CN103199279B - The doping type multi-gradient coating of fuel battery metal double polar plate - Google Patents
The doping type multi-gradient coating of fuel battery metal double polar plate Download PDFInfo
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Abstract
The invention discloses dual polar plates of proton exchange membrane fuel cell of a kind of surface doping multi-gradient film and preparation method thereof, wherein, adopt closed field unbalanced magnetron sputtering technology prepare Ti, Al on metal double polar plates surface or/and Mo doping C/CrN multi-gradient film. This doping type C/CrN multi-gradient coating includes graphite-like carbon coatings, CrN coating and Cr transition zone, and the elements such as Ti, Al, Mo, W, Nb, Ni, Zr, Fe, Si that adulterate in class graphite film and (or) CrN coating carry out organizing and composition regulation and control. Compared with prior art, the metal double polar plates of the PEM of the present invention has the electric conductivity of excellence, decay resistance and the characteristic such as low through-hole rate and low cost, greatly improves the dress heap performance and used life of fuel cell; And it is possible to meet the instructions for use of fuel cell, it is widely applied prospect.
Description
Technical field
The present invention relates to overlay coating of a kind of fuel battery metal double polar plate and preparation method thereof, doping type multi-gradient film particularly relating to a metal double-plate for proton exchange film fuel cell and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) has energy transformation ratio height (40%��60%), zero-emission, quickly startup and specific power advantages of higher, is therefore considered as the ideal device for vehicular energy and distributed power generation station. Bipolar plates is the multi-functional critical component in PEMFC, it accounts for the 80% of PEMFC gross weight, most volume, the 10% of PEMFC totle drilling cost, material cost 20%. The function Supported film electrode group of bipolar plates, collected current, conducting gas and draining etc. act on. It is therefore desirable to bipolar plate material has certain intensity, good toughness, gas impermeability, good surface conductance performance and decay resistance. The cost of bipolar plate material and endurance issues are the key issues that PEMFC application is urgently to be resolved hurrily.
The material being presently used for bipolar plates mainly includes graphite, metal and based composite material of carbon. Metal material is due to high intensity, easy-formation and conducts electricity preferably and heat conductivility, has obvious advantage than other materials in reducing fuel cell volume power ratio and raising power density etc. Wherein, stainless steel material is due to its low cost, high intensity, easy-formation and conducts electricity preferably and heat conductivility, has obvious advantage than other materials in reducing fuel cell cost and raising power density etc. But the decay resistance of stainless steel material and surface conductance performance are not met by its performance requirement as fuel battery double plates, i.e. surface contacted resistance��20m �� cm2, at 0.5M sulphuric acid+5ppmHF solution electric current density��1 �� A/cm at ambient temperature2. There is researcher to propose to start to change alloying component from steel-making, but this is for high cost the commercially producing of most of fuel cells.Also there is researcher to propose to improve the corrosion resistant metal content such as stainless Cr and Mo, adopt heat treatment technics to make part Cr and Mo form, at stainless steel surfaces, the carbide that conduction is anti-corrosion, form the conductive network protruded with metal surface. But, this method needs individually to refine steel on the one hand, and heat treatment is usually sensitized treatment on the other hand, and the carbide of formation protrudes from metal surface, destroy the seriality of stainless steel surfaces passivation layer, it is easy to form intercrystalline corrosion thus aggravating stainless corrosion.
For the bipolar plate of stainless steel problem that decay resistance and surface conductance performance are not enough in fuel cell operating conditions, certain method is adopted to prepare low cost on bipolar plate of stainless steel surface, the anti-corrosion coating material that conducts electricity is a kind of feasible thinking to improve its performance and life-span. Through the literature search of prior art is found, there is researcher to pass through the methods such as plating, chemical plating and deposit the noble metals such as one layer of gold, platinum or silver at stainless steel surfaces. Although the decay resistance and surface conductance performance that improve bipolar plate of stainless steel are had good effect by these noble metals, but noble metal is expensive, and coating processing cost is high, is unfavorable for the commercial applications of bipolar plate of stainless steel; It addition, chemical plating or plating easily produce the waste water of contaminated environment, it is unfavorable for environmental protection. Utilizing physical vapor deposition (PVD) to have corrosion-resistant and electric conductivity coating preferably in stainless steel surfaces preparation is the feasible method of a kind of low cost. Ren Libin etc. propose the protective coating adopting chromium nitride cladding material as metal double polar plates in patent of invention (application number: 200610129486.4), and this coating has good conduction, corrosion-resistant, antioxidation and resistant to elevated temperatures characteristic. (" AninvestigationoftheelectrochemicalpropertiesofPVDTiN-co atedSS410insimulatedPEMfuelcellenvironments ") (PVD deposition titanium nitride plates 410 rustless steels Electrochemical Properties in PEMFC Environment) that Wang etc. deliver on " InternationalJournalofHydrogenEnergy " (international Hydrogen Energy) (32 phase 895-902 pages in 2007) points out, potentiodynamic polarization experiments show that corrosion electric current density has substantial degradation than rustless steel, from 189 �� A/cm2Drop to 1.75 �� A/cm2, but author also points out that electrostatic potential polarization experiment result shows that corrosion electric current density increases three times simultaneously, this illustrates coating hole, and stainless corrosion is had a great impact by these holes. therefore, owing to thin film mostly is column crystal growth in PVD deposition process, thin film would generally be inevitably generated hole. for this problem, there is researcher to have employed PVD deposition multilayer technique and block column crystal growth pattern, thus reduce the hole produced in deposition process as far as possible. the article (" ArcionplatedCr/CrN/Crmultilayerson316Lstainlesssteelasbi polarplatesforpolymerelectrolytemembranefuelcells ") that the Zhang etc. of the Dalian Chemistry and Physics Institute delivers on " JournalofPowerSources " (energy magazine) (196 phase 3249-3254 pages in 2011) adopts arc ion plating technique to deposited Cr/CrN/Cr multilayer film at 316L stainless steel surfaces, result shows that rustless steel is reduced 1 order of magnitude at the corrosion electric current density of anode and cathode environment by Cr/CrN/Cr multilayer film, respectively reach 10-5.4A/cm2With 10-5.9A/cm2;Further, at 150N/cm2Under thrust, ICR reduces 1 order of magnitude, for 30-35m �� cm2. The article (" Chromiumnitride/Crcoated316Lstainlesssteelasbipolarplate forprotonexchangemembranefuelcell ") (chromium nitride/chromium plating 316L rustless steel is as the research of dual polar plates of proton exchange membrane fuel cell) that the Tian of Dalian University Of Communications delivers on " JournalofPowerSources " (energy magazine) (196 phase 1258-1263 pages in 2011) is pointed out, at 0.05MH after plated film2SO4+5ppmF-Solution current density ratio rustless steel under 70 DEG C of conditions reduces an order of magnitude, reaches close to 1 �� A/cm2, at 150N/cm2ICR under thrust is stainless 1/3, for 35m �� cm2��
Relative to TiN and CrN coating material, amorphous carbon coating has more excellent electric conductivity and electrochemical stability, deposits amorphous carbon coating at stainless steel surfaces and can reach the purpose in conjunction with graphite Yu stainless steel material advantage. G.V. reaching rare grade and point out that in patent of invention (application number: 200910164680.X) depositing one layer at bipolar plate surfaces has hydrophilic, has transition Catalytic Layer and metal-doped amorphous carbon coating, this coating includes hydrophilic activating surface. The article (" Carbon-basedfilmscoated316Lstainlesssteelasbipolarplatef orprotonexchangemembranefuelcells ") (the 316L stainless steel as biplar plate for proton exchange membrane fuel cell of plating carbon-base film) that Fu etc. deliver on " InternationalJournalofHydrogenEnergy " (international Hydrogen Energy) (34 phase 405-409 pages in 2009) is prepared for carbon-base film by the method for pulsed bias arc ion plating, it is indicated that the coating that C-Cr thin film (namely makes doping metals with Cr) has good electric conductivity and corrosion resistance. But, the sputtering raste of material with carbon element is extremely low (��0.1), causes that the time of depositing carbon film is longer (carbon film such as depositing 3 �� m thick needs 5-6 hour), is unfavorable for the reduction of preparation cost. The sputtering raste of Cr element is of a relatively high, between 1.0��1.2. Additionally, carbon film differs relatively big with stainless steel base physical property, there is great internal stress (generally reaching GPa level) in usual carbon film, causes that film-substrate cohesion is poor.
Combine difference for PVD deposition amorphous carbon coating sedimentation time length, film base and be easily generated the shortcomings such as hole, those skilled in the art is devoted to develop a kind of method of C/CrN multi-gradient film adopting magnetic controlled sputtering ion plating deposition of elements to adulterate and improving film-substrate cohesion, reducing porosity, reducing cost, thus reaching to prepare at stainless steel surfaces the target of high-quality high connductivity corrosion-resistant coating. C/CrN multi-gradient film is based on outer layer amorphous carbon coating and internal layer CrN thin film, the thin film with chemical composition gradient being transition zone with Cr element between amorphous carbon coating and CrN thin film and between CrN thin film and stainless steel base. Meanwhile, in class graphite film and (or) CrN, the one or more kinds of any combination adulterated in the elements such as Ti, Al, Mo, W, Nb, Ni, Zr, Fe, Si carries out organizing and composition modulation. This coating has the advantages such as outstanding film-substrate cohesion, low porosity, shorter preparation time and low cost, compared to simple C/CrN multi-gradient film, has corrosion-resistant and conductive characteristic more preferably.
Summary of the invention
Because the drawbacks described above of prior art, the technical problem to be solved is to provide a kind of with fuel battery metal double polar plate of overlay coating that conduction is anti-corrosion and adhesion is high and preparation method thereof.
For achieving the above object, doping type multi-gradient film that the invention provides a metal double-plate for proton exchange film fuel cell and preparation method thereof.
It is an object of the invention to realize by following technical solution:
On the one hand, the invention provides a metal double-plate for proton exchange film fuel cell, including: metal double polar plates and the doping type C/CrN multi-gradient coating being deposited on the double; two surface of metal double polar plates; Wherein, the graphite-like carbon coatings of this doping type C/CrN multi-gradient coating includes upwards setting gradually from metal double polar plates surface Cr transition zone, chromium nitride (CrN) coating of doping, the chromium carbon nitrogen transition zone of doping and doping.
In the present invention, described metal double polar plates can be the metal materials such as rustless steel, titanium alloy, aluminium alloy or magnesium alloy.
Doped chemical in described doping type C/CrN multi-gradient coating is the one or more kinds of any combination in the elements such as Ti, Al, Mo, W, Nb, Ni, Zr, Fe, Si. In the specific embodiment of the present invention, the kind of each doped chemical and ratio are by adulterating the selection of target and size of current is controlled.
In the better embodiment of the present invention, the gross thickness of doping type C/CrN multi-gradient coating is 0.1��10 ��m.
In the specific embodiment of the present invention, the ratio of graphite-like carbon coatings and C/CrN multi-gradient coating gross thickness is 0��R(C:C/CrN) < 1, the ratio of CrN coating and C/CrN multi-gradient thickness of coating is 0��R(CrN:C/CrN) < 1, the ratio of Cr transition zone and C/CrN multi-gradient thickness of coating is 0��R(Cr:C/CrN) < 1, the ratio of chromium carbon nitrogen transition zone and C/CrN multi-gradient thickness of coating is 0 < R(CrN:C/CrN) < 1, wherein, R refers to the thickness ratio of any two coating. in the specific implementation, under extreme conditions, in obtained multi-gradient coated article, graphite-like carbon coatings, CrN coating or Cr transition zone are likely to the situation of promising 0, but its value is not 0 simultaneously.
On the other hand, present invention also offers and a kind of prepare above-mentioned surface with conducting electricity the method for dual polar plates of proton exchange membrane fuel cell of anti-corrosion doping type C/CrN multi-gradient coating, the method includes the steps of:
Step one, ion sputtering are cleaned;
First, metal double polar plates clean for chemistry ultrasonic cleaning is put in filming equipment, proceeds by evacuation, make background vacuum maintain 1 �� 10-7��5 �� 10-2Torr, starts to pass into argon, makes vacuum maintain 1 �� 10-3��10Torr;
Secondly, open chromium target current, control at 0.1��10A, the bias that metal double polar plates applies-1000��0V cleans 10min��1 hour, to remove the oxide-film of the possible remaining in metal double polar plates surface, passivating film etc., it is thus achieved that completely clean, and there is the surface of certain surface roughness;
Step 2, deposit pure chromium transition zone;
What control chromium target is biased in-500��0V, chromium target current 0.1��10A, and deposition Cr transition zone 10min��2 hour deposit pure chromium prime coat;
Step 3, deposition CrN coating carry out doping tissue modulation simultaneously;
What control chromium target is biased in-200��0V, pass into nitrogen, Ventilation Rate is 1��100SCCM, deposition CrN plating time is more than 0 and less than or equal to 2 hours, the electric current simultaneously controlling the one or more kinds of any combination target in the elements such as Ti, Al, Mo, W, Nb, Ni, Zr, Fe, Si is 0��40A, CrN coating is organized and composition regulation and control;
Step 4, deposition chromium carbon nitrogen transition zone
Keep chromium target current, substrate bias and nitrogen flow constant, regulate graphite target electric current and become larger to 10A by 0, deposition chromium carbon nitrogen transition zone 10��120 minutes;
Step 5, deposition graphite-like carbon coatings carry out doping tissue modulation simultaneously;
Control to be biased in-200��0V, graphite target electric current is 0.1��10A, the deposition graphite-like carbon coatings time is more than 0 and less than or equal to 10 hours, the electric current simultaneously controlling the one or more kinds of any combination target in the elements such as Ti, Al, Mo, W, Nb, Ni, Zr, Fe, Si is 0.5��40A, graphite-like carbon coating is organized and composition regulation and control.
In the present invention, it is preferred to, the doping type C/CrN multi-gradient coating of dual polar plates of proton exchange membrane fuel cell adopts closed field unbalanced magnetron sputtering ion plating technique to prepare.
In the specific embodiment of the present invention, described filming equipment is the equipment that the art is conventional, and this is not particularly limited by the present invention.
The invention discloses a kind of surface dual polar plates of proton exchange membrane fuel cell with the anti-corrosion doping type C/CrN multi-gradient coating of conduction, compared with prior art, the doping type C/CrN multi-gradient coating of the present invention has organizational structure and the chemical composition of uniqueness; And, the present invention adjusts structure and the composition of C/CrN multi-gradient coating by adjusting the technological parameter such as Cr target and the electric current of graphite target, nitrogen flow, substrate bias and doped chemical type, film-substrate cohesion between coating and metal double polar plates is greatly improved, make electric conductivity and the decay resistance through the fuel battery metal double polar plate that C/CrN multi-gradient coating is modified with excellence, with the characteristic such as low through-hole rate and low cost, thus greatly improving the dress heap performance and used life of fuel cell. Adopt dual polar plates of proton exchange membrane fuel cell prepared by the present invention can meet the instructions for use of fuel cell, be widely applied prospect.
Below with reference to accompanying drawing, the technique effect of the design of the present invention, concrete structure and generation is described further, to be fully understood from the purpose of the present invention, feature and effect.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope surface topography map (50000 times) of the C/CrN multi-gradient coating that embodiments of the invention 1 are deposited on metal double polar plates surface;
Fig. 2 is cross sectional Scanning Electron microscope and element line distribution collection of illustrative plates (20000 times) of the C/CrN multi-gradient coating that embodiments of the invention 1 are deposited on metal double polar plates surface;
The doping type C/CrN multi-gradient coating that Fig. 3 is untreated 316L rustless steel and prepared by embodiments of the invention 1-4 electrochemical tests comparison diagram in fuel cell simulated environment;
The doping type C/CrN multi-gradient coating that Fig. 4 is untreated 316L rustless steel and prepared by embodiments of the invention 1-4 surface contacted resistance comparison diagram under fuel cell typically equipped pressure 120 Ns/square centimeter thrust.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the invention being elaborated, the present embodiment is carried out under premised on technical solution of the present invention, gives detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
In an embodiment of the present invention, the method for physical vapor deposition (PVD) is adopted to deposit doping type C/CrN multi-gradient coating on metal double polar plates.
Embodiment 1
Step one, ion sputtering are cleaned;
First, bipolar plate of stainless steel clean for ultrasonic cleaning is placed in UDP650 closed field unbalanced magnetron sputtering ion beam coating equipment, proceeds by evacuation, make background vacuum lower than 5 �� 10-6Torr, starts to pass into argon, makes vacuum maintain 2 �� 10-2Torr;
Secondly, it is biased to-500V, opens chromium target current, control at 0.5A, bipolar plate of stainless steel is cleaned 30 minutes, to remove the oxide-film of the possible remaining of stainless steel surfaces, passivating film etc., and obtain certain surface roughness;
Step 2, deposit pure chromium transition zone;
Adjust substrate bias to-70V, chromium target current 7A, deposit Cr transition zone 15 minutes.
Step 3, deposition CrN coating carry out doping tissue modulation simultaneously;
Controlling to be biased in-60V, chromium target current maintains 7A, passes into nitrogen, and Ventilation Rate is 25SCCM, deposition CrN coating 30 minutes;
Step 4, deposition chromium carbon nitrogen transition zone;
Open graphite target, make graphite target electric current gradually rise up to 6A from 0A, control to be biased in-60V, chromium target current 7A, deposition chromium carbon nitrogen transition zone 15 minutes;
Step 5, deposition graphite-like carbon coatings;
Chromium target current is made to be gradually reduced from 7A, until stopping chromium target current; Controlling to be biased in-60V, graphite target electric current is 6A, deposition graphite-like carbon coatings 0.5 hour, prepares the surface fuel battery metal double polar plate with multi-gradient coating.
After preparing embodiment 1 sample, adopt the surface topography of sem observation sample. As it is shown in figure 1, the C/CrN multi-gradient film surface prepared is made up of many spherical graphite granules, thin film densification is without obvious hole. Adopt the cross-sectional morphology of sem observation sample and adopt line sweep test sample chemical Elemental redistribution. As in figure 2 it is shown, sample outermost layer is class graphite linings, there is a Cr transition zone subsequently, be CrN coating afterwards, Cr content gradually decreases subsequently, until it reaches matrix. Adopt the decay resistance of linear polarization scanning testing example 1 sample. Being specially employing Germany ZahnerZennium electrochemical workstation, and to adopt three-electrode system, reference electrode be saturated calomel electrode, platinum plate electrode is as to electrode, and sample is as working electrode. Corrosion electrolyte is 0.5M sulphuric acid+5ppm solution, tests, scanning speed 1mV/s under 70 DEG C of conditions. In Fig. 3 shown in embodiment 1 curve, in analog fuel battery corrosion liquid, it is 0.309V that embodiment 1 prepares the corrosion potential of sample, and corrosion electric current density is 1.2 �� 10-7A/cm2, the electric current density when 0.6V is 1.0 �� 10-6A/cm2. In this embodiment, the ratio (C:C/CrN) of graphite-like carbon coatings and C/CrN multi-gradient coating gross thickness is 0.4, the ratio (CrN:C/CrN) of CrN coating and C/CrN multi-gradient thickness of coating is 0.4, the ratio (Cr:C/CrN) of Cr transition zone and C/CrN multi-gradient thickness of coating is 0.1, and the ratio of chromium carbon nitrogen transition zone and C/CrN multi-gradient thickness of coating is 0.1.
The surface contacted resistance test of sample adopts sandwich architecture test system, and two sides is coated with the sample of multi-gradient film and is placed on centre, and two sides Toray carbon paper contacts with sample surfaces, and apply thrust between two carbon papers with copper coin is 120N/cm simultaneously2, between two copper coin, apply the constant current of 0.1A simultaneously, and record resistance along with the change of thrust. Thus can obtain the surface contacted resistance between multi-gradient film and carbon paper, as shown in Figure 4 (unit m �� cm2).As shown in Figure 4 as shown in Example 1, the surface contacted resistance when typical fuel cells thrust of sample is 2.9m �� cm2��
The film-substrate cohesion test of sample adopts the automatic cut testing apparatus of WS-2002 type adhesive force, tests loading speed 60N/min, cut speed 3mm/min, Ending Load 120N. Test adopts tangential force method harmony shooting method, and acoustic emission curve time mainly according to the friction resistance curve of scratch test and breakage of thin film applied observes cut breakage in conjunction with microscope, and comprehensive analysis and judgement go out corresponding critical load. Adopting said method to be carried out example 1 sample and carry out film-substrate cohesion test, recording adhesion is 87N.
Embodiment 2
In the present embodiment, first, second and third step is identical with embodiment 1, it is distinctive in that the present embodiment is when enforcement fourth, fifth, six steps, other parameters keep with embodiment 1 consistent while, open Ti target and Al target carries out element doping and tissue modulation, the target current of Ti target and Al target is held at 2A, and to be gradually lowered in the 5th step process be 0.
Adopt the method for testing identical with embodiment 1 that embodiment 2 sample is detected. In Fig. 3 shown in embodiment 2 curve, in analog fuel battery corrosion liquid, it is 0.382V that embodiment 2 prepares the corrosion potential of sample, and corrosion electric current density is 8.7 �� 10-8A/cm2, the electric current density when 0.6V is 4.2 �� 10-7A/cm2. As shown in Figure 4, shown in Example 2, the surface contacted resistance when typical fuel cells thrust of sample is 2.8m �� cm2. The sample that embodiment 2 is prepared carries out film-substrate cohesion test, and recording its adhesion is 95N.
Embodiment 3
In the present embodiment, the first step is identical with embodiment 1, is distinctive in that:
Second step, control are biased in-50V, chromium target current 5A, deposition Cr transition zone 30 minutes;
3rd step, maintenance chromium target current 5A, control to be biased in-70V, pass into nitrogen, and Ventilation Rate is 20SCCM, opens Mo target and W target simultaneously, and Mo target current controls to control at 1A at 0.5A, W target current. Deposition is doped with the CrN coating 45 minutes of Mo element and W element;
4th step, control are biased in-50V, open graphite target, and electric current gradually rises to 6A from 0A, and chromium target, Mo target and W target current are gradually decrease to 0A, deposition chromium carbon nitrogen transition zone 15 minutes simultaneously;
5th step, closedown chromium target, Mo target and W target, control to be biased in-60V, and graphite target electric current is 6A, deposition graphite-like carbon coatings 1 hour; Obtain the surface fuel battery metal double polar plate product with coating.
In this embodiment, the ratio (C:C/CrN) of graphite-like carbon coatings and C/CrN multi-gradient coating gross thickness is 0.45, the ratio (CrN:C/CrN) of CrN coating and C/CrN multi-gradient thickness of coating is 0.4, the ratio (Cr:C/CrN) of Cr transition zone and C/CrN multi-gradient thickness of coating is 0.1, and the ratio of chromium carbon nitrogen transition zone and C/CrN multi-gradient thickness of coating is 0.05.
Adopt the method for testing identical with embodiment 1 that embodiment 3 sample is detected. In Fig. 3 shown in embodiment 3 curve, in analog fuel battery corrosion liquid, it is 0.368V that embodiment 3 prepares the corrosion potential of sample, and corrosion electric current density is 8.4 �� 10-8A/cm2, the electric current density when 0.6V is 5.1 �� 10-7A/cm2. As shown in Figure 4, shown in Example 3, the surface contacted resistance when typical fuel cells thrust of sample is 2.6m �� cm2. Embodiment 3 sample is carried out film-substrate cohesion test, and recording its adhesion is 102N.
Embodiment 4
In the present embodiment, the first step is identical with embodiment 1, is distinctive in that:
Second step, control are biased in-100V, chromium target current 8A, deposition Cr transition zone 15 minutes;
3rd step, keeping chromium target current 8A, be biased at-70V, pass into nitrogen, Ventilation Rate is 20SCCM, opens Si target simultaneously, and electric current controls at 1.5A, and deposition is doped with the CrN coating 60 minutes of Si element;
4th step, control are biased in-70V, open graphite target, and electric current gradually rises to 8A from 0A, and chromium target current is gradually decrease to 0A, deposition chromium carbon nitrogen transition zone 15 minutes simultaneously;
5th step, closing chromium target, control to be biased in-70V, carbon target current is 8A, Si target current gradually decreases to 0A from 1.5A, closes Si target during deposition graphite-like carbon coatings 30 minutes, little stops deposited plating layer constantly to 1. Obtain the fuel battery metal double polar plate of the present embodiment its surface coating.
Adopt the method for testing identical with embodiment 1 that embodiment 4 sample is detected. In Fig. 3 shown in embodiment 4 curve, in analog fuel battery corrosion liquid, it is 0.374V that embodiment 4 prepares the corrosion potential of sample, and corrosion electric current density is 6.3 �� 10-8A/cm2, the electric current density when 0.6V is 5.2 �� 10-7A/cm2. As shown in Figure 4, shown in Example 4, the surface contacted resistance when typical fuel cells thrust of sample is 2.6m �� cm2. Embodiment 4 sample is carried out film-substrate cohesion test, and recording its adhesion is 98N.
The preferred embodiment of the present invention described in detail above. Should be appreciated that the ordinary skill of this area just can make many modifications and variations according to the design of the present invention without creative work. Therefore, all technical staff in the art, all should in the protection domain being defined in the patent claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (1)
1. the method for the dual polar plates of proton exchange membrane fuel cell preparing surface doping multi-gradient film, it is characterised in that comprise the steps:
Step one, first, puts in filming equipment by metal double polar plates clean for chemistry ultrasonic cleaning, and evacuation makes background vacuum lower than 5 �� 10-6Torr, passes into argon, makes vacuum maintain 2 �� 10-2Torr;
Secondly, it is biased to-500V, opens chromium target current, control at 0.5A, described metal double polar plates is cleaned 30 minutes;
Step 2-(1), the bias controlling chromium target be-70V, and chromium target current 7A deposits Cr transition zone 15 minutes; Or the bias of step 2-(2), control chromium target is-50V, chromium target current 5A, deposition Cr transition zone 30 minutes; Or the bias of step 2-(3), control chromium target is-100V, chromium target current 8A, deposition Cr transition zone 15 minutes;
Step 3-(1) is if the step 2 of completing-(1), then the bias controlling chromium target is-60V, and chromium target current maintains 7A, passes into nitrogen, deposition CrN coating 30 minutes with 25SCCM speed; Or step 3-(2) if the step 2 of completing-(2), the bias then controlling chromium target is-70V, chromium target current maintains 5A, nitrogen is passed into 20SCCM speed, open Mo target and W target simultaneously, Mo target current controls to control at 1A at 0.5A, W target current, and deposition is doped with the CrN coating 45 minutes of Mo element and W element; Or step 3-(3) are if the step 2 of completing-(3), then the bias controlling chromium target is-70V, and chromium target current maintains 8A, nitrogen is passed into 20SCCM speed, opening Si target, electric current controls at 1.5A simultaneously, and deposition is doped with the CrN coating 60 minutes of Si element;
Step 4-(1) if the step 3 of completing-(1), then keep chromium target current, substrate bias and nitrogen flow constant, regulate graphite target electric current and risen to 6A by 0, control to be biased in-60V, chromium target current 7A, deposition chromium carbon nitrogen transition zone 15 minutes, opens Ti target simultaneously and Al target carries out element doping and tissue modulation, the target current of Ti target and Al target is held at 2A; Or step 4-(2) are if the step 3 of completing-(2), then control to be biased in-50V, open graphite target, and electric current gradually rises to 6A from 0A, and chromium target, Mo target and W target current are reduced to 0A, deposition chromium carbon nitrogen transition zone 15 minutes simultaneously; Or step 4-(3) are if the step 3 of completing-(3), then control to be biased in-70V, open graphite target, and electric current gradually rises to 8A from 0A, and chromium target current is reduced to 0A, deposition chromium carbon nitrogen transition zone 15 minutes simultaneously;
Step 5-(1) if the step 4 of completing-(1), then makes chromium target current be gradually reduced from 7A, until stopping chromium target current; The target current making Ti target and Al target reduces to 0; Controlling bias is-60V, and graphite target electric current is 6A, deposition graphite-like carbon coatings 0.5 hour; Or step 5-(2) are if the step 4 of completing-(2), then close chromium target, Mo target and W target, control to be biased in-60V, and graphite target electric current is 6A, deposition graphite-like carbon coatings 1 hour; Or step 5-(3) are if the step 4 of completing-(3), then close chromium target, control to be biased in-70V, carbon target current is 8A, Si target current drops to 0A from 1.5A, closes Si target during deposition graphite-like carbon coatings 30 minutes, little stops deposited plating layer constantly to 1.
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| CN103757614B (en) * | 2014-01-02 | 2016-08-17 | 上海交通大学 | A kind of coating of magnesium and magnesium alloy and preparation method thereof |
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| US8497050B2 (en) * | 2008-07-29 | 2013-07-30 | GM Global Technology Operations LLC | Amorphous carbon coatings for fuel cell bipolar plates |
| CN102723499B (en) * | 2012-06-07 | 2014-08-06 | 上海交通大学 | Metal bipolar plate of fuel cell with surface plating layers and preparation method thereof |
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