CN202585634U - Polyelectrolyte laminated membrane - Google Patents
Polyelectrolyte laminated membrane Download PDFInfo
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- CN202585634U CN202585634U CN2011204566782U CN201120456678U CN202585634U CN 202585634 U CN202585634 U CN 202585634U CN 2011204566782 U CN2011204566782 U CN 2011204566782U CN 201120456678 U CN201120456678 U CN 201120456678U CN 202585634 U CN202585634 U CN 202585634U
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- polyelectrolyte
- membrane
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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 polyelectrolyte laminated membrane, overcomes the defects that when a polymer electrolyte membrane is stored in a long term, folds can increase and the like, and the polymer electrolyte membrane can be easily peeled without any fold and be used. The polyelectrolyte laminated membrane comprises a resin supporting membrane and the polymer electrolyte membrane, wherein the polymer electrolyte membrane is arranged on the resin supporting membrane in laminated mode, thickness of the resin supporting membrane is 5 to 500 micrometers, and thickness of the polymer electrolyte membrane is 1 to 500 micrometers. Corona discharge treatment or plasma discharge treatment is carried out at least to the laminated surface of the resin supporting membrane, openings are cut on the same plane of the whole polymer electrolyte membrane at the thickness direction and a part of the laminated surface of the resin supporting membrane at the thickness direction, the openings are cut according to the shape of paper sheets, or the openings are cut on the same plane along the longitudinal direction or the transverse direction.
Description
Technical field
The utility model relate to a kind of on the resin support membrane lamination the long-pending film of polyelectrolyte layers of polyelectrolyte membrane is arranged.
Background technology
Fuel cell in battery through electrochemical reaction by fuel (hydrogen source) and oxidant (oxygen) acquisition electric energy, the chemical energy of fuel is directly changed into electric energy.The act as a fuel fuels sources of battery is used with the oil that comprises protium headed by the pure hydrogen, natural gas (methane etc.), methyl alcohol etc.
Fuel cell self does not have mechanical part, thereby seldom produces noise, and through from outside sustainable supply fuel and oxidant, can generate electricity on the principle semipermanently.
The electrolyte that uses in the fuel cell is divided into liquid electrolyte and solid electrolyte, wherein uses polyelectrolyte membrane to be called as solid macromolecule shape fuel cell as electrolytical fuel cell.Particularly, solid macromolecule shape fuel cell is compared at low temperatures with the fuel cell of other kinds and also can be worked, thereby expects its replacement power source, home-use co-generation unit, portable purposes with generator as automobile etc.
Solid macromolecule shape fuel cell possesses film/assembly of electrode at least, and said film/assembly of electrode is that gas-diffusion electrode that lamination has electrode catalyst layer and a gas diffusion layers engages on the two sides of polyelectrolyte membrane and forms.Said here polyelectrolyte membrane is meant strong acid groups such as having sulfonic group, carboxylic acid group in the macromolecular chain and the material with character of selective permeation proton.As such polyelectrolyte membrane, suitable what use is that the perfluor of the high Nafion of chemical stability (registered trade mark, du pont company manufacturing) representative is the proton exchange resins film.
The thickness that such polyelectrolyte membrane normally has flexibility is the film of 20～100 μ m, if directly handle with the state of film, then has the shortcoming that is easy to generate fold, damage.Therefore, consider from preservation till making film/assembly of electrode and the aspect in the processing, on the resin support membrane (Backing Film) that the expectation lamination is put down in writing in non-patent literature 1.
Yet the common water absorption of polyelectrolyte membrane is high, and film can swelling under high humility.Thus, if the adaptation of polyelectrolyte membrane and resin support membrane is poor, then can exist under the high humidity environment in summer polyelectrolyte membrane easily from the resin support membrane peel off, or the problem of entering bubble easily.If produce such problem, then when the preservation of laminated film, or laminated film is cut to predetermined size and peels off when using, can become the defective item that in polyelectrolyte membrane, has fold or other shortcomings, have the problem that can't be used for fuel cell.
As being used for solution to the problems described above, disclose in the patent documentation 1 and 2 with one deck at least of laminated film cut fully on the thickness direction, one deck method of on thickness direction, not cutting at least.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2007-114270 communique
Patent documentation 2: TOHKEMY 2007-299551 communique
Non-patent literature
Non-patent literature 1:Dennis E.urtin, Robert D.Lousenberg, Timothy J.Henry, Paul C.Tangeman, Monica E. Tisack, J.Power Sources, 131 (2004), 41-48
The utility model content
But polyelectrolyte membrane is compared more softness with the resin support membrane usually, thereby peels off polyelectrolyte membrane with after long preservation, being difficult to corrugationless.Therefore, when polyelectrolyte being peeled off use, form the defective item that has fold or other shortcomings easily, have the problem that can't be used for fuel cell.
In view of the foregoing; The purpose of the utility model is to provide long-pending film of a kind of polyelectrolyte layers and manufacturing approach thereof; Can not increase shortcomings such as fold even this polyelectrolyte membrane carries out long preservation yet, and can be easily, corrugationless polyelectrolyte membrane is peeled off use.
The inventor finds; The long-pending film of following polyelectrolyte layers can solve above-mentioned problem: it is in that lamination has polyelectrolyte membrane on the resin support membrane that Corona discharge Treatment or plasma discharge handle having implemented with the lamination face side of polyelectrolyte membrane lamination at least; Wherein, The part of the lamination face side on the whole thickness direction with the resin support membrane of the thickness direction of polyelectrolyte membrane in identical plan-position according to page shape (piece blade profile) otch, or indulge or horizontal arbitrary direction otch in identical upper edge, plan-position, accomplished the utility model based on above-mentioned discovery.
That is, the utility model is described below.
[1]
A kind of polyelectrolyte layers amasss film, and it is the long-pending film of polyelectrolyte layers with resin support membrane and polyelectrolyte membrane, wherein,
At thickness be on the resin support membrane of 5～500 μ m lamination thickness is arranged is the polyelectrolyte membrane of 1～500 μ m; Said resin support membrane is being implemented Corona discharge Treatment or plasma discharge processing with the lamination face side of said polyelectrolyte membrane lamination at least
The part of the lamination face side on the whole thickness direction with said resin support membrane of the thickness direction of said polyelectrolyte membrane, is perhaps indulged in identical upper edge, plan position approach or horizontal arbitrary direction has been cut otch according to page shape otch in identical plan position approach.
[2]
Like the long-pending film of above-mentioned [1] described polyelectrolyte layers, wherein, the degree of depth of the portions cut on the thickness direction of the said resin support membrane thickness whole with respect to the resin support membrane is 5～95%.
[3]
Like the long-pending film of above-mentioned [1] or [2] described polyelectrolyte layers, wherein, said polyelectrolyte membrane comprises that to have sulfonic fluorine be polyelectrolyte.
[4]
A kind of manufacturing approach, it is the manufacturing approach with long-pending film of polyelectrolyte layers of resin support membrane and polyelectrolyte membrane, this manufacturing approach comprises following operation:
(1) lamination face side said resin support membrane and said polyelectrolyte membrane lamination is implemented Corona discharge Treatment or plasma discharge treatment procedures;
(2) implement the said polyelectrolyte membrane of lamination on the resin support membrane that said Corona discharge Treatment or plasma discharge handle, obtaining the operation of laminated film;
(3) for said laminated film, the part with lamination face side said polyelectrolyte membrane lamination on the thickness direction of and said resin support membrane whole at the thickness direction of said polyelectrolyte membrane cuts out the operation of otch.
Even the long-pending film of the polyelectrolyte layers of the utility model can not increase the shortcomings such as fold of polyelectrolyte membrane yet after long preservation, and can enough hands easily peel off down to corrugationless polyelectrolyte membrane from the long-pending film of polyelectrolyte layers by the end.
Description of drawings
Fig. 1 representes to cut according to page shape the schematic top plan view of the long-pending film of polyelectrolyte layers of otch.
Fig. 2 representes to cut according to page shape the schematic side view of the long-pending film of polyelectrolyte layers of otch.
Symbol description
1 cuts the long-pending film of polyelectrolyte layers of otch according to page shape
2 polyelectrolyte membranes
3 resin support membranes
4 otch
Embodiment
Below, the embodiment (hereinafter being called " this execution mode ") of the utility model is elaborated.Need to prove that the utility model is not limited to following execution mode, can in the scope of its main points, carry out various distortion and implement.
The long-pending film of the polyelectrolyte layers of this execution mode is the long-pending film of polyelectrolyte layers with resin support membrane and polyelectrolyte membrane, wherein,
At thickness be on the resin support membrane of 5～500 μ m lamination thickness is arranged is the polyelectrolyte membrane of 1～500 μ m; Said resin support membrane is being implemented Corona discharge Treatment or plasma discharge processing with the lamination face side of said polyelectrolyte membrane lamination at least
The part of the lamination face side on the whole thickness direction with said resin support membrane of the thickness direction of said polyelectrolyte membrane, is perhaps indulged in identical upper edge, plan position approach or horizontal arbitrary direction has been cut otch according to page shape otch in identical plan position approach.
" page shape " refers to here, around the in-plane of the long-pending film of such cutting polyelectrolyte layers as depicted in figs. 1 and 2, thus shape that can many ground processing polyelectrolyte membranes.
Do not limit the polyelectrolyte of the polyelectrolyte membrane that constitutes this execution mode is special, suitable especially is following shown in such fluorine be polyelectrolyte.
Being that polyelectrolyte is not special to fluorine limits, and can enumerate Nafion (registered trade mark; The du pont company manufacturing), Aciplex (registered trade mark; The manufacturing of Asahi Chemical Corp of Japan), Flemion (registered trade mark; Asahi Glass Co., Ltd of Japan makes system) etc. have the proton exchange group shown in the formula (1) perfluorocarbon polymer as typical example.
[CF
2CX
1X
2]
a-[CF
2-CF(-O-(CF
2-CF(CF
2X
3))
b-Oc-(CFR
1)
d-(CFR
2)
e-(CF
2)
f-X
4)]
g…(1)
(in the formula, X
1, X
2And X
3Represent independently that respectively halogen atom or carbon number are 1～3 perfluoroalkyl, 0≤a＜1,0＜g≤1, a+g=1,0≤b≤8, c is 0 or 1, d, e and f represent the number (wherein, d+e+f is not equal to 0) of 0～6 scope, R respectively independently
1And R
2Represent independently that respectively halogen atom, carbon number are 1～10 perfluoroalkyl or dichlorodifluoromethan base, X
4Expression-COOH ,-SO
3H ,-PO
3H
2,-PO
3(Z is hydrogen atom, metallic atom (Na, K, Ca etc.) or amine (NH to HZ
4, NH
3R, NH
2R
2, NHR
3, NR
4(R is alkyl or aryl))).)
Wherein, owing to have the tendency that proton conductivity uprises, thereby the perfluorocarbon polymer shown in formula (2) or the general formula (3) more preferably.
[CF
2CF
2]
a-[CF
2-CF(-O-(CF
2-CF(CF
3))
b-O-(CF
2)
f-X
4)]
g …(2)
(in the formula, 0≤a＜1,0＜g≤1, a+g=1,1≤b≤3,1≤f≤8, X
4Expression-COOH ,-SO
3H ,-PO
3H
2Or-PO
3H.)
[CF
2CF
2]
a-[CF
2-CF(-O-(CF
2)f-X
4)]
g…(3)
(in the formula, 0≤a＜1,0＜g≤1, a+g=1,1≤f≤8, X
4Expression-COOH ,-SO
3H ,-PO
3H
2Or-PO
3H.)
Above-mentioned perfluorocarbon polymer can also be the copolymer that further comprises from the unit of comonomers such as perfluoroolefines such as hexafluoropropylene, CTFE or perfluoroalkyl vinyl ether.
As fluorine is the manufacturing approach of polyelectrolyte, for example, can use United States Patent (USP) the 5th, 281, and No. 680 specification, the spy of Japan open the method for putting down in writing in flat 7-252322 communique, the 5th, 608, No. 022 specification of United States Patent (USP).
As fluorine is the polyelectrolyte beyond the polyelectrolyte; For example can enumerate to polyethersulfone resin, polyether-ether-ketone resin, phenol-formaldehyde resin, polystyrene resin, polytrifluorostyrene resin, trifluorostyrene resin, gather (2; 3-diphenyl-1,4-phenylate) resin, gather (allyl ether ketone) resin, gather (allyl ether sulfone) resin, gather (phenyl quinoxaline) resin, gather the material of having introduced sulfonic group, carboxylic acid group in the macromolecule that (benzyl silane) resin, polystyrene-grafting-ETFE resin, polystyrene-grafting-polyvinylidene fluoride resin, polystyrene-grafting-TFE, polyimide resin, polybenzimidazole resin etc. have hydrocarbon portion; The material of phosphoric acid, polyphosphoric acid, inorganic acid has perhaps mixed in these resins, functional group etc.
Do not limit the proton exchange capacity of the polyelectrolyte membrane in this execution mode is special, be preferably 0.5～4.0 milliequivalent/g, more preferably 0.8～4.0 milliequivalent/g further is preferably 0.9～1.5 milliequivalent/g.Through using the bigger polyelectrolyte membrane of proton exchange capacity, can under the low humidified condition of high temperature, demonstrate higher proton-conducting, when using it for fuel cell, can access higher power output.On the other hand, if the proton exchange capacity surpasses 4.0 milliequivalents/g, then has the tendency that the dissolving in hot water increases.
Here; The proton exchange capacity of polyelectrolyte membrane is measured through following manner: behind the weighing polyelectrolyte membrane; Be impregnated in 25 ℃ the saturated sodium-chloride water solution; Stir and carried out ion-exchange reactions in 1 hour, in this solution, add phenolphthalein solution, and carry out acid-base titration with the sodium hydrate aqueous solution of 0.01N as indicator.
As polyelectrolyte membrane, also comprise through carried out the polyelectrolyte membrane that strengthens to the microfibre of the internal mix porous matter reinforcing material of the film that comprises above-mentioned polyelectrolyte, nonwoven fabrics shape sheet material, organic or inorganic etc.
The thickness of the polyelectrolyte membrane in this execution mode is 1～500 μ m, is preferably 2～200 μ m, further is preferably 5～100 μ m, is preferably 10～50 μ m especially.When thickness was thick more, then durability was high more, but then resistance, initial stage characteristic are poor more when being used for fuel cell, in addition, when thickness is thin more, then durability with peel off after processing property poor more.Consider that from above-mentioned aspect the thickness of the polyelectrolyte membrane of this execution mode is adjusted into the scope of 1～500 μ m.
Here, the thickness of polyelectrolyte membrane is measured through the micrometer of contact.
[resin support membrane]
Do not limit the resin support membrane that constitutes the long-pending film of polyelectrolyte layers in this execution mode is special, for example can enumerate by PETG, PEN, polystyrene, polyethylene, polypropylene, Merlon, polyimides, polyether-ketone, polyphenylene sulfide, polyether sulfone, polyketone, gather the common resin support membrane that (ethylene/tetrafluoroethylene) copolymer, polyvinylidene fluoride, polytetrafluoroethylene etc. constitute.Among above-mentioned, the resin molding of PETG system is owing to peel off polyelectrolyte membrane easily in making situation such as film/assembly of electrode, thereby considers it is preferred from the aspect of handling.
The thickness of the resin support membrane in this execution mode is 5～500 μ m, is preferably 10～300 μ m, further is preferably 15～200 μ m, is preferably 20～100 μ m especially.If the thickness of resin support membrane is lower than 5 μ m, then there is fold easily in the resin support membrane, if surpass 500 μ m, then is difficult to utilize hot pressing or lamination etc. to carry out engaging of polyelectrolyte membrane and resin support membrane.
Resin support membrane in this execution mode is being implemented Corona discharge Treatment or plasma discharge processing with the lamination face side of above-mentioned polyelectrolyte membrane lamination at least.Through implement Corona discharge Treatment or plasma discharge processing in the lamination face side of resin support membrane; Hydrophiling has been carried out on the surface of resin support membrane; Thereby good with the adaptability of the strong polyelectrolyte membrane of hydrophily, can obtain the long-pending film of polyelectrolyte layers that the adaptation of resin support membrane and polyelectrolyte membrane is improved.
Said here Corona discharge Treatment is meant following processing etc.: like discharge handbook (exclusive distribution shop Ohmsha; Ltd., clear and 57 years discharge handbook publication committees of revision new edition, electric association compile) p.102～106 in that kind of record; To resin support membrane surface, opposite electrodes such as opposed stainless steel wire, tungsten line, and apply high frequency and high voltage; Thereby in atmosphere, produce corona discharge, functional group such as the carbonyl that generates thus, carboxyl, hydroxyl and electronics are shone directly on the resin support membrane.
In addition; Said here plasma discharge is handled and is meant following processing etc.: like discharge handbook (exclusive distribution shop Ohmsha; Ltd., clear and 57 years discharge handbook publication committees of revision new edition, electric association compile) p.281～329 in that kind of record; In atmosphere, produce plasma discharge through the high-voltage arc plasma discharge; Plasma discharge electron irradiation and activation are carried out in resin support membrane surface, and functionality polar groups such as the carbonyl that will be generated by discharge activation oxygen simultaneously, carboxyl, hydroxyl are imparted to resin support membrane surface.
The wetting of surfaces tension force of the resin support membrane after above-mentioned Corona discharge Treatment or plasma discharge are handled is preferably 40-70mN/m, and more preferably 44-68mN/m further is preferably 48-66mN/m.
Here, wetting tension can utilize the wetting tension experimental liquid to measure according to JIS K-6768.
Polyelectrolyte layers in this execution mode has amassed rete above-mentioned polyelectrolyte membrane and above-mentioned resin support membrane; The part of the lamination face side on the whole thickness direction with said resin support membrane of the thickness direction of said polyelectrolyte membrane, is perhaps indulged in identical upper edge, plan position approach or horizontal arbitrary direction has been cut otch according to page shape otch in identical plan position approach.
Here, " part of the lamination face side on the thickness direction " expression is not at the whole otch that cuts of thickness direction, but cuts otch from the lamination face with the predetermined degree of depth.The predetermined degree of depth is preferably 5～95%, more preferably 10～80%, further is preferably 15～60% with respect to the thickness of resin support membrane.
In addition, " in identical plan position approach " is meant, when observing laminated film from the top, at the same position otch of polyelectrolyte membrane and resin support membrane.
(manufacturing approach of the long-pending film of polyelectrolyte layers)
The manufacturing approach of the long-pending film of the polyelectrolyte layers of this execution mode comprises following operation:
(1) lamination face side said resin support membrane and said polyelectrolyte membrane lamination is implemented Corona discharge Treatment or plasma discharge treatment procedures;
(2) implement the said polyelectrolyte membrane of lamination on the resin support membrane that said Corona discharge Treatment or plasma discharge handle, obtaining the operation of laminated film;
(3) for said laminated film, the part with lamination face side said polyelectrolyte membrane lamination on the thickness direction of and said resin support membrane whole at the thickness direction of said polyelectrolyte membrane cuts out the operation of otch.
Below be that the example of the polyelectrolyte membrane that constitutes of polyelectrolyte describes to having used by fluorine.
Fluorine is that polyelectrolyte can be made with acid treatment through after utilizing following method with the precursor polymer polymerization shown in the formula (4), being hydrolyzed.
[CF
2CX
1X
2]
a-[CF
2-CF(-O-(CF
2-CF(CF
2X
3))
b-O
c-(CFR
1)
d-(CFR
2)
e-(CF
2)
f-X
5)]
g …(4)
(in the formula, X
1, X
2And X
3Represent independently that respectively halogen atom or carbon number are 1～3 perfluoroalkyl, 0≤a＜1,0＜g≤1, a+g=1, b are the number of 0～8 scope, and c is 0 or 1, and d, e and f represent the number (wherein, d+e+f is not equal to 0) of 0～6 scope, R respectively independently
1And R
2Represent independently that respectively halogen atom, carbon number are 1～10 perfluoroalkyl or dichlorodifluoromethan base, X
5Expression-COOR
3,-COR
4Or SO
2R
4(R
3Be that carbon number is 1～3 alkyl (not carrying out fluorine replaces), R
4Be halogen atom).)
Precursor polymer shown in the above-mentioned general formula (4) can be made through making fluorinated olefins compound and the copolymerization of ethylene fluoride based compound.
As the fluorinated olefins compound, for example can enumerate CF
2=CF
2, CF
2=CFCl, CF
2=CCl
2Deng.
As the ethylene fluoride based compound, for example can enumerate CF
2=CFO (CF
2)
z-SO
2F, CF
2=CFOCF
2CF (CF
3) O (CF
2)
z-SO
2F, CF
2=CF (CF
2)
z-SO
2F, CF
2F (OCF
2CF (CF
3))
z-(CF
2)
Z-1-SO
2F, CF
2=CFO (CF
2)
z-CO
2R, CF
2=CFOCF
2CF (CF
3) O (CF
2)
z-CO
2R, CF
2=CF (CF
2)
z-CO
2R, CF
2=CF (OCF
2CF (CF
3))
z-(CF
2)
2-CO
2R (here, Z representes 1～8 integer, and R representes that carbon number is 1～3 alkyl (not carrying out fluorine replaces)) etc.
As the polymerization of above-mentioned precursor polymer, for example can enumerate following method: after being dissolved in the ethylene fluoride based compound in the freon equal solvent, make itself and the gas reaction of fluorinated olefins compound and the solution polymerization process that carries out polymerization; The mass polymerization of not using the freon equal solvent and carrying out polymerization; With the ethylene fluoride based compound with surfactant put into make its emulsification in the water after, with the gas reaction of fluorinated olefins compound and the emulsion polymerization that carries out polymerization; Or the like.In above-mentioned any polymerization, reaction temperature all is preferably 30～90 ℃, and reaction pressure all is preferably 280～1100kPa.
Not special qualification of measuring under 270 ℃, the condition of load 2.16kgf according to JIS K-7210 for above-mentioned precursor polymer of melt flow index (hereafter for " MI "); Be preferably 0.001g/10 minute～1000g/10 minute; More preferably 0.01g/10 minute～100g/10 minute, further be preferably 0.1g/10 minute～10g/10 minute.If the MI of precursor polymer is lower than 0.001g/10 minute, then have the tendency that is difficult to machine-shaping, if surpass 1000g/10 minute, have the tendency of the easy variation of durability when then polyelectrolyte membrane being used for fuel cell.
As precursor polymer being shaped to membranaceous method, use the common method of forming (T modulus method, inflation method, rolling process etc.) that melt extrudes.
Be shaped to membranaceous precursor polymer and contact through making, the ion-exchange based precursor is hydrolyzed, produce polyelectrolyte membrane with reaction liquid.At this moment, the hydrolysis of ion-exchange based precursor can be implemented in alkali metal hydroxide aqueous solution, in order further to increase hydrolysis speed, the preferred solution that uses than higher temperatures.As such method, for example, can enumerate put down in writing in the japanese kokai publication sho 61-19638 communique, use the aqueous solution contain 20～25% NaOH in 16 hours method of 70～90 ℃ of hydrolysis process etc.
In addition, in order to make the film swelling, promote hydrolysis speed, can also use the pure series solvent that utilizes alkali metal hydroxide aqueous solution and methyl alcohol, ethanol, propyl alcohol that kind; The perhaps method that is hydrolyzed of the mixture of water-miscible organic solvent such as dimethyl sulfoxide (DMSO).As such method, for example can enumerate following method: the aqueous solution of putting down in writing in the japanese kokai publication sho 57-139127 communique, use contains 11～13% potassium hydroxide and 30% dimethyl sulfoxide (DMSO) is in 1 hour method of 90 ℃ of hydrolysis process; The aqueous solution of putting down in writing in the japanese kokai publication hei 3-6240 communique, use contains 15～50 quality % alkali metal hydroxides and 0.1～30 quality % water-soluble organic compounds is in 20 minutes～24 hours method of 60～130 ℃ of hydrolysis process; Or the like.
After handle forming ion-exchange group through said hydrolyzed, further utilize inorganic acid such as hydrochloric acid to carry out acid treatment, thereby can produce polyelectrolyte membrane.
As stated, the resin support membrane is being implemented Corona discharge Treatment or plasma discharge processing with the lamination face side of polyelectrolyte membrane lamination at least.The corona discharge surface processing device that Corona discharge Treatment for example can utilize Kasuga Electric K. K. to make carries out with power output 1kW, 50kHz.Plasma discharge is handled the plasma irradiating surface modification device that for example can utilize Kasuga Electric K. K. to make and is carried out with power output 600W, output voltage 10kV.
Will be through the polyelectrolyte membrane and the resin support membrane lamination of having implemented the processing of Corona discharge Treatment or plasma discharge of said method manufacturing; Under the state of lamination,, can obtain the long-pending film of polyelectrolyte layers thus through using known compact technique such as hot pressing, roll-in, vacuum pressing or lamination to engage.
In addition; Also can be with above-mentioned likewise with small pieces (particle, the Powdered) hydrolysis of above-mentioned precursor polymer; Be dissolved or dispersed in the solvent of appropriateness and process uniform solute doping agent, be coated on its curtain coating on the resin support membrane after, distillation removes desolvates; Carry out drying and/or heat-treat, process the long-pending film of polyelectrolyte layers thus at 100～200 ℃.
Make the long-pending film of this polyelectrolyte layers on the platform on plane or on the backing roll that is rotating with the preceding end in contact of cutlery (said cutlery rotates with the polyelectrolyte membrane face of the long-pending film of the polyelectrolyte layers of sending here continuously synchronously); The page shape according to preliminary dimension cuts out otch in identical plan position approach to make the part of the lamination face side on the thickness direction of the whole and resin support membrane of the thickness direction of (a) polyelectrolyte membrane successively, perhaps (b) vertical or horizontal arbitrary direction cuts out otch with preliminary dimension in identical upper edge, plan position approach.The throughput direction of the long-pending film of the polyelectrolyte layers that said here vertical expression is sent here continuously, the Width of horizontal expression film.Page shape is meant the state of cutting otch at the both direction of vertical and horizontal.For the coiling thing of roller shape, be meant the state of cutting otch at the both direction of length direction and Width.
Through cutting out the otch of above-mentioned that kind, can access with the long-pending film of the polyelectrolyte layers of corrugationless, the state lamination that can peel off easily.The degree of depth about the otch of the part on the thickness direction of resin support membrane; Consider from the aspect of even cutting polyelectrolyte membrane; Gross thickness with respect to the resin support membrane is preferably more than 5%; Consider from aspect that improve to handle property, be preferably below 95%, more preferably 10～80%, further be preferably 15～60% with respect to the gross thickness of resin support membrane.Through on the thickness direction of resin support membrane, cutting out the degree of depth is 5～95% otch with respect to the gross thickness of resin support membrane; When peeling off polyelectrolyte membrane; Through bending the resin support membrane lightly at incision site, just can corrugationless ground, easily peel off polyelectrolyte membrane.
(film/assembly of electrode)
When polyelectrolyte membrane is used for solid macromolecule shape fuel cell, use as polyelectrolyte membrane closely being remained on the film/assembly of electrode (membrane/electrode assembly) (hereinafter being also referred to as " MEA ") that forms between anode and the negative electrode.Here, anode is made up of the anode catalyst layer with proton-conducting, and negative electrode is made up of the cathode catalyst layer with proton-conducting.In addition, anode catalyst layer and the cathode catalyst layer outer surface separately object that engages gas diffusion layers respectively is also referred to as MEA.
As the manufacture method of MEA, can use known method.The manufacture method of MEA for example write up in JOURNAL OF APPLIED ELECTROCHEMISTRY, 22 (1992) p.1-7 in.
(solid macromolecule shape fuel cell)
Solid macromolecule shape fuel cell in this execution mode can be mutually combined the anode of above-mentioned MEA and negative electrode by the electronic conductivity material in the outside that is positioned at polyelectrolyte membrane through being situated between and obtain.As the manufacture method of solid macromolecule shape fuel cell, can use known method.The manufacture method of solid macromolecule shape fuel cell for example write up in FUEL CELL HANDBOOK (VAN NOSTRAND REINHOLD, A.J.APPLEBY et.al, ISBN0-442-31926-6), chemical One Point; Fuel cell (second edition); The refined husband in the mouth of a valley; Younger sister's tail learn to be compiled, upright altogether the publication in (1992) etc.The running of solid macromolecule shape fuel cell is through supplying with hydrogen, carrying out to another electrode (negative electrode) supply oxygen or air to an electrode (anode).
Even the long-pending film long preservation of the polyelectrolyte layers of this execution mode can not increase the shortcomings such as fold of polyelectrolyte membrane yet; Can corrugationless when peeling off polyelectrolyte membrane ground, easily peel off, therefore can significantly reduce the disqualification rate when making MEA.
In addition, also can suitably peel off the polyelectrolyte membrane of the long-pending film of polyelectrolyte layers in this execution mode, be used for chloric alkali electrolysis, water electrolysis, halogen acids electrolysis, salt electrolysis, oxygen concentrator, humidity sensor, gas sensor etc.About polyelectrolyte membrane being used for the method for oxygen concentrator, for example, can be with reference to chemical engineering, 56 (3), the method for record in No. the 4th, 879,016, (1992) or the United States Patent (USP) p.178-180.About polyelectrolyte membrane being used for the method for humidity sensor, for example, can be with reference to Japanese ion-exchange association will, 8 (3), p.154-165 (1997) or J.Fangetal., Macromolecules, the methods of record in 35,6070 (2002).About polyelectrolyte membrane being used for the method for gas sensor, for example, can be with reference to analytical chemistry, 50 (9); P.585-594 (2001) or X.Yang, S.Johnson, J.Shi, T.Holesinger; B.Swanson:Sens.Actuators B, the method for 45,887 (1997) middle records.
Embodiment
Below, through embodiment this execution mode is carried out brightly specifically, but this execution mode is not limited to following embodiment.
Each evaluation assessment and determination method in this execution mode are described below.
[thickness]
The thickness of film utilizes the micrometer of contact to measure.
[proton exchange capacity]
The proton exchange capacity of polyelectrolyte membrane is measured through following manner: behind the weighing polyelectrolyte membrane; Be impregnated in 25 ℃ the saturated sodium-chloride water solution; Stir and carried out ion-exchange reactions in 1 hour; In this solution, add phenolphthalein solution, and carry out acid-base titration with the sodium hydrate aqueous solution of 0.01N as indicator.
[embodiment 1]
(making of polyelectrolyte membrane)
As polyelectrolyte membrane, make by [CF as follows
2CF
2]
0.812-[CF
2-CF (O-(CF
2)
2-SO
3H)]
0.188The dielectric film that shown perfluorinated sulfonic acid polymer (hereinafter being called " PFS ") constitutes.
At first, as the precursor polymer of PFS, make tetrafluoroethene and CF
2=CFO (CF
2)
2-SO
2The perfluorocarbon polymer of F (MI:3.0).This precursor polymer is melt extruded and be shaped to the thickness of about 50 μ m, and the film that moulding is obtained contacts 4 hours with the reaction liquid that contains 15 quality % potassium hydroxide, 30 quality % dimethyl sulfoxide (DMSO)s and 55 quality % water at 60 ℃, and processing is hydrolyzed.Thereafter, film was flooded 4 hours in 60 ℃ water, then dipping water-washed away acid with ion-exchange after 3 hours in 60 ℃ 2N aqueous hydrochloric acid solution, obtained polyelectrolyte membrane.
The proton exchange capacity of resulting polyelectrolyte membrane is that 1.22 milliequivalents/g, thickness are 50 μ m.
(making of resin support membrane)
As the resin support membrane, use the PETG system film that has carried out Corona discharge Treatment as follows.
As PETG system film, used thickness is the TEIJIN of the Supreme Being people Du Pont film manufactured of 75 μ m
TMTetoron film (hereinafter being called the PET film).
For the lamination face side PET film and the polyelectrolyte membrane lamination, the corona discharge superficial treatment system that uses Kasuga Electric K. K. to make carries out Corona discharge Treatment with the condition of power output 1kW, 50kHz.The wetting of surfaces tension force of resulting resin support membrane is 58mN/m.
(manufacturing of the long-pending film of polyelectrolyte layers)
Then, the above-mentioned polyelectrolyte membrane that 10cm is square is long-pending with the PET rete of having implemented above-mentioned Corona discharge Treatment, and (300H, thickness 75 μ m) grasp its both sides with the Kapton film.Be set in the compressing forming machine (society of refreshing rattan industry institute of Co., Ltd. makes, VSF-10) it and after being warming up to 100 ℃, with 10kgf/cm
2Suppressed 10 minutes.Compacting stops the back release pressure, be cooled to 30 ℃ after, take out sample A.
(sample A) is put in the constant temperature and humidity cabinet with this laminated film, implements following 3 hours, 10 ℃ wetting-drying tests that the 30%RH condition is following 3 hours of 30 ℃ of 95%RH conditions of repetition.Behind 400 loop terminations, take out laminated film, polyelectrolyte membrane is not peeled off from the PET film of having implemented Corona discharge Treatment as a result.
For above-mentioned sample after being pressed A; Under polyelectrolyte membrane state up; Above the long-pending film of polyelectrolyte layers, be pressed into ceramic knife edge on the platform on plane; This moment, the gap with point of a knife and plane platform was made as 50 μ m; About 1/3 (apart from about 25 μ m of lamination face side) of the thickness direction of and resin support membrane whole to the thickness direction of polyelectrolyte membrane, identical position cuts out otch according to many page shape on in-plane, and the polyelectrolyte layers that obtains this execution mode thus amasss film.
In addition; For above-mentioned sample after being pressed A; At polyelectrolyte membrane state up; The front end of the cutlery that rotates synchronously with the polyelectrolyte membrane face contact with the long-pending film of the polyelectrolyte layers of sending here continuously, at this moment the gap on point of a knife and the backing roll is made as 50 μ m, to about 1/3 (apart from about 25 μ m of lamination face side) of the thickness direction of the thickness direction integral body of polyelectrolyte membrane and resin support membrane; Identical position cuts out otch successively according to many page shape on in-plane, obtains the long-pending film of polyelectrolyte layers of this execution mode thus.
When peeling off down the polyelectrolyte membrane that cut into page shape from the end by the long-pending film of resulting polyelectrolyte layers with hand, the result has easily carried out peeling off and has not produced fold.In addition, also have the adaptation of appropriateness, when the processing polyelectrolyte layers amasss film, nature does not take place yet and peel off.
In addition; Storage stability is also good; With plane by certain big or small range upon range of or in the thermostatic constant wet chamber of 25 ℃ of 50%RH, preserve 3 months with the form of the coiling thing of roller shape after, the page form height molecule dielectric film that the predetermined cuts size also do not occur is peeled off, the situation of intermembranous dislocation or generation fold.In addition, do not occur that polyelectrolyte membrane is peeled off and the situation that bonds to the PET film back side yet.
[comparative example 1]
Do not carry out the PET film of Corona discharge Treatment except using, through obtaining the long-pending film of polyelectrolyte layers with embodiment 1 same method.For the long-pending film of this polyelectrolyte layers, likewise implement wetting-drying test with embodiment 1, polyelectrolyte membrane strips down from the PET film as a result.In addition with the long-pending film of this polyelectrolyte layers and the likewise range upon range of preservation of embodiment 1 or with the form preservation of the coiling thing of roller shape, polyelectrolyte membrane is partly peeled off and is bonded to the PET film back side as a result.
[comparative example 2]
Except in polyelectrolyte membrane and resin support membrane, not cutting out the otch, through obtaining the long-pending film of polyelectrolyte layers with embodiment 1 same method.For the long-pending film of this polyelectrolyte layers; Thickness direction integral body at polyelectrolyte membrane and resin support membrane is cut according to page shape; Likewise peeling off when cutting into the polyelectrolyte membrane of page shape down from the end by the long-pending film of polyelectrolyte layers with hand with embodiment 1, the result has produced fold.
Industrial applicibility
Even the long-pending film of the polyelectrolyte layers of the utility model can not increase the shortcomings such as fold of polyelectrolyte membrane yet after long preservation; Corrugationless when peeling off; Can easily peel off where necessary, therefore can significantly reduce the disqualification rate when making MEA.
Claims (2)
1. a polyelectrolyte layers amasss film, and it is the long-pending film of polyelectrolyte layers with resin support membrane and polyelectrolyte membrane, wherein,
At thickness be on the resin support membrane of 5 μ m～500 μ m lamination thickness is arranged is the polyelectrolyte membrane of 1 μ m～500 μ m; Said resin support membrane is being implemented Corona discharge Treatment or plasma discharge processing with the lamination face side of said polyelectrolyte membrane lamination at least
The part of the lamination face side on the thickness direction integral body of said polyelectrolyte membrane and the thickness direction of said resin support membrane has been cut otch in identical plan position approach according to page shape; Perhaps indulge or horizontal arbitrary direction otch in identical upper edge, plan position approach
Said page shape be the long-pending film of cutting polyelectrolyte layers in-plane around, thereby shape that can many ground processing polyelectrolyte membranes.
2. polyelectrolyte layers as claimed in claim 1 amasss film, and wherein, the degree of depth of a part of otch on the thickness direction of the said resin support membrane thickness whole with respect to the resin support membrane is 5%～95%.
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| CN2011204566782U CN202585634U (en) | 2011-11-17 | 2011-11-17 | Polyelectrolyte laminated membrane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103117401A (en) * | 2011-11-17 | 2013-05-22 | 旭化成电子材料株式会社 | Polyelectrolyte laminated membrane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103117401A (en) * | 2011-11-17 | 2013-05-22 | 旭化成电子材料株式会社 | Polyelectrolyte laminated membrane |
| CN103117401B (en) * | 2011-11-17 | 2015-07-08 | 旭化成电子材料株式会社 | Polyelectrolyte laminated membrane |
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