CN108417846A - Supported oxygen reduction catalyst and application thereof - Google Patents
Supported oxygen reduction catalyst and application thereof Download PDFInfo
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- CN108417846A CN108417846A CN201810077317.3A CN201810077317A CN108417846A CN 108417846 A CN108417846 A CN 108417846A CN 201810077317 A CN201810077317 A CN 201810077317A CN 108417846 A CN108417846 A CN 108417846A
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- oxygen reduction
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- reduction catalyst
- type oxygen
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 52
- 239000001301 oxygen Substances 0.000 title claims abstract description 52
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 239000006230 acetylene black Substances 0.000 claims description 34
- 230000003197 catalytic effect Effects 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 18
- 239000007832 Na2SO4 Substances 0.000 claims description 17
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000000748 compression moulding Methods 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 210000000481 breast Anatomy 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- 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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a supported oxygen reduction catalyst, which is characterized in that the preparation method of the supported oxygen reduction catalyst comprises the following steps: to MnSO4KMnO is added into the aqueous solution in sequence4And BP2000, performing ultrasonic dispersion, heating, preserving heat, filtering, washing and vacuum drying to obtain the supported oxygen reduction catalyst. The invention also discloses the application field of the supported oxygen reduction catalyst. The invention is used for the load type MnO of the air electrode2the/BP 2000 oxygen reduction catalyst has simple and convenient preparation process, cheap raw materials, environmental protection, suitability for large-scale production, more positive half-wave potential and larger extreme compared with commercial Pt/CThe current density is limited, so that the prepared zinc-air battery has excellent performance.
Description
Technical field
The present invention relates to zinc-air battery technical fields, and in particular to a kind of support type oxygen reduction catalyst and its application.
Background technology
With the development of society, fossil fuel economy steering clean energy resource economy is extremely urgent.For a long time, battery is recognized
To be one of the most effectual way of conversion and storage energy, used from original portable electronic device and power grid scale energy storage
To electric vehicle.So far, in many different types of batteries sold on the market, lithium-ion technology compares energy due to it
With power density height as mainstream.However, up to the present, since batteries of electric automobile is of high cost, energy density is insufficient, because
And the market penetration rate of electric vehicle is very low.
The theoretical energy density of zinc-air battery is up to 1086Wh/kg, close to five times of current lithium ion battery, and
Manufacturing cost is very low.Possess wide city in ship-global position system, navigation and underwater operation, beeper, mobile phone etc.
.Especially in terms of electric bicycle and high power battery for electric vehicle and battery pack, zinc-air battery provides any
Available highest energy density in primary battery system, they are often referred to as substituting lithium ion battery for the following electronic vapour
The most viable selection of vehicle application, has broad application prospects.Rich reserves of the zinc in the earth's crust, specific capacity is high, chemically
It can be more stable.In recent years, people are more and more ripe to the research of anode, but to zinc-air battery cathod catalyst
It studies and not perfect.Air electrode (cathode) is the mostly important component part of metal-air battery.Therefore how sky is improved
The catalytic activity and service life of pneumoelectric pole, make it not only meet the requirement of market and environmental protection and energy saving, but also meet the industry political affairs of country
Plan becomes the hot spot of Recent study.
Invention content
Technical problems based on background technology, the present invention propose a kind of support type oxygen reduction catalyst, to realize
Improve the purpose of the chemical property of zinc-air battery.
A kind of support type oxygen reduction catalyst proposed by the present invention, the preparation method packet of the support type oxygen reduction catalyst
Include following steps：To MnSO4KMnO is sequentially added in aqueous solution4, BP2000, ultrasonic disperse, heat up, keep the temperature, filter, washing, very
Sky is dry, obtains support type oxygen reduction catalyst.
Preferably, the MnSO4A concentration of 0.01-0.5mol/L of aqueous solution.
Preferably, the MnSO4With KMnO4Molar ratio be 1：1-5.
Preferably, the MnSO4Mass ratio with BP2000 is 1：5-15.
Preferably, the time of the ultrasonic disperse is 10-30min.
Preferably, the temperature of the heat preservation is 120-180 DEG C, time 12-24h.
Preferably, the washing is repeatedly washs using distilled water, and " multiple " is not construed as limiting herein, as the case may be into
Row selection.
Preferably, the vacuum drying temperature is 40-80 DEG C, time 5-10h.
Preferably, the BP2000 is to pass through pretreated BP2000, and the pretreated method is：BP2000 is disperseed
In HNO3In solution, ultrasonic disperse flows back, and centrifuges, filtering, washs filter residue, dry, obtains pretreated BP2000.
Preferably, BP2000 is dispersed in HNO3In solution, ultrasonic disperse 5-10min.
Preferably, the temperature of the reflux is 60-100 DEG C, time 5-10h.
Preferably, the washing filter residue is to adopt that filter residue is washed with deionized to neutrality.
Preferably, 40-80 DEG C of the temperature of the drying.
Preferably, the HNO3A concentration of 3-10mol/L of solution.
The present invention also provides a kind of air for zinc-air battery prepared using the support type oxygen reduction catalyst
The preparation method of electrode, the air electrode includes the following steps：
S1, by Na2SO4It is dissolved in ethanol water, high electric conductivity carbon black, acetylene black A and the appropriate support type oxygen is added
Reducing catalyst, stirring, is added appropriate binder, and ultrasonic disperse continues to stir, be demulsified in hot bath, and filtering, roll-in obtains
Catalytic Layer；
S2, acetylene black B is added into ethanol water, appropriate binder is added in ultrasonic disperse, stirs, in hot bath
Demulsification, the waterproof ventilative layer that roll-in obtains；
S3, by after roll-in Catalytic Layer and waterproof ventilative layer be sticked to nickel foam both sides respectively, compression moulding, drying obtains
Air electrode.
Preferably, Na2SO4, high electric conductivity carbon black, acetylene black A, acetylene black B mass ratio be 1-5：1-10：1-5：1-10.
Preferably, the time of stirring is 1-3h.
The concentration of above-mentioned ethanol water is not construed as limiting, and is selected as the case may be.
Compared with prior art, the beneficial effects of the invention are as follows：
1) MnO that the present invention will be generated by comproportionation reaction2Nanometer particle load is on BP2000, nanoscale MnO2Have
Very excellent catalytic activity, but individual MnO2Can not efficiently catalytic oxidation-reduction, need to be by being supported on high-specific surface area
On the BP2000 of excellent electrical conductivity, the synergistic effect of both competence exertions makes MnO2Catalytic activity is enhanced；By that will change
Into oxygen reduction catalyst be added in zinc-air battery in the Catalytic Layer of air electrode, due to nanoscale MnO2With high electric conductivity
BP2000 is coupled, and is improved the conductivity of electrode, is thereby reduced the charge mass transfer resistance of battery, promote the quick shifting of electronics
It is dynamic, while the adsorbance of oxygen being made to increase, the hydrogen reduction performance of catalyst is substantially increased, there is good synergy.
2) present invention is used for the support type MnO of air electrode2/ BP2000 oxygen reduction catalysts, preparation process is easy, raw material
It is cheap, it is environmental-friendly, it is suitble to large-scale production, compared with being commercialized Pt/C, there is the limit of the half wave potential and bigger of corrigendum
Current density makes zinc-air battery function admirable obtained.
Description of the drawings
Fig. 1 is LSV test result comparison diagrams in test example 1 of the present invention.
Fig. 2 is 2 middle impedance test result comparison diagram of test example of the present invention.
Specific implementation mode
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
The preparation method of a kind of support type oxygen reduction catalyst, the support type oxygen reduction catalyst includes the following steps：
To MnSO4KMnO is sequentially added in aqueous solution4, BP2000, ultrasonic disperse, heat up, keep the temperature, filter, wash, vacuum drying, obtain
Support type oxygen reduction catalyst.
Air electrode for zinc-air battery prepared by the support type oxygen reduction catalyst, the air electrode
Preparation method includes the following steps：
S1, by Na2SO4It is dissolved in ethanol water, high electric conductivity carbon black, acetylene black A and the appropriate support type oxygen is added
Reducing catalyst, stirring, is added appropriate binder, and ultrasonic disperse continues to stir, be demulsified in hot bath, and filtering, roll-in obtains
Catalytic Layer；
S2, acetylene black B is added into ethanol water, appropriate binder is added in ultrasonic disperse, stirs, in hot bath
Demulsification, the waterproof ventilative layer that roll-in obtains；
S3, by after roll-in Catalytic Layer and waterproof ventilative layer be sticked to nickel foam both sides respectively, compression moulding, drying obtains
Air electrode.
Embodiment 2
The preparation method of a kind of support type oxygen reduction catalyst, the support type oxygen reduction catalyst includes the following steps：
To MnSO4KMnO is sequentially added in aqueous solution4, BP2000, ultrasonic disperse 10min, heat up, keep the temperature, filtering, it is more using distilled water
Secondary washing, vacuum drying, obtains support type oxygen reduction catalyst；
Wherein, the MnSO4A concentration of 0.5mol/L of aqueous solution；
The MnSO4With KMnO4Molar ratio be 1：1；
The MnSO4Mass ratio with BP2000 is 1：15；
The temperature of the heat preservation is 120 DEG C, and the time is for 24 hours；
The vacuum drying temperature is 40 DEG C, time 10h；
The BP2000 is to pass through pretreated BP2000, and the pretreated method is：BP2000 is dispersed in HNO3
In solution, ultrasonic disperse 5min flows back, and centrifuges, filtering, adopts and filter residue is washed with deionized to neutrality, drying is pre-processed
BP2000；
The temperature of the reflux is 100 DEG C, time 5h；
80 DEG C of the temperature of the drying；
The HNO3A concentration of 3mol/L of solution.
Air electrode for zinc-air battery prepared by the support type oxygen reduction catalyst, the air electrode
Preparation method includes the following steps：
S1, by Na2SO4It is dissolved in ethanol water, high electric conductivity carbon black, acetylene black A and the appropriate support type oxygen is added
Reducing catalyst, stirring, is added appropriate binder, and ultrasonic disperse continues to stir, be demulsified in hot bath, and filtering, roll-in obtains
Catalytic Layer；
S2, acetylene black B is added into ethanol water, appropriate binder is added in ultrasonic disperse, stirs, in hot bath
Demulsification, the waterproof ventilative layer that roll-in obtains；
S3, by after roll-in Catalytic Layer and waterproof ventilative layer be sticked to nickel foam both sides respectively, compression moulding, drying obtains
Air electrode；
Wherein, Na2SO4, high electric conductivity carbon black, acetylene black A, acetylene black B mass ratio be 5：1：5：1；
The time of stirring is 3h.
Embodiment 3
The preparation method of a kind of support type oxygen reduction catalyst, the support type oxygen reduction catalyst includes the following steps：
To MnSO4KMnO is sequentially added in aqueous solution4, BP2000, ultrasonic disperse 30min, heat up, keep the temperature, filtering, it is more using distilled water
Secondary washing, vacuum drying, obtains support type oxygen reduction catalyst；
Wherein, the MnSO4A concentration of 0.01mol/L of aqueous solution；
The MnSO4With KMnO4Molar ratio be 1：5；
The MnSO4Mass ratio with BP2000 is 1：5；
The temperature of the heat preservation is 180 DEG C, time 12h；
The vacuum drying temperature is 80 DEG C, time 5h；
The BP2000 is to pass through pretreated BP2000, and the pretreated method is：BP2000 is dispersed in HNO3
In solution, ultrasonic disperse 10min flows back, and centrifuges, filtering, adopts and filter residue is washed with deionized to neutrality, drying obtains pre- place
The BP2000 of reason；
The temperature of the reflux is 60 DEG C, time 10h；
40 DEG C of the temperature of the drying；
The HNO3A concentration of 10mol/L of solution.
Air electrode for zinc-air battery prepared by the support type oxygen reduction catalyst, the air electrode
Preparation method includes the following steps：
S1, by Na2SO4It is dissolved in ethanol water, high electric conductivity carbon black, acetylene black A and the appropriate support type oxygen is added
Reducing catalyst, stirring, is added appropriate binder, and ultrasonic disperse continues to stir, be demulsified in hot bath, and filtering, roll-in obtains
Catalytic Layer；
S2, acetylene black B is added into ethanol water, appropriate binder is added in ultrasonic disperse, stirs, in hot bath
Demulsification, the waterproof ventilative layer that roll-in obtains；
S3, by after roll-in Catalytic Layer and waterproof ventilative layer be sticked to nickel foam both sides respectively, compression moulding, drying obtains
Air electrode；
Wherein, Na2SO4, high electric conductivity carbon black, acetylene black A, acetylene black B mass ratio be 1：10：1：10；
The time of stirring is 1h.
Embodiment 4
The preparation method of a kind of support type oxygen reduction catalyst, the support type oxygen reduction catalyst includes the following steps：
To MnSO4KMnO is sequentially added in aqueous solution4, BP2000, ultrasonic disperse 20min, heat up, keep the temperature, filtering, it is more using distilled water
Secondary washing, vacuum drying, obtains support type oxygen reduction catalyst；
Wherein, the MnSO4A concentration of 0.3mol/L of aqueous solution；
The MnSO4With KMnO4Molar ratio be 1：3；
The MnSO4Mass ratio with BP2000 is 1：10；
The temperature of the heat preservation is 150 DEG C, time 16h；
The vacuum drying temperature is 65 DEG C, time 7h；
The BP2000 is to pass through pretreated BP2000, and the pretreated method is：BP2000 is dispersed in HNO3
In solution, ultrasonic disperse 7min flows back, and centrifuges, filtering, adopts and filter residue is washed with deionized to neutrality, drying is pre-processed
BP2000；
The temperature of the reflux is 70 DEG C, time 7h；
The temperature 50 C of the drying；
The HNO3A concentration of 6mol/L of solution.
Air electrode for zinc-air battery prepared by the support type oxygen reduction catalyst, the air electrode
Preparation method includes the following steps：
S1, by Na2SO4It is dissolved in ethanol water, high electric conductivity carbon black, acetylene black A and the appropriate support type oxygen is added
Reducing catalyst, stirring, is added appropriate binder, and ultrasonic disperse continues to stir, be demulsified in hot bath, and filtering, roll-in obtains
Catalytic Layer；
S2, acetylene black B is added into ethanol water, appropriate binder is added in ultrasonic disperse, stirs, in hot bath
Demulsification, the waterproof ventilative layer that roll-in obtains；
S3, by after roll-in Catalytic Layer and waterproof ventilative layer be sticked to nickel foam both sides respectively, compression moulding, drying obtains
Air electrode；
Wherein, Na2SO4, high electric conductivity carbon black, acetylene black A, acetylene black B mass ratio be 3：5：4：6；
The time of stirring is 2h.
Embodiment 5
The preparation method of a kind of support type oxygen reduction catalyst, the support type oxygen reduction catalyst includes the following steps：
To MnSO4KMnO is sequentially added in aqueous solution4, BP2000, ultrasonic disperse 25min, heat up, keep the temperature, filtering, it is more using distilled water
Secondary washing, vacuum drying, obtains support type oxygen reduction catalyst；
Wherein, the MnSO4A concentration of 0.2mol/L of aqueous solution；
The MnSO4With KMnO4Molar ratio be 1：2；
The MnSO4Mass ratio with BP2000 is 1：8；
130 DEG C of the temperature of the heat preservation, time 20h；
The vacuum drying temperature is 55 DEG C, time 9h；
The BP2000 is to pass through pretreated BP2000, and the pretreated method is：BP2000 is dispersed in HNO3
In solution, ultrasonic disperse 6min flows back, and centrifuges, filtering, adopts and filter residue is washed with deionized to neutrality, drying is pre-processed
BP2000；
The temperature of the reflux is 80 DEG C, time 8h；
75 DEG C of the temperature of the drying；
The HNO3A concentration of 5mol/L of solution.
Air electrode for zinc-air battery prepared by the support type oxygen reduction catalyst, the air electrode
Preparation method includes the following steps：
S1, by Na2SO4It is dissolved in ethanol water, high electric conductivity carbon black, acetylene black A and the appropriate support type oxygen is added
Reducing catalyst, stirring, is added appropriate binder, and ultrasonic disperse continues to stir, be demulsified in hot bath, and filtering, roll-in obtains
Catalytic Layer；
S2, acetylene black B is added into ethanol water, appropriate binder is added in ultrasonic disperse, stirs, in hot bath
Demulsification, the waterproof ventilative layer that roll-in obtains；
S3, by after roll-in Catalytic Layer and waterproof ventilative layer be sticked to nickel foam both sides respectively, compression moulding, drying obtains
Air electrode；
Wherein, Na2SO4, high electric conductivity carbon black, acetylene black A, acetylene black B mass ratio be 2：4：3：7；
The time of stirring is 2.5h.
Comparative example 1
By Na2SO4It is dissolved in ethanol water, high electric conductivity carbon black, acetylene black A and appropriate MnO is added2, stir, be added
Appropriate binder, ultrasonic disperse continue to stir, be demulsified in hot bath, filtering, the Catalytic Layer that roll-in obtains；
Acetylene black B is added into ethanol water, appropriate binder is added in ultrasonic disperse, stirs, and is broken in hot bath
Breast, the waterproof ventilative layer that roll-in obtains；
By after roll-in Catalytic Layer and waterproof ventilative layer be sticked to nickel foam both sides respectively, compression moulding, drying obtains air
Electrode；
Wherein, Na2SO4, high electric conductivity carbon black, acetylene black A, acetylene black B mass ratio be 2：4：3：7；
The time of stirring is 2.5h.
Comparative example 2
By Na2SO4It is dissolved in ethanol water, high electric conductivity carbon black, acetylene black A and appropriate Pt/C is added, stir, be added
Appropriate binder, ultrasonic disperse continue to stir, be demulsified in hot bath, filtering, the Catalytic Layer that roll-in obtains；
Acetylene black B is added into ethanol water, appropriate binder is added in ultrasonic disperse, stirs, and is broken in hot bath
Breast, the waterproof ventilative layer that roll-in obtains；
By after roll-in Catalytic Layer and waterproof ventilative layer be sticked to nickel foam both sides respectively, compression moulding, drying obtains air
Electrode；
Wherein, Na2SO4, high electric conductivity carbon black, acetylene black A, acetylene black B mass ratio be 2：4：3：7；
The time of stirring is 2.5h.
Test example 1
LSV tests are carried out to the air electrode that embodiment 5, comparative example 1 and comparative example 2 obtain respectively, as a result such as Fig. 1 institutes
Show.
As shown in Figure 1, there is larger limiting current density by the air electrode that the hydrogen reduction agent of the present invention is prepared.
Test example 2
Respectively using the air electrode that embodiment 5, comparative example 2 obtain as cathode, using zinc metal sheet electrode as anode, 6mol/L
NaOH forms zinc-air battery as electrolyte, carries out related electrochemical property test, obtained impedance contrast at room temperature
Figure is with reference to Fig. 2.
As shown in Figure 2, zinc-air battery made from the air electrode by the present invention has preferable chemical property.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of support type oxygen reduction catalyst, which is characterized in that the preparation method of the support type oxygen reduction catalyst includes
Following steps：To MnSO4KMnO is sequentially added in aqueous solution4, BP2000, ultrasonic disperse, heat up, keep the temperature, filter, washing, vacuum
It is dry, obtain support type oxygen reduction catalyst.
2. support type oxygen reduction catalyst according to claim 1, which is characterized in that the MnSO4Aqueous solution it is a concentration of
0.01-0.5mol/L；Preferably, the MnSO4With KMnO4Molar ratio be 1：1-5；Preferably, the MnSO4With BP2000
Mass ratio be 1：5-15.
3. support type oxygen reduction catalyst according to claim 1 or claim 2, which is characterized in that the time of the ultrasonic disperse is
10-30min。
4. according to any one of the claim 1-3 support type oxygen reduction catalysts, which is characterized in that the temperature of the heat preservation is
120-180 DEG C, time 12-24h.
5. according to any one of the claim 1-4 support type oxygen reduction catalysts, which is characterized in that the washing is using steaming
Distilled water is repeatedly washed.
6. according to any one of the claim 1-5 support type oxygen reduction catalysts, which is characterized in that the vacuum drying temperature
Degree is 40-80 DEG C, time 5-10h.
7. according to any one of the claim 1-6 support type oxygen reduction catalysts, which is characterized in that the BP2000 is to pass through
Pretreated BP2000, the pretreated method are：BP2000 is dispersed in HNO3In solution, ultrasonic disperse, reflux, from
Filter residue is washed in the heart, filtering, dry, obtains pretreated BP2000；Preferably, BP2000 is dispersed in HNO3In solution, ultrasound
Disperse 5-10min；Preferably, the temperature of the reflux is 60-100 DEG C, time 5-10h；Preferably, the washing filter residue is
It adopts and filter residue is washed with deionized to neutrality；Preferably, 40-80 DEG C of the temperature of the drying；Preferably, the HNO3Solution
A concentration of 3-10mol/L.
8. it is a kind of using any one of the claim 1-7 support type oxygen reduction catalysts prepare for zinc-air battery
Air electrode, which is characterized in that the preparation method of the air electrode includes the following steps：
S1, by Na2SO4It is dissolved in ethanol water, high electric conductivity carbon black, acetylene black A and the appropriate support type hydrogen reduction is added
Catalyst, stirring, is added appropriate binder, and ultrasonic disperse continues to stir, be demulsified in hot bath, and filtering, what roll-in obtained urges
Change layer；
S2, acetylene black B being added into ethanol water, appropriate binder is added in ultrasonic disperse, stirs, is demulsified in hot bath,
The waterproof ventilative layer that roll-in obtains；
S3, by after roll-in Catalytic Layer and waterproof ventilative layer be sticked to nickel foam both sides respectively, compression moulding, drying obtains air
Electrode.
9. air electrode according to claim 8, which is characterized in that Na2SO4, high electric conductivity carbon black, acetylene black A, acetylene black B
Mass ratio is 1-5：1-10：1-5：1-10.
10. air electrode according to claim 8 or claim 9, which is characterized in that the time of stirring is 1-3h.
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