High-temperature insulation nanoceramic fiber membrane material and preparation method thereof

Abstract

The application relates to the technical field of high-temperature heat insulation material preparation, and mainly relates to a high-temperature heat insulation nanometer ceramic fiber membrane material and a preparation method thereof. The method comprises the following steps: dissolving zirconium salt and a spinning aid into a solvent to obtain a spinning solution, performing spinning treatment to obtain a fiber membrane precursor, performing first drying treatment, performing first calcination treatment to obtain a ceramic fiber membrane, immersing the ceramic fiber membrane in a solution containing yttrium salt, taking out, performing second drying treatment, and then performing second calcination treatment to obtain the high-temperature heat insulation nanometer ceramic fiber membrane material. The high-temperature heat insulation nanometer ceramic fiber membrane material has a nanometer-level fiber diameter, small inter-fiber pores, low density, low thermal conductivity, high-temperature resistance, corrosion resistance, excellent thermal shock resistance and structural stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high-temperature thermal insulation material preparation, and mainly relates to a high-temperature thermal insulation nanoceramic fiber membrane material and a preparation method thereof. BACKGROUND

[0002] The ceramic fiber membrane is an ideal thermal insulation material, which has good mechanical properties, high-temperature resistance, corrosion resistance, low thermal conductivity, low density, thermal shock resistance and oxidation resistance, and is widely used in extreme conditions such as high temperature, high pressure and strong radiation. In the field of aerospace, it often involves extreme high-temperature conditions, and light-weight high-strength thermal insulation materials are needed to provide good thermal protection for components and systems, and the ceramic fiber membrane material is currently the most concerned material. In the field of fire fighting, materials with high temperature resistance and excellent thermal insulation performance are needed to protect firefighters, and the ceramic fiber membrane material can be used as a protective clothing interlayer to provide good thermal protection. In the fields of petroleum chemical industry and metallurgy, high-temperature environments are often involved, and ceramic fiber membrane materials are used to protect heat sources, which can effectively protect surrounding personnel and equipment while significantly reducing heat loss, and have broad application prospects. In recent years, new energy devices represented by lithium ion batteries have developed rapidly and are widely used in 3C electronic products, electric vehicles and large-scale energy storage power stations. However, there are still many safety problems. Especially in electric vehicles and large-scale energy storage power stations, the battery pack system is often composed of hundreds or even thousands of single batteries, and a single or multiple batteries can release a large amount of energy instantly due to impact or internal short circuit, causing a fire and leading to the destruction of the entire battery pack system, posing a great risk to personal and property safety. Therefore, how to reduce the safety risk of lithium ion battery packs has become an important problem to be solved. Through analysis, we can see that the fire of the battery pack system is often caused by the chain reaction of a small number of single batteries catching fire, and if the single batteries are well protected from heat, the heat propagation can be blocked in time, which can effectively protect the surrounding batteries and prevent larger fires. In order to achieve this purpose, ceramic fiber membrane materials with high-temperature thermal insulation and corrosion resistance can be used to wrap single batteries, thereby effectively protecting the entire battery pack system and improving its safety, which is conducive to the popularization and application of lithium ion batteries.

[0003] At present, although ceramic fiber membrane materials have broad application prospects in many fields, their shortcomings greatly limit their application. For example, the preparation cost is high, the brittleness is large, and the performance is unstable. Therefore, it is of certain significance to simply and quickly prepare ceramic fiber membrane materials with excellent physical, chemical and mechanical properties. SUMMARY

[0004] In order to overcome the deficiencies of the prior art, the purpose of the present application is to provide a high-temperature thermal insulation nanoceramic fiber membrane material and a preparation method thereof.

[0005] The problem to be solved by the present application is to provide a method for rapidly preparing a ceramic fiber membrane material with low price and excellent physical, chemical and mechanical properties.

[0006] The purpose of the present application is achieved at least by one of the following technical solutions.

[0007] The present application provides a preparation method of a high-temperature thermal insulation nanoceramic fiber membrane material, comprising the following steps:

[0008] The zirconium salt and the spinning aid are dissolved in a solvent, stirred uniformly until completely dissolved to obtain a spinning solution, poured into a solution bin of an electrostatic spinning machine for spinning treatment to obtain a fiber membrane precursor (a white non-woven ceramic fiber membrane precursor can be obtained from the negative electrode of the electrostatic spinning machine), placed in an oven for first drying treatment (sufficient drying to remove the solvent), transferred to a muffle furnace for first calcination treatment (removing the spinning aid by calcination), to obtain a ceramic fiber membrane (a zirconia ceramic fiber membrane with poor crystalline state), the ceramic fiber membrane is soaked in a solution containing yttrium salt, taken out, placed in an oven for second drying treatment, and then in a muffle furnace for second calcination treatment to obtain the high-temperature thermal insulation nanoceramic fiber membrane material.

[0009] Further, the zirconium salt is one or more of zirconyl nitrate (ZrO(NO3)2) and zirconium oxychloride (ZrOCl2);

[0010] Further, the spinning aid is one or more of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and polyvinyl butyral (PVB);

[0011] Further, the weight ratio of the zirconium salt to the spinning aid is 0.1:1 to 1:1.

[0012] Further, the solvent is one or more of water (preferably deionized water) and anhydrous ethanol; the weight ratio of the zirconium salt to the solvent is 0.01:1 to 0.2:1.

[0013] Further, the temperature of the first drying treatment is 110-160℃, and the time of the first drying treatment is 1-4h;

[0014] Further, the temperature of the first calcination treatment is 350-400℃, and the time of the first calcination treatment is 1-4h.

[0015] Further, the solution containing yttrium salt is a mixture of yttrium salt, water, chelating agent and crosslinking agent.

[0016] Further, the yttrium salt is one or more of yttrium nitrate and yttrium chloride; the chelating agent is ammonium citrate; and the cross-linking agent is ethylene glycol.

[0017] Further, the molar ratio of the chelating agent to the yttrium salt is 2:1; the molar ratio of the cross-linking agent to the yttrium salt is 2:1; and the molar volume ratio of the yttrium salt to water is 0.1-0.5:1 mol / L.

[0018] Preferably, the molar ratio of the ammonium citrate to the metal ions in the solution containing the yttrium salt is 2:1.

[0019] Preferably, the molar ratio of the ammonium citrate to the ethylene glycol is 1:1.

[0020] Further, the ceramic fiber membrane is soaked in the solution containing the yttrium salt for 3-5 h.

[0021] Further, the temperature of the second drying treatment is 110-160℃, and the time of the second drying treatment is 1-4 h.

[0022] Further, the temperature of the second calcination treatment is 700-900℃, and the time of the second calcination treatment is 1-4 h.

[0023] Preferably, the temperature of the second calcination treatment is 800℃, and the time of the second calcination treatment is 2.5 h.

[0024] The application provides a high-temperature thermal insulation nanoceramic fiber membrane material prepared by the above preparation method. The high-temperature thermal insulation nanoceramic fiber membrane material has a nanoscale fiber diameter, small fiber interstitial pores, low density, low thermal conductivity, high-temperature resistance, corrosion resistance, excellent thermal shock resistance and structural stability.

[0025] Compared with the prior art, the application has the following advantages and beneficial effects:

[0026] The preparation method of the high-temperature thermal insulation nanoceramic fiber membrane material provided by the application has the advantages of low cost and low price of raw materials, and the prepared high-temperature thermal insulation nanoceramic fiber membrane material has the advantages of high-temperature resistance, good thermal insulation effect, corrosion resistance and easy large-scale production. In addition, the surface of the material is doped with yttrium elements, which can make the surface of the zirconia ceramic fiber membrane be stable tetragonal phase and the inside be transformable monoclinic phase. When a certain high temperature is encountered, the monoclinic phase inside can be transformed into tetragonal phase, thereby absorbing a large amount of heat to form a good thermal insulation and heat resistance effect, and the tetragonal phase on the surface can make the ceramic fiber membrane have a more stable structure, and the zirconia ceramic fiber membrane without doping has more excellent thermal shock resistance and structural stability. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 SEM result picture of high-temperature thermal insulation nanoceramic fiber membrane material prepared for the embodiment 1 of the present application;

[0028] Figure 2 SEM result picture of high-temperature thermal insulation nanoceramic fiber membrane material prepared for the embodiment 2 of the present application;

[0029] Figure 3 SEM result picture of high-temperature thermal insulation nanoceramic fiber membrane material prepared for the embodiment 3 of the present application;

[0030] Figure 4 Thermal insulation performance picture of high-temperature thermal insulation nanoceramic fiber membrane material prepared for the embodiment 3 of the present application. DETAILED DESCRIPTION

[0031] The specific implementation of the present application is further illustrated below in combination with examples, but the implementation and protection of the present application are not limited thereto. It should be noted that, if there are processes not specifically detailed below, they can be implemented or understood by those skilled in the art in reference to the prior art. If the reagents or instruments used are not marked with the manufacturer, they are considered to be conventional products that can be obtained by market purchase.

[0032] Embodiment 1

[0033] A preparation method of a high-temperature thermal insulation nanoceramic fiber membrane material, comprising the following steps:

[0034] Dissolve the zirconium salt and the spinning aid in a solvent, mix uniformly to obtain a spinning solution, perform spinning treatment to obtain a fiber membrane precursor, perform first drying treatment in an oven, then perform first calcination treatment in a muffle furnace to obtain a ceramic fiber membrane, immerse the ceramic fiber membrane in a solution containing a yttrium salt, take out, perform second drying treatment in an oven, and then perform second calcination treatment in a muffle furnace to obtain the high-temperature thermal insulation nanoceramic fiber membrane material.

[0035] The zirconium salt is zirconyl nitrate; the spinning aid is polyvinylpyrrolidone (PVP); and the weight ratio of the zirconium salt to the spinning aid is 0.1:1.

[0036] The solvent is a mixture of deionized water and anhydrous ethanol, and the mass ratio of the deionized water to the anhydrous ethanol is 1:1; and the weight ratio of the zirconium salt to the solvent is 0.2:1.

[0037] The spinning treatment is performed in an electrostatic spinning machine, and the spinning voltage and distance are 20 kV and 15 cm, respectively; after the spinning treatment, the obtained fiber (i.e., the fiber membrane precursor) is collected by a rotary drum;

[0038] The temperature of the first drying treatment is 110℃, and the time of the first drying treatment is 4h.

[0039] The temperature of the first calcination treatment is 350℃, and the time of the first calcination treatment is 4h.

[0040] The solution containing yttrium salt is a mixture of yttrium salt, water, chelating agent and crosslinking agent.

[0041] The yttrium salt is yttrium nitrate; the chelating agent is ammonium citrate; the crosslinking agent is ethylene glycol; the molar ratio of the chelating agent to the yttrium salt is 2:1; the molar ratio of the crosslinking agent to the yttrium salt is 2:1; and the molar volume ratio of the yttrium salt to water is 0.1:1 mol / L.

[0042] The time for which the ceramic fiber membrane is soaked in the solution containing yttrium salt is 5h.

[0043] The temperature of the second drying treatment is 110℃, and the time of the second drying treatment is 4h.

[0044] The temperature of the second calcination treatment is 700℃, and the time of the second calcination treatment is 4h.

[0045] The SEM photograph of the ceramic fiber membrane after the calcination treatment is shown in Figure 1 . Figure 1 As can be seen from the above, the ceramic fiber has a uniform diameter, is in the nanometer level, and has a large porosity, which is conducive to a significant reduction in the density and thermal conductivity of the ceramic fiber membrane.

[0046] Example 2

[0047] A preparation method of a high-temperature thermal insulation nanoceramic fiber membrane material, comprising the following steps:

[0048] A zirconium salt and a spinning aid are dissolved in a solvent to obtain a spinning solution, spinning treatment is performed to obtain a fiber membrane precursor, first drying treatment is performed in an oven, then first calcination treatment is performed in a muffle furnace to obtain a ceramic fiber membrane, the ceramic fiber membrane is soaked in a solution containing a yttrium salt, taken out, second drying treatment is performed in an oven, and then second calcination treatment is performed in a muffle furnace to obtain the high-temperature thermal insulation nanoceramic fiber membrane material.

[0049] The zirconium salt is zirconium oxychloride; the spinning aid is polyvinyl alcohol (PVA); and the weight ratio of the zirconium salt to the spinning aid is 1:1.

[0050] The solvent is a mixture of deionized water and anhydrous ethanol, and the mass ratio of the deionized water to the anhydrous ethanol is 1:1; and the weight ratio of the zirconium salt to the solvent is 0.01:1.

[0051] The spinning treatment is performed in an electrostatic spinning machine, and the spinning voltage and distance are 20 kV and 20 cm respectively; after the spinning treatment, the obtained fiber (i.e. fiber membrane precursor) is collected by a rotating drum;

[0052] The temperature of the first drying treatment is 160℃, and the time of the first drying treatment is 1h.

[0053] The temperature of the first calcination treatment is 400℃, and the time of the first calcination treatment is 1h.

[0054] The solution containing yttrium salt is a mixture of yttrium salt, water, chelating agent and crosslinking agent.

[0055] The yttrium salt is yttrium chloride; the chelating agent is ammonium citrate; the crosslinking agent is ethylene glycol; the molar ratio of the chelating agent to the yttrium salt is 2:1; the molar ratio of the crosslinking agent to the yttrium salt is 2:1; and the molar volume ratio of the yttrium salt to water is 0.5:1 mol / L.

[0056] The time for which the ceramic fiber membrane is soaked in the solution containing yttrium salt is 3h.

[0057] The temperature of the second drying treatment is 160℃; and the time of the second drying treatment is 1h.

[0058] The temperature of the second calcination treatment is 900℃, and the time of the second calcination treatment is 1h.

[0059] The SEM photograph of the ceramic fiber membrane after the calcination treatment is shown in Figure 2 From Figure 2 It can be seen that the ceramic fiber has a uniform diameter, which is in the nanometer level, and has a large porosity, which is conducive to the significant reduction of the density and the thermal conductivity of the ceramic fiber membrane.

[0060] Example 3

[0061] A preparation method of a high-temperature thermal insulation nanoceramic fiber membrane material, comprising the following steps:

[0062] A zirconium salt and a spinning aid are dissolved in a solvent to obtain a spinning solution, the spinning solution is subjected to spinning treatment to obtain a fiber membrane precursor, the fiber membrane precursor is subjected to first drying treatment in an oven, and then subjected to first calcination treatment in a muffle furnace to obtain a ceramic fiber membrane, the ceramic fiber membrane is soaked in a solution containing yttrium salt, taken out, subjected to second drying treatment in an oven, and then subjected to second calcination treatment in a muffle furnace to obtain the high-temperature thermal insulation nanoceramic fiber membrane material.

[0063] The zirconium salt is zirconium oxychloride; the spinning aid is polyvinyl butyl (PVB); and the weight ratio of the zirconium salt to the spinning aid is 0.55:1.

[0064] The solvent is a mixture of deionized water and anhydrous ethanol, and the mass ratio of the deionized water and the anhydrous ethanol is 1:1; the weight ratio of the zirconium salt to the solvent is 0.1:1.

[0065] The spinning treatment is performed in an electrostatic spinning machine, and the spinning voltage and the distance are 20 kV and 20 cm, respectively; after the spinning treatment, the obtained fiber (i.e., the fiber membrane precursor) is collected by a rotating drum;

[0066] The temperature of the first drying treatment is 135℃, and the time of the first drying treatment is 2.5h;

[0067] The temperature of the first calcination treatment is 375℃, and the time of the first calcination treatment is 2.5h.

[0068] The solution containing the yttrium salt is a mixture of the yttrium salt, water, a chelating agent and a crosslinking agent.

[0069] The yttrium salt is yttrium chloride; the chelating agent is ammonium citrate; the crosslinking agent is ethylene glycol; the molar ratio of the chelating agent to the yttrium salt is 2:1; the molar ratio of the crosslinking agent to the yttrium salt is 2:1; and the molar volume ratio of the yttrium salt to water is 0.3:1 mol / L.

[0070] The time for which the ceramic fiber membrane is soaked in the solution containing the yttrium salt is 4h.

[0071] The temperature of the second drying treatment is 135℃; and the time of the second drying treatment is 2.5h.

[0072] The temperature of the second calcination treatment is 800℃, and the time of the second calcination treatment is 2.5h.

[0073] The SEM photograph of the ceramic fiber membrane after the calcination treatment is shown in Figure 3 It can be seen from Figure 3 that the ceramic fiber has a uniform diameter, which is in the nanometer level, and has a large porosity, which is beneficial to the significant reduction of the density and the thermal conductivity of the ceramic fiber membrane. The basic physical performance parameters are shown in Table 1. Table 1 below shows the basic physical performance of the high-temperature thermal insulation nanoceramic fiber membrane material prepared in Example 3.

[0074] Table 1

[0075]

[0076] The thermal insulation performance of the high-temperature thermal insulation nanoceramic fiber membrane material prepared in Example 3 is determined by placing the high-temperature thermal insulation nanoceramic fiber membrane material on a hot stage with a temperature of 600℃, testing the temperature at different distances from the surface of the hot stage over time, and the test results are shown in Figure 4As shown by Table 1 and Figure 4 It can be seen that the ceramic fiber membrane prepared has very low density and excellent thermal insulation performance.

[0077] The above embodiments are only the preferred embodiments of the present application, which are used for explaining the present application, but not limiting the present application. The changes, replacements, modifications, etc. made by the skilled in the art without departing from the spirit and essence of the present application shall all belong to the protection scope of the present application.

Claims

1. A method for preparing a high-temperature thermal insulation nano-ceramic fiber membrane material, characterized in that: The steps include: Dissolving a zirconium salt and a spinning aid in a solvent to obtain a spinning solution, performing a spinning process to obtain a fiber membrane precursor, performing a first drying process, performing a first calcination process to obtain a ceramic fiber membrane, immersing the ceramic fiber membrane in a solution containing an yttrium salt, taking it out, performing a second drying process, and then performing a second calcination process to obtain the high-temperature thermal insulation nano-ceramic fiber membrane material; The solution containing yttrium salt is a mixture of yttrium salt, water, a chelating agent and a cross-linking agent.

2. The method for preparing a high-temperature thermal insulation nano-ceramic fiber membrane material according to claim 1, characterized in that: The zirconium salt is one or more of zirconium oxynitrate and zirconium oxychloride; the spinning aid is one or more of polyvinyl pyrrolidone, polyvinyl alcohol, and polyvinyl butyral; the weight ratio of the zirconium salt to the spinning aid is 0.1:1 to 1:

1.

3. The method for preparing a high-temperature thermal insulation nano-ceramic fiber membrane material according to claim 1, characterized in that: The solvent is one or more of water and anhydrous ethanol; the weight ratio of the zirconium salt to the solvent is 0.01:1 to 0.2:

1.

4. The method for preparing a high-temperature thermal insulation nano-ceramic fiber membrane material according to claim 1, characterized in that: The temperature of the first drying treatment is 110-160° C., and the time of the first drying treatment is 1-4 hours; the temperature of the first calcination treatment is 350-400° C., and the time of the first calcination treatment is 1-4 hours.

5. The method for preparing a high-temperature thermal insulation nano-ceramic fiber membrane material according to claim 1, characterized in that: The yttrium salt is one or more of yttrium nitrate and yttrium chloride; the chelating agent is ammonium citrate; the cross-linking agent is ethylene glycol; the molar ratio of the chelating agent to the yttrium salt is 2:1; the molar ratio of the cross-linking agent to the yttrium salt is 2:1; and the molar volume ratio of the yttrium salt to water is 0.1 to 0.5:1 mol / L.

6. The method for preparing a high-temperature thermal insulation nano-ceramic fiber membrane material according to claim 1, characterized in that: The ceramic fiber membrane is immersed in the solution containing the yttrium salt for 3-5 hours.

7. The method for preparing a high-temperature thermal insulation nano-ceramic fiber membrane material according to claim 1, characterized in that: The temperature of the second drying treatment is 110-160° C.; the time of the second drying treatment is 1-4 hours.

8. The method for preparing a high-temperature thermal insulation nano-ceramic fiber membrane material according to claim 1, characterized in that: The temperature of the second calcination treatment is 700-900° C., and the time of the second calcination treatment is 1-4 hours.

9. A high-temperature thermal insulation nano-ceramic fiber membrane material prepared by the preparation method according to any one of claims 1 to 8.

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