CN104300164B - A kind of preparation method of compound proton exchange membrane - Google Patents
A kind of preparation method of compound proton exchange membrane Download PDFInfo
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- CN104300164B CN104300164B CN201410605875.4A CN201410605875A CN104300164B CN 104300164 B CN104300164 B CN 104300164B CN 201410605875 A CN201410605875 A CN 201410605875A CN 104300164 B CN104300164 B CN 104300164B
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
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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
- H01M50/411—Organic material
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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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides the preparation method of a kind of compound proton exchange membrane, comprise the following steps: the solution of the acid solution of chitosan with CNT class fluid is mixed, obtains mixed solution；Described mixed solution is dried, obtains desciccator diaphragm；Described desciccator diaphragm is carried out alkali cleaning, then is washed to neutrality, then cross-linking reaction occurs under the effect of cross-linking agent, obtains compound proton exchange membrane.The application is during preparing compound proton exchange membrane, use CNT class fluid that chitosan is modified, owing to introducing group on the organic molecule long-chain of CNT class flow surface grafting, the proton conductivity of compound proton exchange membrane can be improved, the mobility of CNT class fluid makes CNT be uniformly dispersed in chitosan basal body simultaneously, achieve the plasticising to chitosan basal body, toughness reinforcing and potentiation, make compound proton exchange membrane have good pliability and intensity.
Description
Technical field
The present invention relates to fuel battery proton exchange film technical field, particularly relate to a kind of compound matter
The preparation method of proton exchange.
Background technology
Chitosan chemical name is [Isosorbide-5-Nitrae]-2-amino-2-deoxidation-β-D glucosan, and it is that chitin takes off
Remove the product after part acetyl group, be a kind of common natural biological copolymer.Chitosan has
Excellent film property, avirulence, antibiotic property and good biocompatibility and degradability,
It is widely used in the fields such as food, medicine, water process, cosmetics and functional material.Chitosan
As a kind of PEM having most research potential, it has cheap, environment friendly,
The feature that suitable environment is the most fastidious and methanol permeability is low.Chitosan is due on molecular structure simultaneously
Rich in-OH and-NH2, controlled chemical modification can be realized by it is carried out MOLECULE DESIGN, relevant
Research becomes focus in recent years.As PEM, there is proton conductivity in chitosan
Low, the pliability of film, mechanical performance and the not enough problem of heat stability.
Stability that composite organic-inorganic material combines inorganic material because of it and organic material
Pliability is it is considered to be used as to improve one of chitosan performance most efficient method.Research shows,
The performance of chitosan/inorganic particulate laminated film be heavily dependent on the filling of inorganic particulate,
Dispersed, particle diameter and the orientation in chitosan basal body thereof.But the nothing of non-surface modification
Machine nanoparticle is difficult to disperse in chitosan basal body, and interfacial adhesion effect simultaneously is more weak, compound
Film performance is difficult to reach to use requirement.
Class fluid is a kind of under conditions of normal temperature and pressure, without any solvent, presents single group
The material of the similar fluid state divided.Class fluid concept is proposed by Giannelis et al., logical
Cross covalent bond or ion exchange long-chain Organic substance in particle surface grafting so that it is at macroscopically table
Reveal the character of fluid.The class fluidisation of material as a kind of material surface modifying technology, due to
The peculiar property of prepared class fluid nanoparticle, there is huge potential using value,
In the self assembly of nanoparticle, the proton membrane of fuel cell, the toughness reinforcing increasing of plasticising of macromolecular material
By force, each neck such as nano composite material, new reaction medium, high temperature lubricating and emr fluid
Territory is expected to be broken through and apply.
Summary of the invention
Present invention solves the technical problem that the preparation side being to provide a kind of compound proton exchange membrane
Method, the proton conduction energy of compound proton exchange membrane prepared by the preparation method provided according to the application
Power, pliability are higher with mechanical performance.
In view of this, this application provides the preparation method of a kind of compound proton exchange membrane, including
Following steps:
The solution of the acid solution of chitosan with CNT class fluid is mixed, obtains mixing molten
Liquid；
Described mixed solution is dried, obtains desciccator diaphragm；
Described desciccator diaphragm is carried out alkali cleaning, then is washed to neutrality, then under the effect of cross-linking agent
Crosslink reaction, obtain compound proton exchange membrane.
Preferably, the acid solution of described chitosan is the acetum of chitosan, and described shell gathers
In the acetum of sugar, the content of chitosan is 1.0wt%～3.0wt%, the matter of described acetum
Amount mark is 1.5wt%～2.5wt%.
Preferably, the ethanol that solution is CNT class fluid of described CNT class fluid is molten
Liquid.
Preferably, the solution of described alkali cleaning is sodium hydroxide solution or potassium hydroxide solution.
Preferably, described cross-linking agent be concentration be the sulphuric acid of 0.1～1.0mol/L.
Preferably, also include after described cross-linking reaction:
The film obtained after cross-linking reaction is dried.
Preferably, the content of CNT class fluid described in described compound proton exchange membrane is
0.5wt%～10wt%.
Preferably, the thickness of described compound proton exchange membrane is 40～60 μm.
Preferably, the molecular weight of described chitosan is 500,000 or 1,000,000.
Preferably, the grafting content of organics of described CNT class fluid is
60wt%～70wt%.
This application provides the preparation method of a kind of compound proton exchange membrane.Preparing composite proton
During exchange membrane, first the application has prepared the mixing of chitosan and CNT class fluid
Solution, then mixed solution is dried, obtain the chitosan containing a small amount of acid solution and carbon
The film of nanometer tubing fluid, cross-links after finally the alkali cleaning of above-mentioned film elder generation being washed to neutrality again,
I.e. obtain compound proton exchange membrane.The application uses CNT class fluid to change chitosan
Property, owing to introducing-SO on the organic molecule long-chain of CNT class flow surface grafting3 -Base
Group, can significantly improve the proton conductivity of compound proton exchange membrane, simultaneously CNT class fluid
Mobility promote CNT dispersed in chitosan basal body, given full play to it to shell
The plasticising of polysaccharide base material, toughness reinforcing and potentiation, and chitosan carry out being cross-linked to form netted
Structure, is effectively increased the stability of PEM, therefore, compound matter prepared by the application
The proton conductivity of proton exchange, pliability and intensity are significantly improved.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment to the preferred embodiment of the invention
It is described, but it is to be understood that these describe simply as further illustrating inventive feature
With advantage rather than limiting to the claimed invention.
The embodiment of the invention discloses the preparation method of a kind of compound proton exchange membrane, including following
Step:
The solution of the acid solution of chitosan with CNT class fluid is mixed, obtains mixing molten
Liquid；
Described mixed solution is dried, obtains desciccator diaphragm；
Described desciccator diaphragm is carried out alkali cleaning, then is washed to neutrality, then under the effect of cross-linking agent
Crosslink reaction, obtain compound proton exchange membrane.
The application uses CNT class fluid to be modified chitosan, due to CNT class
The character of fluid, makes the proton-conducting of the compound proton exchange membrane of preparation, pliability and intensity
It is obtained for and significantly improves.
According to the present invention, first by the solution of the acid solution of chitosan Yu CNT class fluid
Mixing, obtains mixed solution.During preparation mixed solution, the acidity of described chitosan
Solution specifically can configure as follows: preparation acid solution, adds in described acid solution
Enter chitosan, obtain the acid solution of chitosan.Chitosan in the acid solution of described chitosan
Content be preferably 1.0wt%～3.0wt%.Acid solution described herein is preferably acetic acid.
In order to ensure that chitosan can fully dissolve, the concentration of described acid solution is preferably
1.5wt%～2.5wt%.Herein described chitosan preferably molecular weight is 500,000, deacetylation
Be 85% chitosan or molecular weight be 1,000,000, deacetylation is the chitosan of 90%.
CNT class fluid described herein is CNT class fluid of the prior art,
The application is preferably according to method system disclosed in the patent of Application No. 200610124455.X
Standby.The preparation process of described CNT class fluid can be divided into three below step: CNT
Surface oxidation, carbon nano tube surface after oxidation be grafted organic cation salt and carbon nanometer
Manage organic cation salt and nonylphenol polyoxyethylene ether sulfate to carry out ion exchange and connect long-chain and have
Machine anion salt.The grafting content of organics of described CNT class fluid is preferably
60wt%～70wt%.According to the present invention, the preparation of the solution of described CNT class fluid is concrete
For: CNT class fluid is dissolved in solution, ultrasonic disperse, obtains CNT class stream
The solution of body.Above-mentioned solution is preferably dehydrated alcohol, and the time of described ultrasonic disperse is preferably
20～40min.The solution of acid solution with CNT class fluid in order to make chitosan mixes all
Even, after above two solution is preferably mixed by the application, first carry out ultrasonic agitation and carry out ultrasonic again
Deaeration；The time of described ultrasonic agitation is preferably 0.5h～1.5h, and the time of described ultrasonic deaeration is excellent
Elect 20min～40min as.
According to the present invention, after mixed solution has been prepared, then described mixed solution is dried
Dry, obtain desciccator diaphragm.The temperature of described drying is preferably 30～50 DEG C, and the time of drying is preferred
For 18h～36h.Described desciccator diaphragm is that the shell of the mix homogeneously containing a small amount of remaining acid solution gathers
Sugar and the film of CNT class fluid.
In the application, as it has been described above, described desciccator diaphragm is containing chitosan and CNT class stream
The composite membrane of body, in order to improve the proton-conducting of composite membrane, mechanical property and stability, this
Chitosan cross-linking agent need to be cross-linked by application.According to the present invention, need first to be dried described
Film immerses in alkaline solution and carries out alkali cleaning, and is washed to neutrality, makes in alkaline solution and desciccator diaphragm
The acid solution of middle residual, to prevent remaining acid solution from making the compound proton exchange membrane of preparation
Become impact.The effect of described alkaline solution is to neutralize the acid solution of residual, then institute in desciccator diaphragm
State alkaline solution and be preferably potassium hydroxide or sodium hydroxide.The concentration of described alkaline solution is preferably
0.1～1.0mol/L, more preferably 0.5～0.8mol/L, if the concentration of alkaline solution is too low, the most not
Can effectively neutralize the acid solution of residual, if excessive concentration, then the PEM of preparation be made
Becoming impact, it is unfavorable to cause with the post processing to film.
According to the present invention, after having been processed by desciccator diaphragm, the film after the application will process immerses
Cross-linking agent make the chitosan in desciccator diaphragm carry out cross-linking reaction, to improve the matter of PEM
Sub-conductivity, mechanical property and stability.Described cross-linking agent is preferably sulphuric acid, described sulphuric acid
Concentration is preferably 0.1～1.0mol/L, more preferably 0.5～0.8mol/L.Herein described compound
In PEM, described CNT class fluid content is too low, then at compound proton exchange membrane
Middle effect is inconspicuous, and the too high levels of described CNT class fluid, then it is at chitosan basal body
In can reunite, cause the deterioration of compound proton exchange membrane performance, the most described CNT
The content of class fluid is preferably 0.5～10wt%, more preferably 3wt%～7wt%.As preferably side
Case, is washed till neutrality by the film after cross-linking reaction, the most i.e. obtains compound proton exchange membrane.This
The thickness of the compound proton exchange membrane of application preparation is preferably 40～60 μm.
This application provides the preparation method of a kind of compound proton exchange membrane.Preparing composite proton
During exchange membrane, first the application has prepared the mixing of chitosan and CNT class fluid
Solution, then mixed solution is dried, obtain the chitosan containing a small amount of acid solution and carbon
The film of nanometer tubing fluid, cross-links after finally the alkali cleaning of above-mentioned film elder generation being washed to neutrality again,
I.e. obtain compound proton exchange membrane.The application uses CNT class fluid to change chitosan
Property, the organic molecule long-chain of CNT class flow surface grafting introduces-SO3 -Group, can
Significantly improving the proton conductivity of compound proton exchange membrane, CNT class fluid is special simultaneously
Mobility promotes dispersed in chitosan basal body of CNT, has given full play to it to shell
The plasticising of polysaccharide base material, toughness reinforcing and potentiation, and chitosan carry out crosslinked action can be had
Effect improves the stability of PEM, and therefore the compound proton exchange membrane of the application has preferably
Proton-conducting, pliability and intensity.
On the other hand, the application uses biomass castoff chitosan to hand over as fuel cell proton
Change the matrix material of film, realizing while resource recycling turns waste into wealth, be greatly reduced
The cost of material of fuel cell；The organic layer of CNT class flow surface grafting makes carbon nanometer
Pipe can not be connected to each other in chitosan basal body, thus avoids short circuit phenomenon；The shell of the application
Polysaccharide/CNT class fluid compound proton exchange membrane does not produce harmful substance in preparation process,
Environment is not resulted in impact.
In order to be further appreciated by the present invention, the compound matter present invention provided below in conjunction with embodiment
The preparation method of proton exchange is described in detail, and protection scope of the present invention is not by following enforcement
The restriction of example.
Embodiment 1
Take 2g CNT and be scattered in 350～400mL sulphuric acid and (volume in the mixed liquor of nitric acid
Ratio is 3:1, sulfuric acid concentration 98%, concentration of nitric acid 65%), ultrasonic oxidation 2.5～3.5h.Spend
Ionized water dilution CNT acid solution, centrifugal under the speed of 8000～10000r/min
15～25min, then go acid solution, add deionized water, more centrifugal under similarity condition
15～25min, repeat above operation, be drying to obtain surface hydroxyl carbon nano tube.By surface band
The CNT room temperature having hydroxyl is disperseed in deionized water, is slowly added dropwise the water-soluble of sodium hydroxide
The pH value of liquid regulation dispersion liquid is 10, adds 3-(the trimethoxy silicon propyl group) diformazan of 20g
The methanol solution of base octadecyl ammonium chloride (DC5700 silane coupler), by this mixed liquor
Body is at room temperature aged 24h and with intermittent vibration, obtains the nano-inorganic substance of quaternization.
Then the nano-inorganic substance of quaternization is carried out with nonylphenol polyoxyethylene ether sulfate aqueous solution
Mixing, and stirring reaction 24h at 70 DEG C.Remove solvent subsequently, and by gained material difference
By deionized water and methanol filtering and washing 3 times, at 70 DEG C, then it is dried 48h, then at room temperature
Lower vacuum drying 24h, obtains solvent-free CNT class fluid.
The method that CNT class fluid in following example all provides according to embodiment 1 is carried out
Preparation.
Embodiment 2
Weighing chitosan 2g that molecular weight is 500,000 in beaker, the acetic acid pouring 2wt% into is molten
Liquid 100ml, is stirred at room temperature and is completely dissolved to chitosan, weighs CNT class fluid 0.02g
In small sample vial, pour 15mL dehydrated alcohol ultrasonic disperse 30min into being uniformly dispersed.To divide
The CNT class fluid solution dissipated is poured in the chitosan-acetic acid solution being completely dissolved, and stirs
Mixing about 1h, ultrasonic 30min deaeration, being completely dispersed uniform solution until being formed.By above-mentioned
Solution is poured onto in the glass guide channel of clear bottom, dries 24h, by dried film at 40 DEG C
Immerse 0.5mol/L NaOH solution and soak 2h, wash with water to neutrality afterwards, then use 0.5mol/L
H2SO4Solution soaking crosslinking 24h, is washed till neutrality by film after crosslinking, again by washed film glass
Glass plate holder put down, put into 30 DEG C of oven drying 12h, compound proton exchange membrane.
Embodiment 3
Weigh chitosan 1.5g that molecular weight is 500,000 in beaker, pour the acetic acid of 1.5wt% into
Solution 100ml, is stirred at room temperature and is completely dissolved to chitosan, weighs CNT class fluid 0.1g
In small sample vial, pour 15mL dehydrated alcohol ultrasonic disperse 30min into being uniformly dispersed.To divide
The CNT class fluid solution dissipated is poured in the chitosan-acetic acid solution being completely dissolved, and stirs
Mixing about 1h, ultrasonic 30min deaeration, being completely dispersed uniform solution until being formed.By above-mentioned
Solution is poured onto in the glass guide channel of clear bottom, dries 24h, soaked by dried film at 40 DEG C
Enter 0.8mol/L NaOH solution and soak 2h, wash with water to neutrality afterwards, then use 0.8mol/L
H2SO4Solution soaking crosslinking 24h, is washed till neutrality by film after crosslinking, again by washed film glass
Glass plate holder put down, put into 30 DEG C of oven drying 12h, compound proton exchange membrane.
Embodiment 4
Weigh chitosan 2g that molecular weight is 500,000 in beaker, pour the acetum of 2.5% into
100ml, is stirred at room temperature to being completely dissolved, and weighs CNT class fluid 0.2g in small sample vial,
Pour 15mL dehydrated alcohol ultrasonic disperse 30min into being uniformly dispersed.By scattered carbon nanometer
Tubing fluid solution is poured in the chitosan-acetic acid solution being completely dissolved, and stirs about 1h, super
Sound 30min deaeration, is completely dispersed uniform solution until being formed.Above-mentioned solution is poured onto the end
In the glass guide channel that portion is clean, at 40 DEG C, dry 24h, dried film is immersed 0.6mol/L
NaOH solution soaks 2h, washes with water to neutrality afterwards, then uses 0.6mol/L H2SO4Solution soaks
Bubble crosslinking 24h, is washed till neutrality by film again after crosslinking, is put down by washed film glass plate holder, put
Enter 30 DEG C of oven drying 12h, compound proton exchange membrane.
Embodiment 5
Weigh chitosan 2.5g that molecular weight is 1,000,000 in beaker, pour the acetic acid of 1.8% into
Solution 100ml, is stirred at room temperature to being completely dissolved, and weighs CNT class fluid 0.02g in little
Sample bottle, pours 15mL dehydrated alcohol ultrasonic disperse 30min into being uniformly dispersed.By scattered
CNT class fluid solution pour in the chitosan-acetic acid solution being completely dissolved, stirring is big
About 1h, ultrasonic 30min deaeration, it is completely dispersed uniform solution until being formed.By above-mentioned solution
It is poured onto in the glass guide channel of clear bottom, at 40 DEG C, dries 24h, dried film is immersed
0.5mol/L NaOH solution soaks 2h, washes with water to neutrality afterwards, then uses 0.8mol/L H2SO4
Solution soaking crosslinking 24h, is washed till neutrality by film after crosslinking, again by washed film glass plate holder
Flat, put into 30 DEG C of oven drying 12h, compound proton exchange membrane.
Embodiment 6
Weigh chitosan 2.1g that molecular weight is 1,000,000 in beaker, pour into 2% acetic acid molten
Liquid 100ml, is stirred at room temperature to being completely dissolved, and weighs CNT class fluid 0.1g in small sample
Bottle, pours 15mL dehydrated alcohol ultrasonic disperse 30min into being uniformly dispersed.By scattered carbon
Nanometer tubing fluid solution is poured in the chitosan-acetic acid solution being completely dissolved, and stirring is about
1h, ultrasonic 30min deaeration, it is completely dispersed uniform solution until being formed.Above-mentioned solution is inclined
In the glass guide channel of clear bottom, at 40 DEG C, dry 24h, dried film is immersed and uses
0.5mol/L NaOH solution soaks 2h, washes with water to neutrality afterwards, then uses 0.5mol/L H2SO4
Solution soaking crosslinking 24h, is washed till neutrality by film after crosslinking, again by washed film glass plate holder
Flat, put into 30 DEG C of oven drying 12h, compound proton exchange membrane.
Embodiment 7
Weigh chitosan 2g that molecular weight is 1,000,000 in beaker, pour the acetum of 2% into
100ml, is stirred at room temperature to being completely dissolved, and weighs CNT class fluid 0.2g in small sample vial,
Pour 15mL dehydrated alcohol ultrasonic disperse 30min into being uniformly dispersed.By scattered carbon nanometer
Tubing fluid solution is poured in the chitosan-acetic acid solution being completely dissolved, and stirs about 1h, super
Sound 30min deaeration, is completely dispersed uniform solution until being formed.Above-mentioned solution is poured onto the end
In the glass guide channel that portion is clean, at 40 DEG C, dry 24h, by dried film immersion 0.5mol/L
NaOH solution soaks 2h, washes with water to neutrality afterwards, then uses 0.5mol/L H2SO4Solution soaks
Bubble crosslinking 24h, is washed till neutrality by film again after crosslinking, is put down by washed film glass plate holder, put
Enter 30 DEG C of oven drying 12h, compound proton exchange membrane.
The performance data table of the PEM of table 1 embodiment 2～7 preparation
The explanation of above example is only intended to help to understand that the method for the present invention and core thereof are thought
Think.It should be pointed out that, for those skilled in the art, without departing from this
On the premise of bright principle, it is also possible to the present invention is carried out some improvement and modification, these improve and
Modify in the protection domain also falling into the claims in the present invention.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of
Or the use present invention.Those skilled in the art are come by the multiple amendment to these embodiments
Saying and will be apparent from, generic principles defined herein can be without departing from the present invention's
In the case of spirit or scope, realize in other embodiments.Therefore, the present invention will not be by
It is limited to the embodiments shown herein, and is to fit to and principles disclosed herein and new
The widest scope that grain husk feature is consistent.
Claims (9)
1. a preparation method for compound proton exchange membrane, comprises the following steps:
The solution of the acid solution of chitosan with CNT class fluid is mixed, obtains mixed solution；
Described mixed solution is dried, obtains desciccator diaphragm；
Described desciccator diaphragm being carried out alkali cleaning, then is washed to neutrality, then the effect at cross-linking agent issues
Raw cross-linking reaction, obtains compound proton exchange membrane；Carbon nanometer described in described compound proton exchange membrane
The content of tubing fluid is 0.5wt%～10wt%.
Preparation method the most according to claim 1, it is characterised in that the acid of described chitosan
Property solution is the acetum of chitosan, and in the acetum of described chitosan, the content of chitosan is
1.0wt%～3.0wt%, the concentration of described acetum is 1.5wt%～2.5wt%.
Preparation method the most according to claim 1, it is characterised in that described CNT class
The solution of fluid is the ethanol solution of CNT class fluid.
Preparation method the most according to claim 1, it is characterised in that the solution of described alkali cleaning
For sodium hydroxide solution or potassium hydroxide solution.
Preparation method the most according to claim 1, it is characterised in that described cross-linking agent is dense
Degree is the sulphuric acid of 0.1～1.0mol/L.
Preparation method the most according to claim 1, it is characterised in that described cross-linking reaction it
After also include:
The film obtained after cross-linking reaction is dried.
Preparation method the most according to claim 1, it is characterised in that described composite proton is handed over
The thickness changing film is 40～60 μm.
Preparation method the most according to claim 1, it is characterised in that dividing of described chitosan
Son amount is 500,000 or 1,000,000.
Preparation method the most according to claim 1, it is characterised in that described CNT class
The grafting content of organics of fluid is 60wt%～70wt%.
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| CN106935882A (en) * | 2017-04-14 | 2017-07-07 | 湖北工程学院 | A kind of compound proton exchange membrane and preparation method thereof |
| TWI632178B (en) * | 2017-07-24 | 2018-08-11 | 大葉大學 | Green environmental proton exchange membrane synthesis manufacturing method |
| CN107383405B (en) * | 2017-08-02 | 2020-06-30 | 湖北工程学院 | Composite proton exchange membrane 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 |
| CN109818024B (en) * | 2019-01-30 | 2020-12-08 | 湖北工程学院 | Composite proton exchange membrane and preparation method thereof |
| CN109950595A (en) * | 2019-03-27 | 2019-06-28 | 天津工业大学 | Titania modified low-dimensional carbon material/chitosan proton exchange membrane and its preparation method and application |
| CN113178603B (en) * | 2021-04-12 | 2023-05-09 | 武汉氢能与燃料电池产业技术研究院有限公司 | Proton exchange membrane, preparation method thereof and environment-friendly fuel cell |
| CN113410498B (en) * | 2021-06-09 | 2022-03-22 | 深圳市通用氢能科技有限公司 | Preparation method of proton exchange membrane |
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| 刘海等.壳聚糖/高岭土类流体复合质子交换膜的制备及其性能研究.《年全国高分子材料科学与工程研讨会学术论文集（下册）》.2014, * |
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