CN104752665A - Method for preparing polyimide porous nanofiber electrode diaphragm - Google Patents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a method for preparing a polyimide porous nanofiber electrode diaphragm. The method comprises the following steps: carrying out condensation reaction by adopting binary organic amine and binary organic acid anhydride in an organic solvent, thereby obtaining a polyamide acid solution; adding a soluble metal salt to prepare a spinning precursor, preparing a polyamide acid-metal salt electrostatic spinning fiber diaphragm by virtue of high-voltage electrostatic spinning, and performing thermal imidization treatment, thereby obtaining a polyimide-metallic oxide fiber composite diaphragm; and dissolving the composite diaphragm in an inorganic acid aqueous solution for performing acid treatment, so that metallic oxide nanoparticles are converted into soluble metal salts so as to be dissolved in the inorganic acid aqueous solution so as to obtain the polyimide nano/micron porous fiber diaphragm. The method has the advantages that according to the polyimide nano/micron porous fiber diaphragm, the mechanical strength, thermal stability, liquid holdup, permeability, wettability and migration rate of conductive ions of the diaphragm can be effectively improved, and the liquid junction resistance of the diaphragm and electrolyte and the contact resistance of the diaphragm and the electrode can be reduced, so that the electrochemical performance of a supercapacitor is improved.
Description
Technical field
The invention belongs to field of nano material preparation, particularly a kind of preparation method of ultracapacitor polyimide foraminous nano micron fibre electrode diaphragm.
Background technology
Electrode diaphragm is one of important component part of ultracapacitor, be placed between capacitor the two poles of the earth, both positive and negative polarity is separated, prevent the two poles of the earth active material from directly contacting and causing short circuit, do not stop again the migration of capacitor intermediate ion simultaneously, ion is allowed freely to pass through, this just requires that barrier film has certain fibre diameter, aperture and pore-size distribution, and there is stable physical property and chemical property, and little, the electric starting performance of internal resistance is good etc., the barrier film of excellent performance has important effect to the chemical property such as high-power discharge and recharge improving ultracapacitor.
At present, the perforated membrane such as polyethylene, polypropylene of electrode diaphragm materials'use, because melt temperature is low, pyrocondensation is than high and porosity is low, in the situation such as that ultracapacitor produces in high-power charge and discharge process is overheated, overcharge, barrier film pyrocondensation can be caused even to melt causes electrode diaphragm to break, and easily the accident such as thermal runaway and blast occurs.
CN 101974828A and CN 102251307A adopts method of electrostatic spinning to prepare Fypro film, it has that tear resistance is strong, porosity is high, can the feature of high-low temperature resistant and mechanicalness excellence, but the smooth atresia of fiber itself, thus make that the liquid holdup of barrier film is low, ion permeability is not enough.
CN 102277648A adopts the mixed solution of inorganic nano-particle and polyamic acid through electrostatic spinning, machinery roll-in and high-temperature hot imidization obtain inorganic/organic composite polyimide based nano-fiber film, it has the feature such as high porosity and mechanical strength, but inorganic nano-particle add the spinnability and barrier film insulating properties that reduce polymer, cause that electrospun fibers pore-size distribution is uneven, leakage current increases and organic electrolyte can wettability poor.
CN 104213333A adopts method of electrostatic spinning to prepare polyimides/polyolefin composite fiber film, then control heat treatment is carried out, polyolefine fiber is heated micro-melting, fusion point is formed between polyimides superfine fibre, obtained polyimides/polyolefin composite fiber the film with cross-linked structure, to improve mechanical property and the dimensional stability of tunica fibrosa, but the secondary electrostatic spinning masking that the method adopts, technical process poor controllability, the mechanical performance of polyimide diaphragm and chemical property were deteriorated along with the second adding of component.
Summary of the invention
The technical problem to be solved in the present invention be to provide that a kind of ion percent of pass is high, liquid holdup is high, contact resistance is low, mechanical strength is good and Heat stability is good the preparation method of polyimide foraminous nanofiber electrode barrier film.
Technical solution of the present invention is:
A preparation method for polyimide foraminous nanofiber electrode barrier film, its concrete steps are as follows:
1.1, the preparation of polyamic acid solution dimension
Binary organic amine and binary organic acid acid anhydride is adopted to carry out condensation reaction in organic solvent, wherein, the mol ratio of organic two ammoniums and binary organic acid acid anhydride is 0.5:1 ~ 1.5:1, organic solvent addition is 4 times ~ 10 times of organic diamine and binary organic acid acid anhydride total weight, setting-up point is-5 DEG C ~ 10 DEG C, condensation reaction time is 6h ~ 24h, obtained polyamic acid solution;
Described binary organic acid acid anhydride is at least one in cyclobutanetetracarboxylic dianhydride, pyromellitic acid anhydride, bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, Bisphenol A Type Diether Dianhydride;
Described organic diamine is 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, p-phenylenediamine (PPD), m-phenylene diamine (MPD), 3,3 '-diphenyl sulphone (DPS) diamines, 4,4 '-diphenyl sulphone (DPS) diamines, hexamethylene diamine, trimethylhexamethylenediamine, benzidine, 2, at least one in 2 '-bis-[4-(4 amino-benzene oxygen) phenyl] propane;
Described organic solvent is at least one in DMF, DMA, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), carrene, chloroform, dimethyl sulfoxide (DMSO), oxolane, ethyl acetate, trifluoroacetic acid, acetone;
The preparation of 1.2, polyamic acid-slaine electrospun fibers film
In polyamic acid solution prepared by step 1.1, add soluble metallic salt preparation spinning precursor, then prepare polyamic acid-slaine electrospun fibers film by high-voltage electrostatic spinning;
Described soluble metallic salt is at least one in zinc acetate, manganese acetate, Schweinfurt green, cobalt acetate, nickel acetate, stannic chloride, aluminium chloride, iron chloride, zinc chloride, cobalt chloride, silver nitrate, ferrocene, cuprous acetate, dichloro-dimethyl titanium, diethyl zinc, tetra-n-butyl titanate, ethylmagnesium bromide;
In described spinning precursor, polyamic acid and soluble metallic salt mass ratio are 5:1 ~ 1:1;
1.3, the preparation of polyimide-metal oxide fibre composite membrane
Polyamic acid-slaine electrospun fibers film is carried out sub-hot amination treatment, makes the slaine of polyamic acid-slaine tunica fibrosa change metal oxide nanoparticles into, obtain polyimide-metal oxide fibre composite membrane;
Described hot imidization process adopts gradient increased temperature, heats up with the heating rate of 2 DEG C/min ~ 5 DEG C/min; First by room temperature to 100 DEG C, isothermal reaction 0.5h ~ 1.5h; Then 200 DEG C are warming up to by 100 DEG C, isothermal reaction 0.5h ~ 1.5h; Finally be warming up to 350 DEG C by 200 DEG C, isothermal reaction 0.5h ~ 1.5h;
1.4, the preparation of um porous tunica fibrosa received by polyimides
Polyimide-metal oxide fibre composite membrane is dissolved in inorganic acid aqueous solution and carries out acid treatment, make metal oxide nanoparticles in polyimide-metal oxide fibre composite membrane change soluble metallic salt into and be dissolved in inorganic acid aqueous solution, obtain polyimides and receive um porous tunica fibrosa.
The mass percent concentration of polyamic acid solution described in step 1.2 is 5.0% ~ 20.0%.
The mass percent concentration of polyamic acid solution described in step 1.2 is 10.0% ~ 17.0%.
Described electrostatic spinning voltage 10.0kV ~ 30.0kV, spinning spacing is 10.0cm ~ 20.0cm, and the electrostatic spinning time is 30min ~ 120min.
Described inorganic acid is at least one in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid.
Described inorganic acid aqueous solution concentration is 0.01mol/L ~ 1.0mol/L.
Polyamide and soluble metallic salt are dissolved in appropriate solvent and are mixed with spinning presoma by the present invention, utilize high-voltage electrostatic spinning to obtain polyamic acid-slaine electrospun fibers film; Polyamic acid-slaine electrospun fibers film carries out hot imidization process, and slaine changes metal oxide nanoparticles into simultaneously, obtains polyimide-metal oxide fibre composite membrane; By polyimide-metal oxide fibre composite membrane with carrying out the pore of acid treatment stripping metal oxide, obtaining polyimides and receiving um porous tunica fibrosa.Its beneficial effect is:
1, polyimides has good physical and chemical stability and mechanical strength, can guarantee that, under heat treatment and acidic treatment condition, the appearance structure of polyimides nano micron fibre film can not be influenced.
2, in polyimide-metal oxide fibre composite membrane, metal oxide nanoparticles changes soluble metallic salt into and is dissolved in dilute acid soln, hole is formed in polyimide nano-fiber, and the good acid resistance of polyimides makes it not be subject to acid to destroy, and keep good appearance structure, thus obtain porous polyimide and receive um porous tunica fibrosa; Can by regulating the content of soluble metallic salt in spinning precursor, obtain the metal oxide of different-grain diameter size and content, then logical poly-metal deoxide leaching prepares the different polyimide foraminous nano micron fibre of specific surface area and porosity, easily realizes porous nano micron fibre structural controllability.
3, polyimide foraminous nano micron fibre barrier film can effectively improve the mechanical strength of barrier film, thermal stability, liquid holdup, permeability, can the migration rate of wettability and conductive ion, reduce the liquid connecting resistance of barrier film and electrolyte, and the contact resistance of barrier film and electrode, thus the chemical properties such as the power density of raising ultracapacitor, capacity, high-temperature stability and service life cycle.
Accompanying drawing explanation
Fig. 1 is that the scanning electron microscope diagram of um porous fibre diaphragm received by the polyimides of the present invention's (corresponding embodiment 1).
Fig. 2 is that the cyclic voltammetry curve of um porous fibre diaphragm ultracapacitor received by the polyimides of the present invention's (corresponding embodiment 2).
Fig. 3 is that um porous fibre diaphragm ultracapacitor AC impedance curve received by the polyimides of this (corresponding embodiment 3).
Embodiment
Embodiment 1
The preparation of 1, polyamic acid-zinc acetate electrospun fibers
By 5.0g pyromellitic acid anhydride, 5.0g 3,4 '-diaminodiphenyl ether is dissolved in (mass ratio is 1:1:8) in 40.0g DMF, then at-5 DEG C ~ 0 DEG C, reacts 24h, obtains the polyamic acid solution that mass fraction is 17%;
The preparation of 2, polyamic acid-zinc acetate electrospun fibers film
2.0g zinc acetate is joined after stirring 6h in the 12.0g polyamic acid solution that step 1 prepares and carry out electrostatic spinning, needle diameter 1.6 millimeters, copper mesh is receiver, voltage 10kV, syringe needle and receiver spacing (spinning spacing) are 10cm, obtain polyamic acid-zinc acetate electrospun fibers on the receiver, after electrostatic spinning 30min, by for subsequent use for polyamic acid-zinc acetate electrospun fibers 40 DEG C vacuumize 24h;
The preparation of 3, polyimides-zinc oxide fiber composite membrane
Polyamic acid-zinc acetate electrospun fibers film is carried out sub-hot amination treatment, makes the zinc acetate of polyamic acid-zinc acetate tunica fibrosa change zinc oxide nano-particle into, obtain polyimides-zinc oxide fiber composite membrane;
Hot imidization process adopts gradient increased temperature: heat up with the heating rate of 2 DEG C/min; First by room temperature to 100 DEG C, isothermal reaction 0.5h; Then 200 DEG C are warming up to by 100 DEG C, isothermal reaction 1.5h; Finally be warming up to 350 DEG C by 200 DEG C, isothermal reaction 0.5h;
4, the preparation of polyimide foraminous nano micron fibre film
Polyimides-zinc oxide fiber is placed in the hydrochloric acid solution that concentration is 1mol/L, then mechanical agitation, change hydrochloric acid solution, till in solution, inspection does not measure metal ion, after the polyimide foraminous nano micron fibre film deionized water obtained is washed till neutrality, for subsequent use after 80 DEG C of vacuumize 24h, recording its BET specific surface area is 275.1m
2/ g.
With 0.1 μm of thick active carbon of aluminium foil surface that is overlying on for electrode, cut into the electrode slice that diameter is 13.8mm, with polyimide foraminous nano micron fibre film for barrier film, at 120 DEG C after vacuumize 24h, 1.0mol/L tetraethylammonium tetrafluoroborate/propene carbonate is electrolyte, be assembled into button-shaped ultracapacitor, test chemical property is as shown in table 1.Fig. 1 is that the scanning electron microscope diagram of um porous fibre diaphragm received by polyimides, demonstrates obvious porous nano micron fibre feature.
Embodiment 2
The preparation of 1, polyamic acid-diethyl zinc electrospun fibers
5.0g p-phenylenediamine (PPD), 25.0g bibenzene tetracarboxylic dianhydride are dissolved in (mass ratio is 1:5:40) in 200g DMA, then at 0 DEG C ~ 3 DEG C, react 12h, obtain the polyamic acid solution that mass fraction is 13%;
The preparation of 2, polyamic acid-diethyl zinc electrospun fibers film
0.2g diethyl zinc is joined after stirring 6h in the 8.0g polyamic acid solution that step 1 prepares and carry out electrostatic spinning, needle diameter 1.6 millimeters, copper mesh is receiver, voltage 20kV, syringe needle and receiver spacing are 18cm, obtain polyamic acid-diethyl zinc electrospun fibers on the receiver, after electrostatic spinning 60min, by for subsequent use for polyamic acid-slaine electrospun fibers 40 DEG C vacuumize 24h.
The preparation of 3, polyimides-zinc oxide fiber composite membrane
Polyamic acid-diethyl zinc electrospun fibers film is carried out sub-hot amination treatment, makes the diethyl zinc of polyamic acid-diethyl zinc tunica fibrosa change zinc oxide nano-particle into, obtain polyimides-zinc oxide fiber composite membrane;
Hot imidization process adopts gradient increased temperature: heat up with the heating rate of 3 DEG C/min; First by room temperature to 100 DEG C, isothermal reaction 1.0h; Then 200 DEG C are warming up to by 100 DEG C, isothermal reaction 0.5h; Finally be warming up to 350 DEG C by 200 DEG C, isothermal reaction 1.5h;
4, the preparation of polyimide foraminous nano micron fibre film
Polyimide-metal oxide fibre is placed in the sulfuric acid solution that concentration is 0.03mol/L, then mechanical agitation, change sulfuric acid solution, till in solution, inspection does not measure metal ion, the polyimide foraminous nano micron fibre film deionized water obtained is washed till neutrality, by for subsequent use after polyimide foraminous nano micron fibre film 80 DEG C of vacuumize 24h of obtaining, recording its BET specific surface area is 262.7m
2/ g.
With 0.1 μm of thick active carbon of aluminium foil surface that is overlying on for electrode, cut into the electrode slice that diameter is 13.8mm, the fine film of micron is received for barrier film with polyimide foraminous, at 120 DEG C after vacuumize 24h, 1.0mol/L tetraethylammonium tetrafluoroborate/propene carbonate is electrolyte, be assembled into button-shaped ultracapacitor, test chemical property is as shown in table 1.Fig. 2 is the ultracapacitor multiplying power discharging property curve of polyimide foraminous nano micron fibre barrier film, and result demonstrates good high-power charge-discharge performance.
Embodiment 3
The preparation of 1, polyamic acid-ethylmagnesium bromide electrospun fibers
By 6.0g 4,4 '-diphenyl sulphone (DPS) diamines, 5.0g bibenzene tetracarboxylic dianhydride are dissolved in (mass ratio is 1.2:1:20) in 100g dimethyl sulfoxide (DMSO), then at 5 DEG C ~ 10 DEG C, react 6h, obtain the polyamic acid solution that mass fraction is 10%;
The preparation of 2, polyamic acid-ethylmagnesium bromide electrospun fibers film
1.0g ethylmagnesium bromide is joined after stirring 6h in the 20g polyamic acid solution that step 1 prepares and carry out electrostatic spinning, needle diameter 1.6 millimeters, copper mesh is receiver, voltage 15kV, syringe needle and receiver spacing are 15cm, obtain polyamic acid-ethylmagnesium bromide electrospun fibers on the receiver, after electrostatic spinning 120min, by for subsequent use for polyamic acid-ethylmagnesium bromide electrospun fibers 40 DEG C vacuumize 24h.
The preparation of 3, polyimides-magnesia fibers composite membrane
Polyamic acid-ethylmagnesium bromide electrospun fibers film is carried out sub-hot amination treatment, makes the ethylmagnesium bromide of polyamic acid-ethylmagnesium bromide tunica fibrosa change bitter earth nano particle into, obtain polyimides-magnesia fibers composite membrane;
Hot imidization process adopts gradient increased temperature: heat up with the heating rate of 5 DEG C/min; First by room temperature to 100 DEG C, isothermal reaction 1.5h; Then 200 DEG C are warming up to by 100 DEG C, isothermal reaction 1h; Finally be warming up to 350 DEG C by 200 DEG C, isothermal reaction 1h;
4, the preparation of polyimide foraminous nano micron fibre film
Polyimides-magnesia fibers is placed in the perchloric acid solution that concentration is 0.01mol/L, then mechanical agitation, change perchloric acid solution, till in solution, inspection does not measure metal ion, the polyimide foraminous nano micron fibre film deionized water obtained is washed till neutrality, by for subsequent use after polyimide foraminous nano micron fibre film 80 DEG C of vacuumize 24h of obtaining, recording its BET specific surface area is 254.5m
2/ g.
With 0.1 μm of thick active carbon of aluminium foil surface that is overlying on for electrode, cut into the electrode slice that diameter is 13.8mm, the fine film of micron is received for barrier film with polyimide foraminous, at 120 DEG C after vacuumize 24h, 1.0mol/L tetraethylammonium tetrafluoroborate/propene carbonate is electrolyte, be assembled into button-shaped ultracapacitor, test chemical property is as shown in table 1.Fig. 3 is the charge-discharge test curve under the different electric current of ultracapacitor of polyimide foraminous nano micron fibre barrier film, demonstrates minimum internal resistance and high-power charge-discharge characteristic.
Comparative example 1
The preparation of polyimides nano micron fibre barrier film:
P-phenylenediamine (PPD), bibenzene tetracarboxylic dianhydride are dissolved in N, in N-dimethylacetylamide (mass ratio is 1:2:20), then at 0 DEG C ~ 3 DEG C, 12h is reacted, obtain mass fraction be 13% polyamic acid solution carry out electrostatic spinning, needle diameter 1.6 millimeters, copper mesh is receiver, voltage 20kV, syringe needle and receiver spacing are 18cm, obtain polyamic acid electrospun fibers on the receiver, after electrostatic spinning 60min, by for subsequent use for polyamic acid electrospun fibers 40 DEG C of vacuumize 24h.
Polyamic acid electrospun fibers is carried out hot imidization: heating rate 3 DEG C/min, room temperature-100 DEG C of reaction time 1.0h, 100 DEG C-200 DEG C isothermal reaction 0.5h, 200 DEG C-350 DEG C reaction 1.0h.For subsequent use after obtaining polyimides nano micron fibre film 80 DEG C of vacuumize 24h, recording its BET specific surface area is 82.6m
2/ g.With 0.1 μm of thick active carbon of aluminium foil surface that is overlying on for electrode, cut into the electrode slice that diameter is 13.8mm, the fine film of micron is received for barrier film with polyimides, at 120 DEG C after vacuumize 24h, 1.0mol/L tetraethylammonium tetrafluoroborate/propene carbonate is electrolyte, be assembled into button-shaped ultracapacitor, test chemical property is as shown in table 1.
Comparative example 2
With commercial polypropylene diaphragm paper for barrier film, recording its BET specific surface area is 48.3m
2/ g, the active carbon (0.1 μm thick, diameter be 13.8mm) being overlying on aluminium foil surface is electrode, and 1.0mol/L tetraethylammonium tetrafluoroborate/acetonitrile is electrolyte, is assembled into button-shaped ultracapacitor, and test chemical property is as shown in table 1.
The chemical property of table 1 Different electrodes barrier film ultracapacitor
Polyamide receives the power-performance of um porous fibre diaphragm ultracapacitor, internal resistance and efficiency for charge-discharge as can be seen from Table 1, the comprehensive electrochemical that micron nonporous fiber barrier film and commercial polypropylene diaphragm paper had is received compared with polyamide, ultracapacitor internal resistance be can obviously reduce, its power density and efficiency for charge-discharge improved.
Claims (6)
1. a preparation method for polyimide foraminous nanofiber electrode barrier film, is characterized in that:
Concrete steps are as follows:
1.1, the preparation of polyamic acid solution dimension
Binary organic amine and binary organic acid acid anhydride is adopted to carry out condensation reaction in organic solvent, wherein, the mol ratio of organic two ammoniums and binary organic acid acid anhydride is 0.5:1 ~ 1.5:1, organic solvent addition is 4 times ~ 10 times of organic diamine and binary organic acid acid anhydride total weight, setting-up point is-5 DEG C ~ 10 DEG C, condensation reaction time is 6h ~ 24h, obtained polyamic acid solution;
Described binary organic acid acid anhydride is at least one in cyclobutanetetracarboxylic dianhydride, pyromellitic acid anhydride, bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, Bisphenol A Type Diether Dianhydride;
Described organic diamine is 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, p-phenylenediamine (PPD), m-phenylene diamine (MPD), 3,3 '-diphenyl sulphone (DPS) diamines, 4,4 '-diphenyl sulphone (DPS) diamines, hexamethylene diamine, trimethylhexamethylenediamine, benzidine, 2, at least one in 2 '-bis-[4-(4 amino-benzene oxygen) phenyl] propane;
Described organic solvent is at least one in DMF, DMA, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), carrene, chloroform, dimethyl sulfoxide (DMSO), oxolane, ethyl acetate, trifluoroacetic acid, acetone;
The preparation of 1.2, polyamic acid-slaine electrospun fibers film
In polyamic acid solution prepared by step 1.1, add soluble metallic salt preparation spinning precursor, then prepare polyamic acid-slaine electrospun fibers film by high-voltage electrostatic spinning;
Described soluble metallic salt is at least one in zinc acetate, manganese acetate, Schweinfurt green, cobalt acetate, nickel acetate, stannic chloride, aluminium chloride, iron chloride, zinc chloride, cobalt chloride, silver nitrate, ferrocene, cuprous acetate, dichloro-dimethyl titanium, diethyl zinc, tetra-n-butyl titanate, ethylmagnesium bromide;
In described spinning precursor, polyamic acid and soluble metallic salt mass ratio are 5:1 ~ 1:1;
1.3, the preparation of polyimide-metal oxide fibre composite membrane
Polyamic acid-slaine electrospun fibers film is carried out sub-hot amination treatment, makes the slaine of polyamic acid-slaine tunica fibrosa change metal oxide nanoparticles into, obtain polyimide-metal oxide fibre composite membrane;
Described hot imidization process adopts gradient increased temperature, heats up with the heating rate of 2 DEG C/min ~ 5 DEG C/min; First by room temperature to 100 DEG C, isothermal reaction 0.5h ~ 1.5h; Then 200 DEG C are warming up to by 100 DEG C, isothermal reaction 0.5h ~ 1.5h; Finally be warming up to 350 DEG C by 200 DEG C, isothermal reaction 0.5h ~ 1.5h;
1.4, the preparation of um porous tunica fibrosa received by polyimides
Polyimide-metal oxide fibre composite membrane is dissolved in inorganic acid aqueous solution and carries out acid treatment, make metal oxide nanoparticles in polyimide-metal oxide fibre composite membrane change soluble metallic salt into and be dissolved in inorganic acid aqueous solution, obtain polyimides and receive um porous tunica fibrosa.
2. the preparation method of polyimide foraminous nanofiber electrode barrier film according to claim 1, is characterized in that: the mass percent concentration of polyamic acid solution described in step 1.2 is 5.0% ~ 20.0%.
3. the preparation method of polyimide foraminous nanofiber electrode barrier film according to claim 1, is characterized in that: the mass percent concentration of polyamic acid solution described in step 1.2 is 10.0% ~ 17.0%.
4. the preparation method of polyimide foraminous nanofiber electrode barrier film according to claim 1, is characterized in that: described electrostatic spinning voltage 10.0kV ~ 30.0kV, and spinning spacing is 10.0cm ~ 20.0cm, and the electrostatic spinning time is 30min ~ 120min.
5. the preparation method of polyimide foraminous nanofiber electrode barrier film according to claim 1, is characterized in that: described inorganic acid is at least one in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid.
6. the preparation method of polyimide foraminous nanofiber electrode barrier film according to claim 1, is characterized in that: described inorganic acid aqueous solution concentration is 0.01mol/L ~ 1.0mol/L.
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