CN101800298A - Frame laminate material and application thereof in preparing membrane electrode with sealed frame core component - Google Patents
Frame laminate material and application thereof in preparing membrane electrode with sealed frame core component Download PDFInfo
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- CN101800298A CN101800298A CN201010125455A CN201010125455A CN101800298A CN 101800298 A CN101800298 A CN 101800298A CN 201010125455 A CN201010125455 A CN 201010125455A CN 201010125455 A CN201010125455 A CN 201010125455A CN 101800298 A CN101800298 A CN 101800298A
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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
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- 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 frame laminate material and application thereof in preparing a membrane electrode with a sealed frame core component. The frame laminate material has a structure of laminating a support membrane, a first adhesion layer, a frame membrane, a second adhesion layer and a protection membrane in turn. During preparing the membrane electrode with the sealed frame core component, the frame laminate is punched according to a certain rule before the preparation of an anode sealed frame and a cathode sealed frame is finished; and in the preparation process, the thickness and intensity of the frame laminate layer are enhanced in the presence of the support membrane. Therefore, the frame laminate has better processing feasibility and dimension stability; the prepared sealed frame has higher contraposition precision; and the preparation process is more easy to control. After the preparation of the sealed frame is finished, the support membrane is stripped. A catalyst layer is coated on an active region of a polymer ion exchange membrane before or after the preparation of the sealed frame so as to prepare the core component with the sealed frame; and then the core component with the sealed frame is compounded with an anode gas diffusion layer and a cathode gas diffusion layer to prepare the membrane electrode respectively.
Description
Invention field
The present invention relates to a kind of method for preparing the membrane electrode of being with sealed frame core component, wherein the employed in the preparation raw material of anode seal frame and negative electrode sealed frame are a kind of laminated material.
Background of invention
Ion exchange polymer film fuel cell (PEMFC) has high power density; high-energy conversion efficiency; cold-starting; advantages of environment protection; promise to be most the power source of zero disposal of pollutants electric automobile; make it in today that global energy crisis and environment go from bad to worse, become one of focus of international new and high technology competition.Membrane electrode (MEA) is the most key assembly of ion exchange polymer film fuel cell, mainly form by two good porous gas diffusion layer of conductivity and the one layer of polymeric amberplex that is clipped in the middle, on the interface on ion exchange polymer film and gas diffusion layers both sides, be evenly distributed with the catalyst of the caused electrochemical reaction of a large amount of tiny dispersions, hydrogen evenly spreads to catalyst surface generation electrochemical reaction through relative gas diffusion layers respectively with oxygen (air), the electronics that produces in the electrochemical reaction is drawn the forming circuit loop by conductor by external circuit.
Ion exchange polymer film in the ion exchange polymer film fuel cell plays proton conducting, intercept electronics directly constitutes the effect that loop and blocking-up hydrogen and oxygen (air) directly contact at inside battery.In order to reduce the resistance of proton conduction, in the ion-exchange membrane fuel cell field, general in the world used thickness is especially preferentially selected the amberplex of thickness less than 30 μ m less than the amberplex of 50 μ m.
[US3134697, EP700108A2] introduced a kind of membrane electrode, and its ion exchange polymer film size is greater than gas diffusion layers, and when membrane electrode during in sealing, the ion exchange polymer film that exceeds gas diffusion layers is sandwiched between the battery pole plates.
The characteristics of above-mentioned this method are, do not adopt other encapsulant and use ion exchange polymer film as gas and current blocked layer merely.Because ion exchange polymer film thickness is extremely thin, easily causes mechanical damage in the battery pack process of assembling.In use, ion exchange polymer film is subjected to humidity effect easily again and the change of size takes place, further aggravation mechanical damage, thus occur damagedly in use for some time, can't really reach the effect of sealing.So a lot of encapsulating methods occurred at this situation,, made the preparation process of membrane electrode also have nothing in common with each other because the encapsulating method that adopts is varied.
[US6261711] introduced the sealing ring of fuel cell, and the sealing ring that fuel cell comprises is positioned at the groove of fuel cell flow field board.
[US5464700] introduced the gasket system of a kind of fuel cell membrane electrode assembly (MEA) usefulness, be used for reducing as far as possible the amount of polymer dielectric film material in the fuel cell, concrete grammar is to adopt gasket materials at periphery, rather than the polymer dielectric film material.
[CN200480030791.7] introduced a kind of core component and membrane electrode with encapsulant.It adopts thermoplastic polymer, elastic sealed body and thermosetting polymer is encapsulant.There is the encapsulant protection at the edge of amberplex, and gas diffusion layers all adopts encapsulant that negative electrode and anode reactant are completely cut off.
The fuel cell that [US6159628] introduces comprises the porous substrate, and they are full of thermoplastic by periphery.
[CN200380105886.6] and [US6057054] introduced a kind of membrane electrode, and ion exchange polymer film and gas diffusion layers bond by thermoplastics.
[US6165634] discloses a kind of encapsulating method of fuel battery, and the neighboring area of described fuel cell module is flooded by encapsulant or adhered to each other, and described encapsulant has covered the outward flange of described battery component.
[US6159628] and [US2001/0001052] discloses a kind of MEA with edge sealing substrate, and described edge sealing substrate is to form by the periphery of thermoplastic polymer being clamp-oned described base material.Described edge sealing substrate is by thermoplastic, polymeric materials is adhered on the ion exchange polymer film.
[CN200810197098.9] introduced a kind of method for preparing band sealed frame membrane electrode, the characteristics of this method are to be laminated with one deck sealed frame respectively on the two sides of the ion exchange polymer film that extends gas diffusion layers, and this 3-tier architecture has strengthened the intensity of membrane electrode edge seal material greatly.This method need thrust processing completely to the frame lamination of multilayer in the process of preparation sealing frame.
The present invention respectively is laminated with one deck sealed frame on the two sides of the ion exchange polymer film at membrane electrode edge.Different is but with above-mentioned each invention, the present invention is when the preparation sealed frame, part layer to multilayer frame lamination thrusts processing entirely, and part layer partly thrusts processing, and carry out stripping and applying, making has the existence of support membrane all the time to strengthen the thickness and the intensity of frame lamination in the preparation process, make the frame lamination have and process feasibility and dimensional stability preferably, the sealed frame of preparation has higher aligning accuracy, preparation process is easier to control, improve producing feasibility widely, improved the efficient that serialization is produced.
Summary of the invention
The object of the invention aims to provide a kind of frame laminate material and the application on preparation band sealed frame core component membrane electrode thereof.Sealed frame with this frame laminate material preparation has higher aligning accuracy, and preparation process is easier to control, is suitable for large-scale continuous production.
The membrane electrode of band sealed frame core component of the present invention, its structure comprises:
A) ion exchange polymer film, it has an anode surface, a cathode plane, and outward flange;
B) anode catalyst layer, it contacts with at least a portion anode surface of described ion exchange polymer film;
C) cathode catalyst layer, it contacts with at least a portion cathode plane of described ion exchange polymer film;
D) anode seal frame, it has contact-making surface and outward flange, its contact-making surface contacts with at least a portion anode surface of described ion exchange polymer film, the outward flange coplane of its outward flange and ion exchange polymer film or the complete overlie polymer amberplex of anode seal frame outward flange;
E) negative electrode sealed frame, it has contact-making surface and outward flange, its contact-making surface contacts with at least a portion cathode plane of described ion exchange polymer film, its outward flange or negative electrode sealed frame complete overlie polymer amberplex outward flange neat mutually with the outward flange of ion exchange polymer film;
F) anode gas diffusion layer, it contacts with described anode catalyst layer at least a portion;
G) cathode gas diffusion layer, it contacts with described cathode catalyst layer at least a portion.
The present invention uses a kind of frame laminate material when membrane electrode anode seal frame for preparing the band sealed frame core component and negative electrode sealed frame.
Realize the technical scheme of the object of the invention:
A kind of frame laminate material is characterized in that, this frame laminate material is support membrane, first adhesion layer, frame film, second an adhesion layer and diaphragm stack structure mutually successively;
Wherein, described support membrane, it occupy the one side outermost and works to support laminated construction, also has simultaneously the protecting border membrane interaction, support membrane is that resin, rubber, plastics, paper or metal material constitute, or the composite material of above-mentioned any two or more materials formations, and the thickness of support membrane is 0.010～1.000mm, preferred thickness is 0.040～0.200mm, and more preferably thickness is 0.060～0.100mm;
Described first adhesion layer, it is attached to support membrane, play the effect that adheres to support membrane and frame film, the material that constitutes first adhesion layer is the material with cementation, the thickness of first adhesion layer is 0.001～0.100mm, preferred thickness is 0.002～0.050mm, and more preferably thickness is 0.005～0.020mm;
Described frame film, it contacts with first adhesion layer, be when the preparation membrane electrode, constitute the critical material of anode seal frame layer and negative electrode sealed frame layer, have the reaction gas of obstruct, intercept electric current, increase effects such as ion exchange polymer film mechanical strength and protection ion exchange polymer film, described frame film is made of resin, rubber, plastics or paper, or the composite material of above-mentioned any two or more materials formations, the thickness of frame film is 0.005～0.400mm, preferred thickness is 0.010～0.200mm, and more preferably thickness is 0.015～0.100mm;
Described second adhesion layer, it is attached to the frame film, when the preparation membrane electrode, is the important materials that constitutes anode seal frame and negative electrode sealed frame, play the effect of mucoadhesive polymers amberplex and frame film, second adhesion layer is to be made of the material with cementation; The thickness of second adhesion layer is 0.001～0.100mm, and preferred thickness is 0.002～0.050mm, and more preferably thickness is 0.005～0.020mm;
Described diaphragm, it occupy the another side outermost, plays protection second adhesion layer and frame film, and described diaphragm is made of resin, rubber, plastics, paper or metal material, or the composite material that above-mentioned any two or more materials constitute constitutes; Diaphragm thickness is 0.005～0.500mm, and preferred thickness is 0.010～0.100mm, and more preferably thickness is 0.015～0.050mm.
Described frame lamination also comprises following characteristics:
1) when peelling off diaphragm, second adhesion layer can not taken away by protected film, and complete being attached on the frame film;
2) when peelling off support membrane, first adhesion layer can be taken away by supported membrane fully, does not have any part and is attached to the frame film.
Frame laminate material of the present invention is used for preparing the membrane electrode of being with sealed frame core component.
When the present invention adopts the membrane electrode of described frame laminate material preparation band sealed frame core component, before being laminated with ion exchange polymer film, its frame film and the second adhesion layer stamping-out can be gone out the active region; The active region of the active region of described frame film and second adhesion layer is a zone that hollows out, and these regional characteristics are for can allow reactant to be transferred to catalyst layer from gas diffusion layers after being prepared into membrane electrode.
Adopt the process of the membrane electrode of described frame laminate material preparation band sealed frame core component to be:
1), frame lamination stamping-out is divided into non-active region and active region: simultaneously carry out stamping-out towards support membrane from one of diaphragm, the degree of depth of stamping-out is less than gross thickness, be not less than the thickness sum of diaphragm+second adhesion layer+frame film+first adhesion layer, thrusting fully of the diaphragm of active region, second adhesion layer, frame film and first adhesion layer partly thrust support membrane and can be continued to play and support and protective effect;
2), peel off the diaphragm of the active region of frame lamination, second adhesive agent layer of active region, the frame film of active region earlier, and the diaphragm of non-active region, allow the frame lamination utilize second adhesion layer and the ion exchange polymer film of non-active region to be laminated with then, be laminated with finish after, peel off the support membrane and first adhesion layer, obtain ion exchange polymer film with anode seal frame and negative electrode sealed frame;
3), anode catalyst layer and cathode catalyst layer are coated to the active region of the ion exchange polymer film of anode seal frame and negative electrode sealed frame one side respectively, be prepared into the core component of band sealed frame, be laminated with anode gas diffusion layer and cathode gas diffusion layer gas diffusion layers respectively again, promptly make the membrane electrode of band sealed frame core component.
In described preparation process 2) in; perhaps peel off the diaphragm of the non-active region of frame lamination earlier; and the frame film of second adhesion layer of the diaphragm in retentive activity zone, active region and active region; allow the frame lamination utilize second adhesion layer and the ion exchange polymer film of non-active region to be laminated with then; be laminated with finish after; peel off the frame film of support membrane, first adhesion layer, active region, second adhesion layer of active region and the diaphragm of active region, obtain ion exchange polymer film with anode seal frame and negative electrode sealed frame.
Described membrane electrode in the preparation, earlier anode surface and the cathode plane at ion exchange polymer film applies anode catalyst layer and cathode catalyst layer respectively, is laminated with anode seal frame and negative electrode sealed frame then respectively; Perhaps elder generation is laminated with anode seal frame and negative electrode sealed frame respectively at the anode surface and the cathode plane of ion exchange polymer film, and then applies anode catalyst layer and cathode catalyst layer respectively; Be laminated with anode gas diffusion layer and cathode gas diffusion layer at last respectively, make the membrane electrode of band sealed frame core component.
Described ion exchange polymer film is made up of polymer dielectric, has the side chain of band sulfonate group, and does not contain in the aqueous solution polymer of other group that can ionization in the polymer.It can be the polymer that perfluorinated sulfonic resin, sulfonation trifluorostyrene, polymethyl-benzene base sulfonic acid siloxanes, sulfonated polyether-ether-ketone, sulfonated polystyrene-polyethylene and ethylene copolymers, sulfonated polystyrene-polyethylene and butylene-polystyrene and other meet this condition.For example
(Dupont Chemical, Wilmington DE) and FlemionTM (Asahi Glass Co.Ltd., Tokyo, Japan).Described ion exchange polymer film thickness is usually less than 0.100mm, preferably less than 0.050mm, most preferably less than 0.030mm.Described polymer dielectric most preferably is
The equivalent of described polymer dielectric is generally 1200 or littler, and more preferably 1100 or littler, most preferably equivalent about 1000.
The ion exchange polymer film of selecting for use in order to gain in strength, is beneficial to the preparation of anode seal frame and negative electrode sealed frame, can be laminated construction as shown in Figure 4, and 6 is first diaphragm among Fig. 4, and 7 is ion exchange polymer film, and 8 is second diaphragm.First diaphragm and second diaphragm are made of polymer, and polymer comprises resin, rubber or plastics.First diaphragm and the second diaphragm thickness are 0.002～0.2mm, and preferred thickness is 0.005～0.1mm.
In the present invention's practice, the frame film of frame laminate material is selected polymer for use, can be polyamide (PA), heat-resistant polyamide (HPN), PETG (PET), polybutylene terephthalate (PBT) (PBT), ABS resin, polypropylene (PP), polytetrafluoroethylene (PTFE), acrylic, Merlon (PC), polyimides (PI), PPN (polyacrylic a kind of), polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA) or ethylene copolymer.More preferably polyimides (PI), heat-resistant polyamide (HPN), PETG (PET), polybutylene terephthalate (PBT) (PBT) or polytetrafluoroethylene (PTFE).
First adhesion layer and second adhesion layer of frame laminate material are made of the material with adhesive effect.Any suitable material with adhesive effect can be used in the practice of the present invention.Preferred adhesives, comprise epoxide-resin glue, phenolic resins, polyurethane, Lauxite, melmac, butyl rubber, polyisobutene or neoprene adhesive, or natural rubber type pressure-sensitive adhesive, or with butadiene-styrene rubber, polyisobutene, polyisoprene, butyl rubber, butadiene rubber, neoprene, synthetic rubber such as acrylonitrile-butadiene rubber separately or and with being the synthetic rubber and the reclaimed rubber pressure-sensitive adhesive of main body, or be that the thermoplastic elastomer of representative is the thermoplastic elastomer pressure-sensitive adhesive of primary raw material with SIS (SIS) and SBS (SBS), or Acrylic Pressure Sensitive Adhesive, or acrylic glue, or organic pressure-sensitive gel stick, or with polyurethane, polyester, ethylene-vinyl acetate copolymer (EVA), PVC etc. are the pressure-sensitive adhesive of main body, or UV glue.More preferably Acrylic Pressure Sensitive Adhesive, acrylic adhesive, organic pressure-sensitive gel stick or epoxy-phenolic aldehyde pressure-sensitive adhesive.
Coated on both sides has the core component of catalyst layer, and Catalytic Layer is made of noble metal catalyst and the ionic conduction polymer with ionic conduction function.Noble metal catalyst comprises no loaded catalyst and the catalyst that supports is arranged.Noble metal comprises Pt, Pd, Ru, Rh, Ir, Os, Au or Ag.It is the material of high-specific surface area, good conductivity, good stability that the carrier of the catalyst that supports is arranged, and comprising: graphite, carbon black, carbon nano-tube, carbon fiber, C-SBA-15, fullerene, conducting polymer, Al
2O
3, SiO
2, MgO, TiO
2, molecular sieve.Ionic conduction polymer is the anionic polymer that has sulfonate group or carboxylate group side chain, and do not contain in the aqueous solution polymer of other group that can ionization in the polymer, comprise that sulfonation or carboxylated perfluorinated resin, trifluorostyrene, PSI, polyether-ether-ketone, polybenzimidazoles, polybenzoxazole, polybenzothiozole, polyethylene, poly arylidene thio-ester, polystyrene-poly ethylene copolymer, polystyrene-poly ethene and butylene-polystyrene and other meet the polymer of this condition.Catalytic Layer can be coated to by any suitable method and form core component on the ion exchange polymer film.Described method comprises that manual brushing, silk screen printing, notch bar apply, the coating of coiling rod, carrying liqs coating, slit feed blade coating, three roller coat are covered, spraying or medium transfer printing.
Above-mentioned anode and cathode gas diffusion layer are formed by gas diffusion layers matrix and microporous layers.Described gas diffusion layers matrix is generally carbon paper, carbon fiber felt or carbon cloth.Microporous layers is generally the material and the ptfe emulsion of high-specific surface area, good conductivity, good stability and forms.The material of high-specific surface area, good conductivity, good stability comprises graphite, carbon black in the gas diffusion layers microporous layers.The length of gas diffusion layers and width are not less than the length and the width of active region B (seeing accompanying drawing 2b) respectively.
Characteristics of the present invention are that the frame material is designed to a kind of lamination, and through thrusting and partly thrusting processing, the existence that support membrane is arranged in preparation process all the time is to strengthen the thickness and the intensity of frame lamination, make the frame material have the dimensional stability of processing preferably in the feasibility and the course of processing, technology difficulty reduces greatly, operate more easyly, be suitable for large-scale continuous production.If there be not thrusting and partly thrust process in this technology, and be laminated with these two important processing of just peelling off support membrane after finishing, sealed frame is the mid portion disappearance after carrying out complete stamping-out, undercapacity, shape is difficult to control, when being laminated with ion exchange polymer film, operation easier is very big again, also is unwell to continuous batch production.Laminated construction among the present invention and thrust and partly thrust, be laminated with back stripping these process characteristics, for the precision in course of processing control and serialization processing belt great facility, by prepared sealed frame of the present invention, the precision height, process velocity is fast, damage to ion exchange polymer film is little, and the process that is laminated with is convenient and swift.Sealed frame can well support and protect ion exchange polymer film in the process of preparation core component and membrane electrode.Prepared membrane electrode core component, frame intensity is reliable, and performance is secure; In assembling process, also be difficult for sustaining damage, behind the long-play membrane electrode be difficult for collaborating, problem such as gas leakage, good endurance.
Description of drawings
Fig. 1 is a frame laminated construction schematic diagram
Fig. 2 a, be the cross sectional representation of frame lamination after thrusting processing
Fig. 2 b is the vertical plane schematic diagram of frame lamination after thrusting processing
Fig. 3 a is the structural representation that thrusts after frame lamination after the processing is peelled off the diaphragm 5a of non-active region
Fig. 3 b is the frame lamination that thrusts after the processing, peels off the structural representation behind the second adhesion layer 4b of the frame film 3b of diaphragm 5b, active region of active region and active region
Fig. 4 is an ion exchange polymer film laminated construction schematic diagram
Fig. 5 a is after peelling off raw-material first diaphragm 6 of ion exchange polymer film, the structural representation after being laminated with the frame single face shown in Fig. 3 a
Fig. 5 b is after peelling off raw-material first diaphragm 6 of ion exchange polymer film, the structural representation after being laminated with the frame single face shown in Fig. 3 b
Fig. 6 a is the structural representation after the two sides frame of mode shown in Fig. 3 a and ion exchange polymer film are laminated with
Figure Fig. 6 b is the structural representation after the two sides frame of mode shown in Fig. 3 b and ion exchange polymer film are laminated with
Fig. 7 is the ion exchange polymer film structural representation of band anode and cathode sealed frame
Describe this frame laminate material and the application process on preparation band sealed frame core component membrane electrode thereof in detail below in conjunction with accompanying drawing:
A. incite somebody to action frame laminate material as shown in Figure 1, carry out stamping-out from one of diaphragm 5 towards support membrane 1 side by the mode shown in Fig. 2 a, the degree of depth of stamping-out is less than gross thickness, be not less than the thickness sum of the diaphragm 5+ second adhesion layer 4+ frame film 3+ first adhesion layer 2, vertical plane behind the stamping-out such as Fig. 2 b, the a-quadrant is a non-active region, and the B zone is active region (being the stamping-out zone);
B. with following two kinds of optional modes the frame lamination through stamping-out that steps A obtains is handled:
1) shown in Fig. 3 a, peels off the diaphragm 5a of non-active region;
2) shown in Fig. 3 b, peel off the diaphragm 5b of active region, the frame film 3b of active region and the second adhesion layer 4b of active region;
C. the ion exchange polymer film raw material structure as shown in Figure 4,6 is first diaphragm among the figure, 7 is ion exchange polymer film, 8 is second diaphragm;
D. peel off raw-material first diaphragm 6 of ion exchange polymer film, the structure that obtains with step B is laminated with, and the structure after being laminated with is respectively shown in Fig. 5 a and Fig. 5 b;
E. get the process of another batch frame lamination repeating step A, B;
F. after will peelling off second diaphragm 8 through the lamination that step D obtains, be laminated with mutually with the material that step e obtains, the structure after being laminated with is respectively shown in Fig. 6 a and Fig. 6 b;
G. (1) will be as the structure of Fig. 6 a, after peelling off the diaphragm 5b of the first adhesion layer 4b, active region, both sides of frame film 3b, the active region, both sides of first adhesion layer (2a+2b), the active region, both sides of support membrane 1, the both sides of both sides respectively, obtain as shown in Figure 7 the cloudy sealed frame of band and the ion exchange polymer film of anode seal frame;
(2) will be as the structure of Fig. 6 b, peel off first adhesion layer (2a+2b) of support membrane 1, both sides of both sides respectively after, obtain the ion exchange polymer film of band two sides sealed frame as shown in Figure 7;
H. with the anode surface of the ion exchange polymer film of band two sides sealed frame shown in Figure 7 and cathode plane coated anode catalyst and cathod catalyst respectively, obtain core component with sealed frame;
I. will be laminated with the core component of being with sealed frame with the anode gas diffusion layer of microporous layers and the cathode gas diffusion layer of band microporous layers, obtain a kind of membrane electrode with sealed frame core component.
Wherein, the process of described coated anode Catalytic Layer of step H and cathode catalysis layer; also can in step D, realize: the ion exchange polymer film raw material are peelled off first diaphragm 6 and second diaphragm 8; at anode surface and cathode plane difference coated anode catalyst and cathod catalyst; the structure that obtains with step B is laminated with again, continues step e, F, G, I process (deducting second diaphragm, 8 these processes of peelling off in the step F) then.
Embodiment
Illustrate content of the present invention below in conjunction with embodiment.For a person skilled in the art, be not difficult to find out that the present invention has many improvement and alternative form,, should be appreciated that the present invention is not subjected to the restriction of following illustrative embodiments as long as they do not deviate from scope of the present invention and principle.
Among each embodiment, the frame membrane material of frame lamination is polyimides (PI), and first adhesion layer and second adhesion layer are acrylic glue, and support membrane and diaphragm material are polypropylene (PP).
1) employed frame laminate material both sides of the edge are parallel; the thickness of its support membrane, first adhesion layer, frame film, second adhesion layer and diaphragm is respectively 100 μ m, 10 μ m, 20 μ m, 10 μ m, 20 μ m, and first adhesion layer and second adhesion layer are adhesive.The frame lamination is carried out stamping-out; allow cutting die perpendicular to the frame lamination; stamping-out active region towards support membrane from diaphragm; the stamping-out degree of depth is 80～140 μ m; the stamping-out zone is a rectangle; be of a size of 50x50mm, wherein two edges of active region are parallel with the both sides of the edge of frame laminate material, and distance is 25mm.After stamping-out is finished, keep each layer of active region of frame lamination not peel off;
2) be that first diaphragm of the Nafion212 film lamination of 100mm is peelled off with DuPont company width, it is intact to keep second diaphragm and Nafon212 film to adhere to;
3) strip step 1) in through the diaphragm of the lamination non-active region behind the stamping-out, with step 2) in through peeling off the Nafion212 film lamination of first diaphragm, utilize the adhesive of second adhesion layer that non-active region exposes to be laminated with;
4) be laminated with finish after, peel off second diaphragm of Nafion212 film lamination;
5) strip step 1) middle diaphragm through the lamination non-active region behind the stamping-out, the side of exposing with Nafion212 film in the step 4) is laminated with mutually;
6) be laminated with finish after; peel off the support membrane of both sides, first adhesion layer of active region, both sides, first adhesion layer of both sides non-active region, the frame film of active region, both sides, second adhesion layer of active region, both sides, the diaphragm of active region, both sides, obtain Nafion212 film with sealed frame.
7) by the method for spraying, spray catalyst in the active area zone.It is 60% Pt/C catalyst that negative electrode and anode catalyst are all selected mass content for use, anode-catalyzed agent content 0.3mg/cm2, cathode catalysis agent content 0.5mg/cm2.It is 1100 Nafon resin that Catalytic Layer intermediate ion conducting polymer is selected equivalent for use.The mass ratio of catalyst and ionic conduction polymer is 3: 1 in the Catalytic Layer.
8) membrane electrode preparation
The gas diffusion layers that is of a size of the band microporous layers of 52x52mm is hot-pressed onto on the core component of the band sealed frame for preparing in the step 6) and prepares membrane electrode.The gas diffusion layers of band microporous layers is the GDL34BC of SGL company, and hot pressing temperature is 130 ℃, and hot pressing pressure is 1.5Mpa, and hot pressing time is 3 minutes.
9) monocell performance test
The mea for preparing in the step 8) installed in the ion exchange polymer film fuel battery test platform test.Employing is a collector plate at the graphite cake that a side has parallel channel, and end plate is gold-plated corrosion resistant plate.Operating condition is: PCO2=PH2=0MPa, battery temperature are 60 ℃, and anode 100% humidification, humidification temperature are 70 ℃.In current density is under the 600mA/cm2, and the monocell output voltage is 0.72V, and its power density is for being 0.43W/cm2.
Embodiment 2
1) both sides of the edge of employed frame laminate material are parallel; the thickness of its support membrane, first adhesion layer, frame film, second adhesion layer and diaphragm is respectively 150 μ m, 10 μ m, 20 μ m, 10 μ m, 20 μ m; first adhesion layer and second adhesion layer are adhesive; wherein the adhesive of first adhesion layer is certain special state; with can not take place after ion exchange polymer film contacts bondingly, what also do not have adhesive when peeling off partly or entirely is attached to ion exchange polymer film.The frame lamination is carried out stamping-out, allow the edge of a knife of cutting die perpendicular to the lamination plane, stamping-out active region towards support membrane from diaphragm, the stamping-out degree of depth is 80～180 μ m, the stamping-out zone is a rectangle, be of a size of 50x50mm, wherein two edges of active region are parallel with the frame laminate material both sides of the edge, and distance is 25mm;
2) be that first diaphragm of the Nafion212 film lamination of 100mm is peelled off with DuPont company width, it is intact to keep second diaphragm and Nafion212 film to adhere to;
3) peel off in the step 1) through the diaphragm of the frame material active region behind the stamping-out, second adhesion layer of active region, the frame film of active region, peel off the diaphragm of non-active region again, with step 2) in through peeling off the Nafion212 film of first diaphragm, utilize the adhesive of second adhesion layer that non-active region exposes to be laminated with;
4) be laminated with finish after, peel off second diaphragm of Nafion212 film lamination;
5) strip step 1) in through the diaphragm of the frame lamination active region behind the stamping-out, second adhesion layer of active region, the frame film of active region, peel off the diaphragm of non-active region again, the side of exposing with Nafion212 film in the step 4) is laminated with mutually;
6) be laminated with finish after, peel off the support membrane of both sides and first adhesion layer of both sides, obtain Nafion212 film with sealed frame.
7) by the method for spraying, spray catalyst in the active area zone.It is 60% Pt/C catalyst that negative electrode and anode catalyst are all selected mass content for use, anode-catalyzed agent content 0.3mg/cm2, cathode catalysis agent content 0.5mg/cm2.It is 1100 Nafion resin that Catalytic Layer intermediate ion conducting polymer is selected equivalent for use.The mass ratio of catalyst and ionic conduction polymer is 3: 1 in the Catalytic Layer.
8) membrane electrode preparation
The gas diffusion layers that is of a size of the band microporous layers of 52x 52mm is hot-pressed onto on the core component of the band sealed frame for preparing in the step 6) and prepares membrane electrode.The gas diffusion layers of band microporous layers is the GDL34BC of SGL company, and hot pressing temperature is 130 ℃, and hot pressing pressure is 1.5Mpa, and hot pressing time is 3 minutes.
9) monocell performance test
The mea for preparing in the step 8) installed in the ion exchange polymer film fuel battery test platform test.Employing is a collector plate at the graphite cake that a side has parallel channel, and end plate is gold-plated corrosion resistant plate.Operating condition is: PCO2=PH2=0MPa, battery temperature are 60 ℃, and anode 100% humidification, humidification temperature are 70 ℃.In current density is under the 600mA/cm2, and the monocell output voltage is 0.73V, and its power density is 0.44W/cm2.
Claims (17)
1. a frame laminate material is characterized in that, this frame laminate material is the folded mutually successively structure of support membrane (1), first adhesion layer (2), frame film (3), second adhesion layer (4) and diaphragm (5);
Wherein, described support membrane is that resin, rubber, plastics, paper or metal material constitute, or the composite material of above-mentioned any two or more materials formations, and the thickness of support membrane is 0.010～1.000mm;
Described first adhesion layer is made of the material with cementation, and the thickness of first adhesion layer is 0.001～0.100mm;
Described frame film is made of resin, rubber, plastics or paper, or the composite material of above-mentioned any two or more materials formations, and the thickness of frame film is 0.005～0.4mm;
Described second adhesion layer is made of the material with cementation, and the thickness of second adhesion layer is 0.001～0.1mm;
Described diaphragm is made of resin, rubber, plastics, paper or metal material, or the composite material formation of above-mentioned any two or more materials formations, and diaphragm thickness is 0.005～0.5mm.
2. frame laminate material as claimed in claim 1, it is characterized in that, the used material with cementation of described first adhesion layer and second adhesion layer is selected epoxide-resin glue for use, phenolic resins, polyurethane, Lauxite, melmac, butyl rubber, polyisobutene or neoprene adhesive, or natural rubber type pressure-sensitive adhesive, or with butadiene-styrene rubber, polyisobutene, polyisoprene, butyl rubber, butadiene rubber, neoprene or acrylonitrile-butadiene rubber separately or and with being the synthetic rubber or the reclaimed rubber pressure-sensitive adhesive of main body, or with SIS, or SBS is the thermoplastic elastomer pressure-sensitive adhesive of primary raw material, or Acrylic Pressure Sensitive Adhesive, or acrylic glue, or organic pressure-sensitive gel stick, or with polyurethane, polyester, ethylene-vinyl acetate copolymer or PVC are the pressure-sensitive adhesive of main body, or light-cured type UV glue.
3. frame laminate material as claimed in claim 1, it is characterized in that the used material with cementation of described first adhesion layer and second adhesion layer is selected Acrylic Pressure Sensitive Adhesive, acrylic adhesive, organic pressure-sensitive gel stick or epoxy-phenolic aldehyde pressure-sensitive adhesive for use.
4. frame laminate material as claimed in claim 1, it is characterized in that, described frame membrane material is selected polymer for use, comprising: polyamide, heat-resistant polyamide, PETG, polybutylene terephthalate (PBT), ABS resin, polypropylene, polytetrafluoroethylene, acrylic, Merlon, polyimides, polypropylene PPN, polyethylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol or ethylene copolymer.
5. frame laminate material as claimed in claim 1 is characterized in that, described frame membrane material is selected polyimides, heat-resistant polyamide, PETG, polybutylene terephthalate (PBT) or polytetrafluoroethylene for use.
6. frame laminate material as claimed in claim 1 is characterized in that, the thickness of described support membrane is 0.040～0.200mm.
7. frame laminate material as claimed in claim 1 is characterized in that, the thickness of described support membrane is 0.060～0.100mm.
8. frame laminate material as claimed in claim 1 is characterized in that, the thickness of described first adhesion layer is that thickness is 0.002～0.050mm.
9. frame laminate material as claimed in claim 1 is characterized in that, the thickness of described first adhesion layer is that thickness is 0.005～0.020mm.
10. frame laminate material as claimed in claim 1 is characterized in that, the thickness of described frame film is 0.010～0.200mm.，
11. frame laminate material as claimed in claim 1 is characterized in that, the thickness of described frame film is 0.015～0.100mm.
12. frame laminate material as claimed in claim 1 is characterized in that, the thickness of described second adhesion layer is 0.002～0.050mm.
13. frame laminate material as claimed in claim 1 is characterized in that, the thickness of described second adhesion layer is 0.005～0.020mm.
14. the application of the described frame laminate material of claim 1 is characterized in that, is used for preparing the membrane electrode of being with sealed frame.
15. the method with the membrane electrode of the described frame laminate material of claim 1 preparation band sealed frame is characterized in that preparation process is:
1), the frame laminate material stamping-out is divided into non-active region and active region: simultaneously carry out stamping-out towards support membrane from one of diaphragm, the degree of depth of stamping-out is less than gross thickness, be not less than the thickness sum of diaphragm+second adhesion layer+frame film+first adhesion layer, thrusting fully of the diaphragm of active region, second adhesion layer, frame film and first adhesion layer partly thrust support membrane and can be continued to play and support and protective effect;
2), peel off the active region of frame lamination and the diaphragm of non-active region, second adhesive agent layer of active region, the frame film of active region earlier, allow the frame lamination utilize second adhesion layer and the ion exchange polymer film of non-active region to be laminated with then, be laminated with finish after, peel off the support membrane and first adhesion layer, obtain ion exchange polymer film with anode seal frame and negative electrode sealed frame;
3), anode catalyst layer and cathode catalyst layer are coated to the active region of the ion exchange polymer film of anode seal frame and negative electrode sealed frame one side respectively, be prepared into the core component of band sealed frame, be laminated with anode gas diffusion layer and cathode gas diffusion layer respectively again, promptly make the membrane electrode of band sealed frame core component.
16. frame laminate material as claimed in claim 15 is used to prepare the method for the membrane electrode of being with sealed frame; it is characterized in that; in described preparation process 2) in; perhaps peel off the diaphragm of the non-active region of frame lamination earlier; and the diaphragm in retentive activity zone; second adhesion layer and frame film; allow the frame lamination utilize second adhesion layer and the ion exchange polymer film of non-active region to be laminated with then; be laminated with finish after; peel off support membrane; first adhesion layer; the frame film of active region; second adhesion layer of active region and the diaphragm of active region obtain the ion exchange polymer film with anode seal frame and negative electrode sealed frame.
17. frame laminate material as claimed in claim 15 is used to prepare the method for the membrane electrode of being with sealed frame, it is characterized in that, described membrane electrode in the preparation, anode surface and cathode plane at ion exchange polymer film applies anode catalyst layer and cathode catalyst layer respectively earlier, is laminated with anode seal frame and negative electrode sealed frame then respectively; Perhaps elder generation is laminated with anode seal frame and negative electrode sealed frame respectively at the anode surface and the cathode plane of ion exchange polymer film, and then applies anode catalyst layer and cathode catalyst layer respectively; Be laminated with anode gas diffusion layer and cathode gas diffusion layer at last respectively, make the membrane electrode of band sealed frame core component.
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| CN111755726B (en) * | 2020-07-10 | 2024-02-20 | 魔方氢能源科技(江苏)有限公司 | Membrane electrode preparation method, membrane electrode and fuel cell |
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