WO2021179232A1 - 一种溶剂塑化发泡制备气凝胶的方法 - Google Patents

一种溶剂塑化发泡制备气凝胶的方法 Download PDF

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WO2021179232A1
WO2021179232A1 PCT/CN2020/078904 CN2020078904W WO2021179232A1 WO 2021179232 A1 WO2021179232 A1 WO 2021179232A1 CN 2020078904 W CN2020078904 W CN 2020078904W WO 2021179232 A1 WO2021179232 A1 WO 2021179232A1
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foaming
blowing agent
preparation
aerogel
graphene oxide
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PCT/CN2020/078904
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French (fr)
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许震
高超
庞凯
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浙江大学
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Priority to JP2021530993A priority Critical patent/JP7255911B2/ja
Priority to PCT/CN2020/078904 priority patent/WO2021179232A1/zh
Priority to US17/428,639 priority patent/US20220306473A1/en
Publication of WO2021179232A1 publication Critical patent/WO2021179232A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/06—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose

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  • the invention belongs to the technical field of functional materials, and specifically relates to a method for preparing aerogels through solvent plasticization and foaming.
  • Thermoplastic foam materials are widely used in daily life due to their super light weight, insulation, heat insulation, fatigue resistance, etc., such as shock absorption, heat insulation, packaging, sports protection, etc.
  • the thermoplastic foaming process mainly uses polymerization at high temperatures. The disentanglement of the molecular chains of the substance realizes the infiltration of gas, and the cells generated by the gas are fixed inside the polymer after low-temperature setting, and the thermoplastic foam material is obtained.
  • thermoplastic foaming process is only suitable for polymer materials that can be plasticized at lower temperatures, such as polyurethane, polypropylene, etc., while for carbon materials, inorganic materials, metal materials, etc., because they have extremely high plasticization Temperature (up to 3000 °C), so the current thermoplastic process requires extremely high energy consumption to be applied to such materials.
  • Aerogels are generally low-density porous materials prepared from wet gels through a special drying method.
  • the earliest aerogels are silicon aerogels prepared by Kistler, which is the world's least dense solid.
  • Kistler the world's least dense solid.
  • aerogels there are many types of aerogels, mainly focusing on carbon materials, inorganic materials, metal materials, etc., which cannot be achieved by thermoplastic foaming processes.
  • the current preparation process of aerogels is mainly obtained by supercritical drying or freeze-drying preparation methods. , Its energy consumption is high, and its resulting structure is unstable, so it is not conducive to large-scale industrial application.
  • the object of the present invention is to provide a method for preparing an aerogel material by solvent plasticization and foaming, which mainly combines solvent plasticization and in-situ bubble generation to obtain an aerogel material.
  • This method is different from the existing thermoplastic foaming, which is in the solution environment, the plasticizer penetrates into the macroscopic assembly material, reduces the intermolecular force inside the assembly material, and reduces the foaming resistance; at the same time, it is based on the foaming agent. Realize in-situ foaming to obtain aerogel materials; solve the foaming problem of non-thermoplastic polymers.
  • Another object of the present invention is to provide a method for preparing an aerogel material by solvent plasticization and foaming, which mainly combines solvent plasticization and in-situ bubble generation to obtain an aerogel material.
  • This method is different from the existing thermoplastic foaming.
  • the plasticizer penetrates into the macroscopic assembly material to reduce the intermolecular force inside the assembly material to perform in-situ foaming, that is, the molecular level is realized.
  • the structure control of the aerogel can reach the nanometer level, and realize the control of the microscopic composition such as the wall thickness and pore size of the aerogel.
  • Another object of the present invention is to provide a method for preparing a porous aerogel material by solvent plasticization and foaming, which mainly combines solvent plasticization and in-situ bubble generation to obtain the aerogel material. This method does not require heat treatment and can reduce energy consumption.
  • the methods to achieve any of the above objectives are: (1) Mix the material to be foamed with the blowing agent precursor, and then assemble it into a macroscopic material; place the obtained macroscopic material in a plastic solution to plasticize and foam; After plasticization and foaming, the aerogel material is prepared by drying.
  • Method (1) and method (2) are essentially the same, and both use plasticized foaming. The difference is that the foaming method is different.
  • the foaming agent precursor is incorporated before assembly, and then foaming is initiated in the plastic solution; in method (2), the assembled material is directly used to initiate foaming in the plastic solution.
  • the plastic solution is a plasticizer or a solution containing a plasticizer. Therefore, in this application, the plasticizer can be used as a solvent, and can also be used as a solute together with the foaming initiator.
  • the plasticizer is a substance that can reduce the intermolecular force of the material to be foamed.
  • the substance that can reduce the intermolecular force in the film is usually a substance that has affinity with the material.
  • cellulose and polar solvents water, DMF, DMSO, etc.
  • silver nanowires and surfactants where surfactants can reduce the surface tension of silver nanowires (the two have similar HLB values)
  • Mxene and dimethyl Base pyrrolidone polyethylene glycol
  • molybdenum disulfide and dimethylpyrrolidone polyethylene glycol, graphene and dimethylformamide, dimethylacetamide, isopropanol, ethanol, etc.
  • the method for initiating the foaming of the foaming agent precursor includes but is not limited to: adding an initiator and heating; wherein the initiator initiates the foaming agent precursor to generate gas.
  • the combination of the foaming initiator and the foaming agent precursor can be in any form, such as carbonate and acid, sodium borohydride and water, and the like. If it is initiated by heating, the added blowing agent precursor is a substance that can generate gas under heating, such as sodium bicarbonate.
  • the blowing agent includes a self-blowing agent and a reactive blowing agent
  • the reactive blowing agent is a blowing agent that can react with the material to be foamed and generate gas
  • the self-blowing agent is Blowing agent that can decompose to produce gas, such as bicarbonate.
  • the drying can be in any form, for example, direct drying, solvent replacement drying and the like can be used to achieve.
  • energy consumption can be reduced by direct drying.
  • the present invention is suitable for the foaming of all materials, especially for the foaming of non-thermoplastic polymers, such as graphene, molybdenum disulfide, Mxene, cellulose, silver nanowires, and the like.
  • non-thermoplastic polymers such as graphene, molybdenum disulfide, Mxene, cellulose, silver nanowires, and the like.
  • the above method (1) or method (2) is used to prepare graphene aerogel.
  • the purpose is to use the action of gas and liquid to foam graphene-based dense assembly materials, thereby obtaining highly porous graphene aerogel materials.
  • Another purpose is to: mainly use the action of gas and liquid to plasticize and foam graphene-based dense assembly materials.
  • the polar solution reduces the force between the graphene oxide layers and reduces the foaming resistance; due to the dense graphene
  • the base material generally has a layer-by-layer contact structure. Therefore, the internal pores of the graphene aerogel obtained by foaming are mostly face-to-face contact and overlap, so that it has relatively excellent mechanical properties.
  • Another purpose is to use liquid plasticizing and foaming methods to convert dense macroscopic materials assembled by graphene oxide, such as one-dimensional fibers, two-dimensional membranes, etc., into three-dimensional porous aerogel materials.
  • the shape and pattern of the aerogel are controllable and easy to process, and the resulting aerogel structure can depend on dense macroscopic materials, so it has certain structural controllability and can be used in various fields in daily life, such as sound insulation and insulation. Heat, damping, adsorption and electromagnetic shielding, etc.
  • Method (1) The graphene oxide is mixed with the foaming agent precursor, after forming the film, placed in a plastic solution for plasticization and foaming, and dried to obtain the graphene porous aerogel material.
  • the method for initiating the foaming of the foaming agent precursor in the plastic solution includes at least any one of adding an initiator and heating.
  • Method (2) placing the macroscopic material formed by stacking and assembling graphene oxide layers in a plastic solution containing a foaming agent for plasticization and foaming, and then drying to obtain the graphene porous aerogel material.
  • the blowing agent includes a self-blowing agent and a reactive blowing agent.
  • the reactive blowing agent is a blowing agent that can react with graphene oxide oxygen-containing functional groups and generate gas, such as hydration. Hydrazine, borohydride; the self-blowing agent is a blowing agent that can decompose to generate gas, such as bicarbonate.
  • graphene oxide layers with a size larger than 1 um can be stacked and assembled to form a macroscopic graphene oxide material. After being plasticized and foamed by the method described in this application, it has a higher expansion ratio and a better structure. Completeness.
  • the average size is not less than 1um, it can be prepared by Hummers method and improved Hummers method.
  • the obtained graphene aerogel has a volume expansion multiple of 10-800 times compared with the original macroscopic material, which can be extremely useful in the fields of sound insulation, heat insulation, damping, adsorption, and electromagnetic shielding. Potential application value.
  • the above method (1) or method (2) is used to prepare graphene aerogels for electromagnetic shielding. It is mainly used to assemble a large-size graphene oxide film, which is transformed into a three-dimensional porous aerogel material by using plasticized liquid foaming.
  • the shape and pattern of the obtained aerogel are controllable, easy to process, and due to its height
  • the oriented layer-by-layer structure is suitable for the field of electromagnetic shielding and has excellent shielding effects.
  • the density of aerogel is extremely low, which provides the possibility for the development of the next step to prepare micro-nano devices.
  • the specific method can be:
  • graphene oxide with a size greater than 20um and a carbon-oxygen ratio greater than 2 to form a film, then soak it in a plastic solution containing a foaming agent, replace the plastic solution with a volatile solvent, and then dry to remove the volatile solvent.
  • graphene porous material which reduce the defect density by a high temperature annealing process, so that I D / I G 0.01 to 1, to obtain graphene an electromagnetic shielding material.
  • the plastic solution is a plasticizer or a solution containing a plasticizer.
  • the plasticizer can be used as a solvent or as a solute together with the foaming initiator.
  • the plasticizer may be water, an organic solvent, or a mixed solution of water and an organic solvent.
  • the blowing agent can be a gas-generating solution such as hydrazine hydrate, borohydride salt, and bicarbonate salt.
  • the temperature range of the high-temperature annealing treatment is 500-3000°C.
  • Figure 1 shows the porous Mxenes aerogel material obtained in Example 1.
  • Figure 2 shows the porous molybdenum disulfide aerogel material obtained in Example 2.
  • FIG. 3 shows the porous cellulose aerogel material obtained in Example 3.
  • FIG. 4 shows the porous graphene aerogel material obtained in Example 4.
  • FIG. 5 shows the porous graphene aerogel material obtained in Example 2.
  • Figure 6 shows the porous Mxenes aerogel material obtained in Example 2.
  • FIG. 7 shows the dense macroscopic graphene oxide film material used in Example 7 and the resulting aerogel material.
  • FIG. 8 shows the dense macroscopic graphene oxide film material used in Example 8 and the resulting aerogel material.
  • FIG. 9 shows aerogels of different shapes obtained in Example 12.
  • FIG. 10 shows the super-sized aerogel obtained in Example 13.
  • FIG. 11 shows the compression curves of the aerogel material obtained in Example 10 under different compression deformations.
  • the porous Mxenes aerogel material as shown in Fig. 1, has a wall thickness of 195 nm, an average pore diameter of 100 ⁇ m, and a density of 11 mg/cm 3 .
  • the 5mg/ml water suspension of molybdenum disulfide was uniformly mixed with sodium bicarbonate (mass ratio 1:1), dried to form a film, and then placed in 10% hydrochloric acid to generate gas foaming, and the result was obtained after 5 minutes
  • the porous molybdenum disulfide aerogel material as shown in Figure 2, has a wall thickness of 105 nm, an average pore diameter of 87 ⁇ m, and a density of 15 mg/cm 3 .
  • the 11mg/ml aqueous suspension of bacterial cellulose was uniformly mixed with sodium carbonate (mass ratio 1:5), dried to form a film, and then placed in 15% hydrochloric acid to produce gas foaming, and after 1 min, a porous
  • the cellulose aerogel material as shown in Figure 3, has a wall thickness of 360 nm, an average pore size of 230 ⁇ m, and a density of 35 mg/cm 3 .
  • the 8mg/ml graphene oxide suspension was uniformly mixed with the same mass of sulfuric acid, dried to form a film, and then placed in a 10% sodium bicarbonate solution to produce gas foaming. After 1 minute, porous graphite was obtained.
  • the olefin aerogel material as shown in Figure 4, has a wall thickness of 50 nm, an average pore diameter of 310 ⁇ m, and a density of 12 mg/cm 3 .
  • the 8mg/ml graphene oxide suspension was uniformly mixed with the same mass of sulfuric acid, dried to form a film, and then placed in an aqueous solution containing 1% sodium borohydride and DMF, the volume ratio of DMF to water was 1 :1; Gas foaming is generated, and a porous graphene aerogel material is obtained after 10 minutes, as shown in Figure 5, with a wall thickness of 30nm, an average pore diameter of 350 ⁇ m, and a density of 11mg/cm 3 .
  • the porous Mxenes aerogel material as shown in Figure 6, has a wall thickness of 207nm, an average pore size of 122 ⁇ m, and a density of 25mg/cm 3 .
  • a 5mg/ml graphene oxide suspension (GO, purchased from Hangzhou Goene Technology Co., Ltd., size 500-800nm) was prepared by a knife coating method to form a film of about 20um thick graphene oxide film material, and cut it A disc was then placed in a 10wt% hydrazine hydrate aqueous solution. After 5 minutes, a graphene aerogel with a height of about 8 mm was obtained.
  • the 5mg/ml graphene oxide suspension (GO, purchased from Hangzhou Goene Technology Co., Ltd., size 50-100um) was wet-spinned to obtain graphene oxide fiber material with a diameter of 31.4um; It was placed in an 85% by weight hydrazine hydrate aqueous solution, and a highly entangled graphene fiber aerogel material was obtained after 60 minutes.
  • a tensile test was performed on the aerogel using a tensile testing machine, and it was found that the elongation at break of the prepared aerogel was about 6%, and it could be repeatedly stretched for 1000 times under a strain of 5% without breaking.
  • a 10mg/ml graphene oxide suspension was prepared, and a 20um thick graphene oxide non-woven fabric was prepared by suction filtration.
  • the graphene oxide non-woven fabric was placed in a 100mg/ml ammonium bicarbonate aqueous solution, 60 After reacting for 20 minutes at degrees Celsius, a graphene aerogel material with a height of about 7 mm was obtained.
  • a 10mg/ml graphene oxide suspension was prepared, and about 20um thick graphene oxide film material was prepared by the method of scraping and film formation.
  • the graphene oxide film material was placed in a 10mg/ml sodium borohydride aqueous solution for 20 minutes Afterwards, a graphene aerogel material with a height of about 6.5 mm was obtained.
  • a 10 mg/ml graphene oxide suspension was prepared, and a graphene oxide film material with a thickness of about 20 um was prepared by the method of knife coating.
  • Sodium borohydride was added to water and dimethylformamide in a mass-volume ratio of 80 mg/ml, and a mixed solution composed of a volume ratio of 1:1 was used to obtain a foaming agent solution.
  • the graphene oxide film material was placed in the blowing agent solution, and after 20 minutes, a graphene aerogel material with a height of about 6.5 mm was obtained.
  • the foamed graphene aerogel is directly dried to remove the volatile solvent to obtain a graphene porous aerogel material with a density of about 5.9 mg/cm 3 .
  • Example 7 The materials and methods used are the same as in Example 7. The difference is that the graphene oxide membrane material is cut into different shapes, such as rabbits, bears, and dolphins. After liquid foaming, a highly porous aerogel material with a special shape is obtained. , The density is about 5-6mg/cm 3 .
  • Example 7 The materials and methods used are the same as in Example 7. The difference is that a graphene oxide film material with a size of 25*25cm will be prepared, and after liquid foaming, a highly porous large-size graphene aerogel material will be obtained. It is about 5 mg/cm 3 , so it can be seen that the plasticized foaming method of the present application is suitable for large-scale production.
  • the size distribution is between 20-30um, the carbon to oxygen ratio is 2.5, and the concentration of graphene oxide suspension (purchased from Hangzhou Gaoene Technology Co., Ltd.) is about 20um thick.
  • the graphene oxide film material was cut into a disc, and then placed in an 85% hydrazine hydrate solution. One hour later, a graphene aerogel with a height of about 8.1 mm was obtained. The hair was replaced with ethanol. The foaming agent solution was then dried at 60°C to remove ethanol. After high temperature treatment at 1600°C for 1 hour, a graphene aerogel with a density of 3 mg/cm 3 was obtained, with an I D /I G of 0.2 and an electromagnetic field at 5 mm. The shielding effectiveness is 110dB.
  • the size distribution is between 80-100um, the carbon-oxygen ratio is 2.35, the concentration of graphene oxide suspension (purchased from Hangzhou Gaoene Technology Co., Ltd.) is about 50um thick
  • the graphene oxide film material is cut into a wafer, and the graphene oxide film material is placed in a 100mg/ml ammonium bicarbonate aqueous solution. After a period of time, a graphene aerogel with a height of about 12.6mm is obtained.
  • the size distribution is between 100-200um, the carbon-oxygen ratio is 2.14, the concentration of 10mg/ml graphene oxide suspension (purchased from Hangzhou Goene Technology Co., Ltd.) is prepared by suction filtration to obtain about 30um thick oxide
  • the graphene film material is cut into a wafer, and the graphene oxide film material is placed in a 100mg/ml ammonium bicarbonate aqueous solution. After a period of time, a graphene aerogel material with a height of about 8.5mm is obtained.
  • a graphene aerogel with a density of 5.3 mg/cm 3 is obtained, I D / I G is 0.1, and its electromagnetic shielding effectiveness is 102dB at 5mm.
  • the size distribution is between 20-30um, the carbon to oxygen ratio is 2.5, and the concentration of graphene oxide suspension (purchased from Hangzhou Gaoene Technology Co., Ltd.) is about 20um thick.
  • the graphene oxide film material was cut into a wafer (same as Example 14), and the graphene oxide film material was directly subjected to high temperature treatment at 1600°C for 1 hour to obtain a graphene porous film with a density of 100 mg/cm 3 Material, I D /I G is 0.2, and its electromagnetic shielding effectiveness is only 20dB.
  • a suspension of graphene oxide (purchased from Hangzhou Goene Technology Co., Ltd.) with a size distribution of 80-100um, a carbon-oxygen ratio of 2.35 and a concentration of 10mg/ml is mixed with ammonium bicarbonate, and a film is formed by scraping.

Abstract

本发明首次提出一种基于溶剂塑化发泡制备气凝胶的方法，通过溶剂塑化与原位气泡产生从而实现用于制备气凝胶材料，克服了非聚合物难以实现热塑性发泡工艺的难题，具有广泛的应用普适性。此外，此方案可选发泡系较多，且易于实施，无须利用特殊的干燥工艺，因此极大的推动了多孔气凝胶的产业化发展。

Description

一种溶剂塑化发泡制备气凝胶的方法 技术领域
本发明属于功能材料技术领域，具体涉及一种通过溶剂塑化发泡来制备气凝胶的方法。
背景技术
热塑性泡沫材料由于其超轻、绝缘绝热、耐疲劳等优异的性能被广泛的应用于日常生活中，如减震阻尼、隔热、包装、运动防护等等，热塑性发泡工艺主要利用高温下聚合物的分子链的解缠结从而实现气体的渗入，经过低温定形将气体所产生的泡孔固定于聚合物的内部，便得到了热塑性泡沫材料。但是目前热塑性发泡工艺仅仅适用于可以实现在较低温度下塑化的聚合物材料，如聚氨酯、聚丙烯等，而对于碳材料、无机材料、金属材料等，由于它们具有极高的塑化温度(最高可达3000℃)，因此目前的热塑性工艺需要极高的耗能才能应用于此类材料。
气凝胶一般是由湿凝胶通过特殊的干燥方法制备所得的低密度多孔材料，最早的气凝胶是由Kistler制备得到的硅气凝胶，为世界上密度最小的固体。目前气凝胶的种类很多，主要集中于热塑性发泡工艺实现不了的碳材料、无机材料、金属材料等等，但是目前气凝胶的制备工艺主要是采用超临界干燥或冷冻干燥的制备方法所得，其耗能较高，其所得结构不稳定，因此并不利于大规模的产业化应用。
公开于该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不应当被视为承认或以任何形式暗示该信息构成已为本领域一般技术人员所公知的现有技术。
发明内容
本发明的目的在于提供一种溶剂塑化发泡制备气凝胶材料的方法，其主要是结合溶剂塑化和原位气泡的产生，从而得到气凝胶材料。该方法区别于现有的热塑性发泡，其是在溶液环境下，塑化剂渗入到宏观的组装材料中，降低组装材料内部的分子间作用力，降低发泡阻力；同时，基于发泡剂实现原位发泡，从而得到气凝胶材料；解决非热塑性聚合物的发泡难题。
本发明的另一个目的在于提供一种溶剂塑化发泡制备气凝胶材料的方法，其主要是结合溶剂塑化和原位气泡的产生，从而得到气凝胶材料。该方法区别于现有的热塑性发泡，其是在溶液环境下，塑化剂渗入到宏观的组装材料中，降低组装材料内部的分子间作用力来进行原位发泡，即实现了分子层面的结构调 控，可以达到纳米级别，实现气凝胶的壁厚、孔径等微观组成的控制。
本发明的另一个目的在于提供一种溶剂塑化发泡制备多孔气凝胶材料的方法，其主要是结合溶剂塑化和原位气泡的产生，从而得到气凝胶材料。该方法无需热处理，可降低能耗。
实现上述任一目的的方法为：(1)将待发泡的材料与发泡剂前驱体混合，然后组装成宏观材料；将所得宏观材料放置于塑性溶液中，使其塑化和发泡；塑化和发泡后经过干燥便制得气凝胶材料。
或为：(2)将待发泡的材料组装成宏观材料，将所得宏观材料放置于含有发泡剂的塑性溶液中，使其塑化和发泡；塑化和发泡后经过干燥便制得气凝胶材料。
方法(1)和方法(2)实质相同，均采用了塑化发泡，区别在于，发泡方式不同。方法(1)中，在组装前掺入发泡剂前驱体，然后在塑性溶液中引发发泡；方法(2)中，直接采用组装完成的材料，在塑性溶液中引发发泡。
所述的塑性溶液为塑性剂或含有塑性剂的溶液。因此，本申请中，塑化剂可以作为溶剂，也可以与所述的发泡引发剂一同作为溶质。
所述的塑性剂为可降低待发泡材料的分子间作用力的物质，这种可以降低膜内部分子间作用力的物质通常为：与材料具有亲和性的物质。例如：纤维素与极性溶剂(水、DMF、DMSO等)；银纳米线与表面活性剂，其中的表面活性剂可降低银纳米线的表面张力(两者HLB值接近)；Mxene与二甲基吡咯烷酮、聚乙二醇；二硫化钼与二甲基吡咯烷酮、聚乙二醇，石墨烯与二甲基甲酰胺、二甲基乙酰胺、异丙醇、乙醇等。
针对方法(1)，引发发泡剂前驱体发泡的方法包括但不限于：加入引发剂、加热；其中所述的引发剂引发所述发泡剂前驱体产生气体。发泡引发剂和发泡剂前驱体的组合可以为任意形式，例如碳酸盐与酸，硼氢化钠与水等。若采用加热方式引发，则加入的发泡剂前驱体为加热条件下可产生气体的物质，例如碳酸氢钠。
针对方法(2)，发泡剂包括自发泡剂和反应型发泡剂，所述反应型发泡剂为可通过与待发泡材料反应并产生气体的发泡剂；所述自发泡剂为可分解产生气体的发泡剂，如碳酸氢盐。
上述方法中，所述的干燥可以采用任意形式，例如可采用直接干燥、溶剂置换干燥等方式实现。在某些优选的实施例中，可以通过直接干燥降低能耗。
基于上述方法，本发明适用于所有材料的发泡，尤其适用于非热塑性聚合物的发泡，例如石墨烯、二硫化钼、Mxene、纤维素、银纳米线等。
在某些优选的实施例中，采用上述方法(1)或方法(2)来制备石墨烯气凝胶。
目的在于：利用气体及液体的作用实现对石墨烯基致密的组装材料进行发泡，从而得到高度多孔的石墨烯气凝胶材料。
另一个目的在于：主要是利用气体及液体的作用实现对石墨烯基致密的组装材料进行塑化发泡，极性溶液降低氧化石墨烯层间作用力，降低发泡阻力；由于致密的石墨烯基材料一般为层层接触的结构，因此经过发泡所得到的石墨烯气凝胶的内部孔多为面对面接触搭接，从而其具有较为优异的机械性能。
另一个目的在于：采用液体塑化发泡的手段，将利用氧化石墨烯组装得到的致密宏观材料，如一维的纤维、二维的膜等，将其转化为三维多孔的气凝胶材料，所得气凝胶的形状及图案可控，易于加工，且所得气凝胶结构可取决于致密宏观材料，因此具有一定的结构可控性，可用于日常生活的中的各种领域，如隔音、隔热、阻尼、吸附及电磁屏蔽等。
为实现上述目的，采用如下技术方案：
方法(1)：将氧化石墨烯与发泡剂前驱体混合，成膜后，置于塑性溶液中进行塑化发泡，经干燥便可得到石墨烯多孔气凝胶材料。
如前所述，引发发泡剂前驱体在所述塑性溶液中发泡的方法包括：加入引发剂、加热中的至少任意一种。
方法(2)：将由氧化石墨烯层层堆叠组装形成的宏观材料置于含有发泡剂的塑性溶液中进行塑化发泡，经干燥便可得到石墨烯多孔气凝胶材料。
如前所述，所述的发泡剂包括自发泡剂和反应型发泡剂，所述反应型发泡剂为可通过与氧化石墨烯含氧官能团反应并产生气体的发泡剂，如水合肼、硼氢化盐；所述自发泡剂为可分解产生气体的发泡剂，如碳酸氢盐。
在某些优选的实施例中，可以采用尺寸大于1um氧化石墨烯层层堆叠组装形成宏观氧化石墨烯材料，经本申请所述方法塑化发泡后，具有更高膨胀比和更好的结构完整性。
这种平均尺寸要不低于1um，可采用Hummers方法及改进的Hummers等方法制备所得。
在某些实施例中，所得的石墨烯气凝胶相比于原始的宏观材料的体积膨胀倍数可达到10-800倍，可在隔音、隔热、阻尼、吸附及电磁屏蔽等领域具有极大的潜在应用价值。
在某些优选的实施例中，采用上述方法(1)或方法(2)来制备用于电磁屏蔽的石墨烯气凝胶。其主要是将大尺寸氧化石墨烯组装得到的膜，利用塑化 液体发泡将其转化为三维多孔的气凝胶材料，所得气凝胶的形状及图案可控，易于加工，且由于其高度取向的层层排列的结构，适合用于电磁屏蔽领域，具有优异的屏蔽效果，此外，气凝胶的密度极低，为下一步制备微纳器件的发展的集成提供了可能。具体方法可以为：
采用尺寸大于20um、碳氧比大于2的氧化石墨烯成膜，随后将其置于含有发泡剂的塑性溶液中浸泡后，用可挥发溶剂置换塑性溶液，然后干燥处理以除去可挥发溶剂，得到石墨烯多孔材料，通过高温退火处理降低其缺陷密度，使其I D/I G为0.01-1，得到石墨烯电磁屏蔽材料。
如前所述，所述的塑性溶液为塑性剂或含有塑性剂的溶液。塑化剂可以作为溶剂，也可以与所述的发泡引发剂一同作为溶质。塑性剂可以为水、有机溶剂、或水与有机溶剂的混合溶液。
如前所述，所述的发泡剂可以为水合肼、硼氢化盐、碳酸氢盐等可产生气体的溶液。
所述的高温退火处理的温度范围为500-3000℃。
附图说明
图1为实施例1所得到的多孔的Mxenes气凝胶材料。
图2为实施例2所得到的多孔的二硫化钼气凝胶材料。
图3为实施例3所得到的多孔的纤维素气凝胶材料。
图4为实施例4所得到的多孔的石墨烯气凝胶材料。
图5为实施例2所得到的多孔的石墨烯气凝胶材料。
图6为实施例2所得到的多孔的Mxenes气凝胶材料。
图7为实施例7所采用的致密的宏观氧化石墨烯膜材料及其所得气凝胶材料。
图8为实施例8所采用的致密的宏观氧化石墨烯膜材料及其所得气凝胶材料。
图9为实施例12中所得不同形状的气凝胶。
图10为实施例13中所得超大尺寸的气凝胶。
图11为实施例10所得气凝胶材料在不同压缩形变下的压缩曲线。
具体实施方式
下面结合实施例对本发明进一步描述。但本发明的保护范围不仅限于此。
实施例1
将5mg/ml的Mxenes的水悬浮液与碳酸氢钠均匀混合(Mxenes与碳酸氢钠质量比1：1)，干燥成膜，随后将其放置于10％的盐酸中，产生气泡，1min后得到了多孔的Mxenes气凝胶材料，如图1，其壁厚为195nm，平均孔径为100μm， 密度为11mg/cm 3。
实施例2
将5mg/ml的二硫化钼的水悬浮液与碳酸氢钠均匀混合(质量比1：1)，干燥成膜，随后将其放置于10％的盐酸中，产生气体发泡，5min后得到了多孔的二硫化钼气凝胶材料，如图2，其壁厚为105nm，平均孔径为87μm，密度为15mg/cm 3。
实施例3
将11mg/ml的细菌纤维素的水悬浮液与碳酸钠均匀混合(质量比1：5)，干燥成膜，随后将其放置于15％的盐酸中，产生气体发泡，1min后得到了多孔的纤维素气凝胶材料，如图3，其壁厚为360nm，平均孔径为230μm，密度为35mg/cm 3。
实施例4
将8mg/ml的氧化石墨烯的悬浮液与等质量的硫酸均匀混合，进行干燥成膜，随后将其放置于10％的碳酸氢钠溶液中，产生气体发泡，1min后得到了多孔的石墨烯气凝胶材料，如图4，其壁厚为50nm，平均孔径为310μm，密度为12mg/cm 3。
实施例5
将8mg/ml的氧化石墨烯的悬浮液与等质量的硫酸均匀混合，进行干燥成膜，随后将其放置于含有1％的硼氢化钠和DMF的水溶液中，DMF与水的体积比为1:1；产生气体发泡，10min后得到了多孔的石墨烯气凝胶材料，如图5，其壁厚为30nm，平均孔径为350μm，密度为11mg/cm 3。
实施例6
将5mg/ml的Mxenes的水悬浮液与碳酸氢钠均匀混合(Mxenes与碳酸氢钠质量比1：1)，干燥成膜，随后将其放置于水中，40摄氏度加热，产生气泡，1min后得到了多孔的Mxenes气凝胶材料，如图6，其壁厚为207nm，平均孔径为122μm，密度为25mg/cm 3。
实施例7
将5mg/ml的氧化石墨烯的悬浮液(GO，购于杭州高烯科技有限公司，尺寸500～800nm)利用刮涂成膜的方法制备得到约20um厚的氧化石墨烯膜材料，将其裁剪成一个圆片，随后将其放置于10wt％的水合肼水溶液中，5min后便得到了高约为8mm的石墨烯气凝胶。
将发泡后的石墨烯气凝胶浸泡在水中，浸泡15min，置换发泡剂溶液，然后常压干燥处理以除去可挥发溶剂，得到石墨烯多孔气凝胶材料，密度约为5mg/cm 3。
利用压缩试验机对其进行压缩测试，发现所制备气凝胶经过10000次90％应 变压缩后的应力剩余为初始应力的85％，塑性变形为15％。
实施例8
将5mg/ml的氧化石墨烯的悬浮液(GO，购于杭州高烯科技有限公司，尺寸50～100um)进行湿法纺丝便得到了氧化石墨烯的纤维材料，直径为31.4um；随后将其放置于85wt％的水合肼水溶液中，60min后便得到了高度缠绕的石墨烯纤维气凝胶材料。
将发泡后的石墨烯气凝胶浸泡在可挥发溶剂正己烷中，浸泡15min，置换发泡剂溶液，然后直接干燥处理以除去可挥发溶剂，得到石墨烯多孔气凝胶材料，密度约为3mg/cm 3。
利用拉伸试验机对其进行拉伸测试，发现所制备气凝胶的断裂伸长率在6％左右，且可以在5％的应变下反复拉伸1000次不发生断裂。
实施例9
在-10℃下将5g高锰酸钾缓慢加入到快速搅动的40ml浓硫酸中，待充分溶解后，加入1g粒度为300um石墨，60转/分钟缓慢搅拌2h后停止搅拌，在低温(10℃)下反应18h，得到宽分布的氧化石墨晶体；将反应液用浓硫酸稀释并用150um孔径的钛合金网筛将氧化石墨晶体过滤出来(反应液回收)，并缓慢倒入快速搅拌的相对于过滤产物10倍体积的冰水中，静置2h，缓慢加入H 2O 2，以除去反应中多余的高锰酸钾，加入适量的盐酸直到絮状氧化石墨消失，再用钛合金网筛过滤出氧化石墨晶片；摇床缓慢震荡洗涤，得到无碎片超大片的氧化石墨烯，经检测，平均尺寸为10um，分布系数为0.5，测得其碳氧比为1.7。
配制10mg/ml的氧化石墨烯的悬浮液，利用抽滤的方法制备得到约20um厚的氧化石墨烯无纺布，将氧化石墨烯无纺布放置于100mg/ml的碳酸氢铵水溶液中，60摄氏度下反应20min，便得到了高约为7mm的石墨烯气凝胶材料。
将发泡后的石墨烯气凝胶浸泡在可挥发溶剂环己烷中，浸泡15min，置换发泡剂溶液，然后直接干燥处理以除去可挥发溶剂，得到石墨烯多孔气凝胶材料，密度约为2.4mg/cm 3。
利用压缩试验机对其进行压缩测试，发现所制备气凝胶经过50000次90％应变压缩后的应力剩余为初始应力的95％，塑性变形为5％。
实施例10
在-10℃下将5g高锰酸钾缓慢加入到快速搅动的30ml浓硫酸中，待充分溶解后，加入1g粒度为2mm的石墨，60转/分钟缓慢搅拌2h后停止搅拌，在低温(20℃)下反应48h，得到宽分布的氧化石墨晶体；将反应液用浓硫酸稀释并用150um孔径的钛合金网筛将氧化石墨晶体过滤出来(反应液回收)，并缓慢倒入快速搅拌 的相对于过滤产物10倍体积的冰水中，静置2h，缓慢加入H 2O 2，以除去反应中多余的高锰酸钾，加入适量的盐酸直到絮状氧化石墨消失，再用钛合金网筛过滤出氧化石墨晶片；摇床缓慢震荡洗涤，得到无碎片超大片的氧化石墨烯。经检测，平均尺寸为108um，分布系数在0.2，测得其碳氧比为3.1。
配制10mg/ml的氧化石墨烯的悬浮液，利用刮涂成膜的方法制备得到约20um厚的氧化石墨烯膜材料，将氧化石墨烯膜材料放置于10mg/ml的硼氢化钠水溶液中，20min后便得到了高约为6.5mm的石墨烯气凝胶材料。
将发泡后的石墨烯气凝胶浸泡在可挥发溶剂丙酮中，浸泡15min，置换发泡剂溶液，然后直接干燥处理以除去可挥发溶剂，得到石墨烯多孔气凝胶材料，密度约为5.9mg/cm 3。
利用压缩试验机对其进行压缩测试，发现所制备气凝胶经过10000次90％应变压缩后的应力剩余为初始应力的98％，塑性变形为2％。
实施例11
在-10℃下将5g高锰酸钾缓慢加入到快速搅动的30ml浓硫酸中，待充分溶解后，加入1g粒度为2mm的石墨，60转/分钟缓慢搅拌2h后停止搅拌，在20℃、下反应6h，得到氧化石墨烯，经检测，平均尺寸为47um，分布系数在0.5，测得其碳氧比为4.2。
配制10mg/ml的氧化石墨烯的悬浮液，利用刮涂成膜的方法制备得到约20um厚的氧化石墨烯膜材料。
将硼氢化钠按照质量体积比80mg/ml加入到水和二甲基甲酰胺中，按照体积比1：1组成的混合溶液中，得到发泡剂溶液。
将氧化石墨烯膜材料放置于发泡剂溶液中，20min后便得到了高约为6.5mm的石墨烯气凝胶材料。
将发泡后的石墨烯气凝胶直接干燥处理以除去可挥发溶剂，得到石墨烯多孔气凝胶材料，密度约为5.9mg/cm 3。
利用压缩试验机对其进行压缩测试，发现所制备气凝胶经过10000次90％应变压缩后的应力剩余为初始应力的97％，塑性变形为3％。
实施例12
所用材料及方法同实施例7，不同的是将氧化石墨烯膜材料裁剪成不用的形状，如兔子、熊、海豚，经过液体发泡后便得到了高度多孔的具有特殊形状的气凝胶材料，密度约为5-6mg/cm 3。
实施例13
所用材料及方法同实施例7，不同的是将制备一张尺寸为25*25cm的氧化石 墨烯膜材料，经过液体发泡后便得到了高度多孔的大尺寸的石墨烯气凝胶材料，密度约为5mg/cm 3，由此可见，本申请的塑化发泡方法适用于大规模制备。
实施例14
将尺寸分布在20-30um之间，碳氧比为2.5，浓度为5mg/ml的氧化石墨烯的悬浮液(购于杭州高烯科技有限公司)利用刮涂成膜的方法制备得到约20um厚的氧化石墨烯膜材料，将其裁剪成一个圆片，随后将其放置于85％的水合肼溶液中，一小时后便得到了高约为8.1mm的石墨烯气凝胶，用乙醇置换发泡剂溶液，然后60℃干燥处理以除乙醇，经过1600℃高温处理1h后，便得到了密度为3mg/cm 3的石墨烯的气凝胶，I D/I G为0.2，在5mm其电磁屏蔽效能为110dB。
实施例15
将尺寸分布在80-100um之间，碳氧比为2.35，浓度为10mg/ml的氧化石墨烯的悬浮液(购于杭州高烯科技有限公司)利用刮涂成膜的方法制备得到约50um厚的氧化石墨烯膜材料，将其裁剪成一个圆片，将氧化石墨烯膜材料放置于100mg/ml的碳酸氢铵水溶液中，一段时间后便得到了高约为12.6mm的石墨烯气凝胶材料，用异丙醇置换发泡剂溶液，然后60℃干燥处理以除异丙醇，经过1600℃高温处理1h后，便得到了密度为5mg/cm 3的石墨烯的气凝胶，I D/I G为0.15，在5mm其电磁屏蔽效能为70dB。
实施例16
将尺寸分布在100-200um之间，碳氧比为2.14，浓度为10mg/ml的氧化石墨烯的悬浮液(购于杭州高烯科技有限公司)利用抽滤的方法制备得到约30um厚的氧化石墨烯膜材料，将其裁剪成一个圆片，将氧化石墨烯膜材料放置于100mg/ml的碳酸氢铵水溶液中，一段时间后便得到了高约为8.5mm的石墨烯气凝胶材料，用异丙醇置换发泡剂溶液，然后60℃干燥处理以除异丙醇，经过1000℃高温处理1h后，便得到了密度为5.3mg/cm 3的石墨烯的气凝胶，I D/I G为0.1，在5mm其电磁屏蔽效能为102dB。
对比例1
将尺寸分布在20-30um之间，碳氧比为2.5，浓度为5mg/ml的氧化石墨烯的悬浮液(购于杭州高烯科技有限公司)利用刮涂成膜的方法制备得到约20um厚的氧化石墨烯膜材料，将其裁剪成一个圆片(同实施例14)，直接将氧化石墨烯膜材料直接经过1600℃高温处理1h，得到了密度为100mg/cm 3的石墨烯的多孔膜材料，I D/I G为0.2，其电磁屏蔽效能仅有20dB。
对比例2
将尺寸分布在80-100um之间，碳氧比为2.35，浓度为10mg/ml的氧化石墨烯 的悬浮液(购于杭州高烯科技有限公司)中掺入碳酸氢铵，利用刮涂成膜的方法制备得到约50um厚的氧化石墨烯膜材料，将其裁剪成一个圆片，置于200℃下使得碳酸氢铵分解对石墨烯膜进行发泡，得到的发泡材料具有大量不连续的孔洞。

Claims (16)

  1. 一种制备气凝胶材料的方法，其特征在于，该方法基于溶剂塑化发泡实现，具体包括：将待发泡的材料与发泡剂前驱体混合，然后组装成宏观材料；将所得宏观材料放置于塑性溶液中，使其塑化和发泡；塑化和发泡后经过干燥便制得气凝胶材料。
  2. 根据权利要求1所述的制备方法，其特征在于：所述的塑性溶液含有引发所述发泡剂前驱体产生气体的引发剂。
  3. 根据权利要求1所述的制备方法，其特征在于：通过加热的方式引发所述发泡剂前驱体产生气体。
  4. 一种制备气凝胶材料的方法，其特征在于，该方法基于溶剂塑化发泡实现，具体包括：将待发泡的材料组装成宏观材料，将所得宏观材料放置于含有发泡剂的塑性溶液中，使其塑化和发泡；塑化和发泡后经过干燥便制得气凝胶材料。
  5. 根据权利要求4所述的制备方法，其特征在于：所述的发泡剂包括自发泡剂和反应型发泡剂，所述反应型发泡剂为可通过与待发泡的材料反应并产生气体的发泡剂，所述自发泡剂为可分解产生气体的发泡剂。
  6. 根据权利要求1～5任一项所述的制备方法，其特征在于：所述的塑性溶液为塑性剂或含有塑性剂的溶液，所述的塑性剂为可降低待发泡材料的分子间作用力的物质。
  7. 根据权利要求1～5任一项所述的制备方法，其特征在于：所述的待发泡的材料包括石墨烯、二硫化钼、Mxene、纤维素、银纳米线等。
  8. 根据权利要求7所述的制备方法，其特征在于：待发泡的材料为氧化石墨烯，其组装成的宏观材料包括氧化石墨烯膜、氧化石墨烯纤维、氧化石墨烯无纺布、氧化石墨烯气凝胶；所述的塑性溶液为水、有机溶剂、或水与有机溶剂的混合溶液。
  9. 据权利要求8所述的制备方法，其特征在于：所述的有机溶剂选自：二甲基甲酰胺、二甲基乙酰胺、异丙醇、乙醇等。
  10. 据权利要求8所述的制备方法，其特征在于：氧化石墨烯的尺寸大于等于1um。
  11. 根据权利要求8所述的制备方法，其特征在于：该方法为：将氧化石墨烯与发泡剂前驱体混合，成膜后，置于塑性溶液中进行塑化发泡，经干燥便可得到石墨烯多孔气凝胶材料。
  12. 根据权利要求11所述的制备方法，其特征在于：引发发泡剂前驱体在所述塑性溶液中发泡的方法包括：加入引发剂、加热中的至少任意一种；其中 所述的引发剂引发所述发泡剂前驱体产生气体。
  13. 根据权利要求8所述的制备方法，其特征在于：该方法为：将由氧化石墨烯层层堆叠组装形成的宏观材料置于含有发泡剂的塑性溶液中进行塑化发泡，经干燥便可得到石墨烯多孔气凝胶材料。
  14. 根据权利要求13所述的制备方法，其特征在于：所述的发泡剂包括自发泡剂和反应型发泡剂，所述反应型发泡剂为可通过与氧化石墨烯含氧官能团反应并产生气体的发泡剂，所述自发泡剂为可分解产生气体的发泡剂。
  15. 根据权利要求14所述的制备方法，其特征在于：所述的反应型发泡剂包括水合肼、硼氢化盐；所述的自发泡剂包括碳酸氢盐等。
  16. 根据权利要求1～5任一项所述的制备方法，其特征在于：所述的干燥为直接干燥、溶剂置换干燥中的至少任意一种。
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