CN102782919A - Improved polymer membranes, processes for production thereof and use thereof - Google Patents
Improved polymer membranes, processes for production thereof and use thereof Download PDFInfo
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
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- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
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- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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Abstract
The invention relates to improved polymer membranes, to processes for production thereof and to the use thereof.
Description
The present invention relates to improved polymer film, its production method and the purposes in electrochemical reactor such as fuel cell thereof.
Polymer film and the purposes in fuel cell thereof are known.In based on the membrane electrode assembly that gathers azoles film such as polybenzimidazoles (PBI) (MEA), required proton-conducting is through with the realization of phosphate-doped and polymer.With the phosphate-doped low mechanical stability that causes polymer.Simultaneously, high acid content is favourable as far as ionic conductivity.The film that in sol-gel process, produces especially has high phosphorus acid content and low PBI polymer content.This causes the effect current downflow of film at pressure and temperature.In fuel cell, guarantee to be compressed to thickness limited hard packing circle through use and prevent to flow.Not actual film between packing ring; But the so-called subpad circle (subgasket) that constitutes by the polyimides (
) that FEP for example applies, it gives film more than the junction with gas diffusion layers with hermetic seal.It is not the purposes of the gasket materials that is made up of the actual membrane polymer that WO92/22096A2 has for example described.WO2008/014964A2 has described the film with reinforcing element.Film can be weakness with being connected of subpad circle, and this is in the MEA production process defective possibly occur, and in battery-operated, possibly leak.
WO 2004/066428A2 has described the fuel cell with phosphate-doped PBI film, and wherein the PBI film uses with the anacidity form, and the active region is doped with phosphoric acid via the electrode of acid dip in assembling process, and gasket areas keeps mixing.DE 10 2,004 028 141 A1 in gasket areas low-doped or non-impurity-doped has been described and in the active region with the PBI film of phosphoric acid high doped.
The shortcoming that comprises the system of subpad circle is in its production process, to occur defective easily, and its long-time stability are unsatisfactory.This is because the subpad loop material separated with film through the operating time, or becomes fragile.Even in the MEA production process, possibly exist owing to shear the early stage infringement of film, because film is clamp-oned in it and the subpad circle overlapping areas.Usually, production stage is complicated and only can difficulty ground automation.Another shortcoming be mixing subsequently of PBI film cause with sol-gel process in the film that produces compare the acid of less amount.This has adverse effect to conductibility and long-time stability (little sour reservoir).
When providing in incorporating skeleton into, the object of the invention can in gasket areas, improve the improvement film of strengthening.
The present invention relates to a kind of ion-conductive membranes based on polymer P M, it has to become image mode to use on it, adheres on it and based on the layer S of polymer P P powder.
Said layer S is suitable as the packing ring limit among the MEA especially and produces machinery with film and strengthen.Film is particularly useful in the electrochemical reactor, in particular for fuel cell.
Said layer S is especially suitable for use as the packing ring limit among the MEA with spacer ring body.Strengthen being meant that the amount of polymer in the reinforced region compares increase with non-reinforced region.Therefore, film does not flow under as the effect at pressure and temperature in the reinforced region on packing ring limit.
The polymer P M and the PP of film and powder can be identical or different.
Powder PP is preferably the form of paste." one-tenth image mode " is interpreted as referring to not be to be applied on the whole surface of film, but only is applied in the specific region with controlled way.
In preferred embodiments, film is that acid is mixed, and especially is doped with phosphoric acid.Preferred especially polymer film is based on polybenzimidazoles (PBI).
In preferred embodiments, polymer film and powder all comprise polybenzimidazoles or are made up of it, and polymer film especially is phosphate-doped.
The powder that is used for producing zone S preferably comprises following component as solvent:
A) polymer P P, especially polybenzimidazoles (PBI),
B) flexible B component), especially the polytetrafluoroethylene (PTFE) powder and
C) dispersing agent C); Especially sulfonation polytetrafluoroethylene, for example
polymer of aqueous dispersion form.
" flexible " is interpreted as more particularly referring to that consequent packing ring limit can not break with 90 ° of radius bend the time, and polymer beads does not separate.
Preferred flexible B component) is all fluoropolymers, especially FEP (fluorinated polyethylene propylene), PVDF (Kynoar) and PFA (perfluoralkoxy) in principle.
Dispersing agent C is the best and stable additive of mixing that makes the component of powder.Preferred dispersing agent for example is:
Alcohol alkoxylates;
SD 23 for example
Naphthalene sulfonic acid condensate; Especially its sodium salt;
NN890 for example
The Guerbet alcohol ethoxylate;
XP50 for example
Acetylenic glycol (acetylene glycol) base product;
604 for example
Acetylenediol base nonionic double structure surfactant;
104 for example
High molecular weight block copolymer with pigment affinity group;
190-193 for example
Organically-modified polymer with pigment affinity group;
750W/760W for example
The double structure surfactant that contains siloxanes;
Twin 4000 for example
Contain silicon dioxide, not siliceous organic polymer; For example
Foamex 830 and
Fluorine-containing surfactant; Choose wantonly and be and alcohol; The for example mixture of isopropyl alcohol and water, for example
FSA.
The powder that is used for layer S is preferably preferably to be measured as 1-10000mPas under 20 ℃ temperature, especially dispersion in the range of viscosities of 10-1000mPas or the form that flows freely paste are used.
The solid that exists in the powder dispersion used according to the invention is preferably:
A) 30-50 parts by weight polymer PP,
B) the flexible B component of 30-50 weight portion),
C) 5-15 weight portion dispersing agent C).
In addition, preferably contain:
D) the 10-20 weight portion is used to improve the reagent of wetability, alcohols, especially normal propyl alcohol.
In addition, there is preferred 20-60 weight portion, especially the 35-45 weight parts water.
This powder is preferably through following steps production:
1. with the particle of the preferred efflorescence of polymer P P to diameter less than 60 μ m,
2. gained powder in the step 1 and flexible B component and dispersing agent C are scattered in liquid phase, preferred water or alcohol mutually in, and optional it is adjusted to required viscosity.
The invention further relates to the method for a kind of production film of the present invention, it comprises that the powder with polymer P P is applied on the base material (for example carrier film (carrier film)), then it and sour doping is compressed.In preferred embodiments, use the form for lamination printing transferring method, especially continuation method of powder on film.This type lamination printing transferring method for example is described in Electrochimica Acta, the 40th the volume, the 3rd phase, the 355-363 page or leaf, 1995 with J.Appl.Electrochemistry 22 (1992) 1 in.The lamination printing transferring method is also referred to as " applique " method.Because compressing powder, at least a portion powder infiltrate in the film, thus strengthening membrane.
Polymer film of the present invention is suitable for a large amount of electrochemical reactors, especially fuel cells applications.Therefore the present invention also is provided for the membrane electrode assembly (MEA) of fuel cell, and it comprises at least:
I. the polymer film of the present invention that has packing ring limit S,
II. spacer ring body, wherein:
III. the film of layer S periphery embeds and is pressed in the spacer ring body.
In preferred embodiments, spacer ring body is made up of the elastomer according to DE 10 2,004 028 141 A1 basically.In another preferred embodiment, non-resilient spacer is embedded in the spacer ring body that is made up of elastomer, and offset excessive spacer ring body compression, but do not reduce its elastic performance.For example, can use the element or the pad that constitute by metal, plastics or carbon of comparing rigidity more with elastomer.
The invention further relates to the electrochemical reactor that comprises at least one film of the present invention, especially fuel cell.
According to the present invention, can be through with polymer powder PP, especially the powdery polybenzimidazoles (granularity, preferred<60 μ m) be applied on the both sides of film in the gasket areas, then pressure and temperature (for example under 140 ℃, 3 minutes, 3000N/>cm
2) the effect lower compression it and realize, especially at 50-200 ℃, in preferred 70-160 ℃ the temperature range through 0.5-10 minute, especially 1-5 minute, and at common 500-6000N/cm
2, preferred 1000-4000N/cm
2, 2500-3500N/cm especially
2Pressure under.The PBI powder of importantly using absorbs number acid from film, infiltrate in the film and with it to combine.This is increased to 50-90 weight % with the polymer content in the film by 5-10 weight %.The film of strengthening thus even under high pressure and high temperature, no longer flow freely.But it is fully flexible that it keeps.Having another advantage that the subpad circle of different materials compares with use is from activity, and the transition in for example phosphate-doped film surface to reinforcing washer zone is incorporated on the same material, and promptly film does not finish there, but proceeds in the gasket areas to add strong form.
The uniform thickness of the layer S that powder is used is preferably realized by method for printing screen.Find that dispersing additive and the weight ratio of PBI are preferably the polytetrafluoroethylene (PTFE) powder of 0.9:1.1-1.1:0.9, PBI powder and can produce to stablize and printable paste as the mixture of the sulfonation tetrafluoro ethylene polymer of dispersing additive.These can directly be printed on the film with the phosphoric acid acidifying, dry tack free, hot pressing then.This realizes the film reinforcement.Advantage is that PTFE mixes between the PBI particle.After hot pressing, reinforced layer has uniform thickness, smooth and airtight.
In preferred application process, the above-mentioned paste that will be especially constitutes by PBI, PTFE and sulfonation tetrafluoroethene powder by silk screen printing with the administered of packing ring on the carrier substrate that for example constitutes by polyether sulfone (PES) film.It is dry to stick with paste part.To go between two kinds of these coated substrates (grommet frame covers each other) with the PBI mould of phosphoric acid acidifying subsequently.This produces the lamination transfer printing from carrier film to the PBI film.Compression is advantageously at 80 ℃ and 3000N/cm
2Pressure under carried out 1 minute.
PBI film and the gas-diffusion electrode subsequently the edge strengthened are assembled to obtain MEA.This so that the mode of electrode and the about 1-2mm of strengthening membrane imbricate carry out.Compression stress on this realization electrode edge depends on the effect of reinforcement.
For the purpose of the present invention, the polymer P M and the PP that are suitable for producing polymer dielectric film are that itself is known.All proton-conducting materials are suitable.The preferred film that comprises acid that uses, wherein acid can be covalently bonded on the polymer.In addition, can planarization material be mixed to form suitable film with acid.In addition, also can use gel, especially polymer gel is as film, and in this case, with regard to the present invention, specially suitable polymer film for example is described among the DE 102 464 61.
These films can be especially through obtaining as follows: with comprising liquid swelling planarization material such as the polymer film that contains acid compound, or preparation polymer and the mixture that contains acid compound and then through with the flat object moulding and solidify then to form film and form film.
Suitable polymers comprises polyolefin for this reason; For example gather (chlorobutadiene), polyacetylene, polyphenylene, gather (terephthalylidene), gather aryl methylene, polystyrene, polymethylstyrene, polyvinyl alcohol, polyvinyl acetate base ester, polyvingl ether, polyvinylamine, gather (N-vinyl acetamide), polyvinyl imidazol, PVK, PVP, polyvinylpyridine, polyvinyl chloride, Vingon, polytetrafluoroethylene (PTFE), polyhexafluoropropylene; PTFE and hexafluoropropylene, with perfluoro propyl vinyl ether, with trifluoronitrosomethane, with the copolymer of carbalkoxy perfluorinated alkoxy vinyl ether; Polymonochlorotrifluoroethylene, polyvinyl fluoride, Kynoar, polyacrolein, polyacrylamide, polyacrylonitrile, polybutylcyanoacrylate, Polymethacrylimide; Cyclic olefine copolymer is especially formed by ENB;
The polymer that has the C-O key in the main chain; For example polyacetals, polyformaldehyde, polyethers, PPOX, Polyglycol 166-450, PolyTHF, polyphenylene oxide, polyether-ketone, polyester, especially polyglycolic acid, PETG, polybutylene terephthalate (PBT), gather hydroxybenzoate, gather hydracrylic acid, gather pivalolactone, PCL, gather malonic acid, Merlon; The polymer that has the C-S key in the main chain, for example polythiaether, polyphenylene sulfide, polysulfones, polyether sulfone;
The polymer that has the C-N key in the main chain for example gathers imines, gathers isocyanide, polyimide, PEI, polyaniline, Nomex, polyamide, polyhydrazide, polyurethane, polyimides, gathers azoles, gathers azoles ether ketone, polyazine;
Liquid crystal polymer, especially thermoplasticity, liquid crystal polyester, for example Vectra
TMAnd
Inorganic polymer, for example polysilane, Polycarbosilane (polycarbosilane), polysiloxanes, gather silicic acid, polysilicate, silicone (silicone), polyphosphazene and polythiazole.
Preferred here alkaline polymer, wherein especially true to comprising acid or being doped with the film of acid.The useful alkaline polymer film of this type comprises basic all known polymer films that can transmit proton.Here preferably in the no extra acid that can for example transmit proton under water by so-called Grotthuss mechanism.
The alkaline polymer that is used for context of the present invention is preferably has at least one nitrogen, oxygen or sulphur atom in the repetitive, preferably the alkaline polymer of at least one nitrogen-atoms.The alkaline polymer that further preferably comprises at least one heteroaryl.
In preferred embodiments, the repetitive in the alkaline polymer comprises the aromatic ring with at least one nitrogen-atoms.Aromatic ring is preferably 5 or 6 yuan of rings with 1-3 nitrogen-atoms, and it can condense in another ring, especially on another aromatic ring.
In particular aspects of the present invention, use the high thermal stability polymer that in a repetitive or different repeat units, comprises at least one nitrogen, oxygen and/or sulphur atom.
In context of the present invention, but have the polymer of the polymer of high thermal stability for the polymer dielectric long period of operation in the battery that under the temperature more than 120 ℃, acts as a fuel." for a long time " is meant that film of the present invention can be at least 80 ℃; Preferably at least 120 ℃; More preferably operated at least 100 hours down at least 160 ℃; Preferably at least 500 hours, do not reduce greater than any performance of 50% and do not have based on initiation performance, said performance reduces and can measure through the said method of WO 01/18894 A2.
In context of the present invention, can use all above-mentioned polymer separately or as mixture (blend).Especially preferably comprise the blend that gathers azoles and/or polysulfones here.The preferred blends component is polyether sulfone, polyether-ketone and with the polymer of sulfonic acid group modification, and is of German patent application DE 100 522 42 and DE 102 464 61.
In addition, find that also with regard to the present invention useful especially blend polymer is to comprise those of at least a alkaline polymer that weight ratio is 1:99-99:1 and at least a acidic polymer (so-called Acid-Base blend polymer).Particularly suitable at this point acidic polymer comprises the polymer with sulfonic acid and/or phosphonyl group.Very specially suitable Acid-Base blend polymer for example is described in detail among the open EP1073690 A1 according to the present invention.
One group of preferred especially alkaline polymer is to gather azoles.Comprise general formula (I) and/or (II) and/or (III) and/or (IV) and/or (V) and/or (VI) and/or (VII) and/or (VIII) and/or (IX) and/or (X) and/or (XI) and/or (XII) and/or (XIII) and/or (XIV) and/or (XV) and/or (XVI) and/or (XVII) and/or (XVIII) and/or (XIX) and/or (XX) and/or (XXI) and/or azoles repetitive (XXII) based on the alkaline polymer that gathers azoles:
Wherein:
Ar identical or different and respectively do for oneself tetravalence aromatics or heteroaromatic group, it can be single-or many rings,
Ar
1Identical or different and respectively do for oneself divalent aromatic or heteroaromatic group, it can be single-or many rings,
Ar
2Identical or different and respectively do for oneself divalence or trivalent aromatics or heteroaromatic group, it can be single-or many rings,
Ar
3Identical or different and respectively do for oneself trivalent aromatics or heteroaromatic group, it can be single-or many rings,
Ar
4Identical or different and respectively do for oneself trivalent aromatics or heteroaromatic group, it can be single-or many rings,
Ar
5Identical or different and respectively do for oneself tetravalence aromatics or heteroaromatic group, it can be single-or many rings,
Ar
6Identical or different and respectively do for oneself divalent aromatic or heteroaromatic group, it can be single-or many rings,
Ar
7Identical or different and respectively do for oneself divalent aromatic or heteroaromatic group, it can be single-or many rings,
Ar
8Identical or different and respectively do for oneself trivalent aromatics or heteroaromatic group, it can be single-or many rings,
Ar
9Identical or different and respectively do for oneself divalence or trivalent or tetravalence aromatics or heteroaromatic group, it can be single-or many rings,
Ar
10Identical or different and respectively do for oneself divalence or trivalent aromatics or heteroaromatic group, it can be single-or many rings,
Ar
11Identical or different and respectively do for oneself divalent aromatic or heteroaromatic group, it can be single-or many rings, X is identical or different and be oxygen, sulphur or amino; It has hydrogen atom, has the group of 1-20 carbon atom, preferred branched or non-branching alkyl or alkoxyl; Or aryl is as other group
R is identical or different and be hydrogen, alkyl or aromatic group, and in formula (XX), is alkyl or aromatic group, and condition is that the R in the formula (XX) is not hydrogen, and
N, m respectively do for oneself more than or equal to 10, are preferably greater than or equal 100 integer.
Preferred aromatics or heteroaryl groups are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenyl methane, diphenyl dimethylmethane, benzophenone, diphenyl sulphone (DPS), quinoline, pyridine, bipyridine, pyridazine, pyrimidine, pyrazine, benzo
piperazine, triazine, tetrazine, pyrroles, pyrazoles, anthracene, benzopyrrole, BTA, benzo
thiadiazoles, benzo
diazole, benzo pyridine, benzopyrazines, benzopyrazines alkane (benzopyrazidine), benzo pyrimidine, benzopyrazines, phentriazine, indolizine, quinolizine, pyridopyridine, imidazopyrimidine, pyrazine and pyrimidine, carbazole, acridine (aciridine), azophenlyene, benzoquinoline, fen
piperazine, phenthazine, azine, benzo pteridine, phenanthroline and phenanthrene, and it also can be chosen wantonly and be substituted.
Ar
1, Ar
4, Ar
6, Ar
7, Ar
8, Ar
9, Ar
10, Ar
11The replacement mode decide as required; Under the situation of phenylene, Ar for example
1, Ar
4, Ar
6, Ar
7, Ar
8, Ar
9, Ar
10, Ar
11Can for adjacent-,-and right-phenylene.Preferred especially group is derived from benzene and biphenyl, and it also can be chosen wantonly and be substituted.
Preferred alkyl is the short-chain alkyl with 1-4 carbon atom, for example methyl, ethyl, n-pro-pyl or isopropyl and the tert-butyl group.
Preferred aromatic group is a phenyl or naphthyl.Alkyl and aromatic group can be for substituted.
Preferred substituted is a halogen atom, fluorine for example, amino, hydroxyl or short-chain alkyl such as methyl or ethyl.
Preferably gather azoles and have formula (I) repetitive, wherein the X group is identical in a repetitive.
Gather azoles and also can have for example different different repeat units aspect its X group in principle.Yet it preferably only has identical X group in a repetitive.
Other preferably gathers the azoles polymer is polyimidazole; Polybenzothiozole; Polyphenyl is
azoles also; Gather
diazole; Polyquinoxaline; Polythiadiazoles; Gather (pyridine); Gather (pyrimidine); Gather also
piperazine of (four azepine pyrenes) and polyphenyl.
In another embodiment of the present invention, the polymer that comprises the azoles repetitive is copolymer or the blend that comprises at least two formulas that differ from one another (I)-(XXII) unit.Polymer can be the form of block copolymer (diblock, three blocks), random copolymer, periodic copolymer and/or alternating polymer.
In particularly preferred embodiment of the present invention, the polymer that comprises the azoles repetitive for only comprise formula (I) and/or (II) unit gather azoles.
Azoles number of repeat unit in the polymer is preferably more than or equals 10 integer.Preferred especially polymer comprises at least 100 azoles repetitives.
In context of the present invention, preferably comprise the polymer of benzimidazole unit.Some instances of the highly suitable polymer that comprises the benzimidazole repetitive are by following various expression:
Wherein n and m respectively do for oneself more than or equal to 10, are preferably greater than or equal 100 integer.
The used azoles that gathers, but especially polybenzimidazoles is characterised in that HMW.As the measurement of inherent viscosity, this is 0.2dl/g at least, preferred 0.8-10dl/g, especially 1-10dl/g.
Preferred polybenzimidazoles is commercially available with
trade name.
Preferred polymer further comprises polysulfones, especially has the polysulfones of aromatics and/or heteroaromatic group in the main chain.In particular aspects of the present invention, the melt volume speed MVR300/21.6 that records according to ISO 1133 of preferred polysulfones and polyether sulfone is for being less than or equal to 40cm
3/ 10min especially is less than or equal to 30cm
3/ 10min is more preferably less than or equals 20cm
3/ 10min.The polysulfones that preferably has 180-230 ℃ Vicat softening temperature VST/A/50 here.In another preferred embodiment of the present invention, the number-average molecular weight of polysulfones is greater than 30000g/mol.
Polymer based on polysulfones especially comprises the polymer with following repetitive, and said repetitive has the connection sulfuryl group corresponding to general formula A, B, C, D, E, F and/or G:
-O-R-SO
2-R- (A)
-O-R-SO
2-R-O-R- (B)
-O-R-SO
2-R-O-R-R- (C)
-O-R-SO
2-R-R-SO
2-R- (E)
-O-R-SO
2-R-R-SO
2-R-O-R-SO
2-] (F)
Wherein the R group is identical or different, and is aromatics or heteroaromatic group independently of one another, wherein these groups illustrated in detail hereinbefore.These especially comprise 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 4,4 '-biphenyl, pyridine, quinoline, naphthalene, phenanthrene.
Preferred polysulfones comprises homopolymers and copolymer, for example random copolymer in context of the present invention.Preferred especially polysulfones comprises the repetitive of formula H-N:
N wherein>0
Wherein n < 0
The polysulfone can name the following commodities market share:
200P,
720P,
E,
S,
A,
R,
HTA,
and
In addition, special preferred, polyethers ketone, PEKK, polyether-ether-ketone, polyether ether ketone ketone and gather aryl ketones.These high-performance polymers are own known and can be commercial with following trade name:
PEEK
TM,
For producing polymer film, can polymer preferably gather azoles and in another step, be dissolved in polar non-solute such as the dimethylacetylamide (DMAc), and film can be obtained by conventional method.For removing the solvent residues thing, can the film of gained like this be handled according to German patent application DE 101 098 29 usefulness cleaning solutions.The said mechanical performance of solvent residues thing flush away from gather the azoles film being improved surprisingly film of German patent application.These performances especially comprise modulus of elasticity, extension at break and the fracture toughness of film.
In addition, polymer film can have other modification, and is for example through crosslinked, of German patent application DE101 107 52 or WO 00/44816.In preferred embodiments, the used extra crosslinking agent that comprises of polymer film that constitutes by alkaline polymer and at least a blend components, of German patent application DE 101 401 47.
The thickness that gathers the azoles film can be in the wide region.Before dopant acid, the thickness that gathers the azoles film is preferably 5-2000 μ m, more preferably 10-1000 μ m, and especially preferred 20-1000 μ m, this is not intended to give any restriction.
For realizing proton-conducting, with these film dopant acids.Acid comprises all known lewis acid and Bronsted acids among this paper, preferred inorganic Louis and Bronsted acid.
In addition, the use of polyacid also is possible, especially isopolyacid and heteropoly acid, and the mixture of different acid.In context of the present invention; Heteropoly acid refers to have the inorganic polyacid of at least two different central atoms; It is formed by the acid of polynary oxygen as partially mixed acid anhydride, they respectively do for oneself weak, have metal (preferred Cr, Mo, V, W) and nonmetal (preferably As, I, P, Se, Si, Te).They comprise 12-molybdophosphate and 12-tungstophosphoric acid.
Doping level can be used for influencing the conductibility of gathering the azoles film.This conductibility is along with the concentration of dopant improves and improves, until reaching maximum.
According to the present invention, doping level is with the sour molal quantity report of every moles of polymer repetitive.In context of the present invention, preferred doping level is 3-80, suitably 5-60, especially 12-60.
Preferred especially dopant is sulfuric acid and phosphoric acid, or for example discharges these sour compounds during hydrolysis.Preferred very especially dopant is phosphoric acid (H
3PO
4).At this point, use the acid that highly concentrates usually.In particular aspects of the present invention, concentration of phosphoric acid is at least 50 weight %, especially at least 80 weight % based on dopant weight.
In preferred embodiments, film of the present invention is that fiber is strengthened, and like WO 2008/014964 A2, the 17th page the 39th to walk to the 21st page of the 33rd row said.
Film of the present invention can be produced in a manner known way, like WO 2008/014964 A2, the 21st and subsequently the page or leaf said.
Membrane electrode assembly of the present invention comprises film of the present invention and at least two electrochemical activity electrodes (anode and negative electrode) that tunicle separates that at least one has packing ring of the present invention limit S.Electrode is itself known and ability hydrogen catalyzed and/or the oxidation of at least a reformate and the reduction of oxygen.This performance can obtain through electrode is applied with platinum or platinum alloy.Term " electrode " is meant that this material is what conduct electricity.This type electrode is known and for example is described in US 4,191,618, among US 4,212,714 and the US 4,333,805.
Catalyst layer is not self-supporting usually, but is applied to usually on gas diffusion layers and/or the film.At this moment, a part of catalyst layer can for example infiltrate in gas diffusion layers and/or the film, and it forms transition zone.This result also possibly be the part that catalyst layer can be seen gas diffusion layers as.
According to the present invention, the surface of polymer dielectric film contacts with electrode and makes every kind of situation lower part or fully, preferably only partly, and the front side of the first electrode overlie polymer dielectric film, and the dorsal part of the second electrode overlie polymer dielectric film.At this point, the front side of polymer dielectric film and dorsal part refer to respectively polymer dielectric film towards with outlying observation person's side, wherein observe by first electrode (front side), preferred negative electrode, along second electrode (dorsal part), the direction of preferred anodes is carried out.
Be production membrane electrode assembly of the present invention; Mutually combine with folded ground placement of different assemblies of membrane electrode assembly and by pressure and temperature; Wherein lamination is usually at 10-300 ℃, especially under 20-200 ℃ temperature and 1-1000 crust, the especially pressure of 3-300 crust.
Since single fuel cell performance as far as many use usually too low, in context of the present invention preferably by division board with several single fuel cells combinations to form fuel cell (fuel cell pack).At this moment, division board, the optional and interactional division board of other gasket materials should seal the gas compartment in negative electrode and the anode and the outside and between the gas compartment of negative electrode and anode, seal.For this reason, division board preferably places on the membrane electrode assembly hermetically.Sealing function can further strengthen through compressing the complex that is made up of division board and membrane electrode assembly.
Division board preferably has the gas passage that at least one is used for reacting gas separately, and it advantageously places on the side of electrode.The gas passage reaction-ure fluid that should be able to distribute.
Having found wonderful especially is that membrane electrode assembly of the present invention is characterised in that the obvious improvement aspect mechanical stability and intensity, therefore can be used for producing the fuel cell pack with stable especially performance.Simultaneously, no longer observe present common performance change in the gained fuel cell pack, and realize unknown so far quality, reliability and reproducibility.
Demonstrate:
-chemical property does not receive the edge to strengthen influencing,
-strengthen the edge in quickening the strange land storage test than strengthening membrane is more unstable,
-strengthening membrane does not flow under the condition of bedding and padding compression,
-battery (technically) is airtight.
Embodiment
The MEA that edge of the present invention is strengthened is according to following production:
Work embodiment
1. the production of printing paste
At first with the 10g 10% sulfonation tetrafluoro ethylene polymer of packing in the beaker (N
) aqueous solution.At room temperature, in magnetic stirrer, add the 2g normal propyl alcohol, and mixture was stirred 5 minutes again.Be metered into the PBI powder (250 order) of 5g screening then and mixture was stirred 5 minutes again.Add 5g teflon powder (average grain diameter 1 μ m) subsequently.Mixture was at room temperature stirred 30 minutes again.After this, paste has the viscosity of about 1000mPas.
2. will stick with paste silk screen printing on carrier film
3. the lamination transfer printing is with production edge strengthening membrane
By instrument two films that scribble the printing paste are arranged to cover CeltecP film upside and downside.By hot press, under 80 ℃ and with 3000N/cm
2Through proceeding to the lamination transfer printing of film in 1 minute.Printing is stuck with paste part and is infiltrated in the film, and the PBI powder absorbs acid, the fringe region of strengthening membrane thus.The lamination transfer printing is only carried out in the place that instrument is exerted pressure.Therefore, can confirm actual reinforced region via tool geometries.Consequent film has the thickness of 150 μ m in the reinforcing washer district.Do not strengthen the thickness that the active region has 400 μ m.
4. produce MEA by the edge strengthening membrane
Place two gas-diffusion electrodes (anode and negative electrode) with coverlay by location and stamping tool.Gas-diffusion electrode and the about 1-2mm of reinforcement imbricate.The exterior lateral area at strengthening membrane edge keeps not being capped.MEA thickness is 1100 μ m under the uncompressed state.Be compressed in 140 ℃ proceeded to down through 30 seconds spacer (pad) limit thickness limited.The feasible height (500 μ m) that MEA is compressed to fully pad of selection pressure.This makes MEA plasticity and flexibly distortion.Elastic component causes MEA after pressure discharges, to obtain thickness once more.This thickness is about 900 μ m.The thickness at strengthening membrane edge is 125 μ m.
5. fuel cell experiments
Consequent MEA is toasted half an hour down at 160 ℃ in baking oven, make fuel cell then.The current/voltage characteristic is compared the difference that does not demonstrate on any performance with standard MEA.Fig. 1 is presented at the individual features that writes down under the following condition:
T：160℃
The gas of supply: hydrogen, air
Be appointed as 1) characteristic with standard MEA record, be appointed as 2) characteristic with MEA record of the present invention.
Find film of the present invention even in continuous producing method, have high stability and good packing ring performance.
Claims (13)
1. ion-conductive membranes based on polymer P M, it has to become image mode to use on it, adheres on it and based on the layer S of polymer P P powder.
2. according to the film of claim 1, wherein said layer S is suitable as the packing ring limit and produces machinery with film and strengthen.
3. according to the ion-conductive membranes of claim 2, the polymer content in the packing ring limit that wherein is made up of film and layer S is higher than the outside, packing ring limit.
4. according to each film in the aforementioned claim, wherein identical with the polymer P P of powder as film polymer based PM.
5. according to each film in the aforementioned claim, wherein powder does not exist only on the film surface at least in part, and is present in the film itself.
6. according to each film in the aforementioned claim, wherein polymer P P and/or PM are based on polybenzimidazoles (PBI).
7. powder that is used for according to the film of claim 1 comprises basically:
A) polymer P P, especially polybenzimidazoles are the 30-50 weight portion based on powder especially,
B) flexible component, especially polytetrafluorethylepowder powder and
C) dispersant, especially sulfonation polytetrafluoroethylene.
8. method of producing according to each film among the claim 1-6, it comprises that powder with polymer P P is applied on the film and compresses it.
9. according to Claim 8 method, wherein film is that acid is mixed.
10. according to Claim 8 method, wherein powder is with the administered of dispersion or paste.
11. according to the method for claim 10, wherein the paste of powder or dispersion have the viscosity of 1-1000mPas.
12. a membrane electrode assembly (MEA) that is used for fuel cell comprises at least:
I. according to each polymer film among the claim 1-6,
II. spacer ring body, wherein:
III. the film of layer S periphery embeds and is pressed in the spacer ring body.
13. electrochemical reactor that comprises at least one according to the membrane electrode assembly of claim 12.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10155581 | 2010-03-05 | ||
| EP10155581.1 | 2010-03-05 | ||
| PCT/IB2011/050922 WO2011107967A2 (en) | 2010-03-05 | 2011-03-04 | Improved polymer membranes, processes for production thereof and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102782919A true CN102782919A (en) | 2012-11-14 |
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ID=44542664
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800124653A Pending CN102782919A (en) | 2010-03-05 | 2011-03-04 | Improved polymer membranes, processes for production thereof and use thereof |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2543101A4 (en) |
| JP (1) | JP2013521628A (en) |
| KR (1) | KR20130038826A (en) |
| CN (1) | CN102782919A (en) |
| WO (1) | WO2011107967A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112259757A (en) * | 2020-12-17 | 2021-01-22 | 安徽明天氢能科技股份有限公司 | Novel membrane electrode sealing filler and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9095845B2 (en) | 2010-10-21 | 2015-08-04 | Basf Se | Catalyst support material comprising polyazole salt, electrochemical catalyst, and the preparation of a gas diffusion electrode and a membrane-electrode assembly therefrom |
| DK2843743T3 (en) * | 2013-09-02 | 2018-07-16 | Basf Se | Membrane electrode units for high temperature fuel cells with improved stability |
| CN103944079B (en) * | 2014-04-18 | 2016-04-13 | 象山一山工业设计有限公司 | Public change case |
| JP6351739B2 (en) * | 2014-10-10 | 2018-07-04 | 日本ゴア株式会社 | Electrolyte membrane for fuel cell |
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- 2011-03-04 WO PCT/IB2011/050922 patent/WO2011107967A2/en active Application Filing
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| CN112259757B (en) * | 2020-12-17 | 2022-05-17 | 安徽明天氢能科技股份有限公司 | Membrane electrode sealing filler and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2543101A4 (en) | 2014-09-10 |
| EP2543101A2 (en) | 2013-01-09 |
| WO2011107967A2 (en) | 2011-09-09 |
| KR20130038826A (en) | 2013-04-18 |
| JP2013521628A (en) | 2013-06-10 |
| WO2011107967A3 (en) | 2011-12-29 |
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