CN105733004B - A kind of preparation method of full interpenetrating type n-trimethyl chitosan chloride anion-exchange membrane - Google Patents
A kind of preparation method of full interpenetrating type n-trimethyl chitosan chloride anion-exchange membrane Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2212—Natural macromolecular compounds
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2203/16—Applications used for films
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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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
N-trimethyl chitosan chloride (QCS) with macromolecular scaffold structure is completely dissolved, using acetic acid solution as solvent as film base fluid by a kind of preparation method of full interpenetrating type n-trimethyl chitosan chloride anion-exchange membrane.It will be in the acetic acid casting solution with polyhydroxy structure natural polymers cellulose Uniform Doped to n-trimethyl chitosan chloride, utilize glutaraldehyde as cross linker, by above two high molecular polymer, the anion-exchange membrane casting solution with full inierpeneirating network structure is obtained by chemical crosslinking.Using the tape casting on a glass by above-mentioned casting solution, casting film, then the film that drying to constant weight is immersed in potassium hydroxide solution, prepares hydroxide ion type anion-exchange membrane.Anionic membrane prepared by the present invention has excellent alkali stability energy, good mechanical performance, and effectively raises the electric conductivity of film.
Description
Technical field
The invention belongs to field of fuel cell technology, are related to the film electrolyte preparation skill of anion-exchange membrane fuel cells
A kind of art, and in particular to preparation method of the n-trimethyl chitosan chloride film with full inierpeneirating network structure.
Background technique
Direct methanol fuel cell (DMFCs) not only has that energy conversion efficiency is high, environmental-friendly, zero-emission nitrogen, sulphur oxygen
The characteristics of compound, and it is small in size, structure is simple, fuel is easy to store and transport, therefore the extensive concern by all circles.Wherein
Anion-exchange membrane fuel cells (AEMFCs), at low cost using non-precious metal as catalyst, the benefit of higher fuel cell,
Therefore the relevant report studied it is also more and more.As the core of AEMFCs, ideal anion-exchange membrane must have
Excellent alkali stability, stronger mechanically performance ensure that fuel cell can be with the operation of lasting stability.N-trimethyl chitosan chloride
It (QCS) is quaternised modified obtained to natural polymers chitosan (CS) progress.It is with semi-rigid macromolecule
Skeleton and excellent film forming ability, quaternary ammonium group are formed by anion-exchange membrane as anionic electroconductive group and are widely answered
With.Regrettably, because that anion-exchange membrane transmits in a fuel cell is OH-Ion, therefore it must be in alkaline environment
Middle use, there is Hofmann degradation and nucleophilic substitutions in alkaline environment for quaternary ammonium group, can not long-time stable
There are in polymer backbone, so many researchers get down to improve the unstable problem of quaternary ammonium group.It is effectively improved season at present
The method that ammonium group is degraded is to find other alkali resistant cationic electroconductive groups to replace quaternary ammonium group, but these non-quaternary ammonium types
Cationic electroconductive group is difficult to be grafted on chitosan skeleton.Studies have pointed out that can be by conductive group by chemical crosslink technique
" locking " slows down quaternary ammonium group degradation in the internal structure of film.Existing research is pointed out, is made using glutaraldehyde as crosslinking agent
Half interpenetrating network structure is formed inside n-trimethyl chitosan chloride, though slowing down the degradation rate of quaternary ammonium group, its swellbility still has
87%, it is immersed in 2M NaOH solution under room temperature for 24 hours, loss conductivity reaches 7.5%.Its another bone in high concentration alkali solution
Degradation takes place in frame, can not be stable in the presence of in aqueous slkali.
Summary of the invention
The present invention provides a kind of method for preparing full interpenetrating type n-trimethyl chitosan chloride anion-exchange membrane, prepared yin from
Proton exchange membrane material has excellent alkali stability and excellent mechanical performance, and the anion that can be used as alkaline fuel cell is handed over
Change film electrolyte.
The preparation method of full interpenetrating type n-trimethyl chitosan chloride anion-exchange membrane, comprises the following steps that
(1) weighing 2g degree of substitution is 10%-30% n-trimethyl chitosan chloride powder, and 2% (v/v) acetic acid for being added to 30mL is molten
In the flask of agent, lower progress mechanical stirring is heated, until cellulose powder is added, so that negative after n-trimethyl chitosan chloride is completely dissolved
The mass percentage of cellulose is 25-50% in ionic membrane, continues heating stirring, until being completely dissolved, obtains casting solution；
(2) glutaraldehyde solution that mass fraction is 2-5% is added into casting solution, casting solution matter shared by glutaraldehyde solution
Amount score is 1%-5%, continues heating stirring 5min, supersonic oscillations 10min, evacuation and centrifugal degassing；Then using the tape casting in water
Casting film on flat glass plate is taken off spare after film natural air drying.
(3) composite membrane prepared is immersed in 0.1M KOH aqueous solution and carries out ion exchange for 24 hours, then composite membrane is fixed
Between two pieces of polyfluortetraethylene plates, 40 DEG C of drying in oven are placed in film constant weight.
Anionic membrane prepared by the present invention have excellent alkaline resistance properties, by film immersion in 10M NaOH solution 240h
Afterwards, conductivity variations are smaller, tend towards stability, and show excellent alkali stability, meanwhile, the season with full inierpeneirating network structure
Ammonium chitosan anion exchange film immersion deionized water for 24 hours after, minimum reachable 21% (being shown in Table 1) of swellbility illustrates that the method can
The effective alkali stability for improving quaternary ammonium type anion exchange membrane.In conclusion the quaternized shell of full interpenetrating prepared by the present invention
Glycan anionic membrane has the advantage that compared with the composite membrane that existing fuel cell uses
(1) in n-trimethyl chitosan chloride film after cross-linked cellulose, stability of the film in high concentration alkali solution is improved.
(2) the full inierpeneirating network structure formed is by OH-" locking " promotes the ion exchange capacity and electricity of film among micropore cave
Conductance.
(3) some researches show that full inierpeneirating network structure can make more to tamp close, process letter inside anion-exchange membrane
It is single, easily controllable
Detailed description of the invention
Fig. 1 is the preparation process figure of anionic membrane.
Fig. 2 is pure chistosan film, embodiment 1, embodiment 2, the infrared spectrogram of embodiment 3.
Fig. 3 is pure QCS film, embodiment 1, embodiment 2, thermal stability determination of 3 anionic membrane of embodiment in N2 atmosphere
As a result.
Fig. 4 is pure QCS film, embodiment 1, embodiment 2, the conductivity variations of 3 anionic membrane of embodiment at different temperatures
Situation.
Fig. 5 be embodiment 2 prepare anion-exchange membrane room temperature under in 10M NaOH solution impregnate different time after from
Sub- exchange capacity situation of change.
Fig. 6 is 70 DEG C of items after impregnating different time in 10M NaOH solution under anion-exchange membrane prepared by embodiment 2
Conductivity values situation of change under part.
Table 1 be pure QCS film, embodiment 1, embodiment 2, embodiment 3, the swellbility of the anionic membrane of preparation at room temperature,
Moisture content, tensile strength, elongation at break, the measurement result of ion exchange capacity.
Specific embodiment
Method of the invention is further illustrated by the following examples.
Embodiment 1
(1) 20 ± 1.8% n-trimethyl chitosan chloride powder of 2g degree of substitution is weighed, the acetic acid solution containing 2% (v/v) is added to
In the flask of 30ml, in 40 DEG C of progress mechanical stirrings of heating water bath, until cellulose powder is added after n-trimethyl chitosan chloride is completely dissolved
Last 0.67g makes cellulose mass percent 25% in anionic membrane obtained, continues mechanical stirring and obtains until being completely dissolved
Casting solution.
(2) glutaraldehyde solution of mass fraction 2% is added in casting solution, casting solution quality shared by glutaraldehyde solution
Score is 2%, sufficiently reaction 5min, supersonic oscillations 10min, evacuation and centrifugal degassing.Then using the tape casting in horizontal glass plate
Upper casting film is taken off after film natural air drying.
(3) composite membrane is immersed in 0.1M KOH aqueous solution and carries out ion exchange for 24 hours, then composite membrane is fixed on two pieces and is gathered
Between tetrafluoroethene plate, 40 DEG C of drying in oven are placed in film constant weight.
Embodiment 2
(1) weighing 2.0g degree of substitution is 20 ± 1.8% n-trimethyl chitosan chloride powder, is added to the acetic acid containing 2% (v/v)
In the flask of solution 30ml, in 40 DEG C of progress mechanical stirrings of heating water bath, until fiber is added after n-trimethyl chitosan chloride is completely dissolved
Plain powder 1.0g makes cellulose mass percent 33% in anionic membrane obtained, continues mechanical stirring, until completely molten
Solution, obtains casting solution.
(2) glutaraldehyde solution () of mass fraction 2% is added in casting solution, casting solution matter shared by glutaraldehyde solution
Amount is 2%, sufficiently reaction 5min, supersonic oscillations 10min, evacuation and centrifugal degassing.Then using the tape casting on horizontal glass plate
Casting film is taken off after film natural air drying.
(3) composite membrane is immersed in 0.1M KOH aqueous solution and carries out ion exchange for 24 hours, then composite membrane is fixed on two pieces and is gathered
Between tetrafluoroethene plate, 40 DEG C of drying in oven are placed in film constant weight.
Embodiment 3
(1) weighing 2.0g degree of substitution is 20 ± 1.8% n-trimethyl chitosan chloride powder, and it is molten to be added to the acetic acid containing 2% (v/v)
In the flask of liquid 30ml, in 40 DEG C of progress mechanical stirrings of heating water bath, until cellulose is added after n-trimethyl chitosan chloride is completely dissolved
Powder 2.0g makes cellulose mass percent 50% in anionic membrane obtained, continues mechanical stirring, until being completely dissolved,
Obtain casting solution.
(2) glutaraldehyde solution () of mass fraction 2% is added in casting solution, casting solution matter shared by glutaraldehyde solution
Amount is 2%, sufficiently reaction 5min, supersonic oscillations 10min, evacuation and centrifugal degassing.Then using the tape casting on horizontal glass plate
Casting film is taken off after film natural air drying.
(3) composite membrane is immersed in 0.1M KOH aqueous solution and carries out ion exchange for 24 hours, then composite membrane is fixed on two pieces and is gathered
Between tetrafluoroethene plate, 40 DEG C of drying in oven are placed in film constant weight.
Embodiment 4
(1) weighing 2.0g degree of substitution is 10 ± 2.5% n-trimethyl chitosan chloride powder, and it is molten to be added to the acetic acid containing 2% (v/v)
In the flask of liquid 30ml, 40 DEG C of progress mechanical stirrings of heating water bath, until cellulose powder is added after n-trimethyl chitosan chloride is completely dissolved
Last 1.0g continues mechanical stirring until being completely dissolved and obtains casting solution.
(2) glutaraldehyde solution of mass fraction 2% is added in casting solution, casting solution quality shared by glutaraldehyde solution
Score is 2%, sufficiently reaction 5min, ultrasonic oscillation 10min, evacuation and centrifugal degassing.Then using the tape casting in horizontal glass plate
Upper casting film, is taken off after natural air drying.
(3) composite membrane is immersed in 0.1M KOH aqueous solution and carries out ion exchange for 24 hours, then composite membrane is fixed on two pieces and is gathered
Between tetrafluoroethene plate, 40 DEG C of drying in oven are placed in film constant weight.
Embodiment 5
(1) weighing 2.0g degree of substitution is 30 ± 3.1% n-trimethyl chitosan chloride powder, and it is molten to be added to the acetic acid containing 2% (v/v)
In the flask of liquid 30ml, 40 DEG C of progress mechanical stirrings of heating water bath, until cellulose powder is added after n-trimethyl chitosan chloride is completely dissolved
Last 1.0g continues mechanical stirring until being completely dissolved and obtains casting solution.
(2) glutaraldehyde solution of mass fraction 2% is added in casting solution, casting solution quality shared by glutaraldehyde solution
Score is 2%, sufficiently reaction 5min, ultrasonic oscillation 10min, evacuation and centrifugal degassing.Then using the tape casting in horizontal glass plate
Upper casting film, is taken off after natural air drying.
(3) composite membrane is immersed in 0.1M KOH aqueous solution and carries out ion exchange for 24 hours, then composite membrane is fixed on two pieces and is gathered
Between tetrafluoroethene plate, 40 DEG C of drying in oven are placed in film constant weight.
Embodiment 6
(1) weighing 2.0g degree of substitution is 20 ± 1.8% n-trimethyl chitosan chloride powder, and it is molten to be added to the acetic acid containing 2% (v/v)
In the flask of liquid 30ml, 40 DEG C of progress mechanical stirrings of heating water bath, until cellulose powder is added after n-trimethyl chitosan chloride is completely dissolved
Last 1.0g continues mechanical stirring until being completely dissolved and obtains casting solution.
(2) glutaraldehyde solution of mass fraction 2% is added in casting solution, casting solution quality shared by glutaraldehyde solution
Score is 1%, sufficiently reaction 5min, ultrasonic oscillation 10min, evacuation and centrifugal degassing.Then using the tape casting in horizontal glass plate
Upper casting film, is taken off after natural air drying.
(3) composite membrane is immersed in 0.1M KOH aqueous solution and carries out ion exchange for 24 hours, then composite membrane is fixed on two pieces and is gathered
Between tetrafluoroethene plate, 40 DEG C of drying in oven are placed in film constant weight.
Embodiment 7
(1) weighing 2.0g degree of substitution is 20 ± 1.8% n-trimethyl chitosan chloride powder, and it is molten to be added to the acetic acid containing 2% (v/v)
In the flask of liquid 30ml, 40 DEG C of progress mechanical stirrings of heating water bath, until cellulose powder is added after n-trimethyl chitosan chloride is completely dissolved
Last 1.0g continues mechanical stirring until being completely dissolved and obtains casting solution.
(2) glutaraldehyde solution of mass fraction 3% is added in casting solution, casting solution quality shared by glutaraldehyde solution
Score is 3%, sufficiently reaction 5min, ultrasonic oscillation 10min, evacuation and centrifugal degassing.Then using the tape casting in horizontal glass plate
Upper casting film, is taken off after natural air drying.
(3) composite membrane is immersed in 0.1M KOH aqueous solution and carries out ion exchange for 24 hours, then composite membrane is fixed on two pieces and is gathered
Between tetrafluoroethene plate, 40 DEG C of drying in oven are placed in film constant weight.
Embodiment 8
(1) weighing 2.0g degree of substitution is 20 ± 1.8% n-trimethyl chitosan chloride powder, and it is molten to be added to the acetic acid containing 2% (v/v)
In the flask of liquid 30ml, 40 DEG C of progress mechanical stirrings of heating water bath, until cellulose is added after n-trimethyl chitosan chloride is completely dissolved
Powder 1.0g continues mechanical stirring until being completely dissolved and obtains casting solution.
(2) glutaraldehyde solution of mass fraction 4% is added in casting solution, casting solution quality shared by glutaraldehyde solution
Score is 4%, sufficiently reaction 5min, ultrasonic oscillation 10min, evacuation and centrifugal degassing.Then using the tape casting in horizontal glass plate
Upper casting film, is taken off after natural air drying.
(3) composite membrane is immersed in 0.1M KOH aqueous solution and carries out ion exchange for 24 hours, then composite membrane is fixed on two pieces and is gathered
Between tetrafluoroethene plate, 40 DEG C of drying in oven are placed in film constant weight.
Embodiment 9
(1) weighing 2.0g degree of substitution is 20 ± 1.8% n-trimethyl chitosan chloride powder, and it is molten to be added to the acetic acid containing 2% (v/v)
In the flask of liquid 30ml, 40 DEG C of progress mechanical stirrings of heating water bath, until cellulose powder is added after n-trimethyl chitosan chloride is completely dissolved
Last 1.0g continues mechanical stirring until being completely dissolved and obtains casting solution.
(2) glutaraldehyde solution of mass fraction 5% is added in casting solution, casting solution quality shared by glutaraldehyde solution
Score is 5%, sufficiently reaction 5min, ultrasonic oscillation 10min, evacuation and centrifugal degassing.Then using the tape casting in horizontal glass plate
Upper casting film, is taken off after natural air drying.
(3) composite membrane is immersed in 0.1M KOH aqueous solution and carries out ion exchange for 24 hours, then composite membrane is fixed on two pieces and is gathered
Between tetrafluoroethene plate, 40 DEG C of drying in oven are placed in film constant weight.
Table 1
Claims (6)
1. a kind of preparation method of full interpenetrating type n-trimethyl chitosan chloride anion-exchange membrane, it is characterised in that comprise the following steps that
Step (1) weighs 2g n-trimethyl chitosan chloride powder, is added in the flask of the acetic acid solvent of 30mL, heats lower carry out machine
Cellulose powder is added until after n-trimethyl chitosan chloride is completely dissolved in tool stirring so that in anionic membrane cellulose quality percentage
Content is 25-50%, continues heating stirring, until being completely dissolved, obtains casting solution；
Glutaraldehyde solution is added into casting solution step (2), and casting solution mass fraction shared by glutaraldehyde solution is 1%-5%, after
Continuous heating stirring, supersonic oscillations, evacuation and centrifugal degassing；Then the tape casting casting film on horizontal glass plate is used, certainly to film
It is taken off after so air-drying spare；
Step (3) will carry out ion exchange in the composite membrane prepared immersion KOH aqueous solution, then composite membrane be fixed on two pieces
Between polyfluortetraethylene plate, it is dried to film constant weight.
2. a kind of preparation method of full interpenetrating type n-trimethyl chitosan chloride anion-exchange membrane according to claim 1, special
Sign is in the step (1) that n-trimethyl chitosan chloride powder degree of substitution is 10%-30%.
3. a kind of preparation method of full interpenetrating type n-trimethyl chitosan chloride anion-exchange membrane according to claim 1, special
Sign is in the step (1) that acetic acid solvent is the acetic acid solvent of volumetric concentration 2%.
4. a kind of preparation method of full interpenetrating type n-trimethyl chitosan chloride anion-exchange membrane according to claim 1, special
Sign is in the step (2) that the mass fraction of glutaraldehyde solution is 2-5%.
5. a kind of preparation method of full interpenetrating type n-trimethyl chitosan chloride anion-exchange membrane according to claim 1, special
Sign is in the step (2), stirs 5min, supersonic oscillations 10min.
6. a kind of preparation method of full interpenetrating type n-trimethyl chitosan chloride anion-exchange membrane according to claim 1, special
Sign is in the step (3), and the composite membrane prepared is immersed 24 h in 0.1M KOH aqueous solution and carries out ion exchange, is set
In 40oC drying in oven is to film constant weight.
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| CN106374125A (en) * | 2016-09-07 | 2017-02-01 | 辽宁石油化工大学 | Preparation method for full interpenetration type anion exchange membrane containing crosslinked guanidine molecules |
| CN106784949A (en) * | 2016-12-08 | 2017-05-31 | 辽宁石油化工大学 | A kind of preparation method of the full interpenetrating type anion-exchange membranes of crosslinking QCS CM Guanidine |
| CN110433673B (en) * | 2019-07-08 | 2021-02-12 | 淮阴师范学院 | Quaternary ammonium salt functionalized polysulfone-nano attapulgite hybrid anion-exchange membrane and preparation method thereof |
| US20210408567A1 (en) | 2020-02-20 | 2021-12-30 | Industry-University Cooperation Foundation Hanyang University Erica Campus | Complex fiber, solid state electrolyte comprising same, and metal-air battery comprising same |
| CN113801353A (en) * | 2021-09-26 | 2021-12-17 | 辽宁石油化工大学 | Preparation method of quaternized chitosan-ethyl silicate organic/inorganic hybrid membrane |
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