CN105694088B - A kind of preparation method and application of polyvinyl alcohol/chitosan solid electrolytic thin-membrane - Google Patents
A kind of preparation method and application of polyvinyl alcohol/chitosan solid electrolytic thin-membrane Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and applications of polyvinyl alcohol/chitosan solid electrolytic thin-membrane.The lewis acidity inorganic salts aluminum chloride aqueous solution that can dissolve chitosan and plasticization and modification polyvinyl alcohol/Chitosan Composites simultaneously is used as chitosan solvent, avoid the use of the volatile organic acids such as acetic acid in the dissolving of chitosan, original polyvinyl alcohol/chitosan laminated film is prepared, it is crosslinked by way of subsequently adding in formalin and impregnating, and polyvinyl alcohol/chitosan film after crosslinking is put into immersion modification in NaOH solution and obtains polyvinyl alcohol/chitosan solid electrolytic thin-membrane.Prepared polyvinyl alcohol/chitosan solid electrolytic thin-membrane has good water resistance and dimensional stability, and the ionic conductivity of film greatly enhances, and ionic conductivity is up to 1.06 × 10‑2(S·cm‑1), methanol permeability is up to 5.23 × 10‑6(cm2·s‑1)。
Description
Technical field
The invention belongs to material preparation and electrochemical technology field, more particularly to a kind of polyvinyl alcohol/chitosan solid electricity
Solve the preparation method and application of matter film.
Background technology
Polymer electrolyte film can not only be used for solid electrolyte, and can prevent oozing for substance between galvanic anode and cathode
Thoroughly, the Primary Component for obtaining high performance fuel cell has been increasingly becomed.Nafion diaphragms are considered as state-of-the-art be used for
The polymer electrolyte film of direct methanol fuel cell.The chemically and physically stability that Nafion films have had, and have
There is high proton conductivity.But Nafion films are expensive, and commercialized Nafion films have very high methanol permeability
Problem, when making diaphragm using Nafion films, methanol easily penetrates into cathode from anode.
Polyvinyl alcohol is a kind of semicrystalline polymeric, have good chemical stability, hydrophily, corrosion resistance and compared with
Excellent mechanical property, and polyvinyl alcohol derives from a wealth of sources, price is relatively low.Polyvinyl alcohol as a kind of water-soluble high-molecular material, because
It is widely used in fiber, film, gel with good water solubility, film forming, cementability, emulsibility and barrier property
The fields of grade.
Chitosan is existed on the earth next in number only to the main of the second largest natural macromolecular material chitin of cellulose
Derivative.Chitosan is by the product of chitosan moiety N- deacetylations and the most important derivative of chitin.Chitosan is
A kind of water-soluble natural polymer has excellent film forming, antibiotic property and good biodegradable and biofacies
Capacitive, and the reactive group of chitosan（Amino and hydroxyl）To certain electroactive substances have very strong chelating, absorption and
Ion exchange so that chitosan all shows very strong application prospect in fields such as film, fiber, hydrogels.
By polyvinyl alcohol and chitosan it is compound after polyvinyl alcohol/chitosan laminated film, and this THIN COMPOSITE can be prepared
Film has preferable mechanical property and thermal stability.Polyvinyl alcohol and chitosan have preferable methanol barrier property, are prepared into
The polyvinyl alcohol arrived/chitosan laminated film also has preferable methanol barrier property.On polyvinyl alcohol and chitosan molecule chain
Contain a large amount of amino and hydroxyl so that polyvinyl alcohol/chitosan laminated film has preferable ionic conducting property.Polyethylene
Alcohol/chitosan film is expected to apply in solid electrolyte film field, and solid electricity is prepared as raw material using polyvinyl alcohol and chitosan
Solving matter film has very big cost advantage.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of polyvinyl alcohol/chitosan solid electrolyte
The preparation method of film.Prepared polyvinyl alcohol/chitosan solid electrolytic thin-membrane has good water resistance and size
Stability, the ionic conductivity of film greatly enhance, and ionic conductivity is up to 1.06 × 10-2 (S·cm-1), methanol permeability reaches
5.23×10-6 (cm2·s-1)。
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of polyvinyl alcohol/chitosan solid electrolytic thin-membrane, is as follows：
(1) chitosan is dissolved in aluminum chloride aqueous solution, stirring in water bath prepares chitosan solution, and polyvinyl alcohol is added in
In deionized water, stirring in water bath prepares poly-vinyl alcohol solution, by gained chitosan solution with being stirred under poly-vinyl alcohol solution water-bath
0.5 h is blended；
(2) mixed solution obtained by step (1) at 50 ~ 60 DEG C is dried in vacuo 48 h and obtains polyvinyl alcohol/chitosan
Film；
(3) polyvinyl alcohol/chitosan film obtained by step (2) is added in the mixed solution of formaldehyde and acetone, institute
Salt acid as catalyst, wherein formaldehyde are also added into the formaldehyde and the mixed solution of acetone stated：Acetone：The volume ratio of hydrochloric acid is 1:
2:It is taken out after 0.01,1 h of cross-linking reaction, and the organic solvent of film surface is remained in 3 removings of deionized water flushing, obtain first
Crosslinked polyvinyl alcohol/the chitosan film of aldehyde；
（4）Polyvinyl alcohol/the chitosan film of formaldehyde crosslinking prepared in step (3) is done in 50 DEG C of vacuum drying ovens
It after dry 24 h, is put into NaOH solution and 2 h is impregnated at 25 DEG C, polyvinyl alcohol/chitosan solid electrolytic thin-membrane is made.
The mass fraction of aluminium chloride is the wt% of 1 wt% ~ 3 in liquor alumini chloridi described in step (1), shell in chitosan solution
The mass fraction of glycan is the wt% of 2 wt% ~ 5, and poly-vinyl alcohol solution mass fraction is the wt% of 5 wt% ~ 10.
The polyvinyl alcohol and the mass ratio of chitosan added in step (1) is 2 ~ 4:1.
Polyvinyl alcohol/chitosan film and the mass ratio of formaldehyde and the mixed solution of acetone are 1 in step (3):10~20.
Bath temperature is 85 ~ 90 DEG C in step (1).
NaOH solution mass fraction used in step (4) is the wt% of 30 wt% ~ 40.
Prepared polyvinyl alcohol/chitosan solid electrolytic thin-membrane is used for direct solid fuel cell diaphragm field.
The beneficial effects of the present invention are：
（1）Polyvinyl alcohol/chitosan solid electrolytic thin-membrane of the present invention uses aluminum chloride aqueous solution as chitosan solvent,
Film is prepared by solution film formation, and using post-process crosslinked mode improve polyvinyl alcohol/chitosan water resistance and
Dimensional stability；
（2）Chitosan solvent aluminum chloride aqueous solution can also provide chlorion for polyvinyl alcohol/chitosan film, reduce poly- second
The crystal property of enol/chitosan film, improves the ionic conductivity of polyvinyl alcohol/chitosan film, and ionic conductivity reaches
1.06×10-2(S·cm-1), methanol permeability is up to 5.23 × 10-6(cm2·s-1)；
（3）Polyvinyl alcohol provided by the invention/chitosan solid electrolytic thin-membrane can be used for methanol fuel cell diaphragm etc.
Field may replace Nafion films, substantially reduce its cost.
Specific embodiment
The present invention is specifically described below by specific embodiment.It is necessarily pointed out that following embodiment is only
It is used to further illustrate the present invention, it is impossible to be interpreted as limiting the scope of the invention, which is skilled in technique
Personnel can make the present invention according to foregoing invention content some nonessential modifications and adaptations.
Embodiment 1
(1) 2.0 g chitosans are dissolved in 1 wt% aluminum chloride aqueous solutions, 2 h dissolvings is stirred at 90 DEG C of water-bath, are prepared
Chitosan solution is obtained, the mass fraction of chitosan is 2 wt%；4.0 g polyvinyl alcohol are added in deionized water, water-bath 90
2 h are stirred at DEG C, obtain poly-vinyl alcohol solution, poly-vinyl alcohol solution mass fraction is 5 wt%；By gained chitosan solution with gathering
0.5 h is blended under 85 DEG C of water-baths of glycohol solution；
(2) mixed solution obtained by step (1) at 60 DEG C is dried in vacuo 48 h to obtain polyvinyl alcohol/chitosan thin
Film；
(3) polyvinyl alcohol/chitosan film obtained by step (2) is added in the mixed solution of formaldehyde and acetone, institute
Salt acid as catalyst, wherein formaldehyde are also added into the formaldehyde and the mixed solution of acetone stated：Acetone：The volume ratio of hydrochloric acid is 1:
2:It is taken out after 0.01,1 h of cross-linking reaction, and the organic solvent of film surface is remained in 3 removings of deionized water flushing, obtain first
Crosslinked polyvinyl alcohol/the chitosan film of aldehyde；
(4) polyvinyl alcohol/chitosan film of formaldehyde crosslinking prepared in step (3) is done in 50 DEG C of vacuum drying ovens
It after dry, be put into 40 wt%NaOH solution and impregnate 2 h at 25 DEG C, polyvinyl alcohol/chitosan polymer electrolytic thin-membrane is made.
Polyvinyl alcohol/chitosan film and the mass ratio of formaldehyde and the mixed solution of acetone are 1 in step (3):10.
Embodiment 2
(1) 2.0 g chitosans are dissolved in 3 wt% aluminum chloride aqueous solutions, 2 h dissolvings is stirred at 88 DEG C of water-bath, are prepared
Chitosan solution is obtained, the mass fraction of chitosan is 3 wt%；8.0 g polyvinyl alcohol are added in deionized water, water-bath 90
2 h are stirred at DEG C, obtain poly-vinyl alcohol solution, poly-vinyl alcohol solution mass fraction is 8 wt%；By gained chitosan solution with gathering
0.5 h is blended under 88 DEG C of water-baths of glycohol solution；
(2) mixed solution obtained by step (1) at 50 DEG C is dried in vacuo 48 h to obtain polyvinyl alcohol/chitosan thin
Film；
(3) polyvinyl alcohol/chitosan film obtained by step (2) is added in the mixed solution of formaldehyde and acetone, institute
Salt acid as catalyst, wherein formaldehyde are also added into the formaldehyde and the mixed solution of acetone stated：Acetone：The volume ratio of hydrochloric acid is 1:
2:It is taken out after 0.01,1 h of cross-linking reaction, and the organic solvent of film surface is remained in 3 removings of deionized water flushing, obtain first
Crosslinked polyvinyl alcohol/the chitosan film of aldehyde；
(4) polyvinyl alcohol/chitosan film of formaldehyde crosslinking prepared in step (3) is done in 50 DEG C of vacuum drying ovens
It after dry, be put into 30 wt%NaOH solution and impregnate 2 h at 25 DEG C, polyvinyl alcohol/chitosan polymer electrolytic thin-membrane is made.
Polyvinyl alcohol/chitosan film and the mass ratio of formaldehyde and the mixed solution of acetone are 1 in step (3): 15.
Embodiment 3
(1) 2.0 g chitosans are dissolved in 1 wt% aluminum chloride aqueous solutions, 2 h dissolvings is stirred at 85 DEG C of water-bath, are prepared
Chitosan solution is obtained, the mass fraction of chitosan is 5 wt%；6.0 g polyvinyl alcohol are added in deionized water, water-bath 90
2 h are stirred at DEG C, obtain poly-vinyl alcohol solution, poly-vinyl alcohol solution mass fraction is 10 wt%；By gained chitosan solution with
0.5 h is blended under 90 DEG C of water-baths of poly-vinyl alcohol solution；
(2) mixed solution obtained by step (1) at 55 DEG C is dried in vacuo 48 h to obtain polyvinyl alcohol/chitosan thin
Film；
(3) polyvinyl alcohol/chitosan film obtained by step (2) is added in the mixed solution of formaldehyde and acetone, institute
Salt acid as catalyst, wherein formaldehyde are also added into the formaldehyde and the mixed solution of acetone stated：Acetone：The volume ratio of hydrochloric acid is 1:
2:It is taken out after 0.01,0.5 h of cross-linking reaction, and the organic solvent of film surface is remained in 3 removings of deionized water flushing, obtained
Polyvinyl alcohol/chitosan film of formaldehyde crosslinking；
(4) polyvinyl alcohol/chitosan film of formaldehyde crosslinking prepared in step (3) is done in 50 DEG C of vacuum drying ovens
It after dry, be put into 35 wt%NaOH solution and impregnate 2 h at 25 DEG C, polyvinyl alcohol/chitosan polymer electrolytic thin-membrane is made.
Polyvinyl alcohol/chitosan film and the mass ratio of formaldehyde and the mixed solution of acetone are 1 in step (3):20.
Performance test
Polyvinyl alcohol/chitosan is used for the research of methanol fuel cell diaphragm.
Polyvinyl alcohol prepared by embodiment 2/chitosan laminated film is used to detect its ionic conductivity and methanol is saturating
Rate is crossed, experimental procedure is as follows：
The ionic conductivity of film is measured on electrochemical apparatus by double probe AC impedance spectrometries, test frequency range
For 0.1 ~ 1 Hz.Polyvinyl alcohol/chitosan film is put into deionized water before test and impregnates 48 h.By electrochemistry work during test
Make station to be placed in the chest for being placed with deionized water, to ensure that test measures under 100% humidity.The ion-conductance of laminated film
Conductance б (Scm-1) calculate it is as follows：
б = l /Rb * A
In formula,lDistance (cm) between two stainless steel electrodes；A is the cross-sectional area (cm of film2)；RbFor ohmic internal resistance
(Ω), is measured by AC impedence method.
The methanol permeability of laminated film is measured using disperser.Disperser contains supply tank and receiving slit, supply
2 M methanol aqueous solutions are placed in slot, deionized water is placed in receiving slit.It is equipped among two slots and impregnates in deionized water
The polyvinyl alcohol of 24 h/chitosan laminated film.Magnetic agitation is equipped in supply tank and receiving slit.Based on concentration difference, first
Alcohol can be spread from supply tank into receiving slit.The liquid in receiving slit is all changed into deionized water every the set time, and lead to
It crosses gas chromatographic analysis and measures methanol concentration in receiving slit solution.The methanol permeability of laminated film is calculated by following formula：
P is expanding coefficient (cm in formula2·s-1), CB(t) it is the methanol concentration in receiving slit under t moment, toWhen being initial
Between, CAFor the initial methanol concentration in supply tank, V is the volume of supply tank or receiving slit.A is effective infiltrating area, and L is effective
Permeability-thickness.
Subordinate list 1 gives the methanol permeability and ionic conductivity of polyvinyl alcohol/chitosan laminated film
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (7)
1. the preparation method of a kind of polyvinyl alcohol/chitosan solid electrolytic thin-membrane, which is characterized in that be as follows：
(1) chitosan is dissolved in aluminum chloride aqueous solution, stirring in water bath prepares chitosan solution, by polyvinyl alcohol addition go from
In sub- water, stirring in water bath prepares poly-vinyl alcohol solution, by blended under agitation under gained chitosan solution and poly-vinyl alcohol solution water-bath
0.5 h；
(2) mixed solution obtained by step (1) at 50 ~ 60 DEG C is dried in vacuo 48 h and obtains polyvinyl alcohol/chitosan film；
(3) polyvinyl alcohol/chitosan film obtained by step (2) is added in the mixed solution of formaldehyde and acetone, it is described
Salt acid as catalyst, wherein formaldehyde are also added into the mixed solution of formaldehyde and acetone：Acetone：The volume ratio of hydrochloric acid is 1:2:
It is taken out after 0.01,1 h of cross-linking reaction, and the organic solvent of film surface is remained in 3 removings of deionized water flushing, obtain formaldehyde
Crosslinked polyvinyl alcohol/chitosan film；
（4）By the polyvinyl alcohol/chitosan film of formaldehyde crosslinking prepared in step (3) dry 24 in 50 DEG C of vacuum drying ovens
It after h, is put into NaOH solution and 2 h is impregnated at 25 DEG C, polyvinyl alcohol/chitosan solid electrolytic thin-membrane is made.
2. a kind of preparation method of polyvinyl alcohol/chitosan solid electrolytic thin-membrane according to claim 1, feature
It is：The mass fraction of aluminium chloride is the wt% of 1 wt% ~ 3 in aluminum chloride aqueous solution described in step (1), shell in chitosan solution
The mass fraction of glycan is the wt% of 2 wt% ~ 5, and poly-vinyl alcohol solution mass fraction is the wt% of 5 wt% ~ 10.
3. a kind of preparation method of polyvinyl alcohol/chitosan solid electrolytic thin-membrane according to claim 1, feature exist
In：The polyvinyl alcohol and the mass ratio of chitosan added in step (1) is 2 ~ 4:1.
4. a kind of preparation method of polyvinyl alcohol/chitosan solid electrolytic thin-membrane according to claim 1, feature exist
In：Polyvinyl alcohol/chitosan film and the mass ratio of formaldehyde and the mixed solution of acetone are 1 in step (3):10~20.
5. a kind of preparation method of polyvinyl alcohol/chitosan solid electrolytic thin-membrane according to claim 1, feature exist
In：Bath temperature is 85 ~ 90 DEG C in step (1).
6. a kind of preparation method of polyvinyl alcohol/chitosan solid electrolytic thin-membrane according to claim 1, feature exist
In：NaOH solution mass fraction used in step (4) is the wt% of 30 wt% ~ 40.
7. the application of polyvinyl alcohol/chitosan solid electrolytic thin-membrane made from a kind of preparation method as described in claim 1,
It is characterized in that：Prepared polyvinyl alcohol/chitosan solid electrolytic thin-membrane is used for direct solid fuel cell diaphragm field.
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| CN107895812A (en) * | 2017-11-16 | 2018-04-10 | 浙江中科立德新材料有限公司 | A kind of solid electrolyte film preparation method based on the macromolecule modified gelatin polymer of natural polysaccharide |
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| CN108823983B (en) * | 2018-05-29 | 2020-07-07 | 福州大学 | Preparation method of quaternized polyvinyl alcohol/chitosan electrostatic spinning solid electrolyte film |
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| CN101418080A (en) * | 2008-11-13 | 2009-04-29 | 北京科技大学 | Method for preparing chitosan proton exchange membrane for hydrogen sensor |
| CN103601904A (en) * | 2013-11-21 | 2014-02-26 | 福州大学 | Preparation method of chitosan/polyvinyl alcohol composite material |
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2016
- 2016-04-11 CN CN201610219938.1A patent/CN105694088B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418080A (en) * | 2008-11-13 | 2009-04-29 | 北京科技大学 | Method for preparing chitosan proton exchange membrane for hydrogen sensor |
| CN103601904A (en) * | 2013-11-21 | 2014-02-26 | 福州大学 | Preparation method of chitosan/polyvinyl alcohol composite material |
Non-Patent Citations (1)
| Title |
|---|
| "Characterization of chitosan/PVA blended electrolyte doped with NH4I";M.H. Buraidah;《Journal of Non-Crystalline Solids》;20110616(第357期);第3261–3266页 * |
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