CN102637880A - Chromium carbide modified iron-based metal bipolar plate and preparation method thereof - Google Patents
Chromium carbide modified iron-based metal bipolar plate and preparation method thereof Download PDFInfo
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- CN102637880A CN102637880A CN2012101192103A CN201210119210A CN102637880A CN 102637880 A CN102637880 A CN 102637880A CN 2012101192103 A CN2012101192103 A CN 2012101192103A CN 201210119210 A CN201210119210 A CN 201210119210A CN 102637880 A CN102637880 A CN 102637880A
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Abstract
The invention provides a chromium carbide modified iron-based metal bipolar plate for a fuel battery and a preparation method thereof. An iron-based alloy metal plate is subjected to surface modification by using plasma carburization and a combined thermal reactive deposition and diffusion surface modification process. The modified surface of the metal plate is a chromium carbide diffusion layer with high conductivity and corrosion resistance, the thickness is 1-30 microns, and the corrosion speed is lower than 10 microamperes/square centimeter. When the pressure is 150-200 N/square centimeter, the contact resistance is 10-20 micro-ohms*square centimeter, and a chromium carbide diffusion layer is made of Cr3C2 and/or Cr7C3 and/or Cr23C6. According to the method provided by the invention, the corrosion resistance of the metal bipolar plate can be obviously improved in a condition of ensuring the intensity of the bipolar plate and not influencing battery properties of the bipolar plate. The chromium carbide diffusion layer with the modified surface and a base body are in metallurgical combination. Furthermore, components of the chromium carbide diffusion layer can be controlled by adjusting isothermal diffusion temperature and time.
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.Because low surface contacted resistance and excellent corrosion resisting performance, graphite is considered to the polymer electrolyte fuel cells bipolar plate material of standard.Traditional graphite is difficult to prepare the fuel battery of the low volume of low weight because of the fragility hard intensity is low, and it is consuming time and expense is high to process the technology in various flow fields at machining surface.Thereby the cost that causes graphite cake accounts for 80% of Proton Exchange Membrane Fuel Cells cost.It is very potential having good obdurability, conductivity and bubble-tight metal material replacement graphite.Metal not only can be processed into the thin plate that thickness is 0.1～0.3mm; Can also be processed into various flow-field plate through the method for machining and punching press; Be suitable for producing in batches, and then the quality that increases substantially polymer electrolyte fuel cells is than power and volumetric specific power.The metal bipolar panel material that adopts at present has ferrous alloy, nickel-base alloy and aluminium, titanium and alloy thereof etc.
Contain SO in the operational environment of polymer dielectric film fuel cell
4 2-, SO
3 2-, CO
3 2-, HSO
4 -And HSO
3 -Plasma, this degrades relevant with the preparation technology of electrode with the part of PEM.Therefore, electrochemical corrosion so will take place in the rigorous environment in metal double polar plates inevitably.The oxide skin(coating) of the passivation that the metal double polar plates surface generates has also caused nonconforming high surface contacted resistance simultaneously except having suppressed the further corrosion of metal.This will certainly cause the consumption of some electric energy and the reduction of fuel battery gross efficiency, thereby reduces the performance and the power output of battery pack.For this reason, improve its surface conductivity and corrosion resistance through process for modifying surface the preparation and the production of metal double polar plates is had great importance, also will produce far-reaching influence the development and the extensive use of polymer dielectric film fuel cell.Noble coatings is inappropriate for because of its cost is high and produces battery pack cheaply.Nitride and the oxide coating that adopts diverse ways preparations such as physical vapour deposition (PVD), chemical vapour 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 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:
The modifying iron based alloying metal bipolar plates of a kind of chromium carbide is characterized in that: matrix is the ferrous alloy metallic plate, and its thickness is 0.1～3.0mm; Its alloy composition 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%; Said matrix surface is high conductivity and corrosion proof chromium carbide diffusion layer, and thickness of diffusion layer is 1～30 μ m, and corrosion rate is lower than 10 μ A/cm
2When pressure is 150～200N/cm
2, contact resistance is 10～20m Ω cm
2
Said chromium carbide is Cr
3C
2And/or Cr
7C
3And/or Cr
23C
6
The preparation method of the modifying iron based alloying metal bipolar plates of above-mentioned chromium carbide, the matrix surface modified technique was divided into for two steps:
(1) carburizing temperature is 800～1000 ℃ in the stove, and the holding stage glow voltage is 100V～800V, and current density is 0.5～20mA/cm
2, vacuum degree is 50Pa～1330Pa, and carburizing time is 2～8h, and reacting gas is methane or acetylene or propane;
(2) thermal response deposition is 500～1000 ℃ with diffusion temperature, and isothermal diffusion time is 0.5～48h; Spread required Cr and derive from the Cr-Fe powder.
The present invention has outstanding feature and outstanding advantage:
Adopt plasma carburising and thermal response deposition and 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.It after the surface modification metallurgical binding.Can control the composition of chromium carbide diffusion layer through adjusting isothermal diffusion temperature and time.The surface chrome carbide 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 diffusion layer replacement noble coatings cheaply, can reduce cost significantly.Extensive use for quickening 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 carburising 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 the figure, 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 figure, the contact resistance of the ferrous alloy metal double polar plates behind the duplex surface modification tends towards stability along with the incipient stage that is increased in of pressure reduces rapidly then gradually.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 carburising and thermal response deposition and spread the duplex surface modification technology 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, carburizing temperature is 800 ℃; The holding stage glow voltage is 100V, and current density is 0.5mA/cm
2, vacuum degree is 100Pa, and carburizing time is 2h, and reacting gas is a methane.The thermal response deposition is 500 ℃ with diffusion temperature, and be 0.5h diffusion time, the Cr that is generated
7C
3Layer thickness is 1 μ m.Ferrous alloy metal double polar plates interface contact resistance through behind plasma carburising and thermal response deposition and the diffusion duplex surface modification obviously reduces, and is 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 carburising and thermal response deposition and spread the duplex surface modification technology 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, carburizing temperature is 900 ℃; The holding stage glow voltage is 500V, and current density is 15mA/cm
2, vacuum degree is 880Pa, and carburizing time is 5h, and reacting gas is an acetylene.The thermal response deposition is 750 ℃ with diffusion temperature, and be 20h diffusion time, the Cr that is generated
3C
2+ Cr
7C
3Layer thickness is 20 μ m.Ferrous alloy metal double polar plates interface contact resistance through behind plasma carburising and thermal response deposition and the diffusion duplex surface modification obviously reduces, and is 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 carburising and thermal response deposition and spread the duplex surface modification technology 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, carburizing temperature is 1000 ℃; The holding stage glow voltage is 800V, and current density is 0.5～20mA/cm
2, vacuum degree is 1330Pa, and carburizing time is 8h, and reacting gas is a propane.The thermal response deposition is 1000 ℃ with diffusion temperature, and be 45h diffusion time, the Cr that is generated
3C
2+ Cr
23C
6Layer thickness is 30 μ m.Ferrous alloy metal double polar plates interface contact resistance through behind plasma carburising and thermal response deposition and the diffusion duplex surface modification obviously reduces, and is 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 (5)
1. modifying iron based alloying metal bipolar plates of chromium carbide, it is characterized in that: matrix is the ferrous alloy metallic plate, its thickness is 0.1～3.0mm; Its alloy composition 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%; Said matrix surface is high conductivity and corrosion proof chromium carbide diffusion layer, and thickness of diffusion layer is 1～30 μ m, and corrosion rate is lower than 10 μ A/cm
2When pressure is 150～200N/cm
2, contact resistance is 10～20m Ω cm
2
Said chromium carbide is Cr
3C
2And/or Cr
7C
3And/or Cr
23C
6
2. the preparation method of the modifying iron based metal double polar plates of chromium carbide according to claim 1 is characterized in that the matrix surface modified technique was divided into for two steps:
(1) carburizing temperature is 800～1000 ℃ in the stove, and the holding stage glow voltage is 100V～800V, and current density is 0.5～20mA/cm
2, vacuum degree is 50～1330Pa, and carburizing time is 2～8h, and reacting gas is methane or acetylene or propane;
(2) thermal response deposition is 500～1000 ℃ with diffusion temperature, and isothermal diffusion time is 0.5～48h; Spread required Cr and derive from the Cr-Fe powder.
3. the preparation method of metal double polar plates of polymer electrolyte film fuel cell according to claim 2 is characterized in that carburization reaction gas is methane.
4. the preparation method of metal double polar plates of polymer electrolyte film fuel cell according to claim 2 is characterized in that carburization reaction gas is acetylene.
5. the preparation method of metal double polar plates of polymer electrolyte film fuel cell according to claim 2 is characterized in that carburization reaction gas is propane.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066301A (en) * | 2012-12-07 | 2013-04-24 | 上海锦众信息科技有限公司 | Preparation method of chromium-carbon composite plate material for fuel cells |
| CN106997955A (en) * | 2017-04-19 | 2017-08-01 | 大连交通大学 | Cr3C2Modified metal double polar plates of polymer electrolyte film fuel cell and preparation method thereof |
| CN109321875A (en) * | 2018-11-08 | 2019-02-12 | 长沙特耐金属材料科技有限公司 | The surface metal carbide coating processing method of high-alloy steel materials in a kind of middle low-carbon |
| CN112609152A (en) * | 2020-12-15 | 2021-04-06 | 上海治臻新能源装备有限公司 | Continuous equipment for composite deposition of carbon material on surface of bipolar plate and application method |
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| CN106997955A (en) * | 2017-04-19 | 2017-08-01 | 大连交通大学 | Cr3C2Modified metal double polar plates of polymer electrolyte film fuel cell and preparation method thereof |
| CN109321875A (en) * | 2018-11-08 | 2019-02-12 | 长沙特耐金属材料科技有限公司 | The surface metal carbide coating processing method of high-alloy steel materials in a kind of middle low-carbon |
| CN112609152A (en) * | 2020-12-15 | 2021-04-06 | 上海治臻新能源装备有限公司 | Continuous equipment for composite deposition of carbon material on surface of bipolar plate and application method |
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| CN102637880B (en) | 2014-09-03 |
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