CN101170182A - A surface processing method for proton exchange film fuel battery group aluminum alloy terminal board - Google Patents
A surface processing method for proton exchange film fuel battery group aluminum alloy terminal board Download PDFInfo
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- CN101170182A CN101170182A CNA2006101340241A CN200610134024A CN101170182A CN 101170182 A CN101170182 A CN 101170182A CN A2006101340241 A CNA2006101340241 A CN A2006101340241A CN 200610134024 A CN200610134024 A CN 200610134024A CN 101170182 A CN101170182 A CN 101170182A
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- end plate
- aluminum alloy
- proton exchange
- resin
- epoxy resin
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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
Abstract
The invention relates to a surface treatment method for an aluminum alloy end plate of a proton exchange membrane fuel cell group. After an anode of aluminum alloy end plate is oxidized, the surface is coated with one layer of epoxy resin, and the resin is heated for solidification. After being treated with the method, the aluminum alloy surface obtains an insulating function layer with tight corrosion resistance, thereby improving the end plate life in the cell operational environment.
Description
Technical field
The present invention relates to the surface treatment method of Proton Exchange Membrane Fuel Cells group aluminum alloy end plate, can significantly improve the stability of Proton Exchange Membrane Fuel Cells aluminium alloy end plate under the battery operation condition, thereby prolong the life-span of end plate, reduced the harmful effect that battery performance is produced because corrosion takes place end plate simultaneously.
Background technology
Proton Exchange Membrane Fuel Cells is fuel with hydrogen, directly chemical energy is converted into electric energy and is not subjected to the restriction of Carnot cycle, energy conversion efficiency height; Unique product is a water, almost to zero environmental; Simultaneously, but PEMFC also has started quickly at low temperature, and noise is little, and the power density advantages of higher is suitable as electric powered motor source, portable small-sized power supply and underwater engine system power supply etc. very much.Thereby, since the last century the nineties, being subjected to the extensive concern of each side such as the national governments and the energy, automobile, household electrical appliances and military project, technical development is rapid.
Proton Exchange Membrane Fuel Cells belongs to the diaphragm type fuel cell, and the battery pack of the overwhelming majority is all assembled by the filter press mode at present, and common-use tunnel form in adopting mostly.The main body of battery pack is the repetition of MEA (film of fuel cell electrode three-in-one component), bipolar plates and corresponding seal unit.What face mutually with the collector plate at battery pack two ends is the battery pack end plate, also claims clamping plate, and except that being furnished with reaction gas and cooling fluid access way, periphery is the circular hole of uniform some also on end plate.When the assembled battery group, penetrate screw rod in the circular hole, apply certain assembling force to battery, so end-plate material should possess certain intensity.Generally 80 ℃ of operations, end plate should keep original intensity to Proton Exchange Membrane Fuel Cells under this temperature, and softening transform does not take place.Because action need, inlet gas needs humidification; The water that reaction generates is high humility gas or biphase gas and liquid flow also with the eliminating of giving vent to anger so import and export material.Because inside battery is a faintly acid, so end plate is wanted acid corrosion-resistant.In order to guarantee that battery normally starts under low temperature environment, in cooling water, also to add a certain amount of ethylene glycol antifreeze, end plate also should have very high chemical stability in ethylene glycol.Below 150 joints, the voltage ratio about the anti-200V of end plate is safer usually for the high power battery group at present.And gravimetric specific power and volumetric specific power in order to improve whole battery group, end plate is when keeping sufficient intensity, and density is the smaller the better.Thereby desirable Proton Exchange Membrane Fuel Cells group end plate need possess good insulating, and corrosion-resistant, high voltage withstanding, density is little, performances such as intensity height.
At present, Chang Yong end-plate material comprises some metals and glass laminate, engineering plastics, polysulfone material etc.Strength of Metallic Materials height such as titanium plate or corrosion resistant plate, but need between collector plate and end plate, adding make battery system complicated by the insulation board of material preparations such as engineering plastics; Glass laminate exists between each layer collaborates, and also can't address this problem at present; And the thermal stability of engineering plastics and polysulfone material is all good inadequately, easy softening transform under the temperature of battery operation.
Aluminium alloy density small intensity height can form insulating film layer after anodic oxidation, be more satisfactory end-plate material.But what adopt is the anodised technology of fixed voltage before, seals in boiling water then, and inevitably there is defective in rete, still can corrode after operation a period of time in battery pack.The present invention has obtained fine and close more oxidation film layer by the anode oxidation process of constant current density; Seal with epoxy resin then, the basic atresia of epoxy resin rete after the curing, and also insulation property are also fine.Therefore the functional film layer that the present invention obtained can better meet the performance requirement of Proton Exchange Membrane Fuel Cells to end plate.
Relevant patent is as follows:
USP20050048347 proposes the manufacture method of a proton exchanging film fuel battery group end-plate material, this method with heat cured resin with make it after inorganic filler mixes to solidify.Wherein the content of resin is in 1-47% (mass percent); The content of inorganic filler is 50-96%.Selected resin comprises: epoxy resin, maleimide resin, phenolic resin, mylar and silicones etc.
USP20020182470 has proposed a kind of method of injection moulding fuel cell end plate.This end plate is based on thermoplastic resin, and the length that is aided with 30% above mass content surpasses the fiberglass reinforcement of 5mm.Thermoplastic resin comprises: polyarylsulfone (PAS), poly aryl ketone ether etc.
Summary of the invention
The object of the present invention is to provide the surface treatment method of a proton exchanging film fuel battery group aluminum alloy end plate.After the anodic oxidation of aluminium alloy end plate,, and make resin solidification at its surface applied one deck epoxy resin.After the method is handled, obtained fine and close corrosion resistant insulation function layer in aluminum alloy surface, thereby improved the stability of end plate under the battery operation environment.
For achieving the above object, the technical solution used in the present invention is:
The surface treatment method of one proton exchanging film fuel battery group aluminum alloy end plate at first carries out anodic oxidation with the aluminium alloy end plate, makes its surface form oxide-film; At oxide-film surface applied one deck epoxy resin, heating makes resin solidification, thereby obtains fine and close corrosion resistant insulation function layer in end sheet surface then.
The aluminium alloy anode oxide process adopts the technology of constant current density; The technology of described constant current density is, aluminium alloy was placed 30～300 seconds in the NaOH of 5～100g/L of 40～80 ℃ solution, alkaline etching is removed the oxide skin on surface, put into the floating ash of 10%-30% nitric acid flush away then, in the sulfuric acid solution of volume ratio 5%～50%, carry out anodic oxidation again, 8～15 ℃ of temperature adopt constant-current supply, current density 0.5～3A/dm
2, time 20～60min.
Behind end plate oxide-film surface applied resin, 180～250 ℃ of heating 1～8 hour, cool off 1～12 hour at last to room temperature, make resin solidification; Also can add curing agent and/or solvent in the described epoxy resin, when epoxy resin+curing agent, the volume ratio of epoxy resin and curing agent is 4: 1～4: 3; When epoxy resin+solvent, the volume ratio of epoxy resin and solvent is 4: 1～4: 3; When epoxy resin+curing agent+solvent, the volume ratio of epoxy resin, curing agent, solvent is 4: 1: 1～4: 3: 3; Described curing agent contract amine-105 epoxy hardener or 593 epoxy curing agents; Described solvent is ethyl acetate or absolute ethyl alcohol.
The method of application of resin adopts directly and applies or spraying with brush, purges heating so that resin bed is even with hair dryer then; Cooling means comprised natural cooling or forces cooling etc. after resin was heating and curing; The thickness of resin film layer often is 1～2000 μ m.
The present invention has following advantage:
1, the present invention makes aluminium alloy be able to use as the Proton Exchange Membrane Fuel Cells end-plate material, and aluminium alloy density is low, the intensity advantages of higher owing to made full use of, and has effectively reduced the gravimetric specific power and the volumetric specific power of battery pack;
2, the present invention prepares the insulation function layer of corrosion resistance and good, and good stability under the Proton Exchange Membrane Fuel Cells service conditions can not produce harmful effect to battery performance because of corrosion takes place;
3, the functional layer prepared of the present invention is very fine and close, and handling for the sealing behind the aluminium alloy anode oxide provides new thinking.
Embodiment
Below in conjunction with chart and embodiment the present invention is described in further detail.
Embodiment 1
Get 1dm
2LY12 aluminum alloy sample absolute ethyl alcohol wiped clean, dry the back and in the NaOH of 60 ℃ of 50g/L solution, placed 2 minutes, remove the oxide-film on surface; In 10% nitric acid (volume ratio), remove the floating ash in top layer again.Then sample is placed 10% sulfuric acid (volume ratio), at 2A/dm
2Constant current density under anodic oxidation 30 minutes, 10 ℃ of temperature.Washed with de-ionized water is dried.Evenly be coated with the skim bisphenol A type epoxy resin at dried sample surfaces, thickness is 15 μ m.Under 215 ℃ of conditions, in baking oven, placed 6 hours, stop heating, make sample in baking oven natural cooling 12 hours to room temperature.
Every performance of specimen.
1) electrical property: face resistance＞200M Ω; Puncture voltage＞200V;
2) thermal shock experiment: room temperature (about 20 ℃)---100 ℃ (keeping 1 hour)---200 ℃ (keeping 4 hours), circulate 2 times, sample surfaces does not have softening transform;
3) (hydrochloric acid 400ml/L, K in the strong oxidizing solution of strong acid
2Cr
2O
748g/L), (aluminum alloy sample is anodic oxidation in 10% sulfuric acid 8～15 ℃ of volume ratios, constant applied voltage 15V, 30 minutes with adopting common process with sample (A); Take out then, after the washed with de-ionized water in boiling water sealing handled 30 minutes, washed with de-ionized water is dried) sample (B) of preparation compares, and sees Table 1;
Table 1.The aluminum alloy sample corrosion resistance that different process is handled relatively
| Time test piece | A | B |
| 0.1h | \ | Bubble appears in surface scratch and anodised hanger catcher mark place |
| 0.25h | \ | Bubble appears in three points and edge on the face |
| 0.75h | \ | Three spot corrosion are serious on the face |
| 2h | \ | The corrosion aggravation, solution changes color |
| 2.5h | \ | Finish experiment, 3 of test pieces are corroded |
| 5.5h | Bubble appears in anodised hanger trace place | \ |
| 90h | Wide area surface is still intact | \ |
4) sample at room temperature being placed volume ratio is the decay resistance test of 1: 1 glycol water: 200 hours, no corrosion phenomenon took place, and weightlessness is 0.
Embodiment 2
Be with embodiment one difference: NaOH etchant solution temperature is 40 ℃ of 100g/L, standing time 300s; Concentration of nitric acid is (volume ratio) 20%.Anodised solution is 5% sulfuric acid (volume ratio), at 3A/dm
2Constant current density under anodic oxidation 60 minutes, 8 ℃ of temperature.Closed material uses bisphenol A type epoxy resin to add ethyl acetate dilution (volume ratio 3: 1), thicknesses of layers 10 μ m.Under 180 ℃ of conditions, in baking oven, placed 8 hours, stop heating, make sample in baking oven natural cooling 8 hours to room temperature.
Embodiment 3
Be with embodiment one difference: NaOH etchant solution temperature is 80 ℃ of 5g/L, standing time 30s; Concentration of nitric acid is (volume ratio) 30%.Anodised solution is 50% sulfuric acid (volume ratio), at 0.5A/dm
2Constant current density under anodic oxidation 20 minutes, 15 ℃ of temperature.Closed material uses the bisphenol A type epoxy resin+amine that contracts-105 epoxy hardeners+ethyl acetate dilution (volume ratio 3: 1: 1), thicknesses of layers 2000 μ m.Under 250 ℃ of conditions, in baking oven, placed 1 hour, stop heating, make sample in baking oven natural cooling 1 hour to room temperature.
Embodiment 4
Be with embodiment one difference: closed material uses the bisphenol A type epoxy resin+amine that contracts-105 epoxy hardener (volume ratio 3: 1), thicknesses of layers 1 μ m.
Embodiment 5
Be with embodiment one difference: closed material uses bisphenol A type epoxy resin to add absolute ethyl alcohol dilution (volume ratio 4: 1), thicknesses of layers 100 μ m.
Embodiment 6
Be with embodiment one difference: closed material uses bisphenol A type epoxy resin to add ethyl acetate dilution (volume ratio 4: 3).
Embodiment 7
Be with embodiment one difference: closed material uses bisphenol A type epoxy resin+593 epoxy curing agents (volume ratio 4: 1).
Embodiment 8
Be with embodiment one difference: closed material uses the bisphenol A type epoxy resin+amine that contracts-105 epoxy hardener (volume ratio 4: 3), thicknesses of layers 80 μ m.
Embodiment 9
Be with embodiment one difference: closed material uses the bisphenol A type epoxy resin+amine that contracts-105 epoxy hardeners+ethyl acetate dilution (volume ratio 4: 1: 1), 200 ℃ of oven temperatures.
Embodiment 10
Be with embodiment one difference: closed material uses the bisphenol A type epoxy resin+amine that contracts-105 epoxy hardeners+ethyl acetate dilution (volume ratio 4: 3: 3), 220 ℃ of oven temperatures.
Claims (9)
1. the surface treatment method of a proton exchanging film fuel battery group aluminum alloy end plate is characterized in that: at first the aluminium alloy end plate is carried out anodic oxidation, make its surface form oxide-film; At oxide-film surface applied one deck epoxy resin, heating makes resin solidification, thereby obtains fine and close corrosion resistant insulation function layer in end sheet surface then.
2. according to the surface treatment method of the described Proton Exchange Membrane Fuel Cells group aluminum alloy of claim 1 end plate, it is characterized in that: the aluminium alloy anode oxide process adopts the technology of constant current density.
3. according to the surface treatment method of the described Proton Exchange Membrane Fuel Cells group aluminum alloy of claim 2 end plate, it is characterized in that: the technology of described constant current density is, aluminium alloy was placed 30～300 seconds in the NaOH of 5～100g/L of 40～80 ℃ solution, remove the oxide skin on surface, put into the floating ash of 10%-30% nitric acid flush away then, in 5%～50% sulfuric acid solution, carry out anodic oxidation again, 8～15 ℃ of temperature, adopt constant-current supply, current density 0.5～3A/dm
2, time 20～60min.
4. according to the surface treatment method of the described Proton Exchange Membrane Fuel Cells group aluminum alloy of claim 1 end plate, it is characterized in that: behind end plate oxide-film surface applied resin, 180～250 ℃ of heating 1～8 hour, cool off 1～12 hour at last to room temperature, make resin solidification.
5. according to the surface treatment method of claim 1 or 4 described Proton Exchange Membrane Fuel Cells group aluminum alloy end plates, it is characterized in that: also can add curing agent and/or solvent in the described epoxy resin, when epoxy resin+curing agent, the volume ratio of epoxy resin and curing agent is 4: 1～4: 3;
When epoxy resin+solvent, the volume ratio of epoxy resin and solvent is 4: 1～4: 3;
When epoxy resin+curing agent+solvent, the volume ratio of epoxy resin, curing agent, solvent is 4: 1: 1～4: 3: 3.
6. according to the surface treatment method of the described Proton Exchange Membrane Fuel Cells group aluminum alloy of claim 5 end plate, it is characterized in that: described curing agent contract amine-105 epoxy hardener or 593 epoxy curing agents; Described solvent is ethyl acetate or absolute ethyl alcohol.
7. according to the surface treatment method of the described Proton Exchange Membrane Fuel Cells group aluminum alloy of claim 1 end plate, it is characterized in that: the method for application of resin adopts directly and applies or spraying with brush, purges heating so that resin bed is even with hair dryer then.
8. according to the surface treatment method of the described Proton Exchange Membrane Fuel Cells group aluminum alloy of claim 1 end plate, it is characterized in that: cooling means comprised natural cooling or forces cooling etc. after resin was heating and curing.
9. according to the surface treatment method of the described Proton Exchange Membrane Fuel Cells group aluminum alloy of claim 1 end plate, it is characterized in that: the thickness of resin film layer is 1～2000 μ m.
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| CNB2006101340241A CN100533830C (en) | 2006-10-25 | 2006-10-25 | A surface processing method for proton exchange film fuel battery group aluminum alloy terminal board |
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| CNB2006101340241A CN100533830C (en) | 2006-10-25 | 2006-10-25 | A surface processing method for proton exchange film fuel battery group aluminum alloy terminal board |
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| CN100533830C CN100533830C (en) | 2009-08-26 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597784B (en) * | 2008-06-04 | 2012-03-28 | 比亚迪股份有限公司 | Hole-sealing method for anode oxide film of light metal material |
| CN103029247A (en) * | 2011-09-29 | 2013-04-10 | 株式会社东芝 | Electrical insulating cast article and manufacturing method thereof |
| CN105671616A (en) * | 2016-03-16 | 2016-06-15 | 浙江鸿昌铝业有限公司 | Anticorrosive treatment technology for surface of aluminum profile |
| CN107326422A (en) * | 2017-07-03 | 2017-11-07 | 西安强微电气设备有限公司 | A kind of preparation method of aluminum alloy battery surface of shell composite insulation layer |
| CN107732271A (en) * | 2016-08-12 | 2018-02-23 | 丰田自动车株式会社 | Fuel cell unit |
| CN111342078A (en) * | 2020-03-03 | 2020-06-26 | 泰安鼎鑫冷却器有限公司 | Low-conductivity core body for fuel cell and processing technology |
| CN112844997A (en) * | 2020-12-31 | 2021-05-28 | 浙江高成绿能科技有限公司 | Surface insulation treatment method for fuel cell stack end plate |
| CN114277420A (en) * | 2021-12-22 | 2022-04-05 | 佛山泰铝新材料有限公司 | Aluminum substrate with sterilization and antibiosis functions and preparation method thereof |
| CN114381777A (en) * | 2021-12-20 | 2022-04-22 | 佛山泰铝新材料有限公司 | Aluminum alloy anodic oxidation composite sealing method |
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2006
- 2006-10-25 CN CNB2006101340241A patent/CN100533830C/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597784B (en) * | 2008-06-04 | 2012-03-28 | 比亚迪股份有限公司 | Hole-sealing method for anode oxide film of light metal material |
| CN103029247A (en) * | 2011-09-29 | 2013-04-10 | 株式会社东芝 | Electrical insulating cast article and manufacturing method thereof |
| CN103029247B (en) * | 2011-09-29 | 2015-04-15 | 株式会社东芝 | Electrical insulating cast article and manufacturing method thereof |
| CN105671616A (en) * | 2016-03-16 | 2016-06-15 | 浙江鸿昌铝业有限公司 | Anticorrosive treatment technology for surface of aluminum profile |
| CN107732271A (en) * | 2016-08-12 | 2018-02-23 | 丰田自动车株式会社 | Fuel cell unit |
| CN107732271B (en) * | 2016-08-12 | 2020-11-03 | 丰田自动车株式会社 | Fuel cell stack |
| CN107326422A (en) * | 2017-07-03 | 2017-11-07 | 西安强微电气设备有限公司 | A kind of preparation method of aluminum alloy battery surface of shell composite insulation layer |
| CN107326422B (en) * | 2017-07-03 | 2019-11-12 | 西安强微电气设备有限公司 | A kind of preparation method of aluminum alloy battery surface of shell composite insulation layer |
| CN111342078A (en) * | 2020-03-03 | 2020-06-26 | 泰安鼎鑫冷却器有限公司 | Low-conductivity core body for fuel cell and processing technology |
| CN112844997A (en) * | 2020-12-31 | 2021-05-28 | 浙江高成绿能科技有限公司 | Surface insulation treatment method for fuel cell stack end plate |
| CN114381777A (en) * | 2021-12-20 | 2022-04-22 | 佛山泰铝新材料有限公司 | Aluminum alloy anodic oxidation composite sealing method |
| CN114277420A (en) * | 2021-12-22 | 2022-04-05 | 佛山泰铝新材料有限公司 | Aluminum substrate with sterilization and antibiosis functions and preparation method thereof |
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| CN100533830C (en) | 2009-08-26 |
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