CN106654302B - It is a kind of using peanut as proton exchange membrane non-platinum catalyst of raw material and preparation method thereof - Google Patents

It is a kind of using peanut as proton exchange membrane non-platinum catalyst of raw material and preparation method thereof Download PDF

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CN106654302B
CN106654302B CN201610890238.5A CN201610890238A CN106654302B CN 106654302 B CN106654302 B CN 106654302B CN 201610890238 A CN201610890238 A CN 201610890238A CN 106654302 B CN106654302 B CN 106654302B
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peanut
proton exchange
iron
raw material
platinum catalyst
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CN106654302A (en
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徐峰
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Fuzhou University
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Fuzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8817—Treatment of supports before application of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • 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 belongs to the preparation fields of fuel-cell catalyst, more particularly to a kind of using peanut as fuel battery cathode with proton exchange film non-platinum catalyst of raw material and preparation method thereof, the catalyst is to use peanut as the source of carbon and nitrogen, and it is prepared with cerium oxide precursor body and iron forerunner's bluk recombination, wherein the mass ratio of peanut, cerium oxide precursor body and iron presoma is 1-100:1-50:1-35, carbon in catalyst, nitrogen, iron, cerium oxide molar ratio be 1-10:0.3-3:0.1-5:0.1-5.Catalyst of the invention has good oxygen reduction activity, and without precious metal, has very important significance.

Description

It is a kind of using peanut as proton exchange membrane non-platinum catalyst of raw material and preparation method thereof
Technical field
The present invention relates to the preparation fields of fuel-cell catalyst, and in particular to a kind of using peanut as the proton exchange of raw material Membrane fuel battery cathod non-platinum catalyst and preparation method thereof.
Background technique
Proton Exchange Membrane Fuel Cells receives extensive pass with its high efficiency, high power density, advantages of environment protection Note.Proton Exchange Membrane Fuel Cells is mainly using platinum and platinum-base material as catalyst, platinum fancy price and few storage at present Amount hinders the application of Proton Exchange Membrane Fuel Cells.Thus, developing cheap and with excellent activity catalyst seems It is especially urgent and important.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of cheap and there is good hydrogen reduction Active fuel battery cathode with proton exchange film non-platinum catalyst.
To achieve the above object, the present invention adopts the following technical scheme:
It is a kind of using peanut as the fuel battery cathode with proton exchange film non-platinum catalyst of raw material, the catalyst is using flower The source as carbon and nitrogen is given birth to, and is prepared with cerium oxide precursor body and iron forerunner's bluk recombination, wherein peanut, cerium oxide The mass ratio of presoma and iron presoma is 1-100:1-50:1-35, carbon in catalyst, nitrogen, iron, cerium oxide molar ratio be 1-10:0.3-3:0.1-5:0.1-5。
The cerium oxide precursor body is cerous nitrate or ammonium ceric nitrate.
The iron presoma is ferric nitrate, ferric sulfate, iron chloride, ferrocene, iron hydroxide, iron sulfide or ferric perchlorate.
The present invention also provides using peanut as the preparation side of the fuel battery cathode with proton exchange film non-platinum catalyst of raw material Method, comprising the following steps:
1) peanut is mixed with water and peanut slurries is made；
2) cerium oxide precursor body and iron presoma is added, stirs evenly；
3) sodium hydroxide solution is added and stirs evenly, obtains mixed liquor；
4) above-mentioned mixed liquor is placed in autoclave and is sealed, and the heating and thermal insulation 1-24 h at 80-180 DEG C, then It is cooling, liquid is abandoned, it is dry；
5) step 4) products therefrom is placed in reducing atmosphere, and the heating and thermal insulation 1-6 h at 300-500 DEG C, is obtained Fuel battery cathode with proton exchange film non-platinum catalyst with good oxygen reduction activity.
The ratio of step 1), the peanut and water is 100 g:100-1000 mL.Step 3), the sodium hydroxide solution Concentration is 0.5-15 mol/L.Step 5), the reducing atmosphere are one or both of hydrogen, carbon monoxide.
The invention adopts the above technical scheme, by mixing peanut slurries, nano oxidized cerium precursor with iron presoma And be heat-treated, prepare fuel battery cathode with proton exchange film catalyst.The beneficial effects of the present invention are: peanut contains largely Protein, fat and carbohydrate, thus have nitrogen abundant and carbon, meanwhile, cerium oxide has excellent oxygen Storage/releasability can effectively improve the oxygen reduction activity of cathod catalyst.
Detailed description of the invention
Fig. 1 is the electrochemistry that embodiment 1 prepares fuel battery cathode with proton exchange film non-platinum catalyst by raw material of peanut Oxygen reduction reaction performance curve.
Specific embodiment
By the following specific examples further illustrate the invention, but protection scope of the present invention is not limited to following reality Apply example.
It is a kind of using peanut as the preparation method of the fuel battery cathode with proton exchange film non-platinum catalyst of raw material, including it is following Step:
1) peanut and water are mixed in the ratio of 100 g:100-1000 mL and peanut slurries is made；
2) cerium oxide precursor body and iron presoma is added, stirs evenly；
Wherein the mass ratio of peanut, cerium oxide precursor body and iron presoma is 1-100:1-50:1-35, carbon in catalyst, Nitrogen, iron, cerium oxide molar ratio be 1-10:0.3-3:0.1-5:0.1-5；
The cerium oxide precursor body is cerous nitrate or ammonium ceric nitrate；Iron presoma is ferric nitrate, ferric sulfate, iron chloride, two Luxuriant iron, iron hydroxide, iron sulfide, iron halide or ferric perchlorate；
3) sodium hydroxide solution that concentration is 0.5-15mol/L is added and stirs evenly, obtains mixed liquor；
4) above-mentioned mixed liquor is placed in autoclave and is sealed, and the heating and thermal insulation 1-24h at 80-180 DEG C, it is then cold But, liquid is abandoned, it is dry；
5) step 4) products therefrom is placed in reducing atmosphere, and the heating and thermal insulation 1-6 h at 300-500 DEG C, is obtained Fuel battery cathode with proton exchange film non-platinum catalyst with good oxygen reduction activity.
Embodiment 1
A kind of preparation method of the fuel battery cathode with proton exchange film catalyst with good oxygen reduction activity, specifically Step are as follows:
It is put into blender 1. 100 g peanuts are mixed with 100 ml water, prepares peanut slurries；
2. peanut slurries prepared by 0.7 ml step 1 is taken to mix with 4.34g cerous nitrate and 4.04g ferric nitrate, and stir 60 min；
3. the NaOH aqueous solution that concentration is 0.5 M is added into mixed liquor prepared by step 2, and stir 30 min；
It is sealed 4. mixed liquor prepared by step 3 is placed in autoclave, and keeps the temperature 1 hour under 180 oC；
5. the autoclave after heat preservation is cooling, liquid therein is poured out, is filtered and dry；
6. step 5 products therefrom is placed in hydrogen atmosphere, in and in 6 h of heating and thermal insulation at 300 DEG C, obtained after cooling Fuel battery cathode with proton exchange film non-platinum catalyst with good oxygen reduction activity.
C:N:Fe:CeO in catalyst is made in the present embodiment2Molar ratio is 10:3:5:5.
As shown in Figure 1, under 0.9V potential, the current density of Pt/C catalyst is 0.4 mA cm-2, prepared by embodiment 1 The current density of catalyst is 0.6 mA cm-2, close to current density (the 0.4 mA cm of Pt/C catalyst-2), thus the present invention Prepared having using peanut as the fuel battery cathode with proton exchange film non-platinum catalyst of raw material is comparable with Pt/C catalyst Performance.
Embodiment 2
A kind of preparation method of the fuel battery cathode with proton exchange film catalyst with good oxygen reduction activity, tool Body step are as follows:
It is put into blender 1. 100 g peanuts are mixed with 1000 ml water, prepares peanut slurries；
2. peanut slurries prepared by 15 ml steps 1 is taken to mix with 4.3 g cerous nitrates and 4 g ferric sulfate, and stir 60 min；
3. the NaOH aqueous solution that concentration is 15 M is added into mixed liquor prepared by step 2, and stir 30 min；
It is sealed 4. mixed liquor prepared by step 3 is placed in autoclave, and keeps the temperature 24 hours under 80 oC；
5. the autoclave after heat preservation is cooling, liquid therein is poured out, is filtered and dry；
It is cooling 6. step 5 products therefrom is placed in carbon monoxide atmosphere, and in and in 1 h of heating and thermal insulation at 500 DEG C The fuel battery cathode with proton exchange film catalyst of good oxygen reduction activity had both been obtained afterwards.
C:N:Fe:CeO in catalyst is made in the present embodiment2Molar ratio is 1:0.3:0.1:0.1.
Embodiment 3
A kind of preparation method of the fuel battery cathode with proton exchange film catalyst with good oxygen reduction activity, tool Body step are as follows:
It is put into blender 1. 100 g peanuts are mixed with 500 ml water, prepares peanut slurries；
2. peanut slurries prepared by 3 ml steps 1 is taken to mix with 4.34 g cerous nitrates and 1.62 g iron chloride, and stir 60 min；
3. the NaOH aqueous solution that concentration is 7.5 M is added into mixed liquor prepared by step 2, and stir 30 min；
It is sealed 4. mixed liquor prepared by step 3 is placed in autoclave, and keeps the temperature 12 hours under 180 oC；
5. the autoclave after heat preservation is cooling, liquid therein is poured out, filters and dry, had both obtained good oxygen The fuel battery cathode with proton exchange film catalyst of reduction activation.
6. step 5 products therefrom is placed in hydrogen: carbon monoxide volume ratio is in the reducing atmosphere of 1:1, and in 400 3.5 h of heating and thermal insulation at DEG C had both obtained the fuel battery cathode with proton exchange film catalyst of good oxygen reduction activity after cooling.
C:N:Fe:CeO in catalyst is made in the present embodiment2Mass ratio is 5:1.7:2.5:2.5.
Embodiment 4
It is a kind of using peanut as the preparation method of the fuel battery cathode with proton exchange film non-platinum catalyst of raw material, including it is following Step:
1) peanut and water are mixed in the ratio of 100 g:200 mL and peanut slurries is made；
2) cerium oxide precursor body ammonium ceric nitrate and iron presoma iron sulfide is added, stirs evenly；Wherein before peanut, cerium oxide The mass ratio for driving body and iron presoma is 50:1:1；
3) sodium hydroxide solution that concentration is 2mol/L is added and stirs evenly, obtains mixed liquor；
4) above-mentioned mixed liquor is placed in autoclave and is sealed, and the heating and thermal insulation 12h at 120 DEG C, then cooled down, abandoned Liquid, it is dry；
5) step 4) products therefrom is placed in reducing atmosphere, and 6 h of heating and thermal insulation at 300 DEG C, obtains having good The fuel battery cathode with proton exchange film non-platinum catalyst of good oxygen reduction activity.
Embodiment 5
It is a kind of using peanut as the preparation method of the fuel battery cathode with proton exchange film non-platinum catalyst of raw material, including it is following Step:
1) peanut and water are mixed in the ratio of 100 g:600 mL and peanut slurries is made；
2) cerium oxide precursor body ammonium ceric nitrate and iron presoma iron hydroxide is added, stirs evenly；Wherein peanut, cerium oxide The mass ratio of presoma and iron presoma is 1:1:1；
3) sodium hydroxide solution that concentration is 10mol/L is added and stirs evenly, obtains mixed liquor；
4) above-mentioned mixed liquor is placed in autoclave and is sealed, and the heating and thermal insulation 6h at 150 DEG C, then cooled down, abandoned Liquid, it is dry；
5) step 4) products therefrom is placed in reducing atmosphere, and the heating and thermal insulation 2h at 500 DEG C, obtains having good Oxygen reduction activity fuel battery cathode with proton exchange film non-platinum catalyst.
Embodiment 6
It is a kind of using peanut as the preparation method of the fuel battery cathode with proton exchange film non-platinum catalyst of raw material, including it is following Step:
1) peanut and water are mixed in the ratio of 100 g:800 mL and peanut slurries is made；
2) cerium oxide precursor body ammonium ceric nitrate and iron presoma ferric perchlorate's iron sulfide is added, stirs evenly；Wherein peanut, The mass ratio of cerium oxide precursor body and iron presoma is 100:50:35；
3) sodium hydroxide solution that concentration is 8mol/L is added and stirs evenly, obtains mixed liquor；
4) above-mentioned mixed liquor is placed in autoclave and is sealed, and the heating and thermal insulation 16h at 100 DEG C, then cooled down, abandoned Liquid, it is dry；
5) step 4) products therefrom is placed in reducing atmosphere, and 3 h of heating and thermal insulation at 400 DEG C, obtains having good The fuel battery cathode with proton exchange film non-platinum catalyst of good oxygen reduction activity.

Claims (7)

1. a kind of using peanut as the fuel battery cathode with proton exchange film non-platinum catalyst of raw material, it is characterised in that: the catalysis Agent is to use peanut as the source of carbon and nitrogen, and be prepared with cerium oxide precursor body and iron forerunner's bluk recombination, raw material The mass ratio of middle peanut, cerium oxide precursor body and iron presoma is 1-100:1-50:1-35, carbon, nitrogen, iron, oxidation in catalyst The molar ratio of cerium is 1-10:0.3-3:0.1-5:0.1-5.
2. it is according to claim 1 a kind of using peanut as the fuel battery cathode with proton exchange film non-platinum catalyst of raw material, It is characterized by: the cerium oxide precursor body is cerous nitrate or ammonium ceric nitrate.
3. it is according to claim 1 a kind of using peanut as the fuel battery cathode with proton exchange film non-platinum catalyst of raw material, It is characterized by: the iron presoma be ferric nitrate, ferric sulfate, iron chloride, ferrocene, iron hydroxide, iron sulfide, iron halide or Ferric perchlorate.
4. one kind is as described in claim 1 using peanut as the system of the fuel battery cathode with proton exchange film non-platinum catalyst of raw material Preparation Method, it is characterised in that: itself the following steps are included:
1) peanut is mixed with water and peanut slurries is made；
2) cerium oxide precursor body and iron presoma are added in above-mentioned peanut slurries, stirs evenly；
3) it adds sodium hydroxide solution and stirs evenly, obtain mixed liquor；
4) above-mentioned mixed liquor is placed in autoclave and is sealed, and the heating and thermal insulation 1-24 h at 80-180 DEG C, then cooled down, Liquid is abandoned, it is dry；
5) step 4) products therefrom is placed in reducing atmosphere, and the heating and thermal insulation 1-6 h at 300-500 DEG C, is had The fuel battery cathode with proton exchange film non-platinum catalyst of good oxygen reduction activity.
5. according to claim 4 a kind of using peanut as the fuel battery cathode with proton exchange film non-platinum catalyst of raw material Preparation method, it is characterised in that: the ratio of step 1), the peanut and water is 100 g:100-1000 mL.
6. according to claim 4 a kind of using peanut as the fuel battery cathode with proton exchange film non-platinum catalyst of raw material Preparation method, it is characterised in that: step 3), the concentration of sodium hydroxide solution are 0.5-15 mol/L.
7. according to claim 4 a kind of using peanut as the fuel battery cathode with proton exchange film non-platinum catalyst of raw material Preparation method, it is characterised in that: step 5), the reducing atmosphere are one or both of hydrogen, carbon monoxide.
CN201610890238.5A 2016-10-13 2016-10-13 It is a kind of using peanut as proton exchange membrane non-platinum catalyst of raw material and preparation method thereof Active CN106654302B (en)

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EP2059965A4 (en) * 2006-09-13 2012-03-28 Univ Akron Catalysts compositions for use in fuel cells
CN102324531A (en) * 2011-05-26 2012-01-18 东华大学 Carbon-supported CoN fuel-cell catalyst as well as preparation method and application thereof
CN102916203B (en) * 2012-11-07 2014-10-01 武汉理工大学 Cathode non-platinum catalyst of proton exchange membrane fuel cell and preparation method thereof
CN105789644B (en) * 2016-03-02 2018-08-21 中南大学 A kind of preparation method of Fe-N/C oxygen reduction reactions composite electrocatalyst
CN105810982B (en) * 2016-05-05 2019-06-04 福州大学 A kind of catalyst of fuel batter with proton exchange film carrier with high conductivity

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