CN1457112A - Alkaline fuel battery with hydrogen storage alloy as electric catalyst - Google Patents

Alkaline fuel battery with hydrogen storage alloy as electric catalyst Download PDF

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Publication number
CN1457112A
CN1457112A CN03130001A CN03130001A CN1457112A CN 1457112 A CN1457112 A CN 1457112A CN 03130001 A CN03130001 A CN 03130001A CN 03130001 A CN03130001 A CN 03130001A CN 1457112 A CN1457112 A CN 1457112A
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eelctro
bearing alloy
catalyst
hydrogen bearing
alkaline fuel
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CN03130001A
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CN1225048C (en
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胡伟康
高学平
宋德瑛
D·诺若斯
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Nankai University
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Nankai 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 electrocatalyst of anode of the invented battery is alloy with hydrogen stored and without containing noble metal. The electrocatalyst of cathode of the invented battery is ABO3 type of peroviskite structure without containing noble metal and metal oxide of AB2O4 type of spinel structure. The said hydrogen stored alloy is MmNi3.3sCO0.75Mn0.4Al0.3, Mn is mixed rare earth riching in lanthanum. The metal oxide is La1-xCaxMO3, M=Co, Mn or Fe. The new type battery possesses the features of low cost, stable performances applicable to electric devices and electric vehicle etc.

Description

Hydrogen bearing alloy is the alkaline fuel cell of eelctro-catalyst
Technical field
The present invention relates to alkaline fuel cell, it is that hydrogen bearing alloy is the alkaline fuel cell of eelctro-catalyst, particularly the used eelctro-catalyst of cell with hydrogen oxidizing electrode (anode) is not for containing the hydrogen bearing alloy of noble metal, and the used eelctro-catalyst of oxygen reduction electrode (negative electrode) is not for containing the perovskite structure ABO of noble metal 3Type and spinel structure AB 2O 4The metal oxide of type.
Background technology
Fuel cell is a kind of energy conversion device, and it can directly be converted into electric energy to fuel gas.Its advantage: pollution-free, the transformation efficiency height is not subjected to the restriction of Carnot cycle.Can be widely used in electric device and electronic equipment.In recent years, national governments, research institution and company have dropped into a large amount of man power and materials and have carried out correlative study and exploitation.
Fuel cell studies exploitation at present mainly concentrates on Proton Exchange Membrane Fuel Cells (PEMFC), Solid Oxide Fuel Cell (SOFC).This two classes membrane cell is respectively wanted characteristic, but also exists not enough: Proton Exchange Membrane Fuel Cells with regard to present technology, its cost height, and be subjected to the resource limit of noble metal platinum or ruthenium catalyst; Solid Oxide Fuel Cell need at high temperature be carried out.Alkaline fuel cell is to be made of hydroxide electrode (anode) and oxygen reduction electrode (negative electrode).Though also there is CO in alkaline fuel cell 2Poison responsively, but its advantage is also very outstanding: ionic conductivity height, energy conversion efficiency height, can adopt non-platinum eelctro-catalyst and not need expensive acid Nafion film.In the patent that discloses or authorize, Europe with regard to the electrode material application of the fuel cell of alkaline cyclic electrolysis plastidome patent (WO0209214), this patent main feature is that electrode structure adopts gas-liquid-solid or liquid-solid-liquid three phase boundary to help contacting of electrolyte and electro catalytic activity material.Two kinds of disclosed patents of electrocatalyst materials that can be used as the alkaline fuel cell oxygen reduction electrode are arranged at home at present.Chinese patent CN1396308A discloses the Mn oxide compound MnO that can make alkaline fuel cell oxygen reduction electrode eelctro-catalyst 2-Mn 3O 4-Mn 2O 3And preparation method thereof; CN1404178 A is disclosed to relate to a kind of two or more cocatalytic elements (Fe, Co, Ni, Cr, Mn, Pt/C oxygen reduction catalyst Ti) and preparation method thereof of containing.
Summary of the invention
Purpose of the present invention aims to provide the alkaline fuel cell that a kind of hydrogen bearing alloy is an eelctro-catalyst, can overcome the deficiencies in the prior art, and it is the novel low cost and the alkaline fuel cell of stable performance.Utilization of the present invention does not contain the eelctro-catalyst of the hydrogen bearing alloy of noble metal as the hydroxide electrode, and does not contain the eelctro-catalyst of the metal oxide of noble metal as oxygen reduction electrode.The present invention can be applicable to electric device, electronic equipment and motor vehicle etc. with the alkaline fuel cell of this eelctro-catalyst manufacturing.
The present invention includes and contain eelctro-catalyst hydroxide electrode, the oxygen reduction electrode that contains eelctro-catalyst, potassium hydroxide electrolyte and barrier film, the used eelctro-catalyst of described hydroxide electrode is not for containing the hydrogen bearing alloy of noble metal, the used eelctro-catalyst of described oxygen reduction electrode for do not contain noble metal metal oxide.Described hydrogen bearing alloy is rare-earth Ni-base AB 5Type, zirconium base or titanium base or rare-earth Ni-base Laves are AB mutually 2Type, or titanium is Ni-based or ferrotianium base AB type hydrogen storage alloy.Wherein, hydrogen bearing alloy general formula of the present invention is Mm (Ni-Co-Mn-Al) 5, Mm is norium, particularly MmNi 3.35Co 0.75Mn 04Al 0.3
Described metal oxide is perovskite structure ABO 3Type or spinel structure AB 2O 4Type.Wherein, metal oxide of the present invention is La 1-xCa xMO 3, M=Co, Mn or Fe, wherein 0＞x＞1.
Described hydroxide electrode comprises that electro-catalysis layer and gas diffusion layers constitute, and the electro-catalysis layer comprises hydrogen bearing alloy eelctro-catalyst, hydrophobicity polytetrafluoroethylene, Vulcan XC-72R carbon hydroaropic substance, conductive matrices.
Described oxygen reduction electrode comprises that electro-catalysis layer and gas diffusion layers constitute, and the electro-catalysis layer comprises metal oxide eelctro-catalyst, hydrophobicity polytetrafluoroethylene, Vulcan XC-72R carbon hydroaropic substance, conductive matrices.
Above-mentioned gas diffusion layers is made up of carbon dust, hydrophobicity polytetrafluoroethylene and the carbonic hydroammonium gas generation agent of high-ratio surface; Conductive matrices is nickel plated steel strip, perforation nickel strap or foaming nickel.
The present invention adopts general manufacture method preparation.
Specific embodiments of the present invention is described in detail as follows:
The hydrogen-bearing alloy powder particle size can be from several nanometers to several micron, but reduce with particle size, and the hydrogen the evolving path reduces, and the electrode reaction area increases, and can improve electrode reaction speed, improves high current density electrode reaction performance.Therefore, the hydroxide electrode manufacturing method that is used for alkaline fuel cell according to the present invention mainly comprises two parts: 1) hydrogen catalysis layer preparation and 2) gas diffusion layers preparation.Hydrogen catalysis layer manufacturing step comprises: smelting method for preparing hydrogen bearing alloy ingot, become fritter with mechanical crushing, and prepare alloyed powder with hydrogenization method again.So-called hydrogenization method, be put into the hydrogen bearing alloy fritter withstand voltage and the container that can heat in, High Pressure Hydrogen feeds container, under uniform temperature and hydrogen pressure, the hydrogen bearing alloy fritter is inhaled hydrogen, volume is splashed and is risen and pulverize.According to hydrogen bearing alloy kind difference with to the alloyed powder granularity requirements, selected temperature, hydrogen pressure and logical hydrogen time.Mix in certain proportion with conductive material (copper powder or activated carbon powder) and binding agent (PTFE) and be coated on the conductive matrices (conductive matrices, for example perforated metal, foaming metal, net form metal or analog) with this hydrogen-bearing alloy powder.Make the hydrogen catalysis band with rolling method then, thickness is 0.2-0.6mm.The gas diffusion layers preparation process comprises: with carbon black (Vilcan XC-72 or acetylene carbon black powder, average particle size particle size is less than 300nm) mix with certain proportion with hydrophobic binder (PTFE) and gas generation agent (Ammonium bicarbonate food grade), adding ethanol stirs, roll extrusion is prepared into diaphragm, and thickness is 0.3-0.6mm.Add additive to prevent the diaphragm be full of cracks, at room temperature drying is 30 minutes, again 100-150 ° of oven dry 1-3 hour, and then at 250-350 ℃ of sintering 10-40 minute.Gas diffusion layers has a large amount of microcellular structures, can make fuel gas (as hydrogen, oxygen, air, methane etc.) smoothly by arriving catalyst layer, carries out redox reaction.Gas diffusion layers another feature is to prevent that electrolyte from diffusing to gas compartment, guarantees to have higher gas transmission rate.
Again, the hydroxide electrode by hydrogen catalysis layer and gas diffusion layers at 150-200kg/cm 2Cold pressing, and in nitrogen atmosphere, 200-300 ℃ of following sintering made, and makes thickness of electrode at last at 0.2-0.6mm.Hydroxide electrode prepared in accordance with the present invention has very high electrochemical stability and electrocatalysis characteristic.
The present invention is the oxygen reduction electrode that adopts the non precious metal catalyst, this electrode La 1-xCa xMO 3(M=Co, Mn Fe) prepare as oxygen reduction catalyst.This oxide catalyst can prepare with chemical coprecipitation (promptly use three kinds of salt mixed liquors of La, Ca, Co or Mn or Fe, citric acid or oxalic acid are precipitation reagent).Sediment is used deionized water wash 3-5 time, after filtration at 600-800 ℃ of temperature lower calcination 1-5 hour.Catalyst after the calcining mixes with binding agent PTFE and acetylene carbon black again, makes diaphragm with rolling process.The manufacture method of oxygen electrode and the manufacture method of hydrogen electrode are basic identical.At last, oxygen electrode is at 300 ℃, N 2Sintering is made in the atmosphere.
The present invention is the novel low cost and the alkaline fuel cell of stable performance.Utilization of the present invention does not contain the eelctro-catalyst of the hydrogen bearing alloy of noble metal as the hydroxide electrode, and does not contain the eelctro-catalyst of the metal oxide of noble metal as oxygen reduction electrode.The present invention can be applicable to electric device, electronic equipment and motor vehicle etc. with the alkaline fuel cell of this eelctro-catalyst manufacturing.
Description of drawings
Fig. 1 is that hydrogen electrode (hydrogen storage alloy particle 5-30 μ m) is gone up hydroxide electrode potential change curve in time.
Fig. 2 hydrogen electrode (hydrogen storage alloy particle 0.1-5 μ m) is gone up hydroxide electrode potential change curve in time.
Current potential when the alkaline fuel cell of Fig. 3 novel electro-catalytic agent is worked is change curve in time.
Embodiment
Embodiment 1
Use smelting method for preparing AB 5Type hydrogen storage alloy ingot, its chemical composition are MmNi 3.35Co 0.75Mn 04Al 0.3(Mm is a lanthanum rich mischmetal).Pulverize with Mechanical Method then, prepare alloy powder with hydrogenization method again, its particle size is the 5-30 micron.With this hydrogen storing alloy powder and 10wt%PTFE coagulating agent, (it is of a size of the 0.25-0.40 micron to carbon black powder; Specific area is 80m 2/ make the hydrogen catalysis layer g) by 80: 10: 10 mixed, and with rolling method on the net at metallic nickel, its thickness is 0.4mm.Then in nitrogen atmosphere, 280 ℃ of following sintering 5 hours, again with gas diffusion layers at 200kg/cm 2Make the hydrogen catalysis electrode under colding pressing.At 55 ℃, in the 30wt%KOH solution, current density is 50Ma/cm 2, its hydroxide The performance test results is seen Fig. 1.
Embodiment 2
Hydrogen bearing alloy preparation, chemical composition and efflorescence process are identical with embodiment 1.Further reduce particle size to the 0.1-5 micron with the mechanical ball milling method then.The hydrogen catalysis electrode production process is identical with embodiment 1.At 55 ℃, in the 30wt%KOH solution, current density is 100mA/cm 2, its hydroxide The performance test results is seen Fig. 2.
Embodiment 3
The hydrogen catalysis electrode is identical with embodiment 2.Oxygen reduction electrode is by La 0.6Ca 0.4CoO 3Compositions such as catalyst.This catalyst is with coprecipitation (citric acid is a precipitation reagent) preparation, and the back was 650 ℃ of temperature lower calcinations 3 hours.The oxygen reduction electrode preparation process is similar to the hydrogen catalysis electrode, but oxygen reduction electrode is at inert gas N 2Sintering in the atmosphere.Hydrogen catalysis electrode of making and oxygen reduction electrode constitute the anode and the negative electrode of fuel cell respectively.With 30wt% potassium hydroxide is electrolyte, and the asbestos film is as barrier film, and working temperature is 55 ℃, and cell density is 100mA/cm 2Test result is seen Fig. 3.

Claims (10)

1, a kind of hydrogen bearing alloy is the alkaline fuel cell of eelctro-catalyst, and it comprises hydroxide electrode, oxygen reduction electrode, potassium hydroxide electrolyte and barrier film, it is characterized in that:
The used eelctro-catalyst of described hydroxide electrode is not for containing the hydrogen bearing alloy of noble metal, the used eelctro-catalyst of described oxygen reduction electrode for do not contain noble metal metal oxide.
2, be the alkaline fuel cell of eelctro-catalyst according to the described hydrogen bearing alloy of claim 1, it is characterized in that described hydrogen bearing alloy is rare-earth Ni-base AB 5Type, zirconium base or titanium base or rare-earth Ni-base Laves are AB mutually 2Type, or titanium is Ni-based or ferrotianium base AB type hydrogen storage alloy.
3, be the alkaline fuel cell of eelctro-catalyst according to the described hydrogen bearing alloy of claim 1, it is characterized in that described hydrogen bearing alloy is Mm (Ni-Co-Mn-Al) 5, Mm is a norium.
4, be the alkaline fuel cell of eelctro-catalyst according to the described hydrogen bearing alloy of claim 3, it is characterized in that described hydrogen bearing alloy is MmNi 3.35Co 0.75Mn 04Al 0.3, Mm is a lanthanum rich mischmetal.
5, be the alkaline fuel cell of eelctro-catalyst according to the described hydrogen bearing alloy of claim 1, it is characterized in that described metal oxide is perovskite structure ABO 3Type or spinel structure AB 2O 4Type.
6, be the alkaline fuel cell of eelctro-catalyst according to the described hydrogen bearing alloy of claim 4, it is characterized in that described metal oxide is La 1-xCa xMO 3, M=Co, Mn or Fe, wherein 0＞x＞1.
7, be the alkaline fuel cell of eelctro-catalyst according to the described hydrogen bearing alloy of claim 1, it is characterized in that described hydroxide electrode comprises that electro-catalysis layer and gas diffusion layers constitute, the electro-catalysis layer comprises hydrogen bearing alloy eelctro-catalyst, hydrophobicity polytetrafluoroethylene, Vulcan XC-72R carbon hydroaropic substance and conductive matrices.
8, be the alkaline fuel cell of eelctro-catalyst according to the described hydrogen bearing alloy of claim 1, it is characterized in that described oxygen reduction electrode comprises that electro-catalysis layer and gas diffusion layers constitute, the electro-catalysis layer comprises metal oxide eelctro-catalyst, hydrophobicity polytetrafluoroethylene, Vulcan XC-72R carbon hydroaropic substance and conductive matrices.
9,, it is characterized in that described gas diffusion layers is made up of carbon dust, hydrophobicity polytetrafluoroethylene and the carbonic hydroammonium gas generation agent of high-ratio surface according to claim 7 or the 8 described alkaline fuel cells that contain the hydrogen bearing alloy eelctro-catalyst.
10 according to claim 7 or the 8 described alkaline fuel cells that contain the hydrogen bearing alloy eelctro-catalyst, it is characterized in that described conductive matrices is nickel plated steel strip, perforation nickel strap or foaming nickel.
CNB031300014A 2003-06-06 2003-06-06 Alkaline fuel battery with hydrogen storage alloy as electric catalyst Expired - Fee Related CN1225048C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100463275C (en) * 2007-07-13 2009-02-18 西安交通大学 Borohydride alkaline dry cell
CN101800325A (en) * 2010-03-25 2010-08-11 浙江大学 Alkaline direct dimethyl ether fuel cell
CN104307575A (en) * 2014-10-14 2015-01-28 包头稀土研究院 Base metal composite catalyst, preparation method and use thereof
CN111180747A (en) * 2020-01-06 2020-05-19 中国科学技术大学 Anode catalyst, preparation method thereof and alkaline fuel cell
CN113745547A (en) * 2021-09-07 2021-12-03 苏州清德氢能源科技有限公司 Direct liquid organic hydrogen carrier fuel cell based on hydrogen storage alloy electrode

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101908628B (en) * 2010-08-18 2012-11-14 天津久聚能源科技发展有限公司 Transition metal composite oxide catalytic material and microwave preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100463275C (en) * 2007-07-13 2009-02-18 西安交通大学 Borohydride alkaline dry cell
CN101800325A (en) * 2010-03-25 2010-08-11 浙江大学 Alkaline direct dimethyl ether fuel cell
CN101800325B (en) * 2010-03-25 2012-03-14 浙江大学 Alkaline direct dimethyl ether fuel cell
CN104307575A (en) * 2014-10-14 2015-01-28 包头稀土研究院 Base metal composite catalyst, preparation method and use thereof
CN111180747A (en) * 2020-01-06 2020-05-19 中国科学技术大学 Anode catalyst, preparation method thereof and alkaline fuel cell
CN111180747B (en) * 2020-01-06 2021-10-01 中国科学技术大学 Anode catalyst, preparation method thereof and alkaline fuel cell
CN113745547A (en) * 2021-09-07 2021-12-03 苏州清德氢能源科技有限公司 Direct liquid organic hydrogen carrier fuel cell based on hydrogen storage alloy electrode
CN113745547B (en) * 2021-09-07 2023-08-15 苏州清德氢能源科技有限公司 Direct liquid organic hydrogen carrier fuel cell based on hydrogen storage alloy electrode

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