CN106876742A - Modified metal double polar plates of polymer electrolyte film fuel cell of DLC and preparation method thereof - Google Patents
Modified metal double polar plates of polymer electrolyte film fuel cell of DLC and preparation method thereof Download PDFInfo
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- CN106876742A CN106876742A CN201710258069.8A CN201710258069A CN106876742A CN 106876742 A CN106876742 A CN 106876742A CN 201710258069 A CN201710258069 A CN 201710258069A CN 106876742 A CN106876742 A CN 106876742A
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0254—Physical treatment to alter the texture of the surface, e.g. scratching or polishing
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
- H01M8/0208—Alloys
- H01M8/021—Alloys based on iron
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The present invention provides a kind of DLC modified metal double polar plates of polymer electrolyte film fuel cell, is made up of the diamond-like surface modified layer and metallic matrix that are prepared by linear ion beam technology.The preparation method technical maturity, can continuously produce, modified layer growth is uniform, do not damage the performances such as matrix strength, can realize that bipolar plates scale is produced in batches.DLC modified layer has good corrosion resistance, surface conductivity and hydrophobicity, can increase substantially the performance of polymer dielectric film fuel cell, for promoting commercializing fuel cells application significant.
Description
Technical field
The invention belongs to field of fuel cell technology.More particularly to metal double polar plates of polymer electrolyte film fuel cell and
Its surface is modified.
Background technology
Polymer dielectric film fuel cell have energy conversion efficiency high, long lifespan, operating temperature low, environment-friendly and
The features such as started quickly at low temperature, be a kind of general movable power source of the army and the people, is especially suitable for building dispersion power station and as traffic
The power source of means of transport.However, the factors such as of a relatively high cost, weight and volume greatly limit it is poly-
The scale commercial metaplasia of polymer electrolyte membrane cell is produced and applied.Therefore, its each assembly material and preparation cost one are reduced
It is directly national governments and researcher's concern and hot issue anxious to be resolved.
One of multifunctional module as polymer dielectric film fuel cell, the function of bipolar plates mainly includes separating instead
The hydro-thermal for answer conductive gas, afflux, support membrane electrode, passage being provided for reacting gas and makes it be evenly distributed, facilitate battery pack
Management.Graphite has good electric conductivity and chemical stability, is that a kind of preferable polymer dielectric film fuel cell is bipolar
Plate material.However, fragility high, low-intensity and short texture is porous etc. not enough it is difficult to production low weight, the height of low volume
Performance fuel cell unit.Additionally, at graphite cake Surface Machining flow field required complex process and high cost, account for electrostrictive polymer
80% or so of solution membrane fuel cell totle drilling cost.Compared with conventional graphite, metal material is in obdurability, electric conductivity and air-tightness
Etc. aspect have a clear superiority.It is worth noting that, can be each in metal surface processing using machining and the method for punching press
The flow field of shape is planted, is particularly suitable for batch production, the mass ratio of polymer dielectric film fuel cell can be increased substantially
Power and volumetric specific power.Metallic bipolar plate materials conventional at present mainly include ferrous alloy, nickel-base alloy and aluminium, titanium and its
Alloy etc..
Influenceed by PEM Partial digestion and technology for preparing electrode particularity, in polymer dielectric film fuel electricity
SO is commonly present in the working environment in pond4 2-、SO3 2-、CO3 2-、HSO4 -And HSO3 -Plasma.Therefore, metal double polar plates are in this acid
Property under the conditions of occur electrochemical corrosion be inevitable.Although the passivating film that metal bipolar plate surface is formed can effectively press down
Metal processed further corrodes, but the semiconductor property of metal oxide can cause the surface conductivity to reduce in passivating film.Obviously, institute
Having these factors certainly will cause the consumption of some electric energy and the reduction of fuel cell stack power output, so as to influence the resistance to of battery pack
Long property.In order to meet its requirement in electric conductivity and corrosion resistance simultaneously, prepare modified layer in metal bipolar plate surface and can yet be regarded as
A kind of effective ways, this development and application to polymer dielectric film fuel cell will produce material impact.Obviously, price
High modified with noble metals layer is unsuitable for the battery pack of production low cost.Limited by preparation process condition, using PVD, CVD,
Nitride and oxide modifying layer prepared by the different method such as chemical plating and plating is commonly present the micropore and fine fisssure being difficult to avoid that
The tissue defects such as line.These defects can undoubtedly cause metal double polar plates local corrosion and cause modified layer to be peeled off, so as to substantially contract
The service life of short polymer dielectric film fuel cell.More or less foot limit is constantly present based on existing surface modifying method
Property, also disclosure satisfy that current polymer dielectric film fuel electricity without any metal double polar plates by surface modification treatment
The requirement of pond scale market application.Therefore, development cost is cheap, surface conductivity high and corrosion proof bipolar plates are still poly-
The inevitable approach of polymer electrolyte membrane cell, is also necessarily commercialized process and produces important influence to it.
The content of the invention
It is contemplated that in a kind of metal double polar plates of polymer electrolyte film fuel cell preparation method is provided, using linear
Ion beam technology prepares DLC modified layer in metal bipolar plate surface.The method can realize that modified layer large area is uniformly given birth to
It is long, with production efficiency it is high, be readily produced processing the features such as, disclosure satisfy that the requirement of scale market application.DLC changes
Property layer surface it is smooth, low porosity, flawless, can significantly improve the power output of polymer dielectric film fuel cell and makes
Use the life-span.
Metal double polar plates of polymer electrolyte film fuel cell provided by the present invention is by metallic matrix and surface diamond-like
Stone modified layer is constituted.It is specific to be prepared according to following steps using ion beam technology：
1) pre-process：Metallic matrix is through 400~1500#Sand paper is polished successively, is polished with diamond paste；It is sequentially placed into
10min, drying for standby are cleaned in acetone, alcoholic solution with ultrasonic wave；
2) pretreated metallic matrix is put into sample room, when vacuum reaches 2.2 × 10 in sample room-5During Torr,
Being passed through argon gas carries out Ions Bombardment to metal base surface to clean its surface, and the time is 30min；
3) prepared by DLC modified layer：Hydrocarbon gas are passed through, flow is 40sccm, and pressure is 1.2 × 10- 4Torr, ion beam current is 0.2A, and ion beam voltage is 1100V, and substrate bias are -100V, and pulse frequency is 350kHz, temperature
It is 85~95 DEG C to spend, and the time is 0.5~5h.
The method of the invention, metal matrix material is austenitic stainless steel, ferritic stainless steel or two phase stainless steel.
The method of the invention, hydrocarbon gas used by the DLC modified layer are methane, acetylene, ethane
Or propane.
The present invention also provides a kind of DLC of use above method preparation modified polymer dielectric film fuel electricity
Pond metal double polar plates, with metal material as matrix, surface is 0.5~4.5 μm of DLC modified layer；The DLC changes
Property metal double polar plates of polymer electrolyte film fuel cell corrosion rate be less than 5 μ A/cm2, contact resistance is less than 5m Ω
cm2, contact angle is more than 88.5 °.
The present invention provide metal double polar plates advantage be：The present invention prepares metal double polar plates using linear ion beam technology
Surface DLC modified layer, the method have technical maturity, efficiency high, can mass production the features such as.DLC is modified
Layer can increase substantially corrosion resistance, the electric conductivity of metal double polar plates, disclosure satisfy that the performance requirement of fuel cell and facilitate
Hydro-thermal is managed, and potential replacement conventional graphite bipolar plates can apply to polymer dielectric film fuel cell field, for adding
Fast polymer dielectric film fuel cell mass market application has important practical significance.
Brief description of the drawings
Fig. 1 is DLC modified layer surface topography.
The smooth densification of the modified layer surface of DLC as seen from Figure 1, pore-free and micro-crack.
Specific embodiment
Embodiment 1
The metal double polar plates of polymer electrolyte film fuel cell that the DLC that the present embodiment is provided is modified, according to following
Step depositing diamond-like modified layer on the stainless steel bases of AISI 316：
1) matrixes of AISI 316 are through 400~1500#Sand paper is polished successively, is polished with diamond paste；It is sequentially placed into again
10min, drying for standby are cleaned in acetone, alcoholic solution with ultrasonic wave；
2) matrixes of pretreated AISI 316 are put into sample room, when vacuum reaches 2.2 × 10 in sample room-5Torr
When, being passed through argon gas carries out Ions Bombardment to metal base surface to clean its surface, and the time is 30min；
3) DLC modified layer preparation technology parameter：Hydrocarbon gas flow be 40sccm, pressure be 1.2 ×
10-4Torr, ion beam current is 0.2A, and ion beam voltage is 1100V；Substrate bias are -100V, and pulse frequency is 350kHz；
Temperature is 85 DEG C, and the time is 0.5h.
The modified bipolar plate of stainless steel of AISI 316 of DLC manufactured in the present embodiment, modified layer thickness is 0.5 μm.This
The metal double polar plates corrosion rate that DLC prepared by embodiment is modified is less than 5 μ A/cm2, contact resistivity is less than 5m Ω
cm2, contact angle is 88.5 °.
Embodiment 2:
The metal double polar plates of polymer electrolyte film fuel cell that the DLC that the present embodiment is provided is modified, according to following
Step prepares DLC modified layer on the stainless steel bases of AISI 446：
1) stainless steel bases of AISI 446 are through 400~1500#Sand paper is polished successively, is polished with diamond paste.Successively
It is placed in and cleans 10min, drying for standby in acetone, alcoholic solution with ultrasonic wave；
2) stainless steel bases of pretreated AISI 446 are put into sample room, when in sample room vacuum reach 2.2 ×
10-5During Torr, being passed through argon gas carries out Ions Bombardment to metal base surface to clean its surface, and the time is 30min.
3) DLC modified layer preparation technology parameter：Hydrocarbon gas flow be 40sccm, pressure be 1.2 ×
10-4Torr, ion beam current is 0.2A, and ion beam voltage is 1100V.Substrate bias are -100V, and pulse frequency is 350kHz.
Temperature is 90 DEG C, and the time is 1.5h.
The modified bipolar plate of stainless steel of AISI 446 of DLC manufactured in the present embodiment, modified layer thickness is 1.4 μm.This
The metal double polar plates corrosion rate that DLC prepared by embodiment is modified is less than 3.5 μ A/cm2, contact resistivity is less than 4m
Ω·cm2, contact angle is 89 °.
Embodiment 3:
The metal double polar plates of polymer electrolyte film fuel cell that the DLC that the present embodiment is provided is modified, according to following
Step prepares DLC modified layer on the stainless steel bases of AISI 2205：
1) matrixes of AISI 2205 are through 400~1500#Sand paper is polished successively, is polished with diamond paste.It is sequentially placed into third
10min, drying for standby are cleaned in ketone, alcoholic solution with ultrasonic wave；
2) matrixes of pretreated AISI 2205 are put into sample room, when vacuum reaches 2.2 × 10 in sample room- 5During Torr, being passed through argon gas carries out Ions Bombardment to metal base surface to clean its surface, and the time is 30min.
3) DLC modified layer preparation technology parameter：Hydrocarbon gas flow be 40sccm, pressure be 1.2 ×
10-4Torr, ion beam current is 0.2A, and ion beam voltage is 1100V.Substrate bias are -100V, and pulse frequency is 350kHz.
Temperature is 95 DEG C, and the time is 4h.
The modified bipolar plate of stainless steel of AISI 2205 of DLC manufactured in the present embodiment, modified layer thickness is 4 μm.This
The metal double polar plates corrosion rate that DLC prepared by embodiment is modified is less than 2.5 μ A/cm2, contact resistivity is less than 3m
Ω·cm2, contact angle is 90 °.
Claims (4)
1. the metal double polar plates of polymer electrolyte film fuel cell preparation method that DLC is modified, it is characterised in that：In gold
Category matrix surface prepares DLC modified layer；Prepared according to following steps using linear ion beam technology：
1) pre-process：Metallic matrix is through 400~1500#Sand paper is polished successively, is polished with diamond paste；Be sequentially placed into acetone,
10min, drying for standby are cleaned in alcoholic solution with ultrasonic wave；
2) above-mentioned pretreated metallic matrix is put into sample room, when vacuum reaches 2.2 × 10 in sample room-5During Torr,
Being passed through argon gas carries out Ions Bombardment to metal base surface to clean its surface, and the time is 30min；
3) prepared by DLC modified layer：Hydrocarbon gas are passed through, flow is 40sccm, and pressure is 1.2 × 10-4Torr,
Ion beam current is 0.2A, and ion beam voltage is 1100V, and substrate bias are -100V, and pulse frequency is 350kHz, and temperature is 85
~95 DEG C, the time is 0.5~5h.
2. preparation method according to claim 1, it is characterised in that：The metal matrix material be austenitic stainless steel,
Ferritic stainless steel or two phase stainless steel.
3. preparation method according to claim 1, it is characterised in that：Hydrocarbon used by the DLC modified layer
Gas is methane, acetylene, ethane or propane.
4. the polymer dielectric film fuel cell that the DLC that prepared by method any one of claims 1 to 3 is modified
Metal double polar plates, it is characterised in that：With metal material as matrix, its surface is modified for the DLC of 0.5~4.5 μm of thickness
Layer；The corrosion rate of the modified metal double polar plates of polymer electrolyte film fuel cell of the DLC is less than 5 μ A/cm2, connect
Resistance of getting an electric shock is less than 5m Ω cm2, contact angle is more than 88.5 °.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710258069.8A CN106876742A (en) | 2017-04-19 | 2017-04-19 | Modified metal double polar plates of polymer electrolyte film fuel cell of DLC and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710258069.8A CN106876742A (en) | 2017-04-19 | 2017-04-19 | Modified metal double polar plates of polymer electrolyte film fuel cell of DLC and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110875482A (en) * | 2018-08-29 | 2020-03-10 | 北京科技大学 | Method for preparing carbon film on surface of stainless steel bipolar plate by using graphite as carbon source |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1672274B (en) * | 2002-06-05 | 2012-05-02 | 通用汽车公司 | Conductive fluid dispensing members |
| CN103374697A (en) * | 2012-04-20 | 2013-10-30 | 深圳富泰宏精密工业有限公司 | Surface treatment method and product of diamond-like carbon film layer |
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2017
- 2017-04-19 CN CN201710258069.8A patent/CN106876742A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1672274B (en) * | 2002-06-05 | 2012-05-02 | 通用汽车公司 | Conductive fluid dispensing members |
| CN103374697A (en) * | 2012-04-20 | 2013-10-30 | 深圳富泰宏精密工业有限公司 | Surface treatment method and product of diamond-like carbon film layer |
Non-Patent Citations (1)
| Title |
|---|
| 吴国松等: "基于线性离子束技术的镁合金表面类金刚石膜的制备与性能研究", 《材料工程》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110875482A (en) * | 2018-08-29 | 2020-03-10 | 北京科技大学 | Method for preparing carbon film on surface of stainless steel bipolar plate by using graphite as carbon source |
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