CN111653810A - PVA-based molecular sieve composite proton exchange membrane and preparation method thereof - Google Patents
PVA-based molecular sieve composite proton exchange membrane and preparation method thereof Download PDFInfo
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- CN111653810A CN111653810A CN202010476126.1A CN202010476126A CN111653810A CN 111653810 A CN111653810 A CN 111653810A CN 202010476126 A CN202010476126 A CN 202010476126A CN 111653810 A CN111653810 A CN 111653810A
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 170
- 239000012528 membrane Substances 0.000 title claims abstract description 163
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 129
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 129
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 238000010345 tape casting Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005416 organic matter Substances 0.000 claims abstract description 15
- 238000007605 air drying Methods 0.000 claims description 31
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 30
- 238000003760 magnetic stirring Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 15
- 239000001530 fumaric acid Substances 0.000 claims description 15
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical group O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 15
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 238000000265 homogenisation Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000002522 swelling effect Effects 0.000 abstract description 9
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 230000000813 microbial effect Effects 0.000 description 10
- 239000000446 fuel Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000013385 inorganic framework Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 206010016807 Fluid retention Diseases 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
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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
- H01M8/1065—Polymeric electrolyte materials characterised by the form, e.g. perforated or wave-shaped
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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
- H01M8/1086—After-treatment of the membrane other than by polymerisation
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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
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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Abstract
The invention discloses a PVA-based molecular sieve composite proton exchange membrane, which comprises two conducting layers and a multi-stage molecular sieve middle layer, wherein the multi-stage molecular sieve middle layer is positioned between the two conducting layers. The invention also discloses a preparation method thereof, which comprises the following steps: firstly, preparing PVA base membrane liquid by using PVA and organic matters, and forming a conductive membrane by adopting a tape casting method; preparing PVA-based molecular sieve membrane liquid by utilizing a hierarchical pore molecular sieve, polyvinyl alcohol and an organic matter, and forming a conducting layer-hierarchical pore molecular sieve intermediate layer composite membrane by utilizing a tape casting method; finally, the PVA-based membrane liquid is subjected to tape casting to form the PVA-based molecular sieve composite proton exchange membrane. The PVA-based molecular sieve composite proton exchange membrane has good proton conductivity, swelling property and thermal stability, and improves the proton conductivity while inhibiting the swelling property under the condition of ensuring a certain water content.
Description
Technical Field
The invention belongs to the technical field of proton exchange membrane preparation, and particularly relates to a PVA-based molecular sieve composite proton exchange membrane and a preparation method thereof.
Background
Microbial Fuel Cells (MFCs) generate biological electric energy by using bacteria through biomass, have an electricity generating function while treating wastewater, and have important significance in water treatment and new energy development. The membrane material in microbial fuel cells is mainly used in dual chamber MFCs to separate the liquids in the cathode and anode. The primary function of the membrane is to be proton permeable, allowing protons produced at the anode to diffuse to the cathode; and secondly, the transfer of other substances, such as dissolved oxygen and the like, between the two chambers is prevented, so that the coulombic efficiency is improved. At the same time, the membrane will increase the internal resistance of the cell, reducing the electricity production efficiency.
Currently, the commonly used MFC research is a Nafion proton exchange membrane, which has high ion conductivity (10)-2S/cm) of the MFC, which plays an important role in maintaining the pH balance between both ends of the MFC electrode and in normally conducting the electrode reaction. However, in the process of microbial degradation, cations on two sides of the membrane are unbalanced due to limited proton transmission, so that the growth of microorganisms is seriously inhibited, the electrocatalytic activity of the microorganisms is reduced, and the cost is too high and the oxygen diffusion is limited, thereby being not beneficial to industrialization. For the Ultrex CMI 7000 film produced by the American MI company, the price is relatively cheap, the anti-pollution capability is stronger, the mechanical strength is higher, and the defects are that the internal resistance is higher and the coulombic efficiency is lower. Therefore, the development of the proton exchange membrane with low price and excellent performance is the guarantee of the smooth research of the MFC.
Disclosure of Invention
The invention aims to provide a PVA-based molecular sieve composite proton exchange membrane, which solves the problems of poor electricity generation performance and high production cost of the existing proton exchange membrane in the application process of a microbial fuel cell.
The invention also aims to provide a preparation method of the PVA-based molecular sieve composite proton exchange membrane.
The technical scheme adopted by the invention is that the PVA-based molecular sieve composite proton exchange membrane comprises two conducting layers and a multi-stage molecular sieve intermediate layer, wherein the multi-stage molecular sieve intermediate layer is positioned between the two conducting layers; the conducting layer is formed by casting organic matters and polyvinyl alcohol; the intermediate layer of the hierarchical pore molecular sieve is formed by casting the hierarchical pore molecular sieve and polyvinyl alcohol.
The present invention is also characterized in that,
the organic matter is phosphotungstic acid, fumaric acid or glutaraldehyde.
The hierarchical pore molecular sieve is any one or more of ZSM-5 molecular sieve, H-ZSM-11 molecular sieve, X-type molecular sieve and 4A molecular sieve.
The thickness of the PVA-based molecular sieve composite proton exchange membrane is 30-110 mu m.
The invention adopts another technical scheme that a preparation method of the PVA-based molecular sieve composite proton exchange membrane is implemented according to the following steps:
step 1, preparing PVA base membrane liquid; the method specifically comprises the following steps:
dissolving crystalline polyvinyl alcohol in deionized water, magnetically stirring for a certain time, adding organic substances, uniformly mixing, standing and defoaming;
step 2, preparing PVA-based molecular sieve membrane liquid; the method specifically comprises the following steps:
dissolving a hierarchical pore molecular sieve in deionized water, performing first magnetic stirring, adding polyvinyl alcohol and an organic matter, performing second magnetic stirring until the hierarchical pore molecular sieve is completely dissolved, standing for defoaming, and placing the hierarchical pore molecular sieve in an ultrasonic reactor for ultrasonic homogenization to prepare a PVA-based molecular sieve membrane solution;
step 3, preparing a conductive layer;
the method specifically comprises the following steps: pouring the PVA base membrane liquid obtained in the step 1 onto a dry and smooth glass plate, forming a membrane layer by using a tape casting method, and air-drying for a period of time under the conditions of certain temperature and humidity to obtain a conducting layer;
step 4, preparing a conducting layer-hierarchical pore molecular sieve intermediate layer two-layer composite membrane; the method specifically comprises the following steps:
pouring the PVA-based molecular sieve membrane liquid obtained in the step 2 onto a conducting layer by using a tape casting method, and air-drying the membrane liquid for a period of time under the conditions of certain temperature and humidity to prepare a conducting layer-hierarchical pore molecular sieve intermediate layer two-layer composite membrane;
step 5, preparing a PVA-based molecular sieve composite proton exchange membrane; the method specifically comprises the following steps:
pouring the PVA base membrane liquid obtained in the step 1 onto a two-layer composite membrane of a conducting layer-hierarchical pore molecular sieve intermediate layer by using a tape casting method, standing and defoaming for a period of time under the conditions of certain temperature and humidity, and preparing the PVA base molecular sieve composite proton exchange membrane.
The present invention is also characterized in that,
in the step 1, the mass ratio of polyvinyl alcohol to deionized water to organic matters is 6-15: 100: 0.1 to 1.0; the organic matter is phosphotungstic acid, fumaric acid or glutaraldehyde; the rotating speed of the magnetic stirrer is 100-150 rad/min, and the magnetic stirring time is 8-12 h; the standing time is 10-30 h, and the temperature is 10-30 ℃.
In the step 2, the mass ratio of the hierarchical pore molecular sieve, the deionized water, the polyvinyl alcohol and the organic matters is 0.1-2.5: 100: 8-15: 0.1 to 2.0; the organic matter is phosphotungstic acid, fumaric acid or glutaraldehyde; the hierarchical pore molecular sieve is any one or more of a ZSM-5 molecular sieve, an H-ZSM-11 molecular sieve, an X-type molecular sieve and a 4A molecular sieve; the rotating speed of the first magnetic stirring is 100-150 rad/min, and the magnetic stirring time is 1-3 h; the second magnetic stirring speed is 80-120 rad/min, and the magnetic stirring time is 10-12 h; standing for 12-30 h at 10-30 ℃; the ultrasonic reaction time is 2-4 h.
In the step 3, the air drying time is 12-24 hours, the air drying temperature is 20-35 ℃, and the air drying humidity is 40-50% RH.
In the step 4, the air drying time is 24-36 h, the air drying temperature is 25-35 ℃, and the air drying humidity is 45-50% RH.
In the step 5, standing is carried out for 24-48 h at 25-35 ℃ and at 40-50% RH; the thickness of the PVA-based molecular sieve composite proton exchange membrane is 30-110 mu m.
The beneficial effect of the invention is that,
the PVA-based molecular sieve composite proton exchange membrane has good proton conductivity, swelling property and thermal stability, inhibits the swelling property and simultaneously improves the proton conductivity under the condition of ensuring a certain water content, is applied to a diaphragm of a microbial fuel cell, and has beneficial effects in the aspect of water treatment application.
The preparation method of the PVA-based molecular sieve composite proton exchange membrane uses polyvinyl alcohol as a base membrane liquid and a hierarchical molecular sieve as an inorganic framework, and transfers protons with phosphotungstic acid, fumaric acid or glutaraldehyde simultaneously, thereby improving the proton conductivity, thermal stability and mechanical strength of the composite membrane and inhibiting the swelling of the composite membrane. The PVA-based molecular sieve composite proton exchange membrane is prepared by adopting a tape casting step-by-step membrane forming method, and the result shows that the proton conductivity is strong, the mechanical property is good, and the swelling property is low. The preparation method of the PVA-based molecular sieve composite proton exchange membrane has the advantages of simple and convenient actual operation, cheap and easily-obtained raw materials, low economic cost, no toxicity, environmental protection, mild conditions and high synthesis efficiency, provides a new idea for the proton exchange membrane with PVA as the raw material, and simultaneously produces a product with wide application value.
Drawings
FIG. 1 is an SEM spectrogram of a PVA-based molecular sieve composite proton exchange membrane prepared by the invention;
FIG. 2 is a photograph of a PVA-based molecular sieve composite proton exchange membrane prepared by the present invention;
FIG. 3 is a mechanical property diagram of the PVA-based molecular sieve composite proton exchange membrane prepared by the present invention;
FIG. 4 is a power density diagram of a microbial fuel cell in which the PVA-based molecular sieve composite proton exchange membrane prepared by the present invention is located.
Detailed Description
The present invention will be described in detail with reference to the following detailed description and accompanying drawings.
The invention relates to a PVA-based molecular sieve composite proton exchange membrane, which comprises two conducting layers and a multi-stage molecular sieve middle layer, wherein the multi-stage molecular sieve middle layer is positioned between the two conducting layers;
the conducting layer is formed by casting organic matters and polyvinyl alcohol;
the organic matter is phosphotungstic acid, fumaric acid or glutaraldehyde;
the intermediate layer of the hierarchical pore molecular sieve is formed by casting the hierarchical pore molecular sieve and polyvinyl alcohol;
the mass ratio of the hierarchical pore molecular sieve to the polyvinyl alcohol is 0.1-2.5: 8-15;
the hierarchical pore molecular sieve is any one or more of a ZSM-5 molecular sieve, an H-ZSM-11 molecular sieve, an X-type molecular sieve and a 4A molecular sieve;
the thickness of the conducting layer is 10-30 μm; the thickness of the intermediate layer of the hierarchical pore molecular sieve is 20-80 μm; the thickness of the PVA-based molecular sieve composite proton exchange membrane is 30-110 mu m;
the composite proton exchange membrane of the PVA-based molecular sieve is prepared by taking polyvinyl alcohol as a base membrane liquid, phosphotungstic acid, fumaric acid or glutaraldehyde as transfer protons and a hierarchical pore molecular sieve as an inorganic framework, and by adopting a step-by-step tape casting membrane forming method, the water retention of the membrane is improved and ion transmission is promoted while a heteropoly acid carrier is established.
The invention relates to a preparation method of a PVA-based molecular sieve composite proton exchange membrane, which is implemented according to the following steps:
step 1, preparing PVA base membrane liquid;
the method specifically comprises the following steps: dissolving granular PVA in deionized water, magnetically stirring for certain time, adding a certain amount of organic matter, mixing uniformly, taking out after all solids are dissolved, standing and defoaming;
the mass ratio of the polyvinyl alcohol to the deionized water to the organic matters is 6-15: 100: 0.1 to 1.0;
the organic matter is phosphotungstic acid, fumaric acid or glutaraldehyde;
the rotating speed of the magnetic stirrer is 100-150 rad/min, and the magnetic stirring time is 8-12 h;
standing for 10-30 h at 10-30 ℃;
step 2, preparing PVA-based molecular sieve membrane liquid;
the method specifically comprises the following steps: dissolving a hierarchical pore molecular sieve in deionized water, performing first magnetic stirring, adding a certain amount of polyvinyl alcohol and a certain amount of organic matters, performing second magnetic stirring until the polyvinyl alcohol and the organic matters are completely dissolved, standing and defoaming, and placing the mixture into an ultrasonic reactor for ultrasonic homogenization to prepare a PVA-based molecular sieve membrane solution;
the mass ratio of the hierarchical pore molecular sieve to the deionized water to the polyvinyl alcohol to the organic matter is 0.1-2.5: 100: 8-15: 0.1 to 2.0;
the organic matter is phosphotungstic acid, fumaric acid or glutaraldehyde;
the hierarchical pore molecular sieve is any one or more of a ZSM-5 molecular sieve, an H-ZSM-11 molecular sieve, an X-type molecular sieve and a 4A molecular sieve;
the type and the pore structure of the hierarchical pore molecular sieve have certain influence on the proton conduction capability, ammonium ion retention rate, swelling property and mechanical property of the membrane, the pore structure consists of micropores and mesopores, the proportion of the mesopores is 10-30%, the size of the molecular sieve crystal grains is 0.1-1 mu m, and the solid content ratio is 0.1-3.0%.
The rotating speed of the first magnetic stirring is 100-150 rad/min, and the magnetic stirring time is 1-3 h;
the second magnetic stirring speed is 80-120 rad/min, and the magnetic stirring time is 10-12 h;
standing for 12-30 h at 10-30 ℃; the ultrasonic reaction time is 2-4 h.
Step 3, preparing a conductive layer;
the method specifically comprises the following steps: pouring the PVA base membrane liquid obtained in the step 1 onto a dry and smooth glass plate, forming a membrane layer with a certain thickness by using a tape casting method, and air-drying for a period of time under the conditions of a certain temperature and humidity to obtain a conducting layer;
the air drying time is 12-24 h, the air drying temperature is 20-35 ℃, and the air drying humidity is 40-50% RH;
the thickness of the conducting layer is 10-30 μm;
step 4, preparing a conducting layer-hierarchical pore molecular sieve intermediate layer two-layer composite membrane;
the method specifically comprises the following steps: pouring the PVA-based molecular sieve membrane liquid obtained in the step 2 onto a conducting layer by using a tape casting method, and air-drying the membrane liquid for a period of time under the conditions of certain temperature and humidity to prepare a conducting layer-hierarchical pore molecular sieve intermediate layer two-layer composite membrane;
the thickness of the prepared conducting layer-hierarchical pore molecular sieve intermediate layer two-layer composite membrane is 20-80 mu m;
the air drying time is 24-36 h, the air drying temperature is 25-35 ℃, and the air drying humidity is 45-50% RH.
Step 5, preparing a PVA-based molecular sieve composite proton exchange membrane;
when preparing the conducting layer-hierarchical pore molecular sieve intermediate layer-conducting layer three-layer composite membrane, pouring the PVA base membrane solution obtained in the step 1 onto the conducting layer-hierarchical pore molecular sieve intermediate layer two-layer composite membrane by using a tape casting method, standing and defoaming for a period of time under the conditions of certain temperature and humidity, and preparing the three-layer PVA base molecular sieve composite proton exchange membrane;
the thickness of the PVA-based molecular sieve composite proton exchange membrane is 30-110 mu m;
the standing time is 24-48 h, the standing temperature is 25-35 ℃, and the standing humidity is 40-50% RH.
The PVA-based molecular sieve composite proton exchange membrane has good proton conductivity, strong mechanical strength, pollution resistance and thermal stability, and can obviously inhibit the swelling of a polymer membrane.
The PVA-based molecular sieve composite proton exchange membrane comprises two conducting layers and a multi-stage molecular sieve intermediate layer, wherein the conducting layer is made of polyvinyl alcohol containing phosphotungstic acid, fumaric acid or glutaraldehyde, and the multi-stage molecular sieve intermediate layer is: polyvinyl alcohol porous membrane with hierarchical pore molecular sieve uniformly distributed on the surface;
too high polyvinyl alcohol content in the conducting layer can make the membrane liquid sticky and unable to form a membrane, and too low polyvinyl alcohol content can lack viscosity force, resulting in that the membrane can not be taken down. In addition, the thickness of the conductive layer can affect the proton conductivity and ammonium ion rejection rate of the membrane, the thickness range of the conductive layer is preferably 10-30 μm after the test, and the proton conductivity and the ammonium ion rejection rate are both good, so the thickness range of the conductive layer is preferably 10-30 μm;
tests prove that the mass ratio of the hierarchical pore molecular sieve to the polyvinyl alcohol in the middle layer of the hierarchical pore molecular sieve is preferably 0.1-2.5: 8-15, and if the mass ratio of the hierarchical pore molecular sieve to the polyvinyl alcohol is not in the range, the solution is very viscous, the dispersion degree of the molecular sieve in the mixed solution is poor, so that a film cannot be formed, or the mechanical strength of the film is too low, so that the mass ratio of the hierarchical pore molecular sieve to the polyvinyl alcohol is preferably 0.1-2.5: 8-15; the thickness range of the intermediate layer of the hierarchical pore molecular sieve is preferably 20-80 μm.
Example 1
Step 1, dissolving granular PVA in deionized water according to the mass ratio of 8%, adding 0.5% fumaric acid, uniformly mixing, magnetically stirring for 10 hours under the condition that the magnetic stirring rotating speed is 150rad/min, taking out after all solids are dissolved, standing for 12 hours at the temperature of 20 ℃, and defoaming;
step 2, dissolving the hierarchical pore ZSM-5 molecular sieve in deionized water according to the mass ratio of 1.0%, magnetically stirring at the rotating speed of 100rad/min for 1h, continuously adding polyvinyl alcohol with the mass ratio of 10% and fumaric acid with the mass ratio of 1.5%, magnetically stirring at the rotating speed of 100rad/min for 10h until the molecular sieve is completely dissolved, standing at the temperature of 25 ℃ for 12h for defoaming, and putting the molecular sieve into an ultrasonic reactor for ultrasonic treatment for 2h to prepare membrane liquid;
step 3, preparation of conductive layer
Pouring 100mL of the PVA base membrane liquid obtained in the step 1 onto a dry and smooth glass plate with the side length of 20cm square, forming a membrane layer with the thickness of 20 micrometers by using a tape casting method, and air-drying for 12 hours under the conditions that the temperature is kept at 20 ℃ and the humidity is 40-50% RH to prepare a first membrane;
step 4, preparing the intermediate layer of the hierarchical pore molecular sieve
Pouring the PVA-based molecular sieve membrane liquid obtained in the step 2 onto the first membrane by using a tape casting method, forming a membrane layer with the thickness of 50 microns by using the tape casting method, and air-drying for 24 hours under the conditions that the temperature is kept at 25 ℃ and the humidity is 45% RH to prepare a second membrane;
and 5, pouring the PVA base membrane liquid obtained in the step 1 onto the second membrane obtained in the step 4 by using a tape casting method, standing for 36 hours at the temperature of 25 ℃ and the humidity of 40% RH to prepare the three-layer PVA base molecular sieve composite proton exchange membrane.
Example 2
Step 1, dissolving granular PVA in deionized water according to the mass ratio of 10%, adding 1.5% phosphotungstic acid, uniformly mixing, magnetically stirring for 8 hours under the condition that the magnetic stirring rotating speed is 100rad/min, taking out after all solids are dissolved, standing for 10 hours at the temperature of 25 ℃, and defoaming;
step 2, dissolving the hierarchical pore ZSM-11 molecular sieve in deionized water according to the mass ratio of 0.5%, magnetically stirring at the rotating speed of 150rad/min for 2h, continuously adding polyvinyl alcohol with the mass ratio of 10% and phosphotungstic acid with the mass ratio of 2.0%, magnetically stirring at the rotating speed of 100rad/min for 12h until the molecular sieve is completely dissolved, standing at the temperature of 25 ℃ for 18h for defoaming, and then putting the molecular sieve into an ultrasonic reactor for ultrasonic treatment for 4h to prepare membrane liquid;
step 3, preparation of conductive layer
Pouring 150mL of the PVA base membrane liquid obtained in the step 1 onto a dry and smooth glass plate with the side length of 20cm square, forming a membrane layer with the thickness of 25 micrometers by using a tape casting method, and air-drying for 18 hours under the conditions that the temperature is kept at 25 ℃ and the humidity is 50% RH to prepare a first membrane;
step 4, preparing the intermediate layer of the hierarchical pore molecular sieve
Pouring the PVA-based molecular sieve membrane liquid obtained in the step 2 onto the first membrane by using a tape casting method, forming a membrane layer with the thickness of 60 micrometers by using the tape casting method, and air-drying for 24 hours under the conditions that the temperature is kept at 20 ℃ and the humidity is 45% RH to prepare a second membrane;
and 5, pouring the PVA base membrane liquid obtained in the step 1 onto the second membrane obtained in the step 4 by using a tape casting method, standing for 24 hours at the temperature of 20 ℃, and standing at the humidity of 40% RH to prepare the three-layer PVA base molecular sieve composite proton exchange membrane.
Example 3
Step 1, dissolving granular PVA in deionized water according to the mass ratio of 12%, adding 1.0% of glutaraldehyde, uniformly mixing, magnetically stirring for 10 hours under the condition that the magnetic stirring rotating speed is 120rad/min, taking out after all solids are dissolved, standing for 12 hours at the temperature of 25 ℃, and defoaming;
step 2, dissolving the hierarchical porous X-type molecular sieve in deionized water according to the mass ratio of 2.0%, magnetically stirring at the rotating speed of 150rad/min for 1h, continuously adding 12% by mass of polyvinyl alcohol and 1.5% by mass of glutaraldehyde, magnetically stirring at the rotating speed of 150rad/min for 8h until the molecular sieve is completely dissolved, standing at the temperature of 25 ℃ for 12h for defoaming, and then putting the molecular sieve into an ultrasonic reactor for ultrasonic treatment for 2h to prepare membrane liquid;
step 3, preparation of conductive layer
Pouring 200mL of the PVA base membrane liquid obtained in the step 1 onto a dry and smooth glass plate with the side length of 20cm square, forming a membrane layer with the thickness of 30 micrometers by using a tape casting method, and air-drying for 12 hours under the conditions that the temperature is kept at 20 ℃ and the humidity is 40% RH to prepare a first membrane;
step 4, preparing the intermediate layer of the hierarchical pore molecular sieve
Pouring the PVA-based molecular sieve membrane liquid obtained in the step 2 onto the first membrane by using a tape casting method, forming a membrane layer with the thickness of 70 mu m by using the tape casting method, and air-drying for 36h under the conditions that the temperature is kept at 25 ℃ and the humidity is 40% RH to prepare a second membrane;
and 5, pouring the PVA base membrane liquid obtained in the step 1 onto the second membrane obtained in the step 4 by using a tape casting method, standing for 36 hours at the temperature of 25 ℃ and the humidity of 40% RH to prepare the three-layer PVA base molecular sieve composite proton exchange membrane.
The preparation method of the composite proton exchange membrane of the PVA-based molecular sieve is adopted to synthesize the composite proton exchange membrane of the PVA-based molecular sieve, a flow casting method is utilized to firstly prepare a conducting layer, after standing and air drying, a multi-stage pore molecular sieve intermediate layer is continuously prepared, and finally, a conducting layer is prepared to form a multi-layer composite proton exchange membrane;
as shown in fig. 1, the SEM spectrogram of the PVA-based molecular sieve composite proton exchange membrane prepared by the present invention shows that: the synthesized sample hierarchical-pore molecular sieve is uniformly dispersed on the surface of the membrane, the particles are platy, and the size is related to the type of the added molecular sieve.
As shown in fig. 2, the photo of the PVA-based molecular sieve composite proton exchange membrane prepared by the present invention shows: the composite film has compact and smooth surface and better strength and toughness;
as shown in fig. 3, the mechanical strength of the PVA-based molecular sieve composite proton exchange membrane prepared by the present invention is shown in the following results: the strain value of the PVA-based molecular sieve composite proton exchange membrane can reach 28.717-29.192 MPa, the strength of the Nafion membrane can reach 27.263MPa, and the rupture strength of the composite membrane is higher than that of the Nafion membrane, so that the membrane can completely meet the requirement on the mechanical property and can meet the long-term application of the proton exchange membrane in a microbial fuel cell.
As shown in fig. 4, the power density diagram of the microbial fuel cell in which the PVA-based molecular sieve composite proton exchange membrane prepared by the invention is located shows that: power density of 76.88mW/m in microbial fuel cell in which PVA-based molecular sieve composite proton exchange membrane is arranged2The proton conduction effect is provided, and the electricity generation performance is good.
The PVA-based molecular sieve composite proton exchange membrane has good proton conductivity, swelling property and thermal stability, improves the proton conductivity while inhibiting the swelling property, is applied to a diaphragm of a microbial fuel cell, and has beneficial effects in the aspect of water treatment application.
The preparation method of the PVA-based molecular sieve composite proton exchange membrane uses polyvinyl alcohol as a base membrane liquid and a hierarchical molecular sieve as an inorganic framework, transfers protons with phosphotungstic acid, fumaric acid or glutaraldehyde simultaneously, improves thermal stability and inhibits the swelling of the composite membrane. The PVA-based molecular sieve composite proton exchange membrane is prepared by adopting a tape casting step-by-step membrane forming method, and the result shows that the proton conductivity is strong, the mechanical property is good, and the swelling property is low. The preparation method of the PVA-based molecular sieve composite proton exchange membrane has the advantages of simple and convenient actual operation, cheap and easily-obtained raw materials, low economic cost, no toxicity, environmental protection, mild conditions and high synthesis efficiency, provides a new idea for the proton exchange membrane with PVA as the raw material, and simultaneously produces a product with wide application value.
Claims (10)
1. A composite proton exchange membrane of a PVA-based molecular sieve is characterized by comprising two conducting layers and a multi-stage molecular sieve middle layer, wherein the multi-stage molecular sieve middle layer is positioned between the two conducting layers; the conducting layer is formed by casting organic matters and polyvinyl alcohol; the intermediate layer of the hierarchical pore molecular sieve is formed by casting the hierarchical pore molecular sieve and polyvinyl alcohol.
2. The composite PVA-based molecular sieve proton exchange membrane according to claim 1, wherein the organic substance is phosphotungstic acid, fumaric acid or glutaraldehyde.
3. The composite proton exchange membrane of PVA-based molecular sieve of claim 1, wherein the hierarchical pore molecular sieve is any one or more of ZSM-5 molecular sieve, H-ZSM-11 molecular sieve, X-type molecular sieve and 4A molecular sieve.
4. The composite proton exchange membrane of a PVA-based molecular sieve according to claim 1, wherein the thickness of the composite proton exchange membrane of a PVA-based molecular sieve is 30 to 110 μm.
5. A preparation method of a PVA-based molecular sieve composite proton exchange membrane is characterized by comprising the following steps:
step 1, preparing PVA base membrane liquid; the method specifically comprises the following steps:
dissolving crystalline polyvinyl alcohol in deionized water, magnetically stirring for a certain time, adding organic substances, uniformly mixing, standing and defoaming;
step 2, preparing PVA-based molecular sieve membrane liquid; the method specifically comprises the following steps:
dissolving a hierarchical pore molecular sieve in deionized water, performing first magnetic stirring, adding polyvinyl alcohol and an organic matter, performing second magnetic stirring until the hierarchical pore molecular sieve is completely dissolved, standing for defoaming, and placing the hierarchical pore molecular sieve in an ultrasonic reactor for ultrasonic homogenization to prepare a PVA-based molecular sieve membrane solution;
step 3, preparing a conductive layer;
the method specifically comprises the following steps: pouring the PVA base membrane liquid obtained in the step 1 onto a dry and smooth glass plate, forming a membrane layer by using a tape casting method, and air-drying for a period of time under the conditions of certain temperature and humidity to obtain a conducting layer;
step 4, preparing a conducting layer-hierarchical pore molecular sieve intermediate layer two-layer composite membrane; the method specifically comprises the following steps:
pouring the PVA-based molecular sieve membrane liquid obtained in the step 2 onto a conducting layer by using a tape casting method, and air-drying the membrane liquid for a period of time under the conditions of certain temperature and humidity to prepare a conducting layer-hierarchical pore molecular sieve intermediate layer two-layer composite membrane;
step 5, preparing a PVA-based molecular sieve composite proton exchange membrane; the method specifically comprises the following steps:
pouring the PVA base membrane liquid obtained in the step 1 onto a two-layer composite membrane of a conducting layer-hierarchical pore molecular sieve intermediate layer by using a tape casting method, standing and defoaming for a period of time under the conditions of certain temperature and humidity, and preparing the PVA base molecular sieve composite proton exchange membrane.
6. The preparation method of the PVA-based molecular sieve composite proton exchange membrane according to claim 5, wherein in the step 1, the mass ratio of the polyvinyl alcohol to the deionized water to the organic matter is 6-15: 100: 0.1 to 1.0; the organic matter is phosphotungstic acid, fumaric acid or glutaraldehyde; the rotating speed of the magnetic stirrer is 100-150 rad/min, and the magnetic stirring time is 8-12 h; the standing time is 10-30 h, and the temperature is 10-30 ℃.
7. The method for preparing the PVA-based molecular sieve composite proton exchange membrane according to claim 5, wherein in the step 2, the mass ratio of the hierarchical pore molecular sieve, the deionized water, the polyvinyl alcohol and the organic matter is 0.1-2.5: 100: 8-15: 0.1 to 2.0; the organic matter is phosphotungstic acid, fumaric acid or glutaraldehyde; the hierarchical pore molecular sieve is any one or more of a ZSM-5 molecular sieve, an H-ZSM-11 molecular sieve, an X-type molecular sieve and a 4A molecular sieve; the rotating speed of the first magnetic stirring is 100-150 rad/min, and the magnetic stirring time is 1-3 h; the second magnetic stirring speed is 80-120 rad/min, and the magnetic stirring time is 10-12 h; standing for 12-30 h at 10-30 ℃; the ultrasonic reaction time is 2-4 h.
8. The preparation method of the PVA-based molecular sieve composite proton exchange membrane according to claim 5, wherein in the step 3, the air drying time is 12-24 hours, the air drying temperature is 20-35 ℃, and the air drying humidity is 40-50% RH.
9. The preparation method of the PVA-based molecular sieve composite proton exchange membrane according to claim 5, wherein in the step 4, the air drying time is 24-36 hours, the air drying temperature is 25-35 ℃, and the air drying humidity is 45-50% RH.
10. The preparation method of the PVA-based molecular sieve composite proton exchange membrane according to claim 5, wherein in the step 5, the standing time is 24-48 h, the standing temperature is 25-35 ℃, and the standing humidity is 40-50% RH; the thickness of the PVA-based molecular sieve composite proton exchange membrane is 30-110 mu m.
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