CN109830694A - A kind of catalyst and its preparation method and application of double clad structures - Google Patents
A kind of catalyst and its preparation method and application of double clad structures Download PDFInfo
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Abstract
The present embodiments relate to a kind of catalyst and its preparation method and application of double clad structures, specific surface area 320-490m2/ g, the ingredient including parts by weight: 60-80 parts of spinelle, 5-20 parts of Mn oxide and 10-30 parts of carbonaceous material.The present invention increases spinel catalyst catalytic activity, then body mutually coats carbonaceous material, increases electric conductivity, reaches excellent concerted catalysis effect by coating Mn oxide to spinel-type catalyst surface.
Description
Technical field
The present invention relates to metal-air battery technical fields, more particularly, to the catalyst and its system of a kind of double clad structures
Preparation Method and application.
Background technique
As fossil fuel reserves are increasingly deficient, air pollution is on the rise, and the energy that people find sustainable development is compeled
In the eyebrows and eyelashes.Fuel cell has energy transformation ratio height, pollution-free to wait a little, has become the research hotspot in new energy direction.Combustion
Expect that battery includes Proton Exchange Membrane Fuel Cells, solid oxide fuel cell, metal air fuel cell etc..
Metal-air battery plays the advantages of fuel cell, using the oxygen in air as cathode, metal (magnesium, aluminium, zinc etc.)
For anode, oxygen in air can continuously by gas-diffusion electrode reach electrochemical reaction interface and metal (magnesium,
Aluminium, zinc etc.) it reacts and releases electric energy.The outstanding advantages of metal-air battery are that specific energy is big, in alkaline electrolyte solution,
The theoretical specific energy of magnesium-air cell is 6800Wh/kg, and the theoretical specific energy of aluminium-air cell is 8100Wh/kg, magnesium-air
The theoretical specific energy of battery is 1350Wh/kg.But currently, the practical specific energy of metal-air battery only reach 600-800Wh ×
kg-1Left and right, even so, its practical specific energy is also 12 times of lead-acid battery, 9 times of nickel-metal hydride battery, 3 times of left sides of lithium battery
Right (lead-acid battery energy density generally only has 40Wh/kg, and lithium battery energy density also only has 100-200Wh/kg).In metal sky
In pneumoelectric pond, catalyst not only determines the performance of battery, and determines the cost of battery.Currently, noble metal catalyst, such as
Silver, platinum, iridium etc., their d electron orbit is all unfilled, and superficial attractive forces are strong, can guarantee at very high electrode potentials compared with
High output electric current has best catalytic performance, but it is expensive, and the reserves in the earth's crust are low, hinder its big rule
The industrial production of mould.Therefore, in the research of metal-air battery, the catalyst for finding Cheap highly effective has great importance.
Spinel oxide is a kind of widely used catalyst, improves the oxygen of metal-air battery to a certain extent
Reduction catalysts performance, but spinel oxide electron transfer rate is not high, specific surface area still needs to improve, and causes its hydrogen reduction anti-
It answers activity not good enough, limits its application in metal-air battery.CN201510765984.7 discloses one kind, and mangaic acid nickel/
Carbon nano-composite catalyst and its preparation and application, bifunctional catalyst includes nanotube and mangaic acid nickel spinelle, by titanium dioxide
Manganese presoma, nickel acetate and nanotube are dissolved in ammonium hydroxide, ultrasonic disperse, hydrolysis, cooling, are cleaned, dry, and calcining is
?.The discharge energy density of the catalyst is 170mW/cm2, still do not reach the performance of precious metal catalyst.
Summary of the invention
To solve the prior art, the purpose of the present invention is to provide a kind of catalyst of double clad structures, catalyst tools
There is efficient, stable ORR catalytic activity, low production cost is applied in metal-air battery, extends battery and uses the longevity
Life reduces battery cost, improves battery performance.
It is an object of the present invention to provide a kind of preparation methods of the catalyst of double clad structures, and this method is easy to operate, and suitable
Close industrial amplification production.
The present invention is achieved through the following technical solutions:
A kind of catalyst of double clad structures, specific surface area 320-490m2/ g, the ingredient including following weight parts:
60-80 parts of spinelle, 5-20 parts of Mn oxide and 10-30 parts of carbonaceous material.
Further preferably, a kind of catalyst of double clad structures, specific surface area 380-450m2/ g, including it is following heavy
Measure the ingredient of part: 65-75 parts of spinelle, 10-15 parts of Mn oxide and 15-25 parts of carbonaceous material.
The catalyst of double clad structures of the present invention is spinelle surface cladding Mn oxide, body mutually coats and contains again
Carbon material.
Spinelle of the present invention is spinelle AB2O4, and wherein A is a kind of element in Mg, Fe, Co, Ni, Cu and Zn, B
For element a kind of in Al, Cr, Mn, Fe, Co, Ni.It is preferred that A Ni, B Co.Wherein, the molar ratio of A and B is 1:2.
It is preferred that spinelle of the present invention is cobalt acid nickel spinelle, wherein the molar ratio of cobalt and nickel element is 2:1.
The catalyst of double clad structures of the invention aoxidizes to improve hydrogen reduction catalytic performance in spinelle outer cladding manganese
Object.The Mn oxide includes manganese dioxide, manganese sesquioxide managnic oxide, one or more of in mangano-manganic oxide, preferably manganese dioxide, energy
Enough increase spinel catalyst catalytic activity.But Mn oxide conductivity is relatively low, causes electrode anyway slow, results in one
As Mn oxide material actual discharge rate it is lower, affect the conductive capability of catalyst.
The present invention improves the low situation of Mn oxide conductivity, in Mn oxide coating spinelle to enhance electric conductivity
Body mutually coats carbonaceous material to foreign minister again, to improve the utilization rate of Mn oxide, increases capacitance and energy density.Institute of the present invention
Stating carbonaceous material includes but is not limited to graphene, carbon nanotube, graphite, preferably graphene.Graphene compares table since its is biggish
Area can cooperate with the catalysis of Mn oxide coating spinelle, electric action.
The present invention also provides a kind of preparation methods of the catalyst of double clad structures, include the following steps:
(1) preparation of spinelle: weighing metal A salt, and solvent is added in metal B salt, and it is anti-to go to high pressure for stirring, ultrasonic disperse
Kettle is answered, hydro-thermal reaction is cooling, filters, and dries, and calcining obtains spinelle；
(2) it the preparation of Mn oxide coating spinelle: disperses spinelle, Mn oxide, inducer in solvent, stirs
It mixes, ultrasonic disperse, dry, calcining obtains Mn oxide coating spinelle；
(3) preparation of carbonaceous material clad structure spinel catalyst: by Mn oxide coating spinelle, carbonaceous material,
It is scattered in solvent, surfactant is added, ultrasonic disperse, fast decompression is dry, calcining, obtains the catalysis of double clad structures
Agent；
It is preferred that a kind of preparation method of the catalyst of double clad structures, includes the following steps:
(1) preparation of spinelle: weighing 45-60 parts of metal A salt, and solvent, magnetic agitation is added in 90-120 parts of metal B salt
1-2h, re-ultrasonic dispersion 1-2h, goes to autoclave, and 2-4h is reacted at 110-180 DEG C, cooling, filters, drying, 300-
600 DEG C of calcinings, obtain spinelle；
(2) by 60-80 parts of spinelle, 5-20 parts of Mn oxide, induction the preparation of Mn oxide coating spinelle: is added
Agent, magnetic agitation 1-2h, re-ultrasonic dispersion 1-2h, 80 DEG C of oven drying 4-6h, 400-600 DEG C is calcined, and Mn oxide packet is obtained
Cover spinelle；
(3) preparation of carbonaceous material clad structure spinel catalyst: 75-90 parts of Mn oxide coating spinelle contain
10-30 parts of carbon material, it is scattered in solvent, surfactant is added, ultrasonic disperse 6-12h, fast decompression is dry, and 500-800 DEG C
Vacuum calcining obtains the catalyst of double clad structures.
Metal A salt described in above-mentioned steps (1) is sulfuric acid A salt, chlorination A salt, nitric acid A salt etc., preferably nitric acid A salt；Institute
The metal B salt stated is sulfuric acid B salt, chlorination B salt, nitric acid B salt etc., preferably nitric acid B salt.
Wherein A is a kind of element in Mg, Fe, Co, Ni, Cu and Zn, a kind of element in B Al, Cr, Mn, Fe, Co, Ni.It is excellent
Choosing, A Ni, B Co.Wherein, the molar ratio of A and B is 1:2.
Solvent described in above-mentioned steps (1) is one of terpinol, ethyl alcohol, isopropanol, n-butanol and n-hexyl alcohol.This
Invention select ethyl alcohol as solvent, in the fabrication process will not high temperature generation exhaust gas, it is environmentally friendly and harmless.
Mn oxide described in above-mentioned steps (2) includes manganese dioxide, manganese sesquioxide managnic oxide, it is a kind of in mangano-manganic oxide or
It is several, preferred manganese dioxide.
Inducer described in step (2) is one of polyethylene glycol oxide and polyethylene pyrrole network alkanone；Quality is spinelle
With the 1~10% of Mn oxide gross mass.
Solvent described in above-mentioned steps (3) is one of terpinol, ethyl alcohol, isopropanol, n-butanol and n-hexyl alcohol.This
Invention select ethyl alcohol as solvent, in the fabrication process will not high temperature generation exhaust gas, it is environmentally friendly and harmless.
Carbonaceous material described in above-mentioned steps (3) is graphene, carbon nanotube, one or more of in graphite.
Surfactant described in above-mentioned steps (3) is neopelex, dioctyl succinate disulfonate acid, sulphur
It is acidified one of castor oil and glyceride or a variety of, quality is Mn oxide coating spinelle and carbonaceous material gross mass percentage
Than 1~10%.Surfactant makes Catalyst Adsorption in the surface of carbonaceous material by Van der Waals force.
A kind of catalyst of double clad structures provided by the invention is applied to the catalyst of air battery cathode.
Another technical solution of the invention is a kind of preparation method of air battery cathode piece, is included the following steps:
(1) prepare Catalytic Layer: catalyst, conductive agent, binder and solvent mixing, ultrasound stir to get catalyst pulp,
It dries again, compacting forms a film to arrive Catalytic Layer；The air battery cathode catalyst, conductive agent, binder mass parts ratio be
(1-2): (1-3): (2-5)；
(2) waterproof ventilative layer is prepared；Conductive agent, binder and solvent mixing, ultrasound stir to get waterproof ventilative layer slurry
Material, then dry, compacting forms a film up to waterproof ventilative layer；The conductive agent, binder mass parts ratio be (1-3): (2-5).
(3) it prepares air battery cathode piece: Catalytic Layer, waterproof ventilative layer and collector is pressed together, to obtain
Obtain air battery cathode piece.
Catalyst described in above-mentioned steps (1) Catalytic Layer, conductive agent, binder and solvent mass parts ratio be (5-10):
(5-15): (10-20): (60-80)；It is preferred that catalyst, conductive agent, binder and solvent mass parts ratio be (6-8): (8-
12): (12-18): (64-76), still more preferably, catalyst, conductive agent, binder and solvent mass parts ratio be 6.5:
9.8:12.2:71.5.
The mass parts ratio of conductive agent, binder and solvent described in above-mentioned steps (2) waterproof ventilative layer is (5-15): (10-
25): (60-80).It is preferred that the mass parts ratio of conductive agent, binder and solvent is (8-12): (18-24): (64-76)；Further
It is preferred that the mass parts ratio of conductive agent, binder and solvent is 11.8:18.9:69.3.
Conductive agent described in above-mentioned steps (1), (2) is one of carbon black, acetylene black and graphite, preferably carbon black, charcoal
Black particle has very big specific surface area, and accumulation closely is conducive to be in close contact between particle together, constitute in electrode
Conductive network.
Adhesive described in above-mentioned steps (1), (2) is polyvinylidene fluoride, in polytetrafluoroethylene (PTFE), ethyl cellulose
One kind, preferably polyvinylidene fluoride.
For solvent described in above-mentioned steps (1), (2) depending on the property of adhesive, the solvent is terpinol, second
One of alcohol, isopropanol, n-butanol and n-hexyl alcohol.Solvent of the preferred alcohol as polyvinylidene fluoride.The present invention selects second
Alcohol as solvent, in the fabrication process will not high temperature generate exhaust gas, it is environmentally friendly and harmless.
Catalyst of the present invention, conductive agent, binder and solvent quality proportioning be to be screened by a large number of experiments.Metal oxygen
The electric conductivity of compound is bad, and conductive agent is added and increases catalyst electric conductivity, because oxygen is diffused to from waterproof ventilative layer, Catalytic Layer
With the airwater mist cooling interface in electrolyte contacts face, oxygen reduction obtains electronics, and electric conductivity is big, and electronics is transmitted by collector
It is fast.It is preferred that catalyst: conductive agent mass parts ratio is (1-2): the starting voltage and half-wave voltage of (1-3) are all relatively good.Bonding
Agent dosage is also to be set according to catalyst, conductive agent dosage and material, and when binder content is excessive, adhesive, which has obstructed, is urged
Agent and conductive agent, contact area reduction cause stock utilization to reduce, and capacity is reduced；When binder content is very few, viscosity
Not enough, the contact between catalyst and conductive agent is not also close, leads to capacity attenuation in cyclic process.Therefore, catalyst, conduction
Agent, binder optimal proportion are (1-2): (1-3): (2-5).The conductive agent of waterproof ventilative layer of the invention and the proportion of adhesive
It ensure that this layer of waterproof performance, and enhance gas permeability.
Described ultrasonic disperse 0.5-2 hours, preferably 1 hour.
Stirring 1-4 hours, preferably 2-3 hours, including but not limited to magnetic stirring, electric stirring.
Described dry 0.5-2 hours, preferably 1 hour, the drying include but is not limited to dry, be dried in vacuo, drying,
It is preferred that drying.
Beneficial effect
1, spinel oxide is a kind of widely used catalyst, improves metal-air battery to a certain extent
Hydrogen reduction catalytic performance, but spinel oxide electron transfer rate is not high, specific surface area still needs to improve, and leads to its hydrogen reduction
Reactivity is not good enough, limits its application in metal-air battery, by coating manganese to spinel-type catalyst surface
Oxide catalyst increases spinel catalyst catalytic activity, then body mutually coats carbonaceous material, increases electric conductivity, reaches excellent
Concerted catalysis effect.
2, the spinel catalyst of catalyst of the invention and uncoated Mn oxide and carbonaceous material is surveyed in battery discharge
It has a try and is compared in testing, limiting current density of the invention increases, and take-off potential and half wave potential all become just, and hydrogen reduction performance mentions
Height, catalytic activity improve.It is detailed in test example one.
Detailed description of the invention:
Fig. 1 is the discharge test figure of the embodiment of the present invention 1；
Fig. 2 is the discharge test figure of the embodiment of the present invention 2；
Fig. 3 is the discharge test figure of the embodiment of the present invention 3；
Fig. 4 is the discharge test figure of the embodiment of the present invention 4；
Fig. 5 is the discharge test figure of the embodiment of the present invention 5；
Fig. 6 is the polarization curves of oxygen reduction of the embodiment of the present invention 1 Yu comparative example.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in the embodiment of the present invention
Technical solution is clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than complete
The embodiment in portion.Based on the embodiments of the present invention, those of ordinary skill in the art are without creative efforts
Every other embodiment obtained, shall fall within the protection scope of the present invention.Unless otherwise explicitly stated, otherwise entire
In specification and claims, the term " include " or its transformations will be understood as be include institute
The element or component of statement, and do not exclude other elements or other components.
Embodiment 1
(1) nickel nitrate 12g, cobalt nitrate 28g are weighed, ethyl alcohol is added, magnetic agitation 1-2h, re-ultrasonic dispersion 1-2h are gone to
Autoclave reacts 3h at 180 DEG C, cooling, filters, drying, and 400 DEG C of calcinings obtain cobalt acid nickel spinelle；By cobalt acid nickel
Spinelle 16g, manganese dioxide 5g, inducer polyethylene glycol oxide 1.0g are scattered in solvent, magnetic agitation 2h, re-ultrasonic dispersion 2h,
80 DEG C of oven drying 6h, 500 DEG C of calcinings obtain manganese dioxide cladding cobalt acid nickel spinelle；By manganese dioxide cladding cobalt acid nickel point
Spar 20g, graphene 4.0g, are added ethyl alcohol dispersion, and addition surfactant is neopelex 1.0g, then ultrasound point
10h is dissipated, fast decompression is dry, 700 DEG C of vacuum calcinings, obtains the catalyst of double clad structures.
It (2) is 6.5%:9.8%:12.2%:71.5% according to the mass ratio of catalyst, conductive agent, binder and solvent,
Above-mentioned catalyst 16g, conductive black 24g, polyvinylidene fluoride 30g are weighed respectively, and ethyl alcohol 176g is put into beaker and mixes, and surpasses
Sound disperses 1h, then magnetic agitation 3h, obtains catalyst pulp, and then baking oven dries 1h, and compacting film forming obtains Catalytic Layer.It is described to lead
The mass parts ratio of electric agent, binder and solvent is 11.8%:18.9%:69.3%, weighs conductive black 30g respectively, gathers inclined two
Vinyl fluoride 48g, ethyl alcohol 176g, is put into beaker and mixes, ultrasonic disperse 1h, then magnetic agitation 2h, obtains waterproof ventilative layer slurry,
Then baking oven dries 1h, and compacting film forming obtains waterproof ventilative layer slurry.Above-mentioned Catalytic Layer, waterproof ventilative layer and collector are suppressed
In flakes, air battery cathode piece is obtained.
(3) above-mentioned air battery cathode piece and aluminium anodes are assembled into battery in battery tester, electrolyte is
The potassium hydroxide solution of 4mol/L carries out discharge test, as a result as shown in Figure 1.From figure 1 it will be seen that being in discharge voltage
When 1.0V or so, power density 255.5mW/cm2。
Embodiment 2
(1) nickel nitrate 12g, cobalt nitrate 27g are weighed, ethyl alcohol is added, magnetic agitation 1-2h, re-ultrasonic dispersion 1-2h are gone to
Autoclave reacts 2h at 150 DEG C, cooling, filters, drying, and 600 DEG C of calcinings obtain cobalt acid nickel spinelle；By cobalt acid nickel
Spinelle 15g, manganese dioxide 5g, inducer polyethylene pyrrole network alkanone 1.0g are scattered in solvent, plant magnetic agitation 2h, then ultrasound point
2h, 80 DEG C of oven drying 4h are dissipated, 500 DEG C of calcinings obtain manganese dioxide cladding cobalt acid nickel spinelle；By manganese dioxide cladding cobalt acid
Nickel 18g, graphene 4.5g are added ethyl alcohol dispersion, surfactant dioctyl succinate disulfonate acid 1.0g, re-ultrasonic dispersion are added
12h, fast decompression is dry, and 600 DEG C of calcinings obtain the catalyst of double clad structures.
It (2) is 6.5%:9.8%:12.2%:71.5% according to the mass ratio of catalyst, conductive agent, binder and solvent,
Above-mentioned catalyst 16g, conductive black 24g, polyvinylidene fluoride 30g are weighed respectively, and ethyl alcohol 176g is put into beaker and mixes, and surpasses
Sound disperses 1h, then magnetic agitation 3h, obtains catalyst pulp, and then baking oven dries 1h, and compacting film forming obtains Catalytic Layer.It is described to lead
The mass ratio of electric agent, binder and solvent is 11.8%:18.9%:69.3%, weighs conductive black 30g respectively, gathers inclined difluoro
Ethylene 48g, ethyl alcohol 176g, is put into beaker and mixes, ultrasonic disperse 1h, then magnetic agitation 2h, obtains waterproof ventilative layer slurry, so
Baking oven dries 1h afterwards, and compacting film forming obtains waterproof ventilative layer slurry.Above-mentioned Catalytic Layer, waterproof ventilative layer and collector are pressed into
Piece obtains air battery cathode piece.
(3) above-mentioned air battery cathode piece and aluminium anodes are assembled into battery in battery tester, electrolyte is
The potassium hydroxide solution of 4mol/L carries out discharge test, as a result as shown in Figure 2.It can be observed from fig. 2 that being in discharge voltage
When 1.0V or so, power density 293.9mW/cm2。
Embodiment 3
(1) nickel nitrate 13g, cobalt nitrate 26g are weighed, ethyl alcohol is added, magnetic agitation 1-2h, re-ultrasonic dispersion 1-2h are gone to
Autoclave reacts 1h at 110 DEG C, cooling, filters, drying, and 400 DEG C of calcinings obtain cobalt acid nickel spinelle；By cobalt acid nickel
Spinelle 25g, manganese dioxide 6g, inducer polyethylene glycol oxide 1.0g are scattered in solvent, magnetic agitation 1h, re-ultrasonic dispersion 1h,
80 DEG C of oven drying 5h, 500 DEG C of calcinings obtain manganese dioxide cladding cobalt acid nickel spinelle；Manganese dioxide is coated into cobalt acid nickel
28g, carbon nanotube 5.0g are added ethyl alcohol dispersion, surfactant sulfated castor oil 1.0g, re-ultrasonic dispersion 6h are added, fastly
Speed is dried under reduced pressure, and 800 DEG C of calcinings obtain the catalyst of double clad structures.
It (2) is 6.5%:9.8%:12.2%:71.5% according to the mass ratio of catalyst, conductive agent, binder and solvent,
Above-mentioned catalyst 16g, conductive black 24g, polyvinylidene fluoride 30g are weighed respectively, and ethyl alcohol 176g is put into beaker and mixes, and surpasses
Sound disperses 1h, then magnetic agitation 3h, obtains catalyst pulp, and then baking oven dries 1h, and compacting film forming obtains Catalytic Layer.It is described to lead
The mass ratio of electric agent, binder and solvent is 11.8%:18.9%:69.3%, weighs conductive black 30g respectively, gathers inclined difluoro
Ethylene 48g, ethyl alcohol 176g, is put into beaker and mixes, ultrasonic disperse 1h, then magnetic agitation 2h, obtains waterproof ventilative layer slurry, so
Baking oven dries 1h afterwards, and compacting film forming obtains waterproof ventilative layer slurry.Above-mentioned Catalytic Layer, waterproof ventilative layer and collector are pressed into
Piece obtains air battery cathode piece.
(3) above-mentioned air battery cathode piece and aluminium anodes are assembled into battery in battery tester, electrolyte is
The potassium hydroxide solution of 4mol/L carries out discharge test, as a result as shown in Figure 3.As seen from Figure 3, it is in discharge voltage
When 1.0V or so, power density 306.6mW/cm2。
Embodiment 4
(1) it weighs nickel nitrate 13.5g, cobalt nitrate 25.5g, is added ethyl alcohol, magnetic agitation 1-2h, re-ultrasonic dispersion 1-2h,
Autoclave is gone to, 2h is reacted at 160 DEG C, it is cooling, it filters, drying, 300 DEG C of calcinings obtain cobalt acid nickel spinelle；By cobalt
Sour nickel spinelle 16.5g, manganese sesquioxide managnic oxide 3.5g, inducer polyethylene pyrrole network alkanone 1.0g are scattered in solvent, magnetic agitation 2h,
Re-ultrasonic dispersion 2h, 80 DEG C of oven drying 6h, 500 DEG C are calcined, and manganese sesquioxide managnic oxide cladding cobalt acid nickel spinelle is obtained；By three oxidations
Two manganese coat cobalt acid nickel 19g, graphite 5.5g, and ethyl alcohol is added, and surfactant glyceride 1.0g, re-ultrasonic dispersion 10h quickly subtract
Press dry dry, 600 DEG C of calcinings obtain the catalyst of double clad structures.
It (2) is 8.6%:10.3%:18%:63.1% according to the mass ratio of catalyst, conductive agent, binder and solvent,
Above-mentioned catalyst 16g, conductive black 19g, polyvinylidene fluoride 33g are weighed respectively, and ethyl alcohol 117g is put into beaker and mixes, and surpasses
Sound disperses 1h, then magnetic agitation 3h, obtains catalyst pulp, and then baking oven dries 1h, and compacting film forming obtains Catalytic Layer.It is described to lead
The mass ratio of electric agent, binder and solvent is 11.8%:18.9%:69.3%, weighs conductive black 30g respectively, gathers inclined difluoro
Ethylene 48g, ethyl alcohol 220ml, is put into beaker and mixes, ultrasonic disperse 1h, then magnetic agitation 2h, obtains waterproof ventilative layer slurry,
Then baking oven dries 1h, and compacting film forming obtains waterproof ventilative layer slurry.Above-mentioned Catalytic Layer, waterproof ventilative layer and collector are suppressed
In flakes, air battery cathode piece is obtained.
(3) above-mentioned air battery cathode piece and aluminium anodes are assembled into battery in battery tester, electrolyte is
The potassium hydroxide solution of 4mol/L carries out discharge test, as a result as shown in Figure 4.From fig. 4 it can be seen that being in discharge voltage
When 1.0V or so, power density 306.1mW/cm2。
Embodiment 5
(1) nickel nitrate 14g, cobalt nitrate 25g are weighed, ethyl alcohol is added, magnetic agitation 1-2h, re-ultrasonic dispersion 1-2h are gone to
Autoclave reacts 2h at 180 DEG C, cooling, filters, drying, and 600 DEG C of calcinings obtain cobalt acid nickel spinelle；By cobalt acid nickel
Spinelle 17g, mangano-manganic oxide 3g, inducer polyethylene glycol oxide 2.0g are scattered in solvent, magnetic agitation 2h, re-ultrasonic dispersion
2h, 80 DEG C of oven drying 6h, 500 DEG C of calcinings obtain mangano-manganic oxide cladding cobalt acid nickel spinelle；Mangano-manganic oxide is coated into cobalt
Ethyl alcohol, surfactant sodium dodecyl base benzene sulfonic acid sodium salt 2.0g, re-ultrasonic dispersion 10h, fast decompression is added in sour nickel, graphene 6.0
Dry, 500 DEG C of calcinings obtain the catalyst of double clad structures.
It (2) is 8.6%:10.3%:18%:63.1% according to the mass ratio of catalyst, conductive agent, binder and solvent,
Above-mentioned catalyst 16g, conductive black 19g, polyvinylidene fluoride 33g are weighed respectively, and ethyl alcohol 117g is put into beaker and mixes, and surpasses
Sound disperses 1h, then magnetic agitation 3h, obtains catalyst pulp, and then baking oven dries 1h, and compacting film forming obtains Catalytic Layer.It is described to lead
The mass ratio of electric agent, binder and solvent is 11.8%:18.9%:69.3%, weighs conductive black 30g respectively, gathers inclined difluoro
Ethylene 48g, ethyl alcohol 220ml, is put into beaker and mixes, ultrasonic disperse 1h, then magnetic agitation 2h, obtains waterproof ventilative layer slurry,
Then baking oven dries 1h, and compacting film forming obtains waterproof ventilative layer slurry.Above-mentioned Catalytic Layer, waterproof ventilative layer and collector are suppressed
In flakes, air battery cathode piece is obtained.
(3) above-mentioned air battery cathode piece and aluminium anodes are assembled into battery in battery tester, electrolyte is
The potassium hydroxide solution of 4mol/L carries out discharge test, as a result as shown in Figure 5.It is seen from fig 5 that being in discharge voltage
When 1.0V or so, power density 305.4mW/cm2。
Embodiment 6
(1) it weighs nickel nitrate 14.5g, cobalt nitrate 24.5g, is added ethyl alcohol, magnetic agitation 1-2h, re-ultrasonic dispersion 1-2h,
Autoclave is gone to, 2h is reacted at 180 DEG C, it is cooling, it filters, drying, 600 DEG C of calcinings obtain cobalt acid nickel spinelle；By cobalt
Sour nickel spinelle 17.5g, manganese dioxide 2.5g, inducer polyethylene glycol oxide 1.0g are scattered in solvent, magnetic agitation 2h, then ultrasound
Disperse 2h, 80 DEG C of oven drying 6h, 500 DEG C of calcinings obtain manganese dioxide cladding cobalt acid nickel spinelle；Manganese dioxide is coated into cobalt
Ethyl alcohol is added in sour nickel, graphene 6.5, and surfactant dioctyl succinate disulfonate acid 1.0g, re-ultrasonic dispersion 8h quickly subtract
Press dry dry, 600 DEG C of calcinings obtain the catalyst of double clad structures.
(2) above-mentioned catalyst 5g, conductive black 12g, polyvinylidene fluoride 15g, ethyl alcohol 60g are weighed, is put into beaker and mixes
It closes, ultrasonic disperse 1h, then magnetic agitation 3h, obtains catalyst pulp, then baking oven dries 1h, and compacting film forming obtains Catalytic Layer.Point
Conductive black 12g, polyvinylidene fluoride 19g also known as are taken, ethyl alcohol 70g is put into beaker and mixes, and ultrasonic disperse 1h, then magnetic force stir
2h is mixed, waterproof ventilative layer slurry is obtained, then baking oven dries 1h, and compacting film forming obtains waterproof ventilative layer slurry.By above-mentioned catalysis
Layer, waterproof ventilative layer and collector are tabletted, obtain air battery cathode piece.
(3) above-mentioned air battery cathode piece and aluminium anodes are assembled into battery in battery tester.
Embodiment 7
(1) nickel nitrate 15g, cobalt nitrate 24g are weighed, ethyl alcohol is added, magnetic agitation 1-2h, re-ultrasonic dispersion 1-2h are gone to
Autoclave reacts 2h at 110 DEG C, cooling, filters, drying, and 600 DEG C of calcinings obtain cobalt acid nickel spinelle；By cobalt acid nickel
Spinelle 18g, manganese sesquioxide managnic oxide 2g, inducer polyethylene pyrrole network alkanone 0.5g are scattered in solvent, magnetic agitation 2h, then ultrasound point
2h, 80 DEG C of oven drying 6h are dissipated, 500 DEG C of calcinings obtain manganese sesquioxide managnic oxide cladding cobalt acid nickel spinelle；Manganese sesquioxide managnic oxide is coated
Ethyl alcohol, surfactant sulfated castor oil and glyceride 0.5g, re-ultrasonic dispersion 10h is added in cobalt acid nickel, graphene 7.0g,
Fast decompression is dry, and 400 DEG C of calcinings obtain the catalyst of double clad structures.
(2) above-mentioned catalyst 10g, conductive black 12g, polyvinylidene fluoride 20g, ethyl alcohol 80g are weighed, is put into beaker and mixes
It closes, ultrasonic disperse 1h, then magnetic agitation 3h, obtains catalyst pulp, then baking oven dries 1h, and compacting film forming obtains Catalytic Layer.Point
Conductive black 5g, polyvinylidene fluoride 10g also known as are taken, ethyl alcohol 60g is put into beaker and mixes, ultrasonic disperse 1h, then magnetic agitation
2h obtains waterproof ventilative layer slurry, and then baking oven dries 1h, and compacting film forming obtains waterproof ventilative layer slurry.By above-mentioned Catalytic Layer,
Waterproof ventilative layer and collector are tabletted, obtain air battery cathode piece.
(3) above-mentioned air battery cathode piece and aluminium anodes are assembled into battery in battery tester.
Embodiment 8
(1) nickel sulfate 10g is weighed, ethyl alcohol is added in cobaltous sulfate 20g, and magnetic agitation 1-2h, re-ultrasonic dispersion 1-2h go to height
Reaction kettle is pressed, 2h is reacted at 180 DEG C, it is cooling, it filters, drying, 600 DEG C of calcinings obtain cobalt acid nickel spinelle；By cobalt acid nickel point
Spar 16g, manganese dioxide 4g, inducer polyethylene pyrrole network alkanone 1.0g are scattered in solvent, magnetic agitation 2h, re-ultrasonic dispersion
2h, 80 DEG C of oven drying 6h, 500 DEG C of calcinings obtain manganese dioxide cladding cobalt acid nickel spinelle；By manganese dioxide cladding cobalt acid
Nickel, graphene 5g are added ethyl alcohol, surfactant sodium dodecyl base benzene sulfonic acid sodium salt 1.0g, re-ultrasonic dispersion 10h, and fast decompression is dry
Dry, 500 DEG C of calcinings obtain the catalyst of double clad structures.
(2) above-mentioned catalyst 8g, conductive black 15g, polyvinylidene fluoride 25g, ethyl alcohol 80g are weighed, is put into beaker and mixes
It closes, ultrasonic disperse 1h, then magnetic agitation 3h, obtains catalyst pulp, then baking oven dries 1h, and compacting film forming obtains Catalytic Layer.Point
Conductive black 8g, polyvinylidene fluoride 18g also known as are taken, ethyl alcohol 64g is put into beaker and mixes, ultrasonic disperse 1h, then magnetic agitation
2h obtains waterproof ventilative layer slurry, and then baking oven dries 1h, and compacting film forming obtains waterproof ventilative layer slurry.By above-mentioned Catalytic Layer,
Waterproof ventilative layer and collector are tabletted, obtain air battery cathode piece.
(3) above-mentioned air battery cathode piece and aluminium anodes are assembled into battery in battery tester.
Embodiment 9
(1) nickel chloride 8g, cobalt chloride 16g are weighed, ethyl alcohol is added, magnetic agitation 1-2h, re-ultrasonic dispersion 1-2h go to height
Reaction kettle is pressed, 2h is reacted at 180 DEG C, it is cooling, it filters, drying, 600 DEG C of calcinings obtain cobalt acid nickel spinelle；By cobalt acid nickel point
Spar 12g, manganese dioxide 3g, inducer polyethylene pyrrole network alkanone 1.0g are scattered in solvent, magnetic agitation 2h, re-ultrasonic dispersion
2h, 80 DEG C of oven drying 6h, 500 DEG C of calcinings obtain manganese dioxide cladding cobalt acid nickel spinelle；By manganese dioxide cladding cobalt acid
Ethyl alcohol is added in nickel, graphene 4g, and surfactant sulfated castor oil 1.0g, re-ultrasonic dispersion 10h, fast decompression is dry,
600 DEG C of calcinings obtain the catalyst of double clad structures.
(2) above-mentioned catalyst 10g, conductive black 12g, polyvinylidene fluoride 18g, ethyl alcohol 80g are weighed, is put into beaker and mixes
It closes, ultrasonic disperse 1h, then magnetic agitation 3h, obtains catalyst pulp, then baking oven dries 1h, and compacting film forming obtains Catalytic Layer.Point
Conductive black 12g, polyvinylidene fluoride 24g also known as are taken, ethyl alcohol 76g is put into beaker and mixes, and ultrasonic disperse 1h, then magnetic force stir
2h is mixed, waterproof ventilative layer slurry is obtained, then baking oven dries 1h, and compacting film forming obtains waterproof ventilative layer slurry.By above-mentioned catalysis
Layer, waterproof ventilative layer and collector are tabletted, obtain air battery cathode piece.
(3) above-mentioned air battery cathode piece and aluminium anodes are assembled into battery in battery tester
Test example one
In metal-air battery, Mn oxide surface cladding is not carried out to spinel catalyst, carbonaceous material body mutually wraps
It covers, only cobalt acid nickel spinelle only carries out Mn oxide surface cladding to cobalt acid nickel spinelle and make as catalyst (comparative example 1)
For catalyst (comparative example 2), with rotating circular disk testing example 1 compared with, 1,2 polarization curves of oxygen reduction, as a result as Fig. 6,
Shown in table 1,
The oxygen reduction reaction of 1 catalyst of table
Conclusion: compared with comparative example 1,2 catalyst, 1 catalyst of embodiment, limiting current density increase, take-off potential and
Half wave potential all becomes just, and hydrogen reduction performance improves, and catalytic activity improves, and the present invention is by coating spinel-type catalyst surface
Manganese oxide catalyst increases spinel catalyst catalytic activity, then body mutually coats carbonaceous material, increases electric conductivity, reaches association
Same catalytic effect.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of catalyst of double clad structures, specific surface area 320-490m2/ g, the ingredient including following weight parts: point is brilliant
60-80 parts of stone, 5-20 parts of Mn oxide and 10-30 parts of carbonaceous material；It is preferred that a kind of catalyst of double clad structures, compares table
Area is 380-450m2/ g, the ingredient including following weight parts: 65-75 parts of spinelle, 10-15 parts of Mn oxide and contain carbon materials
15-25 parts of material.
2. the catalyst of double clad structures as described in claim 1, it is characterised in that: the spinelle surface cladding manganese oxidation
Object, body mutually coats carbonaceous material again.
3. the catalyst of double clad structures as described in claim 1, it is characterised in that: the spinelle chemical formula AB2O4,
Middle A is a kind of element in Mg, Fe, Co, Ni, Cu and Zn, a kind of element in B Al, Cr, Mn, Fe, Co, Ni；It is preferred that A Ni, B
For Co, the spinelle is cobalt acid nickel spinelle.
4. the catalyst of double clad structures as described in claim 1, it is characterised in that: the Mn oxide includes titanium dioxide
Manganese, manganese sesquioxide managnic oxide, one or more of mangano-manganic oxide, preferred manganese dioxide.
5. the catalyst of clad structures as described in claim 1 double, it is characterised in that: the carbonaceous material include graphene,
It is one or more of in carbon nanotube, graphite, preferred graphene.
6. a kind of preparation method of the catalyst of double clad structures, includes the following steps:
(1) preparation of spinelle: weighing metal A salt, and solvent is added in metal B salt, and stirring, ultrasonic disperse go to reaction under high pressure
Kettle, hydro-thermal reaction is cooling, filters, and dries, and calcining obtains spinelle；
(2) preparation of Mn oxide coating spinelle: dispersing spinelle, Mn oxide, inducer in solvent, stirs, and surpasses
Sound dispersion, dry, calcining obtains Mn oxide coating spinelle；
(3) preparation of carbonaceous material clad structure spinel catalyst: by Mn oxide coating spinelle, carbonaceous material, dispersion
In solvent, surfactant is added, ultrasonic disperse, fast decompression is dry, calcining, obtains the catalyst of double clad structures；
It is preferred that a kind of preparation method of the catalyst of double clad structures, includes the following steps:
(1) preparation of spinelle: weighing 45-60 parts of metal A salt, 90-120 parts of metal B salt, is added solvent, magnetic agitation 1-2h,
Re-ultrasonic dispersion 1-2h, goes to autoclave, and 2-4h is reacted at 110-180 DEG C, cooling, filters, drying, and 300-600 DEG C
Calcining, obtains spinelle；
(2) by 60-80 parts of spinelle, 5-20 parts of Mn oxide, inducer, magnetic the preparation of Mn oxide coating spinelle: is added
Power stirs 1-2h, and re-ultrasonic dispersion 1-2h, 80 DEG C of oven drying 4-6h, 400-600 DEG C is calcined, and it is brilliant to obtain Mn oxide cladding point
Stone；
(3) preparation of carbonaceous material clad structure spinel catalyst: by 75-90 parts of Mn oxide coating spinelle, contain carbon materials
10-30 parts of material is scattered in solvent, surfactant is added, ultrasonic disperse 6-12h, fast decompression is dry, 500-800 DEG C of vacuum
Calcining obtains the catalyst of double clad structures.
7. the preparation method of the catalyst of double clad structures as claimed in claim 6, which is characterized in that in the step (1)
The metal A salt is sulfuric acid A, chlorination A, nitric acid A etc., preferably nitric acid A；The metal B salt is sulfuric acid B, chlorination B, nitric acid B
Deng preferably nitric acid B.
8. the preparation method of the catalyst of double clad structures as claimed in claim 6, which is characterized in that in step (1), (3)
The solvent is one of terpinol, ethyl alcohol, isopropanol, n-butanol and n-hexyl alcohol；
Inducer described in step (2) is one of polyethylene glycol oxide and polyethylene pyrrole network alkanone；Quality is spinelle and manganese
The 1~10% of oxide gross mass；
Surfactant described in step (3) is neopelex, dioctyl succinate disulfonate acid, sulphation castor-oil plant
Oil and one of glyceride are a variety of, quality be Mn oxide coating spinelle and carbonaceous material gross mass percentage 1~
10%.
9. a kind of preparation method of air battery cathode piece, includes the following steps:
(1) prepare Catalytic Layer: the described in any item catalyst of claim 1-5, conductive agent, binder and solvent mix, ultrasound,
Catalyst pulp is stirred to get, then is dried, compacting forms a film to arrive Catalytic Layer；The quality of the catalyst, conductive agent, binder
Part is than being (1-2): (1-3): (2-5)；
(2) waterproof ventilative layer is prepared；Conductive agent, binder and solvent mixing, ultrasound stir to get waterproof ventilative layer slurry, then
Drying, compacting form a film up to waterproof ventilative layer；The conductive agent, binder mass parts ratio be (1-3): (2-5)；
(3) it prepares air battery cathode piece: Catalytic Layer, waterproof ventilative layer and collector is pressed together, to obtain sky
Gas battery cathode piece.
10. the preparation method of air battery cathode piece as claimed in claim 9, which is characterized in that step (1) Catalytic Layer
Described in air cathode catalyst, conductive agent, binder and solvent mass parts ratio be (5-10): (5-15): (10-20):
(60-80)；It is preferred that air cathode catalyst, conductive agent, binder and solvent mass parts ratio be (6-8): (8-12): (12-
18): (64-76), still more preferably, air cathode catalyst, conductive agent, binder and solvent mass parts ratio be 6.5:
9.8:12.2:71.5；
The mass parts ratio of conductive agent, binder and solvent described in step (2) waterproof ventilative layer is (5-15): (10-25):
(60-80)；It is preferred that the mass parts ratio of conductive agent, binder and solvent is (8-12): (18-24): (64-76)；It is further excellent
Choosing, the mass parts ratio of conductive agent, binder and solvent are 11.8:18.9:69.3.
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