CN101752566A - Bonding agent and membrane electrode group thereof - Google Patents
Bonding agent and membrane electrode group thereof Download PDFInfo
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- CN101752566A CN101752566A CN200810188126A CN200810188126A CN101752566A CN 101752566 A CN101752566 A CN 101752566A CN 200810188126 A CN200810188126 A CN 200810188126A CN 200810188126 A CN200810188126 A CN 200810188126A CN 101752566 A CN101752566 A CN 101752566A
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Abstract
The present invention provides a bonding agent used by a membrane electrode group. The bonding agent comprises a solvent system, a hyperbranched polymer and an organic polymer capable of conducting ions, wherein the branching degree of the hyperbranched polymer is bigger than 0.5, and the hyperbranched polymer and the organic polymer capable of conducting ions are dispersed in the solvent system.
Description
Technical field
The present invention relates to a kind of bond and comprise its mea, particularly a kind of bond that can at high temperature move and comprise its mea.
Background technology
Fuel cell (Fuel Cell, FC) be a kind of Blast Furnace Top Gas Recovery Turbine Unit (TRT) of utilizing chemical energy directly to be converted to electric energy, under traditional generation mode comparison, fuel cell has low pollution, low noise, high-energy-density and higher advantages such as energy conversion efficiency, be to have following prospective clean energy, applicable scope comprises various fields such as portable electric product, household system, means of transportation, military equipment, space industry and large generating system.The operation principles of fuel cell has a little difference according to the difference of its kind, with Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane fuel Cell, PEMFC) be example, hydrogen carries out oxidation reaction at anode catalyst layer, produces hydrogen ion (or being called proton) (H
+) and electronics (e
-), wherein hydrogen ion (or being called proton) can be passed to negative electrode via proton-conductive films, electronics is passed to negative electrode after then transferring to the load work done via external circuit again, and the oxygen that supply with cathode terminal this moment can carry out reduction reaction and produce water in cathode catalyst layer with hydrogen ion and electronics.
Figure 1A is traditional three-dimensional exploded view with fuel cell of mea, and Figure 1B is the profile of mea among Figure 1A.Shown in Figure 1A and Figure 1B, conventional fuel cell 10 its compositions comprise one by anode catalyst electrode 121, proton exchange membrane 122 (Proton Exchange Membrane, PEM) add mea 12 (the Membrane ElectrodeAssembly that cathod catalyst electrode 123 is combined, MEA), can utilize a bond 124 to engage between this anode catalyst electrode 121, proton exchange membrane 122 and the cathod catalyst electrode 123; And, the battery pack that is combined as the termination electrode plate 11 at the bipolar plates 13 (Bipolar Plate) of indivedual mea 12 series connection and two ends.In addition, the function of termination electrode plate 11 and bipolar plates 13 is except being connected in series as battery, and inner also design has runner 111 and 131 service ducts as hydrogen and oxygen.
The Nafion that the general employed bond of mea adopts E.I.Du Pont Company mostly to be produced though rerum natura, voltinism and proton-conducting all meet the requirements, in the application of reality, often derives following problem as Main Ingredients and Appearance:
With Nafion is that the bond of main composition runs into the easy dilatancy of aqueous solvent, therefore causes the difficulty of coating precision regulation and control; And under the environment of higher temperatures (＞80 ℃), Nafion can produce ruckbildung, even produces phase change and have influence on the usefulness of overall transfer mechanism.Yet when carrying out low temperature (＜80 ℃) operation, can't avoid CO to poison phenomenon, therefore cause catalyst efficiency variation and reduction of service life; In addition, be that the bond of main composition still exists suitable difficulty to the Mechanism Design of water management merely, when being in high current density, be easy to cause the negative electrode waterflooding with Nafion, and cause oxygen can't normal conduction to catalyst surface, caused the limit of proton conduction.In addition, Nafion is when carrying out high-temperature operation (more than 100 ℃), because its water retention coefficient (water retention coefficient) is relatively poor, its proton conduction degree is significantly subtracted to fall, and extend the problem of structure deterioration, make with Nafion to be that the application of the bond of main composition is limited in the operation below 80 ℃.
Therefore, for addressing the deficiencies of the prior art, the employed bond of mea that present industry urgent need develops a kind of novelty replaces the bond that traditional Nafion is main composition, in order to overcome traditional mea bond problem in the use.
Summary of the invention
The object of the present invention is to provide the employed bond of a kind of mea, can form membrane electrode layer or close catalyst layer admittedly and electrode formation catalyst electrode in order to close proton exchange membrane and catalyst electrode layer admittedly.Layer is closed in consolidating that this bond constituted, but have air guide, lead proton and the sub multiple functional structure of conduction, and has the proton channel that connects proton exchange membrane and mea, or the electronics channel of perforation catalyst layer and conductive carbon layer, in order to subtract the impedance disturbances of falling interface, promote the overall efficiency of battery.
The employed bond of mea of the present invention comprises: a solvent system; One hyper branched polymer (hyper-branched polymer), wherein this hyper branched polymer base material has a degree of branching greater than 0.5; And the organic polymer with conducting ion ability, wherein this hyper branched polymer and this organic polymer with conducting ion ability are scattered in this solvent system.
In addition, the present invention also provides a kind of mea, comprises: an anode catalyst electrode; One cathod catalyst electrode; One proton exchange membrane is disposed between this anode catalyst electrode and this cathod catalyst electrode; And one close layer admittedly, in order to respectively in conjunction with this cathod catalyst electrode, this anode catalyst electrode and this proton exchange membrane, wherein this to close layer admittedly be that the above-mentioned employed bond of mea is formed.This mea also can be applicable to lithium ion battery and bio-battery except being applicable to fuel cell (hydrogen or methanol fuel cell).
The advantage of bond of the present invention is: closing film by consolidating of its gained is that solid water coefficient and mechanical strength all are better than merely the rete as material with s-PEEK or s-PI, and also be difficult for dilatancy in the water of high temperature, can obviously improve swelling and the fragility of film under height is warm and humid; In addition, the consolidating of bond gained of the present invention closed the film tensile strength and obviously improves, and also can not soften and embrittlement in high-temperature water.
Below by several embodiment and comparing embodiment, illustrating further method of the present invention, feature and advantage, but be not to be used for limiting the scope of the invention, scope of the present invention should be as the criterion with the scope of appending claims.
Description of drawings
Figure 1A has the three-dimensional exploded view of the fuel cell of mea for tradition.
Figure 1B is the profile of mea among Figure 1A.
Fig. 2 A and Fig. 2 B are the structural representation that closes film of consolidating of the described bond gained of the present invention's one preferred embodiments.
Fig. 3 consolidates the chemical constitution of closing film and the conduct the relation schematic diagram of hydrone and proton for the described bond gained of the present invention's one preferred embodiments.
Wherein, primary clustering symbol description:
10～tradition has the fuel cell of mea; 11～termination electrode plate;
111～runner; 12～mea; 121～anode catalyst electrode;
122～proton-conductive films; 124～bond; 123～cathod catalyst electrode;
13～bipolar plates; 131～runner;
Admittedly 201～close layer; 202～electrode layer; 203 proton exchange membrane;
204～polyelectrolyte main structure; 205～conductive material;
206～catalyst material; 207～hydrogen proton; 208～electronics;
209～oxygen.
Embodiment
The present invention proposes the employed bond of a kind of mea, it comprises a hyper branched polymer (for example STOBA of the following stated of the present invention (Self-terminated Oligomer with hyper-branchedarchitecture) polymer), and the organic polymer with conducting ion ability, be dispersed in the solvent system.
Hyper branched polymer of the present invention is defined as one and has the polymer of the degree of branching (degree of branching, DB) greater than 0.5, and the degree of branching can be calculated gained by following formula:
DB＝(∑D+∑T)/(∑D+∑L+∑T)
Wherein, DB: the degree of branching, D: tree-shaped unit (dendritic unit, at least have three and extend binding key (1inkage bonds), do not contain any reactive group in the unit), L: linear unit (linear unit, two ends in unit are extendible binding key), T: terminal unit (terminal unit, the unit contains terminal key and at least one the tool reactive group of linking).
According to a preferred embodiment of the present invention, this hyper branched polymer can be the STOBA polymer, for example by the high degree of branching macromolecular material that reactant constituted that contains bismaleimides (Bismaleimide) group compound and barbituric acid (Barbituric acid).
This contains dimaleoyl imino group compound and comprises replacement or unsubstituted bismaleimide amine monomers or bismaleimides oligomerization compound, can have following structure:
In addition, described bismaleimides can have structure shown in the following formula:
R wherein
1For-RCH
2-(alkyl) ,-RNH
2R-,-C (O) CH
2-,-CH
2OCH
2-,-C (O)-,-O-,-O-O-,-S-,-S-S-,-S (O)-,-CH
2S (O) CH
2-,-(O) S (O)-,-C
6H
4-,-CH
2(C
6H
4) CH
2-,-CH
2(C
6H
4) (O)-, penylene base, biphenylene base, the penylene base of replacement or the biphenylene base of replacement, and R
2For-RCH
2-,-C (O)-,-C (CH
3)
2-,-O-,-O-O-,-S-,-S-S-,-(O) S (O)-, or-S (O)-, for example can select free N, N '-bismaleimides-4,4 '-diphenyl is for methane (N, N '-bismaleimide-4,4 '-diphenylmethane), 1,1 '-(di-2-ethylhexylphosphine oxide-4, the 1-phenylene) bismaleimides [1,1 '-(methylenedi-4,1-phenylene) bismaleimide], N, N '-(1,1 '-diphenyl-4,4 '-dimethylene) bismaleimides [N, N '-(1,1 '-biphenyl-4,4 '-diyl) bismaleimide], N, N '-(4-methyl isophthalic acid, the 3-phenylene) bismaleimides [N, N '-(4-methyl-1,3-phenylene) bismaleimide], 1,1 '-(3,3 '-dimethyl-1,1 '-diphenyl-4,4 '-dimethylene) bismaleimides [1,1 '-(3,3 ' dimethyl-1,1 '-biphenyl-4,4 '-diyl) bismaleimide], N, and N '-vinyl dimaleimide (N, N '-ethylenedimaleimide), N, N '-(1, the 2-phenylene) dimaleimide [N, N '-(1,2-phenylene) dimaleimide], N, N '-(1, the 3-phenylene) dimaleimide [N, N '-(1,3-phenylene) dimaleimide], N, N '-bismaleimides sulphur (N, N '-thiodimaleimid), N, and N '-bismaleimides two sulphur (N, N '-dithiodimaleimid), N, N '-bismaleimides ketone (N, N '-ketonedimaleimid), N, and N '-di-2-ethylhexylphosphine oxide maleimide (N, N '-methylene-bis-maleinimid), bismaleimides first-ether (bis-maleinimidomethyl-ether), 1,2-dimaleoyl imino-1,2-ethylene glycol [1,2-bis-(maleimido)-1,2-ethandiol], N, N '-4,4 '-diphenyl ether-bismaleimides (N, N '-4,4 '-diphenylether-bis-maleimid), and 4, (4,4 '-bis (maleimido)-diphenylsulfone) forms group to 4 '-bismaleimides-hexichol.
In addition, this barbituric acid can have the structure shown in the following formula:
Wherein, R
1, R
2, R
3And R
4Be identical or different substituting group, described substituting group comprises H, CH
3, C
2H
5, C
6H
5, CH (CH
3)
2, CH
2CH (CH
3)
2, CH
2CH
2CH (CH
3)
2, or
Above-mentioned STOBA (by the reactant that contains dimaleoyl imino group's compound and barbituric acid) polymer, its preparation method can be and carries out polymerization reaction with containing dimaleoyl imino group's compound and barbituric acid, and wherein this reaction also can be carried out in the presence of an initator.Wherein, this mol ratio that contains dimaleoyl imino group compound and barbituric acid can be between 20: 1 to 1: 5, and is preferable between 5: 1 to 1: 2.
This initator can be the compound that can produce free radical; such as: peroxide radical initiator or azo-compound radical initiator; can for example be 2; 2 '-azobis isobutyronitrile; 2; 2 '-azo two (2-cyano group-2-butane); dimethyl-2; 2 '-azo two (methyl isobutyrate); 4; 4 '-azo two (4-cyanopentanoic acid); 1; 1 '-two (cyclohexane nitriles of azo; 2-(tert-butyl group azo)-2-dicyanopropane; 2; 2 '-two [2-methyl-N-(1 of azo; 1)-and two (methylol)-2-ethoxys] propionamide; 2; 2 '-two [2-methyl-N-the ethoxy]-propionamides of azo; 2; 2 '-two (N of azo; N '-dimethylene butyronitrile two hydrochloric acids); 2; 2 '-two (2-nitrile propane) two hydrochloric acids of azo; 2; 2 '-two (N of azo; N '-dimethylene isobutyl amine); 2; 2 '-two (2-methyl-N-[1 of azo; two (the methylol)-2-ethoxys of 1-] the propionyl imines); 2; 2 '-two (2-methyl-N-[1 of azo; two (methylol) ethyls of 1-] the propionyl imines); 2; 2 '-azo two [2-methyl-N-(2-ethoxy) propionyl imines]; 2; 2 '-two (isobutyramide) dihydrates of azo; 2; 2 '-azo two (2; 2; the 4-trimethylpentane); 2,2 '-azo two (2-methylpropane); t-butyl peroxy-acetate; the t-butyl peroxy acetate; the t-butyl peroxy benzoic ether; the t-butyl peroxy caprylate; t-butyl peroxy neodecanoic acid ester; the t-butyl peroxy isobutyrate; tertiary pentyl peroxide trimethylacetic acid ester; t-butyl peroxy trimethylacetic acid ester; diisopropyl peroxydicarbonate; dicyclohexyl peroxide two carbonic esters; dicumyl peroxide; the dibenzoyl peroxide; two bay acyl peroxides; potassium peroxydisulfate; peroxo disulfate acid ammonium; di-tert-butyl peroxide; di-t-butyl time nitrite; dicumyl time nitrite.
According to preferred embodiment of the present invention, described organic polymer is the organic polymer with conducting ion ability, perfluorinated sulfonic resin (Nafion) for example, Sulfonated polyether-ether-ketone (sulfonated poly (etherether ketone, s-PEEK), Sulfonated polyimides (sulfonated polyimides, s-PI), polyphosphoric acid/polybenzimidazoles macromolecule (Phosphoric Acid/Polybenzimidazole Polymer, p-PBI), Sulfonated polyphenylene oxide (sulfonated poly (phenylene oxide), s-PPO), Sulfonated polyether sulphone (sulfonated poly (arylene ether sulfone), s-PES), Sulfonated poly-4-phenoxy group 1,4 Ben Ji Benzyl base ester (sulfonated poly (4-phenoxybenzoyl-1,4-phenylene), s-PPBP) or its mixing.
Solvent system used in the present invention and indefinite, can for example be gamma-butyrolacton (γ-butyrolactone, GBL), N-methyl pyrrolidone (1-methyl-2-pyrrolidinone, NMP), N, N-dimethylacetylamide (dimethylacetamide, DMAC), dimethyl formamide (N, N-dimethylformamide, DMF), dimethyl sulfoxide (DMSO) (Dimethyl sulfoxide, DMSO), dimethylamine (Dimethylamine, DMA), oxolane (tetrahydrofuran, THF), butanone (methyl ethyl ketone, MEK), propene carbonate (propylene carbonate, PC), water, isopropyl alcohol (isopropylalcohol, IPA), or its mixing.Percentage by weight that it should be noted that this hyper branched polymer is 5% to 30%, is preferably 10% to 25%, is benchmark with this hyper branched polymer and this organic macromolecule gross weight with conducting ion ability.
In addition, the employed bond of this mea can more comprise a conductive material, this conductive material can comprise organic conductive material, organic and inorganic electric conducting material, inorganic conductive material, metal material, organic-metallic material or inorganic-metal material, for example carbon material (as Vulcan XC-72), lithium and cobalt oxides, lithium manganese oxide, lithium nickel oxide, lithium-cobalt-nickel oxide, lithium nickel cobalt manganese oxidation thing, lithium iron phosphate oxide etc.In other preferred embodiment of the present invention, the employed bond of this mea can comprise a catalyst material, for example platinum (Pt), ruthenium (Ru), platinum-ruthenium alloys, platinum ashbury metal (Pt-Sn), platinum-tungsten alloys (Pt-W), platinum molybdenum alloy (Pt-Mo) etc.
Please refer to shown in Fig. 2 A and Fig. 2 B, by the formed layer 201 that closes admittedly of this bond, be that electrode layer 202 and proton exchange membrane 203 are linked, the organic polymer of its hyper branched polymer of the employed bond of this mea and tool conducting ion ability is the polyelectrolyte main structure 204 of closing layer 201 as this admittedly, and see through the performance assembly and the structural design of himself material, use mixing/disperse/adhere to/technology such as self-organizing/structure is fixing, conductive material (for example nano carbon material) 205 that this bond comprised and the catalyst material platinum of activity (for example have) 206 built structure tool class linearity (Linear-like) (please refer to Fig. 2 A) or class netted (Network-like) three-dimensional structures such as (please refer to Fig. 2 B), present air guide, lead proton, conduction, the feature passage of water guide (Characteristic Channels), reach the gain battery performance effect.For instance, hydrogen enters and closes layer admittedly after be attached to catalyst reaction on the carbon material and generate the hydrogen proton (reaction equation is H
2-＞2H
++ 2e
-).Hydrogen proton 207 can enter consolidating that this bond material constituted by this proton exchange membrane 203 and close layer 201 passage; 208 of electronics can enter consolidating that this bond material constituted by cathode electrode 202 and close layer 201 passage; The oxygen 209 also passage by this air guide and electronics and hydrogen proton carries out chemical reaction.In addition, oxygen imports and to close in the layer admittedly, and (reaction equation is 1/2O with proton and electron reaction
2+ 2H
++ 2e
--＞H
2O), produce water.By as can be known above-mentioned, the high branched structure of utilization upgrading type tool is from the main composition of termination type macromolecule (STOBA) as bond, and be directed in Sulfonated polyether-ether-ketone (s-PEEK) or perfluorinated sulfonic resin (Nafion), Sulfonated polyether-ether-ketone (s-PEEK), Sulfonated polyimides (s-PI), polyphosphoric acid/polybenzimidazoles macromolecule (p-PBI), Sulfonated polyphenylene oxide (s-PPO), Sulfonated polyether sulphone (s-PES), Sulfonated poly-4-phenoxy group 1,4 Ben Ji Benzyl base ester (s-PPBP) or its mixing, can build to constitute and have the structure of proton channel (proton channel), water holding capacity when strengthening high-temperature operation with this, anti-chemistry and electrochemical stability, mechanical strength, thermal endurance and flexibility, simultaneously can enhance the conductivity of proton and avoid acidleach to go out (acid leaching out), in order to reach high-performance, the mea bond that quality is good and cost is low.
Please refer to Fig. 3, be the above-mentioned chemical constitution of polyelectrolyte structure 204 (organic polymer by hyper branched polymer and tool conducting ion ability is constituted) of layer 201 (by the formed retes of this bond) and the conduct the relation schematic diagram of hydrone and proton of closing admittedly of explanation, wherein this proton exchange membrane is by STOBA and s-PEEK is prepared forms, and the s-PEEK segment is about
, and this STOBA be by bismaleimides (BMI) group and barbituric acid group constituted, its weight average molecular weight is about 9000 to 12000.
Below by the following example and comparing embodiment the preparation and the character thereof of proton exchange membrane of the present invention are described, in order to further to illustrate technical characterictic of the present invention.
The preparation of hyper branched polymer
Embodiment 1-3:
(its structure is respectively will to contain dimaleoyl imino group compound
,
(structure is with barbituric acid respectively
Be dissolved in (mol ratio that contains dimaleoyl imino group's compound and barbituric acid is 2: 1, and solid content is 20wt%) among the GBL (gamma-butyrolacton), and reacted 6 hours down at 130 ℃.After filtration is drained, obtain hyper branched polymer (A)-(C) respectively, its degree of branching is about 50%.
The preparation of mea bond
Embodiment 4:
With embodiment 1 resulting hyper branched polymer (A, solid content 20%, solvent is GBL) and s-PEEK (Sulfonated polyether-ether-ketone, solid content 20%, sulfonated 67%, solvent is NMP) at room temperature fully stir 1 hour after, use the low-temperature reduced-pressure mode to take out to residue in the bubble in the solution again, can obtain bond (A), wherein hyper branched polymer (A) is 15: 85 with the solid weight percentage of s-PEEK.
Embodiment 5:
With embodiment 1 resulting hyper branched polymer (A, solid content 20%, solvent is GBL) and s-PI (Sulfonated polyimides, solid content 3%, solvent is a m-cresol) at room temperature fully stir 1 hour after, use the low-temperature reduced-pressure mode to take out again and residue in the interior bubble of solution, can obtain bond (B), wherein hyper branched polymer (A) is 18: 82 with the weight ratio of s-PI.
Embodiment 6:
With embodiment 1 resulting hyper branched polymer (A, solid content 20%, solvent is GBL) at room temperature fully stir 1 hour with Nafion2020 (make and sell) by E.I.Du Pont Company after, be that room temperature left standstill 5 days, can obtain bond (C), wherein hyper branched polymer (A) is 10: 90 with the weight ratio of Nafion.A layer property detection closed in consolidating that bond constituted
With the bond (A) of embodiment 4,5 gained and (B) coat respectively (dry film is estimated and is about 25um) on the glass substrate, program according to 80 ℃/30min → 100 ℃/60min → 130 ℃/120min is toasted operation, peels off from glass substrate after cooling and can be closed layer (A) and dry film (B) respectively admittedly.To close admittedly layer (A) and (B) with known materials Naflon 112, s-PEEK, and rete that s-PI formed carry out water holding capacity (water retention ability), mechanical strength, and soak into the test of degrees of expansion, its test condition and result are respectively shown in following table 1～3:
The water retention coefficient of each composition of table 1STOBA-SPEEK material
| ??STOBA | ??-SO 3H | ??PEEK | ??BMI | |
| Free water (Free water) (＜100 ℃-TGA) | ??0.1904 | ??5.7614 | ??-0.5438 | ??-1.8956 |
| Bond water (Bound water) (100 ℃～200 ℃-TGA) | ??0.1429 | ??-0.4771 | ??0.0960 | ??-0.0568 |
Remarks 1: each composition water retention coefficient is the Unit Weight water conservation contribution rate that weight provided (water retention contribution) of the overall water retention coefficient of this STOBA-SPEEK composition at indivedual compositions.
Remarks 2: the boiling water that the STOBA-SPEEK film of various combination composition is soaked in 100 ℃ was dried after 1 hour, carried out the TGA inspection immediately and analysed.The loss amount of institute below 100 ℃ is defined as the weight of free water, and institute's loss amount then is defined as bond water in 100 ℃～200 ℃ scopes.
List the water retention coefficient of each composition the STOBA-SPEEK structure from table 1, can learn that STOBA has water holding capacity really, especially structure can have stronger hydrogen bond bonding interaction with water, and this part is better than sulfonic acid group (SO
3H), PEEK, and BMI monomer need can apply to higher temperatures to promote the operating environment of battery efficiency.
The comparison of the film engineering properties of table 2 comparative example and embodiment
| ??Nafion??112 | ??s-PEEK | Admittedly close layer (A) (STOBA: s-PEE K=20: 80) | ??s-PI | Admittedly close layer (B) (STOBA: s-P I=18: 82) | |
| Thickness (μ m) | ??54 | ??25 | ?42 | ??26 | ??26 |
| Tensile strength (Kgf/mm 2) | ??2.25 | ??4.94 | ?5.87 | ??2.69 | ??4.22 |
| Prolongation property (%) | ??103.3 | ??5.48 | ?5.28 | ??5.00 | ??6.37 |
Add STOBA as known from Table 2 in the structure of SPEEK or SPI, all can promote the tensile strength of general structure effectively,, can strengthen the mechanical performance of overall electrode group material with this bond as the electrode group.
The comparison of the anti-high humidity swelling of the film of table 3 comparative example and embodiment intensity
| ??Naflon??112 | ??s-PEEK | Admittedly close layer (A) (STOBA: s-P EEK=20: 80) | ??s-PI | Admittedly close layer (B) (STOBA: s-PI=18: 82) | |
| ??ΔL | ??17％ | ??X | ??5％ | ??2.5％ | ??3.75％ |
| ??ΔW | ??3％ | ??X | ??10％ | ??12％ | ??0％ |
| ??ΔT | ??12％ | ??X | ??19％ | ??53.9％ | ??4.5％ |
| Film | Softening | Dissolving | No embrittlement | Embrittlement | No embrittlement |
Remarks: test mode continues 120 minutes for material being immersed in the water under 100 ℃; Wherein Δ L, Δ W, Δ T represent that respectively material is at length and width, thick expansion percentage.
Add STOBA as known from Table 3 in the structure of SPEEK or SPI, all can subtract the size changing rate that falls general structure effectively, the dimensional stability of material is higher, and can overcome the problem of dissolving of SPEEK under the high temperature and SPI embrittlement.
Warpage and then degree test
The bond (C) of embodiment 6 gained is coated a side surface of one first gas diffusion layers (carbonaceous paper) and one second gas diffusion layers (carbonaceous paper) and the both side surface of a proton exchange membrane (being made of STOBA, s-PEEK and s-PI) respectively, structural order according to first gas diffusion layers-proton exchange membrane-second gas diffusion layers utilizes hot pressing mode with above-mentioned rete hot pressing together, and toasts 15 minutes down at 70 ℃ and 130 ℃.
Then, above-mentioned mea is soaked in 1,25 ℃ pure water 15 hours respectively; 2,100 ℃ pure water is after 1.5 hours, and no warpage or peeling phenomenon take place.
Can confirm from The above results, consolidating of bond gained of the present invention closes no matter film (with STOBA collocation s-PEEK or s-PI) is solid water coefficient and mechanical strength, all be better than merely the rete as material, and also be difficult for dilatancy in the water of high temperature with s-PEEK or s-PI.This represents STOBA really with s-PEEK or the s-PI upgrading and its usefulness that gains, and can obviously improve film at height warm and humid down (100 ℃/100%RH) swelling and fragility.In addition, the consolidating of bond gained of the present invention closed film and compares with traditional Naflon 112 retes, and tensile strength obviously improves, and also can not soften and embrittlement in high-temperature water.Moreover under the test of conductivity, its conductivity of 25 ℃ (1 * 10 of film is closed in consolidating of bond gained of the present invention
-2～5 * 10
-2S/cm) suitable with Nafion, and be 1 * 10 at 120 ℃ conductivity
-1～5 * 10
-1S/cm.
Though the present invention with preferred embodiment openly as above; right its is not in order to limit the present invention; any those skilled in the art; without departing from the spirit and scope of the present invention; when can doing a little change and retouching, so protection scope of the present invention is as the criterion when looking the accompanying Claim book scope person of defining.
Claims (19)
1. employed bond of mea comprises:
One solvent system;
One hyper branched polymer, wherein said hyper branched polymer base material has a degree of branching greater than 0.5; And
One has the organic polymer of conducting ion ability,
Wherein said hyper branched polymer and described organic polymer with conducting ion ability are scattered in the described solvent system.
2. the employed bond of mea according to claim 1, wherein said hyper branched polymer are the macromolecular material that reactant constituted that contains dimaleoyl imino group's compound and barbituric acid.
3. the employed bond of mea according to claim 2, the wherein said mol ratio of dimaleoyl imino group's compound and barbituric acid that contains is between 20: 1 to 1: 5.
4. the employed bond of mea according to claim 2, the wherein said mol ratio of dimaleoyl imino group's compound and barbituric acid that contains is between 5: 1 to 1: 2.
5. the employed bond of mea according to claim 2, the wherein said dimaleoyl imino group compound that contains comprises bismaleimide amine monomers replacement or unsubstituted or bismaleimides oligomerization compound.
6. the employed bond of mea according to claim 2, the wherein said dimaleoyl imino group compound that contains comprises:
7. the employed bond of mea according to claim 1, the percentage by weight of wherein said hyper branched polymer is 5% to 30%, is benchmark with described hyper branched polymer and described organic macromolecule gross weight with conducting ion ability.
8. the employed bond of mea according to claim 1, the percentage by weight of wherein said hyper branched polymer is 10% to 25%, is benchmark with described hyper branched polymer and described organic macromolecule gross weight with conducting ion ability.
9. the employed bond of mea according to claim 1, wherein said organic polymer with conducting ion ability is perfluorinated sulfonic resin, Sulfonated polyether-ether-ketone, Sulfonated polyimides, polyphosphoric acid/polybenzimidazoles macromolecule, Sulfonated polyphenylene oxide, Sulfonated polyether sulphone or Sulfonated poly-4-phenoxy group 1,4 Ben Ji Benzyl base ester.
10. the employed bond of mea according to claim 1, wherein said solvent system is gamma-butyrolacton, N-methyl pyrrolidone, N, N-dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), dimethylamine, oxolane, butanone, propene carbonate, water, isopropyl alcohol or its mixing.
11. the employed bond of mea according to claim 1 also comprises an electric conducting material.
12. the employed bond of mea according to claim 11, wherein said electric conducting material are organic conductive material, organic and inorganic electric conducting material, inorganic conductive material, metal material, organic-metallic material or inorganic-metal material.
13. the employed bond of mea according to claim 11, wherein said electric conducting material are carbon material, lithium and cobalt oxides, lithium manganese oxide, lithium nickel oxide, lithium-cobalt-nickel oxide, lithium nickel cobalt manganese oxidation thing or lithium iron phosphate oxide.
14. the employed bond of mea according to claim 1 also comprises a catalyst material.
15. the employed bond of mea according to claim 14, wherein this catalyst material is platinum, ruthenium, platinum-ruthenium alloys, platinum ashbury metal, platinum-tungsten alloys or platinum molybdenum alloy.
16. the employed bond of mea according to claim 1, wherein said bond are to connect and change a film and an electrode in order to unify proton admittedly.
17. the employed bond of mea according to claim 1, wherein said bond are in order to unify a catalyst layer and an electrode admittedly.
18. a mea comprises:
One anode catalyst electrode;
One cathod catalyst electrode;
One proton exchange membrane is disposed between described anode catalyst electrode and the described cathod catalyst electrode; And
One closes layer admittedly, and in conjunction with described cathod catalyst electrode, described anode catalyst electrode and described proton exchange membrane, the wherein said layer that closes admittedly is made up of the employed bond of the described mea of claim 1 in order to respectively.
19. mea according to claim 18, wherein said mea are to be applied to fuel cell, lithium ion battery, or bio-battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105762336A (en) * | 2014-12-19 | 2016-07-13 | 江苏华东锂电技术研究院有限公司 | An anode composite material, a preparing method thereof and a lithium ion battery |
| JPWO2016063813A1 (en) * | 2014-10-21 | 2017-08-03 | 日本電気株式会社 | Secondary battery electrode and secondary battery using the same |
| CN107732163A (en) * | 2016-08-12 | 2018-02-23 | 微宏动力系统（湖州）有限公司 | A kind of lithium rechargeable battery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100505395C (en) * | 2006-09-15 | 2009-06-24 | 中国电子科技集团公司第十八研究所 | Self-humidifying proton exchange film fuel cell membrane electrode preparation method |
| CN101210073B (en) * | 2006-12-30 | 2010-12-08 | 财团法人工业技术研究院 | Composition containing bismaleimide oligomer and preparing method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2016063813A1 (en) * | 2014-10-21 | 2017-08-03 | 日本電気株式会社 | Secondary battery electrode and secondary battery using the same |
| CN105762336A (en) * | 2014-12-19 | 2016-07-13 | 江苏华东锂电技术研究院有限公司 | An anode composite material, a preparing method thereof and a lithium ion battery |
| CN105762336B (en) * | 2014-12-19 | 2019-06-25 | 江苏华东锂电技术研究院有限公司 | Anode material and preparation method thereof and lithium ion battery |
| CN107732163A (en) * | 2016-08-12 | 2018-02-23 | 微宏动力系统（湖州）有限公司 | A kind of lithium rechargeable battery |
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