CN102623720A - Fuel cell metal bipolar plate containing tungsten-modified layer and manufacture method thereof - Google Patents
Fuel cell metal bipolar plate containing tungsten-modified layer and manufacture method thereof Download PDFInfo
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- CN102623720A CN102623720A CN2012100934939A CN201210093493A CN102623720A CN 102623720 A CN102623720 A CN 102623720A CN 2012100934939 A CN2012100934939 A CN 2012100934939A CN 201210093493 A CN201210093493 A CN 201210093493A CN 102623720 A CN102623720 A CN 102623720A
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- tungsten
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- modified layer
- bipolar plate
- bipolar plates
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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
Abstract
The invention relates to a fuel cell metal bipolar plate containing a tungsten-modified layer and a manufacture method thereof. The bipolar plate consists of a bipolar plate substrate and a surface modified layer, wherein the bipolar plate substrate is made from a ferrous alloy austenitic stainless steel thin sheet; and the surface modified layer comprises a pure tungsten layer with high electrical conductivity and corrosion resistance and a tungsten-diffusion solid solution layer which is located on a subsurface between the pure tungsten layer and the bipolar plate substrate. The fuel cell metal bipolar plate containing the tungsten-modified layer and the manufacture method of the fuel cell metal bipolar plate containing the tungsten-modified layer have the advantages that the cost can be greatly lowered due to the adoption of the tungsten-alloyed modified layer with low cost, and high electrical conductivity and corrosion resistance; the bonding between the modified layer and the substrate is of compact and pinhole-free metallurgical bonding, and the failure arising from corrosion spalling cannot occur, so that the bipolar plate can have long-term stability and good mechanical properties within the range of operating potential of a fuel cell; the manufacture method is simple, the ultrathin metal bipolar plate can be manufactured, and thus the mass specific power and the volume specific power of a cell are improved; and the fuel cell metal bipolar plate containing the tungsten-modified layer can be produced in a batch, so that the fuel cell metal bipolar plate containing the tungsten-modified layer and the manufacture method of the fuel cell metal bipolar plate containing the tungsten-modified layer have good application prospects.
Description
Technical field
The invention belongs to the fuel cell technology field.Be particularly related to the process for modifying surface of the metal double polar plates of Proton Exchange Membrane Fuel Cells.
Background technology
Bipolar plates is one of Proton Exchange Membrane Fuel Cells critical component, and the metal double polar plates of prior art is prone to take place electrochemical corrosion in the Proton Exchange Membrane Fuel Cells environment; The passivating film that the metal surface forms causes interface contact resistance to increase, thereby reduces the performance and the power output of battery pack.Therefore, for decay resistance and the surface conductivity that improves metal double polar plates, prior art mainly is that metal is carried out surface treatment or surface modification.Disclosed at present technology is only relevant for the report of noble metal-coated, nitride, carbide and oxide coating in the metal surface.Noble coatings is inappropriate for because of its cost is high and produces battery pack cheaply.Nitride, carbide and oxide coating adopt methods preparations such as PVD, CVD, plating, thermal spraying, because of the restriction of its preparation technology's inherent feature, make the coating of generation have defectives such as pin hole, thereby cause that the coating spot corrosion peels off early failure.Simultaneously, also there are problems such as coating and basal body binding force deficiency.
Summary of the invention
The object of the invention just provides a kind of have good conductivity and corrosion resistance; Low-cost, be easy to make, can satisfy the dual polar plates of proton exchange membrane fuel cell and the manufacturing approach thereof of Proton Exchange Membrane Fuel Cells development and mass market application requirements.
Technical solution of the present invention is: a kind of fuel battery metal double polar plate of tungstenic modified layer; Bipolar plates matrix and surface reforming layer by the ferrous alloy austenitic stainless steel thin plate is processed are formed; It is characterized in that said surface reforming layer comprises the tungsten solid solution diffusion body layer on top layer high conductivity and corrosion proof pure tungsten layer and the inferior top layer between pure tungsten layer (1) and bipolar plates matrix.
The fuel battery metal double polar plate of a kind of tungstenic modified layer of the present invention is characterized in that, said pure tungsten layer is 100% tungsten; The mass concentration of said tungsten solid solution diffusion body layer tungsten reduces to bipolar plates matrix place from next-door neighbour's pure tungsten layer gradually, and the mass concentration of next-door neighbour's pure tungsten layer place tungsten is 10-100wt%, and the mass concentration of bipolar plates matrix place tungsten is the W content of bipolar plates matrix.
The fuel battery metal double polar plate of a kind of tungstenic modified layer of the present invention is characterized in that, said bipolar plates basis material is the ferrous alloy austenitic stainless steel; Its alloy content by weight percentage, Cr is 15-25%, Ni is 5-28%; Mo is 0-4%, and Mn is 0-15%, and Ti is 0-1%; Cu is 0-3%, and Nb is 0-2%, and all the other are Fe.
The fuel battery metal double polar plate of a kind of tungstenic modified layer of the present invention is characterized in that, the thickness of said bipolar plates matrix is 0.1-1mm, and pure tungsten layer thickness is 0.1-10 μ m, and the thickness of tungsten solid solution diffusion body layer is 1-30 μ m.
The manufacturing approach of the fuel battery metal double polar plate of a kind of tungstenic modified layer of the present invention comprises the ferrous alloy austenitic stainless steel thin plate and to process the bipolar plates semi-finished product through mold pressing or stamp out the input and output gas flow field channel; The bipolar plates semi-finished product are placed in the seal of plasma atmosphere and carry out surface treatment; It is characterized in that; Carrying out surface treatment in the said seal that the bipolar plates semi-finished product is placed plasma atmosphere is in the tungstenic plasma atmosphere bipolar plates semi-finished product to be applied 350-550V direct current or pulsed dc voltage; Under temperature 700-1150 ℃, handled 0.3-8 hour, obtain surface reforming layer.
The manufacturing approach of the fuel battery metal double polar plate of tungstenic modified layer of the present invention; It is characterized in that; Described tungstenic plasma atmosphere is obtained by following method: the tungsten source is placed in the seal, apply the 600-900V pulsed dc voltage to the tungsten source, current density is 0.1-15mA/cm
2, argon Ar is as working gas, and operating air pressure is 0.01-2kPa, obtains the tungstenic plasma atmosphere with argon gas bombardment tungsten source.
The invention has the advantages that: adopting cheaply, high conductivity and corrosion proof tungstenic modified layer can significantly reduce cost; Be combined into metallurgical binding between modified layer and the matrix, can not produce corrosion spalling and lose efficacy; Manufacturing approach is simple, can produce in batches, thereby the quality of raising battery pack is than power and volumetric specific power; The present invention is easy to implement, uses the low-cost Proton Exchange Membrane Fuel Cells of the metal double polar plates production of this technical finesse to can be used for large-scale fuel cells production.
Description of drawings
The present invention has accompanying drawing two width of cloth, wherein
Fig. 1 is a double-polar plate surface modifying layer structural representation,
Fig. 2 is the interface contact resistance of bipolar plates loads solid pressure power with fuel cell stack a change curve.Among the figure, 1, pure tungsten layer, 2, tungsten solid solution diffusion body layer, 3, the bipolar plates matrix.In the accompanying drawing 2, abscissa is a fastening pressure, its unit be newton/centimetre
2(N/cm
2); Ordinate is a surface contacted resistance, and unit is a milliohm centimetre
2(m Ω cm
2); ● the interface contact resistance of the bipolar plates of the curve representation prior art that the black round dot forms loads the change curve of solid pressure power with fuel cell stack, and the interface contact resistance of the curve representation bipolar plates of the present invention that the ■ black forms loads the change curve of solid pressure power with fuel cell stack.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described further.
Embodiment
With commercial thickness is that 304 austenitic stainless steel thin plate of 1.5mm are cut into the plate that is of a size of 50X150mm as requested; Prepare metal bipolar boards half-finished product with flow field through mold pressing; The bipolar plates semi-finished product are placed negative electrode; The tungsten plate links to each other with the source metal electrode as source electrode, and bipolar plates semi-finished product and tungsten source electrode all are arranged in the seal that the bilayer anode hollow cap is formed.Vacuumize, and feed argon gas, making the interior pressure of seal is 40Pa; Apply the 550V pulsed dc voltage to the bipolar plates semi-finished product; On the tungsten source electrode, apply the 900V pulsed dc voltage, source metal is overflowed, form tungstenic plasma atmosphere bombardment specimen surface thereby produce glow discharge; 1000 ℃ of Temperature Treatment 4 hours, forming thickness in the bipolar plates surface of semi-finished was that 5 μ m pure tungsten layers 1 and thickness are 2 μ m tungsten solid solution diffusion body layers 2.Bipolar plates to embodiment produces is made electrochemistry experiment, anodic polarization curves and at the constant potential polarization under the Proton Exchange Membrane Fuel Cells condition of work all under 70 ℃, experiment is at 0.05M H
2SO
4Carry out in the solution of+2ppm F-, modified layer can make stainless corrosion potential bring up to-90mV from-300mV (with respect to saturated calomel electrode, down with), and with its current density from 21 μ A/cm
2Be reduced to 1 μ A/cm
2Below, corrosion resistance significantly improves.In order to simulate the operational environment of Proton Exchange Membrane Fuel Cells, all in solution, feed H in all electrochemistry experiment processes
2Or air.Electrochemistry experiment shows that bipolar plate of stainless steel interface contact resistance of the present invention obviously reduces, be under the same thrust original 304 austenitic stainless steel bipolar plate surfaces contact resistances 1/10, have surface of good conductivity.
Claims (6)
1. the fuel battery metal double polar plate of a tungstenic modified layer; Bipolar plates matrix (3) and surface reforming layer by the ferrous alloy austenitic stainless steel thin plate is processed are formed; It is characterized in that said surface reforming layer comprises the tungsten solid solution diffusion body layer (2) on top layer high conductivity and corrosion proof pure tungsten layer (1) and the inferior top layer between pure tungsten layer (1) and bipolar plates matrix (3).
2. the fuel battery metal double polar plate of a kind of tungstenic modified layer according to claim 1 is characterized in that, said pure tungsten layer (1) is 100% tungsten; The mass concentration of said tungsten solid solution diffusion body layer (2) tungsten is located to reduce gradually to bipolar plates matrix (3) from next-door neighbour's pure tungsten layer (1); The mass concentration that next-door neighbour's pure tungsten layer (1) is located tungsten is 10-100wt%, and the mass concentration that bipolar plates matrix (1) is located tungsten is the W content of bipolar plates matrix.
3. the fuel battery metal double polar plate of a kind of tungstenic modified layer according to claim 1 is characterized in that, said bipolar plates matrix (3) material is the ferrous alloy austenitic stainless steel; Its alloy content by weight percentage, Cr is 15-25%, Ni is 5-28%; Mo is 0-4%, and Mn is 0-15%, and Ti is 0-1%; Cu is 0-3%, and Nb is 0-2%, and all the other are Fe.
4. the fuel battery metal double polar plate of a kind of tungstenic modified layer according to claim 1 is characterized in that, the thickness of said bipolar plates matrix (3) is 0.1-1mm, and pure tungsten layer (1) thickness is 0.1-10 μ m, and the thickness of tungsten solid solution diffusion body layer (2) is 1-30 μ m.
5. the manufacturing approach of the fuel battery metal double polar plate of a tungstenic modified layer comprises the ferrous alloy austenitic stainless steel thin plate and to process the bipolar plates semi-finished product through mold pressing or stamp out the input and output gas flow field channel; The bipolar plates semi-finished product are placed in the seal of plasma atmosphere and carry out surface treatment; It is characterized in that; Carrying out surface treatment in the said seal that the bipolar plates semi-finished product is placed plasma atmosphere is in the tungstenic plasma atmosphere bipolar plates semi-finished product to be applied 350-550V direct current or pulsed dc voltage; Under temperature 700-1150 ℃, handled 0.3-8 hour, obtain surface reforming layer.
6. the manufacturing approach of the fuel battery metal double polar plate of tungstenic modified layer according to claim 5; It is characterized in that; Described tungstenic plasma atmosphere is obtained by following method: the tungsten source is placed in the seal; Apply the 600-900V pulsed dc voltage to the tungsten source, current density is 0.1-15mA/cm
2, argon Ar is as working gas, and operating air pressure is 0.01-2kPa, obtains the tungstenic plasma atmosphere with argon gas bombardment tungsten source.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100934939A CN102623720A (en) | 2012-04-01 | 2012-04-01 | Fuel cell metal bipolar plate containing tungsten-modified layer and manufacture method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100934939A CN102623720A (en) | 2012-04-01 | 2012-04-01 | Fuel cell metal bipolar plate containing tungsten-modified layer and manufacture method thereof |
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| CN102623720A true CN102623720A (en) | 2012-08-01 |
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| CN2012100934939A Pending CN102623720A (en) | 2012-04-01 | 2012-04-01 | Fuel cell metal bipolar plate containing tungsten-modified layer and manufacture method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336371A (en) * | 2018-02-05 | 2018-07-27 | 大连融科储能技术发展有限公司 | A kind of bipolar plates used for all-vanadium redox flow battery |
| CN111471939A (en) * | 2020-04-09 | 2020-07-31 | 大连理工大学 | High Ni stainless steel suitable for proton exchange membrane fuel cell bipolar plate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050202305A1 (en) * | 2004-02-24 | 2005-09-15 | Markoski Larry J. | Fuel cell apparatus and method of fabrication |
| CN101694879A (en) * | 2009-10-22 | 2010-04-14 | 大连海事大学 | Mo-nitride-containing surface modification fuel cell stainless steel bipolar plate and manufacturing method thereof |
| CN101743657A (en) * | 2007-07-09 | 2010-06-16 | 蒂森克虏伯钢铁欧洲股份公司 | Bipolar plate for a fuel cell and fuel cell stack |
| CN101752575A (en) * | 2008-12-04 | 2010-06-23 | 上海空间电源研究所 | Preparation method of metal bipolar plate surface coating of proton exchange membrane fuel cell |
-
2012
- 2012-04-01 CN CN2012100934939A patent/CN102623720A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050202305A1 (en) * | 2004-02-24 | 2005-09-15 | Markoski Larry J. | Fuel cell apparatus and method of fabrication |
| CN101743657A (en) * | 2007-07-09 | 2010-06-16 | 蒂森克虏伯钢铁欧洲股份公司 | Bipolar plate for a fuel cell and fuel cell stack |
| CN101752575A (en) * | 2008-12-04 | 2010-06-23 | 上海空间电源研究所 | Preparation method of metal bipolar plate surface coating of proton exchange membrane fuel cell |
| CN101694879A (en) * | 2009-10-22 | 2010-04-14 | 大连海事大学 | Mo-nitride-containing surface modification fuel cell stainless steel bipolar plate and manufacturing method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336371A (en) * | 2018-02-05 | 2018-07-27 | 大连融科储能技术发展有限公司 | A kind of bipolar plates used for all-vanadium redox flow battery |
| CN111471939A (en) * | 2020-04-09 | 2020-07-31 | 大连理工大学 | High Ni stainless steel suitable for proton exchange membrane fuel cell bipolar plate |
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Application publication date: 20120801 |