CN101800318B - Metal bipolar plate for proton exchange membrane fuel cell and preparation method thereof - Google Patents

Metal bipolar plate for proton exchange membrane fuel cell and preparation method thereof Download PDF

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Publication number
CN101800318B
CN101800318B CN2010101440138A CN201010144013A CN101800318B CN 101800318 B CN101800318 B CN 101800318B CN 2010101440138 A CN2010101440138 A CN 2010101440138A CN 201010144013 A CN201010144013 A CN 201010144013A CN 101800318 B CN101800318 B CN 101800318B
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carbon
titanium
intermediate layer
fuel cell
proton exchange
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CN101800318A (en
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付宇
潘欢欢
侯中军
刘常福
明平文
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Sunrise Power Co Ltd
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Sunrise Power Co Ltd
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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

Abstract

The invention discloses a metal bipolar plate for a proton exchange membrane fuel cell. A modifying layer is arranged on the surface of the metal bipolar plate and comprises a metallic titanium intermediate layer contiguous to a metal substrate and a carbon-based film composite layer on the metallic titanium intermediate layer. The carbon-based film composite layer on the metallic titanium intermediate layer is a carbon-based film composite layer which is formed by mixing carbon, titanium carbide and metallic titanium. The invention has the advantages that a metal bipolar plate matrix is provided with multilayer protection; protective layers can be mutually compensated, so that the bipolar plate has extremely-strong corrosion resistant performance and thereby remarkably prolongs the service life of the bipolar plate; meanwhile, the bipolar plate has excellent conductive performance, can remarkably reduce the internal resistance of the proton exchange membrane fuel cell and improve the output performance of the cell; and the modifying layer has low cost, which is beneficial to reduce the cost of the whole fuel cell system, thereby improving the overall competitiveness.

Description

A kind of used in proton exchange membrane fuel cell metal double polar plates and preparation method thereof
Technical field
The present invention relates to the fuel cell technology field, relate in particular to the fuel battery double plates manufacturing technology.
Background technology
In the prior art, the surface of metal double polar plates is all passed through surface modification treatment or is constituted by two kinds of components, satisfies bipolar plates to conductivity and corrosion proof requirement.The patent No. is that the patented technology of CN200610125191.X relates to a kind of dual polar plates of proton exchange membrane fuel cell and preparation method thereof; Bipolar plates is mixed after hot pressed sintering forms by conductivity ceramics and graphite two components, and its deficiency is that the mechanical property of this bipolar plates is difficult to compare with metal double polar plates with conductive capability.The patent No. is CN200810086375.9; The patented technology of CN200810086374.4 and CN200810086373.X relates to the preparation method of three kinds of ceramic modified films of metal double polar plates surface conductance; Its deficiency is that the conductivity of common conductivity ceramics is difficult to reach very high level, and the decay resistance under fuel cell environment also remains to be investigated.
Summary of the invention
The object of the present invention is to provide a kind of used in proton exchange membrane fuel cell metal double polar plates and surface modifying method thereof, make metal double polar plates have superior corrosion resistance ability and conductive capability.Technical scheme of the present invention is: a kind of used in proton exchange membrane fuel cell metal double polar plates; There is modified layer on the metal double polar plates surface, it is characterized in that said metal double polar plates surface reforming layer comprises: with the Titanium intermediate layer of metal substrate adjacency and the carbon-based films composite bed on the Titanium intermediate layer.
A kind of used in proton exchange membrane fuel cell metal double polar plates of the present invention is characterized in that the carbon-based films composite bed on the said Titanium intermediate layer is the carbon-based films composite bed that carbon, titanium carbide and Titanium mix.
A kind of used in proton exchange membrane fuel cell metal double polar plates of the present invention is characterized in that the carbon atomic percent accounts for 50%～95% in the carbon-based films composite bed on the said Titanium intermediate layer, and the titanium elements atomic percent accounts for 5%～50%.
A kind of used in proton exchange membrane fuel cell metal double polar plates of the present invention, the thickness that it is characterized in that said Titanium intermediate layer is between 0.2～5 micron; The thickness of the carbon-based films composite bed on the said Titanium intermediate layer is between 0.2～5 micron.
The preparation method of a kind of used in proton exchange membrane fuel cell metal double polar plates of the present invention; Comprise: cleaning of parent metal thin sheet surface and metal sheet surface modification are handled; Cleaning comprises passivating film and the impurity of removing the parent metal thin sheet surface to the parent metal thin sheet surface; The processing method that it is characterized in that said metal double polar plates surface modification treatment layer comprises with arc ion plating and multi-target magnetic control sputtering method; But be not limited to said method, in metal sheet surface plated metal titanium intermediate layer, deposit carbon basement membrane composite bed on the Titanium intermediate layer again.
The preparation method of a kind of used in proton exchange membrane fuel cell metal double polar plates of the present invention; It is characterized in that said on the Titanium intermediate layer deposit carbon basement membrane composite bed be that the Titanium intermediate layer to metal double polar plates is carried out titanium target and carbon target reaction magnetocontrol sputtering simultaneously in deposition vacuum chamber: titanium target 40W power; 0.25KV voltage, the 0.20A electric current is work down; Carbon target 80W power, 0.25KV voltage, the 0.40A electric current is work down; Time 30min.
The preparation method of a kind of used in proton exchange membrane fuel cell metal double polar plates of the present invention is characterized in that saidly on the Titanium intermediate layer, during deposit carbon basement membrane composite bed, with the reaction of carbon and titanium, generating titanium carbide.
The present invention has following advantage: the surface modification layer material of bipolar plates is main with carbon.Carbon is most widely used material among the PEMFC, catalyst carrier, diffusion layer and traditional pure graphite bi-polar plate, usefulness all be material with carbon element, the stability of carbon in PEMFC is by extensive confirmation.And bipolar plate surfaces carbon film and diffusion layer carbon paper are identical material, and contact resistance is expected to drop to low-down degree.Make bipolar plates have good electric conductivity, can significantly reduce the internal resistance of Proton Exchange Membrane Fuel Cells, improve cell output.
Secondly, the TiC in the surperficial carbon-coating helps to strengthen the adhesion between carbon-based films and titanium intermediate layer.TiC is on the basis in titanium intermediate layer, in the deposition process of surperficial carbon film, generates through reaction.Therefore between TiC and titanium layer there be good the combination, and carbon is had " rivet " effect, make surperficial carbon-coating difficult drop-off.Excellent properties such as that TiC has is high temperature resistant, anti-oxidant, intensity is high, thermal conductivity is good.Conductivity that TiC is good and the decay resistance under simulation PEMFC environment are proved.Therefore, a small amount of TiC in the carbon-based films can significantly strengthen the stability of compound structure film and not influence serviceability.
The 3rd, to have certain thickness Titanium as the intermediate layer.Titanium itself has the very strong anti-strong acid and the ability of alkali corrosion.Research shows, adopts corrosion resistant intermediate layer material can improve the decay resistance of whole bipolar plates.Titanium is captured the very capable of oxygen, is prone to generate the oxide film of one deck densification as thin as a wafer on the titanium surface, and the effect that can resist strong acid even chloroazotic acid shows strong corrosion resistance.Therefore, even the top layer carbon-base film is damaged, the titanium that exposes also can generate diaphragm naturally, prevents to corrode further generation.Have the multilayer protective effect is arranged, protective layer can remedy mutually, thus the useful life of significant prolongation bipolar plates.
The 4th, lower cost for material helps to reduce the cost of whole fuel cell system, improves whole competitiveness.
Description of drawings
The present invention has accompanying drawing 1 width of cloth, is the structural representation of bipolar plates of the present invention, in the accompanying drawing, and 1, the bipolar plates matrix, 2, the Titanium intermediate layer, 3, the carbon-based films composite bed, 4, the Titanium in the carbon-based films composite bed, 5, the titanium carbide in the carbon-based films composite bed.
Embodiment
Embodiment 1
Embodiment 1 is that the surface modification layer thickness is the pure titanium bipolar plates of 3mm.On pure titanium bipolar plates, prepare modified layer through magnetron sputtering technique.Modified layer is respectively Titanium intermediate layer 2 and carbon-based films composite bed 3, in carbon-based films composite bed 3, contains Titanium particle 4 and titanium carbide granule 5.When preparing this modified layer, 6 symmetrical target position are arranged in the magnetron sputtering apparatus, 3 titanium targets and 3 carbon targets are respectively relatively.In the film forming procedure, revolve round the sun around vacuum chamber when being plated the sample rotation.Titanium target and carbon target purity are 99.99%, and thickness is 40mm, and diameter is 80mm.The bipolar plates matrix that will be of a size of 100mm * 100mm * 1.0mm is clipped on the hanger.After the vacuum chamber sealing, be evacuated to 2Pa, be evacuated to 3 * 10 with molecular pump then with mechanical pump -3Pa.At 100 ℃, 40W power, 0.25KV voltage, the titanium target carries out reaction magnetocontrol sputtering under the 0.20A electric current, and the time is 30min.This moment, Titanium intermediate layer 2 thickness were 1 micron.Then at 100 ℃, titanium target and carbon target carry out reaction magnetocontrol sputtering simultaneously: titanium target 40W power, and 0.25KV voltage, the 0.20A electric current is work down; Carbon target 80W power, 0.25KV voltage, the 0.40A electric current is work down; Time 30min, this moment, carbon-based films composite bed 3 thickness were 2 microns.The cooling back is taken out and had both been obtained the bipolar plates that the surface has the carbon-based films composite bed.
Embodiment 2
Embodiment 2 is that the surface modification layer thickness is the titanium alloy bipolar plates of 3mm.On the titanium alloy bipolar plates, prepare modified layer through magnetron sputtering technique.Modified layer is respectively Titanium intermediate layer 2 and carbon-based films composite bed 3, in carbon-based films composite bed 3, contains Titanium particle 4 and titanium carbide granule 5.When preparing this modified layer, on the titanium alloy bipolar plates, prepare modified layer through ion plating technique.6 symmetrical target position are arranged in the equipment, and 3 titanium targets and 3 carbon targets are respectively relatively.In the film forming procedure, revolve round the sun around vacuum chamber when being plated the sample rotation.Titanium target and carbon target purity are 99.99%, and thickness is 40mm, and diameter is 80mm.The bipolar plates matrix that will be of a size of 100mm * 100mm * 1.0mm is clipped on the hanger.After the vacuum chamber sealing, be evacuated to 2Pa, be evacuated to 3 * 10-3Pa with molecular pump then with mechanical pump.At 100 ℃, 60W power, 0.25KV voltage, the titanium target carries out reaction magnetocontrol sputtering under the 0.20A electric current, and the time is 10min.This moment, Titanium intermediate layer 2 thickness were 0.5 micron.Then at 100 ℃, titanium target and carbon target carry out reaction magnetocontrol sputtering simultaneously: titanium target 60W power, and 0.25KV voltage, the 0.20A electric current is work down; Carbon target 100W power, 0.25KV voltage, the 0.40A electric current is work down; Time 60min, this moment, carbon-based films composite bed 3 thickness were 1.5 microns.The cooling back is taken out and had both been obtained to show the bipolar plates with carbon-based films composite bed.

Claims (6)

1. used in proton exchange membrane fuel cell metal double polar plates; There is modified layer on the metal double polar plates surface; Surface reforming layer comprises the Titanium intermediate layer (2) with metal substrate (1) adjacency; It is characterized in that said metal double polar plates surface reforming layer also comprises the carbon-based films composite bed (3) on the Titanium intermediate layer (2), the carbon-based films composite bed (3) on the said Titanium intermediate layer (2) is the carbon-based films composite bed that carbon, titanium carbide (5) and Titanium (4) mix.
2. a kind of used in proton exchange membrane fuel cell metal double polar plates according to claim 1; It is characterized in that in the carbon-based films composite bed (3) on the said Titanium intermediate layer (2); The carbon atomic percent accounts for 50%～95%, and the titanium elements atomic percent accounts for 5%～50%.
3. a kind of used in proton exchange membrane fuel cell metal double polar plates according to claim 2, the thickness that it is characterized in that said Titanium intermediate layer (2) is between 0.2～5 micron; The thickness of the carbon-based films composite bed (3) on the said Titanium intermediate layer (2) is between 0.2～5 micron.
4. the preparation method of the described a kind of used in proton exchange membrane fuel cell metal double polar plates of claim 1; Comprise: cleaning of parent metal thin sheet surface and metal sheet surface modification are handled; Cleaning comprises passivating film and the impurity of removing the parent metal thin sheet surface to the parent metal thin sheet surface; It is characterized in that processing method that said metal sheet surface modification is handled comprises with arc ion plating and multi-target magnetic control sputtering method in metal sheet surface plated metal titanium intermediate layer (2), again deposit carbon basement membrane composite bed (3) on the Titanium intermediate layer.
5. the preparation method of a kind of used in proton exchange membrane fuel cell metal double polar plates according to claim 4; It is characterized in that said on the Titanium intermediate layer deposit carbon basement membrane composite bed (3) be that the Titanium intermediate layer to metal double polar plates is carried out titanium target and carbon target reaction magnetocontrol sputtering simultaneously in deposition vacuum chamber: titanium target 40W power; 0.25KV voltage, the 0.20A electric current is work down; Carbon target 80W power, 0.25KV voltage, the 0.40A electric current is work down; Time 30min.
6. the preparation method of a kind of used in proton exchange membrane fuel cell metal double polar plates according to claim 5 is characterized in that saidly on the Titanium intermediate layer, during deposit carbon basement membrane composite bed (3), with the reaction of carbon and titanium, generating titanium carbide.
CN2010101440138A 2010-04-09 2010-04-09 Metal bipolar plate for proton exchange membrane fuel cell and preparation method thereof Active CN101800318B (en)

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CN102074708A (en) * 2010-12-14 2011-05-25 天津理工大学 Boron-doping diamond film modification-based PEMFC (Proton Exchange Membrane Fuel Cell) bipolar plate and preparation method thereof
CN105322184B (en) * 2014-07-07 2018-06-22 江苏冰城氢能科技有限公司 The preparation process of used in proton exchange membrane fuel cell metal double polar plates
CN105261769B (en) * 2014-07-14 2017-10-03 江苏冰城电材股份有限公司 Hydrogen power supply based on metal double polar plates
CN106637112B (en) * 2016-11-16 2019-01-18 上海交通大学 Horizontal magnetic control sputtering system and coating process for fuel battery metal double polar plate
CN106887599B (en) * 2017-01-20 2020-01-24 大连理工大学 Long-life bipolar plate of fuel cell with surface titanium palladium carbon film and preparation method thereof
CN106887600B (en) * 2017-01-20 2020-01-24 大连理工大学 High-performance bipolar plate of fuel cell with titanium tantalum carbon film on surface and preparation method thereof
CN106784916B (en) * 2017-01-20 2020-04-07 大连理工大学 Long-life bipolar plate of fuel cell with surface titanium-molybdenum-nickel-carbon film and preparation method thereof
CN109728307A (en) * 2017-10-27 2019-05-07 中国科学院大连化学物理研究所 A kind of preparation and bipolar plates and application of the metal double polar plates based on carbon film modification
EP3604606A1 (en) 2018-08-02 2020-02-05 Centre de Recherches Métallurgiques ASBL - Centrum voor Research in de Metallurgie VZW Coating for reducing the contact resistance of a passive metal substrate prior to application of a conductive layer providing corrosion resistance
CN109755592B (en) * 2018-12-26 2023-10-27 浙江锋源氢能科技有限公司 Metal bipolar plate, preparation method thereof and fuel cell
CN110707340B (en) * 2019-09-27 2022-07-15 佛山科学技术学院 Composite multilayer corrosion-resistant film and application thereof
CN111146465B (en) * 2019-12-19 2022-04-08 南京理工大学 Method for improving corrosion resistance of titanium-based bipolar plate of proton exchange membrane fuel cell
CN114277344A (en) * 2021-11-16 2022-04-05 中国船舶重工集团公司第七二五研究所 Preparation method of titanium-based fuel cell bipolar plate coating
WO2023222930A1 (en) 2022-05-17 2023-11-23 Universidad Carlos Iii De Madrid Bipolar plate of a proton-exchange membrane fuel cell and methods of manufacturing same

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JP3908359B2 (en) * 1997-10-21 2007-04-25 日新製鋼株式会社 Low temperature fuel cell separator
CN101604756B (en) * 2008-06-11 2011-05-18 财团法人工业技术研究院 Bipolar plate and fuel cell
CN201717318U (en) * 2010-04-09 2011-01-19 新源动力股份有限公司 Metal bipolar plate for proton exchange membrane fuel cell

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