CN109589802B - Porous separation membrane for zinc-bromine flow battery and preparation method thereof - Google Patents
Porous separation membrane for zinc-bromine flow battery and preparation method thereof Download PDFInfo
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- CN109589802B CN109589802B CN201811315735.8A CN201811315735A CN109589802B CN 109589802 B CN109589802 B CN 109589802B CN 201811315735 A CN201811315735 A CN 201811315735A CN 109589802 B CN109589802 B CN 109589802B
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- 238000000926 separation method Methods 0.000 title claims abstract description 110
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- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 title claims description 16
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
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- 229920000573 polyethylene Polymers 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
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- 239000000463 material Substances 0.000 claims description 9
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- 238000001704 evaporation Methods 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 6
- 239000011118 polyvinyl acetate Substances 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229960001484 edetic acid Drugs 0.000 claims description 4
- 229920002681 hypalon Polymers 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
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- 239000002356 single layer Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 4
- 230000010287 polarization Effects 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 239000013557 residual solvent Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
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Images
Classifications
-
- 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
- B01D71/26—Polyalkenes
-
- 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
- B01D69/04—Tubular membranes
-
- 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
- B01D71/08—Polysaccharides
- B01D71/10—Cellulose; Modified cellulose
-
- 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
- B01D71/28—Polymers of vinyl aromatic compounds
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a porous separation membrane, a preparation method thereof and a battery manufactured by using the porous separation membrane, wherein the porous separation membrane comprises the following raw materials in percentage by mass: 9.8 to 60wt% of a film substrate, 0.1 to 18wt% of a conductive agent, 20 to 90wt% of a solvent, and 0.1 to 2wt% of a dispersant. The preparation method comprises the following steps: (1) mixing a film matrix material, a conductive agent, a solvent and a dispersing agent, and stirring and grinding at 20-60 ℃ to obtain slurry; (2) extruding the slurry through a spinning nozzle, performing phase transformation molding in water or ethanol, and curing to obtain a porous separation membrane blank; (3) and drying and cutting the porous separation membrane blank to obtain the porous separation membrane. The battery is manufactured using a porous separation membrane. The porous separation membrane has good mechanical property and simple preparation; in addition, the mass transfer resistance applied as the battery diaphragm is small, and the ohmic impedance and the polarization impedance of the battery can be effectively reduced.
Description
Technical Field
The invention relates to a separation membrane, in particular to a porous separation membrane, a preparation method thereof and a battery manufactured by using the porous separation membrane.
Background
The zinc-bromine flow battery is a novel electrochemical energy storage technology, and the battery completes the mutual conversion of electric energy and chemical energy by the mutual conversion of positive side bromide ions and complex bromine in electrolyte and negative side zinc ions and zinc simple substances, thereby realizing the storage and release of the electric energy. In the charging process, positive electrode bromine ions lose electrons to generate complex bromine, oxidation reaction occurs, negative electrode zinc ions obtain electrons to generate a zinc simple substance, reduction reaction occurs, and conversion from electric energy to chemical energy is realized. Compared with other energy storage technologies, the zinc-bromine flow battery has the following advantages: 1. the safety is higher, 2, deep charging and discharging can be carried out, 3, safety and environmental protection are realized, 4, the price is low, 5, the system design is more flexible, and the configuration of the battery power and the energy is more independent. The zinc-bromine flow battery has excellent application prospect in wind power, solar energy and other new energy consumption, power grid peak regulation and frequency modulation, user side energy storage, emergency power supply system and the like.
The zinc-bromine flow battery mainly comprises three parts, including an electric pile, electrolyte, a pipeline system and the like. The electric pile is a bipolar structure, and electrolyte is uniformly distributed to each single battery through a pipeline system. As a core component of the zinc-bromine flow battery, the stack generally needs to include a separator, electrodes, an electrolyte distribution device, a current collecting device, and the like. The diaphragm plays a role in blocking chemical reaction between the positive electrode and the negative electrode, providing an ion channel and preventing self-discharge of the battery. Porous separation membranes are commonly used in zinc-bromine flow batteries and prevent the passage of complexed bromine generated at the positive electrode of the battery, but provide a pathway for bromide and zinc ions in the electrolyte. The thickness, pore size, porosity, resistivity, mechanical strength, chemical stability and the like of the porous separation membrane directly influence the internal resistance and service life of the battery, and in addition, the shape and structure of the porous separation membrane can also change the flow mode of electrolyte, thereby influencing the polarization impedance of the battery. From the performance perspective of zinc-bromine flow batteries, porous separation membranes are generally required to have lower sheet resistance and lower complex bromine permeability, as well as better mechanical strength and chemical stability.
At present, the separation membrane used in the domestic zinc-bromine flow battery is mainly a flat porous separation membrane, and is generally prepared by a plane extrusion method, a rolling method or a casting method. The separation membrane prepared by the method has the defects of high tortuosity factor (4-10), low porosity (less than or equal to 30%) and the like; and the flat membrane bears larger shearing force in the using process, the phenomena of membrane matrix fatigue or breakage and the like are easy to occur, and in order to ensure the mechanical strength of the separation membrane in the using process, the thickness of the membrane is only increased, so that the mass transfer resistance of the separation membrane is further increased. The traditional film making process usually adopts extraction method, pore-forming agent method and other pore-forming techniques, and the pore structure produced by the method is often disordered spongy pore canals, and has high tortuosity factor and large mass transfer resistance. When the flat membrane is applied to a flow battery, the flow field of electrolyte in the galvanic pile needs to be finely planned so as to avoid the phenomena of uneven flow, even dead zones and the like when the electrolyte flows on the surface of the membrane.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a porous separation membrane with good mechanical property, and the invention also aims to provide a preparation method of the porous separation membrane which is not easy to cause the phenomena of fatigue or damage of a membrane matrix and the like.
The technical scheme is as follows: the porous separation membrane provided by the invention comprises the following raw materials in percentage by mass: 9.8 to 60wt% of a film substrate, 0.1 to 18wt% of a conductive agent, 20 to 90wt% of a solvent, and 0.1 to 2wt% of a dispersant. Preferably, the raw materials comprise the following substances in percentage by mass: 25-40 wt% of a film substrate, 1-2 wt% of a conductive agent, 60-70 wt% of a solvent and 1-2 wt% of a dispersant.
The film base material is one or more of polyethylene and polyvinyl acetate copolymer, polyvinyl acetate, chlorosulfonated polyethylene, sulfonated polyethylene and polystyrene copolymer, poly N, N-butyl dimethacrylate and sulfonated polyethylene copolymer, polyisoprene and ethyl cellulose, and the polyethylene is preferably ultrahigh molecular weight polyethylene with molecular weight of more than 200 ten thousand or HDPE high density polyethylene with molecular weight of less than 30 ten thousand.
The conductive agent is single-layer graphene, multi-layer graphene, acetylene black, silver powder, copper powder or nickel powder, and after the conductive agent is added, the surface resistance of the porous separation membrane is less than 2 omega dm-2。
The solvent is one or more of N-methyl pyrrolidone, dimethylformamide, dimethylacetamide and dimethyl sulfoxide.
The dispersant is one or more of polyvinylpyrrolidone, nitrilotriacetic acid, ethylene diamine tetraacetic acid and polyethylene glycol.
The porous separation membrane is of a hollow tubular structure, the outer diameter of the porous separation membrane is 0.5-200 mm, preferably 1.5-2 mm, and the thickness of the membrane wall is 0.05-10 mm, preferably 0.08-0.12 mm. The pore diameter of the porous separation membrane is 2-50 nm, preferably 10-20 nm, and the porosity is 20-65%, preferably 30-40%.
The preparation method of the porous separation membrane comprises the following steps:
(1) mixing a film substrate material, a conductive agent, a solvent and a dispersing agent, stirring and grinding at 20-60 ℃ to obtain slurry, and preferably, the stirring and grinding temperature is 25-40 ℃;
(2) extruding the slurry through a spinneret, performing phase inversion molding in water or ethanol, and curing to obtain a porous separation membrane blank, wherein the phase inversion molding comprises the following steps: performing convection evaporation in an environment with the temperature of 15-25 ℃ and the relative humidity of 45-60%, standing in a gel bath at the temperature of 19-21 ℃ for 22-28 hours after a solvent begins to volatilize, then placing in ultrapure water at the temperature of 20-30 ℃, standing for 4-8 hours, and removing a small amount of residual solvent and non-solvent additives in the film;
(3) and drying and cutting the porous separation membrane blank to obtain the porous separation membrane.
The spinneret for extruding slurry consists of two concentric circular tubes, the inner diameter of the inner tube is the same as that of the porous separation membrane, and the inner diameter of the outer tube is the same as that of the porous separation membrane.
A tubular zinc-bromine flow battery prepared by the porous separation membrane.
Has the advantages that: compared with the prior art, the invention has the following remarkable characteristics:
1. the pipe diameter of the porous separation membrane with a hollow tubular structure is usually below 2mm, so that the effective membrane area filled in a unit volume can be increased by about 1 order of magnitude compared with that of a flat-plate type separation membrane;
2. the hollow tubular structure of the porous separation membrane is symmetrically distributed along the stress of each section, the mechanical strength of the tubular separation membrane with the same thickness is higher than that of a flat-plate separation membrane, so that the porous separation membrane can bear larger internal and external hydraulic pressure difference, the membrane thickness of the tubular separation membrane is lower than that of the flat-plate separation membrane under the condition of tolerating the same hydraulic pressure difference, and the ohmic impedance caused by the membrane thickness can be reduced;
3. the concentration polarization of the battery can be greatly reduced by the straight hole structure with the radial low-tortuosity factor prepared by the phase inversion method;
4. the tubular membrane is convenient for liquid to flow due to the hollow tubular structure, the difficulty of planning the flow field of the electrolyte is greatly reduced, and fine planning is not needed;
5. polymers such as chlorosulfonated polyethylene, sulfonated polyethylene and polystyrene copolymer in the membrane substrate contain polar groups such as sulfonic groups, a molecular structure contains chlorosulfonyl active groups, chemical corrosion resistance is achieved, meanwhile, the sulfonic groups have strong interaction with water, membrane pores with different sizes can be formed through regulation and control, and the permeation of bromine generated in the electrochemical reaction process is controlled.
Drawings
FIG. 1 is a schematic view of the structure of a spinneret used in the present invention;
fig. 2 is a radial cross-sectional profile of the porous separation membrane of the present invention under an electron microscope.
Detailed Description
The stirring and grinding in each of the following examples were carried out using a planetary ball mill, and the grinding time was 48 hours. The surface resistance of the porous separation membrane in each of the following examples was measured in accordance with GB/T1410-2006 test method for volume resistivity and surface resistivity of solid insulating material.
As shown in figure 1, the spinning nozzle for extruding the slurry is two concentric circular tubes and has a sandwich structure, the outer diameter of an inner tube 2 is the same as the inner diameter of the porous separation membrane, the inner diameter of an outer tube 1 is the same as the outer diameter of the porous separation membrane, and the wall thickness of the porous separation membrane is 0.05-10 mm. The inner diameter of the outer tube 1 of the concentric circular tube is 0.5-200 mm. Preferably, the wall thickness of the porous separation membrane is 0.08-0.12 mm, and the inner diameter of the outer pipe 1 is 1.5-2 mm. The slurry enters an outer flow channel 4 of the spinning nozzle through extrusion, and filling gas such as nitrogen enters an inner flow channel 3 of the spinning nozzle, the extrusion pressure in the extrusion step is not particularly limited, preferably, the extrusion pressure of the slurry in the outer flow channel 4 of the spinning nozzle is 0.01-0.15 Mpa, and the nitrogen of 0.01-0.2 Mpa is introduced into the inner flow channel 3 of the spinning nozzle.
Example 1
A method of preparing a porous separation membrane, comprising the steps of:
(1) mixing 9.8wt% of polyethylene and polyvinyl acetate copolymer polyethylene film base material, 0.1wt% of single-layer graphene conductive agent, 90wt% of N-methyl pyrrolidone solvent and 0.1wt% of polyvinylpyrrolidone dispersing agent, and stirring and grinding at 20 ℃ to obtain slurry;
(2) extruding the slurry through a spinneret with the outer diameter of an inner pipe 2 being 0.45mm and the inner diameter of an outer pipe 1 being 0.5mm, carrying out phase transformation forming in water or ethanol, and solidifying to obtain a porous separation membrane blank, wherein the phase transformation forming step comprises the following steps: performing convection evaporation at 15 deg.C and relative humidity of 45%, standing in 19 deg.C gel bath for 22 hr, adding into 20 deg.C ultrapure water, standing for 4 hr, and removing residual solvent and non-solvent additive;
(3) and drying and cutting the porous separation membrane blank at 50 ℃ to prepare the porous separation membrane.
The prepared porous separation membrane is of a hollow tubular structure, the outer diameter of the porous separation membrane is 0.5mm, and the thickness of the membrane wall is 0.05 mm. The pore diameter of the porous separation membrane is 2nm, the porosity is 20%, and the surface resistance of the porous separation membrane is less than 2 omega dm-2。
The polyethylene is ultra-high molecular weight polyethylene with molecular weight of more than 200 ten thousand or HDPE high density polyethylene with molecular weight of less than 30 ten thousand.
Fig. 2 is a radial cross-sectional profile of the porous separation membrane under an electron microscope, and it can be seen that the porous separation membrane has uniform pore channels, thin tube walls controlled at 0.1-0.3 mm, and low pore channel tortuosity factor, and reduces resistance in the mass transfer process.
Example 2
A method of preparing a porous separation membrane, comprising the steps of:
(1) mixing 60wt% of polyvinyl acetate film base material, 18wt% of multilayer graphene conductive agent, 20wt% of dimethylformamide solvent and 2wt% of nitrilotriacetic acid dispersing agent, and stirring and grinding at 60 ℃ to obtain slurry;
(2) extruding the slurry through a spinneret with the outer diameter of an inner pipe 2 being 190mm and the inner diameter of an outer pipe 1 being 200mm, carrying out phase transformation forming in water or ethanol, and curing to obtain a porous separation membrane blank, wherein the phase transformation forming step comprises the following steps: performing convection evaporation at 25 deg.C and relative humidity of 60%, standing in 21 deg.C gel bath for 28 hr, adding into 30 deg.C ultrapure water, standing for 8 hr, and removing residual solvent and non-solvent additive;
(3) and drying and cutting the porous separation membrane blank at 90 ℃ to obtain the porous separation membrane.
The prepared porous separation membrane is of a hollow tubular structure, the outer diameter of the porous separation membrane is 200mm, and the thickness of the membrane wall is 10 mm. The porous separation membrane has a pore diameter of 50 nm and a porosity of 65%, and has a surface resistance of less than 2 Ω dm-2。
Example 3
A method of preparing a porous separation membrane, comprising the steps of:
(1) mixing 25wt% of chlorosulfonated polyethylene film base material, 1wt% of acetylene black conductive agent, 73wt% of dimethylacetamide solvent and 1wt% of ethylenediamine tetraacetic acid dispersing agent, and stirring and grinding at 25 ℃ to obtain slurry;
(2) extruding the slurry through a spinneret with the outer diameter of the inner pipe 2 being 1.42mm and the inner diameter of the outer pipe 1 being 1.5mm, carrying out phase transformation molding in water or ethanol, and solidifying to obtain a porous separation membrane blank, wherein the phase transformation molding step comprises the following steps: performing convection evaporation at 20 deg.C and relative humidity of 53%, standing in 20 deg.C gel bath for 25 hr, adding into 25 deg.C ultrapure water, standing for 6 hr, and removing residual solvent and non-solvent additive;
(3) and drying and cutting the porous separation membrane blank at 60 ℃ to prepare the porous separation membrane.
The prepared porous separation membrane is of a hollow tubular structure, the outer diameter of the porous separation membrane is 1.5mm, and the thickness of the membrane wall is 0.08 mm. The porous separation membrane has a pore diameter of 10nm and a porosity of 30%, and has a surface resistance of less than 2 Ω dm-2。
Example 4
A method of preparing a porous separation membrane, comprising the steps of:
(1) mixing 40wt% of sulfonated polyethylene film base material, 2wt% of silver powder conductive agent, 56wt% of dimethyl sulfoxide solvent and 2wt% of polyethylene glycol dispersant, and stirring and grinding at 40 ℃ to obtain slurry;
(2) extruding the slurry through a spinneret with the outer diameter of the inner pipe 2 being 1.88mm and the inner diameter of the outer pipe 1 being 2mm, carrying out phase transformation molding in water or ethanol, and curing to obtain a porous separation membrane blank, wherein the phase transformation molding step comprises the following steps: performing convection evaporation at 17 deg.C and relative humidity of 50%, standing in 19 deg.C gel bath for 23 hr, adding into 22 deg.C ultrapure water, standing for 5 hr, and removing residual solvent and non-solvent additive;
(3) and drying and cutting the porous separation membrane blank at 80 ℃ to prepare the porous separation membrane.
The prepared porous separation membrane is of a hollow tubular structure, the outer diameter of the porous separation membrane is 2mm, and the thickness of the membrane wall is 0.12 mm. The pore diameter of the porous separation membrane is 20nm, the porosity is 40%, and the surface resistance of the porous separation membrane is less than 2 omega dm-2。
Example 5
A method of preparing a porous separation membrane, comprising the steps of:
(1) mixing 32wt% of sulfonated polyethylene and polystyrene copolymer film base material, 1.5wt% of copper powder conductive agent, 65wt% of mixed solvent of N-methyl pyrrolidone and dimethyl formamide, 1.5wt% of polyvinyl pyrrolidone and aminotriacetic acid dispersing agent, and stirring and grinding at 33 ℃ to obtain slurry;
(2) extruding the slurry through a spinneret with the outer diameter of the inner pipe 2 being 1.6mm and the inner diameter of the outer pipe 1 being 1.7mm, carrying out phase transformation forming in water or ethanol, and solidifying to obtain a porous separation membrane blank, wherein the phase transformation forming step comprises the following steps: performing convection evaporation at 23 deg.C and relative humidity of 55%, standing in 21 deg.C gel bath for 26 hr, adding into 28 deg.C ultrapure water, standing for 7 hr, and removing residual solvent and non-solvent additive;
(3) and drying and cutting the porous separation membrane blank at 70 ℃ to prepare the porous separation membrane.
The prepared porous separation membrane is of a hollow tubular structure, the outer diameter of the porous separation membrane is 1.7mm, and the thickness of the membrane wall is 0.10 mm. The pore diameter of the porous separation membrane is 15nm, the porosity is 35 percent, and the surface electricity of the porous separation membraneResistance less than 2 omega dm-2。
Example 6
A method of preparing a porous separation membrane, comprising the steps of:
(1) mixing 55wt% of poly-N, N-butyl dimethacrylate or poly-N, N-butyl dimethacrylate and sulfonated polyethylene copolymer membrane matrix material, 18wt% of nickel powder conductive agent, 26.5wt% of dimethylacetamide and dimethyl sulfoxide solvent, 0.5 wt% of ethylene diamine tetraacetic acid and polyethylene glycol dispersant, stirring and grinding at 50 ℃ to obtain slurry;
(2) extruding the slurry through a spinneret with the outer diameter of the inner pipe 2 being 95mm and the inner diameter of the outer pipe 1 being 100mm, carrying out phase transformation forming in water or ethanol, and curing to obtain a porous separation membrane blank, wherein the phase transformation forming step comprises the following steps: evaporating by convection at 16 deg.C and relative humidity of 58%, volatilizing part of solvent, standing in 20 deg.C gel bath for 23 hr, adding into 24 deg.C ultrapure water, standing for 7 hr, and removing residual solvent and non-solvent additive;
(3) and drying and cutting the porous separation membrane blank at 85 ℃ to obtain the porous separation membrane.
The film base material can also be polyisoprene or ethyl cellulose.
The prepared porous separation membrane is of a hollow tubular structure, the outer diameter of the porous separation membrane is 100mm, and the thickness of the membrane wall is 5 mm. The pore diameter of the porous separation membrane is 35 nm, the porosity is 55%, and the surface resistance of the porous separation membrane is less than 2 omega dm-2。
Claims (6)
1. A porous separation membrane for a zinc-bromine flow battery is characterized in that the raw material of the porous separation membrane comprises the following substances in percentage by mass: 9.8-60 wt% of a film substrate, 0.1-18 wt% of a conductive agent, 20-90 wt% of a solvent and 0.1-2 wt% of a dispersant; the dispersing agent is one or more of polyvinylpyrrolidone, nitrilotriacetic acid, ethylene diamine tetraacetic acid and polyethylene glycol; the porous separation membrane is of a hollow tubular structure, the outer diameter of the porous separation membrane is 1.5-2 mm, and the thickness of the membrane wall is 0.08-0.12 mm; the porous separation membrane has a pore diameter of 2-50 nm and a porosity of 20-65%.
2. The porous separation membrane for a zinc-bromine flow battery of claim 1, wherein: the film base material is one or more of polyethylene and polyvinyl acetate copolymer, polyvinyl acetate, chlorosulfonated polyethylene, sulfonated polyethylene and polystyrene copolymer, poly N, N-butyl dimethacrylate and sulfonated polyethylene copolymer, polyisoprene and ethyl cellulose.
3. The porous separation membrane for a zinc-bromine flow battery of claim 1, wherein: the conductive agent is single-layer graphene, multi-layer graphene, acetylene black, silver powder, copper powder or nickel powder.
4. The porous separation membrane for a zinc-bromine flow battery of claim 1, wherein: the solvent is one or more of N-methyl pyrrolidone, dimethylformamide, dimethylacetamide and dimethyl sulfoxide.
5. The preparation method of the porous separation membrane for the zinc-bromine flow battery as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
(1) mixing a film substrate, a conductive agent, a solvent and a dispersing agent, and stirring and grinding at 20-60 ℃ to obtain slurry;
(2) extruding the slurry through a spinning nozzle, performing phase transformation molding in water or ethanol, and curing to obtain a porous separation membrane blank;
(3) and drying and cutting the porous separation membrane blank to obtain the porous separation membrane.
6. The method of claim 5, wherein the step of phase inversion forming comprises: the method is carried out in an environment with the temperature of 15-25 ℃ and the relative humidity of 45-60%, after the solvent begins to volatilize through convection evaporation, the gel is placed in a gel bath at the temperature of 19-21 ℃ for 22-28 hours, then the gel is placed in ultrapure water at the temperature of 20-30 ℃ and placed for 4-8 hours.
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