CN1266312C - Air electrode catalyst and its preparing process - Google Patents

Air electrode catalyst and its preparing process Download PDF

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Publication number
CN1266312C
CN1266312C CNB021333092A CN02133309A CN1266312C CN 1266312 C CN1266312 C CN 1266312C CN B021333092 A CNB021333092 A CN B021333092A CN 02133309 A CN02133309 A CN 02133309A CN 1266312 C CN1266312 C CN 1266312C
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Prior art keywords
catalyst
air electrode
electrode catalyst
cocatalyst
mno
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Expired - Fee Related
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CN1396308A (en
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魏子栋
朱伟
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Chongqing University
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Chongqing 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)

Abstract

The present invention relates to an air electrode catalyst which is prepared from composite oxide of manganese of MnO2-Mn3O4/Mn2O3, wherein MnO2 is a main catalyst and Mn3O4 or Mn2O3 is a cocatalyst. MnO2 as the main catalyst is obtained by heating and decomposing a manganese nitrate solution absorbed on carbon carriers, and Mn3O4 or Mn2O3 powder need to be added to the carbon powder carriers before manganese nitrate is thermally decomposed. The catalyst has the advantages of simple preparation technology and wide sources and low price of raw materials, and an air electrode prepared from the catalyst has the advantages of high catalytic activity and small cathode polarization. The present invention can be applied to air electrodes working in alkali or neutral media, such as anodes of metal-air cells and alkali fuel cells and cathodes for substituted hydrogen evolution in chlor-alkali industry.

Description

Air electrode catalyst and preparation method thereof
(1) technical field:
The present invention relates to fuel cell, the metal-air battery of electrochemical field.
(2) background technology:
Air electrode is a main building block in fuel cell, the metal-air battery, and it is the positive pole of fuel cell and metal-air battery, and the quality of its performance has determined the size of battery output rating.Improve the catalytic activity of air electrode catalyst, mean: under certain working current density, take air electrode as anodal fuel cell or metal-air battery, higher output potential is arranged.
Directly with electrolysis MnO 2With the mixture of carbon black be that the air electrode of catalyzer is poor because of its mixing uniformity, cause prepared air electrode performance not good; Produce MnO by thermal degradation uniform distribution, the manganous nitrate that is adsorbed on the carbon support 2, because of MnO 2Catalyzer dispersing uniformity on carbon support is good, and prepared air electrode performance is improved, and problem does not still solve but air electrode descends faster with current density increase output services voltage.
Chinese patent CN1312595A discloses a kind of " catalyst of zinc-air battery air electrode ", its objective is that it is with electrolysis MnO in order to improve the output services voltage of zinc-air battery 2Be predecessor, by sol-gal process and the synthetic metal oxide air electrode catalyst LiMn with spinel-type crystalline structure of high-temperature calcination 2-XCo xO 4The shortcoming of sol-gel method is: water loss is big, drying process is long, energy consumption is high, the purpose product that only contains minute quantity in bulky colloidal sol, the gel, this catalyzer has used expensive Li, Co element in addition, and the catalyzer for preparing with this method costs an arm and a leg.
(3) summary of the invention:
The object of the present invention is to provide a kind ofly than under the high current density, can export big operating voltage, and the preparation method is simple, raw material resources is cheap air electrode catalyst again extensively.
Purpose of the present invention reaches by the following technical programs:
Air electrode catalyst, its component and mass percent are: the MnO of 5.4-6.2% 2Major catalyst, the Mn of 0.1-14% 3O 4Perhaps Mn 2O 3The carbon black of cocatalyst and 79.8-94.5% or acetylene black or ratio are 1: 1 carbon black, acetylene black catalyst carrier.
The preparation method of air electrode catalyst is:
The first step infiltrates catalyst carrier
With 95% or dehydrated alcohol to soak into the carbon black of 79.8-94.5% that weight is air electrode catalyst or acetylene black or ratio be 1: 1 carbon black, acetylene black support of the catalyst, with the support of the catalyst complete wetting;
Second step absorption manganese nitrate solution
Under the room temperature, in the catalyst carrier after the first step infiltrates, drip while stirring manganese nitrate solution, fully mix;
The 3rd step added cocatalyst
In the mixture of second step preparation, adding weight is the Mn of air electrode catalyst 0.1-14% 3O 4Perhaps Mn 2O 3The cocatalyst powder, fully mixing is a pastel;
The 4th step preparation air electrode catalyst
With the mashed prod of the 3rd step preparation, under 100-110 ℃ of temperature, to dry earlier, the back is at 250-400 ℃ of roasting temperature, and roasting time is 3-1 hour, and manganous nitrate is decomposed into Primary Catalysts MnO fully 2, its MnO 2The content of Primary Catalysts just makes air electrode catalyst by the 5.4-6.2% of air electrode catalyst weight for being.Should note the interpolation order of cocatalyst in the making, cocatalyst Mn 3O 4Or Mn 2O 3Powder must join in the carrier carbon dust before the manganese nitrate thermal decomposition.
The present invention compared with prior art has following advantage:
(1) than under the high current density, can export big operating voltage.As shown in table 1, current density is 80mA/cm 2The time, air electrode with the present invention's preparation is that the air electrode that anodal " zinc-air battery " voltage ratio traditional method prepares is that anodal " zinc-air battery " exceeds 110-250mV, and increase with current density, the speed that operating potential descends is delayed on the air electrode of Preparation of Catalyst of the present invention.
(2) compare with the disclosed catalyzer of Chinese patent CN1312595A with catalyzer of the present invention, used raw material resources is extensive, cheap, production technique is simple, production efficiency is high.
The comparison of the air electrode of table 1 the present invention and traditional catalyst preparation
Air electrode Air electrode catalyst forms * " zinc-air battery " current potential/V under the different current densities
30mA/cm 2 50mA/cm 2 80mA/cm 2 100mA/cm 2
The present invention 5.5%MnO 212.3%Mn 2O 482.2%C 1.220 1.150 1.070 1.030
The present invention 6.1%MnO 22.7%Mn 2O 391.2%C 1.210 1.140 1.060 1.020
Conventional method 6.3%MnO 2(thermal decomposition) 93.7%C 1.180 1.050 0.960 0.900
Conventional method 6.3%MnO 2(electrolysis) 93.7%C 1.020 0.940 0.820 0.700
*C represents catalyst carrier carbon
(4) description of drawings:
Fig. 1, catalyst MnO 2-Mn 3O 4In, Mn 3O 4Content is to the impact of " zinc-air battery " volt-ampere performance.
Fig. 2, catalyst MnO 2-Mn 3O 4In, Mn 3O 4The interpolation order is to the impact of " zinc-air battery " volt-ampere performance.。
Fig. 3, catalyst MnO 2-Mn 2O 3In, Mn 2O 3Content is to the impact of " zinc-air battery " volt-ampere performance.
The corresponding catalyzer of curve numbering is formed and content among the figure:
Curve a 6.3%MnO 2, 93.7%C
Curve b 5.8%MnO 2, 7.0%Mn 3O 4, 87.2%C, Mn 3O 4Before the manganese nitrate thermal decomposition, join in the carrier carbon
Curve c 5.5%MnO 2, 12.3%Mn 3O 4, 82.2%C, Mn 3O 4Before the manganese nitrate thermal decomposition, join in the carrier carbon
Curve d 5.3%MnO 2, 15.8%Mn 3O 4, 78.9%C, Mn 3O 4Before the manganese nitrate thermal decomposition, join in the carrier carbon
Curve e 13.0%Mn 3O 4, 87.0%C, Mn 3O 4Directly mix with carrier carbon
Curve f 5.5%MnO 2, 12.3%Mn 3O 4, 82.2%C, Mn 3O 4After the manganese nitrate thermal decomposition, join in the carrier carbon
Curve g 6.2%MnO 2, 0.9%Mn 2O 3, 92.9%C, Mn 2O 3Before the manganese nitrate thermal decomposition, join in the carrier carbon
Curve h 6.1%MnO 2, 2.7%Mn 2O 3, 91.2%C, Mn 2O 3Before the manganese nitrate thermal decomposition, join in the carrier carbon
Curve k 6.0%MnO 2, 4.5%Mn 2O 3, 89.5%C, Mn 2O 3Before the manganese nitrate thermal decomposition, join in the carrier carbon
(5) embodiment:
Embodiment 1
A certain amount of carbon black or acetylene black or their mixture are infiltrated with ethanol, under the room temperature, drip while stirring manganese nitrate aqueous solution, and add commercially available Mn 3O 4Powder is mixed into pastel.Under 100 ℃ of-110 ℃ of temperature, dry, grind unity thing powdered gently, 340 ℃ of calcinings 1.5 hours, manganous nitrate is decomposed fully again, naturally cool to room temperature.
The gained catalyzer is made air electrode according to traditional method, as anodal, zinc metal sheet is negative pole, 7 mol KOH are electrolyte solution, constitute zinc-air battery, record the voltage of the zinc-air battery that is constituted by different components and content air electrode and current density curve under the room temperature as depicted in figs. 1 and 2.As can be seen from Figure 1, cocatalyst Mn 3O 4Content not simultaneously, the C-V characteristic of zinc-air battery is different, wherein curve c is the C-V characteristic of catalyst when being best composition and content.As can be seen from Figure 2, cocatalyst Mn 3O 4Only before the manganese nitrate thermal decomposition, join in the catalyst carrier, could effectively improve the catalytic activity of air electrode.
Embodiment 2
With Mn 2O 3Replace the Mn among the embodiment 1 3O 4, adopt the preparation method identical with embodiment 1, prepare air electrode, and form zinc-air battery in the same manner as in Example 1, record the voltage of the zinc-air battery that is consisted of by different component and content air electrode and current density curve as shown in Figure 3.Wherein curve h is the volt-ampere characteristic of this catalyzer when being best composition and content.

Claims (4)

1, a kind of air electrode catalyst is characterized in that its component and percentage by weight are: the MnO of 5.4-6.2% 2Major catalyst, the Mn of 0.1-14% 3O 4Perhaps Mn 2O 3The carbon black of cocatalyst and 79.8-94.5% or acetylene black or ratio are 1: 1 carbon black, acetylene black catalyst carrier.
2, air electrode catalyst according to claim 1 is characterized in that a kind of with Mn 3O 4For component and the percentage by weight of the air electrode catalyst of cocatalyst is: 5.5% MnO 2Major catalyst, 12.3% Mn 3O 4Cocatalyst and 82.2% carbon black catalyst carrier.
3, air electrode catalyst according to claim 1 is characterized in that a kind of with Mn 2O 3For component and the percentage by weight of the air electrode catalyst of cocatalyst is: 6.1% MnO 2Major catalyst, 2.7% Mn 2O 3Cocatalyst and 91.2% carbon black catalyst carrier.
4, a kind of preparation method of air electrode catalyst is characterized in that its method steps is as follows:
The first step infiltrates catalyst carrier
With 95% or dehydrated alcohol to soak into the carbon black of 79.8-94.5% that weight is air electrode catalyst or acetylene black or ratio be 1: 1 carbon black, acetylene black support of the catalyst, with the support of the catalyst complete wetting;
Second step absorption manganese nitrate solution
Under the room temperature, in the catalyst carrier after the first step infiltrates, drip while stirring manganese nitrate solution, fully mix;
The 3rd step added cocatalyst
In the mixture of second step preparation, adding weight is the Mn of air electrode catalyst 0.1-14% 3O 4Perhaps Mn 2O 3The cocatalyst powder, fully mixing is a pastel;
The 4th step preparation air electrode catalyst
With the mashed prod of the 3rd step preparation, under 100-110 ℃ of temperature, to dry earlier, the back is at 250-400 ℃ of roasting temperature, and roasting time is 3-1 hour, and manganous nitrate is decomposed into Primary Catalysts MnO fully 2, its MnO 2The content of Primary Catalysts is for being the 5.4-6.2% of air electrode catalyst weight.
CNB021333092A 2002-06-17 2002-06-17 Air electrode catalyst and its preparing process Expired - Fee Related CN1266312C (en)

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CN1266312C true CN1266312C (en) 2006-07-26

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100373672C (en) * 2003-11-06 2008-03-05 北京双威富能科技有限公司 Technique for making manganese catalytic air cathode of metal-air battery
CN100454626C (en) * 2007-02-07 2009-01-21 施建 Anode catalysis electrode of improved aluminum and magnesium alloy fuel battery and its making method
CN101901916B (en) * 2010-08-17 2013-03-27 天津久聚能源科技发展有限公司 Carbon-carried manganese tetraoxide composite catalytic material and preparation method thereof
CN102476054B (en) * 2010-11-29 2013-12-04 中国科学院大连化学物理研究所 Ag/MnyOx/C catalyst and preparation and application thereof
CN110093621B (en) * 2019-04-24 2020-08-25 浙江工业大学 Hydrogen-free continuous electrochemical oxidation IO3-Transformation to IO4-Method (2)
CN112340782B (en) * 2020-11-06 2021-10-01 中国科学技术大学 Preparation method of carbon-supported metal oxide catalyst

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