-2).
优选地，步骤(1)中，所述加热反应的温度为100℃-200℃，加热反应的时间为20-40小时。Preferably, in step (1), the temperature of the heating reaction is 100°C-200°C, and the time of the heating reaction is 20-40 hours.
优选地，步骤(1)中，所述加热反应的过程中是在无水无氧的条件下进行的。Preferably, in step (1), the heating reaction is carried out under anhydrous and oxygen-free conditions.
优选地，步骤(2)中，所述醇与邻苯二甲酸酐的液固比为(1-5)：1L/kg。Preferably, in step (2), the liquid-solid ratio of the alcohol to phthalic anhydride is (1-5): 1L/kg.
优选地，步骤(2)中，所述所述醇为乙醇、甲醇、丙醇或丁醇中的一种。Preferably, in step (2), the alcohol is one of ethanol, methanol, propanol or butanol.
优选地，步骤(2)中，所述反应的时间为10-30min。Preferably, in step (2), the reaction time is 10-30 min.
优选地，所述邻苯二胺与邻苯二甲酸酐的质量比为(1-1.2)：1。Preferably, the mass ratio of the o-phenylenediamine to phthalic anhydride is (1-1.2):1.
邻苯二甲酸酐与负极材料混合反应改性是通过使是邻苯二甲酸酐***到石墨层间，使邻苯二甲酸酐与负极材料紧密结合。经邻苯二甲酸酐改性的负极材料与邻苯二胺反应，在负极材料的表面形成聚酰亚胺，形成一层均匀且薄的改性膜层包覆在负极材料表面。由于聚酰亚胺材料具有耐高低温、优良的机械性能、抗氧化性、小的热膨胀系数，通过对石墨负极材料本身进行了化学改性，可以从材料特性上改良负极的电化学性质，从而提升整体电池的性能及稳定性。The mixed reaction modification of phthalic anhydride and the negative electrode material is by inserting phthalic anhydride into the graphite layer, so that the phthalic anhydride and the negative electrode material are closely combined. The negative electrode material modified by phthalic anhydride reacts with o-phenylenediamine to form polyimide on the surface of the negative electrode material, and a uniform and thin modified film layer is formed to coat the surface of the negative electrode material. Because the polyimide material has high and low temperature resistance, excellent mechanical properties, oxidation resistance, and small thermal expansion coefficient, by chemically modifying the graphite anode material itself, the electrochemical properties of the anode can be improved from the material characteristics, thereby Improve overall battery performance and stability.
优选地，步骤(3)中，所述加热的温度为50℃-100℃，加热的时间为10-30小时。Preferably, in step (3), the heating temperature is 50°C-100°C, and the heating time is 10-30 hours.
优选地，步骤(3)中，所述热水的温度为60℃-100℃。Preferably, in step (3), the temperature of the hot water is 60°C-100°C.
一种改性石墨，是由上述方法制得，所述改性石墨包括石墨及其表面形成的改性膜层，所述改性膜层的厚度为2-20nm；所述改性石墨的比表面积为1.0-1.8m 2·g -1。 A modified graphite is prepared by the above method, the modified graphite comprises graphite and a modified film layer formed on the surface thereof, the thickness of the modified film layer is 2-20 nm; the ratio of the modified graphite is 2-20 nm. The surface area is 1.0-1.8 m 2 ·g -1 .
相对于现有技术，本发明的有益效果如下：With respect to the prior art, the beneficial effects of the present invention are as follows:
1.本发明采用的处理工艺简单，采用邻苯二甲酸酐来对石墨进行改性处理，处理步骤少，反应原料廉价易得，对负极石墨材料进行改性处理具有重要的应用价值，更贴合实际生产过程中的工业化应用需求，适合大规模生产应用。1. The treatment process adopted in the present invention is simple, and phthalic anhydride is used to modify the graphite. The treatment steps are few, the reaction raw materials are cheap and easy to obtain, and the modification treatment of the negative electrode graphite material has important application value. It meets the needs of industrial applications in the actual production process and is suitable for large-scale production applications.
2.本发明采用化学改性法对石墨负极材料进行改性处理，具有改性膜层稳定不易脱落的优点。同时，由于对石墨负极材料本身进行了化学改性，邻苯二甲酸酐与负极材 料混合反应改性是通过使是邻苯二甲酸酐***到石墨层间，使邻苯二甲酸酐与负极材料紧密结合，经邻苯二甲酸酐改性的负极材料与邻苯二胺反应，在负极材料的表面形成聚酰亚胺，形成一层均匀且薄的改性膜层包覆在负极材料表面，可以从材料特性上改良负极的电化学性质，从而提升整体电池的性能及稳定性。2. The present invention adopts the chemical modification method to modify the graphite negative electrode material, and has the advantage that the modified film layer is stable and not easy to fall off. At the same time, due to the chemical modification of the graphite negative electrode material itself, the mixed reaction modification of phthalic anhydride and the negative electrode material is made by inserting phthalic anhydride into the graphite layers, so that phthalic anhydride and the negative electrode material are modified. Closely combined, the negative electrode material modified by phthalic anhydride reacts with o-phenylenediamine to form polyimide on the surface of the negative electrode material, forming a uniform and thin modified film layer covering the surface of the negative electrode material, The electrochemical properties of the negative electrode can be improved from the material properties, thereby improving the performance and stability of the overall battery.
3.本发明采用的改性方法可以在石墨负极表面形成一层均匀且薄的改性膜层，膜层的厚度为2-20nm，反应物用量少且不会对负极石墨材料本身特性产生较大影响。3. The modification method adopted in the present invention can form a uniform and thin modified film layer on the surface of the graphite negative electrode. greater impact.
附图说明Description of 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 embodiments, wherein:
图1为本发明的实施例1的改性石墨的SEM图。FIG. 1 is a SEM image of the modified graphite of 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, characteristics and effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative efforts are all within the scope of The scope of protection of the present invention.
实施例1Example 1
本实施例的锂电池负极材料石墨的改性方法，包括以下具体步骤：The modification method of the lithium battery negative electrode material graphite of the present embodiment comprises the following specific steps:
(1)取适量石墨负极材料与邻苯二甲酸酐以质量比1:2混合，并将反应物在无水无氧条件下加热反应，反应温度控制在100℃，反应20小时直至充分反应，得到混合物；(1) Mix an appropriate amount of graphite negative electrode material and phthalic anhydride in a mass ratio of 1:2, and heat the reactant under anhydrous and oxygen-free conditions, the reaction temperature is controlled at 100 ° C, and the reaction is performed for 20 hours until fully reacted, get a mixture;
(2)将乙醇加入步骤(1)混合物中除去未反应完全的有机原料，再进行抽滤，使得固液分离，制备得到预改性石墨材料；(2) adding ethanol to the mixture in step (1) to remove unreacted organic raw materials, and then performing suction filtration to separate solid-liquid to prepare a pre-modified graphite material;
(3)将预改性石墨材料与改性剂邻苯二胺混合均匀，并在50℃区间范围内加热进行反应，反应10小时直至反应充分；(3) Mixing the pre-modified graphite material and the modifier o-phenylenediamine evenly, and heating in the range of 50°C for reaction, and reacting for 10 hours until the reaction is sufficient;
(4)将步骤(3)反应的产物加入75℃的热水中，充分溶解搅拌后进行抽滤，固液分离后，除去步骤(3)中未反应完全的有机原料，即得改性石墨负极材料。(4) adding the reaction product of step (3) into hot water at 75° C., fully dissolving and stirring, and then performing suction filtration. After solid-liquid separation, remove the unreacted organic raw materials in step (3) to obtain modified graphite negative electrode material.
图1为本发明的实施例1的改性石墨的SEM图，从图1中可以看出，本发明采用的改性方法可以在石墨负极表面形成均匀且薄的改性膜层。FIG. 1 is an SEM image of the modified graphite in Example 1 of the present invention. It can be seen from FIG. 1 that the modification method adopted in the present invention can form a uniform and thin modified film layer on the surface of the graphite negative electrode.
实施例2Example 2
本实施例的锂电池负极材料石墨的改性方法，包括以下具体步骤：The modification method of the lithium battery negative electrode material graphite of the present embodiment comprises the following specific steps:
(1)取石墨负极材料与邻苯二甲酸酐以质量比为1:1混合，并将反应物在无水无氧条件下加热反应，反应温度控制在150℃区间范围内，反应30小时直至充分反应，得到混合物；(1) get the graphite negative electrode material and phthalic anhydride to mix with the mass ratio of 1:1, and the reactant is heated and reacted under anhydrous and oxygen-free conditions, the reaction temperature is controlled within the range of 150 ° C, and the reaction is performed for 30 hours until Fully react to obtain a mixture;
(2)将乙醇加入步骤(1)混合物中除去未反应完全的有机原料，并进行抽滤，使得固液分离，得到预改性石墨材料；(2) ethanol is added to the mixture of step (1) to remove unreacted organic raw materials, and suction filtration is performed to separate solid-liquid to obtain pre-modified graphite material;
(3)将预改性石墨材料与邻苯二胺混合均匀，并在75℃区间范围内加热进行反应，反应20小时直至反应充分；(3) Mixing the pre-modified graphite material and o-phenylenediamine evenly, and heating in the range of 75°C for reaction, and reacting for 20 hours until the reaction is sufficient;
(4)将步骤(3)反应的产物加入70℃的热水中，充分溶解搅拌后进行抽滤，固液分离后，除去步骤(3)中未反应完全的有机原料，即得改性石墨负极材料。(4) adding the reaction product of step (3) into hot water at 70° C., fully dissolving and stirring, and then performing suction filtration. After solid-liquid separation, remove the unreacted organic raw materials in step (3) to obtain modified graphite negative electrode material.
实施例3Example 3
本实施例的锂电池负极材料石墨的改性方法，包括以下具体步骤：The modification method of the lithium battery negative electrode material graphite of the present embodiment comprises the following specific steps:
(1)取适量石墨负极材料与邻苯二甲酸酐以质量比为2:1混合，并将反应物在无水无氧条件下加热反应，反应温度控制在200℃，反应40小时直至充分反应，得到混合物；(1) Mix an appropriate amount of graphite anode material and phthalic anhydride in a mass ratio of 2:1, and heat the reactant under anhydrous and oxygen-free conditions, and the reaction temperature is controlled at 200 ° C, and the reaction is performed for 40 hours until fully reacted , to get a mixture;
(2)将乙醇加入步骤(1)混合物中除去未反应完全的有机原料，并进行抽滤，使得固液分离，制备得到预改性石墨材料；(2) adding ethanol to the mixture in step (1) to remove unreacted organic raw materials, and performing suction filtration to separate solid-liquid to prepare a pre-modified graphite material;
(3)将预改性石墨材料与改性剂邻苯二胺混合均匀，并在100℃区间范围内加热进行反应，反应30小时直至反应充分；(3) Mixing the pre-modified graphite material and the modifier o-phenylenediamine evenly, and heating in the range of 100 ° C to carry out the reaction, and reacting for 30 hours until the reaction is sufficient;
(4)将步骤(3)反应的产物加入100℃的热水中，充分溶解搅拌后进行抽滤，固液分离后，除去步骤(3)中未反应完全的有机原料，即得改性石墨负极材料。(4) adding the reaction product of step (3) into hot water at 100° C., fully dissolving and stirring, and then performing suction filtration. After solid-liquid separation, remove the unreacted organic raw materials in step (3) to obtain modified graphite negative electrode material.
对比例1Comparative Example 1
本对比例的PVA物理包覆改性的石墨负极材料的方法，包括以下步骤：The method of PVA physical coating modified graphite negative electrode material of this comparative example comprises the following steps:
(1)取适量PVA材料，溶于去离子水中，得到PVA水溶液；(1) Take an appropriate amount of PVA material and dissolve it in deionized water to obtain an aqueous PVA solution;
(2)将石墨负极材料与PVA水溶液搅拌混合，并放置于球磨机中进行球磨处理，完成后干燥处理，即得PVA物理包覆改性的石墨负极材料。(2) stirring and mixing the graphite negative electrode material and the PVA aqueous solution, placing it in a ball mill for ball milling treatment, and completing the post-drying treatment to obtain a PVA physical coating modified graphite negative electrode material.
对比例1是以石墨负极材料和聚乙烯醇(PVA)为原料，采用浸渍法进行物理包覆。In Comparative Example 1, the graphite negative electrode material and polyvinyl alcohol (PVA) were used as raw materials, and the physical coating was carried out by the impregnation method.
对比例2Comparative Example 2
本对比例的锂电池负极材料石墨的改性方法，包括以下具体步骤：The modification method of the lithium battery anode material graphite of this comparative example includes the following specific steps:
(1)取适量石墨负极材料与邻苯二甲酸酐以质量比1:2混合，并将反应物在无水无 氧条件下加热反应，反应温度控制在100℃，反应20小时直至充分反应，得到混合物；(1) Mix an appropriate amount of graphite negative electrode material and phthalic anhydride in a mass ratio of 1:2, and heat the reactant under anhydrous and oxygen-free conditions, the reaction temperature is controlled at 100 ° C, and the reaction is performed for 20 hours until fully reacted, get a mixture;
(2)将乙醇加入步骤(1)混合物中除去未反应完全的有机原料，再进行抽滤，使得固液分离，制备得到预改性石墨材料；(2) adding ethanol to the mixture in step (1) to remove unreacted organic raw materials, and then performing suction filtration to separate solid-liquid to prepare a pre-modified graphite material;
(3)将预改性石墨材料与十二碳二胺混合均匀，并在50℃区间范围内加热进行反应，反应10小时直至反应充分；(3) mixing the pre-modified graphite material and dodecanediamine evenly, and heating in the range of 50°C for reaction, and reacting for 10 hours until the reaction is sufficient;
(4)将步骤(3)反应的产物加入75℃的热水中，充分溶解搅拌后进行抽滤，固液分离后，除去步骤(3)中未反应完全的有机原料，即得改性石墨负极材料。(4) adding the reaction product of step (3) into hot water at 75° C., fully dissolving and stirring, and then performing suction filtration. After solid-liquid separation, remove the unreacted organic raw materials in step (3) to obtain modified graphite negative electrode material.
电化学性能：Electrochemical properties:
表1为将实施例1、2、3与对比例1制备得到改性后的石墨负极材料应用于锂离子电池中，测试得到电池的电化学性能参数，具体数据是通过电化学工作站等设备测试得到。由表1可知，实施例中制备得到的石墨负极材料在应用于电池中时，电池的电化学性能明显比对比例1要好，特别是实施例2。Table 1 shows that the modified graphite anode materials prepared in Examples 1, 2, 3 and Comparative Example 1 are applied to lithium ion batteries, and the electrochemical performance parameters of the batteries are obtained by testing. The specific data are tested by equipment such as electrochemical workstations. get. It can be seen from Table 1 that when the graphite anode material prepared in the example is used in a battery, the electrochemical performance of the battery is obviously better than that of the comparative example 1, especially the example 2.
表1改性后的石墨负极材料应用于锂离子电池中电池的电化学性能对比Table 1 Comparison of electrochemical performance of modified graphite anode materials used in lithium-ion batteries
Figure PCTCN2021142807-appb-000001
Figure PCTCN2021142807-appb-000001
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 in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned embodiments, and within the scope of knowledge possessed by those of ordinary skill in the art, various Variety. Furthermore, the embodiments of the present invention and features in the embodiments may be combined with each other without conflict.

Claims (10)

  1. 一种锂电池负极材料石墨的改性方法，其特征在于，包括以下步骤：A method for modifying lithium battery negative electrode material graphite, characterized in that it comprises the following steps:
    (1)取石墨负极材料和邻苯二甲酸酐混合，加热反应，得到混合物；(1) get graphite negative electrode material and phthalic anhydride and mix, heating reaction, obtain mixture;
    (2)将醇加入所述混合物中反应，并进行抽滤，得到预改性石墨材料；(2) adding alcohol to the mixture to react, and performing suction filtration to obtain a pre-modified graphite material;
    (3)将所述预改性石墨材料与改性剂混合，加热进行反应后，反应的产物加入热水中溶解搅拌，再进行抽滤，即得改性石墨；步骤(3)中，所述改性剂为邻苯二胺。(3) mixing the pre-modified graphite material with the modifier, heating and reacting, adding the reaction product into hot water to dissolve and stir, and then performing suction filtration to obtain modified graphite; in step (3), the The modifier is o-phenylenediamine.
  2. 根据权利要求1所述的改性方法，其特征在于，步骤(1)中，所述石墨负极材料和邻苯二甲酸酐的质量比为(1-2)：(1-2)。The modification method according to claim 1, wherein in step (1), the mass ratio of the graphite negative electrode material and phthalic anhydride is (1-2): (1-2).
  3. 根据权利要求1所述的改性方法，其特征在于，步骤(1)中，所述加热反应的温度为100℃-200℃，加热反应的时间为20-40小时。The modification method according to claim 1, wherein in step (1), the temperature of the heating reaction is 100°C-200°C, and the time of the heating reaction is 20-40 hours.
  4. 根据权利要求1所述的改性方法，其特征在于，步骤(1)中，所述加热反应的过程中是在无水无氧的条件下进行的。The modification method according to claim 1, characterized in that, in step (1), the heating reaction is carried out under anhydrous and oxygen-free conditions.
  5. 根据权利要求1所述的改性方法，其特征在于，步骤(2)中，所述醇与邻苯二甲酸酐的液固比为(1-5)：1L/kg。The modification method according to claim 1, wherein in step (2), the liquid-solid ratio of the alcohol to phthalic anhydride is (1-5): 1L/kg.
  6. 根据权利要求1所述的改性方法，其特征在于，步骤(2)中，所述醇为乙醇、甲醇、丙醇或丁醇中的一种。The modification method according to claim 1, wherein in step (2), the alcohol is one of ethanol, methanol, propanol or butanol.
  7. 根据权利要求1所述的改性方法，其特征在于，所述邻苯二胺与邻苯二甲酸酐的质量比为(1-1.2)：1。The modification method according to claim 1, wherein the mass ratio of the o-phenylenediamine to the phthalic anhydride is (1-1.2):1.
  8. 根据权利要求1所述的改性方法，其特征在于，步骤(3)中，所述加热的温度为50℃-100℃，加热的时间为10-30小时。The modification method according to claim 1, wherein in step (3), the heating temperature is 50°C-100°C, and the heating time is 10-30 hours.
  9. 根据权利要求1所述的改性方法，其特征在于，步骤(3)中，所述热水的温度为60℃-100℃。The modification method according to claim 1, wherein in step (3), the temperature of the hot water is 60°C-100°C.
  10. 一种改性石墨，其特征在于，是由权利要求1-9任一项所述的方法制得，所述改性石墨包括石墨及其表面形成的改性膜层，所述改性膜层的厚度为2-20nm；所述改性石墨的比表面积为1.0-1.8m 2·g -1。 A modified graphite, characterized in that it is prepared by the method of any one of claims 1-9, the modified graphite comprises a modified film layer formed on graphite and its surface, and the modified film layer The thickness of the modified graphite is 2-20 nm; the specific surface area of the modified graphite is 1.0-1.8 m 2 ·g -1 .
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