CN108598497A - A kind of nano metal layer and preparation method for fuel battery metal pole plate - Google Patents
A kind of nano metal layer and preparation method for fuel battery metal pole plate Download PDFInfo
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- CN108598497A CN108598497A CN201810404258.6A CN201810404258A CN108598497A CN 108598497 A CN108598497 A CN 108598497A CN 201810404258 A CN201810404258 A CN 201810404258A CN 108598497 A CN108598497 A CN 108598497A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 112
- 239000002184 metal Substances 0.000 title claims abstract description 112
- 239000000446 fuel Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010410 layer Substances 0.000 claims abstract description 130
- 239000010953 base metal Substances 0.000 claims abstract description 86
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 71
- 238000000576 coating method Methods 0.000 claims abstract description 70
- 239000011248 coating agent Substances 0.000 claims abstract description 64
- 230000008021 deposition Effects 0.000 claims abstract description 27
- 239000011247 coating layer Substances 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims description 32
- 150000004706 metal oxides Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- 239000010931 gold Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 238000001020 plasma etching Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012495 reaction gas Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000007740 vapor deposition Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 19
- 238000005260 corrosion Methods 0.000 abstract description 19
- 239000011651 chromium Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 10
- 239000002905 metal composite material Substances 0.000 description 10
- 239000010936 titanium Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- FXNGWBDIVIGISM-UHFFFAOYSA-N methylidynechromium Chemical compound [Cr]#[C] FXNGWBDIVIGISM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8867—Vapour deposition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- 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 present invention provides a kind of nano metal coatings for fuel battery metal pole plate, the base layer constituted including a metal polar plate, deposition has at least one layer of base metal layer on base layer, there is one layer to replace the mixed layer constituted with noble metal by base metal in the upper surface of base metal layer deposition, noble metal is located at the outermost of the nano metal coating, 1 500 nm of thickness of the base metal layer, in the mixed layer that base metal and noble metal are constituted, the mass ratio of base metal and noble metal is 1 90：100,1 100 nm of mixed layer coating layer thickness.The present invention also provides a kind of preparation methods of above-mentioned nano metal coating for fuel battery metal pole plate.The present invention can substantially reduce the dosage of noble metal compared with existing coating, hence it is evident that enhance the surface conductance performance and corrosion resistance of metal polar plate, improve fuel battery pole board endurance quality.
Description
Technical field
The invention belongs to chemical fields, are related to a kind of fuel battery metal pole plate, specifically a kind of for fuel electricity
The nano metal layer and preparation method of pond metal polar plate.
Background technology
Proton Exchange Membrane Fuel Cells is a kind of novel energy device, has and starts fast, pollution-free, efficient, variable load sound
The features such as fast is answered, in automobile, stationary electric power plant, portable power etc. is with a wide range of applications.Typical proton exchange
Membrane cell includes mainly membrane electrode assembly, pole plate, sealing ring, the components such as end plate.Wherein pole plate is crucial in fuel cell
One of component primarily serves support membrane electrode, distributes reaction gas, collected current, the main functions such as water that discharge reaction generates.
Pole plate accounts for the 80% of fuel cell total weight, cost 30%-40%.Traditional graphite electrode plate is due to processing difficulties, shock resistance
Difference is gradually replaced by metal polar plate.But metal polar plate running surface in fuel cell acidic environment is passivated, and causes to connect
The metal ion pollution catalyst that resistance of getting an electric shock increases, while being precipitated, reduces proton exchange membrane conductivity.Therefore in metal surface system
Standby one layer of conduction and erosion-resisting coating are the important research directions for improving metal polar plate performance and promoting commercializing fuel cells.
Metal polar plate face coat more mature at present is broadly divided into noble coatings and carbon-base coating.Class graphite is carbon-based
Coating has good electric conductivity and corrosion resistance, is widely studied in recent years.Patent publication No. CN102800871A is public
It has opened and one layer of chromium underlayer is first deposited in stainless steel surface deposition using the method for closed field unbalanced magnetron sputtering technology, then sunk
Product chromium carbon doped layer, finally deposits one layer of amorphous carbon layer, by adjusting chromium target current, carbon target electric current, argon flow amount, substrate bias
It waits technological parameters to adjust coating structure ingredient, significantly reduces metal polar plate contact resistance and corrosion resistance.Carbon coating
In the presence of major problem is that durability is poor, class equadag coating is a kind of non crystalline structure, and there are many defects, in fuel cell acid
Property environment in for a long time corrosion cause amorphous carbon surface to aoxidize, cause contact resistance to dramatically increase.With platinum, Jin Dengwei is represented expensive
Metal has preferable stability and electric conductivity, is applicable in fuel cell environment.Electroplating gold on surface is a kind of common system
Standby technique, but since electroplating gold coating compactness is poor, required gold thin film thickness is at least in 100 nm or more, and cost is too
Height is unsuitable for metal polar plate commercialization demand.Therefore a kind of low cost is prepared, the metal polar plate coating of high-durability becomes particularly
It is important.
Invention content
For above-mentioned technical problem in the prior art, the present invention provides a kind of receiving for fuel battery metal pole plate
Rice metal layer and preparation method, this nano metal layer and preparation method for fuel battery metal pole plate will solve
Fuel battery metal pole plate electric conductivity in the prior art, corrosion resistance are bad, and coating is under fuel cell acidic environment
The not high technical problem of endurance quality.
The present invention provides a kind of nano metal coatings for fuel battery metal pole plate, including a metal polar plate structure
At base layer, deposition has at least one layer of base metal or non-noble metal oxide or base metal time on the base layer
Oxide skin(coating) has one layer in the upper surface of the base metal or non-noble metal oxide or base metal suboxide layer deposition
Replace the mixed layer constituted, noble metal position with noble metal by base metal or non-noble metal oxide or base metal suboxide
In the outermost of the nano metal coating, the base metal layer element is Cr elements, Ni elements, Ti elements, Nb members
Element, Ta elements, W elements, Zr elements, the non-noble metal oxide or base metal suboxide are the oxide of Cr elements
Or suboxide, the oxide of Ni elements or suboxide, the oxide of Ti elements or suboxide, Nb elements oxide or
The oxide or secondary of suboxide, the oxide of Ta elements or suboxide, the oxide of W elements or suboxide or Zr elements
The thickness 1-500 nm of oxide, the base metal or non-noble metal oxide or base metal suboxide layer, your gold
It is Pt elements, Au elements, Y element or Ru elements to belong to, in base metal or time oxidation of non-noble metal oxide or base metal
In the mixed layer that nitride layer and noble metal are constituted, base metal or non-noble metal oxide or base metal suboxide layer and your gold
The mass ratio of category is 1-90：100, the thickness of the mixed layer coating is 1-100 nm.
Further, layer of precious metal is dots structure.
Further, the mixed layer replace by base metal with noble metal it is compound constitute, alternately at least twice.
The present invention also provides a kind of preparation method of above-mentioned nano metal coating for fuel battery metal pole plate,
Include the following steps：
1）Using vacuum vapor deposition method at least one layer of one layer of base metal or base metal oxygen are deposited on metal polar plate surface
Compound or base metal suboxide layer；The base metal layer element is Cr elements, Ni elements, Ti elements, Nb elements, Ta
Element, W elements, Zr elements, the non-noble metal oxide or base metal suboxide are the oxide or secondary of Cr elements
Oxide, the oxide of Ni elements or suboxide, the oxide of Ti elements or suboxide, the oxide of Nb elements or secondary oxygen
The oxide or secondary oxidation of compound, the oxide of Ta elements or suboxide, the oxide of W elements or suboxide or Zr elements
The thickness 1-500 nm of object, the base metal or non-noble metal oxide or base metal suboxide layer；In deposition
In the process, depositing temperature is less than 200 DEG C, and deposition pressure is less than 0.1 Pa；
2）The mixed layer that one deposition base metal or non-noble metal oxide or base metal suboxide are constituted with noble metal
The step of；Noble metal is Pt elements, Au elements, Y element or Ru elements, in base metal or non-noble metal oxide or non-expensive
In the mixed layer that metal suboxide and noble metal are constituted, base metal or non-noble metal oxide or base metal suboxide
Mass ratio with noble metal is 1-90：100, the mixed layer coating layer thickness 1-100 nm；, during deposition, deposition
Temperature at 200 DEG C -800 DEG C, deposition pressure between 0.1 Pa-1 Pa,
3）One using plasma etching base metal or non-noble metal oxide or base metal suboxide and noble metal
The step of mixed layer of composition, is passed through reaction gas in the vacuum chamber, and for etch period between 1-100 s, removal surface is non-expensive
Metal layer；
4）The step of one vacuum annealing process；Temperature control between 200-1000 DEG C, processing time between 0.1-2h, very
Reciprocal of duty cycle is more than 1 Pa, eliminates the cavity blemish that etching processing leaves.
Specifically, the reaction gas is hydrogen.
The first step deposited metal layer material of the present invention is the elements such as Cr, Ni, Ti, Nb, Ta, W or Zr, or Cr,
On the one hand binding force between nano metal layer and matrix can be improved in the oxide or suboxide of Ni, Ti, Nb, Ta, W or Zr, another
The metal material corrosion resistance of aspect deposition is strong, enhances the corrosion resistance of matrix.Third walks plasma etching and removes table
Face base metal layer, using the gas reacted with surface layer non-noble metal j element is passed through in vacuum chamber, etching depth is in 1-100 nm.
As in the nano metal layer of titanium and gold, needed metal polar plate being put in CF4Plasma in, control etch period ensures to carve
Lose depth.4th step vacuum annealing process, to eliminate the cavity blemish that etching processing leaves, the combination for improving outer layer noble metal is strong
Degree.The base metal layer oxidation processes that etching is exposed simultaneously, to achieve the purpose that enhance corrosion resistance.
When the first step of the present invention prepares base metal bottom, depositing temperature is less than 200 DEG C, and deposition pressure is less than 0.1 Pa,
The fabric of deposition compact；Second step deposits base metal and noble metal mixed coating, and deposition pressure is in 0.1-1 Pa, deposition
Temperature forms stable column structure at 200-1000 DEG C.Third walks plasma etching treatment surface base metal layer, etching
Depth removes surface base metal layer in 1-100nm..4th step vacuum annealing process, 200-1000 DEG C of annealing temperature, time
0.1-2 h, vacuum degree eliminate holiday due to 1 Pa, improve the bond strength of outer layer noble metal.
The nano metal coating internal layer of the present invention can be that base metal layer, base metal and noble metal composite layer are alternately more
Layer periodic structure, periodic thickness 1-100nm enhance coating corrosion resistance.Outermost layer is by plasma etching, vacuum
Dotted layer of precious metal after heat treatment ensures conductive coating performance, and for coating layer thickness between 1-100nm, enhancing coating is anticorrosive
Performance.Outermost layer is the dotted layer of precious metal after plasma etching, vacuum heat, ensures conductive coating performance.
Multi-arc ion coating, magnetron sputtering, the physical vapour deposition (PVD)s such as pulsed laser deposition can be used in the preparation method of the present invention
It is prepared by method.
It is analog fuel cell acidic environment pH3 that the present invention, which uses the fast appraisement method of constant potential polarization, etchant solution,
H2SO4+ 0.1 ppm HF+80 DEG C, application current potential are 0.84 VSHEWith 1.6 VSHE, contact resistance test pressure is 1.4 MPa.
In a preferred embodiment of the present invention, a kind of described 1.6 V-5h of nano metal composite coating constant potential and
The contact resistance of coating does not occur significantly to change between 1-1.5m Ω cm2 after 0.84V_200h polarization experiments, molten after corrosion
Liquid ion concentration testing result shows that each ion concentration is far below other coating process results.Therefore nanogold proposed by the present invention
Belong to the endurance quality that coating can effectively improve metal polar plate.
A kind of nano metal layer for fuel battery metal pole plate proposed by the present invention has higher electric conductivity,
Endurance quality under acidic environment is suitable for various variable load operating modes；Coating tool is well bonded simultaneously, lower interior
Stress, can significantly increase the durability of metal polar plate at the problem of coating shedding will not occurring during long-play use.
Compared with traditional electroplating technology or sputter deposition noble metal film, coating structure proposed by the present invention and preparation process can
Noble metal usage amount is greatly decreased, reduces production cost, is suitable for mass production.
The present invention is compared with prior art, and technological progress is significant.The technique can compared with existing coating by the present invention
To substantially reduce the dosage of noble metal, the present invention can significantly increase metal polar plate surface conductance performance, corrosion resistance, and
Coating endurance quality under fuel cell acidic environment, meeting the durability under fuel cell environment for metal polar plate needs
It asks.Metal polar plate coating manufacture efficiency is improved simultaneously, reduces production cost.The present invention is applied particularly to fuel cell field, subtracts
Few noble metal usage amount, reduces contact resistance between metal polar plate and gas diffusion layers, improves fuel battery metal pole plate durability
Energy.
Description of the drawings
Fig. 1 is one layer of nano metal composite coating, wherein 11 be metallic matrix, 12 be base metal layer, and 13 be your non-gold
Belong to and noble metal mixed layer；
Fig. 2 is one layer of nano metal composite coating, wherein 21 be metallic matrix, 22 be non-metallic layer, and 23 be dotted layer of precious metal；
Fig. 3 is that multilayer replaces nano metal composite coating, wherein 31 metallic matrixes, 32 be base metal layer, and 33 be base metal
With noble metal composite layer；
Fig. 4 is that multilayer replaces nano metal composite coating, wherein 41 metallic matrixes, 42 be base metal layer, and 43 be base metal
With noble metal composite layer, 44 shape layer of precious metal；
Fig. 5 is the nano metal coating preparation flow schematic diagram for fuel battery metal pole plate, the advance nano metal of the first step
Composite coating, second step carry out corona treatment under vacuum conditions, and third walks coating post-processing and obtains nano metal coating.
The same treatment process is also applied for the processing of multilayered cylindrical shell coating.
Fig. 6 is a kind of structural schematic diagram of nano metal coating for fuel battery metal pole plate of the present invention.
Fig. 7 is 7 obtained corrosion curve of present example（A）With contact resistance figure before and after corrosion（B）.
Specific implementation mode
Detailed description is proposed to the present invention with reference to specific embodiment of implementing.Some embodiments will be helpful to ability
The technical staff in domain further understands the present invention, but the invention is not limited in any way.Before not departing from present inventive concept
It puts, those skilled in the art make several modifications and improvements and belong to protection scope of the present invention.
Embodiment 1
A kind of nano metal layer for fuel battery metal pole plate, structure as shown in Figure 1, the nano metal layer first in pole
Deposit underlying metal 12 on plate 11, then deposit base metal and noble metal mixed coating 13, base metal and noble metal it is mixed
Composition and division in a proportion example is between 1%-90%.
Embodiment 2
A kind of nano metal layer for fuel battery metal pole plate, structure as shown in Fig. 2, the nano metal layer first in pole
Bottom 22 is deposited on plate 21, then deposits base metal and noble metal mixed coating, the mixed proportion of base metal and noble metal
Between 0%-90%, finally and corona treatment and post-processing is carried out, obtain dotted noble metal conductive layer 23.
Embodiment 3
A kind of nano metal coating for fuel battery metal pole plate, structure is as shown in figure 3, the nano metal layer exists first
Bottom base metal layer 32 is deposited on pole plate 31, base metal layer and noble metal composite layer 33, period alternating deposit carry out later
Plasma etching and vacuum annealing process, obtain nano-multilayered structures.
Embodiment 4
A kind of nano metal coating for fuel battery metal pole plate, structure is as shown in figure 4, the nano metal layer exists first
Bottom base metal layer 42 is deposited on pole plate 41, base metal layer and noble metal composite layer 43, period alternating deposit are finally gone forward side by side
Row corona treatment and post-processing obtain dotted noble metal conductive layer 44.
Embodiment 5
As shown in Figure 5,6, a kind of nano metal layer for fuel battery metal pole plate, may be used technique system in detail below
It is standby：
The first step：Metal polar plate 1 is sequentially placed into deionized water ultrasonic cleaning equipment in advance, removes product surface greasy dirt, it is miscellaneous
The pollutants such as matter improve sample surfaces cleannes, and then drying etc. is housed in furnace chamber.
Second step：Cleaned 1 product of metal polar plate is put into vacuum coating cavity and carries out plasma cleaning, is removed
Sample surfaces oxide layer and adsorbed gas enhance coating binding force.
Third walks：In the 1 surface deposited metal Cr layers 2 of metal polar plate cleaned out, Cr layer thickness is 50 nm；
4th step：In 2 surface of the bottom deposition Cr and Au doped layers 3, Cr deposited：Au atomic ratios are classified as 1:1, deposition pressure
0.2 Pa, 30 nm of depositing coating thickness.
Embodiment 6
As shown in Figure 5,6, a kind of nano metal layer for fuel battery metal pole plate, may be used technique system in detail below
It is standby：
The first step：Metal polar plate 1 is sequentially placed into deionized water ultrasonic cleaning equipment in advance, removes product surface greasy dirt, it is miscellaneous
The pollutants such as matter improve sample surfaces cleannes, and then drying etc. is housed in furnace chamber.
Second step：Cleaned 1 product of metal polar plate is put into vacuum coating cavity and carries out plasma cleaning, is removed
Sample surfaces oxide layer and adsorbed gas enhance coating binding force.
Third walks：In the 1 surface deposited metal Cr layers 2 of metal polar plate cleaned out, Cr layer thickness is 50 nm；
4th step：Cr and Y doped layers 3, Cr are deposited in the bottom surface 2 deposited：Y atomic ratios are classified as 1:1, depositing temperature 300
DEG C, 0.2 Pa of deposition pressure, 30 nm of depositing coating thickness；
5th step：The metal polar plate deposited is put into plasma etching cavity, Cl is passed through at radio frequency source2And O2Mixing is anti-
Answer gas, removal metal polar plate surface base metal Cr elements；In the mixed reaction gas, Cl2And O2Volume ratio be 1：
1；
6th step：The metal polar plate etched is put into vacuum drying oven, 1Pa is evacuated to, temperature is heated to 300 DEG C, heat preservation
1h then passes to protective gas argon gas and is cooled to room temperature, and eliminates holiday.
Embodiment 7
Technique preparation in detail below may be used in a kind of nano metal layer for fuel battery metal pole plate：
The first step：Metal polar plate 1 is sequentially placed into deionized water ultrasonic cleaning equipment in advance, removes product surface greasy dirt, it is miscellaneous
The pollutants such as matter improve sample surfaces cleannes, and then drying etc. is housed in furnace chamber.
Second step：Cleaned 1 product of metal polar plate is put into vacuum coating cavity and carries out plasma cleaning, is removed
Sample surfaces oxide layer and adsorbed gas enhance coating binding force.
Third walks：In the 1 surface deposited metal Ta layers 2 of metal polar plate cleaned out, Ta layer thickness is 30 nm；
4th step：Using magnetically controlled sputter method, Ta is sputtered2O5Target deposits Ta in the bottom surface deposited2O5Layer, oxide
Layer thickness is 20nm；
5th step：Continue to deposit Ta on 1 surface of metal polar plate for depositing aerobic compound layer2O5With the mixed layer 3 of Pt, Ta and Pt are former
Sub- ratio is 7：3；
6th step：The metal polar plate for having deposited coating is put into progress plasma etching removing in vacuum cavity, from radio frequency source
Place is passed through H2, remove coating surface oxide；
7th step：The metal polar plate prepared is put into the metal polar plate for being about to etch in vacuum drying oven, is evacuated to
1Pa, temperature are heated to 400 DEG C, keep the temperature 0.5 h, then pass to protective gas argon gas and be cooled to room temperature, and eliminate holiday.
8th step：The metal polar plate prepared is subjected to measuring contact resistance and electrochemistry in fuel cell simulated environment
Evaluation of Corrosion Resistance.As a comparison with traditional metal polar plate coating simultaneously.From the point of view of test result, nanometer prepared by the present invention
Metal coating initial contact resistance is under 1.4 MPa assembling pressures by the 3-4 m Ω cm of conventional coatings2It is reduced to 1m Ω cm2, can
Significantly reduce fuel battery inside Ohmic resistance.Prepared nano metal coating corrosion performance significantly improves simultaneously, and electric current is close
Degree is substantially reduced than conventional coatings, after long-time accelerated test（pH3 H2SO4+ 80 DEG C of solution, constant potential polarization 1.6
VSHE1 h）, coating morphology is complete, does not there is evidence of corrosion.Sample resistance after test corrosion compares, after traditional coating corrosion
Contact resistance dramatically increases, and after the experience accelerated corrosion of the sample contact resistance of present example 7, contact resistance is basically unchanged
（Fig. 7）.
Claims (4)
1. a kind of nano metal coating for fuel battery metal pole plate includes the base layer of metal polar plate composition,
It is characterized in that：Deposition has at least one layer of base metal or non-noble metal oxide or base metal time oxygen on the base layer
Compound layer, the upper surface of the base metal or non-noble metal oxide or base metal suboxide layer deposition have one layer by
Base metal or non-noble metal oxide or base metal suboxide replace the mixed layer constituted with noble metal, and noble metal is located at
The outermost of the nano metal coating, the base metal layer element be Cr elements, Ni elements, Ti elements, Nb elements,
Ta elements, W elements, Zr elements, the non-noble metal oxide or base metal suboxide be Cr elements oxide or
The oxide or secondary of suboxide, the oxide of Ni elements or suboxide, the oxide of Ti elements or suboxide, Nb elements
The oxide or secondary oxygen of oxide, the oxide of Ta elements or suboxide, the oxide of W elements or suboxide or Zr elements
The thickness 1-500 nm of compound, the base metal or non-noble metal oxide or base metal suboxide layer, noble metal
For Pt elements, Au elements, Y element or Ru elements, in base metal or non-noble metal oxide or base metal suboxide
Layer in the mixed layer of noble metal composition, base metal or non-noble metal oxide or base metal suboxide layer and noble metal
Mass ratio be 1-90：100, the thickness of the mixed layer coating is 1-100 nm.
2. according to claim 1 a kind of for fuel battery metal pole plate nano metal coating, it is characterised in that：Your gold
Category layer is dots structure.
3. according to claim 1 a kind of for fuel battery metal pole plate nano metal coating, it is characterised in that：It is described
Mixed layer replace by base metal with noble metal it is compound constitute, alternately at least twice.
4. a kind of preparation method of nano metal coating for fuel battery metal pole plate described in claim 1, feature
It is to include the following steps：
1）Using vacuum vapor deposition method at least one layer of one layer of base metal or base metal oxygen are deposited on metal polar plate surface
Compound or base metal suboxide layer；The base metal layer element is Cr elements, Ni elements, Ti elements, Nb elements, Ta
Element, W elements, Zr elements, the non-noble metal oxide or base metal suboxide are the oxide or secondary of Cr elements
Oxide, the oxide of Ni elements or suboxide, the oxide of Ti elements or suboxide, the oxide of Nb elements or secondary oxygen
The oxide or secondary oxidation of compound, the oxide of Ta elements or suboxide, the oxide of W elements or suboxide or Zr elements
The thickness 1-500 nm of object, the base metal or non-noble metal oxide or base metal suboxide layer；In deposition
In the process, depositing temperature is less than 200 DEG C, and deposition pressure is less than 0.1 Pa；
2）The mixed layer that one deposition base metal or non-noble metal oxide or base metal suboxide are constituted with noble metal
The step of；Noble metal is Pt elements, Au elements, Y element or Ru elements, in base metal or non-noble metal oxide or non-expensive
In the mixed layer that metal suboxide and noble metal are constituted, base metal or non-noble metal oxide or base metal suboxide
Mass ratio with noble metal is 1-90：100, the mixed layer coating layer thickness 1-100 nm；During deposition, deposition temperature
Degree is at 200 DEG C -800 DEG C, and deposition pressure is between 0.1 Pa-1 Pa；
3）One using plasma etching base metal or non-noble metal oxide or base metal suboxide and noble metal
The step of mixed layer of composition, is passed through reaction gas in the vacuum chamber, and for etch period between 1-100 s, removal surface is non-expensive
Metal layer；
4）The step of one vacuum annealing process；Temperature control between 200-1000 DEG C, processing time between 0.1-2 h,
Vacuum degree is more than 1 Pa, eliminates the cavity blemish that etching processing leaves.
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