WO2020177461A1 - 覆碳泡沫铝复合材料及其制备方法、集流体及过滤材料 - Google Patents

覆碳泡沫铝复合材料及其制备方法、集流体及过滤材料 Download PDF

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WO2020177461A1
WO2020177461A1 PCT/CN2019/128882 CN2019128882W WO2020177461A1 WO 2020177461 A1 WO2020177461 A1 WO 2020177461A1 CN 2019128882 W CN2019128882 W CN 2019128882W WO 2020177461 A1 WO2020177461 A1 WO 2020177461A1
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carbon
coated
aluminum
composite material
foam composite
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PCT/CN2019/128882
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English (en)
French (fr)
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缪永华
张刚
杨智皋
骞伟中
金鹰
崔超婕
张抒婷
杨周飞
刘莎
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中天储能科技有限公司
江苏中天科技股份有限公司
清华大学
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Publication of WO2020177461A1 publication Critical patent/WO2020177461A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/02—Loose filtering material, e.g. loose fibres
    • B01D39/06—Inorganic material, e.g. asbestos fibres, glass beads or fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66—Current collectors
    • H01G11/68—Current collectors characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66—Current collectors
    • H01G11/70—Current collectors characterised by their structure
    • 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
    • H01M4/64—Carriers or collectors
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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

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  • the invention relates to the field of materials, in particular to a carbon-coated aluminum foam composite material and a preparation method thereof, a current collector and a filter material.
  • Aluminum-based materials are widely used in industry, mainly including various electrical conduction, heat dissipation, sound insulation applications and mechanical applications (such as buffering, weight reduction and strength support).
  • the positive electrode current collector materials are all Aluminum
  • aluminum is prepared into porous film-like materials, which can be used as current collectors for various electrochemical energy storage.
  • the method of preparing porous aluminum includes depositing an aluminum layer on a porous polymer film, and then removing the polymer substrate; it can also be obtained by bonding aluminum powder and then sintering; it can also be obtained by melting aluminum, blowing in gas, and blowing .
  • the through-hole porous aluminum film has the disadvantages of large porosity, low mechanical strength, and inconvenient and rapid preparation of electrode pads.
  • porous aluminum when porous aluminum is placed in the air, or even under the protection of a protective gas, it is easy to form an oxide film on the surface.
  • it When it is in contact with the electrode material, it has poor contact and high resistance, which is useful for improving the power of the device.
  • the density is unfavorable.
  • a carbon-coated aluminum foam composite material has a coated core-shell structure.
  • the core is aluminum foam formed by an aluminum wire skeleton and three-dimensional connected holes.
  • the shell layer is a carbon layer. It is uniformly coated on the surface of the aluminum wire skeleton, and the thickness of the carbon layer is 0.34 nm to 4 ⁇ m.
  • the foamed aluminum is an open-pore particle, block or film-like material, and the porosity on the foamed aluminum is 50-99%.
  • the diameter of the three-dimensional communicating hole is within 1 mm, and the aluminum wire skeleton is tens of microns in thickness.
  • a method for preparing the carbon-coated aluminum foam composite material includes the following steps:
  • Step 1 Coat the organic compound on the foamed aluminum, and in the presence of a solvent, dry at 50-100°C for 0.1-5 hours to volatilize the solvent;
  • Step 2 Raise the temperature to 250-660°C in a protective atmosphere for carbonization for 0.5-8 hours to form a carbon film on the surface of the foamed aluminum, and then take it out after the temperature drops to room temperature in a protective atmosphere, where the heating rate is 10-50°C every minute;
  • Step 3 Repeat Step 1 and Step 2 until the desired carbon film thickness is reached.
  • the organic compound in the step 1 is liquid, solid or paste.
  • the organic compound in step 1 includes one of epoxy resin, polyacrylonitrile, polyolefin, unsaturated polyester resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, liquid rubber, or Multiple combinations.
  • the solvent in the step 1 includes one or more of ethers, alcohols, ketones, aromatic hydrocarbons, halogenated hydrocarbons, phenols, esters, amides, sulfones and sulfoxides.
  • the gas in the protective atmosphere is argon and one or more combinations of argon.
  • a current collector is made of the above-mentioned carbon-coated aluminum foam composite material.
  • the two sides of the carbon-coated aluminum foam are provided with uncoated carbon areas, and the uncoated carbon areas are used for welding tabs.
  • a filter material is made of the carbon-coated aluminum foam composite material.
  • the filter material is used for filtering or adsorbing substances, and can be used for filtering or adsorbing cations, cells, heavy metals, non-polar organics and particles.
  • the carbon-coated aluminum foam composite material provided by the present invention has a coated core-shell structure, the core body is aluminum foam formed by an aluminum wire skeleton and three-dimensional connected holes, the shell layer is a carbon layer, and the carbon layer is evenly coated on the On the surface of the aluminum wire skeleton, the thickness of the carbon layer is 0.34 nm to 4 ⁇ m.
  • the present invention wraps a continuous carbon film on the foam aluminum structure to increase the mechanical strength of the multi-foam aluminum film material by 20-80%; when used as a current collector material for energy storage devices (batteries, capacitors, battery capacitors, etc.) Compared with the carbon-coated aluminum foam current collector, the contact resistance of the carbon-coated aluminum foam current collector and the electrode material is reduced by 50%-99.5%.
  • Fig. 1 is a schematic flow chart of a method for preparing a carbon-coated aluminum foam composite material in an embodiment of the present invention.
  • Fig. 2 is a schematic diagram of the microstructure of the carbon-coated aluminum foam composite prepared by the preparation method described in Fig. 1.
  • Fig. 3 is a further enlarged schematic diagram of the microstructure of the carbon-coated aluminum foam composite material of Fig. 2.
  • FIG. 4 is a schematic diagram of the microstructure of a foamed aluminum composite material coated with a non-dense continuous carbon layer in an embodiment of the present invention.
  • Fig. 5 is a further enlarged schematic view of the microstructure of the non-dense continuous carbon layer coated foam aluminum composite material of Fig. 4.
  • FIG. 1 is a schematic flow diagram of a method for preparing a carbon-coated aluminum foam composite material in an embodiment of the present invention, which specifically includes the following steps:
  • Step S11 coating the organic compound on the foamed aluminum, and in the presence of a solvent, drying at 50-100°C for 0.1-5 hours to volatilize the solvent;
  • Step S12 heat up to 250-660°C in a protective atmosphere for carbonization for 0.5-8 hours to form a carbon film on the surface of the foamed aluminum, and then take it out after the temperature drops to room temperature in a protective atmosphere, where the heating rate is 10-50°C every minute;
  • Step S13, step S11 and step S12 are repeated until the desired carbon film thickness is reached.
  • the organic compound in step S11 is liquid, solid or paste.
  • the organic compound in step S11 includes epoxy resin, polyacrylonitrile, polyolefin, unsaturated polyester resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, and liquid rubber. One or more combinations.
  • the solvent in step S11 includes one or more of ethers, alcohols, ketones, aromatic hydrocarbons, halogenated hydrocarbons, phenols, esters, amides, sulfones and sulfoxides.
  • ethers organic radicals
  • aromatic hydrocarbons organic radicals
  • halogenated hydrocarbons organic radicals
  • phenols organic radicals
  • esters organic radicals
  • amides organic radicals
  • sulfones sulfones
  • sulfoxides sulfoxides.
  • the protective atmosphere in the step S12 is one or more combinations of argon and nitrogen.
  • Figures 2 and 3 are schematic diagrams of the microstructure of the carbon-coated aluminum foam composite prepared by the above preparation method.
  • the carbon-coated aluminum foam composite prepared by the above preparation method has a coated core-shell structure.
  • the core body is aluminum foam formed by an aluminum wire skeleton and three-dimensional connected pores
  • the shell layer is a carbon layer
  • the carbon layer uniformly coats the surface of the aluminum wire skeleton
  • the thickness of the carbon layer is 0.34 nm to 4 ⁇ m.
  • the foamed aluminum is an open-pored particle, block or film material with a porosity of 50-99%.
  • the aluminum wire skeleton is composed of several aluminum wires tens of microns thick, and the surface of each aluminum wire is uniformly and continuously covered with a carbon layer, and the foamed aluminum is provided with three-dimensional interconnected holes, The aperture of the three-dimensional communicating hole is within 1 mm. Since there are closed-cell aluminum foams on the market, open-cell aluminum foams or through-cell aluminum foams are for closed-cell aluminum foams. At present, the closed-cell aluminum foam is prepared by the foaming method, so the pore size cannot be below millimeters, and it is currently mainly used for strength materials or sound insulation materials.
  • the commercially available porous aluminum foil is made by rolling on the aluminum foil with a laser or a dense needle cylinder, so this hole is a vertical hole, that is, two adjacent holes are parallel and not connected.
  • Aluminum foil and porous aluminum foil are basically flat, so the adhesion of the carbon layer will not cause major problems, and the thickness of the carbon layer is relatively large in the micron or tens of microns.
  • the aluminum wire in this application is only tens of micrometers thick, so the contact surface between the large carbon particles and the fine aluminum wire is very small, and the bonding force is not strong, which will cause falling off (as shown in Figure 4 and Figure 5). Higher technical requirements.
  • the epoxy resin and ethanol (or xylene) are prepared into a slurry and coated on the middle of the film-like foamed aluminum with a porosity of 50%, leaving a blank area directly around or on both sides to facilitate the use of welding tabs. Then it was dried at 50°C for 5 hours, heated to 250°C in a nitrogen atmosphere for carbonization for 8 hours to form a carbon film on the surface of the foamed aluminum. The heating rate was 50°C per minute, and then the temperature was lowered. The product is taken out under the action of the atmosphere, and the obtained foamed aluminum with continuous dense carbon film has a thickness of 0.34 nm.
  • the phenolic resin is configured into a slurry in acetone, and it is coated on the middle of the film-like foamed aluminum material with a porosity of 95%, leaving a blank area directly around or on both sides to facilitate the use of welding tabs. Then it was dried at 100°C for 0.1 hour, heated to 640°C in a hydrogen atmosphere for 3 hours, the heating rate was 30°C per minute, and then the temperature was lowered to room temperature. Repeat the above steps 5 times to get on the foamed aluminum surface A carbon film is formed, the hydrogen is switched to nitrogen when the temperature drops to room temperature, the product is taken out under the action of a nitrogen atmosphere, and the resulting aluminum foam with a continuous and dense carbon-coated film has a thickness of 4 ⁇ m.
  • Polyvinylidene chloride is dissolved in polychlorinated benzene to prepare a slurry, which is coated on the middle of the film-like aluminum foam with a porosity of 99%, leaving blank areas directly on the periphery or on both sides to facilitate the use of welding tabs. Then dry at 60°C for 2.5 hours, heat up to 600°C in an argon atmosphere for carbonization for 4 hours, where the heating rate is 20°C per minute, then cool down, and the temperature is lowered to room temperature. Repeat the above steps 3 times to A carbon film is formed on the surface, and the product is taken out under the action of a nitrogen atmosphere when the temperature is lowered to room temperature. The resulting foamed aluminum with a continuous and dense carbon-coated film has a thickness of 2 ⁇ m.
  • the tensile and mechanical strength of carbon-coated aluminum foam composites are increased by 80%.
  • the contact resistance with the electrode material (graphene) is reduced by 40%.
  • the polyvinyl chloride is configured into a slurry in chloroform, and it is coated on the middle of the film-like foamed aluminum with a porosity of 93%, leaving a blank area directly around or on both sides, which is convenient for welding the tabs.
  • carbonization was carried out at 500°C for 6 hours under an atmosphere of 5% hydrogen and 95% argon. Then lower the temperature and turn off the hydrogen gas, and take out the product under the protection of nitrogen when it reaches room temperature.
  • the obtained foamed aluminum with continuous dense carbon film has a thickness of 1.5 ⁇ m.
  • Polypropylene is dissolved in dimethylformamide to prepare a slurry, and it is coated on the middle of the film-like foamed aluminum with a porosity of 93%, leaving a blank area directly around or on both sides to facilitate the use of welding tabs. After drying, it was carbonized at 630°C for 4 hours in an argon atmosphere. Then the temperature is lowered, and the product is taken out under the protection of argon when it reaches room temperature.
  • the obtained foamed aluminum with a continuous dense carbon film has a thickness of 3 ⁇ m.
  • the liquid rubber is directly coated on the middle of the film-like foamed aluminum, leaving a blank area directly around or on both sides to facilitate the use of welding tabs. Dry at 50°C for 5 hours, then heat up in hydrogen to 350°C for carbonization for 6 hours, where the temperature rise rate is 50°C per minute, then cool down, and take out the product under nitrogen protection when it drops to room temperature.
  • the obtained foamed aluminum with continuous dense carbon film has a thickness of 200 nm.
  • the tensile and mechanical strength of carbon-coated aluminum foam composite materials are increased by 40%.
  • the contact resistance with the electrode material (activated carbon) is reduced by 90%.
  • the unsaturated polyester resin is swelled with dichloromethane and prepared into a slurry, and then coated on foamed aluminum particles with a particle size of 0.2-10 mm. Dry at 70°C for 3 hours. Then program the temperature to 580°C for 3 hours in an atmosphere of 50% nitrogen and 50% hydrogen for carbonization, where the heating rate is 40°C per minute, and then cool down and shut off the hydrogen. When it falls to room temperature, take out the product under nitrogen protection .
  • the obtained foamed aluminum with a continuous dense carbon film has a thickness of 150 nm.
  • the polyvinyl alcohol and water are prepared into a slurry, uniformly coated on the block foam aluminum, and dried at 60° C. for 5 hours. Then program the temperature to 500°C for carbonization in a nitrogen atmosphere for 6 hours, where the temperature rise rate is 35°C per minute, and then lower the temperature. When it is lowered to room temperature, the product is taken out under the protection of nitrogen.
  • the obtained foamed aluminum with continuous dense carbon film has a thickness of 50 nm.
  • Polyethylene and decahydronaphthalene are prepared into a slurry, which is uniformly coated on block foamed aluminum with a porosity of 90%, and dried at 100°C for 5 hours. Then program the temperature to 250°C for carbonization in a nitrogen atmosphere for 6 hours, where the temperature rise rate is 25°C per minute, and then lower the temperature. When it is lowered to room temperature, the product is taken out under argon protection.
  • the obtained foamed aluminum with continuous dense carbon film has a thickness of 4 ⁇ m.
  • the carbon-coated aluminum foam composite material provided by the present invention wraps a continuous carbon film on the foam aluminum structure to increase the mechanical strength of the multi-foam aluminum film material by 20-80%; it is used as an energy storage device (battery, capacitor, battery capacitor, etc.) ), the contact resistance between the carbon-coated aluminum foam current collector and the electrode material is reduced by 50% to 99.5% compared with the foam aluminum current collector without carbon coating.

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Abstract

本发明提供一种覆碳泡沫铝复合材料，所述覆碳泡沫铝复合材料为包覆型核壳结构，核体为铝丝骨架和三维连通孔形成的泡沫铝，壳层为碳层，所述碳层均匀包覆在所述铝丝骨架的表面，所述碳层的厚度为0.34nm～4μm。本发明提供的覆碳泡沫铝复合材料，在泡沫铝结构上包覆连续碳膜，使多泡沫铝膜材料的机械强度提高20-80％；用做储能器件(电池，电容器，电池电容等)的集流体材料时，与不涂覆碳的泡沫铝集流体相比，涂覆碳的泡沫铝集流体与电极材料的接触电阻降低50％-99.5％。

Description

覆碳泡沫铝复合材料及其制备方法、集流体及过滤材料 技术领域
本发明涉及材料领域，尤其涉及覆碳泡沫铝复合材料及其制备方法、集流体及过滤材料。
背景技术
铝基材料在工业中应用广泛，主要包括各种导电、散热、隔音用途及机械用途(如缓冲、减重与强度支撑)，目前2-4.5V锂离子电池中，正极的集流体材料全是铝的，铝材制备成多孔薄膜状材料，可以用作各种电化学储能的集流体。制备多孔铝的方法包括在多孔高分子薄膜上沉积铝层，然后去除高分子基板；也可以将铝粉进行粘合后烧结而得；也可以通过将铝熔融，通入气体，吹泡而得。但通孔型的多孔铝薄膜具有孔隙率大，机械强度低，不方便快速制备电极极片的缺点。同时，多孔铝在空气中放置时，或即使是在保护气体保护下，也容易在表面生成一层氧化膜，在与电极材料接触时，接触性较差，电阻较高，对于提高器件的功率密度不利。
发明内容
有鉴于此，有必要提供一种改进的覆碳泡沫铝复合材料，其能够有效提高泡沫铝的机械强度以及降低与电极材料的接触电阻。
一种覆碳泡沫铝复合材料，所述覆碳泡沫铝复合材料为包覆型核壳结构，核体为铝丝骨架和三维连通孔形成的泡沫铝，壳层为碳层，所述碳层均匀包覆在所述铝丝骨架的表面，所述碳层的厚度为0.34nm～4μm。
进一步的，所述泡沫铝为开孔状的颗粒、块状或薄膜状材料，所述泡沫铝上的孔隙率为50-99％。
进一步的，所述三维连通孔的孔径为1毫米以内，所述铝丝骨架为数十微米粗细。
一种所述覆碳泡沫铝复合材料的制备方法，包括以下步骤：
步骤1，将有机化合物涂覆在泡沫铝上，在有溶剂存在的情况下，在50-100℃下干燥0.1-5小时，使溶剂挥发；
步骤2，在保护气氛下升温至250-660℃进行碳化0.5-8小时以在泡沫铝表面形成碳膜，然后在保护气氛作用下，温度降至室温后取出，其中升温速率为10-50℃每分钟；
步骤3，重复步骤1和步骤2，直至达到所需的碳膜的厚度。
进一步的，所述步骤1中的有机化合物为液态、固态或膏状。
进一步的，所述步骤1中的有机化合物包括环氧树脂、聚丙烯腈、聚烯烃、不饱和聚酯树脂、聚氯乙烯、聚偏二氯乙烯、聚乙烯醇、液体橡胶中的一种或多种组合。
进一步的，所述步骤1中的溶剂包括醚类、醇类、酮类、芳烃类、卤代烃类、酚类、酯类、酰胺、砜及亚砜类中的一种或多种。
进一步的，所述保护气氛中的气体为氩气、氩气中的一种或多种组合。
一种集流体，采用上述的覆碳泡沫铝复合材料制成，所述覆碳泡沫铝的两侧设有未包覆碳的区域，所述未包覆碳的区域用于焊接极耳。
一种过滤材料，采用上述的覆碳泡沫铝复合材料制成，所述过滤材料用于过滤或吸附物质，可以用于过滤或吸附阳离子、细胞、重金属、非极性有机物以及颗粒等。
本发明提供的覆碳泡沫铝复合材料，为包覆型核壳结构，核体为铝丝骨架和三维连通孔形成的泡沫铝，壳层为碳层，所述碳层均匀包覆在所述铝丝骨架的表面，所述碳层的厚度为0.34nm～4μm。本发明在泡沫铝结构上包覆连续碳膜，使多泡沫铝膜材料的机械强度提高20-80％；用做储能器件(电池，电容器，电池电容等)的集流体材料时，与不涂覆碳的泡沫铝集流体相比，涂覆碳的泡沫铝集流体与电极材料的接触电阻降低50％-99.5％。
附图说明
图1为本发明一实施方式中的覆碳泡沫铝复合材料的制备方法的流程示意图。
图2为图1所述制备方法制备的覆碳泡沫铝复合材料的微观结构示意图。
图3为图2的覆碳泡沫铝复合材料的进一步放大微观结构示意图。
图4为本发明一实施方式中的非致密连续碳层包覆的泡沫铝复合材料的微观结构示意图。
图5为图4的非致密连续碳层包覆的泡沫铝复合材料的进一步放大微观结构示意图。
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
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。本文所使用的术语“或/及”包括一个或多个相关的所列项目的任意的和所有的组合。
请参阅图1，图1为本发明一实施方式中的覆碳泡沫铝复合材料的制备方法的流程示意图，具体包括以下步骤：
步骤S11，将有机化合物涂覆在泡沫铝上，在有溶剂存在的情况下，在50-100℃下干燥0.1-5小时，使溶剂挥发；
步骤S12，在保护气氛下升温至250-660℃进行碳化0.5-8小时以在泡沫铝表面形成碳膜，然后在保护气氛作用下，温度降至室温后取出，其中升温速率为10-50℃每分钟；
步骤S13，重复步骤S11和步骤S12，直至达到所需的碳膜的厚度。
在本实施方式中，所述步骤S11中的有机化合物为液态、固态或膏状。
在本实施方式中，所述步骤S11中的有机化合物包括环氧树脂、聚丙烯腈、聚烯烃、不饱和聚酯树脂、聚氯乙烯、聚偏二氯乙烯、聚乙烯醇、液体橡胶中的一种或多种组合。
在本实施方式中，所述步骤S11中的溶剂包括醚类、醇类、酮类、芳烃类、卤代烃类、酚类、酯类、酰胺、砜及亚砜类中的一种或多种。
在本实施方式中，所述步骤S12中的保护气氛为氩气、氮气中的一种或多种组合。
如图2和图3所示，图2及图3为上述制备方法制备的覆碳泡沫铝复合材料的微观结构示意图，上述制备方法制备的覆碳泡沫铝复合材料为包覆型核壳结构，核体为铝丝骨架和三维连通孔形成的泡沫铝，壳层为碳层，所述碳层均匀包覆在所述铝丝骨架的表面，所述碳层的厚度为0.34nm～4μm。
所述泡沫铝为开孔状的颗粒、块状或薄膜状材料，孔隙率为50-99％。
在本实施方式中，所述铝丝骨架由若干个数十微米粗的铝丝组成，每一所述铝丝表面均匀连续包覆碳层，且所述泡沫铝上设有三维连通的孔，所述三维连通孔的孔径为1毫米以内。由于市场上存在闭孔的泡沫铝，所以开孔泡沫铝或通孔的泡沫铝是针对闭孔泡沫铝来说的。目前闭孔泡沫铝是用发泡法制备的，所以孔径做不到到毫米以下，目前主要用于强度材料或隔音材料。另外市售的多孔铝箔是在铝箔上用激光或密集的针筒进行滚压而成，所以这种孔是垂直的孔，即两个相邻的孔是平行的且不相通。铝箔、多孔铝箔基本是平整的，所以碳层的附着力不会出现大的问题，其碳层厚度较大在微米级或数十微米级。本申请中的铝丝只有数十微米粗，因此大的碳颗粒与细的铝丝之间的接触面特别小，结合力不牢固，会导致脱落(如图4和图5所示)，制备技术要求较高。
下面将通过具体的实施方式对覆碳泡沫铝复合材料及其应用做进一步的说明。
实施例1
将环氧树脂与乙醇(或二甲苯)配置成浆料，涂覆在孔隙率为50％的薄膜状泡沫铝的中部，在四周或两边直接留出空白区，方便焊接极耳使用。然后在50℃下干燥5小时，在氮气气氛下升温至250℃进行碳化8小时以在泡沫铝表面形成碳膜，其中升温速率为50℃每分钟，然后进行降温，温度降至室温时在氮气气氛作用下将产品取出，所得具有连续致密覆碳膜的泡沫铝，碳膜厚度为0.34nm。
与不覆碳的产品(空心铝丝的壁厚7-100μm，空隙率85-99％，拉伸强度0.4-2MPa，抗压强度1-3.5MPa)相比，覆碳泡沫铝复合材料的拉伸及机械强 度提高20％。该产品用作3-4.5V的双电层超级电容器的集流体时，与电极材料(活性炭)的接触电阻降低50％。
实施例2
将聚丙烯腈溶在二甲基甲酰胺中配置成浆料，涂覆在孔隙率为99％的薄膜状泡沫铝材料的中部，在四周或两边直接留出空白区，方便焊接极耳使用。然后在50℃下干燥5小时，在氩气气氛下升温至620℃进行碳化0.5小时，其中升温速率为10℃每分钟，温度降至室温，重复上述步骤2次以在泡沫铝表面形成碳膜，温度降至室温时在氩气气氛作用下将产品取出；所得具有连续致密的覆碳膜的泡沫铝，碳膜厚度为0.5μm。
与不覆碳的产品相比，覆碳泡沫铝复合材料的拉伸及机械强度提高50％。该产品用作3-4.5V的锂离子电池正极侧的集流体时，与电极材料(磷酸铁锂)的接触电阻降低99.5％。
实施例3
将酚醛树脂在丙酮中配置成浆料，涂覆在孔隙率为95％的薄膜状泡沫铝材料的中部，在四周或两边直接留出空白区，方便焊接极耳使用。然后在100℃下干燥0.1小时，在氢气气氛下升温至640℃进行碳化3小时，其中升温速率为30℃每分钟，然后进行降温，温度降至室温，重复上述步骤5次以在泡沫铝表面形成碳膜，温度降至室温时将氢气切换为氮气，在氮气气氛作用下将产品取出，所得具有连续致密的覆碳膜的泡沫铝，碳膜厚度为4μm。
与不覆碳的产品相比，覆碳泡沫铝复合材料的拉伸及机械强度提高80％。该产品用作3-4.5V的锂离子电池正极侧的集流体时，与电极材料(镍钴锰三元材料)的接触电阻降低60％。
实施例4
将聚偏二氯乙烯溶解于多氯代苯中配置成浆料，涂覆在孔隙率99％的薄膜状泡沫铝的中部，在四周或两边直接留出空白区，方便焊接极耳使用。然后在60℃下干燥2.5小时，在氩气气氛下升温至600℃进行碳化4小时，其中升温速率为20℃每分钟，然后进行降温，温度降至室温，重复上述步骤3次以在泡沫铝表面形成碳膜，温度降至室温时在氮气气氛作用下将产品取出，所得具有连续致密的覆碳膜的泡沫铝，碳膜厚度为2μm。
与不覆碳的产品相比，覆碳泡沫铝复合材料的拉伸及机械强度提高80％。 该产品用作3-4.5V的双电层超级电容器的集流体时，与电极材料(石墨烯)的接触电阻降低40％。
实施例5
将聚氯乙烯在氯仿中配置成浆料，涂覆在孔隙率93％的薄膜状泡沫铝的中部，在四周或两边直接留出空白区，方便焊接极耳使用。干燥后，在5％氢气与95％氩气气氛下在500℃下碳化6小时。然后降温并关闭氢气，至室温时在氮气保护下，将产品取出。所得具有连续致密覆碳膜的泡沫铝，碳膜厚度为1.5μm。
与不覆碳的产品相比，覆碳泡沫铝复合材料的拉伸及机械强度提高75％。该产品用作3-4.5V的锂离子超级电容器的集流体时，与电极材料(活性炭或含锂化合物)的接触电阻降低70％。
实施例6
将聚丙烯溶于二甲基甲酰胺配置成浆料，涂覆在孔隙率93％的薄膜状泡沫铝的中部，在四周或两边直接留出空白区，方便焊接极耳使用。干燥后，在氩气气氛下在630℃下碳化4小时。然后进行降温，至室温时在氩气保护下，将产品取出。所得具有连续致密覆碳膜的泡沫铝，碳膜厚度为3μm。
与不覆碳的产品相比，覆碳泡沫铝复合材料的拉伸及机械强度提高70％。该产品用作3-4.5V的双电层超级电容器的集流体时，与电极材料(碳纳米管)的接触电阻降低60％。
实施例7
将液体橡胶直接涂覆在薄膜状泡沫铝的中部，在四周或两边直接留出空白区，方便焊接极耳使用。在50℃下干燥5小时，然后在氢气中升温至350℃进行碳化6小时，其中升温速率为50℃每分钟，然后进行降温，降至室温时在氮气保护下，将产品取出。所得具有连续致密覆碳膜的泡沫铝，碳膜厚度为200nm。
与不覆碳的产品相比，覆碳泡沫铝复合材料的拉伸及机械强度提高40％。该产品用作3-4.5V的双电层超级电容器的集流体时，与电极材料(活性炭)的接触电阻降低90％。
实施例8
将不饱和聚酯树脂用二氯甲烷溶胀与配置成浆料，涂敷在粒径为0.2-10mm 的泡沫铝颗粒。在70℃下干燥3小时。然后在50％氮气与50％氢气的气氛中程序升温至580℃进行碳化3小时，其中升温速率为40℃每分钟，然后进行降温并关闭氢气，降至室温时在氮气保护下，将产品取出。所得具有连续致密覆碳膜的泡沫铝，碳膜厚度为150nm。
与不覆碳的产品相比，覆碳泡沫铝复合材料的拉伸及机械强度提高40％。该材料可用作高性能过滤材料。
实施例9
将聚乙烯醇与水配置成浆料，均匀涂覆在块状泡沫铝上，在60℃下干燥5小时。然后在氮气气氛中程序升温至500℃进行碳化6小时，其中升温速率为35℃每分钟，然后进行降温，降至室温时在氮气保护下，将产品取出。所得具有连续致密覆碳膜的泡沫铝，碳膜厚度为50nm。
与不覆碳的产品相比，覆碳泡沫铝复合材料的拉伸及机械强度提高20％。该材料可用作高性能过滤材料。
实施例10
将聚乙烯与十氢萘配置成浆料，均匀涂覆在孔隙率为90％的块状泡沫铝上，在100℃下干燥5小时。然后在氮气气氛中程序升温至250℃进行碳化6小时，其中升温速率为25℃每分钟，然后进行降温，降至室温时在氩气保护下，将产品取出。所得具有连续致密覆碳膜的泡沫铝，碳膜厚度为4μm。
与不覆碳的产品相比，覆碳泡沫铝复合材料的拉伸及机械强度提高20％。该材料可用作高性能过滤材料。
本发明提供的覆碳泡沫铝复合材料，在泡沫铝结构上包覆连续碳膜，使多泡沫铝膜材料的机械强度提高20-80％；用做储能器件(电池，电容器，电池电容等)的集流体材料时，与不涂覆碳的泡沫铝集流体相比，涂覆碳的泡沫铝集流体与电极材料的接触电阻降低50％-99.5％。
本技术领域的普通技术人员应当认识到，以上的实施方式仅是用来说明本发明，而并非用作为对本发明的限定，只要在本发明的实质精神范围内，对以上实施方式所作的适当改变和变化都落在本发明要求保护的范围内。

Claims (10)

  1. 一种覆碳泡沫铝复合材料，其特征在于：所述覆碳泡沫铝复合材料为包覆型核壳结构，核体为铝丝骨架和三维连通孔形成的泡沫铝，壳层为碳层，所述碳层均匀包覆在所述铝丝骨架的表面，所述碳层的厚度为0.34nm～4μm。
  2. 如权利要求1所述的覆碳泡沫铝复合材料，其特征在于：所述泡沫铝为开孔状的颗粒、块状或薄膜状材料，所述泡沫铝上的孔隙率为50-99％。
  3. 如权利要求1所述的覆碳泡沫铝复合材料，其特征在于：所述三维连通孔的孔径为1毫米以内，所述铝丝骨架为数十微米粗细。
  4. 一种如权利要求1-3任意一项所述的覆碳泡沫铝复合材料的制备方法，其特征在于，包括以下步骤：
    步骤1，将有机化合物涂覆在泡沫铝上，在有溶剂存在的情况下，在50-100℃下干燥0.1-5小时，使溶剂挥发；
    步骤2，在保护气氛下升温至250-660℃进行碳化0.5-8小时以在泡沫铝表面形成碳膜，然后在保护气氛作用下，温度降至室温后取出，其中升温速率为10-50℃每分钟；
    步骤3，重复步骤1和步骤2，直至达到所需的碳膜的厚度。
  5. 如权利要求4所述的覆碳泡沫铝复合材料的制备方法，其特征在于：所述步骤1中的有机化合物为液态、固态或膏状。
  6. 如权利要求4所述的覆碳泡沫铝复合材料的制备方法，其特征在于：所述步骤1中的有机化合物包括环氧树脂、聚丙烯腈、聚烯烃、不饱和聚酯树脂、聚氯乙烯、聚偏二氯乙烯、聚乙烯醇、液体橡胶中的一种或多种组合。
  7. 如权利要求4所述的覆碳泡沫铝复合材料的制备方法，其特征在于：所述步骤1中的溶剂包括醚类、醇类、酮类、芳烃类、卤代烃类、酚类、酯类、酰胺、砜及亚砜类中的一种或多种。
  8. 如权利要求4所述的覆碳泡沫铝复合材料的制备方法，其特征在于：所述保护气氛中的气体为氩气、氩气中的一种或多种组合。
  9. 一种集流体，其特征在于：采用如权利要求1-3任意一所述的覆碳泡沫铝复合材料制成，所述集流体的两侧设有未包覆碳的区域，所述未包覆碳的区域用于焊接极耳。
  10. 一种过滤材料，其特征在于：采用如权利要求1-3任意一所述的覆碳泡沫铝复合材料制成，所述过滤材料用于过滤或吸附物质。
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