CN107383405B - A kind of composite proton exchange membrane and preparation method thereof - Google Patents

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

A kind of composite proton exchange membrane and preparation method thereof

technical field

The invention relates to the field of fuel cells, and in particular to a composite proton exchange membrane and a preparation method thereof.

Background technique

As a proton exchange membrane with potential research, chitosan has the characteristics of low price and environmental friendliness. At the same time, it also has the characteristics that its applicable environment is not critical and the permeability of methanol is low.

However, the direct use of chitosan to prepare proton exchange membranes, or the composite proton exchange membranes prepared by modifying the single group (-OH, -NH ₂ ) carried by the chitosan parent, all have the flexibility and mechanical properties of the membrane. and insufficient thermal stability.

In view of this, the present invention is proposed.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a method for preparing a composite proton exchange membrane, which uses super-strong solid acid-sulfided zirconia with good hydrophilicity and proton conductivity to form a coating layer on the surface of carbon nanotubes. The coating can effectively weaken the interaction between carbon nanotubes (CNTs), improve the dispersion and compatibility with the matrix, and give full play to the reinforcing effect of carbon nanotubes. proton conduction pathway.

Another object of the present invention is to provide a composite proton exchange membrane prepared by the above-mentioned preparation method of the composite proton exchange membrane, which has good water absorption, proton conductivity, mechanical properties and thermal stability. The battery has broad application prospects.

The present invention solves its technical problems by adopting the following technical solutions.

The present invention provides a preparation method of a composite proton exchange membrane, comprising:

The carbon nanotubes covered by sulfide zirconia are made into dispersion liquid, and the dispersion liquid is mixed with the acid solution of chitosan and dried to obtain a dry film. The dry film is washed with alkali and then washed to neutrality. A composite proton exchange membrane was obtained.

A composite proton exchange membrane is prepared according to the above-mentioned preparation method of the composite proton exchange membrane.

The beneficial effects of the manufacturing process of the embodiment of the present invention are:

In the preparation method of the composite proton exchange membrane of the embodiment of the present invention, the sulfided zirconia with good hydrophilicity and proton conductivity is used to form a coating layer on the surface of carbon nanotubes, which can improve the dispersion of carbon nanotubes in the polymer matrix. properties, so as to better play the role of carbon nanotubes. In addition, because the sulfide zirconia itself has good proton conductivity, the proton conductivity of the composite proton exchange membrane is further improved.

The composite proton exchange membrane of the embodiment of the present invention is prepared according to the above-mentioned preparation method of the composite proton exchange membrane. The composite proton exchange membrane made of carbon nanotubes coated with chitosan and sulfided zirconia has good water absorption, proton conductivity, mechanical properties and thermal stability, and has broad application prospects in polymer-based fuel cells .

Description of drawings

In order to illustrate the technical solutions of the embodiments of the present invention more clearly, the following briefly introduces the accompanying drawings used in the embodiments. It should be understood that the following drawings only show some embodiments of the present invention, and therefore do not It should be regarded as a limitation of the scope, and for those of ordinary skill in the art, other related drawings can also be obtained according to these drawings without any creative effort.

FIG. 1 is a transmission electron microscope image of the carbon nanotubes coated with sulfided zirconia prepared in Example 1 of the present invention.

Detailed ways

In order to make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not indicated in the examples, it is carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used without the manufacturer's indication are conventional products that can be purchased from the market.

The composite proton exchange membrane and the preparation method thereof according to the embodiments of the present invention will be specifically described below.

A preparation method of a composite proton exchange membrane, comprising:

According to the mass ratio of sulfided zirconia-coated carbon nanotubes to chitosan of 0.1 to 10:100, sulfided zirconia-coated carbon nanotubes and chitosan were prepared respectively. Wherein, the prepared chitosan is made into an acidic solution of chitosan.

Sulfurized zirconia coated carbon nanotubes can be prepared by the following methods:

Add each 1g of carbon nanotubes to every 50-100mL of the acid solution and mix evenly, carry out the oxidation treatment at a temperature of 20-120°C for 1-8h, and then cool it down to 20-25°C to facilitate the follow-up. deal with. Filtration, washing with water until neutrality, and drying at a temperature of 60 to 100° C. are performed in this order to obtain acid-oxidized carbon nanotubes. By oxidizing carbon nanotubes with acid, oxygen-containing functional groups are introduced into the surface of carbon nanotubes. While improving the hydrophilicity of carbon nanotubes, the oxygen-containing functional groups introduced on the surface of carbon nanotubes make the surface electronegative in aqueous solution. sex.

Among them, the acid solution is preferably concentrated nitric acid, and its mass fraction is about 68%. In addition, in order to fully mix the carbon nanotubes and concentrated nitric acid uniformly, the mixing can be carried out by means of ultrasonic stirring.

The acid-oxidized carbon nanotubes and the aqueous solution of zirconium oxychloride are mixed to obtain a mixed solution. A precipitant is slowly added dropwise to the mixed solution to adjust the pH value of the mixed solution to 9-10. During the dropwise addition of the precipitant, zirconium oxychloride is hydrolyzed to form hydrated zirconia. Since the surface of acid-oxidized carbon tubes is electronegative, there is electrostatic interaction with zirconium cations, so that hydrated zirconia is deposited on the surface of carbon nanotubes to form a hydrated zirconia coating layer. After the mixture was kept stirring for 10-30 h within the pH value, the precipitate was obtained by separation. After the precipitate is washed with water until neutral, it is dried at a temperature of 60-100° C. to obtain an initial sample.

Wherein, the precipitant is selected from at least one of ammonia water and urea. Preferably, the precipitating agent is selected from ammonia water.

The initial sample is added to the vulcanizing agent, stirred for 30-90 min at a speed of 600-800 rpm, washed with water and dried at a temperature of 60-100 ℃, and then calcined at a temperature of 550-620 ℃ for 1-3 hours to obtain sulfided zirconia Coated carbon nanotubes.

Wherein, the vulcanizing agent is selected from at least one of H ₂ SO ₄ , (NH ₄ ) ₂ SO ₄ , SO ₃ , H ₂ S and CS ₂ . The vulcanizing agent is preferably H ₂ SO ₄ with a concentration of 0.5-2 mol/L.

The sulfided zirconia-coated carbon nanotubes were prepared into a dispersion. Specifically, after adding the sulfided zirconia-coated carbon nanotubes into the alcohol, ultrasonic stirring is performed.

Among them, the alcohol is an aliphatic hydrocarbon alcohol, such as methanol, ethanol, propanol and butanol.

In order to ensure the effect of the dispersion liquid system, 0.5-5 mg of sulfided zirconia-coated carbon nanotubes are dispersed in every 10 ml of the alcohol solution.

Sulfurized zirconia is a super-strong solid acid. Due to the existence of SO ₄ ^2- on its surface, it has excellent hydrophilicity and proton conductivity (5×10 ^-2 S/cm, 60～150℃). The carbon nanotubes are coated with zirconia sulfide. On the one hand, the surface coating can effectively weaken the interaction between the carbon nanotubes, improve the dispersion and compatibility with the matrix, and give full play to the reinforcing effect of the carbon nanotubes; On the other hand, the existence of surface proton conductors provides a new proton conduction pathway for composite membranes.

Based on the above, the use of sulfided zirconia with good hydrophilicity and proton conductivity to form a coating layer on the surface of carbon nanotubes can improve the dispersibility of carbon nanotubes in the polymer matrix, so that carbon nanotubes can be better used. enhanced effect. In addition, the existence of surface proton conductors provides a new proton conduction pathway for composite membranes.

Prepare an acidic solution of chitosan. Chitosan is dissolved in an aqueous solution of 1-3 vt% acid at 1-3 wt%.

Wherein, the molecular weight of chitosan is 500,000 to 1,000,000, for example, the molecular weight of chitosan is 500,000, 700,000, 800,000, or 1,000,000. By selecting chitosan with appropriate molecular weight, the prepared composite proton exchange membrane has better mechanical properties.

The acidic solution is an aqueous solution of an organic acid, such as formic acid, acetic acid, or propionic acid. Wherein, the volume fraction of acid in the acid aqueous solution is 1-3%.

The dispersion liquid is mixed with the acidic solution of chitosan and dried to obtain a dry film. Specifically, the dispersion liquid was added to the acidic solution of chitosan, stirred and then dispersed by ultrasonic. By stirring, the carbon nanotubes coated with sulfided zirconia can be uniformly dispersed in the matrix; by ultrasonic dispersion, the dispersion can be further promoted and the prepared composite proton exchange membrane can be prevented from containing air bubbles, which affects its performance.

After that, it is put into a film casting tank, and dried at a temperature of 30 to 50° C. to obtain a dry film.

In order to prevent the mixed solution of the dispersion liquid and the acidic solution of chitosan from reacting with the film casting tank during the drying process, the film casting tank is made of polytetrafluoroethylene film casting tank, plexiglass film casting tank or glass film casting tank.

During the drying process, by controlling the drying temperature to be 30-50°C, the excess moisture in the dry film can be effectively removed, and the properties of the dry film can be ensured that the drying process does not affect the dry film.

Since the dry film is obtained by mixing sulfided zirconia-coated carbon nanotubes with an acidic solution of chitosan, a certain amount of acid remains in the dry film. Therefore, it is necessary to clean the residual acid in the dry membrane by means of alkaline washing to prevent the residual acid from affecting the prepared composite proton exchange membrane.

At least one of an alkali metal hydroxide solution and an alkaline earth metal hydroxide solution can be used for the alkaline washing. The alkali metal hydroxide is, for example, NaOH, KOH, or the like. The alkaline earth metal hydroxide is, for example, Mg(OH) ₂ or Ca(OH) ₂ or the like.

Preferably, the solution of alkali metal hydroxide is used for alkali washing, which can be NaOH solution, KOH solution, or a mixed solution of NaOH and KOH. Further, the concentration of the alkaline solution used for alkaline washing should not be too low nor too high. Too low alkali concentration cannot guarantee that the residual acid in the dry membrane can be washed clean, and too high alkali concentration will affect the prepared composite proton exchange membrane. The concentration of the NaOH solution, the KOH solution or the mixed solution thereof is preferably 2 to 5 wt %.

The dry membrane after alkali washing is washed with water until neutral, and the residual alkali solution in the dry membrane is washed to avoid affecting the prepared composite proton exchange membrane.

The washed dry film is added to the crosslinking agent. Cross-linking of chitosan. Wherein, the crosslinking agent is selected from glutaraldehyde or sulfuric acid.

In order to ensure the cross-linking effect of chitosan, the concentration of the cross-linking agent is 0.5-2 mol/L, for example, 0.5 mol/L, 1 mol/L, 1.5 mol/L or 2 mol/L.

Preferably, the cross-linking agent is selected from sulfuric acid with a concentration of 0.5-2 mol/L. By selecting and controlling the type and concentration of the cross-linking agent, the cross-linking speed and effect can be guaranteed.

Based on the above, by using sulfuric acid to cross-link chitosan, the stability, proton conductivity and mechanical properties of the prepared composite proton exchange membrane can be improved.

The cross-linked product is washed with water to remove the residual cross-linking agent on its surface; then, the washed cross-linked product is dried at a temperature of 30-50° C. to remove excess water on its surface. Through the above operations, a composite proton exchange membrane was obtained.

A composite proton exchange membrane is prepared according to the above-mentioned preparation method of the composite proton exchange membrane. The thickness of the prepared composite proton exchange membrane is 50-100 μm, and within the thickness range, it has better comprehensive performance. In addition, the thickness of the composite proton exchange membrane can also be set within this range according to actual needs by those skilled in the art.

Based on the above, the composite proton exchange membrane made of carbon nanotubes coated with chitosan and sulfided zirconia has good water absorption, stability, proton conductivity and mechanical properties. It has broad application prospects in polymer-based fuel cells.

The features and performances of the present invention will be further described in detail below in conjunction with the embodiments.

Reagent description: Carbon nanotubes are multi-walled carbon nanotubes, with a diameter of 40-60nm and a tube length of <2μm, purchased from Shenzhen Nanoport Co., Ltd.; zirconium oxychloride octahydrate is analytical pure AR, purchased from Sinopharm Group Chemical Reagent Co., Ltd.; the molecular weight of chitosan is 1 million and the degree of deacetylation is 90%, purchased from Zhejiang Aoxing Biological Co., Ltd.

Example 1

According to the mass ratio of sulfide zirconia-coated carbon nanotubes to chitosan of 0.1:100, a composite proton exchange membrane was prepared.

Take 1 g of carbon nanotubes in 60 mL of concentrated nitric acid and oxidize at 30 °C for 7 h, then cool to 20 °C, filter, wash with deionized water until neutral, and dry at 60 °C to obtain acid oxidation. carbon nanotubes. Mix acid-oxidized carbon nanotubes with 0.2 mol/L zirconium oxychloride aqueous solution, add ammonia water dropwise to adjust the pH value between 9 and 10, stir for 24 h, filter, wash with deionized water until neutral, Drying at a temperature of 80°C gave the initial sample. The initial sample was added to a 0.5 mol/L sulfuric acid solution, stirred at 200 rpm for 1 h, filtered, washed with deionized water until neutral, dried at 80 °C, and calcined at 620 °C for 1 h to obtain Sulfurized zirconia-coated carbon nanotubes.

Put 0.7 g of chitosan with a molecular weight of 1 million in the first beaker, add 25 mL of 2vt% acetic acid solution, and stir at a temperature of 20 to 25° C. until it is completely dissolved. Weigh 0.7 mg of the prepared zirconia sulfide-coated carbon nanotubes into a second beaker, add 10 mL of ethanol, and disperse uniformly by ultrasonic. The dispersed carbon nanotubes coated with sulfided zirconia were added to the acetic acid solution of chitosan, stirred for 1 hour, and then ultrasonically deaerated for 1 hour until a completely uniform mixed solution was formed. The above mixed solution was poured into a clean glass tank, and dried at a temperature of 50° C. for 12 h to obtain a dry film. The dry film was immersed in a 5wt% NaOH solution for 3h, washed with deionized water until neutral, immersed in a 2mol/L H ₂ SO ₄ solution for crosslinking for 24 h, washed with deionized water until neutral, and washed with a glass plate After being flattened, put it into an oven at 40°C to dry.

The thickness of the prepared composite proton exchange membrane was 50 μm.

The sulfided zirconia-coated carbon nanotubes prepared in Example 1 of the present invention were observed by a transmission electron microscope (TEM), and the results are shown in FIG. 1 . It can be clearly observed from Fig. 1 that the sulfided zirconia completely coats the carbon nanotubes, and the coating effect is better.

Example 2

The composite proton exchange membrane was prepared according to the mass ratio of sulfide zirconia-coated carbon nanotubes to chitosan of 0.5:100.

Take 1 g of carbon nanotubes and put them in 70 mL of concentrated nitric acid and oxidize them at a temperature of 40 °C for 6 h, then cool to 25 °C, filter, wash with deionized water until neutral, and dry at a temperature of 60 °C to obtain acid oxidation. carbon nanotubes. Mix acid-oxidized carbon nanotubes with 0.2 mol/L zirconium oxychloride aqueous solution, add ammonia water dropwise to adjust the pH value between 9 and 10, stir for 26 h, filter, wash with deionized water until neutral, Drying at a temperature of 85°C gave the initial sample. The initial sample was added to 0.5mol/L sulfuric acid solution, stirred at 200rpm for 1.5h, filtered, washed with deionized water until neutral, dried at 85°C, and calcined at 600°C for 1.5h , to obtain sulfided zirconia-coated carbon nanotubes.

Put 0.7 g of chitosan with a molecular weight of 1 million in the first beaker, add 25 mL of 2vt% acetic acid solution, and stir at a temperature of 20 to 25° C. until it is completely dissolved. Weigh 3.5 mg of the prepared zirconia sulfide-coated carbon nanotubes into the second beaker, add 10 mL of ethanol, and disperse uniformly by ultrasonic. The dispersed carbon nanotubes coated with sulfided zirconia were added to the acetic acid solution of chitosan, stirred for 1 hour, and then ultrasonically deaerated for 1 hour until a completely uniform mixed solution was formed. The above mixed solution was poured into a clean glass tank, and dried at a temperature of 50° C. for 12 h to obtain a dry film. The dry film was immersed in a 5wt% NaOH solution for 3h, washed with deionized water until neutral, immersed in a 2mol/L H ₂ SO ₄ solution for crosslinking for 24 h, washed with deionized water until neutral, and washed with a glass plate After being flattened, put it into an oven at 40°C to dry.

The thickness of the prepared composite proton exchange membrane was 55 μm.

Example 3

According to the mass ratio of sulfide zirconia-coated carbon nanotubes to chitosan of 1:100, a composite proton exchange membrane was prepared.

Take 1 g of carbon nanotubes in 80 mL of concentrated nitric acid and oxidize at 50 °C for 7 h, then cool to 20 °C, filter, wash with deionized water until neutral, and dry at 60 °C to obtain acid oxidation carbon nanotubes. Mix acid-oxidized carbon nanotubes with 0.2 mol/L zirconium oxychloride aqueous solution, add ammonia water dropwise to adjust the pH value between 9 and 10, stir for 24 h, filter, wash with deionized water until neutral, Drying at a temperature of 80°C gave the initial sample. The initial sample was added to a 0.5 mol/L sulfuric acid solution, stirred at 200 rpm for 1 h, filtered, washed with deionized water until neutral, dried at 80 °C, and calcined at 600 °C for 1 h to obtain Sulfurized zirconia-coated carbon nanotubes.

Put 0.7 g of chitosan with a molecular weight of 1 million in the first beaker, add 25 mL of 2vt% acetic acid solution, and stir at a temperature of 20 to 25° C. until it is completely dissolved. Weigh 7 mg of the prepared zirconia sulfide-coated carbon nanotubes into a second beaker, add 10 mL of ethanol, and disperse uniformly by ultrasonic. The dispersed carbon nanotubes coated with sulfided zirconia were added to the acetic acid solution of chitosan, stirred for 1 hour, and then ultrasonically deaerated for 1 hour until a completely uniform mixed solution was formed. The above mixed solution was poured into a clean glass tank, and dried at a temperature of 45° C. for 12 h to obtain a dry film. The dry film was immersed in a 5wt% NaOH solution for 3h, washed with deionized water until neutral, immersed in a 2mol/L H ₂ SO ₄ solution for crosslinking for 24 h, washed with deionized water until neutral, and washed with a glass plate After being flattened, put it into an oven at 40°C to dry.

The thickness of the prepared composite proton exchange membrane was 70 μm.

Example 4

According to the mass ratio of zirconia sulfide coated carbon nanotubes to chitosan of 3:100, a composite proton exchange membrane was prepared.

Take 1 g of carbon nanotubes and place them in 50-100 mL of concentrated nitric acid, and after oxidation treatment at 30 °C for 7 hours, cool to 20 °C, filter, wash with deionized water until neutral, and dry at 60 °C to obtain Acid oxidizes carbon nanotubes. Mix acid-oxidized carbon nanotubes with 0.2 mol/L zirconium oxychloride aqueous solution, add ammonia water dropwise to adjust the pH value between 9 and 10, stir for 24 h, filter, wash with deionized water until neutral, Drying at a temperature of 80°C gave the initial sample. The initial sample was added to a 0.5 mol/L sulfuric acid solution, stirred at 200 rpm for 1 h, filtered, washed with deionized water until neutral, dried at 80 °C, and calcined at 620 °C for 1 h to obtain Sulfurized zirconia-coated carbon nanotubes.

Put 0.7 g of chitosan with a molecular weight of 1 million in the first beaker, add 25 mL of 2vt% acetic acid solution, and stir at a temperature of 20 to 25° C. until it is completely dissolved. Weigh 21 mg of the prepared zirconia sulfide-coated carbon nanotubes into a second beaker, add 10 mL of ethanol, and disperse uniformly by ultrasonic. The dispersed carbon nanotubes coated with sulfided zirconia were added to the acetic acid solution of chitosan, stirred for 1 hour, and then ultrasonically deaerated for 1 hour until a completely uniform mixed solution was formed. The above mixed solution was poured into a clean glass tank, and dried at a temperature of 50° C. for 12 h to obtain a dry film. The dry film was immersed in a 5wt% NaOH solution for 3h, washed with deionized water until neutral, immersed in a 2mol/L H ₂ SO ₄ solution for crosslinking for 24 h, washed with deionized water until neutral, and washed with a glass plate After being flattened, put it into an oven at 40°C to dry.

The thickness of the prepared composite proton exchange membrane was 80 μm.

Comparative Example 1

Prepared by the existing production method of chitosan proton exchange membrane: put 0.7 g of chitosan with a molecular weight of 1 million in a beaker, add 25 mL of 2vt% acetic acid solution, and stir at a temperature of 20 to 25 ° C to After complete dissolution, the above solution was poured into a clean glass tank and dried at a temperature of 50° C. for 12 h to obtain a dry film. The dry film was immersed in a 5wt% NaOH solution for 3h, filtered, washed with deionized water until neutral, and then the washed dry film was immersed in a _2mol /L _H2SO4 solution for crosslinking for 24h, filtered, Use deionized water to wash to neutrality, and put it into an oven at 40°C for drying to obtain a proton exchange membrane of pure chitosan.

The composite proton exchange membranes provided in Examples 1 to 4 of the present invention and Comparative Example 1 were tested for mechanical properties and proton conductivity in the same environment, and the results are shown in Table 1 and Table 2.

Table 1 Test results of mechanical properties of composite proton exchange membranes

sample 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 Test results of proton conductivity of composite proton exchange membrane

It can be seen from Table 1 and Table 2 that the tensile strength and elongation at break of the composite proton exchange membranes prepared in Examples 1 to 4 of the present invention are better than those of Comparative Example 1; Under the conditions of ℃ and 80 ℃, the proton conductivity of the composite proton exchange membranes prepared in Examples 1 to 4 of the present invention is also significantly better than that of Comparative Example 1.

To sum up, in the preparation method of the composite proton exchange membrane of the embodiment of the present invention, the sulfided zirconia with good hydrophilicity is used to form a coating layer on the surface of carbon nanotubes, which can improve the adhesion of carbon nanotubes in the polymer matrix. Dispersibility, so as to better play the role of carbon nanotubes. In addition, since the sulfide zirconia itself has good proton conductivity, the proton conductivity of the composite proton exchange membrane is further improved.

The composite proton exchange membrane of the embodiment of the present invention is prepared according to the above-mentioned preparation method of the composite proton exchange membrane. The composite proton exchange membrane made of carbon nanotubes coated with chitosan and sulfided zirconia has good water absorption, proton conductivity, mechanical properties and thermal stability, and has broad application prospects in polymer-based fuel cells .

The embodiments described above are some, but not all, embodiments of the present invention. The detailed descriptions of the embodiments of the invention are not intended to limit the scope of the invention as claimed, but are merely representative of selected embodiments of the invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts 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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