CN102364738A - Polymeric electrolyte membrane fuel cell bulk metallic glass bipolar plate and manufacturing method thereof - Google Patents

Polymeric electrolyte membrane fuel cell bulk metallic glass bipolar plate and manufacturing method thereof Download PDF

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Publication number
CN102364738A
CN102364738A CN201110361563XA CN201110361563A CN102364738A CN 102364738 A CN102364738 A CN 102364738A CN 201110361563X A CN201110361563X A CN 201110361563XA CN 201110361563 A CN201110361563 A CN 201110361563A CN 102364738 A CN102364738 A CN 102364738A
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fuel cell
metallic glass
bulk metallic
dielectric film
zirconium
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CN102364738B (en
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田如锦
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Dalian Jiaotong University
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Dalian Jiaotong University
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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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Abstract

The invention discloses a polymeric electrolyte membrane fuel cell bulk metallic glass bipolar plate and a manufacturing method thereof. Materials are prepared according to a required atomic moore proportion of a composition formula, namely Zr60-xNbxCu20Al10Ni10 (x is equal to a value ranging from 0 to 20). A mother alloy ingot is smelted by electric arc under the protection of argon; and the mother alloy ingot is re-smelted for at least three times, so that the chemical uniformity can be guaranteed. Current of a vacuum electric arc furnace is 150 to 250 amperes; and a zirconium-base bulk metallic glass plate with a thickness of between 0.1 and 3 millimeters is cast and formed by a Cu die. The purity of elements, namely Zr, Nb, Cu, Ni and Al is more than or equal to 99.95 weight percent; the zirconium-base bulk metallic glass at least contains 95 vol percent of amorphous phase; a corrosion speed is lower than 16 mu A per square centimeters; and the conductivity is more than 5,000 S per centimeters. The polymeric electrolyte membrane fuel cell bulk metallic glass bipolar plate has higher conductivity and high corrosion resistance, and the cost can be reduced greatly; and the polymeric electrolyte membrane fuel cell bulk metallic glass bipolar plate can be applied to the field of manufacturing of fuel cells.

Description

Polymer dielectric film fuel cell blocky metal-glass bipolar plates and method for making thereof
Technical field
The invention belongs to the fuel cell electrode technical field.Be particularly related to the bipolar plates of polymer dielectric film fuel cell.
Background technology
Except having characteristics such as energy conversion efficiency height, life-span length, environmental friendliness, polymer dielectric film fuel cell is low because of its working temperature, startup as the power source in communications and transportation and construction dispersion power station, is the general removable power supplys of a kind of the army and the people soon.Yet, factor such as expensive, weight and volume to a great extent limit the large-scale commercial applications application of polymer dielectric film fuel cell.Therefore, reduce cost and become national governments and researcher's the focus of attention.
Bipolar plates is one of multifunctional module important in the polymer dielectric film fuel cell; Not only have the reacting gas of separation, afflux conduction, support membrane electrode and conductive force; Can also passage be provided so that it is evenly distributed through being combined into reacting gas, and the water that generates is discharged with flow-field plate.Graphite has good electrical conductivity and chemical stability, is considered to desirable polymer dielectric film fuel cell bipolar plate material always.But its fragility is big, the low fuel battery that is difficult to prepare low weight, low volume of intensity.In addition, consuming time and expense is high through machining mode in the technology in various flow fields, surface, thus cause the cost of graphite cake to account for 80% of Proton Exchange Membrane Fuel Cells cost.Metal material is because of the potential replacement graphite of good obdurability, conductivity and air-tightness.Metal not only can be processed into the thin plate that thickness is 0.1～0.3mm; Can also adopt the method for machining and punching press to be processed into various flow-field plate; Be more suitable in production in enormous quantities, and then the quality that increases substantially polymer dielectric film fuel cell 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.
In the process of polymer dielectric film fuel cell operation, because the peculiar preparation technology of degraded of the part of PEM and electrode causes containing in the operational environment SO 4 2-, SO 3 2-, CO 3 2-, HSO 4 -And HSO 3 -Plasma [1]Therefore, electrochemical corrosion will take place in metal double polar plates inevitably.Although the oxide skin(coating) of the passivation that the metal double polar plates surface generates can suppress the further corrosion of metal, also caused simultaneously to be difficult to satisfy the actual high surface contacted resistance that requires [2-4]All of these factors taken together 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.Adopt PVD [5-10], CVD [11-13]And plating [14,15]Then generate defectives such as the micropore that is difficult to avoid and micro-crack and can peel off Deng the nitride of diverse ways preparation and oxide coating, thereby cause the reduction in useful life of polymer dielectric film fuel cell because of local corrosion because of its preparation technology's restriction.Up to the present, also do not have a kind ofly to be able to large-scale application market through the surface-treated metal double polar plates.Therefore, the bipolar plates of development low cost, high surface conductivity and good corrosion resistance 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.
List of references
[1]Li?Y，Meng?W，Swathirajan?S，Harris?S，et?al.US?Patent?5624769，20?April1997.
[2]Scholta?J，Rohland?B，Garche?J.Proceedings?of?the?Second?International?Symposium?on?New?Materials?for?Fuel?Cell?and?Modern?Battery?Systems，Ecole?Polytechnique?de?Montreal，Canada，1997，p330-334.
[3]Davies?D?P，Adcock?P?L，Turpin?M，et?al.J.Appl.Electrochem.2000，30：101-105.
[4]Hentall?P?L，Barry?L，Mepsted?Gary?O.J.Power?Sources?1999，80：235-241.
[5]Ma?L，Warthesen?S，Shores?D?A.J.New?Mater.Electrochem.Syst.2000，3：221-228.
[6]Li?M，Luo?S，Zeng?C，et?al.Corros.Sci.2004，46：1369-1380.
[7]Cho?E?A，Jeon?U.-S，Hong?S.-A，et?al.J.Power?Sources?2005，142：177-183.
[8]Wang?Y，Northwood?D.O.Int.J.Hydrogen?Energy?2007，32：895-902.
[9]Wang?Y，Northwood?D.O.J.Power?Sources?2007，165：293-298.
[10]Jeon?W.-S，Kim?J.-G，Kim?Y.-J，et?al.Thin?Solid?Films?2008，516：3669-3672.
[11]Wang?H，Turner?J?A.J.Power?Sources?2007，170：387-394.
[12]Wang?H，Turner?J?A，Lin?X，et?al.J.Power?Sources?2007，171：567-574.
[13]Wang?H，Turner?J?A，Lin?X，et?al.J.Power?Sources?2008，178(2008)：238-274.
[14]Lee?S-J，Lai?J-J，Huang?C-H.J.Power?Sources?2005，145：362-368.
[15]Lee?S-J，Huang?C-H，Lai?J-J，et?al.J.Power?Sources?2004，131：162-168.
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 polymer dielectric film fuel cell blocky metal-glass bipolar plates of mass market application requirements and preparation method thereof.
In order to achieve the above object, the present invention adopts following technical scheme:
Polymer dielectric film fuel cell zirconium matrix shape metal glass bipolar plates provided by the present invention, thickness is 0.1～3mm.Zirconium matrix shape metal glass is a constituent element with zirconium, niobium, copper, nickel and aluminium, and it forms formula: Zr 60-xNb xCu 20Al 10Ni 10(x=0-20).The purity of each element Zr, Nb, Cu, Ni, Al raw material all is not less than 99.95wt% (percentage by weight).Described zirconium matrix shape metal glass contains the amorphous phase of 95vol% (percent by volume) at least.Corrosion rate is lower than 10 μ A/cm 2When pressure is 150～250N/cm 2The time, contact resistance is lower than 10m Ω cm 2
The preparation method of zirconium matrix shape metal glass provided by the present invention comprises following step: according to forming formula Zr 60-xNb xCu 20Al 10Ni 10(x=0-20) needed atomic molar ratio batching.Master alloy ingot forms through electric arc melting under argon shield, and remelting 3 times is to guarantee its chemical uniformity at least.The vacuum arc furnace ignition electric current is 150～250A.Adopt the Cu die cast to be prepared into the zirconium matrix shape metal glass sheet material that thickness is 0.1～3mm then.
Zirconium matrix shape metal glass bipolar plates advantage provided by the invention is: zirconium matrix shape metal glass can be applied to polymer dielectric film fuel cell bipolar plate material field.The required critical cooling rate of zirconium matrix shape metal glass of the present invention's preparation is low, and it is strong to suppress crystallizing power, is easier to form large-sized non-crystaline amorphous metal than additive method.Owing to have the supercooling liquid phase region of broad and higher glass transformation temperature and crystallization temperature, the thermal stability of zirconium matrix shape metal glass is higher, helps it and is able to use in higher temperature.Preparation zirconium matrix shape metal glass provided by the invention is to adopt more cheap common metal preparation, and preparation method's technology is simple, and low processing cost is easy to produce in batches thin metal glass bipolar plates.
This zirconium matrix shape metal glass has surface of good conductivity and higher corrosion resistance.Adopt zirconium matrix shape metal glass to replace traditional graphite to be expected to realize cost degradation significantly and the mass industrialized production and large-scale application market of polymer dielectric film fuel cell to have important and practical meanings for the extensive use of accelerating metal double polar plates of polymer electrolyte film fuel cell as bipolar plate material.
Embodiment
Embodiment 1
According to forming formula Zr 60-xNb xCu 20Al 10Ni 10(x=0) needed atomic molar ratio batching.The purity of each element Zr, Nb, Cu, Ni, Al raw material all is not less than 99.95wt%.Master alloy ingot forms through electric arc melting under argon shield, and remelting 3 times is to guarantee its chemical uniformity at least.The vacuum arc furnace ignition electric current is 150A.Adopt the Cu die cast to be prepared into the zirconium matrix shape metal glass sheet material that thickness is 0.1～3mm then.Anodic polarization curves and the constant potential polarization under the polymer dielectric film fuel cell condition of work are all at 0.05MH 2SO 4+ 2ppmF -Solution in carry out.For the operational environment of simulating polymer dielectric film fuel cell, all in solution, feed H in all electrochemistry experiment processes 2Or air.Corrosion rate is lower than 16 μ A/cm 2Conductivity is higher than 5000S/cm.
Embodiment 2
According to forming formula Zr 60-xNb xCu 20Al 10Ni 10(x=5) needed atomic molar ratio batching.The purity of each element Zr, Nb, Cu, Ni, Al raw material all is not less than 99.95wt%.Master alloy ingot forms through electric arc melting under argon shield, and remelting 3 times is to guarantee its chemical uniformity at least.The vacuum arc furnace ignition electric current is 150A.Adopt the Cu die cast to be prepared into the zirconium matrix shape metal glass sheet material that thickness is 0.1～3mm then.Anodic polarization curves and the constant potential polarization under the polymer dielectric film fuel cell condition of work are all at 0.05MH 2SO 4+ 2ppmF -Solution in carry out.For the operational environment of simulating polymer dielectric film fuel cell, all in solution, feed H in all electrochemistry experiment processes 2Or air.Corrosion rate is lower than 16 μ A/cm 2Conductivity is higher than 5000S/cm.
Embodiment 3
According to forming formula Zr 60-xNb xCu 20Al 10Ni 10(x=15) needed atomic molar ratio batching.The purity of each element Zr, Nb, Cu, Ni, Al raw material all is not less than 99.95wt%.Master alloy ingot forms through electric arc melting under argon shield, and remelting 3 times is to guarantee its chemical uniformity at least.The vacuum arc furnace ignition electric current is 200A.Adopt the Cu die cast to be prepared into the zirconium matrix shape metal glass sheet material that thickness is 0.1～3mm then.Anodic polarization curves and the constant potential polarization under the polymer dielectric film fuel cell condition of work are all at 1MH 2SO 4+ 2ppmF -Solution in carry out.For the operational environment of simulating polymer dielectric film fuel cell, all in solution, feed H in all electrochemistry experiment processes 2Or air.Corrosion rate is lower than 10 μ A/cm 2Conductivity is higher than 5000S/cm.
Embodiment 4
According to forming formula Zr 60-xNb xCu 20Al 10Ni 10(x=20) needed atomic molar ratio batching.The purity of each element Zr, Nb, Cu, Ni, Al raw material all is not less than 99.95wt%.Master alloy ingot forms through electric arc melting under argon shield, and remelting 3 times is to guarantee its chemical uniformity at least.The vacuum arc furnace ignition electric current is 250A.Adopt the Cu die cast to be prepared into the zirconium matrix shape metal glass sheet material that thickness is 0.1～3mm then.Anodic polarization curves and the constant potential polarization under the polymer dielectric film fuel cell condition of work are all at 1MH 2SO 4+ 2ppmF -+ 0.01M CH 3The 1M H of OH and bubbling air 2SO 4+ 2ppmF -+ 1MCH 3Carry out in the solution of OH.Corrosion rate is lower than 10 μ A/cm 2Conductivity is higher than 5000S/cm.

Claims (3)

1. polymer dielectric film fuel cell blocky metal-glass bipolar plates.It is characterized in that thickness is 0.1～3.0mm, zirconium matrix shape metal glass is a constituent element with zirconium, niobium, copper, nickel and aluminium, and it forms formula: Zr 60-xNb xCu 20Al 10Ni 10, x=0-20 wherein; The purity of each element Zr, Nb, Cu, Ni, Al raw material all is not less than 99.95wt%, and zirconium matrix shape metal glass contains the amorphous phase of 95vol% at least; Corrosion rate is lower than 16 μ A/cm 2Conductivity is higher than 5000S/cm.
2. the method for making of polymer dielectric film fuel cell blocky metal-glass bipolar plates according to claim 1 is characterized in that preparing with following technology: according to forming formula Zr 60-xNb xCu 20Al 10Ni 10(x=0-20) needed atomic molar ratio batching.Master alloy ingot forms through vacuum arc furnace melting under argon shield, and remelting 3 times is to guarantee its chemical uniformity at least; Adopt the Cu die cast to be prepared into the zirconium matrix shape metal glass sheet material that thickness is 0.1～3mm then.
3. according to the method for making of the said polymer dielectric film fuel cell blocky metal-glass of claim 2 bipolar plates, it is characterized in that the vacuum arc furnace ignition electric current is 150-250A.
CN201110361563XA 2011-11-15 2011-11-15 Polymeric electrolyte membrane fuel cell bulk metallic glass bipolar plate and manufacturing method thereof Expired - Fee Related CN102364738B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104521048B (en) * 2012-05-28 2017-02-22 株式会社中山非晶质 Separator material for solid polymer fuel cells having excellent corrosion resistance, conductivity and formability, and method for manufacturing same
CN108063269A (en) * 2017-12-29 2018-05-22 成都新柯力化工科技有限公司 It is a kind of using glassy metal as the fuel-cell catalyst and preparation method of carrier

Citations (1)

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Publication number Priority date Publication date Assignee Title
US20050109434A1 (en) * 2003-08-22 2005-05-26 Samsung Sdi Co., Ltd. Separator for fuel cell

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
US20050109434A1 (en) * 2003-08-22 2005-05-26 Samsung Sdi Co., Ltd. Separator for fuel cell

Non-Patent Citations (1)

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Title
柳林等: "Zr－Cu－Ni－Al－Nb大块非晶合金的晶化行为、力学性能及电化学腐蚀行为的研究", 《物理学报》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104521048B (en) * 2012-05-28 2017-02-22 株式会社中山非晶质 Separator material for solid polymer fuel cells having excellent corrosion resistance, conductivity and formability, and method for manufacturing same
US9959950B2 (en) 2012-05-28 2018-05-01 Nakayama Amorphous Co., Ltd. Thin plate having excellent corrosion resistance, conductivity and formability, and method for manufacturing same
US10032537B2 (en) 2012-05-28 2018-07-24 Nakayama Amorphous Co., Ltd. Separator material for polymer electrolyte fuel cell having excellent corrosion resistance, conductivity and formability, and method for manufacturing same
CN108063269A (en) * 2017-12-29 2018-05-22 成都新柯力化工科技有限公司 It is a kind of using glassy metal as the fuel-cell catalyst and preparation method of carrier

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