CN108774808B - Polyimide nanofiber membrane with cross-linked appearance and zirconium dioxide coated surface and preparation method thereof - Google Patents
Polyimide nanofiber membrane with cross-linked appearance and zirconium dioxide coated surface and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
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Abstract
A polyimide nanofiber membrane with cross-linking appearance and zirconium dioxide coated on the surface and a preparation method thereof. Firstly, preparing a polyimide nano-fiber membrane by an electrostatic spinning method, treating the polyimide nano-fiber membrane by using a zirconium dioxide polymer solution, then treating the polyimide nano-fiber membrane in an ammonia atmosphere formed by dilute ammonia water for a certain time, and finally performing heat treatment to obtain the polyimide nano-fiber membrane with a cross-linking appearance and the surface coated with zirconium dioxide. The method disclosed by the invention is simple in implementation process, high in coating efficiency and good in application prospect.
Description
Technical Field
The invention belongs to the technical field of polyimide fiber membranes, and particularly relates to a cross-linked polyimide nanofiber membrane with a zirconium dioxide-coated surface and a preparation method thereof.
Background
Lithium ion batteries have many advantages such as environmental protection, long service life, and high low-temperature adaptability, and are therefore gaining favor of researchers in recent years. The lithium ion battery diaphragm is one of the key inner layer components of the lithium ion battery, and plays a very important role in the lithium ion battery. Firstly, it can avoid the direct contact of lithium cell positive negative pole, prevents the short circuit, and it can guarantee the normal through of ion when charging and discharging simultaneously, guarantees the normal work of battery. The performance of the lithium ion battery separator directly influences the performance of the battery, and therefore, the research of the separator material becomes a hot problem in the current lithium ion battery research.
Electrospinning, also known as electrospinning, has attracted more and more attention of researchers in various countries in the world in recent years due to the rapid development of nanotechnology, and has become the most popular method for producing nanofibers in the world. The nanofiber prepared by the electrostatic spinning method has the characteristics of small diameter, large specific surface area and the like, and can be widely applied to a plurality of fields and play an important role, such as filter materials, biomedical functional materials, sensor materials, electrode materials, reinforcing materials, sound absorption materials and the like.
The polyimide material has the advantages of excellent high temperature resistance, low temperature resistance, high strength and high modulus, high creep resistance, high dimensional stability, low thermal expansion coefficient, high electrical insulation, low dielectric constant and loss, radiation resistance, corrosion resistance and the like, and has the characteristics of space materials such as low vacuum volatile component, less volatile condensable substances and the like. The nano-scale PI fiber not only has many characteristics of polyimide, but also has the advantage of large specific surface area, and is particularly suitable for energy storage, energy conversion, environmental protection and the like. The polyimide/inorganic particle composite material prepared by the method for coating the inorganic particles on the surface has more characteristics of the polyimide nano-fiber, and is also a current research hotspot. For example, patent CN105970485A has used a sol-gel method to prepare a polyimide/zirconium dioxide composite nanofiber membrane. The method adopted by the invention is simple, the zirconium dioxide inorganic nano-layer is uniformly coated, and the obtained composite nano-fiber membrane has higher porosity and liquid absorption rate and excellent mechanical property, and is an ideal candidate material for a lithium ion battery diaphragm.
Disclosure of Invention
The invention provides a polyimide nanofiber membrane with a cross-linked appearance and a zirconium dioxide-coated surface and a preparation method thereof. The nanofiber membrane combines the advantages of polyimide and zirconium dioxide, and has high porosity, excellent chemical stability, excellent thermal dimensional stability and excellent mechanical properties. The preparation method comprises the specific steps of preparing a polyamic acid nanofiber membrane by an electrostatic spinning method, then performing heat treatment to convert a polyamic acid part into polyimide, then placing the polyimide in a zirconium dioxide polymer solution for soaking for a certain time, taking out the polyimide, then placing the polyimide in a steam atmosphere of dilute ammonia water for treating for a certain time to form a layer of zirconium dioxide sol on the surface of the fiber, and finally performing heat treatment to convert the zirconium dioxide sol into zirconium dioxide and form a cross-linked structure, thereby finally obtaining the zirconium dioxide-coated polyimide nanofiber membrane with a cross-linked appearance.
The preparation method of the polyimide nanofiber membrane with the cross-linked appearance and the zirconium dioxide-coated surface comprises the following specific steps:
a: preparing ethanol and deionized water into a mixed solvent according to the mass ratio of 1:1, dissolving zirconium salt into the mixed solvent, adding hydrogen peroxide with the mass fraction of 30%, and reacting for 20min to obtain a zirconium dioxide polymer solution;
b: preparing a polyamic acid solution with the solid content of 8-30% into a polyamic acid nanofiber membrane by adopting an electrostatic spinning method, performing program-controlled heating imidization treatment, heating from room temperature to 200-250 ℃, and preserving heat for 1-2h to obtain a polyimide nanofiber membrane which is not completely imidized;
c: soaking the polyimide nano fiber membrane which is not completely imidized in the zirconium dioxide polymer solution obtained in the step A, and performing ultrasonic treatment for 5-10 min;
d: placing the polyimide nanofiber membrane obtained by the treatment in the step C in an ammonia atmosphere, and carrying out constant-temperature treatment at 40-70 ℃ for 1-4 h;
e: and D, heating the polyimide nanofiber membrane obtained by the treatment in the step D for 2 hours at the temperature of 300 ℃ to obtain the polyimide nanofiber membrane with the cross-linked appearance and the zirconium dioxide-coated surface.
Wherein, the zirconium salt in the step A is zirconium nitrate, zirconium citrate, zirconium tetrachloride or zirconium oxychloride, and the concentration of zirconium ions in the solution is 0.5-4 mol/L; the molar ratio of hydrogen peroxide to zirconium salt is 4-6. And D, heating and volatilizing the ammonia gas atmosphere in the step D by using a dilute ammonia water solution, wherein the concentration of the dilute ammonia water is 0.001-0.005 mol/L.
Compared with the prior art, the method has the following excellent effects:
1. the preparation method has the advantages of simple preparation process, easy satisfaction of conditions, simple and convenient operation and easy repetition, and can realize the controllability of the thickness of the zirconium dioxide layer through the adjustment of preparation process parameters in the treatment process.
2. The polyimide nanofiber membrane with the cross-linked morphology and the zirconium dioxide-coated surface, which is prepared by the invention, has high porosity, excellent chemical stability, excellent thermal dimensional stability and excellent mechanical properties.
3. The zirconium dioxide layer of the polyimide nanofiber membrane with the zirconium dioxide-coated surface prepared by the method disclosed by the invention has the characteristics of compactness, uniformity and high adhesive force.
Drawings
FIG. 1 is a scanning electron micrograph of a surface-coated zirconium dioxide polyimide nanofiber membrane with cross-linked morphology, prepared according to example 1, at 200000 times magnification.
FIG. 2 is a scanning electron micrograph of a surface-coated zirconium dioxide polyimide nanofiber membrane with cross-linked morphology, prepared according to example 2, at 200000 times magnification.
FIG. 3 is a scanning electron micrograph of a surface-coated zirconium dioxide polyimide nanofiber membrane with cross-linked morphology, prepared according to example 3, at 200000 times magnification.
FIG. 4 is a scanning electron micrograph of a surface-coated zirconium dioxide polyimide nanofiber membrane with cross-linked morphology, prepared according to example 4, at 200000 times magnification.
FIG. 5 is a scanning electron micrograph of a surface-coated zirconium dioxide polyimide nanofiber membrane with cross-linked morphology, prepared according to example 5, at 200000 times magnification.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be noted that: the following examples are only for illustrating the present invention and are not intended to limit the technical solutions described in the present invention. Thus, while the present invention has been described in detail with reference to the following examples, it will be understood by those skilled in the art that the present invention may be modified and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Example 1
Preparing a PMDA/ODA system polyamide acid fiber membrane, performing thermal imidization to obtain a polyimide nano fiber membrane, placing the polyimide nano fiber membrane in a 1mol/L zirconium polymer solution, performing ultrasonic treatment for 5min, placing the polyimide nano fiber membrane in a dilute ammonia steam atmosphere for 1h, and finally performing heat treatment to obtain a surface coating with a cross-linking appearanceA polyimide nanofiber membrane of zirconium dioxide. (1) Weighing 2.0g of pyromellitic dianhydride (PMDA) and 1.8g of 4, 4' -diaminodiphenyl ether (ODA) in a molar ratio of 1:1, completely dissolving ODA in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanically stirring, after completely dissolving ODA in DMF, adding PMDA step by step under the condition of ice-water bath to obtain a polyamic acid solution with moderate viscosity, mechanically stirring for 2 hours, filling the polyamic acid solution into a 20ml injector, and preparing the polyamic acid fiber membrane by using an electrostatic spinning technology, wherein the parameters of the electrostatic spinning machine are spinning voltage: 20 kV; spinning temperature: room temperature; spinning humidity: 20 percent; diameter of syringe needle: number 12; receiving roller rotating speed: 80.0 m/min; receiving distance: 20 cm. Placing the prepared polyamic acid fiber membrane in a super clean bench for 12 h; and (3) placing the obtained polyamide acid fiber membrane in a heating furnace, gradually heating to 300 ℃ at the heating rate of 2 ℃/min, and keeping for 2 hours to obtain the polyimide nanofiber membrane. (2) 20ml of deionized water and 25ml of absolute ethyl alcohol are weighed and mixed evenly in a beaker. 14g of zirconium oxychloride was weighed, added to a mixed solvent of ethanol and deionized water, and stirred to be sufficiently dissolved. The measuring amount is 7.87mlH2O2Adding the mixture into a beaker, and fully reacting for 20min to obtain the solution of the zirconium dioxide polymer. (3) Soaking the polyimide nano-fiber membrane in a zirconium dioxide polymer solution, performing ultrasonic treatment for 5min, taking out and drying. (4) And (3) placing the nanofiber membrane obtained by the last step in the steam atmosphere of dilute ammonia water, and keeping the constant temperature of 60 ℃ for 1 h. (5) And (3) placing the nanofiber membrane obtained by the previous step in an oven at 300 ℃ for heat preservation for 2h to obtain the polyimide nanofiber membrane with the surface coated with zirconium dioxide, wherein the appearance of the obtained fiber is shown in figure 1.
Example 2
Preparing a PMDA/ODA system polyamide acid fiber membrane, performing thermal imidization to obtain a polyimide nano fiber membrane, placing the polyimide nano fiber membrane in a 2mol/L zirconium polymer solution, performing ultrasonic treatment for 5min, placing the polyimide nano fiber membrane in a dilute ammonia steam atmosphere for 1h, and finally performing heat treatment to obtain the polyimide nano fiber membrane with a cross-linking appearance and the surface coated with zirconium dioxide. (1) 2.0g of pyromellitic dianhydride (PMDA) and 1.8g of 4, 4' -diaminodiphenyl ether (ODA) are weighed according to the molar ratio of 1:1,dissolving ODA in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanically stirring, after dissolving ODA in DMF, adding PMDA step by step in the condition of ice-water bath to obtain polyamic acid solution with moderate viscosity, mechanically stirring for 2h, filling the polyamic acid solution into a 20ml injector, and preparing the polyamic acid fiber membrane by applying an electrostatic spinning technology, wherein the parameters of the electrostatic spinning machine are spinning voltage: 20 kV; spinning temperature: room temperature; spinning humidity: 20 percent; diameter of syringe needle: number 12; receiving roller rotating speed: 80.0 m/min; receiving distance: 20 cm. Placing the prepared polyamic acid fiber membrane in a super clean bench for 12 h; and (3) placing the obtained polyamide acid fiber membrane in a heating furnace, gradually heating to 300 ℃ at the heating rate of 2 ℃/min, and keeping for 2 hours to obtain the polyimide nanofiber membrane. (2) 20ml of deionized water and 25ml of absolute ethyl alcohol are weighed and mixed evenly in a beaker. 28g of zirconium oxychloride was weighed, added to a mixed solvent of ethanol and deionized water, and stirred to be sufficiently dissolved. 7.87ml of H are metered in2O2Adding the mixture into a beaker, and fully reacting for 20min to obtain the solution of the zirconium dioxide polymer. (3) Soaking the polyimide nanofiber membrane in a zirconium dioxide polymer solution, performing ultrasonic treatment for 5min, taking out and drying in the air. (4) And (3) placing the nanofiber membrane obtained by the last step in the steam atmosphere of dilute ammonia water, and keeping the constant temperature of 60 ℃ for 1 h. (5) And (3) placing the nanofiber membrane obtained by the previous step in an oven at 300 ℃ for heat preservation for 2h to obtain the polyimide nanofiber membrane with the surface coated with zirconium dioxide, wherein the appearance of the obtained fiber is shown in figure 2.
Example 3
Preparing a BTDA/ODA system polyamide acid fiber membrane, performing thermal imidization to obtain a polyimide nano fiber membrane, placing the polyimide nano fiber membrane in a 2mol/L zirconium polymer solution, performing ultrasonic treatment for 5min, placing the polyimide nano fiber membrane in a dilute ammonia steam atmosphere for 1h, and finally performing thermal treatment to obtain the polyimide nano fiber membrane with a cross-linking appearance and the surface coated with zirconium dioxide. (1) Weighing 2.0g of BTDA2 and 1.8g of 4, 4' -diaminodiphenyl ether (ODA) in a molar ratio of 1:1, completely dissolving ODA in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanically stirring, after completely dissolving ODA in DMF, adding BTDA step by step under the condition of ice-water bath to obtain poly (N-bromosuccinimide) with moderate viscosityAfter the polyamic acid solution is mechanically stirred for 2 hours, the polyamic acid solution is filled into a 20ml syringe, and a polyamic acid fiber membrane is prepared by applying an electrostatic spinning technology, wherein the parameters of the electrostatic spinning machine are spinning voltage: 20 kV; spinning temperature: room temperature; spinning humidity: 20 percent; diameter of syringe needle: number 12; receiving roller rotating speed: 80.0 m/min; receiving distance: 20 cm. Placing the prepared polyamic acid fiber membrane in a super clean bench for 12 h; and (3) placing the obtained polyamide acid fiber membrane in a heating furnace, gradually heating to 300 ℃ at the heating rate of 2 ℃/min, and keeping for 2 hours to obtain the polyimide nanofiber membrane. (2) 20ml of deionized water and 25ml of absolute ethyl alcohol are weighed and mixed evenly in a beaker. 28g of zirconium oxychloride was weighed, added to a mixed solvent of ethanol and deionized water, and stirred to be sufficiently dissolved. The measuring amount is 7.87mlH2O2Adding the mixture into a beaker, and fully reacting for 20min to obtain the solution of the zirconium dioxide polymer. (3) Soaking the polyimide nanofiber membrane in a zirconium dioxide polymer solution, performing ultrasonic treatment for 5min, taking out and drying in the air. (4) And (3) placing the nanofiber membrane obtained by the last step in the steam atmosphere of dilute ammonia water, and keeping the constant temperature of 60 ℃ for 1 h. (5) And (3) placing the nanofiber membrane obtained by the previous step in an oven at 300 ℃ for heat preservation for 2h to obtain the polyimide nanofiber membrane with the surface coated with zirconium dioxide, wherein the morphology of the obtained fiber is shown in figure 3.
Example 4
Preparing an ODPA/ODA system polyamide acid fiber membrane, performing thermal imidization to obtain a polyimide nano fiber membrane, placing the polyimide nano fiber membrane in a 2mol/L zirconium polymer solution, performing ultrasonic treatment for 5min, placing the polyimide nano fiber membrane in a dilute ammonia steam atmosphere for 1h, and finally performing thermal treatment to obtain the polyimide nano fiber membrane with a cross-linking appearance and the surface coated with zirconium dioxide. (1) 2.0g of ODPA2 and 1.8g of 4, 4' -diaminodiphenyl ether (ODA) in a molar ratio of 1:1 are weighed, the ODA is completely dissolved in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanical stirring is carried out, after the ODA is completely dissolved in the DMF, the ODPA is added step by step under the condition of ice water bath to obtain polyamic acid solution with moderate viscosity, the polyamic acid solution is filled into a 20ml injector after mechanical stirring is carried out for 2h, the polyamic acid fiber membrane is prepared by applying an electrostatic spinning technology, and the parameters of the electrostatic spinning machine are thatSpinning voltage: 20 kV; spinning temperature: room temperature; spinning humidity: 20 percent; diameter of syringe needle: number 12; receiving roller rotating speed: 80.0 m/min; receiving distance: 20 cm. Placing the prepared polyamic acid fiber membrane in a super clean bench for 12 h; and (3) placing the obtained polyamide acid fiber membrane in a heating furnace, gradually heating to 300 ℃ at the heating rate of 2 ℃/min, and keeping for 2 hours to obtain the polyimide nanofiber membrane. (2) 20ml of deionized water and 25ml of absolute ethyl alcohol are weighed and mixed evenly in a beaker. 28g of zirconium oxychloride was weighed, added to a mixed solvent of ethanol and deionized water, and stirred to be sufficiently dissolved. The measuring amount is 7.87mlH2O2Adding the mixture into a beaker, and fully reacting for 20min to obtain the solution of the zirconium dioxide polymer. (3) Soaking the polyimide nanofiber membrane in a zirconium dioxide polymer solution, performing ultrasonic treatment for 5min, taking out and drying in the air. (4) And (3) placing the nanofiber membrane obtained by the last step in the steam atmosphere of dilute ammonia water, and keeping the constant temperature of 60 ℃ for 1 h. (5) And (3) placing the nanofiber membrane obtained by the previous step in an oven at 300 ℃ for heat preservation for 2h to obtain the polyimide nanofiber membrane with the surface coated with zirconium dioxide, wherein the appearance of the obtained fiber is shown in figure 4.
Example 5
Preparing a 6FDA/ODA system polyamide acid fiber membrane, performing thermal imidization to obtain a polyimide nano fiber membrane, placing the polyimide nano fiber membrane in a 2mol/L zirconium polymer solution, performing ultrasonic treatment for 5min, placing the polyimide nano fiber membrane in a dilute ammonia steam atmosphere for 1h, and finally performing heat treatment to obtain the polyimide nano fiber membrane with a cross-linking appearance and the surface coated with zirconium dioxide. (1) Weighing 4.0g of 6FDA and 1.8g of 4, 4' -diaminodiphenyl ether (ODA) in a molar ratio of 1:1, completely dissolving ODA in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanically stirring, after completely dissolving ODA in DMF, adding 6FDA step by step under the condition of ice-water bath to obtain a polyamic acid solution with moderate viscosity, mechanically stirring for 2h, filling the polyamic acid solution into a 20ml syringe, and preparing the polyamic acid fiber membrane by using an electrostatic spinning technology, wherein the parameters of an electrostatic spinning machine are spinning voltage: 20 kV; spinning temperature: room temperature; spinning humidity: 20 percent; diameter of syringe needle: number 12; receiving roller rotating speed: 80.0 m/min; receiving distance: 20 cm. The prepared polyimidePlacing the amino acid fiber membrane in a super clean bench for 12 h; and (3) placing the obtained polyamide acid fiber membrane in a heating furnace, gradually heating to 300 ℃ at the heating rate of 2 ℃/min, and keeping for 2 hours to obtain the polyimide nanofiber membrane. (2) 20ml of deionized water and 25ml of absolute ethyl alcohol are weighed and mixed evenly in a beaker. 28g of zirconium oxychloride was weighed, added to a mixed solvent of ethanol and deionized water, and stirred to be sufficiently dissolved. 7.87ml of H are metered in2O2Adding the mixture into a beaker, and fully reacting for 20min to obtain the solution of the zirconium dioxide polymer. (3) Soaking the polyimide nanofiber membrane in a zirconium dioxide polymer solution, performing ultrasonic treatment for 5min, taking out and drying in the air. (4) And (3) placing the nanofiber membrane obtained by the last step in the steam atmosphere of dilute ammonia water, and keeping the constant temperature of 60 ℃ for 1 h. (5) And (3) placing the nanofiber membrane obtained by the previous step in an oven at 300 ℃ for heat preservation for 2h to obtain the polyimide nanofiber membrane with the surface coated with zirconium dioxide, wherein the appearance of the obtained fiber is shown in figure 5.
Claims (3)
1. A preparation method of a polyimide nanofiber membrane with a cross-linked appearance and a zirconium dioxide-coated surface is characterized by comprising the following steps:
a: preparing ethanol and deionized water into a mixed solvent according to the mass ratio of 1:1, dissolving zirconium salt into the mixed solvent, adding hydrogen peroxide with the mass fraction of 30%, and reacting for 20min to obtain a zirconium dioxide polymer solution;
b: preparing a polyamic acid solution with the solid content of 8-30% into a polyamic acid nanofiber membrane by adopting an electrostatic spinning method, performing program-controlled heating imidization treatment, heating from room temperature to 200-250 ℃, and preserving heat for 1-2h to obtain a polyimide nanofiber membrane which is not completely imidized;
c: soaking the polyimide nano fiber membrane which is not completely imidized in the zirconium dioxide polymer solution obtained in the step A, and performing ultrasonic treatment for 5-10 min;
d: placing the polyimide nanofiber membrane obtained by the treatment in the step C in an ammonia atmosphere, and carrying out constant-temperature treatment at 40-70 ℃ for 1-4 h;
e: and D, heating the polyimide nanofiber membrane obtained by the treatment in the step D for 2 hours at the temperature of 300 ℃ to obtain the polyimide nanofiber membrane with the cross-linked appearance and the zirconium dioxide-coated surface.
2. The method according to claim 1, wherein the zirconium salt in step a is zirconium nitrate, zirconium citrate, zirconium tetrachloride or zirconium oxychloride, and the concentration of zirconium ions in the solution is 0.5 to 4 mol/L; the molar ratio of hydrogen peroxide to zirconium salt is 4-6.
3. The method of claim 1, wherein the ammonia gas atmosphere in step D is formed by heating and volatilizing a dilute ammonia solution, and the concentration of the dilute ammonia solution is 0.001mol/L-0.005 mol/L.
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| CN111472055A (en) * | 2020-04-03 | 2020-07-31 | 北京宇程科技有限公司 | High-temperature-resistant polymer nanofiber membrane densely coated with zirconium dioxide layer on surface and preparation method thereof |
| CN113494020B (en) * | 2020-04-05 | 2022-11-25 | 北京化工大学 | Method for coating surface of polyimide nanofiber membrane with boehmite ceramic layer |
| CN113529404B (en) * | 2020-04-17 | 2024-02-02 | 北京化工大学 | Polyimide nanofiber membrane with surface uniformly coated with controllable nano zirconium dioxide inorganic layer and preparation method thereof |
| CN113622089B (en) * | 2021-09-08 | 2022-09-13 | 北京化工大学常州先进材料研究院 | Polyimide/cerium dioxide composite nanofiber membrane and preparation method thereof |
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| CN102766270B (en) * | 2012-07-25 | 2013-11-20 | 北京化工大学 | Polyimide nano-fiber membrane with crosslinked structure and preparation thereof |
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| CN105970485B (en) * | 2016-06-06 | 2018-07-06 | 北京化工大学常州先进材料研究院 | A kind of polyimides/zirconium dioxide composite nano-fiber membrane and preparation method thereof |
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