CN111495218A - Multilayer composite membrane for flow battery or water treatment and preparation method and application thereof - Google Patents

Multilayer composite membrane for flow battery or water treatment and preparation method and application thereof Download PDF

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CN111495218A
CN111495218A CN202010200591.2A CN202010200591A CN111495218A CN 111495218 A CN111495218 A CN 111495218A CN 202010200591 A CN202010200591 A CN 202010200591A CN 111495218 A CN111495218 A CN 111495218A
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layer
functional layer
multilayer composite
composite membrane
auxiliary layer
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赵天寿
万昱含
范新庄
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Hong Kong University of Science and Technology HKUST
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Hong Kong University of Science and Technology HKUST
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0221—Organic resins; Organic polymers
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • 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
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/39—Electrospinning
    • 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 relates to the technical field of flow batteries and water treatment, in particular to a multilayer composite membrane for flow batteries or water treatment and a preparation method and application thereof. The multilayer composite membrane has a functional layer/auxiliary layer or an auxiliary layer/functional layer/auxiliary layer structure, wherein the functional layer is a barrier layer and can block specific ions in electrolyte or specific particles in aqueous solution, the auxiliary layer is a supporting layer and can provide good mechanical property for the functional layer, and the layers are manufactured into an integrated membrane assembly in a heating, hot-pressing, crosslinking and other modes. In addition, in the multilayer composite film, the functional layer is thinner, so that the ion conduction or flow resistance is ensured while the ion or particle blocking capability is good; the porosity of the auxiliary layer is large, the transmission of ions or particles in the solution can not be influenced on the premise of ensuring the supporting effect, and the number and the thickness of the auxiliary layer can be adjusted according to the implementation effect.

Description

Multilayer composite membrane for flow battery or water treatment and preparation method and application thereof
Technical Field
The invention relates to the technical field of flow batteries and water treatment, in particular to a multilayer composite membrane for flow batteries or water treatment and a preparation method and application thereof.
Background
In recent years, with the development and utilization of clean and renewable energy sources such as solar energy, wind energy and the like, the research and development of safe and efficient large-scale energy storage systems become the key for the development and application of the new energy sources so as to deal with the problem of time and regional dependence. Flow Batteries (FBs) are a battery technology based on the oxidation-reduction reaction of inorganic or organic couples in electrolyte, and have the advantages of high efficiency, safety, reliability, long cycle life, deep discharge, environmental protection and the like, so that the Flow batteries attract extensive attention in academic and industrial fields, and are ideal energy storage systems matched with solar and wind power generation technologies. The separator, as one of the core components of an all-vanadium flow battery, has a significant impact on battery performance (energy efficiency, coulombic efficiency, voltage efficiency, and cycle life) and stack cost. An ideal separator should meet the following requirements: excellent proton conductivity, active ion migration resistance, good chemical and mechanical stability and low cost.
Currently, the Nafion series perfluorosulfonic acid membranes, manufactured by dupont, usa, are the most widely used in flow batteries. Although Nafion membrane has high proton conductivity and chemical stability, its poor vanadium-blocking capability and expensive price (its cost is 41% of the total cost of the stack) directly affect the commercialization process of flow batteries. Therefore, the search for a substitute diaphragm with excellent performance and low cost becomes a research focus of researchers at home and abroad. A compact membrane formed by Polybenzimidazole (PBI) and other polymers is proved to have excellent vanadium resistance, but the proton conductivity of the compact membrane is poor, so that high internal resistance is introduced into a battery, and the voltage efficiency of the battery is difficult to improve. The internal resistance of the diaphragm can be greatly reduced by reducing the thickness of the compact polybenzimidazole diaphragm, but the mechanical property of the diaphragm is poor and the like. On the premise of ensuring certain vanadium resistance and mechanical stability of the diaphragm, the internal resistance of the diaphragm is reduced, which becomes a key for further commercial application of the diaphragm of the all-vanadium redox flow battery.
In recent years, the problem of pollution of natural environments, particularly water environments, caused by industrial development and urban construction has become more serious, and the demand for water treatment of drinking water, industrial and domestic sewage has become stronger. The earliest water treatment technology is a sewage aeration test, and then through a biomembrane method and an artificial biological treatment method, the technology develops to the high and new technologies such as an ion exchange method, an electrochemical method and the like which have pertinence at present. The membrane technology is increasingly applied to water treatment in domestic and foreign waterworks, and intercepts suspended particles, microorganisms, toxic and harmful organic matters and inorganic matters in water, reduces the content of disinfection byproducts, and ensures the sanitary safety of drinking water. In addition, the membrane technology has the advantages of small occupied area, simple equipment, convenient operation, wide separation range, high separation effect and the like, but also has the problem of contradiction between the separation effect and the flow resistance. Therefore, how to solve the efficient synergistic problem of the selective separability and the flow resistance in the membrane technology is a key problem for solving the membrane water treatment technology.
Disclosure of Invention
The invention aims to provide a multilayer composite membrane for a flow battery or water treatment, a preparation method and application thereof, and solves the contradiction problem between selective separability and ion transmission/flow channel resistance in the flow battery or membrane separation technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a multilayer composite membrane for flow batteries or water treatment having a functional layer/auxiliary layer or auxiliary layer/functional layer/auxiliary layer structure, wherein: the functional layer is a barrier layer and blocks specific ions in the electrolyte or specific particles in the aqueous solution; the auxiliary layer is a supporting layer and provides mechanical property for the functional layer, and the layers are manufactured into an integrated diaphragm component in a bonding heating, hot pressing or crosslinking mode.
The flow battery or the multilayer composite membrane for water treatment has the advantages that the auxiliary layer is positioned on one side or two sides of the functional layer, the auxiliary layer is one layer or more than two layers, or the auxiliary layer is one or more than two fiber materials.
The multilayer composite membrane for the flow battery or the water treatment has the advantages that the thickness of the functional layer is thin, the specific thickness of the functional layer can be freely regulated and controlled according to the implementation effect, and the premise is that the capability of blocking ions or particles is provided while the smaller ion conduction or flow resistance is ensured; the auxiliary layer has larger porosity, and the specific porosity is freely regulated according to the implementation effect on the premise that the transmission of ions or particles in the solution is not influenced while the supporting effect is ensured.
The preparation method of the multilayer composite membrane for the flow battery or the water treatment adopts one of the following methods:
(1) coating a binding agent on the functional layer in a spraying or casting mode, and tightly combining the functional layer and the auxiliary layer by heating;
(2) tightly bonding the functional layer and the auxiliary layer by hot pressing with or without using a binder;
(3) the functional layer is tightly bonded to the auxiliary layer by physical or chemical crosslinking.
The preparation method of the multilayer composite membrane for the flow battery or the water treatment comprises the steps of dissolving a polymer raw material in an organic solvent to form a polymer solution, and evaporating the solvent to form a membrane by adopting a solution casting method; the auxiliary layer is formed by dissolving polymer raw materials in an organic solvent to form a polymer solution and forming a porous fiber layer through an electrostatic spinning method.
The preparation method of the multilayer composite membrane for the flow battery or the water treatment comprises the following steps of: the heating and dissolving temperature of the polymer solution is 40-100 ℃, and the mass percentage is 1-25%; and then carrying out ultrasonic treatment or standing treatment on the obtained polymer solution to remove bubbles and impurities, casting the polymer solution on a flat and smooth glass plate by adopting a solution casting method, and carrying out constant-temperature treatment at 50-120 ℃ for 0.5-24 h to realize the evaporation of the solvent and complete the forming of a functional layer, wherein the thickness of the functional layer is 1-30 mu m.
The preparation method of the multilayer composite membrane for the flow battery or the water treatment comprises the following preparation processes of the auxiliary layer: the heating and dissolving temperature of the polymer solution is 40-100 ℃, and the mass percentage is 1-25%; and then carrying out ultrasonic or standing treatment on the obtained polymer solution to remove bubbles and impurities, and preparing the polymer solution into a porous carbon fiber membrane by adopting an electrostatic spinning method, wherein the thickness of the porous carbon fiber membrane is 10-100 mu m, the porosity is 60-95%, and the average pore diameter is 500 nm-500 mu m.
The preparation method of the multilayer composite membrane for the flow battery or the water treatment comprises the following steps of preparing a functional layer and an auxiliary layer, wherein the main components of the functional layer and the auxiliary layer are one or more than two of the following materials: polybenzimidazole (PBI), polyphenylene sulfone (PPSU), Polysulfone (PSF), Polyethersulfone (PES), sulfonated polyether ether ketone (SPEEK), Sulfonated Polyimide (SPI), Polyfluoroether (PFE), polyfluoroether ketone (PAEK), Polyphthalacetone Ether Ketone (PEK), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), Polyimide (PI), Polyurethane (PU), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), Polytetrafluoroethylene (PTFE), Polyethylene (PE), polyethylene terephthalate (PET), Polyetherimide (PEI), ethylene-tetrafluoroethylene copolymer (ETFE), Polysulfone (PSF), polyphthalamide (PPA), polyvinyl pyrrolidone (PVP), and polypropylene (PP); the organic solvent is one or more of N-methyl pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide and dichloromethane.
When the multilayer composite membrane is used for the flow battery, the functional layer is a compact layer, the thickness of the compact layer is 1-10 mu m, the compact layer is responsible for blocking the migration of active ions between a positive electrode and a negative electrode, and a proton conduction path is provided to form a loop.
When the multilayer composite membrane is used for membrane separation, a functional layer is a porous layer, but the porosity of the porous layer is small enough, the thickness of the porous layer is 5-30 mu m, the porosity is 5-60%, the average pore diameter is 5-100 nm, a channel is required to be provided for water transmission, and pollutants in water need to be blocked.
The design idea of the invention is as follows:
in a flow battery, the separator functions to block the migration of active ions between the positive and negative electrodes while providing a proton conduction pathway to form a circuit. Generally, the ion conduction resistance is reduced by adopting a method of membrane thickness, but the mechanical property of the membrane is deteriorated and the like. Similarly, in water treatment, the diaphragm serves to provide a water transmission channel and simultaneously isolate pollutants in water, and a method for increasing the thickness and density of the diaphragm is generally adopted to provide the separation effect, but the transmission resistance is increased.
Based on the structure, the multilayer composite membrane is constructed, and the multilayer composite membrane has a functional layer/auxiliary layer or an auxiliary layer/functional layer/auxiliary layer structure, wherein the functional layer is a barrier layer and can block specific ions in electrolyte or specific particles in aqueous solution, the auxiliary layer is a support layer and can provide good mechanical property for the functional layer, and the functional layer is manufactured into an integrated membrane component in a heating, hot-pressing, crosslinking and other modes. The functional layer is thin, and the porosity of the auxiliary layer is high, so that the selective permeability is ensured, the flow resistance of the auxiliary layer is not additionally increased, and finally the problem of contradiction between the selective separability and the ion transmission/flow channel resistance in the flow battery or the membrane separation technology is perfectly solved.
The invention has the following advantages and beneficial effects:
1. according to the invention, through the design combination of the functional layer and the auxiliary layer, a multilayer composite membrane is constructed, and the separation performance and the mechanical performance of the diaphragm are ensured on the premise of not improving the flow resistance of the membrane.
2. The prepared functional membrane and the auxiliary membrane are compounded in a heating, hot-pressing or crosslinking mode, and the preparation method is low in price, simple, flexible, easy to control and suitable for industrial large-scale production.
3. The composite membrane provided by the invention has flexible structural design, and can be used for a flow battery when the functional layer is a compact layer; when the functional layer is a porous layer, it can be used for membrane separation.
Drawings
FIGS. 1(a) - (b) are schematic structural diagrams of multilayer composite films. Wherein, (a) is one structure of the multilayer composite film, and (b) is the other structure of the multilayer composite film.
Fig. 2 is a photograph (a) and a cross-sectional Scanning Electron Microscope (SEM) image (b) of the composite membrane for a flow cell prepared in example 1.
Fig. 3 is a comparison graph (a) of the sheet resistance and the vanadium ion permeability of the composite membrane for a flow battery prepared in example 1 and a comparison Nafion membrane of a control group.
Fig. 4 is a comparative graph of mechanical tensile testing of the composite membrane for flow batteries prepared in example 1 and a control group Nafion membrane.
Detailed Description
In the specific implementation process, the multilayer composite membrane has a functional layer/auxiliary layer or an auxiliary layer/functional layer/auxiliary layer structure, wherein the functional layer is a barrier layer and can block specific ions in electrolyte or specific particles in aqueous solution, the auxiliary layer is a support layer and can provide good mechanical property for the functional layer, and the layers are manufactured into an integrated membrane component through heating, hot pressing, crosslinking and the like. Wherein the specific ion is V2+、V3+、VO2+、VO2 +And SO4 2-The specific particles include fine particles, microorganisms, metal ions, organic substances, and the like.
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The present invention will be described in further detail below by way of examples and figures.
Example 1:
this example is a specific process for preparing a multilayer composite membrane for a flow battery, comprising the following specific steps:
1. weighing 1g of Polybenzimidazole (PBI) into a glass bottle, adding 21ml of N, N-dimethylacetamide, heating and stirring at 60 ℃ to dissolve for 12h, and standing for 12h to obtain the PBI casting solution with the concentration of 5 wt%.
2. And (2) placing a clean glass plate on a flat experiment table, dropping 2ml of the casting film obtained in the step (1) on the glass plate, immediately placing the glass plate in an oven after the solution is uniformly diffused, heating and drying the glass plate at 60 ℃ for 12h, and completely volatilizing the solvent to obtain the compact PBI film with the thickness of about 5 microns.
3. Weighing 2g of Polybenzimidazole (PBI) into a glass bottle, adding 8.5ml of N, N-dimethylacetamide, heating and stirring at 60 ℃ for dissolving for 12h, and standing for 12h to obtain PBI spinning solution with the concentration of 20 wt%.
4. And (3) preparing the spinning solution obtained in the step (3) into a porous PBI carbon fiber membrane by adopting an electrostatic spinning method under the environmental conditions of room temperature and relative humidity lower than 50%, wherein the thickness of the porous PBI carbon fiber membrane is 15 microns, the porosity is 90%, and the average pore diameter is 50 microns. Wherein the electrostatic spinning conditions are as follows: the voltage is 18V, the glue pushing speed is 0.3ml/h, the roller rotating speed is 100rpm, and the effective distance from the tip of the needle to the roller is 20 cm.
5. And (3) spraying the compact PBI film obtained in the step (2) with an N, N-dimethylacetamide dilute solution with the concentration of 2 wt% of PBI as a binder, coating the porous PBI carbon fiber film on the compact PBI film, placing the compact PBI carbon fiber film in an oven, and heating and drying for 2 hours at the temperature of 60 ℃ to obtain the PBI composite film.
6. And (3) soaking the PBI composite membrane obtained in the step (3) in sulfuric acid with the molar concentration of 3M for 3 days to obtain an acidified PBI composite membrane.
The structure and performance of the composite membrane for the all-vanadium redox flow battery of the embodiment are characterized as follows:
fig. 1(a) - (b) are schematic diagrams of two structures of the composite membrane for the all-vanadium flow battery. Wherein (a) the functional layer of the diagram is positioned on the auxiliary layer to form a functional layer/auxiliary layer structure; (b) the functional layer of the figure is located between two auxiliary layers, forming an auxiliary layer/functional layer/auxiliary layer structure.
Fig. 2(a) is a photograph of a physical representation of the PBI composite membrane prepared in example 1. Fig. 2(b) is a cross-sectional SEM image of the prepared composite membrane for an all-vanadium redox flow battery. As can be seen, the dense layer and the polymer fiber layer are tightly bonded, no delamination occurs, and the total thickness is about 30 μm.
Fig. 3(a) is a comparison graph of the surface resistance of the prepared composite membrane for the all-vanadium redox flow battery and a control group Nafion membrane. As can be seen from the figure, the sheet resistance of the composite film (0.041 omega cm)2) Proximity to control Nafion membrane (0.035. omega. cm)2) FIG. 3(b) is a graph comparing the vanadium ion permeability of the composite membrane for the all-vanadium flow battery prepared with that of a control Nafion membrane, from which it can be seen that the vanadium ion permeability of the composite membrane (3.15 × 10)- 7cm2h-1) Is obviously lower than that of Nafion film (2.02 × 10)-5cm2h-1) The composite film has excellent vanadium resistance.
Fig. 4 is a comparison graph of the mechanical tensile test of the prepared composite membrane for the all-vanadium redox flow battery and a control group Nafion membrane, wherein the tensile speed is 10mm/min, and it can be seen that the tensile breaking strength and the elastic modulus of the composite membrane are far higher than those of a commercial Nafion membrane.
Example 2:
the same procedure as in example 1 was followed, except that Polyacrylonitrile (PAN) was used as the material for the auxiliary layer in step 3.
Example 3:
the same method as that of example 1, except that in step 3, the PBI fiber layer is coated on both sides of the PBI dense layer by hot pressing to form a sandwich structure.
Example 4:
the same method as that of example 1, except that step 3 adopts a chemical crosslinking mode, the PBI fiber layer is coated on one side of the PBI dense layer and is soaked in a potassium persulfate aqueous solution with the concentration of 5 wt% for crosslinking and compounding.
Example 5:
this example is a specific process for preparing a multilayer composite membrane for membrane separation, comprising the following steps:
1. weighing 2g of Polyacrylonitrile (PAN) in a glass bottle, adding 8.5ml of N, N-dimethylacetamide, heating and stirring at 60 ℃ for dissolving for 12h to obtain PAN spinning solution with the concentration of 20 wt%.
2. And (2) preparing the solution obtained in the step (1) into a porous PAN carbon fiber membrane (with low porosity) by adopting an electrostatic spinning method under the environmental conditions of room temperature and relative humidity lower than 50%, wherein the thickness of the porous PAN carbon fiber membrane is 10 microns, the porosity of the porous PAN carbon fiber membrane is 20%, and the average pore diameter of the porous PAN carbon fiber membrane is 500 nm. Wherein the electrostatic spinning conditions are as follows: the voltage is 25KV, the glue pushing speed is 0.3ml/h, the rotating speed of the roller is 100rpm, and the effective distance from the tip of the needle to the roller is 20 cm.
3. And (2) preparing the solution obtained in the step (1) into a porous PAN carbon fiber membrane (with macroporosity) by adopting an electrostatic spinning method under the environmental conditions of room temperature and relative humidity lower than 50%, wherein the thickness of the porous PAN carbon fiber membrane is 20 microns, the porosity of the porous PAN carbon fiber membrane is 95%, and the average pore diameter of the porous PAN carbon fiber membrane is 100 microns. Wherein the electrostatic spinning conditions are as follows: the voltage is 18KV, the glue pushing speed is 0.3ml/h, the roller rotating speed is 100rpm, and the effective distance from the tip of the needle to the roller is 20 cm.
4. And (3) taking the low-porosity PAN fiber membrane obtained in the step (2), spraying an N, N-dimethylacetamide dilute solution with the concentration of 2 wt% of PAN on the low-porosity PAN fiber membrane to serve as a binder, covering the high-porosity PAN fiber membrane obtained in the step (3) on the low-porosity PAN fiber membrane, putting the high-porosity PAN fiber membrane into an oven, and heating and drying the high-porosity PAN fiber membrane for 2 hours at the temperature of 60 ℃ to obtain the PAN composite membrane.
When the membrane is used in water treatment, the transfer resistance can be greatly reduced without reducing the separation efficiency.
The example results show that, in the multilayer composite film of the present invention, the functional layer has a small thickness, which can provide good ion or particle blocking capability and ensure small ion conduction or flow resistance, the auxiliary layer has a large porosity, and the transmission of ions or particles in a solution is not affected on the premise of ensuring the supporting effect, wherein the number and thickness of the auxiliary layer can be adjusted according to the implementation effect. The multilayer composite membrane structure has the advantages of strong specific ion/particle blocking capability, small ion conduction/flow resistance, good mechanical property, low cost, simple preparation method and the like, and is suitable for the fields of flow batteries and membrane separation.

Claims (10)

1. A multilayer composite membrane for flow batteries or water treatment, characterized in that it has a functional layer/auxiliary layer or auxiliary layer/functional layer/auxiliary layer structure, wherein: the functional layer is a barrier layer and blocks specific ions in the electrolyte or specific particles in the aqueous solution; the auxiliary layer is a supporting layer and provides mechanical property for the functional layer, and the layers are manufactured into an integrated diaphragm component in a bonding heating, hot pressing or crosslinking mode.
2. A multilayer composite membrane for flow batteries or water treatment according to claim 1, wherein an auxiliary layer is located on one or both sides of the functional layer, the auxiliary layer being one or more than two layers, or the auxiliary layer being one or more than two fibrous materials.
3. The multilayer composite membrane for flow batteries or water treatment according to claim 1, wherein the functional layer has a small thickness, and the specific thickness thereof is freely controlled according to the implementation effect, provided that the ability to block ions or particles is provided while ensuring a small ion conduction or flow resistance; the auxiliary layer has larger porosity, and the specific porosity is freely regulated according to the implementation effect on the premise that the transmission of ions or particles in the solution is not influenced while the supporting effect is ensured.
4. A method of preparing a multilayer composite membrane for flow batteries or water treatment according to any one of claims 1 to 3, characterized in that one of the following methods is used:
(1) coating a binding agent on the functional layer in a spraying or casting mode, and tightly combining the functional layer and the auxiliary layer by heating;
(2) tightly bonding the functional layer and the auxiliary layer by hot pressing with or without using a binder;
(3) the functional layer is tightly bonded to the auxiliary layer by physical or chemical crosslinking.
5. The method of claim 4, wherein the functional layer is formed by dissolving a polymer material in an organic solvent to form a polymer solution, and evaporating the solvent to form a film by a solution casting method; the auxiliary layer is formed by dissolving polymer raw materials in an organic solvent to form a polymer solution and forming a porous fiber layer through an electrostatic spinning method.
6. A method of making a multilayer composite membrane for flow batteries or water treatment according to claim 5, wherein the functional layer is made by: the heating and dissolving temperature of the polymer solution is 40-100 ℃, and the mass percentage is 1-25%; and then carrying out ultrasonic treatment or standing treatment on the obtained polymer solution to remove bubbles and impurities, casting the polymer solution on a flat and smooth glass plate by adopting a solution casting method, and carrying out constant-temperature treatment at 50-120 ℃ for 0.5-24 h to realize the evaporation of the solvent and complete the forming of a functional layer, wherein the thickness of the functional layer is 1-30 mu m.
7. A method of making a multilayer composite membrane for flow batteries or water treatment according to claim 5, wherein the auxiliary layer is made by: the heating and dissolving temperature of the polymer solution is 40-100 ℃, and the mass percentage is 1-25%; and then carrying out ultrasonic or standing treatment on the obtained polymer solution to remove bubbles and impurities, and preparing the polymer solution into a porous carbon fiber membrane by adopting an electrostatic spinning method, wherein the thickness of the porous carbon fiber membrane is 10-100 mu m, the porosity is 60-95%, and the average pore diameter is 500 nm-500 mu m.
8. A process for preparing a multilayer composite membrane for flow batteries or water treatment according to claim 5, characterized in that the functional layer and the auxiliary layer are mainly composed of one or more of the following materials: polybenzimidazole (PBI), polyphenylene sulfone (PPSU), Polysulfone (PSF), Polyethersulfone (PES), sulfonated polyether ether ketone (SPEEK), Sulfonated Polyimide (SPI), Polyfluoroether (PFE), polyfluoroether ketone (PAEK), Polyphthalacetone Ether Ketone (PEK), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), Polyimide (PI), Polyurethane (PU), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), Polytetrafluoroethylene (PTFE), Polyethylene (PE), polyethylene terephthalate (PET), Polyetherimide (PEI), ethylene-tetrafluoroethylene copolymer (ETFE), Polysulfone (PSF), polyphthalamide (PPA), polyvinyl pyrrolidone (PVP), and polypropylene (PP); the organic solvent is one or more of N-methyl pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide and dichloromethane.
9. Use of a multilayer composite membrane for flow batteries or water treatment according to any one of claims 1 to 3, wherein when the multilayer composite membrane is used in a flow battery, the functional layer is a dense layer having a thickness of 1 to 10 μm and is responsible for blocking the migration of active ions between the positive and negative electrodes and providing a proton conduction path to form a circuit.
10. Use of a multilayer composite membrane for flow batteries or water treatment according to any one of claims 1 to 3, wherein when the multilayer composite membrane is used for membrane separation, the functional layer is a porous layer, but the porosity is sufficiently small, the thickness is 5 to 30 μm, the porosity is 5 to 60%, the average pore diameter is 5 to 100nm, and not only channels for water transport are provided, but also contaminants in water need to be blocked.
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