CN109589802A - A kind of porous diffusion barrier and its preparation method utilize the made battery of the porous diffusion barrier - Google Patents
A kind of porous diffusion barrier and its preparation method utilize the made battery of the porous diffusion barrier Download PDFInfo
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- CN109589802A CN109589802A CN201811315735.8A CN201811315735A CN109589802A CN 109589802 A CN109589802 A CN 109589802A CN 201811315735 A CN201811315735 A CN 201811315735A CN 109589802 A CN109589802 A CN 109589802A
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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Abstract
The invention discloses a kind of porous diffusion barrier and its preparation method, using the made battery of the porous diffusion barrier, the porous diffusion barrier raw material includes the substance of following mass fraction: 9.8~60wt% of film base material, 0.1~18wt% of conductive agent, 20~90wt% of solvent, 0.1~2wt% of dispersing agent.The preparation method comprises the following steps: (1) by film basis material, conductive agent, solvent, dispersant, obtaining slurry after 20~60 DEG C of agitation grindings；(2) by slurry by spinning head squeeze out, in water or ethyl alcohol carry out inversion of phases molding, solidification obtain porous diffusion barrier green body；(3) porous diffusion barrier green body dried, cut, can be prepared by porous diffusion barrier.The battery exploitation right porous diffusion barrier is made.Porous diffusion barrier good mechanical property of the invention, preparation are simple；In addition, the resistance to mass tranfer as battery diaphragm application is small, the ohmage and polarization impedance of battery can be effectively reduced.
Description
Technical field
The present invention relates to seperation film, specially a kind of porous diffusion barrier and its preparation method utilize the made electricity of the porous diffusion barrier
Pond.
Background technique
Zinc-bromine flow battery is a kind of novel electrochemical energy storage technology, this battery by side of the positive electrode bromine in electrolyte from
Son and complexing bromine and negative side zinc ion and zinc simple substance mutually convert, and complete mutually converting for electric energy and chemical energy, realize electricity
The storage and release of energy.In charging process, positive bromide ion, which loses, is electronically generated complexing bromine, occur oxidation reaction, cathode zinc from
Son obtains being electronically generated zinc simple substance, and reduction reaction occurs, and realizes the conversion of electric energy to chemical energy.Other energy storage technologies are compared, zinc
Bromine flow battery has the advantage that 1. safeties are higher, and 2. can carry out the charge and discharge of depth, 3. safety and environmental protections, 4. valences
Lattice are cheap, and the design of 5. systems is more flexible, and the configuration of the power of battery and energy is more independent.Zinc-bromine flow battery in wind-powered electricity generation, too
Before new energy consumption, peak load regulation network frequency modulation, user side energy storage, the emergency power systems such as positive energy etc. conveniently have splendid application
Scape.
Zinc-bromine flow battery mainly consists of three parts, including pile, electrolyte, pipe-line system etc..Wherein pile is double
Polar structure, electrolyte are evenly distributed in every monocell by pipe-line system.Core as zinc-bromine flow battery
Part, pile are generally required comprising diaphragm, electrode, electrolyte distributor and current-collecting device etc..Wherein, it is positive and negative to play barrier for diaphragm
Chemical reaction between pole provides ion channel and prevents the effect of self-discharge of battery.It is generally used in zinc-bromine flow battery
Porous diffusion barrier, the complexing bromine that this seperation film can prevent anode from generating pass through, but can be the bromine in electrolyte
Ion and zinc ion provide channel.Thickness, pore size, porosity, resistivity, mechanical strength, the chemistry of porous diffusion barrier are steady
The internal resistance and service life for directly influencing battery such as qualitative, furthermore the shape and structure of porous diffusion barrier also can change electrolyte
The type of flow, and then the polarization impedance of battery is impacted.It is general to require from the performance perspective of zinc-bromine flow battery
Porous diffusion barrier has lower surface resistance and lower complexing bromine permeability, while also to have preferable mechanical strength and chemistry
Stability.
Seperation film used in country's zinc-bromine flow battery is mainly flat porous diffusion barrier at present, usually using flat
Face extrusion molding, roll-in method or the tape casting preparation.There are tortuosity high (4~10), porosity for the seperation film of this method preparation
The disadvantages of low (≤30%)；And plate membrane receiving shearing force is larger in use, is easy to appear film matrix fatigue or damaged
Phenomena such as, in order to guarantee the mechanical strength of seperation film in use, only increase the thickness of film, which further increases divide
Resistance to mass tranfer from film.The boring techniques such as extraction, pore creating material method, the hole that this method is produced often are selected in traditional filming technology
For structure usually from unordered spongy duct, tortuosity is high, and resistance to mass tranfer is big.When plate membrane is applied to flow battery, electricity
The flow field of electrolyte needs fine planning in heap, occurs the uneven even dead zone etc. of flowing when film surface flows to avoid it
Phenomenon.
Summary of the invention
Goal of the invention: it is an object of the present invention to provide a kind of porous diffusion barrier of good mechanical property, another object of the present invention
It is to provide a kind of preparation method of porous diffusion barrier for being not easy to occur phenomena such as film matrix fatigue or breakage, of the invention is another
Purpose is to provide a kind of electrolyte flow and uniformly utilizes tubular type zinc-bromine flow battery made from porous diffusion barrier.
Technical solution: a kind of porous diffusion barrier of the present invention, raw material include the substance of following mass fraction: film base
9.8~60wt% of material, 0.1~18wt% of conductive agent, 20~90wt% of solvent, 0.1~2wt% of dispersing agent.Preferably, raw material packet
Include the substance of following mass fraction: 25~40wt% of film base material, 1~2wt% of conductive agent, 60~70wt% of solvent, dispersing agent 1~
2wt%.
Film base material is polyethylene and polyvinyl acetate copolymer, polyvinyl acetate, chlorosulfonated polyethylene, the poly- second of sulfonation
Alkene, sulfonated polyethylene and polystyrene copolymer, poly- N, N- dimethyl allene acid butyl ester, poly- N, N- dimethyl allene acid butyl ester and
One of sulfonated polyethylene copolymer, polyisoprene, ethyl cellulose are a variety of, polyethylene preferred molecular weight 2,000,000 with
On ultra-high molecular weight polyethylene or the HDPE high density polyethylene (HDPE) below of molecular weight 300,000.
Conductive agent is single-layer graphene, multi-layer graphene, acetylene black, silver powder, copper powder or nickel powder, after adding conductive agent, institute
The surface resistance of porous diffusion barrier is stated less than 2 Ω dm-2。
Solvent is one of N-Methyl pyrrolidone, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide or more
Kind.
Dispersing agent is one of polyvinylpyrrolidone, aminotriacetic acid, ethylenediamine tetra-acetic acid, polyethylene glycol or more
Kind.
Porous diffusion barrier is hollow tubular structure, and outer diameter is 0.5~200mm, preferably 1.5~2mm, wall thickness
For 0.05~10mm, preferably 0.08~0.12mm.The aperture of porous diffusion barrier is 2~50nm, preferably 10~20nm, hole
Rate is 20~65%, preferably 30~40%.
The preparation method of above-mentioned porous diffusion barrier, comprising the following steps:
(1) by film basis material, conductive agent, solvent, dispersant, slurry is obtained after 20~60 DEG C of agitation grindings,
It is preferred that agitation grinding temperature is 25~40 DEG C；
(2) by slurry by spinning head squeeze out, in water or ethyl alcohol carry out inversion of phases molding, solidification obtain porous separation
It is 15~25 DEG C that the step of film green body, inversion of phases forms, which includes: in temperature, and relative humidity carries out in the environment of being 45~60%,
By after solvent starts volatilization, being statically placed in 19~21 DEG C of coagulation baths 22~28 hours, placing into 20~30 DEG C to flow evaporator
In ultrapure water, 4~8 hours are stood, except a small amount of solvent and nonsolvent additive remaining in striping；
(3) porous diffusion barrier green body dried, cut, can be prepared by porous diffusion barrier.
For the spinning head that slurry squeezes out, it is made of two concentric round tubes, inner tube outside diameter and porous diffusion barrier internal diameter phase
Together, outer tube diameter is identical as porous diffusion barrier outer diameter.
It is a kind of to utilize tubular type zinc-bromine flow battery made from above-mentioned porous diffusion barrier.
The utility model has the advantages that compared to the prior art the present invention, has the characteristics that following conspicuousness:
1, the caliber of the porous diffusion barrier of hollow tubular structure is usually at 2 millimeters hereinafter, therefore in its unit volume
About 1 order of magnitude can be improved in effective membrane area of filling compared with flat seperation film；
2, the hollow tubular structure of porous diffusion barrier is symmetrical along the stress of each section, the tubular type separation of same thickness
The mechanical strength of film is higher than flat seperation film, therefore can bear bigger inside and outside hydraulic pressure difference, is resistant to identical hydraulic pressure difference
Under the conditions of, the film thickness of tubular type seperation film will be lower than flat seperation film, it can reduce by film thickness bring ohmage, this
The tube wall for inventing the hollow fiber tubular type seperation film of preparation is relatively thin, and usually 0.1~0.3 millimeter, the resistance in mass transport process is big
It is big to reduce；
3, the straight hole structure for the radially low tortuosity that phase inversion is prepared, can substantially reduce the concentration polarization of battery
Change；
4, since its hollow tubular structure is convenient for liquid flowing, electrolyte flow field planning difficulty substantially reduces tubular membrane,
It does not need finely to plan；
5, the chlorosulfonated polyethylene in film base material, the polymerization such as sulfonated polyethylene, sulfonated polyethylene and polystyrene copolymer
Object contains sulfonic group isopolarity group, and chlorine sulphonyl active group is contained in molecular structure, resistant to chemical etching, at the same sulfonic acid group with
Water has compared with strong interaction, can form various sizes of fenestra by regulation, control the bromine generated in electrochemical reaction process
Simple substance penetrates.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of spinning head used herein；
Fig. 2 is the radial cross-section morphology figure of porous diffusion barrier of the invention under an electron microscope.
Specific embodiment
Agitation grinding in following embodiment is carried out using planetary ball mill, and milling time is 48 hours.It is following
The surface resistance of porous diffusion barrier in embodiment is according to GB/T 1410-2006 " solid insulating material volume resistivity and surface
Resistivity test method " it is measured.
Such as Fig. 1, the spinning head squeezed out for slurry is two concentric round tubes, has sandwich, 2 outer diameter of inner tube and more
Pore separation membrane internal diameter is identical, and 1 internal diameter of outer tube is identical as porous diffusion barrier outer diameter, and the wall thickness of porous diffusion barrier is 0.05~10 milli
Rice.1 internal diameter of outer tube of concentric round tube is 0.5~200 millimeter.Preferably, the wall thickness of porous diffusion barrier is 0.08~0.12 millimeter,
1 internal diameter of outer tube is 1.5~2 millimeters.Slurry enters spinning head by being squeezed into spinning head outer flow passage 4, the filling gas such as nitrogen
Inner flow passage 3, the present invention are not particularly limited the extrusion pressure in the extrusion step, it is preferable that expect in spinning head outer flow passage 4
The extrusion pressure of slurry is 0.01~0.15Mpa, and the nitrogen of 0.01~0.2Mpa is passed through in spinning head inner flow passage 3.
Embodiment 1
A kind of preparation method of porous diffusion barrier, comprising the following steps:
(1) by 9.8wt% polyethylene and polyvinyl acetate copolymer polyethylene film basis material, 0.1wt% single layer stone
Black alkene conductive agent, 90wt%N- methyl pyrrolidone solvent, 0.1wt% polyvinylpyrrolidone dispersant, are stirred through 20 DEG C
Slurry is obtained after mixing grinding；
(2) the spinning head that is 0.45mm by 2 outer diameter of inner tube by slurry, 1 internal diameter of outer tube is 0.5mm squeezes out, with water or
It is 15 that the step of progress inversion of phases molding in ethyl alcohol, solidification obtain porous diffusion barrier green body, and inversion of phases forms, which includes: in temperature,
DEG C, relative humidity carries out in the environment of being 45%, by after solvent starts volatilization, being statically placed in 19 DEG C of coagulation baths to flow evaporator
It 22 hours, places into 20 DEG C of ultrapure water, 4 hours is stood, except a small amount of solvent and nonsolvent additive remaining in striping；
(3) porous diffusion barrier green body dried at 50 DEG C, cut, can be prepared by porous diffusion barrier.
Obtained porous diffusion barrier is hollow tubular structure, outer diameter 0.5mm, wall thickness 0.05mm.It is more
The aperture of pore separation membrane is 2nm, and porosity 20%, the surface resistance of porous diffusion barrier is less than 2 Ω dm-2。
Above-mentioned polyethylene selects the ultra-high molecular weight polyethylene or the HDPE below of molecular weight 300,000 of 2,000,000 or more molecular weight
High density polyethylene (HDPE).
Fig. 2 is the radial cross-section morphology figure of porous diffusion barrier of the invention under an electron microscope, it can be seen that porous point
Uniform from duct in film, tube wall is relatively thin, controls at 0.1~0.3 millimeter, duct tortuosity is lower, reduces mass transport process
In resistance.
Embodiment 2
A kind of preparation method of porous diffusion barrier, comprising the following steps:
(1) by 60wt% polyvinyl acetate film basis material, 18wt% multi-layer graphene conductive agent, 20wt% dimethyl
Formamide solvent, 2wt% aminotriacetic acid dispersant, obtain slurry after 60 DEG C of agitation grindings；
(2) the spinning head that is 190mm by 2 outer diameter of inner tube by slurry, 1 internal diameter of outer tube is 200mm squeezes out, with water or second
It is 25 DEG C that the step of progress inversion of phases molding in alcohol, solidification obtain porous diffusion barrier green body, and inversion of phases forms, which includes: in temperature,
Relative humidity carries out in the environment of being 60%, and by flow evaporator, after solvent starts volatilization, it is small to be statically placed in 21 DEG C of coagulation baths 28
When, it places into 30 DEG C of ultrapure water, 8 hours is stood, except a small amount of solvent and nonsolvent additive remaining in striping；
(3) porous diffusion barrier green body dried at 90 DEG C, cut, can be prepared by porous diffusion barrier.
Obtained porous diffusion barrier is hollow tubular structure, outer diameter 200mm, wall thickness 10mm.It is porous
The aperture of seperation film is 50nm, and porosity 65%, the surface resistance of porous diffusion barrier is less than 2 Ω dm-2。
Embodiment 3
A kind of preparation method of porous diffusion barrier, comprising the following steps:
(1) by 25wt% chlorosulfonated polyethylene film basis material, 1wt% acetylene black conductor, 73wt% dimethylacetamide
Amine solvent, 1wt% ethylenediamine tetra-acetic acid dispersant, obtain slurry after 25 DEG C of agitation grindings；
(2) the spinning head that is 1.42mm by 2 outer diameter of inner tube by slurry, 1 internal diameter of outer tube is 1.5mm squeezes out, with water or
It is 20 that the step of progress inversion of phases molding in ethyl alcohol, solidification obtain porous diffusion barrier green body, and inversion of phases forms, which includes: in temperature,
DEG C, relative humidity carries out in the environment of being 53%, by after solvent starts volatilization, being statically placed in 20 DEG C of coagulation baths to flow evaporator
It 25 hours, places into 25 DEG C of ultrapure water, 6 hours is stood, except a small amount of solvent and nonsolvent additive remaining in striping；
(3) porous diffusion barrier green body dried at 60 DEG C, cut, can be prepared by porous diffusion barrier.
Obtained porous diffusion barrier is hollow tubular structure, outer diameter 1.5mm, wall thickness 0.08mm.It is more
The aperture of pore separation membrane is 10nm, and porosity 30%, the surface resistance of porous diffusion barrier is less than 2 Ω dm-2。
Embodiment 4
A kind of preparation method of porous diffusion barrier, comprising the following steps:
It (1) will be molten in 40wt% sulfonated polyethylene film basis material, 2wt% silver powder conductive agent, 56wt% dimethyl sulfoxide
Agent, 2wt% polyethylene glycol dispersant, obtain slurry after 40 DEG C of agitation grindings；
(2) the spinning head that is 1.88mm by 2 outer diameter of inner tube by slurry, 1 internal diameter of outer tube is 2mm squeezes out, with water or second
It is 17 DEG C that the step of progress inversion of phases molding in alcohol, solidification obtain porous diffusion barrier green body, and inversion of phases forms, which includes: in temperature,
Relative humidity carries out in the environment of being 50%, and by flow evaporator, after solvent starts volatilization, it is small to be statically placed in 19 DEG C of coagulation baths 23
When, it places into 22 DEG C of ultrapure water, 5 hours is stood, except a small amount of solvent and nonsolvent additive remaining in striping；
(3) porous diffusion barrier green body dried at 80 DEG C, cut, can be prepared by porous diffusion barrier.
Obtained porous diffusion barrier is hollow tubular structure, outer diameter 2mm, wall thickness 0.12mm.It is porous
The aperture of seperation film is 20nm, and porosity 40%, the surface resistance of porous diffusion barrier is less than 2 Ω dm-2。
Embodiment 5
A kind of preparation method of porous diffusion barrier, comprising the following steps:
(1) by 32wt% sulfonated polyethylene and polystyrene copolymer film basis material, 1.5wt% copper powder conductive agent,
65wt%N- methyl pyrrolidone and dimethylformamide mixed solvent, 1.5wt% polyvinylpyrrolidone and aminotriacetic acid
Dispersant obtains slurry after 33 DEG C of agitation grindings；
(2) the spinning head that is 1.6mm by 2 outer diameter of inner tube by slurry, 1 internal diameter of outer tube is 1.7mm squeezes out, with water or second
It is 23 DEG C that the step of progress inversion of phases molding in alcohol, solidification obtain porous diffusion barrier green body, and inversion of phases forms, which includes: in temperature,
Relative humidity carries out in the environment of being 55%, and by flow evaporator, after solvent starts volatilization, it is small to be statically placed in 21 DEG C of coagulation baths 26
When, it places into 28 DEG C of ultrapure water, 7 hours is stood, except a small amount of solvent and nonsolvent additive remaining in striping；
(3) porous diffusion barrier green body dried at 70 DEG C, cut, can be prepared by porous diffusion barrier.
Obtained porous diffusion barrier is hollow tubular structure, outer diameter 1.7mm, wall thickness 0.10mm.It is more
The aperture of pore separation membrane is 15nm, and porosity 35%, the surface resistance of porous diffusion barrier is less than 2 Ω dm-2。
Embodiment 6
A kind of preparation method of porous diffusion barrier, comprising the following steps:
(1) by the poly- N of 55wt%, N- dimethyl allene acid butyl ester or poly- N, N- dimethyl allene acid butyl ester and sulfonated polyethylene
Co-polymer membrane basis material, 18wt% nickel powder conductive agent, 26.5wt% dimethyl acetamide and dimethyl sulfoxide solvent,
0.5wt% ethylenediamine tetra-acetic acid, polyethylene glycol dispersant, obtain slurry after 50 DEG C of agitation grindings；
(2) the spinning head that is 95mm by 2 outer diameter of inner tube by slurry, 1 internal diameter of outer tube is 100mm squeezes out, with water or second
It is 16 DEG C that the step of progress inversion of phases molding in alcohol, solidification obtain porous diffusion barrier green body, and inversion of phases forms, which includes: in temperature,
Relative humidity carries out in the environment of being 58%, by flow evaporator, volatile fraction solvent, then is statically placed in 20 DEG C of coagulation baths and sets 23
Hour, it places into 24 DEG C of ultrapure water, 7 hours is stood, except a small amount of solvent and nonsolvent additive remaining in striping；
(3) porous diffusion barrier green body dried at 85 DEG C, cut, can be prepared by porous diffusion barrier.
Polyisoprene or ethyl cellulose also can be selected in above-mentioned film basis material.
Obtained porous diffusion barrier is hollow tubular structure, outer diameter 100mm, wall thickness 5mm.Porous point
Aperture from film is 35nm, and porosity 55%, the surface resistance of porous diffusion barrier is less than 2 Ω dm-2。
Claims (10)
1. a kind of porous diffusion barrier, it is characterised in that the raw material of porous diffusion barrier includes the substance of following mass fraction: film base material
9.8~60wt%, 0.1~18wt% of conductive agent, 20~90wt% of solvent, 0.1~2wt% of dispersing agent.
2. porous diffusion barrier according to claim 1, it is characterised in that: the film base material is polyethylene and polyvinyl acetate
Ester copolymer, polyvinyl acetate, chlorosulfonated polyethylene, sulfonated polyethylene, sulfonated polyethylene and polystyrene copolymer, poly- N,
N- dimethyl allene acid butyl ester, poly- N, N- dimethyl allene acid butyl ester and sulfonated polyethylene copolymer, polyisoprene, ethyl are fine
Tie up one of element or a variety of.
3. porous diffusion barrier according to claim 1, it is characterised in that: the conductive agent is single-layer graphene, multilayer stone
Black alkene, acetylene black, silver powder, copper powder or nickel powder.
4. porous diffusion barrier according to claim 1, it is characterised in that: the solvent is N-Methyl pyrrolidone, diformazan
One of base formamide, dimethyl acetamide, dimethyl sulfoxide are a variety of.
5. porous diffusion barrier according to claim 1, it is characterised in that: the dispersing agent is polyvinylpyrrolidone, ammonia
One of base triacetic acid, ethylenediamine tetra-acetic acid, polyethylene glycol are a variety of.
6. porous diffusion barrier according to claim 1, it is characterised in that: the porous diffusion barrier is hollow tubular type knot
Structure, outer diameter are 0.5~200mm, and wall thickness is 0.05~10mm.
7. porous diffusion barrier according to claim 1 or 6, it is characterised in that: the aperture of the porous diffusion barrier be 2~
50nm, porosity are 20~65%.
8. a kind of preparation method of porous diffusion barrier described in claim 1, it is characterised in that the following steps are included:
(1) by film basis material, conductive agent, solvent, dispersant, slurry is obtained after 20~60 DEG C of agitation grindings；
(2) by slurry by spinning head squeeze out, in water or ethyl alcohol carry out inversion of phases molding, solidification obtain porous diffusion barrier base
Body；
(3) porous diffusion barrier green body dried, cut, can be prepared by porous diffusion barrier.
9. a kind of preparation method of porous diffusion barrier according to claim 8, it is characterised in that the inversion of phases is molding
It is 15~25 DEG C that step, which includes: in temperature, and relative humidity carries out in the environment of being 45~60%, by the way that flow evaporator, solvent is opened
Begin to be statically placed in 19~21 DEG C of coagulation baths 22~28 hours, place into 20~30 DEG C of ultrapure water after volatilization, it is small to stand 4~8
When.
10. a kind of utilize tubular type zinc-bromine flow battery made from any porous diffusion barrier of claim 1~7.
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