CN109546170A - A kind of preparation method of combination electrode catalyst and its application in metal-air battery - Google Patents
A kind of preparation method of combination electrode catalyst and its application in metal-air battery Download PDFInfo
- Publication number
- CN109546170A CN109546170A CN201811507315.XA CN201811507315A CN109546170A CN 109546170 A CN109546170 A CN 109546170A CN 201811507315 A CN201811507315 A CN 201811507315A CN 109546170 A CN109546170 A CN 109546170A
- Authority
- CN
- China
- Prior art keywords
- graphene
- electrode catalyst
- air
- metal
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
-
- 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
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- Y02E60/10—Energy storage using batteries
Abstract
Metal-air battery the present invention relates to a kind of mullite-graphene composite electrocatalyst preparation method and using the catalyst as electrode active material；The method that the present invention uses hydrothermal synthesis, is successfully prepared graphene-supported mullite catalysis material, solves the problems, such as mullite poorly conductive；In the test of metal-air full battery, above-mentioned composite catalyst has higher power generation peak power density and more preferably charge and discharge cycles stability compared with conventional precious metal catalyst.
Description
Technical field
The present invention relates to metal-air battery field, in particular to a kind of metal-air battery electrode catalyst and its preparation
Method.
Background technique
It is all scientific research circle and work all the time that research and development, which have high-performance, the electrochemical energy storage of high capacity and reforming unit,
One of the hot spot of industry concern, especially demand of the today's society to the energy, which are in from traditional fossil energy to low-carbon, cleans energy
The critical stage of source transformation.Metal-air battery has commercial much higher than at present as the next-generation battery technology being concerned
The theoretical energy density of lithium ion battery and relatively cheap cost of electricity-generating (Chem.Soc.Rev., 2014,43,5257),
Extensive concern by many researchers.Metal-air battery is using the oxygen in air as anode reactant, metal
The battery of (zinc, iron, aluminium, magnesium etc.) as a kind of air of cathode reactant has specific capacity height, safety and environmental protection, raw material valence
Many advantages, such as lattice are cheap.The technology of metal-air battery is very mature, has been successfully applied to medical instrument and long-range
Communication etc. needs low current, length to continue a journey, in the working environment of safety and stability (US Patent, 6660680B1,2003).,
However for the new demand of current industrial circle, such as electric car and mobile phone, there is also several for metal-air battery
The crucial technological difficulties of item need to break through.First, the reaction efficiency of air electrode, which is still, restricts metal-air battery performance
Key factor, although good (the Journal of Apply of traditional noble metal catalyst power generation performance
Electrochemistry, 1986,16,527；French Patent, 127069,1878), but it is expensive, reserves are rare,
It is not able to satisfy the demand of high-incidence electrical power；Second, stability is to measure the important indicator of a battery performance, noble metal catalyst
Easily poisoned in metal-air battery reaction environment semi-open in this way, itself there is also self-corrosion and reunite ask
Topic is not able to satisfy long-time or nonexpondable demand；Third, high potential ring when the unbearable battery of platinum catalyst charges
Border can lose activity quickly.Therefore, one of the key technology for promoting metal-air battery be development cost it is low, it is active it is high,
Still with the novel electrode catalyst of higher stability after repeated charge.Transition metal oxide catalysis with higher is lived
Property and the cost of relative moderate and be concerned.H.Dai et al. has synthesized the carbon nanotube of supported by cobalt oxide as air electricity
The catalyst preparation of pole oxygen reduction reaction has gone out generated output density and has been up to 265mW/cm2Zinc-air battery (Nature
Communications, 2013,4,1805) when charging, but under high currents, cobalt oxide particle will appear serious agglomeration
Battery performance is caused to reduce.Mn oxide is as one of electrode catalyst of greatest concern, stability (US with higher
Patent, 4894296A, 1987；US Patent, 7001439B2,2003), but generated output it is lower (Nano Letter,
2011,11,5362.).
Summary of the invention
Problem of the present invention is that proposing the preparation method and the use catalyst of a kind of combination electrode catalyst
Metal-air battery as electrode catalyst.
[electrode catalyst of the invention]
Heretofore described combination electrode catalyst is characterized in that, is following catalyst: two components are included at least,
One of group is divided into manganese base mullite type oxide, and the general formula having is RMn2O5, wherein R bit element is lanthanide series or yttrium
One or more of element；Another one group is divided into graphene perhaps graphene oxide or redox graphene,
Perhaps nitrogen-doping redox graphene or above several mixture.
[preparation method of electrode catalyst of the invention]
The preparation method of the combination electrode catalyst is hydro-thermal method, specifically includes the following steps:
1) salt containing R element of certain mass is weighed according to stoichiometric ratio and the salt containing manganese element is dissolved in solvent；
2) graphene or derivatives thereof being added into mixture obtained by step 1)；
3) aqueous slkali is added into mixture obtained by step 2)；
4) mixture obtained by step 2) is transferred in reaction kettle, is reacted at a certain temperature；
5) by the resulting product separation of step 3), drying, the catalysis material is obtained after grinding.
The preparation method of the combination electrode catalyst, temperature when executing step 1) to step 3) are not particularly limited,
Usually carried out under room temperature (20-30 DEG C).
The order of addition of the preparation method of the combination electrode catalyst, salt containing R element and the salt containing manganese element is not special
Limitation, suitably selects according to synthesis condition.
The preparation method of the combination electrode catalyst, solvent are water, hydrochloric acid, nitric acid, ethyl alcohol, isopropanol, ethylene glycol, first
One or more of benzene, preferably water；
The preparation method of the combination electrode catalyst, wherein graphene or derivatives thereof includes graphene, graphene point
One or more of dispersion liquid, graphene oxide, graphene oxide dispersion, N doping redox graphene.
The preparation method of the combination electrode catalyst, aqueous slkali be sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide,
One or more of tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, preferably sodium hydroxide solution.
The preparation method of the combination electrode catalyst, the reaction temperature of hydro-thermal reaction are 150-250 DEG C, preferably 180-
240 DEG C, more preferable 180-200 DEG C.
The preparation method of the combination electrode catalyst, reaction time of hydro-thermal reaction are 6-48h, preferably 12-48h, more
It is preferred that 12-24h.
The preparation method of the combination electrode catalyst, isolated method are not particularly limited, and can be natural filtration, true
Empty pump filter and centrifugation, suitably select according to synthesis condition；Dry condition is not particularly limited, can be dry for air blast
Dry, vacuum drying and freeze-drying, preferably freeze drying；The dry time is not particularly limited, usually 2h or more, preferably
6h or more, more preferable 12h or more, the upper limit are not particularly limited, usually three days hereinafter, it is preferred that two days hereinafter, more preferably for 24 hours
Below.
[zinc-air battery]
Zinc-air battery belongs to one kind of metal-air battery.One of electrode (referred to as air electricity of zinc-air battery
Pole) during discharge absorb air in oxygen.Reduction reaction occurs under the effect of the catalyst for oxygen, is reduced to OH-,
Metallic zinc is oxidized to Zn in another electrode (referred to as zinc electrode) simultaneously2+.During the charging process, the OH in electrolyte-Meeting exists
O is oxidized under the action of catalyst2(oxygen evolution reaction), and Zn2+Metallic zinc is reduced in zinc electrode.Alkaline zinc-air electricity
Reaction equation of the pond in electric discharge are as follows:
Cathode: O2+2H2O+4e-→4OH-
Anode: Zn → Zn2++2e-
Reaction equation when charging are as follows:
Cathode: Zn2++2e-→Zn
Anode: 4OH-→O2+2H2O+4e-
Zinc-air battery using the compound electrode catalyst as electrode catalyst, including zinc electrode, electrolyte
And air electrode.
The zinc-air battery, anode material are one of zine plate, zinc foil, zinc metal sheet, zinc powder.
The zinc-air battery, electrolyte are potassium hydroxide solution or potassium hydroxide and zinc acetate mixed aqueous solution.
The zinc-air battery, collector and oxygen evolution reaction catalyst are nickel foam or hydrotalcite.
The zinc-air battery, the air electrode include the active layer, collector and waterproof and breathable that load has catalyst
Film.
[aluminium-air cell]
Aluminium-air cell belongs to one kind of metal-air battery.One of electrode (referred to as air electricity of aluminium-air cell
Pole) oxygen in air is absorbed during discharge, reduction reaction occurs under the effect of the catalyst, is reduced to OH oxygen-,
Metallic aluminium is oxidized into Al in another electrode (referred to as aluminium electrode) simultaneously3+.Reaction of the alkaline aluminium-air cell in electric discharge
Equation are as follows:
Cathode: O2+2H2O+4e-→4OH-
Anode: Al → Al3++3e-
Aluminium-air cell using the compound electrode catalyst as electrode catalyst, including aluminium electrode, electrolyte
And air electrode.
The aluminium-air cell, anode material are one of aluminium sheet, aluminium foil, aluminium flake, aluminium powder.
The aluminium-air cell, electrolyte are sodium hydrate aqueous solution.
The aluminium-air cell, wherein air electrode includes the active layer, collector and waterproof and breathable that load has catalyst
Film.
In the present invention, " generated output density ", " specific capacity ", " energy density " and " stability " is based on following fixed
Justice: generated output density refers to the result that the area of active layer is normalized in electric power generation cell；Specific capacity refers at certain
Under the conditions of one specific, constant current discharge, what the quality of reaction consumption metal was normalized in the actual capacity of battery
As a result；Energy density refers to that the actual discharge energy of battery disappears to reaction under the conditions of a certain specific, constant current discharge
The result that the quality of consumption metal is normalized；Stability refers to that battery in charge and discharge process repeatedly, is keeping charging
Difference is at any time or cycle-index under the premise of electric current, discharge current are constant, between battery charging voltage and discharge voltage
Increased variation degree.
[The effect of invention]
The preparation method of electrode catalyst proposed by the present invention, the advantage is that, chemically synthesized presoma is stored up in earth's surface
Amount is abundant, preparation process is relatively easy, repeatable good, and material itself has the adjustability of height.Using described compound
Metal-air battery of the electrode catalyst as air-electrode catalyst material, with the battery phase using noble metal as catalysis material
Than under identical testing conditions, there are higher power generation peak power density, higher energy density and more preferably charge and discharge
Cyclical stability.
Detailed description of the invention
Fig. 1 is the XRD spectrum of electrode catalyst in embodiment
Fig. 2 is the TEM photo of electrode catalyst in embodiment 1
Fig. 3 is the TEM photo of electrode catalyst in embodiment 2 and embodiment 3
Fig. 4 is the nitrogen xps energy spectrum of electrode catalyst in embodiment 2 and embodiment 3
The power generation curve of zinc-air battery in Fig. 5 embodiment 1
Fig. 6 is the power generation curve of zinc-air battery in embodiment 2
Fig. 7 is the power generation curve of aluminium-air cell in embodiment 3
Fig. 8 is the power generation curve of zinc-air battery in comparative example
Fig. 9 be in embodiment 1 zinc-air battery in 50mA/cm2Under constant-current discharge curve
Figure 10 be in embodiment 2 zinc-air battery in 50mA/cm2Under constant-current discharge curve
Figure 11 be in embodiment 3 aluminium-air cell in 50mA/cm2Under constant-current discharge curve
Figure 12 be in comparative example zinc-air battery in 50mA/cm2Under constant-current discharge curve
Figure 13 be in embodiment 2 and comparative example zinc-air battery in 5mA/cm2Under charging and discharging curve
Specific embodiment
[measurement of powder X-ray RD]
Use the electrode catalyst sample obtained after agate mortar artificial pulverizing.The device of test is Rigaku company
Ultima IV type X-ray diffractometer, incident light source are Cu K αRunning parameter is 40kV, 40mA, scans model
10 °~80 ° are enclosed, sweeping speed is 8 °/min, and scanning step is 0.02 °.
[measurement of powder TEM]
Using the combination electrode catalyst sample obtained after agate mortar artificial pulverizing, takes and be distributed to dehydrated alcohol on a small quantity
In, it is not particularly limited about the quality of sample and the volume of ethyl alcohol.Ultrasonic disperse 30min suspension derived above.It takes a small amount of
Above-mentioned suspended drop is supported on film in carbon, wait spontaneously dry.The device of test is that 2100 type of Jeol Ltd. JEM is saturating
Penetrate electron microscope, acceleration voltage 200kV.
[air electrode preparation]
The composition of air electrode in the present invention has the active layer, collector and hydrophobic breathable layer of catalyst including loading.
The active layer generally refers to the ventilative backing material of the conduction coated with electrode catalyst, can be nickel foam, carbon
Cloth or carbon paper, the present invention in preferred carbon paper.The coating of the electrode catalyst carries out: as follows firstly, by electrode
Catalyst, which mixes to be dispersed in dispersion liquid with conductive material, is prepared into suspension, and the suspension is coated in carbon paper surface certainly
It is so dry.It should be noted that the conductive material is not particularly limited, it is typically chosen voltage window cheap, in battery
Mouthful physics and the stable material of chemical property, can be conductive black, acetylene black, Ketjen black；The dispersion liquid is without special
Limitation, can be water, ethyl alcohol and 5%The mixture of solution, wherein the ratio of water and ethyl alcohol is not particularly limited, and 5%The percentage that the volume of solution accounts for dispersion liquid is generally 20% hereinafter, preferably 10% hereinafter, particularly preferably 5%
Below.
The collector can be carbon paper, carbon cloth, metallic nickel, metallic copper, Titanium and other conductive materials, the present invention
Middle preferred foams nickel.The size of nickel foam is not particularly limited with thickness, chooses according to the actual situation.
Heretofore described air electrode, prepares in accordance with the following steps: by active layer, (electrode coated catalyst one is faced
On), collector and hydrophobic breathable layer be from top to bottom sequentially placed, be transferred in flat-bed press and apply pressure and kept for a period of time
Up to air electrode.It is not particularly limited it should be noted that applying stressed temperature, preferably under room temperature (20-30 DEG C)；It applies
The pressure added is not particularly limited, generally 10MPa hereinafter, preferably 5MPa hereinafter, particularly preferably 2MPa or less.
[electro-chemical test]
To the power generation of zinc-air battery test, the equipment used for Autolab PGSTAT128N type electrochemical workstation,
Sweep current range 0-325mA/cm2, sweep speed 5mV/s.Constant-current discharge test and charge-discharge test, the equipment used for
Eight channel battery analysis instrument of LAND, data acquisition rate 1point/5s.The current density of constant-current discharge is 50mA/cm2, fill
Each circulation of discharging includes 20min constant-current charge and 20min constant-current discharge process, and current density is 5mA/cm2。
Below will by specific example, the present invention is further illustrated, but the scope of application of the invention is not limited by it
System.
[embodiment 1]
Firstly, preparing redox graphene load SmMn using hydrothermal synthesis method2O5Catalyst, comprising the following steps:
1) Sm (NO is weighed according to molar ratio 5: 7: 33)3·6H2O、Mn(CH3COO)2·6H2O and KMnO4It is dissolved in 47ml
In deionized water, persistently stirs 30min and obtain solution A；
2) 3ml 10mg/ml graphene oxide water solution is added dropwise in the solution A into stirring, continues to stir 30min
Obtain solution B；
3) 5.5ml 1M NaOH solution is added dropwise in the solution B into stirring, continues stirring 5min and obtains solution C；
4) solution C is moved in 100ml reaction kettle, and reaction kettle is transferred in baking oven at 180 DEG C and is reacted for 24 hours；
5) mixture in reaction kettle is taken out into filtering, and uses 1%HNO3Solution and deionized water repeated flushing three times, obtain
To sediment；
6) gained precipitating is transferred in freeze drier dry 12h, grinding obtains redox graphene after taking-up
Load SmMn2O5Combination electrode catalyst.
The XRD analysis result of the combination electrode catalysis material prepared according to the method described above is as shown in Figure 1, electrode catalyst has
There is mullite-type oxide structure, does not observe that other are miscellaneous.Its pattern is as shown in Fig. 2, irregular particle homoepitaxial exists
Graphene-based bottom.Using above-mentioned composite catalyzing material as zinc-air battery electrode catalyst, assembling the following steps are included:
1) it weighs redox graphene described in 5mg and loads SmMn2O5Composite catalyzing material is led with 5mg Vulcan XC-72
Electric carbon black (Cabot Corp.), is added to 250ul deionized water, 1ml dehydrated alcohol and 50ul 5%Mixing it is molten
In liquid, ultrasonic 30min obtains dispersion liquid M；
2) appropriate dispersion liquid M is measured, is coated uniformly on carbon paper, so that the load capacity of final catalyst is 1.5mg/cm2；
3) carbon paper (one side of coating catalyst is upward), nickel foam and waterproof ventilated membrane are from top to bottom sequentially placed, are turned
It moves on in flat-bed press, applies the pressure of 2MPa at room temperature, take out after keeping 1min up to air cathode；
4) zine plate (99.99%) and gained air cathode is fixed in fixture, 6M KOH solution is added to get empty to zinc
Pneumoelectric pond.
The concrete outcome tested is generated electricity as shown in figure 5, zinc-air battery peak power density reaches 222mW/cm2.Constant-current discharge
In test and charge-discharge test, when with 50mA/cm2Current density when carrying out constant-current discharge, zinc-air battery specific capacity can be high
Up to 652mAh/g, corresponding energy density is up to 730kWh/kg, as a result as shown in Figure 9.
[embodiment 2]
Firstly, preparing N doping redox graphene load SmMn using hydrothermal synthesis method2O5Catalyst, including it is following
Step:
1) Sm (NO is weighed according to molar ratio 5: 7: 33)3·6H2O、Mn(CH3COO)2·6H2O and KMnO4It is dissolved in 47ml
In deionized water, persistently stirs 30min and obtain solution A；
2) 3ml 10mg/ml graphene oxide water solution is added dropwise in the solution A into stirring, continues to stir 30min
Obtain solution B；
3) 5.5ml 1M NaOH solution is added dropwise in the solution B into stirring, continues stirring 5min and obtains solution C；
4) concentrated ammonia liquor of 1ml 36-38% is added dropwise in the solution C into stirring, continues stirring 5min and obtains solution D
5) solution D is moved in 100ml reaction kettle, and reaction kettle is transferred in baking oven at 180 DEG C and is reacted for 24 hours；
6) mixture in reaction kettle is taken out into filtering, and uses 1%HNO3Solution and deionized water repeated flushing three times, obtain
To sediment；
7) gained precipitating is transferred in freeze drier dry 12h, grinding obtains N doping reduction-oxidation after taking-up
Graphene-supported SmMn2O5Combination electrode catalyst.
The XRD analysis result of the combination electrode catalysis material prepared according to the method described above is as shown in Figure 1, electrode catalyst has
There is mullite-type oxide structure, does not observe that other are miscellaneous.Its pattern is as shown in figure 3, irregular particle homoepitaxial exists
Graphene-based bottom.XPS shown in Fig. 4 the result shows that, the characteristic peak of nitrogen is observed at 399.5eV, illustrate nitrogen success
It is doped in material.Using above-mentioned composite catalyzing material as zinc-air battery electrode catalyst, assembling the following steps are included:
1) it weighs N doping redox graphene described in 5mg and loads SmMn2O5Composite catalyzing material and 5mg Vulcan
XC-72 conductive black (Cabot Corp.), is added to 250ul deionized water, 1ml dehydrated alcohol and 50ul 5%'s
In mixed solution, ultrasonic 30min obtains dispersion liquid M；
2) appropriate dispersion liquid M is measured, is coated uniformly on carbon paper, so that the load capacity of final catalyst is 1.5mg/cm2；
3) carbon paper (one side of coating catalyst is upward), nickel foam and waterproof ventilated membrane are from top to bottom sequentially placed, are turned
It moves on in flat-bed press, applies the pressure of 2MPa at room temperature, take out after keeping 1min up to air cathode；
4) zine plate (99.99%) and gained air cathode is fixed in fixture, 6M KOH and 0.2M Zn is added
(CH3COO)2Mixed solution solution to get arrive zinc-air battery.
The concrete outcome tested is generated electricity as shown in fig. 6, zinc-air battery peak power density reaches 243mW/cm2.Constant-current discharge
In test and charge-discharge test, when with 50mA/cm2Current density when carrying out constant-current discharge, zinc-air battery specific capacity can be high
Up to 657mAh/g, corresponding energy density is up to 780kWh/kg, and the results are shown in Figure 10.Charge-discharge test result shown in Figure 13
Show zinc-air battery after about 70h, 100 charge and discharge cycles, charging/discharging voltage difference is increased from 0.60V
0.65V has only changed 8.3%, shows excellent cyclical stability.
[embodiment 3]
Firstly, preparing N doping redox graphene load SmMn using hydrothermal synthesis method2O5Catalyst, including it is following
Step:
1) Sm (NO is weighed according to molar ratio 5: 7: 33)3·6H2O、Mn(CH3COO)2·6H2O and KMnO4It is dissolved in 47ml
In deionized water, persistently stirs 30min and obtain solution A；
2) 3ml 10mg/ml graphene oxide water solution is added dropwise in the solution A into stirring, continues to stir 30min
Obtain solution B；
3) 5.5ml 1M NaOH solution is added dropwise in the solution B into stirring, continues stirring 5min and obtains solution C；
4) concentrated ammonia liquor of 1ml 36-38% is added dropwise in the solution C into stirring, continues stirring 5min and obtains solution D
5) solution D is moved in 100ml reaction kettle, and reaction kettle is transferred in baking oven at 180 DEG C and is reacted for 24 hours；
6) mixture in reaction kettle is taken out into filtering, and uses 1%HNO3Solution and deionized water repeated flushing three times, obtain
To sediment；
7) gained precipitating is transferred in freeze drier dry 12h, grinding obtains N doping reduction-oxidation after taking-up
Graphene-supported SmMn2O5Combination electrode catalyst.
The XRD analysis result of the combination electrode catalysis material prepared according to the method described above is as shown in Figure 1, electrode catalyst has
There is mullite-type oxide structure, does not observe that other are miscellaneous.Its pattern is as shown in figure 3, irregular particle homoepitaxial exists
Graphene-based bottom.XPS shown in Fig. 4 the result shows that, the characteristic peak of nitrogen is observed at 399.5eV, illustrate nitrogen success
It is doped in material.Using above-mentioned composite catalyzing material as aluminium-air cell electrode catalyst, assembling the following steps are included:
1) it weighs N doping redox graphene described in 5mg and loads SmMn2O5Composite catalyzing material and 5mg Vulcan
XC-72 conductive black (Cabot Corp.), is added to 250ul deionized water, 1ml dehydrated alcohol and 50ul 5%'s
In mixed solution, ultrasonic 30min obtains dispersion liquid M；
2) appropriate dispersion liquid M is measured, is coated uniformly on carbon paper, so that the load capacity of final catalyst is 1.5mg/cm2；
3) carbon paper (one side of coating catalyst is upward), nickel foam and waterproof ventilated membrane are from top to bottom sequentially placed, are turned
It moves on in flat-bed press, applies the pressure of 2MPa at room temperature, take out after keeping 1min up to air cathode；
4) aluminium sheet (99.99%) and gained air cathode is fixed in fixture, 4M NaOH solution is added to get aluminium is arrived
Air cell.
The concrete outcome tested is generated electricity as shown in fig. 7, aluminium-air cell peak power density reaches 190mW/cm2.Constant-current discharge
In test and charge-discharge test, when with 50mA/cm2Current density carry out constant-current discharge when, aluminium-air cell specific capacity is reachable
480mAh/g, corresponding energy density reach 530kWh/kg, as a result as shown in figure 11.
[comparative example]
As comparative example, zinc-air battery is used as using commercial platinum carbon catalyst (Pt/C 20%, Sigma Aldrich)
Cathod catalyst.The assembling of zinc-air battery the following steps are included:
1) 10mg 20%Pt/C is weighed, 250ul deionized water, 1ml dehydrated alcohol and 50ul 5% are added to
Mixed solution in, ultrasonic 30min obtains dispersion liquid M；
2) appropriate dispersion liquid M is measured, is coated uniformly on carbon paper, so that the load capacity of final Pt/C is 1.5mg/cm2；
3) carbon paper (one side of coating catalyst is upward), nickel foam and waterproof ventilated membrane are from top to bottom sequentially placed, are turned
It moves on in flat-bed press, applies 1000 pounds of pressure at room temperature, take out after keeping 1min up to air cathode；
4) zine plate (99.99%) and gained air cathode is fixed in fixture, 6M KOH and 0.2M Zn is added
(CH3COO)2Mixed solution to get arrive zinc-air battery.
The concrete outcome tested is generated electricity as shown in figure 8, zinc-air battery peak power density is about 170mW/cm2.Constant current is put
In electrical testing and charge-discharge test, when with 50mA/cm2Current density carry out constant-current discharge when, the specific capacity of zinc-air battery
For up to 642mAh/g, corresponding energy density is 767kWh/kg, as a result as shown in figure 12.Charge-discharge test knot shown in Figure 13
Fruit shows zinc-air battery after only passing through about 25h, 37 charge and discharge cycles, has already appeared obvious decaying, between charge and discharge
The difference of voltage increases to 0.96V by 0.68V, has changed 41.2%.
The above results show that electrode catalyst of the invention has in metal-air battery better than business precious metal catalyst
The performance of agent.
Claims (9)
1. a kind of combination electrode catalyst for metal-air battery, which is characterized in that the electrode catalyst includes at least
Two components, one of group is divided into manganese base mullite type oxide, and the general formula having is RMn2O5, wherein R bit element is group of the lanthanides
One or more of element or yttrium；Another one group is divided into graphene perhaps graphene oxide or reduction-oxidation
Graphene perhaps nitrogen-doping redox graphene or above several mixture.
2. electrode catalyst according to claim 1, which is characterized in that the preparation method of the electrode catalyst is hydro-thermal
Method, comprising the following steps:
1) salt and the salt containing manganese element that the element of bit containing R of certain mass is weighed according to stoichiometric ratio are dissolved in solvent；
2) graphene or derivatives thereof is added into step 1) acquired solution；
3) aqueous slkali is added into step 2) acquired solution；
4) step 3) acquired solution is transferred in reaction kettle, is reacted at a certain temperature；
5) by the resulting product separation of step 4), drying, the catalyst is obtained after grinding.
3. the preparation method of electrode catalyst according to claim 2, which is characterized in that the solvent is water, hydrochloric acid, nitre
One or more of acid, ethyl alcohol, isopropanol, ethylene glycol, toluene.
4. the preparation method of electrode catalyst according to claim 2, which is characterized in that described graphene or derivatives thereof
Including in graphene, graphene dispersing solution, graphene oxide, graphene oxide dispersion, N doping redox graphene
It is one or more of.
5. the preparation method of electrode catalyst according to claim 2, which is characterized in that the aqueous slkali is sodium hydroxide
One or more of solution, potassium hydroxide solution, ammonium hydroxide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide.
6. a kind of air electrode, which is characterized in that the air electrode includes electrode catalyst described in any one of claim 1-5
Agent.
7. air electrode according to claim 6, which is characterized in that the air electrode includes at least hydrophobic breathable layer, collection
The active layer of fluid and supported catalyst.
8. a kind of metal-air battery, which is characterized in that the metal-air battery includes the electricity of air described in claim 6-7
Pole.
9. metal-air battery according to claim 7, which is characterized in that the metal include zinc, aluminium, magnesium, iron, lithium,
Any and its alloy in sodium, potassium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811507315.XA CN109546170A (en) | 2018-12-11 | 2018-12-11 | A kind of preparation method of combination electrode catalyst and its application in metal-air battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811507315.XA CN109546170A (en) | 2018-12-11 | 2018-12-11 | A kind of preparation method of combination electrode catalyst and its application in metal-air battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109546170A true CN109546170A (en) | 2019-03-29 |
Family
ID=65854525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811507315.XA Pending CN109546170A (en) | 2018-12-11 | 2018-12-11 | A kind of preparation method of combination electrode catalyst and its application in metal-air battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109546170A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110176658A (en) * | 2019-05-28 | 2019-08-27 | 中国科学技术大学 | Available composite zinc air secondary battery in a kind of oxygen-free environment |
| CN110299532A (en) * | 2019-06-21 | 2019-10-01 | 天津大学 | A kind of preparation method of water system aluminum-air battery device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105742654A (en) * | 2016-03-24 | 2016-07-06 | 南开大学 | Preparation method for mixed-phase mullite electrocatalyst and catalyst layer used for negative electrode of fuel cell |
| CN106159289A (en) * | 2016-07-05 | 2016-11-23 | 张启辉 | Composite of Mn oxide Surface coating graphite and preparation method thereof |
| CN108232213A (en) * | 2017-12-01 | 2018-06-29 | 复旦大学 | A kind of nitrogen-doped graphene-carbon nanotube-cobaltosic oxide hybrid material and preparation method thereof |
| CN108448121A (en) * | 2018-03-14 | 2018-08-24 | 南开大学 | A kind of preparation method of electrode catalyst and its application in zinc-air battery |
-
2018
- 2018-12-11 CN CN201811507315.XA patent/CN109546170A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105742654A (en) * | 2016-03-24 | 2016-07-06 | 南开大学 | Preparation method for mixed-phase mullite electrocatalyst and catalyst layer used for negative electrode of fuel cell |
| CN106159289A (en) * | 2016-07-05 | 2016-11-23 | 张启辉 | Composite of Mn oxide Surface coating graphite and preparation method thereof |
| CN108232213A (en) * | 2017-12-01 | 2018-06-29 | 复旦大学 | A kind of nitrogen-doped graphene-carbon nanotube-cobaltosic oxide hybrid material and preparation method thereof |
| CN108448121A (en) * | 2018-03-14 | 2018-08-24 | 南开大学 | A kind of preparation method of electrode catalyst and its application in zinc-air battery |
Non-Patent Citations (2)
| Title |
|---|
| 董超: ""氧空位可调的非晶莫来石催化剂应用于高效的氧还原反应"", 《万方数据知识服务平台》 * |
| 马士精: ""基于SmMn2O5纳米晶体表面形貌的调控及其NO催化氧化性能的研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110176658A (en) * | 2019-05-28 | 2019-08-27 | 中国科学技术大学 | Available composite zinc air secondary battery in a kind of oxygen-free environment |
| CN110299532A (en) * | 2019-06-21 | 2019-10-01 | 天津大学 | A kind of preparation method of water system aluminum-air battery device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111001427B (en) | Cobalt-nitrogen co-doped carbon-based electrocatalyst material and preparation method thereof | |
| CN112090441B (en) | Preparation method, product and application of cobalt-based carbon nanomaterial | |
| CN111001428B (en) | Metal-free carbon-based electrocatalyst, preparation method and application | |
| CN105552393A (en) | Bi-functional catalyst for alkaline water system metal/air battery and preparation method thereof | |
| CN109802150B (en) | Non-noble metal bifunctional oxygen electrode catalyst, preparation method thereof, zinc-air battery anode and zinc-air battery | |
| CN110247068B (en) | Preparation method and application of iron/copper aza graphene zinc air battery cathode catalyst | |
| CN112349921B (en) | Nitrogen-doped graphene hollow sphere catalyst, preparation method and application | |
| CN110797541B (en) | Cathode dual-function electrocatalyst for molten salt iron air battery and application of cathode dual-function electrocatalyst | |
| CN111933961B (en) | Binary CoFe alloy loaded g-C3N4Catalyst and preparation method thereof | |
| CN112886029B (en) | Preparation and application of bifunctional oxygen electrocatalyst with hollow carbon nanotube as carrier | |
| CN113611881B (en) | Atomic-level dispersed Fe/nitrogen-doped mesoporous carbon spheres and preparation method and application thereof | |
| CN110247071A (en) | A kind of positive electrode, and its preparation method and application | |
| CN112002915B (en) | Oxygen electrode bifunctional catalyst, preparation method and application | |
| CN113649011A (en) | Non-noble metal carbon-based catalyst and preparation method and application thereof | |
| CN112968184A (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| CN111326745A (en) | Two-dimensional zinc monoatomic/carbon nitrogen composite material and preparation method and application thereof | |
| CN109546170A (en) | A kind of preparation method of combination electrode catalyst and its application in metal-air battery | |
| CN115411276B (en) | Preparation method of core-shell nano-cage electrocatalyst for oxygen reduction reaction | |
| CN114944495B (en) | Difunctional oxygen electrocatalyst with CoN/MnO double active sites and preparation and application thereof | |
| CN114628696B (en) | Preparation method of porous carbon-supported cobalt-based bifunctional oxygen catalyst | |
| WO2024031917A1 (en) | Bimetallic single-atom nitrogen-doped porous carbon electrocatalyst and preparation method therefor | |
| CN110120526A (en) | A kind of preparation method and application of transition metal alloy/multidimensional carbon-based composite electrode material | |
| CN108448121A (en) | A kind of preparation method of electrode catalyst and its application in zinc-air battery | |
| CN113659151A (en) | Graphene composite copper sulfide/nickel sulfide catalytic material and preparation method and application thereof | |
| CN110247073A (en) | A kind of chargeable zinc-air battery anode catalyst, preparation method and applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190329 |