WO2017107807A1 - Method for fabricating lithium-ion battery cathode material and application thereof - Google Patents

Method for fabricating lithium-ion battery cathode material and application thereof Download PDF

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WO2017107807A1
WO2017107807A1 PCT/CN2016/109638 CN2016109638W WO2017107807A1 WO 2017107807 A1 WO2017107807 A1 WO 2017107807A1 CN 2016109638 W CN2016109638 W CN 2016109638W WO 2017107807 A1 WO2017107807 A1 WO 2017107807A1
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graphene
gas
carbon
coated
composite material
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French (fr)
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王海波
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苏州格瑞动力电源科技有限公司
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 field of new energy materials and electrochemical research, and particularly relates to a preparation method and application of a lithium ion battery anode material.
  • a single graphene material is used as an electrode material and is limited by many factors.
  • the graphene is too large in surface area (theoretical value is 2630 m 2 /g), and the sheets are easily agglomerated, which greatly increases the irreversible capacity loss (lower first time).
  • Coulomb efficiency ( ⁇ 73%)) and its electrical conductivity as an electrode material which has an adverse effect on the electrode production process.
  • the capacity decays too fast.
  • Core/shell material composite means that a single or multiple layers of organic or inorganic materials are coated around the organic or inorganic core particles, which is an effective way to improve the stability and surface chemical properties of the core particles, and it is impossible. A unique physicochemical property obtained from a material.
  • tea residue formed after industrial extraction of biochemical components such as tea polyphenols; the other is the tea residue formed in the tea beverage industry.
  • the comprehensive utilization of biomass such as dregs is a worldwide problem. At present, most of the domestic dregs are disposed of in landfills, and a small part is used as feed and fertilizer, thus causing serious environmental problems such as sewage and odor, and some dregs are dangerous. Waste, the state has separate provisions on hazardous waste treatment, the requirements are more stringent.
  • the analysis shows that the crude fiber content in the tea residue is as high as (16%-18%), the protein content is high, the crude protein content is 17%-19%, the amino acid composition is reasonable, and the lysine and methionine contents are 1.5 respectively. % ⁇ 2% and 0.5 ⁇ 0.7%, also contains a certain amount of vitamins, tea polyphenols, caffeine and a small amount of tea saponin.
  • the present invention is based on the above background and has been invented.
  • the invention aims to provide a method for preparing a carbon-coated graphene composite material for a lithium ion battery anode material with high rate and long life, simple preparation process and good experimental reproducibility.
  • the technical solution adopted by the present invention is: a method for preparing a carbon-coated graphene composite material, which comprises the following steps:
  • the mixture prepared in the step (2) is ground and placed in a flowing protective gas to be heated for high-temperature thermal reduction and carbonization reaction, and the heating temperature is 250 to 950 ° C.
  • the carbon-coated graphene composite material can be obtained by reacting the reaction time to 0.2 to 20 hours and finally dropping to room temperature in a flowing protective gas.
  • step (1)
  • the tea leaf residue is one of black tea, black tea, oolong tea and Pu'er tea slag.
  • step (2)
  • the graphite oxide or graphene is produced by the modified Hummers method.
  • the tea slag is added in an amount of 0.1 to 10 times the mass of the graphene oxide. .
  • step (3)
  • reaction temperature is maintained at 0 to 5 ° C, and the reaction time is maintained for 4 to 6 hours.
  • the heating is carried out by introducing a flow shielding gas into the tube furnace or directly heating in a box type electric resistance furnace or a muffle furnace.
  • the shielding gas is one or several inert gases of argon, nitrogen and helium, or one of argon, nitrogen and hydrogen or a mixed gas of inert gas and hydrogen.
  • the purity of the mixed gas of inert gas and hydrogen is ⁇ 99.99%, and the content of hydrogen in the mixed gas is 0.1 to 99.9%.
  • the mechanism included in the above technical solution is that the carbonization of the tea leaf slag can be converted into nitrogen-doped hard carbon at a high temperature, and the hard carbon and the graphene are composited, which reduces the specific surface of the graphene to a certain extent, and reduces the partial The capacity of lithium adsorbed between the layers of graphene nanosheets enhances the stability of the graphene structure; and the hard carbon is doped into the layers of graphene oxide to enhance the longitudinal electrical conductivity between the graphene sheets.
  • the carbonization of the tea slag can be turned into a hard carbon soft carbon composite material at a high temperature, and the advantages of the two can be fully utilized to avoid the embedded induced peeling caused by the electrolyte, thereby improving the rate and cycle performance of the active material.
  • the invention also provides a carbon-coated graphene composite material prepared by using the above technical solution as a negative electrode material application of a lithium ion battery, and mixing the carbon-coated graphene composite material with polyvinylidene fluoride PVDF and carbon black Super-P.
  • the slurry is stirred, coated on the surface of the copper foil, and dried to punch the negative electrode sheet of the lithium battery.
  • the method of the present invention will waste tea leaves
  • the slag is converted into the raw material of the negative electrode material of the lithium ion battery, which not only reduces the pollution caused by the environment, but also the cost of the negative electrode material; at the same time, the invention does not require any special equipment, so the preparation method is simple and easy, and the reaction process is easy to control. , low risk, low cost, mass production, easy to promote.
  • the carbon-coated graphene product with different carbon coating amounts can be prepared according to the requirements of the properties of the product, by changing the mass-to-volume ratio of the raw materials, and the experimental conditions such as the reaction temperature and the reaction time.
  • graphite oxide is prepared by a modified Hummers method, specifically: 1 g of graphite is slowly added to a round bottom flask containing 35 ml of 98% sulfuric acid under stirring, and then 0.5 g of sodium nitrate is added. The temperature was maintained at 0 ° C and stirred rapidly for 2 hours. Slowly add 5g potassium permanganate (temperature control below 20 °C), dark green, remove the ice water bath after adding potassium permanganate, control temperature at (35 ⁇ 3) °C, maintain for 2h under stirring, slowly add 100ml distilled water (The temperature rose to 98 ° C), stirred rapidly at this temperature for 2.5 h, and slowly stirred for 15 h.
  • a modified Hummers method specifically: 1 g of graphite is slowly added to a round bottom flask containing 35 ml of 98% sulfuric acid under stirring, and then 0.5 g of sodium nitrate is added. The temperature was maintained at 0 ° C and stirred rapidly for 2 hours.
  • the product was washed first with a 30% aqueous solution of H 2 O 2 and then with a 5% aqueous solution of hydrochloric acid and washed with deionized water until the filtrate was free of SO 4 2 (the white precipitate was not detected by BaCl 2 ) and dried in vacuo.
  • the mixture prepared in the step (3) is ground and placed in a flowing protective gas to be heated for high-temperature thermal reduction and carbonization reaction, and the heating temperature is 250 to 950 ° C.
  • the carbon-coated graphene composite material can be obtained by reacting the reaction time to 0.2 to 20 hours and finally dropping to room temperature in a flowing protective gas.
  • the preparation method of this embodiment is the same as that of the first embodiment, wherein the mass of the graphite oxide in the step (3) and the ratio of the tea leaf residue are adjusted to 1:2, and the concentration of the sulfuric acid solution increases according to a certain proportion of the amount of the tea residue. Increasing, under the same conditions, the black product is also obtained, that is, carbon-coated graphene is obtained.
  • the preparation method of this embodiment is the same as that of the first embodiment, wherein the mass of the graphite oxide in the step (3) and the ratio of the tea leaf residue are adjusted to 1:10, and the concentration of the sulfuric acid solution increases correspondingly according to the increase of the amount of the tea residue. , unchanged in other conditions In the case, a black product is also obtained, that is, carbon-coated graphene is obtained.
  • the carbon-coated graphene After the carbon-coated graphene is obtained according to the above embodiment, it can be used as a negative electrode of a lithium ion battery, specifically: carbon-coated graphene and polyvinylidene fluoride PVDF and carbon black Super-P according to a mass ratio of 85:10 The ratio of 5 is agitated, and then coated on a surface of a circular copper foil having a thickness of 14 ⁇ m, vacuum-dried, rolled to a thickness of 40 ⁇ m, and then punched into a disk having a diameter of 12 ⁇ m to form a lithium ion battery. Negative electrode sheet.
  • the carbon coated graphene is prepared by the method of the present invention.
  • the above embodiments are merely preferred embodiments of the present invention and are not intended to limit the present invention.

Abstract

Disclosed are a method for fabricating a carbon-coated graphene composite material and an application thereof; the fabrication method is: dispersing graphite oxide or graphene in a dilute acid solution; adding different amounts of polymer/monomer to the solution and stirring continuously, then slowly adding a polymerization initiator to cause a polymerization reaction to occur in the solution; using deionized water and ethanol to rinse several times the polymer-coated graphite oxide or graphene generated by the polymerization reaction, then performing vacuum drying; grinding the obtained polymer-coated graphite oxide or graphene, then placing into a flowing protective gas, heating, and performing high-temperature thermal reduction and a carbonization reaction; lastly, reducing the flowing protective gas to ambient temperature to obtain a carbon-coated graphene material. The carbon-coated graphene has high magnification and a long service life, solves such problems in preparation as those caused by the specific surface area of current individual graphene electrode materials being excessively large, as well as the problem of rapid attenuation of capacity at large magnifications, and may be used as a lithium-ion battery cathode material.

Description

一种锂离子电池负极材料的制备方法及应用Preparation method and application of anode material for lithium ion battery
技术领域Technical field
本发明涉及新能源材料与电化学研究领域，具体涉及一种锂离子电池负极材料的制备方法及应用。The invention relates to the field of new energy materials and electrochemical research, and particularly relates to a preparation method and application of a lithium ion battery anode material.
背景技术Background technique
单一的石墨烯材料用作电极材料，受到诸多因素的限制，如石墨烯比表面过大(理论值2630m2/g)，片层之间容易团聚，大大提高了不可逆容量损失(较低的首次库仑效率(＜73％))并降低了其作为电极材料电导率，从而给电极制片工艺方面带来不良影响。特别是，单一的石墨烯电极材料在大倍率充放电时，容量衰减太快。A single graphene material is used as an electrode material and is limited by many factors. For example, the graphene is too large in surface area (theoretical value is 2630 m 2 /g), and the sheets are easily agglomerated, which greatly increases the irreversible capacity loss (lower first time). Coulomb efficiency (<73%)) and its electrical conductivity as an electrode material, which has an adverse effect on the electrode production process. In particular, when a single graphene electrode material is charged and discharged at a large rate, the capacity decays too fast.
近来，核/壳纳米结构如金属氧化物/碳、导电聚合物/碳、金属氧化物/金属氮化物等复合材料已被广泛用于研究。核/壳材料复合是指单层或多层的有机或无机材料包覆在有机或无机核颗粒的周围，这是提高该核颗粒的稳定性和表面化学性能的有效方式，而且可以达到不可能从一种材料上获得的独一无二的物理化学特性。Recently, composite materials such as metal/shell nanostructures such as metal oxide/carbon, conductive polymer/carbon, metal oxide/metal nitride have been widely used for research. Core/shell material composite means that a single or multiple layers of organic or inorganic materials are coated around the organic or inorganic core particles, which is an effective way to improve the stability and surface chemical properties of the core particles, and it is impossible. A unique physicochemical property obtained from a material.
此外，我国是茶产品生产消耗大国，每年有大量的茶渣产生。茶渣的主要来源有两个：一是工业提取茶多酚等生化成分之后所形成的茶渣；二是茶饮料工业中形成的茶渣。药渣等生物质综合利用是一个世界性问题，目前国内的药渣大部分做填埋处理，少部分用作饲料和肥料，因而造成严重的污水和气味等环境问题，另外部分药渣属于危险废物，国家在危废处理上有另行规定，要求比较严格。经分析表明：茶渣中仅粗纤维含量就高达(16％～18％)，蛋白质含量较高，粗蛋白含量达17％～19％，氨基酸组成较合理，赖氨酸和蛋氨酸含量分别为1.5％～2％和0.5～0.7％，还含有一定量的维生素、茶多酚、咖啡碱及少量的茶皂素等。In addition, China is a big country in the production of tea products, and a large amount of tea residue is produced every year. There are two main sources of tea residue: one is the tea residue formed after industrial extraction of biochemical components such as tea polyphenols; the other is the tea residue formed in the tea beverage industry. The comprehensive utilization of biomass such as dregs is a worldwide problem. At present, most of the domestic dregs are disposed of in landfills, and a small part is used as feed and fertilizer, thus causing serious environmental problems such as sewage and odor, and some dregs are dangerous. Waste, the state has separate provisions on hazardous waste treatment, the requirements are more stringent. The analysis shows that the crude fiber content in the tea residue is as high as (16%-18%), the protein content is high, the crude protein content is 17%-19%, the amino acid composition is reasonable, and the lysine and methionine contents are 1.5 respectively. % ~ 2% and 0.5 ~ 0.7%, also contains a certain amount of vitamins, tea polyphenols, caffeine and a small amount of tea saponin.
本发明正是基于上述背景而进行的发明创造。The present invention is based on the above background and has been invented.
发明内容Summary of the invention
本发明目的在于提供一种高倍率和长寿命、制备工艺简单，实验重现性好的用于锂离子电池负极材料的碳包覆石墨烯复合材料的制备方法。The invention aims to provide a method for preparing a carbon-coated graphene composite material for a lithium ion battery anode material with high rate and long life, simple preparation process and good experimental reproducibility.
为了达到上述目的，本发明所采用的技术方案为：一种碳包覆石墨烯复合材料制备方法，它包括如下步骤： In order to achieve the above object, the technical solution adopted by the present invention is: a method for preparing a carbon-coated graphene composite material, which comprises the following steps:
(1)茶叶渣的预处理：将茶叶渣进行干燥，粉碎和过筛得固态物质；(1) Pretreatment of tea slag: drying the tea slag, pulverizing and sieving to obtain a solid substance;
(2)混合物的制备：将氧化石墨烯或石墨烯分散在硫酸溶液中，向所述溶液中加入不同量的(1)中所述固态物质并持续搅拌，充分混合后干燥；(2) Preparation of the mixture: dispersing graphene oxide or graphene in a sulfuric acid solution, adding different amounts of the solid matter in (1) to the solution and continuously stirring, thoroughly mixing and drying;
(3)碳包覆石墨烯复合材料的制成：将步骤(2)中制得的混合物研磨后置于流动的保护气体中加热进行高温热还原和碳化反应，加热温度为250～950℃，反应时间为0.2～20小时，最后在流动的保护气体中降至室温即可获得所述的碳包覆石墨烯复合材料。(3) Preparation of carbon-coated graphene composite material: the mixture prepared in the step (2) is ground and placed in a flowing protective gas to be heated for high-temperature thermal reduction and carbonization reaction, and the heating temperature is 250 to 950 ° C. The carbon-coated graphene composite material can be obtained by reacting the reaction time to 0.2 to 20 hours and finally dropping to room temperature in a flowing protective gas.
根据上述技术方案所进一步优化和变换的方式为：The manner of further optimization and transformation according to the above technical solution is:
步骤(1)中，In step (1),
所述的茶叶渣为红茶、黑茶、乌龙茶和普洱茶叶渣中的一种。The tea leaf residue is one of black tea, black tea, oolong tea and Pu'er tea slag.
步骤(2)中，In step (2),
所述的氧化石墨或石墨烯采用改进的Hummers法制得。The graphite oxide or graphene is produced by the modified Hummers method.
所述的茶叶渣的添加量为氧化石墨烯质量的0.1～10倍。。The tea slag is added in an amount of 0.1 to 10 times the mass of the graphene oxide. .
步骤(3)中，In step (3),
所述的反应中，反应温度维持在0～5℃，反应时间维持4～6小时。In the above reaction, the reaction temperature is maintained at 0 to 5 ° C, and the reaction time is maintained for 4 to 6 hours.
所述的加热是在管式炉中通入流动保护气体加热，或者直接在箱式电阻炉或马弗炉中加热。The heating is carried out by introducing a flow shielding gas into the tube furnace or directly heating in a box type electric resistance furnace or a muffle furnace.
所述的保护气体为氩气、氮气、氦气中的一种或几种惰性气体，或者为氩气、氮气、氢气中的一种或几种惰性气体与氢气的混合气体。The shielding gas is one or several inert gases of argon, nitrogen and helium, or one of argon, nitrogen and hydrogen or a mixed gas of inert gas and hydrogen.
在所述的混合气体中，所述的惰性气体和氢气混合气的纯度≥99.99％，且氢气在混合气体中的含量为0.1～99.9％。In the mixed gas, the purity of the mixed gas of inert gas and hydrogen is ≥99.99%, and the content of hydrogen in the mixed gas is 0.1 to 99.9%.
上述技术方案所包含的机理为：茶叶渣在高温下碳化可以转化为氮掺杂的硬碳，将硬碳与石墨烯进行复合，在一定程度上降低了石墨烯的比表面，减少了部分由于吸附脱附于石墨烯纳米片层间的锂带来的容量，增强了石墨烯结构的稳定性；而且硬碳掺杂到氧化石墨烯的层间，增强了石墨烯片层间纵向电导率。所以，茶叶渣高温下碳化可变成硬碳软碳复合材料，充分发挥二者的优势，避免电解液造成的嵌入式诱导剥离，从而提高活性材料的倍率和循环性能。The mechanism included in the above technical solution is that the carbonization of the tea leaf slag can be converted into nitrogen-doped hard carbon at a high temperature, and the hard carbon and the graphene are composited, which reduces the specific surface of the graphene to a certain extent, and reduces the partial The capacity of lithium adsorbed between the layers of graphene nanosheets enhances the stability of the graphene structure; and the hard carbon is doped into the layers of graphene oxide to enhance the longitudinal electrical conductivity between the graphene sheets. Therefore, the carbonization of the tea slag can be turned into a hard carbon soft carbon composite material at a high temperature, and the advantages of the two can be fully utilized to avoid the embedded induced peeling caused by the electrolyte, thereby improving the rate and cycle performance of the active material.
本发明还提供利用上述技术方案制得的碳包覆石墨烯复合材料作为锂离子电池负极材料应用，将所述的碳包覆石墨烯复合材料与聚偏氟乙烯PVDF以及炭黑Super-P混合搅浆，涂膜于铜箔表面，干燥后冲孔即制得锂电池负极片。The invention also provides a carbon-coated graphene composite material prepared by using the above technical solution as a negative electrode material application of a lithium ion battery, and mixing the carbon-coated graphene composite material with polyvinylidene fluoride PVDF and carbon black Super-P. The slurry is stirred, coated on the surface of the copper foil, and dried to punch the negative electrode sheet of the lithium battery.
由于上述技术方案的运用，本发明相对现有技术的优点：本发明方法将废弃物茶叶 渣转化为锂离子电池负极材料的原料，既减少了其对环境造成的污染，又能为负极材料的成本；同时本发明不需要其它任何专用设备，所以制备方法简便易行，反应过程易于控制，危险性小，成本低，可批量生产，极易推广使用。Due to the use of the above technical solutions, the advantages of the present invention over the prior art: the method of the present invention will waste tea leaves The slag is converted into the raw material of the negative electrode material of the lithium ion battery, which not only reduces the pollution caused by the environment, but also the cost of the negative electrode material; at the same time, the invention does not require any special equipment, so the preparation method is simple and easy, and the reaction process is easy to control. , low risk, low cost, mass production, easy to promote.
具体实施方式detailed description
本发明可以根据对产品的性质的需要，通过改变原料质量体积比以及反应温度、反应时间等实验条件，制备出不同碳包覆量的碳包覆石墨烯产物。下面将给出几个具体实施例：According to the invention, the carbon-coated graphene product with different carbon coating amounts can be prepared according to the requirements of the properties of the product, by changing the mass-to-volume ratio of the raw materials, and the experimental conditions such as the reaction temperature and the reaction time. Several specific embodiments will be given below:
实施例1Example 1
(1)原料氧化石墨烯的制备方法：采用改进的Hummers法制备氧化石墨，具体为：将1g石墨在搅拌下缓慢加入到装有35ml 98％硫酸的圆底烧瓶中，再加入0.5g硝酸钠，温度维持在0℃，快速搅拌2小时。缓慢加入5g高锰酸钾(控温在20℃以下)，呈墨绿色，高锰酸钾加毕后撤去冰水浴，控温在(35±3)℃，搅拌下维持2h，缓慢加入100ml蒸馏水(温度上升至98℃)，在此温度下快速搅拌2.5h，再缓慢搅拌15h。产物先用30％的H2O2水溶液洗涤，再用5％的盐酸溶液清洗，用去离子水清洗至滤液中无SO4 2-(BaCl2检测无白色沉淀)，真空干燥。(1) Preparation method of raw material graphene oxide: graphite oxide is prepared by a modified Hummers method, specifically: 1 g of graphite is slowly added to a round bottom flask containing 35 ml of 98% sulfuric acid under stirring, and then 0.5 g of sodium nitrate is added. The temperature was maintained at 0 ° C and stirred rapidly for 2 hours. Slowly add 5g potassium permanganate (temperature control below 20 °C), dark green, remove the ice water bath after adding potassium permanganate, control temperature at (35 ± 3) °C, maintain for 2h under stirring, slowly add 100ml distilled water (The temperature rose to 98 ° C), stirred rapidly at this temperature for 2.5 h, and slowly stirred for 15 h. The product was washed first with a 30% aqueous solution of H 2 O 2 and then with a 5% aqueous solution of hydrochloric acid and washed with deionized water until the filtrate was free of SO 4 2 (the white precipitate was not detected by BaCl 2 ) and dried in vacuo.
(2)将茶叶渣进行干燥和粉碎，得固态物质；(2) drying and pulverizing the tea residue to obtain a solid substance;
(3)将1g氧化石墨烯分散在含有0.1M的硫酸溶液中，向所述溶液中加入1g茶叶渣并持续搅拌，充分混合后干燥；(3) Dispersing 1 g of graphene oxide in a 0.1 M sulfuric acid solution, adding 1 g of tea leaf residue to the solution, stirring continuously, thoroughly mixing, and drying;
(3)碳包覆石墨烯复合材料的制成：将步骤(3)中制得的混合物研磨后置于流动的保护气体中加热进行高温热还原和碳化反应，加热温度为250～950℃，反应时间为0.2～20小时，最后在流动的保护气体中降至室温即可获得所述的碳包覆石墨烯复合材料。(3) Preparation of carbon-coated graphene composite material: the mixture prepared in the step (3) is ground and placed in a flowing protective gas to be heated for high-temperature thermal reduction and carbonization reaction, and the heating temperature is 250 to 950 ° C. The carbon-coated graphene composite material can be obtained by reacting the reaction time to 0.2 to 20 hours and finally dropping to room temperature in a flowing protective gas.
实施例2Example 2
本实施例制备方法同实施例1，其中步骤(3)中氧化石墨的质量和茶叶渣的比例两笔调至1∶2，硫酸溶液的浓度随着茶叶渣的量的增加按照一定的比例相应的增加，在其它条件不变情况下，同样得到黑色产品，即得到碳包覆石墨烯。The preparation method of this embodiment is the same as that of the first embodiment, wherein the mass of the graphite oxide in the step (3) and the ratio of the tea leaf residue are adjusted to 1:2, and the concentration of the sulfuric acid solution increases according to a certain proportion of the amount of the tea residue. Increasing, under the same conditions, the black product is also obtained, that is, carbon-coated graphene is obtained.
实施例3Example 3
本实施例制备方法同实施例1，其中步骤(3)中氧化石墨的质量和茶叶渣的比例调至1∶10，硫酸溶液的浓度随着茶叶渣的量的增加按照一定的比例相应的增加，在其它条件不变 情况下，同样得到黑色产品，即得到碳包覆石墨烯。The preparation method of this embodiment is the same as that of the first embodiment, wherein the mass of the graphite oxide in the step (3) and the ratio of the tea leaf residue are adjusted to 1:10, and the concentration of the sulfuric acid solution increases correspondingly according to the increase of the amount of the tea residue. , unchanged in other conditions In the case, a black product is also obtained, that is, carbon-coated graphene is obtained.
按照上述实施例制得碳包覆石墨烯后，其可作为锂离子电池负极应用，具体为：将碳包覆石墨烯与聚偏氟乙烯PVDF以及炭黑Super-P按照质量比为85∶10∶5的比例搅浆，然后涂膜于厚度为14um的圆形铜箔表面上，真空干燥后将其滚压至40um厚度，再冲孔成直径为12um的圆片，即可形成锂离子电池负极电极片。After the carbon-coated graphene is obtained according to the above embodiment, it can be used as a negative electrode of a lithium ion battery, specifically: carbon-coated graphene and polyvinylidene fluoride PVDF and carbon black Super-P according to a mass ratio of 85:10 The ratio of 5 is agitated, and then coated on a surface of a circular copper foil having a thickness of 14 μm, vacuum-dried, rolled to a thickness of 40 μm, and then punched into a disk having a diameter of 12 μm to form a lithium ion battery. Negative electrode sheet.
本发明所述方法制备碳包覆石墨烯，上述实施例仅为本发明的较佳实施例而已，并不用以限制本发明。 The carbon coated graphene is prepared by the method of the present invention. The above embodiments are merely preferred embodiments of the present invention and are not intended to limit the present invention.

Claims (2)

  1. 一种碳包覆石墨烯复合材料制备方法制备的碳包覆石墨烯复合材料作为锂离子电池负极材料的应用，其特征在于，所述的制备方法包括如下步骤：The invention relates to a carbon-coated graphene composite material prepared by using a carbon-coated graphene composite material as a negative electrode material for a lithium ion battery, characterized in that the preparation method comprises the following steps:
    (1)茶叶渣的预处理：将茶叶渣进行干燥，粉碎和过筛得固态物质；(1) Pretreatment of tea slag: drying the tea slag, pulverizing and sieving to obtain a solid substance;
    (2)混合物的制备：将氧化石墨烯或石墨烯分散在硫酸溶液中，向所述溶液中加入不同量的(1)中所述固态物质并持续搅拌，充分混合后干燥；(2) Preparation of the mixture: dispersing graphene oxide or graphene in a sulfuric acid solution, adding different amounts of the solid matter in (1) to the solution and continuously stirring, thoroughly mixing and drying;
    (3)碳包覆石墨烯复合材料的制成：将步骤(2)中制得的混合物研磨后置于流动的保护气体中加热进行高温热还原和碳化反应，加热温度为250-950℃，反应时间为0.2-20小时，最后在流动的保护气体中降至室温即可获得所述的碳包覆石墨烯复合材料；(3) Preparation of carbon-coated graphene composite material: the mixture prepared in the step (2) is ground and placed in a flowing protective gas for heating at a high temperature for thermal reduction and carbonization, and the heating temperature is 250-950 ° C. The reaction time is 0.2-20 hours, and finally the carbon-coated graphene composite material can be obtained by dropping to room temperature in a flowing shielding gas;
    步骤(1)中，所述的茶叶渣20～25℃干燥至恒重；In the step (1), the tea leaf residue is dried to a constant weight at 20 to 25 ° C;
    步骤(1)中，所述的茶叶渣粉碎，过40～80目筛；In the step (1), the tea leaf slag is crushed and passed through a 40-80 mesh sieve;
    步骤(2)中，所述的氧化石墨或石墨烯采用改进的Hummers法制得；In the step (2), the graphite oxide or graphene is prepared by a modified Hummers method;
    步骤(2)中，所述的硫酸溶液浓度为0.1～1M；In step (2), the concentration of the sulfuric acid solution is 0.1 to 1 M;
    步骤(2)中，所述的茶叶渣和氧化石墨或石墨烯的质量比为0.1∶1～10∶1；In step (2), the mass ratio of the tea leaf residue to graphite oxide or graphene is from 0.1:1 to 10:1;
    步骤(3)中，所述的反应中，反应温度维持在0～5℃，反应时间维持4～6小时；In the step (3), in the reaction, the reaction temperature is maintained at 0 to 5 ° C, and the reaction time is maintained for 4 to 6 hours;
    步骤(3)中，所述的加热是在管式炉中通入流动保护气体加热，或者直接在箱式电阻炉或马弗炉中加热；In the step (3), the heating is performed by introducing a flow shielding gas into the tube furnace, or directly heating in a box type electric resistance furnace or a muffle furnace;
    步骤(3)中，所述的保护气体为氩气、氮气、氦气中的一种或几种惰性气体，或者为氩气、氮气、氢气中的一种或几种惰性气体与氢气的混合气体；In the step (3), the shielding gas is one or several inert gases of argon gas, nitrogen gas, helium gas, or one of argon gas, nitrogen gas, hydrogen gas or a mixture of several inert gases and hydrogen gas. gas;
    在所述的混合气体中，所述的惰性气体和氢气混合气的纯度≥99.99％，且氢气在混合气体中的含量为0.1～99.9％。In the mixed gas, the purity of the mixed gas of inert gas and hydrogen is ≥99.99%, and the content of hydrogen in the mixed gas is 0.1 to 99.9%.
  2. 根据权利要求1所述的应用，其特征在于：将所述的碳包覆石墨烯复合材料与聚偏氟乙烯PVDF以及炭黑Super-P混合搅浆，涂膜于铜箔表面，干燥后冲孔即制得锂电池负极片。 The invention according to claim 1, wherein the carbon-coated graphene composite material is mixed with polyvinylidene fluoride PVDF and carbon black Super-P, and the film is coated on the surface of the copper foil, dried and then washed. The hole is a negative electrode of a lithium battery.
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