CN113493958A - Polyimide nanofiber membrane coaxially coated with boehmite and preparation method thereof - Google Patents
Polyimide nanofiber membrane coaxially coated with boehmite and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
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- D01F1/02—Addition of substances to the spinning solution or to the melt
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- 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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- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
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Abstract
A polyimide nanofiber membrane coaxially coated with boehmite is prepared by the steps of firstly preparing a polyamic acid nanofiber membrane by an electrostatic spinning method and performing thermal imidization to obtain the polyimide nanofiber membrane; and then sequentially immersing the polyimide nano-fiber membrane into a potassium hydroxide solution and a dilute acetic acid solution for etching, ring opening and acidification, immersing the nano-fiber membrane into an aluminum salt alcohol solution for in-situ adsorption and complexation, immersing the nano-fiber membrane into ammonia water for hydrolysis, and finally performing heat treatment to obtain the polyimide nano-fiber membrane coaxially coated with boehmite. The polyimide nanofiber membrane coaxially coated with boehmite prepared by the method disclosed by the invention is excellent in surface wettability and thermal stability, and the boehmite ceramic layer is uniformly coated; the high-temperature-resistant lithium ion battery diaphragm can effectively improve the battery safety and has a good application prospect. The preparation method disclosed by the invention is simple in implementation process, high in coating efficiency, small in environmental pollution and promising in industrial production prospect.
Description
Technical Field
The invention belongs to the technical field of polyimide nano-fiber membranes, and particularly relates to a polyimide nano-fiber membrane coaxially coated with boehmite and a preparation method thereof.
Background
With the rapid development of the modern industrial process and the rapid increase of population, the traditional fossil fuel is rapidly consumed, the requirement of people on environmental protection is increasingly improved, and the development and utilization of novel green and environment-friendly energy sources are not slow. The lithium ion battery with long service life, wide working temperature range and high energy density becomes one of the most important new energy development directions in the future. The diaphragm is used as a third electrode, plays a role in preventing the anode and the cathode of the battery from being in direct contact and allowing lithium ions to be transmitted, plays an important role in the working of the battery, and has direct influence on the performance of the battery. The separator material research is the focus of battery research in recent years.
Electrospinning, also known as electrospinning, is a process that can produce nanofibers simply and efficiently, and has received much attention at present. The nanofiber with large length-diameter ratio and large specific surface area can be prepared by utilizing an electrostatic spinning technology, and the fiber diameter, the pore structure and the fiber accumulation state can be regulated and controlled by regulating the conditions of polymer types, molecular weight, solvents and the like, so that the nanofiber has excellent performance. The advantages of high porosity and uniform and adjustable aperture of the electrospun nanofiber membrane allow the electrospun nanofiber membrane to have great potential in the application field of lithium ion battery separators.
The Polyimide (PI) material has the advantages of high temperature resistance, low temperature resistance, high strength, high modulus, high creep resistance, high dimensional stability and the like. The PI nano-fiber has small diameter and large specific surface area, and is applied to the fields of composite material reinforcement, lithium battery diaphragms, fuel cells, sensors and the likeGreat application potential. Further properties can also be imparted to the nanofibers by modifying the PI nanofibers. In modification of battery separator, inorganic particle slurry coating is one of the most common modification methods, and aluminum ceramics such as aluminum oxide (Al)2O3) Boehmite (AlOOH) is low in price, excellent in thermodynamic property and capable of greatly improving electrolyte wettability of the diaphragm, and is widely used for modification of lithium battery diaphragms, for example, an aluminum oxide coating with the thickness of 1-4 mu m is coated on the surface of a base film in patent CN106299204A, and a high-safety lithium battery diaphragm is prepared. However, loading the inorganic material using a coating method will inevitably increase the thickness of the separator, reduce the energy density of the battery, reduce the uniformity of the separator, and also risk the inorganic layer falling off. In view of the defects, the invention provides a polyimide nano-fiber membrane coaxially coated with boehmite and a preparation method thereof. The method adopted by the invention is simple, the obtained fiber membrane has higher porosity and liquid absorption rate, and is different from the traditional coating method, the adsorption and complexation effect brought by the functional group of the PI nano-fiber is utilized to uniformly coat the boehmite ceramic on the surface of the fiber, the ceramic layer is not easy to fall off and has thin thickness, and the thermal stability of the diaphragm is excellent.
Disclosure of Invention
In order to improve the defects of increasing the thickness of the diaphragm, reducing the uniformity of the diaphragm, easily causing coating shedding and the like caused by loading an inorganic material on the surface of the diaphragm by a coating method, the invention provides a polyimide nano-fiber membrane coaxially coated with boehmite and a preparation method thereof.
The polyimide nanofiber membrane coaxially coated with boehmite is characterized in that the diameter of polyimide nanofibers is 20-600nm, and the surfaces of the nanofibers are coated with boehmite ceramic layers with the thickness of 10-100 nm.
Furthermore, the diameter of the polyimide nano-fiber is 30-500nm, and the surface of the nano-fiber is coated with a boehmite ceramic layer with the thickness of 20-90 nm.
Further, the contact angle of the polyimide nanofiber membrane coaxially coated with boehmite is 4-18 °, preferably 5-16 °;
further, the polyimide nanofiber membrane coaxially coated with boehmite has a porosity of 60 to 85%, preferably 62 to 82%;
further, the thermal deformation temperature of the polyimide nanofiber membrane coaxially coated with boehmite under 0.02N is 270-320 ℃, preferably 280-315 ℃.
A preparation method of a polyimide nanofiber membrane coaxially coated with boehmite is characterized by comprising the following steps:
a: preparing an aluminum salt alcohol solution with the concentration of 0.05-0.5 mol/L;
b: preparing a polyamic acid solution with the solid content of 8-12% into a polyamic acid nanofiber membrane by adopting an electrostatic spinning method, and carrying out heat treatment to obtain a polyimide nanofiber membrane;
c: b, placing the polyimide nanofiber membrane prepared in the step B in 0.05-6mol/L alkali solution for etching to obtain a polyimide nanofiber membrane with an alkaline hydrolysis ring on the surface;
d: placing the polyimide nanofiber membrane obtained by the treatment in the step C in an acid solution with the mass fraction of 0.3-15% for acidification to obtain the polyimide nanofiber membrane with the nanofiber surface containing carboxyl active functional groups;
e: d, placing the polyimide nanofiber membrane obtained through the treatment in the step D into the aluminum salt alcohol solution prepared in the step A;
f: and E, soaking the nanofiber membrane obtained after the treatment in the step E in 0.002-0.09mol/L of dilute ammonia water, and then carrying out heat treatment on the nanofiber membrane to obtain the polyimide nanofiber membrane coaxially coated with boehmite.
The aluminum salt in the step A is at least one of aluminum sulfate and anhydrous aluminum chloride.
The concentration of the aluminum salt alcohol solution in the step A is preferably 0.1-0.4mol/L, and the alcohol as the solvent is at least one of methanol, ethanol and isopropanol.
The polyamic acid in the step B is prepared by solution condensation polymerization of any one of a dicarboxylic anhydride and a diamine, wherein the dicarboxylic anhydride and the diamine are preferably pyromellitic dianhydride/4, 4 '-diaminodiphenyl ether (PMDA/ODA), 3', 4,4 '-benzophenonetetracarboxylic dianhydride/4, 4' -diaminodiphenyl ether (BTDA/ODA), hexafluoro dianhydride/4, 4 '-diaminodiphenyl ether (6FDA/ODA), 3', 4,4 '-biphenyltetracarboxylic dianhydride/4, 4' -diaminodiphenyl ether (BPDA/ODA), 4,4 '-biphenylether dianhydride/4, 4' -diaminodiphenyl ether (ODPA/ODA). The conditions of the heat treatment are as follows: the temperature is 290-350 ℃, preferably 300-330 ℃, and the temperature is kept for 1-5h, preferably 1.5-3.5 h.
The alkali in the step C is at least one of sodium hydroxide and potassium hydroxide, the concentration of the alkali solution is preferably 0.1-5mol/L, and the time for treating the nanofiber membrane in the alkali is 20s-40min, preferably 30s-30 min. Further, the alkali solution is treated and then washed to be neutral by deionized water. The mass ratio of the alkali solution to the polyimide nanofiber membrane prepared in the step B is more than 10: 1, preferably 20: 1-105：1。
The acid in the step D is at least one of acetic acid, sulfuric acid, hydrochloric acid and nitric acid, the mass fraction of the acid is preferably 0.5-10%, and the time for treating the nanofiber membrane in the acid is 20min-4h, preferably 30min-3 h. Further, after acidification, washing with deionized water to neutrality. And D, the mass ratio of the acid solution to the polyimide nanofiber membrane obtained by the treatment in the step C is more than 10: 1, preferably 20: 1-104：1。
And E, treating the nanofiber membrane in the aluminum salt alcohol solution for 20min-4h, preferably 30min-3h, so that the aluminum salt is subjected to adsorption complexation on the surface of the polyimide nanofiber, and further, taking out the polyimide nanofiber membrane and then ultrasonically cleaning the polyimide nanofiber membrane in deionized water for 10-60min, preferably 20-50 min. And D, the mass ratio of the aluminum salt alcohol solution to the polyimide nanofiber membrane obtained by the treatment in the step D is more than 10: 1, preferably 20: 1-105: 1. the concentration of the dilute ammonia water in the step F is preferably 0.004-0.08mol/L, and the soaking time of the nanofiber membrane in the dilute ammonia water is 20min-3h, preferably 30min-2 h; aluminum salt is hydrolyzed and deposited on the surface of the fiber, and further, the fiber is taken out and ultrasonically cleaned in deionized water for 10 to 60min, preferably 20 to 50 min. And E, the weight ratio of the dilute ammonia water to the nanofiber membrane obtained after treatment in the step E is more than 10: 1, preferably 20: 1-104: 1. the conditions of the heat treatment are as follows: the temperature is 290-350 ℃, preferably 300-330 ℃, and the temperature is kept for 1-5h, preferably 1.5-3.5 h.
Compared with the prior art, the invention has the following excellent effects:
1. the polyimide nano-fiber membrane coated with boehmite coaxially can be prepared by soaking the polyimide nano-fiber membrane in different solutions and then heating, the preparation method is relatively simple, acid, alkali, aluminum salt and solvent used in the preparation process are common and easy to obtain, the cost is low, and the industrial production is favorably realized.
2. According to the polyimide nanofiber membrane coaxially coated with boehmite, polyimide nanofibers can provide excellent thermal stability, the boehmite ceramic layer can provide excellent electrolyte wettability, and the two materials can be simultaneously utilized by combining the polyimide nanofibers and the boehmite ceramic layer.
3. Compared with the composite diaphragm modified by a coating method, the polyimide nanofiber membrane coaxially coated with boehmite prepared by the invention does not cause a multi-layer diaphragm structure, has higher porosity, better uniformity, thinner functional layer thickness, better wettability and flame retardance, and can effectively improve the safety of a battery when being used as a high-performance lithium battery diaphragm.
Drawings
FIG. 1 is a scanning electron micrograph of a polyimide nanofiber membrane coaxially coated with boehmite prepared according to example 1, magnified 50000 times.
FIG. 2 is a scanning electron micrograph of a polyimide nanofiber membrane coaxially coated with boehmite prepared according to example 2, magnified 50000 times.
FIG. 3 is a scanning electron micrograph of a polyimide nanofiber membrane coaxially coated with boehmite prepared according to example 3, magnified 50000 times.
FIG. 4 is a scanning electron micrograph of a polyimide nanofiber membrane coaxially coated with boehmite prepared according to example 4, magnified 50000 times.
FIG. 5 is a scanning electron micrograph of a polyimide nanofiber membrane coaxially coated with boehmite prepared according to example 5, magnified 50000 times.
FIG. 6 is a scanning electron micrograph of a fiber cross-section of a polyimide nanofiber membrane coaxially coated with boehmite prepared according to example 5, magnified 50000 times.
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
(1) Weighing 4.17g of anhydrous aluminum chloride, slowly adding the anhydrous aluminum chloride into 80ml of ethanol, and completely dissolving the anhydrous aluminum chloride into 0.4mol/L anhydrous aluminum chloride ethanol solution; (2) weighing 2.0g of pyromellitic dianhydride (PMDA) and 1.84g 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 in batches under the condition of ice-water bath to obtain a polyamic acid solution with moderate viscosity, mechanically stirring for 2h for homogenization, finally filling the polyamic acid solution into a 20ml syringe, and preparing the polyamic acid nanofiber membrane by using an electrostatic spinning technology, wherein the specific parameters in the electrostatic spinning process are spinning voltage: 17 kV; spinning temperature: room temperature; spinning humidity: 30 percent; diameter of syringe needle: number 12; receiving roller rotating speed: 400 rpm; receiving distance: 20 cm. Placing the prepared polyamic acid nanofiber membrane in a super clean bench for 12h, then placing the polyamic acid nanofiber membrane in a heating furnace, gradually heating to 300 ℃ at the heating speed of 2 ℃/min, and keeping the temperature for 2h to obtain a polyimide nanofiber membrane; (3) weighing 8.98g of potassium hydroxide, dissolving the potassium hydroxide in 80ml of deionized water to prepare a 2mol/L potassium hydroxide solution, and then weighing acetic acid to prepare an acetic acid solution with the mass concentration of 5%; (4) soaking the polyimide nano-fiber membrane in a potassium hydroxide solution for 1min, taking out, ultrasonically cleaning for 5min, soaking in acetic acid for 1h, taking out, ultrasonically cleaning for 30min, and obtaining the polyimide nano-fiber membrane with the surface containing carboxyl active functional groups; (5) measuring ammonia water to prepare 0.04mol/L dilute ammonia water solution; (6) soaking a polyimide nanofiber membrane with a surface containing carboxyl active functional groups in an anhydrous aluminum chloride ethanol solution for 1h, taking out, ultrasonically cleaning for 30min, soaking the polyimide nanofiber membrane in dilute ammonia water for 1h, taking out, ultrasonically cleaning for 30 min; (7) and (3) placing the nanofiber membrane obtained by the treatment in the step (6) in an oven at 300 ℃ for heat preservation for 2h to obtain the polyimide nanofiber membrane coaxially coated with boehmite, wherein the diameter of the nanofiber is 380nm, the thickness of a boehmite coating layer of the nanofiber is 58nm, the tensile strength is 12.1Mpa, the contact angle of an electrolyte is 5.7 degrees, the thermal deformation temperature under 0.02N is 285 ℃, and the porosity is 74.5 percent. The morphology of the obtained fiber membrane is shown in figure 1.
Example 2
(1) Weighing 4.17g of anhydrous aluminum chloride, slowly adding the anhydrous aluminum chloride into 80ml of ethanol, and completely dissolving the anhydrous aluminum chloride into 0.4mol/L anhydrous aluminum chloride ethanol solution; (2) weighing 2.0g of pyromellitic dianhydride (PMDA) and 1.84g 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 in batches under the condition of ice-water bath to obtain a polyamic acid solution with moderate viscosity, mechanically stirring for 2h for homogenization, finally filling the polyamic acid solution into a 20ml syringe, and preparing the polyamic acid nanofiber membrane by using an electrostatic spinning technology, wherein the specific parameters in the electrostatic spinning process are spinning voltage: 17 kV; spinning temperature: room temperature; spinning humidity: 30 percent; diameter of syringe needle: number 12; receiving roller rotating speed: 400 rpm; receiving distance: 20 cm. Firstly, placing the prepared polyamic acid nanofiber membrane in a super clean bench, standing for 12h, then placing the polyamic acid nanofiber membrane in a heating furnace, gradually heating to 300 ℃ at the heating rate of 2 ℃/min, and keeping for 2h to prepare the polyimide nanofiber membrane; (3) weighing 4.49g of potassium hydroxide, dissolving the potassium hydroxide in 80ml of deionized water to prepare 1mol/L potassium hydroxide solution, and then weighing acetic acid to prepare acetic acid solution with the mass fraction of 5%; (4) soaking the polyimide nano-fiber membrane in a potassium hydroxide solution for 1min, taking out, ultrasonically cleaning for 5min, soaking in acetic acid for 1h, taking out, ultrasonically cleaning for 30min, and obtaining the polyimide nano-fiber membrane with the surface containing carboxyl active functional groups; (5) measuring ammonia water to prepare 0.04mol/L dilute ammonia water solution; (6) soaking a polyimide nanofiber membrane with a surface containing carboxyl active functional groups in an anhydrous aluminum chloride ethanol solution for 1h, taking out, ultrasonically cleaning for 30min, soaking the polyimide nanofiber membrane in dilute ammonia water for 1h, taking out, ultrasonically cleaning for 30 min; (7) and (3) placing the nanofiber membrane obtained by the treatment in the step (6) in a 300 ℃ oven for heat preservation for 2h to obtain the polyimide nanofiber membrane coaxially coated with boehmite, wherein the diameter of the nanofiber is 320nm, the thickness of a boehmite coating layer of the nanofiber is 44nm, the tensile strength is 46.2Mpa, the contact angle of an electrolyte is 7.5 degrees, the thermal deformation temperature is 308 ℃ under 0.02N, and the porosity is 78.5 percent. The morphology of the obtained fiber membrane is shown in figure 2.
Example 3
(1) Weighing 4.17g of anhydrous aluminum chloride, slowly adding the anhydrous aluminum chloride into 80ml of ethanol, and completely dissolving the anhydrous aluminum chloride into 0.4mol/L anhydrous aluminum chloride ethanol solution; (2) 2.0g of pyromellitic dianhydride (PMDA) and 1.84g 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, and the PMDA is added in batches under the condition of ice-water bath after the ODA is completely dissolved in the DMF; and after obtaining a polyamic acid solution with moderate viscosity, mechanically stirring for 2h for homogenization, finally filling the polyamic acid solution into a 20ml syringe, and preparing the polyamic acid nanofiber membrane by applying an electrostatic spinning technology, wherein the specific parameters of the electrostatic spinning process are spinning voltage: 17 kV; spinning temperature: room temperature; spinning humidity: 30 percent; diameter of syringe needle: number 12; receiving roller rotating speed: 400 rpm; receiving distance: 20 cm. Firstly, placing the prepared polyamic acid nanofiber membrane in a super clean bench, standing for 12h, then placing the polyamic acid nanofiber membrane in a heating furnace, gradually heating to 300 ℃ at the heating rate of 2 ℃/min, and keeping for 2h to prepare the polyimide nanofiber membrane; (3) weighing 4.49g of potassium hydroxide, dissolving the potassium hydroxide in 80ml of deionized water to prepare 1mol/L potassium hydroxide solution, and then weighing acetic acid to prepare acetic acid solution with the mass fraction of 5%; (4) soaking the polyimide nano-fiber membrane in a potassium hydroxide solution for 2min, taking out, ultrasonically cleaning for 5min, soaking in acetic acid for 1h, taking out, ultrasonically cleaning for 30min, and obtaining the polyimide nano-fiber membrane with the surface containing carboxyl active functional groups; (5) measuring ammonia water to prepare 0.04mol/L dilute ammonia water solution; (6) soaking a polyimide nanofiber membrane with a surface containing carboxyl active functional groups in an anhydrous aluminum chloride ethanol solution for 1h, taking out, ultrasonically cleaning for 30min, soaking the polyimide nanofiber membrane in dilute ammonia water for 1h, taking out, ultrasonically cleaning for 30 min; (7) and (3) placing the nanofiber membrane obtained by the treatment in the step (6) in an oven at 300 ℃ for heat preservation for 2h to obtain the polyimide nanofiber membrane coaxially coated with boehmite, wherein the diameter of the nanofiber is 350nm, the thickness of a boehmite coating layer of the nanofiber is 51nm, the tensile strength is 31.4Mpa, the contact angle of an electrolyte is 6.4 degrees, the thermal deformation temperature under 0.02N is 291 ℃, and the porosity is 72.3%. The morphology of the obtained fiber membrane is shown in figure 3.
Example 4
(1) Weighing 4.17g of anhydrous aluminum chloride, slowly adding the anhydrous aluminum chloride into 80ml of ethanol, and completely dissolving the anhydrous aluminum chloride into 0.4mol/L anhydrous aluminum chloride ethanol solution; (2) 2.0g of pyromellitic dianhydride (PMDA) and 1.84g 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, and the PMDA is added in batches under the condition of ice-water bath after the ODA is completely dissolved in the DMF; and after obtaining a polyamic acid solution with moderate viscosity, mechanically stirring for 2h for homogenization, finally filling the polyamic acid solution into a 20ml syringe, and preparing the polyamic acid nanofiber membrane by applying an electrostatic spinning technology, wherein the specific parameters of the electrostatic spinning process are spinning voltage: 17 kV; spinning temperature: room temperature; spinning humidity: 30 percent; diameter of syringe needle: number 12; receiving roller rotating speed: 400 rpm; receiving distance: 20 cm. Firstly, placing the prepared polyamic acid nanofiber membrane in a super clean bench, standing for 12h, then placing the polyamic acid nanofiber membrane in a heating furnace, gradually heating to 300 ℃ at the heating rate of 2 ℃/min, and keeping for 2h to prepare the polyimide nanofiber membrane; (3) weighing 4.49g of potassium hydroxide, dissolving the potassium hydroxide in 80ml of deionized water to prepare 1mol/L potassium hydroxide solution, and then weighing acetic acid to prepare acetic acid solution with the mass fraction of 5%; (4) soaking the polyimide nano-fiber membrane in a sodium hydroxide solution for 2min, taking out, ultrasonically cleaning for 5min, soaking in acetic acid for 2h, taking out, ultrasonically cleaning for 30min, and obtaining the polyimide nano-fiber membrane with the surface containing carboxyl active functional groups; (5) measuring ammonia water to prepare 0.04mol/L dilute ammonia water solution; (6) soaking a polyimide nanofiber membrane with a surface containing carboxyl active functional groups in an anhydrous aluminum chloride ethanol solution for 1h, taking out, ultrasonically cleaning for 30min, soaking the polyimide nanofiber membrane in dilute ammonia water for 1h, taking out, ultrasonically cleaning for 30 min; (7) and (3) placing the nanofiber membrane obtained by the treatment in the step (6) in a 300 ℃ oven for heat preservation for 2h to obtain the polyimide nanofiber membrane coaxially coated with boehmite, wherein the diameter of the nanofiber is 420nm, the thickness of a boehmite coating layer of the nanofiber is 64nm, the tensile strength is 14.4Mpa, the contact angle of an electrolyte is 5.5 degrees, the thermal deformation temperature under 0.02N is 285 ℃, and the porosity is 70.8%. The morphology of the obtained fiber membrane is shown in figure 4.
Example 5
(1) Weighing 3.12g of anhydrous aluminum chloride, slowly adding the anhydrous aluminum chloride into 80ml of ethanol, and completely dissolving the anhydrous aluminum chloride to obtain 0.3mol/L (the concentration of the part is 0.1 or not) anhydrous aluminum chloride ethanol solution; (2) 2.0g of pyromellitic dianhydride (PMDA) and 1.84g 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, and the PMDA is added in batches under the condition of ice-water bath after the ODA is completely dissolved in the DMF; and after obtaining a polyamic acid solution with moderate viscosity, mechanically stirring for 2h for homogenization, finally filling the polyamic acid solution into a 20ml syringe, and preparing the polyamic acid nanofiber membrane by applying an electrostatic spinning technology, wherein the specific parameters of the electrostatic spinning process are spinning voltage: 17 kV; spinning temperature: room temperature; spinning humidity: 30 percent; diameter of syringe needle: number 12; receiving roller rotating speed: 400 rpm; receiving distance: 20 cm. Firstly, placing the prepared polyamic acid nanofiber membrane in a super clean bench, standing for 12h, then placing the polyamic acid nanofiber membrane in a heating furnace, gradually heating to 300 ℃ at the heating rate of 2 ℃/min, and keeping for 2h to prepare the polyimide nanofiber membrane; (3) weighing 4.49g of potassium hydroxide, dissolving the potassium hydroxide in 80ml of deionized water to prepare 1mol/L potassium hydroxide solution, and then weighing acetic acid to prepare acetic acid solution with the mass fraction of 5%; (4) soaking the polyimide nanofiber membrane in a potassium hydroxide solution for 2min, taking out the polyimide nanofiber membrane, ultrasonically cleaning the polyimide nanofiber membrane for 5min, soaking the polyimide nanofiber membrane in sulfuric acid for 2h, taking out the polyimide nanofiber membrane, ultrasonically cleaning the polyimide nanofiber membrane for 30min, and obtaining the polyimide nanofiber membrane with the surface containing carboxyl active functional groups; (5) measuring ammonia water to prepare 0.04mol/L dilute ammonia water solution; (6) soaking a polyimide nanofiber membrane with a surface containing carboxyl active functional groups in an anhydrous aluminum chloride ethanol solution for 1h, taking out, ultrasonically cleaning for 30min, soaking the polyimide nanofiber membrane in dilute ammonia water for 1h, taking out, ultrasonically cleaning for 30 min; (7) and (3) placing the nanofiber membrane obtained by the treatment in the step (6) in a 300 ℃ oven for heat preservation for 2h to obtain the polyimide nanofiber membrane coaxially coated with boehmite, wherein the diameter of the nanofiber is 395nm, the thickness of a boehmite coating layer of the nanofiber membrane is 35nm, the tensile strength is 10.5Mpa, the contact angle of an electrolyte is 8.8 degrees, the thermal deformation temperature is 290 ℃ at 0.02N, and the porosity is 71.4%. The morphology of the obtained fiber membrane is shown in figure 5; the fiber membrane was embedded with resin and quenched in liquid nitrogen, and the obtained fiber cross-sectional morphology is shown in fig. 6.
Claims (10)
1. The polyimide nanofiber membrane coaxially coated with boehmite is characterized in that the diameter of polyimide nanofibers is 20-600nm, and the surfaces of the nanofibers are coated with boehmite ceramic layers with the thickness of 10-100 nm.
2. The polyimide nanofiber membrane of claim 1, wherein the diameter of the polyimide nanofibers is 30-500nm, and the surface of the nanofibers is coated with a boehmite ceramic layer having a thickness of 20-90 nm.
3. A method for preparing a polyimide nanofiber membrane coaxially coated with boehmite according to claim 1, characterized by comprising the steps of:
a: preparing an aluminum salt alcohol solution with the concentration of 0.05-0.5 mol/L;
b: preparing a polyamic acid solution with the solid content of 8-12% into a polyamic acid nanofiber membrane by adopting an electrostatic spinning method, and carrying out heat treatment to obtain a polyimide nanofiber membrane;
c: b, placing the polyimide nanofiber membrane prepared in the step B in 0.05-6mol/L alkali solution for etching to obtain a polyimide nanofiber membrane with an alkaline hydrolysis ring on the surface;
d: placing the polyimide nanofiber membrane obtained by the treatment in the step C in an acid solution with the mass fraction of 0.3-15% for acidification to obtain the polyimide nanofiber membrane with the nanofiber surface containing carboxyl active functional groups;
e: d, placing the polyimide nanofiber membrane obtained through the treatment in the step D into the aluminum salt alcohol solution prepared in the step A;
f: and E, soaking the nanofiber membrane obtained after the treatment in the step E in 0.002-0.09mol/L of dilute ammonia water, and then carrying out heat treatment on the nanofiber membrane to obtain the polyimide nanofiber membrane coaxially coated with boehmite.
4. The method according to claim 3, wherein the aluminum salt in step A is at least one of aluminum sulfate and anhydrous aluminum chloride, and the alcohol as the solvent is at least one of methanol, ethanol and isopropanol.
5. The method according to claim 3, wherein the concentration of the alcoholic aluminum salt solution in step A is preferably 0.1 to 0.4 mol/L.
6. A method according to claim 3, characterized in that the conditions of the heat treatment in steps B and F are: the temperature is 290 ℃ and 350 ℃, and the temperature is kept for 1-5 h.
7. A method according to claim 3, characterized in that the time for treating the nanofibrous membrane in alkali in step C is 20s-40min, preferably 30s-30 min.
8. The method according to claim 3, wherein the time for treating the nanofiber membrane in acid in step D is 20min-4 h.
9. The method according to claim 3, wherein the time for treating the nanofiber membrane in the aluminum salt alcohol solution in the step E is 20min-4 h.
10. The method according to claim 3, wherein the soaking time of the nanofiber membrane in the dilute ammonia water in the step F is 20min-3 h.
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