CN106887599A - A kind of fuel cell long-life bipolar plates with surface titanium palladium carbon film and preparation method thereof - Google Patents
A kind of fuel cell long-life bipolar plates with surface titanium palladium carbon film and preparation method thereof Download PDFInfo
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- CN106887599A CN106887599A CN201710032998.7A CN201710032998A CN106887599A CN 106887599 A CN106887599 A CN 106887599A CN 201710032998 A CN201710032998 A CN 201710032998A CN 106887599 A CN106887599 A CN 106887599A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/8626—Porous electrodes characterised by the form
- H01M4/8631—Bipolar electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8867—Vapour deposition
- H01M4/8871—Sputtering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to a kind of fuel cell long-life bipolar plates with surface titanium palladium carbon film and preparation method thereof, belong to fuel cell and material surface modifying technology field.Bipolar plates are made up of titanium sheet metal bipolar plates base material, titanium palladium nano-crystal transition zone and surface titanium palladium carbon film.Transition zone of the invention and surface recombination film using New Arc ion electroplating method because being prepared, therefore it is the quasi- Welding Metallurgy connection of polynary counterdiffusion of the material in interface in matrix and transition interlayer, the connection between transition zone and surface film, the few consistency of defect is high in modified layer film, wherein top layer laminated film has the electric conductivity and high hydrophobicity not worse than silver, transition zone has the ability of the long-term resistance to spot corrosion under battery context, therefore the bipolar plates for being prepared with the method have combination property very high, life-span service requirement when can meet long under battery pile high power.
Description
Technical field
The present invention relates to a kind of fuel cell long-life bipolar plates with surface titanium palladium carbon film and preparation method thereof, category
In fuel cell and technical field of metal material surface modification.
Background technology
The chemical energy that fuel battery energy will be stored in fuel and oxidant is converted into electric energy, its transformation efficiency is high,
It is environment-friendly, highly reliable, it is considered to be current first-selected efficient sustainable development power technology.In each types of fuel cells, matter
Proton exchange film fuel cell (Proton Exchange Membrane Fuel Cell, PEMFC) have start fast, long lifespan,
The advantages of specific power is high, in addition to suitable for terrestrial power generation station, is also particularly well suited for removable power source and various portable electricity
Source, is one of ideal source of new-energy automobile.
Bipolar plates are the critical pieces of Proton Exchange Membrane Fuel Cells, account for more than the 70% of battery weight, in battery assembly
Also accounted for close to half in this, its effect is to separate reacting gas, collected current, each cells in series gets up and by flow field
For the discharge that reaction gas passes in and out electrode and water provides passage etc..Metal is the bipolar plate of preferable Proton Exchange Membrane Fuel Cells
Material, but its subject matter is easily corroded under battery context, including chemical attack and electrochemical corrosion, its consequence is not only
It is to make bipolar plates disabler, but also PEM " poisoning " can be caused.To metal double polar plates application modern times surface work
Journey technology carries out the effective means that surface modification treatment is solve problem.Therefore, in the industrialization process of fuel cell, for
The modified research and development of metal bipolar plate surface are always one of emphasis public relations technology, in recent years in surface modifying material and system
Breakthrough is achieved in standby technique.Such as ZL200810086374.4 technologies, with PVD arc ions electroplating methods in stainless steel
The bipolar plate surfaces deposition nano compound film such as carbon chromium, makes in the original performance of modified bipolar plates electric conductivity close to noble metal
Silver, corrosion resisting property is improved more than 2 orders of magnitude than stainless steel base, and hydrophobic performance water contact angle is more than 110 °, has been reached with honest and clean
The purpose that valency surface modifying material substitutes noble metal to prepare bipolar plates so that cost is greatly lowered.
But found in lasting research in the recent period, through the bipolar plates of above-mentioned technical face modification in the actually accumulative operation of dress heap
After thousands of hours, pile occurs that combination property decays rapidly, the phenomenon that power output drops suddenly.Sent out through the analysis and research of system
Existing, its reason is that the modified film of bipolar plate surfaces is inevitably present pin hole, the corrosive medium in During Process of Long-term Operation
Pin hole can be gradually passed through and enter film inside directly contact stainless steel base surface, so as to cause ulcer formula to corrode, so existed
While causing contact resistance to increase considerably, modified film can also floated and avalanche, finally make fuel cell pile too early
Failure.
Therefore, problem demanding prompt solution is wanted on fuel battery double plates at present, is how to ensure bipolar plates in reality
The problem of overlength time limit operation is met in pile environment, the problem that must so solve has two, and one is how to improve surface to be modified
To reduce the problem of pin hole quantity, two is the point of resistance to pin hole for how improving bipolar plates body upper surface under film to the consistency of film
Corrosion can be maintaining the problem of high-level combination property when ensureing that bipolar plates are long.
The content of the invention
It is an object of the invention to provide a kind of low cost, high-quality, long-life used in proton exchange membrane fuel cell
The preparation method of bipolar plates and its surface modified film, the bipolar plates prepared using structures and methods of the invention, while having
The combination property such as anti-corrosion, conductive and hydrophobic of high target, and ensure that these initial performance indexs took in 10000 hours long
Fall is not more than 5% after labour, meets the long-life service requirement in Proton Exchange Membrane Fuel Cells.
Technology design of the invention is that one layer is further added by between metal double polar plates matrix and surface modified film in fuel
The special overcoat of resistance to spot corrosion under battery context, protection coating materials are according to ligand field alloy design theory and carry out experimental verification
To determine, outmost surface is material modified to use new carbon-based nano compound film, and in order to strengthen interface compatibility, carbon-based nano is multiple
The constituent element composition of condensation material determines on the premise of performance is ensured according to composition close friend's principle.It is wherein particularly critical, should
Intervening guard layer and surface modifying material application are accompanied with the electricity of large area gas ion source and the electric discharge of heated filament plasma enhancing
Prepared by arc ion electroplating method, wherein can launch a large amount of electronics to promote the ionization level of plasma using heated filament, can carry significantly
" suture " ability at film high/base interface；Using large area gas ion source, ion etching can be carried out to the interface between each layer clear
Wash, can significantly eliminate needle pore defect quantity and improve film entirety compactness extent.
It is of the present invention in order to reach its purpose on the basis of substantial amounts of theoretical and experimental studies results
Technical scheme：
A kind of fuel cell long-life bipolar plates with surface titanium palladium carbon film, including sheet metal bipolar plates base material 1,
The middle transition zone of resistance to spot corrosion 2 and surface titanium palladium carbon film 3；The thickness of sheet metal bipolar plates base material 1 is 0.1mm-0.5mm；In
Between the transition zone of resistance to spot corrosion 2 material be titanium palladium nano-crystal alloy-layer, wherein the weight/mass percentage composition of palladium be 0.1%-1.0%, titanium
The thickness of palladium nano-crystal alloy-layer is 0.3 μm -3.0 μm, and it is in many of interface that it is used between sheet metal bipolar plates base material 1
First quasi- Welding Metallurgy connected mode of counterdiffusion；The material of surface titanium palladium carbon film 3 is carbon amorphous titanium palladium nano-crystal laminated film, its
The atomic percentage conc of middle carbon amorphous is 60%-100%, and remaining is titanium palladium nano-crystal, both titanium and palladium in the titanium palladium nano-crystal
Relative components content and the middle transition zone of resistance to spot corrosion 2 it is identical, the thickness of surface titanium palladium carbon film 3 is 0.1 μm -1 μm, its with
Using the quasi- Welding Metallurgy connected mode of polynary counterdiffusion in interface between the middle transition zone of resistance to spot corrosion 2.
The material of described sheet metal bipolar plates matrix 1 is TA1 industrially pure titanium thin plate bipolar plates or 316L Thin Stainless Steels
Plate bipolar plates.
A kind of preparation method of the fuel cell long-life bipolar plates with surface titanium palladium carbon film, is strengthened using there is heated filament
Discharge and be aided with gas ion source enhancing ise arc ions electroplating method on the surface of sheet metal bipolar plates matrix 1 successively
The transition zone of resistance to spot corrosion 2 and surface carbon titanium palladium membranes 3, comprise the following steps that in the middle of deposition：
(1) arc ion plating apparatus vacuum chamber side being arranged in vacuum environment can launch a large amount of thermionic heated filament dresses
Put, opposite side is installed again enables inert gas to obtain the gas ion source device for being electrically excited ionization, has in vacuum chamber inner wall even distribution
Tubular heater device；Distinguish on equally distributed multiple negative electrode target position and carbon target and titanium palldium alloy target are separately installed, wherein
The weight/mass percentage composition of palladium is 0.1%~1.0% in titanium palldium alloy target；
(2) sheet metal bipolar plates matrix 1 through being cleaned by ultrasonic and after drying and processing, is placed in arc ion plating vacuum chamber
Workpiece holder on, vacuum chamber vacuum is extracted into 5 × 10 by closing chamber by vacuum system behind the door-3More than Pa, starting heater makes
Sheet metal bipolar plates matrix 1 is heated to 200 DEG C~350 DEG C, and argon gas is filled with afterwards, and partial pressure of ar gas is 0.4Pa~1.0Pa, plus
It is 500V~1000V to bias, and triggers glow plasma, and restarting hot-wire device carries out plasma discharge enhancing, is passed through heat
The electric current of silk is 3A~30A, and the voltage at heated filament two ends is 10V~50V, and the bias of heated filament grid bias power supply is 10V~50V, is carried out
The enhanced sputter clean of the surface plasma of sheet metal bipolar plates matrix 1, the time is 5min~30min, and heat is then stopped afterwards
Silk device work, reductions partial pressure of ar gas be 0.1Pa~0.4Pa, start gas ion source device, adjustment ion beam current for 1A~
3A, carries out the surface ion ise of sheet metal bipolar plates matrix 1 and activation process, and the time is 5min~20min；
(3) then afterwards stop ion source device work, adjustment partial pressure of ar gas be 0.5Pa~2Pa, reduce bias be 50V~
200V, starts titanium palldium alloy target electric arc and obtains metallic plasma, and titanium palldium alloy target arc current is adjusted to 40A~120A, enters
In the middle of row prepared by the deposition of the transition zone of resistance to spot corrosion 2, and the time is 30min~180min；
(4) then stop titanium palldium alloy target electric arc afterwards, then reduce partial pressure of ar gas for 0.1Pa~0.4Pa, start gas ion
Source device, adjustment ion beam current is 1A~3A, and it is 500V~1000V to improve bias, carries out the surface of the middle transition zone of resistance to spot corrosion 2
The removal of ion sputtering defect treatment, the time be 5min~20min；
(5) then afterwards stop ion source device work, adjustment partial pressure of ar gas be 0.5Pa~2Pa, reduce bias be 50V~
200V, starts carbon target electric arc, and carbon target arc current is 60A~100A, restarts titanium palldium alloy target electric arc, titanium palldium alloy target electric arc
Electric current is adjusted to 0A~120A, carries out the surface titanium palladium carbon film 3 i.e. deposition of carbon amorphous titanium palladium nano-crystal laminated film and prepares, when
Between be 10min~90min；Then carry out stopping alloys target and the work of carbon target electric arc afterwards, unload bias, stop supply, stop heating,
Through abundant stove it is cold after i.e. can be taken off the good metal double polar plates of surface modification treatment.
The beneficial effects of the invention are as follows sheet metal bipolar plates deposited on substrates be prepared for thickness for 0.3 μm -3.0 μm,
The weight/mass percentage composition of palladium is the transition zone of resistance to spot corrosion 2 in the middle of the titanium palladium nano-crystal of 0.1%-1.0%, and thickness is 0.1 μm of -1 μ
M, carbon amorphous atomic percentage composition are the carbon titanium palladium amorphous nano-crystalline surface titanium palladium carbon film 3 of 60%-100%, wherein transition zone
Between base material, and between surface modified film and transition zone, because employing plasma enhancing and being aided with gas ion beam
Stream carries out ise and is pre-processed, and its connection is the quasi- Welding Metallurgy connection of polynary counterdiffusion of the material in interface, such as
This surface layer material consistency is high and defect is few, substantially increases the surface property of metal double polar plates, and contact resistance is reduced to 5m
Ω·cm2(under 1.2MPa thrusts) below, corrosion resistance is improved more than 3 orders of magnitude, particularly in bipolar plates fashionable dress heap fortune long
Power output can be kept under row, and at 10000 hours, decay was less than 5% afterwards.
Brief description of the drawings
Fig. 1 is the cross-sectional profile structure chart of bipolar plates of the present invention.
In figure：1 sheet metal bipolar plates base material；The transition zone of resistance to spot corrosion in the middle of 2；
3 surface titanium palladium carbon films.
Specific embodiment
Below in conjunction with accompanying drawing and technical scheme, specific embodiment of the invention is further illustrated.
Embodiment 1：
(1) hot-wire device is installed in arc ion plating apparatus vacuum chamber side, opposite side installs gas ion source device again,
Installation tubulose heater assembly also is uniformly distributed in vacuum chamber interior walls, is distinguished separately on equally distributed 10 negative electrode target position
Pure carbon target and titanium palldium alloy target are installed, the quality percentage component content of palladium is 0.2% wherein in titanium palldium alloy target；
(2) 0.1mm thick 316L stainless sheet steel bipolar plates base material 1 through being cleaned by ultrasonic and after drying and processing, is placed in
On the workpiece holder of arc ion plating vacuum chamber, vacuum chamber vacuum is extracted into 5 × 10 by closing chamber by vacuum system behind the door-3Pa, opens
Dynamic heater makes base material workpiece heat to 300 DEG C, and argon gas is filled with afterwards, and partial pressure of ar gas is 0.8Pa, is biased at 800V, is drawn
Hair glow plasma, restarting hot-wire device carries out plasma discharge enhancing, is passed through the electric current of heated filament for 10A, heated filament two
The voltage at end is 20V, and the bias of heated filament grid bias power supply is 30V, carries out the sputter clean of substrate surface plasma enhancing, time
Be 10min, then afterwards stop hot-wire device work, reductions partial pressure of ar gas be 0.2Pa, startup gas ion source device, adjust from
Electron-beam current is 2A, carries out substrate surface ion sputtering etching and activation process, and the time is 10min；
(3) ion source device work is stopped, adjustment partial pressure of ar gas is 1Pa, it is 200V to reduce bias, starts titanium palldium alloy target
Electric arc obtains metallic plasma, and alloys target arc current is adjusted to 90A, prepared by the deposition for carrying out the transition zone of resistance to spot corrosion 2, the time
It is 40min；
(4) stop titanium palldium alloy target electric arc, then reduce partial pressure of ar gas for 0.2Pa, start gas ion source device, adjust from
Electron-beam current is 2A, and it is 800V to improve bias, carries out the ion sputtering defect removal treatment of resistance to spot corrosion transition layer surface, and the time is
10min；
(5) ion source device work is stopped, adjustment partial pressure of ar gas is 1Pa, it is 200V to reduce bias, starts carbon target electric arc,
Carbon target arc current is 60A, restarts titanium palldium alloy target electric arc, and alloys target arc current is adjusted to 40A, carries out surface titanium palladium carbon
Film 3 is prepared by the deposition of carbon amorphous titanium palladium nano-crystal laminated film, and the time is 20min；
(6) stop alloys target and carbon target electric arc work, unload bias, stop supply, stop heating, through abundant stove it is cold after taking-up
Good metal double polar plates of surface modification treatment.
It is 1 μm accurate with the polynary counterdiffusion that base material is material in interface so in bipolar plate surfaces deposition synthesis thickness
The titanium palladium nano-crystal intermediate layer of resistance to spot corrosion of Welding Metallurgy connection, and 0.5 μm with transition zone is also material in interface
The surface high performance carbon amorphous composite modified film of titanium palladium nano-crystal of the polynary quasi- Welding Metallurgy connection of counterdiffusion, makes bipolar plates synthesis
Performance is significantly lifted, contact resistance≤5m Ω cm2(under 1.2MPa), corrosion current i under simulation PEMFC corrosive environmentscor≤
1.0×10- 7A/cm2, particularly through that can keep power output under fashionable dress stack operation long, at 10000 hours, attenuation rate was less than afterwards
5%.
Claims (3)
1. a kind of fuel cell long-life bipolar plates with surface titanium palladium carbon film, it is characterised in that the fuel cell is long-lived
Life bipolar plates and its surface titanium palladium carbon film include sheet metal bipolar plates base material (1), the middle transition zone of resistance to spot corrosion (2) and surface
Titanium palladium carbon film (3)；The thickness of sheet metal bipolar plates base material (1) is 0.1mm~0.5mm；The middle transition zone of resistance to spot corrosion (2)
Material is titanium palladium nano-crystal alloy-layer, and wherein the weight/mass percentage composition of palladium is 0.1%~1.0%, titanium palladium nano-crystal alloy-layer
Thickness is 0.3 μm~3.0 μm；The material on surface titanium palladium carbon film (3) is carbon amorphous titanium palladium nano-crystal laminated film, and wherein carbon is non-
Brilliant atomic percentage conc is 60%~100%, and remaining is titanium palladium nano-crystal, the titanium and relative both palladium in the titanium palladium nano-crystal
Component content and the middle transition zone of resistance to spot corrosion (2) are identical, and the thickness on surface titanium palladium carbon film (3) is 0.1 μm~1 μm.
2. fuel cell long-life bipolar plates with surface titanium palladium carbon film according to claim 1, it is characterised in that
The material of described sheet metal bipolar plates matrix (1) is that TA1 industrially pure titanium thin plate bipolar plates or 316L stainless sheet steels are bipolar
Plate.
3. a kind of preparation method of the fuel cell long-life bipolar plates with surface titanium palladium carbon film, is put using there is heated filament to strengthen
Electricity and be aided with gas ion source enhancing ise arc ions electroplating method on sheet metal bipolar plates matrix (1) surface successively
The transition zone of resistance to spot corrosion (2) and surface carbon titanium palladium membranes (3) in the middle of deposition, it is characterised in that comprise the following steps that：
(1) arc ion plating apparatus vacuum chamber side being arranged in vacuum environment can launch a large amount of thermionic hot-wire devices,
Opposite side is installed again enables inert gas to obtain the gas ion source device for being electrically excited ionization, has tubulose in vacuum chamber inner wall even distribution
Heater assembly；Distinguish on equally distributed multiple negative electrode target position and carbon target and titanium palldium alloy target, wherein titanium palladium are separately installed
The weight/mass percentage composition of palladium is 0.1%~1.0% in alloys target；
(2) sheet metal bipolar plates matrix (1) through being cleaned by ultrasonic and after drying and processing, are placed in arc ion plating vacuum chamber
On workpiece holder, vacuum chamber vacuum is extracted into 5 × 10 by closing chamber by vacuum system behind the door-3More than Pa, starting heater makes gold
Metal thin plate bipolar plates matrix (1) are heated to 200 DEG C~350 DEG C, and argon gas is filled with afterwards, and partial pressure of ar gas is 0.4Pa~1.0Pa, plus
It is 500V~1000V to bias, and triggers glow plasma, and restarting hot-wire device carries out plasma discharge enhancing, is passed through heat
The electric current of silk is 3A~30A, and the voltage at heated filament two ends is 10V~50V, and the bias of heated filament grid bias power supply is 10V~50V, is carried out
The enhanced sputter clean of sheet metal bipolar plates matrix (1) surface plasma, the time is 5min~30min, is then stopped afterwards
Hot-wire device works, and reduction partial pressure of ar gas is 0.1Pa~0.4Pa, starts gas ion source device, and adjustment ion beam current is 1A
~3A, carries out sheet metal bipolar plates matrix (1) surface ion ise and activation process, and the time is 5min~20min；
(3) ion source device work is then stopped afterwards, adjustment partial pressure of ar gas is 0.5Pa~2Pa, it is 50V~200V to reduce bias,
Start titanium palldium alloy target electric arc and obtain metallic plasma, titanium palldium alloy target arc current is adjusted to 40A~120A, carries out centre
Prepared by the deposition of the transition zone of resistance to spot corrosion (2), the time is 30min~180min；
(4) then stop titanium palldium alloy target electric arc afterwards, then reduce partial pressure of ar gas for 0.1Pa~0.4Pa, start gas ion source dress
Put, adjustment ion beam current is 1A~3A, it is 500V~1000V to improve bias, carries out the middle transition zone of resistance to spot corrosion (2) surface
The removal of ion sputtering defect is processed, and the time is 5min~20min；
(5) ion source device work is then stopped afterwards, adjustment partial pressure of ar gas is 0.5Pa~2Pa, it is 50V~200V to reduce bias,
Start carbon target electric arc, carbon target arc current is 60A~100A, restarts titanium palldium alloy target electric arc, titanium palldium alloy target arc current
0A~120A is adjusted to, prepared by the deposition for carrying out surface titanium palladium carbon film (3) i.e. carbon amorphous titanium palladium nano-crystal laminated film, the time
It is 10min~90min；Then carry out stopping alloys target and the work of carbon target electric arc afterwards, unload bias, stop supply, stop heating, warp
The good metal double polar plates of surface modification treatment are can be taken off after abundant stove is cold.
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| 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 |
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| CN114388834A (en) * | 2020-10-16 | 2022-04-22 | 丰田自动车株式会社 | Separator and method for producing separator |
| 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 |
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