WO2024040429A1 - 一种具有温度响应特性的电磁屏蔽复合材料及其制备方法和应用 - Google Patents

一种具有温度响应特性的电磁屏蔽复合材料及其制备方法和应用 Download PDF

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WO2024040429A1
WO2024040429A1 PCT/CN2022/114200 CN2022114200W WO2024040429A1 WO 2024040429 A1 WO2024040429 A1 WO 2024040429A1 CN 2022114200 W CN2022114200 W CN 2022114200W WO 2024040429 A1 WO2024040429 A1 WO 2024040429A1
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electromagnetic shielding
composite material
vanadium dioxide
temperature response
response characteristics
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French (fr)
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万艳君
廖思远
王晓允
胡友根
朱朋莉
孙蓉
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Shenzhen Institute of Advanced Technology of CAS
Shenzhen Institute of Advanced Electronic Materials
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Shenzhen Institute of Advanced Technology of CAS
Shenzhen Institute of Advanced Electronic Materials
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C1/00—Details
    • H01C1/06—Electrostatic or electromagnetic shielding arrangements

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  • the invention belongs to the technical field of electromagnetic shielding materials and relates to an electromagnetic shielding composite material with temperature response characteristics and its preparation method and application.
  • Intelligent electromagnetic shielding composite materials refer to the ability to change the electromagnetic properties of composite materials through external stimuli, including force, electricity, magnetism and heat.
  • Existing intelligent electromagnetic shielding composite materials have basically undergone certain structural designs and respond to electromagnetic waves through structural deformation.
  • Existing smart shielding composite materials cannot start from the intrinsic characteristics of the material. When responding to external stimuli, the composite material will deform, which is a great challenge to the reliability of the material.
  • Heat is one of the very important stimulating factors, because the high-speed operation of electronic devices will inevitably be accompanied by the generation of a large amount of heat. Therefore, heat is an unavoidable problem when the chip is working. It is necessary to develop an intrinsic type that can respond to heat. Composite materials with tunable electromagnetic response have broad application prospects.
  • the present invention provides an electromagnetic shielding composite material with temperature response characteristics and its preparation method and application.
  • the present invention uses the phase change material vanadium dioxide as a functional material to be compounded with the matrix material.
  • the vanadium dioxide is used when its temperature exceeds The phase transition temperature changes from the insulating state to the metallic state to achieve the electromagnetic shielding performance of the composite material with temperature response characteristics.
  • the present invention provides an electromagnetic shielding composite material with temperature response characteristics, using vanadium dioxide as a functional material, and the functional material is composited with a matrix material.
  • the vanadium dioxide is in the form of fibers, sheets, or granules.
  • the vanadium dioxide is doped before use, and the doping element is tungsten element or germanium element.
  • the matrix material is polymer, cellulose fiber, or graphene material.
  • the ratio of the amount of vanadium dioxide to the matrix material is 1:1 to 10:1.
  • the present invention also provides a method for preparing the above-mentioned electromagnetic shielding composite material with temperature response characteristics, which includes the following steps:
  • the gel, solution or dispersion of vanadium dioxide and the matrix material is ball-milled and blended in a certain proportion;
  • the base material is cellulose fiber
  • the preparation method includes the following steps:
  • the vanadium dioxide and cellulose fiber gel are ball-milled and blended in a certain proportion
  • the base material is a polymer
  • the preparation method includes the following steps:
  • the vanadium dioxide and polymer solution are ball milled and blended in a certain proportion
  • the base material is graphene
  • the preparation method includes the following steps:
  • the vanadium dioxide and graphene dispersion are ball milled and blended in a certain proportion
  • the present invention also provides the application of the electromagnetic shielding composite material with temperature response characteristics.
  • the electromagnetic shielding composite material with temperature response characteristics is used as an intelligent temperature-controlled electromagnetic shielding switch in a device.
  • the electromagnetic shielding composite material with temperature response characteristics of the present invention uses the phase change material vanadium dioxide as a functional material to be compounded with the matrix material, and uses the vanadium dioxide to change from an insulating state to a metallic state when its temperature exceeds the phase change temperature, thereby realizing the composite
  • the electromagnetic shielding performance of the material has temperature response characteristics;
  • the electromagnetic shielding composite material with temperature response characteristics of the present invention is an intrinsic composite material that can make a tunable electromagnetic response to heat, has recyclable characteristics, and avoids the traditional smart electromagnetic Shielding composite materials need to respond to external stimuli through deformation of the designed structure, which greatly improves the reliability of the material.
  • the preparation method of the electromagnetic shielding composite material with temperature response characteristics of the present invention is simple and can be industrially produced.
  • the electromagnetic shielding composite material with temperature response characteristics of the present invention has broad application prospects and is of great significance for application in devices as an intelligent temperature-controlled electromagnetic shielding switch.
  • Figure 1 shows the XRD patterns of vanadium dioxide at different temperatures
  • Figure 2 is a cross-sectional microscopic view of the vanadium dioxide/nanocellulose fiber film in Example 1 of the present invention
  • Figure 3 shows the electrical conductivity of vanadium dioxide/nanocellulose fibers in Example 1 at different temperatures
  • Figure 4 shows the electromagnetic shielding effectiveness of the vanadium dioxide/nanocellulose fibers in Example 1 at different temperatures
  • Figure 5 shows the electromagnetic shielding effectiveness of vanadium dioxide/polyurethane in Example 2 at different temperatures
  • Figure 6 shows the electromagnetic shielding effectiveness of vanadium dioxide/graphene in Example 3 at different temperatures.
  • Vanadium dioxide (VO 2 ) has a monoclinic rutile crystal structure at room temperature. It has poor conductivity and is in an insulating state.
  • the XRD patterns of vanadium dioxide at different temperatures are shown in Figure 1. When its temperature exceeds the phase transition temperature, it can transform from an insulating state to a metallic state. Before and after the phase change, the reflectivity, absorptivity, resistivity and magnetic susceptibility of vanadium dioxide will undergo huge changes. In particular, the change in resistivity reaches 3 to 5 orders of magnitude, which allows vanadium dioxide to become a A filler with excellent thermo-electromagnetic response tunable.
  • the invention provides an electromagnetic shielding composite material with temperature response characteristics, which uses vanadium dioxide as a functional material and is prepared by compounding the functional material with a matrix material.
  • vanadium dioxide can be in the form of fibers, sheets, or granules.
  • the particle size of the vanadium dioxide particles ranges from 0.1 to 5 ⁇ m.
  • vanadium dioxide is in the form of fibers, it is easier to form a conductive network with each other, followed by flakes, and particles are the most difficult.
  • the conductivity of the fibrous vanadium dioxide composite material is the highest, and the electromagnetic shielding of the material is Performance is again directly proportional to conductivity.
  • Vanadium dioxide can also be doped before use.
  • the doping element is tungsten or germanium. Usually doping will change the phase transition temperature of vanadium dioxide and also reduce the conductivity of vanadium dioxide, thereby reducing its Electromagnetic shielding performance.
  • the matrix material may be polymer, cellulose fiber, graphene material, etc. The ratio of the amount of vanadium dioxide to the matrix material is 1:1 to 10:1, preferably 10:1, and the prepared composite material has better electromagnetic shielding effect.
  • the present invention also provides a method for preparing the above-mentioned electromagnetic shielding composite material with temperature response characteristics, which includes the following steps:
  • the gel, solution or dispersion of vanadium dioxide and the matrix material is ball-milled and blended in a certain proportion;
  • the matrix material is cellulose fiber
  • the preparation method includes the following steps:
  • the vanadium dioxide and cellulose fiber gel are ball-milled and blended in a certain proportion
  • the matrix material is a polymer
  • the preparation method includes the following steps:
  • the vanadium dioxide and polymer solution are ball-milled and blended in a certain proportion;
  • the polymer can be thermoplastic polyurethane, preferably polyester type or polyether type, with a Shore hardness range of 40-90A and a molecular weight range of 30-20W. ;
  • the base material is graphene
  • the preparation method includes the following steps:
  • the vanadium dioxide and graphene dispersion are ball milled and blended in a certain proportion; wherein, the dispersant in the graphene dispersion is water or an organic solvent, and the organic solvent is mainly methanol, ethanol, isopropyl alcohol, dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, etc.;
  • the present invention also provides the application of the electromagnetic shielding composite material with temperature response characteristics.
  • the electromagnetic shielding composite material with temperature response characteristics is used as an intelligent temperature-controlled electromagnetic shielding switch in a device.
  • Vanadium dioxide/nanocellulose fiber film the preparation process is as follows:
  • the dried vanadium dioxide/nanocellulose fiber gel is mechanically pressed into a film at a pressure of 50MPa and a compression time of 1 minute to finally obtain a vanadium dioxide/nanocellulose fiber film with a thickness of approximately 0.6mm.
  • Figure 2 is a cross-sectional microscopic view of the vanadium dioxide/nanocellulose fiber film. It can be seen from the figure that the vanadium dioxide particles are confined in the nanocellulose fiber network, which enhances the mechanical stability of the composite material.
  • the freeze-dried vanadium dioxide/nanocellulose fiber gel is pressed into a regular block of 20*10*2mm (l*w*h), and then adhered to the block with copper foil coated with conductive silver paste. Both sides serve as electrodes. Finally, a resistance meter is used to measure the resistance of the material, and the conductivity is calculated.
  • the measured conductivity of the vanadium dioxide/nanocellulose fiber at different temperatures is shown in Figure 3. It can be seen from the figure , the conductivity of vanadium dioxide/nanocellulose fibers increases sharply between 65 and 70°C, indicating that the vanadium dioxide phase transition begins to occur.
  • the conductivity of the vanadium dioxide/nanocellulose fiber composite reaches a stable value, and then the conductivity does not increase when the temperature is raised.
  • the conductivity of the material is directly proportional to the electromagnetic shielding effectiveness, so it proves that the electromagnetic shielding effectiveness will not be further improved after the phase change of the vanadium dioxide/nanocellulose fiber composite material.
  • Vanadium dioxide/polyurethane composite material the preparation process is as follows:
  • the vanadium dioxide/polyurethane composite material into a 22.86mm*10.16mm (l*w) block sample (the size corresponds to the size of the 8.2-12.4GHz band test fixture), and then place the sample into a high-temperature waveguide test device for testing
  • the vector network analyzer model is N5227B.
  • the heating rate was 1°C per minute.
  • the electromagnetic shielding performance of the material was tested, as shown in Figure 5. It can be seen from the figure that vanadium dioxide/polyurethane
  • the electromagnetic shielding effectiveness of the composite material increases as the temperature increases. When the temperature is 70°C, the vanadium dioxide undergoes a phase change and completely transforms into a metal conductor, and the electromagnetic shielding effectiveness of the vanadium dioxide/polyurethane composite material reaches stability.
  • Vanadium dioxide/graphene composite material the preparation process is as follows:
  • the dried vanadium dioxide/graphene gel is mechanically pressed into a film at a pressure of 50MPa and a compression time of 1 minute to finally obtain a vanadium dioxide/graphene film with a thickness of approximately 0.6mm.
  • the vector network analyzer model is N5227B.
  • the heating rate was 1°C per minute.
  • the electromagnetic shielding effectiveness of the vanadium dioxide/graphene film increases as the temperature increases.
  • the temperature is 70°C
  • the vanadium dioxide undergoes a phase change and completely transforms into a metal conductor.
  • the vanadium dioxide/graphene film The electromagnetic shielding efficiency of graphene film reaches stability.
  • the electromagnetic shielding composite material with temperature response characteristics of the present invention uses the phase change material vanadium dioxide as a functional material to be compounded with the matrix material, and uses the vanadium dioxide to change from an insulating state to a metallic state when its temperature exceeds the phase change temperature, thereby realizing the composite
  • the electromagnetic shielding performance of the material has temperature response characteristics;
  • the electromagnetic shielding composite material with temperature response characteristics of the present invention is an intrinsic composite material that can make a tunable electromagnetic response to heat, has recyclable characteristics, and avoids the traditional smart electromagnetic Shielding composite materials need to respond to external stimuli through deformation of the designed structure, which greatly improves the reliability of the material.
  • the preparation method of the electromagnetic shielding composite material with temperature response characteristics of the present invention is simple and can be industrially produced.
  • the electromagnetic shielding composite material with temperature response characteristics of the present invention has broad application prospects and is of great significance for application in devices as an intelligent temperature-controlled electromagnetic shielding switch.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

提供了一种具有温度响应特性的电磁屏蔽复合材料及其制备方法和应用，属于电磁屏蔽材料技术领域。该复合材料为具有温度响应特性的电磁屏蔽复合材料，采用二氧化钒作为功能材料，所述功能材料与基体材料复合制备而成。还提供了上述具有温度响应特性的电磁屏蔽复合材料的制备方法和应用。上述复合材料利用二氧化钒在其温度超过相变温度时从绝缘状态转变为金属状态，实现复合材料的电磁屏蔽性能具有温度响应特性，本征型地对热量做出可调谐电磁响应且不需要发生结构的形变，还具有可循环特征，这大大提高了材料的可靠性，具有广阔的应用前景，对应用在器件中作为一种智能温控电磁屏蔽开关具有重要意义。

Description

一种具有温度响应特性的电磁屏蔽复合材料及其制备方法和应用 技术领域
本发明属于电磁屏蔽材料技术领域，涉及一种具有温度响应特性的电磁屏蔽复合材料及其制备方法和应用。
背景技术
随着电子通讯技术的迅速发展，电子器件朝向高集成度和多功能化方向发展，传统的电磁屏蔽复合材料功能单一，无法对外界的刺激做出电磁响应。智能电磁屏蔽复合材料指的是可以通过外部的刺激，包括力、电、磁和热等，来改变复合材料的电磁特性。现有的智能电磁屏蔽复合材料，基本都是进行过一定的结构设计，通过结构的形变对电磁波发生响应。现有的智能屏蔽复合材料无法从材料本征特性出发，对外界刺激响应时，复合材料都会发生形变，这对材料的可靠性是一个很大的挑战。
热量是其中一个很重要的刺激因素，因为电子器件的高速运行不可避免会伴随着大量的热量产生，所以，热量是芯片工作时不可回避的一个问题，开发一种本征型的能对热量作出可调谐电磁响应的复合材料，具有广阔的应用前景。
因此，开发一种热响应的具有可循环特性电磁屏蔽复合材料，对应用在器件中作为一种智能温控电磁屏蔽开关具有重要意义。
发明内容
有鉴于此，本发明提供一种具有温度响应特性的电磁屏蔽复合材料及其制备方法和应用，本发明采用相变材料二氧化钒作为功能材料与基体材料复合，利用二氧化钒在其温度超过相变温度时从绝缘状态转变为金属状态，实现复合材料的电磁屏蔽性能具有温度响应特性。
为实现上述目的，本发明提供一种具有温度响应特性的电磁屏蔽复合材料，采用二氧化钒作为功能材料，所述功能材料与基体材料复合制备而成。
优选地，二氧化钒为纤维状，或为片状，或为颗粒状。
优选地，二氧化钒在使用前经掺杂处理，掺杂元素为钨元素，或锗元素。
优选地，所述基体材料为聚合物，或纤维素纤维，或石墨烯材料。
优选地，二氧化钒与所述基体材料的物质的量之比为1:1～10:1。
本发明还提供上述具有温度响应特性的电磁屏蔽复合材料的制备方法，包括以下步骤：
将二氧化钒与所述基体材料的凝胶或溶液或分散液按一定比例球磨共混均匀；
之后冷冻成型再冷冻干燥，然后机械压膜成薄膜；或者，加热固化成型。
优选地，所述基体材料为纤维素纤维，制备方法包括以下步骤：
将二氧化钒与纤维素纤维凝胶按一定比例球磨共混均匀；
之后冷冻成型再冷冻干燥；
然后进行机械压膜得到二氧化钒/纤维素纤维薄膜。
优选地，所述基体材料为聚合物，制备方法包括以下步骤：
将二氧化钒与聚合物溶液按一定比例球磨共混均匀；
之后加热固化成型得到二氧化钒/聚合物复合材料。
优选地，所述基体材料为石墨烯，制备方法包括以下步骤：
将二氧化钒与石墨烯分散液按一定比例球磨共混均匀；
之后冷冻成型再冷冻干燥；
然后进行机械压膜得到二氧化钒/石墨烯薄膜。
本发明还提供上述具有温度响应特性的电磁屏蔽复合材料的应用，所述具有温度响应特性的电磁屏蔽复合材料在器件中作为智能温控电磁屏蔽开关使用。
本发明采用上述技术方案的优点是：
本发明的具有温度响应特性的电磁屏蔽复合材料，采用相变材料二氧化钒作为功能材料与基体材料复合，利用二氧化钒在其温度超过相变温度时从绝缘状态转变为金属状态，实现复合材料的电磁屏蔽性能具有温度响应特性；本发明的具有温度响应特性的电磁屏蔽复合材料为本征型的能对热量做出可调谐电磁响应的复合材料，具有可循环特征，避免了传统智能电磁屏蔽复合材料需 要通过设计结构上的形变对外界刺激做出响应，大大提高了材料的可靠性。本发明的具有温度响应特性的电磁屏蔽复合材料的制备方法简单，可工业化生产。本发明的具有温度响应特性的电磁屏蔽复合材料具有广阔的应用前景，对应用在器件中作为一种智能温控电磁屏蔽开关具有重要意义。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。
图1为二氧化钒在不同温度下的XRD图谱；
图2为本发明实施例1中二氧化钒/纳米纤维素纤维薄膜的截面微观图；
图3为不同温度下实施例1中的二氧化钒/纳米纤维素纤维的电导率；
图4为不同温度下实施例1中的二氧化钒/纳米纤维素纤维的电磁屏蔽效能；
图5为不同温度下实施例2中的二氧化钒/聚氨酯的电磁屏蔽效能；
图6为不同温度下实施例3中的二氧化钒/石墨烯的电磁屏蔽效能。
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它实施例，都属于本发明保护的范围。
二氧化钒(VO 2)，在常温下是单斜金红石的晶体结构，导电性差，呈现绝缘状态，二氧化钒在不同温度下的XRD图谱如图1所示。当其温度超过相变温度后，可以从绝缘状态转变到金属状态。在相变前后，二氧化钒的反射率、吸收率、电阻率和磁化率等均会发生巨大的改变，尤其是电阻率的变化达到了3～5个数量级，这使得二氧化钒可以成为一种出色的热-电磁响应可调谐的填料。
本发明提供一种具有温度响应特性的电磁屏蔽复合材料，采用二氧化钒作为功能材料，所述功能材料与基体材料复合制备而成。其中，二氧化钒可以为纤维状，或为片状，或为颗粒状。当二氧化钒为颗粒状时，二氧化钒颗粒的粒径范围为0.1-5μm。当二氧化钒为纤维状时更容易相互形成导电网络，片状次之，颗粒最难，在相同基体材料相同填充比下纤维状的二氧化钒复合材料的电导率最高，而材料的电磁屏蔽性能又与电导率成正比。二氧化钒在使用前还可以经掺杂处理，掺杂元素为钨元素，或锗元素，通常掺杂会改变二氧化钒的相变温度，也会降低二氧化钒的电导率，从而降低其电磁屏蔽性能。所述基体材料可以为聚合物，或纤维素纤维，或石墨烯材料等。二氧化钒与所述基体材料的物质的量之比为1:1～10:1，优选为10∶1，制备的复合材料的电磁屏蔽效果较佳。
本发明还提供上述具有温度响应特性的电磁屏蔽复合材料的制备方法，包括以下步骤：
将二氧化钒与所述基体材料的凝胶或溶液或分散液按一定比例球磨共混均匀；
之后冷冻成型再冷冻干燥，然后机械压膜成薄膜；或者，加热固化成型。
在一些实施例中，所述基体材料为纤维素纤维，制备方法包括以下步骤：
将二氧化钒与纤维素纤维凝胶按一定比例球磨共混均匀；
之后冷冻成型再冷冻干燥；
然后进行机械压膜得到二氧化钒/纤维素纤维薄膜。
在一些实施例中，所述基体材料为聚合物，制备方法包括以下步骤：
将二氧化钒与聚合物溶液按一定比例球磨共混均匀；其中，聚合物可以为热塑性聚氨酯，优选为聚酯型或者聚醚型，邵氏硬度范围为40-90A，分子量范围为30-20W；
之后加热固化成型得到二氧化钒/聚合物复合材料。
在一些实施例中，所述基体材料为石墨烯，制备方法包括以下步骤：
将二氧化钒与石墨烯分散液按一定比例球磨共混均匀；其中，石墨烯分散液中分散剂为水或者有机溶剂，有机溶剂主要为甲醇、乙醇、异丙醇、二甲基亚砜、N，N-二甲基甲酰胺、N-甲基吡咯烷酮等；
之后冷冻成型再冷冻干燥；
然后进行机械压膜得到二氧化钒/石墨烯薄膜。
本发明还提供上述具有温度响应特性的电磁屏蔽复合材料的应用，所述具有温度响应特性的电磁屏蔽复合材料在器件中作为智能温控电磁屏蔽开关使用。
实施例1
二氧化钒/纳米纤维素纤维薄膜，制备过程如下：
称取0.1mol的二氧化钒颗粒(粒径约为200nm)与0.01mol的纳米纤维素纤维凝胶(纳米纤维素纤维的质量分数为百分之一)球磨共混，转速100-2000r/min，球磨1-60min；
将搅拌均匀的二氧化钒/纳米纤维素纤维凝胶倒入塑料培养皿，在冰箱中 -20℃下冷冻4小时，然后将冷冻成型后的二氧化钒/纳米纤维素纤维凝胶进行冷冻干燥24小时；
将干燥后的二氧化钒/纳米纤维素纤维凝胶进行机械压膜，压强为50MPa，压缩时间1分钟，最后得到二氧化钒/纳米纤维素纤维薄膜，厚度约为0.6mm。
图2为二氧化钒/纳米纤维素纤维薄膜的截面微观图，从图中可以看出，二氧化钒颗粒被限定在纳米纤维素纤维网络中，增强了复合材料的力学稳定性。
将冷冻干燥后的二氧化钒/纳米纤维素纤维凝胶压成20*10*2mm(l*w*h)的规则块状体，然后用表面涂有导电银浆的铜箔黏附在块体两侧作为电极，最后用电阻仪测量出材料的电阻，换算得出电导率，测得不同温度下的二氧化钒/纳米纤维素纤维的电导率如图3所示，从图中可以看出，在65～70℃之间二氧化钒/纳米纤维素纤维的电导率急剧变大，说明开始发生二氧化钒相变。当温度达到70℃后，二氧化钒/纳米纤维素纤维复合材料的电导率达到了稳定值，随后再提升温度，电导率也不会随着上升。材料的电导率又和电磁屏蔽效能成正比，所以佐证了二氧化钒/纳米纤维素纤维复合材料发生相变后电磁屏蔽效能不会进一步提升。
将二氧化钒/纳米纤维素纤维薄膜制成22.86mm*10.16mm(l*w)的块状体样品(尺寸对应8.2-12.4GHz波段测试夹具的尺寸)，然后将样品放入高温波导测试装置中进行测试，矢量网络分析仪的型号为N5227B。测试时，升温速率为每分钟1℃，加热至目标测试温度后，保温20分钟后，测试得出材料的电磁屏蔽性能。测得不同温度下的二氧化钒/纳米纤维素纤维的电磁屏蔽效能如图4所示，从图中可以看出，在没有达到二氧化钒的相变温度时，二氧化钒/纳米纤维素纤维薄膜仍为绝缘体，电磁屏蔽效能几乎没有提升。当温度为70℃时，二氧化钒发生相变，转变为金属导体，二氧化钒/纳米纤维素纤维薄 膜的电磁屏蔽效能急剧提升，但当达到相变温度后再提升温度，响应的电磁屏蔽效能并不会进一步提升。
实施例2
二氧化钒/聚氨酯复合材料，制备过程如下：
称取0.1mol的二氧化钒颗粒(粒径约为200nm)与0.01mol的热塑性聚氨酯(聚酯型，邵氏硬度范围为50A，分子量范围为20W)进行球磨共混，转速100-2000r/min，球磨1-60min；
将搅拌均匀的二氧化钒/聚氨酯倒入模具中，放入烘箱中80℃下加热3小时，最后得到二氧化钒/聚氨酯复合材料。
将二氧化钒/聚氨酯复合材料制成22.86mm*10.16mm(l*w)的块状体样品(尺寸对应8.2-12.4GHz波段测试夹具的尺寸)，然后将样品放入高温波导测试装置中进行测试，矢量网络分析仪的型号为N5227B。测试时，升温速率为每分钟1℃，加热至目标测试温度后，保温20分钟后，测试得出材料的电磁屏蔽性能，如图5所示，从图中可以看出，二氧化钒/聚氨酯复合材料的电磁屏蔽效能随着温度的增加而增加，当温度为70℃时，二氧化钒发生相变，完全转变为金属导体，二氧化钒/聚氨酯复合材料的电磁屏蔽效能达到稳定。
实施例3
二氧化钒/石墨烯复合材料，制备过程如下：
称取0.1mol的二氧化钒颗粒(粒径约为200nm)与0.01mol的石墨烯分散液(分散剂为水)球磨共混，转速100-2000r/min，球磨1-60min；
将搅拌均匀的二氧化钒/石墨烯溶液倒入塑料培养皿，在冰箱中-20℃下冷 冻4小时，然后将冷冻成型后的二氧化钒/石墨烯凝胶进行冷冻干燥24小时；
将干燥后的二氧化钒/石墨烯凝胶进行机械压膜，压强为50MPa，压缩时间1分钟，最后得到二氧化钒/石墨烯薄膜，厚度约为0.6mm。
将二氧化钒/石墨烯薄膜制成22.86mm*10.16mm(l*w)的块状体样品(尺寸对应8.2-12.4GHz波段测试夹具的尺寸)，然后将样品放入高温波导测试装置中进行测试，矢量网络分析仪的型号为N5227B。测试时，升温速率为每分钟1℃，加热至目标测试温度后，保温20分钟后，测试得出材料的电磁屏蔽性能，如图6所示。从图中可以看出，二氧化钒/石墨烯薄膜的电磁屏蔽效能随着温度的增加而增加，当温度为70℃时，二氧化钒发生相变，完全转变为金属导体，二氧化钒/石墨烯薄膜的电磁屏蔽效能达到稳定。
本发明采用上述技术方案的优点是：
本发明的具有温度响应特性的电磁屏蔽复合材料，采用相变材料二氧化钒作为功能材料与基体材料复合，利用二氧化钒在其温度超过相变温度时从绝缘状态转变为金属状态，实现复合材料的电磁屏蔽性能具有温度响应特性；本发明的具有温度响应特性的电磁屏蔽复合材料为本征型的能对热量做出可调谐电磁响应的复合材料，具有可循环特征，避免了传统智能电磁屏蔽复合材料需要通过设计结构上的形变对外界刺激做出响应，大大提高了材料的可靠性。本发明的具有温度响应特性的电磁屏蔽复合材料的制备方法简单，可工业化生产。本发明的具有温度响应特性的电磁屏蔽复合材料具有广阔的应用前景，对应用在器件中作为一种智能温控电磁屏蔽开关具有重要意义。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种具有温度响应特性的电磁屏蔽复合材料，其特征在于，采用二氧化钒作为功能材料，所述功能材料与基体材料复合制备而成。
  2. 根据权利要求1所述的具有温度响应特性的电磁屏蔽复合材料，其特征在于，二氧化钒为纤维状，或为片状，或为颗粒状。
  3. 根据权利要求1所述的具有温度响应特性的电磁屏蔽复合材料，其特征在于，二氧化钒在使用前经掺杂处理，掺杂元素为钨元素，或锗元素。
  4. 根据权利要求1所述的具有温度响应特性的电磁屏蔽复合材料，其特征在于，所述基体材料为聚合物，或纤维素纤维，或石墨烯材料。
  5. 根据权利要求1所述的具有温度响应特性的电磁屏蔽复合材料，其特征在于，二氧化钒与所述基体材料的物质的量之比为1:1～10:1。
  6. 根据权利要求1-5任意一项所述的具有温度响应特性的电磁屏蔽复合材料的制备方法，其特征在于，包括以下步骤：
    将二氧化钒与所述基体材料的凝胶或溶液或分散液按一定比例球磨共混均匀；
    之后冷冻成型再冷冻干燥，然后机械压膜成薄膜；或者，加热固化成型。
  7. 根据权利要求6所述的具有温度响应特性的电磁屏蔽复合材料的制备方法，其特征在于，所述基体材料为纤维素纤维，制备方法包括以下步骤：
    将二氧化钒与纤维素纤维凝胶按一定比例球磨共混均匀；
    之后冷冻成型再冷冻干燥；
    然后进行机械压膜得到二氧化钒/纤维素纤维薄膜。
  8. 根据权利要求6所述的具有温度响应特性的电磁屏蔽复合材料的制备方 法，其特征在于，所述基体材料为聚合物，制备方法包括以下步骤：
    将二氧化钒与聚合物溶液按一定比例球磨共混均匀；
    之后加热固化成型得到二氧化钒/聚合物复合材料。
  9. 根据权利要求6所述的具有温度响应特性的电磁屏蔽复合材料的制备方法，其特征在于，所述基体材料为石墨烯，制备方法包括以下步骤：
    将二氧化钒与石墨烯分散液按一定比例球磨共混均匀；
    之后冷冻成型再冷冻干燥；
    然后进行机械压膜得到二氧化钒/石墨烯薄膜。
  10. 一种权利要求1-5任意一项所述的具有温度响应特性的电磁屏蔽复合材料的应用，其特征在于，所述具有温度响应特性的电磁屏蔽复合材料在器件中作为智能温控电磁屏蔽开关使用。
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