CN107383405B - Composite proton exchange membrane and preparation method thereof - Google Patents

Composite proton exchange membrane and preparation method thereof Download PDF

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CN107383405B
CN107383405B CN201710653736.2A CN201710653736A CN107383405B CN 107383405 B CN107383405 B CN 107383405B CN 201710653736 A CN201710653736 A CN 201710653736A CN 107383405 B CN107383405 B CN 107383405B
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exchange membrane
proton exchange
composite proton
carbon nano
chitosan
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汪杰
欧颖
刘海
文胜
龚春丽
汪广进
郑根稳
覃彩芹
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Hubei Engineering University
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Abstract

The invention provides a composite proton exchange membrane and a preparation method thereof, relating to the field of fuel cells. The preparation method of the composite proton exchange membrane comprises the following steps: preparing carbon nano tubes coated with zirconium sulfide into dispersion liquid, mixing the dispersion liquid with an acid solution of chitosan, drying to obtain a dry film, washing the dry film with alkali, washing with water to neutrality, and obtaining the composite proton exchange membrane under the action of a cross-linking agent. The prepared composite proton exchange membrane has good water absorption, proton conductivity, mechanical property and thermal stability, and has wide application prospect in polymer-based fuel cells.

Description

Composite proton exchange membrane and preparation method thereof
Technical Field
The invention relates to the field of fuel cells, in particular to a composite proton exchange membrane and a preparation method thereof.
Background
As a proton exchange membrane with research potential, the chitosan has the characteristics of low price, environmental friendliness and the like, and also has the characteristics of no restriction on applicable environment and low permeability with methanol.
However, the proton exchange membrane is prepared directly using chitosan, or the mono-group (-OH, -NH) carried on the chitosan matrix2) The composite proton exchange membranes prepared after modification all have the problems of insufficient flexibility, mechanical property and thermal stability of the membranes.
The invention is provided in view of the above.
Disclosure of Invention
The invention aims to provide a preparation method of a composite proton exchange membrane, which uses super-strong solid acid-zirconium sulfide oxide with good hydrophilicity and proton conductivity to form a coating layer on the surface of a carbon nano tube, on one hand, the surface coating can effectively weaken the interaction between the Carbon Nano Tubes (CNTs), improve the dispersion and the compatibility with a matrix, and fully play the reinforcing role of the carbon nano tube; on the other hand, the existence of the surface proton conductor provides a new proton conduction path for the composite membrane.
The invention also aims to provide a composite proton exchange membrane which is prepared by the preparation method of the composite proton exchange membrane, has good water absorption, proton conductivity, mechanical property and thermal stability, and has wide application prospect in polymer-based fuel cells.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a preparation method of a composite proton exchange membrane, which comprises the following steps:
preparing carbon nano tubes coated with zirconium sulfide into dispersion liquid, mixing the dispersion liquid with an acid solution of chitosan, drying to obtain a dry film, washing the dry film with alkali, washing with water to neutrality, and obtaining the composite proton exchange membrane under the action of a cross-linking agent.
A composite proton exchange membrane is prepared according to the preparation method of the composite proton exchange membrane.
The manufacturing process of the embodiment of the invention has the beneficial effects that:
according to the preparation method of the composite proton exchange membrane, the vulcanized zirconia with good hydrophilicity and proton conductivity is used for forming the coating layer on the surface of the carbon nano tube, so that the dispersibility of the carbon nano tube in the polymer matrix can be improved, and the reinforcing effect of the carbon nano tube can be better exerted. In addition, the sulfide zirconia has better proton conductivity, so the proton conductivity of the composite proton exchange membrane is further improved.
The composite proton exchange membrane of the embodiment of the invention is prepared according to the preparation method of the composite proton exchange membrane. The composite proton exchange membrane prepared from the carbon nano tube coated by the chitosan and the zirconium sulfide oxide has good water absorption rate, proton conductivity, mechanical property and thermal stability, and has wide application prospect in polymer-based fuel cells.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a transmission electron microscope image of a carbon nanotube coated with zirconium sulfide oxide prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The composite proton exchange membrane and the preparation method thereof according to the embodiment of the present invention are specifically described below.
A preparation method of a composite proton exchange membrane comprises the following steps:
according to the mass ratio of the carbon nano tube coated with the zirconium sulfide oxide to the chitosan of 0.1-10: 100, preparing the carbon nano tube coated with the zirconium sulfide oxide and the chitosan respectively. Wherein the prepared chitosan is prepared into an acid solution of chitosan.
The carbon nano tube coated by the zirconium sulfide can be prepared by the following method:
adding every 1g of carbon nano tube into every 50-100 mL of acid solution, uniformly mixing, carrying out oxidation treatment at the temperature of 20-120 ℃ for 1-8 h, cooling to 20-25 ℃ preferably to facilitate subsequent treatment. And sequentially filtering, washing with water to neutrality and drying at the temperature of 60-100 ℃ to obtain the acid oxidation carbon nano tube. The carbon nano tube is oxidized by using acid, so that the oxygen-containing functional group is introduced to the surface of the carbon nano tube, and the carbon nano tube is electronegative in an aqueous solution by the oxygen-containing functional group introduced to the surface of the carbon nano tube while the hydrophilicity of the carbon nano tube is improved.
Wherein, the acid solution is preferably concentrated nitric acid, and the mass fraction of the acid solution is about 68 percent. In addition, in order to mix the carbon nanotubes and the concentrated nitric acid fully and uniformly, the mixing can be carried out by adopting an ultrasonic stirring mode.
And mixing the acid oxidized carbon nanotube with a zirconium oxychloride aqueous solution to obtain a mixed solution. And adding a precipitant into the mixed solution slowly dropwise to adjust the pH value of the mixed solution to 9-10, and hydrolyzing zirconium oxychloride to generate hydrous zirconium oxide in the dropwise adding process of the precipitant. Because the surface of the acid carbon oxide tube is electronegative, the acid carbon oxide tube and zirconium cations have electrostatic interaction, so that the hydrous zirconia is deposited on the surface of the carbon nano tube to form a hydrous zirconia coating layer. And keeping stirring the mixed solution within the pH value for 10-30 h, and separating to obtain a precipitate. And washing the precipitate to be neutral, and drying at the temperature of 60-100 ℃ to obtain an initial sample.
Wherein the precipitant is at least one of ammonia water and urea. Preferably, the precipitating agent is selected from ammonia.
Adding the initial sample into a vulcanizing agent, stirring for 30-90 min at the rotating speed of 600-800 rpm, washing with water, drying at the temperature of 60-100 ℃, and calcining at the temperature of 550-620 ℃ for 1-3 h to obtain the carbon nano tube coated with the vulcanized zirconia.
Wherein the vulcanizing agent is selected from H2SO4、(NH4)2SO4、SO3、H2S and CS2At least one of (1). H with the concentration of 0.5-2 mol/L for the vulcanizing agent2SO4It is preferable.
And preparing the carbon nano tube coated by the zirconium sulfide oxide into dispersion liquid. Specifically, the carbon nanotubes coated with the zirconium sulfide oxide were added to alcohol, and then subjected to ultrasonic stirring.
Among them, the alcohol is an aliphatic hydrocarbon alcohol such as methanol, ethanol, propanol and butanol.
In order to ensure the effect of a dispersion liquid system, 0.5-5 mg of carbon nano tubes coated by zirconium sulfide oxide are dispersed in 10ml of alcoholic solution.
Zirconium sulfide oxide is a super strong solid acid due to its surface SO4 2-Has excellent hydrophilicity and proton conductivity (5 × 10)-2S/cm, 60-150 ℃). The surface coating treatment is carried out on the carbon nano tubes by adopting the zirconium sulfide oxide, on one hand, the surface coating can effectively weaken the interaction among the carbon nano tubes, improve the dispersion and the compatibility with a matrix, and fully play the reinforcing role of the carbon nano tubes; on the other hand, the existence of the surface proton conductor provides a new proton conduction path for the composite membrane.
As described above, the use of the zirconium sulfide having excellent hydrophilicity and proton conductivity to form a coating layer on the surface of the carbon nanotube can improve the dispersibility of the carbon nanotube in the polymer matrix, thereby more effectively enhancing the carbon nanotube. In addition, the presence of surface proton conductors provides a new proton conduction pathway for the composite membrane.
Preparing an acidic solution of chitosan. Dissolving chitosan in 1-3 wt% of acid aqueous solution with 1-3 vt%.
Wherein the molecular weight of the chitosan is 50-100 ten thousand, for example, the molecular weight of the chitosan is 50 ten thousand, 70 ten thousand, 80 ten thousand or 100 ten thousand. The chitosan with proper molecular weight is selected, so that the prepared composite proton exchange membrane has better mechanical property.
The acidic solution is an aqueous solution of an organic acid, such as formic acid, acetic acid, propionic acid, or the like. Wherein the volume fraction of the acid in the acid water solution is 1-3%.
And mixing the dispersion liquid with an acid solution of chitosan and drying to obtain a dry film. Specifically, the dispersion is added to an acidic solution of chitosan, stirred and ultrasonically dispersed. The carbon nano tube coated by the zirconium sulfide oxide can be uniformly dispersed in the matrix by stirring; through ultrasonic dispersion, the dispersion can be further promoted, and the prepared composite proton exchange membrane is prevented from containing bubbles and influencing the performance of the composite proton exchange membrane.
And then, adding the mixture into a film casting tank, and drying at the temperature of 30-50 ℃ to obtain a dry film.
In order to prevent the mixed solution of the dispersion liquid and the acid solution of chitosan from reacting with the film casting tank in the drying process, the film casting tank is a polytetrafluoroethylene film casting tank, an organic glass film casting tank or a glass film casting tank.
In the drying process, the drying temperature is controlled to be 30-50 ℃, so that the redundant moisture in the dry film can be effectively removed, and the drying process can be ensured not to influence the property of the dry film.
The dry film is obtained by mixing the carbon nano tube coated by the zirconium sulfide oxide with the acid solution of the chitosan, and a certain amount of acid remains in the dry film. Therefore, the residual acid in the dry film needs to be cleaned by means of alkali cleaning to prevent the residual acid from affecting the prepared composite proton exchange membrane.
The alkali washing may use at least one of a solution of an alkali metal hydroxide and a solution of an alkaline earth metal hydroxide. The alkali metal hydroxide is, for example, NaOH or KOH. Alkaline earth metal hydroxides such as Mg (OH)2Or Ca (OH)2And the like.
Preferably, the alkali washing is performed using a solution of an alkali metal hydroxide, which may be a NaOH solution, a KOH solution, or a mixed solution of NaOH and KOH. Further, the concentration of the alkali solution used for alkali washing is not too low and is not too high. Too low alkali concentration cannot ensure that the residual acid in the dry film is washed cleanly, and too high alkali concentration causes influence on the prepared composite proton exchange membrane. The concentration of NaOH solution, KOH solution or the mixture thereof is preferably 2 to 5 wt%.
And washing the alkali-washed dry film to be neutral, and washing the alkali solution remained in the dry film to avoid influencing the prepared composite proton exchange membrane.
And adding the dried film after washing into a cross-linking agent. And (3) performing crosslinking treatment on the chitosan. Wherein the cross-linking agent is selected from glutaraldehyde or sulfuric acid.
In order to ensure the crosslinking effect of the chitosan, the concentration of the crosslinking agent is 0.5-2 mol/L, such as 0.5mol/L, 1mol/L, 1.5mol/L or 2 mol/L.
Preferably, the cross-linking agent is selected from sulfuric acid with the concentration of 0.5-2 mol/L. The crosslinking speed and effect can be ensured by selecting and controlling the type and concentration of the crosslinking agent.
According to the method, the stability, the proton conductivity and the mechanical property of the prepared composite proton exchange membrane can be improved by crosslinking the chitosan by using the sulfuric acid.
Washing the crosslinked product with water to remove the residual crosslinking agent on the surface of the product; and then, drying the cross-linked product after water washing at the temperature of 30-50 ℃ to remove excessive water on the surface of the cross-linked product. And (3) obtaining the composite proton exchange membrane through the operation.
A composite proton exchange membrane is prepared according to the preparation method of the composite proton exchange membrane. The thickness of the prepared composite proton exchange membrane is 50-100 mu m, and the composite proton exchange membrane has better comprehensive performance within the thickness range. In addition, the thickness of the composite proton exchange membrane can be set within the range according to the actual requirement by workers in the field.
According to the above, the composite proton exchange membrane prepared by the carbon nano tube coated by the chitosan and the zirconium sulfide oxide has good water absorption rate, stability, proton conductivity and mechanical property. Has wide application prospect in polymer-based fuel cells.
The features and properties of the present invention are described in further detail below with reference to examples.
Description of the agent: the carbon nano tube is a multi-walled carbon nano tube, has the tube diameter of 40-60 nm and the tube length of <2 mu m, and is purchased from Shenzhen Nangang Limited; zirconium oxychloride octahydrate is analytically pure AR and is purchased from chemical reagents of national drug group, Inc.; the chitosan has the molecular weight of 100 ten thousand and the deacetylation degree of 90 percent, and is purchased from Aoxing biology Limited company in Zhejiang.
Example 1
According to the mass ratio of the carbon nano tube coated with the zirconium sulfide oxide to the chitosan of 0.1: 100, preparing the composite proton exchange membrane.
And (2) putting 1g of carbon nano tube into 60mL of concentrated nitric acid, carrying out oxidation treatment at the temperature of 30 ℃ for 7h, cooling to 20 ℃, filtering, washing to be neutral by using deionized water, and drying at the temperature of 60 ℃ to obtain the acid oxidized carbon nano tube. Mixing the acid oxidized carbon nanotube with 0.2mol/L aqueous solution of zirconium oxychloride, dropwise adding ammonia water into the mixture to adjust the pH value of the mixture to be 9-10, stirring the mixture for 24 hours, filtering the mixture, washing the mixture to be neutral by using deionized water, and drying the mixture at the temperature of 80 ℃ to obtain an initial sample. Adding the initial sample into a 0.5mol/L sulfuric acid solution, stirring for 1h at the rotating speed of 200rpm, filtering, washing to be neutral by using deionized water, drying at the temperature of 80 ℃, and calcining for 1h at the temperature of 620 ℃ to obtain the carbon nano tube coated by the vulcanized zirconia.
0.7g of chitosan with the molecular weight of 100 ten thousand is put into a first beaker, 25mL of 2 vt% acetic acid solution is added, and the mixture is stirred at the temperature of 20-25 ℃ until the chitosan is completely dissolved. 0.7mg of the prepared carbon nanotube coated with the zirconium sulfide oxide was weighed in a second beaker, and was ultrasonically dispersed uniformly after 10mL of ethanol was added. And adding the dispersed carbon nano tube coated with the zirconium sulfide oxide into an acetic acid solution of chitosan, stirring for 1h, and then performing ultrasonic defoaming for 1h until a completely uniform mixed solution is formed. And pouring the mixed solution into a clean glass tank, and drying at the temperature of 50 ℃ for 12 hours to obtain a dry film. Immersing the dry film into 5 wt% NaOH solution for 3H, washing the dry film to be neutral by using deionized water, and immersing the dry film into 2mol/L H2SO4Crosslinking the solution for 24 hours, washing the solution to be neutral by using deionized water, flattening the solution by using a glass plate, and then putting the glass plate into a drying oven at 40 ℃ for drying to obtain the product.
The thickness of the prepared composite proton exchange membrane is 50 μm.
The carbon nanotubes coated with the zirconium sulfide oxide prepared in example 1 of the present invention were observed by a Transmission Electron Microscope (TEM), and the results are shown in fig. 1. As can be clearly observed from fig. 1, the carbon nanotubes are completely coated with the zirconium sulfide oxide, and the coating effect is good.
Example 2
According to the mass ratio of the carbon nano tube coated with the zirconium sulfide oxide to the chitosan of 0.5: 100, preparing the composite proton exchange membrane.
And (2) putting 1g of carbon nano tube into 70mL of concentrated nitric acid, carrying out oxidation treatment at the temperature of 40 ℃ for 6h, cooling to 25 ℃, filtering, washing to be neutral by using deionized water, and drying at the temperature of 60 ℃ to obtain the acid oxidized carbon nano tube. Mixing the acid oxidized carbon nanotube with 0.2mol/L aqueous solution of zirconium oxychloride, dropwise adding ammonia water into the mixture to adjust the pH value of the mixture to be 9-10, stirring the mixture for 26 hours, filtering the mixture, washing the mixture to be neutral by using deionized water, and drying the mixture at the temperature of 85 ℃ to obtain an initial sample. Adding the initial sample into 0.5mol/L sulfuric acid solution, stirring at the rotating speed of 200rpm for 1.5h, filtering, washing to neutrality by using deionized water, drying at the temperature of 85 ℃, and calcining at the temperature of 600 ℃ for 1.5h to obtain the carbon nano tube coated by the zirconium sulfide oxide.
0.7g of chitosan with the molecular weight of 100 ten thousand is put into a first beaker, 25mL of 2 vt% acetic acid solution is added, and the mixture is stirred at the temperature of 20-25 ℃ until the chitosan is completely dissolved. 3.5mg of the prepared carbon nanotube coated with the zirconium sulfide oxide is weighed in a second beaker, and is added with 10mL of ethanol for uniform ultrasonic dispersion. And adding the dispersed carbon nano tube coated with the zirconium sulfide oxide into an acetic acid solution of chitosan, stirring for 1h, and then performing ultrasonic defoaming for 1h until a completely uniform mixed solution is formed. And pouring the mixed solution into a clean glass tank, and drying at the temperature of 50 ℃ for 12 hours to obtain a dry film. Immersing the dry film into 5 wt% NaOH solution for 3H, washing the dry film to be neutral by using deionized water, and immersing the dry film into 2mol/L H2SO4Crosslinking the solution for 24 hours, washing the solution to be neutral by using deionized water, flattening the solution by using a glass plate, and then putting the glass plate into a drying oven at 40 ℃ for drying to obtain the product.
The thickness of the prepared composite proton exchange membrane is 55 mu m.
Example 3
According to the mass ratio of the carbon nano tube coated with the zirconium sulfide oxide to the chitosan of 1: 100, preparing the composite proton exchange membrane.
And (2) putting 1g of carbon nano tube into 80mL of concentrated nitric acid, carrying out oxidation treatment at the temperature of 50 ℃ for 7h, cooling to 20 ℃, filtering, washing to be neutral by using deionized water, and drying at the temperature of 60 ℃ to obtain the acid oxidized carbon nano tube. Mixing the acid oxidized carbon nanotube with 0.2mol/L aqueous solution of zirconium oxychloride, dropwise adding ammonia water into the mixture to adjust the pH value of the mixture to be 9-10, stirring the mixture for 24 hours, filtering the mixture, washing the mixture to be neutral by using deionized water, and drying the mixture at the temperature of 80 ℃ to obtain an initial sample. Adding the initial sample into 0.5mol/L sulfuric acid solution, stirring for 1h at the rotating speed of 200rpm, filtering, washing to be neutral by using deionized water, drying at the temperature of 80 ℃, and calcining for 1h at the temperature of 600 ℃ to obtain the carbon nano tube coated by the vulcanized zirconia.
0.7g of chitosan with the molecular weight of 100 ten thousand is put into a first beaker, 25mL of 2 vt% acetic acid solution is added, and the mixture is stirred at the temperature of 20-25 ℃ until the chitosan is completely dissolved. And weighing 7mg of the prepared carbon nano tube coated by the zirconium sulfide oxide in a second beaker, adding 10mL of ethanol, and performing ultrasonic dispersion uniformly. And adding the dispersed carbon nano tube coated with the zirconium sulfide oxide into an acetic acid solution of chitosan, stirring for 1h, and then performing ultrasonic defoaming for 1h until a completely uniform mixed solution is formed. And pouring the mixed solution into a clean glass tank, and drying at the temperature of 45 ℃ for 12 hours to obtain a dry film. Immersing the dry film into 5 wt% NaOH solution for 3H, washing the dry film to be neutral by using deionized water, and immersing the dry film into 2mol/L H2SO4Crosslinking the solution for 24 hours, washing the solution to be neutral by using deionized water, flattening the solution by using a glass plate, and then putting the glass plate into a drying oven at 40 ℃ for drying to obtain the product.
The thickness of the prepared composite proton exchange membrane is 70 mu m.
Example 4
According to the mass ratio of the carbon nano tube coated with the zirconium sulfide oxide to the chitosan being 3: 100, preparing the composite proton exchange membrane.
And (2) putting 1g of carbon nano tube into 50-100 mL of concentrated nitric acid, carrying out oxidation treatment at the temperature of 30 ℃ for 7h, cooling to 20 ℃, filtering, washing to be neutral by using deionized water, and drying at the temperature of 60 ℃ to obtain the acid oxidized carbon nano tube. Mixing the acid oxidized carbon nanotube with 0.2mol/L aqueous solution of zirconium oxychloride, dropwise adding ammonia water into the mixture to adjust the pH value of the mixture to be 9-10, stirring the mixture for 24 hours, filtering the mixture, washing the mixture to be neutral by using deionized water, and drying the mixture at the temperature of 80 ℃ to obtain an initial sample. Adding the initial sample into a 0.5mol/L sulfuric acid solution, stirring for 1h at the rotating speed of 200rpm, filtering, washing to be neutral by using deionized water, drying at the temperature of 80 ℃, and calcining for 1h at the temperature of 620 ℃ to obtain the carbon nano tube coated by the vulcanized zirconia.
0.7g of chitosan with the molecular weight of 100 ten thousand is put into a first beaker, 25mL of 2 vt% acetic acid solution is added, and the mixture is stirred at the temperature of 20-25 ℃ until the chitosan is completely dissolved. 21mg of the prepared carbon nanotube coated with the zirconium sulfide oxide is weighed in a second beaker, and is added with 10mL of ethanol for uniform ultrasonic dispersion. And adding the dispersed carbon nano tube coated with the zirconium sulfide oxide into an acetic acid solution of chitosan, stirring for 1h, and then performing ultrasonic defoaming for 1h until a completely uniform mixed solution is formed. And pouring the mixed solution into a clean glass tank, and drying at the temperature of 50 ℃ for 12 hours to obtain a dry film. Immersing the dry film into 5 wt% NaOH solution for 3H, washing the dry film to be neutral by using deionized water, and immersing the dry film into 2mol/L H2SO4Crosslinking the solution for 24 hours, washing the solution to be neutral by using deionized water, flattening the solution by using a glass plate, and then putting the glass plate into a drying oven at 40 ℃ for drying to obtain the product.
The thickness of the prepared composite proton exchange membrane is 80 μm.
Comparative example 1
The preparation method of the existing chitosan proton exchange membrane comprises the following steps: adding 0.7g of chitosan with the molecular weight of 100 ten thousand into a beaker, adding 25mL of 2 vt% acetic acid solution, stirring at the temperature of 20-25 ℃ until the chitosan is completely dissolved, pouring the solution into a clean glass tank, and drying at the temperature of 50 ℃ for 12 hours to obtain a dry film. Immersing the dry film into a 5 wt% NaOH solution for 3H, filtering, washing with deionized water to be neutral, and then immersing the washed dry film into 2mol/L H2SO4Crosslinking the solution for 24 hours, filtering, washing the solution to be neutral by using deionized water, and putting the solution into an oven for drying at 40 ℃ to obtain the pure chitosan proton exchange membrane.
The composite proton exchange membranes provided in examples 1 to 4 of the present invention and comparative example 1 were subjected to mechanical property test and proton conductivity test in the same environment, and the results are shown in tables 1 and 2.
Table 1 mechanical property test results of composite proton exchange membrane
Sample (I) Tensile Strength (MPa) Elongation at Break (%)
Example 1 25.89(±1.74) 27.25(±2.48)
Example 2 27.55(±1.68) 18.83(±3.40)
Example 3 36.51(±3.15) 27.53(±4.52)
Example 4 31.78(±0.64) 25.54(±2.99)
Comparative example 1 29.84(±0.43) 24.39(±3.26)
Table 2 proton conductivity test results for composite proton exchange membranes
Figure BDA0001367866650000111
Figure BDA0001367866650000121
As can be seen from tables 1 and 2, the tensile strength and the elongation at break of the composite proton exchange membranes prepared in the embodiments 1 to 4 of the invention are superior to those of the comparative example 1; moreover, the proton conductivity of the composite proton exchange membrane prepared in the embodiment 1-4 is also obviously superior to that of the comparative example 1 under the conditions of 20 ℃, 40 ℃, 60 ℃ and 80 ℃.
In summary, in the preparation method of the composite proton exchange membrane according to the embodiment of the present invention, the zirconium sulfide having good hydrophilicity is used to form the coating layer on the surface of the carbon nanotube, so that the dispersibility of the carbon nanotube in the polymer matrix can be improved, and the carbon nanotube enhancing effect can be better exerted. In addition, the sulfide zirconia has better proton conductivity, so the proton conductivity of the composite proton exchange membrane is further improved.
The composite proton exchange membrane of the embodiment of the invention is prepared according to the preparation method of the composite proton exchange membrane. The composite proton exchange membrane prepared from the carbon nano tube coated by the chitosan and the zirconium sulfide oxide has good water absorption rate, proton conductivity, mechanical property and thermal stability, and has wide application prospect in polymer-based fuel cells.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (6)

1. A preparation method of a composite proton exchange membrane is characterized by comprising the following steps:
preparing carbon nano tubes coated with zirconium sulfide into dispersion liquid, mixing the dispersion liquid with an acidic solution of chitosan, drying to obtain a dry film, washing the dry film with alkali, washing with water to neutrality, and obtaining the composite proton exchange membrane under the action of a cross-linking agent; the mass ratio of the carbon nano tube coated with the zirconium sulfide to the chitosan is (0.1-10): 100, respectively;
the dispersion is prepared by the following method: adding every 1g of carbon nano tube into every 50-100 ml of acid solution, mixing, treating at the temperature of 20-120 ℃ for 1-8 h, filtering, washing with water to be neutral, and drying to obtain an acid oxidized carbon nano tube, mixing the acid oxidized carbon nano tube with a zirconium oxychloride solution, adding a precipitator to adjust the pH value to 9-10, stirring for 10-30 h, drying at the temperature of 60-100 ℃ to obtain an initial sample, mixing the initial sample with a vulcanizing agent, stirring for 30-90 min, washing with water, drying at the temperature of 60-100 ℃, and calcining at the temperature of 550-620 ℃ for 1-3 h to obtain the carbon nano tube coated with the vulcanized zirconium oxide; adding the carbon nano tube coated by the zirconium sulfide oxide into alcohol, and then stirring and ultrasonically dispersing; the precipitant is selected from ammonia water.
2. The process for the preparation of a composite proton exchange membrane according to claim 1, wherein said vulcanizing agent is selected from H2SO4、(NH4)2SO4、SO3And CS2At least one of (1).
3. The preparation method of the composite proton exchange membrane according to claim 1, wherein the dispersion is added into the acidic solution of chitosan, and the acidic solution is added into a membrane casting tank after being subjected to ultrasonic stirring, and the dry membrane is obtained by drying at a temperature of 30-50 ℃.
4. The method for preparing a composite proton exchange membrane according to claim 1, wherein the acid solution of chitosan is an aqueous solution of chitosan dissolved in 1-3 vol% of acetic acid at 1-3 wt%.
5. The method of preparing a composite proton exchange membrane according to claim 1 wherein the cross-linking agent is selected from sulfuric acid;
the concentration of the cross-linking agent is 0.5-2 mol/L.
6. A composite proton exchange membrane, characterized in that, the composite proton exchange membrane is prepared by the preparation method of the composite proton exchange membrane according to any one of claims 1 to 5.
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