CN115247049A - A kind of graphite foam-based phase change energy storage material and preparation method thereof - Google Patents

A kind of graphite foam-based phase change energy storage material and preparation method thereof Download PDF

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CN115247049A
CN115247049A CN202210112352.0A CN202210112352A CN115247049A CN 115247049 A CN115247049 A CN 115247049A CN 202210112352 A CN202210112352 A CN 202210112352A CN 115247049 A CN115247049 A CN 115247049A
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polyurethane foam
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姜丽丽
赵乐
于海涛
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Lanzhou University of Technology
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract

本发明公开了一种石墨泡沫基相变储能材料及制备方法,属于相变储能材料技术领域,包括:聚氨酯泡沫预处理,其中,所述聚氨酯泡沫预处理包括对聚氨酯泡沫进行氢氧化钠溶液浸泡;经预处理的聚氨酯泡沫浸泡于酚醛树脂‑石墨溶液中,经干燥、固化和烧结,制备得到石墨泡沫;将有机相变材料填充到所述石墨泡沫内部以得到所述石墨泡沫基相变储能材料。本发明获得的石墨泡沫基相变储能材料储热性能好,防泄露性能好,且成本低,更适合在低温余热回收利用应用。

Figure 202210112352

The invention discloses a graphite foam-based phase-change energy storage material and a preparation method, which belong to the technical field of phase-change energy storage materials, and include: polyurethane foam pretreatment, wherein the polyurethane foam pretreatment includes sodium hydroxide on the polyurethane foam solution soaking; the pretreated polyurethane foam is soaked in a phenolic resin-graphite solution, dried, cured and sintered to prepare a graphite foam; an organic phase change material is filled into the graphite foam to obtain the graphite foam base phase energy storage materials. The graphite foam-based phase-change energy storage material obtained by the invention has good heat storage performance, good anti-leakage performance and low cost, and is more suitable for application in low-temperature waste heat recovery and utilization.

Figure 202210112352

Description

一种石墨泡沫基相变储能材料及制备方法A graphite foam-based phase change energy storage material and preparation method thereof

技术领域technical field

本发明涉及相变储能材料技术领域,特别是涉及一种石墨泡沫基相变储能材料及制备方法。The invention relates to the technical field of phase-change energy storage materials, in particular to a graphite foam-based phase-change energy storage material and a preparation method thereof.

背景技术Background technique

以风能、太阳能为代表的可再生能源具有间歇性、波动性和随机性的特征,一直困扰着可再生能源的发展,找到理想的储能解决方案显得十分重要。热能存储,作为一种清洁高效的储能方式为解决可再生能源利用中遇到的难点提供了很好的思路。储能技术广泛的应用于太阳能热利用、工业废热和余热回收、建筑物空调节能等领域,是提高能源利用效率和保护环境的重要技术。相变储能技术是将介质的热量先储存在相变材料中,使相变材料发生相变,以潜热的形式将能量储存,当需要能量时,相变材料再次发生相变,将潜热释放出来,完成热能交换。Renewable energy represented by wind energy and solar energy has the characteristics of intermittency, volatility and randomness, which have always plagued the development of renewable energy. It is very important to find an ideal energy storage solution. Thermal energy storage, as a clean and efficient energy storage method, provides a good idea to solve the difficulties encountered in the utilization of renewable energy. Energy storage technology is widely used in solar heat utilization, industrial waste heat and waste heat recovery, building air conditioning energy saving and other fields. It is an important technology to improve energy utilization efficiency and protect the environment. Phase change energy storage technology is to store the heat of the medium in the phase change material first, make the phase change material undergo a phase change, and store energy in the form of latent heat. When energy is needed, the phase change material undergoes a phase change again to release the latent heat. Come out to complete the heat exchange.

相变材料(phase change materials,PCM)或称相变储能材料,是指能被利用其在物态变化时所吸收或放出的大量热能用于能量储存的材料,因其具有储能密度大、成本低、输出的温度和能量相当稳定的特点而被广泛研究。但传统的相变材料导热性能低下(0.1-1W/(m·K)),影响了相变材料在储/放热过程中的传热效率。此外,传统的有机相变材料由于具备一定流动性,还存在着封闭难题,难以广泛应用到各个应用场景中。因此泄露、导热性低仍然是限制相变材料应用的主要问题。Phase change materials (phase change materials, PCM) or phase change energy storage materials refer to materials that can be used for energy storage by utilizing a large amount of heat energy absorbed or released when the state of matter changes, because of its high energy storage density , low cost, stable output temperature and energy, and has been extensively studied. However, the thermal conductivity of traditional phase change materials is low (0.1-1W/(m·K)), which affects the heat transfer efficiency of phase change materials in the process of heat storage/discharge. In addition, due to the certain fluidity of traditional organic phase change materials, there is still a sealing problem, which makes it difficult to be widely used in various application scenarios. Therefore, leakage and low thermal conductivity are still the main problems that limit the application of phase change materials.

发明内容SUMMARY OF THE INVENTION

本发明的目的是提供一种石墨泡沫基相变储能材料及制备方法,以解决上述现有技术存在的问题,采用石墨泡沫复合相变材料,既可以解决泄露及导热率低的问题,还能极大程度上保留相变材料的储热能力。The purpose of the present invention is to provide a graphite foam-based phase-change energy storage material and its preparation method to solve the above-mentioned problems in the prior art. The use of graphite-foam composite phase-change materials can solve the problems of leakage and low thermal conductivity, and also The heat storage capacity of the phase change material can be preserved to a great extent.

为实现上述目的,本发明提供了如下方案:To achieve the above object, the present invention provides the following scheme:

本发明提供一种石墨泡沫基相变储能材料的制备方法,包括以下步骤:The invention provides a preparation method of a graphite foam-based phase change energy storage material, comprising the following steps:

聚氨酯泡沫预处理,其中,所述聚氨酯泡沫预处理包括对聚氨酯泡沫进行氢氧化钠溶液浸泡;Polyurethane foam pretreatment, wherein, the polyurethane foam pretreatment comprises sodium hydroxide solution soaking the polyurethane foam;

经预处理的聚氨酯泡沫浸泡于酚醛树脂-石墨溶液中,经干燥、固化和烧结,制备得到石墨泡沫;Soak the pretreated polyurethane foam in the phenolic resin-graphite solution, dry, solidify and sinter to prepare the graphite foam;

将有机相变材料填充到所述石墨泡沫内部以得到所述石墨泡沫基相变储能材料,其中,所述有机相变材料与所述石墨泡沫的质量比为7-9:1。Filling the interior of the graphite foam with an organic phase change material to obtain the graphite foam-based phase change energy storage material, wherein the mass ratio of the organic phase change material to the graphite foam is 7-9:1.

进一步地,所述聚氨酯泡沫预处理包括:Further, the polyurethane foam pretreatment includes:

聚氨酯泡沫浸泡于氢氧化钠溶液中60-120min后,用去离子水洗涤至中性,再用无水乙醇冲洗,真空干燥,得到经预处理的聚氨酯泡沫;The polyurethane foam is soaked in sodium hydroxide solution for 60-120 minutes, washed with deionized water until neutral, then rinsed with absolute ethanol, and dried in vacuum to obtain pretreated polyurethane foam;

其中,所述氢氧化钠溶液的质量分数为40%,所述氢氧化钠溶液浸泡的温度为80℃。Wherein, the mass fraction of the sodium hydroxide solution is 40%, and the soaking temperature of the sodium hydroxide solution is 80°C.

聚氨酯泡沫在氢氧化钠溶液中刻蚀封闭孔,清洗并干燥后获得高开孔率的聚氨酯泡沫,氢氧化钠溶液浸泡可以打开更多的封闭孔获得更高的孔隙率,从而有利于获得更高的填充率,以获得储热能力强的复合相变材料。Polyurethane foam is etched with closed pores in sodium hydroxide solution, washed and dried to obtain polyurethane foam with high open porosity, soaking in sodium hydroxide solution can open more closed pores to obtain higher porosity, which is beneficial to obtain more High filling rate to obtain composite phase change materials with strong heat storage capacity.

进一步地,所述酚醛树脂-石墨溶液的制备方法包括:Further, the preparation method of described phenolic resin-graphite solution comprises:

间苯二酚溶解于水和乙醇的混合物中,混匀后加入盐酸溶液,混匀,然后在搅拌条件下滴加甲醛溶液,剧烈搅拌获得均相溶液;Dissolve resorcinol in a mixture of water and ethanol, mix well, add hydrochloric acid solution, mix well, then add formaldehyde solution dropwise under stirring condition, stir vigorously to obtain a homogeneous solution;

在所述均相溶液中加入合成石墨和硝酸镍,得到所述酚醛树脂-石墨溶液。Add synthetic graphite and nickel nitrate into the homogeneous solution to obtain the phenolic resin-graphite solution.

进一步地,所述混合物中水和乙醇的质量比为1:1;所述间苯二酚和所述混合物的质量比为1:3.2-4。Further, the mass ratio of water and ethanol in the mixture is 1:1; the mass ratio of the resorcinol to the mixture is 1:3.2-4.

进一步地,所述盐酸溶液的质量分数为37%;所述盐酸溶液与所述甲醛溶液的质量比为1:7.1。Further, the mass fraction of the hydrochloric acid solution is 37%; the mass ratio of the hydrochloric acid solution to the formaldehyde solution is 1:7.1.

进一步地,所述合成石墨和硝酸镍的质量比为1:1;所述合成石墨与所述均相溶液的质量比为1:4。Further, the mass ratio of the synthetic graphite to nickel nitrate is 1:1; the mass ratio of the synthetic graphite to the homogeneous solution is 1:4.

进一步地,所述经预处理的聚氨酯泡沫浸泡于所述酚醛树脂-石墨溶液中5min,取出后去除多余溶液,随后80℃真空干燥12h,然后在150℃下固化24h,然后再以2℃/min的加热速率在氩气流下加热至1000℃,碳化1h,以制备得到所述石墨泡沫。Further, the pretreated polyurethane foam was soaked in the phenolic resin-graphite solution for 5 minutes, and the excess solution was removed after taking it out, then vacuum-dried at 80°C for 12h, then cured at 150°C for 24h, and then heated at 2°C/ The graphite foam was prepared by heating at a heating rate of min to 1000° C. under an argon flow and carbonizing for 1 h.

进一步地,将有机相变材料填充到所述石墨泡沫内部的步骤采用熔融浸渍与真空浸渍相结合的方法进行。Further, the step of filling the interior of the graphite foam with the organic phase change material is carried out by a combined method of melt impregnation and vacuum impregnation.

进一步地,所述熔融浸渍与真空浸渍相结合的方法包括:Further, the method of combining melt impregnation and vacuum impregnation includes:

将所述有机相变材料融化后,加入所述石墨泡沫浸泡12h;然后将浸泡体系转移至抽滤瓶中,堵住所述抽滤瓶的瓶口,抽气1min后保持30s,重复2-3次,得到复合材料样品,将所述复合材料样品置于滤纸上,真空干燥,连续更换滤纸,直至滤纸上没有液体泄露,得到所述石墨泡沫基相变储能材料。After the organic phase change material is melted, add the graphite foam and soak for 12 hours; then transfer the soaking system to a suction filtration bottle, block the mouth of the suction filtration bottle, keep it for 30 seconds after pumping for 1 minute, repeat 2- 3 times to obtain a composite material sample, place the composite material sample on filter paper, vacuum dry, and continuously replace the filter paper until there is no liquid leakage on the filter paper, and obtain the graphite foam-based phase change energy storage material.

进一步地,所述有机相变材料包括石蜡、癸醇、十四醇、十六醇或十八胺。更进一步地,所述有机相变材料为十八胺。Further, the organic phase change material includes paraffin, decyl alcohol, myristyl alcohol, cetyl alcohol or octadecylamine. Furthermore, the organic phase change material is octadecylamine.

本发明还提供一种石墨泡沫基相变储能材料,采用如上任一所述的石墨泡沫基相变储能材料的制备方法制备得到。The present invention also provides a graphite foam-based phase-change energy storage material, which is prepared by any of the above-mentioned preparation methods for graphite-foam-based phase-change energy storage materials.

本发明还提供一种如上所述的石墨泡沫基相变储能材料在低温余热回收领域的应用。The present invention also provides an application of the above-mentioned graphite foam-based phase change energy storage material in the field of low-temperature waste heat recovery.

本发明公开了以下技术效果:The invention discloses the following technical effects:

本发明通过将多孔材料与有机相变材料结合,不仅可以解决相变材料的泄露问题还可以提高其导热性,多孔材料具有优良的结构,具有更高的孔体积、比表面积和存储容量,同时还具有优异的吸附性能,使得相变材料能够很容易地被结合到孔中。由于范德华力、氢键、表面张力等各种力,相变材料被固定在支撑基质中,从而避免相变材料从孔隙中泄漏,多孔材料负责在相变过程中保持所有结构的整体形态。这样,相变材料不仅与支撑基体接合,而且有可能改善导热性能、化学稳定性,以及提升相变储能材料的封装性能和导热性能。By combining the porous material with the organic phase change material, the present invention can not only solve the leakage problem of the phase change material but also improve its thermal conductivity. The porous material has an excellent structure, higher pore volume, specific surface area and storage capacity, and at the same time It also has excellent adsorption properties, enabling phase change materials to be easily incorporated into pores. Due to various forces such as van der Waals force, hydrogen bonding, surface tension, etc., the phase change material is fixed in the support matrix, thereby avoiding the leakage of the phase change material from the pores, and the porous material is responsible for maintaining the overall shape of all structures during the phase change process. In this way, the phase change material is not only bonded to the supporting substrate, but also may improve thermal conductivity, chemical stability, and improve the packaging performance and thermal conductivity of the phase change energy storage material.

本发明通过氢氧化钠对聚氨酯泡沫进行孔刻蚀,可以有效打开聚氨酯泡沫模板更多封闭孔,从而提高石墨泡沫基相变储能材料的填充率、导热率,并改善其泄露性能。The invention uses sodium hydroxide to etch the pores of the polyurethane foam, which can effectively open more closed pores of the polyurethane foam template, thereby increasing the filling rate and thermal conductivity of the graphite foam-based phase change energy storage material, and improving its leakage performance.

本发明获得的石墨泡沫基相变储能材料储热性能好,防泄露性能好,且成本低,更适合在低温余热回收利用应用。The graphite foam-based phase-change energy storage material obtained by the invention has good heat storage performance, good leakage prevention performance and low cost, and is more suitable for low-temperature waste heat recovery and utilization.

附图说明Description of drawings

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他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the accompanying drawings required in the embodiments. Obviously, the accompanying drawings in the following description are only some of the present invention. Embodiments, for those of ordinary skill in the art, other drawings can also be obtained based on these drawings without any creative effort.

图1为氢氧化钠溶液预处理前后的聚氨酯泡沫图,左图未经氢氧化钠溶液处理,右图经氢氧化钠溶液处理;Fig. 1 is the polyurethane foam figure before and after sodium hydroxide solution pretreatment, and the left figure is not treated with sodium hydroxide solution, and the right figure is treated with sodium hydroxide solution;

图2为实施例1的石墨泡沫基相变储能材料的扫描电镜图;Fig. 2 is the scanning electron micrograph of the graphite foam-based phase-change energy storage material of embodiment 1;

图3为实施例1的石墨泡沫基相变储能材料的差示扫描量热曲线图;Fig. 3 is the differential scanning calorimetry curve figure of the graphite foam-based phase change energy storage material of embodiment 1;

图4为纯十八胺与实施例1的石墨泡沫基相变储能材料的泄露实验图,左侧两图为纯十八胺,右侧两图为实施例1的石墨泡沫基相变储能材料。Fig. 4 is the leakage test diagram of pure octadecylamine and the graphite foam-based phase change energy storage material of Example 1. energy material.

具体实施方式Detailed ways

现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。Various exemplary embodiments of the present invention will now be described in detail. The detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features and embodiments of the present invention.

应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。It should be understood that the terminology described in the present invention is only used to describe specific embodiments, and is not used to limit the present invention. In addition, regarding the numerical ranges in the present invention, it should be understood that each intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated value or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded from the range.

除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only the preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and/or materials in connection with which the documents are described. In case of conflict with any incorporated document, the contents of this specification control.

在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本发明说明书和实施例仅是示例性的。It will be apparent to those skilled in the art that various modifications and changes can be made in the specific embodiments of the present invention described herein without departing from the scope or spirit of the present invention. Other embodiments will be apparent to the skilled person from the description of the present invention. The description and examples of the invention are illustrative only.

关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。As used herein, "comprising", "comprising", "having", "comprising" and so on are all open terms, meaning including but not limited to.

实施例1Example 1

(1)聚氨酯泡沫(PU泡沫)的预处理:(1) Pretreatment of polyurethane foam (PU foam):

将密度为13kg/m3的聚氨酯泡沫(PU泡沫)切割为3×2×1cm大小的块,浸泡于80℃质量分数40%的氢氧化钠溶液60min后,用去离子水反复冲洗至中性,然后用无水乙醇冲洗1-2遍,置于80℃真空干燥箱干燥12h,得到水解度为15%的聚氨酯泡沫。Polyurethane foam (PU foam) with a density of 13kg/ m3 was cut into 3×2×1cm blocks, soaked in a 40% sodium hydroxide solution at 80°C for 60 minutes, and then rinsed repeatedly with deionized water until neutral , and then rinsed with absolute ethanol for 1-2 times, and dried in a vacuum oven at 80° C. for 12 hours to obtain a polyurethane foam with a degree of hydrolysis of 15%.

图1为氢氧化钠溶液预处理前后的聚氨酯泡沫图,左图未经氢氧化钠溶液处理,右图经氢氧化钠溶液处理,可以明显看出,右图中的聚氨酯泡沫孔隙率更高。Figure 1 is the picture of polyurethane foam before and after sodium hydroxide solution pretreatment. The left picture is not treated with sodium hydroxide solution, and the right picture is treated with sodium hydroxide solution. It can be clearly seen that the polyurethane foam in the right picture has a higher porosity.

(2)石墨泡沫的制备:(2) Preparation of graphite foam:

间苯二酚溶解在水和乙醇的混合物(水和乙醇的质量比为1:1)中,间苯二酚与混合物的质量比为1:3.2,并搅拌(300r/min)混合物15min;向上述混合物中加入质量分数37%的盐酸溶液(混合物与盐酸溶液质量比30:1)并搅拌1h(800r/min),在磁力搅拌下逐滴加入质量分数37%的甲醛溶液,盐酸溶液与甲醛溶液的质量比为1:7.1。将反应混合物进一步剧烈搅拌1h(1200r/min),然后获得均相溶液。Resorcinol was dissolved in a mixture of water and ethanol (the mass ratio of water and ethanol was 1:1), the mass ratio of resorcinol to the mixture was 1:3.2, and the mixture was stirred (300r/min) for 15min; Add a 37% mass fraction of hydrochloric acid solution to the above mixture (the mass ratio of the mixture to the hydrochloric acid solution is 30:1) and stir for 1 h (800 r/min), add dropwise a 37% mass fraction of formaldehyde solution under magnetic stirring, and the hydrochloric acid solution and formaldehyde The mass ratio of the solution is 1:7.1. The reaction mixture was further vigorously stirred for 1 h (1200 r/min), then a homogeneous solution was obtained.

将合成石墨和硝酸镍添加到上述均相溶液中并搅拌2h(1000r/min),合成石墨和硝酸镍的质量比为1:1,合成石墨与均相溶液的质量比为1:4,得到酚醛树脂-石墨溶液。Synthetic graphite and nickel nitrate are added in the above-mentioned homogeneous solution and stirred 2h (1000r/min), the mass ratio of synthetic graphite and nickel nitrate is 1:1, the mass ratio of synthetic graphite and homogeneous solution is 1:4, obtains Phenolic resin-graphite solution.

将PU泡沫浸渍于上述酚醛树脂-石墨溶液中5min,用玻璃棒除去多余溶液,随后在80℃的真空干燥箱中干燥12h,然后在150℃下固化24h。聚合物复合泡沫在管式炉中以2℃/min的加热速率在氩气流下在1000℃下碳化1h,获得高度互连的三维(3D)石墨泡沫。The PU foam was immersed in the above-mentioned phenolic resin-graphite solution for 5 min, and the excess solution was removed with a glass rod, then dried in a vacuum oven at 80 °C for 12 h, and then cured at 150 °C for 24 h. Polymer syntactic foams were carbonized in a tube furnace at a heating rate of 2 °C/min at 1000 °C for 1 h under an argon flow to obtain highly interconnected three-dimensional (3D) graphite foams.

(3)石墨泡沫基相变储能材料的制备:(3) Preparation of graphite foam-based phase change energy storage materials:

烧杯称取十八胺置于80℃烘箱完全融化后,加入石墨泡沫浸泡12h,十八胺和石墨泡沫的质量比为50:1,然后将十八胺及石墨泡沫转移至抽滤瓶,抽滤瓶口放一培养皿堵住瓶口,抽气1min后保持30s,重复两到三次,得到复合相变材料,将复合材料样品至于滤纸上,滤纸置于真空干燥箱中除去液体十八胺,连续更换滤纸,直到滤纸上没有液体泄漏,得到石墨泡沫基相变储能材料。Weigh octadecylamine in a beaker and place it in an oven at 80°C to completely melt, add graphite foam to soak for 12 hours, the mass ratio of octadecylamine to graphite foam is 50:1, then transfer octadecylamine and graphite foam to a suction filter bottle, and pump Put a petri dish at the mouth of the filter bottle to block the mouth of the bottle, pump air for 1 minute and keep it for 30 seconds, repeat two to three times to obtain a composite phase change material, put the composite material sample on the filter paper, and put the filter paper in a vacuum drying oven to remove the liquid octadecylamine , and continuously replace the filter paper until there is no liquid leakage on the filter paper, and a graphite foam-based phase change energy storage material is obtained.

最终所制备得到的石墨泡沫基相变储能材料的填充率为88.64%,其中,十八胺和石墨泡沫的质量比为8.9:1。The filling ratio of the finally prepared graphite foam-based phase change energy storage material was 88.64%, wherein the mass ratio of octadecylamine to graphite foam was 8.9:1.

该石墨泡沫基相变储能材料的扫描电镜图(SEM)如图2所示,可见,石墨泡沫的开孔和大孔互连网络结构。The scanning electron microscope image (SEM) of the graphite foam-based phase change energy storage material is shown in Figure 2. It can be seen that the graphite foam has an interconnected network structure of open cells and macropores.

该石墨泡沫基相变储能材料的DSC(差示扫描量热仪)曲线如图3所示,凝固温度为41.33℃,凝固潜热为227.8J/g,纯十八胺相变材料的凝固潜热为217.9J/g。The DSC (differential scanning calorimeter) curve of the graphite foam-based phase change energy storage material is shown in Figure 3, the solidification temperature is 41.33°C, the solidification latent heat is 227.8J/g, the solidification latent heat of pure octadecylamine phase change material It is 217.9 J/g.

通过热导仪对该石墨泡沫基相变储能材料的导热系数进行表征,测得的导热系数为0.72W/m·k,相比之下纯十八胺的导热系数为0.32W/m·k,由此可见通过本申请实施例1所提供的石墨泡沫基相变储能材料的热导系数提高了125%。The thermal conductivity of the graphite foam-based phase change energy storage material was characterized by a thermal conductivity meter, and the measured thermal conductivity was 0.72W/m·k, compared with 0.32W/m·k for pure octadecylamine. k, it can be seen that the thermal conductivity of the graphite foam-based phase-change energy storage material provided by Example 1 of the present application is increased by 125%.

如图4所示,将十八胺与复合材料放置于80℃真空干燥箱30min,纯十八胺相变材料发生明显泄露,而复合材料未发生泄漏,证明复合材料有很好的防泄漏性能。As shown in Figure 4, when octadecylamine and the composite material were placed in a vacuum oven at 80°C for 30 minutes, the pure octadecylamine phase change material leaked obviously, but the composite material did not leak, which proved that the composite material had good leak-proof performance. .

对比例1Comparative Example 1

将密度为13kg/m3的聚氨酯泡沫切割为3×2×1cm大小的块,浸泡于80℃质量分数40%的氢氧化钠溶液180min后,用去离子水反复冲洗至中性,然后用无水乙醇冲洗1-2遍,由于浸泡时间过长,水解过度,在冲洗过程中聚氨酯泡沫结构破裂,失去回弹性,置于80℃真空干燥箱干燥12h,其水解度为30.11%。Cut the polyurethane foam with a density of 13kg/m3 into 3 ×2×1cm blocks, soak them in 40% sodium hydroxide solution at 80°C for 180 minutes, rinse them repeatedly with deionized water until neutral, and then use Rinse with water and ethanol for 1-2 times. Due to the excessive soaking time and excessive hydrolysis, the structure of the polyurethane foam is broken during the rinsing process and loses resilience. Place it in a vacuum oven at 80°C for 12 hours, and the degree of hydrolysis is 30.11%.

对比例2Comparative Example 2

将密度为13kg/m3的聚氨酯泡沫切割为3×2×1cm大小的块,浸泡于80℃质量分数40%的氢氧化钠溶液30min后,用去离子水反复冲洗至中性,然后用无水乙醇冲洗1-2遍,置于80℃真空干燥箱干燥12h,得到水解度为0.75%的聚氨酯泡沫。Cut the polyurethane foam with a density of 13kg/m3 into 3 ×2×1cm blocks, soak them in 40% sodium hydroxide solution at 80°C for 30 minutes, rinse them repeatedly with deionized water until neutral, and then use Rinse with water and ethanol for 1-2 times, and dry in a vacuum oven at 80° C. for 12 hours to obtain a polyurethane foam with a degree of hydrolysis of 0.75%.

对比例3Comparative Example 3

与实施例1的不同之处在于,不包括步骤(1),即不对聚氨酯泡沫进行预处理,后续步骤直接采用未经预处理的聚氨酯泡沫。The difference from Example 1 is that the step (1) is not included, that is, the polyurethane foam is not pretreated, and the unpretreated polyurethane foam is directly used in subsequent steps.

最终所制备得到的石墨泡沫基相变储能材料的填充率为54%,其中,十八胺和石墨泡沫的质量比为5:1。The final filling rate of the prepared graphite foam-based phase change energy storage material is 54%, wherein the mass ratio of octadecylamine to graphite foam is 5:1.

该石墨泡沫基相变储能材料的凝固温度为39.56℃,凝固潜热为177.2J/g,导热系数为0.36W/m·k。The solidification temperature of the graphite foam-based phase change energy storage material is 39.56°C, the solidification latent heat is 177.2J/g, and the thermal conductivity is 0.36W/m·k.

实施例2Example 2

(1)聚氨酯泡沫(PU泡沫)的预处理:(1) Pretreatment of polyurethane foam (PU foam):

将密度为13kg/m3的聚氨酯泡沫(PU泡沫)切割为3×2×1cm大小的块,浸泡于80℃质量分数40%的氢氧化钠溶液120min后,用去离子水反复冲洗至中性,然后用无水乙醇冲洗1-2遍,置于80℃真空干燥箱干燥12h,得到水解度为26.8%的聚氨酯泡沫,泡沫回弹性较差。Polyurethane foam (PU foam) with a density of 13kg/ m3 was cut into 3×2×1cm blocks, soaked in 80°C 40% sodium hydroxide solution for 120min, then rinsed repeatedly with deionized water until neutral , and then rinsed with absolute ethanol for 1-2 times, and placed in a vacuum oven at 80° C. for 12 hours to obtain a polyurethane foam with a degree of hydrolysis of 26.8%, and the resilience of the foam is relatively poor.

(2)石墨泡沫的制备:(2) Preparation of graphite foam:

间苯二酚溶解在水和乙醇的混合物(水和乙醇的质量比为1:1)中,间苯二酚与混合物的质量比为1:4,并搅拌(300r/min)混合物15min;向上述混合物中加入质量分数37%的盐酸溶液(混合物与盐酸溶液质量比30:1)并搅拌1h(500r/min),在磁力搅拌下逐滴加入质量分数37%的甲醛溶液,盐酸溶液与甲醛溶液的质量比为1:7.1。将反应混合物进一步剧烈搅拌1h(1000r/min),然后获得均相溶液。Resorcinol was dissolved in a mixture of water and ethanol (the mass ratio of water and ethanol was 1:1), the mass ratio of resorcinol to the mixture was 1:4, and the mixture was stirred (300r/min) for 15min; Add 37% mass fraction of hydrochloric acid solution to the above mixture (mass ratio of mixture to hydrochloric acid solution 30:1) and stir for 1 h (500r/min), add dropwise 37% mass fraction of formaldehyde solution under magnetic stirring, hydrochloric acid solution and formaldehyde The mass ratio of the solution is 1:7.1. The reaction mixture was further vigorously stirred for 1 h (1000 r/min), then a homogeneous solution was obtained.

将合成石墨和硝酸镍添加到上述均相溶液中并搅拌2h(800r/min),合成石墨和硝酸镍的质量比为1:1,合成石墨与所述均相溶液的质量比为1:4,得到酚醛树脂-石墨溶液。Add synthetic graphite and nickel nitrate to the above-mentioned homogeneous solution and stir for 2h (800r/min), the mass ratio of synthetic graphite and nickel nitrate is 1:1, and the mass ratio of synthetic graphite to the homogeneous solution is 1:4 , to obtain a phenolic resin-graphite solution.

将PU泡沫浸渍于上述酚醛树脂-石墨溶液中5min,用玻璃棒除去多余溶液,随后在80℃的真空干燥箱中干燥12h,然后在150℃下固化24h。聚合物复合泡沫在管式炉中以2℃/min的加热速率在氩气流下在1000℃下碳化1h,获得高度互连的三维(3D)石墨泡沫。The PU foam was immersed in the above-mentioned phenolic resin-graphite solution for 5 min, and the excess solution was removed with a glass rod, then dried in a vacuum oven at 80 °C for 12 h, and then cured at 150 °C for 24 h. Polymer syntactic foams were carbonized in a tube furnace at a heating rate of 2 °C/min at 1000 °C for 1 h under an argon flow to obtain highly interconnected three-dimensional (3D) graphite foams.

(3)石墨泡沫基相变储能材料的制备:(3) Preparation of graphite foam-based phase change energy storage materials:

烧杯称取十八胺置于80℃烘箱完全融化后,加入石墨泡沫浸泡12h,十八胺和石墨泡沫的质量比为50:1,然后将十八胺及石墨泡沫转移至抽滤瓶,抽滤瓶口放一培养皿堵住瓶口,抽气1min后保持30s,重复两到三次,得到复合相变材料,将复合材料样品至于滤纸上,滤纸置于真空干燥箱中除去液体十八胺,连续更换滤纸,直到滤纸上没有液体泄漏,得到石墨泡沫基相变储能材料。Weigh octadecylamine in a beaker and place it in an oven at 80°C to completely melt, add graphite foam to soak for 12 hours, the mass ratio of octadecylamine to graphite foam is 50:1, then transfer octadecylamine and graphite foam to a suction filter bottle, and pump Put a petri dish at the mouth of the filter bottle to block the mouth of the bottle, pump air for 1 minute and keep it for 30 seconds, repeat two to three times to obtain a composite phase change material, put the composite material sample on the filter paper, and put the filter paper in a vacuum drying oven to remove the liquid octadecylamine , and continuously replace the filter paper until there is no liquid leakage on the filter paper, and a graphite foam-based phase change energy storage material is obtained.

最终所制备得到的石墨泡沫基相变储能材料的填充率为77.58%,其中,十八胺和石墨泡沫的质量比为7.6:1。The final filling ratio of the prepared graphite foam-based phase change energy storage material was 77.58%, wherein the mass ratio of octadecylamine to graphite foam was 7.6:1.

该石墨泡沫基相变储能材料的凝固温度为39.22℃,凝固潜热为207.5J/g,导热系数为0.43W/m·k。The solidification temperature of the graphite foam-based phase change energy storage material is 39.22°C, the solidification latent heat is 207.5J/g, and the thermal conductivity is 0.43W/m·k.

以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。The above-mentioned embodiments are only to describe the preferred mode of the present invention, not to limit the scope of the present invention. Without departing from the design spirit of the present invention, those skilled in the art may make various Variations and improvements should fall within the scope of protection defined by the claims of the present invention.

Claims (10)

1. A preparation method of a graphite foam-based phase change energy storage material is characterized by comprising the following steps:
pretreating polyurethane foam, wherein the pretreatment of the polyurethane foam comprises soaking the polyurethane foam in a sodium hydroxide solution;
soaking the pretreated polyurethane foam in a phenolic resin-graphite solution, and drying, curing and sintering to prepare graphite foam;
filling an organic phase-change material into the graphite foam to obtain the graphite foam-based phase-change energy storage material, wherein the mass ratio of the organic phase-change material to the graphite foam is 7-9.
2. The method of claim 1, wherein the polyurethane foam pre-treatment comprises:
soaking polyurethane foam in a sodium hydroxide solution for 60-120min, washing with deionized water to neutrality, washing with absolute ethyl alcohol, and vacuum drying to obtain pretreated polyurethane foam;
wherein the mass fraction of the sodium hydroxide solution is 40%, and the soaking temperature of the sodium hydroxide solution is 80 ℃.
3. The method according to claim 1, wherein the method for preparing the phenolic resin-graphite solution comprises:
dissolving resorcinol in a mixture of water and ethanol, adding a hydrochloric acid solution after uniformly mixing, then dropwise adding a formaldehyde solution under the stirring condition, and violently stirring to obtain a homogeneous solution;
and adding synthetic graphite and nickel nitrate into the homogeneous phase solution to obtain the phenolic resin-graphite solution.
4. The preparation method according to claim 3, wherein the mass ratio of water to ethanol in the mixture is 1; the mass ratio of the resorcinol to the mixture is 1.2-4.
5. The preparation method according to claim 3, wherein the mass fraction of the hydrochloric acid solution is 37%; the mass ratio of the hydrochloric acid solution to the formaldehyde solution is 1.
6. The production method according to claim 3, wherein the mass ratio of the synthetic graphite to the nickel nitrate is 1; the mass ratio of the synthetic graphite to the homogeneous solution is 1.
7. The method of claim 1, wherein the pre-treated polyurethane foam is soaked in the phenolic resin-graphite solution for 5min, taken out, excess solution is removed, and then dried in vacuum at 80 ℃ for 12h, and then cured at 150 ℃ for 24h, and then heated to 1000 ℃ under argon flow at a heating rate of 2 ℃/min, and carbonized for 1h to prepare the graphite foam.
8. The preparation method according to claim 1, wherein the step of filling the interior of the graphite foam with the organic phase change material is performed by a method combining melt impregnation and vacuum impregnation, and comprises the following steps:
after the organic phase change material is melted, adding the graphite foam for soaking for 12 hours; and then transferring the soaking system into a filter flask, blocking the mouth of the filter flask, keeping for 30s after 1min of air suction, repeating for 2-3 times to obtain a composite material sample, placing the composite material sample on filter paper, performing vacuum drying, and continuously replacing the filter paper until no liquid leaks on the filter paper, thereby obtaining the graphite foam-based phase-change energy storage material.
9. A graphite foam-based phase-change energy storage material, which is prepared by the preparation method of the graphite foam-based phase-change energy storage material as claimed in any one of claims 1 to 8.
10. The application of the graphite foam-based phase-change energy storage material as claimed in claim 9 in the field of low-temperature waste heat recovery.
CN202210112352.0A 2022-01-29 2022-01-29 A kind of graphite foam-based phase change energy storage material and preparation method thereof Pending CN115247049A (en)

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