CN108258290B - Method for preparing high-temperature proton exchange membrane with layer-by-layer assembly structure based on spin coating technology by doping phosphoric acid - Google Patents
Method for preparing high-temperature proton exchange membrane with layer-by-layer assembly structure based on spin coating technology by doping phosphoric acid Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the technical field of fuel cells, relates to a preparation technology of proton exchange membrane electrolyte, and particularly relates to a proton exchange membrane electrolyteA method for preparing a phosphoric acid doped high-temperature proton exchange membrane with a layer-by-layer assembly structure based on a spin coating technology. Respectively spin-coating Kevlar nanofiber, cadmium telluride nanocrystal and phosphoric acid to complete 2-5 layers of assembly, and preparing the (Kevlar-CdTe-PA) with an ordered structure2‑5Compounding film; the film dried by the oven is hermetically soaked in phosphoric acid solution with the mass fraction of 40-85 percent to prepare phosphoric acid doped cadmium telluride nanocrystal (Kevlar-CdTe-PA)2‑5/(40-85%) PA composite membrane. The invention realizes the assembly of the Kevlar nano-fiber and the cadmium telluride nanocrystal, prepares the high-temperature proton exchange membrane with an ordered structure and good proton conductivity, and has potential application value in the field of fuel cells. In addition, the invention provides a new research method and thought for preparing a novel composite membrane based on the nano material and the Kevlar nano fiber.
Description
Technical Field
The invention belongs to the technical field of fuel cells, relates to a preparation technology of proton exchange membrane electrolyte, and particularly relates to a method for preparing a high-temperature proton exchange membrane with a layer-by-layer assembly structure and doped with phosphoric acid based on a spin coating technology.
Background
Molecular assembly refers to a process of spontaneously forming molecular aggregates having a specific structure and shape by weak forces such as hydrogen bonds, electrostatic forces, van der waals forces, hydrophobic lipophillic forces, and the like at the molecular level. Molecular assembly techniques are commonly used in the field of assembly of nanomaterials and preparation of ultrathin films. The technology has the advantages of simple and convenient operation, no need of special equipment, controllable thickness of the film in a nanoscale range and the like. Layer-by-layer assembly is taken as a specific form of molecular assembly technology application, great development is achieved in the field of ultrathin composite material preparation, and the prepared material is widely applied to the fields of biomedicine, energy, environmental protection and the like. However, the membrane electrolyte is prepared by layer-by-layer assembly techniques, which typically require several hundred layers to be assembled to achieve a thickness of 10 μm. Therefore, there is a disadvantage that the preparation period is long.
The spin coating method is a coating process in which coating liquid drops falling on a substrate are distributed on the surface of a workpiece all over by the centrifugal force and the gravity generated when the substrate rotates. Compared with the film preparation technologies such as an electrochemical method, a physical/chemical vapor deposition method and the like, the spin-coating method has the unique advantages of mild process conditions, simplicity in operation and control and the like, and the thickness of the prepared film is 30-200nm and is accurately controllable. Therefore, the membrane electrolyte prepared by the spin coating method has obvious effects on the aspects of reducing pollution, saving energy, improving cost performance and the like. In recent years, the spin coating method has been receiving attention, and its application has been gradually popularized in the fields of materials science, physics, medicine, biology, and the like.
The proton exchange membrane is one of the core components of the proton exchange membrane fuel cell, and the increase of the operating temperature thereof will directly determine the development and commercialization process of the high temperature proton exchange membrane fuel cell. Proton exchange membranes are both dense permselective membranes and are the substrate material for electrolytes (for proton transfer) and electrode active materials (electrocatalysts). According to the statement of the institute of chemical and physical research, the proton exchange membrane is mainly required to have the following 6 points: (1) the high proton conductivity can reduce the internal resistance of the battery, reduce the ohmic overpotential to improve the current density and realize high battery efficiency; (2) the permeability of gas in the membrane is as small as possible, so that the phenomenon that hydrogen and oxygen react on the surface of the counter electrode to cause local overheating of the electrode and influence the coulomb efficiency of the battery is avoided; (3) the membrane has stability to oxidation, reduction and hydrolysis, and is not degraded under the oxidation/reduction and acidic action of active substances; (4) has sufficiently high mechanical strength and thermal stability to withstand mechanical and thermal impacts that are not uniform during cell processing and operation, thereby meeting the requirements of mass production; (5) the surface properties of the membrane are suitable for binding with the catalyst; (6) appropriate performance/price ratio.
Kevlar is a high-performance aramid fiber, Kevlar is used for short, the Kevlar is also called aramid fiber 1414 prepared in China, the original name of the Kevlar is poly (p-phenylene terephthalamide) (PPTA), and the basic unit of the Kevlar is [ -CO-C [ -C ]6H4-CONH-C6H4NH-]And (2). Kevlar has the common advantages of common fiber materials: high strength, high modulus, high temperature resistance and the like, and has the advantages of light weight, chemical corrosion resistance, strong flame retardance, good insulativity, fatigue resistance, good textile performance, strong stability and the like. The Kevlar nano-fiber has the diameter of about 10-20nm and the specific gravity of only 1.44g/cm3The tensile strength is up to 2760N/mm2The elongation at break was low at 2.5%. At present, most reports of making bulletproof materials by using Kevlar nanofibers in the world exist, and most researches are focused on the modification aspect of Kevlar, but because the interfacial acting force between the Kevlar nanofibers and polymers is weak, the researches on preparing polymer membrane electrolytes based on the Kevlar nanofibers are less, and the reports on applying the Kevlar nanofibers and nano material composite prepared membrane electrolytes to high-temperature proton exchange membrane batteries are not available. For the invention, the characteristics of a molecular assembly principle and a spin coating technology are comprehensively considered, and the research progress of the Kevlar nano fiber at present is combined, so that the high-temperature proton exchange membrane which is doped with phosphoric acid and has a layer-by-layer assembly structure and good performance and is prepared by utilizing the spin coating method based on the Kevlar nano fiber and a cadmium telluride nano material has theoretical feasibility and strong application prospect.
Disclosure of Invention
The invention provides a method for preparing a high-temperature proton exchange membrane with a layer-by-layer assembly structure by using a spin coating technology based on Kevlar nanofibers and cadmium telluride nanocrystals, and the purpose of preparing the high-temperature proton exchange membrane with high proton conductivity, good mechanical properties and stability is achieved.
The technical scheme of the invention is as follows:
a method for preparing a high-temperature proton exchange membrane with a layer-by-layer assembly structure based on a spin coating technology by doping phosphoric acid comprises the following steps:
(1) adding 400-600ml of dimethyl sulfoxide, 4-6g of Kevlar nano fiber and 2-4g of potassium hydroxide into a 1000ml reagent bottle with a plug, and stirring for 5-7 days to form a Kevlar nano fiber homogeneous solution with the concentration of 9-11 g/L;
(2) dripping 4-6ml Kevlar nanofiber homogeneous phase solution on a glass sheet treated by the piranha solution at the temperature of 20-35 ℃, spin-coating for 15-25 seconds on a spin-coating machine at the speed of 500-1500 revolutions per minute, and then soaking the glass sheet in deionized water for 5-10 seconds; wherein, the piranha solution: concentrated sulfuric acid with the concentration of 98wt% and hydrogen peroxide with the concentration of 30wt% are mixed according to the volume ratio of 7: 3, mixing;
(3) dripping 1-3ml of cadmium telluride aqueous solution on the glass sheet at 20-35 ℃, drying in a drying oven at 75-85 ℃ for 2-4 hours, dripping 2-4ml of cadmium telluride aqueous solution again, and continuously drying in the drying oven at 75-85 ℃ for 2-4 hours;
(4) dripping 2-5ml of phosphoric acid solution with the concentration of 85wt% on a glass sheet at the temperature of 20-35 ℃, and spin-coating for 30-10 seconds on a spin-coating machine at the speed of 300-1000 revolutions per minute;
(5) repeating the step (3) to finish a layer of self-assembly, which is marked as (Kevlar-CdTe-PA)1A self-assembled film;
(6) repeating the steps (2) - (5) for 2-5 times to obtain (Kevlar-CdTe-PA) with 2-5 layers of self-assembled structure2-5Compounding film;
(7) will (Kevlar-CdTe-PA)2-5The composite film is stripped from the glass sheet and dried in an oven at 75-85 ℃ for 1-3 hours, and is marked as (Kevlar-CdTe-PA)2-5Compounding film;
(8) at 20-30 deg.C, the composite film (Kevlar-CdTe-PA)2-5Soaking in 40-85 wt% phosphoric acid water solution in a container with plug for 1-4 days to obtain (Kevlar-CdTe-PA)2-5/(40% -85%) PA composite membrane.
The method for preparing the high-temperature proton exchange membrane with the layer-by-layer assembly structure based on the spin coating technology by doping phosphoric acid preferably comprises the steps of adding 500ml of dimethyl sulfoxide, 5g of Kevlar fiber and 3g of potassium hydroxide into a 1000ml reagent bottle with a plug in step (1), and stirring for 5-7 days to form a Kevlar fiber homogeneous solution with the concentration of 10 g/L.
Preferably, in the step (2), 5ml of Kevlar nanofiber homogeneous phase solution is dripped on a glass sheet treated by the piranha solution at the temperature of 20-35 ℃, and after the glass sheet is spin-coated for 20 seconds on a spin-coating machine at the speed of 500-1500 revolutions per minute, the glass sheet is soaked in deionized water for 5-10 seconds.
The phosphoric acid-doped spin coating-based method for preparing the high-temperature proton exchange membrane with the layer-by-layer assembly structure preferably comprises the steps of (3) dropwise adding 1-3ml of cadmium telluride aqueous solution on a glass sheet at 20-35 ℃, drying in an oven at 80 ℃ for 2-4 hours, dropwise adding 2-4ml of cadmium telluride aqueous solution again, and continuously drying in the oven at 80 ℃ for 2-4 hours.
The phosphoric acid-doped spin coating-based method for preparing the high-temperature proton exchange membrane with the layer-by-layer assembly structure preferably comprises the step (7) of mixing (Kevlar-CdTe-PA)2-5The composite film was peeled from the glass sheet and dried in an oven at 80 ℃ for 2 hours and recorded as (Kevlar-CdTe-PA)2-5A composite membrane.
The phosphoric acid-doped high-temperature proton exchange membrane with a layer-by-layer assembly structure prepared by the method based on the spin coating technology (Kevlar-CdTe-PA)2-5In the/PA composite membrane, the mass ratio of phosphoric acid PA to other substances is 50-130%.
The phosphoric acid-doped high-temperature proton exchange membrane with a layer-by-layer assembly structure prepared by the method based on the spin coating technology (Kevlar-CdTe-PA)2-5/(40-85%) the PA composite film has a thickness of 30-100 μm and each self-assembled film has a thickness of 15-20 μm.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
1. the phosphoric acid-doped high-temperature proton exchange membrane with the layer-by-layer assembly structure is prepared based on the spin coating technology, so that the fine regulation and control of the membrane composition and the structure are facilitated, and the membrane material with stable properties is obtained. Compared with a membrane material prepared by a solution pouring method, the membrane prepared by the method has an ordered structure, is beneficial to proton conduction, and further improves the proton conduction capability of the composite membrane.
2. Prepared by the invention (Kevlar-CdTe-PA)4The composite membrane has good thermal stability, and the thermal decomposition temperature reaches 180 ℃; according to (Kevlar-CdTe-PA)4The surface and cross section of the composite film can be known by an electronic scanning electron microscope picture: (Kevlar-CdTe-PA)4The composite film has obvious layer-by-layer ordered structure and is compact, and is prepared by (Kevlar-CdTe-PA)4Soaking the composite membrane in phosphoric acid solutionPreparation (Kevlar-CdTe-PA)4A/PA composite membrane. (Kevlar-CdTe-PA)4the/PA composite membrane has good proton conductivity, and (Kevlar-CdTe-PA) under the condition of no humidification at 160 DEG C4The proton conductivity of the/85% PA composite membrane is 2.3 multiplied by 10-1S/cm。
Drawings
FIG. 1 shows (Kevlar-CdTe-PA) prepared in example 6 of the invention4Picture of the real object of the composite film; wherein: (A) the overall appearance of the composite membrane; (B) the composite film and A4 paper are subjected to a thickness comparison graph;
FIG. 2 shows (Kevlar-CdTe-PA) prepared in example 64The thermal weight loss curve of the composite membrane and the pure Kevlar membrane;
FIG. 3 is (Kevlar-CdTe-PA) prepared in example 64Scanning an electron microscope picture by using the composite film; wherein: (A) is a surface electron microscope picture of the composite film; (B) scanning electron microscope pictures of the cross section of the composite film;
FIG. 4 shows examples 7 to 9 (Kevlar-CdTe-PA)4The composite membrane is prepared by soaking in 40-85 wt% phosphoric acid solution (Kevlar-CdTe-PA)4Conductivity of the/PA composite membrane and the un-soaked phosphoric acid membrane.
Detailed Description
The process of the present invention is further illustrated by the following examples.
Example 1
(1) 500ml of dimethyl sulfoxide, 5g of Kevlar nano fiber and 3g of potassium hydroxide are added into a 1000ml reagent bottle with a plug, and stirred for 5-7 days to form a Kevlar nano fiber homogeneous solution with the concentration of 10 g/L.
(2) At the temperature of 20-35 ℃, 5ml of Kevlar nanofiber homogeneous phase solution is dripped on a glass sheet treated by a piranha solution (concentrated sulfuric acid with the concentration of 98wt% and hydrogen peroxide with the concentration of 30wt% are mixed according to the volume ratio of 7: 3), spin-coated on a spin-coating machine at the speed of 1500 rpm for 20 seconds, and then the glass sheet is soaked in deionized water for 5-10 seconds.
(3) Dropping 1ml of cadmium telluride aqueous solution on the glass sheet at 20-35 ℃, drying in an oven at 80 ℃ for 4 hours, dropping 4ml of cadmium telluride aqueous solution again, and continuously drying in the oven at 80 ℃ for 4 hours.
(4) 2ml of a 85% strength phosphoric acid solution are added dropwise to the glass plate at 20-35 ℃ and the plate is spun on a spin coater at 1000 rpm for 20 seconds.
(5) Repeating the step (3) to finish a layer of self-assembly, which is marked as (Kevlar-CdTe-PA)1Self-assembled film, PA is Phosphoric acid (Phosphoric acid).
(6) Repeating the steps (2) - (5) 4 times to obtain (Kevlar-CdTe-PA) with 4 layers of self-assembled structure4A composite membrane.
(7) Will (Kevlar-CdTe-PA)4The composite film was peeled from the glass sheet and dried in an oven at 80 ℃ for 2 hours, and the mark was (Kevlar-CdTe-PA)4A composite membrane.
(8) At 25 deg.C, the composite film (Kevlar-CdTe-PA)4Soaking in 85% phosphoric acid water solution with plug for 1-4 days to obtain (Kevlar-CdTe-PA)4The thickness of the/85% PA composite membrane is about 60-80 μm, the thickness of each self-assembled membrane is about 15-20 μm, and the mass ratio of the phosphoric acid PA to other substances in the composite membrane is about 50-70%.
Example 2
(1) 450ml of dimethyl sulfoxide, 4g of Kevlar nano fiber and 2g of potassium hydroxide are added into a 1000ml reagent bottle with a plug, and stirred for 5-7 days to form a Kevlar nano fiber homogeneous solution with the concentration of 9 g/L.
(2) At the temperature of 20-35 ℃, 6ml of Kevlar nanofiber homogeneous phase solution is dripped on a glass sheet treated by a piranha solution (concentrated sulfuric acid with the concentration of 98wt% and hydrogen peroxide with the concentration of 30wt% are mixed according to the volume ratio of 7: 3), spin-coated for 15 seconds on a spin-coating machine at the speed of 1000 revolutions per minute, and then the glass sheet is soaked in deionized water for 5-10 seconds.
(3) Dropping 1ml of cadmium telluride aqueous solution on the glass sheet at 20-35 ℃, drying in a 75 ℃ oven for 4 hours, dropping 4ml of cadmium telluride aqueous solution again, and continuously drying in the 75 ℃ oven for 4 hours.
(4) 2ml of a 85% strength phosphoric acid solution are added dropwise to the glass plate at 20-35 ℃ and the plate is spun on a spin coater at 500 rpm for 20 seconds.
(5) Repeating the step (3) to finish a layer of self-assembly, and recording as (Ke)vlar-CdTe-PA)1Self-assembled film, PA is Phosphoric acid (Phosphoric acid).
(6) Repeating the steps (2) - (5) 4 times to obtain (Kevlar-CdTe-PA) with 4 layers of self-assembled structure4A composite membrane.
(7) Will (Kevlar-CdTe-PA)4The composite film was peeled from the glass sheet and dried in an oven at 75 ℃ for 2 hours, and it was designated (Kevlar-CdTe-PA)4A composite membrane.
(8) At 20 deg.C, the composite film (Kevlar-CdTe-PA)4Soaking in 85% phosphoric acid water solution with plug for 1-4 days to obtain (Kevlar-CdTe-PA)4The thickness of the/85% PA composite membrane is about 60-80 μm, the thickness of each self-assembled membrane is about 15-20 μm, and the mass ratio of the phosphoric acid PA to other substances in the composite membrane is about 60-80%.
Example 3
(1) 550ml of dimethyl sulfoxide, 6g of Kevlar nano fiber and 4g of potassium hydroxide are added into a 1000ml reagent bottle with a plug, and stirred for 5-7 days to form a Kevlar nano fiber homogeneous solution with the concentration of 11 g/L.
(2) 4ml of Kevlar nanofiber homogeneous phase solution is dripped on a glass sheet treated by a piranha solution (concentrated sulfuric acid with the concentration of 98wt% and hydrogen peroxide with the concentration of 30wt% are mixed according to the volume ratio of 7: 3) at the temperature of 20-35 ℃, spin-coated on a spin-coating machine at the speed of 500 revolutions per minute for 25 seconds, and then the glass sheet is soaked in deionized water for 5-10 seconds.
(3) Dropping 1ml of cadmium telluride aqueous solution on the glass sheet at 20-35 ℃, drying in an oven at 85 ℃ for 4 hours, dropping 4ml of cadmium telluride aqueous solution again, and continuously drying in the oven at 85 ℃ for 4 hours.
(4) 2ml of a 85% strength phosphoric acid solution are added dropwise to the glass plate at 20-35 ℃ and the plate is spun on a spin coater at 300 revolutions per minute for 30 seconds.
(5) Repeating the step (3) to finish a layer of self-assembly, which is marked as (Kevlar-CdTe-PA)1Self-assembled film, PA is Phosphoric acid (Phosphoric acid).
(6) Repeating the steps (2) - (5) 4 times to obtain (Kevlar-CdTe-PA) with 4 layers of self-assembled structure4A composite membrane.
(7) Will (Kevlar-CdTe-PA)4The composite film was peeled from the glass sheet and dried in an oven at 85 ℃ for 2 hours, and the title was (Kevlar-CdTe-PA)4A composite membrane.
(8) At 30 deg.C, the composite film (Kevlar-CdTe-PA)4Soaking in 85% phosphoric acid water solution with plug for 1-4 days to obtain (Kevlar-CdTe-PA)4The thickness of the/85% PA composite membrane is about 60-80 μm, the thickness of each self-assembled membrane is about 15-20 μm, and the mass ratio of the phosphoric acid PA to other substances in the composite membrane is about 70-90%.
Example 4
(1) 500ml of dimethyl sulfoxide, 5g of Kevlar nano fiber and 3g of potassium hydroxide are added into a 1000ml reagent bottle with a plug, and stirred for 5-7 days to form a Kevlar nano fiber homogeneous solution with the concentration of 10 g/L.
(2) At the temperature of 20-35 ℃, 5ml of Kevlar nanofiber homogeneous phase solution is dripped on a glass sheet treated by a piranha solution (concentrated sulfuric acid with the concentration of 98wt% and hydrogen peroxide with the concentration of 30wt% are mixed according to the volume ratio of 7: 3), spin-coated on a spin-coating machine at the speed of 1000 revolutions per minute for 20 seconds, and then the glass sheet is soaked in deionized water for 5-10 seconds.
(3) Dropping 2ml of cadmium telluride aqueous solution on the glass sheet at 20-35 ℃, drying in an oven at 80 ℃ for 4 hours, dropping 3ml of cadmium telluride aqueous solution again, and continuously drying in the oven at 80 ℃ for 4 hours.
(4) 4ml of a 85% strength phosphoric acid solution are added dropwise to the glass plate at 20-35 ℃ and the plate is spun on a spin coater at 500 rpm for 20 seconds.
(5) Repeating the step (3) to finish a layer of self-assembly, which is marked as (Kevlar-CdTe-PA)1Self-assembled film, PA is Phosphoric acid (Phosphoric acid).
(6) Repeating the steps (2) - (5) 4 times to obtain (Kevlar-CdTe-PA) with 4 layers of self-assembled structure4A composite membrane.
(7) Will (Kevlar-CdTe-PA)4The composite film was peeled from the glass sheet and dried in an oven at 80 ℃ for 2 hours, and the mark was (Kevlar-CdTe-PA)4A composite membrane.
(8) At 25 ℃, the composite membrane (Kevl)ar-CdTe-PA)4Soaking in 85% phosphoric acid water solution with plug for 1-4 days to obtain (Kevlar-CdTe-PA)4The thickness of the/85% PA composite membrane is about 60-80 μm, the thickness of each self-assembled membrane is about 15-20 μm, and the mass ratio of the phosphoric acid PA to other substances in the composite membrane is about 100% -110%.
Example 5
(1) 500ml of dimethyl sulfoxide, 5g of Kevlar nano fiber and 3g of potassium hydroxide are added into a 1000ml reagent bottle with a plug, and stirred for 5-7 days to form a Kevlar nano fiber homogeneous solution with the concentration of 10 g/L.
(2) At the temperature of 20-35 ℃, 5ml of Kevlar nanofiber homogeneous phase solution is dripped on a glass sheet treated by a piranha solution (concentrated sulfuric acid with the concentration of 98wt% and hydrogen peroxide with the concentration of 30wt% are mixed according to the volume ratio of 7: 3), spin-coated on a spin-coating machine at the speed of 500 revolutions per minute for 20 seconds, and then the glass sheet is soaked in deionized water for 5-10 seconds.
(3) At the temperature of 20-35 ℃, 3ml of cadmium telluride aqueous solution is dripped on the glass sheet, and after the glass sheet is dried in an oven at the temperature of 80 ℃ for 3 hours, 2ml of cadmium telluride aqueous solution is dripped again, and the glass sheet is continuously dried in the oven at the temperature of 80 ℃ for 3 hours.
(4) 5ml of a 85% strength phosphoric acid solution are added dropwise to the glass plate at 20-35 ℃ and the plate is spun on a spin coater at 300 revolutions per minute for 30 seconds.
(5) Repeating the step (3) to finish a layer of self-assembly, which is marked as (Kevlar-CdTe-PA)1Self-assembled film, PA is Phosphoric acid (Phosphoric acid).
(6) Repeating the steps (2) - (5) 4 times to obtain (Kevlar-CdTe-PA) with 4 layers of self-assembled structure4A composite membrane.
(7) Will (Kevlar-CdTe-PA)4The composite film was peeled from the glass sheet and dried in an oven at 80 ℃ for 2 hours, and the mark was (Kevlar-CdTe-PA)4A composite membrane.
(8) At 25 deg.C, the composite film (Kevlar-CdTe-PA)4Soaking in 85% phosphoric acid water solution with plug for 1-4 days to obtain (Kevlar-CdTe-PA)4The thickness of the/85% PA composite film is about 60-80 μm, the thickness of each self-assembled film is about 15-20 μm, and the composite film is preparedThe mass ratio of the phosphoric acid PA to other substances in the film is about 100-130%.
Example 6
(1) 500ml of dimethyl sulfoxide, 5g of Kevlar nano fiber and 3g of potassium hydroxide are added into a 1000ml reagent bottle with a plug, and stirred for 5-7 days to form a Kevlar nano fiber homogeneous solution with the concentration of 10 g/L.
(2) At the temperature of 20-35 ℃, 5ml of Kevlar nanofiber homogeneous phase solution is dripped on a glass sheet treated by a piranha solution (concentrated sulfuric acid with the concentration of 98wt% and hydrogen peroxide with the concentration of 30wt% are mixed according to the volume ratio of 7: 3), spin-coated on a spin-coating machine at the speed of 1500 rpm for 20 seconds, and then the glass sheet is soaked in deionized water for 5-10 seconds.
(3) Dropping 2ml of cadmium telluride aqueous solution on the glass sheet at 20-35 ℃, drying in an oven at 80 ℃ for 4 hours, dropping 3ml of cadmium telluride aqueous solution again, and continuously drying in the oven at 80 ℃ for 4 hours.
(4) 4ml of a 85% strength phosphoric acid solution are added dropwise to the glass plate at 20-35 ℃ and the plate is spun on a spin coater at 1000 rpm for 20 seconds.
(5) Repeating the step (3) to finish a layer of self-assembly, which is marked as (Kevlar-CdTe-PA)1Self-assembled film, PA is Phosphoric acid (Phosphoric acid).
(6) Repeating the steps (2) - (5) 4 times to obtain (Kevlar-CdTe-PA) with 4 layers of self-assembled structure4A composite membrane.
(7) Will (Kevlar-CdTe-PA)4The composite film was peeled from the glass sheet and dried in an oven at 80 ℃ for 2 hours, and the mark was (Kevlar-CdTe-PA)4A composite membrane.
(8) At 25 deg.C, the composite film (Kevlar-CdTe-PA)4Soaking in 85% phosphoric acid water solution with plug for 1-4 days to obtain (Kevlar-CdTe-PA)4The thickness of the/85% PA composite membrane is about 60-80 μm, the thickness of each self-assembled membrane is about 15-20 μm, and the mass ratio of the phosphoric acid PA to other substances in the composite membrane is about 80% -100%.
As shown in FIG. 1, (Kevlar-CdTe-PA) prepared from inventive example 64The picture of the composite film can be seen, (Kevlar-CdTe-PA)4The composite membrane is dark gray and opaque as a whole, the surface is uniform, the thickness of the membrane is equivalent to that of A4 paper, and the composite membrane has good flexibility and can meet the requirement of the proton exchange membrane fuel cell on the strength of the proton exchange membrane.
As shown in FIG. 2, prepared from example 6 (Kevlar-CdTe-PA)4The thermal weight loss curve of the composite film and the pure Kevlar film can be seen that the thermal decomposition temperature of the pure Kevlar film reaches nearly 450 ℃, and the film is formed after CdTe nanocrystals and PA molecules are introduced (Kevlar-CdTe-PA)4The thermal stability of the composite film is reduced, the quality of the composite film is reduced by 5% at 180 ℃, mainly caused by the evaporation of water molecules in the composite film, and finally at the temperature of nearly 200 ℃, caused by the decomposition of phosphoric acid (Kevlar-CdTe-PA)4The quality of the composite film is rapidly reduced.
As shown in FIG. 3, prepared from example 6 (Kevlar-CdTe-PA)4The composite film can be seen by a scanning electron microscope picture, (Kevlar-CdTe-PA)4The surface of the composite membrane has a fiber structure which is uniform, the cross section of the composite membrane has an obvious layer-by-layer structure which is ordered, and the thickness of the composite membrane is about 22-25 μm.
Example 7
(1) 500ml of dimethyl sulfoxide, 5g of Kevlar nano fiber and 3g of potassium hydroxide are added into a 1000ml reagent bottle with a plug, and stirred for 5-7 days to form a Kevlar nano fiber homogeneous solution with the concentration of 10 g/L.
(2) At the temperature of 20-35 ℃, 5ml of Kevlar nanofiber homogeneous phase solution is dripped on a glass sheet treated by a piranha solution (concentrated sulfuric acid with the concentration of 98wt% and hydrogen peroxide with the concentration of 30wt% are mixed according to the volume ratio of 7: 3), spin-coated on a spin-coating machine at the speed of 1000 revolutions per minute for 20 seconds, and then the glass sheet is soaked in deionized water for 5-10 seconds.
(3) Dropping 2ml of cadmium telluride aqueous solution on the glass sheet at 20-35 ℃, drying in an oven at 80 ℃ for 2 hours, dropping 2ml of cadmium telluride aqueous solution again, and continuously drying in the oven at 80 ℃ for 2 hours.
(4) 3ml of a 85% strength phosphoric acid solution are added dropwise to the glass plate at 20-35 ℃ and the plate is spun on a spin coater at 500 rpm for 20 seconds.
(5) Repeating the step (3) to finish a layer of self-assembly, which is marked as (Kevlar-CdTe-PA)1Self-assembled film, PA is Phosphoric acid (Phosphoric acid).
(6) Repeating the steps (2) - (5) 4 times to obtain (Kevlar-CdTe-PA) with 4 layers of self-assembled structure4A composite membrane.
(7) Will (Kevlar-CdTe-PA)4The composite film was peeled from the glass sheet and dried in an oven at 80 ℃ for 2 hours, and the mark was (Kevlar-CdTe-PA)4A composite membrane.
(8) At 25 deg.C, the composite film (Kevlar-CdTe-PA)4Soaking in 40% phosphoric acid water solution with plug for 1-4 days to obtain (Kevlar-CdTe-PA)4The thickness of the/40% PA composite membrane is about 60-80 μm, the thickness of each self-assembled membrane is about 15-20 μm, and the mass ratio of the phosphoric acid PA to other substances in the composite membrane is about 50-70%.
Example 8
(1) 500ml of dimethyl sulfoxide, 5g of Kevlar nano fiber and 3g of potassium hydroxide are added into a 1000ml reagent bottle with a plug, and stirred for 5-7 days to form a Kevlar nano fiber homogeneous solution with the concentration of 10 g/L.
(2) At the temperature of 20-35 ℃, 5ml of Kevlar nanofiber homogeneous phase solution is dripped on a glass sheet treated by a piranha solution (concentrated sulfuric acid with the concentration of 98wt% and hydrogen peroxide with the concentration of 30wt% are mixed according to the volume ratio of 7: 3), spin-coated on a spin-coating machine at the speed of 1000 revolutions per minute for 20 seconds, and then the glass sheet is soaked in deionized water for 5-10 seconds.
(3) Dropping 1-3ml of cadmium telluride aqueous solution on the glass sheet at 20-35 ℃, drying in an oven at 80 ℃ for 2 hours, dropping 2ml of cadmium telluride aqueous solution again, and continuously drying in the oven at 80 ℃ for 2 hours.
(4) 3ml of a 85% strength phosphoric acid solution are added dropwise to the glass plate at 20-35 ℃ and the plate is spun on a spin coater at 500 rpm for 20 seconds.
(5) Repeating the step (3) to finish a layer of self-assembly, which is marked as (Kevlar-CdTe-PA)1Self-assembled film, PA is Phosphoric acid (Phosphoric acid).
(6) Repeating the steps (2) - (5)4 times, obtaining (Kevlar-CdTe-PA) with 4 layers of self-assembled structure4A composite membrane.
(7) Will (Kevlar-CdTe-PA)4The composite film was peeled from the glass sheet and dried in an oven at 80 ℃ for 2 hours, and the mark was (Kevlar-CdTe-PA)4A composite membrane.
(8) At 25 deg.C, the composite film (Kevlar-CdTe-PA)4Soaking in 60% phosphoric acid water solution with plug for 1-4 days to obtain (Kevlar-CdTe-PA)4The thickness of the/60% PA composite membrane is about 60-80 μm, the thickness of each self-assembled membrane is about 15-20 μm, and the mass ratio of the phosphoric acid PA to other substances in the composite membrane is about 60-80%.
Example 9
(1) 500ml of dimethyl sulfoxide, 5g of Kevlar nano fiber and 3g of potassium hydroxide are added into a 1000ml reagent bottle with a plug, and stirred for 5-7 days to form a Kevlar nano fiber homogeneous solution with the concentration of 10 g/L.
(2) At the temperature of 20-35 ℃, 5ml of Kevlar nanofiber homogeneous phase solution is dripped on a glass sheet treated by a piranha solution (concentrated sulfuric acid with the concentration of 98wt% and hydrogen peroxide with the concentration of 30wt% are mixed according to the volume ratio of 7: 3), spin-coated on a spin-coating machine at the speed of 1000 revolutions per minute for 20 seconds, and then the glass sheet is soaked in deionized water for 5-10 seconds.
(3) Dropping 2ml of cadmium telluride aqueous solution on the glass sheet at 20-35 ℃, drying in an oven at 80 ℃ for 2 hours, dropping 2ml of cadmium telluride aqueous solution again, and continuously drying in the oven at 80 ℃ for 2 hours.
(4) 3ml of a 85% strength phosphoric acid solution are added dropwise to the glass plate at 20-35 ℃ and the plate is spun on a spin coater at 500 rpm for 20 seconds.
(5) Repeating the step (3) to finish a layer of self-assembly, which is marked as (Kevlar-CdTe-PA)1Self-assembled film, PA is Phosphoric acid (Phosphoric acid).
(6) Repeating the steps (2) - (5) 4 times to obtain (Kevlar-CdTe-PA) with 4 layers of self-assembled structure4A composite membrane.
(7) Will (Kevlar-CdTe-PA)4The composite film was peeled from the glass sheet and dried in an oven at 80 ℃ for 2 hours and was designated (Kevlar-CdT)e-PA)4A composite membrane.
(8) At 25 deg.C, the composite film (Kevlar-CdTe-PA)4Soaking in 85% phosphoric acid water solution with plug for 1-4 days to obtain (Kevlar-CdTe-PA)4The thickness of the/85% PA composite membrane is about 60-80 μm, the thickness of each self-assembled membrane is about 15-20 μm, and the mass ratio of the phosphoric acid PA to other substances in the composite membrane is about 70-90%.
As shown in FIG. 4, examples 7 to 9 (Kevlar-CdTe-PA)4The composite membrane is prepared by soaking in 40-85 wt% phosphoric acid solution (Kevlar-CdTe-PA)4The electrical conductivity of the/PA composite membrane and the non-soaked phosphoric acid membrane can be seen, under the condition of no humidification at 80-160 ℃, the electrical conductivity of the prepared composite membrane is increased along with the temperature rise, and the composite membrane is formed by soaking in a phosphoric acid solution (Kevlar-CdTe-PA)4The electrical conductivity of the/PA composite film is obviously higher than that of (Kevlar-CdTe-PA)4Composite membrane conductivity and higher concentration of the soaking phosphoric acid solution (Kevlar-CdTe-PA)4The larger the electrical conductivity of the/PA composite membrane. Wherein, (Kevlar-CdTe-PA)4The composite film is formed by soaking in 85% phosphoric acid solution (Kevlar-CdTe-PA)4The conductivity of the PA composite membrane of 85 percent reaches 2.3 multiplied by 10 at 160 DEG C-1S/cm。
Example 10
(1) 500ml of dimethyl sulfoxide, 5g of Kevlar nano fiber and 3g of potassium hydroxide are added into a 1000ml reagent bottle with a plug, and stirred for 5-7 days to form a Kevlar nano fiber homogeneous solution with the concentration of 10 g/L.
(2) At the temperature of 20-35 ℃, 5ml of Kevlar nanofiber homogeneous phase solution is dripped on a glass sheet treated by a piranha solution (concentrated sulfuric acid with the concentration of 98wt% and hydrogen peroxide with the concentration of 30wt% are mixed according to the volume ratio of 7: 3), spin-coated on a spin-coating machine at the speed of 1000 revolutions per minute for 20 seconds, and then the glass sheet is soaked in deionized water for 5-10 seconds.
(3) Dropping 2ml of cadmium telluride aqueous solution on the glass sheet at 20-35 ℃, drying in an oven at 80 ℃ for 2 hours, dropping 2ml of cadmium telluride aqueous solution again, and continuously drying in the oven at 80 ℃ for 2 hours.
(4) 3ml of a 85% strength phosphoric acid solution are added dropwise to the glass plate at 20-35 ℃ and the plate is spun on a spin coater at 500 rpm for 20 seconds.
(5) Repeating the step (3) to finish a layer of self-assembly, which is marked as (Kevlar-CdTe-PA)1Self-assembled film, PA is Phosphoric acid (Phosphoric acid).
(6) Repeating the steps (2) - (5) 5 times to obtain (Kevlar-CdTe-PA) with 5 layers of self-assembled structure5A composite membrane.
(7) Will (Kevlar-CdTe-PA)5The composite film was peeled from the glass sheet and dried in an oven at 80 ℃ for 2 hours, and the mark was (Kevlar-CdTe-PA)5A composite membrane.
(8) At 25 deg.C, the composite film (Kevlar-CdTe-PA)5Soaking in 85% phosphoric acid water solution with plug for 1-4 days to obtain (Kevlar-CdTe-PA)5The thickness of the/85% PA composite membrane is about 80-100 μm, the thickness of each self-assembled membrane is about 15-20 μm, and the mass ratio of the phosphoric acid PA to other substances in the composite membrane is about 60-80%.
Example 11
(1) 500ml of dimethyl sulfoxide, 5g of Kevlar nano fiber and 3g of potassium hydroxide are added into a 1000ml reagent bottle with a plug, and stirred for 5-7 days to form a Kevlar nano fiber homogeneous solution with the concentration of 10 g/L.
(2) At the temperature of 20-35 ℃, 5ml of Kevlar nanofiber homogeneous phase solution is dripped on a glass sheet treated by a piranha solution (concentrated sulfuric acid with the concentration of 98wt% and hydrogen peroxide with the concentration of 30wt% are mixed according to the volume ratio of 7: 3), spin-coated on a spin-coating machine at the speed of 1000 revolutions per minute for 20 seconds, and then the glass sheet is soaked in deionized water for 5-10 seconds.
(3) At the temperature of 20-35 ℃, 3ml of cadmium telluride aqueous solution is dripped on the glass sheet, and after the glass sheet is dried in an oven at the temperature of 80 ℃ for 2 hours, 2ml of cadmium telluride aqueous solution is dripped again, and the glass sheet is continuously dried in the oven at the temperature of 80 ℃ for 2 hours.
(4) 3ml of a 85% strength phosphoric acid solution are added dropwise to the glass plate at 20-35 ℃ and the plate is spun on a spin coater at 500 rpm for 20 seconds.
(5) Repeating the step (3) to finish a layer of self-assembly, which is marked as (Kevlar-CdTe-PA)1Self-organizingAnd (4) loading the membrane, wherein PA is Phosphoric acid (Phosphoric acid).
(6) Repeating the steps (2) - (5) for 2 times to obtain (Kevlar-CdTe-PA) with 2 layers of self-assembled structure2A composite membrane.
(7) Will (Kevlar-CdTe-PA)2The composite film was peeled from the glass sheet and dried in an oven at 80 ℃ for 2 hours, and the mark was (Kevlar-CdTe-PA)2A composite membrane.
(8) At 25 deg.C, the composite film (Kevlar-CdTe-PA)2Soaking in 85% phosphoric acid water solution with plug for 1-4 days to obtain (Kevlar-CdTe-PA)2The thickness of the/85% PA composite membrane is about 30-40 μm, the thickness of each self-assembled membrane is about 15-20 μm, and the mass ratio of the phosphoric acid PA to other substances in the composite membrane is about 70% -90%.
Example 12
(1) 500ml of dimethyl sulfoxide, 5g of Kevlar nano fiber and 3g of potassium hydroxide are added into a 1000ml reagent bottle with a plug, and stirred for 5-7 days to form a Kevlar nano fiber homogeneous solution with the concentration of 10 g/L.
(2) At the temperature of 20-35 ℃, 5ml of Kevlar nanofiber homogeneous phase solution is dripped on a glass sheet treated by a piranha solution (concentrated sulfuric acid with the concentration of 98wt% and hydrogen peroxide with the concentration of 30wt% are mixed according to the volume ratio of 7: 3), spin-coated on a spin-coating machine at the speed of 1000 revolutions per minute for 20 seconds, and then the glass sheet is soaked in deionized water for 5-10 seconds.
(3) Dropping 2ml of cadmium telluride aqueous solution on the glass sheet at 20-35 ℃, drying in an oven at 80 ℃ for 2 hours, dropping 2ml of cadmium telluride aqueous solution again, and continuously drying in the oven at 80 ℃ for 2 hours.
(4) 3ml of a 85% strength phosphoric acid solution are added dropwise to the glass plate at 20-35 ℃ and the plate is spun on a spin coater at 500 rpm for 20 seconds.
(5) Repeating the step (3) to finish a layer of self-assembly, which is marked as (Kevlar-CdTe-PA)1Self-assembled film, PA is Phosphoric acid (Phosphoric acid).
(6) Repeating the steps (2) - (5) for 3 times to obtain (Kevlar-CdTe-PA) with 3 layers of self-assembled structure3A composite membrane.
(7) Will (Kevla)r-CdTe-PA)3The composite film was peeled from the glass sheet and dried in an oven at 80 ℃ for 2 hours, and the mark was (Kevlar-CdTe-PA)3A composite membrane.
(8) At 25 deg.C, the composite film (Kevlar-CdTe-PA)3Soaking in 85% phosphoric acid water solution with plug for 1-4 days to obtain (Kevlar-CdTe-PA)3The thickness of the/85% PA composite membrane is about 45-60 μm, the thickness of each self-assembled membrane is about 15-20 μm, and the mass ratio of the phosphoric acid PA to other substances in the composite membrane is about 80-100%.
The embodiment result shows that the invention realizes the assembly of the Kevlar nano-fiber and the cadmium telluride nanocrystal to prepare the high-temperature proton exchange membrane with an ordered structure and good proton conductivity, and has potential application value in the field of fuel cells. In addition, the invention provides a new research method and thought for preparing a novel composite membrane based on the nano material and the Kevlar nano fiber.
Claims (7)
1. A method for preparing a high-temperature proton exchange membrane with a layer-by-layer assembly structure based on a spin coating technology by doping phosphoric acid is characterized by comprising the following steps:
(1) adding 400-600ml of dimethyl sulfoxide, 4-6g of Kevlar nano fiber and 2-4g of potassium hydroxide into a 1000ml reagent bottle with a plug, and stirring for 5-7 days to form a Kevlar nano fiber homogeneous solution with the concentration of 9-11 g/L;
(2) dripping 4-6ml Kevlar nanofiber homogeneous phase solution on a glass sheet treated by the piranha solution at the temperature of 20-35 ℃, spin-coating for 15-25 seconds on a spin-coating machine at the speed of 500-1500 revolutions per minute, and then soaking the glass sheet in deionized water for 5-10 seconds; wherein, the piranha solution: concentrated sulfuric acid with the concentration of 98wt% and hydrogen peroxide with the concentration of 30wt% are mixed according to the volume ratio of 7: 3, mixing;
(3) dripping 1-3ml of cadmium telluride aqueous solution on the glass sheet at 20-35 ℃, drying in a drying oven at 75-85 ℃ for 2-4 hours, dripping 2-4ml of cadmium telluride aqueous solution again, and continuously drying in the drying oven at 75-85 ℃ for 2-4 hours;
(4) dripping 2-5ml of phosphoric acid solution with the concentration of 85wt% on a glass sheet at the temperature of 20-35 ℃, and spin-coating for 30-10 seconds on a spin-coating machine at the speed of 300-1000 revolutions per minute;
(5) repeating the step (3) to finish a layer of self-assembly, which is marked as (Kevlar-CdTe-PA)1A self-assembled film;
(6) repeating the steps (2) - (5) for 2-5 times to obtain (Kevlar-CdTe-PA) with 3-6 layers of self-assembled structure3-6Compounding film;
(7) will (Kevlar-CdTe-PA)3-6The composite film is stripped from the glass sheet and dried in an oven at 75-85 ℃ for 1-3 hours, and is marked as (Kevlar-CdTe-PA)3-6Compounding film;
(8) at 20-30 deg.C, the composite film (Kevlar-CdTe-PA)3-6Soaking in 40-85 wt% phosphoric acid water solution in a container with plug for 1-4 days to obtain (Kevlar-CdTe-PA)3-6/(40% -85%) PA composite membrane.
2. The method for preparing the high-temperature proton exchange membrane with the layer-by-layer assembly structure based on the spin coating technology doped with phosphoric acid according to claim 1, wherein in the step (1), 500ml of dimethyl sulfoxide, 5g of Kevlar fiber and 3g of potassium hydroxide are added into a 1000ml reagent bottle with a plug, and the mixture is stirred for 5 to 7 days to form a Kevlar fiber homogeneous solution with the concentration of 10 g/L.
3. The method for preparing the high-temperature proton exchange membrane with the layer-by-layer assembly structure based on the spin coating technology doped with phosphoric acid as claimed in claim 1, wherein in the step (2), 5ml of the homogeneous phase solution of Kevlar nanofibers is dripped on the glass sheet treated by the piranha solution at 20-35 ℃, and after the glass sheet is spin coated for 20 seconds at a speed of 500-1500 rpm on a spin coating machine, the glass sheet is soaked in deionized water for 5-10 seconds.
4. The phosphoric acid-doped spin-coating-based method for preparing a high-temperature proton exchange membrane with a layer-by-layer assembly structure according to claim 1, wherein in the step (3), 1-3ml of cadmium telluride aqueous solution is dripped on the glass sheet at 20-35 ℃, and after the glass sheet is baked in an oven at 80 ℃ for 2-4 hours, 2-4ml of cadmium telluride aqueous solution is dripped again, and the baking is continued in the oven at 80 ℃ for 2-4 hours.
5. The phosphoric acid-doped spin-coating-based method for preparing a high-temperature proton exchange membrane with a layer-by-layer assembly structure as claimed in claim 1, wherein in the step (7), (Kevlar-CdTe-PA)3-6The composite film was peeled from the glass sheet and dried in an oven at 80 ℃ for 2 hours and recorded as (Kevlar-CdTe-PA)3-6A composite membrane.
6. The phosphoric acid-doped spin-coating-based method for preparing a high-temperature proton exchange membrane with a layer-by-layer assembly structure as claimed in claim 1, wherein the prepared (Kevlar-CdTe-PA)3-6In the/PA composite membrane, the mass ratio of phosphoric acid PA to other substances is 50-130%.
7. The phosphoric acid-doped spin-coating-based method for preparing a high-temperature proton exchange membrane with a layer-by-layer assembly structure as claimed in claim 1, wherein the prepared (Kevlar-CdTe-PA)3-6/(40-85%) the PA composite film has a thickness of 30-100 μm and each self-assembled film has a thickness of 15-20 μm.
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