CN100442578C - A nanometer electro-catalyst for fuel cell and its manufacture method - Google Patents

A nanometer electro-catalyst for fuel cell and its manufacture method Download PDF

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CN100442578C
CN100442578C CNB200610135293XA CN200610135293A CN100442578C CN 100442578 C CN100442578 C CN 100442578C CN B200610135293X A CNB200610135293X A CN B200610135293XA CN 200610135293 A CN200610135293 A CN 200610135293A CN 100442578 C CN100442578 C CN 100442578C
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catalyst
fuel cell
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naoh
value
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CN1964115A (en
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廖代伟
符显珠
梁营
王新
林敬东
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Xiamen University
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Xiamen 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 preparation method for electric catalyst of fuel cell comprises: selecting 3-50nm nano Ni as core and thin Pt or PtRu as shell, wherein the rate between Ni and Pt or PtRu is 10:10~100; selecting the load capacity of Pt or PtRu on C carrier as 10-60%; preparing the glycol solution of NiSO4, NiCl2 or Ni(NO3)2; adding C carrier and N2H4, adjusting pH value by KOH or NaOH; adding glycol solution of HPtCl6 or mixture of HPtCl6 and RuCl3; adjusting pH value; separating, cleaning, and drying. This invention can improve noble metal utility and reduces cell cost.

Description

Nanometer electro-catalyst for fuel cell and preparation method thereof
Technical field
The present invention relates to a kind of fuel cell electro-catalyst, especially relating to a kind of is nuclear with nanometer Ni metal, and thin layer Pt or PtRu alloy noble metal are fuel cell electro-catalyst of shell and preparation method thereof.
Background technology
Environmental pollution and fossil energy exhaustion are to influence human survival and the very important problem of development at present.Because fuel cell is a kind ofly will be stored in the device that chemical energy in fuel and the oxidant directly changes electric energy into by electrochemical reaction, have incomparable advantages of traditional hot function source reforming unit such as energy conversion efficiency height and product be environmentally friendly, so the research and development of fuel cell are subjected to people and pay attention to greatly.When operation of fuel cells, be by eelctro-catalyst with the fuel in the anode (as H 2, N 2H 4, organic molecule such as sodium borohydride, methyl alcohol) and negative electrode in oxygen or H 2O 2Thereby carry out redox catalysis reaction respectively and provide electric energy Deng oxidant fluid, eelctro-catalyst is the very crucial material of fuel cell.In middle low-temperature fuel cell (as phosphoric acid type fuel cell, alkaline fuel cell, pem fuel and direct methanol fuel cell), in order to obtain preferable electro catalytic activity, generally use your eelctro-catalyst such as Pt base, be widely used as H as Pt 2Oxidation and O 2The eelctro-catalyst of reduction, the PtRu alloy has splendid anodic oxidation of methanol ability.Yet the Pt resource-constrained costs an arm and a leg, and makes the fuel cell cost high, seriously hinders its commercialization.Though reduce the catalyst based particle diameter of Pt and can effectively improve the catalyst based utilization ratio of Pt on the carrier such as carbon and reach about 40% with disperseing to be supported on, if but Pt base electricity greatly reduces electro catalytic activity when urging agent less than 2nm then be easy to stop up the micropore of carrier carbon and assemble because of particle size is easy to send out on the contrary.The top layer atom that during electrocatalytic reaction mainly is eelctro-catalyst plays effect, and inner precious metal atom does not play effect and wasted.(Zhao D such as Dan Zhao, Xu BQ ANGEWANDTE CHEMIE-INTERNATIONAL EDITION.2006,45 (30): 4955-4959) thin layer Pt is wrapped on the Au nuclear about 10nm, thereby obtained nearly 100%Pt utilization ratio, yet Au also is a noble metal, price is also somewhat expensive, and the degree that reduces the fuel cell cost is limited.
Summary of the invention
The object of the present invention is to provide a class can improve the catalysis utilance of noble metal, reduce the fuel cell cost, is nuclear with nanometer Ni metal, and thin layer Pt or PtRu alloy noble metal are nanometer electro-catalyst for fuel cell of shell and preparation method thereof.
Technical scheme of the present invention is to coat the layer of precious metal that has only several atomic layers on nano level base metal particle, fully allows the noble metal catalyst atom be distributed in the surface.
The composition and the content thereof of nanometer electro-catalyst for fuel cell of the present invention are as follows:
Catalyst consist of C, Ni, Pt or C, Ni, PtRu, Ni karyosome footpath size is 3～50nm, be 100 by the content of mass ratio Ni and shell Pt or PtRu: (10～100), Pt or the PtRu load capacity on the C carrier is 10%～60%.
Pt in the composition of catalyst: Ru=1: 1.
Its step of nanometer electro-catalyst for fuel cell preparation method of the present invention is as follows:
1. prepare NiSO 4, NiCl 2Or Ni (NO 3) 2Ethylene glycol solution 200mL;
2. add carbon carrier 0.025～2.5g, and abundant mixing;
3. add 5～20g N 2H 4
4. the pH value with KOH or NaOH adjustment system is 10～13;
5. add HPtCl 6Or HPtCl 6With RuCl 3Ethylene glycol solution 20～the 200mL that mixes;
6. the pH value with KOH or NaOH adjustment system is 9～13;
7. reaction finishes the back centrifugation and washing of precipitate, the oven dry that obtains is promptly obtained product.
In step 1, NiSO 4, NiCl 2Or Ni (NO 3) 2Concentration be 1～100 * 10 -3M.
In step 3, N 2H 4Concentration be 50%.
In step 4, the concentration of KOH or NaOH is 1M, and the temperature of adjusting the pH value of system with KOH or NaOH is preferably 30～90 ℃, and adds the N of 5～20g concentration 50% behind stirring reaction 0.5～5h 2H 4
In step 5, MHPtCl 6Or HPtCl 6With RuCl 3Concentration be 1～100 * 10 -3M.
In step 6, the concentration of KOH or NaOH is 1M, and the temperature of adjusting the pH value of system with KOH or NaOH is preferably 30～90 ℃, and stirring reaction 0.5～5h.
Because the present invention is a nuclear with nanometer Ni metal, thin layer Pt or PtRu alloy noble metal are shell, promptly on nano level base metal particle, coat the layer of precious metal that has only several atomic layers, fully allow the noble metal catalyst atom be distributed in the surface, therefore can improve the catalysis utilance of noble metal, reduce the fuel cell cost.The eelctro-catalyst NP1 (seeing specific embodiment) that as Ni: Pt is 10: 1 is 315mA/mgPt to the catalytic activity of methyl alcohol, far above the 61mA/mgPt of pure Pt eelctro-catalyst contrast sample.
Embodiment
Embodiment 1
Preparation 1 * 10 -3M NiSO 4Ethylene glycol solution 200mL, add Carbot VC-72R carbon carrier 0.025g, and abundant mixing, add N again 2H 4(50%) 5g is 12 with the KOH of 1M or the pH value of NaOH adjustment system, adds N behind 90 ℃ of following stirring reaction 5h 2H 4(50%) 5g and 1 * 10 -3MHPtCl 6Ethylene glycol solution 20mL, the pH value of adjusting system with the NaOH of 1M is 12, continuation is at 90 ℃ of following stirring reaction 5h, and reaction finishes the back centrifugation and the clean vacuum drying of the washing of precipitate that obtains is promptly obtained carbon that to carry Pt and Ni ratio be 1: 10 nucleocapsid structure eelctro-catalyst product, sample note NP1.
Embodiment 2
Preparation 10 * 10 -3MNiCl 2Ethylene glycol solution 200mL, add Carbot VC-72R carbon carrier 0.25g, and abundant mixing, add N again 2H 4(50%) 10g is 11 with the KOH of 1M or the pH value of NaOH adjustment system, adds N behind 80 ℃ of following stirring reaction 3h 2H 4(50%) 10g and 10 * 10 -3MHPtCl 6Ethylene glycol solution 40mL, the pH value of adjusting system with the KOH of 1M is 11, continuation is at 80 ℃ of following stirring reaction 3h, and reaction finishes the back centrifugation and the clean vacuum drying of the washing of precipitate that obtains is promptly obtained carbon that to carry Pt and Ni ratio be 2: 10 nucleocapsid structure eelctro-catalyst product, sample note NP2.
Embodiment 3
Preparation 50 * 10 -3M Ni (NO 3) 2Ethylene glycol solution 200mL, add Carbot VC-72R carbon carrier 1g, and abundant mixing, add N again 2H 4(50%) 20g, the pH value of adjusting system with the NaOH of 1M is 12, adds N behind 60 ℃ of following stirring reaction 2h 2H 4(50%) 20g and 50 * 10 -3MHPtCl 6Ethylene glycol solution 100mL, the pH value of adjusting system with the KOH of 1M is 12, continuation is at 60 ℃ of following stirring reaction 2h, and reaction finishes the back centrifugation and the clean vacuum drying of the washing of precipitate that obtains is promptly obtained carbon that to carry Pt and Ni ratio be 5: 10 nucleocapsid structure eelctro-catalyst product, sample note NP3.
Embodiment 4
Preparation 100 * 10 -3M NiCl 2Ethylene glycol solution 200mL, add Carbot VC-72R carbon carrier 2.5g, and abundant mixing, add N again 2H 4(50%) 20g, the pH value of adjusting system with the NaOH of 1M is 13, adds N behind 30 ℃ of following stirring reaction 0.5h 2H 4(50%) 20g and 100 * 10 -3MHPtCl 6Ethylene glycol solution 200mL, the pH value of adjusting system with the KOH of 1M is 13, continuation is at 30 ℃ of following stirring reaction 0.5h, and reaction finishes the back centrifugation and the clean vacuum drying of the washing of precipitate that obtains is promptly obtained carbon that to carry Pt and Ni ratio be 10: 10 nucleocapsid structure eelctro-catalyst product, sample note NP4.
Embodiment 5
Preparation 10 * 10 -3M NiCl 2Ethylene glycol solution 200mL, add Carbot VC-72R carbon carrier 0.2g, and abundant mixing, add N again 2H 4(50%) 10g, the pH value of adjusting system with the NaOH of 1M is 11.5, adds N behind 60 ℃ of following stirring reaction 0.5h 2H 4(50%) 10g and 5 * 10 -3MHPtCl 6And RuCl 3Ethylene glycol solution 20mL, the pH value of adjusting system with the KOH of 1M is 11.5, continuation is at 30 ℃ of following stirring reaction 0.5h, reaction finishes the back centrifugation and the clean vacuum drying of the washing of precipitate that obtains is promptly obtained carbon that to carry PtRu and Ni ratio be 1: 10 nucleocapsid structure eelctro-catalyst product, and sample is designated as NP5.
Reference
0.025g5g Carbot VC-72R carbon carrier is added 1 * 10 -3MHPtCl 6Ethylene glycol solution 20mL, add the N of 5g again 2H 4(50%), the pH value of adjusting system with the NaOH of 1M is 12, and at 90 ℃ of following stirring reaction 5h, reaction finishes centrifugation afterwards and the clean vacuum drying of the washing of precipitate that obtains is promptly obtained carbon to carry Pt eelctro-catalyst reference, and sample is designated as NP (seeing table).
The sample name NP NP1 NP2 NP3 NP4 NP5
Catalytic activity (mA/mgPt) 61 315 287 239 186 412

Claims (6)

1. nanometer electro-catalyst for fuel cell, it is characterized in that it consists of C, Ni, Pt or C, Ni, PtRu, Ni karyosome footpath size is 3～50nm, and be 100 by the content of mass ratio Ni and shell Pt or PtRu: (10～100), Pt or the PtRu load capacity on the C carrier is 10%～60%.
2. nanometer electro-catalyst for fuel cell as claimed in claim 1 is characterized in that Pt in the composition of catalyst: Ru=1: 1.
3. nanometer electro-catalyst for fuel cell preparation method as claimed in claim 1 is characterized in that its step is as follows:
1) preparation NiSO 4, NiCl 2Or Ni (NO 3) 2Ethylene glycol solution 200mL;
2) add carbon carrier 0.025～2.5g, and abundant mixing;
3) adding 5～20g concentration is 50% N 2H 4
4) the pH value of adjusting system with KOH or NaOH is 10～13, adds 5～20g concentration behind stirring reaction 0.5～5h and be 50% N 2H 4
5) add H 2PtCl 6Or H 2PtCl 6With RuCl 3Ethylene glycol solution 20～the 200mL that mixes, H 2PtCl 6Or H 2PtCl 6With RuCl 3Concentration be 1 * 10 -3M～100 * 10 -3M;
6) the pH value with KOH or NaOH adjustment system is 9～13, stirring reaction 0.5～5h;
7) reaction finishes the back centrifugation and washing of precipitate, the vacuum drying that obtains is promptly obtained product.
4. nanometer electro-catalyst for fuel cell preparation method as claimed in claim 3 is characterized in that in step 1 NiSO 4, NiCl 2Or Ni (NO 3) 2Concentration be 1 * 10 -3M～100 * 10 -3M.
5. nanometer electro-catalyst for fuel cell preparation method as claimed in claim 3 is characterized in that in step 4, and the concentration of KOH or NaOH is 1M, and the temperature of adjusting the pH value of system with KOH or NaOH is 30～90 ℃.
6. nanometer electro-catalyst for fuel cell preparation method as claimed in claim 3 is characterized in that in step 6, and the concentration of KOH or NaOH is 1M, and the temperature of adjusting the pH value of system with KOH or NaOH is 30～90 ℃.
CNB200610135293XA 2006-12-06 2006-12-06 A nanometer electro-catalyst for fuel cell and its manufacture method Expired - Fee Related CN100442578C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8236462B2 (en) * 2008-01-28 2012-08-07 Toyota Jidosha Kabushiki Kaisha Electrode catalyst for fuel cell, method for producing the electrode catalyst, and polymer electrolyte fuel cell using the electrode catalyst
US20130084385A1 (en) * 2010-06-13 2013-04-04 Mingjie Zhou Method for producing core-shell magnetic alloy nanoparticle
US10505197B2 (en) 2011-03-11 2019-12-10 Audi Ag Unitized electrode assembly with high equivalent weight ionomer
US20150255798A1 (en) * 2012-10-22 2015-09-10 United Technologies Corporation Platinum alloy nano catalyst with a non-platinum core
CN103861584A (en) * 2012-12-11 2014-06-18 浙江海洋学院 Preparation method of binary palladium-platinum core-shell oxygen reduction catalyst with high catalytic activity
JP2016507611A (en) 2012-12-21 2016-03-10 トヨタ自動車株式会社 Proton exchange material and method for producing the same
WO2014098910A1 (en) 2012-12-21 2014-06-26 United Technologies Corporation Electrolyte membrane, dispersion and method therefor
WO2014098907A1 (en) 2012-12-21 2014-06-26 Utc Power Corporation Method of fabricating an electrolyte material
CN103285880B (en) * 2013-05-28 2015-09-16 浙江科技学院 A kind of preparation method of catalyst of fuel batter with proton exchange film
CN104037427B (en) * 2014-06-26 2016-01-20 大连交通大学 A kind of preparation method of high active core shell structure catalyst and application thereof
CN104646026B (en) * 2015-02-11 2016-03-30 青岛大学 The three-dimensional composite catalyst of a kind of hollow core-shell PtNi/ Graphene and preparation method
CN110911700B (en) * 2019-11-21 2020-12-04 深圳氢时代新能源科技有限公司 Catalyst, preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1524711A2 (en) * 2003-10-06 2005-04-20 Nissan Motor Co., Ltd. Electrode catalyst for fuel cell and method for production thereof
CN1783559A (en) * 2004-10-28 2006-06-07 三星Sdi株式会社 Catalyst for fuel cell,method for preparing the same,and membrane-electrode assembly and fuel cell system comprising same
US20060135359A1 (en) * 2004-12-22 2006-06-22 Radoslav Adzic Platinum- and platinum alloy-coated palladium and palladium alloy particles and uses thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1524711A2 (en) * 2003-10-06 2005-04-20 Nissan Motor Co., Ltd. Electrode catalyst for fuel cell and method for production thereof
CN1783559A (en) * 2004-10-28 2006-06-07 三星Sdi株式会社 Catalyst for fuel cell,method for preparing the same,and membrane-electrode assembly and fuel cell system comprising same
US20060135359A1 (en) * 2004-12-22 2006-06-22 Radoslav Adzic Platinum- and platinum alloy-coated palladium and palladium alloy particles and uses thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Effect of Ni addition over PtRu/C based electrocatalysts forfuel cell applications. M.V. Martinez-Huerta et al.Applied Catalysis B: Environmental,Vol.69 . 2006
Effect of Ni addition over PtRu/C based electrocatalysts forfuel cell applications. M.V. Martinez.Huerta et al.Applied Catalysis B: Environmental,Vol.69. 2006 *
Enhancement of Pt Utilization in Electrocatalystsby Using Gold Nanoparticles. Dan Zhao and Bo-Qing Xu.Angewandte Chemie International Edition,Vol.45 No.30. 2006
Enhancement of Pt Utilization in Electrocatalystsby Using Gold Nanoparticles. Dan Zhao and Bo.Qing Xu.Angewandte Chemie International Edition,Vol.45 No.30. 2006 *

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