CN102629690A - Chromium nitride modified metal bipolar plate for fuel cells and manufacturing method thereof - Google Patents
Chromium nitride modified metal bipolar plate for fuel cells and manufacturing method thereof Download PDFInfo
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- CN102629690A CN102629690A CN2012101190536A CN201210119053A CN102629690A CN 102629690 A CN102629690 A CN 102629690A CN 2012101190536 A CN2012101190536 A CN 2012101190536A CN 201210119053 A CN201210119053 A CN 201210119053A CN 102629690 A CN102629690 A CN 102629690A
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Abstract
The invention provides a chromium nitride modified metal bipolar plate for fuel cells and a manufacturing method thereof, which adopts a surface modified technique combing plasma nitriding and thermal reaction sedimentation and diffusion for achieving surface modification of an iron-base alloy metal plate. The surface of the modified iron-base alloy metal plate is a chromium nitride layer when a thickness of the plate is 1-50 mu m and the corrosion rate is below 10 muA/cm<2>; when the pressure is 150-200 N/cm<2>, a contact resistance is 10-20 m omega.cm<2>; and the chromium nitride of the modified layer is CrN and / or Cr2N. Under conditions that the intensity of the bipolar plate is guaranteed and the cell performance of the bipolar plate is not affected, the method improves corrosion-resistance of the metal bipolar plate; metallurgical bonding is achieved between the chromium nitride modified layer with the modified surface and the substrate; and components of the chromium nitride modified layer can be controlled by adjustment of the isothermal diffusion temperature and time, and the surface chromium nitride modified layer has good electrical conductivity and corrosion resistance.
Description
Technical field
The invention belongs to the fuel cell electrode technical field.Be particularly related to metal double polar plates of polymer dielectric film fuel cell and preparation method thereof.
Background technology
Except having characteristics such as energy conversion efficiency height, life-span length, environmental friendliness; Polymer electrolyte fuel cells is low because of its working temperature, startup becomes the power source that is applied to communications and transportation and builds the dispersion power station soon, is the general removable power supplys of a kind of the army and the people.Yet factor such as expensive, weight and volume limit has to a great extent hindered the large-scale commercial applications application of polymer electrolyte fuel cells.Therefore, reduce cost and become national governments and researcher's the focus of attention.
As one of multifunctional module important in the polymer electrolyte fuel cells; Bipolar plates not only has the reacting gas of separation, afflux conduction, support membrane electrode and conductive force; Can also be combined into reacting gas with flow-field plate passage is provided, reacting gas is evenly distributed, and the water that generates is discharged.Bipolar plates must be by conduction and satisfactory mechanical property, chemically stable hyposmosis material preparation, thereby reduces the energy loss of battery pack and increase the service life.As a kind of important multifunctional module, the performance of bipolar plates directly influences useful life and the power output of PEMFC.Traditional graphite bi-polar plate, big because of fragility, intensity is low, is difficult to prepare fuel battery in light weight, that volume is little, and also it is consuming time and expense is high to process the technology in various flow fields at its machining surface.These have all limited the practical application of graphite bi-polar plate in transportation with broad prospect of application and portable removable power supply.Metal material has outstanding features such as obdurability height, conductivity, thermal conductivity and compactness are good; Avoided the deficiency such as high fragility and low-intensity of conventional graphite bipolar plates; Can adopt methods such as machining and punching press in the various flow fields of Surface Machining, be more suitable in the fuel battery of producing low weight, low volume in enormous quantities.Replacing graphite to make bipolar plates with metal material has become at present the research focus of fuel cell field in the world, also has been to have one of challenging research field.Concerning metal material, be unfavorable for forming passivating film in the reducing atmosphere of anode one side, some metals also possibly dissolve; The oxidizing atmosphere of negative electrode one side then helps the formation of passivating film.In recent years, the researcher attempts to replace graphite as bipolar plates with metal material always, comprises aluminium and aluminium alloy, titanium or titanium alloy, stainless steel and nickel-base alloy etc.Big quantity research shows owing to receive the restriction of Proton Exchange Membrane Fuel Cells (PEMFC) condition of work, also do not have a kind of low-cost metal material can satisfy the requirement of corrosion resistance, conductivity and long-time stability in the redox mediator simultaneously.Therefore research emphasis turns to carries out suitable surface modification to metal material.Conducting polymer, metal nitride (TiN, TaN, CrN, ZrN, NbN etc.), oxide (IrO
2, SnO
2: F, RuO
2) and the cheap relatively coating of cost such as carbon-base film caused domestic and international researcher's concern; Nitride and the oxide coating that adopts diverse ways preparations such as physical vapor deposition (PVD), chemical vapor deposition (CVD) and plating then generate because of its preparation technology's restriction defectives such as the micropore that is difficult to avoid and micro-crack can because local corrosion peel off, thereby reduce the useful life that causes polymer dielectric film fuel cell.Therefore; The metal double polar plates that develops low cost, high surface conductivity and good corrosion resistance through a kind of new surface modifying method is the inexorable trend of polymer dielectric film fuel cell, also will produce significant effects to the commercialization process of polymer dielectric film fuel cell.
Summary of the invention
The object of the present invention is to provide and a kind ofly have good electric conductivity, corrosion resistance cheaply, be easy to production and processing and can satisfy the polymer electrolyte fuel cells service requirement and the metal double polar plates of polymer electrolyte film fuel cell of mass market application requirements and preparation method thereof.
In order to achieve the above object, the present invention adopts following technical scheme:
Fuel cell is with chromium nitride modified metal bipolar plates, and matrix is the ferrous alloy metallic plate; Said matrix surface is high conductivity and corrosion proof chromium nitride modified layer, and thickness is 1～50 μ m, and corrosion rate is lower than 10 μ A/cm
2The time; When pressure is 150～200N/cm
2, contact resistance is 10～20m Ω cm
2
Said chromium nitride is CrN and/or Cr
2N.
The chemical composition of said matrix iron-based alloying metal plate is C≤0.50%, 0.17～0.37%Si by weight percentage, 0.35～0.80%Mn; Cr≤0.25%, Ni≤0.30%, Cu≤0.25%; P＜0.35%, S≤0.04%, plate thickness are 0.1～3.0mm.
The preparation method of above-mentioned modified metal bipolar plates, its matrix surface modified technique comprises the steps:
(1) plasma nitrided reaction: nitriding temperature is 500～600 ℃ in the stove, and the holding stage glow voltage is 200V～700V, and current density is 0.5～20mA/cm
2, vacuum degree is 50～1330Pa, and nitridation time is 1～10h, and reacting gas is the mixed gas of ammonia or nitrogen or nitrogen one hydrogen;
(2) ferrous alloy after step (1) processing is carried out thermal response deposition and diffusion, temperature is 500～1000 ℃, and isothermal time is 0.5～48h; Spread required Cr and derive from the Cr-Fe powder.
When the said nitridation reaction gas of step (1) was the mixed gas of nitrogen-hydrogen, according to volume ratio, the content of nitrogen was 5-95% in the hybrid reaction gas.
The present invention has outstanding feature and outstanding advantage:
Adopt plasma nitrided the deposition with the diffusion duplex surface modification to handle the ferrous alloy bipolar plates,, obviously improve the corrosion resistance of metal double polar plates guaranteeing bipolar plates intensity and not influencing under the situation of bipolar plates battery performance with thermal response.It after the surface modification metallurgical binding.Can control the composition of chromium nitride modified layer through adjusting isothermal diffusion temperature and time.Surface chromium nitride modified layer has good electrical conductivity and corrosion resistance.This surface modification technology is simple, the basis material wide material sources, and material and low processing cost can be produced thin metal dual-pole board in batches, adopt high conductivity and corrosion proof chromium nitride modified layer replacement noble coatings cheaply, can reduce cost significantly.Extensive use for accelerating metal double polar plates of polymer electrolyte film fuel cell has important and practical meanings.Be expected to realize cost degradation and the mass industrialized production and large-scale application market of polymer dielectric film fuel cell through this technology.
Description of drawings
Fig. 1 be plasma nitrided and thermal response deposition with the diffusion duplex surface modification after ferrous alloy metal double polar plates and the interface contact resistance comparison diagram of graphite.
Abscissa is a contact pressure among Fig. 1, and its unit is N/cm
2Ordinate is an interface contact resistance, and its unit is m Ω cm
2Black round dot ● represent this patent modification bipolar plates, black ■ represents graphite bi-polar plate.Visible from Fig. 1, the contact resistance of ferrous alloy metal double polar plates tends towards stability along with the incipient stage that is increased in of pressure reduces rapidly then gradually behind the duplex surface modification.When pressure is 150～200N/cm
2The time, contact resistance is 10～20m Ω cm
2
Embodiment
Following embodiment can make those of ordinary skill in the art more fully understand the present invention, but does not limit the present invention in any way.
Embodiment 1
Adopt plasma nitrided and thermal response deposition and diffusion duplex surface modification technology to ferrous alloy (0.42～0.50%C, 0.17～0.37%Si, 0.35～0.80%Mn; Cr≤0.25%, Ni≤0.30%, Cu≤0.25%; P＜0.35%, S≤0.04%) carry out surface modification, nitriding temperature is 500 ℃; The holding stage glow voltage is 200V, and current density is 1mA/cm
2, vacuum degree is 50Pa, and nitridation time is 1h, and reacting gas is an ammonia.The thermal response deposition is 500 ℃ with diffusion temperature, and the time is 0.5h, and the CrN modified layer thickness that is generated is 1 μ m.Ferrous alloy metal double polar plates interface contact resistance through behind plasma nitrided and thermal response deposition and the diffusion duplex surface modification obviously reduces, a little more than graphite.As shown in Figure 1, current density is less than 10 μ A/cm under the condition of work of simulating polymer dielectric film fuel cell
2
Embodiment 2
Adopt plasma nitrided and thermal response deposition and diffusion duplex surface modification technology to ferrous alloy (0.17～0.23%C, 0.17～0.37%Si, 0.35～0.80%Mn; Cr≤0.25%, Ni≤0.30%, Cu≤0.25%; P＜0.35%, S≤0.04%) carry out surface modification, nitriding temperature is 550 ℃; The holding stage glow voltage is 500V, and current density is 10mA/cm
2, vacuum degree is 500Pa, and nitridation time is 5h, and reacting gas is a nitrogen.The thermal response deposition is 750 ℃ with diffusion temperature, and the time is 20h, the CrN+Cr that is generated
2N modified layer thickness is 20 μ m.Ferrous alloy metal double polar plates interface contact resistance through behind plasma nitrided and thermal response deposition and the diffusion duplex surface modification obviously reduces, a little more than graphite.As shown in Figure 1.Current density is less than 10 μ A/cm under the condition of work of simulating polymer dielectric film fuel cell
2
Embodiment 3
Adopt plasma nitrided and thermal response deposition and diffusion duplex surface modification technology to ferrous alloy (0.07～0.14%C, 0.17～0.37%Si, 0.35～0.80%Mn; Cr≤0.25%, Ni≤0.30%, Cu≤0.25%; P＜0.35%, S≤0.04%) carry out surface modification, nitriding temperature is 600 ℃; The holding stage glow voltage is 700V, and current density is 20mA/cm
2, vacuum degree is 50Pa～1330Pa, and nitridation time is 10h, and reacting gas is an ammonia.The thermal response deposition is 1000 ℃ with diffusion temperature, and the time is 45h, the Cr that is generated
2N modified layer thickness is 50 μ m.Ferrous alloy metal double polar plates interface contact resistance through behind plasma nitrided and thermal response deposition and the diffusion duplex surface modification obviously reduces, a little more than graphite.As shown in Figure 1.Current density is less than 10 μ A/cm under the condition of work of simulating polymer dielectric film fuel cell
2
Claims (6)
1. fuel cell is characterized in that with chromium nitride modified metal bipolar plates: matrix is the ferrous alloy metallic plate; Said matrix surface is high conductivity and corrosion proof chromium nitride modified layer, and thickness is 1～50 μ m, and corrosion rate is lower than 10 μ A/cm
2The time; When pressure is 150～200N/cm
2, contact resistance is 10～20m Ω cm
2
Said chromium nitride is CrN and/or Cr
2N.
2. modified metal bipolar plates according to claim 1 is characterized in that: the chemical composition of said matrix iron-based alloying metal plate is C≤0.50%, 0.17～0.37%Si; 0.35～0.80%Mn, Cr≤0.25%, Ni≤0.30%; Cu≤0.25%; P＜0.35%, S≤0.04%, plate thickness are 0.1～3.0mm.
3. the preparation method of modified metal bipolar plates as claimed in claim 1 is characterized in that the matrix surface modified technique comprises the steps:
(1) plasma nitrided reaction: nitriding temperature is 500～600 ℃ in the stove, and the holding stage glow voltage is 200V～700V, and current density is 0.5～20mA/cm
2, vacuum degree is 50～1330Pa, and nitridation time is 1～10h, and reacting gas is the mixed gas of ammonia or nitrogen or nitrogen-hydrogen;
(2) the thermal response deposition is 500～1000 ℃ with diffusion temperature, and isothermal time is 0.5～48h; Spread required Cr and derive from the Cr-Fe powder.
4. preparation method according to claim 3 is characterized in that: the said nitridation reaction gas of step (1) is ammonia.
5. preparation method according to claim 3 is characterized in that: the said nitridation reaction gas of step (1) is nitrogen.
6. preparation method according to claim 3 is characterized in that: the said nitridation reaction gas of step (1) is the mixed gas of nitrogen-hydrogen, and according to volume ratio, the content of nitrogen is 5-95% in the hybrid reaction gas.
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| CN201210119053.6A CN102629690B (en) | 2012-04-20 | 2012-04-20 | Chromium nitride modified metal bipolar plate for fuel cells and manufacturing method thereof |
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| CN201210119053.6A CN102629690B (en) | 2012-04-20 | 2012-04-20 | Chromium nitride modified metal bipolar plate for fuel cells and manufacturing method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066289A (en) * | 2012-12-07 | 2013-04-24 | 上海锦众信息科技有限公司 | Preparation method of chromium-nitrogen composite cathode material of lithium ion battery |
| CN104638274A (en) * | 2015-02-03 | 2015-05-20 | 大连交通大学 | Nano-TiO2-modified metal bipolar plate of fuel cell with polymer electrolyte membrane and preparation method of nano-TiO2-modified metal bipolar plate |
| CN104638273A (en) * | 2015-02-03 | 2015-05-20 | 大连交通大学 | RuO2-modified bipolar plate of fuel cell and preparation method of RuO2-modified bipolar plate |
| CN111933965A (en) * | 2020-07-24 | 2020-11-13 | 苏州敦胜新能源科技有限公司 | High-temperature fuel cell bipolar plate oxidation-resistant coating |
| CN112952130A (en) * | 2021-03-12 | 2021-06-11 | 大连交通大学 | Metal bipolar plate with chromium nitride functional coating on surface and preparation method thereof |
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| CN1851967A (en) * | 2006-05-26 | 2006-10-25 | 大连海事大学 | Metal double-polar board of solid polymer dielectric film fuel cell and making method therefor |
| 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 |
| CN101148769A (en) * | 2007-10-30 | 2008-03-26 | 华南理工大学 | Method for directly growing nano-crystal chromium nitride film on steel products |
| CN101601158A (en) * | 2006-12-28 | 2009-12-09 | Posco公司 | Improve the method for the stainless surface property of the bipolar plates that is used for polymer dielectric film fuel cell |
| CN102400059A (en) * | 2011-09-28 | 2012-04-04 | 南京钢铁股份有限公司 | Production technology of corrosion resisting steel plate used for crude oil cargo tank |
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2012
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Patent Citations (5)
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| CN1851967A (en) * | 2006-05-26 | 2006-10-25 | 大连海事大学 | Metal double-polar board of solid polymer dielectric film fuel cell and making method therefor |
| 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 |
| CN101601158A (en) * | 2006-12-28 | 2009-12-09 | Posco公司 | Improve the method for the stainless surface property of the bipolar plates that is used for polymer dielectric film fuel cell |
| CN101148769A (en) * | 2007-10-30 | 2008-03-26 | 华南理工大学 | Method for directly growing nano-crystal chromium nitride film on steel products |
| CN102400059A (en) * | 2011-09-28 | 2012-04-04 | 南京钢铁股份有限公司 | Production technology of corrosion resisting steel plate used for crude oil cargo tank |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066289A (en) * | 2012-12-07 | 2013-04-24 | 上海锦众信息科技有限公司 | Preparation method of chromium-nitrogen composite cathode material of lithium ion battery |
| CN104638274A (en) * | 2015-02-03 | 2015-05-20 | 大连交通大学 | Nano-TiO2-modified metal bipolar plate of fuel cell with polymer electrolyte membrane and preparation method of nano-TiO2-modified metal bipolar plate |
| CN104638273A (en) * | 2015-02-03 | 2015-05-20 | 大连交通大学 | RuO2-modified bipolar plate of fuel cell and preparation method of RuO2-modified bipolar plate |
| CN104638274B (en) * | 2015-02-03 | 2017-02-22 | 大连交通大学 | Nano-TiO2-modified metal bipolar plate of fuel cell with polymer electrolyte membrane and preparation method of nano-TiO2-modified metal bipolar plate |
| CN104638273B (en) * | 2015-02-03 | 2017-07-11 | 大连交通大学 | RuO2Modified fuel battery double plates and preparation method thereof |
| CN111933965A (en) * | 2020-07-24 | 2020-11-13 | 苏州敦胜新能源科技有限公司 | High-temperature fuel cell bipolar plate oxidation-resistant coating |
| CN112952130A (en) * | 2021-03-12 | 2021-06-11 | 大连交通大学 | Metal bipolar plate with chromium nitride functional coating on surface and preparation method thereof |
| CN112952130B (en) * | 2021-03-12 | 2023-08-29 | 大连交通大学 | Metal bipolar plate with chromium nitride functional coating on surface and preparation method thereof |
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| CN102629690B (en) | 2014-09-24 |
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