WO2020253094A1 - Boron nitride nanotube aerogel/phase change heat conductive composite material and preparation method therefor - Google Patents

Boron nitride nanotube aerogel/phase change heat conductive composite material and preparation method therefor Download PDF

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WO2020253094A1
WO2020253094A1 PCT/CN2019/119879 CN2019119879W WO2020253094A1 WO 2020253094 A1 WO2020253094 A1 WO 2020253094A1 CN 2019119879 W CN2019119879 W CN 2019119879W WO 2020253094 A1 WO2020253094 A1 WO 2020253094A1
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boron nitride
phase change
nitride nanotube
composite material
aerogel
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PCT/CN2019/119879
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Chinese (zh)
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曾小亮
王明媚
孙蓉
张涛
韩猛
叶振强
许建斌
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中国科学院深圳先进技术研究院
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    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa

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  • the invention relates to the technical field of phase change thermally conductive composite materials, and in particular to a method for preparing a phase change composite material based on boron nitride nanotube aerogel.
  • phase change material can absorb or release heat from the environment, thereby being able to store and release thermal energy, which effectively improves the utilization rate of energy. Therefore, in recent years, phase change energy storage materials have gradually become a hot spot in energy utilization and materials research. It can be widely used in the fields of solar thermal utilization, building energy saving and thermal management.
  • Organic phase change materials have many advantages, such as small phase change temperature fluctuations, large phase change latent heat, and stable chemical properties, so they have been extensively studied. However, organic phase change materials have low thermal conductivity, large volume changes during phase change, and easy leakage, which limit their application.
  • the three-dimensional porous material composite composed of an organic phase change material and a high thermal conductivity filler can provide a heat conduction path while playing a supporting role, and is one of the effective means to improve the performance of the phase change material.
  • boron nitride nanotubes The crystal structure of boron nitride nanotubes is similar to that of carbon nanotubes. It is a tubular structure formed by bonding of B nuclei and N atoms with SP 2 hybridization. Boron nitride nanotubes have high thermal conductivity, high temperature oxidation resistance, good chemical stability, excellent dielectric properties, and high elastic modulus, making them very promising in the field of thermally conductive composite materials.
  • Song et al. used carbon aerogel as a template and prepared a boron nitride nanotube/nanosheet hybrid porous aerogel by chemical vapor deposition under high temperature and high pressure conditions. Due to the strong hydrophobicity of boron nitride nanotubes and the lack of surface functional groups, there are still huge challenges in constructing three-dimensional porous structures based on boron nitride nanotubes by simple methods.
  • the composite of organic phase change material and three-dimensional boron nitride nanotube aerogel can achieve shape stability while improving its heat transfer performance and heat storage performance.
  • the purpose of the present invention is to overcome the above-mentioned defects in the prior art and provide a method for preparing a boron nitride nanotube aerogel/phase change thermally conductive composite material.
  • One aspect of the present invention provides a boron nitride nanotube aerogel/phase change thermally conductive composite material, which includes a boron nitride nanotube aerogel skeleton composed of boron nitride nanotubes and graphene oxide, and filled in Solid-liquid organic phase change material inside and around the aerogel skeleton.
  • One aspect of the present invention provides a method for preparing a boron nitride nanotube aerogel/phase change thermally conductive composite material, which includes the following steps:
  • the concentration of the graphene oxide solution in step (1) is 2-6 mg/ml, preferably 3-5 mg/ml, more preferably 4 mg/ml.
  • the mass ratio of the boron nitride nanotubes to graphene oxide in step (1) is 1: (0.1-20), preferably 1: (0.5-15), more preferably 1 : (1-9).
  • the uniform mixing and dispersion in step (1) is dispersed by ultrasonic and stirring.
  • the magnetic stirring is continued for 1-2 hours.
  • the reducing agent in step (2) is selected from one or a mixture of at least two of hydrazine hydrate, hydrogen iodide, vitamin C, ammonium sulfide, tea polyphenols or ethylene diamine, Preferably, ethylene diamine; its volume ratio to the boron nitride nanotube/graphene oxide dispersion is 100-200, preferably 120-180, more preferably 150:1.
  • the conditions for hydrothermal reduction under heating conditions in step (2) are: in a sealed environment, the heating temperature is 50-150°C, preferably 75-105°C, more preferably 85-95°C ;
  • the heating time is 5-20h, preferably 6-15h, more preferably 8-12h.
  • the freeze-drying process in step (2) is: taking out the hydrogel after the reaction, and freeze-drying the hydrogel under vacuum conditions using a vacuum freeze dryer for 24-48 hours, and the freezing temperature is -20 ⁇ - 80°C, preferably -50°C, and the vacuum degree is 10-100 Pa, preferably 33 Pa.
  • step (3) all operations in step (3) are completed under heating conditions, and the heating temperature is 60-90°C, preferably 80-90°C, more preferably 85°C.
  • the solid-liquid organic phase change material described in step (3) is one or more of polyethylene glycol, paraffin wax, polyols, and fatty acids, preferably polyethylene glycol Alcohol, more preferably polyethylene glycol, has a relative molecular weight of 4000-10000.
  • step (3) the operation time of transferring to heating under vacuum to remove residual bubbles is 12-24h.
  • step (3) in the operation of cooling after heating under vacuum to remove residual bubbles, the cooling temperature is room temperature, and the cooling time is 10-20 min.
  • Another aspect of the present invention provides a boron nitride nanotube aerogel/phase change thermal conductive composite material prepared by the above method of the present invention.
  • the present invention solves the problems of difficult dispersion and assembly of boron nitride nanotubes, and graphene oxide is used as boron nitride nanotubes.
  • the dispersant and cross-linking agent are used to obtain the boron nitride nanotube aerogel through the process of hydrothermal reduction and freeze-drying of the uniformly dispersed boron nitride nanotube/graphene oxide solution.
  • the phase change material is filled in the three-dimensional structure of the boron nitride nanotube aerogel through a vacuum impregnation method, which effectively prevents the phase change material from permeating and improves its thermal conductivity.
  • the boron nitride nanotubes make the surface of the aerogel rough and hydrophobic, and the capillary force generated by them can further increase the adsorption capacity of the phase change material, thereby improving the shape stability of the phase change composite material.
  • the phase change heat storage capacity of the composite material has also been improved.
  • Graphene oxide is amphiphilic.
  • the present invention first uses the surface activity of graphene oxide as a dispersant to disperse boron nitride nanotubes to obtain a uniformly dispersed boron nitride nanotube/graphene oxide solution. Therefore, boron nitride nanotubes of different masses can be added, but the mass ratio of boron nitride nanotubes to graphene oxide does not exceed 1:1, otherwise a uniformly dispersed boron nitride nanotube/graphene oxide dispersion liquid cannot be formed. And a solution with a mass ratio of 0:1 between the two was prepared, that is, without adding boron nitride nanotubes, to compare the effects of graphene nanosheets on composite materials.
  • the present invention uses graphene oxide as a dispersant and crosslinking agent to obtain a uniformly dispersed boron nitride nanotube/graphene oxide solution, and uses the reducing agent ethylenediamine to initiate self-assembly under hydrothermal conditions to make oxidation While graphene is reduced, a hybrid three-dimensional porous aerogel with uniformly dispersed boron nitride nanotubes is obtained.
  • the present invention finds that the addition amount of boron nitride nanotubes can adjust the performance of the composite material, thereby obtaining a composite material with adjustable heat storage performance and thermal conductivity.
  • the boron nitride nanotubes in the present invention exist on the surface of the graphene sheets or between the interlayers, and are cross-linked to form a three-dimensional network structure.
  • the boron nitride nanotubes with excellent thermal conductivity can be used as thermally conductive fillers to improve the thermal conductivity of phase change materials.
  • phase change composite material prepared by the invention not only improves the thermal conductivity, but also improves the heat storage performance.
  • the preparation method of the invention is simple and has good repeatability.
  • the boron nitride nanotube aerogel is used as a thermally conductive framework, and is combined with a solid-liquid phase change organic material to effectively improve the shape stability and thermal conductivity of the phase change composite material. It can effectively solve the technical problems that are easy to leak and has good application prospects.
  • Figure 1 is a field emission scanning electron microscope image of the graphene aerogel prepared in Example 1 under different magnifications
  • Example 2 is a field emission scanning electron micrograph of the boron nitride nanotube aerogel prepared in Example 2 under different magnifications;
  • Figure 3 is a DSC curve diagram of the composite material and polyethylene glycol prepared in Examples 1-4;
  • Figure 4 is a thermal conductivity diagram of composite materials prepared in Examples 1-4 and polyethylene glycol.
  • phase change material Use polyethylene glycol as the phase change material, heat it and melt it and slowly add it dropwise to the boron nitride nanotube aerogel, then transfer it into a vacuum drying oven, and heat it at 85°C for 12 hours under vacuum conditions. The residual bubbles are removed, and the boron nitride nanotube aerogel phase change thermal conductive composite material is obtained when the sample is cooled to room temperature.
  • Figures 1 and 2 are respectively scanning electron micrographs of graphene aerogel in Example 1 and boron nitride nanotube aerogel in Example 2. It can be observed that the prepared graphene aerogel and boron nitride nanotube aerogel are both three-dimensional porous honeycomb structures, but the boron nitride nanotube aerogel can see that the boron nitride nanotubes are uniformly distributed Graphene sheet surface or in the interlayer.
  • phase change material Use polyethylene glycol as the phase change material, heat it and melt it and slowly add it dropwise to the boron nitride nanotube aerogel, then transfer it into a vacuum drying oven, and heat it at 85°C for 12 hours under vacuum conditions. The residual bubbles are removed, and the boron nitride nanotube aerogel phase change thermal conductive composite material is obtained when the sample is cooled to room temperature.
  • phase change material Use polyethylene glycol as the phase change material, heat it and melt it and slowly add it dropwise to the boron nitride nanotube aerogel, then transfer it into a vacuum drying oven, and heat it at 85°C for 12 hours under vacuum conditions. The residual bubbles are removed, and the boron nitride nanotube aerogel phase change thermal conductive composite material is obtained when the sample is cooled to room temperature.
  • the thermal conductivity of the composite material is shown in Figure 4, and the thermal conductivity of the composite material is significantly improved.

Abstract

The present invention relates to a boron nitride nanotube aerogel/phase change heat conductive composite material and a preparation method therefor. The preparation method comprises the following steps: (1) mixing and uniformly dispersing a boron nitride nanotube raw material in a graphene oxide solution, in order to obtain a uniform boron nitride nanotube/graphene oxide dispersion; (2) dropwise adding a reducing agent into the boron nitride nanotube/graphene oxide dispersion, subjecting same to a hydrothermal reduction under heating conditions to obtain a hydrogel, and then subjecting same to vacuum freeze-drying to obtain a boron nitride nanotube aerogel; and (3) under heating conditions, dropwise adding a thawed solid-liquid organic phase change material into the boron nitride nanotube aerogel, then transferring same and heating same under a vacuum to remove the remaining air bubbles, and cooling same to room temperature so as to obtain the boron nitride nanotube aerogel/phase change heat conductive composite material. The phase change composite material prepared in the present invention has a high heat-conducting property and heat-storing property.

Description

一种氮化硼纳米管气凝胶/相变导热复合材料及其制备方法Boron nitride nanotube aerogel/phase change thermal conductive composite material and preparation method thereof 技术领域Technical field
本发明涉及相变导热复合材料技术领域，尤其是涉及一种基于氮化硼纳米管气凝胶的相变复合材料的制备方法。The invention relates to the technical field of phase change thermally conductive composite materials, and in particular to a method for preparing a phase change composite material based on boron nitride nanotube aerogel.
背景技术Background technique
目前，能源问题已成为制约人类物质和精神生活进一步提高的瓶颈。相变材料在其相变过程中，能够从环境吸收或放出热量，从而能够储存和释放热能，有效地提高了能源的利用率。因而近年来，相变储能材料逐渐成为能源利用和材料研究方面的热点。可被广泛应用于太阳能热利用、建筑节能以及热管理等领域。有机相变材料具有相变温度波动小、相变潜热大、化学性能稳定等诸多优点，因而受到广泛的研究。但是有机相变材料导热性能较低、相变过程中体积变化大、易泄露等缺点，使其在应用过程中受到一定的限制。有机相变材料与高导热填料组成的三维多孔材料复合可以在提供导热通路的同时起到支撑作用，是提高相变材料性能的有效手段之一。At present, the energy issue has become a bottleneck restricting the further improvement of human material and spiritual life. In the process of phase change, the phase change material can absorb or release heat from the environment, thereby being able to store and release thermal energy, which effectively improves the utilization rate of energy. Therefore, in recent years, phase change energy storage materials have gradually become a hot spot in energy utilization and materials research. It can be widely used in the fields of solar thermal utilization, building energy saving and thermal management. Organic phase change materials have many advantages, such as small phase change temperature fluctuations, large phase change latent heat, and stable chemical properties, so they have been extensively studied. However, organic phase change materials have low thermal conductivity, large volume changes during phase change, and easy leakage, which limit their application. The three-dimensional porous material composite composed of an organic phase change material and a high thermal conductivity filler can provide a heat conduction path while playing a supporting role, and is one of the effective means to improve the performance of the phase change material.
氮化硼纳米管与碳纳米管晶体结构相似，是由B原子核N原子已SP 2杂化成键形成的管状结构。氮化硼纳米管具有高导热性、高温抗氧化性，良好的化学稳定性、优异的介电性能以及高弹性模量，使其在导热复合材料领域有非常有潜力的应用价值。Song等人使用碳气凝胶作为模板，并通过化学气相沉积法在高温高压条件下制备氮化硼纳米管/纳米片杂化多孔气凝胶。由于氮化硼纳米管强疏水性和表面官能团缺失，通过简单方法构建基于氮化硼纳米管的三维多孔结构仍存在巨大挑战。 The crystal structure of boron nitride nanotubes is similar to that of carbon nanotubes. It is a tubular structure formed by bonding of B nuclei and N atoms with SP 2 hybridization. Boron nitride nanotubes have high thermal conductivity, high temperature oxidation resistance, good chemical stability, excellent dielectric properties, and high elastic modulus, making them very promising in the field of thermally conductive composite materials. Song et al. used carbon aerogel as a template and prepared a boron nitride nanotube/nanosheet hybrid porous aerogel by chemical vapor deposition under high temperature and high pressure conditions. Due to the strong hydrophobicity of boron nitride nanotubes and the lack of surface functional groups, there are still huge challenges in constructing three-dimensional porous structures based on boron nitride nanotubes by simple methods.
有机相变材料与三维氮化硼纳米管气凝胶复合可实现形状稳定的同时，提高其传热性能和储热性能。The composite of organic phase change material and three-dimensional boron nitride nanotube aerogel can achieve shape stability while improving its heat transfer performance and heat storage performance.
发明内容Summary of the invention
本发明的目的就是为了克服上述现有技术存在的缺陷，提供一种氮化硼纳米管气凝胶/相变导热复合材料的制备方法。The purpose of the present invention is to overcome the above-mentioned defects in the prior art and provide a method for preparing a boron nitride nanotube aerogel/phase change thermally conductive composite material.
本发明一个方面提供了一种氮化硼纳米管气凝胶/相变导热复合材料，其包括由氮化硼纳米管和氧化石墨烯构成的氮化硼纳米管气凝胶骨架，以及填充在气凝胶骨架内部和四周的固-液有机相变材料。One aspect of the present invention provides a boron nitride nanotube aerogel/phase change thermally conductive composite material, which includes a boron nitride nanotube aerogel skeleton composed of boron nitride nanotubes and graphene oxide, and filled in Solid-liquid organic phase change material inside and around the aerogel skeleton.
本发明一个方面提供了一种氮化硼纳米管气凝胶/相变导热复合材料的制备方法，包括以下步骤：One aspect of the present invention provides a method for preparing a boron nitride nanotube aerogel/phase change thermally conductive composite material, which includes the following steps:
(1)将氮化硼纳米管原料与氧化石墨烯溶液混合分散均匀，得到均匀的氮化硼纳米管/氧化石墨烯分散液；(1) Mix and disperse the boron nitride nanotube raw materials and the graphene oxide solution uniformly to obtain a uniform boron nitride nanotube/graphene oxide dispersion;
(2)向所述氮化硼纳米管/氧化石墨烯分散液中滴加还原剂，在加热条件下水热还原得到水凝胶，接着进行真空冷冻干燥得到氮化硼纳米管气凝胶；(2) Add a reducing agent dropwise to the boron nitride nanotube/graphene oxide dispersion, hydrothermally reduce it under heating to obtain a hydrogel, and then perform vacuum freeze drying to obtain a boron nitride nanotube aerogel;
(3)在加热条件下，向所述石墨烯增强的氮化硼纳米管气凝胶中加入融化的固-液有机相变材料，接着转入真空条件下加热以除去残留气泡，冷却至室温即得到氮化硼纳米管气凝胶/相变导热复合材料。(3) Under heating conditions, add melted solid-liquid organic phase change material to the graphene-enhanced boron nitride nanotube aerogel, then heat under vacuum to remove residual bubbles, and cool to room temperature That is, the boron nitride nanotube aerogel/phase change thermal conductivity composite material is obtained.
在本发明的技术方案中，步骤(1)中所述氧化石墨烯溶液的浓度为2-6mg/ml，优选为3-5mg/ml，更优选为4mg/ml。In the technical scheme of the present invention, the concentration of the graphene oxide solution in step (1) is 2-6 mg/ml, preferably 3-5 mg/ml, more preferably 4 mg/ml.
在本发明的技术方案中，步骤(1)中所述氮化硼纳米管与氧化石墨烯的质量比为1：(0.1-20)，优选为1：(0.5-15)，更优选为1：(1-9)。In the technical scheme of the present invention, the mass ratio of the boron nitride nanotubes to graphene oxide in step (1) is 1: (0.1-20), preferably 1: (0.5-15), more preferably 1 : (1-9).
在本发明的技术方案中，步骤(1)中所述混合分散均匀是通过超声和搅拌进行分散，优选为，低功率超声分散6-12h后，转入磁力搅拌继续分散1-2h。In the technical scheme of the present invention, the uniform mixing and dispersion in step (1) is dispersed by ultrasonic and stirring. Preferably, after 6-12 hours of low-power ultrasonic dispersion, the magnetic stirring is continued for 1-2 hours.
在本发明的技术方案中，步骤(2)中所述的还原剂选自水合肼、碘化氢、维生素C、硫化铵、茶多酚或乙二胺中一种或至少两种的混合物，优选乙二胺；其与所述氮化硼纳米管/氧化石墨烯分散液的体积比例为100-200，优选为120-180，更优选为150：1。In the technical scheme of the present invention, the reducing agent in step (2) is selected from one or a mixture of at least two of hydrazine hydrate, hydrogen iodide, vitamin C, ammonium sulfide, tea polyphenols or ethylene diamine, Preferably, ethylene diamine; its volume ratio to the boron nitride nanotube/graphene oxide dispersion is 100-200, preferably 120-180, more preferably 150:1.
在本发明的技术方案中，步骤(2)中在加热条件下水热还原的条件为：在密封环境下，加热温度为50～150℃，优选为75-105℃，更优选为85-95℃；加热时间为5-20h，优选为6-15h，更优选为8-12h。In the technical scheme of the present invention, the conditions for hydrothermal reduction under heating conditions in step (2) are: in a sealed environment, the heating temperature is 50-150°C, preferably 75-105°C, more preferably 85-95°C ; The heating time is 5-20h, preferably 6-15h, more preferably 8-12h.
在本发明的技术方案中，步骤(2)中冷冻干燥过程为：取出反应后的水凝胶，使用真空冻干机在真空条件下冷冻干燥24-48h，所述冷冻温度为-20～-80℃，优选为-50℃，所述真空度为10-100Pa，优选为33Pa。In the technical scheme of the present invention, the freeze-drying process in step (2) is: taking out the hydrogel after the reaction, and freeze-drying the hydrogel under vacuum conditions using a vacuum freeze dryer for 24-48 hours, and the freezing temperature is -20~- 80°C, preferably -50°C, and the vacuum degree is 10-100 Pa, preferably 33 Pa.
在本发明的技术方案中，步骤(3)中所有操作都在加热条件下完成，加热温度为60-90℃，优选为80-90℃，更优选为85℃。In the technical scheme of the present invention, all operations in step (3) are completed under heating conditions, and the heating temperature is 60-90°C, preferably 80-90°C, more preferably 85°C.
在本发明的技术方案中，步骤(3)中所述的固-液有机相变材料为聚乙二醇、石蜡、多元醇类、脂肪酸类中的一种或多种，优选为聚乙二醇，更优选为聚乙二醇相对分子量大小为4000-10000。In the technical scheme of the present invention, the solid-liquid organic phase change material described in step (3) is one or more of polyethylene glycol, paraffin wax, polyols, and fatty acids, preferably polyethylene glycol Alcohol, more preferably polyethylene glycol, has a relative molecular weight of 4000-10000.
在本发明的技术方案中，步骤(3)中，所述转入真空条件下加热以除去残留气泡的操作时间为12-24h。In the technical scheme of the present invention, in step (3), the operation time of transferring to heating under vacuum to remove residual bubbles is 12-24h.
在本发明的技术方案中，步骤(3)中，所述置于真空条件下加热以除去残留气泡后进行冷却的操作中，冷却温度为室温，冷却时间为10-20min。In the technical scheme of the present invention, in step (3), in the operation of cooling after heating under vacuum to remove residual bubbles, the cooling temperature is room temperature, and the cooling time is 10-20 min.
本发明再一个方面提供了一种由本发明上述方法制备得到的氮化硼纳米管气凝胶/相变导热复合材料。Another aspect of the present invention provides a boron nitride nanotube aerogel/phase change thermal conductive composite material prepared by the above method of the present invention.
本发明为了解决现有技术中存在相变储能材料热导率低、电绝缘等问题本发明为解决氮化硼纳米管难分散、难组装的问题，以氧化石墨烯作为氮化硼纳 米管的分散剂和交联剂，将分散均匀的氮化硼纳米管/氧化石墨烯溶液通过水热还原和冷冻干燥过程得到氮化硼纳米管气凝胶。随后通过真空浸渍方法使得相变材料填充于在石氮化硼纳米管气凝胶三维结构中，有效防止相变材料的渗流，并且提高其导热性能。氮化硼纳米管使气凝胶表面变得粗糙和疏水，其产生的毛细力可以进一步提高对相变材料的吸附能力，从而提高相变复合材料的形状稳定性。另外由于独特的氮化硼纳米管杂化结构，复合材料的相变储热能力也得到了提高。In order to solve the problems of low thermal conductivity and electrical insulation of phase-change energy storage materials in the prior art, the present invention solves the problems of difficult dispersion and assembly of boron nitride nanotubes, and graphene oxide is used as boron nitride nanotubes. The dispersant and cross-linking agent are used to obtain the boron nitride nanotube aerogel through the process of hydrothermal reduction and freeze-drying of the uniformly dispersed boron nitride nanotube/graphene oxide solution. Subsequently, the phase change material is filled in the three-dimensional structure of the boron nitride nanotube aerogel through a vacuum impregnation method, which effectively prevents the phase change material from permeating and improves its thermal conductivity. The boron nitride nanotubes make the surface of the aerogel rough and hydrophobic, and the capillary force generated by them can further increase the adsorption capacity of the phase change material, thereby improving the shape stability of the phase change composite material. In addition, due to the unique hybrid structure of boron nitride nanotubes, the phase change heat storage capacity of the composite material has also been improved.
氧化石墨烯具有两亲性，本发明首先利用氧化石墨烯的表面活性，使其作为分散剂，分散氮化硼纳米管，得到均匀分散的氮化硼纳米管/氧化石墨烯溶液。因此可以加入不同质量的氮化硼纳米管，但是氮化硼纳米管与氧化石墨烯的质量比不超过1:1，否则无法形成均匀分散的氮化硼纳米管/氧化石墨烯分散液。并且制备了两者质量比为0:1的溶液，即不加入氮化硼纳米管，以此进行对比，比较石墨烯纳米片对复合材料的影响。Graphene oxide is amphiphilic. The present invention first uses the surface activity of graphene oxide as a dispersant to disperse boron nitride nanotubes to obtain a uniformly dispersed boron nitride nanotube/graphene oxide solution. Therefore, boron nitride nanotubes of different masses can be added, but the mass ratio of boron nitride nanotubes to graphene oxide does not exceed 1:1, otherwise a uniformly dispersed boron nitride nanotube/graphene oxide dispersion liquid cannot be formed. And a solution with a mass ratio of 0:1 between the two was prepared, that is, without adding boron nitride nanotubes, to compare the effects of graphene nanosheets on composite materials.
往均匀分散的氮化硼纳米管/氧化石墨烯分散液滴加还原剂乙二胺随后进行水热还原，温度为85-95℃，时间为8-12h。由于氧化石墨烯的导热性差，通过水热反应可将其还原，并且形成三维的网络。实验过程中，分散液凝胶化随着氮化硼纳米管含量的增加而增加，反应的还原程度还与反应温度有关，采用本发明中的条件，氧化石墨烯均可得到有效的还原。Add the reducing agent ethylenediamine dropwise to the uniformly dispersed boron nitride nanotube/graphene oxide dispersion liquid followed by hydrothermal reduction at a temperature of 85-95°C and a time of 8-12h. Due to the poor thermal conductivity of graphene oxide, it can be reduced by a hydrothermal reaction and form a three-dimensional network. During the experiment, the gelation of the dispersion increases as the content of the boron nitride nanotubes increases, and the reduction degree of the reaction is also related to the reaction temperature. Using the conditions of the present invention, graphene oxide can be effectively reduced.
有益效果Beneficial effect
(1)本发明以氧化石墨烯为分散剂和交联剂，得到均匀分散的氮化硼纳米管/氧化石墨烯溶液，并通过还原剂乙二胺在水热条件下引发自组装，使氧化石墨烯还原的同时得到氮化硼纳米管均匀分散的杂化的三维多孔气凝胶。本发明发现氮化硼纳米管添加量可以调节复合材料的性能，从而获得储热性能和导热 性能可调的复合材料。(1) The present invention uses graphene oxide as a dispersant and crosslinking agent to obtain a uniformly dispersed boron nitride nanotube/graphene oxide solution, and uses the reducing agent ethylenediamine to initiate self-assembly under hydrothermal conditions to make oxidation While graphene is reduced, a hybrid three-dimensional porous aerogel with uniformly dispersed boron nitride nanotubes is obtained. The present invention finds that the addition amount of boron nitride nanotubes can adjust the performance of the composite material, thereby obtaining a composite material with adjustable heat storage performance and thermal conductivity.
(2)不同于三维石墨烯气凝胶，本发明中氮化硼纳米管存在于石墨烯片层表面或者夹层之间，并且相互交联形成三维网络状结构。具有优异导热性能的氮化硼纳米管作为导热填料可以提高相变材料的导热性。(2) Different from the three-dimensional graphene aerogel, the boron nitride nanotubes in the present invention exist on the surface of the graphene sheets or between the interlayers, and are cross-linked to form a three-dimensional network structure. The boron nitride nanotubes with excellent thermal conductivity can be used as thermally conductive fillers to improve the thermal conductivity of phase change materials.
(3)氮化硼纳米管气凝胶的三维多孔结构能吸收相变材料，其中氮化硼纳米管的加入使得气凝胶表面疏水、粗糙，从而更有利于吸附相变材料，提高相变材料的形状稳定性。本发明制备的相变复合材料不仅提高了导热性能，其储热性能也得到了提高。(3) The three-dimensional porous structure of boron nitride nanotube aerogels can absorb phase change materials. The addition of boron nitride nanotubes makes the surface of the aerogel hydrophobic and rough, which is more conducive to the adsorption of phase change materials and improves phase change. The shape stability of the material. The phase change composite material prepared by the invention not only improves the thermal conductivity, but also improves the heat storage performance.
(4)本发明制备方法简单，可重复性好。以氮化硼纳米管气凝胶作为导热骨架，与固-液相变的有机材料复合，有效改善相变复合材料的形状稳定性和热导率。能有效解决易泄漏的技术问题，具有很好应用前景。(4) The preparation method of the invention is simple and has good repeatability. The boron nitride nanotube aerogel is used as a thermally conductive framework, and is combined with a solid-liquid phase change organic material to effectively improve the shape stability and thermal conductivity of the phase change composite material. It can effectively solve the technical problems that are easy to leak and has good application prospects.
附图说明Description of the drawings
图1为实施例1制备的石墨烯气凝胶在不同放大倍数下的场发射扫描电镜图；Figure 1 is a field emission scanning electron microscope image of the graphene aerogel prepared in Example 1 under different magnifications;
图2为实施例2制备的氮化硼纳米管气凝胶在不同放大倍数下的场发射扫描电镜图；2 is a field emission scanning electron micrograph of the boron nitride nanotube aerogel prepared in Example 2 under different magnifications;
图3为实施例1-4制备的复合材料和聚乙二醇的DSC曲线图；Figure 3 is a DSC curve diagram of the composite material and polyethylene glycol prepared in Examples 1-4;
图4为实施例1-4制备的复合材料和聚乙二醇的热导率图。Figure 4 is a thermal conductivity diagram of composite materials prepared in Examples 1-4 and polyethylene glycol.
具体实施方式Detailed ways
本发明通过下述实施例和附图对本发明进行详细说明。但本领域技术人员了解，下述实施例不是对本发明保护范围的限制，任何在本发明基础上做出的 改进和变化，都在本发明的保护范围之内。The present invention is described in detail through the following embodiments and drawings. However, those skilled in the art understand that the following embodiments do not limit the scope of protection of the present invention, and any improvements and changes made on the basis of the present invention fall within the scope of protection of the present invention.
实施例1Example 1
(1)取3ml氧化石墨烯溶液(4mg/ml)将其置于样品瓶内，并加入20μL的乙二胺作为还原剂，在95℃下水热还原反应12h。反应结束后取出石墨烯柱状凝胶，使用真空冻干机进行真空冻干24h，得到石墨烯气凝胶。(1) Take 3ml of graphene oxide solution (4mg/ml) and place it in a sample bottle, add 20μL of ethylenediamine as a reducing agent, and hydrothermally reduce it at 95°C for 12h. After the reaction, the graphene columnar gel was taken out, and vacuum freeze-dried for 24 hours using a vacuum freeze dryer to obtain a graphene aerogel.
(2)使用聚乙二醇作为相变材料，将其加热融化后缓慢滴加到石墨烯气凝胶上，接着转入真空干燥箱内，在真空条件和85℃下加热12h，除去残留气泡，待样品降到室温即得到石墨烯气凝胶相变导热复合材料。(2) Use polyethylene glycol as a phase change material, heat it and melt it and slowly add it dropwise to the graphene aerogel, then transfer it into a vacuum drying oven, and heat it at 85°C for 12 hours under vacuum conditions to remove residual bubbles After the sample is cooled to room temperature, the graphene aerogel phase change thermal conductive composite material is obtained.
实施例2Example 2
(1)取3ml氧化石墨烯溶液(4mg/ml)置于样品瓶内，加入一定量的氮化硼纳米管，其中氮化硼纳米管与氧化石墨烯的质量比为1：9，超声6h，搅拌1h得到氮化硼纳米管/氧化石墨烯分散液。(1) Take 3ml of graphene oxide solution (4mg/ml) into the sample bottle, add a certain amount of boron nitride nanotubes, where the mass ratio of boron nitride nanotubes to graphene oxide is 1:9, ultrasonic for 6h , Stirring for 1 h to obtain a dispersion of boron nitride nanotubes/graphene oxide.
(2)将其置于样品瓶内，并加入20μL的乙二胺作为还原剂，在95℃下水热还原反应12h。反应结束后取出氮化硼纳米管/石墨烯柱状凝胶，使用真空冻干机进行真空冻干24h，得到氮化硼纳米管气凝胶。(2) Put it in a sample bottle, and add 20 μL of ethylenediamine as a reducing agent, and perform a hydrothermal reduction reaction at 95°C for 12 hours. After the reaction, the boron nitride nanotube/graphene columnar gel was taken out, and vacuum freeze-dried using a vacuum freeze dryer for 24 hours to obtain the boron nitride nanotube aerogel.
(3)使用聚乙二醇作为相变材料，将其加热融化后缓慢滴加到氮化硼纳米管气凝胶上，接着转入真空干燥箱内，在真空条件和85℃下加热12h，除去残留气泡，待样品降到室温即得到氮化硼纳米管气凝胶相变导热复合材料。(3) Use polyethylene glycol as the phase change material, heat it and melt it and slowly add it dropwise to the boron nitride nanotube aerogel, then transfer it into a vacuum drying oven, and heat it at 85°C for 12 hours under vacuum conditions. The residual bubbles are removed, and the boron nitride nanotube aerogel phase change thermal conductive composite material is obtained when the sample is cooled to room temperature.
图1和图2分别为实施例1中石墨烯气凝胶和实施例2中氮化硼纳米管气凝胶的扫描电镜图。可以观察到所制备的石墨烯气凝胶和氮化硼纳米管气凝胶均为为三维多孔蜂窝状结构，但氮化硼纳米管气凝胶可以看到氮化硼纳米管均匀的分布在石墨烯片层表面或者夹层里。Figures 1 and 2 are respectively scanning electron micrographs of graphene aerogel in Example 1 and boron nitride nanotube aerogel in Example 2. It can be observed that the prepared graphene aerogel and boron nitride nanotube aerogel are both three-dimensional porous honeycomb structures, but the boron nitride nanotube aerogel can see that the boron nitride nanotubes are uniformly distributed Graphene sheet surface or in the interlayer.
实施例3Example 3
(1)取3ml氧化石墨烯溶液(4mg/ml)置于样品瓶内，加入一定量的氮化硼纳米管，其中氮化硼纳米管与氧化石墨烯的质量比为3:7，超声6h，搅拌1h得到氮化硼纳米管/氧化石墨烯分散液。(1) Take 3ml of graphene oxide solution (4mg/ml) into the sample bottle, add a certain amount of boron nitride nanotubes, where the mass ratio of boron nitride nanotubes to graphene oxide is 3:7, ultrasonic for 6h , Stirring for 1 h to obtain a dispersion of boron nitride nanotubes/graphene oxide.
(2)将其置于样品瓶内，并加入20μL的乙二胺作为还原剂，在95℃下水热还原反应12h。反应结束后取出氮化硼纳米管/石墨烯柱状凝胶，使用真空冻干机进行真空冻干24h，得到氮化硼纳米管气凝胶。(2) Put it in a sample bottle, and add 20 μL of ethylenediamine as a reducing agent, and perform a hydrothermal reduction reaction at 95°C for 12 hours. After the reaction, the boron nitride nanotube/graphene columnar gel was taken out, and vacuum freeze-dried using a vacuum freeze dryer for 24 hours to obtain the boron nitride nanotube aerogel.
(3)使用聚乙二醇作为相变材料，将其加热融化后缓慢滴加到氮化硼纳米管气凝胶上，接着转入真空干燥箱内，在真空条件和85℃下加热12h，除去残留气泡，待样品降到室温即得到氮化硼纳米管气凝胶相变导热复合材料。(3) Use polyethylene glycol as the phase change material, heat it and melt it and slowly add it dropwise to the boron nitride nanotube aerogel, then transfer it into a vacuum drying oven, and heat it at 85°C for 12 hours under vacuum conditions. The residual bubbles are removed, and the boron nitride nanotube aerogel phase change thermal conductive composite material is obtained when the sample is cooled to room temperature.
实施例4Example 4
(1)取3ml氧化石墨烯溶液(4mg/ml)置于样品瓶内，加入一定量的氮化硼纳米管，其中氮化硼纳米管与氧化石墨烯的质量比为1：1，超声6h，搅拌1h得到氮化硼纳米管/氧化石墨烯分散液。(1) Take 3ml of graphene oxide solution (4mg/ml) into the sample bottle, add a certain amount of boron nitride nanotubes, where the mass ratio of boron nitride nanotubes to graphene oxide is 1:1, ultrasonic for 6h , Stirring for 1 h to obtain a dispersion of boron nitride nanotubes/graphene oxide.
(2)将其置于样品瓶内，并加入20μL的乙二胺作为还原剂，在95℃下水热还原反应12h。反应结束后取出氮化硼纳米管/石墨烯柱状凝胶，使用真空冻干机进行真空冻干24h，得到氮化硼纳米管气凝胶。(2) Put it in a sample bottle, and add 20 μL of ethylenediamine as a reducing agent, and perform a hydrothermal reduction reaction at 95°C for 12 hours. After the reaction, the boron nitride nanotube/graphene columnar gel was taken out, and vacuum freeze-dried using a vacuum freeze dryer for 24 hours to obtain the boron nitride nanotube aerogel.
(3)使用聚乙二醇作为相变材料，将其加热融化后缓慢滴加到氮化硼纳米管气凝胶上，接着转入真空干燥箱内，在真空条件和85℃下加热12h，除去残留气泡，待样品降到室温即得到氮化硼纳米管气凝胶相变导热复合材料。(3) Use polyethylene glycol as the phase change material, heat it and melt it and slowly add it dropwise to the boron nitride nanotube aerogel, then transfer it into a vacuum drying oven, and heat it at 85°C for 12 hours under vacuum conditions. The residual bubbles are removed, and the boron nitride nanotube aerogel phase change thermal conductive composite material is obtained when the sample is cooled to room temperature.
上述1-4实施例中的所制备的氮化硼纳米管气凝胶相变导热复合材料的DSC曲线如图3所示，可以看出复合材料的相变温度几乎不变，相变焓也并没有损失。The DSC curve of the boron nitride nanotube aerogel phase change thermally conductive composite material prepared in the foregoing Examples 1-4 is shown in Figure 3. It can be seen that the phase change temperature of the composite material is almost constant, and the phase change enthalpy is also There is no loss.
复合材料的热导率如图4所示，复合材料的导热性能得到明显提高。The thermal conductivity of the composite material is shown in Figure 4, and the thermal conductivity of the composite material is significantly improved.
上述实施例1-4中制备的氮化硼纳米管气凝胶相变导热复合材料。The boron nitride nanotube aerogel phase change thermally conductive composite material prepared in the foregoing Examples 1-4.
以及聚乙二醇的热性能具体见下表1。And the thermal properties of polyethylene glycol are shown in Table 1 below.
表1Table 1
Figure PCTCN2019119879-appb-000001
Figure PCTCN2019119879-appb-000001
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的。The foregoing description of the embodiments is for the convenience of those skilled in the art to understand and use the invention. Those skilled in the art can obviously make various modifications to these embodiments and apply the general principles described here to other embodiments without creative work. Therefore, the present invention is not limited to the above-mentioned embodiments. According to the disclosure of the present invention, those skilled in the art make improvements and modifications without departing from the scope of the present invention.

Claims (10)

  1. 一种氮化硼纳米管气凝胶/相变导热复合材料的制备方法，其特征在于，包括以下步骤：A preparation method of boron nitride nanotube aerogel/phase change thermal conductivity composite material is characterized in that it comprises the following steps:
    (1)将氮化硼纳米管原料以氧化石墨烯溶液混合分散均匀，得到均匀的氮化硼纳米管/氧化石墨烯分散液；(1) Mix and disperse boron nitride nanotube raw materials with graphene oxide solution uniformly to obtain a uniform boron nitride nanotube/graphene oxide dispersion;
    (2)向所述氮化硼纳米管/氧化石墨烯分散液中滴加还原剂，在加热条件下水热还原得到水凝胶，接着进行真空冷冻干燥得到氮化硼纳米管气凝胶；(2) Add a reducing agent dropwise to the boron nitride nanotube/graphene oxide dispersion, hydrothermally reduce it under heating to obtain a hydrogel, and then perform vacuum freeze drying to obtain a boron nitride nanotube aerogel;
    (3)在加热条件下，向所述氮化硼纳米管气凝胶中滴加融化的固-液有机相变材料，接着转入真空条件下加热以除去残留气泡，冷却至室温即得到氮化硼纳米管气凝胶/相变导热复合材料。(3) Under heating conditions, the molten solid-liquid organic phase change material is added dropwise to the boron nitride nanotube aerogel, then heated under vacuum to remove residual bubbles, and cooled to room temperature to obtain nitrogen Boron nanotube aerogel/phase change thermal conductivity composite material.
  2. 如权利要求1所述的一种氮化硼纳米管气凝胶/相变导热复合材料的制备方法，步骤(1)中所述氮化硼纳米管与氧化石墨烯的质量比为1：(0.1-20)，优选为1：(0.5-15)，更优选为1：(1-9)。The method for preparing a boron nitride nanotube aerogel/phase change thermally conductive composite material according to claim 1, wherein the mass ratio of the boron nitride nanotube to graphene oxide in step (1) is 1:( 0.1-20), preferably 1:(0.5-15), more preferably 1:(1-9).
  3. 其特征在于，步骤(1)中所述氧化石墨烯的浓度为1-10mg/ml，优选为3-5mg/ml，更优选为4mg/ml。It is characterized in that the concentration of the graphene oxide in step (1) is 1-10 mg/ml, preferably 3-5 mg/ml, more preferably 4 mg/ml.
  4. 如权利要求1所述的一种氮化硼纳米管气凝胶/相变导热复合材料的制备方法，其特征在于，步骤(2)中所述的还原剂为乙二胺，其与所述氮化硼纳米管/氧化石墨烯分散液的体积比例为100-200，优选为120-180，更优选为150：1。A method for preparing boron nitride nanotube aerogel/phase change thermally conductive composite material according to claim 1, wherein the reducing agent in step (2) is ethylene diamine, which is compatible with The volume ratio of the boron nitride nanotube/graphene oxide dispersion is 100-200, preferably 120-180, and more preferably 150:1.
  5. 如权利要求1所述的一种氮化硼纳米管气凝胶/相变导热复合材料的制 备方法，其特征在于，步骤(2)中在加热条件下水热还原的操作为：在密封环境下，加热温度为50～150℃，优选为75-105℃，更优选为85-95℃，加热时间为5-20h，优选为6-15h，更优选为8-12h。The method for preparing a boron nitride nanotube aerogel/phase change thermal conductive composite material according to claim 1, wherein the hydrothermal reduction operation under heating conditions in step (2) is: in a sealed environment The heating temperature is 50-150°C, preferably 75-105°C, more preferably 85-95°C, and the heating time is 5-20h, preferably 6-15h, more preferably 8-12h.
  6. 如权利要求1所述的一种氮化硼纳米管气凝胶/相变导热复合材料的制备方法，其特征在于，步骤(2)中冷冻干燥过程为：取出反应后的水凝胶，使用真空条件下冷冻干燥24-48h，所述冷冻温度为-50℃，所述真空度为33Pa。The method for preparing a boron nitride nanotube aerogel/phase change thermally conductive composite material according to claim 1, wherein the freeze-drying process in step (2) is: taking out the reacted hydrogel and using Freeze drying under vacuum conditions for 24-48 hours, the freezing temperature is -50°C, and the vacuum degree is 33 Pa.
  7. 如权利要求1所述的一种氮化硼纳米管气凝胶/相变导热复合材料的制备方法，其特征在于，步骤(3)中所述的固-液有机相变材料为聚乙二醇、石蜡、多元醇类、脂肪酸类中的一种或多种，优选为聚乙二醇，更优选为聚乙二醇相对分子量大小为4000-10000。The method for preparing a boron nitride nanotube aerogel/phase change thermally conductive composite material according to claim 1, wherein the solid-liquid organic phase change material in step (3) is polyethylene dioxide One or more of alcohols, paraffins, polyhydric alcohols, and fatty acids, preferably polyethylene glycol, and more preferably polyethylene glycol with a relative molecular weight of 4000-10000.
  8. 如权利要求1所述的一种氮化硼纳米管气凝胶/相变导热复合材料的制备方法，其特征在于，步骤(3)中所有操作都在加热条件下完成，加热温度为60-90℃，优选为80-90℃，更优选为85℃。The method for preparing a boron nitride nanotube aerogel/phase change thermal conductivity composite material according to claim 1, wherein all operations in step (3) are completed under heating conditions, and the heating temperature is 60- 90°C, preferably 80-90°C, more preferably 85°C.
  9. 如权利要求1-8任一项所述的一种氮化硼纳米管气凝胶/相变导热复合材料的制备方法所得的氮化硼纳米管气凝胶/相变导热复合材料。The boron nitride nanotube aerogel/phase change thermally conductive composite material obtained by the preparation method of the boron nitride nanotube aerogel/phase change thermally conductive composite material according to any one of claims 1-8.
  10. 一种氮化硼纳米管气凝胶/相变导热复合材料，其包括由氮化硼纳米管和氧化石墨烯构成的氮化硼纳米管气凝胶骨架，以及填充在气凝胶骨架内部和四周的固-液有机相变材料；A boron nitride nanotube aerogel/phase change thermal conductive composite material, which includes a boron nitride nanotube aerogel skeleton composed of boron nitride nanotubes and graphene oxide, and a boron nitride nanotube aerogel skeleton filled in the aerogel skeleton and Surrounding solid-liquid organic phase change materials;
    优选地，所述氮化硼纳米管与氧化石墨烯的质量比为1：(0.1-20)；固-液有机相变材料为聚乙二醇、石蜡、多元醇类、脂肪酸类中的一种或多种。Preferably, the mass ratio of the boron nitride nanotubes to the graphene oxide is 1: (0.1-20); the solid-liquid organic phase change material is one of polyethylene glycol, paraffin wax, polyols, and fatty acids. Kind or more.
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