WO2022127046A1 - Preparation method for modified graphite electrode material - Google Patents

Preparation method for modified graphite electrode material Download PDF

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WO2022127046A1
WO2022127046A1 PCT/CN2021/098368 CN2021098368W WO2022127046A1 WO 2022127046 A1 WO2022127046 A1 WO 2022127046A1 CN 2021098368 W CN2021098368 W CN 2021098368W WO 2022127046 A1 WO2022127046 A1 WO 2022127046A1
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reactant
electrode material
graphite electrode
modified graphite
material according
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Chinese (zh)
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彭飞
仰永军
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广东凯金新能源科技股份有限公司
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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
    • 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
    • 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
    • H01M4/58—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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • 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 relates to the technical field of batteries, in particular to a preparation method of a modified graphite electrode material.
  • Electrochemical energy storage has high operating energy efficiency, controllable replay time and good cycle performance, and has become a hot spot in current new energy research.
  • Carbon materials especially heteroatom-doped carbon materials, have the characteristics of high specific surface area, high electrical conductivity, high thermal conductivity, etc.
  • the supercapacitors prepared with them have high specific capacitance, high current charge-discharge performance, high power density and long cycle life. It is one of the most important electrode materials in supercapacitors, with abundant resources, diverse structures and moderate cost.
  • traditional carbon materials often have problems such as small specific surface area, low mass specific capacitance, and low power density, which requires a series of process operations such as modification to improve their performance as electrode materials. Yun et al. (Journal of Power Sources 2014; 262(0):79-85) and Yan et al.
  • a method for preparing a modified graphite electrode material is provided.
  • the battery has a higher lithium ion storage capacity, and the distribution of sulfur element is uniform. There will be no precipitation of elemental sulfur particles.
  • a preparation method of modified graphite electrode material comprising the following preparation steps.
  • step S1 the mass concentration of the nitric acid solution is 1%, and the cationic polymer is one or a combination of two of aluminum hydroxy and zirconium hydroxy.
  • step S1 the mass ratio of the graphite to the cationic polymer is 1:0.01-0.1.
  • the ionic liquid is 1-butyl-3-methylimidazolium bromide or 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid.
  • step S2 the mass ratio of the first reactant and ionic liquid, carbon oxysulfide is 1: 0.01-0.1: 0.1-0.2.
  • the inert gas is nitrogen or argon.
  • step S3 the temperature of the carbonization treatment is 600°C-800°C, the pressure is 30 MPa-50 MPa, and the reaction time is 10h-20h.
  • step S4 the mass ratio of the third reactant to the conductive agent, anhydrous ethanol and the binder is 1:0.3-0.5:1-3:0.01-0.05.
  • the conductive agent is one of acetylene black, carbon nanotubes, nanocarbon fibers, and expanded graphite.
  • the binder is one of polyvinylidene fluoride, polyvinyl chloride polyvinyl alcohol, and sodium hydroxymethyl cellulose.
  • the hydroxyl group of the cationic polymer forms coordination in the graphite, and then in the ionic liquid, the uncoordinated hydroxyl group in the cationic polymer reacts with carbon oxysulfide to generate a sulfur-containing compound on the surface of the graphite, and then, Through the curing process and the carbonization process, the sulfur-containing element compound is fixed and uniformly distributed on the surface of the graphite, and the finally obtained modified graphite electrode material has good charge-discharge performance and cycle performance.
  • a preparation method of modified graphite electrode material comprising the following preparation steps.
  • the cationic polymer is hydroxyaluminum; the mass ratio of the graphite to the cationic polymer is 1:0.01; the ionic liquid is 1-butyl-3-methylimidazolium bromide; the first reactant and the ionic liquid, The mass ratio of carbon oxysulfide is 1: 0.01: 0.1; the conductive agent is acetylene black, the adhesive is polyvinylidene fluoride, and the mass ratio of the third reactant to the conductive agent, absolute ethanol, and the adhesive is 1: 0.3:1:0.01.
  • the obtained modified graphite electrode material is used as a negative electrode material for lithium ion batteries.
  • the discharge specific capacity is 856mAh/g, and the first charge-discharge efficiency is 88.9%.
  • the capacity retention rate is 91.3%, and no sulfur particles were precipitated during the charging and discharging process.
  • a preparation method of modified graphite electrode material comprising the following preparation steps.
  • the cationic polymer is hydroxyaluminum; the mass ratio of the graphite to the cationic polymer is 1:0.05; the ionic liquid is 1-butyl-3-methylimidazolium bromide; the first reactant and the ionic liquid, The mass ratio of carbon oxysulfide is 1: 0.01: 0.2; the conductive agent is acetylene black, the adhesive is polyvinylidene fluoride, and the mass ratio of the third reactant to the conductive agent, absolute ethanol, and the adhesive is 1: 0.3:1:0.01.
  • the obtained modified graphite electrode material is used as a negative electrode material for lithium-ion batteries.
  • the discharge specific capacity after the first charge-discharge cycle is 882mAh/g, and the first charge-discharge efficiency is 90.3%. 93.1%, and no sulfur particles were precipitated during the charging and discharging process.
  • a preparation method of modified graphite electrode material comprising the following preparation steps.
  • the cationic polymer is hydroxyaluminum; the mass ratio of the graphite to the cationic polymer is 1:0.1; the ionic liquid is 1-butyl-3-methylimidazolium bromide; the first reactant and the ionic liquid, The mass ratio of carbon oxysulfide is 1: 0.01: 0.2; the conductive agent is acetylene black, the adhesive is polyvinylidene fluoride, and the mass ratio of the third reactant to the conductive agent, absolute ethanol, and the adhesive is 1: 0.3:1:0.01.
  • the obtained modified graphite electrode material is used as a negative electrode material for lithium ion batteries.
  • the discharge specific capacity after the first charge-discharge cycle is 906mAh/g, and the first charge-discharge efficiency is 92.3%. After 100 cycles, the capacity retention rate is 92.7%, and no sulfur particles were precipitated during the charging and discharging process.
  • a preparation method of modified graphite electrode material comprising the following preparation steps.
  • the cationic polymer is hydroxyaluminum; the mass ratio of the graphite to the cationic polymer is 1:0.01; the ionic liquid is 1-butyl-3-methylimidazolium bromide; the first reactant and the ionic liquid, The mass ratio of carbon oxysulfide is 1: 0.01: 0.4; the conductive agent is acetylene black, the adhesive is polyvinylidene fluoride, and the mass ratio of the third reactant to the conductive agent, absolute ethanol, and the adhesive is 1: 0.3:1:0.01.
  • the obtained modified graphite electrode material is used as a negative electrode material for lithium ion batteries.
  • the discharge specific capacity after the first charge-discharge cycle is 610mAh/g, and the first charge-discharge efficiency is 68.9%. After 100 cycles, the capacity retention rate is 77.5%, and there will be sulfur elemental particles precipitated during the charging and discharging process.

Abstract

Disclosed is a preparation method for a modified graphite electrode material, comprising the following preparation steps: adding nitric acid solution into graphite, then adding a cationic polymer, and reacting in a constant temperature water bath while stirring to obtain a first reactant; sequentially introducing an ionic liquid and carbonyl sulfide into the first reactant to obtain a second reactant; washing the second reactant using deionized water, placing in a drying oven for curing treatment, ball milling using a ball mill, then placing the ball-milled powder in a high-temperature heating furnace for carbonization treatment to obtain a third reactant; mixing the third reactant and a conductive agent, grinding, then dispersing in anhydrous ethanol, adding an adhesive and potassium oxalate, stirring evenly, drying, and pelleting to obtain a modified graphite electrode material. The modified graphite electrode material obtained in the present invention has good charge and discharge performance and cycle performance.

Description

一种改性石墨电极材料的制备方法A kind of preparation method of modified graphite electrode material
相关申请的交叉引用。CROSS-REFERENCE TO RELATED APPLICATIONS.
本申请要求于2020年12月15日提交中国专利局，申请号为202011477581.X，发明名称为“一种改性石墨电极材料的制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed on December 15, 2020 with the application number 202011477581.X and the invention titled "A method for preparing a modified graphite electrode material", the entire contents of which are by reference Incorporated in this application.
技术领域technical field
本发明涉及电池技术领域，尤其涉及一种改性石墨电极材料的制备方法。The invention relates to the technical field of batteries, in particular to a preparation method of a modified graphite electrode material.
背景技术Background technique
随着全球能源使用量的日益增长，化石燃料等不可再生的能源日益枯竭，并且会对环境造成严重的污染，因此迫切需要人们去开发氢能、风能、核能、地热能、太阳能等可再生新能源，但是这些新能源均存在供应间歇性，不易控制等问题，在使用这些新能源之前需要解决的问题是将其储存后再集中释放利用，因此需要建设大规模的储能***。电化学储能运行能量效率高，并且重放时间可控制，循环性能好，已经成为目前新能源研究的热点。With the increasing use of global energy, non-renewable energy sources such as fossil fuels are increasingly exhausted, and will cause serious pollution to the environment. Therefore, it is urgent to develop renewable energy such as hydrogen, wind, nuclear, geothermal, and solar energy. However, these new energies all have problems such as intermittent supply and difficult control. The problem that needs to be solved before using these new energies is to store them and then release them centrally. Therefore, a large-scale energy storage system needs to be built. Electrochemical energy storage has high operating energy efficiency, controllable replay time and good cycle performance, and has become a hot spot in current new energy research.
技术问题technical problem
碳材料特别是杂原子掺杂的碳材料具有高比表面积、高导电率、高导热率等特性，用其制备的超级电容器具有比电容高、大电流充放电性能、大功率密度和循环寿命长等特性，且资源丰富、结构多样、成本适中，是超级电容器中最为重要的电极材料之一。然而，传统的碳材料往往存在比表面积小，质量比电容低，功率密度小等问题，这就需要通过对其进行改性等一系列工艺操作达到提高其作为电极材料性能的目的。Yun等人(Journal of Power Sources2014；262(0):79-85)和Yan等人(Chemical Communications 2012；48(86):10663-10665)的报道均表明硫掺杂的碳材料比未掺杂的碳材料具有更高的锂离子存储容量。但传统技术中，由于硫元素含量过高并且硫的分布不均一，在充放电过程中会有硫单质颗粒析出，从而不利于电池能量密度的提高。Carbon materials, especially heteroatom-doped carbon materials, have the characteristics of high specific surface area, high electrical conductivity, high thermal conductivity, etc. The supercapacitors prepared with them have high specific capacitance, high current charge-discharge performance, high power density and long cycle life. It is one of the most important electrode materials in supercapacitors, with abundant resources, diverse structures and moderate cost. However, traditional carbon materials often have problems such as small specific surface area, low mass specific capacitance, and low power density, which requires a series of process operations such as modification to improve their performance as electrode materials. Yun et al. (Journal of Power Sources 2014; 262(0):79-85) and Yan et al. (Chemical Communications 2012; 48(86):10663-10665) both showed that sulfur-doped carbon materials are more efficient than undoped carbon materials The carbon material has a higher lithium-ion storage capacity. However, in the traditional technology, due to the high content of sulfur and the uneven distribution of sulfur, elemental sulfur particles will be precipitated during the charging and discharging process, which is not conducive to the improvement of the energy density of the battery.
技术解决方案technical solutions
根据本申请的各种实施例，提供一种改性石墨电极材料的制备方法，其通过掺杂硫元素，使电池具有更高的锂离子存储容量，并且硫元素的分布均一，在充放电过程中不会有硫单质颗粒析出。According to various embodiments of the present application, a method for preparing a modified graphite electrode material is provided. By doping sulfur element, the battery has a higher lithium ion storage capacity, and the distribution of sulfur element is uniform. There will be no precipitation of elemental sulfur particles.
一种改性石墨电极材料的制备方法，包括如下制备步骤。A preparation method of modified graphite electrode material, comprising the following preparation steps.
S1：向石墨中加入硝酸溶液，调节pH至4-6，再加入阳离子聚合物，在100℃-120℃下，恒温水浴搅拌反应，得到第一反应物。S1: adding a nitric acid solution to the graphite, adjusting the pH to 4-6, then adding a cationic polymer, and stirring the reaction in a constant temperature water bath at 100°C-120°C to obtain the first reactant.
S2：向第一反应物中依次通入离子液体、氧硫化碳，在100℃-150℃下，反应0.5 h -2h，得到第二反应物。S2: The ionic liquid and carbon oxysulfide are sequentially introduced into the first reactant, and the reaction is carried out at 100° C. to 150° C. for 0.5 h to 2 h to obtain the second reactant.
S3：将第二反应物用去离子水进行洗涤，然后放入220℃-300℃的干燥箱中固化处理10h-15h，再用球磨机球磨2h-3h，使球磨后的粉体粒径小于2µm，接着，在惰性气体的保护下，将球磨后的粉体置于高温加热炉中，进行碳化处理，得到第三反应物。S3: Wash the second reactant with deionized water, then put it into a drying oven at 220°C-300°C for curing for 10h-15h, and then use a ball mill for 2h-3h, so that the particle size of the powder after ball milling is less than 2µm and then, under the protection of an inert gas, the ball-milled powder is placed in a high-temperature heating furnace for carbonization to obtain a third reactant.
S4：将第三反应物和导电剂混合后，进行研磨，再分散于无水乙醇中，加入粘合剂和草酸钾，搅拌均匀，干燥，压片，即得改性石墨电极材料。S4: After mixing the third reactant and the conductive agent, grind, disperse in absolute ethanol, add a binder and potassium oxalate, stir evenly, dry, and press to obtain a modified graphite electrode material.
进一步地，在步骤S1中，硝酸溶液的质量浓度为1%，阳离子聚合物为羟基铝、羟基锆中的一种或者两种组合。Further, in step S1, the mass concentration of the nitric acid solution is 1%, and the cationic polymer is one or a combination of two of aluminum hydroxy and zirconium hydroxy.
进一步地，在步骤S1中，所述石墨与所述阳离子聚合物的质量比为1:0.01-0.1。Further, in step S1, the mass ratio of the graphite to the cationic polymer is 1:0.01-0.1.
进一步地，在步骤S2中，所述离子液体为1-丁基-3-甲基咪唑溴盐或者1-丁基-3-甲基咪唑六氟磷酸离子液体。Further, in step S2, the ionic liquid is 1-butyl-3-methylimidazolium bromide or 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid.
进一步地，在步骤S2中，第一反应物与离子液体、氧硫化碳的质量比为1: 0.01-0.1: 0.1-0.2。Further, in step S2, the mass ratio of the first reactant and ionic liquid, carbon oxysulfide is 1: 0.01-0.1: 0.1-0.2.
进一步地，在步骤S3中，惰性气体为氮气或氩气。Further, in step S3, the inert gas is nitrogen or argon.
进一步地，在步骤S3中，碳化处理的温度为600℃-800℃，压力为30 MPa -50MPa，反应时间为10h-20h。Further, in step S3, the temperature of the carbonization treatment is 600°C-800°C, the pressure is 30 MPa-50 MPa, and the reaction time is 10h-20h.
进一步地，步骤S4中，第三反应物与导电剂、无水乙醇、粘合剂的质量比为1:0.3-0.5:1-3:0.01-0.05。Further, in step S4, the mass ratio of the third reactant to the conductive agent, anhydrous ethanol and the binder is 1:0.3-0.5:1-3:0.01-0.05.
进一步地，所述导电剂为乙炔黑、碳纳米管、纳米碳纤维、膨胀石墨中的一种。Further, the conductive agent is one of acetylene black, carbon nanotubes, nanocarbon fibers, and expanded graphite.
进一步地，所述粘合剂为聚偏二氟乙烯、聚氯乙烯聚乙烯醇、羟甲基纤维素钠中的一种。Further, the binder is one of polyvinylidene fluoride, polyvinyl chloride polyvinyl alcohol, and sodium hydroxymethyl cellulose.
有益效果beneficial effect
本发明先通过阳离子聚合物的羟基在石墨中形成配位，然后在离子液体中，阳离子聚合物中未配位的羟基与氧硫化碳进行反应，在石墨的表面生成含硫元素化合物，接着，通过固化工艺和碳化工艺，使含硫元素化合物固定且均匀分布在石墨的表面，最终得到的改性石墨电极材料具有良好的充放电性能和循环性能。In the present invention, the hydroxyl group of the cationic polymer forms coordination in the graphite, and then in the ionic liquid, the uncoordinated hydroxyl group in the cationic polymer reacts with carbon oxysulfide to generate a sulfur-containing compound on the surface of the graphite, and then, Through the curing process and the carbonization process, the sulfur-containing element compound is fixed and uniformly distributed on the surface of the graphite, and the finally obtained modified graphite electrode material has good charge-discharge performance and cycle performance.
本发明的实施方式Embodiments of the present invention
为了便于理解本发明，下面将对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。In order to facilitate understanding of the present invention, the present invention will be described more fully below. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that a thorough and complete understanding of the present disclosure is provided.
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used herein in the description of the present invention are for the purpose of describing specific embodiments only, and are not intended to limit the present invention.
实施例1。Example 1.
一种改性石墨电极材料的制备方法，包括如下制备步骤。A preparation method of modified graphite electrode material, comprising the following preparation steps.
S1：向石墨中加入质量浓度为1%的硝酸溶液，调节pH至4-6，再加入阳离子聚合物，在100℃-120℃下，恒温水浴搅拌反应，得到第一反应物。S1: adding a nitric acid solution with a mass concentration of 1% to the graphite, adjusting the pH to 4-6, then adding a cationic polymer, and stirring the reaction in a constant temperature water bath at 100°C-120°C to obtain the first reactant.
S2：向第一反应物中依次通入离子液体、氧硫化碳，在100℃-150℃下，反应0.5 h -2h，得到第二反应物。S2: The ionic liquid and carbon oxysulfide are sequentially introduced into the first reactant, and the reaction is carried out at 100° C. to 150° C. for 0.5 h to 2 h to obtain the second reactant.
S3：将第二反应物用去离子水进行洗涤，然后放入220℃-300℃的干燥箱中固化处理10h-15h，再用球磨机球磨2h-3h，使球磨后的粉体粒径小于2µm，接着，在氮气的保护下，将球磨后的粉体置于高温加热炉中，进行碳化处理，碳化处理的温度为600℃-800℃，压力为30 MPa -50MPa，反应时间为10h-20h，得到第三反应物。S3: Wash the second reactant with deionized water, then put it into a drying oven at 220°C-300°C for curing for 10h-15h, and then use a ball mill for 2h-3h, so that the particle size of the powder after ball milling is less than 2µm , and then, under the protection of nitrogen, the ball-milled powder is placed in a high-temperature heating furnace for carbonization treatment. , the third reactant is obtained.
S4：将第三反应物和导电剂混合后，进行研磨，再分散于无水乙醇中，加入粘合剂和草酸钾，搅拌均匀，干燥，压片，即得改性石墨电极材料。S4: After mixing the third reactant and the conductive agent, grind, disperse in absolute ethanol, add a binder and potassium oxalate, stir evenly, dry, and press to obtain a modified graphite electrode material.
其中，阳离子聚合物为羟基铝；所述石墨与所述阳离子聚合物的质量比为1:0.01；离子液体为1-丁基-3-甲基咪唑溴盐；第一反应物与离子液体、氧硫化碳的质量比为1: 0.01: 0.1；导电剂为乙炔黑，粘合剂为聚偏二氟乙烯，第三反应物与导电剂、无水乙醇、粘合剂的质量比为1:0.3:1:0.01。Wherein, the cationic polymer is hydroxyaluminum; the mass ratio of the graphite to the cationic polymer is 1:0.01; the ionic liquid is 1-butyl-3-methylimidazolium bromide; the first reactant and the ionic liquid, The mass ratio of carbon oxysulfide is 1: 0.01: 0.1; the conductive agent is acetylene black, the adhesive is polyvinylidene fluoride, and the mass ratio of the third reactant to the conductive agent, absolute ethanol, and the adhesive is 1: 0.3:1:0.01.
经测试，所得的改性石墨电极材料用作锂离子电池负极材料，在首次充放电循环后的放电比容量856mAh/g，首次充放电效率为88.9％，经过100次循环后，容量保持率为91.3％，且在充放电过程中没有硫单质颗粒析出。After testing, the obtained modified graphite electrode material is used as a negative electrode material for lithium ion batteries. After the first charge-discharge cycle, the discharge specific capacity is 856mAh/g, and the first charge-discharge efficiency is 88.9%. After 100 cycles, the capacity retention rate is 91.3%, and no sulfur particles were precipitated during the charging and discharging process.
实施例2。Example 2.
一种改性石墨电极材料的制备方法，包括如下制备步骤。A preparation method of modified graphite electrode material, comprising the following preparation steps.
S1：向石墨中加入质量浓度为1%的硝酸溶液，调节pH至4-6，再加入阳离子聚合物，在100℃-120℃下，恒温水浴搅拌反应，得到第一反应物。S1: adding a nitric acid solution with a mass concentration of 1% to the graphite, adjusting the pH to 4-6, then adding a cationic polymer, and stirring the reaction in a constant temperature water bath at 100°C-120°C to obtain the first reactant.
S2：向第一反应物中依次通入离子液体、氧硫化碳，在100℃-150℃下，反应0.5 h -2h，得到第二反应物。S2: The ionic liquid and carbon oxysulfide are sequentially introduced into the first reactant, and the reaction is carried out at 100° C. to 150° C. for 0.5 h to 2 h to obtain the second reactant.
S3：将第二反应物用去离子水进行洗涤，然后放入220℃-300℃的干燥箱中固化处理10h-15h，再用球磨机球磨2h-3h，使球磨后的粉体粒径小于2µm，接着，在氮气的保护下，将球磨后的粉体置于高温加热炉中，进行碳化处理，碳化处理的温度为600℃-800℃，压力为30 MPa -50MPa，反应时间为10h-20h，得到第三反应物。S3: Wash the second reactant with deionized water, then put it into a drying oven at 220°C-300°C for curing for 10h-15h, and then use a ball mill for 2h-3h, so that the particle size of the powder after ball milling is less than 2µm , and then, under the protection of nitrogen, the ball-milled powder is placed in a high-temperature heating furnace for carbonization treatment. , the third reactant is obtained.
S4：将第三反应物和导电剂混合后，进行研磨，再分散于无水乙醇中，加入粘合剂和草酸钾，搅拌均匀，干燥，压片，即得改性石墨电极材料。S4: After mixing the third reactant and the conductive agent, grind, disperse in absolute ethanol, add a binder and potassium oxalate, stir evenly, dry, and press to obtain a modified graphite electrode material.
其中，阳离子聚合物为羟基铝；所述石墨与所述阳离子聚合物的质量比为1:0.05；离子液体为1-丁基-3-甲基咪唑溴盐；第一反应物与离子液体、氧硫化碳的质量比为1: 0.01: 0.2；导电剂为乙炔黑，粘合剂为聚偏二氟乙烯，第三反应物与导电剂、无水乙醇、粘合剂的质量比为1:0.3:1:0.01。Wherein, the cationic polymer is hydroxyaluminum; the mass ratio of the graphite to the cationic polymer is 1:0.05; the ionic liquid is 1-butyl-3-methylimidazolium bromide; the first reactant and the ionic liquid, The mass ratio of carbon oxysulfide is 1: 0.01: 0.2; the conductive agent is acetylene black, the adhesive is polyvinylidene fluoride, and the mass ratio of the third reactant to the conductive agent, absolute ethanol, and the adhesive is 1: 0.3:1:0.01.
经测试，所得的改性石墨电极材料用作锂离子电池负极材料，在首次充放电循环后的放电比容量882mAh/g，首次充放电效率为90.3％，经过100次循环后，容量保持率为93.1％，且在充放电过程中没有硫单质颗粒析出。After testing, the obtained modified graphite electrode material is used as a negative electrode material for lithium-ion batteries. The discharge specific capacity after the first charge-discharge cycle is 882mAh/g, and the first charge-discharge efficiency is 90.3%. 93.1%, and no sulfur particles were precipitated during the charging and discharging process.
实施例3。Example 3.
一种改性石墨电极材料的制备方法，包括如下制备步骤。A preparation method of modified graphite electrode material, comprising the following preparation steps.
S1：向石墨中加入质量浓度为1%的硝酸溶液，调节pH至4-6，再加入阳离子聚合物，在100℃-120℃下，恒温水浴搅拌反应，得到第一反应物。S1: adding a nitric acid solution with a mass concentration of 1% to the graphite, adjusting the pH to 4-6, then adding a cationic polymer, and stirring the reaction in a constant temperature water bath at 100°C-120°C to obtain the first reactant.
S2：向第一反应物中依次通入离子液体、氧硫化碳，在100℃-150℃下，反应0.5 h -2h，得到第二反应物。S2: The ionic liquid and carbon oxysulfide are sequentially introduced into the first reactant, and the reaction is carried out at 100° C. to 150° C. for 0.5 h to 2 h to obtain the second reactant.
S3：将第二反应物用去离子水进行洗涤，然后放入220℃-300℃的干燥箱中固化处理10h-15h，再用球磨机球磨2h-3h，使球磨后的粉体粒径小于2µm，接着，在氮气的保护下，将球磨后的粉体置于高温加热炉中，进行碳化处理，碳化处理的温度为600℃-800℃，压力为30 MPa -50MPa，反应时间为10h-20h，得到第三反应物。S3: Wash the second reactant with deionized water, then put it into a drying oven at 220°C-300°C for curing for 10h-15h, and then use a ball mill for 2h-3h, so that the particle size of the powder after ball milling is less than 2µm , and then, under the protection of nitrogen, the ball-milled powder is placed in a high-temperature heating furnace for carbonization treatment. , the third reactant is obtained.
S4：将第三反应物和导电剂混合后，进行研磨，再分散于无水乙醇中，加入粘合剂和草酸钾，搅拌均匀，干燥，压片，即得改性石墨电极材料。S4: After mixing the third reactant and the conductive agent, grind, disperse in absolute ethanol, add a binder and potassium oxalate, stir evenly, dry, and press to obtain a modified graphite electrode material.
其中，阳离子聚合物为羟基铝；所述石墨与所述阳离子聚合物的质量比为1:0.1；离子液体为1-丁基-3-甲基咪唑溴盐；第一反应物与离子液体、氧硫化碳的质量比为1: 0.01: 0.2；导电剂为乙炔黑，粘合剂为聚偏二氟乙烯，第三反应物与导电剂、无水乙醇、粘合剂的质量比为1:0.3:1:0.01。Wherein, the cationic polymer is hydroxyaluminum; the mass ratio of the graphite to the cationic polymer is 1:0.1; the ionic liquid is 1-butyl-3-methylimidazolium bromide; the first reactant and the ionic liquid, The mass ratio of carbon oxysulfide is 1: 0.01: 0.2; the conductive agent is acetylene black, the adhesive is polyvinylidene fluoride, and the mass ratio of the third reactant to the conductive agent, absolute ethanol, and the adhesive is 1: 0.3:1:0.01.
经测试，所得的改性石墨电极材料用作锂离子电池负极材料，在首次充放电循环后的放电比容量906mAh/g，首次充放电效率为92.3％，经过100次循环后，容量保持率为92.7％，且在充放电过程中没有硫单质颗粒析出。After testing, the obtained modified graphite electrode material is used as a negative electrode material for lithium ion batteries. The discharge specific capacity after the first charge-discharge cycle is 906mAh/g, and the first charge-discharge efficiency is 92.3%. After 100 cycles, the capacity retention rate is 92.7%, and no sulfur particles were precipitated during the charging and discharging process.
对比例1。Comparative Example 1.
一种改性石墨电极材料的制备方法，包括如下制备步骤。A preparation method of modified graphite electrode material, comprising the following preparation steps.
S1：向石墨中加入质量浓度为1%的硝酸溶液，调节pH至4-6，再加入阳离子聚合物，在100℃-120℃下，恒温水浴搅拌反应，得到第一反应物。S1: adding a nitric acid solution with a mass concentration of 1% to the graphite, adjusting the pH to 4-6, then adding a cationic polymer, and stirring the reaction in a constant temperature water bath at 100°C-120°C to obtain the first reactant.
S2：向第一反应物中依次通入离子液体、氧硫化碳，在100℃-150℃下，反应0.5 h -2h，得到第二反应物。S2: The ionic liquid and carbon oxysulfide are sequentially introduced into the first reactant, and the reaction is carried out at 100° C. to 150° C. for 0.5 h to 2 h to obtain the second reactant.
S3：将第二反应物用去离子水进行洗涤，然后放入220℃-300℃的干燥箱中固化处理10h-15h，再用球磨机球磨2h-3h，使球磨后的粉体粒径小于2µm，接着，在氮气的保护下，将球磨后的粉体置于高温加热炉中，进行碳化处理，碳化处理的温度为600℃-800℃，压力为30 MPa -50MPa，反应时间为10h-20h，得到第三反应物。S3: Wash the second reactant with deionized water, then put it into a drying oven at 220°C-300°C for curing for 10h-15h, and then use a ball mill for 2h-3h, so that the particle size of the powder after ball milling is less than 2µm , and then, under the protection of nitrogen, the ball-milled powder is placed in a high-temperature heating furnace for carbonization treatment. , the third reactant is obtained.
S4：将第三反应物和导电剂混合后，进行研磨，再分散于无水乙醇中，加入粘合剂和草酸钾，搅拌均匀，干燥，压片，即得改性石墨电极材料。S4: After mixing the third reactant and the conductive agent, grind, disperse in absolute ethanol, add a binder and potassium oxalate, stir evenly, dry, and press to obtain a modified graphite electrode material.
其中，阳离子聚合物为羟基铝；所述石墨与所述阳离子聚合物的质量比为1:0.01；离子液体为1-丁基-3-甲基咪唑溴盐；第一反应物与离子液体、氧硫化碳的质量比为1: 0.01: 0.4；导电剂为乙炔黑，粘合剂为聚偏二氟乙烯，第三反应物与导电剂、无水乙醇、粘合剂的质量比为1:0.3:1:0.01。Wherein, the cationic polymer is hydroxyaluminum; the mass ratio of the graphite to the cationic polymer is 1:0.01; the ionic liquid is 1-butyl-3-methylimidazolium bromide; the first reactant and the ionic liquid, The mass ratio of carbon oxysulfide is 1: 0.01: 0.4; the conductive agent is acetylene black, the adhesive is polyvinylidene fluoride, and the mass ratio of the third reactant to the conductive agent, absolute ethanol, and the adhesive is 1: 0.3:1:0.01.
经测试，所得的改性石墨电极材料用作锂离子电池负极材料，在首次充放电循环后的放电比容量610mAh/g，首次充放电效率为68.9％，经过100次循环后，容量保持率为77.5％，且在充放电过程中会有硫单质颗粒析出。After testing, the obtained modified graphite electrode material is used as a negative electrode material for lithium ion batteries. The discharge specific capacity after the first charge-discharge cycle is 610mAh/g, and the first charge-discharge efficiency is 68.9%. After 100 cycles, the capacity retention rate is 77.5%, and there will be sulfur elemental particles precipitated during the charging and discharging process.
上述实施方式仅为本发明的优选实施方式，不能以此来限定本发明保护的范围，本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。The above-mentioned embodiments are only preferred embodiments of the present invention, and cannot be used to limit the scope of protection of the present invention. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention belong to the scope of the present invention. Scope of protection claimed.

Claims (10)

  1. 一种改性石墨电极材料的制备方法，其特征在于，包括如下制备步骤：A preparation method of modified graphite electrode material, characterized in that, comprising the following preparation steps:
    S1：向石墨中加入硝酸溶液，调节pH至4-6，再加入阳离子聚合物，在100℃-120℃下，恒温水浴搅拌反应，得到第一反应物；S1: adding a nitric acid solution to the graphite, adjusting the pH to 4-6, then adding a cationic polymer, and stirring the reaction in a constant temperature water bath at 100°C-120°C to obtain the first reactant;
    S2：向第一反应物中依次通入离子液体、氧硫化碳，在100℃-150℃下，反应0.5 h -2h，得到第二反应物；S2: successively feeding ionic liquid and carbon oxysulfide into the first reactant, and reacting at 100°C-150°C for 0.5 h-2h to obtain the second reactant;
    S3：将第二反应物用去离子水进行洗涤，然后放入220℃-300℃的干燥箱中固化处理10h-15h，再用球磨机球磨2h-3h，使球磨后的粉体粒径小于2µm，接着，在惰性气体的保护下，将球磨后的粉体置于高温加热炉中，进行碳化处理，得到第三反应物；S3: Wash the second reactant with deionized water, then put it into a drying oven at 220°C-300°C for curing for 10h-15h, and then use a ball mill for 2h-3h, so that the particle size of the powder after ball milling is less than 2µm , and then, under the protection of inert gas, the ball-milled powder is placed in a high-temperature heating furnace for carbonization to obtain the third reactant;
    S4：将第三反应物和导电剂混合后，进行研磨，再分散于无水乙醇中，加入粘合剂和草酸钾，搅拌均匀，干燥，压片，即得改性石墨电极材料。S4: After mixing the third reactant and the conductive agent, grind, disperse in absolute ethanol, add a binder and potassium oxalate, stir evenly, dry, and press to obtain a modified graphite electrode material.
  2. 根据权利要求1所述的改性石墨电极材料的制备方法，其特征在于，在步骤S1中，硝酸溶液的质量浓度为1%，阳离子聚合物为羟基铝、羟基锆中的一种或者两种组合。The method for preparing modified graphite electrode material according to claim 1, characterized in that, in step S1, the mass concentration of the nitric acid solution is 1%, and the cationic polymer is one or both of aluminum hydroxy and zirconium hydroxy. combination.
  3. 根据权利要求1所述的改性石墨电极材料的制备方法，其特征在于，在步骤S1中，所述石墨与所述阳离子聚合物的质量比为1:0.01-0.1。The method for preparing a modified graphite electrode material according to claim 1, wherein in step S1, the mass ratio of the graphite to the cationic polymer is 1:0.01-0.1.
  4. 根据权利要求1所述的改性石墨电极材料的制备方法，其特征在于，在步骤S2中，所述离子液体为1-丁基-3-甲基咪唑溴盐或者1-丁基-3-甲基咪唑六氟磷酸离子液体。The method for preparing a modified graphite electrode material according to claim 1, wherein in step S2, the ionic liquid is 1-butyl-3-methylimidazolium bromide or 1-butyl-3- Methylimidazole hexafluorophosphate ionic liquid.
  5. 根据权利要求1所述的改性石墨电极材料的制备方法，其特征在于，在步骤S2中，第一反应物与离子液体、氧硫化碳的质量比为1: 0.01-0.1: 0.1-0.2。The preparation method of modified graphite electrode material according to claim 1, is characterized in that, in step S2, the mass ratio of first reactant and ionic liquid, carbon oxysulfide is 1: 0.01-0.1: 0.1-0.2.
  6. 根据权利要求1所述的改性石墨电极材料的制备方法，其特征在于，在步骤S3中，惰性气体为氮气或氩气。The method for preparing a modified graphite electrode material according to claim 1, wherein in step S3, the inert gas is nitrogen or argon.
  7. 根据权利要求1所述的改性石墨电极材料的制备方法，其特征在于，在步骤S3中，碳化处理的温度为600℃-800℃，压力为30 MPa -50MPa，反应时间为10h-20h。The preparation method of the modified graphite electrode material according to claim 1, characterized in that, in step S3, the temperature of the carbonization treatment is 600°C-800°C, the pressure is 30 MPa-50 MPa, and the reaction time is 10h-20h.
  8. 根据权利要求1所述的改性石墨电极材料的制备方法，其特征在于，步骤S4中，第三反应物与导电剂、无水乙醇、粘合剂的质量比为1:0.3-0.5:1-3:0.01-0.05。The method for preparing a modified graphite electrode material according to claim 1, wherein in step S4, the mass ratio of the third reactant to the conductive agent, anhydrous ethanol and the binder is 1:0.3-0.5:1 -3:0.01-0.05.
  9. 根据权利要求8所述的改性石墨电极材料的制备方法，其特征在于，所述导电剂为乙炔黑、碳纳米管、纳米碳纤维、膨胀石墨中的一种。The method for preparing a modified graphite electrode material according to claim 8, wherein the conductive agent is one of acetylene black, carbon nanotubes, nanocarbon fibers, and expanded graphite.
  10. 根据权利要求8所述的改性石墨电极材料的制备方法，其特征在于，所述粘合剂为聚偏二氟乙烯、聚氯乙烯聚乙烯醇、羟甲基纤维素钠中的一种。The method for preparing a modified graphite electrode material according to claim 8, wherein the binder is one of polyvinylidene fluoride, polyvinyl chloride polyvinyl alcohol, and sodium hydroxymethyl cellulose.
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