CN114031870A - Proton exchange membrane and preparation method and application thereof - Google Patents

Proton exchange membrane and preparation method and application thereof Download PDF

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CN114031870A
CN114031870A CN202111279466.6A CN202111279466A CN114031870A CN 114031870 A CN114031870 A CN 114031870A CN 202111279466 A CN202111279466 A CN 202111279466A CN 114031870 A CN114031870 A CN 114031870A
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proton exchange
composite material
titanium dioxide
exchange membrane
mxene
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张海宁
赵胜球
孟子寒
唐浩林
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Foshan Xianhu Laboratory
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Abstract

The invention belongs to the technical field of battery materials, and discloses a proton exchange membrane and a preparation method and application thereof. The proton exchange membrane comprises a composite materialA material, a fluoropolymer; the composite material is prepared by loading titanium dioxide nanowires on MXene-Ti3C2The composite material is coated with fluoropolymer on the surface. The invention uniformly loads the one-dimensional titanium dioxide nanowire material on the two-dimensional layered nano carbide MXene-Ti in an electrostatic self-assembly mode3C2The surface of the proton exchange membrane is formed with a composite material, the composite material is coated by the fluorine-containing polymer, a proton transmission channel is constructed in the formed proton exchange membrane, the proton transmission path is shortened, the water retention of the proton membrane is increased, and the electrical conductivity and the dimensional stability of the proton exchange membrane are obviously improved.

Description

Proton exchange membrane and preparation method and application thereof
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a proton exchange membrane and a preparation method and application thereof.
Background
A fuel cell (fuel cell) is a power generation device that can directly convert chemical energy into electrical energy, hydrogen is oxidized at an anode into protons, and the protons are transported through a proton exchange membrane to a cathode to be combined with oxygen to be reduced into water. The fuel cell has the advantages of high power generation efficiency, less environmental pollution and the like.
The proton exchange membrane is used as a core component of the fuel cell, and the conductivity and the dimensional stability of the proton exchange membrane have important significance for the efficient and stable operation of the fuel cell. The proton exchange membranes developed at present mostly fail to achieve both electrical conductivity and dimensional stability. For example, the swelling ratio of the existing proton exchange membrane is generally over 12%, which indicates that the size stability of the proton exchange membrane is poor and is not beneficial to the normal use of the fuel cell. The proton conductivity of the existing proton exchange membrane at 30 ℃ is generally not more than 40 mS/cm.
Therefore, it is highly desirable to provide a proton exchange membrane, which has both high electrical conductivity and dimensional stability, and further provides thermal stability of the proton exchange membrane, which is more beneficial to the development and application of fuel cells.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. The proton exchange membrane has the characteristics of high conductivity and dimensional stability, the swelling rate for measuring the dimensional stability is lower than 10%, and the proton conductivity at 30 ℃ exceeds 42mS/cm, even can reach 50 mS/cm.
The invention conception of the invention is as follows: two-dimensional layered nano carbide MXene-Ti3C2(MXene represents a two-dimensional material) is a graphene-like structure material that can be made of ternary lamellar MAX-phase ceramics Ti3AlC2The powder is selectively corroded to obtain two-dimensional layered nano carbide MXene-Ti3C2Has large area ratio and hydrophilicity; the one-dimensional titanium dioxide nanowire has a large length-diameter ratio and a large number of hydrophilic hydroxyl groups on the surface. The invention uniformly loads the one-dimensional titanium dioxide nanowire material on the two-dimensional layered nano carbide MXene-Ti in an electrostatic self-assembly mode3C2The surfaces of the two membranes are coated by the fluorine-containing polymer, and a proton transmission channel is constructed in the formed proton exchange membrane, so that the proton transmission path is shortened, the water retention of the proton membrane is increased, and the proton conductivity and the dimensional stability of the proton exchange membrane are remarkably improved.
In a first aspect of the invention, a proton exchange membrane is provided.
In particular to a proton exchange membrane which comprises a composite material and a fluorine-containing polymer; the composite material is prepared by loading titanium dioxide nanowires on MXene-Ti3C2A surface, the composite material being coated with a fluoropolymer.
Preferably, the fluoropolymer is selected from polytetrafluoroethylene and perfluoro-3, 6-diepoxy-4-methyl-7-decene-sulfuric acid copolymer (Nafion for short).
Preferably, the fluoropolymer, MXene-Ti3C2The mass ratio of the titanium dioxide nanowire is (100-500): (3-20): 1; more preferably, the fluoropolymer and MXene-Ti are3C2The mass ratio of the titanium dioxide nanowire is (110) -425): (5-16): 1.
the second aspect of the invention provides a preparation method of a proton exchange membrane.
Specifically, the preparation method of the proton exchange membrane comprises the following steps:
MXene-Ti3C2the preparation of (1): the acid is mixed with the fluorine salt and,then adding Ti3AlC2Reacting, collecting bottom-layer products, then carrying out ultrasonic treatment and centrifugation, and collecting supernatant fluid containing MXene-Ti3C2；
Preparing a titanium dioxide nanowire: dissolving titanium dioxide in alkali liquor, dispersing, then carrying out hydrothermal reaction, and purifying to obtain titanium dioxide nanowires;
preparing a composite material: mixing the cationic surfactant with the solvent, then adding the titanium dioxide nano-wire, stirring and mixing, and then dropwise adding the MXene-Ti-containing nano-wire3C2Purifying the supernatant to obtain the composite material;
and mixing the composite material with a solvent to obtain a composite material mixture, dripping the composite material mixture into a solution containing a fluorine polymer, mixing to obtain a membrane casting solution, pouring the membrane casting solution onto a carrier, and drying to obtain the proton exchange membrane.
Preferably, the MXene-Ti3C2In the preparation process of (3), the acid is hydrochloric acid.
Preferably, the concentration of the hydrochloric acid is 8-15 mol/L; further preferably, the concentration of the hydrochloric acid is 9-12 mol/L.
Preferably, the acid, fluoride salt, Ti3AlC2The dosage ratio of (A) is 10 mL: (0.6-1.5) g: (0.5-1.0) g; further preferably, the acid, fluorine salt and Ti are3AlC2The dosage ratio of (A) is 10 mL: (0.8-1.2) g: (0.5-0.9) g.
Preferably, the Ti is3AlC2Is ternary laminated MAX phase ceramic Ti3AlC2。
Preferably, the MXene-Ti3C2In the preparation process of (3), the fluorine salt is LiF or NaF.
Preferably, the MXene-Ti3C2In the preparation process of (2), the reaction temperature is 30-40 ℃, and the reaction time is 24-48 hours; further preferably, the reaction temperature is 33-38 ℃, and the reaction time is 36-48 hours.
Preferably, the MXene-Ti3C2Prepared byIn the process, the bottom product is centrifugally washed to be neutral, the washed product is dispersed in water, and nitrogen or argon is introduced for ultrasonic treatment.
Preferably, the MXene-Ti3C2In the preparation process, the supernatant is stored at the temperature of 0-7 ℃.
Preferably, in the preparation process of the titanium dioxide nanowire, the reaction temperature of the hydrothermal reaction is 140-190 ℃; the reaction time is 18-36 hours; further preferably, the reaction temperature of the hydrothermal reaction is 150-160 ℃; the reaction time is 20-24 hours.
Preferably, in the preparation process of the titanium dioxide nanowire, the alkali solution is selected from a sodium hydroxide solution or a potassium hydroxide solution.
Further preferably, the concentration of the sodium hydroxide solution or the potassium hydroxide solution is 6 to 14mol/L, and more preferably 8 to 12 mol/L.
Preferably, in the preparation process of the titanium dioxide nanowire, after the hydrothermal reaction is finished, the specific process of purification is as follows: and washing the product after the hydrothermal reaction to be neutral (pH 7) by using deionized water, then collecting bottom precipitates through high-speed centrifugation, and freeze-drying the bottom precipitates to finally obtain the one-dimensional titanium dioxide nanowires.
Preferably, in the preparation process of the composite material, the cationic surfactant is selected from at least one of cetyltrimethyl ammonium bromide, octadecyltrimethyl ammonium chloride, octadecyltrimethyl ammonium bromide, hexadecyltrimethyl ammonium chloride or dodecyltrimethyl ammonium chloride (bromide).
Preferably, in a mixture formed by mixing the cationic surfactant and the solvent, the mass concentration of the cationic surfactant is 0.05-1%; preferably 0.05-0.5%.
Preferably, the cationic surfactant is mixed with the solvent to form a mixture, and then the titanium dioxide nanowires are added, wherein the concentration of the titanium dioxide nanowires in the mixture is 0.05-0.8 mg/mL; more preferably 0.05-0.5 mg/mL.
Preferably, the MXene-Ti is contained3C2The supernatant is diluted to MXene-Ti before use3C2The concentration of (A) is 0.1-1.2 mg/mL; preferably 0.1-1 mg/mL.
Preferably, the titanium dioxide nanowire and MXene-Ti in the supernatant fluid3C2The mass ratio of (1), (3-15); the preferred mass ratio is 1 (5-10).
Preferably, in the preparation process of the composite material, the solvent is water, preferably deionized water. Two-dimensional MXene-Ti3C2The surface of the material is negatively charged, while the surface of the one-dimensional titanium dioxide nanowire material is uncharged (or has small positive electricity), and the surface of the one-dimensional titanium dioxide nanowire can be positively charged by modifying the one-dimensional titanium dioxide nanowire with a cationic surfactant. Thus, when a positively charged one-dimensional titanium dioxide nanowire encounters a negatively charged two-dimensional MXene-Ti3C2When the material is prepared, the one-dimensional titanium dioxide nanowire and the two-dimensional MXene-Ti nanowire can be quickly adsorbed to the two-dimensional MXene-Ti under the action of electrostatic attraction force3C2On materials, the process is electrostatic self-assembly.
Preferably, during the preparation of the composite material, the purification comprises centrifugation, washing and freeze drying.
Preferably, in the mixing of the composite material and the solvent, the solvent is an organic solvent, and preferably, the organic solvent is at least one of N, N-dimethylacetamide, dimethyl sulfoxide or N, N-dimethylformamide.
Preferably, the solvent in the solution of the fluoropolymer is at least one of N, N-dimethylacetamide, dimethylsulfoxide, or N, N-dimethylformamide.
Preferably, the mass ratio of the fluoropolymer to the solvent in the solution of the fluoropolymer is 1: (3-85), more preferably 1: (3-80).
Preferably, the mass ratio of the composite material to the fluoropolymer is 1: (5-120), more preferably 1: (10-100).
Preferably, the solvent mixed with the composite material and the solvent in the solution of the fluoropolymer are the same solvent.
Preferably, the carrier is a plastic mold or a glass plate.
Preferably, the drying temperature is 60-160 ℃, and the drying time is 10-24 hours; further preferably, the drying temperature is 60-150 ℃, and the drying time is 12-24 hours.
Preferably, after the proton exchange membrane is prepared, the proton exchange membrane is soaked and washed by hydrogen peroxide solution, sulfuric acid solution and deionized water in sequence, and finally dried at 50-60 ℃.
In a third aspect, the present invention provides the use of the proton exchange membrane described above.
A battery comprising the proton exchange membrane of the present invention.
Preferably, the cell is a fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention uniformly loads the one-dimensional titanium dioxide nanowire material on the two-dimensional layered nano carbide MXene-Ti in an electrostatic self-assembly mode3C2The composite material is formed on the surface and is coated by the fluorine-containing polymer, a proton transmission channel is constructed in the formed proton exchange membrane, the path of proton transmission is shortened, the water retention of the proton exchange membrane is increased, and the proton conductivity (the proton conductivity of the proton exchange membrane exceeds 42mS/cm at 30 ℃) and the dimensional stability (the swelling ratio of the proton exchange membrane is less than 10%) of the proton exchange membrane are remarkably improved.
(2) The preparation process of the proton exchange membrane has the advantages of low energy consumption and mild conditions, and is suitable for large-scale production.
Drawings
FIG. 1 shows MXene-Ti obtained in step (1) of example I of the present invention3C2SEM (scanning electron microscope) picture of (a);
FIG. 2 is a TEM (transmission electron microscope) image of a titanium dioxide nanowire produced in step (2) in example l of the present invention;
FIG. 3 is an SEM photograph of the composite material obtained in step (3) of example l of the present invention;
FIG. 4 is a cross-sectional view of a proton exchange membrane obtained in step (4) of example l of the present invention;
FIG. 5 is a graph showing the results of thermal stability tests of proton exchange membranes prepared in examples 1 to 3 of the present invention and a commercial Nafion115 proton membrane in a comparative example;
FIG. 6 is a graph showing the results of swelling ratio tests of proton exchange membranes produced in examples 1 to 3 of the present invention and a Nafion115 commercial proton membrane in a comparative example;
FIG. 7 is a graph showing the results of proton conductivity tests of proton exchange membranes produced in examples 1 to 3 of the present invention and a Nafion115 commercial proton membrane in a comparative example.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1: preparation of proton exchange membranes
A proton exchange membrane comprising a composite material, a fluoropolymer; the composite material is prepared by loading titanium dioxide nanowires on MXene-Ti3C2The surface of the composite material is coated by fluorine-containing polymer, and the fluorine-containing polymer is copolymer of polytetrafluoroethylene and perfluoro-3, 6-diepoxy-4-methyl-7-decene-sulfuric acid (Nafion for short).
Fluoropolymer, MXene-Ti3C2The mass ratio of the titanium dioxide nanowires is 120: 5: 1.
a preparation method of a proton exchange membrane comprises the following steps:
(1)MXene-Ti3C2the preparation of (1): 10mL of 9mol/L hydrochloric acid is poured into a plastic container filled with 0.8g of LiF to be uniformly stirred, and then 0.5g of ternary laminar MAX phase ceramic Ti is added3AlC2Reacting the powder at the constant temperature of 35 ℃ for 48 hours, collecting a bottom product, centrifugally washing the bottom product to be neutral, and dispersing a product obtained after washing inIntroducing nitrogen into water for ultrasonic treatment for 1 hour, collecting supernatant containing MXene-Ti3C2；
(2) Preparing a titanium dioxide nanowire: dissolving 1g of titanium dioxide powder in 9mol/L NaOH solution, uniformly dispersing titanium dioxide by adopting mechanical stirring and ultrasonic treatment to obtain a mixture, transferring the mixture into an autoclave with a PTFE (polytetrafluoroethylene) lining, sealing, putting the autoclave into a high-temperature drying box at 170 ℃ for hydrothermal reaction for 20 hours, washing the autoclave with deionized water until the pH value of supernatant is 7, then centrifugally collecting bottom precipitates, and freeze-drying the bottom precipitates to obtain one-dimensional titanium dioxide nanowires;
(3) preparing a composite material: adding 0.05g of hexadecyl trimethyl ammonium bromide into 100g of deionized water, stirring until the hexadecyl trimethyl ammonium bromide is dissolved to obtain a hexadecyl trimethyl ammonium bromide solution with the mass concentration of 0.05%, then adding 5mg of titanium dioxide nanowires prepared in the step (2), stirring and mixing to obtain a titanium dioxide nanowire solution with the mass concentration of 0.05mg/mL and modified by a cationic surfactant (hexadecyl trimethyl ammonium bromide), and slowly dripping 20mL (0.05mg/mL) of the titanium dioxide nanowire solution with the cationic surfactant (hexadecyl trimethyl ammonium bromide) into 10mL (0.5mg/mL) of titanium dioxide nanowire solution containing MXene-Ti and prepared in the step (1) at the room temperature of 20 DEG C3C2Centrifuging, washing, freeze-drying and collecting the obtained product to obtain the composite material (the titanium dioxide nanowires are loaded on MXene-Ti)3C2A surface);
(4) adding 0.5g of the composite material prepared in the step (3) into 50g N N-dimethylformamide to be uniformly dispersed to prepare a composite material mixture, then dripping the composite material mixture into a solution containing the fluoropolymer (10g of Nafion and 50g N N-dimethylformamide are mixed to form the solution containing the fluoropolymer), fully and uniformly mixing to prepare a casting solution, pouring the casting solution into a tetrafluoroethylene mold, drying at 80 ℃ for 24 hours to prepare the proton exchange membrane, then soaking and washing the proton exchange membrane for 1 hour by sequentially using a hydrogen peroxide solution with the mass concentration of 3%, a 1mol/L sulfuric acid solution and deionized water, and finally drying in a 60 ℃ forced air drying oven.
FIG. 1 shows MXene-Ti obtained in step (1) of example I of the present invention3C2SEM picture of (1); as can be seen from FIG. 1, MXene-Ti obtained in step (1)3C2Has the characteristic of two-dimensional layered structure.
FIG. 2 is a TEM image of titanium dioxide nanowires obtained in step (2) in example l of the present invention; as can be seen from FIG. 2, the titanium dioxide nanowires prepared in step (2) have the characteristic of one-dimensional linear shape.
FIG. 3 is an SEM photograph of the composite material obtained in step (3) of example l of the present invention; as can be seen from FIG. 3, the titanium dioxide nanowires in the composite material prepared in step (3) are supported on MXene-Ti3C2A surface.
FIG. 4 is a cross-sectional view of a proton exchange membrane obtained in step (4) of example l of the present invention. As can be seen from FIG. 4, the composite material (the titanium dioxide nanowires are loaded on MXene-Ti)3C2The surface) is coated by Nafion, the composite material is uniformly dispersed in the Nafion, the phenomenon of composite material agglomeration does not occur, and the composite material and the Nafion have good interface compatibility.
Example 2: preparation of proton exchange membranes
A proton exchange membrane comprising a composite material, a fluoropolymer; the composite material is prepared by loading titanium dioxide nanowires on MXene-Ti3C2The surface of the composite material is coated by fluorine-containing polymer, and the fluorine-containing polymer is copolymer of polytetrafluoroethylene and perfluoro-3, 6-diepoxy-4-methyl-7-decene-sulfuric acid (Nafion for short).
Fluoropolymer, MXene-Ti3C2The mass ratio of the titanium dioxide nanowires is 425: 16: 1.
a preparation method of a proton exchange membrane comprises the following steps:
(1)MXene-Ti3C2the preparation of (1): 20mL of 10mol/L hydrochloric acid is poured into a plastic container filled with 1.8g of LiF to be uniformly stirred, and then 1.2g of ternary laminar MAX phase ceramic Ti is added3AlC2Reacting the powder at the constant temperature of 35 ℃ for 48 hours, collecting bottom products, centrifugally washing the bottom products to be neutral, and washingDispersing the product obtained after washing in water, introducing nitrogen for ultrasonic treatment for 1.2 hours, collecting supernatant containing MXene-Ti3C2；
(2) Preparing a titanium dioxide nanowire: dissolving 1g of titanium dioxide powder in 10mol/L NaOH solution, uniformly dispersing titanium dioxide by adopting mechanical stirring and ultrasonic treatment to obtain a mixture, transferring the mixture into an autoclave with a PTFE (polytetrafluoroethylene) lining, sealing, putting the autoclave into a high-temperature drying box at 160 ℃ for hydrothermal reaction for 24 hours, washing the autoclave with deionized water until the pH value of supernatant is 7, then centrifugally collecting bottom precipitates, and freeze-drying the bottom precipitates to obtain one-dimensional titanium dioxide nanowires;
(3) preparing a composite material: adding 0.1g of octadecyltrimethyl ammonium chloride into 100g of deionized water, stirring until the solution is dissolved to obtain a solution of octadecyltrimethyl ammonium chloride with the mass concentration of 0.1%, then adding 10mg of titanium dioxide nanowires prepared in the step (2), stirring and mixing to obtain a 0.1mg/mL solution of titanium dioxide nanowires modified by cationic surfactant (octadecyltrimethyl ammonium chloride), and slowly dripping 50mL (0.1mg/mL) of the solution of titanium dioxide nanowires modified by cationic surfactant (octadecyltrimethyl ammonium chloride) into 80mL (1mg/mL) of the solution of titanium dioxide nanowires modified by cationic surfactant (octadecyltrimethyl ammonium chloride) and prepared in the step (1) at the room temperature of 20 DEG C3C2Centrifuging, washing, freeze-drying and collecting the obtained product to obtain the composite material (the titanium dioxide nanowires are loaded on MXene-Ti)3C2A surface);
(4) adding 1g of the composite material prepared in the step (3) into 75g N N-dimethylacetamide to be uniformly dispersed to prepare a composite material mixture, then dripping the composite material mixture into a solution containing fluoropolymer (25g of Nafion and 75g N N-dimethylacetamide are mixed to form the solution containing fluoropolymer), fully and uniformly mixing to prepare a casting solution, pouring the casting solution into a tetrafluoroethylene mold, drying at 120 ℃ for 24 hours to prepare a proton exchange membrane, then soaking and washing the proton exchange membrane for 1 hour by using a hydrogen peroxide solution with the mass concentration of 3%, a 1mol/L sulfuric acid solution and deionized water in sequence, and finally drying in a blast drying oven at 60 ℃.
Example 3: preparation of proton exchange membranes
A proton exchange membrane comprising a composite material, a fluoropolymer; the composite material is prepared by loading titanium dioxide nanowires on MXene-Ti3C2The surface of the composite material is coated by fluorine-containing polymer, and the fluorine-containing polymer is copolymer of polytetrafluoroethylene and perfluoro-3, 6-diepoxy-4-methyl-7-decene-sulfuric acid (Nafion for short).
Fluoropolymer, MXene-Ti3C2The mass ratio of the titanium dioxide nanowires is 110: 10: 1.
a preparation method of a proton exchange membrane comprises the following steps:
(1)MXene-Ti3C2the preparation of (1): 30mL of 12mol/L hydrochloric acid is poured into a plastic container filled with 3.6g of LiF to be uniformly stirred, and then 2.7g of ternary laminar MAX phase ceramic Ti is added3AlC2Reacting the powder at the constant temperature of 35 ℃ for 48 hours, collecting a bottom product, centrifugally washing the bottom product to be neutral, dispersing the washed product in water, introducing nitrogen to perform ultrasonic treatment for 1.5 hours, and collecting an upper layer liquid containing MXene-Ti3C2；
(2) Preparing a titanium dioxide nanowire: dissolving 1g of titanium dioxide powder in 12mol/L NaOH solution, uniformly dispersing titanium dioxide by adopting mechanical stirring and ultrasonic treatment to obtain a mixture, transferring the mixture into an autoclave with a PTFE (polytetrafluoroethylene) lining, sealing, putting the autoclave into a high-temperature drying box at 180 ℃ for hydrothermal reaction for 36 hours, washing the autoclave with deionized water until the pH value of supernatant is 7, then centrifugally collecting bottom precipitates, and freeze-drying the bottom precipitates to obtain one-dimensional titanium dioxide nanowires;
(3) preparing a composite material: adding 0.5g of octadecyl trimethyl ammonium bromide into 100g of deionized water, stirring until the octadecyl trimethyl ammonium bromide is dissolved to obtain an octadecyl trimethyl ammonium bromide solution with the mass concentration of 0.5%, then adding 50mg of titanium dioxide nanowires prepared in the step (2), stirring and mixing to obtain 0.5mg/mL titanium dioxide nanowires passing through a cation tableSlowly dripping 20mL (0.5mg/mL) of titanium dioxide nanowire solution modified by cationic surfactant (octadecyl trimethyl ammonium bromide) into 100mL (1mg/mL) of titanium dioxide nanowire solution modified by surfactant (octadecyl trimethyl ammonium bromide) at room temperature of 20 ℃ to obtain solution containing MXene-Ti, wherein the solution is prepared in the step (1)3C2Centrifuging, washing, freeze-drying and collecting the obtained product to obtain the composite material (the titanium dioxide nanowires are loaded on MXene-Ti)3C2A surface);
(4) adding 1.5g of the composite material prepared in the step (3) into 150g of dimethyl sulfoxide for uniform dispersion to prepare a composite material mixture, then dripping the composite material mixture into a solution containing a fluoropolymer (15g of Nafion and 150g of dimethyl sulfoxide are mixed to form the solution containing the fluoropolymer), fully and uniformly mixing to prepare a casting solution, pouring the casting solution into a tetrafluoroethylene mold, drying at 140 ℃ for 24 hours to prepare a proton exchange membrane, then soaking and washing the proton exchange membrane for 1 hour by sequentially using a hydrogen peroxide solution with the mass concentration of 3%, a 1mol/L sulfuric acid solution and deionized water, and finally drying in a 60 ℃ forced air drying oven.
Comparative example
The comparative example is a Nafion115 commercial proton membrane.
Product effectiveness testing
1. Proton exchange membrane thermal stability test
The proton exchange membranes prepared in examples 1 to 3 and the commercial proton membrane of Nafion115 in comparative example were taken and tested for thermal stability under the same conditions, and the results are shown in fig. 5.
FIG. 5 is a graph showing the results of thermal stability tests of proton exchange membranes prepared in examples 1 to 3 of the present invention and a commercial Nafion115 proton membrane in a comparative example; as can be seen from FIG. 5 (in FIG. 5, the abscissa "Temperature" represents Temperature and the ordinate "Weight" represents Weight), the decrease in Weight of the proton exchange membranes prepared in examples 1-3 of the present invention is smaller than that of the comparative example in the range of 100-400 ℃, indicating that the thermal stability of the proton exchange membranes prepared in examples 1-3 of the present invention is significantly better than that of the Nafion115 commercial proton membrane in the comparative example.
2. Proton exchange membrane dimensional stability test
The swelling ratios of the proton exchange membranes prepared in examples 1 to 3 and the commercial proton membrane Nafion115 of comparative example were measured under the same conditions, and the smaller the swelling ratio, the more stable the dimensional stability, and the results are shown in FIG. 6.
The swelling ratio test conditions were: cutting the proton exchange membrane into rectangular strips with the length of 5cm and the width of 1cm, soaking in deionized water at 80 ℃ for 8h, taking out the proton exchange membrane, slightly wiping off water on the surface of the proton exchange membrane by using filter paper, and then rapidly measuring the length A of the proton exchange membrane1. The swelling ratio is calculated according to the formula: swelling ratio [ (A)1-5)/5]*100％。
FIG. 6 is a graph showing the results of swelling ratio tests of proton exchange membranes produced in examples 1 to 3 of the present invention and a Nafion115 commercial proton membrane in a comparative example; as can be seen from FIG. 6, the swelling ratio of the proton exchange membranes obtained in examples 1 to 3 of the present invention is less than 10%, which is significantly less than 12% of that of the Nafion115 commercial proton membrane of the comparative example, indicating that the proton exchange membranes obtained in examples 1 to 3 of the present invention have good dimensional stability, and particularly that the swelling ratio of the proton exchange membranes obtained in example 3 is less than 6% and the dimensional stability is the best.
3. Proton conductivity test for proton exchange membranes
The proton conductivity of the proton exchange membranes prepared in examples 1 to 3 and the commercial proton membrane of Nafion115 of comparative example was measured under the same conditions (100% relative humidity, 30 to 90 ℃ C.), and the results are shown in FIG. 7.
FIG. 7 is a graph showing the results of proton conductivity tests of proton exchange membranes produced in examples 1 to 3 of the present invention and a Nafion115 commercial proton membrane in a comparative example. As can be seen from fig. 7, the proton conductivity of the proton exchange membranes prepared in examples 1 to 3 of the present invention is significantly better than that of the Nafion115 commercial proton membrane in the comparative example at 30 to 90 ℃ under 100% relative humidity. For example, the proton conductivity of the proton exchange membranes obtained in examples 1 to 3 was 77mS/cm, 75mS/cm, 84mS/cm, and 64mS/cm, respectively, at 60 ℃. The proton conductivity of the proton exchange membranes prepared in examples 1-3 exceeded 42mS/cm, and could even be as high as 50mS/cm at 30 deg.C, while the proton conductivity of the comparative example was less than 40 mS/cm.

Claims (10)

1. A proton exchange membrane is characterized by comprising a composite material and a fluorine-containing polymer; the composite material is prepared by loading titanium dioxide nanowires on MXene-Ti3C2A surface, the composite material being coated with the fluoropolymer.
2. The proton exchange membrane according to claim 1 wherein said fluoropolymer is selected from the group consisting of polytetrafluoroethylene and perfluoro-3, 6-diepoxy-4-methyl-7-decene-sulfuric acid copolymer.
3. The proton exchange membrane according to claim 1 wherein said fluoropolymer, MXene-Ti3C2The mass ratio of the titanium dioxide nanowire is (100-500): (3-20): 1.
4. a process for the preparation of a proton exchange membrane according to any one of claims 1 to 3, comprising the steps of:
MXene-Ti3C2the preparation of (1): mixing the acid with the fluoride salt and then adding Ti3AlC2Reacting, collecting bottom-layer products, then carrying out ultrasonic treatment and centrifugation, and collecting supernatant fluid containing MXene-Ti3C2；
Preparing a titanium dioxide nanowire: dissolving titanium dioxide in alkali liquor, dispersing, then carrying out hydrothermal reaction, and purifying to obtain titanium dioxide nanowires;
preparing a composite material: mixing a cationic surfactant with a solvent, adding titanium dioxide nanowires, stirring and mixing, then dropwise adding the supernatant, and then purifying to obtain a composite material;
and mixing the composite material with a solvent to obtain a composite material mixture, dripping the composite material mixture into a solution containing a fluorine polymer, mixing to obtain a membrane casting solution, pouring the membrane casting solution onto a carrier, and drying to obtain the proton exchange membrane.
5. The method according to claim 4, wherein the MXene-Ti is3C2In the preparation, the acid is hydrochloric acid, and the concentration of the hydrochloric acid is 8-15 mol/L; the acid, fluoride salt, Ti3AlC2The dosage ratio of (A) is 10 mL: (0.6-1.5) g: (0.5-1.0) g.
6. The method according to claim 4, wherein the Ti is3AlC2Is ternary laminated MAX phase ceramic Ti3AlC2。
7. The method as claimed in claim 4, wherein the reaction temperature of the hydrothermal reaction is 140 ℃ to 190 ℃ during the preparation of the titanium dioxide nanowires; the reaction time of the hydrothermal reaction is 18-36 hours.
8. The preparation method according to claim 4, wherein the titanium dioxide nanowires and MXene-Ti in the supernatant liquid3C2The mass ratio of (1) to (3-15).
9. The method according to claim 4, wherein the mass ratio of the composite material to the fluoropolymer is 1: (5-120).
10. A cell comprising the proton exchange membrane of any one of claims 1 to 3.
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