CN106784949A - A kind of preparation method of the full interpenetrating type anion-exchange membranes of crosslinking QCS CM Guanidine - Google Patents
A kind of preparation method of the full interpenetrating type anion-exchange membranes of crosslinking QCS CM Guanidine Download PDFInfo
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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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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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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- 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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
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Abstract
A kind of crosslinking QCS, CM and Guanidine and the fuel cell anion-exchange membrane with excellent alkali stability, mechanical performance and high conductivity and preparation method thereof, belong to field of fuel cell technology.With acetic acid solution as solvent, the quaternised modified rear n-trimethyl chitosan chloride powder with semi-rigid macromolecular scaffold structure is completely dissolved, as film base fluid.Using simple chemical crosslink technique, will there is relatively strong rigid cellulose and the molecule guanidine with double amino to be uniformly doped in casting solution.Immersed in potassium hydroxide solution using the tape casting film that casting film will be dried again in glass plate, prepare hydroxide ion type anion-exchange membrane.Anionic membrane prepared by the present invention has excellent alkali stability, mechanical performance and electric conductivity higher, and the performance for solving anion-exchange membrane generally existing optimizes incomplete problem.
Description
Technical field
The invention belongs to field of fuel cell technology, it is related to the film electrolyte of anion-exchange membrane fuel cells to prepare skill
Art, and in particular to one kind crosslinking full interpenetrating type anion exchange membrane preparation methods of QCS-CM-Guanidine, the method is prepared into
To the fuel cell anion-exchange membrane for having superior electrical conductivity energy, alkali stability and mechanical performance concurrently simultaneously.
Background technology
In recent years, with the aggravation of environmental pollution and consuming excessively for the energy, demand day of the people to new cleaning fuel
Benefit increases, wherein, fuel cell the features such as its generating efficiency is high, environmental pollution is small because receiving much concern.With traditional energy technology
Compare, fuel cell is not limited by Carnot cycle, with power density higher, and pollution is few, environmentally friendly, with hydrogen
For fuel can realize noxious material zero-emission, had a wide range of applications in fields such as space flight, military affairs, the energy and traffic.
Used as the key component of fuel cell, the research of anion-exchange membrane focuses on that balancing fuel cell properties refer to
Mark such as the relation between electrical conductivity, alkali resistance, mechanical strength.The most of conducting films for working out at present are all in some aspect of performances
Performance is excellent, and multinomial performance but can not be comprehensively taken into account relatively, therefore, finding a kind of preparation means simply, can comprehensively have
The method that effect improves film multinomial performance is imperative.
N-trimethyl chitosan chloride (QCS) be natural polymerses shitosan (CS) is carried out it is quaternised modified obtained by
, with semi-rigid macromolecular scaffold and excellent film forming ability, the moon that quaternary ammonium group is formed as anionic electroconductive group
Amberplex is widely used.Guanidine (Guanidine) is a kind of important organic base, and it has 3 N atoms and center C
Atom conjugation special construction, this conjugated structure decide guanidine be just provided with some properties such as electric charge degree of scatter it is high,
Chemically and thermally stability is strong etc., and substituent R on N atoms can freely replace and adjust, and biology is mainly used at present
Pharmacy aspect, application in a fuel cell but rarely has report.Cellulose (CM) is that most wide, content is distributed in nature is most
Natural polysaccharide, its intramolecular and it is intermolecular can be formed hydrogen bond, particularly intramolecular hydrogen bond cause glycosidic bond can not rotate so as to
Rigidity is greatly enhanced, and the water insoluble and general organic solvent of cellulose, it is swelling very limited in a solvent.By guanidine and fibre
Dimension element is incorporated into the middle of basement membrane n-trimethyl chitosan chloride, and the introducing of one side guanidine radicals can improve the alkali resistance and electrical conductivity of film,
On the other hand introducing cellulose can improve the mechanical strength and the stability under liquid environment of film again, effectively solve the moon
The performance of amberplex generally existing optimizes incomplete problem.What is be related in the present invention leads to QCS, CM and Guanidine
Cross crosslinked action and form full inierpeneirating network structure, the method for preparing the anion-exchange membrane with excellent properties is not yet appeared in the newspapers
Road.
The content of the invention
The present invention provides a kind of preparation method of the full interpenetrating type anion-exchange membrane of crosslinking QCS-CM-Guanidine, institute
The anion exchange membrane material of preparation has superior electrical conductivity energy, alkali stability and mechanical performance concurrently simultaneously, can be used as alkaline combustion
Expect the anion-exchange membrane electrolyte of battery.
The preparation method of the full interpenetrating type anion-exchange membrane of QCS-CM-Guanidine is crosslinked, its step is as follows：(1) claim
2.0g n-trimethyl chitosan chloride powder is taken, is added in the flask of the acetic acid solution of 2% (v/v), 50 DEG C of stirrings are heated to, to quaternary ammonium
Change after shitosan is completely dissolved and be cooled to room temperature, add cellulose, stirred under normal temperature, until substantially uniformity mixes；
(2) 2mL cross-linking agent solutions are added into mixed liquor, continues to stir 1min；
(3) Guanidine molecular solution is added, is stirred under normal temperature, until substantially uniformity mixes, obtain casting solution；
(4) 2mL cross-linking agent solutions are added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation 5min, centrifugation
Deaeration, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying, obtain composite membrane；
(5) composite membrane is immersed into 0.1molL-124h is kept in the KOH aqueous solution carries out ion exchange, then composite membrane is consolidated
It is scheduled between two pieces of polyfluortetraethylene plates, is placed in 60 DEG C of drying in oven to film constant weight.
Further, the substitution value of n-trimethyl chitosan chloride is 10%~30% in step (1) of the present invention.
Further, in step (1) of the present invention the mass percent of cellulose account for raw material gross mass 10%~
50%.
Further, the mass percent of Guanidine molecular fluids accounts for raw material gross mass in step (3) of the present invention
0.5%~2.5%.
Further, crosslinking agent is glutaraldehyde in step (2) of the present invention and (4), and the mass concentration of crosslinking agent is 0.5
~3.0%.
Anionic membrane prepared by the present invention has good mechanical strength and alkali stability, while having taken into account electricity higher
Conductance, electrical conductivity can reach 5.13 × 10 under the conditions of 70 DEG C-2S·cm-1, through 4molL-1NaOH concentrated solutions in impregnate 96h,
The loss amount of the electrical conductivity of film is only 4%, and the loss amount of ion exchange capacity is 7%, illustrate the method can effectively improve the moon from
The combination property of proton exchange.In sum, the full interpenetrating type anionic membranes of QCS-CM-Guanidine that prepared by the present invention, it is and existing
The composite membrane that some fuel cells are used is compared, with advantages below：
(1) introducing of CM improves the mechanical performance and the stability under liquid environment of film, Guanidine molecular fluids
Be introduced into the electrical conductivity and the stability in high concentration alkali solution that improve film.
(2) the full inierpeneirating network structure that CM and Guanidine and n-trimethyl chitosan chloride are formed by OH- " locking " in micropore cave
Among, lift the ion exchange capacity and electrical conductivity of film.
Brief description of the drawings
Fig. 1 is the preparation process figure of anionic membrane.
Fig. 2 is pure CS films, pure QCS films, QCS-CM films, the infrared spectrogram of the film of embodiment 2.
Fig. 3 is anionic membrane conductivity variations situation at different temperatures prepared by 1~example of embodiment 5.
Impregnated not in 10molL-1NaOH solution under the anion-exchange membrane normal temperature that Fig. 4 is prepared for 1~example of embodiment 5
With ion exchange capacity situation of change after the time.
Fig. 5 is that anion-exchange membrane prepared by 1~example of embodiment 5 impregnates different time in 10molL-1NaOH solution
Afterwards, conductivity values situation of change under the conditions of 70 DEG C.
Table 1 is pure QCS films, and embodiment 2, embodiment 6, embodiment 7, embodiment 8, anionic membrane prepared by embodiment 9 exists
Swellbility at room temperature, moisture content, tensile strength, the measurement result of elongation at break.
Specific embodiment
The method of the present invention is further illustrated by the following examples.
Embodiment 1
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 20 ± 1.8%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 0.4g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 2wt% is added into mixed liquor, continues to stir 1min.
(3) 0.2g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 2wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation
5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 2
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 20 ± 1.8%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 0.4g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 2wt% is added into mixed liquor, continues to stir 1min.
(3) 0.4g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 2wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation
5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 3
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 20 ± 1.8%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 0.4g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 2wt% is added into mixed liquor, continues to stir 1min.
(3) 0.6g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 2wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation
5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 4
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 20 ± 1.8%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 0.4g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 2wt% is added into mixed liquor, continues to stir 1min.
(3) 0.8g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 2wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation
5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 5
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 20 ± 1.8%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 0.4g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 2wt% is added into mixed liquor, continues to stir 1min.
(3) 1.0g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 2wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation
5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 6
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 20 ± 1.8%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out under heating, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, add 0.2g
Cellulose powder, stirs under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 2wt% is added into mixed liquor, continues to stir 1min.
(3) 0.4g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 2wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation
5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 7
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 20 ± 1.8%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 0.6g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 2wt% is added into mixed liquor, continues to stir 1min.
(3) 0.4g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 2wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation
5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 8
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 20 ± 1.8%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 0.8g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 2wt% is added into mixed liquor, continues to stir 1min.
(3) 0.4g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 2wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation
5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 9
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 20 ± 1.8%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 1.0g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 2wt% is added into mixed liquor, continues to stir 1min.
(3) 0.4g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 2wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation
5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 10
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 20 ± 1.8%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 0.4g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 0.5wt% is added into mixed liquor, continues to stir 1min.
(3) 0.4g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 0.5wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic wave shake
Swing 5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 11
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 20 ± 1.8%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 0.4g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 1wt% is added into mixed liquor, continues to stir 1min.
(3) 0.4g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 1wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation
5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 12
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 20 ± 1.8%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 0.4g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 1.5wt% is added into mixed liquor, continues to stir 1min.
(3) 0.4g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 1.5wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic wave shake
Swing 5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 13
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 20 ± 1.8%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 0.4g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 2.5wt% is added into mixed liquor, continues to stir 1min.
(3) 0.4g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 2.5wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic wave shake
Swing 5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 14
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 20 ± 1.8%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 0.4g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 3wt% is added into mixed liquor, continues to stir 1min.
(3) 0.4g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 3wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation
5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 15
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 10 ± 3.1%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 0.4g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 2wt% is added into mixed liquor, continues to stir 1min.
(3) 0.4g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 2wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation
5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Embodiment 16
(1) 2.0g n-trimethyl chitosan chlorides powder (substitution value 30 ± 1.2%) is weighed, the acetic acid containing 2% (v/v) is added to molten
In the flask of liquid solvent, mechanical agitation is carried out at being heated to 50 DEG C, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, plus
Enter 0.4g cellulose powders, stirred under normal temperature, until substantially uniformity mixes.
(2) glutaraldehyde solution of 2mL 2wt% is added into mixed liquor, continues to stir 1min.
(3) 0.4g Guanidine molecular solution (5wt%) are added, is stirred under normal temperature, until substantially uniformity mixes.
(4) glutaraldehyde solution of 2mL 2wt% is added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation
5min, evacuation and centrifugal degassing, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying.
(5) composite membrane is immersed into 0.1molL-124h carries out ion exchange in the KOH aqueous solution, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
Table 1
Claims (5)
1. a kind of preparation method of the full interpenetrating type anion-exchange membranes of crosslinking QCS-CM-Guanidine, its feature includes following steps
Suddenly：
(1) 2.0g n-trimethyl chitosan chloride powder is weighed, is added in the flask of the acetic acid solution of 2% (v/v), be heated to 50 DEG C and stir
Mix, room temperature is cooled to after being completely dissolved to n-trimethyl chitosan chloride, add cellulose, stirred under normal temperature, until substantially uniformity mixes；
(2) 2mL cross-linking agent solutions are added into mixed liquor, continues to stir 1min；
(3) Guanidine molecular solution is added, is stirred under normal temperature, until substantially uniformity mixes, obtain casting solution；
(4) 2mL cross-linking agent solutions are added into above-mentioned casting solution, continues to stir 1min, ultrasonic oscillation 5min, centrifugation is de-
Bubble, using the tape casting in horizontal glass plate casting film, it is standby after being taken off after film natural air drying, obtain composite membrane；
(5) composite membrane is immersed into 0.1molL-124h is kept in the KOH aqueous solution carries out ion exchange, then composite membrane is fixed on
Between two pieces of polyfluortetraethylene plates, 60 DEG C of drying in oven to film constant weight are placed in.
2. the preparation side of the full interpenetrating type anion-exchange membranes of a kind of crosslinking QCS-CM-Guanidine as claimed in claim 1
Method, it is characterised in that the substitution value of n-trimethyl chitosan chloride is 10%~30% in the step (1).
3. the preparation side of the full interpenetrating type anion-exchange membranes of a kind of crosslinking QCS-CM-Guanidine as claimed in claim 1
Method, it is characterised in that the cellulose added in the step (1), should make its mass percent account for raw material gross mass 10%~
50%.
4. the preparation method of a kind of crosslinking QCS-CM-Guanidine full interpenetrating type anion-exchange membranes as claimed in claim 1,
It is characterized in that step (3) add Guanidine molecular fluids make its mass percent account for raw material gross mass 0.5%~
2.5%.
5. the preparation method of a kind of crosslinking QCS-CM-Guanidine full interpenetrating type anion-exchange membranes as claimed in claim 1,
It is characterized in that crosslinking agent is glutaraldehyde in step (2) and (4), the mass concentration of crosslinking agent is 0.5~3.0%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111359453A (en) * | 2020-03-21 | 2020-07-03 | 山东科技大学 | Imidazole-doped ionic liquid/modified chitosan homogeneous anion exchange membrane and preparation method thereof |
| 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 |
| JP2023515491A (en) * | 2020-02-20 | 2023-04-13 | 漢陽大学校エリカ産学協力団 | Composite fiber, solid electrolyte containing the same, and metal-air battery containing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104966843A (en) * | 2015-04-28 | 2015-10-07 | 大连理工大学 | Cross-linking type anion membrane and preparation method thereof |
| CN105733004A (en) * | 2016-04-21 | 2016-07-06 | 辽宁石油化工大学 | Preparation method of full-interpenetrating-type quaternized chitosan anion exchange membrane |
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2016
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104966843A (en) * | 2015-04-28 | 2015-10-07 | 大连理工大学 | Cross-linking type anion membrane and preparation method thereof |
| CN105733004A (en) * | 2016-04-21 | 2016-07-06 | 辽宁石油化工大学 | Preparation method of full-interpenetrating-type quaternized chitosan anion exchange membrane |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023515491A (en) * | 2020-02-20 | 2023-04-13 | 漢陽大学校エリカ産学協力団 | Composite fiber, solid electrolyte containing the same, and metal-air battery containing the same |
| JP7448998B2 (en) | 2020-02-20 | 2024-03-13 | 漢陽大学校エリカ産学協力団 | Composite fiber, solid electrolyte containing the same, and metal-air battery containing the same |
| CN111359453A (en) * | 2020-03-21 | 2020-07-03 | 山东科技大学 | Imidazole-doped ionic liquid/modified chitosan homogeneous anion exchange membrane and preparation method thereof |
| 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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