CN109023282A - A kind of preparation method preparing CrMoTiN nitride film nano coating in bipolar plate surfaces - Google Patents
A kind of preparation method preparing CrMoTiN nitride film nano coating in bipolar plate surfaces Download PDFInfo
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- CN109023282A CN109023282A CN201811105800.4A CN201811105800A CN109023282A CN 109023282 A CN109023282 A CN 109023282A CN 201811105800 A CN201811105800 A CN 201811105800A CN 109023282 A CN109023282 A CN 109023282A
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- 150000004767 nitrides Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002103 nanocoating Substances 0.000 title claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000151 deposition Methods 0.000 claims abstract description 14
- 230000008021 deposition Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000005498 polishing Methods 0.000 claims abstract description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 9
- 244000137852 Petrea volubilis Species 0.000 claims abstract description 7
- 239000006071 cream Substances 0.000 claims abstract description 7
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 7
- 239000010432 diamond Substances 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims abstract description 7
- 239000010935 stainless steel Substances 0.000 claims abstract description 7
- 239000000356 contaminant Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012495 reaction gas Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims description 9
- 238000004062 sedimentation Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 229910000619 316 stainless steel Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000007733 ion plating Methods 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 description 12
- 230000010287 polarization Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
Classifications
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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
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
-
- 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
- C23C14/0641—Nitrides
-
- 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
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
A kind of preparation method preparing CrMoTiN nitride film nano coating in bipolar plate surfaces, comprising the following steps: 1) polished respectively 316 bipolar plate of stainless steel matrixes with SiC sand paper, then with diamond polishing cream to the matrix looking-glass finish degree of grinding；2) before plated film, surface and oil contaminant is removed, obtains pretreatment matrix；3) pretreatment matrix is put into vacuum chamber cavity, deposits quaternary nitride film CrMoTiN on its surface using unbalanced magnetron sputter ion plating technique and is modified to carry out surface to stainless steel base.The present invention adds Ti element using physical gas phase deposition technology on the basis of the bipolar plates of CrMoN coating surface modifying, a kind of new quaternary nitride CrMoTiN coating is provided, it is mixed by elements such as Mo, Ti, further increase the corrosion resistance of bipolar plate material and guarantees electric conductivity.
Description
Technical field
The present invention relates to a kind of preparation methods of coating on dual polar plates of proton exchange membrane fuel cell material, that is, pass through closure
Field unbalanced magnetron sputtering technique deposits CrMoTiN quaternary nitride film in bipolar plate surfaces to improve the resistance to of fuel battery double plates
Corrosion and conductivity guarantee unfailing performance and prolong the service life that battery uses.
Background technique
Not only energy conversion rate is high, environmental-friendly for Proton Exchange Membrane Fuel Cells, and can be in room temperature quick start, nothing
Electrolysis is lost, the service life is long, specific power and specific energy are high.It is particularly suitable for being used as removable power source, is electric vehicle and dispersion
One of the ideal source in power station has wide practical use in terms of substituting traditional fossil energy.
Bipolar plates are one of significant components of fuel cell, it accounts for the 70% of the 80% of battery pile total volume, quality, and
The 30% of cost.It has afflux, heat dissipation, evenly dispersed reaction medium and cooling effect, while have support membrane electrode, every
The requirement of exhausted reaction gas and leakproofness.So ideal bipolar plate material should have good electric conductivity, high-air-tightness,
High mechanical strength and it is easy to process the features such as.Graphite and its compound have good electric conductivity, easy to process, still
Material fragility is big, bad mechanical property, processing cost are higher, is unfavorable for large-scale business application.Metallic bipolar plate materials have
High mechanical strength, good electric conductivity, easy to process, cost is relatively low, can be extensive commercial.However it is handed in acid proton
Change in membrane cell environment, metallic bipolar plate materials are easily corroded, and form passivating film, increase bipolar plates and gas diffusion membrane it
Between contact resistance, while polluting membrane electrode, damage battery pile.It is modified so needing to carry out bipolar plate of stainless steel surface to mention
High corrosion-resistant, electric conductivity.
Summary of the invention
Corrosion resistance in order to overcome the shortcomings of existing bipolar plate material is lower and electric conductivity is poor, and the present invention provides one
Kind prepares the preparation method of CrMoTiN nitride film nano coating in bipolar plate surfaces, using physical gas phase deposition technology in CrMoN
Ti element is added on the basis of the bipolar plates of coating surface modifying, and a kind of new quaternary nitride CrMoTiN coating is provided, is passed through
The elements such as Mo, Ti mix, and further increase the corrosion resistance of bipolar plate material and guarantee electric conductivity.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of preparation method preparing CrMoTiN nitride film nano coating in bipolar plate surfaces, the preparation method include
Following steps:
1) it is polished respectively 316 bipolar plate of stainless steel matrixes with SiC sand paper, then with diamond polishing cream to grinding
Matrix looking-glass finish degree；
2) before plated film, surface and oil contaminant is removed, obtains pretreatment matrix；
3) pretreatment matrix is put into vacuum chamber cavity, closes door for vacuum chamber, is evacuated to preset threshold, has in cavity
Two pieces of symmetrically placed high-purity Cr targets, one piece of high-purity Mo target and one piece of high-purity Ti target, argon gas run as protective gas and plate
Film program；
In the case where -520V~-480V bias and all target currents are both configured to 0.2~0.4A, ion sputtering bombardment
Pre-process 25~35min of matrix surface；
Cr target current is promoted to 3~5A, Mo target and Ti target current it is corresponding it is small be promoted to 0.4~0.6A, deposit 3~8min
Cr transition zone is obtained to increase film-substrate cohesion；
Nitrogen is passed through as reaction gas and deposits 10~20min in Cr layer surface, obtains CrN film；
Mo target current is adjusted to 3~5A, 10~20min is deposited, obtains CrMoN film；
CrMoTiN film is finally deposited, Ti target current range is 0.3A-6A, and sedimentation time is 40~80min, to be contained
The CrMoTiN coating of Ti.
Further, in the step 3), the preset threshold is 2.5 × 10-5torr；In -500V bias and all targets electricity
In the case that stream is both configured to 0.3A, matrix surface 30min is bombarded in ion sputtering, and Cr target current is promoted to 4A, Mo target and Ti target
Electric current is accordingly small to be promoted to 0.5A, and deposition 5min obtains Cr transition zone, and it is heavy in Cr layer surface as reaction gas to be passed through nitrogen
Product 15min, obtains CrN film；Mo target current is adjusted to 4A, 15min is deposited, obtains CrMoN film；Finally deposit CrMoTiN film, Ti
Target current range is 0.3A-6A, sedimentation time 60min, to obtain the CrMoTiN coating containing Ti.
Further, it in the step 1), to 316 stainless steel bars wire cuttings, is machined to be sized to obtain bipolar plates
Matrix respectively polishes to matrix with the SiC sand paper that granularity is 400#, 800#, 1200#, 1500#, 2000#, then uses grain
Matrix looking-glass finish degree of the diamond polishing cream that degree is 0.1 μm to grinding.
Further, in the step 2), with ultrasonic device polishing matrix be respectively put into acetone, dehydrated alcohol, go from
15~25min of ultrasound in sub- water.
In the present invention, physical gas phase deposition technology prepares that resulting coating purity is high, compactness is good, coating is in conjunction with matrix
Power is high, and it is more satisfactory double-polar plate surface modifying technology, and especially with nitride that coating performance is not influenced by basis material
Coating prepares in the majority.But defect existing for the single nitride coatings of physical gas phase deposition technology preparation will form primary battery,
Lead to local corrosion.The appearance of this problem can be effectively avoided deposition composite membrane and by way of adding extra elements.
Closed field unbalanced magnetron sputtering ion plating equipment combines the advantages of magnetron sputtering technique and ion plating technique, and thicknesses of layers is equal
Even, tool is by higher binding force between coating and matrix, while having very high flexibility, can be used to prepare gradient membrane coat
With the depositing multilayer coatings on same matrix.
Beneficial effects of the present invention are mainly manifested in: carrying out including dynamic polarization test, stable state to it by three-electrode system
The electro-chemical test of polarization test and electrochemical impedance spectroscopy simulates PEMFCs use environment, and test result shows: new quaternary
Nitride CrMoTiN coating surface modifying bipolar plates have very big promotion with respect to 316 stainless steel base corrosion potentials, and corrosion current is close
Degree has dropped two orders of magnitude；It can be enhanced about more than once than CrTiN coating corrosion resistance.Film-substrate cohesion about 46N.
Specific embodiment
The invention will be further described below.
A kind of preparation method preparing CrMoTiN nitride film nano coating in bipolar plate surfaces, the preparation method include
Following steps:
1) it is polished respectively 316 bipolar plate of stainless steel matrixes with SiC sand paper, then with diamond polishing cream to grinding
Matrix looking-glass finish degree；
2) before plated film, surface and oil contaminant is removed, obtains pretreatment matrix；
3) pretreatment matrix is put into vacuum chamber cavity, closes door for vacuum chamber, is evacuated to preset threshold, has in cavity
Two pieces of symmetrically placed high-purity Cr targets, one piece of high-purity Mo target and one piece of high-purity Ti target, argon gas run as protective gas and plate
Film program；
In the case where -520V~-480V bias and all target currents are both configured to 0.2~0.4A, ion sputtering bombardment
Pre-process 25~35min of matrix surface；
Cr target current is promoted to 3~5A, Mo target and Ti target current it is corresponding it is small be promoted to 0.4~0.6A, deposit 3~8min
Cr transition zone is obtained to increase film-substrate cohesion；
Nitrogen is passed through as reaction gas and deposits 10~20min in Cr layer surface, obtains CrN film；
Mo target current is adjusted to 3~5A, 10~20min is deposited, obtains CrMoN film；
CrMoTiN film is finally deposited, Ti target current range is 0.3A-6A, and sedimentation time is 40~80min, to be contained
The CrMoTiN coating of Ti.
Further, in the step 3), the preset threshold is 2.5 × 10-5torr；In -500V bias and all targets electricity
In the case that stream is both configured to 0.3A, matrix surface 30min is bombarded in ion sputtering, and Cr target current is promoted to 4A, Mo target and Ti target
Electric current is accordingly small to be promoted to 0.5A, and deposition 5min obtains Cr transition zone, and it is heavy in Cr layer surface as reaction gas to be passed through nitrogen
Product 15min, obtains CrN film；Mo target current is adjusted to 4A, 15min is deposited, obtains CrMoN film；Finally deposit CrMoTiN film, Ti
Target current range is 0.3A-6A, sedimentation time 60min, to obtain the CrMoTiN coating containing Ti.
Further, it in the step 1), to 316 stainless steel bars wire cuttings, is machined to be sized to obtain bipolar plates
Matrix respectively polishes to matrix with the SiC sand paper that granularity is 400#, 800#, 1200#, 1500#, 2000#, then uses grain
Matrix looking-glass finish degree of the diamond polishing cream that degree is 0.1 μm to grinding.
Further, in the step 2), with ultrasonic device polishing matrix be respectively put into acetone, dehydrated alcohol, go from
15~25min of ultrasound in sub- water.
The present invention provides the bipolar plates and its surface reforming layer of a kind of 316 stainless steels preparation.I.e. using 316 stainless steels as base
Body, using unbalanced magnetron sputter ion plating technique its surface deposit quaternary nitride film CrMoTiN come to stainless steel base into
Row surface is modified, and the corrosion resistance of surface modified membrane is characterized by potentiodynamic polarization test.PEMFCs use environment is simulated, is surveyed
Test result shows: new quaternary nitride CrMoTiN coating surface modifying bipolar plates have with respect to 316 stainless steel base corrosion potentials
Very big promotion, corrosion electric current density have dropped two orders of magnitude；It can be enhanced about more than once than CrTiN coating corrosion resistance.Film base
Binding force about 46N.
Embodiment 1
Pretreatment matrix is put into vacuum chamber cavity, door for vacuum chamber is closed, is evacuated to 2.5 × 10-5torr.In cavity
There are two pieces of symmetrically placed high-purity Cr targets, one piece of high-purity Mo target and one piece of high-purity Ti target.Argon gas is run as protective gas
Plating run.In the case where -520V bias and all target currents are both configured to 0.2A, matrix surface is bombarded in ion sputtering
25min has reached the purpose of removal surface film oxide and impurity.Cr target current is promoted to 3A, and Mo target and Ti target current are accordingly micro-
Small to be promoted to 0.4A, deposition 3min obtains Cr transition zone to increase film-substrate cohesion.Nitrogen is passed through as reaction gas at Cr layers
Surface deposits 10min, obtains CrN film.Mo target current is adjusted to 3A, 10min is deposited, obtains CrMoN film.Ti target current is still tieed up
It holds in 0.3A, continues to deposit 40min, complete coating process, it is to be cooled, take out sample.
The corrosion electric current density that this example prepares resulting CrMoTiN composite membrane bipolar plates potentiodynamic polarization test is 2.62
×10-7A cm-2, in 1.5MPa, the interface contact resistance between coating and carbon paper is 6.2m Ω cm2。
Embodiment 2
Pretreatment matrix is put into vacuum chamber cavity, door for vacuum chamber is closed, is evacuated to 2.5 × 10-5torr.In cavity
There are two pieces of symmetrically placed high-purity Cr targets, one piece of high-purity Mo target and one piece of high-purity Ti target.Argon gas is run as protective gas
Plating run.In the case where -500V bias and all target currents are both configured to 0.3A, matrix surface is bombarded in ion sputtering
30min has reached the purpose of removal surface film oxide and impurity.Cr target current is promoted to 4A, and Mo target and Ti target current are accordingly micro-
Small to be promoted to 0.5A, deposition 5min obtains Cr transition zone to increase film-substrate cohesion.Nitrogen is passed through as reaction gas at Cr layers
Surface deposits 15min, obtains CrN film.Mo target current is adjusted to 4A, 15min is deposited, obtains CrMoN film.Finally deposit
CrMoTiN film, Ti target current are raised to 2A, sedimentation time 60min.
This example prepares the corrosion electric current density that resulting CrMoTiN composite membrane bipolar plates potentiodynamic polarization is tested
1.170×10-7A cm-2, under the pressure of 1.5MPa, the interface contact resistance between coating and carbon paper is 5.8m Ω cm2。
Embodiment 3
Pretreatment matrix is put into vacuum chamber cavity, door for vacuum chamber is closed, is evacuated to 2.5 × 10-5torr.In cavity
There are two pieces of symmetrically placed high-purity Cr targets, one piece of high-purity Mo target and one piece of high-purity Ti target.Argon gas is run as protective gas
Plating run.In the case where -480V bias and all target currents are both configured to 0.4A, matrix surface is bombarded in ion sputtering
35min has reached the purpose of removal surface film oxide and impurity.Cr target current is promoted to 5A, and Mo target and Ti target current are accordingly micro-
Small to be promoted to 0.6A, deposition 8min obtains Cr transition zone to increase film-substrate cohesion.Nitrogen is passed through as reaction gas at Cr layers
Surface deposits 20min, obtains CrN film.Mo target current is adjusted to 5A, 20min is deposited, obtains CrMoN film.Finally deposit
CrMoTiN film, Ti target current are 6A, sedimentation time 80min.
This example prepares the corrosion electric current density that resulting CrMoTiN composite membrane bipolar plates potentiodynamic polarization is tested
5.884×10-8A cm2, under the pressure of 1.5MPa, the interface contact resistance between coating and carbon paper is 5.2m Ω cm2。
Claims (4)
1. a kind of preparation method for preparing CrMoTiN nitride film nano coating in bipolar plate surfaces, which is characterized in that the preparation
Method the following steps are included:
1) it is polished respectively 316 bipolar plate of stainless steel matrixes with SiC sand paper, then with diamond polishing cream to the base of grinding
Body looking-glass finish degree；
2) before plated film, surface and oil contaminant is removed, obtains pretreatment matrix；
3) pretreatment matrix is put into vacuum chamber cavity, closes door for vacuum chamber, is evacuated to preset threshold, there are two pieces in cavity
Symmetrically placed high-purity Cr target, one piece of high-purity Mo target and one piece of high-purity Ti target, argon gas run plated film journey as protective gas
Sequence；
In the case where -520V~-480V bias and all target currents are both configured to 0.2~0.4A, the pre- place of ion sputtering bombardment
Manage 25~35min of matrix surface；
Cr target current is promoted to 3~5A, Mo target and Ti target current it is corresponding it is small be promoted to 0.4~0.6A, 3~8min of deposition is obtained
Cr transition zone is to increase film-substrate cohesion；
Nitrogen is passed through as reaction gas and deposits 10~20min in Cr layer surface, obtains CrN film；
Mo target current is adjusted to 3~5A, 10~20min is deposited, obtains CrMoN film；
CrMoTiN film is finally deposited, Ti target current range is 0.3A-6A, and sedimentation time is 40~80min, to obtain containing Ti's
CrMoTiN coating.
2. a kind of preparation method that CrMoTiN nitride film nano coating is prepared in bipolar plate surfaces as described in claim 1,
It is characterized in that, in the step 3), the preset threshold is 2.5 × 10-5torr；It is all set in -500V bias and all target currents
In the case where being set to 0.3A, matrix surface 30min is bombarded in ion sputtering, and Cr target current is promoted to 4A, Mo target and Ti target current phase
Answer it is small be promoted to 0.5A, deposition 5min obtains Cr transition zone, is passed through nitrogen as reaction gas in Cr layer surface deposition
15min obtains CrN film；Mo target current is adjusted to 4A, 15min is deposited, obtains CrMoN film；Finally deposit CrMoTiN film, Ti target
Current range is 0.3A-6A, sedimentation time 40min, to obtain the CrMoTiN coating of different Ti contents.
3. a kind of preparation side for preparing CrMoTiN nitride film nano coating in bipolar plate surfaces as claimed in claim 1 or 2
Method, which is characterized in that in the step 1), to 316 stainless steel bars wire cuttings, be machined to be sized to obtain bipolar plates base
Body respectively polishes to matrix with the SiC sand paper that granularity is 400#, 800#, 1200#, 1500#, 2000#, then uses granularity
It is 0.1 μm of diamond polishing cream to the matrix looking-glass finish degree of grinding.
4. a kind of preparation side for preparing CrMoTiN nitride film nano coating in bipolar plate surfaces as claimed in claim 1 or 2
Method, which is characterized in that in the step 2), polishing matrix is respectively put into acetone, dehydrated alcohol, deionized water with ultrasonic device
Middle ultrasonic 15~25min.
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| CN201811105800.4A CN109023282B (en) | 2018-09-21 | 2018-09-21 | Preparation method for preparing CrMoTiN nitride film nano coating on surface of bipolar plate |
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| CN201811105800.4A CN109023282B (en) | 2018-09-21 | 2018-09-21 | Preparation method for preparing CrMoTiN nitride film nano coating on surface of bipolar plate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111224121A (en) * | 2020-01-15 | 2020-06-02 | 辽宁科技大学 | In-situ preparation method of surface composite modified layer of stainless steel bipolar plate of proton exchange membrane fuel cell |
| CN114959577A (en) * | 2022-06-09 | 2022-08-30 | 中国科学院宁波材料技术与工程研究所 | Cr-based multi-principal-element nitride coating and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102723499A (en) * | 2012-06-07 | 2012-10-10 | 上海交通大学 | Metal bipolar plate of fuel cell with surface plating layers and preparation method thereof |
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| CN114959577B (en) * | 2022-06-09 | 2024-05-14 | 中国科学院宁波材料技术与工程研究所 | Cr-based multi-principal element nitride coating and preparation method and application thereof |
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