CN101710620A - Proton exchange membrane fuel cell stainless steel bipolar plate and modification method thereof - Google Patents
Proton exchange membrane fuel cell stainless steel bipolar plate and modification method thereof Download PDFInfo
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- CN101710620A CN101710620A CN200910231657A CN200910231657A CN101710620A CN 101710620 A CN101710620 A CN 101710620A CN 200910231657 A CN200910231657 A CN 200910231657A CN 200910231657 A CN200910231657 A CN 200910231657A CN 101710620 A CN101710620 A CN 101710620A
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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 an improvement on a surface property of a proton exchange membrane fuel cell metal bipolar plate, which is characterized in that: a substrate surface is plated with a nickel layer and a Ni-Cu-P double-plating layer, wherein Ni-Cu-P adopts electroless deposition. The improvement not only greatly reduces contact resistance of the bipolar plate and a gas diffusion layer, but also improves corrosion resistant. Electrical conductivity and the corrosion resistance can basically reach the level of those of the stainless steel bipolar plate plated with precious metal. The improvement is simple in modification, low in cost and superior in performance after modification.
Description
Technical field
The present invention is the improvement to the dual polar plates of proton exchange membrane fuel cell surface property, relates in particular to the bipolar plate of stainless steel that there is Ni-Cu-P coating on a kind of surface of adopting chemical plating method to obtain, and surface modifying method.
Background technology
Bipolar plates is one of Proton Exchange Membrane Fuel Cells (PEMFC) critical component, cost accounts for more than 46% of fuel cell total cost, be to cause one of high major reason of Proton Exchange Membrane Fuel Cells price, and quality good or not directly determine fuel cell pack power output size and useful life length.
Characteristics such as stainless steel has high-termal conductivity, easily machine-shaping, and price is low, and can improve fuel cell output power, improve the fuel cell heat management, reduce the fuel cell pile cost, be a kind of dual polar plates of proton exchange membrane fuel cell base material that has future.But stainless steel not only self-resistance is higher, and surface passivated membrane and corrosion product produce additional resistance, makes to have bigger contact resistance when contacting with gas diffusion layers, can cause the internal resistance of fuel cell increase, directly influences battery power output and useful life.Secondly, stainless steel corrosion resistance under battery context is relatively poor, and corrosion product can poison proton exchange membrane, reduces battery performance and life-span.And noble metals such as use gold, silver can improve conductivity and corrosion resistance, but cost is higher, is unfavorable for commercially producing.People take in type bipolar plate of stainless steel is carried out surface treatment for this reason, to overcome above-mentioned deficiency.For example:
The disclosed dual polar plates of proton exchange membrane fuel cell of U.S. Pat 7.247.403B2 contains the chromium nitrogen treatment at stainless steel surfaces, forms the series modified layer of chromium nitride, thus the corrosion resistance that acquisition is become reconciled than low contact resistance.Yet this method needs at 800 ℃ to 1200 ℃ nitrogen treatment, the one, the processing cost height, the 2nd, the high temperature utmost point like this can make thin bipolar plate of stainless steel (thickness only is 0.1mm usually) deform, and then influence the planarization and the result of use of bipolar plates, cause and the diffusion layer loose contact, can increase contact resistance equally.
The disclosed bipolar plate for fuel cell of U.S. Pat 2008/0038619A1 is that 5～20nm noble metal film such as Au, Pt etc. are compound with 0.1mm stainless sheet steel and thickness, obtains having the low contact resistance bipolar plates, satisfies battery output energy requirement.Yet adopt the compound meeting of noble metal that the bipolar plates cost is improved a lot, be unfavorable for the commercialization promotion and application.
Japan Patent (JP-A) 11-121018 discloses at bipolar plate of stainless steel surface deposition carbon particle, to reduce the contact resistance of bipolar plates and gas diffusion layers.Deposit carbon particle and stainless steel adhesion are not strong, not only can cause carbon particle to come off because of the friction that vibration in the use causes, and the deposit carbon particle are not obvious to improving the corrosion resistance effect.
Chinese patent CN1776946 discloses a kind of surface modified stainless steel as biplar plate for proton exchange membrane fuel cell preparation method, by adopting heat treatment and surface applied silver salt technology, form conduction, corrosion-resistant particles such as chromium carbide and silver at stainless steel surfaces as conductive network, and then employing electrochemistry or chemical passivation technology, between the above-mentioned conductive network without the current-carrying part passivation, not only conducted electricity but also corrosion resistant bipolar plate of stainless steel.Its complex procedures not only, and need carry out high-temperature process, can cause ultra-thin bipolar plate of stainless steel surface irregularity, objectively be difficult to leveling, can assemble uniformity to pile and bring adverse effect, this method is difficult to commercial applications.
The disclosed proton exchange membrane fuel cell stainless steel bipolar plate of Chinese patent CN101092688, by the diamond like carbon modification plated film of ion film plating, make bipolar plates have anti-corrosion, conduction simultaneously, strengthen and composite performance such as not hydrophilic at its surface sputtering deposition chromium nickel, chromium nitride or doping metals chromium.Ion film plating is higher to equipment requirements, needs special-purpose arc ion plating apparatus, and technique process is more and complicated, causes the modification cost big equally.
The disclosed PEMFC stainless steel double-polar plate surface modifying method of Chinese patent CN101289755, with the PTFE emulsion with after surfactant evenly mixes, add in the cyanide-free silver plating solution, the electro-deposition on bipolar plate of stainless steel of employing plating mode, silver-PTFE composite deposite that adhesion is good, densification is corrosion-resistant, conductivity is strong improve the performance of bipolar plate of stainless steel under the PEMFC operational environment.But silver is precious metal, and silver-plated meeting causes the bipolar plates cost that bigger increase is arranged, and is unfavorable for the commercialization promotion and application equally.
The disclosed used in proton exchange membrane fuel cell bipolar plates of Chinese patent CN101136479 is a base material with the aluminium alloy, adopts alkalescence and acid two solution system chemical plating nickel-phosphorus alloy method, and bipolar plates is carried out surface modification.Corrosion resisting property is better than 316 stainless steels, and the thick bipolar plates specific insulation of 3mm is 8～10 μ Ω .cm, and is suitable with pure nickel, is 316 stainless steels 1/10～1/7, graphite cake 1/20～1/15.But this method is except that soaking the zinc processing, also need carry out the two solution system chemical plating nickel-phosphorus alloys of alkalescence and acidity and could obtain required coating, preparation section is many, cause the modification cost higher, aluminium alloy is that base material thickness is big in addition, can cause assembling pile volumetric specific power to descend, and the traditional plating noble metal of nickel-phosphorus coating effect have certain gap.
Though the various of above-mentioned proposition carry out surface modification to stainless steel or metal polar plate, can both overcome simple metal pole plate contact resistance and corrosion proof deficiency to a certain extent, still there is shortcoming separately in they, all fail to reach simultaneously the low-cost and high-performance modification.Therefore still having is worth improved place.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned prior art, provides a kind of not only preparation cost low, and method is simple, and can obtain the proton exchange membrane fuel cell stainless steel bipolar plate near plating noble metal performance.
Another purpose of the present invention is to provide a kind of method of modifying of above-mentioned stainless steel metal bipolar plates.
The present invention's first purpose realizes, the main improvement is on the bipolar plate of stainless steel surface, successively deposit nickel dam and the two coating of ambrose alloy phosphorus on the surface by applying the coating mode, not only reduced bipolar plate of stainless steel and gas diffusion layers contact resistance, and increased substantially bipolar plate of stainless steel decay resistance in the PEMFC battery context, and the coating material price is low, applying method is simple, the coating cost is low, thereby has overcome above-mentioned the deficiencies in the prior art, has realized the object of the invention.Specifically, proton exchange membrane fuel cell stainless steel bipolar plate of the present invention comprises moulding Thin Stainless Steel substrate, it is characterized in that substrate surface is coated with nickel dam and the two coating of ambrose alloy phosphorus.
Bipolar plate of stainless steel of the present invention, the base material stainless steel is not particularly limited, and the stainless sheet steel that uses as pole plate in the prior art all can be employed, for example 304,316,316L, 2Cr13,1Cr18Ni9Ti etc., electrode thickness is also basic identical with prior art, for example about 0.1mm.
Top layer ambrose alloy phosphorus owing to add the Cu element at Ni-P coating, test card is understood the corrosion resistance that has improved coating, under the normal temperature at 0.5mol/L H
2SO
4+ 0.5 * 10
-6In the HF solution, the Ni-P coating bipolar plates corrosion potential that does not add copper is-0.3178V, and Ni-Cu-P coating bipolar plates corrosion potential is-0.0842V.Corrosion potential has improved 233mV, and the corrosion current that match draws through the tafel empirical equation has also reduced by 1 order of magnitude; Also having reduced contact resistance simultaneously, is 150N/cm at pressure for example
2Down, the contact resistance of Ni-Cu-P coating bipolar plates and graphite cake is 15m Ω cm
2, and Ni-P coating bipolar plates contact resistance is 79m Ω cm
2Through test relatively, ambrose alloy phosphorus three atomic ratio is Ni: Cu: P=15-45: 0.05-3 simultaneously: during 55-85, performance is comparatively desirable, and existing lower contact resistance has stronger corrosion resistance again.
Proton exchange membrane fuel cell stainless steel bipolar plate method of modifying of the present invention, be included in moulding bipolar plate of stainless steel substrate surface and apply the coat of metal, it is characterized in that applying the coat of metal divides secondary to carry out, earlier at stainless steel substrate plating nickel on surface layer, again at nickel coating surface chemical plating ambrose alloy phosphorus mixing coating.
In the inventive method, first nickel coating connects transition zone as follow-up ambrose alloy phosphorus mixing coating, helps ambrose alloy phosphorus coating and matrix and forms excellent combination, guarantees that coating can not come off, and selects nickel coating simultaneously, can also guarantee low resistance.Nickel dam applies, for example can adopt in the prior art electroplate, chemical plating method.
The ambrose alloy phosphorus chemistry plates, and makes by the nickel-clad copper P elements by chemical action to be deposited on nickel coating surface.Chemical plating solution by the mixed solution that comprises nickel ion, copper ion, ortho phosphorous acid radical ion, and helps the plating additive to form.Nickel ion wherein, by soluble nickel salt, such as but not limited to nickel chloride, nickelous sulfate, nickel acetates etc. provide; Copper ion is by soluble copper salt, such as but not limited to copper chloride, and copper sulphate, Schweinfurt greens etc. provide; Wherein soluble nickel salt and mantoquita better adopt corresponding sulfate, for example seven water nickelous sulfates, cupric sulfate pentahydrate, better effects if; The ortho phosphorous acid radical ion, by the soluble-salt that contains the ortho phosphorous acid root, such as but not limited to inferior sodium phosphate, ortho phosphorous acid potassium, ammonium hypophosphite etc. provide, and wherein are preferably inferior sodium phosphate.The ortho phosphorous acid radical ion is the source of sedimentary phosphor element in plating bath, uses as reducing agent again, and nickel, copper ion in the plating bath are reduced into metal simple-substance, can omit chemical plating like this and add reducing agent in addition.Test shows, nickel ion concentration 0.071～0.142mol/L among the present invention, copper ion concentration 4 * 10
-4～6 * 10
-3Mol/L, ortho phosphorous acid radical ion concentration 0.189～0.377mol/L, comparatively suitable, show more best performance.
Other additives in the plating bath; similar with common chemical plating additive therefor kind and function; be mainly and improve the chemical plating effect; and improve coating uniformity and compactness; employed additive in the prior art chemical plating, the complexing agent, PH buffer, surfactant, the stabilizer that for example improve covering power and covering power all can be employed.
Complexing agent, main effect are to discharge by the complexing later stage at initial stage, and it is poor to regulate the deposition ion concentration gradient, plays stably depositing ion concentration effect in the whole chemical plating process.For example the complex ni-ion later stage at chemical plating initial stage discharges, and alleviates course of reaction nickel ion concentration gradient difference, makes in the whole chemical plating process nickel ion even, prevents that effectively the initial reaction stage nickel ion is excessive.Can complexing the complex compound of deposition ion all can be employed, for example some aliphatic carboxylic acids and substitutive derivative thereof, as succinic acid, hydroxysuccinic acid, amion acetic acid, citric acid, pyrophosphoric acid, lactic acid, malic acid, butanedioic acid and glycine etc. or their salt, and hydroxide, thiosulfate, sulphite and replacement acid.
PH buffer, main effect are to keep the weighing apparatus of pH value in the course of reaction to decide, and controls reaction speed obtains homogeneous coating, and existing PH buffer all can be utilized, for example acetate, sodium acetate, boric acid etc.Consumption is looked used buffering agents and is correlated with, and can determine according to test, so that keep basicly stable pH value in the whole chemical plating process.
Surfactant, effect are to reduce the plating bath surface tension, help the effusion of surface of the work generation gas in the chemical plating process, to reduce the porosity of coating.Various surfactants all can be employed in the same prior art, for example the described anion of Chinese patent CN101289755, cation, non-ionic surface active agent are all passable, and commonly used have lauryl sulfate, dodecane sulfonate and a n-octyl sodium sulphate etc.Look the gas flow test that produces in the chemical plating process and determine use amount, can in time overflow, can not make bottom produce striped or pit so that the surface generates gas.
Stabilizer, main effect is stablize plating bath, by being preferentially adsorbed on some that produce in the plating bath active particles surface of catalytic effect is arranged, thus the inhibition catalytic reaction, the reduction of nickel ion is only occurred in by on the plating surface, so the strong inorganic or organic compound of adsorptivity all can be used.
For obtaining to stablize good coating, test relatively, chemical plating of the present invention is 70～90 ℃ of bath temperatures, bath pH value 8～10, chemical plating 1～3h has better effect.
In addition, for improving coating and the stainless bond strength of matrix, same as the prior art, usually need earlier stamping forming bipolar plate of stainless steel to be carried out pre-treatment, remove substrate surface impurity, greasy dirt, oxide layer etc., the binding ability of raising and coating, electro-plating pre-treatment method all can be employed in the prior art.For example surface chemistry or electrochemical method oil removing, pickling, deoxidation film, surface active etc.
Interval range described in the present invention is the preferable interval range of test assessment, is not accurate extremum on the mathematical meaning, suitably depart from a small quantity neither, just effect has minor variations.
Other additives in the above-mentioned plating bath, and preliminary treatment before the plating are prior art.
Proton exchange membrane fuel cell stainless steel bipolar plate of the present invention, owing to be coated with corrosion resistance on the stainless steel substrate surface and conductivity is all better, and cheap ambrose alloy phosphorus coating, the contact resistance of gained bipolar plates and gas diffusion layers is reduced greatly, load under the pressure at battery, the stainless steel and the graphite cake contact resistance that do not add the coating modification are 200～300m Ω cm
2, Ni-Cu-P coating stainless steel polar plate contact resistance of the present invention is 12～15m Ω cm
2, only be original 4-7.5%; And because the existence of middle nickel coating, not only coating is firm, and improved coating compactness, atresia is corroded voltage and is improved fully, and anti-corrosion capability strengthens, under the simulated battery corrosive environment, bipolar plates corrosion potential of the present invention has improved 20～40mv, and corrosion current has reduced an order of magnitude, makes bipolar plates decay resistance under the pem cell environment of preparing obtain bigger raising.And chemical plating prepares technology and equipment is simple, only needs electroless plating tank, does not need other special equipments, and plating rate of finished products height.Coating ambrose alloy P elements price is relatively low, wide material sources, and the coating cost is low.Than Chinese patent CN101136479 chemical nickel phosphorus plating, owing to increased copper, corrosion potential is increased to-0.0842V by-0.3178V, has improved 233mV, the corrosion current that draws through the match of tafel empirical equation has also reduced by 1 order of magnitude, is 150N/cm at pressure
2Under contact resistance be by 79m Ω cm
2Be reduced to 15m Ω cm
2, only be original 18%, and price there is no obvious increase, conductivity and corrosion resistance can reach the stainless steel double polar plate level of plating noble metal substantially.Bipolar plate of stainless steel of the present invention can pass through to detect the coating element, and the bipolar plates Performance Detection, is different from prior art.
Below in conjunction with two specific embodiments; the present invention is further understood in exemplary illustration and help; but the embodiment detail only is for the present invention is described; do not represent the present invention to conceive whole technical schemes down; therefore should not be construed as the technical scheme qualification total to the present invention, some are In the view of the technical staff, and the unsubstantiality that does not depart from the present invention's design increases and/or change; for example simple the change or replacement of technical characterictic to have same or similar technique effect all belongs to protection range of the present invention.
Description of drawings
Ni-Cu-P modification test piece and Ni-P modification test piece and carbon paper contact resistance are relatively under Fig. 1 different pressures.
Under Fig. 2 normal temperature at 0.5mol/L H
2SO
4+ 0.5 * 10
-6Ni-Cu-P modification test piece and Ni-P modification test piece polarization curve are relatively in the HF solution.
Embodiment
Embodiment 1: bipolar plates base material 316L stainless steel.
The preliminary treatment of moulding bipolar plates: with bipolar plates after the moulding, through electrochemical deoiling 10min, washing.Carrying out white picking, is that 10% hydrochloric acid, volume fraction are that 8% nitric acid and volume fraction are pickling 8min in the mixed acid of 82% distilled water in volume fraction for the first time, washing.For the second time in volume fraction is 20% hydrochloric acid, activate 30s and remove surface oxide layer, washing.
Electronickelling: make anode with sheet nickel, with 120g/L seven water nickel chlorides, 8mL/L hydrochloric acid, the 5mL/L surfactant is formed electronickelling solution, and temperature is 20 ℃, and cathode-current density is 1.2A/dm
2Electroplate 2min, washing.
Chemical plating ambrose alloy phosphorus ambrose alloy phosphorus composite plating liquor, by seven water nickelous sulfate 35g/L, cupric sulfate pentahydrate 1.2g/L, inferior sodium phosphate 30g/L, trisodium citrate 70g/L, sodium acetate 30g/L, add surfactant dodecyl sodium sulfate 10mL/L, stabilizer lead acetate 1mg/L.Put into electroless plating tank, 85 ℃ of control bath temperatures, plating bath pH=9, chemical plating 2h.Obtain coating outward appearance even compact, the ambrose alloy phosphorus coating of no peeling, bubbling.
Service check: after the bipolar plates that will be coated with above-mentioned coating is put into 300 ℃ of Muffle furnace heat treatment 1h, water-cooled, 3 times repeatedly.Observe with 10 times of magnifying glasses, coating does not have peeling or comes off.When pressure is 150Ncm
-2The time, recording contact resistance is 12m Ω cm
2With saturated calomel electrode is reference electrode, and platinum electrode is to electrode, and the gained bipolar plates is that work electrode carries out electrokinetic potential scanning in 25 ℃ of simulated battery corrosive environments, and the corrosion current that records bipolar plates is 10
-6A/dm
2, than untreated Corrosion of Stainless Steel electric current little an order of magnitude.The result shows that the coating of preparation can reach the contact resistance that reduces bipolar plates and gas diffusion layers, improves the decay resistance requirement of bipolar plates in battery context.
Embodiment 2: bipolar plates base material 304 stainless steels.
Moulding bipolar plates preliminary treatment: electrochemical deoiling 10min, washing.In volume fraction is that 10% hydrochloric acid, volume fraction are that 8% nitric acid and volume fraction are pickling 6min in the mixed acid of 82% distilled water, washing.In being 20% hydrochloric acid, volume fraction carries out active 30s pickling, washing.
Electronickelling: sheet nickel is made anode, and with 120g/L seven water nickel chlorides, 8mL/L hydrochloric acid, the 5mL/L surfactant is formed electronickelling solution, is 20 ℃ in temperature, and cathode-current density is 1.2A/dm
2Electroplate 2min.Washing.
Chemical plating ambrose alloy phosphorus composite plating bath is formed: 30g/L seven water nickelous sulfates, 0.8g/L cupric sulfate pentahydrate, 25g/L inferior sodium phosphate, 60g/L trisodium citrate, 30g/L sodium acetate, 10mL/L surfactant dodecyl sodium sulfate, 1mg/L stabilizer lead acetate.At 80 ℃ of bath temperatures, plating bath pH=8.5, chemical plating 2h.Obtain the outward appearance even compact, defective coating such as no peeling, bubbling.
Service check: after the coating bipolar plates put into 300 ℃ of Muffle furnace heat treatment 1h, water-cooled, 3 times repeatedly.Observe with 10 times of magnifying glasses, coating does not have peeling or comes off.When pressure is 150Ncm
-2The time, surveying its contact resistance is 15m Ω cm
2With saturated calomel electrode is reference electrode, and platinum electrode is to electrode, and the gained bipolar plates is that work electrode carries out electrokinetic potential scanning in 25 ℃ of simulated battery corrosive environments, and the corrosion potential that records bipolar plates is-0.134v that corrosion current is 10
-6A/dm
2, than stainless corrosion current little an order of magnitude.The result shows that too the coating of this prepared can reach the contact resistance that reduces bipolar plates and gas diffusion layers, improves the decay resistance requirement of bipolar plates in battery context.
To those skilled in the art; under this patent design and specific embodiment enlightenment; some distortion that can directly derive or associate from this patent disclosure and general knowledge; those of ordinary skills will recognize also can adopt additive method; or the substituting of known technology commonly used in the prior art; and the mutual various combination between feature; for example the difference of plating bath is formed; the variation of the process conditions of chemical plating; or the like unsubstantiality change, can be employed equally, can both realize and basic identical function of the foregoing description and effect; launch for example no longer one by one to describe in detail, all belong to this patent protection range.
Brief Description Of Drawings:
Fig. 1, contrast and experiment shows: the bipolar plates through the Ni-Cu-P surface modification is 150N/cm at pressure
2Under contact resistance be 15m Ω/cm
2And the Ni-P modification bipolar plates contact resistance that does not add copper is 79m Ω/cm
2Show that adding copper is bigger to the influence of contact resistance, add the contact resistance that a certain amount of copper can reduce bipolar plates greatly.
Fig. 2 shows: under the analog fuel battery context, the Ni-P modification bipolar plates corrosion potential that does not add copper is-0.3178V, and process Ni-Cu-P surface modification bipolar plates corrosion potential is-0.0842V that corrosion potential has improved 233mV.The corrosion current that match draws through the tafel empirical equation has also reduced by 1 order of magnitude.Bipolar plate corrosion resistant is greatly improved than the corrosion resistance that does not add copper after showing adding copper.
Claims (8)
1. proton exchange membrane fuel cell stainless steel bipolar plate comprises moulding Thin Stainless Steel substrate, it is characterized in that substrate surface is coated with nickel dam and the two coating of ambrose alloy phosphorus.
2. according to the described proton exchange membrane fuel cell stainless steel bipolar plate of claim 1, it is characterized in that top layer ambrose alloy phosphorus three atomic ratio is Ni: Cu: P=15-45: 0.05-3: 55-85.
3. proton exchange membrane fuel cell stainless steel bipolar plate method of modifying, be included in moulding bipolar plate of stainless steel substrate surface and apply the coat of metal, it is characterized in that applying the coat of metal and divide secondary to carry out, earlier at stainless steel substrate plating nickel on surface layer, again at nickel coating surface chemical plating ambrose alloy phosphorus mixing coating.
4. according to the described proton exchange membrane fuel cell stainless steel bipolar plate method of modifying of claim 3, it is characterized in that nickel ion concentration 0.071～0.142mol/L in the ambrose alloy phosphor bath, copper ion concentration 4 * 10
-4～6 * 10
-3Mol/L, ortho phosphorous acid radical ion concentration 0.189～0.377mol/L.
5. according to claim 3 or 4 described proton exchange membrane fuel cell stainless steel bipolar plate method of modifying, it is characterized in that nickel source in the ambrose alloy phosphor bath, copper source are nickel, the copper compound of sulfur-bearing acid group, the phosphorus source is an ortho phosphorous acid root salt.
6. according to the described proton exchange membrane fuel cell stainless steel bipolar plate method of modifying of claim 5, it is characterized in that nickel source in the plating bath, Tong Yuan, phosphorus source, be respectively seven water nickelous sulfates, cupric sulfate pentahydrate, inferior sodium phosphate.
7. according to claim 3,4 or 6 described proton exchange membrane fuel cell stainless steel bipolar plate method of modifying, it is characterized in that 70～90 ℃ of chemical plating bath temperature, bath pH value 8～10, chemical plating time 1～3h.
8. according to the described proton exchange membrane fuel cell stainless steel bipolar plate method of modifying of claim 5, it is characterized in that 70～90 ℃ of chemical plating bath temperature, bath pH value 8～10, chemical plating time 1～3h.
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| CN106684394A (en) * | 2015-11-06 | 2017-05-17 | 中国科学院大连化学物理研究所 | Surface modification method of proton-exchange membrane fuel cells' stainless steel bipolar plates |
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| CN104600272A (en) * | 2014-12-19 | 2015-05-06 | 华侨大学 | Mesh-shaped nickel-copper-phosphorus amorphous alloy electrode material and preparation method thereof |
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| CN110699647A (en) * | 2019-10-31 | 2020-01-17 | 宇石能源(南通)有限公司 | Method for modifying stainless steel bipolar plate of fuel cell |
| CN112055460A (en) * | 2020-09-01 | 2020-12-08 | 王川川 | Resistance material, copper-clad plate containing resistance layer and manufacturing method of printed circuit board |
| CN112055460B (en) * | 2020-09-01 | 2022-12-06 | 王川川 | Resistance material, copper-clad plate containing resistance layer and manufacturing method of printed circuit board |
| CN113328110A (en) * | 2021-05-25 | 2021-08-31 | 上海电力大学 | Surface modified stainless steel bipolar plate of proton exchange membrane fuel cell and preparation method thereof |
| CN113328111A (en) * | 2021-05-25 | 2021-08-31 | 上海电力大学 | Stainless steel bipolar plate with chromium-based nitride composite coating and preparation method thereof |
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