CN107937871A - A kind of fuel battery double plates composite coating and preparation method thereof - Google Patents
A kind of fuel battery double plates composite coating and preparation method thereof Download PDFInfo
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- CN107937871A CN107937871A CN201710983891.0A CN201710983891A CN107937871A CN 107937871 A CN107937871 A CN 107937871A CN 201710983891 A CN201710983891 A CN 201710983891A CN 107937871 A CN107937871 A CN 107937871A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0635—Carbides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
- C23C14/0057—Reactive sputtering using reactive gases other than O2, H2O, N2, NH3 or CH4
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
- C23C14/0084—Producing gradient compositions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/048—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with layers graded in composition or physical properties
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Abstract
The present invention relates to a kind of fuel battery double plates composite coating and preparation method thereof, composite coating includes the metal carbide layer on setting metal polar plate and the amorphous carbon layer being arranged in metal carbide layer, in metal carbide layer, the tenor at metal polar plate is most, and carbon content is minimum；Tenor at amorphous carbon layer is minimum, and carbon content is most；Preparation process includes metal polar plate surface preparation, deposited metal carbide layer and deposited amorphous carbon-coating successively.Compared with prior art, in the present invention, tenor in metal carbide layer changes with carbon content in steps change or continuity, effectively enhance the combination power between matrix and coating, coating and coating, with excellent conduction and corrosion resistance, the method for the reactive sputtering alloys target that coating introduces in preparing can efficiently reduce target poison ing phenomenon, it is easier to reaction gas flow be controlled, to prepare the metal carbide layer of different metal content.
Description
Technical field
The invention belongs to field of fuel cell technology, is related to a kind of fuel battery double plates composite coating and its preparation side
Method.
Background technology
Fuel cell is a kind of hair that the chemical energy of fuel and oxidant is directly changed into electric energy by electrochemical reaction
Electric installation.With the continuous development of new energy technology, the Proton Exchange Membrane Fuel Cells (Proton using hydrogen as main fuel
Exchange Membrane Fuel Cell, PEMFC) have become one of hot spot of research in recent years.Since its energy is changed
Process need not be through overheated machine process, therefore energy conversion efficiency limits from Carnot cycle, and the generating efficiency of battery pack can reach
To more than 50%, and its exclusive product is water, very friendly to environment.The operating temperature of Proton Exchange Membrane Fuel Cells is low,
Startup speed is fast, specific power is high, long working life, is preferable mobile power and independent power supply device, in the vehicles, electronics
The fields such as product, national defense and military and stationary electric power plant are with a wide range of applications.
Traditional pemfc stack mainly includes the structures such as membrane electrode, bipolar plates, wherein, bipolar plates have accounted for the big of pile
Part mass and cost.One of core component as Proton Exchange Membrane Fuel Cells, bipolar plates have following functions：(1) divide
Oxygen barrier agent and reducing agent；(2) collected current and the heat dissipation of battery system is undertaken；(3) it is the inflow of reacting gas and the stream of water
Go out to provide passage (i.e. flow field)；(4) membrane electrode is supported.Therefore, preferable bipolar plate material must be good conductor electrically and thermally, tool
There is good gas barrier property, there is good corrosion resistance in certain operating temperature and potential range, density is low, and intensity is high, and
And easily processed into type and mass production.At present, the bipolar plate material of PEMFC mainly has three kinds：Graphite material, composite material
And metal material.Wherein, the thermal conductance of graphite material and electrical conductance are good, and chemical property is stablized, corrosion resistance and good, but due to
Graphite material brittleness is big, bad mechanical property, is not easy to produce in enormous quantities；Composite material double pole plate manufacturing process is simple, light weight,
Corrosion resistance is good, but there are the problems such as electric conductivity difference and gas infiltration at the same time；Metal material bipolar plates have high intensity and
Good conduction, heat conductivility, and raw material are cheap, are adapted to high-volume to process, and are fuel cell productions generally acknowledged at present
Industryization is preferred.However, metal polar plate easily corrodes in the strong acid, high-temperature work environment of fuel cell, catalyst is polluted,
The serious service life for reducing fuel cell, and metal polar plate can form passivating film, Jin Erzeng in sour environment on surface
The big contact resistance of pole plate and gas diffusion layers.Therefore, improve the corrosion resistance of metal polar plate, reduce pole plate contact resistance
It is the Main way of metal polar plate development.
Pass through PVD (physical vapour deposition (PVD)), CVD (chemical vapor deposition), ion plating or plating etc. on metal polar plate surface
It is the effective way for improving metal polar plate corrosion resistance and electric conductivity that mode, which prepares one or more layers protective coating, at present,
Metal-carbide coating and amorphous carbon coating have been used widely due to its good corrosion resistance and electric conductivity.It is right
In metal-carbide coating, if directly bombarding sputtering compound target with working gas, gaseous state or solid compounds can be caused to send out
Solution estranged, causing to deposit has very big difference on obtained film and target, and the stronger constituent content of electronegativity, which can generally be less than, to be changed
The correct content of compound, so that the compound film of corresponding stoicheiometry can not be obtained.Reactive magnetron sputtering is a kind of deposition chemical combination
The major way of thing film, i.e., using high purity metal target, be passed through a certain amount of reacting gas and carry out reactive deposition film.Pass through tune
Section deposition process parameters can prepare the compound film of stoicheiometry or non-chemical proportion, so as to fulfill by adjusting film group
Into regulating and controlling film characteristics.
As shown in Figure 1, generally as the increase of reaction gas flow, deposition film can occur three patterns successively：Metal
Modes I (in figure AB sections), transition mode II (in figure BC sections) and reaction pattern III (in figure CD sections).In the mistake of reaction magnetocontrol sputtering
Cheng Zhong, when the reaction gas flow in sputtering settling chamber is relatively low (in figure AB sections), sedimentation rate is higher at this time, and deposition film is substantially
Belong to metallic state, therefore this sputtering state is known as metal mode.When reaction gas flow constantly increases above critical point B,
Metallic target is acted on reacting gas, in target surface generating layer compound layer.Since the secondary electron yield of compound is generally high
In metal, sputtering yield reduces, and the flow of reacting gas somewhat increases (in figure BC sections) at this time, and sputter rate can occur significantly
Decline, this process is known as transition mode.If reaction gas flow further increases, the change of sedimentation rate is little,
Deposition film is rendered as compound film, and sputtering state at this time is known as reaction pattern (in figure CD sections).Reaction pattern is in sputtering
When, reaction gas flow (in figure DE, EF sections) is gradually reduced, sputter rate will not return to B points along former rate curve, but directly
To some critical point E is reduced to, numerical value when sharp rising to metal mode sputtering state just occurs, this is because target table
Face is covered with compound, and need to sputter removing is exposed metal targets afterwards, and material is thus formed the lag loop of closure.One
As high-speed reactive sputtering process occur mainly in transition mode, but II scope of transition mode is relatively narrow, and control is improper, can cause
Target poison ing, target poison ing can not only reduce the sedimentation rate of film, can also damage the quality of deposition film.Prevent target poison ing at present
Method mainly has following 4 kinds：(1) intermediate frequency or radio-frequency power supply are used；(2) closed-loop control reaction gas flow；(3) using twin
Target；(4) film coating mode conversion is controlled.
Authorization Notice No. discloses one kind for the Chinese invention patent of CN103820761B and uses multi-target magnetic control sputtering equipment
The method for preparing metal carbides coating, accurately controls carbon content, but can not obtain the metal-carbide coating of high-purity.Award
The Chinese invention patent that power notification number is CN103668092B discloses a kind of new plasma ion assisted deposition method, passes through
It is improved to magnetron sputtering coater or using magnetic-controlled sputtering coating equipment, it can be ensured that high deposition rate, film deposition mistake
Cheng Wending, obtains high-purity compound film of high stoichiometric ratio, overcomes target poison ing phenomenon.Authorization Notice No. is
The Chinese utility model patent of CN205741199U discloses a kind of plasma enhancing magnetron sputtering apparatus for preventing target poison ing,
It can prevent the aggregation of target surface reacting gas particle.However, technical solution disclosed in above-mentioned patent is from optimization filming equipment
Angle improve the quality of coating carbide coating, add the cost of equipment, and application range is restricted.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of fuel cell bipolar
Plate composite coating and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of fuel battery double plates composite coating, the composite coating are arranged on metal polar plate, the composite coating
Including the amorphous carbon layer for setting the metal carbide layer on metal polar plate and being arranged in metal carbide layer, the metal
In carbide lamella, the tenor at metal polar plate is most, and carbon content is minimum；Tenor at amorphous carbon layer is most
Few, carbon content is most.The surface of metal polar plate can be modified by applying the composite coating being plated on metal polar plate.Amorphous carbon layer
Painting is plated in metal carbide layer surface, can significantly reduce the contact resistance of metal polar plate, improves the corrosion resistance of metal polar plate
Energy.
Further, in the metal carbide layer, continuously subtract along metal polar plate to amorphous carbon layer direction, tenor
Few, carbon content continuously increases.Tenor and carbon content i.e. in metal carbide layer change in continuity.
Further, the metal carbide layer includes the sub- coating of metal carbides that at least two is overlapped mutually setting,
And along metal polar plate to amorphous carbon layer direction, the tenor in multiple sub- coatings of metal carbides is reduced successively, carbon content
Increase successively.Tenor and carbon content i.e. in metal carbide layer are in steps change, and along metal polar plate to amorphous
Carbon-coating direction, the tenor in the adjacent sub- coating of two metal carbides are reduced, and carbon content increases.
Further, the metal carbide layer includes the 2-10 sub- coatings of metal carbides for being overlapped mutually setting.
Further, in the metal carbide layer, along metal polar plate to amorphous carbon layer direction, tenor by
50wt% is decremented to 0wt%, and carbon content is incremented to 100wt% by 50wt%.Being located at the tenor at metal polar plate is
50wt%, carbon content 50wt%；Tenor at amorphous carbon layer is 0wt%, carbon content 100wt%.
Further, the material of the metal polar plate includes one in stainless steel, titanium alloy, aluminium alloy or magnesium alloy
Kind.
Further, the thickness of the metal polar plate is 0.1-2mm, and the thickness of the metal carbide layer is 10-
200nm, the thickness of the amorphous carbon layer is 1-100nm.
A kind of preparation method of fuel battery double plates composite coating, this method comprise the following steps：
1) metal polar plate surface preparation：After metal polar plate is cleaned up, handled with ultrasonic wave；
2) deposited metal carbide layer：Working gas and reacting gas are passed through into vacuum tank, sputters alloys target afterwards,
In metal polar plate surface deposited metal carbide layer；
3) deposited amorphous carbon-coating：Working gas is passed through, reacting gas is simultaneously closed off, sputters carbon target afterwards, in metallic carbide
Nitride layer surface deposited amorphous carbon-coating.
Further, in step 1), after metal polar plate is cleaned up with deionized water or distilled water, then it is sequentially placed into third
Ultrasonic vibration treatment is carried out in ketone, absolute ethyl alcohol.
Further, in step 2), the material of the alloys target is the carbide of metal, and the working gas is argon
Gas, the reacting gas are hydrocarbon gas.
As preferable technical solution, the carbide of the metal includes chromium carbide (Cr3C2), titanium carbide (TiC), carbon
Change the one or more in zirconium (ZrC), niobium carbide (NbC) or molybdenum carbide (MoC), the hydrocarbon gas includes methane
(CH4), butane (C4H10) or acetylene (C2H2) in one or more.
Further, in step 2), by controlling technological parameter to sputter alloys target, in metal polar plate surface deposited metal carbon
Compound layer.
As preferable technical solution, in step 2), it is 10-100sccm to control and be passed through argon flow amount, is passed through reacting gas
Flow is 5-80sccm, is biased as -20V to -300V, sedimentation time 5-60min.
Further, in step 2) and step 3), the vacuum in vacuum tank is 10-4-10-1Torr。
As preferable technical solution, in step 3), it is 5-90sccm to control argon flow amount, is biased as -10V to -500V,
Sedimentation time is 5-30min.
During reactive magnetron sputtering alloys target prepares composite coating, argon inlet mouth can be tieed up effectively close to target
Hold plasma；The air inlet of reacting gas is close to metal polar plate, it is possible to increase the sedimentation rate of metal carbides, and avoid
Metal carbides are deposited on the region beyond metal polar plate.
The present invention uses reactive magnetron sputtering alloy target technology, and metal carbon is prepared on fuel battery metal Polar plate matrix surface
Compound-amorphous carbon composite coating, wherein, metal carbide layer is prepared by reactive magnetron sputtering alloys target, which is a kind of
Steps coating or continuity coating, it is upward from metal polar plate surface, the tenor in metal carbide layer it is steps or
Continuity is reduced, and tenor is controlled under different film coating modes by varying reaction gas flow；Amorphous carbon layer then passes through work
Make gas bombardment carbon target material sputtering sedimentation.Composite coating prepared by this method is improved between matrix and coating, coating and coating
Combination power, there is excellent conduction and corrosion resistance, the method for the reactive sputtering alloys target that coating introduces in preparing can have
Effect reduces target poison ing phenomenon, it is easier to controls reaction gas flow, prepares the metal carbide layer of different metal content.
Compared with prior art, the invention has the characteristics that：
1) tenor in metal carbide layer changes with carbon content in steps change or continuity, effectively strengthens
Combination power between matrix and coating, coating and coating, avoids coating from peeling off, and the amorphous carbon layer of coating surface is effective
Ground improves the resistance to corrosion of whole coating, reduces the contact resistance of metal polar plate；
2) metal carbides-amorphous carbon composite coating is prepared using closed field unbalanced reactive magnetron sputtering alloys target, its
In, metal carbide layer is prepared using the method for reactive magnetron sputtering alloys target, can be in original metal carbide chemical
Different film coating modes are adjusted on proportioning to regulate and control the tenor in whole coating, obtain the metal of different metal content
Carbide lamella, and effectively suppress target poison ing phenomenon and occur；
3) preparation process of coating is improved, metal carbides applies the ratio of layer number, thickness and carbide
Can freely it control, technique adjustment control is flexible.
Brief description of the drawings
Hysteresis phenomenon schematic diagram when Fig. 1 is general reactive magnetron sputtering pure metal targets；
Fig. 2 is the structure diagram of composite coating in embodiment 3；
Fig. 3 is the structure diagram of composite coating in embodiment 4；
Description of symbols in figure：
1-metal polar plate, 2-metal carbide layer, 3-amorphous carbon layer, I-metal mode, II-transition mode, III-
Reaction pattern.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention
Premised on implemented, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to
Following embodiments.
Embodiment 1：
Using bipolar plate of stainless steel as matrix, the compound painting of chromium carbide-amorphous carbon is coated with its surface using reactive magnetron sputtering
Layer, technical process are as follows：
1) metal polar plate pre-processes：Successively using deionized water, acetone, absolute ethyl alcohol to stainless steel double polar plate surface ultrasound
Cleaning；
2) bipolar plate of stainless steel after cleaning is hung in closed field unbalanced magnetron sputtering ion plating furnace chamber, taken out true
It is empty to be extremely less than 3 × 10-5After Torr, argon working gas is filled with, and operating air pressure is maintained at 4 × 10-4Torr, substrate bias
For -500V, the passivation layer that ion bombardment removes matrix surface is carried out, scavenging period 30min, wherein pole plate hang on planet and turn
On pallet, rotating speed 4r/min；
3) 60sccm argon gas is passed through as protective gas, and it is each to be passed through 30sccm-35sccm-40sccm reacting gas butane
10min, keeps substrate bias -80V, opens alloy target current, reactive sputter-deposition Cr2C3Layer, sedimentation time 30min；
4) reactant gas passage and alloy target current are closed, opens carbon target electric current, sputtering sedimentation amorphous carbon layer, sedimentation time
20min；
5) target current and blow vent are closed, carries out cooling 20min, coating is prepared and finished.
Embodiment 2：
Reactive magnetron sputtering prepares titanium carbide-amorphous carbon composite coating, and technical process is as follows：
1) metal polar plate pre-processes：It is clear to stainless steel polar plate surface ultrasound using deionized water, acetone, absolute ethyl alcohol successively
Wash；
2) bipolar plate of stainless steel after cleaning is hung in closed field unbalanced magnetron sputtering ion plating furnace chamber, taken out true
It is empty to be extremely less than 3 × 10-5After Torr, argon working gas is filled with, and operating air pressure is maintained at 4 × 10-4Torr, substrate bias
For -500V, the passivation layer that ion bombardment removes matrix surface is carried out, scavenging period 30min, wherein pole plate hang on planet and turn
On pallet, rotating speed 4r/min；
3) 40sccm argon gas is passed through as protective gas, and is passed through 20-40sccm reacting gas acetylene 30min, reaction gas
Body flow is linearly increasing, keeps substrate bias -100V, opens alloy target current, reactive sputter-deposition TiC layer, and sedimentation time is
30min；
4) reactant gas passage and alloy target current are closed, opens carbon target electric current, sputtering sedimentation amorphous carbon layer, sedimentation time
20min；
5) target current and blow vent are closed, carries out cooling 20min, coating is prepared and finished.
Embodiment 3：
A kind of fuel battery double plates composite coating, the composite coating are arranged on metal polar plate 1, and composite coating includes setting
Put the metal carbide layer 2 on metal polar plate 1 and the amorphous carbon layer 3 being arranged in metal carbide layer 2, metal carbide layer
In 2, the tenor at metal polar plate 1 is most, and carbon content is minimum；Tenor at amorphous carbon layer 3 is minimum, carbon
Content is most.
As shown in Fig. 2, in the composite coating, metal carbide layer 2 is continuity coating, along metal polar plate 1 to amorphous carbon
3 direction of layer, tenor are continuously reduced, and carbon content continuously increases.
In metal carbide layer 2, it is decremented to along metal polar plate 1 to 3 direction of amorphous carbon layer, tenor by 50wt%
0wt%, carbon content are incremented to 100wt% by 50wt%.
The material of metal polar plate 1 is stainless steel.The thickness of metal polar plate 1 is 0.1mm, and the thickness of metal carbide layer 2 is
200nm, the thickness of amorphous carbon layer 3 is 1nm.
The preparation method of the composite coating comprises the following steps：
1) 1 surface preparation of metal polar plate：After metal polar plate 1 is cleaned up, handled with ultrasonic wave；
2) deposited metal carbide layer 2：Working gas and reacting gas are passed through into vacuum tank, sputters alloy afterwards
Target, in 1 surface deposited metal carbide layer 2 of metal polar plate；
3) deposited amorphous carbon-coating 3：Working gas is passed through, reacting gas is simultaneously closed off, sputters carbon target afterwards, in metallic carbide
2 surface deposited amorphous carbon-coating 3 of nitride layer.
In step 2), the material of alloys target is the carbide of metal, and working gas is argon gas, and reacting gas is hydro carbons gas
Body.In step 2) and step 3), the vacuum in vacuum tank is 10-4-10-3Torr。
Embodiment 4：
A kind of fuel battery double plates composite coating, the composite coating are arranged on metal polar plate 1, and composite coating includes setting
Put the metal carbide layer 2 on metal polar plate 1 and the amorphous carbon layer 3 being arranged in metal carbide layer 2, metal carbide layer
In 2, the tenor at metal polar plate 1 is most, and carbon content is minimum；Tenor at amorphous carbon layer 3 is minimum, carbon
Content is most.
As shown in figure 3, in the composite coating, metal carbide layer 2 is steps coating, and metal carbide layer 2 includes 5
It is overlapped mutually the sub- coating of metal carbides of setting, and along metal polar plate 1 to 3 direction of amorphous carbon layer, 5 metal carbides
Tenor in coating is reduced successively, and carbon content increases successively.1 ' gradually decreases to n ' tenors i.e. in figure.
In metal carbide layer 2, it is decremented to along metal polar plate 1 to 3 direction of amorphous carbon layer, tenor by 50wt%
0wt%, carbon content are incremented to 100wt% by 50wt%.
The material of metal polar plate 1 is titanium alloy.The thickness of metal polar plate 1 is 2mm, and the thickness of metal carbide layer 2 is
10nm, the thickness of amorphous carbon layer 3 is 100nm.
The preparation method of the composite coating comprises the following steps：
1) 1 surface preparation of metal polar plate：After metal polar plate 1 is cleaned up, handled with ultrasonic wave；
2) deposited metal carbide layer 2：Working gas and reacting gas are passed through into vacuum tank, sputters alloy afterwards
Target, in 1 surface deposited metal carbide layer 2 of metal polar plate；
3) deposited amorphous carbon-coating 3：Working gas is passed through, reacting gas is simultaneously closed off, sputters carbon target afterwards, in metallic carbide
2 surface deposited amorphous carbon-coating 3 of nitride layer.
In step 2), the material of alloys target is the carbide of metal, and working gas is argon gas, and reacting gas is hydro carbons gas
Body.In step 2) and step 3), the vacuum in vacuum tank is 10-3-10-2Torr。
Embodiment 5：
A kind of fuel battery double plates composite coating, the composite coating are arranged on metal polar plate 1, and composite coating includes setting
Put the metal carbide layer 2 on metal polar plate 1 and the amorphous carbon layer 3 being arranged in metal carbide layer 2, metal carbide layer
In 2, the tenor at metal polar plate 1 is most, and carbon content is minimum；Tenor at amorphous carbon layer 3 is minimum, carbon
Content is most.
Metal carbide layer 2 includes 2 sub- coatings of the metal carbides for being overlapped mutually setting, and along metal polar plate 1 to
3 direction of amorphous carbon layer, the tenor in 2 sub- coatings of metal carbides are reduced successively, and carbon content increases successively.
In metal carbide layer 2, it is decremented to along metal polar plate 1 to 3 direction of amorphous carbon layer, tenor by 50wt%
0wt%, carbon content are incremented to 100wt% by 50wt%.
The material of metal polar plate 1 is aluminium alloy.The thickness of metal polar plate 1 is 1mm, and the thickness of metal carbide layer 2 is
100nm, the thickness of amorphous carbon layer 3 is 50nm.
The preparation method of the composite coating comprises the following steps：
1) 1 surface preparation of metal polar plate：After metal polar plate 1 is cleaned up, handled with ultrasonic wave；
2) deposited metal carbide layer 2：Working gas and reacting gas are passed through into vacuum tank, sputters alloy afterwards
Target, in 1 surface deposited metal carbide layer 2 of metal polar plate；
3) deposited amorphous carbon-coating 3：Working gas is passed through, reacting gas is simultaneously closed off, sputters carbon target afterwards, in metallic carbide
2 surface deposited amorphous carbon-coating 3 of nitride layer.
In step 2), the material of alloys target is the carbide of metal, and working gas is argon gas, and reacting gas is hydro carbons gas
Body.In step 2) and step 3), the vacuum in vacuum tank is 10-2-10-1Torr。
Embodiment 6：
A kind of fuel battery double plates composite coating, the composite coating are arranged on metal polar plate 1, and composite coating includes setting
Put the metal carbide layer 2 on metal polar plate 1 and the amorphous carbon layer 3 being arranged in metal carbide layer 2, metal carbide layer
In 2, the tenor at metal polar plate 1 is most, and carbon content is minimum；Tenor at amorphous carbon layer 3 is minimum, carbon
Content is most.
Metal carbide layer 2 includes 10 sub- coatings of the metal carbides for being overlapped mutually setting, and along metal polar plate 1 to
3 direction of amorphous carbon layer, the tenor in 10 sub- coatings of metal carbides are reduced successively, and carbon content increases successively.
In metal carbide layer 2, it is decremented to along metal polar plate 1 to 3 direction of amorphous carbon layer, tenor by 50wt%
0wt%, carbon content are incremented to 100wt% by 50wt%.
The material of metal polar plate 1 is magnesium alloy.The thickness of metal polar plate 1 is 1.5mm, and the thickness of metal carbide layer 2 is
150nm, the thickness of amorphous carbon layer 3 is 70nm.
The preparation method of the composite coating comprises the following steps：
1) 1 surface preparation of metal polar plate：After metal polar plate 1 is cleaned up, handled with ultrasonic wave；
2) deposited metal carbide layer 2：Working gas and reacting gas are passed through into vacuum tank, sputters alloy afterwards
Target, in 1 surface deposited metal carbide layer 2 of metal polar plate；
3) deposited amorphous carbon-coating 3：Working gas is passed through, reacting gas is simultaneously closed off, sputters carbon target afterwards, in metallic carbide
2 surface deposited amorphous carbon-coating 3 of nitride layer.
In step 2), the material of alloys target is the carbide of metal, and working gas is argon gas, and reacting gas is hydro carbons gas
Body.In step 2) and step 3), the vacuum in vacuum tank is 10-4-10-1Torr。
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously easily can make these embodiments various modifications, and described herein general
Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel disclose according to the present invention, do not depart from improvement that scope made and modification all should be the present invention's
Within protection domain.
Claims (10)
1. a kind of fuel battery double plates composite coating, which is arranged on metal polar plate (1), it is characterised in that institute
The composite coating stated includes the metal carbide layer (2) on setting metal polar plate (1) and is arranged in metal carbide layer (2)
Amorphous carbon layer (3),
In the metal carbide layer (2), the tenor positioned at metal polar plate (1) place is most, and carbon content is minimum；Positioned at non-
The tenor at brilliant carbon-coating (3) place is minimum, and carbon content is most.
A kind of 2. fuel battery double plates composite coating according to claim 1, it is characterised in that the metallic carbide
In nitride layer (2), continuously reduced along metal polar plate (1) to amorphous carbon layer (3) direction, tenor, carbon content continuously increases.
A kind of 3. fuel battery double plates composite coating according to claim 1, it is characterised in that the metallic carbide
Nitride layer (2) includes at least two and is overlapped mutually the sub- coating of metal carbides of setting, and along metal polar plate (1) to amorphous carbon layer
(3) direction, the tenor in multiple sub- coatings of metal carbides are reduced successively, and carbon content increases successively.
A kind of 4. fuel battery double plates composite coating according to claim 3, it is characterised in that the metallic carbide
Nitride layer (2) includes the 2-10 sub- coatings of metal carbides for being overlapped mutually setting.
A kind of 5. fuel battery double plates composite coating according to claim 1, it is characterised in that the metallic carbide
In nitride layer (2), along metal polar plate (1) to amorphous carbon layer (3) direction, tenor is decremented to 0wt% by 50wt%, carbon content by
50wt% is incremented to 100wt%.
A kind of 6. fuel battery double plates composite coating according to claim 1, it is characterised in that the metal polar plate
(1) material includes one kind in stainless steel, titanium alloy, aluminium alloy or magnesium alloy.
A kind of 7. fuel battery double plates composite coating according to claim 1, it is characterised in that the metal polar plate
(1) thickness is 0.1-2mm, and the thickness of the metal carbide layer (2) is 10-200nm, the amorphous carbon layer (3)
Thickness is 1-100nm.
It is 8. a kind of as the preparation method of claim 1 to 7 any one of them fuel battery double plates composite coating, its feature exist
In this method comprises the following steps：
1) metal polar plate (1) surface preparation：After metal polar plate (1) is cleaned up, handled with ultrasonic wave；
2) deposited metal carbide layer (2)：Working gas and reacting gas are passed through into vacuum tank, sputters alloys target afterwards,
In metal polar plate (1) surface deposited metal carbide layer (2)；
3) deposited amorphous carbon-coating (3)：Working gas is passed through, reacting gas is simultaneously closed off, sputters carbon target afterwards, in metal carbides
Layer (2) surface deposited amorphous carbon-coating (3).
A kind of 9. preparation method of fuel battery double plates composite coating according to claim 8, it is characterised in that step
2) in, the material of the alloys target is the carbide of metal, and the working gas is argon gas, and the reacting gas is hydrocarbon
Class gas.
A kind of 10. preparation method of fuel battery double plates composite coating according to claim 8, it is characterised in that step
Rapid 2) and in step 3), the vacuum in vacuum tank is 10-4-10-1Torr。
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| CN111029606A (en) * | 2019-12-20 | 2020-04-17 | 佛山国防科技工业技术成果产业化应用推广中心 | Metal boride-based composite coating for fuel cell bipolar plate and preparation method thereof |
| CN112609165A (en) * | 2020-12-15 | 2021-04-06 | 辽宁科技大学 | Composite coating on surface of bipolar plate of stainless steel-based fuel cell and preparation method thereof |
| CN113025980A (en) * | 2021-03-01 | 2021-06-25 | 森科五金(深圳)有限公司 | Corrosion-resistant film layer for fuel cell bipolar plate and preparation method thereof |
| CN113097522A (en) * | 2021-03-29 | 2021-07-09 | 纳狮新材料有限公司 | Bipolar plate and method for producing the same |
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