CN101694879B - Mo-nitride-containing surface modification fuel cell stainless steel bipolar plate and manufacturing method thereof - Google Patents
Mo-nitride-containing surface modification fuel cell stainless steel bipolar plate and manufacturing method thereof Download PDFInfo
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- CN101694879B CN101694879B CN2009101880597A CN200910188059A CN101694879B CN 101694879 B CN101694879 B CN 101694879B CN 2009101880597 A CN2009101880597 A CN 2009101880597A CN 200910188059 A CN200910188059 A CN 200910188059A CN 101694879 B CN101694879 B CN 101694879B
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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 solid polymer electrolyte film fuel cell metal bipolar plate, a surface modification layer of which comprises a surface layer modification layer and a sub-surface layer alloy diffusion layer, wherein the surface layer modification layer is Mo nitride with high conductivity and anti-corrosion property, and the sub-surface layer alloy diffusion layer is Mo and N diffusion solid solution. The metal bipolar plate has the advantages that the diffusion Mo nitride modification layer with low cost, high conductivity and anti-corrosion property is adopted to greatly reduce the cost; the modification layer is combined with a matrix by metallurgical bonding, so that corrosion stripping failure can not be caused; and the manufacturing method has simple technique and is suitable for batch production, thus improving the mass ratio power and the volume ratio power of a battery pack. A low cost solid polymer electrolyte film fuel cell produced by the metal bipolar plate processed by the technology can be applied to large-scale fuel cell production.
Description
Technical field
The invention belongs to the fuel cell technology field.Be particularly related to the bipolar plate of stainless steel of solid polymer dielectric film fuel cell.
Background technology
Solid polymer dielectric film fuel cell (comprising Proton Exchange Membrane Fuel Cells and direct alcohol fuel battery) has outstanding features such as room temperature startup fast, high efficiency, no electrolyte loss, zero pollution, easy draining and life-span length.Not only can be used for building and disperse the power station, also be the general removable power supplys of a kind of the army and the people.
Fuel battery double plates has graphite bi-polar plate and metal double polar plates in the prior art, and graphite bi-polar plate adopts flexible graphite to make now usually.Graphite bi-polar plate has good electrical conductivity and corrosion resistance, and its deficiency is because of its porousness, makes its air-tightness deficiency, is difficult to the battery pack of processing and fabricating low weight, low volume because of fragility makes it.In addition, the cost of graphite cake accounts for solid polymer dielectric film fuel cell and piles this 60%, and volume energy density and mass energy density are lower.The material that metal double polar plates adopts usually has ferrous alloy, aluminium and aluminium alloy thereof, titanium and alloy thereof etc.Metal material has good obdurability, conductivity and air-tightness, is a kind of good material for preparing bipolar plates.Adopt metal material to make the solid polymer dielectric film fuel cell bipolar plates and can improve the quality of battery pack than power and volumetric specific power.Its deficiency is: contain SO in the operational environment of solid polymer dielectric film fuel cell
4 2-, SO
3 2-, CO
3 2-, HSO
4 -And HSO
3 -Plasma.In rigorous environment like this, metal double polar plates will be corroded inevitably.On the one hand, the metal ion of corrosion dissolution can poison the eelctro-catalyst of electrode and block the proton channel of solid electrolyte film, reduces the conductive capability of catalyst activity and reduction dielectric film; On the other hand, the passivating film that forms in the metal surface causes interface contact resistance to increase, and two aspects all reduce the performance and the power output of battery pack.In order to address the above problem, prior art is to improve metal double polar plates surface conductivity and corrosion resistance by process for modifying surface.Now disclosed technology is only relevant for the report at metal surface noble metal-coating, nitride and oxide coating.Noble coatings is unsuitable for producing battery pack cheaply because of its cost is high.Nitride and oxide coating adopt methods preparations such as CVD, PVD, plating, then because of the intrinsic characteristic limitations of its preparation technology, can have the defectives such as pin hole that are difficult to avoid in coating, thereby cause that the coating spot corrosion peels off early failure.Simultaneously, the adhesion deficiency of coating and matrix also causes spalling failure.
The relevant patent that relates to has: CN 02 155 187.1, and 2002; CN 1 271 027-A, 2001; CN200610046735.3,2006; CN200710051303.6,2007.
Summary of the invention
The purpose of this invention is to provide a kind of have good surface conductivity and corrosion resistance, low-cost, be easy to make, can satisfy the solid polymer dielectric film fuel cell Fe-Base Metal bipolar plates and the manufacture method thereof of solid polymer dielectric film fuel cell development and mass market application requirements.
For achieving the above object, technical solution of the present invention is:
Contain Mo nitride surface denatured fuel battery bipolar plate of stainless steel, comprise bipolar plates and surface reforming layer thereof that austenitic stainless steel thin plate is made, it is characterized in that described surface reforming layer comprises top layer modified layer and time top layer alloying diffusion layer, the top layer modified layer is high conductivity and corrosion proof Mo nitride, and inferior top layer alloying diffusion layer is the solid solution diffusion body of Mo, N.
The Mo nitride surface denatured fuel battery bipolar plate of stainless steel that contains of the present invention is characterized in that described Mo nitride top layer modified layer is single-phase MoN, single-phase Mo
2N and single-phase Mo
3N
2In the mixture of any one or above-mentioned phase; The solid solution diffusion body of described Mo, N time top layer is the alloy solid solution body of Mo, Mo and N mass concentration reduce Mo, the N content that carries out the transition to matrix gradually from the high concentration of next-door neighbour's nitride surface layer, described Mo and N mass concentration are 10wt%～40wt% at the high concentration Mo of next-door neighbour's nitride surface layer, and N is 0.4wt%～2wt%.
The Mo nitride surface denatured fuel battery bipolar plate of stainless steel that contains of the present invention, it is characterized in that, the alloy content of described austenitic stainless steel thin plate by weight percentage, Cr is 15-25%, Ni is 5-28%, Mo is 0-4%, Mn is 0～15%, and Ti is 0～1%, and Cu is 0～3%, Nb is 0-2%, and all the other are Fe.
The Mo nitride surface denatured fuel battery bipolar plate of stainless steel that contains of the present invention, it is characterized in that, the thickness of described ferrous alloy austenitic stainless steel thin plate is 0.1～3mm, and Mo nitride modified layer thickness is 1～40 μ m, and the thickness on Mo, N solid solution diffusion body time top layer is 1-50 μ m.
The manufacture method that contains Mo nitride surface denatured fuel battery bipolar plate of stainless steel of the present invention, comprise austenitic stainless steel thin plate be prepared into the semi-finished product bipolar plates that has fluid course and passage and to the surface modification treatment of semi-finished product bipolar plates, it is characterized in that described surface modification treatment to the semi-finished product bipolar plates may further comprise the steps:
A) surface with the semi-finished product bipolar plates places in the seal that contains the Mo plasma atmosphere, in containing the Mo plasma atmosphere, the semi-finished product bipolar plates is applied 600-950V direct current or pulsed dc voltage, under 700～1150 ℃ of temperature, handled 0.5～8 hour, obtain the alloying layer of high Mo, wherein, the described Mo of containing plasma atmosphere is: metal M o source is placed in the seal, apply the 400-900V direct voltage to the Mo source, current density is 0.1～15mA/cm
2, operating air pressure is 0.01～2kPa, uses hydrogen H
2Or argon Ar bombardment metal M o source obtain contain the Mo plasma atmosphere.
B) will place in the seal of nitrogenous plasma atmosphere through the semi-finished product bipolar plates that step a handles then, the semi-finished product bipolar plates of handling through step a is applied 500-900V direct current or pulsed dc voltage, current density is 0.1～6mA/cm
2, under 0.1～3kPa air pressure, to handle, treatment temperature is 400-900 ℃, and the processing time is 0.5～6 hour, forms Mo, N solid solution diffusion body time top layer under Mo nitride top layer modified layer and the top layer modified layer, and described nitrogenous plasma atmosphere is that working gas is N
2And H
2Mist, by volume, N in the mist
2Gas content is 5～50%.
The manufacture method that contains Mo nitride surface denatured fuel battery bipolar plate of stainless steel of the present invention is characterized in that, the working gas of described nitrogenous plasma atmosphere is an ammonia.
The beneficial effect that the present invention reached is:
Adopt high conductivity and the corrosion proof expansion molybdenum nitride modified layer of oozing cheaply, can reduce cost significantly; Be combined into metallurgical binding between modified layer and the matrix, do not exist corrosion spalling to lose efficacy; Manufacturing approach craft is simple, can produce thin metal dual-pole board in batches; The quality that can improve battery pack is than power and volumetric specific power.Metal double polar plates with this technical finesse can be applied to large-scale fuel cells production.
Description of drawings
The present invention has accompanying drawing 1 width of cloth, is the interface contact resistance of bipolar plates loads solid pressure power with fuel cell stack change curve.
Among the figure, abscissa is a fastening pressure, its unit be newton/centimetre
2(N/cm
2); Ordinate is a surface contacted resistance, and unit is milliohm centimetre 2 (m Ω cm
2); The interface contact resistance of the curve representation original material bipolar plates 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 ■ black square forms loads the change curve of solid pressure power with fuel cell stack.
Embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments.
With commercial thickness is that the 304L austenitic stainless steel thin plate of 1mm is prepared into the semi-finished product bipolar plates that has fluid course and passage, then the semi-finished product bipolar plates is placed the low-voltage vacuum container, charge into argon gas to 2.2kPa, apply the 800V pulsed dc voltage to the semi-finished product bipolar plates, metal molybdenum places the low-voltage vacuum container, on metal molybdenum, apply the 750V direct voltage, contain the Mo plasma atmosphere in the formation of the space of low-voltage vacuum container, the control temperature was 850 ℃ of Temperature Treatment 4 hours, and the surface forms the homogeneous structure of Mo diffusion; Then, cancel the direct voltage on the metal molybdenum in the low-voltage vacuum container, only apply the 700V pulsed dc voltage on the semi-finished product bipolar plates, the temperature in the low-voltage vacuum container is reduced to 600 ℃, charging into volume ratio is 80%H
2+ 20%N
2Mist was handled 3 hours at 600 ℃, generated the molybdenum nitride layer at the semi-finished product bipolar plate surfaces, and the molybdenum nitride layer thickness is 15 μ m, and inferior top layer is the diffusion layer of Mo, N, and thickness is 30 μ m.The bipolar plates that embodiment produces is made electrochemistry experiment, and anodic polarization curves and the constant potential polarization under the solid polymer dielectric film fuel cell condition of work are all at 0.05M H
2SO
4+ 2ppm F
-Solution in carry out, passivation current density is less than 10 μ A/cm
2, all in solution, feed H in the electrochemistry experiment process
2Or air.Electrochemistry experiment shows that metal double polar plates interface contact resistance of the present invention obviously reduces, and is 1/10 of original 304L austenitic stainless steel bipolar plate surfaces contact resistance.
Claims (6)
1. contain Mo nitride surface denatured fuel battery bipolar plate of stainless steel, comprise bipolar plates and surface reforming layer thereof that austenitic stainless steel thin plate is made, it is characterized in that described surface reforming layer comprises top layer modified layer and time top layer alloying diffusion layer, the top layer modified layer is high conductivity and corrosion proof Mo nitride, and inferior top layer alloying diffusion layer is the solid solution diffusion body of Mo, N.
2. the Mo nitride surface denatured fuel battery bipolar plate of stainless steel that contains according to claim 1 is characterized in that described Mo nitride top layer modified layer is single-phase MoN, single-phase Mo
2N and single-phase Mo
3N
2In the mixture of any one or above-mentioned phase; Mo, N content that described top layer alloying diffusion layer Mo and N mass concentration reduce to carry out the transition to the stainless steel double polar board substrate from the high concentration of next-door neighbour top layer modified layer gradually, described Mo and N mass concentration are 10wt%～40wt% at the Mo of high concentration place of next-door neighbour top layer modified layer, and N is 0.4wt%～2wt%.
3. the Mo nitride surface denatured fuel battery bipolar plate of stainless steel that contains according to claim 2, it is characterized in that, the alloy content of described austenitic stainless steel thin plate by weight percentage, Cr is 15-25%, Ni is 5-28%, Mo is 0-4%, Mn is 0～15%, and Ti is 0～1%, and Cu is 0～3%, Nb is 0-2%, and all the other are Fe.
4. the Mo nitride surface denatured fuel battery bipolar plate of stainless steel that contains according to claim 3, it is characterized in that, the thickness of described ferrous alloy austenitic stainless steel thin plate is 0.1～3mm, and top layer modified layer thickness is 1～40 μ m, and the thickness of inferior top layer alloying diffusion layer is 1-50 μ m.
5. the manufacture method that contains Mo nitride surface denatured fuel battery bipolar plate of stainless steel, comprise austenitic stainless steel thin plate be prepared into the semi-finished product bipolar plates that has fluid course and passage and to the surface modification treatment of semi-finished product bipolar plates, it is characterized in that described surface modification treatment to the semi-finished product bipolar plates may further comprise the steps:
A) surface with the semi-finished product bipolar plates places in the seal that contains the Mo plasma atmosphere, in containing the Mo plasma atmosphere, the semi-finished product bipolar plates is applied 600-950V direct current or pulsed dc voltage, under 700～1150 ℃ of temperature, handled 0.5～8 hour, obtain the alloying layer of high Mo, wherein, the described Mo of containing plasma atmosphere is: metal M o source is placed in the seal, apply the 400-900V direct voltage to the Mo source, current density is 0.1～15mA/cm
2, operating air pressure is 0.01～2kPa, uses hydrogen H
2Or argon Ar bombardment metal M o source obtain contain the Mo plasma atmosphere;
B) will place in the seal of nitrogenous plasma atmosphere through the semi-finished product bipolar plates that step a handles then, the semi-finished product bipolar plates of handling through step a is applied 500-900V direct current or pulsed dc voltage, current density is 0.1～6mA/cm
2Handle under 0.1～3kPa air pressure, treatment temperature is 400-900 ℃, and the processing time is 0.5～6 hour, form Mo, N solid solution diffusion body time top layer alloying diffusion layer under Mo nitride top layer modified layer and the top layer modified layer, described nitrogenous plasma atmosphere is: working gas is N
2And H
2Mist, by volume, N in the mist
2Gas content is 5～50%.
6. the manufacture method that contains Mo nitride surface denatured fuel battery bipolar plate of stainless steel according to claim 5 is characterized in that, the working gas of described nitrogenous plasma atmosphere is an ammonia.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101880597A CN101694879B (en) | 2009-10-22 | 2009-10-22 | Mo-nitride-containing surface modification fuel cell stainless steel bipolar plate and manufacturing method thereof |
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|---|---|---|---|
| CN2009101880597A CN101694879B (en) | 2009-10-22 | 2009-10-22 | Mo-nitride-containing surface modification fuel cell stainless steel bipolar plate and manufacturing method thereof |
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| CN101694879A CN101694879A (en) | 2010-04-14 |
| CN101694879B true CN101694879B (en) | 2011-08-10 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324528A (en) * | 2011-09-21 | 2012-01-18 | 大连海事大学 | Surface-modified fuel cell stainless steel bipolar plate with Nb nitride and manufacturing method thereof |
| CN102623720A (en) * | 2012-04-01 | 2012-08-01 | 大连海事大学 | Fuel cell metal bipolar plate containing tungsten-modified layer and manufacture method thereof |
| 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 |
|---|---|---|---|---|
| CN1271027A (en) * | 1999-04-19 | 2000-10-25 | 住友金属工业株式会社 | Stainless steel material for solid polymer fuel battery |
| US6300001B1 (en) * | 1997-01-22 | 2001-10-09 | Siemens Aktiengesellschaft | Fuel cell and use of iron-based alloys for the construction of fuel cells |
| CN1446383A (en) * | 2000-08-05 | 2003-10-01 | 伊尼尔斯科劳尔有限公司 | Stainless steel substrate treatment |
| CN1885600A (en) * | 2006-05-26 | 2006-12-27 | 大连海事大学 | Solid electrolyte membrane fuel cell metal bipolar plate containing nitrogen carbon surface and method for manufacturing same |
-
2009
- 2009-10-22 CN CN2009101880597A patent/CN101694879B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6300001B1 (en) * | 1997-01-22 | 2001-10-09 | Siemens Aktiengesellschaft | Fuel cell and use of iron-based alloys for the construction of fuel cells |
| CN1271027A (en) * | 1999-04-19 | 2000-10-25 | 住友金属工业株式会社 | Stainless steel material for solid polymer fuel battery |
| CN1446383A (en) * | 2000-08-05 | 2003-10-01 | 伊尼尔斯科劳尔有限公司 | Stainless steel substrate treatment |
| CN1885600A (en) * | 2006-05-26 | 2006-12-27 | 大连海事大学 | Solid electrolyte membrane fuel cell metal bipolar plate containing nitrogen carbon surface and method for manufacturing same |
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