WO2022012075A1 - 一种多孔碳-石墨烯复合材料及其制备方法 - Google Patents

一种多孔碳-石墨烯复合材料及其制备方法 Download PDF

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WO2022012075A1
WO2022012075A1 PCT/CN2021/082188 CN2021082188W WO2022012075A1 WO 2022012075 A1 WO2022012075 A1 WO 2022012075A1 CN 2021082188 W CN2021082188 W CN 2021082188W WO 2022012075 A1 WO2022012075 A1 WO 2022012075A1
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composite material
porous carbon
graphene oxide
graphene
graphene composite
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French (fr)
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闵永刚
朋小康
张诗洋
刘屹东
廖松义
刘荣涛
黄兴文
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Guangdong University of Technology
Dongguan South China Design and Innovation Institute
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Guangdong University of Technology
Dongguan South China Design and Innovation Institute
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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
    • 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
    • H01M4/583—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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, in particular to a porous carbon-graphene composite material and a preparation method thereof.
  • the positive and negative electrodes of lithium-ion batteries are the basis of battery performance, which directly determine the battery's specific energy, specific power, cycle stability and safety and other performance indicators.
  • carbon materials are commonly used in negative electrodes, and among them, porous carbon materials are the most widely used due to their excellent electrical conductivity, low cost, and simple preparation process.
  • the super absorbent resin can absorb hundreds of times of water equivalent to the volume of the resin, and can effectively expand its volume. After water absorption and drying, a large number of channels and holes will be formed in the water absorbent resin. After carbonization, it can form a carbon material with a high specific surface area. Very low cost and good electrical conductivity.
  • the present invention provides a porous carbon-graphene composite material and a preparation method thereof in order to solve the technical problem that the structure of the existing lithium battery negative electrode material is easily collapsed during the carbonization process, which is unfavorable for use.
  • the embodiment of the present invention provides a preparation method of a porous carbon-graphene composite material, comprising the following steps:
  • the super absorbent resin is one or more of starch grafted acrylic acid, grafted acrylamide, high degree of substitution cross-linked carboxymethyl cellulose, cross-linked carboxymethyl cellulose grafted acrylamide or sodium polyacrylate. kind.
  • the graphene oxide solution adopts one or more of intrinsic state graphene oxide, nitrogen-doped graphene oxide and sulfur-doped graphene oxide.
  • the size of the graphene oxide is 500-2000 nm, and the number of layers of the graphene oxide is in the range of 1-100 layers.
  • the concentration of the graphene oxide solution is 0.1-2 g/L.
  • step S1 the mass ratio of the superabsorbent resin to the volume of the graphene oxide solution is 1 g: (0.05-1) L.
  • the protective gas is nitrogen or argon.
  • step S3 the drying time is 60-180 min.
  • step S3 the heating temperature for carbonization is 500-1000°C.
  • the present invention also provides a porous carbon-graphene composite material, and the porous carbon-graphene composite material is prepared by the preparation method.
  • the beneficial effects of the present invention are: in the embodiment of the present invention, superabsorbent resin, water and a small amount of graphene oxide are used as raw materials, the cost is low, the graphene oxide solution fills the superabsorbent resin, and the porous carbon-graphene composite obtained after carbonization
  • the structure of the material does not collapse, and graphene oxide has excellent electrical conductivity after thermal reduction, which is filled in porous carbon, which greatly increases the electrical conductivity and specific surface area of porous carbon, and improves the reactivity and reaction rate.
  • the superabsorbent resin is rich in carbon elements and contains other beneficial elements (N, S, P, etc.), thereby improving the cycle performance of lithium-ion batteries.
  • the invention has simple preparation steps, no toxic and harmful solvents, environmental protection and high efficiency.
  • Example 1 is a SEM image of the reduction of the porous carbon-graphene composite material obtained in Example 1 of the present invention.
  • first and second are only used for descriptive purposes, and should not be construed as indicating or implying relative importance or implying the number of indicated technical features. Thus, a feature defined as “first” or “second” may expressly or implicitly include one or more of that feature.
  • “plurality” means two or more, unless otherwise expressly and specifically defined.
  • the terms “installed”, “connected”, “connected”, “fixed” and other terms should be understood in a broad sense, for example, it may be a fixed connection or a detachable connection , or integrally connected; it can be a mechanical connection or an electrical connection; it can be a direct connection, or an indirect connection through an intermediate medium, or the internal communication between the two components.
  • installed e.g., it may be a fixed connection or a detachable connection , or integrally connected; it can be a mechanical connection or an electrical connection; it can be a direct connection, or an indirect connection through an intermediate medium, or the internal communication between the two components.
  • a first feature "on” or “under” a second feature may include the first and second features in direct contact, or may include the first and second features Not directly but through additional features between them.
  • the first feature being “above”, “over” and “above” the second feature includes the first feature being directly above and obliquely above the second feature, or simply means that the first feature is level higher than the second feature.
  • the first feature is “below”, “below” and “below” the second feature includes the first feature being directly below and diagonally below the second feature, or simply means that the first feature has a lower level than the second feature.
  • the embodiment of the present invention provides a preparation method of a porous carbon-graphene composite material, comprising the following steps:
  • superabsorbent resin, water and a small amount of graphene oxide are used as raw materials, the cost is low, and the graphene oxide solution fills the superabsorbent resin, and the structure of the porous carbon-graphene composite material obtained after carbonization will not collapse, And graphene oxide has excellent electrical conductivity after thermal reduction, and it is filled in porous carbon, which greatly increases the electrical conductivity and specific surface area of porous carbon, and improves the reaction activity and reaction rate.
  • the superabsorbent resin is rich in carbon elements and contains other beneficial elements (N, S, P, etc.), thereby improving the cycle performance of lithium-ion batteries.
  • the invention has simple preparation steps, no toxic and harmful solvents, environmental protection and high efficiency.
  • the superabsorbent resin is starch grafted acrylic acid, grafted acrylamide, high-degree croscarmellose, croscarmellose grafted acrylamide or sodium polyacrylate one or more of.
  • the graphene oxide solution adopts one or more of intrinsic state graphene oxide, nitrogen-doped graphene oxide and sulfur-doped graphene oxide.
  • the size of the graphene oxide is 500-2000 nm, and the number of layers of the graphene oxide is in the range of 1-100 layers.
  • the concentration of the graphene oxide solution is 0.1-2 g/L.
  • step S1 the mass ratio of the superabsorbent resin to the volume of the graphene oxide solution is 1 g: (0.05-1) L.
  • the protective gas is nitrogen or argon.
  • the drying time is 60-180min.
  • the heating temperature for carbonization is 500-1000°C.
  • the present invention also provides a porous carbon-graphene composite material, and the porous carbon-graphene composite material is prepared by the preparation method.
  • superabsorbent resin, water and a small amount of graphene oxide are used as raw materials, the cost is low, and the graphene oxide solution fills the superabsorbent resin, and the structure of the porous carbon-graphene composite material obtained after carbonization will not collapse, And graphene oxide has excellent electrical conductivity after thermal reduction, and it is filled in porous carbon, which greatly increases the electrical conductivity and specific surface area of porous carbon, and improves the reaction activity and reaction rate.
  • the superabsorbent resin is rich in carbon elements and contains other beneficial elements (N, S, P, etc.), thereby improving the cycle performance of lithium-ion batteries.
  • the invention has simple preparation steps, no toxic and harmful solvents, environmental protection and high efficiency.
  • the graphene oxide solution with a concentration of 0.5 g/L was ultrasonicated for 30 min, and 1 g of sodium polyacrylate was added to 100 ml of the intrinsic state graphene oxide solution and stirred. Dry to constant weight, heat at 800° C. for 120 min under nitrogen atmosphere, wash, dry to constant weight, and grind to obtain porous carbon-graphene composite material after carbonization is completed.
  • the porous carbon-graphene composite was fabricated into a coin cell battery. After the electrochemical performance test, when the current density is 0.1C, the first discharge specific capacity is 353.81mAh/g, after 100 cycles, the discharge specific capacity is 383.90mAh/g, the capacity retention rate is 108.50%, and the cycle performance is excellent.
  • Fig. 1 is the SEM image of graphene oxide obtained after reduction of graphene oxide in the present embodiment, as can be seen from Fig. 1, graphene oxide has good dispersibility, and it is a single layer, which can give full play to its high conductivity and high specific surface area effect.
  • a nitrogen-doped graphene oxide solution with a concentration of 0.5 g/L was prepared by ultrasonic for 30 min, 1 g of sodium polyacrylate was added to 100 ml of graphene oxide solution and stirred to make it evenly distributed, freeze-dried to a constant weight, under a nitrogen atmosphere, the temperature Heating at 500° C. for 30 min, after carbonization is completed, washing to remove salt ions, drying to constant weight, and grinding to obtain a porous carbon-graphene composite material.
  • the porous carbon-graphene composite material was used as the anode material of lithium ion battery to make a button battery.
  • the first discharge specific capacity is 334.29mAh/g
  • the discharge specific capacity is 340.28mAh/g
  • the capacity retention rate is 101.79%
  • the cycle performance is better.
  • the nitrogen-doped graphene oxide solution with a concentration of 1 g/L was ultrasonicated for 30 min, and 1 g of starch grafted acrylic acid was added to 200 ml of graphene oxide solution and stirred to make it evenly distributed, freeze-dried to constant weight, and in a nitrogen atmosphere, the temperature was Heating at 900° C. for 180 min, after carbonization is completed, washing to remove impurities, drying to constant weight, and grinding to obtain a porous carbon-graphene composite material.
  • the porous carbon-graphene composite material was used as the anode material of lithium ion battery to make a button battery.
  • the first discharge specific capacity is 329.34mAh/g
  • the discharge specific capacity is 322.85mAh/g
  • the capacity retention rate is 98.02%
  • the cycle performance is better.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Manufacturing & Machinery (AREA)
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Abstract

本发明提供了一种多孔碳-石墨烯复合材料及其制备方法，包括以下步骤：将高吸水树脂加入超声处理的氧化石墨烯溶液中，冷冻成型；在真空环境下冷冻干燥，得高吸水树脂-氧化石墨烯复合材料；在保护气氛下，在500～1000℃对所得复合材料依次进行碳化、洗涤、干燥至恒重、研磨后多孔碳-石墨烯复合材料。本发明实施例以高吸水树脂、水和少量氧化石墨烯为原料，成本较低，氧化石墨烯溶液将高吸水树脂填满，碳化后得到的多孔碳-石墨烯复合材料的结构不会坍塌，并且氧化石墨烯经过热还原后具有优异的导电性，其填充在多孔碳中，极大地增加多孔碳的导电性和比表面积，提高反应活性和反应速率。本发明制备步骤简单，无有毒有害溶剂，环保高效。

Description

一种多孔碳-石墨烯复合材料及其制备方法 技术领域
本发明涉及新能源领域，尤其涉及一种多孔碳-石墨烯复合材料及其制备方法。
背景技术
锂离子电池的正极和负极是电池性能的基础，直接决定了电池的比能量、比功率、循环稳定性和安全性等各项性能指标。目前负极普遍碳材料，而其中多孔碳材料由于其导电性优异，成本不高，制备工艺简单应用最为广泛。高吸水树脂可以吸收相当于树脂体积几百倍的水分，可以在有效扩大其体积，吸水干燥后，会在吸水树脂中形成大量的孔道和孔洞，碳化后可形成高比表面积的碳材料，其成本极低，导电性良好。
高吸水树脂在碳化过程中，由于其体积增加较多，形成的孔无材料支撑，多孔结构易坍塌，从而影响其性能，如何防止其在碳化过程中结构坍塌，增大其比表面积，具有重要的研究的意义。
发明内容
本发明为解决现有锂电池负极材料在碳化过程中结构结易坍塌，不利于使用的技术问题，提供了一种多孔碳-石墨烯复合材料及其制备方法。
本发明实施例提供了一种多孔碳-石墨烯复合材料的制备方法，包括以下步骤：
S1、将高吸水树脂加入超声处理的氧化石墨烯溶液中，冷冻成型；
S2、在真空环境下冷冻干燥，得高吸水树脂-氧化石墨烯复合材料；
S3、在保护气氛下，在500～1000℃对所得复合材料依次进行碳化、洗涤、干燥至恒重、研磨后多孔碳-石墨烯复合材料。
进一步地，所述高吸水树脂为淀粉接枝丙烯酸、接枝丙烯酰胺、高取代度交联羧甲基纤维素、交联羧甲基纤维素接枝丙烯酰胺或聚丙烯酸钠的一种或多种。
进一步地，所述氧化石墨烯溶液采用本征态氧化石墨烯、氮掺杂氧化石墨烯和硫掺杂氧化石墨烯中的一种或多种。
进一步地，氧化石墨烯的尺寸为500～2000nm，氧化石墨烯的层数范围在1～100层。
进一步地，所述氧化石墨烯溶液的浓度为0.1～2g/L。
进一步地，步骤S1中，高吸水树脂的质量和氧化石墨烯溶液的体积比为1g：(0.05～1)L。
进一步地，步骤S3中，保护气为氮气或氩气。
进一步地，步骤S3中，干燥的时间为60～180min。
进一步地，步骤S3中，碳化的加热温度为500～1000℃。
另一方面，本发明还提供一种多孔碳-石墨烯复合材料，所述多孔碳-石墨烯复合材料采用所述的制备方法制得。
本发明的有益效果是：本发明实施例以高吸水树脂、水和少量氧化石墨烯为原料，成本较低，氧化石墨烯溶液将高吸水树脂填满，碳化后得到的多孔碳-石墨烯复合材料的结构不会坍塌，并且氧化石墨烯经过热还原后具有优异的导电性，其填充在多孔碳中，极大地增加多孔碳的导电性和比表面积，提高反应活性和反应速率。另外，高吸水树脂碳元素丰富，且含有其它有益的元素(N、S、P等)，从而提高锂离子电池的循环性能。本发明制备步骤简单，无有毒有害溶剂，环保高效。
附图说明
图1为本发明实施例1所得多孔碳-石墨烯合材料还原的SEM图。
具体实施方式
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。
在本发明的描述中，需要理解的是，术语“中心”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”“内”、“外”、“顺时针”、“逆时针”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。
在本发明中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”、“固定”等术语应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本发明中的具体含义。
在本发明中，除非另有明确的规定和限定，第一特征在第二特征之“上”或之“下”可以包括第一和第二特征直接接触，也可以包括第一和第二特征不是直接接触而是通过它们之间的另外的特征接触。而且，第一特征在第二特征“之上”、“上方”和“上面”包括第一特征在第二特征正上方和斜上方，或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”包括第一特征在第二特征正下方和斜下方，或仅仅表示第一特征水平高度小于第二特征。
下面通过具体实施方式结合附图对本发明作进一步详细说明。
本发明实施例提供了一种多孔碳-石墨烯复合材料的制备方法，包括以下步骤：
S1、将高吸水树脂加入超声处理的氧化石墨烯溶液中，冷冻成型；
S2、在真空环境下冷冻干燥，得高吸水树脂-氧化石墨烯复合材料；
S3、在保护气氛下，在500～1000℃对所得复合材料依次进行碳化、洗涤、干燥至恒重、研磨后多孔碳-石墨烯复合材料。
本发明实施例以高吸水树脂、水和少量氧化石墨烯为原料，成本较低，氧化石墨烯溶液将高吸水树脂填满，碳化后得到的多孔碳-石墨烯复合材料的结构不会坍塌，并且氧化石墨烯经过热还原后具有优异的导电性，其填充在多孔碳中，极大地增加多孔碳的导电性和比表面积，提高反应活性和反应速率。另外，高吸水树脂碳元素丰富，且含有其它有益的元素(N、S、P等)，从而提高锂离子电池的循环性能。本发明制备步骤简单，无有毒有害溶剂，环保高效。
在一个可选实施例中，所述高吸水树脂为淀粉接枝丙烯酸、接枝丙烯酰胺、高取代度交联羧甲基纤维素、交联羧甲基纤维素接枝丙烯酰胺或聚丙烯酸钠的一种或多种。
在一个可选实施例中，所述氧化石墨烯溶液采用本征态氧化石墨烯、氮掺杂氧化石墨烯和硫掺杂氧化石墨烯中的一种或多种。
在一个可选实施例中，氧化石墨烯的尺寸为500～2000nm，氧化石墨烯的层数范围在1～100层。
在一个可选实施例中，所述氧化石墨烯溶液的浓度为0.1～2g/L。
在一个可选实施例中，步骤S1中，高吸水树脂的质量和氧化石墨烯溶液的体积比为1g：(0.05～1)L。
在一个可选实施例中，步骤S3中，保护气为氮气或氩气。干燥的时间为60～180min。步骤S3中，碳化的加热温度为500～1000℃。
另一方面，本发明还提供一种多孔碳-石墨烯复合材料，所述多孔碳-石墨烯复合材料采用所述的制备方法制得。
本发明实施例以高吸水树脂、水和少量氧化石墨烯为原料，成本较低，氧化石墨烯溶液将高吸水树脂填满，碳化后得到的多孔碳-石墨烯复合材料的结构不会坍塌，并且氧化石墨烯经过热还原后具有优异的导电性，其填充在多孔碳中，极大地增加多孔碳的导电性和比表面积，提高反应活性和反应速率。另外，高吸水树脂碳元素丰富，且含有其它有益的元素(N、S、P等)，从而提高锂离子电池的循环性能。本发明制备步骤简单，无有毒有害溶剂，环保高效。
具体实施例如下：
实施例1
配置浓度为0.5g/L的氧化石墨烯溶液超声30min，取1g聚丙烯酸钠加入到100ml本征态氧化石墨烯溶液中搅拌，氧化石墨烯为单层，使其均匀分布，冷冻成型，真空冷冻干燥至恒重，在氮气气氛下，温度为800℃加热120min，碳化完成后，洗涤，干燥至恒重，研磨，即得多孔碳-石墨烯复合材料。
将多孔碳-石墨烯复合材料制成纽扣电池。经过电化学性能测试，在电流密度为0.1C时，首次放电比容量353.81mAh/g，100周循环后放电比容量为383.90mAh/g,容量保持率为108.50％，循环性能优异。
图1为本实施例中氧化石墨烯还原后得到石墨烯的SEM图，从图1中可以看出，氧化石墨烯分散性良好，其为单层，能够充分发挥其高导电性和高比表面积的作用。
实施例2
配置浓度为0.5g/L的氮掺杂氧化石墨烯溶液超声30min，取1g聚丙烯酸钠加入到100ml氧化石墨烯溶液中搅拌，使其均匀分布，冷冻干燥至恒重，在氮气气氛下，温度为500℃加热30min，碳化完成后，洗涤去除其中的盐离子，干燥至恒重，研磨，即得多孔碳-石墨烯复合材料。
将多孔碳-石墨烯复合材料作为锂离子电池负极材料制成纽扣电池。经过电 化学性能测试，在电流密度为0.1C时，首次放电比容量334.29mAh/g，100周循环后放电比容量为340.28mAh/g,容量保持率为101.79％，循环性能较佳。
实施例3
配置浓度为1g/L的氮掺杂氧化石墨烯溶液超声30min，取1g淀粉接枝丙烯酸加入到200ml氧化石墨烯溶液中搅拌，使其均匀分布，冷冻干燥至恒重，在氮气气氛下，温度为900℃加热180min，碳化完成后，洗涤去除杂质，干燥至恒重，研磨，即得多孔碳-石墨烯复合材料。
将多孔碳-石墨烯复合材料作为锂离子电池负极材料制成纽扣电池。经过电化学性能测试，在电流密度为0.1C时，首次放电比容量329.34mAh/g，100周循环后放电比容量为322.85mAh/g,容量保持率为98.02％，循环性能较佳。
在本说明书的描述中，参考术语“一个实施方式”、“一些实施方式”、“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上内容是结合具体的实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单推演或替换。

Claims (10)

  1. 一种多孔碳-石墨烯复合材料的制备方法，其特征在于，包括以下步骤：
    S1、将高吸水树脂加入超声处理的氧化石墨烯溶液中，冷冻成型；
    S2、在真空环境下冷冻干燥，得高吸水树脂-氧化石墨烯复合材料；
    S3、在保护气氛下，在500～1000℃对所得复合材料依次进行碳化、洗涤、干燥至恒重、研磨后多孔碳-石墨烯复合材料。
  2. 如权利要求1所述的多孔碳-石墨烯复合材料的制备方法，其特征在于，所述高吸水树脂为淀粉接枝丙烯酸、接枝丙烯酰胺、高取代度交联羧甲基纤维素、交联羧甲基纤维素接枝丙烯酰胺或聚丙烯酸钠的一种或多种。
  3. 如权利要求1所述的多孔碳-石墨烯复合材料的制备方法，其特征在于，所述氧化石墨烯溶液采用本征态氧化石墨烯、氮掺杂氧化石墨烯和硫掺杂氧化石墨烯中的一种或多种。
  4. 如权利要求1所述的多孔碳-石墨烯复合材料的制备方法，其特征在于，氧化石墨烯的尺寸为500～2000nm，氧化石墨烯的层数范围在1～100层。
  5. 如权利要求1所述的多孔碳-石墨烯复合材料的制备方法，其特征在于，所述氧化石墨烯溶液的浓度为0.1～2g/L。
  6. 如权利要求1所述的多孔碳-石墨烯复合材料的制备方法，其特征在于，步骤S1中，高吸水树脂的质量和氧化石墨烯溶液的体积比为1g：(0.05～1)L。
  7. 如权利要求1所述的多孔碳-石墨烯复合材料的制备方法，其特征在于，步骤S3中，保护气为氮气或氩气。
  8. 如权利要求1所述的多孔碳-石墨烯复合材料的制备方法，其特征在于，步骤S3中，干燥的时间为60～180min。
  9. 如权利要求1所述的多孔碳-石墨烯复合材料的制备方法，其特征在于，步骤S3中，碳化的加热温度为500～1000℃。
  10. 一种多孔碳-石墨烯复合材料，其特征在于，所述多孔碳-石墨烯复合材料采用权利要求1～9任一项所述的制备方法制得。
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