CN105206848B - The method for preparing the graphene-supported mixed catalyst of air electrode of zinc-air cell - Google Patents
The method for preparing the graphene-supported mixed catalyst of air electrode of zinc-air cell Download PDFInfo
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- CN105206848B CN105206848B CN201510509185.3A CN201510509185A CN105206848B CN 105206848 B CN105206848 B CN 105206848B CN 201510509185 A CN201510509185 A CN 201510509185A CN 105206848 B CN105206848 B CN 105206848B
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- 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
Abstract
The present invention relates to a kind of air electrode of zinc-air cell catalyst, and in particular to a method of prepare the graphene-supported mixed catalyst of air electrode of zinc-air cell.The following steps are included: one: graphene oxide water solution will be prepared into graphene oxide ultrasonic disperse and water；Two: mixed catalyst is prepared using coprecipitation；Three: ultrasound will be continued to being uniformly dispersed in mixed catalyst obtained in two, graphene oxide water solution of the active carbon through ultrasonic disperse Yu Yizhong；Four: by the mixed system in three through being dried to obtain solid powder, this solid powder obtains target product through high temperature reduction.The present invention is added in the air electrode of zinc-air battery by the way that graphene and mixed catalyst are made into composite material, is accelerated catalytic efficiency, is improved the conductivity of electrode, is greatly improved the performance of zinc-air battery, is extended it and is used field.
Description
Technical field
The present invention relates to a kind of air electrode of zinc-air cell catalyst, and in particular to a kind of to prepare zinc-air battery sky
The method of the extremely graphene-supported mixed catalyst of pneumoelectric.
Background technique
Zinc-air battery is a kind of metal-air battery, makees positive active material, metallic zinc conduct with the oxygen in air
Cathode, neutral or alkalinity electrolyte aqueous solution is as electrolyte.
Outside due to positive active material from battery, without occupying the space of battery, in same volume, the feelings of weight
Under condition, more negative electrode active materials can be packed into zinc-air battery, so that zinc-air battery is higher than the capacity of common batteries
Many out, theoretical specific energy reaches 1350Wh/kg or more, and practical specific energy belongs to large capacity high energy in 1000Wh/kg or more
Electrochmical power source.Zinc-air battery also has many advantages, such as that specific energy is high, cheap, pollution-free, thus the application of zinc-air battery
Field is quite wide, be mainly used for navigation light in navigation, unmanned observation station, radio relay station, military radio transmitter,
Electric power car etc., but zinc-air battery still remains wretched insufficiency, such as: air electrode poorly conductive, catalytic efficiency are low, electric
Pond heavy-current discharge fever etc. seriously limits the development of zinc-air battery.
In recent years, graphene as a kind of good conductivity, paid close attention to, and is widely applied by the two-dimensional material of large specific surface area
In super capacitance electrode material field.Graphene is a kind of two-dimensional material of individual layer laminated structure being made of carbon atom, by list
Layer carbon atom passes through sp2Its tightly packed formation honeycomb crystal structure.This structure makes graphene have special mechanics
Light thermal property, single-molecule detection device, functional composite material, energy storage material, in terms of have and widely answer
Use prospect.Particularly, graphene has the electric conductivity of superelevation, resistivity only about 10~6Ω cm is current resistivity in the world
The smallest material, while graphene has good heating conduction again, is expected to improve the deficiency of new air cell.
Summary of the invention
It is graphene-supported mixed the present invention provides air electrode of zinc-air cell is prepared in order to solve the deficiencies in the prior art
The method of mould assembly catalyst, to improve, zinc-air battery poorly conductive, catalytic efficiency be low, high-rate battery discharge fever is asked
Topic, in order to achieve the above object, the technical solution adopted by the present invention are as follows:
A method of prepare the graphene-supported mixed catalyst of air electrode of zinc-air cell, preparation method include with
Lower step:
Step 1: graphene oxide ultrasonic disperse Yu Shuizhong is obtained into graphene oxide aqueous dispersions；
Step 2: nickel manganese mixed catalyst is prepared；
Step 3: by oxidation of the nickel manganese mixed catalyst ultrasonic disperse obtained in active carbon and step 2 in step 1
Graphene
In aqueous dispersions, continue ultrasound to being uniformly dispersed to obtain mixed dispersion liquid；
Step 4: the mixed dispersion liquid in step 3 is dried to obtain solid powder, solid powder is obtained through high temperature reduction
Target product.
Preferably, graphene oxide aqueous dispersions concentration is 0.1~20.0mg/ml, ultrasonic time in the step 1
For 2~12h.
Preferably, the step 2 includes following procedure:
(1) alkaline solution is prepared；
(2) Ni (NO is prepared3)2With Mn (NO3)2Mixed liquor；
(3) mixed liquor in (2) and the alkaline solution in (1) are slowly dropped into beaker, and control pH and is use up to drop is mixed,
Obtain suspension；
(4) lasting stirring, until the color of the suspension in (3) no longer changes；
(5) suspension in (4) is filtered, washing to neutrality obtains solid；
(6) solid in (5) is dry, grinding obtains solid powder, and the solid powder is nickel Mn catalyst.
Preferably, alkaline solution in (1) is NaOH, KOH, any one in ammonium hydroxide, alkaline solution pH value
It is 8~14.
Preferably, Ni (NO in (2) mixed liquor3)2With Mn (NO3)2Mass ratio be 1:9~9:1.
Preferably, pH value is 8~14 in (3).
Preferably, mixing time is 2~20h in (4).
Preferably, activated carbon raw material granularity is 800~10000 mesh in the step 3.
Preferably, mixed catalyst in the step three: active carbon: the molar ratio of graphene oxide is 10:8:7
~1:1:1, ultrasonic time are 1~18h.
Preferably, restoring method is heating reduction method in the step 4, reduction temperature is 150~800 DEG C, when reduction
Between be 2~12h, N is used when reduction2As protective atmosphere.
Compared with prior art, the advantages and positive effects of the present invention are: graphene has biggish specific surface area, excellent
Good electric conductivity, by the way that graphene and mixed catalyst are made into the air electrode that composite material is added to zinc-air battery
In, the active site of catalyst is increased, catalytic efficiency is accelerated, the introducing of graphene improves the conductivity of electrode again, into
And improve the high rate performance of battery.
Its catalytic activity of catalyst prepared by the present invention is higher, using the polarized current density density in potential range compared with
Greatly, the requirement of more high current density can be met.The addition of graphene can increase leading for electrode while improving catalytic efficiency again
The high rate performance for electrically improving battery, is greatly improved the performance of zinc-air battery, extends it and uses field.
It can be seen that compared with prior art, the present invention implementing with substantive distinguishing features outstanding and significant progress
Beneficial effect be also obvious.
Specific embodiment
Keep the object, technical solutions and advantages of the present invention clearer, embodiment of the present invention is made further below
Detailed description.
Embodiment 1:
The method provided by the invention for preparing the graphene-supported mixed catalyst of air electrode of zinc-air cell, step is such as
Under:
Step 1: the preparation of graphene oxide aqueous dispersions:
It weighs graphene oxide 0.1g to be scattered in 1000ml deionized water (concentration 0.1mg/ml), is ultrasonically treated 4h,
It is completely dispersed to graphene oxide.
Step 2: nickel manganese mixed catalyst is prepared:
It weighs NaOH solid 5.0g to be dissolved in the beaker equipped with 100ml deionized water, and is stirred, add deionized water tune
Section to pH value is 8, weighs Ni (NO3)20.29g (is with Ni (NO under the usual state of nickel nitrate3)2·6H2O form exists, molecular weight
For 290), weigh Mn (NO3)2(molar ratio is Ni (NO to solid 2.25g3)2: Mn (NO3)2=1:9) it is dissolved in 10ml deionized water
Mixed liquor is prepared, mixed liquor is slowly dropped into beaker with NaOH solution, control pH value keeps its constant 8, until mixing drop is most.
2h is persistently stirred, until the color of suspension, which no longer changes, obtains suspension.Then the suspension of preparation is filtered, wash to
PH value obtains solid for 7.By solid, dry, grind into powder, spare.
Step 3: the preparation of graphene oxide-loaded mixed catalytic agent solution
The catalyst fines 0.14g prepared in step 2, active carbon 0.11g are weighed, it is aerobic that containing for step 1 preparation is added
In the aqueous dispersions of graphite alkene 0.1g (nickel manganese mixed catalyst: active carbon: graphene oxide=10:8:7).Ultrasonic 1h, until
It is uniformly dispersed, obtains mixed dispersion liquid.
Step 4: the preparation of graphene-supported mixed catalyst
By the mixed dispersion liquid in step 3 through being dried to obtain solid powder, this solid powder is in N2Through 400 DEG C under protection
Heating reductase 12 h obtains target product.
Embodiment 2:
The method provided by the invention for preparing the graphene-supported mixed catalyst of air electrode of zinc-air cell, step is such as
Under:
Step 1: the preparation of graphene oxide aqueous dispersions:
It weighs graphene oxide 0.13g to be scattered in 130ml deionized water (concentration 1mg/ml), is ultrasonically treated 2h, until
Graphene oxide is completely dispersed.
Step 2: nickel manganese mixed catalyst is prepared:
It weighs KOH solid 5.0g to be dissolved in the beaker equipped with 100ml deionized water, and is stirred, distilled water is added to adjust
PH value is controlled 11, weighs Ni (NO3)20.29g, Mn (NO is weighed3)2(molar ratio is Ni (NO to solid 1.5g3)2: Mn (NO3)2=
It 1:6) is dissolved in 10ml deionized water and prepares mixed liquor, mixed liquor is slowly dropped into beaker with alkaline solution, control pH value makes it
It is constant 11, until mixing drop is to the greatest extent.4h is persistently stirred, until the color of suspension no longer changes.Preparation is hanged
Turbid is filtered, is washed, until pH value is 7.Filter cake obtained is put in beaker, it is dry, and by the powder mull after drying,
It is spare.
Step 3: the preparation of graphene oxide-loaded mixed catalytic agent solution
The catalyst fines 0.17g prepared in step 2, active carbon 0.15g are weighed, it is aerobic that containing for step 1 preparation is added
In the aqueous dispersions of graphite alkene 0.13g (nickel manganese mixed catalyst: active carbon: graphene oxide=9:8:7).Ultrasonic 6h, until
It is uniformly dispersed, obtains mixed dispersion liquid.
Step 4: the preparation of graphene-supported mixed catalyst
By the mixed system in step 3 through being dried to obtain solid powder, this solid powder is in N2Through 150 DEG C of heat under protection
Reduction 5h obtains target product.
Embodiment 3:
The method provided by the invention for preparing the graphene-supported mixed catalyst of air electrode of zinc-air cell, step is such as
Under:
Step 1: the preparation of graphene oxide aqueous dispersions:
It weighs graphene oxide 0.13g to be scattered in 43ml deionized water (concentration 3mg/ml), 5h is ultrasonically treated, until oxygen
Graphite alkene is completely dispersed.
Step 2: nickel manganese mixed catalyst is prepared:
Take 50mlNH3·H2O adds distilled water to adjust pH value control 10, weighs Ni (NO in beaker3)20.29g, it weighs
Mn(NO3)2(molar ratio is Ni (NO to solid 2g3)2: Mn (NO3)2=1:8) it is dissolved in 10ml deionized water and prepares mixed liquor, it will mix
It closes liquid and is slowly dropped into beaker with alkaline solution, control pH value keeps its constant 10, until mixing drop is to the greatest extent.Lasting stirring
6h, until the color of suspension no longer changes.The suspension of preparation is filtered, is washed, until pH value is 7.It will be obtained
Filter cake is put in beaker, dry, and by the powder mull after drying, spare.
Step 3: the preparation of graphene oxide-loaded mixed catalytic agent solution
The catalyst fines 0.13g prepared in step 2, active carbon 0.13g are weighed, it is aerobic that containing for step 1 preparation is added
In the aqueous dispersions of graphite alkene 0.13g (nickel manganese mixed catalyst: active carbon: graphene oxide=1:1:1).Ultrasonic 6h, until
It is uniformly dispersed, obtains mixed dispersion liquid.
Step 4: the preparation of graphene-supported mixed catalyst
Solid powder is obtained by the mixed system in step 3 is spray-dried, this solid powder is in N2Through 600 under protection
DEG C thermal reduction 7h obtain target product.
Embodiment 4:
The method provided by the invention for preparing the graphene-supported mixed catalyst of air electrode of zinc-air cell, step is such as
Under:
Step 1: the preparation of graphene oxide aqueous dispersions:
It weighs graphene oxide 0.36g to be scattered in 18ml deionized water (concentration 20mg/ml), is ultrasonically treated 5h, until
Graphene oxide is completely dispersed.
Step 2: nickel manganese mixed catalyst is prepared:
It weighs KOH solid 5.0g to be dissolved in the beaker equipped with 100ml deionized water, and is stirred, distilled water is added to adjust
PH value is controlled 14, weighs Ni (NO3)20.29g, Mn (NO is weighed3)2(molar ratio is Ni (NO to solid 0.75g3)2: Mn (NO3)2=
It 1:3) is dissolved in 10ml deionized water and prepares mixed liquor, mixed liquor is slowly dropped into beaker with alkaline solution, control pH value makes it
It is constant 14, until mixing drop is to the greatest extent.18h is persistently stirred, until the color of suspension no longer changes.Preparation is hanged
Turbid is filtered, is washed, until pH value is 7.Filter cake obtained is put in beaker, it is dry, and by the powder mull after drying,
It is spare.
Step 3: the preparation of graphene oxide-loaded mixed catalytic agent solution
The catalyst fines 0.84g prepared in step 2, active carbon 0.48g are weighed, it is aerobic that containing for step 1 preparation is added
In the aqueous dispersions of graphite alkene 0.36g (nickel manganese mixed catalyst: active carbon: graphene oxide=7:4:3).Ultrasonic 12h, until
It is uniformly dispersed, obtains mixed dispersion liquid.
Step 4: the preparation of graphene-supported mixed catalyst
By the mixed system in step 3 through being dried to obtain solid powder, this solid powder is in N2Through 800 DEG C of heat under protection
Reduction 8h obtains target product.
Embodiment 5:
The method provided by the invention for preparing the graphene-supported mixed catalyst of air electrode of zinc-air cell, step is such as
Under:
Step 1: the preparation of graphene oxide aqueous dispersions:
It weighs graphene oxide 0.4g to be scattered in 40ml deionized water (concentration 10mg/ml), is ultrasonically treated 10h, until
Graphene oxide is completely dispersed.
Step 2: nickel manganese mixed catalyst is prepared:
Take 50mlNH3·H2O adds distilled water to adjust pH value control 12, weighs Ni (NO in beaker3)22.61g, weigh
Mn(NO3)2(molar ratio is Ni (NO to solid 0.25g3)2: Mn (NO3)2=9:1) it is dissolved in 10ml deionized water and prepares mixed liquor,
Mixed liquor is slowly dropped into beaker with alkaline solution, control pH value keeps its constant 12, until mixing drop is to the greatest extent.Persistently stir
20h is mixed, until the color of suspension no longer changes.The suspension of preparation is filtered, is washed, until pH value is 7.It will be made
Filter cake be put in beaker, it is dry, and by the powder mull after drying, it is spare.
Step 3: the preparation of graphene oxide-loaded mixed catalytic agent solution
The catalyst fines 2.4g prepared in step 2, active carbon 2.0g are weighed, step 1 preparation is added contains oxidation
In the aqueous dispersions of graphene 0.4g (nickel manganese mixed catalyst: active carbon: graphene oxide=6:5:1).Ultrasonic 10h, until point
It dissipates uniformly, obtains mixed dispersion liquid.
Step 4: the preparation of graphene-supported mixed catalyst
By the mixed system in step 3 through being dried to obtain solid powder, this solid powder is in N2Through 600 DEG C of heat under protection
Reduction 10h obtains target product.
Embodiment 6:
The method provided by the invention for preparing the graphene-supported mixed catalyst of air electrode of zinc-air cell, step is such as
Under:
Step 1: the preparation of graphene oxide aqueous dispersions:
It weighs graphene oxide 0.1g to be scattered in 20ml deionized water (concentration 5mg/ml), 8h is ultrasonically treated, until oxygen
Graphite alkene is completely dispersed.
Step 2: nickel manganese mixed catalyst is prepared:
It weighs KOH solid 5.0g to be dissolved in the beaker equipped with 100ml deionized water, and is stirred, distilled water is added to adjust
PH value is controlled 9, weighs Ni (NO3)20.58g, Mn (NO is weighed3)2(molar ratio is Ni (NO to solid 0.25g3)2: Mn (NO3)2=
It 2:1) is dissolved in 10ml deionized water and prepares mixed liquor, mixed liquor is slowly dropped into beaker with alkaline solution, control pH value makes it
It is constant 9, until mixing drop is to the greatest extent.When persistently stirring 15h, until the color of suspension no longer changes.To preparation
Suspension is filtered, is washed, until pH value is 7.Filter cake obtained is put in beaker, it is dry, and the powder after drying is ground
Mill, it is spare.
Step 3: the preparation of graphene oxide-loaded mixed catalytic agent solution
The catalyst fines 0.7g prepared in step 2, active carbon 0.5g are weighed, step 1 preparation is added contains oxidation
In the aqueous dispersions of graphene 0.1g (nickel manganese mixed catalyst: active carbon: graphene oxide=7:5:1).Ultrasonic 9h, until dispersion
Uniformly, mixed dispersion liquid is obtained.
Step 4: the preparation of graphene-supported mixed catalyst
By the mixed system in step 3 through being dried to obtain solid powder, this solid powder is in N2Through 700 DEG C of heat under protection
Reduction 9h obtains target product.
Embodiment 7:
The method provided by the invention for preparing the graphene-supported mixed catalyst of air electrode of zinc-air cell, step is such as
Under:
Step 1: the preparation of graphene oxide aqueous dispersions:
It weighs graphene oxide 0.5g to be scattered in 83ml deionized water (concentration 6mg/ml), 8h is ultrasonically treated, until oxygen
Graphite alkene is completely dispersed.
Step 2: nickel manganese mixed catalyst is prepared:
It weighs NaOH solid 5.0g to be dissolved in the beaker equipped with 100ml deionized water, and is stirred, distilled water is added to adjust
PH value is controlled 13, weighs Ni (NO3)20.29g, Mn (NO is weighed3)2(molar ratio is Ni (NO to solid 1.25g3)2: Mn (NO3)2=
It 1:5) is dissolved in 10ml deionized water and prepares mixed liquor, mixed liquor is slowly dropped into beaker with alkaline solution, control pH value makes it
It is constant 13, until mixing drop is to the greatest extent.16h is persistently stirred, until the color of suspension no longer changes.Preparation is hanged
Turbid is filtered, is washed, until pH value is 7.Filter cake obtained is put in beaker, it is dry, and by the powder mull after drying,
It is spare.
Step 3: the preparation of graphene oxide-loaded mixed catalytic agent solution
The catalyst fines 0.8g prepared in step 2, active carbon 0.3g are weighed, step 1 preparation is added contains oxidation
In the aqueous dispersions of graphene 0.5g (nickel manganese mixed catalyst: active carbon: graphene oxide=8:3:5).Ultrasonic 16h, until point
It dissipates uniformly, obtains mixed dispersion liquid.
Step 4: the preparation of graphene-supported mixed catalyst
By the mixed system in step 3 through being dried to obtain solid powder, this solid powder is in N2Through 300 DEG C of heat under protection
Reduction 12h obtains target product.
Embodiment 8:
Embodiment prepares a kind of activated carbon supported mixed catalyst steps are as follows the present embodiment as a comparison:
Step 1: nickel manganese mixed catalyst is prepared:
It weighs NaOH solid 5.0g to be dissolved in the beaker equipped with 100ml deionized water, and is stirred, distilled water is added to adjust
PH value is controlled 13, weighs Ni (NO3)20.29g, Mn (NO is weighed3)2(molar ratio is Ni (NO to solid 1.25g3)2: Mn (NO3)2=
It 1:5) is dissolved in 10ml deionized water and prepares mixed liquor, mixed liquor is slowly dropped into beaker with alkaline solution, control pH value makes it
It is constant 13, until mixing drop is to the greatest extent.16h is persistently stirred, until the color of suspension no longer changes.Preparation is hanged
Turbid is filtered, is washed, until pH value is 7.Filter cake obtained is put in beaker, it is dry, and by the powder mull after drying,
It is spare.
Step 2: the preparation of activated carbon supported mixed catalytic agent solution
The powder prepared in step 1, active carbon are proportionally added into aqueous solution, wherein nickel manganese mixed catalyst: living
Property charcoal=8:3.Ultrasonic 16h, until being uniformly dispersed.
Step 3: the preparation of activated carbon supported mixed catalyst
By the mixed system in step 3 through being dried to obtain solid powder, this solid powder is in N2Through 300 DEG C of heat under protection
Reduction 12h obtains target product.
Technological parameter by Examples 1 to 7 and embodiment 8 (comparative example) and products thereof performance detection data comparison knot
Fruit is as follows:
It is analyzed from comparing result it is found that after graphene is added ,~0.3V polarized current density value is bright when other conditions are constant
It is aobvious to increase, illustrate that the addition of graphene improves the catalytic effect of catalyst.The present invention electric conductivity excellent using graphene,
It is added in the air electrode of zinc-air battery by the way that graphene and mixed catalyst are made into composite material, increases catalyst
Active site, accelerate catalytic efficiency, the introducing of graphene improves the conductivity of electrode again, and then improves the multiplying power of battery
Performance.Its catalytic activity of catalyst prepared by the present invention is higher, is using the polarized current density density in potential range larger,
The requirement of more high current density can be met.The addition of graphene can increase the electric conductivity of electrode again while improving catalytic efficiency
The high rate performance for improving battery, is greatly improved the performance of zinc-air battery, extends it and uses field.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
It imitates embodiment and is applied to other fields, but without departing from the technical solutions of the present invention, according to the technical essence of the invention
Any simple modification, equivalent variations and remodeling to the above embodiments, still fall within the protection scope of technical solution of the present invention.
Claims (9)
1. a kind of preparation method of the graphene-supported mixed catalyst for air electrode of zinc-air cell, feature exist
In: preparation method the following steps are included:
Step 1: graphene oxide ultrasonic disperse Yu Shuizhong is obtained into graphene oxide aqueous dispersions；
Step 2: nickel manganese mixed catalyst is prepared；
Step 3: by graphite oxide of the nickel manganese mixed catalyst ultrasonic disperse obtained in active carbon and step 2 in step 1
In alkene aqueous dispersions, continue ultrasound to being uniformly dispersed to obtain mixed dispersion liquid；
Step 4: the mixed dispersion liquid in step 3 is dried to obtain solid powder, solid powder obtains target through high temperature reduction
Product；
The step 2 includes following procedure:
(1) alkaline solution is prepared；
(2) Ni (NO is prepared3)2With Mn (NO3)2Mixed liquor；
(3) mixed liquor in (2) and the alkaline solution in (1) are slowly dropped into beaker, and control pH and is use up to mixing drop, obtained
Suspension；
(4) lasting stirring, until the color of the suspension in (3) no longer changes；
(5) suspension in (4) is filtered, washing to neutrality obtains solid；
(6) solid in (5) is dry, grinding obtains solid powder, and the solid powder is nickel Mn catalyst.
2. a kind of graphene-supported mixed catalyst for air electrode of zinc-air cell according to claim 1
Preparation method, it is characterised in that: graphene oxide aqueous dispersions concentration is 0.1~20.0mg/ml in the step 1, when ultrasonic
Between be 2~12h.
3. a kind of graphene-supported mixed catalyst for air electrode of zinc-air cell according to claim 1
Preparation method, it is characterised in that: (1) the neutral and alkali solution ph is 8~14.
4. a kind of graphene-supported mixed catalyst for air electrode of zinc-air cell according to claim 3
Preparation method, it is characterised in that: Ni (NO in (2) mixed liquor3)2With Mn (NO3)2Mass ratio be 1:9~9:1.
5. a kind of graphene-supported mixed catalyst for air electrode of zinc-air cell according to claim 3
Preparation method, it is characterised in that: pH value is 8~14 in (3).
6. a kind of graphene-supported mixed catalyst for air electrode of zinc-air cell according to claim 3
Preparation method, it is characterised in that: mixing time is 2~20h in (4).
7. a kind of graphene-supported mixed catalyst for air electrode of zinc-air cell according to claim 1
Preparation method, it is characterised in that: the active carbon activated carbon raw material granularity is 800~10000 mesh.
8. a kind of graphene-supported mixed catalyst for air electrode of zinc-air cell according to claim 1
Preparation method, it is characterised in that: mixed catalyst in the step three: active carbon: the molar ratio of graphene oxide is 10:
8:7~1:1:1；Ultrasonic time is 1~18h in the step three.
9. a kind of graphene-supported mixed catalyst for air electrode of zinc-air cell according to claim 1
Preparation method, it is characterised in that: restoring method is heating reduction method in the step 4, and reduction temperature is 150~800 DEG C, also
The former time is 2~12h, and N is used when reduction2As protective atmosphere.
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| CN104475172A (en) * | 2014-11-21 | 2015-04-01 | 东华大学 | Preparation method and application of three-dimensional porous heteroatom-doped graphene |
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