CN104300164A - Preparation method for complex proton exchange membrane - Google Patents
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- CN104300164A CN104300164A CN201410605875.4A CN201410605875A CN104300164A CN 104300164 A CN104300164 A CN 104300164A CN 201410605875 A CN201410605875 A CN 201410605875A CN 104300164 A CN104300164 A CN 104300164A
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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
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- 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
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Abstract
The invention provides a preparation method for a complex proton exchange membrane. The preparation method comprises the steps as follows: firstly, the acid solution of chitosan is mixed with the solution of CNT (Carbon Nano Tube) fluid so as to obtain a mixed solution; secondly, the mixed solution is dried so as to obtain a dried membrane; thirdly, the dried membrane is subjected to alkali washing, and is then washed by water until the pH value reaches 7; fourthly, the membrane is subjected to cross-linking reaction under the function of a cross-linking agent so as to obtain the complex proton exchange membrane. During the preparation process of the complex proton exchange membrane, through the adoption of CNT fluid to modify the chitosan, and as perssad is introduced to the organic molecule long chain grafted on the surface of the CNT fluid, the proton electrical conductivity of the complex proton exchange membrane is improved; besides, the fluidity of the CNT fluid enables the CNT to be distributed in the base body of the chitosan uniformly, so that the plasticizing, toughening and strengthening functions for the base body of the chitosan are realized, and the complex proton exchange membrane is good in flexibility and strength.
Description
Technical field
The present invention relates to fuel battery proton exchange film technical field, particularly relate to a kind of preparation method of compound proton exchange membrane.
Background technology
Shitosan chemical name is [Isosorbide-5-Nitrae]-2-amino-2-deoxidation-β-D glucan, and it is the product after chitin sloughs part acetyl group, is a kind of common natural biological copolymer.Shitosan has excellent film forming, nontoxicity, antibiotic property and good biocompatibility and degradability, is widely used in the fields such as food, medicine, water treatment, cosmetics and functional material.Shitosan is as a kind of proton exchange membrane having research potential most, and it has cheap, environment friendly, the not fastidious feature low with methanol permeability of suitable environment.Shitosan is owing to molecular structure being rich in-OH and-NH2 simultaneously, and realize controlled chemical modification by carrying out MOLECULE DESIGN to it, correlative study becomes focus in recent years.Shitosan, as proton exchange membrane, exists that proton conductivity is low, the problem of the pliability of film, mechanical performance and thermal stability deficiency.
Composite organic-inorganic material combines the stability of inorganic material and the pliability of organic material because of it, is considered to as improving one of most effective method of shitosan performance.Research shows, the performance of shitosan/inorganic particulate laminated film depends on the filling of inorganic particulate, dispersed, particle diameter and the orientation in chitosan basal body thereof to a great extent.But the inorganic nano-particle of non-surface modification is difficult to dispersion in chitosan basal body, interfacial adhesion effect is more weak simultaneously, and laminated film performance is difficult to reach instructions for use.
Class fluid is a kind of under the condition of normal temperature and pressure, not containing any solvent, presents the material of the similar fluid state of one-component.Class fluid concept is proposed by people such as Giannelis, and the long-chain organic substance in particle surface grafting by covalent bond or ion-exchange, makes it in the character macroscopically showing fluid.The class fluidisation of material is as a kind of material surface modifying technology, due to the peculiar property of prepared class fluid nano particle, there is huge potential using value, be expected to be broken through and apply in the self assembly of nano particle, the proton membrane of fuel cell, the plasticising toughen and intensify of macromolecular material, nano composite material, new reaction medium, the every field such as high temperature lubricating and emr fluid.
Summary of the invention
The technical problem that the present invention solves is the preparation method providing a kind of compound proton exchange membrane, and the proton conductivity of compound proton exchange membrane prepared by the preparation method provided according to the application, pliability and mechanical performance are higher.
In view of this, this application provides a kind of preparation method of compound proton exchange membrane, comprise the following steps:
The solution of the acid solution of shitosan with carbon nano-tube 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 under the effect of crosslinking agent, cross-linking reaction occurs, obtain compound proton exchange membrane.
Preferably, the acid solution of described shitosan is the acetum of shitosan, and in the acetum of described shitosan, the content of shitosan is 1.0wt% ~ 3.0wt%, and the mass fraction of described acetum is 1.5wt% ~ 2.5wt%.
Preferably, the solution of described carbon nano-tube class fluid is the ethanolic solution of carbon nano-tube class fluid.
Preferably, the solution of described alkali cleaning is sodium hydroxide solution or potassium hydroxide solution.
Preferably, the sulfuric acid of described crosslinking agent to be concentration be 0.1 ~ 1.0mol/L.
Preferably, also comprise after described cross-linking reaction:
The film obtained after cross-linking reaction is carried out drying.
Preferably, the content of the fluid of carbon nano-tube class 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 shitosan is 500,000 or 1,000,000.
Preferably, the grafting content of organics of described carbon nano-tube class fluid is 60wt% ~ 70wt%.
This application provides a kind of preparation method of compound proton exchange membrane.In the process preparing compound proton exchange membrane, first the application has prepared the mixed solution of shitosan and carbon nano-tube class fluid, again mixed solution is carried out drying, obtain the film of shitosan containing a small amount of acid solution and carbon nano-tube class fluid, be cross-linked after finally first for above-mentioned film alkali cleaning being washed to neutrality again, namely obtain compound proton exchange membrane.The application adopts carbon nano-tube class fluid to carry out modification to shitosan, and the organic molecule long-chain due to the grafting of carbon nano-tube class flow surface introduces-SO
3 -group, significantly can improve the proton conductivity of compound proton exchange membrane, the mobility of carbon nano-tube class fluid impels carbon nano-tube dispersed in chitosan basal body simultaneously, its plasticising to shitosan base material, toughness reinforcing and humidification are given full play to, and shitosan carries out being cross-linked to form network structure, effectively improve the stability of proton exchange membrane, therefore, the proton conductivity of compound proton exchange membrane prepared by the application, pliability and intensity are significantly improved.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of preparation method of compound proton exchange membrane, comprise the following steps:
The solution of the acid solution of shitosan with carbon nano-tube 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 under the effect of crosslinking agent, cross-linking reaction occurs, obtain compound proton exchange membrane.
The application adopts carbon nano-tube class fluid to carry out modification to shitosan, due to the character of carbon nano-tube class fluid, makes the proton-conducting of the compound proton exchange membrane of preparation, pliability and intensity be obtained for remarkable improvement.
According to the present invention, first the solution of the acid solution of shitosan with carbon nano-tube class fluid is mixed, obtain mixed solution.In the process of preparation mixed solution, the acid solution of described shitosan specifically can configure in the following manner: preparation acid solution, adds shitosan, obtain the acid solution of shitosan in described acid solution.In the acid solution of described shitosan, the content of shitosan is preferably 1.0wt% ~ 3.0wt%.Described in the application, acid solution is preferably acetic acid.In order to ensure that shitosan can fully dissolve, the concentration of described acid solution is preferably 1.5wt% ~ 2.5wt%.Shitosan described in the application is preferably that molecular weight is 500,000, deacetylation be 85% shitosan or molecular weight be 1,000,000, deacetylation is the shitosan of 90%.
The class of carbon nano-tube described in the application fluid is carbon nano-tube class fluid of the prior art, and the application is preferably prepared according to application number method disclosed in the patent of 200610124455.X.The preparation process of described carbon nano-tube class fluid can be divided into following three steps: the surface oxidation of carbon nano-tube, carbon nano tube surface grafting organic cation salt after oxidation and carbon nano-tube organic cation salt and nonylphenol polyoxyethylene ether sulfate carry out ion-exchange and connect the organic anion salt of long-chain.The grafting content of organics of described carbon nano-tube class fluid is preferably 60wt% ~ 70wt%.According to the present invention, the preparation of the solution of described carbon nano-tube class fluid is specially: be dissolved in solution by carbon nano-tube class fluid, ultrasonic disperse, obtain the solution of carbon nano-tube class fluid.Above-mentioned solution is preferably absolute ethyl alcohol, and the time of described ultrasonic disperse is preferably 20 ~ 40min.In order to make the acid solution of shitosan mix with the solution of carbon nano-tube class fluid, the application preferably by after above-mentioned two kinds of solution mixing, first carries out ultrasonic agitation and carries out ultrasonic deaeration again; The time of described ultrasonic agitation is preferably 0.5h ~ 1.5h, and the time of described ultrasonic deaeration is preferably 20min ~ 40min.
According to the present invention, after mixed solution has been prepared, then described mixed solution is dried, obtained desciccator diaphragm.The temperature of described oven dry is preferably 30 ~ 50 DEG C, and the time of oven dry is preferably 18h ~ 36h.Described desciccator diaphragm is the film of the shitosan mixed containing a small amount of remaining acid solution and carbon nano-tube class fluid.
In the application, as mentioned above, described desciccator diaphragm is the composite membrane containing shitosan and carbon nano-tube class fluid, and in order to improve the proton-conducting of composite membrane, mechanical property and stability, shitosan crosslinking agent need be cross-linked by the application.According to the present invention, need first described desciccator diaphragm to be immersed in alkaline solution to carry out alkali cleaning, and be washed to neutrality, make in alkaline solution and acid solution residual in desciccator diaphragm, impact to prevent the compound proton exchange membrane of remaining acid solution to preparation.The effect of described alkaline solution be in and acid solution residual in desciccator diaphragm, then described alkaline solution is preferably potassium hydroxide or NaOH.The concentration of described alkaline solution is preferably 0.1 ~ 1.0mol/L, is more preferably 0.5 ~ 0.8mol/L, if the concentration of alkaline solution is too low, then can not effectively neutralize residual acid solution, if excessive concentration, then the proton exchange membrane of preparation is impacted, unfavorable to cause the reprocessing of film.
According to the present invention, after desciccator diaphragm process being completed, the film after process immerses in crosslinking agent and makes the shitosan in desciccator diaphragm carry out cross-linking reaction by the application, to improve the proton-conducting of proton exchange membrane, mechanical property and stability.Described crosslinking agent is preferably sulfuric acid, and the concentration of described sulfuric acid is preferably 0.1 ~ 1.0mol/L, is more preferably 0.5 ~ 0.8mol/L.In compound proton exchange membrane described in the application, described carbon nano-tube class fluid content is too low, then act on not obvious in compound proton exchange membrane, the too high levels of described carbon nano-tube class fluid, then it can reunite in chitosan basal body, cause the deterioration of compound proton exchange membrane performance, therefore the content of described carbon nano-tube class fluid is preferably 0.5 ~ 10wt%, is more preferably 3wt% ~ 7wt%.Preferably, the film after cross-linking reaction is washed till neutrality, after drying, namely obtains compound proton exchange membrane.The thickness of compound proton exchange membrane prepared by the application is preferably 40 ~ 60 μm.
This application provides a kind of preparation method of compound proton exchange membrane.In the process preparing compound proton exchange membrane, first the application has prepared the mixed solution of shitosan and carbon nano-tube class fluid, again mixed solution is carried out drying, obtain the film of shitosan containing a small amount of acid solution and carbon nano-tube class fluid, be cross-linked after finally first for above-mentioned film alkali cleaning being washed to neutrality again, namely obtain compound proton exchange membrane.The application adopts carbon nano-tube class fluid to carry out modification to shitosan, and the organic molecule long-chain of carbon nano-tube class flow surface grafting introduces-SO
3 -group, significantly can improve the proton conductivity of compound proton exchange membrane, the mobility that simultaneously carbon nano-tube class fluid is special impels dispersed in chitosan basal body of carbon nano-tube, its plasticising to shitosan base material, toughness reinforcing and humidification are given full play to, and shitosan carries out the stability that crosslinked action effectively can improve proton exchange membrane, and therefore the compound proton exchange membrane of the application has good proton-conducting, pliability and intensity.
On the other hand, the application adopts biomass castoff shitosan as the basis material of fuel battery proton exchange film, is realizing while resource recycling turns waste into wealth, greatly reducing the cost of material of fuel cell; The organic layer of carbon nano-tube class flow surface grafting makes carbon nano-tube can not be connected to each other in chitosan basal body, thus avoids short circuit phenomenon; Shitosan/carbon nano-tube class fluid the compound proton exchange membrane of the application does not produce harmful substance, can not impact environment in preparation process.
In order to understand the present invention further, below in conjunction with embodiment, the preparation method to compound proton exchange membrane provided by the invention is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Get 2g carbon nanotube dispersed (volume ratio is 3:1, sulfuric acid concentration 98%, concentration of nitric acid 65%) in the mixed liquor of 350 ~ 400mL sulfuric acid and nitric acid, ultrasonic oxidation 2.5 ~ 3.5h.By deionized water dilution carbon nano-tube acid solution, centrifugal 15 ~ 25min, the then liquid of falling disacidify under the speed of 8000 ~ 10000r/min, add deionized water, centrifugal 15 ~ 25min under similarity condition again, repeats above operation, is drying to obtain surface hydroxyl carbon nano tube.The carbon nano-tube room temperature of surface with hydroxyl is disperseed in deionized water, the aqueous solution of slow dropping NaOH regulates the pH value of dispersion liquid to be 10, add the methanol solution of the 3-(trimethoxy silicon propyl group) dimethyl stearyl ammonium chloride (DC5700 silane coupler) of 20g again, by the at room temperature ageing 24h also adjoint intermittent vibration of this mixing material, obtain the nano-inorganic substance of quaternization.Then the nano-inorganic substance of quaternization is mixed with the nonylphenol polyoxyethylene ether sulfate aqueous solution, and at 70 DEG C stirring reaction 24h.Subsequently except desolventizing, and gained material is used respectively deionized water and methyl alcohol filtering and washing 3 times, then dry 48h at 70 DEG C, then in the dry 24h of ambient temperature in vacuum, obtain solvent-free carbon nano-tube class fluid.
The method that carbon nano-tube class fluid in following examples all provides according to embodiment 1 is prepared.
Embodiment 2
Taking molecular weight is that the shitosan 2g of 500,000 is in beaker, pour the acetum 100ml of 2wt% into, stirring at room temperature is dissolved completely to shitosan, takes carbon nano-tube class fluid 0.02g in small sample vial, pours 15mL absolute ethyl alcohol ultrasonic disperse 30min into being uniformly dispersed.Scattered carbon nano-tube class fluid solution is poured in consoluet chitosan-acetic acid solution, stirs about 1h, ultrasonic 30min deaeration, until form complete finely dispersed solution.Above-mentioned solution 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 and soaks 2h, wash with water to neutrality afterwards, then use 0.5mol/LH
2sO
4solution soaks crosslinked 24h, again film is washed till neutrality, is put down by washed film glass plate holder, put into 30 DEG C of oven drying 12h after crosslinked, compound proton exchange membrane.
Embodiment 3
Taking molecular weight is that the shitosan 1.5g of 500,000 is in beaker, pour the acetum 100ml of 1.5wt% into, stirring at room temperature is dissolved completely to shitosan, takes carbon nano-tube class fluid 0.1g in small sample vial, pours 15mL absolute ethyl alcohol ultrasonic disperse 30min into being uniformly dispersed.Scattered carbon nano-tube class fluid solution is poured in consoluet chitosan-acetic acid solution, stirs about 1h, ultrasonic 30min deaeration, until form complete finely dispersed solution.Above-mentioned solution is poured onto in the glass guide channel of clear bottom, at 40 DEG C, dries 24h, dried film is immersed 0.8mol/L NaOH solution and soaks 2h, wash with water to neutrality afterwards, then use 0.8mol/LH
2sO
4solution soaks crosslinked 24h, again film is washed till neutrality, is put down by washed film glass plate holder, put into 30 DEG C of oven drying 12h after crosslinked, compound proton exchange membrane.
Embodiment 4
Take molecular weight be the shitosan 2g of 500,000 in beaker, pour the acetum 100ml of 2.5% into, stirring at room temperature to dissolving completely, taking carbon nano-tube class fluid 0.2g in small sample vial, pouring 15mL absolute ethyl alcohol ultrasonic disperse 30min into being uniformly dispersed.Scattered carbon nano-tube class fluid solution is poured in consoluet chitosan-acetic acid solution, stirs about 1h, ultrasonic 30min deaeration, until form complete finely dispersed solution.Above-mentioned solution is poured onto in the glass guide channel of clear bottom, at 40 DEG C, dries 24h, dried film is immersed 0.6mol/LNaOH solution and soaks 2h, wash with water to neutrality afterwards, then use 0.6mol/L H
2sO
4solution soaks crosslinked 24h, again film is washed till neutrality, is put down by washed film glass plate holder, put into 30 DEG C of oven drying 12h after crosslinked, compound proton exchange membrane.
Embodiment 5
Take molecular weight be the shitosan 2.5g of 1,000,000 in beaker, pour the acetum 100ml of 1.8% into, stirring at room temperature to dissolving completely, taking carbon nano-tube class fluid 0.02g in small sample vial, pouring 15mL absolute ethyl alcohol ultrasonic disperse 30min into being uniformly dispersed.Scattered carbon nano-tube class fluid solution is poured in consoluet chitosan-acetic acid solution, stirs about 1h, ultrasonic 30min deaeration, until form complete finely dispersed solution.Above-mentioned solution 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 and soaks 2h, wash with water to neutrality afterwards, then use 0.8mol/L H
2sO
4solution soaks crosslinked 24h, again film is washed till neutrality, is put down by washed film glass plate holder, put into 30 DEG C of oven drying 12h after crosslinked, compound proton exchange membrane.
Embodiment 6
Take molecular weight be the shitosan 2.1g of 1,000,000 in beaker, pour the acetum 100ml of 2% into, stirring at room temperature to dissolving completely, taking carbon nano-tube class fluid 0.1g in small sample vial, pouring 15mL absolute ethyl alcohol ultrasonic disperse 30min into being uniformly dispersed.Scattered carbon nano-tube class fluid solution is poured in consoluet chitosan-acetic acid solution, stirs about 1h, ultrasonic 30min deaeration, until form complete finely dispersed solution.Above-mentioned solution is poured onto in the glass guide channel of clear bottom, at 40 DEG C, dries 24h, dried film immersion 0.5mol/L NaOH solution is soaked 2h, washes with water to neutrality afterwards, then use 0.5mol/L H
2sO
4solution soaks crosslinked 24h, again film is washed till neutrality, is put down by washed film glass plate holder, put into 30 DEG C of oven drying 12h after crosslinked, compound proton exchange membrane.
Embodiment 7
Take molecular weight be the shitosan 2g of 1,000,000 in beaker, pour the acetum 100ml of 2% into, stirring at room temperature to dissolving completely, taking carbon nano-tube class fluid 0.2g in small sample vial, pouring 15mL absolute ethyl alcohol ultrasonic disperse 30min into being uniformly dispersed.Scattered carbon nano-tube class fluid solution is poured in consoluet chitosan-acetic acid solution, stirs about 1h, ultrasonic 30min deaeration, until form complete finely dispersed solution.Above-mentioned solution is poured onto in the glass guide channel of clear bottom, at 40 DEG C, dries 24h, dried film immersion 0.5mol/LNaOH solution is soaked 2h, washes with water to neutrality afterwards, then use 0.5mol/L H
2sO
4solution soaks crosslinked 24h, again film is washed till neutrality, is put down by washed film glass plate holder, put into 30 DEG C of oven drying 12h after crosslinked, compound proton exchange membrane.
The performance data table of proton exchange membrane prepared by table 1 embodiment 2 ~ 7
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection range of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a preparation method for compound proton exchange membrane, comprises the following steps:
The solution of the acid solution of shitosan with carbon nano-tube 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 under the effect of crosslinking agent, cross-linking reaction occurs, obtain compound proton exchange membrane.
2. preparation method according to claim 1, it is characterized in that, the acid solution of described shitosan is the acetum of shitosan, and in the acetum of described shitosan, the content of shitosan is 1.0wt% ~ 3.0wt%, and the concentration of described acetum is 1.5wt% ~ 2.5wt%.
3. preparation method according to claim 1, is characterized in that, the solution of described carbon nano-tube class fluid is the ethanolic solution of carbon nano-tube class fluid.
4. preparation method according to claim 1, is characterized in that, the solution of described alkali cleaning is sodium hydroxide solution or potassium hydroxide solution.
5. preparation method according to claim 1, is characterized in that, the sulfuric acid of described crosslinking agent to be concentration be 0.1 ~ 1.0mol/L.
6. preparation method according to claim 1, is characterized in that, also comprises after described cross-linking reaction:
The film obtained after cross-linking reaction is carried out drying.
7. preparation method according to claim 1, is characterized in that, the content of the fluid of carbon nano-tube class described in described compound proton exchange membrane is 0.5wt% ~ 10wt%.
8. preparation method according to claim 1, is characterized in that, the thickness of described compound proton exchange membrane is 40 ~ 60 μm.
9. preparation method according to claim 1, is characterized in that, the molecular weight of described shitosan is 500,000 or 1,000,000.
10. preparation method according to claim 1, is characterized in that, the grafting content of organics of described carbon nano-tube class fluid is 60wt% ~ 70wt%.
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| 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 |
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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 |
| CN107383405A (en) * | 2017-08-02 | 2017-11-24 | 湖北工程学院 | A kind of compound proton exchange membrane and preparation method thereof |
| CN107383405B (en) * | 2017-08-02 | 2020-06-30 | 湖北工程学院 | Composite proton exchange membrane and preparation method thereof |
| CN107834089A (en) * | 2017-10-19 | 2018-03-23 | 武汉氢阳能源有限公司 | A kind of high temperature proton exchange film available for membrane cell and its preparation method and application |
| 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 |
| CN109818024A (en) * | 2019-01-30 | 2019-05-28 | 湖北工程学院 | A kind of compound 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 |
| CN113178603A (en) * | 2021-04-12 | 2021-07-27 | 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 |
| 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 |
| CN113410498A (en) * | 2021-06-09 | 2021-09-17 | 深圳市通用氢能科技有限公司 | Preparation method of proton exchange membrane |
| 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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