CN105924865B - A kind of acidic proton exchange membrane and preparation method thereof - Google Patents
A kind of acidic proton exchange membrane and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to ion exchange field of membrane preparation, more particularly to a kind of acidic proton exchange membrane and preparation method thereof.A kind of preparation method of acidic proton exchange membrane, comprises the following steps：Prepare the mixed liquor containing PVA, PRDS and carbon nanotubes；Mixed liquor forms a film；Film and more aldehyde compounds are subjected to aldolisation, are then immersed in strong acid, then obtain the acidic proton exchange membrane after washing.The preparation method of acidic proton exchange membrane provided by the invention, load body using high molecular dye PRDS as membrane material, PVA is as base material, carbon nanotubes is added into film, film forming is blended in three, then carries out crosslinking Treatment by aldolisation, forms Semi-IPN structure, the heat endurance and oxidation stability of membrane material are improved, improves the properties such as the electrical conductivity of membrane material, moisture content, mechanical performance.
Description
Technical field
The present invention relates to ion exchange field of membrane preparation, in particular to a kind of acidic proton exchange membrane and its preparation
Method.
Background technology
In recent years, many fuel cell barrier film researchers added various inorganic nano fillers, such as Al into film2O3、
SiO2、TiO2Etc., to which every stability of film can be obviously improved on the premise of electrical conductivity is stablized.In these materials,
Carbon nanotubes receives the concern of developers with its unique performance, some fuel cell carbon nanotubes addition dielectric film should
With and give birth to.Carbon nanotubes has special aspect ratio and huge specific surface area, and special biography can be formed after adding various base materials
Guideway, so the nanocomposite formed possesses the mechanical performance that other materials are difficult to match in excellence or beauty, thermal property, chemically
Energy and electric property.For example Liu et al. people with the addition of 0.05% multi-walled carbon nanotube into Nafion membrane, it turns out that, with original
Nafion membrane is compared, and the ionic conductance for adding the film after multi-walled carbon nanotube lifts 5 times, and mechanical performance improves 1.5 times.
Joo et al. adds a kind of functionalized carbon nano-tube into sPAS materials, the fracture strength of the nano composite membrane formed and flexible
Performance is significantly improved, while its ionic conductance also makes moderate progress.Yun et al. with the addition of one kind into SPVA membrane materials
Sulfonic acid multi-walled carbon nano-tube, as a result the moisture content of film declined, heat endurance and mechanical performance are improved.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of preparation method of acidic proton exchange membrane, by high molecular dye PRDS
As the load body of membrane material, PVA adds carbon nanotubes into film as base material, and film forming is blended in three, then crosslinking Treatment,
Semi-IPN structure is formed, improves the properties of membrane material.
The second object of the present invention is to provide acid made from a kind of preparation method of the acidic proton exchange membrane
Proton exchange membrane, relative to existing acidic proton exchange membrane, its heat endurance, electrical conductivity, moisture content, oxidation stability and machine
Tool performance is obviously improved.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of preparation method of acidic proton exchange membrane, comprises the following steps：
Prepare the mixed liquor containing PVA, PRDS and carbon nanotubes；
The mixed liquor film forming；
The film and more aldehyde compounds are subjected to aldolisation, are then immersed in strong acid, then obtain the acid after washing
Property proton exchange.
The preparation method of a kind of acidic proton exchange membrane provided by the invention, using high molecular dye PRDS as membrane material
Load body, PVA add carbon nanotubes into film, three is blended film forming, is then carried out by aldolisation at crosslinking as base material
Reason, forms Semi-IPN structure, improves the heat endurance and oxidation stability of membrane material, improve the electrical conductivity of membrane material, contain
The properties such as water rate, mechanical performance.
In order to which each component distributing in obtained film is homogeneous, each component bridging property is good, and obtained film properties are stablized, preferably
Ground, in the mixed liquor, the weight ratio of PVA, PRDS and carbon nanotubes is 2:0.5-1.5:0.025-0.105.
It is highly preferred that in the mixed liquor, the weight ratio of PVA, PRDS and carbon nanotubes is 2:1:0.025-0.105.
It is distributed in mixed liquor containing PVA, PRDS and carbon nanotubes between each component more uniform；It is more preferable in order to reach
Film-formation result, preferably each distributed components.Preparing the mixed liquor can be prepared by existing technology, can also use with
It is prepared by lower section method：
Further, the mixed liquor is prepared by the following method：
PVA aqueous solutions, PRDS aqueous solutions and carbon nanotubes aqueous dispersions are prepared respectively；
PRDS aqueous solutions are added dropwise in the PVA aqueous solutions, obtain the first mixed liquor；
The carbon nanotubes aqueous dispersions are added dropwise to first mixed liquor, obtain the mixed liquor；
Wherein, it is kept stirring during dropwise addition.
PRDS is directly mixed with PVA to be not easy to mix, and therefore, PRDS aqueous solutions are added to by the present invention in a manner of being added dropwise
In PVA aqueous solutions, it is kept stirring at the same time, mixes both, phase is formed by intermolecular force and interpenetrating structure between the two
Interaction；Further, since carbon nanotube molecule is small, it is not easy to mix, therefore, carbon nanotubes aqueous dispersions are first made, then
It is added in a manner of dropwise addition in the first mixed liquor, is kept stirring at the same time, makes to be distributed between each component homogeneous.Due to carbon nanotubes
Particle diameter is small, and specific surface area is big, has very strong suction-operated, and it can also form hydrogen bond action with other compositions.Therefore,
More homogeneous mixed liquor is formed between each raw material.
PVA contents are high in PVA aqueous solutions, then obtained aqueous solution is not easy to mix；And if PVA contents in PVA aqueous solutions
Low, then water content is too many, the washiness removed after follow-up film forming, processing trouble, it is preferable that in the PVA aqueous solutions, PVA's
Mass concentration is 8%-15%.
Similarly, it is preferable that in the PRDS aqueous solutions, the mass concentration of PRDS is 3%-8%.
PVA aqueous solutions are that PVA is added in deionized water, then heat to 80 ± 5 DEG C, are stirred until dissolved to completely
Dissolving, obtains transparent homogeneous PVA aqueous solutions.
PRDS aqueous solutions are that PRDS is added in deionized water, then heat to 80 ± 5 DEG C, have stirred until dissolved to
Fully dissolved, obtains transparent homogeneous PRDS aqueous solutions.
For the ease of the mutual mixing between each component, and reduce and go water after follow-up film forming, further, the carbon
In nanotube aqueous dispersions, the mass concentration of carbon nanotubes is 0.5%-1.5%.Mass concentration such as carbon nanotubes can be
0.5%th, 0.8%, 1% and 1.5% etc..
Carbon nanotubes particle diameter is small, strong adsorption, it is not easy to is evenly distributed in water, therefore, addition dispersant is so that its point
Cloth is more homogeneous, and empirical tests dispersant selects cetyl trimethylammonium bromide to reach good dispersion effect.Preferably, institute
It is cetyl trimethylammonium bromide to state the dispersant used in carbon nanotubes aqueous dispersions.
In order to which carbon nanotubes distribution is homogeneous in obtained carbon nanotubes aqueous dispersions, further, the carbon nanotubes water
Dispersion liquid is prepared by the following method：
After carbon nanotubes, dispersant and water are mixed, the carbon nanotubes moisture is obtained after ultrasonication is disperseed
Dispersion liquid.
By ultrasonication, to increase the dispersiveness of carbon nanotubes.
Empirical tests, it is preferable that the ultrasonication is：With the Power Processing 40-80min of 80-150W.By the ultrasound
Ripple processing, adds the dispersiveness of carbon nanotubes, meets the demand being subsequently added dropwise well.
In order to which obtained film more fully carries out aldolisation with more aldehyde compounds, it is preferable that the thickness of the film is
50-120μm。
Aldehyde compound need at least two aldehyde radicals so that occur aldolisation after component between can be connected with each other, shape
Reticulate structure, it is preferable that more aldehyde compounds are the compound containing at least two aldehyde radical.Such as：Glyoxal, butanedial,
Malonaldehyde, glutaraldehyde, hexandial, terephthalaldehyde, o-phthalaldehyde, equal benzene trioxin etc..Chemical combination more than general three aldehyde
Thing is using less, synthesis difficulty, therefore, generally using dialdehyde compounds.
Glutaraldehyde is a kind of dialdehyde compounds commonly used in the art, it is preferable that more aldehyde compounds are glutaraldehyde.
The aldolisation is：The film is immersed in more aldehyde compound solution, instills strong acid, it is anti-at 28-32 DEG C
More than 20min is answered, is preferably 25-35min.
More aldehyde compound solution are the aqueous solution or acetone soln of more aldehyde compounds；In more aldehyde compound solution,
The mass concentration of more aldehyde compounds is preferably 8%-12%；Instill strong acid and play catalytic action, strong acid can be hydrochloric acid, sulfuric acid, nitre
Any of acid.
Carry out the film after aldolisation and immerse strong acid, be the SO made in film component3Na types change SO3H-type.Strong acid is generally adopted
With the strong acid of 1.0mol/L, strong acid can be any of hydrochloric acid, sulfuric acid, nitric acid.For the ease of operation, generally film is cut into
The fritter of fritter, such as 1.0 × 2.0cm sizes, is then immersed in strong acid.
Then film water is washed till neutrality, and preserved in deionized water stand-by.
In the present invention, PVA is the english abbreviation of polyvinyl alcohol；PRDS is water soluble chitosan high molecular dye, PRDS's
Chemical formula is：
It is as follows that it prepares reaction equation：
Chitosan and Reactive Brilliant Blue KN-R are subjected to nucleophilic substitution, obtained product in alkaline conditions with chloroethene
Acid carries out substitution reaction, then purified to obtain PRDS up to the product containing PRDS.
Comprise the following steps that：
The synthesis of first step shitosan macromolecule dyestuff
Weigh 5g chitosans (deacetylation 96.31%, 7.9 × 105Da of molecular weight, the limited public affairs of Zhejiang gold section biotechnology
Department) it is placed in 250mL three-neck flasks, distilled water 150mL is added, is sufficiently stirred until chitosan is thoroughly dispersed in graininess
In ionized water, 60 DEG C are warming up to, Reactive Brilliant Blue KN-R (Wujiang Land of Peach Blossoms Dye Co., Ltd, China) 50mL that 10g/L is added dropwise fills
Divide reaction 3h.After reaction, repeatedly washing and filtering product until filtrate it is colourless.Product is placed in baking oven at 60 DEG C to constant temperature is done
It is dry 24 it is small when.
The synthesis of second step water soluble chitosan high molecular dye
The high molecular dye based on CTS that the first step synthesizes is placed in the three-neck flask of 250mL, adds isopropanol
(Changzhou edifies Chemical Co., Ltd., China) 100mL, NaOH6.75g, so that first step synthetic product alkalescence pretreatment
60min.It is accurate to weigh monoxone (Chemical Co., Ltd. of Changzhou Xintai City, China) 7.5g, dissolved with 50mL isopropanols, chlorine can be obtained
One aqueous isopropanol of acetic acid.The temperature of reaction system is raised to 55 DEG C, one aqueous isopropanol of monoxone is added dropwise.It is added dropwise follow-up
Continuous insulation reaction 4h, obtains product water soluble chitosan high molecular dye.
The purification of 3rd step water soluble polymer dyestuff
Contain reaction medium isopropanol, unreacted monoxone and reaction product sodium chloride in second step products therefrom,
Carry out purification processes.
By second step products therefrom isopropanol washing and filtering, to remove unreacted monoxone；Again with 80% ethanol
Solution washing and filtering, to remove the sodium chloride of solvent isopropanol and reaction generation；Finally it is placed in baking oven and dries 24h at 55 DEG C,
Obtain final product.
In addition, the carbon nanotubes in the present invention can be multi-walled carbon nanotube (MWCNTs), or single
Pipe, the performance played are similar.But due to single-walled carbon nanotube higher price, it is therefore preferable that using multi-walled carbon nanotube.
Compared with prior art, beneficial effects of the present invention are：
(1) preparation method of a kind of acidic proton exchange membrane provided by the invention, using high molecular dye PRDS as membrane material
The load body of material, PVA add carbon nanotubes into film, three is blended film forming, is then handed over by aldolisation as base material
Connection processing, forms Semi-IPN structure, improves the heat endurance and oxidation stability of membrane material, improve the conductance of membrane material
The properties such as rate, moisture content, mechanical performance.
(2) present invention also defines PVA, PRDS and the adding proportion of carbon nanotubes, make coordinated between each component, make
The acidic proton exchange membrane obtained forms Semi-IPN structure, improves the heat endurance and oxidation stability of membrane material, improves membrane material
Electrical conductivity, moisture content, the properties such as mechanical performance.
(3) present invention also offers the hybrid mode between the preparation method of each raw material and each raw material so that each raw material
Between form more homogeneous mixed liquor, for be made function admirable acidic proton exchange membrane good basis is provided.
(4) the present invention also provides acidic proton exchange membrane relative to existing acidic proton exchange membrane, its heat endurance,
Electrical conductivity, moisture content, oxidation stability and mechanical performance are obviously improved.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described.
Fig. 1 is the infrared spectrogram of chitosan and PRDS in the embodiment of the present invention 1；
Fig. 2 is uncrosslinked PVA/PRDS films in the embodiment of the present invention 1, crosslinking PVA/PRDS films, uncrosslinked PVA/PRDS/
MWCNTs films and the infrared spectrogram for being crosslinked PVA/PRDS/MWCNTs films；
Fig. 3 is the electron microscope that the section of PVA/PRDS films in the embodiment of the present invention 1 is scanned under 2000 times of Electronic Speculum；
Fig. 4 is the electron microscope that the section of PVA/PRDS films in the embodiment of the present invention 1 is scanned under 5000 times of Electronic Speculum；
Fig. 5 is the electron microscope that the section of PVA/PRDS films in the embodiment of the present invention 1 is scanned under 10000 times of Electronic Speculum；
Fig. 6 is the electricity that the section of PVA/PRDS/MWCNTs films in the embodiment of the present invention 1 is scanned under 2000 times of Electronic Speculum
Mirror figure；
Fig. 7 is the electricity that the section of PVA/PRDS/MWCNTs films in the embodiment of the present invention 1 is scanned under 5000 times of Electronic Speculum
Mirror figure；
Fig. 8 is that what is obtained scanned in the section of PVA/PRDS/MWCNTs films in the embodiment of the present invention 1 under 10000 times of Electronic Speculum
Electron microscope；
Fig. 9 is the electron-microscope scanning figure of PVA/PRDS/MWCNTs film surfaces in the embodiment of the present invention 1；
Figure 10 is the structure diagram of the PVA/PRDS/MWCNTs films in the embodiment of the present invention 1；
Figure 11 is uncrosslinked PVA/PRDS films in the embodiment of the present invention 1, crosslinking PVA/PRDS films and crosslinking PVA/PRDS/
The thermal gravimetric analysis curve figure of MWCNTs films；
Figure 12 is the impedance scatterplot of acidic proton exchange membrane made from different content of carbon nanotubes in the embodiment of the present invention 2
Figure；
Figure 13 is the electrical conductivity cylindricality of acidic proton exchange membrane made from different content of carbon nanotubes in the embodiment of the present invention 2
Figure；
Figure 14 is the moisture content cylindricality of acidic proton exchange membrane made from different content of carbon nanotubes in the embodiment of the present invention 2
Figure；
Figure 15 be in the embodiment of the present invention 2 fracture strength of acidic proton exchange membrane made from different content of carbon nanotubes and
Breaking ductility curve map；
Figure 16 is steady to add and being not added with the oxidation of acidic proton exchange membrane made from carbon nanotubes in the embodiment of the present invention 3
Qualitative scatter diagram.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person, the condition suggested according to normal condition or manufacturer carry out.Reagents or instruments used without specified manufacturer, is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
PVA and PRDS are placed in deionized water respectively, is warming up at 80 DEG C and is sufficiently stirred up to being completely dissolved, be made
Transparent homogeneous 10%PVA solution and 5%PRDS solution；
According to mass ratio PVA/PRDS=1:0.5 mixing, wherein, it is to instill PRDS solution in PVA solution, is sufficiently stirred
Uniformly, PVA/PRDS mixed solutions are obtained；
Take a certain amount of MWCNTs (AlphaNano Technology Co., Ltd., China) selection cetyl trimethylammonium bromide (tall building
Retail sales apex Science and Technology Ltd., China) it is dispersant, 1% carbon nano-tube solution is made into, with the power ultrasonic of 80-150W
Scattered 40-80min, then instills in PVA/PRDS mixed solutions, and the addition weight of MWCNTs is the 3% of PVA and PRDS weight,
Then by mixed solution casting film, the thickness of film is 50-120 μm；
Film after gel is placed in 10% glutaraldehyde (GA) acetone soln, few drops of HCl is instilled, acetal is carried out at 30 DEG C
30min is reacted, so as to be chemically crosslinked between each component；
Film after crosslinking is cut into the fritter of 1.0 × 2.0cm sizes, is dipped in 12h in 1.0M HCl solutions, make its from
SO3Na types change SO3H-type；
It is washed with deionized water to neutrality, and preserves in deionized water stand-by, film is black.
1st, by chitosan, PRDS, uncrosslinked PVA/PRDS films, crosslinking PVA/PRDS films, uncrosslinked PVA/PRDS/MWCNTs
Film and crosslinking PVA/PRDS/MWCNTs films are utilized respectively FTIR-4200 types infrared spectrometric analyzer (Shimadzu, Japan) decay
Total reflection method (ATR) carries out test analysis to the molecular structure of film, and reference background is used as using air.Obtained chitosan and PRDS
Infrared spectrum as shown in Figure 1, uncrosslinked PVA/PRDS films, crosslinking PVA/PRDS films, uncrosslinked PVA/PRDS/MWCNTs films and
The infrared spectrum for being crosslinked PVA/PRDS/MWCNTs films is as shown in Figure 2.
Fig. 1 is Chitosan powder and the infrared spectrogram of water soluble chitosan high molecular dye powder, contrasts two curves
It can be seen that, in 1260cm-1Locate C-N stretching vibration peak remitted its furys, this shows that reactive dye are successfully grafted to chitosan high score
On the free amine group of subchain.1420cm-1、1620cm-1The peak height at place significantly increases, this is because 1420cm-1There is-COO at place-'s
Symmetrical stretching vibration, 1620cm-1There is-COO at place-Antisymmetric stretching vibration, therefore water soluble chitosan high molecular dye may have
There is carboxymethyl structure, show etherification modified more successful.In 1120cm-1The new peak that place occurs is stretched for typical sulfonic group asymmetry
Contracting vibration, 1270-1380cm-1The peak intensity at place substantially increases, and may be caused due to the introducing of sulfuryl.Above analytic explanation dyestuff
Small molecule has been successfully introduced among chitosan macromolecular.
Fig. 2 is uncrosslinked PVA/PRDS films, is crosslinked PVA/PRDS films, uncrosslinked PVA/PRDS/MWCNTs and PVA/PRDS/
The infrared spectrogram of MWCNTs films, can not see the peak in relation to multi-walled carbon nanotube in figure, this is probably because carbon nanotubes
Based on C-C keys, and it is too strong to infrared absorption, and peak type is very weak, is submerged in the spectrogram of matrix；And cross-linking process is brought
C=O keys and C-O-C keys exist in original molecule structure, but be also difficult to embody in spectrogram.
2nd, PVA/PRDS films and PVA/PRDS/MWCNTs films use Quanta200 type scanning electron microscope to the micro- of film
See pattern (FEI, the U.S.) and carry out observation analysis, its morphosis is observed under the conditions of amplification after section metal spraying, as a result such as Fig. 3-5
With shown in Fig. 6-8.Fig. 3-5 is respectively that the section of PVA/PRDS films is carried out respectively at 2000 times, 5000 times and 10000 times of Electronic Speculum
Scan obtained figure；Fig. 6-8 is respectively the section of PVA/PRDS/MWCNTs films respectively at 2000 times, 5000 times and 10000 times
The figure that Electronic Speculum is scanned；Fig. 9 is the electron-microscope scanning figure of PVA/PRDS/MWCNTs film surfaces.
By Fig. 3-5 it can be seen that PVA/PRDS films section is more coarse, there is more fold, there are certain phase separation to show
As membrane material does not occur obvious opening structure, this explanation PVA/PRDS macromolecular chain segment can preferably be accumulated in process of setting.
After adding carbon nanotubes, there are many micropores in film section, this is because drying and process of setting in blended liquid casting film
In, the multi-walled carbon nanotube hydrophily being evenly distributed in film is preferable, can adsorb certain moisture, but it divides greatly in polymer
Play inhibition in subchain section banking process, therefore generate compared with concrete dynamic modulus, and the presence of these holes accelerate it is more
Wall carbon nano tube institute's adsorption moisture is sloughed, so that the number of apertures in film further increases.And multi-walled carbon nanotube
The shear action enhanced to polymer macromolecule segment is added, the molecule segment of smaller can be caused to accumulate, can also be promoted micro-
The formation of pore structure.From surface electron microscope it is also seen that in the preferably embedded film of carbon nanotubes, effectively enhance each in film
The link of composition.Whole film microcosmic surface seems out-of-flatness that this is probably the agglomeration due to CNTs, makes film surface part convex
Rise, destroy the flatness of film.
In addition, the part by weight for changing PVA, PRDS is 2:0.5 and 2：1.5, the PVA/ in obtained infrared spectrum and Fig. 2
PRDS/MWCNTs films are basically identical；Electron-microscope scanning figure is also basically identical with PVA/PRDS/MWCNTs films.
Change the additive amount of carbon nanotubes, the addition of carbon nanotubes is changed into 1%, in obtained infrared spectrum and Fig. 2
PVA/PRDS/MWCNTs films it is basically identical；Electron-microscope scanning figure is also basically identical with PVA/PRDS/MWCNTs films.
According to the infrared absorption spectroscopy of said determination and scanning electron microscope as a result, and according to the principle of reaction it is inferred that this
The structure diagram of acidic proton exchange membrane made from invention is as shown in Figure 10.Each component shape of obtained acidic proton exchange membrane
Structure is reticulated, mesh is thin and close, and PRDS is clamped wherein.
3rd, uncrosslinked PVA/PRDS films, crosslinking PVA/PRDS films and crosslinking PVA/PRDS/MWCNTs films are used
SAT449C types thermogravimetric analyzer (NETSCH, Germany) measures analysis to the heat endurance of film, takes about 10mg sample qualities to put
Enter alumina crucible, with 10 DEG C of min in air atmosphere-1Heating rate rise to 650 DEG C from 30 DEG C, empty alumina crucible is made
Reference, system automatic data collection obtain the weightless value of sample, and obtained thermal gravimetric analysis curve is as shown in figure 11.
It can be seen from figure 11 that three kinds of films show as four-stage.The 80-180 DEG C of volatilization for water and glutaraldehyde；200-
350 DEG C are the fracture of PRDS macromolecular dyestuffs molecular side chain and decomposition, the fracture of PVA partial side-chains of small molecule；400-450 DEG C is
The fracture of two kinds of macromolecular chain skeletons of PVA, PRDS and oxygenolysis, the size formed after 450-550 DEG C of macromolecular chain fracture is not
Deng lower-molecular substance further oxygenolysis.Collection of illustrative plates is contrasted, it can be found that carrying out crosslinking Treatment and adding carbon nanotubes
The heat endurance of membrane material, the T of uncrosslinked PVA/PRDS films can be improved- 10%For 215 DEG C, second stage maximum decomposition temperature is
239℃；It is crosslinked the T of PVA/PRDS films- 10%For 242 DEG C, second stage maximum decomposition temperature is 294 DEG C；It is crosslinked PVA/PRDS/
MWCNTs films T- 10%For 252 DEG C, second stage maximum decomposition temperature is 301 DEG C.Data above also further illustrates crosslinked action
And the addition of carbon nanotubes component enhances the hydrogen bond action in film between each component, the heat endurance of film is improved.
In addition, the part by weight for changing PVA, PRDS is 2:0.5 and 2：1.5, obtained film T- 10%More than 250 DEG C,
Second stage maximum decomposition temperature is more than 300 DEG C；Change the additive amount of carbon nanotubes, the addition of carbon nanotubes is changed into
1%, obtained film T- 10%More than 248 DEG C, second stage maximum decomposition temperature more than 298 DEG C
Embodiment 2
The acidic proton exchange membrane of different content of carbon nanotubes is prepared using method same as Example 1, measure is different
Influence of the content of carbon nanotubes to the electrical conductivity of acidic proton exchange membrane, moisture content, mechanical performance
1st, electrical conductivity and moisture content
Measure respectively and do not add carbon nanotubes, 1% carbon nanotubes, 3% carbon nanotubes, 5% carbon nanotubes, 7% carbon nanometer
The impedance of acidic proton exchange membrane made from pipe and moisture content, according to the impedance of measure, are calculated electrical conductivity, finally obtain
Impedance diagram, conductivity map and the moisture content figure difference of film are as shown in figs. 12-14.
As can be seen from Figure 13, as proton exchange membrane, when MWCNTs additive amounts are 1%-3%, PVA/PRDS/MWCNTs
The conductivity value of film is 1.5 × 10-2More than S/cm, although the electrical conductivity 1.0 × 10 apart from industry mark post Nafion membrane-1S/cm
There is a certain distance.But since conductive group is less in high molecular dye structure, an only sulfonic acid in the unit that success is grafted
Base, although two carboxyls of etherification modified introducing, it is acid weaker as conductive group for carboxyl, causes membrane conductance relatively low；And film
The mass ratio 0.5 of inner macromolecule dyestuff and base material:1 is relatively low, if but further improving high molecular dye containing in film
Amount, two kinds of macromolecular components compatibility poors, mechanical performance decline seriously, are easily broken, therefore must be to two kinds of macromoleculars
Further modification, to improve their compatibility, or find can improve electrical conductivity and can improve toughness the 3rd,
4th component.
From the point of view of Figure 13 and Figure 14, its electrical conductivity, moisture content first increase with the increase of content of carbon nanotubes and reduce afterwards, this
It is because a small amount of multi-walled carbon nanotube is added in film can improve the hydrophily of film, increases its porosity, and it is a certain amount of more
Wall carbon nano tube mutually can be built to form hydrophilic transmission channel in film, thus improve the water content of film, promote film
To the conducting power of ion, but excess moisture, the diluting effect of carrier is increased, causes its electrical conductivity to be declined slightly.If again
Continue to increase multi-walled carbon nanotube, the structure in film will become compact, reduce space existing for hydrone, film it is aqueous
Rate declines, and the transmission of the reduction of moisture to ion has a negative impact.If continuing to improve multi-walled carbon nanotube content, excessive is more
Serious reunion will occur for wall carbon nano tube, destroy the hydrophilic network structure originally tended to be perfect, therefore the moisture content of film is further
Decline, its electrical conductivity also declines therewith.
2nd, mechanical performance
The fracture strength and breaking ductility of the PVA/PRDS/MWCNTs blending proton membranes of different MWCNTs contents are measured,
Ultimate strength and breaking ductility are measured using H5K-S type universal material testings instrument (Hounsfield, Britain), and condition is
Room temperature, relative humidity 65%, draw speed 12mm/min, load 5000N.Sample is cut into the strip of 1 × 5cm, is measured 5 times,
Take its average value.As a result it is as shown in figure 15.
As seen from the figure, with the increase of MWCNTs contents in film, fracture strength and breaking ductility are generally in rising
Trend, fracture strength scope are 16.43MPa-33.6MPa, and breaking ductility scope is 4.1-12.48%.It rises main
Reason one is the link and the motive power that strengthen in film between each component because carbon nanotubes, is advantageously formed tight
The three-dimensional structure gathered；Second, carbon nanotubes has high intensity, toughness and elasticity modulus in terms of mechanics, its mechanical strength exceedes
Any existing material, its mutual supplement with each other's advantages with the compound achievable component material of polymer, but carbon nanotubes have very strong
Van der Waals force, dosage is excessive easily to form beam, so as to influence the performance of its excellent performance.The chitosan-based height used in the present invention
Molecular dye can effectively alleviate this unfavorable factor, this because chitosan macromolecular has complicated double-spiral structure
Double-spiral structure is conducive to the surface that chitosan parcel is wrapped in carbon nanotubes, so as to contribute to the uniform of the carbon nanotubes to be formed
Distribution.Therefore PVA/PRDS/MWCNTs blendings proton membrane mechanical performance is generally in the increase of MWCNTs contents in film
Ascendant trend.If MWCNTs too high levels can still trigger agglomeration in film, phase separation is aggravated, the Microphase Structure of film is destroyed, leads
Strength is caused to decline.
The weight ratio for changing PVA, PRDS is 2:0.5 or 2:1.5 carry out above-mentioned experiments, as a result with the weight ratio of PVA, PRDS
For 2:1 result is basically identical.
Embodiment 3
The oxidation stability of film is an important indicator of fuel cell film practical application.
The present embodiment will prepare the PVA/PRDS/ containing 3% multi-walled carbon nanotube according to the preparation method of embodiment 1
MWCNTs films are not added with the PVA/PRDS films of multi-walled carbon nanotube as a control group, both are immersed in room temperature 30% as test group
(w)H2O2In solution, their quality of Timing measurement, as a result as shown in figure 16.
As seen from the figure, it is larger to be not added with the PVA/PRDS film qualities loss of carbon nanotubes, its interior quality of 250h drops to original
The 67.9% of quality, and the PVA/PRDS/MWCNTs films for adding carbon nanotubes have 11.8% mass loss in preceding 50h, and
After tend towards stability, quality still keeps former film quality 78.8% in 250h, therefore, has also further proved multi-walled carbon nanotube
The formation for being conducive to three-dimensional net structure is added, improves the oxidation stability of film.
In addition, other preparation processes are constant, the content for changing multi-walled carbon nanotube exists for 1%, PVA/PRDS/MWCNTs films
There is 12.1% mass loss in preceding 50h, then tend towards stability, quality still keeps former film quality 76.8% in 250h, obtains
The oxidation stability of film be obviously improved than being not added with the film of multi-walled carbon nanotube.
Similarly, other preparation processes are constant, and the weight ratio for changing PVA, PRDS is 2:0.5 or 2:1.5, PVA/PRDS/
MWCNTs films have less than 12.5% mass loss in preceding 50h, then tend towards stability, and quality still keeps former film quality in 250h
Amount more than 78%, the oxidation stability of obtained film is obviously improved than being not added with the film of multi-walled carbon nanotube.
In addition, uncrosslinked PVA/PRDS films, crosslinking PVA/PRDS films, uncrosslinked PVA/PRDS/ in the embodiment of the present invention
MWCNTs films and crosslinking PVA/PRDS/MWCNTs films in crosslinking with it is uncrosslinked be to be crosslinked with glutaraldehyde, i.e., it is uncrosslinked
PVA/PRDS films are to save addition MWCNTs and and the step of glutaraldehyde cross-linking；It is then to save addition to be crosslinked PVA/PRDS films
The step of MWCNTs, but still be crosslinked with glutaraldehyde；Uncrosslinked PVA/PRDS/MWCNTs films refer to save in whole process with
The step of glutaraldehyde cross-linking.Wherein, it is acidic proton exchange membrane provided by the invention to be crosslinked PVA/PRDS/MWCNTs films.
The present invention also changes the glutaraldehyde in embodiment for glyoxal, butanedial, malonaldehyde, hexandial, terephthaldehyde
Aldehyde, o-phthalaldehyde, equal benzene trioxin etc., it is as a result consistent with glutaraldehyde.
Although being illustrated and the invention has been described with specific embodiment, but will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (14)
1. a kind of preparation method of acidic proton exchange membrane, it is characterised in that comprise the following steps：
Prepare the mixed liquor containing PVA, PRDS and carbon nanotubes；
The mixed liquor film forming；
The film and more aldehyde compounds are subjected to aldolisation, are then immersed in strong acid, then obtain the Acidity after washing
Proton exchange；
In the mixed liquor, the mass ratio of PVA, PRDS and carbon nanotubes is 2:0.5-1.5:0.025-0.105；
PRDS is water soluble chitosan high molecular dye, and the chemical formula of PRDS is：
2. the preparation method of acidic proton exchange membrane according to claim 1, it is characterised in that in the mixed liquor,
The weight ratio of PVA, PRDS and carbon nanotubes is 2:1:0.025-0.105.
3. the preparation method of acidic proton exchange membrane according to claim 1, it is characterised in that the mixed liquor by with
It is prepared by lower section method：
PVA aqueous solutions, PRDS aqueous solutions and carbon nanotubes aqueous dispersions are prepared respectively；
PRDS aqueous solutions are added dropwise in the PVA aqueous solutions, obtain the first mixed liquor；
The carbon nanotubes aqueous dispersions are added dropwise to first mixed liquor, obtain the mixed liquor；
Wherein, it is kept stirring during dropwise addition.
4. the preparation method of acidic proton exchange membrane according to claim 3, it is characterised in that in the PVA aqueous solutions,
The mass concentration of PVA is 8%-15%；
In the PRDS aqueous solutions, the mass concentration of PRDS is 3%-8%；
In the carbon nanotubes aqueous dispersions, the mass concentration of carbon nanotubes is 0.5%-1.5%.
5. the preparation method of acidic proton exchange membrane according to claim 4, it is characterised in that the carbon nanotubes moisture
Dispersant used in dispersion liquid is cetyl trimethylammonium bromide.
6. the preparation method of acidic proton exchange membrane according to claim 4, it is characterised in that the carbon nanotubes moisture
Dispersion liquid is prepared by the following method：
After carbon nanotubes, dispersant and water are mixed, the carbon nanotubes aqueous dispersions are obtained after ultrasonication is disperseed.
7. the preparation method of acidic proton exchange membrane according to claim 6, it is characterised in that the ultrasonication
For：With the Power Processing 40-80min of 80-150W.
8. the preparation method of acidic proton exchange membrane according to claim 1, it is characterised in that the thickness of the film is
50-120μm。
9. the preparation method of acidic proton exchange membrane according to claim 1, it is characterised in that more aldehyde compounds
For the compound containing at least two aldehyde radical.
10. the preparation method of acidic proton exchange membrane according to claim 1, it is characterised in that more aldehyde radical chemical combination
Thing is glyoxal, appointing in butanedial, malonaldehyde, glutaraldehyde, hexandial, terephthalaldehyde, o-phthalaldehyde, equal benzene trioxin
It is one or more.
11. the preparation method of acidic proton exchange membrane according to claim 1, it is characterised in that the aldolisation is：
The film is immersed in more aldehyde compound solution, instills strong acid, more than 20min is reacted at 28-32 DEG C.
12. the preparation method of acidic proton exchange membrane according to claim 1, it is characterised in that the aldolisation is：
The film is immersed in more aldehyde compound solution, strong acid is instilled, reacts 25-35min at 28-32 DEG C.
13. the preparation method of the acidic proton exchange membrane according to claim 11 or 12, it is characterised in that the strong acid is
Any of hydrochloric acid, sulfuric acid, nitric acid.
14. acidic proton exchange membrane made from the preparation method of claim 1-13 any one of them acidic proton exchange membranes.
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