CN203415656U - Membrane electrode assembly and flow battery - Google Patents
Membrane electrode assembly and flow battery Download PDFInfo
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- CN203415656U CN203415656U CN201320524773.0U CN201320524773U CN203415656U CN 203415656 U CN203415656 U CN 203415656U CN 201320524773 U CN201320524773 U CN 201320524773U CN 203415656 U CN203415656 U CN 203415656U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The utility model provides a membrane electrode assembly and a flow battery. The membrane electrode assembly comprises two electrodes and an ion exchange membrane, wherein the ion exchange membrane is clamped between the two electrodes; the two electrodes include a first electrode and a second electrode; the reaction surface of the first electrode is provided with a first concave part; a reaction space is formed between the opposite reaction surfaces of the first electrode and the second electrode; the reaction surface of the second electrode is provided with a first convex part matched with a first concave part; and the ion exchange membrane has a concave-convex structure which is formed between the first electrode and the second electrode and is matched with the reaction space. Because the ion exchange membrane has a concave-convex structure which is formed between the first electrode and the second electrode and is matched with the reaction space, the effective ion exchange area (contact area) of the ion exchange membrane and the electrode is increased, thus improving the electric current density and the conductive performance of the flow battery are improved; and meanwhile, the membrane electrode assembly has the characteristics of simple structure and low manufacturing cost.
Description
Technical field
The utility model relates to flow battery technical field, more specifically, relates to a kind of membrane electrode assembly and flow battery.
Background technology
As depicted in figs. 1 and 2, flow battery of the prior art (for example vanadium cell) comprises amberplex 10 ', the first electrode 20 ', the second electrode 30 ', two collector plate 50 ' and two liquid flow frames 40 ', amberplex 10 ' is clamped between the first electrode 20 ' and the second electrode 30 ', two collector plate 50 ' are separately positioned on the both sides of the first electrode 20 ' and the second electrode 30 ', and two liquid flow frames 40 ' are separately positioned on two collector plate 50 ' away from a side of amberplex 10 '.When the flow battery of a plurality of said structures stacks when arranging and assembling successively, form liquid stream battery stack.
Because the first electrode 20 ' and the second electrode 30 ' conduct electricity by ion-exchange with amberplex 10 ', thereby the effective ion exchange area (namely contact area) of the first electrode 20 ' and the second electrode 30 ' and amberplex 10 ' is determining the size of current density in flow battery, is also determining that whether the electric conductivity of flow battery is good.The material of the first electrode 20 ' of the prior art and the second electrode 30 ' is carbon felt, and the structure of the first electrode 20 ' and the second electrode 30 ' is slab construction.Because the first electrode 20 ' of the prior art and the second electrode 30 ' and the effective ion exchange area (contact area) of amberplex 10 ' equal the area of plane of the first electrode 20 ' and the second electrode 30 ', thereby cause that effective ion exchange area in flow battery is little, current density is low, power density is low, thereby make the electric conductivity of flow battery be difficult to improve.
Utility model content
The utility model aims to provide a kind of membrane electrode assembly and flow battery, to solve the flow battery of prior art, has the problem that ion-exchange area is little, current density is low, electric conductivity is difficult to raising.
For solving the problems of the technologies described above, according to an aspect of the present utility model, provide a kind of membrane electrode assembly, comprise two electrodes and amberplex, amberplex is clamped between two electrodes, and two electrodes comprise: the first electrode, and the reaction surface of the first electrode has the first recess; The second electrode, between the first electrode and the second electrode reaction surface respect to one another, form reaction compartment, the reaction surface of the second electrode has the first protuberance coordinating with the first recess, and amberplex forms the concaveconvex structure adapting with reaction compartment shape between the first electrode and the second electrode.
Further, the first recess is bar shaped, and the two ends of the first recess extend to the edge of the first electrode on the reaction surface of the first electrode.
Further, the first recess is a plurality of, and a plurality of the first recesses arrange at intervals.
Further, the first recess has U-shaped or V-arrangement cross section.
Further, the first recess is block, and the first recess is a plurality of, and a plurality of the first recesses arrange at intervals along first direction and second direction, between first direction and second direction, have angle.
Further, the reaction surface of the first electrode also comprises the second protuberance, and the reaction surface of the second electrode also comprises the second recess coordinating with the second protuberance.
Further, the first recess and the second protuberance are bulk, and the first recess and the second protuberance are a plurality of, and the second protuberance and the first recess arrange at intervals, a plurality of the first recesses and a plurality of the second protuberance are arranged alternately successively along first direction and second direction, between first direction and second direction, have angle.
Further, the first recess and the second protuberance are bulk, and the first recess and the second protuberance are a plurality of, a plurality of the first recesses are divided into many groups, and the first recess in same group arranges at intervals along first direction, a plurality of the second protuberances are divided into many groups, and the second protuberance in same group arranges at intervals along first direction, and many groups the first recess is arranged alternately along second direction successively with many groups the second protuberance, between first direction and second direction, has angle.
Further, the first recess and the first protuberance, the second protuberance and the second recess are cylindrical or hemisphere or cuboid.
According to another aspect of the present utility model, a kind of flow battery is provided, comprise membrane electrode assembly, membrane electrode assembly is above-mentioned membrane electrode assembly.
Between the first electrode in the utility model and the second electrode reaction surface respect to one another, form reaction compartment, the first electrode reaction surface there is the first recess, the reaction surface of the second electrode has the first protuberance coordinating with the first recess, amberplex forms the concaveconvex structure adapting with reaction compartment shape between the first electrode and the second electrode, thereby increased the effective ion exchange area (contact area) of amberplex and electrode, thereby current density and the electric conductivity of flow battery have been improved.Meanwhile, the membrane electrode assembly in the utility model has feature simple in structure, low cost of manufacture.
Accompanying drawing explanation
The accompanying drawing that forms the application's a part is used to provide further understanding of the present utility model, and schematic description and description of the present utility model is used for explaining the utility model, does not form improper restriction of the present utility model.In the accompanying drawings:
Fig. 1 has schematically shown the structural representation of flow battery of the prior art;
Fig. 2 has schematically shown the structural representation of electrode of the prior art and amberplex;
Fig. 3 has schematically shown electrode in first embodiment in the utility model and the cutaway view of amberplex;
Fig. 4 has schematically shown electrode in second embodiment in the utility model and the cutaway view of amberplex;
Fig. 5 has schematically shown the structural representation of the electrode in second embodiment in the utility model;
Fig. 6 has schematically shown the structural representation of the electrode in the 3rd embodiment in the utility model; And
Fig. 7 has schematically shown the structural representation of the electrode in the 4th embodiment in the utility model.
Reference numeral in figure: 10, amberplex; 20, the first electrode; 21, the first recess; 22, the second protuberance; 30, the second electrode; 31, the first protuberance; 10 ', amberplex; The 20 ', first electrode; The 30 ', second electrode; 40 ', liquid flow frame; 50 ', collector plate.
Embodiment
Below in conjunction with accompanying drawing, embodiment of the present utility model is elaborated, but the multitude of different ways that the utility model can be defined by the claims and cover is implemented.
As first aspect of the present utility model, provide a kind of membrane electrode assembly.As shown in Fig. 3 to Fig. 7, membrane electrode assembly comprises two electrodes and amberplex 10, and amberplex 10 is clamped between two electrodes, and two electrodes comprise: the reaction surface of the first electrode 20, the first electrodes 20 has the first recess 21; The second electrode 30, between the first electrode 20 and the second electrode 30 reaction surface respect to one another, form reaction compartment, the reaction surface of the second electrode 30 has the first protuberance 31 coordinating with the first recess 21, and amberplex 10 forms the concaveconvex structure adapting with reaction compartment shape between the first electrode 20 and the second electrode 30.Because amberplex 10 forms the concaveconvex structure adapting with reaction compartment shape between the first electrode 20 and the second electrode 30, thereby increased the effective ion exchange area (contact area) of amberplex 10 with electrode, thereby (for example: current density vanadium cell) and electric conductivity improved flow battery.Meanwhile, the membrane electrode assembly in the utility model has feature simple in structure, low cost of manufacture.
In embodiment as shown in Figures 3 to 5, the first recess 21 is bar shaped, and the two ends of the first recess 21 extend to the edge of the first electrode 20 on the reaction surface of the first electrode 20.Preferably, the strip structure of the first protuberance 31 for matching with the first recess 21.Because the first recess 21 is bar shaped, thereby more easily make to be clamped between two electrodes after amberplex 10 distortion.
The first recess 21 in the present invention is a plurality of, and a plurality of the first recesses 21 arrange (please refer to Fig. 3 to Fig. 5) at intervals.Because the first recess 21 is a plurality of, thereby further increase the response area of electrode and amberplex, thereby improved current density and the electric conductivity of flow battery.
Preferably, the first recess 21 has U-shaped or V-arrangement cross section (please refer to Fig. 3 to Fig. 5).
In first embodiment as shown in Figure 3, the first recess 21 is a plurality of, and a plurality of the first recesses 21 are adjacent to arrange successively, and the junction of adjacent two the first recesses 21 is a straight line, thereby makes the reaction surface zigzag triangular in shape of electrode.There is the jagged electrode of the triangle clamping amberplex 10 that cooperatively interacts due to two, thereby increased the effective ion exchange area between amberplex 10 and electrode, thereby reduced ionic conduction resistance, improved current density and electric conductivity.
In second embodiment as shown in Figure 4 and Figure 5, because the first recess 21 is U-shaped, thereby make the reaction surface of the first electrode 20 zigzag that is square.There is the square jagged electrode clamping amberplex 10 that cooperatively interacts due to two, thereby increased the effective ion exchange area between amberplex 10 and electrode, thereby reduced ionic conduction resistance, improved current density and electric conductivity.
Preferably, the first recess 21 is block, and the first recess 21 is a plurality of, and a plurality of the first recesses 21 arrange at intervals along first direction and second direction, have angle (please refer to Fig. 6 and Fig. 7) between first direction and second direction.In a not shown embodiment, on the reaction surface of the first electrode 20, be provided with and on the reaction surface of a plurality of the first recess 21, the second electrodes 30, be provided with and the first recess 21 the first protuberance 31 of corresponding setting one by one.Owing to thering is a plurality of the first recesses 21 and a plurality of the first protuberance 31, thereby increase the response area of electrode and amberplex 10, thereby reduced ionic conduction resistance, improved current density and electric conductivity.
The reaction surface of the first electrode 20 in the present invention also comprises that the reaction surface of the second protuberance 22, the second electrodes 30 also comprises the second recess coordinating with the second protuberance 22.Because the reaction surface of the first electrode 20 also comprises the second protuberance 22, thereby further increase the response area of the first electrode 20 with amberplex 10, thereby further reduced ionic conduction resistance, improved current density and electric conductivity.
In the 3rd embodiment as shown in Figure 6 and in the 4th embodiment shown in Fig. 7, the first recess 21 and the second protuberance 22 are bulk, and the first recess 21 and the second protuberance 22 are a plurality of, and the second protuberance 22 and the first recess 21 arrange at intervals, a plurality of the first recesses 21 are arranged alternately along first direction and second direction successively with a plurality of the second protuberances 22, between first direction and second direction, have angle.Owing to there being a plurality of the first recesses 21 to coordinate with a plurality of the first protuberances 31, a plurality of the second protuberances 22 coordinate with a plurality of the second recesses, thereby further increased the response area of electrode and amberplex 10, thereby further reduced ionic conduction resistance, improved current density and electric conductivity.Meanwhile, owing to there being a plurality of the first recesses 21 to coordinate with a plurality of the first protuberances 31, a plurality of the second protuberances 22 coordinate with a plurality of the second recesses, thereby amberplex 10 is coordinated firmly with electrode, have reduced the problem that the changing of the relative positions in use occurs flow battery.
Preferably, in a not shown embodiment, the first recess 21 and the second protuberance 22 are bulk, and the first recess 21 and the second protuberance 22 are a plurality of, a plurality of the first recesses 21 are divided into many groups, and the first recess 21 in same group arranges at intervals along first direction, a plurality of the second protuberances 22 are divided into many groups, and the second protuberance 22 in same group arranges at intervals along first direction, and many group the first recesses 21 are arranged alternately along second direction successively with many groups the second protuberance 22, between first direction and second direction, have angle.
Preferably, angle is 90 degree.Certainly, the angle between first direction and second direction can not be 90 degree, and staff can, according to using needs, determine the angular dimension between first direction and second direction.
Preferably, the height of the first protuberance 31 in the present invention and the deep equality of the first recess 21.
The first recess 21 in the present invention and the first protuberance 31, the second protuberance 22 and the second recess are cylindrical or hemisphere or cuboid (please refer to Fig. 6 and Fig. 7).Certainly, the first recess 21 and the first protuberance 31, the second protuberance 22 and the second recess can also be other shapes that adapt.
As second aspect of the present utility model, provide a kind of flow battery.Flow battery (for example: vanadium cell) comprise membrane electrode assembly, membrane electrode assembly is above-mentioned membrane electrode assembly.Preferably, the first electrode 20, the second electrode 30 are plane with the surface that collector plate fits.The first electrode 20 and the mutual interlock of the second electrode 30, and the first electrode 20 is contrary with the polarity of the second electrode 30.Because amberplex 10 is concaveconvex structure, be clamped between the first electrode 20 and the second electrode 30, thereby increased the response area of amberplex 10 with electrode, thereby improved current density, power density and the electric conductivity of flow battery.
As the 3rd aspect of the present invention, provide a kind of preparation method of electrode.Preparation method comprises:
Steps A 1: electrode material is carried out to foamable reaction to form porous electrode material;
Steps A 2: after porous electrode material cooled, carry out processing and forming to form above-mentioned electrode.
First, electrode material is formed for carrying out with amberplex the porous electrode material of ion-exchange after foamable reaction; Then, by by porous electrode material cooled, make porous electrode material become the raw material that can carry out processing and forming; Then, by above-mentioned raw materials is processed, thereby obtain the electrode with concaveconvex structure.
Preferably, the method for processing forming in the steps A in the present invention 2 is by cutting or polish manufacture electrode.
Preferably, the method for processing forming in the steps A in the present invention 2 is casting.
Preferably, the electrode material in the present invention is metal material, and steps A 1 also comprises:
Step S1: metal material is heated to molten condition;
Step S2: to adding 0.1～10% the thickener that weight content is metal material in the metal material of molten condition;
Step S3: add gas in the metal material of molten condition, and stir to form porous electrode material.
Metal material can be stainless steel, aluminium, molybdenum, lead, titanium, tantalum, zirconium, nickel etc.Due to metal material abundant raw material, thereby facilitate staff to produce electrode.
Preferably, the steps A in the present invention 1 also comprises:
Step S10: be heated to molten condition to be prepared into electrode material after be thermoplastic resin by thermoplastic resin and weight content 1～20% conductive auxiliary agent mixes;
Step S20: to add gas or weight content in electrode material be thermoplastic resin 1～10% blowing agent to form porous electrode material.
Thermoplastic resin can be polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl acetate etc.Because thermoplastic resin raw materials is abundant, thereby facilitate staff to produce electrode.
In a preferred embodiment, be first thermoplastic resin by thermoplastic resin and weight content 1～20% conductive auxiliary agent (such as carbon black, carbon nano-tube etc.) is mixed and heated to molten condition; Then, to passing into gas in mixture or adding weight content, be 1～10% blowing agent of thermoplastic resin; Then cooling and shaping, forms conductive foaming thermoplastics (being porous electrode material); Then, by cutting or the machining such as polishing, make cooled conductive foaming thermoplastics form concaveconvex structure.Certainly, can also in the process of thermoplastic resin polymerization, directly add weight content is 1～20% conductive auxiliary agent (for example conductive black) of thermoplastic resin and weight content be thermoplastic resin 1～10% blowing agent, the foaming of generation in-situ polymerization, thus conductive foaming thermoplastics obtained.
Preferably, the steps A in the present invention 1 also comprises:
Step S100: being thermosetting resin by thermosetting resin and weight content, 1～20% conductive auxiliary agent mixes to be prepared into electrode material;
Step S200: add electrode material and weight content and be 1～10% blowing agent of thermosetting resin monomer in reactor to form porous electrode material.
Thermosetting resin can be polyurethane, phenolic resins, Lauxite and epoxy resin etc.Due to thermosetting resin abundant raw material, thereby facilitate staff to produce porous electrode.
Preferably, by changing the adding proportion of conductive auxiliary agent, blowing agent, initator, curing agent, can regulate material is aperture, porosity, hardness and the conductivity of the porous electrode of conductive foaming thermoset plastics.Because aperture, porosity, hardness and the conductivity of porous electrode can change, thereby can prepare the porous electrode that meets different instructions for uses.
According to above-mentioned preparation method, be prepared as follows the electrode of stating in embodiment 1 to 9, and the electrode in the electrode in following comparative example 1, monocell and embodiment 1 to 9, monocell are carried out to contrast test, and obtain experimental data as shown in table 1.
Comparative example 1: select graphite felt to prepare porous electrode, the overall dimension of this electrode is that 30cm*30cm(profile is slab construction).And this porous electrode and collector plate, liquid flow frame, amberplex are assembled into monocell.
Embodiment 1: metal material is nickel.Implementation process: first metallic nickel should be heated in high temperature furnace to molten condition; Then to adding weight content in the melt in high temperature furnace, be 0.1% the carborundum (as thickener, certainly can also select other thickener particle, such as: aluminium oxide and magnesium oxide etc.) of metal material, thereby improve the viscosity of melt; Then, melt is cast in mould, and passes into nitrogen (certainly, can also pass into the mist of the gases such as air, argon gas or above-mentioned gas), stir; Then place coolingly, form foaming metal nickel (be porous electrode, please refer to Fig. 4).Then this porous electrode (projected area is 30cm*30cm) and collector plate, liquid flow frame, amberplex are assembled into monocell.Above-mentioned mould has concaveconvex structure, and because mould has concaveconvex structure, thereby the porous electrode of cooling forming has concaveconvex structure.Certainly, can also, by cutting or the machining such as polishing, make cooled foaming metal nickel form concaveconvex structure.
Embodiment 2: metal material is titanium.Implementation process: first Titanium should be heated in high temperature furnace to molten condition; Then to adding weight content in the melt in high temperature furnace, be 10% the aluminium oxide (as thickener, certainly can also select other thickener, such as: carborundum and magnesium oxide etc.) of metal material, thereby improve the viscosity of melt; Then, melt is cast in mould, and passes into nitrogen (certainly, can also pass into the mist of the gases such as air, argon gas or above-mentioned gas), stir; Then place coolingly, form foaming metal titanium (be porous electrode, please refer to Fig. 4).Then this porous electrode (projected area is 30cm*30cm) and collector plate, liquid flow frame, amberplex are assembled into monocell.Above-mentioned mould has concaveconvex structure, and because mould has concaveconvex structure, thereby the porous electrode of cooling forming has concaveconvex structure.Certainly, can also, by cutting or the machining such as polishing, make cooled foaming metal titanium form concaveconvex structure.
Embodiment 3: metal material is plumbous.Implementation process: first metallic lead should be heated in high temperature furnace to molten condition; Then to adding weight content in the melt in high temperature furnace, be 5% the silica (as thickener, certainly can also select other thickener, such as: aluminium carbide and magnesium oxide etc.) of metal material, thereby improve the viscosity of melt; Then, melt is cast in mould, and passes into nitrogen (certainly, can also pass into the mist of the gases such as air, argon gas or above-mentioned gas), stir; Then place coolingly, form foaming metal plumbous (be porous electrode, please refer to Fig. 4).Then this porous electrode (projected area is 30cm*30cm) and collector plate, liquid flow frame, amberplex are assembled into monocell.Above-mentioned mould has concaveconvex structure, and because mould has concaveconvex structure, thereby the porous electrode of cooling forming has concaveconvex structure.Certainly, can also, by cutting or the machining such as polishing, make the plumbous concaveconvex structure that forms of cooled foaming metal.
Embodiment 4: thermoplastic resin is polyvinyl chloride (matrix).Implementation process: by vinyl chloride (monomer), conductive black (conductive auxiliary agent), DOP(plasticizer), azodiisobutyronitrile (initator), Celogen Az (blowing agent) mix (in polymerization process in kneader according to the ratio of 105:20:3:2:1 under room temperature, the vinyl chloride of 105 parts is converted into the polyvinyl chloride of 100 parts as thermoplastic resin, reacts and prepares electrode with the conductive black that accounts for polyvinyl chloride percentage by weight 20%); Then compound is packed in mould, and heating-up temperature is promoted to 100～110 ℃, now compound polymerization reaction take place heat release, impel temperature to rise to 180～200 ℃, and plasticizing sizing at this temperature, 130～200 ℃ of bottom knockouts, thereby obtain conductive foaming polyvinyl chloride electrode (be porous electrode, please refer to Fig. 4).Then this porous electrode (projected area is 30cm*30cm) and collector plate, liquid flow frame, amberplex are assembled into monocell.Above-mentioned mould has concaveconvex structure, and because mould has concaveconvex structure, thereby the porous electrode of cooling forming has concaveconvex structure.Certainly, can also, by cutting or the machining such as polishing, make cooled conductive foaming polyvinyl chloride form concaveconvex structure.
Embodiment 5: thermoplastic resin is polystyrene (matrix).Implementation process: deionized water (solvent), styrene (monomer), hydroxyethylcellulose (dispersant), benzoyl peroxide (initator), pentane (blowing agent), carbon nano-tube (conductive auxiliary agent) are carried out to proportioning (in polymerization process according to 110:105:2:5:10:1, the styrene conversion of 105 parts be the polystyrene of 100 parts as thermoplastic resin, react and prepare electrode with the carbon nano-tube that accounts for polystyrene percentage by weight 1%); First, deionized water, styrene, hydroxyethylcellulose, benzoyl peroxide and carbon nano-tube are added in reactor, control mixing speed, be warming up to 90 ℃ and logical nitrogen protection; When reaction is carried out, after 5 hours, reactor being cooled to 80 ℃, and add pentane, then continue to be warming up to 100 ℃, when slaking is after 1 hour, reactor is cooled to 40 ℃, emptying discharging; And obtain by washing, dry, screening the polystyrene bead that contains blowing agent; Then the polystyrene bead that contains blowing agent is first placed in to the reactor prefoam 2 hours of 85 ℃, then at room temperature slaking 24 hours again; Expanded polystyrene particle after slaking is packed in mould, and lead to steam heated in mould, rear water flowing to be formed is cooling, thereby obtains conductive foaming polystyrene electrode (be porous electrode, please refer to Fig. 4).Then this porous electrode (projected area is 30cm*30cm) and collector plate, liquid flow frame, amberplex are assembled into monocell.Above-mentioned mould has concaveconvex structure, and because mould has concaveconvex structure, thereby the porous electrode of cooling forming has concaveconvex structure.Certainly, can also, by cutting or the machining such as polishing, make cooled conductive foaming polystyrene form concaveconvex structure.
Embodiment 6: thermoplastic resin is polypropylene (matrix).Implementation process: polypropylene (matrix), conductive black (conductive auxiliary agent), cumyl peroxide (crosslinking agent), divinylbenzene (assistant crosslinking agent), Celogen Az (blowing agent) are joined in single screw extrusion machine according to the ratio of 100:10:4:1:5, each section of temperature setting of extruder is set to 170 ℃, 210 ℃, 220 ℃, 190 ℃, screw speed is 40r/min, thereby extrudes the expanded polypropylene of the cuboid obtaining; Then by cutting or the machining such as polishing, make cooled expanded polypropylene form the electrode (be porous electrode, please refer to Fig. 4) with concaveconvex structure.Then this porous electrode (projected area is 30cm*30cm) and collector plate, liquid flow frame, amberplex are assembled into monocell.
Embodiment 7: thermosetting resin is polyurethane.Implementation process: first by 4, 4-methyl diphenylene diisocyanate (the first monomer), PPG (the second monomer), triethanolamine (catalyst), diethyl ethylene diamine (co-catalyst), silicone oil (surfactant), distilled water (blowing agent) and conductive black (conductive auxiliary agent) according to the ratio of 53:53:3:0.5:1.5:10:20 join with in the blender of high speed agitator (in polymerization process, 53 parts 4, the PPG of 4-methyl diphenylene diisocyanate and 53 parts is converted into the polyurethane of 100 parts as thermoplastic resin, react and prepare electrode with the conductive black that accounts for weight polyurethane percentage 20%), after blender stirs, material is discharged in blender, flow on the conveyer belt of continuous operation, now, material starts foaming, and within 30 minutes, post-foaming is complete, then slaking 72 hours at 70～100 ℃, thus obtain conductive foaming polyurethane plate (being porous electrode material), then by this sheet material by cutting or the machining such as polishing, make cooled conductive foaming polyurethane form concaveconvex structure (please refer to Fig. 4).Then this porous electrode (projected area is 30cm*30cm) and collector plate, liquid flow frame, amberplex are assembled into monocell.
Embodiment 8: thermosetting resin is phenolic resins.Implementation process: first phenol (the first monomer) and formaldehyde (the second monomer) are joined in reactor according to the ratio of 1:1, start stirring the heating water bath to 80 ℃ of certain speed; Then adding weight content is 3% hydrogen chloride (catalyst), weight content of thermosetting resin be thermosetting resin 1% carbon nano-tube (conductive auxiliary agent), continue to be heated to 95 ℃, react after 2 hours, with cold bath, mixture is cooled to below 70 ℃, by decompression dehydration, thereby obtain foaminess phenolic resins; After then foaminess phenolic resins (matrix), pentane (blowing agent), aliphatic alcohol polyethenoxy (surfactant), hydrochloric acid (curing agent) being joined to reactor high speed and are uniformly mixed according to the ratio of 100:5:1.5:3.5, inject mould, then in the thermostatic chamber of 75 ℃, carry out foamable reaction, after foamable reaction 8 hours, can obtain the porous electrode shown in Fig. 7.Then this porous electrode (projected area is 30cm*30cm) and collector plate, liquid flow frame, amberplex are assembled into monocell.Above-mentioned mould has concaveconvex structure, and because mould has concaveconvex structure, thereby the porous electrode of cooling forming has concaveconvex structure.
Embodiment 9: thermosetting resin is bisphenol A type epoxy resin.Implementation process: first bisphenol A type epoxy resin (matrix), triethylene tetramine (curing agent), Celogen Az (main foaming agent), toluene (blowing promotor), conductive black (conductive auxiliary agent), polysorbas20 (surfactant) are joined in reactor according to the ratio of 100:5:0.7:0.3:5:1.5, after rapid stirring mixes, inject mould; Then at 30 ℃, carry out foamable reaction, foamable reaction is after 30 minutes, at room temperature cooling standing, thereby obtains conductive foaming epoxy resin (being porous electrode) as shown in Figure 6.Then this porous electrode (projected area is 30cm*30cm) and collector plate, liquid flow frame, amberplex are assembled into monocell.Above-mentioned mould has concaveconvex structure, and because mould has concaveconvex structure, thereby the porous electrode of cooling forming has concaveconvex structure.
Table 1: embodiment 1 to 9 and the electrode of comparative example 1 and the test result of monocell
Experimental data by table 1 is known, compare with the monocell that the electrode assembling of slab construction of the prior art becomes, the monocell of the porous electrode assembling in the present invention has the advantages that current density is high, power density is large, and the electric conductivity of the monocell in the present invention is improved.
The foregoing is only preferred embodiment of the present utility model, be not limited to the utility model, for a person skilled in the art, the utility model can have various modifications and variations.All within spirit of the present utility model and principle, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection range of the present utility model.
Claims (10)
1. a membrane electrode assembly, comprises two electrodes and amberplex (10), and described amberplex (10) is clamped between two described electrodes, it is characterized in that, described two electrodes comprise:
The first electrode (20), the reaction surface of described the first electrode (20) has the first recess (21);
The second electrode (30), between described the first electrode (20) and described the second electrode (30) reaction surface respect to one another, form reaction compartment, the reaction surface of described the second electrode (30) has the first protuberance (31) coordinating with described the first recess (21), and described amberplex (10) forms the concaveconvex structure adapting with described reaction compartment shape between described the first electrode (20) and described the second electrode (30).
2. membrane electrode assembly according to claim 1, is characterized in that, described the first recess (21) is bar shaped, and the two ends of described the first recess (21) extend to the edge of described the first electrode (20) on the reaction surface of described the first electrode (20).
3. membrane electrode assembly according to claim 2, is characterized in that, described the first recess (21) is a plurality of, and a plurality of described the first recesses (21) arrange at intervals.
4. membrane electrode assembly according to claim 2, is characterized in that, described the first recess (21) has U-shaped or V-arrangement cross section.
5. membrane electrode assembly according to claim 1, it is characterized in that, described the first recess (21) is block, and described the first recess (21) is a plurality of, a plurality of described the first recesses (21) arrange at intervals along first direction and second direction, between described first direction and described second direction, have angle.
6. membrane electrode assembly according to claim 1, it is characterized in that, the reaction surface of described the first electrode (20) also comprises the second protuberance (22), and the reaction surface of described the second electrode (30) also comprises the second recess coordinating with described the second protuberance (22).
7. membrane electrode assembly according to claim 6, it is characterized in that, described the first recess (21) and described the second protuberance (22) are bulk, and described the first recess (21) and described the second protuberance (22) are a plurality of, and described the second protuberance (22) arranges at intervals with described the first recess (21), a plurality of described the first recesses (21) are arranged alternately along first direction and second direction successively with a plurality of described the second protuberances (22), between described first direction and described second direction, have angle.
8. membrane electrode assembly according to claim 6, it is characterized in that, described the first recess (21) and described the second protuberance (22) are bulk, and described the first recess (21) and described the second protuberance (22) are a plurality of, a plurality of described the first recesses (21) are divided into many groups, and described the first recess (21) in same group arranges at intervals along first direction, a plurality of described the second protuberances (22) are divided into many groups, and described the second protuberance (22) in same group arranges at intervals along described first direction, and described the first recess of many groups (21) is arranged alternately along second direction successively with described the second protuberance of many groups (22), between described first direction and described second direction, there is angle.
9. membrane electrode assembly according to claim 6, is characterized in that, described the first recess (21) and described the first protuberance (31), described the second protuberance (22) and described the second recess are cylindrical or hemisphere or cuboid.
10. a flow battery, comprises membrane electrode assembly, it is characterized in that, described membrane electrode assembly is the membrane electrode assembly described in any one in claim 1 to 9.
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| CN103413954A (en) * | 2013-08-26 | 2013-11-27 | 中国东方电气集团有限公司 | Membrane electrode assembly, flow cell and preparation method of electrode |
| CN103413954B (en) * | 2013-08-26 | 2016-03-02 | 中国东方电气集团有限公司 | The preparation method of membrane electrode assembly, flow battery and electrode |
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