CN105047975B - A kind of fuel cell metal double polar plates and preparation method thereof - Google Patents
A kind of fuel cell metal double polar plates and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02B90/10—Applications of fuel cells in buildings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a kind of fuel cell metal double polar plates, including stainless steel substrate and its surface reforming layer, the surface reforming layer includes being attached to the continuous insulating layer and discontinuous conduction particle on stainless steel substrate surface.The fuel cell of the present invention is with metal double polar plates by the process of surface treatment that surface deposits continuous insulating layer and discontinuous conduction particle is combined; the protective layer of densification can not only be formed; greatly reduce the corrosion rate of metal double polar plates; and contact resistance can be reduced, extend the service life of metal double polar plates.Discontinuous conduction particle is deposited by plasma plasma spray technology, conductive particle can be made to form micro metallurgic bonding with stainless steel substrate, improves the adhesive force of discontinuous conduction particle, reduces and prepares cost.
Description
Technical field
The present invention relates to fuel cell field, particularly relates to a kind of fuel cell metal double polar plates and preparation method thereof.
Background technology
There is Hydrogen Proton exchange film fuel battery (PEMFC) environment-friendly, high conversion efficiency, room temperature quickly to start, noise
Low advantage, for fields such as packaged type power supply, stand-by power supply, electrical source of power, fixed power stations, currently as dual-use
Clean energy resource equipment widely favored.
One of PEMFC critical component bipolar plates are often from graphite as base material, but traditional graphite bi-polar plate bulk
Greatly, mechanical strength is low, cost is high, it is difficult to is had breakthrough improving power density, antidetonation etc., so as to limit it in power
The application of power supply etc..One of solution method is to use new stainless steel metal bipolar plates, and stainless steel material has good
The advantages such as electric conductivity, gas barrier property are good, easy processing shaping, high mechanical strength, ductility are good, can largely improve PEMFC's
Volume, mass power density and reduce cost.
But often contain F-, SO in PEMFC running environment4 2-、SO3 2-、CO3 2-、HSO3 -Plasma, and when starting
Negative electrode is maximum up to 1V with anode voltage difference, and running temperature is typically at 60-90 DEG C, and under these conditions, stainless steel material can be sent out
Raw electrochemical corrosion, reduce the service life of metal double polar plates.In addition, although the self-passivation film of stainless steel surfaces can play protection
Effect, but be insulation, the contact resistance between pole plate and carbon paper is added, this is to need to consider in bipolar plates preparation process
Solve the problems, such as.
In order to improve the surface conductivity of metal double polar plates and decay resistance, existing method is mainly carried out at surface to it
Reason is modified.In the prior art, main use prepares the films such as noble metal, carbons film, melt-ceramic compound in metal surface.
Noble coatings are unsuitable for the inexpensive battery pack of production because its cost is high.With the process of lower cost in stainless steel plate
On prepare melt-ceramic compound and be advantageous for industrialized approach.Patent CN201110027099.0 invented it is a kind of using from
The method of mode depositing Ti C nano laminated film on stainless steel substrate of son plating, can be reduced to 10 by corrosion current-7A/
cm2.Patent CN20111028193.6 and CN200610046733.4 individually disclose to enter stainless steel surfaces with vacuum environment
The method of row plasma nitridation process, NbN and CrN film are prepared, significantly reduce surface contacted resistance, improve corrosion resistant
Corrosion energy.But single thin film prepared by these methods and material is difficult the presence for eliminating pin hole, and pin hole or bulky grain etc. lack
Local pitting, galvanic corrosion caused by falling into, can accelerate the failure of metal double polar plates.In patent CN201310116099 and
Carbon, nitride film that PVD methods prepare multi-layer C r are disclosed in CN201210438569, to reduce the generation of needle pore defect,
But the structure of plural layers adds the complexity of technique.
The content of the invention
In view of this, it is an object of the invention to propose a kind of fuel cell metal double polar plates and preparation method thereof, carry
The high anticorrosive property of metal double polar plates, reduce the surface contacted resistance of metal double polar plates.
Based on a kind of above-mentioned purpose fuel cell metal double polar plates provided by the invention, including stainless steel substrate and its table
Face modified layer, the surface reforming layer include being attached to the continuous insulating layer on stainless steel substrate surface and are attached to stainless steel substrate
Discontinuous conduction particle on surface, that excellent electric contact is formed with stainless steel substrate.
In some embodiments of the invention, the continuous insulating layer is selected from chemical passivation layer, titanium dioxide layer, tin oxide
Any one or two kinds of layer and diamond-like rock layers.The discontinuous conduction particle is selected from chromium nitride, chromium carbide, tungsten carbide, platinum
With any one golden.
In one embodiment of the invention, the continuous insulating layer is chemical passivation layer and titanium dioxide layer, in this hair
In another bright embodiment, the continuous insulating layer is chemical passivation layer and stannic oxide layer.
Alternatively, the thickness of the continuous insulating layer is 135~270nm.
Present invention also offers a kind of preparation method of fuel cell metal double polar plates, first in stainless steel substrate surface system
Standby continuous insulating layer, then using plasma heat spraying method spray anti-corrosion electric conducting molten mass to stainless steel substrate, described resistance to
Etching conductive molten mass penetrates continuous insulating layer and forms discontinuous conduction particle on stainless steel substrate surface.
In some embodiments of the invention, the stainless steel substrate of preheating is placed in vacuum chamber, by plasma gun
Stainless steel substrate upright position is placed on, the anti-corrosion electric conducting particle of melt surface is carried to not with hydrogen by argon gas or argon gas
The steel substrate that becomes rusty sprays, and the nozzle of the plasma gun and the horizontal range of stainless steel substrate are 50~120mm, and gas flow is
30~150L/min, spray gun translational speed are 3~40mm/ strokes, and spray power is 15~30kW, spray time is 120~
350s, obtain discontinuous conduction particle.
Alternatively, the particle diameter of the discontinuous conduction particle is 0.3~10 μm.
In some embodiments of the invention, before discontinuous conduction particle is prepared, first in stainless steel substrate surface system
Standby continuous insulating layer, the continuous insulating layer are oozed using chemical passivation, vacuum film deposition, ullrasonic spraying thin film deposition and high temperature
Any one or two methods of nitrogen are prepared.
In one embodiment of the invention, if in stainless steel substrate surface deposition of titanium oxide layer or stannic oxide layer,
Chemical passivation layer is first deposited, titanium dioxide layer is on the one hand improved in chemical passivation layer surface deposition of titanium oxide layer or stannic oxide layer
Or the adhesion of stannic oxide layer and stainless steel substrate, on the other hand make up the defects of chemical passivation layer there may be.
In another embodiment of the present invention, it is if pre- in stainless steel substrate surface depositing diamond-like carbon class film, elder generation
One layer of carbonization layers of chrome of plating, to improve the adhesion of DLC carbons film and stainless steel substrate.
In some embodiments of the invention, before continuous insulating layer is prepared, stainless steel substrate is subjected to degreasing and gone
Except self-passivation film process, first it is cleaned by ultrasonic in ethanol to remove grease, then with volume ratio is 10：1 sulfuric acid and hydrogen fluorine
The acid solution cleaning that acid mixes, to remove the self-passivation film on stainless steel substrate surface, finally cleans stainless steel with deionized water
The acid solution of substrate surface, is preserved in a nitrogen atmosphere after drying.
From the above it can be seen that fuel cell metal double polar plates provided by the invention and preparation method thereof have with
Lower beneficial effect：
First, metal bipolar plate surface provided by the invention is combined using continuous insulating layer and discontinuous conduction particle
Process of surface treatment, not only increases the anticorrosive property of metal double polar plates, and reduces surface contacted resistance, and it is double to extend metal
The service life of pole plate.
Secondly, stainless steel substrate surface first using the mode such as chemical passivation or vacuum coating deposit chemical passivation layer,
The continuous insulating layer such as titanium dioxide layer, stannic oxide layer or diamond-like rock layers, this dielectric film can avoid pin hole from asking
Topic, the protective layer of densification is formed, greatly reduce the corrosion rate of metal double polar plates.
3rd, on surface, the method deposition discontinuous conduction particle of thermal spraying, improves discontinuous conduction particle and gold
Belong to the adhesion of bipolar plates matrix, reduce metal double polar plates surface contacted resistance.In addition, ensureing that surface contacted resistance is enough
On the premise of small, the surface density number of conductive particle can be reduced as far as possible, dramatically saves on material cost, such as your gold
The high materials of cost such as category, can also realize commercial applications.
Finally, using plasma thermal sprayed method, make anti-corrosion electric conducting particle formed molten mass through continuous insulating layer with not
Rust steel matrix forms local micro metallurgic bonding, adds the adhesive force of conductive particle and stainless steel substrate.In addition, plasma is warm
The arc temperature of spraying is very high, can reach 30000K, can melt any difficulty and melt material, is preparing discontinuous conduction particle
When, selectable sprayed on material is extensive, and any material for meeting performance requirement can use this method to spray.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, below in conjunction with specific embodiment, to this hair
Bright further description.
Embodiment 1
Pretreatment, by the 316L stainless steel substrate punch formings that thickness is 0.1mm.Stainless steel substrate is carried out in ethanol
It is cleaned by ultrasonic, to remove the grease on surface.Then it is 10 with volume ratio：1 sulfuric acid cleans with the acid solution that hydrofluoric acid mixes,
The self-passivation film on stainless steel substrate surface is removed, the acid solution on stainless steel substrate surface, drying, in nitrogen are finally cleaned with deionized water
Preserved in gas.
Prepare continuous insulating layer：
1) chemical passivation layer is deposited：Stainless steel substrate is immersed in 30% salpeter solution and be passivated, temperature is maintained at 50
Stainless steel substrate is taken out after~60 DEG C, 30 minutes, with deionized water rinsing two to three times, drying preserves, the table of stainless steel substrate
The fine and close passivation layer that a layer thickness is 40nm, hereinafter referred to as chemical passivation layer are formed after face is passivated.Chemical passivation layer is than stainless
Steel substrate self-passivation layer is finer and close, stainless steel substrate can be protected not to be corroded.But may be because of stainless steel substrate surface
The defects of and cause passivation layer produce defect, to prevent defective part from producing, one layer of TiO of redeposition on chemical passivation layer2
Layer.
2) depositing Ti O2Layer：The stainless steel substrate of surface deposition chemical passivation layer is cleaned by ultrasonic 10min in ethanol,
To remove surface grease and dust, then twice, drying are cleaned with deionized water.
Stainless steel substrate is placed on the substrate of vacuum chamber, background vacuum pressure is maintained at 10-4Pa, face purity are
The horizontal range of 99.99% Ti targets, Ti targets and stainless steel substrate is maintained at 20cm, and substrate temperature is heated to 200 DEG C,
The adhesion between film and stainless steel substrate can be not only improved at this temperature, and can ensure that stainless steel substrate will not occur
Deformation.Argon working gas carries reacting gas oxygen and is passed through in vacuum chamber, oxygen flow 200sccm, and argon pressure is
2Pa, target current 150A, reaction time 10min, obtain the TiO that average thickness is 96nm2Layer.In depositing Ti O2Before layer first
Chemical passivation layer is prepared, TiO can not only be improved2The adhesion of layer and stainless steel substrate, and can overcome the disadvantages that may be because of stainless base steel
Plate surface defect and cause chemical passivation layer flaw the defects of, chemical passivation layer and TiO2Layer complements each other as surface more
Add the continuous insulating layer of densification, reduce the probability for producing pin hole, improve the anticorrosive property of stainless steel substrate.
Chemical passivation layer is deposited using the method for chemical passivation and uses reactive sputtering magnetic control method deposition of titanium oxide
Layer, the two complements each other as the finer and close continuous insulating layer in surface, is not only avoided that pin hole problems, and can be more efficiently
Stainless steel substrate is protected not to be corroded.
Prepare discontinuous conduction particle：
Using plasma spraying method in continuous insulating layer surface spraying CrC conductive particles.
The stainless steel substrate of preheating is placed on the rotating disk of vacuum chamber, stainless steel substrate need not continue to heat, background
Vacuum is maintained at 10-2Pa, plasma gun is vertical with stainless steel substrate, and the horizontal range of nozzle and stainless steel substrate is
70mm, the CrC particles that melt surface is carried by argon gas spray to stainless steel substrate, argon flow amount 120sccm, spray gun movement
Speed is 15~40mm/ strokes, and spraying general power is 15kW, spray time 300s.The CrC particles hits of melt surface are not to
The titanium dioxide layer surface of rust steel substrate simultaneously penetrates certain thickness continuous insulating layer, is formed in stainless steel substrate surface crystallization
CrC particles, excellent electric contact is formed with stainless steel base, i.e., deposits CrC discontinuous conduction particles, the CrC particles on surface
Particle diameter be 3.2~4.5 μm, 0.8~5 μm of distribution.
Performance detection：Will not pass through the stainless steel substrate of punching press, that is, do not contain the stainless steel substrate of flow field structure, using with
Surface, which is prepared, in the identical method of embodiment 1 has the stainless steel substrate of continuous insulating layer and discontinuous conduction particle as sample
Product, wherein continuous insulating layer are chemical passivation layer and titanium dioxide layer, and discontinuous conduction particle is chromium carbide particles.The two of sample
Titanium oxide layer is microstructure, and surface is very fine and close, can play good corrosion-resisting function.The face of the chromium carbide particles of sample
Density is 6.3~32.5 μ g/cm2。
Contact resistance test is carried out to sample, when the surface density of CrC particles reaches 12.5 μ g/cm2During left and right, contact resistance
In 150N/cm2It is 14.5m Ω cm under pressure2, reached and be less than 20m Ω cm2Application standard.
The test of electrochemistry corrosion resistance is carried out to sample, under conditions of vs.SCE, pH=3,80 DEG C of 0.8V, corrosion
Current density is less than 10-8A/cm2, the life-span is tested under the same conditions, can reach more than 1000h.
Embodiment 2
Pre-treatment step is same as Example 1.
Prepare continuous insulating layer：
1) preplating CrC layers：Stainless steel substrate is put into load lock chamber, the base of vacuum chamber is sent to by load lock chamber
Piece position, the background vacuum pressure of vacuum chamber are maintained at 10-3Pa, substrate heating temperature are 200 DEG C, at such a temperature not only can be with
The adhesion between film and stainless steel substrate is improved, and can ensure that stainless steel substrate will not deform.Substrate rotation speed
Spend and carry reacting gas acetylene for 2rmp, argon working gas and be passed through in vacuum chamber, acetylene flow is 50sccm, and target is
Chromium, target current 120A, biasing 500V, after reacting 1min, chromium target is closed, now in stainless steel substrate surface preplating one
For layer CrC as transition zone, the thickness of CrC layers is 20nm.
2) after closing chromium target, by acetylene gas Flow-rate adjustment to 300sccm, bias adds to 800V, is tied after reacting 10min
Beam, treat that stainless steel substrate is cooled to room temperature taking-up, the DLC carbons film (abbreviation DLC) that thickness is 250nm is prepared.
Before preparing DLC carbons film, first in one layer of CrC transition zone of stainless steel substrate surface preplating, it is possible to increase DLC layer with not
The adhesion of rust steel substrate.
Prepare discontinuous conduction particle：
Continuous insulating layer surface spraying gold conductive particle of the using plasma hot spray process in deposition.
The stainless steel substrate of preheating is placed on the rotating disk of vacuum chamber, stainless steel substrate need not continue to heat, background
Vacuum is maintained at 10-2Pa, plasma torch is vertical with stainless steel substrate, and the distance of nozzle and stainless steel substrate is 60mm,
The gold grain that melt surface is carried by argon gas sprays to stainless steel substrate, argon flow amount 220sccm, and spray gun translational speed is
9~25mm/ strokes, spraying general power are 30kW, spray time 200s.Gold grain is impinged upon in eka-gold with melt surface state
Hard rock carbons film surface, because the melt and dissolved state temperature of contact point is very high, gold melting physical efficiency passes through Diamond-like Carbon film layer, in stainless steel substrate
Surface crystallization forms gold grain, forms excellent electric contact with stainless steel substrate, the particle diameter of the gold grain is 2.2~3.5 μm.
Performance detection：Will not pass through the stainless steel substrate of punching press, that is, do not contain the stainless steel substrate of flow field structure, using with
Surface, which is prepared, in the identical method of embodiment 2 has the stainless steel substrate of continuous insulating layer and discontinuous conduction particle as sample
Product, wherein continuous insulating layer are CrC layers and DLC carbons film, and discontinuous conduction particle is gold grain.The gold grain of sample
Surface density be 2.4~25.2 μ g/cm2。
Contact resistance test is carried out to sample, when gold grain surface density is 2.4 μ g/cm2, its surface contacted resistance can
Reach 8.2m Ω cm2, and traditional carbon material bipolar plates are suitable.
The test of electrochemistry corrosion resistance is carried out to sample, under conditions of vs.SCE, pH=3,80 DEG C of 0.8V, corrosion
Current density can reach 10-9A/cm2, test under the same conditions the life-span, the life-span can be more than 1500 hours.For 300cm2
Stainless steel substrate, golden dosage only has 0.72mg, greatly saves cost.It is fresh few in electric Microscopic observation, gold grain edge
The defects of hole, produces, and illustrates that continuous insulating layer prepared by this method can effectively act as protecting stainless steel surfaces, drop
The effect of low contact resistance.
Embodiment 3
Pre-treatment step is same as Example 1.
Prepare continuous insulating layer：
1) chemical passivation layer is deposited：Method is same as Example 1.
2) SnO layers are deposited：The stainless steel substrate of surface deposition chemical passivation layer is cleaned by ultrasonic 10min in ethanol,
To remove surface grease and dust, then twice, drying are cleaned with deionized water.
Stainless steel substrate is placed on the substrate of vacuum chamber, background vacuum pressure is maintained at 10-4Pa, face purity are
The horizontal range of 99.98% Sn targets, Sn targets and stainless steel substrate is maintained at 20cm, and substrate temperature is heated to 200 DEG C,
The adhesion between film and stainless steel substrate can be not only improved at this temperature, and can ensure that stainless steel substrate will not occur
Deformation.Argon working gas carries reacting gas oxygen and is passed through in vacuum chamber, gas flow 210sccm, and target current is
150A, air pressure 2Pa, reaction time 15min, obtain the SnO layers that average thickness is 100nm.Deposition SnO layers it
It is preceding first to prepare chemical passivation layer, the adhesion of SnO layers and stainless steel substrate can not only be improved, and can overcome the disadvantages that may be because of stainless steel
Substrate surface defects and cause chemical passivation layer flaw the defects of, chemical passivation layer and SnO layers complement each other as surface
Finer and close continuous insulating layer, the probability for producing pin hole is reduced, improve the anticorrosive property of stainless steel substrate.
Prepare discontinuous conduction particle：
Using plasma spraying method deposition continuous insulating layer surface spraying CrN conductive particles.
The stainless steel substrate of preheating is placed on the rotating disk of vacuum chamber, stainless steel substrate need not continue to heat, background
Vacuum is maintained at 10-2Pa, plasma gun is vertical with stainless steel substrate, and the horizontal range of nozzle and stainless steel substrate is
100mm, the CrN particles that melt surface is carried by argon gas spray to stainless steel substrate, and argon flow amount 120sccm, spray gun moves
Dynamic speed is 15~40mm/ strokes, and spraying general power is 20kW, spray time 150s.The CrN particles hits of melt surface arrive
The SnO layer surfaces of stainless steel substrate, because the melt and dissolved state temperature of contact point is very high, CrN molten masses pass through Diamond-like Carbon film layer, stainless
Steel substrate surface crystallization forms CrN particles, and excellent electric contact is formed with stainless steel substrate, the particle diameters of the CrN particles for 3.2~
4.5 μm, 0.8~5 μm of distribution.
Performance detection：Will not pass through the stainless steel substrate of punching press, that is, do not contain the stainless steel substrate of flow field structure, using with
Surface, which is prepared, in the identical method of embodiment 3 has the stainless steel substrate of continuous insulating layer and discontinuous conduction particle as sample
Product, wherein continuous insulating layer are chemical passivation layer and stannic oxide layer, and discontinuous conduction particle is chromium nitride particle.The oxidation of sample
Tin layers surface is very fine and close, can play good corrosion-resisting function.The surface density of the chromium nitride particle of sample is 7.3~30.5
μg/cm2。
Contact resistance test is carried out to sample, when the surface density of CrC particles reaches 12.5 μ g/cm2During left and right, contact resistance
In 150N/cm2It is 13.6m Ω cm under pressure2, reached and be less than 20m Ω cm2Application standard.
The test of electrochemistry corrosion resistance is carried out to sample, under conditions of vs.SCE, pH=3,80 DEG C of 0.8V, corrosion
Current density is less than 10-8A/cm2, the life-span is tested under the same conditions, can reach more than 1000h.
Fuel cell metal double polar plates provided by the invention and preparation method thereof, have it can be seen from foregoing description
Following beneficial effect：
First, the present invention first deposits continuous insulating layer on stainless steel substrate surface, it is ensured that forms the protective layer of densification, avoids
Pin hole problems, the corrosion rate of metal double polar plates can be greatly reduced, redeposited discontinuous conduction particle, metal can be reduced
The contact resistance of bipolar plate surfaces.In addition, on the premise of ensureing that surface contacted resistance is sufficiently small, the surface density number of conductive particle
Can be small as much as possible, material cost is dramatically saves on, for example for the high material of the costs such as noble metal, business can also be realized
Industry application.
Secondly, using plasma spraying method, anti-corrosion electric conducting particle is formed molten mass and pass through continuous insulating layer, it is and stainless
Steel matrix forms local micro metallurgic bonding, adds the adhesive force of conductive particle and stainless steel substrate.In addition, plasma spraying
Arc temperature it is very high, 30000K can be reached, any insoluble material can be melted, can when preparing discontinuous conduction particle
The sprayed on material of selection is extensive, and any material for meeting performance requirement can use this method to spray.
Those of ordinary skills in the art should understand that：The discussion of any of the above embodiment is exemplary only, not
It is intended to imply that the scope of the present disclosure (including claim) is limited to these examples；Under the thinking of the present invention, above example
Or can also be combined between the technical characteristic in different embodiments, step can be realized with random order, and exist such as
Many other changes of upper described different aspect of the invention, for simplicity, they are not provided in details.Therefore, it is all
Within the spirit and principles in the present invention, any omission for being made, modification, equivalent substitution, improvement etc., it should be included in the present invention's
Within protection domain.
Claims (9)
- A kind of 1. fuel cell metal double polar plates, it is characterised in that including stainless steel substrate and its surface reforming layer, the table Face modified layer includes the continuous insulating layer and discontinuous conduction particle for being attached to stainless steel substrate surface；The continuous insulation layer choosing From any one or two kinds of chemical passivation layer, titanium dioxide layer, stannic oxide layer and diamond-like rock layers；The discontinuous conduction Grain-by-grain seed selection from chromium nitride, chromium carbide, tungsten carbide, platinum and gold any one；The chemical passivation layer is to soak stainless steel substrate It is passivated and is made in 30% salpeter solution.
- 2. fuel cell metal double polar plates according to claim 1, it is characterised in that the continuous insulating layer is chemistry Passivation layer and titanium dioxide layer, or chemical passivation layer and stannic oxide layer.
- 3. fuel cell metal double polar plates according to claim 1, it is characterised in that the thickness of the continuous insulating layer For 135~270nm.
- 4. a kind of preparation method of the fuel cell metal double polar plates described in claims 1 to 3 any one, its feature exist In first resistance to stainless steel substrate injection in stainless steel substrate surface preparation continuous insulating layer, then using plasma spraying method Etching conductive molten mass, the anti-corrosion electric conducting molten mass, which penetrates continuous insulating layer and formed in stainless steel substrate surface crystallization, not to be connected Continuous conductive particle.
- 5. preparation method according to claim 4, it is characterised in that preheat the stainless steel substrate for depositing continuous insulating layer After be placed in vacuum chamber, by plasma gun be placed on stainless steel substrate upright position, pass through argon gas or argon gas and hydrogen The anti-corrosion electric conducting particle for carrying melt surface sprays to stainless steel substrate, the nozzle and stainless steel substrate of the plasma gun Horizontal range be 50~120mm, gas flow is 30~150L/min, and spray gun translational speed is 3~40mm/ strokes, spraying Power is 15~30kW, and spray time is 120~350s, obtains discontinuous conduction particle.
- 6. the preparation method according to claim 4 or 5, it is characterised in that the particle diameter of the discontinuous conduction particle is 0.3 ~10 μm.
- 7. preparation method according to claim 4, it is characterised in that the continuous insulating layer is using chemical passivation, vacuum Any one or two methods of thin film deposition, ullrasonic spraying thin film deposition and high temperature nitriding are prepared.
- 8. preparation method according to claim 7, it is characterised in that if in stainless steel substrate surface deposition of titanium oxide layer Or stannic oxide layer, then first deposit chemical passivation layer；If in stainless steel substrate surface depositing diamond-like carbon class film, first one layer of carbonization layers of chrome of preplating.
- 9. preparation method according to claim 4, it is characterised in that before continuous insulating layer is prepared, by stainless steel substrate Carry out degreasing and remove self-passivation film process, be first cleaned by ultrasonic in ethanol to remove grease, then with volume ratio be 10： 1 sulfuric acid and hydrofluoric acid mix acid liquor cleaning, to remove the self-passivation film on stainless steel substrate surface, is finally cleaned with deionized water The acid solution on stainless steel substrate surface, is preserved in a nitrogen atmosphere after drying.
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| CN107681173A (en) * | 2017-08-03 | 2018-02-09 | 上海交通大学 | A kind of point-like conduction composite coating for fuel battery metal pole plate |
| CN109768295B (en) * | 2018-12-11 | 2022-03-04 | 上海治臻新能源股份有限公司 | Production method of corrosion-resistant high-conductivity fuel cell metal bipolar plate |
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| JP3857873B2 (en) * | 2000-11-09 | 2006-12-13 | 三洋電機株式会社 | FUEL CELL SEPARATOR, ITS MANUFACTURING METHOD, AND FUEL CELL |
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Effective date of registration: 20200914 Address after: 102600 No.17 yard, Yongchang South Road, Beijing Economic and Technological Development Zone, Daxing District, Beijing Patentee after: BEIJING LONG MARCH TIANMIN HI-TECH Co.,Ltd. Address before: 4003, room 2, building 17, South Yongchang Road, Beijing economic and Technological Development Zone, Beijing, Daxing District 100076, China Patentee before: AEROSPACE NEW LONG MARCH ELECTRIC VEHICLE TECHNOLOGY Co.,Ltd. |