CN115010501A - Elastic ceramic micro-nanofiber aerogel heat insulation material and preparation method and application thereof - Google Patents
Elastic ceramic micro-nanofiber aerogel heat insulation material and preparation method and application thereof Download PDFInfo
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- CN115010501A CN115010501A CN202210645190.7A CN202210645190A CN115010501A CN 115010501 A CN115010501 A CN 115010501A CN 202210645190 A CN202210645190 A CN 202210645190A CN 115010501 A CN115010501 A CN 115010501A
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- solution
- aerogel
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- spinnable
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Abstract
The application discloses an elastic ceramic micro-nanofiber aerogel heat insulation material and a preparation method and application thereof, and relates to the field of heat insulation materials. The preparation method comprises the following steps: preparing a spinnable raw material mixed solution: dissolving a polymer in a solvent, and stirring until the solution is uniform to form a polymer solution; adding the catalyst, the polymer solution and the compound or the compound, the polymer solution and the catalyst into a stirrer according to the charging sequence, stirring and standing to obtain a spinnable raw material mixed solution; preparing a precursor: spinning the spinnable mixed solution into solid micro-nano fibers by using a centrifugal spinning device, and accumulating the micro-nano fibers to obtain an elastic ceramic micro-nano fiber aerogel precursor; sintering a precursor: and (3) sintering the elastic ceramic micro-nanofiber aerogel precursor at a high temperature to obtain the elastic ceramic micro-nanofiber aerogel heat insulation material. The preparation method is simple in preparation process and low in production cost, and can be applied to battery diaphragms or super capacitors.
Description
Technical Field
The application relates to a heat insulation material, in particular to an elastic ceramic micro-nano fiber aerogel heat insulation material and a preparation method and application thereof.
Background
The ceramic aerogel has excellent performances of low density, high porosity, high specific surface area, low thermal conductivity, chemical and thermal stability and the like, is an ideal heat-insulating, fireproof, sound-insulating and diaphragm material, and has huge application potential in the fields of energy, environmental protection, buildings, ships, fire fighting and the like.
The existing ceramic aerogel mainly adopts organic matters such as organic silicon or organic salt and the like as raw materials and is prepared under the supercritical drying or normal pressure drying condition, the technical condition is harsh, and the manufacturing cost is high. The microstructure of the obtained ceramic aerogel is zero-dimensional granular or two-dimensional flaky, the ceramic aerogel is poor in mechanical property and easy to break, the construction operation difficulty is very high, and the engineering application is difficult to realize. In order to increase the mechanical properties of ceramic aerogel, realize the engineering application, prior art all smashes the aerogel that obtains preparing, makes into powder, then mixes with the short-staple that uses in traditional thermal insulation material, and the short-staple includes: glass fiber, rock wool fiber, aramid fiber and the like, and then are bonded by using a bonding agent to finally prepare the aerogel composite material.
The prior aerogel composite material has the following defects: 1. the binder solution enters the gaps of part of the aerogel, so that the porosity of the aerogel is reduced, the heat conductivity coefficient of the aerogel is increased, the liquid absorption rate of the aerogel is reduced, and the heat insulation effect and the liquid absorption capacity are influenced; 2. the powder and slag fall seriously, which is harmful to the respiratory tract of constructors and easily causes environmental pollution; 3. because the binder is added, the high temperature limit generally cannot exceed 650 ℃, and the application range of the aerogel is greatly limited; 4. because of containing organic matters such as adhesive and the like, the anti-aging performance is poor, and the service life of the aerogel composite material is generally not more than 5 years; 5. it does not have good mechanical properties such as compressibility, resilience, and bendability. 6. The ceramic aerogel is prepared by adopting organic matters as raw materials, and the production of the ceramic aerogel is limited and the production cost is high due to the high market price and unstable market conditions of the organic matters. 7. Only organic matters are used as raw materials to prepare the ceramic aerogel, so that the selection of the raw materials has certain limitation and is not beneficial to the selection of the diversification of the raw materials.
Disclosure of Invention
It is an object of the present application to overcome the above problems or to at least partially solve or mitigate the above problems.
According to an aspect of this application, it is simple to provide a preparation procedure, low in production cost, and the little nanofiber aerogel that the drying formed is handled through the sintering again under the normal atmospheric temperature condition, obtains elasticity ceramic little nanofiber aerogel thermal insulation material.
According to another aspect of the application, a preparation method of the elastic ceramic micro-nanofiber aerogel heat insulation material is provided, and comprises the following steps:
(1) preparing a spinnable raw material mixed solution:
firstly, according to an empirical formula obtained by mathematical modeling, aiming at the physical and chemical properties of raw materials, introducing the raw materials into a mathematical model for analog simulation calculation, designing the mass proportion of a spinnable raw material mixed solution, dissolving a polymer in a solvent according to the result in the model, and stirring at a first stirring speed for a first stirring time until the solution is uniform to form a polymer solution; adding the catalyst, the polymer solution and the compound or the compound, the polymer solution and the catalyst into a stirrer according to the charging sequence, stirring for a second stirring time at a second stirring speed, and standing to obtain a spinnable raw material mixed solution;
the compound is selected from at least one of silicon source, inorganic salt and organic salt;
(2) preparing a precursor: according to the setting of control parameters in a mathematical model, spinning spinnable mixed solution into solid micro-nano fibers by using a centrifugal spinning device and controlling corresponding parameters, and accumulating the micro-nano fibers to obtain an elastic ceramic micro-nano fiber aerogel precursor;
(3) sintering a precursor: and (3) sintering the elastic ceramic micro-nanofiber aerogel precursor at a high temperature to obtain the elastic ceramic micro-nanofiber aerogel heat insulation material.
Optionally, the polymer is selected from at least one of polyvinylpyrrolidone PVP, polyethylene oxide PEO, polyethylene glycol PEG, polyacrylamide PAM, and polyvinyl alcohol PVA; the mass ratio of the polymer to the solvent in the polymer solution is 1: 99-20: 80.
Optionally, the solvent is selected from at least one of deionized water, absolute ethanol, acetonitrile, acetone, and dimethylformamide.
Optionally, the compound is selected from at least one of tetraethyl silicate, ethyl silicate 32, ethyl silicate 40, sodium silicate, barium acetate, aluminum chloride hexahydrate, tetrabutyl titanate, zirconium acetate, zirconium citrate, zirconium oxychloride octahydrate, magnesium acetate tetrahydrate, and magnesium citrate.
Optionally, the catalyst is selected from at least one of phosphoric acid, hydrochloric acid, citric acid, acetic acid, urea, and cetyltrimethylammonium bromide.
Optionally, the mass ratio of the polymer solution, the compound, and the catalyst is 1:0.25-0.8: 0.0025-0.008.
Optionally, the first stirring speed is 500-; the second stirring speed is 700-1000rpm, the second stirring time is 1-5 hours, and the standing time is 0-3 hours.
Optionally, the centrifugal spinning device adopts a motor with a rotating speed of 3000-.
Optionally, the sintering process is as follows: raising the temperature from room temperature to 1700 ℃ at the temperature raising rate of 2-5 ℃/min, keeping sintering for 1-2 hours in the environment of 1700 ℃ at 500 ℃, and then lowering the temperature from 1700 ℃ at the temperature lowering rate of 5-10 ℃ to room temperature.
The elastic ceramic micro-nanofiber aerogel heat-insulating material provided by the invention is prepared according to the preparation method.
The invention also provides application of the elastic ceramic micro-nanofiber aerogel heat-insulating material as a battery diaphragm and a super capacitor.
The invention has the following advantages:
1. the invention adopts normal temperature and normal pressure drying technology to replace the prior supercritical drying and normal pressure drying technology, reduces the manufacturing cost of the aerogel and improves the market competitiveness of the product.
2. The invention belongs to pure inorganic aerogel. Organic matters such as a binder, aramid short fibers and the like used in the existing aerogel composite material are removed to prepare the pure inorganic aerogel, so that the heat-resistant temperature of the aerogel heat-insulating material exceeds 650 ℃, the application requirement of a higher-temperature environment is met, and the thermal stability and the chemical stability of the aerogel are improved. The invention removes the binder, avoids the increase of the thermal conductivity coefficient of the aerogel caused by filling the gaps of the aerogel with the binder, and achieves the effect of more energy-saving and heat-preservation. The invention removes the fibers such as glass fiber, aramid fiber, rock wool and the like, and achieves the purpose of improving the porosity, the liquid absorption rate and the wettability of the aerogel thermal insulation material.
3. The invention relates to micro-nano fibrous aerogel. Has the following effects: a. the preparation microstructure is the aerogel of one-dimensional micro-nano fiber structure, it is the aerogel of zero-dimensional granule or two-dimentional slice to replace current microstructure, promote the mechanical properties such as compression performance, resilience performance, folding angle, tensile strength of aerogel by a wide margin, can solve the aerogel simultaneously and fall the powder, fall the problem that the sediment or even mechanical structure collapses, improve the life of aerogel greatly, increase aerogel material's life cycle, promote aerogel material's economic nature, the feature of environmental protection, energy-conservation nature. b. In the field of heat insulation application, traditional short fiber heat insulation materials (such as rock wool fibers, glass fibers, aramid fibers and the like) used in the existing aerogel composite material are removed, a pure aerogel heat insulation material product is prepared, the porosity and the specific surface area of the heat insulation material are improved to the maximum extent, and the excellent heat insulation, sound insulation and noise reduction performances of the aerogel are exerted to the maximum extent. c. In the application field of the battery diaphragm, the thermal stability, the chemical stability, the electrochemical inertia, the fire resistance, the wettability, the liquid absorption rate, the porosity and other properties of the diaphragm are improved, the safety stability of the battery can be guaranteed while the energy density of the battery is improved, the internal resistance is reduced, and the purpose of light weight of the battery is achieved.
4. According to the invention, inorganic salt is used as a raw material to replace organic matters completely or partially, so that the cost of the raw material is reduced, the risk resistance capability of market quotations of the raw material is improved, and the diversified selection of the raw material is increased.
5. According to the elastic ceramic micro-nano fiber aerogel precursor prepared in the first step and the second step, the existing mathematical model is optimized on the basis of basic theoretical calculation of fluid mechanics and a large amount of experimental verification, and the mathematical model specially aiming at the mechanism of preparing the elastic ceramic micro-nano fiber aerogel precursor by a centrifugal spinning method is established, so that the numerical values corresponding to all parameters can be designed according to the microstructure (such as fiber diameter, aperture clearance and the like) required in actual production application, and the microstructure corresponding to the required product is finally directly prepared. Therefore, the trial production cost for producing various products with different microstructures can be reduced, the equipment manufacturing cost is reduced, and the production line construction efficiency is improved. The invention extracts a theoretical calculation model from experimental exploration, and is beneficial to the standardized production of products.
Drawings
FIG. 1 is a flow chart of a preparation method of the elastic ceramic micro-nanofiber aerogel heat insulation material provided by the invention;
FIG. 2 is a schematic diagram of a preparation of a one-dimensional micro-nanofiber according to the present invention;
FIG. 3 is a schematic diagram of three stages of formation of a one-dimensional micro-nanofiber material provided by the present invention;
FIG. 4 is a diagram showing the pressure distribution of the solution in the spinning needle pipe during the simulation analysis of the spinning process;
FIG. 5 is a cross-sectional solution pressure distribution (a) and solution velocity distribution (b) at the outlet of a spinning channel in a simulation analysis spinning process;
FIG. 6 is a schematic diagram of an elastic micro-nanofiber aerogel formed by stacking micro-nanofibers according to the present invention;
FIG. 7 is a scanning electron microscope image of the silicon-based elastic ceramic micro-nanofiber aerogel provided by the invention;
fig. 8 is a real object diagram of the silicon-based elastic ceramic micro-nanofiber aerogel provided by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Referring to fig. 1, the invention provides a preparation method of an elastic ceramic micro-nanofiber aerogel heat insulation material, which comprises the following steps:
(1) preparing a spinnable raw material mixed solution:
firstly, according to an empirical formula obtained by mathematical modeling, aiming at the physical and chemical properties of raw materials, introducing the raw materials into a mathematical model for analog simulation calculation, designing the mass proportion of a spinnable raw material mixed solution, dissolving a polymer in a solvent according to the result in the model, and stirring the solution at a first stirring speed of 500 plus materials and 800rpm for 2 to 8 hours until the solution is uniform to form a polymer solution; adding the catalyst, the polymer solution and the compound or the compound, the polymer solution and the catalyst into a stirrer according to the adding sequence of the catalyst, the polymer solution and the compound or the adding sequence of the compound, the polymer solution and the catalyst, stirring for 1-2.5 hours at a second stirring speed of 700-1000rpm, and standing for 0-3 hours to obtain a spinnable raw material mixed solution;
preferably, the mass ratio of the polymer solution, the compound and the catalyst is 1:0.25-0.8: 0.0025-0.008.
Wherein the polymer is selected from at least one of polyvinylpyrrolidone (PVP), polyethylene oxide (PEO), polyethylene glycol (PEG), Polyacrylamide (PAM) and polyvinyl alcohol (PVA); the mass ratio of the polymer to the solvent in the polymer solution is 1: 99-20: 80.
The solvent is at least one selected from deionized water, absolute ethyl alcohol, acetonitrile, acetone and dimethyl amide.
The compound is at least one of tetraethyl silicate, ethyl silicate 32, ethyl silicate 40, sodium silicate, barium acetate, aluminum chloride hexahydrate, tetrabutyl titanate, zirconium acetate, zirconium citrate, zirconium oxychloride octahydrate, magnesium acetate tetrahydrate and magnesium citrate.
The catalyst is at least one selected from phosphoric acid, hydrochloric acid, citric acid, acetic acid, urea and cetyl trimethyl ammonium bromide.
The invention uses ethyl silicate 40 to have the following advantages compared with tetraethyl silicate: the content of silicon dioxide in the ethyl silicate 40 is 40%, the content of silicon dioxide in the tetraethyl silicate is only 28%, and the chemical component of the material to be finally obtained is silicon dioxide, so that when two types of organic silicon with the same mass are used, more silicon dioxide is finally generated by the ethyl silicate 40, and the production efficiency is higher. In addition, tetraethyl silicate is a monomer, ethyl silicate 40 is a polymer, and the molecular structure of ethyl silicate 40 is more stable.
The solvent, the polymer, the compound and the catalyst are prepared into a spinnable raw material mixed solution of the non-Newtonian fluid according to a certain formula proportion. In the process of preparing the mixed solution, strict control of the sequence of putting raw materials, the stirring speed of a stirrer and the stirring time of the solution is required to be followed, so that the compound can be fully and uniformly hydrolyzed to obtain the ideal non-Newtonian fluid mixed solution with spinnability. By adopting the feeding sequence of the invention, the problem that partial small amount of compounds are fully contacted with the catalyst before the solution is not uniformly mixed and stirred, so that the hydrolysis degree of the partial compounds is greater than that of other partial compounds, and the local rheological property of the spinnable non-Newtonian fluid mixed solution is abnormal, thereby influencing the spinnability of the solution is avoided.
(2) Preparing a precursor: according to the setting of control parameters in a mathematical model, spinning spinnable mixed solution into solid micro-nano fibers by using a centrifugal spinning device and controlling corresponding parameters, and accumulating the micro-nano fibers to obtain an elastic ceramic micro-nano fiber aerogel precursor;
in this step, as shown in fig. 1, the centrifugal spinning device includes a feeding device, a spinning device, and a collecting device, and the feeding device, the spinning device, and the collecting device are connected to the control sensing system, and the operation of the control sensing system is controlled. As shown in fig. 2, the prepared spinnable solution is injected into a liquid storage tank 2 of a continuous feeding device of a centrifugal spinning device, the solution is conveyed into a spinning device according to a set feeding speed, the high-viscosity spinnable solution in the liquid storage tank 2 is ejected from a needle at a high speed by using centrifugal force generated by the spinning device to form a fine elastic mucus thread, the elastic mucus thread is rapidly stretched under the common acting force of the centrifugal force, elastic tension, air resistance and surface tension, and the solution is solidified into micro-nano fibers 1 and falls on a collecting device along with the volatilization of the solvent in the solution. As shown in fig. 3, in principle, the process of forming micro-nanofibers from a spinnable non-newtonian fluid mixed solution can be divided into three stages: stage (a), initial stage of solution filament formation: the motor rotating at high speed drives the solution storage tank to generate huge centrifugal force to spray the solution out of a fine spinning nozzle of the solution storage tank; stage (b), solution yarn drawing stage: the sprayed solution can be rapidly stretched under the actions of centrifugal force, inertia force, capillary force, air resistance, elastic tension of the solution and the like, and the solution is stretched into a filament with the length-diameter ratio exceeding 100; stage (c), solvent evaporation stage: the specific surface area of the solution filaments which are rapidly elongated is increased, the solvent can be rapidly volatilized under the action of rapidly flowing air, and finally, the micro-nano fibers are formed after drying and curing and are accumulated on a collecting device. Elastic micro-nanofiber aerogel with a low-density and porous 3D structure, namely an elastic ceramic micro-nanofiber aerogel precursor, is formed after the micro-nanofibers are accumulated in a large quantity. As shown in fig. 6, a schematic diagram of elastic micro-nanofiber aerogel is formed after stacking micro-nanofibers, which is a schematic diagram of micro-nanofiber aerogel in a compressed state and a rebounded state respectively. The microstructure of the elastic ceramic micro-nanofiber aerogel is photographed by a scanning electron microscope and is shown in fig. 7. The obtained silicon-based elastic ceramic micro-nanofiber aerogel is shown in fig. 8.
The invention also combines the German industry 4.0 concept of digital twins, and the elastic ceramic micro-nano fiber aerogel heat-insulating material is mainly equipped with an experience formula (see the formulas 1-3) for calculating the fiber diameter, and the experience formula is established by establishing a virtual model, carrying out structural modeling simulation (see the formulas 2 and 3) on a new process production line to be built, and carrying out simulation calculation analysis (see the formulas 4 and 5) on the new process production line, so that the equipment manufacturing cost is reduced, and the production line building efficiency is improved. Specifically, main equipment of a process production line is subjected to 1:1 virtual manufacturing according to the real size, and then all parts are subjected to size positioning and equipment assembly by simulating a real environment. And carrying out simulation analysis and detection on the assembled virtual production line, finding out design defects, and carrying out corresponding optimization. And after the optimization is finished, processing and manufacturing the parts required by the virtualized production line equipment according to the proportion of 1:1, and assembling and debugging to obtain the real process production line of the elastic ceramic micro-nanofiber aerogel heat insulation material.
Wherein D is f Is the fiber diameter, R 0 Is the inner bore diameter of the spinning nozzle, P e Is a number of elastic processability, L n Is the length of the needle tube, and omega is the rotation speed.
Wherein L is the rotating radius of the spinneret, V n Is the spinneret line speed.
Wherein k is the fiber diameter coefficient, h m Lambda is the solution filament draw down time for the mass transfer coefficient.
In FIG. 5, the Path Points on the abscissa are waypoints; absolute pressure is absolute pressure and Velocity is Velocity.
The parameters needing to be controlled in the process of spinning the micro-nano fiber comprise: motor rotation speed, spinneret aperture, spinneret rotation radius, collection distance, and the like. The motor rotating speed range is as follows: 3000-5000 rpm, the aperture of a spinning nozzle: 0.08-0.3mm, spinning nozzle rotation radius: 3-15cm, collection distance: 20-50 cm. The ambient temperature of the spinning is 0-35 deg.C, the ambient relative humidity is 20-65% RH, and the preferred ambient relative humidity is 35-45% RH.
The motor with the medium and low rotating speed is adopted in the application, the dependence on high-speed motor equipment can be reduced, and the universality of the motor equipment is improved. Ambient temperature and humidity have a severe impact on the solvent evaporation rate during the second and third stages of the spinning process. If the humidity is too high, the solvent can not be volatilized rapidly, the sprayed solution can not form fibers, but the solution state is kept to fall into a collecting device, and the spinning effect is influenced. The spinning temperature and the spinning humidity can ensure good spinning effect.
(3) Sintering a precursor: and (3) sintering the elastic ceramic micro-nanofiber aerogel precursor at a high temperature to obtain the elastic ceramic micro-nanofiber aerogel heat insulation material.
In this step, the elastic micro-nanofiber aerogel obtained by spinning is filled in a mold or wound and stacked according to design requirements, then the elastic micro-nanofiber aerogel is placed in a boiler for high-temperature sintering, the elastic micro-nanofiber aerogel is led into the mold and sintered at high temperature to obtain the 3D elastic ceramic micro-nanofiber aerogel with the opposite three-dimensional structure, and the elastic ceramic micro-nanofiber aerogel felt is formed after the elastic micro-nanofiber aerogel is wound and stacked and sintered at high temperature. The control of the boiler temperature gradient during the sintering process was set according to the following temperature gradient. The initial temperature in the sintering process is room temperature, the temperature is raised from the room temperature to 500-1700 ℃ at the temperature rise rate of 2-5 ℃/min, the sintering is kept for 1-2 hours in the environment of 500-1700 ℃, and then the temperature is lowered from 500-1700 ℃ to the room temperature at the temperature decrease rate of 5-10 ℃.
(4) Laser cutting and shaping:
carrying out the fastening type with 3D elasticity ceramic micro-nano fiber aerogel, obtain 3D elasticity ceramic micro-nano fiber aerogel finished product, carry out laser cutting packing with elasticity ceramic micro-nano fiber aerogel felt, obtain elasticity ceramic micro-nano fiber aerogel finished product.
Based on the technical characteristics of centrifugal spinning and the physicochemical properties of the raw materials of the elastic ceramic micro-nano fiber aerogel, a spinnable raw material mixed solution is prepared, the solution is prepared into an elastic ceramic micro-nano fiber aerogel precursor by using centrifugal spinning equipment, and then the precursor is sintered at high temperature to obtain the elastic ceramic micro-nano fiber aerogel heat insulation material. The invention realizes the whole process from sol to aerogel at normal temperature and pressure. Has the advantages of simple preparation process and saving a large amount of equipment cost and labor cost. The elastic ceramic micro-nanofiber aerogel disclosed by the invention is pure aerogel without other short fibers and binders. On the basis of retaining the excellent performance of the ceramic aerogel, the mechanical performance is greatly enhanced, and the ceramic aerogel has the characteristics of compressibility, resilience, foldability and the like.
The elastic ceramic micro-nanofiber aerogel heat-insulating material can be applied to the field of batteries and used as a battery diaphragm, compared with the existing battery diaphragm, the thermal stability, the chemical stability, the electrochemical inertia, the fire resistance, the wettability, the liquid absorption rate, the porosity and other properties of the diaphragm are improved, and by using the diaphragm material, the safety and the stability of the battery can be guaranteed while the energy density of the battery is improved, the internal resistance is reduced, and the light weight of the battery is realized.
Meanwhile, the elastic ceramic micro-nanofiber aerogel heat insulation material has the characteristics of low density, low loss, low temperature rise, long service life, excellent insulating property, excellent specific property and the like, and has a huge prospect in the application of capacitor diaphragms.
The present application is further illustrated by the following specific examples:
example 1
Firstly, preparing a spinnable raw material mixed solution, mixing PVP and deionized water according to the mass ratio of 15:85, and stirring at 600rpm for 5 hours until the solution is uniform to obtain a polymer solution. Mixing phosphoric acid, urea and hexadecyl trimethyl ammonium bromide according to the mass ratio of 8:1:1 to obtain the catalyst. Putting the polymer solution, the compound and the catalyst in a mass ratio of 1:0.5:0.005 into a stirrer according to the charging sequence of the catalyst, the polymer solution, the tetraethyl silicate and the sodium silicate, stirring at the speed of 1000rpm for 1.5 hours, and standing for 0.2 hours to obtain a spinnable raw material mixed solution; wherein, the tetraethyl silicate and the sodium silicate can be in any proportion, and the sum of the tetraethyl silicate and the sodium silicate after mixing meets the proportion of the tetraethyl silicate and the polymer solution.
Injecting a spinnable raw material mixed solution into a liquid storage device, regulating the rotating speed of a motor to 4000 revolutions per minute, adopting a spinning nozzle with the aperture of 0.2mm and the rotating radius of the spinning nozzle of 10cm, spraying the solution from the spinning nozzle by utilizing centrifugal force to form micro-nano fibers, collecting the micro-nano fibers on a collecting device at a position 35cm away from the spinning nozzle, and winding and stacking the micro-nano fibers to form a layered micro-nano fiber aerogel felt. The spinning ambient temperature was 25 ℃ and the ambient humidity was 40% RH.
Wherein, the PVP and deionized water are used as the fiber diameter coefficient k of the polymer solution is 0.5; the solution yarn draw attenuation time lambda is 5.3 x 10 calculated by shooting with a high-speed video camera -2 s, combining thermogravimetric analysis data calculation and high-speed camera shooting verification, and obtaining a mass conversion coefficient h m ＝4.2ⅹ10 -3 Hole diameter R of spinneret 0 ＝1.6ⅹ10 -4 m, length L of needle tube n ＝1.3ⅹ10 - 2 m, spinning nozzle rotary radius L0.15 m, spinning nozzle linear velocity V n 52.3 m/s. According to the mathematical model formula 3,
the resulting fiber diameter D f ＝0.575ⅹ10 -6 m。
And (3) putting the collected micro-nanofiber aerogel felt into a muffle furnace for sintering, heating the micro-nanofiber aerogel felt from room temperature to 1000 ℃ at the heating rate of 3 ℃/min, keeping the micro-nanofiber aerogel felt at the temperature of 1000 ℃ for 1.5 hours, and then cooling the micro-nanofiber aerogel felt to the room temperature at the cooling rate of 8 ℃/min. The material obtained after sintering is the elastic ceramic micro-nanofiber aerogel felt. And finally, carrying out laser cutting and cutting on the aerogel felt to obtain the elastic ceramic micro-nanofiber aerogel felt with the required size. Aerogel obtained in this exampleThe heat conductivity of the felt at room temperature is less than or equal to 0.021 (W/m.K), and the density: 8mg/cm 3 Compression deformation is more than or equal to 85 percent, bending angle is more than or equal to 175 degrees, liquid absorption rate is more than or equal to 1003 percent, porosity is more than or equal to 99 percent, thermal shrinkage rate is less than or equal to 0.1 percent (keeping for 1 hour at 105 ℃), and temperature application range is as follows: and the temperature is-196-1000 ℃, and the powder and the slag are not dropped.
Example 2:
firstly, preparing a spinnable raw material mixed solution, mixing PEO and deionized water according to the mass ratio of 1:99, and stirring at the speed of 500rpm for 8 hours until the solution is uniform to obtain a polymer solution. Putting the polymer solution, the compound and the catalyst into a stirrer according to the charging sequence of tetraethyl silicate, magnesium citrate, the polymer solution and hydrochloric acid according to the mass ratio of 1:0.8:0.0025, stirring at the speed of 800rpm for 2.5 hours, and standing for 3 hours to obtain a spinnable raw material mixed solution; wherein, the tetraethyl silicate and the magnesium citrate can be in any proportion, and the sum of the tetraethyl silicate and the magnesium citrate after mixing meets the proportion of the tetraethyl silicate and the magnesium citrate to the polymer solution.
Injecting a spinnable raw material mixed solution into a liquid storage device, regulating the rotating speed of a motor to 5000 revolutions per minute, adopting a spinning nozzle with the aperture of 0.3mm and the rotating radius of the spinning nozzle of 3cm, spraying the solution from the spinning nozzle by utilizing centrifugal force to form micro-nano fibers, collecting the micro-nano fibers on a collecting device at a position 50cm away from the spinning nozzle, and winding and stacking the micro-nano fibers to form a layered micro-nano fiber aerogel felt. The spinning ambient temperature was 15 ℃ and the ambient humidity was 65% RH. And (3) putting the collected micro-nanofiber aerogel felt into a muffle furnace for sintering, heating from room temperature to 500 ℃ at the heating rate of 2 ℃/min, keeping at 500 ℃ for 2 hours, and then cooling to room temperature at the cooling rate of 10 ℃/min. The material obtained after sintering is the elastic ceramic micro-nanofiber aerogel felt. And finally, carrying out laser cutting and cutting on the aerogel felt to obtain the elastic ceramic micro-nanofiber aerogel felt with the required size. The aerogel blanket obtained in this example had a room temperature thermal conductivity of 0.028 (W/m.K) or less, a density: 90mg/cm 3 Compression deformation is more than or equal to 80 percent, bending angle is more than or equal to 170 degrees, liquid absorption rate is more than or equal to 853 percent, porosity is more than or equal to 95 percent, heat shrinkage rate is less than or equal to 0.1 percent (keeping for 1 hour under 105 ℃) environment), and the material is used at temperatureThe range is as follows: the temperature is 196 ℃ below zero to 1400 ℃, and powder and slag cannot fall off.
Example 3:
firstly, preparing a spinnable raw material mixed solution, selecting a mixture of PVP and PVA according to a mass ratio of 1:1 as a polymer, mixing the polymer and a solvent according to a mass ratio of 12:88, wherein the solvent is a mixture of deionized water and acetone in any ratio, and stirring at 800rpm for 3 hours until the solution is uniform to obtain a polymer solution. Putting the polymer solution, the compound and the catalyst in a mass ratio of 1:0.25:0.008 in a stirrer according to the charging sequence of acetic acid, the polymer solution, tetrabutyl titanate and barium acetate, stirring at 700rpm for 1 hour, and standing for 0.5 hour to obtain a spinnable raw material mixed solution; wherein, tetrabutyl titanate and barium acetate can be in any proportion, and the sum of the tetrabutyl titanate and the barium acetate satisfies the proportion of the polymer solution.
Injecting a spinnable raw material mixed solution into a liquid storage device, regulating the rotating speed of a motor to 3000 r/min, adopting a spinning nozzle with the aperture of 0.08mm and the rotating radius of the spinning nozzle of 15cm, spraying the solution from the spinning nozzle by utilizing centrifugal force to form micro-nano fibers, collecting the micro-nano fibers on a collecting device at a position 20 away from the spinning nozzle, and winding and stacking the micro-nano fibers to form a layered micro-nano fiber aerogel felt. The spinning ambient temperature was 20 ℃ and the ambient humidity was 60% RH. And (3) putting the collected micro-nanofiber aerogel felt into a muffle furnace for sintering, heating the micro-nanofiber aerogel felt from room temperature to 700 ℃ at the heating rate of 5 ℃/min, keeping the micro-nanofiber aerogel felt at the temperature of 700 ℃ for 2 hours, and then cooling the micro-nanofiber aerogel felt to the room temperature at the cooling rate of 5 ℃/min. The material obtained after sintering is the elastic ceramic micro-nanofiber aerogel felt. And finally, carrying out laser cutting and cutting on the aerogel felt to obtain the elastic ceramic micro-nanofiber aerogel felt with the required size. The aerogel blanket obtained in this example had a room temperature thermal conductivity of 0.027 (W/m.K) or less, a density: 80mg/cm 3 Compression deformation is more than or equal to 80%, bending angle is more than or equal to 175 degrees, liquid absorption rate is more than or equal to 935%, porosity is more than or equal to 95%, thermal shrinkage rate is less than or equal to 0.1% (keeping for 1 hour at 105 ℃), temperature application range: and the temperature is 196 ℃ below zero to 800 ℃, and the powder and the slag are not dropped.
Example 4:
firstly, preparing a spinnable raw material mixed solution, mixing PVP and absolute ethyl alcohol according to the mass ratio of 20:80, and stirring at the speed of 700rpm for 6 hours until the solution is uniform to obtain a polymer solution. Putting the polymer solution, the compound and the catalyst in a mass ratio of 1:0.3:0.007 in a stirrer according to the charging sequence of citric acid, the polymer solution, aluminum chloride hexahydrate and zirconium citrate, stirring at 900rpm for 2 hours, and standing for 2 hours to obtain a spinnable raw material mixed solution; wherein, the aluminum chloride hexahydrate and the zirconium citrate can be in any proportion, and the combination of the aluminum chloride hexahydrate and the zirconium citrate meets the proportion of the polymer solution.
The spinnable raw material mixed solution is injected into a liquid storage device, the rotating speed of a motor is adjusted to 5000 r/min, the aperture of a spinning nozzle is 0.1mm, the rotating radius of the spinning nozzle is 12cm, the solution is sprayed out of the spinning nozzle by using centrifugal force to form micro-nano fibers, the micro-nano fibers are collected on a collecting device which is 30cm away from the spinning nozzle, and the micro-nano fibers are wound and stacked mutually to form a layered micro-nano fiber aerogel felt. The spinning ambient temperature was 30 ℃ and the ambient humidity was 25% RH. And (3) putting the collected micro-nanofiber aerogel felt into a muffle furnace for sintering, heating from room temperature to 800 ℃ at the heating rate of 3 ℃/min, keeping at the temperature of 800 ℃ for 2 hours, and then cooling to room temperature at the cooling rate of 8 ℃/min. The material obtained after sintering is the elastic ceramic micro-nanofiber aerogel felt. And finally, carrying out laser cutting and cutting on the aerogel felt to obtain the elastic ceramic micro-nanofiber aerogel felt with the required size. The aerogel blanket obtained in this example had a room temperature thermal conductivity of 0.025 (W/m.K) or less, a density: 50mg/cm 3 Compression deformation is more than or equal to 82 percent, bending angle is more than or equal to 170 degrees, liquid absorption rate is more than or equal to 901 percent, porosity is more than or equal to 96 percent, thermal shrinkage rate is less than or equal to 0.1 percent (keeping for 1 hour at 105 ℃), and temperature application range is as follows: and the temperature is-196-1200 ℃, and the powder and the slag are not dropped.
Example 5:
firstly, preparing a spinnable raw material mixed solution, mixing PVP, deionized water and absolute ethyl alcohol according to the mass ratio of 16:56:28, and stirring for 3 hours at the stirring speed of 500rpm until the solution is uniform to obtain a polymer solution. Putting the polymer solution, the compound and the catalyst in a mass ratio of 1:0.6:0.003 into a stirrer according to the charging sequence of aluminum chloride hexahydrate, the polymer solution and hydrochloric acid, stirring for 2 hours at a stirring speed of 800rpm, and standing for 1 hour to obtain a spinnable raw material mixed solution;
and (3) injecting the spinnable raw material mixed solution into a liquid storage device, wherein the spinning environment temperature is 10 ℃, and the environment humidity is 35% RH. And (3) regulating the rotating speed of a motor to 5000 revolutions per minute, adopting a spinning nozzle with the aperture of 0.2mm and the rotating radius of 4cm, ejecting the solution from the spinning nozzle by utilizing centrifugal force to form micro-nano fibers, collecting the micro-nano fibers on a collecting device at a position 45cm away from the spinning nozzle, introducing the micro-nano fibers into a mold, putting the mold into a muffle furnace for sintering, heating the temperature to 800 ℃ from room temperature at the heating rate of 4 ℃/minute, keeping the temperature for 2 hours at the temperature of 800 ℃, and then cooling the temperature to room temperature at the cooling rate of 6 ℃/minute. The material obtained after sintering is 3D elastic ceramic micro-nanofiber aerogel. And finally, tightly fixing the composite material to obtain a 3D elastic ceramic micro-nanofiber aerogel finished product. The aerogel blanket obtained in this example had a room temperature thermal conductivity of 0.023(W/m · K) or less, a density: 20mg/cm 3 Compression deformation is more than or equal to 85%, bending angle is more than or equal to 175 degrees, liquid absorption rate is more than or equal to 988%, porosity is more than or equal to 98%, thermal shrinkage rate is less than or equal to 0.1% (keeping for 1 hour at 105 ℃), temperature application range: and the temperature is 196 ℃ below zero to 1300 ℃, and the powder and the slag are not dropped.
Example 6:
firstly, preparing a spinnable raw material solution, namely mixing PVP, PEG, deionized water and absolute ethyl alcohol according to a mass ratio of 12: 5: 51: 32, and stirring at the stirring speed of 800rpm for 4 hours until the solution is uniform to obtain a polymer solution. And mixing the polymer solution, the compound and the catalyst in a mass ratio of 1: 0.375: 0.00375, putting the polymer solution, the ethyl silicate 40 and the phosphoric acid into a stirrer in the order of adding the polymer solution, the ethyl silicate 40 and the phosphoric acid, stirring for 2 hours at the speed of 700rpm, and standing for 1 hour to obtain a spinnable raw material mixed solution;
and (3) injecting the spinnable raw material mixed solution into a liquid storage device, wherein the spinning environment temperature is 15 ℃, and the environment humidity is 45% RH. Adjusting the rotating speed of a motor to 5000 revolutions per minute, adopting a spinning nozzle with the aperture of 0.2mm and the rotating radius of 9cm, spraying the solution from the spinning nozzle by utilizing centrifugal force to form micro-nano fibers, collecting the micro-nano fibers on a collecting device at a position 30cm away from the spinning nozzle, and forming a layered micro-nano fiber net after the micro-nano fibers are mutually staggered and stacked. And (3) putting the collected micro-nano fiber net into a muffle furnace for sintering, raising the temperature to 1000 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 1 hour at the temperature of 1000 ℃, and then reducing the temperature to room temperature at a cooling rate of 6 ℃/min. The material obtained after sintering is a 3D elastic ceramic micro-nanofiber aerogel felt. And finally, cutting and tailoring the aerogel felt to obtain the 3D elastic ceramic micro-nanofiber aerogel felt with the required size. The aerogel blanket obtained in this example had a room temperature thermal conductivity of 0.021 (W/m. K) or less, a density: 20mg/cm3, compression deformation is more than or equal to 85%, bending angle is more than or equal to 175 degrees, liquid absorption rate is more than or equal to 967%, porosity is more than or equal to 98%, thermal shrinkage rate is less than or equal to 0.1% (keeping for 1 hour at 105 ℃), temperature application range: and the temperature is-196-1000 ℃, and the powder and the slag are not dropped.
Comparative example 1
Aerogel blankets were prepared according to the method of example 1, except that the ambient humidity was 70% RH. Obtaining the micro-nano fiber aerogel felt with a large amount of liquid beads. And (4) placing the collected micro-nano fiber aerogel felt with a large amount of liquid beads into a muffle furnace for sintering.
The aerogel blanket obtained in this example had a room temperature thermal conductivity of 0.041 (W/m. K), density: 200mg/cm 3 Compression deformation is more than or equal to 25%, bending angle is more than or equal to 86%, liquid absorption rate is about 463%, porosity is about 79%, thermal shrinkage rate is less than or equal to 0.1% (keeping for 1 hour at 105 ℃), and temperature application range is as follows: and (4) removing powder and slag at the temperature of-196-1000 ℃. The comparative example shows that under the condition that the humidity is 70% RH, the density of the obtained heat-insulating material is greatly improved, the heat conductivity of the material is also improved in detail, and the performance indexes of other materials are much worse than those of the example 1. Therefore, the environment humidity is too high, and the elastic ceramic micro-nanofiber aerogel felt with the required performance cannot be obtained.
Comparative example 2
Aerogel blankets were prepared according to the method of example 1, except that the ambient humidity was 19% RH. After about 15 minutes of spinning, the needle is blocked and the remaining mass of spinnable solution in the reservoir cannot be spun out. And putting a small amount of collected micro-nano fiber aerogel felt into a muffle furnace for sintering.
The aerogel blanket obtained in this example had a room temperature thermal conductivity of 0.021 (W/m. K) or less, a density: 8mg/cm 3 Compression deformation is more than or equal to 85 percent, bending angle is more than or equal to 175 degrees, liquid absorption rate is more than or equal to 1003 percent, porosity is more than or equal to 99 percent, thermal shrinkage rate is less than or equal to 0.1 percent (keeping for 1 hour at 105 ℃), and temperature application range is as follows: and the temperature is-196-1000 ℃, and the powder and the slag are not dropped. It can be seen from the comparative example that, under the condition that the humidity is 19% RH, the spinnability of the solution is not changed, but the solution is dried too fast in the spinning nozzle due to the over-dry environment, so that the spinning nozzle is blocked, the material cannot be continuously and uninterruptedly prepared, the working efficiency is affected, and the amount of finally obtained micro-nanofibers is greatly reduced. And the solution can not be sprayed out of the liquid storage tank for a long time, and the solution can be excessively hydrolyzed, so that the solution can not have spinnability any more, and a great deal of raw materials are wasted.
Comparative example 3
An aerogel blanket was prepared as in example 1, except that phosphoric acid, tetraethyl silicate, sodium silicate and polymer solution were added in the order of addition to the mixer. After about 19 minutes of spinning, part of the needle heads are blocked, the retention time of the spinnable solution in the liquid storage tank is too long, so that the solution is excessively hydrolyzed, and the residual large amount of solution has no spinnability and cannot be spun.
Comparative example 4
An aerogel blanket was prepared as in example 1, except that the polymer solution, tetraethyl silicate, sodium silicate and phosphoric acid were added in the order of addition to the mixer. After about 19 minutes of spinning, part of the needle heads are blocked, the retention time of the spinnable solution in the liquid storage tank is too long, so that the solution is excessively hydrolyzed, and the residual large amount of solution has no spinnability and cannot be spun.
From this example, it can be seen that when raw material is added into a mixer in the order of polymer solution, tetraethyl silicate, sodium silicate and phosphoric acid, the partial acid concentration of tetraethyl silicate and sodium silicate is too high, which makes the partial hydrolysis reaction excessive, resulting in a so-called "spinnable solution" that is finally obtained, and actually, the partial solution is partially non-spinnable, and the capillary coefficient of the partial solution without spinnability is very large, which easily blocks the needle head, and affects the spinning continuity and production efficiency.
Comparative example 5
An aerogel blanket was prepared according to the method of example 1, except that the raw material mixed solution was obtained after stirring at 1000rpm for 3 hours and then left to stand for 0.2 hours; finally, the micro-nanofiber aerogel material cannot be obtained. Because the hydrolysis reaction time of tetraethyl silicate and sodium silicate in acid environment is too long during the second stirring, the solution is hydrolyzed excessively, and the non-Newtonian fluid mixed solution has no spinnability.
After the hydrolysis reaction of tetraethyl silicate and sodium silicate in an acid environment exceeds 3 hours, the solution becomes gel. According to the invention, through the first stirring and the second stirring, the raw materials are sequentially mixed twice, the hydrolysis reaction time is preferably 2 hours, and the spinnability solution is prepared, once the stirring time exceeds 2.5 hours, the spinnability of the solution is obviously deteriorated, and the solution does not have spinnability after 3 hours.
Comparative example 6
An aerogel blanket was prepared according to the method of example 1, except that the raw material mixed solution was obtained after stirring at 1000rpm for 0.5 hour and then left to stand for 0.2 hour; the aerogel blanket obtained in this example had a room temperature thermal conductivity of 0.031(W/m · K) and a density: 124mg/cm 3 Compression deformation is more than or equal to 65%, bending angle is more than or equal to 115%, liquid absorption rate is more than or equal to 463%, porosity is more than or equal to 82%, thermal shrinkage rate is less than or equal to 0.1% (keeping for 1 hour at 105 ℃), temperature application range: and (4) dropping powder and slag at the temperature of-196-1000 ℃. Compared with the example 1, the obtained material has high thermal conductivity, high density and poor mechanical property, and does not meet the requirements of developing the material. Because the hydrolysis reaction time of the tetraethyl silicate and the sodium silicate is too short, the spinnability of the raw material mixed solution obtained finally is poor, and the spun fiber contains a large amount of liquid tetraethyl silicate and liquid beads of the sodium silicate.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which this application belongs.
The above description is only for the preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present application should be covered within the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of an elastic ceramic micro-nanofiber aerogel heat insulation material comprises the following steps:
(1) preparing a spinnable raw material mixed solution:
dissolving a polymer in a solvent, and stirring at a first stirring speed for a first stirring time until the solution is uniform to form a polymer solution; adding the catalyst, the polymer solution and the compound or the compound, the polymer solution and the catalyst into a stirrer according to the charging sequence, stirring for a second stirring time at a second stirring speed, and standing to obtain a spinnable raw material mixed solution;
the compound is selected from at least one of silicon source, inorganic salt and organic salt;
(2) preparing a precursor: spinning the spinnable mixed solution into solid micro-nano fibers by using a centrifugal spinning device, and accumulating the micro-nano fibers to obtain an elastic ceramic micro-nano fiber aerogel precursor;
(3) sintering a precursor: and (3) sintering the elastic ceramic micro-nanofiber aerogel precursor at a high temperature to obtain the elastic ceramic micro-nanofiber aerogel heat insulation material.
2. The method of claim 1, wherein the step (1) of dissolving the polymer in the solvent further comprises:
firstly, according to an empirical formula obtained by mathematical modeling, aiming at the physical and chemical properties of raw materials, introducing the raw materials into a mathematical model for analog simulation calculation, designing the mass proportion of a spinnable raw material mixed solution, and carrying out subsequent steps according to the result in the model;
in the step (2), according to the setting of the control parameters in the mathematical model, the spinnable mixed solution is spun into the solid micro-nano fiber by using a centrifugal spinning device and controlling the corresponding parameters.
3. The production method according to claim 1,
the polymer is selected from at least one of polyvinylpyrrolidone (PVP), polyethylene oxide (PEO), polyethylene glycol (PEG), Polyacrylamide (PAM) and polyvinyl alcohol (PVA); the mass ratio of the polymer to the solvent in the polymer solution is 1: 99-20: 80;
and/or the solvent is at least one selected from deionized water, absolute ethyl alcohol, acetonitrile, acetone and dimethyl amide.
4. The method of claim 1, wherein the compound is at least one selected from the group consisting of tetraethyl silicate, ethyl silicate 32, ethyl silicate 40, sodium silicate, barium acetate, aluminum chloride hexahydrate, tetrabutyl titanate, zirconium acetate, zirconium citrate, zirconium oxychloride octahydrate, magnesium acetate tetrahydrate, and magnesium citrate;
and/or the catalyst is selected from at least one of phosphoric acid, hydrochloric acid, citric acid, acetic acid, urea and cetyl trimethyl ammonium bromide.
5. The production method according to claim 1, wherein the mass ratio of the polymer solution, the compound and the catalyst is 1:0.25-0.8: 0.0025-0.008.
6. The production method according to any one of claims 1 to 5, wherein the first stirring speed is 500-800 rpm; the first stirring time is 2-8 hours; the second stirring speed is 700-1000 rpm; the second stirring time is 1-2.5 hours, and the standing time is 0-3 hours.
7. The method as claimed in claim 6, wherein the centrifugal spinning device employs a motor rotating speed of 3000-5000 rpm, a spinneret aperture of 0.08-0.3mm, a spinneret rotation radius of 3-15cm, a collection distance of 20-50cm, an ambient temperature of 0-35 ℃ and an ambient relative humidity of 20-65% RH.
8. The method according to claim 6, wherein the sintering process comprises: raising the temperature from room temperature to 1700 ℃ at the temperature raising rate of 2-5 ℃/min, keeping sintering for 1-2 hours in the environment of 1700 ℃ at 500 ℃, and then lowering the temperature from 1700 ℃ at the temperature lowering rate of 5-10 ℃ to room temperature.
9. An elastic ceramic micro-nanofiber aerogel heat insulation material, which is characterized by being prepared according to the preparation method of any one of claims 1-8.
10. Use of the elastic ceramic micro-nanofiber aerogel thermal insulation material of claim 9 as a battery separator or a supercapacitor.
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