WO2022148460A1 - 纤维复合气凝胶材料及其制备方法和应用 - Google Patents

纤维复合气凝胶材料及其制备方法和应用 Download PDF

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WO2022148460A1
WO2022148460A1 PCT/CN2022/071020 CN2022071020W WO2022148460A1 WO 2022148460 A1 WO2022148460 A1 WO 2022148460A1 CN 2022071020 W CN2022071020 W CN 2022071020W WO 2022148460 A1 WO2022148460 A1 WO 2022148460A1
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fiber composite
composite aerogel
aerogel material
nanofiber
silicon source
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PCT/CN2022/071020
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English (en)
French (fr)
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林继铭
赵园
仇若翔
魏欢饴
曾献
邹青
段承杰
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中广核研究院有限公司
中国广核集团有限公司
中国广核电力股份有限公司
岭东核电有限公司
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Publication of WO2022148460A1 publication Critical patent/WO2022148460A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B30/00—Compositions for artificial stone, not containing binders
    • C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/158—Purification; Drying; Dehydrating

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  • the invention relates to the field of aerogel materials, in particular to a fiber composite aerogel material and a preparation method and application thereof.
  • Silica aerogel materials have poor mechanical properties and are brittle, making it difficult to directly apply in practical engineering. Combining aerogel materials with fibers is currently the main modification method to improve the mechanical properties of silica aerogels. However, the commonly used modified fibers have a large thermal conduction effect, which greatly reduces the thermal insulation performance of aerogel materials.
  • the traditional technology discloses a method for preparing high-efficiency aerogel fiber felt by using fiber felt and aerogel through siphon effect.
  • the effect enhances the binding effect of the aerogel material and the fiber.
  • Another technology discloses a preparation method of a fiber composite aerogel in which fibers are soaked in an alcohol sol and then gelled and dried. The preparation method is simple and the manufacturing cost is low.
  • the aerogel cannot be fully contacted and combined with the fibers, which will easily lead to the phenomenon of "powdering" of the material.
  • Another technology discloses a method for preparing electrospinning nanofiber reinforced silica aerogel by using electrospinning nanofibers as reinforcements through compounding process, solvent exchange, surface modification and normal pressure drying.
  • the nanofibers prepared by the method contain more organic components, and the organic components will be oxidized and decomposed at high temperature, thereby reducing the mechanical and thermal insulation properties of the material.
  • a preparation method of a fiber composite aerogel material comprising the following steps:
  • Part of the silicon source is hydrolyzed to prepare a silicon hydrolyzate, the silicon hydrolyzate is mixed with a polymer, and electrospinning is performed to prepare a nanofiber membrane;
  • the heat-treated nanofiber membrane is dipped in the silica sol, and mixed under negative pressure to prepare a nanofiber sol;
  • the nanofiber sol is subjected to gel aging treatment and then dried to prepare a fiber composite aerogel material.
  • the temperature of the heat treatment is 300°C to 900°C
  • the time of the heat treatment is 0.5h to 5h
  • the heat treatment is performed under vacuum conditions or under the protection of an inert gas.
  • the spinning voltage is 10kV-20kV
  • the receiving distance is 5cm-25cm
  • the injection flow rate is 0.3mL/h-3mL/h.
  • the drying method is carbon dioxide supercritical drying.
  • the temperature of the carbon dioxide supercritical drying is 32° C. ⁇ 50° C.
  • the pressure is 7.4 MPa ⁇ 18 MPa.
  • nitrates or oxides of rare earth elements are also added.
  • the rare earth element is lanthanum, cerium, neodymium or gadolinium; and/or,
  • the mass ratio of the nitrate of the rare earth element or the oxide of the rare earth element to the remaining silicon source is (1-35):100.
  • the polymer in the step of mixing the silicon hydrolyzate with the polymer, is polyvinyl alcohol; and/or,
  • the silicon hydrolyzate is mixed with the polymer aqueous solution, and the mass ratio of the silicon hydrolyzate to the polymer aqueous solution is 1: (0.6-1.4), the mass percentage concentration of the aqueous solution of the polymer is 5%-15%.
  • the nanofiber sol in the step of subjecting the nanofiber sol to gel ageing treatment, is allowed to stand for 0.5 h to 3 h to prepare a nanofiber gel, and then the nanofiber sol is The gel is placed in an alcohol reagent and aged at 60°C to 70°C for 1 to 3 days.
  • the step of hydrolyzing part of the silicon source includes: mixing part of the silicon source and water in a molar ratio of 1:(2-10), then adjusting the pH to 2-5, stirring 1h ⁇ 10h.
  • the step of mixing the remaining silicon source with water and an alcohol reagent includes: dispersing the remaining silicon source in the alcohol reagent, then adding water to adjust the pH to be 2 ⁇ 5, stir for 1h ⁇ 10h, and then adjust the pH to 6 ⁇ 9.
  • the molar ratio of the remaining silicon source, alcohol reagent and water is 1:(5 ⁇ 20 ): (2 to 10).
  • the silicon source is ethyl orthosilicate, methyl orthosilicate or butyl orthosilicate; and/or, the alcoholic solvent is ethanol, methanol or propanol.
  • a fiber composite aerogel material is prepared by the above-mentioned preparation method of the fiber composite aerogel material.
  • the preparation method of the above-mentioned fiber composite aerogel material is based on the characteristics that inorganic fibers can obtain enhanced flexibility when the nano-scale diameter and size distribution are uniform.
  • the fiber reinforcement of the material, and the polymer in the nanofiber is removed by heat treatment, the fiber structure is inorganic, and the oxidation and decomposition of the polymer at high temperature are avoided to reduce the mechanical and thermal insulation properties of the material, so that the material has better resistance.
  • High temperature performance and thermal insulation properties By immersing the heat-treated nanofiber membrane in silica sol and mixing under negative pressure conditions, the nanofiber membrane is fully impregnated by the silica sol, and the silica sol is fully dispersed in the nanofiber skeleton and gaps.
  • the silicone gel and the fiber form a stronger bonding force, which enhances the mechanical properties and avoids the phenomenon of "powder drop".
  • this dispersion also effectively reduces the macropore content in the composite material, thereby further improving the thermal insulation performance of the material. Therefore, the above-mentioned preparation method of the fiber composite aerogel material can simultaneously improve the thermal insulation performance and flexibility of the fiber composite aerogel material without losing powder.
  • FIG. 1 is a process flow diagram of a method for preparing a fiber composite aerogel material according to an embodiment.
  • a method for preparing a fiber composite aerogel material includes the following steps:
  • Step S110 hydrolyzing part of the silicon source to prepare a silicon hydrolyzate, mixing the silicon hydrolyzate with a polymer, and performing electrospinning to prepare a nanofiber membrane.
  • the silicon source is ethyl orthosilicate, methyl orthosilicate or butyl orthosilicate.
  • the step of hydrolyzing part of the silicon source includes: mixing part of the silicon source and water in a molar ratio of 1:(2-10), then adjusting the pH to 2-5, and stirring for 1-10h.
  • hydrochloric acid is added to adjust the pH.
  • other acidic reagents may also be added to adjust the pH.
  • the silicon hydrolyzate is mixed with the aqueous solution of the polymer, and the mass ratio of the silicon hydrolyzate to the aqueous solution of the polymer is 1: (0.6-1.4), and the mass ratio of the polymer
  • the mass percentage concentration of the aqueous solution is 5% to 15%.
  • the polymer is polyvinyl alcohol.
  • the preparation step of the aqueous solution of the polymer includes: mixing and stirring the polymer with water to dissolve the polymer. Specifically, during the mixing and stirring process, heating can be performed to speed up the dissolution rate.
  • the spinning voltage is 10kV-20kV
  • the receiving distance is 5cm-25cm
  • the injection flow rate is 0.3mL/h-3mL/h.
  • the receiving distance is 8cm ⁇ 15cm.
  • the nanofibers prepared by electrospinning have the characteristics of small fiber diameter, large specific surface area, and uniform fiber diameter distribution, and the nanofibers can be well dispersed in the silica sol to form a uniform and complex three-dimensional network structure, making the composite material It has good mechanical properties and good flexibility.
  • Inorganic silica nanofibers have a great impact on the properties of fiber composite aerogels.
  • the inventors have found through a lot of experiments that by adjusting the ratio of the spinning precursor solution, spinning parameters and coordinating with the subsequent heat treatment process, the prepared Inorganic silica nanofibers performed better.
  • the above-mentioned inorganic fibers have the characteristics of enhanced flexibility when they have a nano-scale diameter and a uniform size distribution.
  • Electrospinning is used to prepare flexible fibers with a nano-scale diameter as a fiber reinforcement for aerogel materials.
  • Silica nanofibers have the characteristics of good compatibility with silica aerogels, large specific surface area, good flexibility, and low thermal conductivity.
  • the flexible fiber materials can not only withstand certain The degree of bending can also effectively prevent the expansion of cracks in the aerogel material during the deformation process, thereby enhancing the mechanical properties of the aerogel material. thermal insulation properties.
  • Step S120 heat-treating the nanofiber membrane to remove the polymer.
  • the temperature of the heat treatment is 300°C to 900°C
  • the time of the heat treatment is 0.5h to 5h
  • the heat treatment is performed under vacuum conditions or under the protection of inert gas.
  • Nanofibers prepared by electrospinning mostly contain more organic components, which will oxidize and decompose at high temperature, thereby reducing the mechanical and thermal insulation properties of the material.
  • the nanofiber membrane is heat-treated to inorganicize the fiber structure without destroying the fiber structure, remove organic components, and make the material have better high temperature resistance and heat insulation properties.
  • the temperature of the heat treatment can be adjusted according to the cracking temperature of the polymer.
  • the inert gas is nitrogen or argon.
  • Step S130 Mix the remaining silicon source with water and an alcohol solvent to prepare a silica sol.
  • the step of mixing the remaining silicon source with water and the alcohol reagent includes: dispersing the remaining silicon source in the alcohol reagent, then adding water, adjusting the pH to 2-5, stirring for 1-10 hours, and then adjusting the pH 6 to 9.
  • hydrochloric acid is added to adjust the pH. It can be understood that in the step of adjusting the pH to 2-5, other acidic reagents may also be added to adjust the pH.
  • ammonia water is added to adjust the pH.
  • other alkaline reagents may also be added to adjust the pH.
  • the molar ratio of the remaining silicon source, alcohol reagent and water is 1:(5-20):(2-10).
  • the inventors found that by controlling the molar ratio of silicon source, alcohol reagent and water, as well as the pH value of the reaction, the time for the silica sol to form gel can be controlled, so as to avoid the silica sol gelling too fast, which will affect the subsequent negative pressure conditions and nanometers.
  • the alcohol solvent is ethanol, methanol or propanol.
  • the alcoholic solvent is ethanol.
  • nitrates of rare earth elements or oxides of rare earth elements are also added.
  • neutron irradiation in the primary circuit shell of nuclear power plants, and neutron irradiation will accelerate the aging of conventional aerogel materials and degrade the material properties. Therefore, in this embodiment, by adding rare earth element nitrate or rare earth element oxide in the preparation process of the silica sol, the rare earth element has strong absorption and shielding effects on neutron irradiation, so that the material has a higher Neutron tolerance expands the application of aerogel insulation materials in nuclear power insulation scenarios.
  • the mass ratio of the rare earth element nitrate or rare earth element oxide to the remaining silicon source is (1 ⁇ 35):100.
  • the rare earth element is lanthanum, cerium, neodymium or gadolinium.
  • the rare earth element is gadolinium.
  • gadolinium nitrate or gadolinium oxide is also added.
  • the nitrate of rare earth element is mixed with the remaining silicon source, water and alcohol solvent in the form of an aqueous solution.
  • the oxides of rare earth elements are mixed with the remaining silicon source, water and alcohol solvent by ultrasonic dispersion.
  • step S130 and step S120 are not in sequence, step S130 may be performed first, then step S120, or step S120 may be performed first, then step S130, or step S120 and step S130 may be performed simultaneously.
  • Step S140 Immerse the heat-treated nanofiber membrane in silica sol, and mix under negative pressure to prepare nanofiber sol.
  • the silica sol was placed on the lower layer of the mold, and the nanofiber film was placed on the upper layer of the mold, so that the silica sol was completely immersed in the nanofiber film.
  • the mold can be a mold commonly used in the field, and details are not described herein again.
  • the nanofiber membrane in the process of immersing the heat-treated nanofiber membrane in the silica sol in step S140, can be one or more layers, and the specific thickness and mechanical properties of the fiber aerogel material to be obtained can be determined. etc. to adjust.
  • One or more layers of the nanofiber membrane can improve the thermal insulation performance, high temperature resistance and mechanical properties of the fiber composite aerogel material, and the number of layers of the nanofiber membrane is very important to the prepared fiber composite aerogel material. The thermal conductivity and high temperature resistance have little effect.
  • the bottom-injection negative pressure dipping method is used to make the nanofiber membrane fully impregnated with silica sol, and the silica sol is fully dispersed in the nanofiber skeleton and gaps.
  • the silicone gel and the fiber form a stronger bonding force, which enhances the mechanical properties and avoids the phenomenon of "powder drop".
  • this dispersion also effectively reduces the macropore content in the composite material, thereby further improving the thermal insulation performance of the material.
  • Step S150 subjecting the nanofiber sol to gel aging treatment, and then drying, to prepare a fiber composite aerogel material.
  • the nanofiber sol is allowed to stand for 0.5 h to 3 h to prepare a nanofiber gel, and then the nanofiber gel is placed in an alcohol reagent at 60° C. to 70° C.
  • the aging treatment is carried out for 1 to 3 days.
  • the alcohol solvent is ethanol, methanol or propanol.
  • the alcoholic solvent is ethanol.
  • the drying method is carbon dioxide supercritical drying.
  • the temperature of carbon dioxide supercritical drying is 32°C ⁇ 50°C, and the pressure is 7.4MPa ⁇ 18MPa.
  • the carbon dioxide supercritical drying method saves the period of surface modification of the material, and reduces the collapse of the inner pore size of the material during the drying process, so that the material has better thermal insulation and mechanical properties. .
  • the preparation method of the above-mentioned fiber composite aerogel material is based on the characteristics that inorganic fibers can obtain enhanced flexibility when they have a nano-scale diameter and a uniform size distribution. Electrospinning is used to prepare flexible fibers with nano-scale diameters as aerogels. The fiber reinforcement of the material, and the polymer in the nanofiber is removed by heat treatment, the fiber structure is inorganic, and the oxidation and decomposition of the polymer at high temperature are avoided to reduce the mechanical and thermal insulation properties of the material, so that the material has better resistance. High temperature performance and thermal insulation properties. Inorganic silica nanofibers have the characteristics of good compatibility with silica aerogel, large specific surface area, good flexibility, and low thermal conductivity.
  • nanofibers When nanofibers are compounded with aerogel materials, flexible fiber materials not only It can withstand a certain degree of bending, and can also effectively prevent the expansion of cracks in the aerogel material during the deformation process, thereby enhancing the mechanical properties of the aerogel material. Has stronger thermal insulation properties.
  • silica sol By immersing the heat-treated nanofiber membrane in silica sol and mixing under negative pressure conditions, the nanofiber membrane is fully impregnated by the silica sol, and the silica sol is fully dispersed in the nanofiber skeleton and gaps.
  • the silicone gel and the fiber form a stronger bonding force, which enhances the mechanical properties and avoids the phenomenon of "powder drop".
  • this dispersion also effectively reduces the macropore content in the composite material, thereby further improving the thermal insulation performance of the material. Therefore, the above-mentioned preparation method of the fiber composite aerogel material can simultaneously improve the thermal insulation performance and flexibility of the fiber composite aerogel material without losing powder.
  • Rare earth elements are added in the preparation process of the fiber composite aerogel material, so that the rare earth elements are dispersed in the fiber composite aerogel material.
  • the rare earth elements have strong absorption and shielding effects on neutron irradiation, so that the material has higher The neutron tolerance can be used in nuclear power insulation materials.
  • the fiber composite aerogel material of one embodiment is prepared by the above-mentioned preparation method of the fiber composite aerogel material.
  • the fiber composite aerogel material has both good thermal insulation performance and flexibility, and has good high temperature resistance, no powder drop, and neutron radiation resistance.
  • the application of the fiber composite aerogel material in one embodiment in the preparation of nuclear power thermal insulation materials has good thermal insulation performance and flexibility, and has good high temperature resistance, no powder drop, and neutron radiation resistance, and can be used in nuclear power thermal insulation materials.
  • step (1) The nanofiber membrane prepared in step (1) is kept at 700° C. for 1.5 hours in a vacuum environment to prepare a high temperature resistant nanofiber membrane.
  • the nanofiber sol prepared in step (4) was allowed to stand for 2 hours in a constant temperature water bath in an airtight environment, and after it was gelled, the gelled material was placed in a container filled with ethanol at 70°C for ageing in a constant temperature water bath for 3 days . Then, the aged nanofiber gel is dried with supercritical carbon dioxide to prepare fiber composite aerogel. The drying temperature was 40° C. and the pressure was 10 MPa.
  • step (1) The nanofiber membrane prepared in step (1) is kept at 700° C. for 1 hour in a vacuum environment to prepare a high temperature resistant nanofiber membrane.
  • the nanofiber sol prepared in step (4) was allowed to stand for 2 hours in a constant temperature water bath in an airtight environment, and after it was gelled, the gelled material was placed in a container filled with ethanol at 70°C for ageing in a constant temperature water bath for 3 days . Then, the aged nanofiber gel is dried with supercritical carbon dioxide to prepare fiber composite aerogel. The drying temperature was 40° C. and the pressure was 10 MPa.
  • the preparation process of the fiber composite aerogel material in this embodiment is similar to the preparation process of the fiber composite aerogel material in Example 1, the difference is that the sol ratio of step (3) is different.
  • the step (3) is: uniformly mix ethyl orthosilicate, ethanol and water (molar ratio 1:5:5), adjust the pH to 3 with hydrochloric acid, continue to stir slowly for 6h and adjust the pH to 7 with ammonia water , to prepare silica sol.
  • step (3) is as follows: uniformly mix ethyl orthosilicate, ethanol and water (molar ratio 1:20:5), adjust pH to 3 with hydrochloric acid, continue to stir slowly for 6h and adjust pH to 7 with ammonia water , to prepare silica sol.
  • step (3) is as follows: uniformly mix 10 mL of ethyl orthosilicate and 40 mL of ethanol to form solution A, add 4.5 mL of a solution containing 1 g of gadolinium nitrate dropwise to solution A, and adjust the pH to 3 with hydrochloric acid , continue to stir slowly for 6h and then adjust the pH to 7 with ammonia water to prepare silica sol.
  • step (3) is as follows: uniformly mix 10 mL of ethyl orthosilicate and 40 mL of ethanol to form solution A, add 4.5 mL of solution containing 3 g of gadolinium nitrate dropwise to solution A, and adjust the pH to 3 with hydrochloric acid , continue to stir slowly for 6h and then adjust the pH to 7 with ammonia water to prepare silica sol.
  • the preparation process of the fiber composite aerogel material of Comparative Example 1 is similar to the preparation process of the fiber composite aerogel material of Example 1, except that the heat treatment of step (2) is not performed in Comparative Example 1.
  • the preparation process of the fiber composite aerogel material of Comparative Example 2 is similar to the preparation process of the fiber composite aerogel material of Example 1, except that the heat treatment temperature in Comparative Example 2 is 1200°C.
  • the preparation process of the fiber composite aerogel material of Comparative Example 3 is as follows:
  • step (3) collecting and dispersing the PVA fiber membrane of step (2) through the silica sol of step (1), adding a certain amount of ammonia water to make the silica sol form a gel.
  • step (3) The gel of step (3) was placed in ethanol and aged at 70°C for 3 days. Then, the aged nanofiber gel is dried with supercritical carbon dioxide to prepare fiber composite aerogel. The drying temperature was 40° C. and the pressure was 10 MPa.
  • Parameters such as temperature resistance, thermal conductivity at 25° C., and density of the fiber composite aerogel materials prepared in the examples and comparative examples were tested, and the experimental data shown in the following table were obtained.
  • the specific test methods are as follows: the high temperature resistance test adopts calcination at 750 °C for not less than 6 hours, and the properties of the material still meet the performance index requirements.
  • the room temperature thermal conductivity of fiber composite aerogel materials was tested by GB/T 10295-2008 test standard.
  • the density of fiber composite aerogel materials was tested by GB/T 17911-2006.
  • the fiber composite aerogel materials prepared in Examples 1 to 6 have good temperature resistance, which can reach 750 ° C, and the thermal conductivity at room temperature is 0.022 mW/(mK) ⁇ 0.025 mW/(mK), and the density is 0.08 to 0.16 g/cm 3 .
  • the temperature resistance of the fiber composite aerogel materials of Comparative Example 1 and Comparative Example 3 is only 350 °C, which is poor in temperature resistance, and the spinning fibers are cracked at higher temperatures, resulting in material fragmentation.
  • the thermal conductivity at room temperature is 0.028-0.032mW/(mK), and the heat preservation performance is worse than that of Examples 1-6.
  • the heat treatment temperature was too high, resulting in embrittlement and fragmentation of the electrospun fibers, which could not be formed.

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Abstract

本发明涉及一种纤维复合气凝胶材料及其制备方法和应用。上述纤维复合气凝胶材料的制备方法包括如下步骤：使部分硅源水解，制备硅水解液，将硅水解液与聚合物混合，进行静电纺丝，制备纳米纤维膜；将纳米纤维膜进行热处理以除去聚合物；将剩余的硅源与水和醇类溶剂混合，制备硅溶胶；将热处理后的纳米纤维膜浸渍在硅溶胶中，在负压条件下混合，制备纳米纤维溶胶；以及将纳米纤维溶胶进行凝胶老化处理，然后干燥，制备纤维复合气凝胶材料。上述纤维复合气凝胶材料的制备方法能够同时提高纤维复合气凝胶材料的保温性能、柔韧性且不掉粉。

Description

纤维复合气凝胶材料及其制备方法和应用
本申请要求于2021年01月11日提交国家知识产权局、申请号为202110029140.1、发明名称为“纤维复合气凝胶材料及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及气凝胶材料领域，特别是涉及一种纤维复合气凝胶材料及其制备方法和应用。
背景技术
二氧化硅气凝胶材料的力学性能较差、质脆，难以直接在实际工程中应用。将气凝胶材料与纤维复合是目前提高二氧化硅气凝胶的力学性能的主要改性方法。然而常用的改性纤维的热传导效应大，极大降低了气凝胶材料的隔热性能。
传统技术公开了一种利用纤维毡通过虹吸作用与气凝胶复合制备高效气凝胶纤维毡的方法，通过选用特定密度和直径的纤维毡以保障材料的加工性能和隔热性能，并通过虹吸作用增强气凝胶材料与纤维的结合效果。然而采用常规的纤维毡很难同时兼顾材料的柔韧性与隔热性能。另有一种技术公开了一种纤维浸泡在醇溶胶后再进行凝胶及干燥的纤维复合气凝胶的制备方法，其制备方法简便，制造成本较低。然而通过该种方法气凝胶不能与纤维充分接触结合，从而会导致材料很容易发生“掉粉”现象。另有一种技术公开了以静电纺丝纳米纤维为增强体，通过复合工艺、溶剂交换、表面改性和常压干燥制备静电纺纳米纤维增强型二氧化硅气凝胶的方法。该方法制备的纳米纤维含有较多的有机组分，在高温下有机组分会发生氧化与分解从而降低材料的机械与隔热性能。
发明内容
基于此，有必要提供一种能够同时提高纤维复合气凝胶材料的保温性能和 柔韧性且不掉粉的纤维复合气凝胶材料的制备方法。
此外，还有必要提供一种纤维复合气凝胶材料和应用。
一种纤维复合气凝胶材料的制备方法，包括如下步骤：
使部分硅源水解，制备硅水解液，将所述硅水解液与聚合物混合，进行静电纺丝，制备纳米纤维膜；
将所述纳米纤维膜进行热处理以除去所述聚合物；
将剩余的所述硅源与水和醇类溶剂混合，制备硅溶胶；
将热处理后的所述纳米纤维膜浸渍在所述硅溶胶中，在负压条件下混合，制备纳米纤维溶胶；及
将所述纳米纤维溶胶进行凝胶老化处理，然后干燥，制备纤维复合气凝胶材料。
在其中一个实施例中，所述热处理的温度为300℃～900℃，所述热处理的时间为0.5h～5h，所述热处理是在真空条件或惰性气体保护下进行。
在其中一个实施例中，在所述静电纺丝的步骤中，纺丝电压为10kV～20kV，接收距离为5cm～25cm，注射流量为0.3mL/h～3mL/h。
在其中一个实施例中，所述干燥的方式为二氧化碳超临界干燥。
在其中一个实施例中，所述二氧化碳超临界干燥的温度为32℃～50℃，压力为7.4MPa～18MPa。
在其中一个实施例中，在所述将剩余的所述硅源与水和醇类试剂混合的步骤中，还加入了稀土元素的硝酸盐或稀土元素的氧化物。
在其中一个实施例中，所述稀土元素为镧、铈、钕或钆；及/或，
所述稀土元素的硝酸盐或所述稀土元素的氧化物与剩余的所述硅源的质量比为(1～35)：100。
在其中一个实施例中，在所述将所述硅水解液与聚合物混合的步骤中，所述聚合物为聚乙烯醇；及/或，
在所述将所述硅水解液与所述聚合物混合的步骤中，将所述硅水解液与所述聚合物的水溶液混合，所述硅水解液与所述聚合物的水溶液的质量比为1:(0.6～1.4)，所述聚合物的水溶液的质量百分浓度为5％～15％。
在其中一个实施例中，在所述将所述纳米纤维溶胶进行凝胶老化处理的步骤中，将所述纳米纤维溶胶静置0.5h～3h，制备纳米纤维凝胶，然后将所述纳米纤维凝胶置于醇类试剂中，在60℃～70℃下进行老化处理1天～3天。
在其中一个实施例中，所述使部分硅源水解的步骤包括：将部分所述硅源与水按摩尔比为1:(2～10)的比例混合，然后调节pH为2～5，搅拌1h～10h。
在其中一个实施例中，所述将剩余的所述硅源与水和醇类试剂混合的步骤包括：将剩余的所述硅源分散在所述醇类试剂中，然后加入水，调节pH为2～5，搅拌1h～10h，再调节pH为6～9。
在其中一个实施例中，在所述将剩余的所述硅源与水和醇类试剂混合的步骤中，剩余的所述硅源、醇类试剂和水的摩尔比为1:(5～20):(2～10)。
在其中一个实施例中，所述硅源为正硅酸乙酯、正硅酸甲酯或正硅酸丁酯；及/或，所述醇类溶剂为乙醇、甲醇或丙醇。
一种纤维复合气凝胶材料，由上述的纤维复合气凝胶材料的制备方法制备得到。
上述的纤维复合气凝胶材料在制备核电保温材料中的应用。
上述纤维复合气凝胶材料的制备方法基于无机纤维在纳米级直径且大小分布均匀时会获得增强柔韧性的特点，利用静电纺丝法制备纳米级直径且分布均匀的柔性纤维，作为气凝胶材料的纤维增强体，并通过热处理除去纳米纤维中的聚合物，使纤维结构无机化，避免高温下聚合物发生氧化与分解而降低材料的机械与隔热性能，从而使材料具有更好的耐高温性能和隔热性能。通过将热处理后的纳米纤维膜浸渍在硅溶胶中，在负压条件下混合，使纳米纤维膜被硅溶胶充分浸渍，硅溶胶充分分散在纳米纤维骨架及缝隙中，在凝胶与老化过程中，硅凝胶与纤维形成更强的结合力，增强了机械性能，避免了“掉粉”现象。同时，这种分散作用也有效降低了复合材料中的大孔含量，从而进一步提升材料的隔热性能。因此，上述纤维复合气凝胶材料的制备方法能够同时提高纤维复合气凝胶材料的保温性能、柔韧性且不掉粉。
附图说明
图1为一实施方式的纤维复合气凝胶材料的制备方法的工艺流程图。
具体实施方式
为了便于理解本发明，下面将结合具体实施方式对本发明进行更全面的描述。具体实施方式中给出了本发明的较佳的实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体地实施例的目的，不是旨在于限制本发明。
请参阅图1，一实施方式的纤维复合气凝胶材料的制备方法，包括如下步骤：
步骤S110：使部分硅源水解，制备硅水解液，将硅水解液与聚合物混合，进行静电纺丝，制备纳米纤维膜。
其中，硅源为正硅酸乙酯、正硅酸甲酯或正硅酸丁酯。
使部分硅源水解的步骤包括：将部分硅源与水按摩尔比为1:(2～10)的比例混合，然后调节pH为2～5，搅拌1h～10h。优选地，在调节pH为2～5的步骤中，加入盐酸调节pH。可以理解，在调节pH为2～5的步骤中，还可以加入其他酸性试剂调节pH。
具体地，在将硅水解液与聚合物混合的步骤中，将硅水解液与聚合物的水溶液混合，硅水解液与聚合物的水溶液的质量比为1:(0.6～1.4)，聚合物的水溶液的质量百分浓度为5％～15％。
在其中一个实施例中，聚合物为聚乙烯醇。
聚合物的水溶液的制备步骤包括：将聚合物与水混合搅拌，使聚合物溶解。具体地，混合搅拌的过程中，可以加热以加快溶解速度。
具体地，在静电纺丝的步骤中，纺丝电压为10kV～20kV，接收距离为5cm～25cm，注射流量为0.3mL/h～3mL/h。优选地，在静电纺丝的步骤中，接收距离为8cm～15cm。
通过静电纺丝制备的纳米纤维具有纤维直径小、比表面积大、纤维直径分 布均匀的特点，并且纳米纤维在二氧化硅溶胶中可以较好地分散，形成均匀复杂的三维网络结构，使得复合材料具有较好的力学性能和较好的柔韧性。
无机二氧化硅纳米纤维对纤维复合气凝胶的性能有较大的影响，发明人经过大量实验发现，调节纺丝前驱体溶液的配比、纺丝参数并与后续热处理工艺配合，所制备的无机二氧化硅纳米纤维的性能更好。上述无机纤维在纳米级直径且大小分布均匀时会获得增强柔韧性的特点，利用静电纺丝法制备纳米级直径的柔性纤维，作为气凝胶材料的纤维增强体。二氧化硅纳米纤维具有与二氧化硅气凝胶相容性好，比表面积大、柔韧性好、热传导系数小等特点，将纳米纤维与气凝胶材料复合，柔性的纤维材料不仅可以承受一定程度的弯折，还可以有效阻止气凝胶材料在形变过程中裂纹的扩展，进而增强气凝胶材料的机械性能，同时，纳米级纤维直径更细，热传导效应更低，使材料具有更强的隔热性能。
步骤S120：将纳米纤维膜进行热处理以除去聚合物。
具体地，热处理的温度为300℃～900℃，热处理的时间为0.5h～5h，热处理是在真空条件或惰性气体保护下进行。通过静电纺丝法制备的纳米纤维多含有较多的有机组分，在高温下有机组分会发生氧化与分解从而降低材料的机械与隔热性能。在本实施方式中，将纳米纤维膜进行热处理，在不破坏纤维结构的同时将纤维结构无机化，除去有机组分，使材料具有更好的耐高温性能和隔热性能。
具体地，热处理的温度可以根据聚合物的裂解温度进行调整。
在其中一个实施例中，惰性气体为氮气或氩气。
步骤S130：将剩余的硅源与水和醇类溶剂混合，制备硅溶胶。
具体地，将剩余的硅源与水和醇类试剂混合的步骤包括：将剩余的硅源分散在醇类试剂中，然后加入水，调节pH为2～5，搅拌1h～10h，再调节pH为6～9。
优选地，在调节pH为2～5的步骤中，加入盐酸调节pH。可以理解，在调节pH为2～5的步骤中，还可以加入其他酸性试剂调节pH。
优选地，在调节pH为6～8的步骤中，加入氨水调节pH。可以理解，在调节pH为6～8的步骤中，还可以加入其他碱性试剂调节pH。
优选地，在将剩余的硅源与水和醇类试剂混合的步骤中，剩余的硅源、醇类试剂和水的摩尔比为1:(5～20):(2～10)。发明人发现，通过控制硅源、醇类试剂和水的摩尔比，以及反应的pH值，控制硅溶胶生成凝胶的时间，避免硅溶胶凝胶过快，而影响后续负压条件下与纳米纤维膜混合浸渍的过程。
在其中一个实施例中，醇类溶剂为乙醇、甲醇或丙醇。优选地，醇类溶剂为乙醇。
进一步地，在将剩余的硅源与水和醇类试剂混合的步骤中，还加入了稀土元素的硝酸盐或稀土元素的氧化物。核电厂一回路壳体中存在较强的中子辐照，中子辐照会加速常规气凝胶材料的老化，使材料性能发生退化。因此，在本实施方式中，通过在硅溶胶的制备过程中添加稀土元素硝酸盐或者稀土元素的氧化物的方法，稀土元素对中子辐照有强吸收和屏蔽效应，使材料具有更高的中子耐受性，拓展了气凝胶保温材料在核电保温场景的应用。
在其中一个实施例中，稀土元素的硝酸盐或稀土元素的氧化物与剩余的硅源的质量比为(1～35)：100。
具体地，稀土元素为镧、铈、钕或钆。优选地，稀土元素为钆。在将剩余的硅源与水和醇类试剂混合的步骤中，还加入了硝酸钆或氧化钆。
具体地，稀土元素的硝酸盐以水溶液的形式与剩余的硅源、水和醇类溶剂混合。稀土元素的氧化物通过超声分散的方式与剩余的硅源、水和醇类溶剂混合。
进一步地，步骤S130和步骤S120没有先后顺序，可以先进行步骤S130，再进行步骤S120，也可以先进行步骤S120，再进行步骤S130，或者，步骤S120和步骤S130同时进行。
步骤S140：将热处理后的纳米纤维膜浸渍在硅溶胶中，在负压条件下混合，制备纳米纤维溶胶。
具体地，将硅溶胶置于模具的下层，纳米纤维膜置于模具的上层，使硅溶胶完全浸没纳米纤维膜。可以理解，模具可以为本领域常用的模具，在此不再赘述。
可以理解，在步骤S140中将热处理后的纳米纤维膜浸渍在硅溶胶的过程中， 纳米纤维膜可以为一层或多层，具体可根据实际所要得到的纤维气凝胶材料的厚度和机械性能等情况进行调整。纳米纤维膜为一层或多层均能够起到提高纤维复合气凝胶材料的保温性能、耐高温性和机械性能的作用，且纳米纤维膜的层数对所制备的纤维复合气凝胶材料的热导率和耐高温性能影响较小。
区别于简单的浸渍凝胶法，本实施方式中采用底注式负压浸渍法使纳米纤维膜被硅溶胶充分浸渍，硅溶胶充分分散在纳米纤维骨架及缝隙中，在凝胶与老化过程中，硅凝胶与纤维形成更强的结合力，增强了机械性能，避免了“掉粉”现象。同时，这种分散作用也有效降低了复合材料中的大孔含量，从而进一步提升材料的隔热性能。
步骤S150：将纳米纤维溶胶进行凝胶老化处理，然后干燥，制备纤维复合气凝胶材料。
在将纳米纤维溶胶进行凝胶老化处理的步骤中，将纳米纤维溶胶静置0.5h～3h，制备纳米纤维凝胶，然后将纳米纤维凝胶置于醇类试剂中，在60℃～70℃下进行老化处理1天～3天。
具体地，醇类溶剂为乙醇、甲醇或丙醇。优选地，醇类溶剂为乙醇。
干燥的方式为二氧化碳超临界干燥。二氧化碳超临界干燥的温度为32℃～50℃，压力为7.4MPa～18MPa。采用二氧化碳超临界干燥方法，相较于真空干燥与常压干燥方法，节省了材料表面改性的周期，并且降低了干燥过程中材料内部孔径的坍塌，使材料具有更好的隔热和机械性能。
上述纤维复合气凝胶材料的制备方法至少具有以下优点：
(1)上述纤维复合气凝胶材料的制备方法基于无机纤维在纳米级直径且大小分布均匀时会获得增强柔韧性的特点，利用静电纺丝法制备纳米级直径的柔性纤维，作为气凝胶材料的纤维增强体，并通过热处理除去纳米纤维中的聚合物，使纤维结构无机化，避免高温下聚合物发生氧化与分解而降低材料的机械与隔热性能，从而使材料具有更好的耐高温性能和隔热性能。无机化的二氧化硅纳米纤维具有与二氧化硅气凝胶相容性好、比表面积大、柔韧性好、热传导系数小等特点，将纳米纤维与气凝胶材料复合，柔性的纤维材料不仅可以承受一定程度的弯折，还可以有效阻止气凝胶材料在形变过程中裂纹的扩展，进而 增强气凝胶材料的机械性能，同时，纳米级纤维直径更细，热传导效应更低，使材料具有更强的隔热性能。通过将热处理后的纳米纤维膜浸渍在硅溶胶中，在负压条件下混合，使纳米纤维膜被硅溶胶充分浸渍，硅溶胶充分分散在纳米纤维骨架及缝隙中，在凝胶与老化过程中，硅凝胶与纤维形成更强的结合力，增强了机械性能，避免了“掉粉”现象。同时，这种分散作用也有效降低了复合材料中的大孔含量，从而进一步提升材料的隔热性能。因此，上述纤维复合气凝胶材料的制备方法能够同时提高纤维复合气凝胶材料的保温性能、柔韧性且不掉粉。
(2)在纤维复合气凝胶材料的制备过程中加入稀土元素，使稀土元素分散在纤维复合气凝胶材料中，稀土元素对中子辐照有强吸收和屏蔽效应，使材料具有更高的中子耐受性，能够应用在核电保温材料中。
(3)采用二氧化碳超临界干燥方法，相较于真空干燥与常压干燥方法，节省了材料表面改性的周期，并且降低了干燥过程中材料内部孔径的坍塌，使材料具有更好的隔热和机械性能。
一实施方式的纤维复合气凝胶材料，由上述的纤维复合气凝胶材料的制备方法制备得到。该纤维复合气凝胶材料兼具较好的保温隔热性能和柔韧性，且耐高温性好、不掉粉、耐中子辐射。
一实施方式的纤维复合气凝胶材料在制备核电保温材料中的应用。该纤维复合气凝胶材料兼具较好的保温隔热性能和柔韧性，且耐高温性好、不掉粉、耐中子辐射，能够应用在核电保温材料中。
以下为具体实施例部分：
实施例1
本实施例的纤维复合气凝胶材料的制备过程具体如下：
(1)将正硅酸乙酯与去离子水(摩尔比1:8)均匀混合后用盐酸调节pH为3，搅拌12h后与PVA溶液(质量百分浓度为10％)按1:1的质量比均匀混合，然后将混合液进行静电纺丝，制备纳米纤维膜，纺丝过程中的工艺参数为：电压10kV，接收距离12cm，注射流速2mL/h。
(2)将步骤(1)制备的纳米纤维膜在真空环境下700℃保温1.5h，制备耐高温的纳米纤维膜。
(3)将正硅酸乙酯、乙醇和水(摩尔比1:10:5)均匀混合，通过盐酸将pH调至3，继续缓慢搅拌6h后用氨水调节pH为7，制备硅溶胶。
(4)将多层步骤(2)制备的耐高温的纳米纤维膜置于模具上层，步骤(3)制备的硅溶胶液置于模具下层，在负压条件下将多层纳米纤维膜与硅溶胶混合，制备纳米纤维溶胶。
(5)步骤(4)制备的纳米纤维溶胶在密闭环境中恒温水浴下静置2h，待其凝胶后，将凝胶后的材料放置于盛有乙醇的容器中70℃恒温水浴老化3天。然后将老化后的纳米纤维凝胶利用超临界二氧化碳进行干燥，制备纤维复合气凝胶。干燥的温度为40℃，压力为10MPa。
实施例2
本实施例的纤维复合气凝胶材料的制备过程具体如下：
(1)将正硅酸乙酯与去离子水(摩尔比1:8)均匀混合后用盐酸调节pH为3，搅拌12h后与PVA溶液(质量百分浓度为10％)按1:1的质量比均匀混合，然后将混合液进行静电纺丝，制备纳米纤维膜，纺丝过程中的工艺参数为：电压10kV，接收距离12cm，注射流速2mL/h。
(2)将步骤(1)制备的纳米纤维膜在真空环境下700℃保温1h，制备耐高温的纳米纤维膜。
(3)将10mL正硅酸乙酯(9.3g,0.045mol)、40mL(31.56g,0.685mol)乙醇均匀混合成溶液A，将4.5mL(4.5g,0.25mol)(正硅酸乙酯、乙醇和水的摩尔比为1:15:5.5)含有0.5g硝酸钆的水溶液逐滴加入到溶液A中，通过盐酸将pH调至3，继续缓慢搅拌6h后用氨水调节pH为7，制备硅溶胶。
(4)将多层步骤(2)制备的耐高温的纳米纤维膜置于模具上层，步骤(3)制备的硅溶胶液置于模具下层，在负压条件下将多层纳米纤维膜与硅溶胶混合，制备纳米纤维溶胶。
(5)步骤(4)制备的纳米纤维溶胶在密闭环境中恒温水浴下静置2h，待其凝胶后，将凝胶后的材料放置于盛有乙醇的容器中70℃恒温水浴老化3天。 然后将老化后的纳米纤维凝胶利用超临界二氧化碳进行干燥，制备纤维复合气凝胶。干燥的温度为40℃，压力为10MPa。
实施例3
本实施例的纤维复合气凝胶材料的制备过程与实施例1的纤维复合气凝胶材料的制备过程相似，区别在于：步骤(3)的溶胶配比不同。具体地，步骤(3)为：将正硅酸乙酯、乙醇和水(摩尔比1:5:5)均匀混合，通过盐酸将pH调至3，继续缓慢搅拌6h后用氨水调节pH为7，制备硅溶胶。
实施例4
本实施例的纤维复合气凝胶材料的制备过程与实施例1的纤维复合气凝胶材料的制备过程相似，区别在于：步骤(3)的溶胶配比不同。具体地，步骤(3)为：将正硅酸乙酯、乙醇和水(摩尔比1:20:5)均匀混合，通过盐酸将pH调至3，继续缓慢搅拌6h后用氨水调节pH为7，制备硅溶胶。
实施例5
本实施例的纤维复合气凝胶材料的制备过程与实施例2的纤维复合气凝胶材料的制备过程相似，区别在于：步骤(3)的稀土元素的配比不同。具体地，步骤(3)为：将10mL正硅酸乙酯、40mL乙醇均匀混合成溶液A，将4.5mL含有1g硝酸钆的溶解液逐滴加入到溶液A中，通过盐酸将pH调至3，继续缓慢搅拌6h后用氨水调节pH为7，制备硅溶胶。
实施例6
本实施例的纤维复合气凝胶材料的制备过程与实施例2的纤维复合气凝胶材料的制备过程相似，区别在于：步骤(3)的稀土元素的配比不同。具体地，步骤(3)为：将10mL正硅酸乙酯、40mL乙醇均匀混合成溶液A，将4.5mL含有3g硝酸钆的溶解液逐滴加入到溶液A中，通过盐酸将pH调至3，继续缓慢搅拌6h后用氨水调节pH为7，制备硅溶胶。
对比例1
对比例1的纤维复合气凝胶材料的制备过程与实施例1的纤维复合气凝胶材料的制备过程相似，区别在于：对比例1中没有进行步骤(2)的热处理。
对比例2
对比例2的纤维复合气凝胶材料的制备过程与实施例1的纤维复合气凝胶材料的制备过程相似，区别在于：对比例2中热处理温度为1200℃。
对比例3
对比例3的纤维复合气凝胶材料的制备过程具体如下：
(1)将正硅酸乙酯、乙醇和水(摩尔比1:10:5)均匀混合，通过盐酸将pH调至3，继续缓慢搅拌12h，制备硅溶胶。
(2)将10％质量分数的PVA溶液静电纺丝，制备纳米纤维膜，纺丝过程中的工艺参数为：电压10KV，接收距离12cm，注射流速2mL/h。
(3)将步骤(2)的PVA纤维膜通过步骤(1)的硅溶胶收集和分散，加入一定量的氨水，使硅溶胶形成凝胶。
(4)将步骤(3)的凝胶放置于乙醇中70℃老化3天。然后将老化后的纳米纤维凝胶利用超临界二氧化碳进行干燥，制备纤维复合气凝胶。干燥的温度为40℃，压力为10MPa。
以下为测试部分：
对实施例和对比例所制备的纤维复合气凝胶材料的耐温性、25℃热导率、密度等参数进行测试，得到如下表所示的实验数据。具体测试方法如下：耐高温测试采用在750℃煅烧不少于6h后，材料各项性能仍然满足性能指标要求。采用GB/T 10295-2008测试标准对纤维复合气凝胶材料的常温导热率进行测试。采用GB/T 17911-2006对纤维复合气凝胶材料的密度进行测试。
表1 实施例1～6和对比例1～3的纤维复合气凝胶材料的性能数据
Figure PCTCN2022071020-appb-000001
Figure PCTCN2022071020-appb-000002
从上述表1中可以看出，实施例1～实施例6所制备的纤维复合气凝胶材料的耐温性较好，可以达到750℃，常温热导率在0.022mW/(m.K)～0.025mW/(m.K)，密度为0.08～0.16g/cm 3。而对比例1和对比例3的纤维复合气凝胶材料的耐温性仅为350℃，耐温性较差，在较高温度下纺丝纤维裂解导致材料碎裂。常温热导率为0.028-0.032mW/(m.K)，保温性能较实施例1～6差。对比例2中热处理的温度过高，导致静电纺丝纤维脆化碎裂，不能成型。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (15)

  1. 一种纤维复合气凝胶材料的制备方法，其特征在于，包括如下步骤：
    使部分硅源水解，制备硅水解液，将所述硅水解液与聚合物混合，进行静电纺丝，制备纳米纤维膜；
    将所述纳米纤维膜进行热处理以除去所述聚合物；
    将剩余的所述硅源与水和醇类溶剂混合，制备硅溶胶；
    将热处理后的所述纳米纤维膜浸渍在所述硅溶胶中，在负压条件下混合，制备纳米纤维溶胶；及
    将所述纳米纤维溶胶进行凝胶老化处理，然后干燥，制备纤维复合气凝胶材料。
  2. 根据权利要求1所述的纤维复合气凝胶材料的制备方法，其特征在于，所述热处理的温度为300℃～900℃，所述热处理的时间为0.5h～5h，所述热处理是在真空条件或惰性气体保护下进行。
  3. 根据权利要求1所述的纤维复合气凝胶材料的制备方法，其特征在于，在所述静电纺丝的步骤中，纺丝电压为10kV～20kV，接收距离为5cm～25cm，注射流量为0.3mL/h～3mL/h。
  4. 根据权利要求1所述的纤维复合气凝胶材料的制备方法，其特征在于，所述干燥的方式为二氧化碳超临界干燥。
  5. 根据权利要求4所述的纤维复合气凝胶材料的制备方法，其特征在于，所述二氧化碳超临界干燥的温度为32℃～50℃，压力为7.4MPa～18MPa。
  6. 根据权利要求1所述的纤维复合气凝胶材料的制备方法，其特征在于，在所述将剩余的所述硅源与水和醇类试剂混合的步骤中，还加入了稀土元素的硝酸盐或稀土元素的氧化物。
  7. 根据权利要求6所述的纤维复合气凝胶材料的制备方法，其特征在于，所述稀土元素为镧、铈、钕或钆；及/或，
    所述稀土元素的硝酸盐或所述稀土元素的氧化物与剩余的所述硅源的质量比为(1～35)：100。
  8. 根据权利要求1所述的纤维复合气凝胶材料的制备方法，其特征在于，所 述聚合物为聚乙烯醇；及/或，
    在所述将所述硅水解液与聚合物混合的步骤中，将所述硅水解液与所述聚合物的水溶液混合，所述硅水解液与所述聚合物的水溶液的质量比为1:(0.6～1.4)，所述聚合物的水溶液的质量百分浓度为5％～15％。
  9. 根据权利要求1所述的纤维复合气凝胶材料的制备方法，其特征在于，在所述将所述纳米纤维溶胶进行凝胶老化处理的步骤中，将所述纳米纤维溶胶静置0.5h～3h，制备纳米纤维凝胶，然后将所述纳米纤维凝胶置于醇类试剂中，在60℃～70℃下进行老化处理1天～3天。
  10. 根据权利要求1～9任一项所述的纤维复合气凝胶材料的制备方法，其特征在于，所述使部分硅源水解的步骤包括：将部分所述硅源与水按摩尔比为1:(2～10)的比例混合，然后调节pH为2～5，搅拌1h～10h。
  11. 根据权利要求1～9任一项所述的纤维复合气凝胶材料的制备方法，其特征在于，所述将剩余的所述硅源与水和醇类试剂混合的步骤包括：将剩余的所述硅源分散在所述醇类试剂中，然后加入水，调节pH为2～5，搅拌1h～10h，再调节pH为6～9。
  12. 根据权利要求11所述的纤维复合气凝胶材料的制备方法，其特征在于，在所述将剩余的所述硅源与水和醇类试剂混合的步骤中，剩余的所述硅源、醇类试剂和水的摩尔比为1:(5～20):(2～10)。
  13. 根据权利要求1～9及11任一项所述的纤维复合气凝胶材料的制备方法，其特征在于，所述硅源为正硅酸乙酯、正硅酸甲酯或正硅酸丁酯；及/或，所述醇类溶剂为乙醇、甲醇或丙醇。
  14. 一种纤维复合气凝胶材料，其特征在于，由权利要求1～13任一项所述的纤维复合气凝胶材料的制备方法制备得到。
  15. 权利要求14所述的纤维复合气凝胶材料在制备核电保温材料中的应用。
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