CN105406091B - A kind of preparation method of Kynoar heteropoly acid chitosan compound proton exchange membrane - Google Patents
A kind of preparation method of Kynoar heteropoly acid chitosan compound proton exchange membrane Download PDFInfo
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- CN105406091B CN105406091B CN201511000301.5A CN201511000301A CN105406091B CN 105406091 B CN105406091 B CN 105406091B CN 201511000301 A CN201511000301 A CN 201511000301A CN 105406091 B CN105406091 B CN 105406091B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to field of fuel cell technology, specifically discloses a kind of preparation method of Kynoar heteropoly acid chitosan compound proton exchange membrane.This method obtains polyvinylidene fluoride film by electrostatic spinning first, heteropoly acid is coated on by fiber surface by the superpower poly-dopamine of adhesiveness again, then the natural polymer chitosan of lotus positive electricity is filled into the hole of tunica fibrosa, losing issue of the heteropoly acid during battery use can be effectively prevented using electrostatic interactions strong between chitosan and heteropoly acid, the mechanical performance of tunica fibrosa can be also greatly increased simultaneously, and obtained composite membrane is respectively provided with high proton conductivity and mechanical performance at a room temperature and a high temperature.The Kynoar heteropoly acid chitosan compound proton exchange membrane of the present invention is expected to have broad application prospects in Proton Exchange Membrane Fuel Cells field.
Description
Technical field
The present invention relates to field of fuel cell technology, and in particular to a kind of Kynoar-compound matter of heteropoly acid-chitosan
The preparation method of proton exchange.
Background technology
Proton Exchange Membrane Fuel Cells due to have the advantages that can room temperature start, energy conversion efficiency it is high, compact-sized,
Had broad application prospects in terms of electric automobile and compact power.Critical components as Proton Exchange Membrane Fuel Cells
One of, PEM can separate fuel and oxidant, it is allowed to which proton is by but to electronic isolation, and it or electrolyte
With the substrate of catalyst, therefore excellent PEM must have high proton conductivity and excellent mechanical performance.Mesh
The preceding Nafion series perfluorosulfonic acid type PEMs for generally using DuPont to develop, but it is in high temperature and low
It can cause that proton conductivity drastically declines, alcohol-rejecting ability is poor because of strong dehydration under humidity and expensive but limit
The extensive commercialization of Nafion membrane.Thus develop and the substitute of exploitation Nafion membrane is very urgent.
Method of electrostatic spinning is that polymer solution or melt carry out injection stretching by electrostatic interaction and obtain continuous micro-nano
The method of meter level fiber.U.S. Pintauro professor research groups [Macromolecules, 2008,41,4569.] utilize electrostatic
Spining technology is first prepared for the sulfonated polyether sulphone nano fibrous membrane of three-dimensional IPN, then by a kind of excellent inertia of mechanical performance
For polymer-filled into the space of tunica fibrosa to improve alcohol-rejecting ability and mechanical performance, the proton conductivity of final gained film can be with
The commercial films of Nafion 117 are suitable, but the not up to expected perfect condition of the nano shape structure being separated, and to poly- electricity
Relation between electrolyte solution property and electrospinning performance is not inquired into.Domestic that brightness professor research group [Journal of
Membrane Science,2006,281:1.] sulfonated polyether-ether-ketone (SPEEK) film is also prepared for using electrostatic spinning technique, grind
Study carefully the sulfonic acid group shown in electrospinning film aggregation is more easy in preparation process and form ion cluster, but its follow-up study and battery performance
But have not been reported.Zhongshan University Meng Yue medium [Chinese patent ZL201110393309.8] is non-with another kind by sulfonated polymer
Sulfonated polymer carries out electrospinning after dissolving respectively, obtains the heterogeneous electrospun fibers film of chemistry, and the composite membrane has higher
Chemical stability and proton conductivity.As a whole, current research has focused largely on carries out electrospinning to make with sulfonated polymer
Standby PEM, but due to strong repulsion interference between the ionic group on sulfonated polymer molecule be present so that polymer
Show rod-like conformation in the solution, the condition of electrostatic spinning not easy-regulating, it is difficult to large-scale industrial production.
Kynoar (PVDF) is a kind of hemicrystalline fluoropolymer, its excellent combination property, has excellent machine
The advantages that tool performance, electrochemistry and heat endurance, high-k, easy electrostatic spinning film forming, and intensity and pliability after film forming
It is excellent, but PVDF in itself and does not have a proton-conducting, thus by PVDF and inorganic solid proton conductor such as heteropoly acid it is compound be to improve
The effective way of its proton conductivity, but heteropoly acid is soluble in water, in the running of Proton Exchange Membrane Fuel Cells, holds very much
Easily it is lost in the water of electrode generation, therefore, how to solve loss of the heteropoly acid in electrospinning film is that can this kind of film actually answer
Key issue.
The content of the invention
For the shortcomings of the prior art, it is an object of the invention to provide a kind of Kynoar-miscellaneous more
The preparation method of acid-chitosan compound proton exchange membrane.
For achieving the above object, this invention takes following technical measures：
A kind of preparation method of Kynoar-heteropoly acid-chitosan compound proton exchange membrane, this method successively include with
Lower step：
(1) Kynoar is dissolved in mixed organic solvents, it is 5wt%~30wt% to be made into Kynoar concentration
Electrostatic spinning solution；
The Kynoar is preferably trade mark HSV900 Kynoar；
The mixed organic solvents are made up of amide solvent and ketones solvent, wherein, ketones solvent is organic molten in mixing
Volume percent content in agent is 2~40%；
The amide solvent is DMF or DMA, and ketones solvent is acetone or fourth
Ketone；
(2) electrostatic spinning solution obtained by step (1) is added in the syringe of electrostatic spinning apparatus, is in environment temperature
10~30 DEG C, spinning voltage is 20~40kV, and spinning syringe needle flow carries out electrostatic spinning under conditions of being 0.1~1mL/h, obtained
Kynoar electrospun fibers film；
(3) the Tris-HCl buffer solutions that three (methylol) aminomethane concentration are 1~10mmol/L, the Tris- are configured
HCl pH of cushioning fluid is 8.0~9.0, and Kynoar electrospun fibers film obtained by step (2) is soaked in into the Tris-HCl
In buffer solution；
(4) toward obtained by step (3) immersed with being added in the Tris-HCl buffer solutions of Kynoar electrospun fibers film
The ratio of dopamine hydrochloride, dopamine hydrochloride and Tris-HCl buffer solutions is (0.5~8) mg：1mL, room temperature magnetic agitation
After making 10~48h of dopamine oxidation polymerization, the Kynoar electrospun fibers film of poly-dopamine processing is obtained；
(5) it is 2wt% the Kynoar electrospun fibers film of poly- bar of amine processing obtained by step (4) to be added into concentration
In~25wt% heteropoly acid the aqueous solution, 8~24h of soaking at room temperature, take out tunica fibrosa, and through deionized water washing be drying to obtain it is poly-
Vinylidene-heteropoly acid film；The heteropoly acid is phosphotungstic acid, phosphomolybdic acid or silico-tungstic acid；
(6) acetic acid aqueous solution that acetic acid concentration is 0.5wt%~3wt% is configured, then dissolves chitosan in the acetic acid
The chitosan solution that chitosan concentration is 0.2wt%~5wt% is made into the aqueous solution, by Kynoar obtained by step (5)-miscellaneous
More sorrels are added in the chitosan solution, and 15~45min of soaking at room temperature, taking-up is dried, and are repeated immersion, are dried 2~6 times,
Finally it is drying to obtain Kynoar-heteropoly acid-chitosan compound proton exchange membrane.
The present invention compared with prior art, has the following advantages that and beneficial effect：
1st, compared with heteropoly acid directly is doped into Kynoar, the present invention is using a kind of superpower poly- DOPA of adhesiveness
Amine can firmly wrap heteropoly acid on the surface for being attached to polyvinylidene fluoride as intermediate layer (see accompanying drawing 3)；
2nd, compared with inert polymer to be only filled into mechanical performance of the electrospinning fibre membrane pores to increase film, the present invention will
The natural polymer chitosan of lotus positive electricity is filled into the hole of tunica fibrosa, utilizes electrostatic phase strong between chitosan and heteropoly acid
Interreaction force can effectively prevent losing issue of the heteropoly acid during battery use, and also can be significantly after chitosan filling
Increase the mechanical performance of electrospinning film；
3rd, composite membrane prepared by the present invention is due to having the introducing of inorganic solid proton conductor heteropoly acid, proton conductivity height；
4th, preparation technology of the present invention is simple, and the compound proton exchange membrane cost of preparation is far below Nafion commercial membranes, easily production
Industry, the development of fuel cell can be promoted.
In summary, Kynoar-heteropoly acid-chitosan compound proton exchange membrane that prepared by the present invention is expected in proton
Exchange film fuel battery field has broad application prospects.
Brief description of the drawings
Fig. 1 and 2 is respectively the scanning electron microscope (SEM) photograph and energy of Kynoar electrospun fibers film prepared in embodiment 1
Spectrogram；
Fig. 3 and 4 is respectively that Kynoar-phosphotungstic acid tunica fibrosa after phosphotungstic acid prepared in embodiment 1 coats is swept
Retouch electron microscope and energy spectrum diagram.
The diameter of polyvinylidene fluoride film prepared by electrostatic spinning is more uniform as can be seen from Figure 1, and diameter exists substantially
500nm or so；There was only C, F element in energy spectrum diagram detection tunica fibrosa in Fig. 2；As can be seen from Figure 3 after Chitosan-coated, fiber
Coated with uniform have thick shell；The appearance of the element such as obvious P, W, O can prove that clad is in Fig. 4 energy spectrum diagrams
Phosphotungstic acid.
Embodiment
Applicant will be described in further detail to technical scheme in conjunction with specific embodiments below, purpose
It is those skilled in the art is more clearly understood and recognize the application.
Following specific embodiment should not be understood or be construed in any degree to ask the application claims
The limitation of protection domain.
In example 1 below -5：
Raw materials used Kynoar (trade mark HSV900), it is purchased from French A Ke codes company；Chitosan (deacetylation
92.5%, ten thousand) molecular weight is purchased from Zhejiang Ao Xing bio tech ltd for 10.
Other reagents and raw material are conventional commercial commodity.
Embodiment 1
A kind of preparation method of Kynoar-heteropoly acid-chitosan compound proton exchange membrane, step are as follows：
5g Kynoar is dissolved in volume ratio as 9.5:0.5 DMAC N,N' dimethyl acetamide and the mixed solvent of acetone
In, it is made into 10wt% Kynoar electrostatic spinning solution；The electrostatic spinning solution is added to the note of electrostatic spinning apparatus
It it is 25 DEG C, spinning voltage 25kV in environment temperature, spinning syringe needle flow carries out electrostatic under conditions of being 0.3mL/h in emitter
Spinning, obtain Kynoar electrospun fibers film；Configure the Tris- that three (methylol) aminomethane concentration are 4mmol/L
HCl buffer solutions, the Tris-HCl pH of cushioning fluid are 8.5, and Kynoar electrospun fibers film then is immersed in into this
In cushioning liquid, then (ratio is dopamine hydrochloride and Tris-HCl buffer solutions are consolidated toward 4mg/mL is added in the buffer solution
Liquor ratio, following examples are same, do not repeat) dopamine hydrochloride, after room temperature magnetic agitation 24h, obtain poly-dopamine processing
Kynoar electrospun fibers film；The Kynoar electrospun fibers film by poly-dopamine processing is added to concentration again
In 15wt% phosphotungstic acid aqueous solution, soaking at room temperature 12h, to take out tunica fibrosa, and be drying to obtain and gather partially through deionized water washing
PVF-phosphotungstic acid film；The acetic acid aqueous solution that acetic acid concentration is 1wt% is configured, it is water-soluble then to dissolve chitosan in the acetic acid
The chitosan solution that chitosan concentration is 1wt% is made into liquid, then Kynoar-phosphotungstic acid film is added to the chitosan is molten
In liquid, soaking at room temperature 30min, taking-up is dried, and is repeated immersion, is dried 5 times, be finally drying to obtain Kynoar-phosphotungstic acid-
Chitosan compound proton exchange membrane.The performance test results of film are as shown in table 1.
Table 1
As can be seen from Table 1, Kynoar-phosphotungstic acid prepared by the present embodiment-chitosan composite proton is handed over
The proton conductivity for changing film is above the films of Nafion 112 under room temperature and high temperature (80 DEG C), and proton conducts especially at 80 DEG C
Rate is about 3 times of the films of Nafion 112 with the conditions of；While the mechanical performance of the compound proton exchange membrane is relatively not filled by shell and gathered
Kynoar-phosphotungstic acid film of sugar greatly improves.This composite membrane is expected to be used in Proton Exchange Membrane Fuel Cells.
Embodiment 2
A kind of preparation method of Kynoar-heteropoly acid-chitosan compound proton exchange membrane, step are as follows：
5g Kynoar is dissolved in volume ratio as 9.8:0.2 N,N-dimethylformamide and the mixed solvent of butanone
In, it is made into 5wt% Kynoar electrostatic spinning solution；The electrostatic spinning solution is added to the injection of electrostatic spinning apparatus
It is 10 DEG C, spinning voltage 20kV in environment temperature in device, spinning syringe needle flow carries out electrostatic spinning under conditions of being 1mL/h,
Obtain Kynoar electrospun fibers film；The Tris-HCl that three (methylol) aminomethane concentration of configuration are 1mmol/L delays
Fliud flushing, the Tris-HCl pH of cushioning fluid are 8.0, and it is molten that Kynoar electrospun fibers film then is immersed in into the buffering
In liquid, then toward the dopamine hydrochloride that 0.5mg/mL is added in the buffer solution, after room temperature magnetic agitation 10h, poly-dopamine is obtained
The Kynoar electrospun fibers film of processing；The Kynoar electrospun fibers film by poly-dopamine processing adds again
In the phosphomolybdic acid aqueous solution for being 2wt% to concentration, soaking at room temperature 24h, tunica fibrosa is taken out, and be drying to obtain through deionized water washing
Kynoar-phosphomolybdic acid film；The acetic acid aqueous solution that acetic acid concentration is 0.5wt% is configured, then dissolves chitosan in the second
Chitosan concentration is made into aqueous acid and is 0.2wt% chitosan solution, then Kynoar-phosphomolybdic acid film is added to this
In chitosan solution, soaking at room temperature 15min, taking-up is dried, and is repeated immersion, is dried 6 times, is finally drying to obtain polyvinylidene fluoride
Alkene-phosphomolybdic acid-chitosan compound proton exchange membrane.
Embodiment 3
A kind of preparation method of Kynoar-heteropoly acid-chitosan compound proton exchange membrane, step are as follows：
5g Kynoar is dissolved in volume ratio as 6:4 DMF and the in the mixed solvent of butanone,
It is made into 30wt% Kynoar electrostatic spinning solution；The electrostatic spinning solution is added to the syringe of electrostatic spinning apparatus
In, it is 30 DEG C, spinning voltage 40kV in environment temperature, spinning syringe needle flow carries out electrostatic spinning under conditions of being 0.1mL/h,
Obtain Kynoar electrospun fibers film；The Tris-HCl that three (methylol) aminomethane concentration of configuration are 10mmol/L delays
Fliud flushing, the Tris-HCl pH of cushioning fluid are 9.0, and it is molten that Kynoar electrospun fibers film then is immersed in into the buffering
In liquid, then toward the dopamine hydrochloride that 8mg/mL is added in the buffer solution, after room temperature magnetic agitation 48h, obtain at poly-dopamine
The Kynoar electrospun fibers film of reason；The Kynoar electrospun fibers film by poly-dopamine processing is added to again
Concentration is soaking at room temperature 12h in 25wt% silicon tungsten acid solution, takes out tunica fibrosa, and be drying to obtain through deionized water washing
Kynoar-silico-tungstic acid film；The acetic acid aqueous solution that acetic acid concentration is 3wt% is configured, then dissolves chitosan in the acetic acid
Chitosan concentration is made into the aqueous solution and is 5wt% chitosan solution, then Kynoar-silico-tungstic acid film is added to the shell and gathered
In sugar juice, soaking at room temperature 45min, taking-up is dried, and is repeated immersion, is dried 2 times, is finally drying to obtain Kynoar-silicon
Wolframic acid-chitosan compound proton exchange membrane.
Embodiment 4
A kind of preparation method of Kynoar-heteropoly acid-chitosan compound proton exchange membrane, step are as follows：
5g Kynoar is dissolved in volume ratio as 8:2 DMA and the in the mixed solvent of butanone,
It is made into 15wt% Kynoar electrostatic spinning solution；The electrostatic spinning solution is added to the syringe of electrostatic spinning apparatus
In, it is 20 DEG C, spinning voltage 30kV in environment temperature, spinning syringe needle flow carries out electrostatic spinning under conditions of being 0.5mL/h,
Obtain Kynoar electrospun fibers film；The Tris-HCl that three (methylol) aminomethane concentration of configuration are 6mmol/L delays
Fliud flushing, the Tris-HCl pH of cushioning fluid are 8.2, and it is molten that Kynoar electrospun fibers film then is immersed in into the buffering
In liquid, then toward the dopamine hydrochloride that 5mg/mL is added in the buffer solution, after room temperature magnetic agitation 16h, obtain at poly-dopamine
The Kynoar electrospun fibers film of reason；The Kynoar electrospun fibers film by poly-dopamine processing is added to again
Concentration is soaking at room temperature 16h in 10wt% phosphotungstic acid aqueous solution, takes out tunica fibrosa, and be drying to obtain through deionized water washing
Kynoar-phosphotungstic acid film；The acetic acid aqueous solution that acetic acid concentration is 2wt% is configured, then dissolves chitosan in the acetic acid
Chitosan concentration is made into the aqueous solution and is 2wt% chitosan solution, then Kynoar-phosphotungstic acid film is added to the shell and gathered
In sugar juice, soaking at room temperature 25min, taking-up is dried, and is repeated immersion, is dried 3 times, is finally drying to obtain Kynoar-phosphorus
Wolframic acid-chitosan compound proton exchange membrane.
Embodiment 5
A kind of preparation method of Kynoar-heteropoly acid-chitosan compound proton exchange membrane, step are as follows：
5g Kynoar is dissolved in volume ratio as 7:3 DMF and the in the mixed solvent of acetone,
It is made into 25wt% Kynoar electrostatic spinning solution；The electrostatic spinning solution is added to the syringe of electrostatic spinning apparatus
In, it is 25 DEG C, spinning voltage 35kV in environment temperature, spinning syringe needle flow carries out electrostatic spinning under conditions of being 0.8mL/h,
Obtain Kynoar electrospun fibers film；The Tris-HCl that three (methylol) aminomethane concentration of configuration are 2mmol/L delays
Fliud flushing, the Tris-HCl pH of cushioning fluid are 8.2, and it is molten that Kynoar electrospun fibers film then is immersed in into the buffering
In liquid, then toward the dopamine hydrochloride that 2mg/mL is added in the buffer solution, after room temperature magnetic agitation 30h, obtain at poly-dopamine
The Kynoar electrospun fibers film of reason；The Kynoar electrospun fibers film by poly-dopamine processing is added to again
Concentration be 20wt% the phosphomolybdic acid aqueous solution in, soaking at room temperature 8h, take out tunica fibrosa, and through deionized water washing be drying to obtain it is poly-
Vinylidene-phosphomolybdic acid film；The acetic acid aqueous solution that acetic acid concentration is 1.5wt% is configured, then dissolves chitosan in the acetic acid
Chitosan concentration is made into the aqueous solution and is 3wt% chitosan solution, then Kynoar-phosphomolybdic acid film is added to the shell and gathered
In sugar juice, soaking at room temperature 35min, taking-up is dried, and is repeated immersion, is dried 4 times, is finally drying to obtain Kynoar-phosphorus
Molybdic acid-chitosan compound proton exchange membrane.
Table 2 lists the items of Kynoar-heteropoly acid-chitosan compound proton exchange membrane made from embodiment 2-5
Performance indications data.
Table 2
Film properties test condition Unify legislation prepared by various embodiments above is as follows：
(1) proton conductivity：The resistance of film is tested on frequency response analyzer, frequency sweeping ranges 1-
107Hz, AC signal amplitude are 100mV.The film cut (4cm × 5cm) is tested using four electrode AC impedance methods, surveyed
Before examination, membrane sample, which is placed in deionized water at room temperature, reaches saturation.The proton conductivity σ (S/cm) of film is calculated by following formula：
In formula, L and A are respectively the effective cross section product of film to be measured between the spacing of two electrodes and two electrodes, and R is the electricity of film
Resistance, the Nyquist figures as obtained by ac impedance measurement are asked for.
(2) tensile strength and elongation at break：Film is cut into long 50mm, wide 20mm rectangular specimens, in electronics pulling force
Tested on machine using 2mm/min draw speed.
(3) turnover rate of heteropoly acid：The quality for weighing dry film first is W1, then film is soaked in deionized water at room temperature
Taken out after 24h, it is W to weigh its quality after drying to constant weight2, the turnover rate of heteropoly acid calculated by following formula：
Above-described embodiment is better embodiment of the invention, but embodiments of the present invention are not by above-described embodiment
Limitation.Other any changes made without departing from spirit of the invention and principle, modification, replacement, combination, simplification, all should be regarded
For equivalent replacement mode, within the scope of the present invention.
Claims (1)
1. a kind of preparation method of Kynoar-heteropoly acid-chitosan compound proton exchange membrane, this method includes following successively
Step：
（1）Kynoar is dissolved in mixed organic solvents, is made into the electrostatic that Kynoar concentration is 5wt% ~ 30wt%
Spinning solution；
The mixed organic solvents are made up of amide solvent and ketones solvent, wherein, ketones solvent is in mixed organic solvents
Volume percent content be 2 ~ 40%；
The amide solvent is DMF or DMA, and ketones solvent is acetone or butanone；
（2）By step（1）Gained electrostatic spinning solution is added in the syringe of electrostatic spinning apparatus, environment temperature be 10 ~
30 DEG C, spinning voltage be 20 ~ 40 kV, spinning syringe needle flow carry out electrostatic spinning under conditions of being 0.1 ~ 1 mL/h, obtain poly- inclined
PVF electrospun fibers film；
（3）Configuration three（Methylol）Aminomethane concentration is 1 ~ 10 mmol/L Tris-HCl buffer solutions, and the Tris-HCl delays
Fliud flushing pH value is 8.0 ~ 9.0, by step（2）Gained Kynoar electrospun fibers film is soaked in the Tris-HCl buffer solutions
In；
（4）Toward step（3）Gained in the Tris-HCl buffer solutions of Kynoar electrospun fibers film immersed with adding DOPA
The ratio of amine hydrochlorate, dopamine hydrochloride and Tris-HCl buffer solutions is 0.5 ~ 8 mg：1mL, room temperature magnetic agitation make DOPA
After 10 ~ 48h of amine oxidation polymerization, the Kynoar electrospun fibers film of poly-dopamine processing is obtained；
（5）By step（4）A Kynoar electrospun fibers film for poly- bar of amine processing of gained be added to concentration for 2wt% ~
In the 25wt% heteropoly acid aqueous solution, 8 ~ 24h of soaking at room temperature, tunica fibrosa is taken out, and poly- inclined fluorine is drying to obtain through deionized water washing
Ethene-heteropoly acid film；
The heteropoly acid is one kind in phosphotungstic acid, phosphomolybdic acid or silico-tungstic acid；
（6）The acetic acid aqueous solution that acetic acid concentration is 0.5wt% ~ 3wt% is configured, is then dissolved chitosan in the acetic acid aqueous solution
The chitosan solution that chitosan concentration is 0.2wt% ~ 5wt% is made into, by step（5）Gained Kynoar-heteropoly acid film adds
Into the chitosan solution, 15 ~ 45min of soaking at room temperature, taking-up is dried, and is repeated immersion, is dried 2 ~ 6 times, finally dry to gather
Vinylidene-heteropoly acid-chitosan compound proton exchange membrane.
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| CN107093760A (en) * | 2017-05-05 | 2017-08-25 | 湖北工程学院 | The preparation method of Kynoar loading chitosan PEM |
| CN107248584A (en) * | 2017-06-22 | 2017-10-13 | 长春工业大学 | Chitosan phosphotungstic acid ionic liquid compound proton exchange membrane of novel porous structure and preparation method thereof |
| CN107834089B (en) * | 2017-10-19 | 2022-02-18 | 武汉氢阳能源有限公司 | High-temperature proton exchange membrane for membrane fuel cell and preparation method and application thereof |
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| CN111261913B (en) * | 2018-11-30 | 2021-09-03 | 中国科学院大连化学物理研究所 | Composite membrane for alkaline zinc-based flow battery and preparation and application thereof |
| CN110635157B (en) * | 2019-09-25 | 2022-06-14 | 东北大学 | Preparation method of anion exchange membrane with sandwich structure |
| CN114447382B (en) * | 2020-10-31 | 2024-05-31 | 中国石油化工股份有限公司 | Proton exchange membrane containing concentric shaft microstructure and preparation method thereof |
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