CN102364738B - 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

Info

Publication number
CN102364738B
CN102364738B CN201110361563XA CN201110361563A CN102364738B CN 102364738 B CN102364738 B CN 102364738B CN 201110361563X A CN201110361563X A CN 201110361563XA CN 201110361563 A CN201110361563 A CN 201110361563A CN 102364738 B CN102364738 B CN 102364738B
Authority
CN
China
Prior art keywords
fuel cell
metallic glass
bulk metallic
dielectric film
zirconium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201110361563XA
Other languages
Chinese (zh)
Other versions
CN102364738A (en
Inventor
田如锦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Jiaotong University
Original Assignee
Dalian Jiaotong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Jiaotong University filed Critical Dalian Jiaotong University
Priority to CN201110361563XA priority Critical patent/CN102364738B/en
Publication of CN102364738A publication Critical patent/CN102364738A/en
Application granted granted Critical
Publication of CN102364738B publication Critical patent/CN102364738B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Fuel Cell (AREA)

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
The characteristics such as energy conversion efficiency is high except having, life-span length, environmental friendliness, polymer dielectric film fuel cell is low because of its working temperature, start soon as communications and transportation and build the power source that disperses the power station, is the general movable power sources of a kind of the army and the people.Yet the factor such as expensive, weight and volume has limited the large-scale commercial applications application of polymer dielectric film fuel cell to a great extent.Therefore, reduce costs the focus of attention that becomes national governments and researcher.
Bipolar plates is one of multifunctional module important in polymer dielectric film fuel cell, not only have the reacting gas of separation, afflux conduction, support membrane electrode and conductive force, can also provide passage in order to it is evenly distributed by being combined into reacting gas with flow-field plate, and the water that generates is discharged.Graphite has good conductivity and chemical stability, is considered to desirable polymer dielectric film fuel cell bipolar plate material always.But its fragility is large, the low fuel cell unit that is difficult to prepare low weight, low volume of intensity.In addition, consuming time and expense is high in the technique in various flow fields, surface by machining mode, 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 plate 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 Partial digestion of proton exchange membrane and the peculiar preparation technology of electrode cause containing in operational environment SO 4 2-, SO 3 2-, CO 3 2-, HSO 4 -And HSO 3 -Plasma [1]Therefore, metal double polar plates is inevitably wanted electrochemical corrosion.Although the oxide skin(coating) of the passivation of metal double polar plates Surface Creation can suppress the further corrosion of metal, also caused the high surface contacted resistance that is difficult to satisfy actual requirement simultaneously [2-4]All of these factors taken together will certainly cause the consumption of some electric energy and the reduction of fuel cell unit gross efficiency, thereby reduces performance and the power stage of battery pack.For this reason, improve its surface conductivity and corrosion resistance by process for modifying surface preparation and the production of metal double polar plates is had great importance, also will produce far-reaching influence to development and the extensive use of polymer dielectric film fuel cell.Noble coatings is unsuitable for producing battery pack cheaply because its cost is high.Adopt PVD [5-10], CVD [11-13]And plating [14,15]Deng the nitride of diverse ways preparation and oxide coating generate because of its preparation technology's restriction the 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.Up to the present, also do not have a kind ofly to be able to large-scale market by the surface-treated metal double polar plates and to use.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 important impact 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 cheaply good conductivity, corrosion resistance, 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 can to achieve the above object, the present invention by the following technical solutions:
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 take zirconium, niobium, copper, nickel and aluminium as constituent element, 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.Then adopt the Cu die cast to be prepared into the zirconium matrix shape metal glass sheet material that thickness is 0.1～3mm.
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, suppresses crystallizing power strong, is easier to form large-sized non-crystaline amorphous metal than additive method.Owing to having wider supercooling liquid phase region and higher glass transformation temperature and crystallization temperature, the thermal stability of zirconium matrix shape metal glass is higher, is conducive to it and is used 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 technique is simple, and low processing cost is easy to produce in batches thin metal glass bipolar plates.
This zirconium matrix shape metal glass has good surface conductivity and higher corrosion resistance.Adopt zirconium matrix shape metal glass to replace traditional graphite to be expected to realize significantly cost degradation and mass industrialized production and the application of large-scale market of polymer dielectric film fuel cell as bipolar plate material, have important practical significance for the extensive use of accelerating metal double polar plates of polymer electrolyte film fuel cell.
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.Then adopt the Cu die cast to be prepared into the zirconium matrix shape metal glass sheet material that thickness is 0.1～3mm.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 pass into H in all electrochemistry experiment processes in solution 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.Then adopt the Cu die cast to be prepared into the zirconium matrix shape metal glass sheet material that thickness is 0.1～3mm.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 pass into H in all electrochemistry experiment processes in solution 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.Then adopt the Cu die cast to be prepared into the zirconium matrix shape metal glass sheet material that thickness is 0.1～3mm.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 pass into H in all electrochemistry experiment processes in solution 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.Then adopt the Cu die cast to be prepared into the zirconium matrix shape metal glass sheet material that thickness is 0.1～3mm.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 3OH and the 1M H that passes into 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, is characterized in that thickness is 0.1～3.0mm, and zirconium matrix shape metal glass is take zirconium, niobium, copper, nickel and aluminium as constituent element, 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 as claimed in claim 1, is characterized in that being prepared with following technique: 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; Then adopt the Cu die cast to be prepared into the zirconium matrix shape metal glass sheet material that thickness is 0.1～3mm.
3. the method for making of polymer dielectric film fuel cell blocky metal-glass bipolar plates according to claim 2, 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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110361563XA CN102364738B (en) 2011-11-15 2011-11-15 Polymeric electrolyte membrane fuel cell bulk metallic glass bipolar plate and manufacturing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110361563XA CN102364738B (en) 2011-11-15 2011-11-15 Polymeric electrolyte membrane fuel cell bulk metallic glass bipolar plate and manufacturing method thereof

Publications (2)

Publication Number Publication Date
CN102364738A CN102364738A (en) 2012-02-29
CN102364738B true CN102364738B (en) 2013-05-08

Family

ID=45691294

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110361563XA Expired - Fee Related CN102364738B (en) 2011-11-15 2011-11-15 Polymeric electrolyte membrane fuel cell bulk metallic glass bipolar plate and manufacturing method thereof

Country Status (1)

Country Link
CN (1) CN102364738B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5973790B2 (en) 2012-05-28 2016-08-23 株式会社中山アモルファス Thin plate excellent in corrosion resistance, conductivity and moldability, and method for producing the same
CN108063269B (en) * 2017-12-29 2018-12-07 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 of carrier and preparation method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050020380A (en) * 2003-08-22 2005-03-04 삼성에스디아이 주식회사 Materials for bipolar plate and other metal parts for fuel cell

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
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》.2006,第55卷(第4期),第1930-1935页. *

Also Published As

Publication number Publication date
CN102364738A (en) 2012-02-29

Similar Documents

Publication Publication Date Title
CN101800318B (en) Metal bipolar plate for proton exchange membrane fuel cell and preparation method thereof
CN101369667B (en) Metal double polar plates of polymer electrolyte film fuel cell and method of manufacturing the same
CN108914156B (en) Fe-Co-Mo-P-C amorphous alloy electrocatalyst and preparation method and application thereof
CN109023161A (en) A kind of Fe-Ni-P-C system amorphous alloy elctro-catalyst and its preparation method and application
CN109576679A (en) A kind of fuel battery double plates carbon coating continuous deposition system and its application
CN102290595A (en) All-solid state long-cycle life thin-film lithium cell and production method thereof
CN114481048B (en) High-conductivity corrosion-resistant amorphous/nanocrystalline composite coexisting coating and preparation method and application thereof
CN103510136B (en) A kind of method at ultra-fine tungsten wires surface electrical deposition of aluminum magnesium alloy film
CN102364738B (en) Polymeric electrolyte membrane fuel cell bulk metallic glass bipolar plate and manufacturing method thereof
CN107761060B (en) Surface corrosion-resistant conductive composite coating of metal polar plate for battery, metal polar plate for battery and preparation method of metal polar plate
CN115275213A (en) Composite current collector for lithium battery cathode and preparation method and application thereof
CN102629690B (en) Chromium nitride modified metal bipolar plate for fuel cells and manufacturing method thereof
CN100391663C (en) Process for preparing nano nickel powder
CN105332029A (en) Preparing method for electric-conduction and anti-corrosion cobalt and manganese spinel coating
CN106920977A (en) ITO/Nb composite modified metal double polar plates of polymer electrolyte film fuel cell and preparation method thereof
CN102637880B (en) Chromium carbide modified iron-based metal bipolar plate and preparation method thereof
CN101174687A (en) Production method for nickel oxide anode thin film used for full solid-state thin-film lithium ion battery
CN201717318U (en) Metal bipolar plate for proton exchange membrane fuel cell
CN101250705B (en) Method for manufacturing nickel-cuprum metallic baseband layer of highly oriented double-shaft texture
CN114695866B (en) Preparation method of double transition metal oxide negative electrode material of lithium ion battery
CN101369668B (en) Metal double polar plates of polymer electrolyte film fuel cell and method of manufacturing the same
CN1851967A (en) Metal double-polar board of solid polymer dielectric film fuel cell and making method therefor
CN101694879B (en) Mo-nitride-containing surface modification fuel cell stainless steel bipolar plate and manufacturing method thereof
CN112952130B (en) Metal bipolar plate with chromium nitride functional coating on surface and preparation method thereof
CN100382367C (en) Solid electrolyte membrane fuel cell metal bipolar plate containing nitrogen carbon surface and method for manufacturing same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130508

Termination date: 20151115

EXPY Termination of patent right or utility model