CN106785241B - Metal air battery cathodes and preparation method thereof - Google Patents
Metal air battery cathodes and preparation method thereof Download PDFInfo
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- 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
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Abstract
The present invention provides a kind of preparation methods of metal air battery cathodes, comprising: A) conductive agent, binder and solvent are mixed, stirring obtains slurry；In the slurry by current collector layer raw material dipping, firing obtains hydrophobic layer；B) lubricant, conductive agent, binder and solvent are mixed, obtain slurry；The slurry is squeezed out, is stretched, drying obtains mixture；The mixture is squeezed into film in hydrophobic layer surface；C catalyst, binder and solvent) are mixed to get slurry, slurry is sprayed on the film, Catalytic Layer is obtained；D the Catalytic Layer and hydrophobic layer hot pressing, firing) are obtained into metal air battery cathodes.Battery of the invention first prepares a tunic in hydrophobic layer surface, and as the carrier of catalyst, the component of film stronger can be fixed on hydrophobic layer by squeezing out and being drawn into fibrosis distribution, have preferable structural strength, then be sprayed catalyst by thermal spraying.Catalytic Layer of the invention has excellent battery performance and stability.
Description
Technical field
The present invention relates to battery technology fields, more particularly, to a kind of metal air battery cathodes and preparation method thereof.
Background technique
The energy is developing national economy and the important material base uplifted the people's living standard, and directly affects economic hair
One key factor of exhibition.Since the 21th century, facing mankind realize economy and society sustainable development significant challenge,
How to keep rapid development of economy to have become global hot spot under the dual restriction of the limited and environmentally friendly strict demand of resource to ask
Topic.And the problems such as shortage of resources brought by traditional energy utilization patterns, environmental pollution, greenhouse effects, will more protrude, because
This traditional energy structure and its Land use systems are increasingly difficult to adapt to the needs of survival and development of mankind.In order to efficiently, reasonably make
With non-renewable energy resources and environment and the ecological balance are kept, Basic Ways are exactly to develop using these resources as the fuel of fuel electricity
Pool technology.
Metal-air battery is a kind of between primary battery and fuel cell " half fuel " battery, has both primary battery and fuel
The characteristics of battery, has many advantages, such as that capacity is big, specific energy is high, at low cost, it is considered to be there are development and application prospect in future very much
Novel battery material.Metal-air battery is generally made of air cathode, electrolyte and metal anode, and metal anode is business
Rafifinal and aluminium alloy, therefore, cell cathode directly determines battery performance.Cathode includes current collector layer, hydrophobic layer and catalysis
Redox reaction occurs in Catalytic Layer for layer, battery, and three-phase reaction interface is that the place of above-mentioned reaction, phase reaction circle occurs
Face area has large effect to the performance of air electrode.
Application No. is 201310282853.4 Chinese patents to disclose catalyst, active carbon, acetylene black and binder
Ptfe emulsion is uniformly mixed according to a certain percentage, using dehydrated alcohol as solvent, after 20~50min of ultrasonic disperse, is turned
It moves in 70~90 DEG C of water-baths after removing ethyl alcohol and obtains rubber pureed mixture, the catalytic membrane after being rolled into 0.2~0.5mm, this
For the Catalytic Layer of battery.Hydrophobic layer uses same method, with active carbon, acetylene black, the preparation of polyfluortetraethylene of binding element lotion
It forms, is then hot pressed into the cathode of air cell according to the sequence of waterproof membrane, collector, catalytic membrane.The cathode of the method preparation
Catalytic Layer is easy water suction cracking during the test, therefore the long-time stability of battery are poor, pass through 200mA/cm2Constant-current discharge
Mode is tested 40 hours, and in 1.24V, output energy density is only 1.902kWh/ (Kg, Al).In addition, this method preparation process
Complexity is unfavorable for the amplification and commercialized popularization of product.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of preparation side of metal air battery cathodes
Method, the metal air battery cathodes stability that the present invention is prepared are good.
The present invention provides a kind of preparation methods of metal air battery cathodes, comprising:
A) conductive agent, binder and solvent are mixed, stirring obtains slurry；In the slurry by current collector layer dipping, dry,
Firing obtains hydrophobic layer；
B) by lubricant, conductive agent, binder and solvent mixing, precompressed, extrusion, stretching, drying, mixture is obtained；It will
The mixture squeezes to obtain catalytic substrate film in hydrophobic layer surface；
C catalyst, binder and solvent) are mixed to get slurry, slurry thermal jet is coated on the catalytic substrate film, is obtained
To Catalytic Layer；
D the Catalytic Layer and hydrophobic layer) are obtained into metal air battery cathodes in hot pressing, firing.
Preferably, the step A) in conductive agent be selected from one of active carbon, carbon black and polyethylene alkynes or a variety of；It is described
Binder is selected from one of ptfe micropowder, ptfe emulsion, Kynoar and fluorinated ethylene propylene or more
Kind；The solvent is selected from one of terpinol, ethyl alcohol and isopropanol or a variety of；The current collector layer raw material is selected from nickel foam, nickel
One or more of net and steel mesh；
The step B) in lubricant be selected from one or more of silicone oil, fatty acid amide, oleic acid and polyester；It is described to lead
Electric agent is selected from one of active carbon, carbon black and polyethylene alkynes or a variety of；The binder is selected from ptfe micropowder, poly- four
One of vinyl fluoride lotion, Kynoar and fluorinated ethylene propylene are a variety of；The solvent is selected from terpinol, ethyl alcohol and different
One of propyl alcohol is a variety of；
The step C) in catalyst be selected from MnO2、MnO、Mn3O4And Mn2O3One or more of；Binder is selected from poly-
One of tetrafluoroethene micro mist, ptfe emulsion, Kynoar and fluorinated ethylene propylene are a variety of；The solvent choosing
From one of terpinol, ethyl alcohol and isopropanol or a variety of.
Preferably, the step A) in conductive agent, binder and solvent mass ratio be preferably (0.1~5): (0.5~
5): (10~300)；
The step B) in lubricant, conductive agent, binder and solvent mass ratio be (0.5~10): (0.1~3):
(0.1~10): (20~400).
Preferably, the step B) in precompressed obtain slurry density be 100~10000kg/cm3；Extrusion pressure be 1~
30MPa；Squeezing out number is 2~20 times；Rate of extension is 0.1~10MPa/s；Drawing numbers are 3~10 times.
Preferably, the step B) in drawn material drying temperature be 80~500 DEG C；The time of drying is 1~50h；It squeezes
Pressure pressure is 1~20MPa.
Preferably, the step C) in catalyst, binder and solvent mass ratio (1~50): (1~40): (50~
1500)。
Preferably, the step C) in thermal spraying temperature be 100~500 DEG C；Pressure is 0.1~10MPa；Catalytic Layer thickness
For 0.01~1mm.
Preferably, the step D) in hot pressing pressure be 5~50MPa；Time is 0.5~5min；The temperature of firing is
200~1000 DEG C, the firing time is 0.1~20h.
The present invention provides a kind of metal air battery cathodes, the preparation method as described in above-mentioned technical proposal is prepared into
It arrives.
The present invention provides a kind of metal-air batteries, are prepared including preparation method described in above-mentioned technical proposal
Cathode.
Compared with prior art, the present invention provides a kind of preparation methods of metal air battery cathodes, comprising: A) it will lead
Electric agent, binder and solvent mixing, stirring obtain slurry；In the slurry by current collector layer dipping, drying, firing obtain hydrophobic layer；
B) by lubricant, conductive agent, binder and solvent mixing, precompressed, extrusion, stretching, drying, mixture is obtained；By the mixing
Object squeezes to obtain catalytic substrate film in hydrophobic layer surface；C catalyst, binder and solvent) are mixed to get slurry, by slurry heat
It sprays on the catalytic substrate film, obtains Catalytic Layer；D the Catalytic Layer and hydrophobic layer) are obtained into metal sky in hot pressing, firing
Pneumoelectric pool cathode.Metal-air battery provided by the invention first prepares a tunic in hydrophobic layer surface, as the carrier of catalyst,
The component of film stronger can be fixed on hydrophobic layer by squeezing out and being drawn into fibrosis distribution, have preferable structural strength,
Then catalyst is sprayed by thermal spraying.The Catalytic Layer that method of the invention is prepared has more three phase boundary, and
And be firmly combined with hydrophobic layer, therefore there is excellent battery performance and stability, the experimental results showed that, electricity prepared by the present invention
Pond long-term intermittent discharges 24 times, and attenuation rate is only 6%.
Detailed description of the invention
Fig. 1 is the cell performance curve that the embodiment of the present invention 1~4 is prepared；
Fig. 2 is the battery long-term intermittent discharge performance curve that the embodiment of the present invention 1 is prepared；
Fig. 3 is the cell performance curve that embodiment 1 and comparative example 1 are prepared.
Specific embodiment
The present invention provides a kind of preparation methods of metal air battery cathodes, comprising:
A) conductive agent, binder and solvent are mixed, stirring obtains slurry；In the slurry by current collector layer dipping, dry,
Firing obtains hydrophobic layer；
B) by lubricant, conductive agent, binder and solvent mixing, precompressed, extrusion, stretching, drying, mixture is obtained；It will
The mixture squeezes to obtain catalytic substrate film in hydrophobic layer surface；
C catalyst, binder and solvent) are mixed to get slurry, slurry thermal jet is coated on the catalytic substrate film, is obtained
To Catalytic Layer；
D the Catalytic Layer and hydrophobic layer) are obtained into metal air battery cathodes in hot pressing, firing.
The preparation method of metal air battery cathodes provided by the invention first mixes conductive agent, binder and solvent,
Stirring, obtains slurry；Current collector layer raw material is immersed in the slurry, firing obtains hydrophobic layer.
In the present invention, the current collector layer is selected from one or more of nickel foam, nickel screen and steel mesh.The conductive agent is excellent
Choosing is selected from one of active carbon, carbon black and polyethylene alkynes or a variety of；The binder is preferably selected from ptfe micropowder, gathers
One of tetrafluoroethene lotion, Kynoar and fluorinated ethylene propylene are a variety of；The solvent is preferably selected from terpinol, second
One of pure and mild isopropanol is a variety of.The mass ratio of the conductive agent, binder and solvent is preferably (0.1~5): (0.5~
5): (10~300)；More preferably (0.5~4): (1~4): (50~250).Most preferably (1~3): (2~3): (100~
200)。
The present invention for the mixing concrete mode without limit, it is well known to those skilled in the art.
Current collector layer raw material is immersed in the slurry, firing obtains hydrophobic layer；The current collector layer raw material be selected from nickel foam,
One or more of nickel screen and steel mesh.The current collector layer raw material is preferably nickel foam.
Current collector layer raw material is immersed in the slurry, drying, firing obtain hydrophobic layer；The dipping time is preferably 1
~10 times；More preferably 2~8 times；Most preferably 3~5 times；The temperature of the firing is preferably 200~600 DEG C；More preferably
300~500 DEG C；Most preferably 350~450 DEG C；The firing time is preferably 0.1~10h；More preferably 0.5~4h；It is optimal
It is selected as 1~3h.
After obtaining hydrophobic layer, lubricant, conductive agent, binder and solvent mixing, precompressed, extrusion, stretching, drying obtain
To mixture；The mixture is squeezed to obtain catalytic substrate film in hydrophobic layer surface.
Catalytic substrate film of the present invention is preferably prepared by following methods:
Lubricant, conductive agent, binder and solvent are mixed, slurry is obtained.It is preferred that be specially by lubricant, conductive agent,
Binder is added to solvent mixing, and heating makes its flocculation, obtains powdery lotion；Lotion obtains slurry through precompressed.
In the present invention, the flocculated temperature of heating is preferably 40~120 DEG C；More preferably 60~100 DEG C；Most preferably
It is 80~90 DEG C；The present invention for the precompressed without limit, precompressed mode well known to those skilled in the art, preferably
The precompressed in cylinder occlusion tubular die.The density of slurry is preferably 100~10000kg/cm after the precompressed3, more preferably
For 500~8000kg/cm3, most preferably 2000~6000kg/cm3。
In the present invention, the lubricant is preferably selected from one of silicone oil, fatty acid amide, oleic acid and polyester or several
Kind；It is more preferably selected from one or more of silicone oil, fatty acid amide and oleic acid；The conductive agent is preferably selected from active carbon, charcoal
One of black and polyethylene alkynes is a variety of；The binder is preferably selected from ptfe micropowder, ptfe emulsion, gathers
One of vinylidene and fluorinated ethylene propylene are a variety of；The solvent is preferably selected from terpinol, ethyl alcohol and isopropanol
It is one or more.
In the present invention, the mass ratio of the lubricant, conductive agent, binder and solvent is preferably (0.5~10): (0.1
~3): (0.1~10): (20~400)；More preferably (3~8): (0.5~2.5): (2~8): (100~350)；Most preferably
(4~6): (1~2): (3~5): (150~300)
After obtaining slurry, the slurry is squeezed out, is stretched, drying obtains mixture.
The slurry is squeezed out in an extruder, recycles repeated processing under certain speed, extrusion pressure is preferably 1~
30MPa；More preferably 5~20MPa；Most preferably 10~15MPa；Squeezing out number is preferably 2~20 times, more preferably 5~15
It is secondary；Most preferably 9~12 times；In extrusion process, under the action of compression and shearing force fibrosis occurs for binder particle, more
Secondary extrusion can significantly improve the degree of fibrosis.
Post-tensioning is squeezed out, the rate of extension of the stretching is preferably 0.1~10MPa/s, more preferably 1~8MPa/s；Most
Preferably 3~5MPa；Drawing numbers are preferably 3~10 times；More preferably 4~8 times；Most preferably 5~7 times.
It stretches so that microfibre further elongation, and cleaves, form gap.
The drawn material is dried, mixture is obtained.The temperature of the drying is preferably 80~500 DEG C；More preferably
150~400 DEG C；Most preferably 200~300 DEG C；The time of the drying is preferably 1~50h；More preferably 10~40h；It is optimal
It is selected as 20~30h.
After drying, lubricant is volatilized, and is conducive to the preparation of film.
The mixture is squeezed into film in hydrophobic layer surface, forms catalytic substrate film at this time, the film compactness is high, but
Still there is more hole, plays the role of completely cutting off electrolyte exudation while guaranteeing gas permeability；The pressure of the extruding is preferably 1
~20MPa；More preferably 5~15MPa；Most preferably 7~10MPa.
Catalyst, binder and solvent are mixed to get slurry, slurry is sprayed on the catalytic substrate film, is urged
Change layer.
In the present invention, the catalyst is selected from MnO2、MnO、Mn3O4And Mn2O3One or more of；Binder is selected from
One of ptfe micropowder, ptfe emulsion, Kynoar and fluorinated ethylene propylene are a variety of；The solvent
Selected from one of terpinol, ethyl alcohol and isopropanol or a variety of.
In the present invention, the mass ratio of the catalyst, binder and solvent is preferably (1~50): (1~40): (50~
1500)；More preferably (10~40): (10~30): (150~1200)；Most preferably (20~30): (15~25): (200~
1000)。
The mixing is preferably high speed ball milling.The thermal spraying temperature is preferably 100~800 DEG C；More preferably 200~
600℃；Override is 300~500 DEG C；Thermal spraying pressure is preferably 0.1~10MPa；More preferably 1~8MPa；Most preferably 2
~5MPa；The thickness of catalytic substrate film is preferably 0.01~1mm；More preferably 0.1~0.7mm；Most preferably 0.3~0.5mm.
The Catalytic Layer and hydrophobic layer hot pressing, firing are obtained into metal air battery cathodes.
In the present invention, the pressure of the hot pressing is preferably 5~50MPa；More preferably 10~40MPa；Most preferably 20
~30MPa；The hot pressing time is preferably 0.5~5min；More preferably 1~4min；Most preferably 2~3min.
In the present invention, hot pressing makes the binder particle in binder particle and catalytic substrate film in hydrophobic layer mutual
Connection, can play the role of fixed catalyst, increase the structural strength of Catalytic Layer.Further, since having in catalytic substrate film
More is mesoporous, by thermal spraying it is also possible that catalyst and binder particle enter in mesoporous, increases spatial depth
The content of upper catalyst, this is the second tunic of Catalytic Layer, and voidage is high, and the contact surface of electrolyte and catalyst can be improved
Product, improves the catalytic performance of catalyst.
After Catalytic Layer and hydrophobic layer after hot pressing are fired, cathode is obtained.The temperature of the firing is preferably 200~1000
DEG C, more preferably 300~800 DEG C；Most preferably 340~500 DEG C；The firing time is preferably 0.1~20h；More preferably
0.2~10h；Most preferably 0.5~5h.
The present invention provides a kind of metal air battery cathodes, the preparation method as described in above-mentioned technical proposal is prepared into
It arrives.
The present invention provides a kind of metal-air batteries, are prepared including preparation method described in above-mentioned technical proposal
Cathode.
The present invention provides a kind of preparation methods of metal air battery cathodes, comprising: A) by conductive agent, binder and molten
Agent mixing, stirring obtain slurry；In the slurry by current collector layer dipping, drying, firing obtain hydrophobic layer；B) by lubricant, conduction
Agent, binder and solvent mixing, precompressed, extrusion, stretching, drying, obtain mixture；The mixture is squeezed in hydrophobic layer surface
Pressure obtains catalytic substrate film；C catalyst, binder and solvent) are mixed to get slurry, slurry thermal jet is coated onto the catalysis base
On counterdie, Catalytic Layer is obtained；D the Catalytic Layer and hydrophobic layer) are obtained into metal air battery cathodes in hot pressing, firing.This hair
The metal-air battery of bright offer first prepares one layer of catalytic substrate film in hydrophobic layer surface, as the carrier of catalyst, the group of film
Lease making crosses extrusion and is drawn into fibrosis distribution, stronger can be fixed on hydrophobic layer, have preferable structural strength, then lead to
Thermal spraying is crossed to spray catalyst.The Catalytic Layer that method of the invention is prepared have more three phase boundary, and with
Hydrophobic layer is firmly combined, therefore has excellent battery performance and stability.
Present invention preferably employs such as under type to carry out performance measurement to the metal air battery cathodes that the present invention is prepared:
Stability Determination: using test one day, then pouring out electrolyte, and Catalytic Layer and air is allowed to contact one day.
In order to further illustrate the present invention, metal air battery cathodes provided by the invention are carried out with reference to embodiments
Detailed description.
Embodiment 1
Polyethylene alkynes, binder PTFE powder are weighed according to the ratio of 1:2:100, etoh solvent is uniformly mixed, obtains hydrophobic
Layer slurry.Nickel foam is impregnated in the slurry 3 times, after being dried to drying, firing 3h at 350 DEG C can be obtained hydrophobic layer.
Lubricant fatty acid amide, nano carbon black, PTFE micro mist and ethyl alcohol mixing are weighed according to the mass ratio of 4:1:3:150
Uniformly, 80 DEG C are heated to and brings it about flocculation, obtains powdery lotion, lotion is carried out in cylinder occlusion tubular die pre-
Pressure, the density for obtaining slurry is 2000kg/cm3；Raw material is transferred to extruder, squeezes out 12 times under 10MPa pressure, then exists
It is stretched 7 times under 3MPa pulling force, is elongated microfibre further, and cleave, form gap；The product of stretching is placed on
Dry 30h at 200 DEG C, is then pressed into film in hydrophobic layer surface for it at room temperature 7MPa in baking oven；
Catalyst MnO is weighed according to the mass ratio of 4:3:202, binder PTFE micro mist and etoh solvent, then clipping the ball
Mill obtains Catalytic Layer spray liniment, and at 300 DEG C, thermal jet is coated on Catalytic Layer basilar memebrane under 2MPa, obtains with a thickness of 0.3mm catalysis
Film, the then hot pressing 3min at 20MPa, by after hot pressing Catalytic Layer and hydrophobic layer fire 5h at 340 DEG C, metal can be obtained
The cathode of air cell.
Metal aluminium-air cell is applied to using the cathode that the embodiment of the present invention is prepared, anode use is commercially available in the market
The quaternary aluminium alloy bought, and be measured using method of the present invention, as shown in FIG. 1, FIG. 1 is the embodiment of the present invention for performance
1~4 battery performance figure being prepared, as seen from Figure 1, when voltage is 1.0V, to the electricity of battery prepared by embodiment 1
Current density is 255mA/cm2, power density 260mW/cm2。
Stability is as shown in Fig. 2, Fig. 2 is the battery long-term intermittent discharge performance curve that the embodiment of the present invention 1 is prepared
Figure, as seen from Figure 2, when battery carries out 24 intermittent discharges, the attenuation rate of battery is only 6%, is illustrated using the method
The cell catalyst layer of preparation improves a lot with hydrophobic layer firmness, is not easy to take off exposure in air after electric discharge
It falls.
Embodiment 2
Polyethylene alkynes, binder PTFE powder are weighed according to the ratio of 3:3:200, etoh solvent is uniformly mixed, obtains hydrophobic
Layer slurry.Nickel foam is impregnated in the slurry 5 times, after being dried to drying, firing 1h at 450 DEG C can be obtained hydrophobic layer.
Lubricant fatty acid amide, nano carbon black, PTFE micro mist and ethyl alcohol mixing are weighed according to the mass ratio of 6:2:5:300
Uniformly, 90 DEG C are heated to and brings it about flocculation, obtains powdery lotion, lotion is carried out in cylinder occlusion tubular die pre-
Pressure, the density for obtaining slurry is 6000kg/cm3；Raw material is transferred to extruder, squeezes out 9 times under 15MPa pressure, then exists
It is stretched 5 times under 5MPa pulling force, is elongated microfibre further, and cleave, form gap；The product of stretching is placed on
Dry 20h at 300 DEG C, is then pressed into film in hydrophobic layer surface for it at room temperature 10MPa in baking oven；
Catalyst MnO is weighed according to the mass ratio of 6:5:2002, binder PTFE micro mist and etoh solvent, then clipping the ball
Mill obtains Catalytic Layer spray liniment, and at 500 DEG C, thermal jet is coated on Catalytic Layer basilar memebrane under 5MPa, obtains with a thickness of 0.5mm catalysis
Film, the then hot pressing 2min at 30MPa, by after hot pressing Catalytic Layer and hydrophobic layer fire 0.5h at 500 DEG C, gold can be obtained
Belong to the cathode of air cell.
Metal aluminium-air cell is applied to using the cathode that the embodiment of the present invention is prepared, anode use is commercially available in the market
The quaternary aluminium alloy bought, and be measured using method of the present invention, as shown in FIG. 1, FIG. 1 is the embodiment of the present invention for performance
1~4 battery performance figure being prepared, as seen from Figure 1, when voltage is 1.0V, to the electricity of battery prepared by embodiment 2
Current density is 243mA/cm2, power density 250mW/cm2。
The battery being prepared is subjected to the test of long-term intermittent discharge performance, when battery carries out 24 intermittent discharges, electricity
The attenuation rate in pond is 8%, illustrates to improve a lot using the cell catalyst layer of the method preparation with hydrophobic layer firmness, even if
Exposure is also not easy to fall off in air after electric discharge.
Embodiment 3
Polyethylene alkynes, binder PTFE powder are weighed according to the ratio of 0.5:1:50, etoh solvent is uniformly mixed, obtains hydrophobic
Layer slurry.Nickel foam is impregnated in the slurry 2 times, after being dried to drying, firing 4h at 300 DEG C can be obtained hydrophobic layer.
Lubricant fatty acid amide is weighed according to the mass ratio of 3:0.5:2:100, nano carbon black, PTFE micro mist and ethyl alcohol are mixed
It closes uniformly, is heated to 60 DEG C and brings it about flocculation, obtain powdery lotion, lotion is carried out in cylinder occlusion tubular die pre-
Pressure, the density for obtaining slurry is 500kg/cm3；Raw material is transferred to extruder, is squeezed out 15 times under 5MPa pressure, then in 1MPa
It is stretched 8 times under pulling force, is elongated microfibre further, and cleave, form gap；The product of stretching is placed on baking oven
In dry 40h at 150 DEG C, it is then pressed into film in hydrophobic layer surface at room temperature 5MPa；
Catalyst MnO is weighed according to the mass ratio of 10:10:1502, binder PTFE micro mist and etoh solvent, then high speed
Ball milling obtains Catalytic Layer spray liniment, and at 200 DEG C, thermal jet is coated on Catalytic Layer basilar memebrane under 8MPa, obtains with a thickness of 0.1mm catalysis
Film, the then hot pressing 4min at 10MPa, by after hot pressing Catalytic Layer and hydrophobic layer fire 10h at 300 DEG C, gold can be obtained
Belong to the cathode of air cell.
Metal aluminium-air cell is applied to using the cathode that the embodiment of the present invention is prepared, anode use is commercially available in the market
The quaternary aluminium alloy bought, and be measured using method of the present invention, as shown in FIG. 1, FIG. 1 is the embodiment of the present invention for performance
1~4 battery performance figure being prepared, as seen from Figure 1, when voltage is 1.0V, to the electricity of battery prepared by embodiment 3
Current density is 230mA/cm2, power density 245mW/cm2。
The battery being prepared is subjected to the test of long-term intermittent discharge performance, when battery carries out 24 intermittent discharges, electricity
The attenuation rate in pond is 10%, illustrates to improve a lot using the cell catalyst layer of the method preparation with hydrophobic layer firmness, i.e.,
Keep exposure after electric discharge also not easy to fall off in air.
Embodiment 4
Polyethylene alkynes, binder PTFE powder are weighed according to the ratio of 4:4:250, etoh solvent is uniformly mixed, obtains hydrophobic
Layer slurry.Nickel foam is impregnated in the slurry 8 times, after being dried to drying, firing 0.5h at 500 DEG C can be obtained hydrophobic layer.
Lubricant fatty acid amide is weighed according to the mass ratio of 8:2.5:8:350, nano carbon black, PTFE micro mist and ethyl alcohol are mixed
It closes uniformly, is heated to 100 DEG C and brings it about flocculation, obtain powdery lotion, lotion is carried out in cylinder occlusion tubular die
Precompressed, the density for obtaining slurry is 8000kg/cm3；Raw material is transferred to extruder, squeezes out 5 times under 20MPa pressure, then exists
It is stretched 4 times under 8MPa pulling force, is elongated microfibre further, and cleave, form gap；The product of stretching is placed on
Dry 10h at 400 DEG C, is then pressed into film in hydrophobic layer surface for it at room temperature 15MPa in baking oven；
Catalyst MnO is weighed according to the mass ratio of 40:30:12002, binder PTFE micro mist and etoh solvent, it is then high
Fast ball milling obtains Catalytic Layer spray liniment, and at 600 DEG C, thermal jet is coated on Catalytic Layer basilar memebrane under 1MPa, obtains urging with a thickness of 0.7mm
Change film, the then hot pressing 1min at 40MPa, by after hot pressing Catalytic Layer and hydrophobic layer fire 0.2h at 800 DEG C, can be obtained
The cathode of metal-air battery.
Metal aluminium-air cell is applied to using the cathode that the embodiment of the present invention is prepared, anode use is commercially available in the market
The quaternary aluminium alloy bought, and be measured using method of the present invention, as shown in FIG. 1, FIG. 1 is the embodiment of the present invention for performance
1~4 battery performance figure being prepared, as seen from Figure 1, when voltage is 1.0V, to the electricity of battery prepared by embodiment 4
Current density is 220mA/cm2, power density 230mW/cm2。
The battery being prepared is subjected to the test of long-term intermittent discharge performance, when battery carries out 24 intermittent discharges, electricity
The attenuation rate in pond is 9%, illustrates to improve a lot using the cell catalyst layer of the method preparation with hydrophobic layer firmness, even if
Exposure is also not easy to fall off in air after electric discharge.
Comparative example 1
Polyethylene alkynes, binder PTFE powder are weighed according to the ratio of 1:2:100, etoh solvent is uniformly mixed, obtains hydrophobic
Layer slurry.Nickel foam is impregnated in the slurry 3 times, after being dried to drying, firing 3h at 350 DEG C can be obtained hydrophobic layer.
In order to be contrasted with embodiment 1, in Catalytic Layer preparation process, removal extruding, stretching and thermal spray process,
When preparing catalytic substrate film, directly catalyst is added thereto, compares the variation of its battery performance, detailed process are as follows: according to 4:
The mass ratio of 1:3:4:150 weighs lubricant fatty acid amide, nano carbon black, PTFE micro mist, MnO2It is uniformly mixed, adds with ethyl alcohol
Heat brings it about flocculation to 80 DEG C, obtains powdery lotion, and lotion is carried out precompressed in cylinder occlusion tubular die, is starched
The density of material is 2000kg/cm3；Slurry is placed into dry 30h at 200 DEG C in an oven, then at room temperature 7MPa by its
Hydrophobic layer surface is pressed into film, and cathode forms Catalytic Layer at this time, then the hot pressing 3min at 20MPa, by urging after hot pressing
Change layer and hydrophobic layer fires 5h at 340 DEG C, the cathode of metal-air battery can be obtained.
Metal aluminium-air cell is applied to using the cathode that the embodiment of the present invention is prepared, anode use is commercially available in the market
The quaternary aluminium alloy bought, and be measured using method of the present invention, performance is as shown in figure 3, Fig. 3 is the embodiment of the present invention
1 and the battery performance figure that is prepared of comparative example 1, as seen from Figure 3, when voltage is 1.0V, electricity prepared by embodiment 1
The current density in pond is 255mA/cm2, power density 260mW/cm2, the current density of battery prepared by comparative example 1 is
175mA/cm2, power density 185mW/cm2。
The battery being prepared is subjected to the test of long-term intermittent discharge performance, when battery carries out 24 intermittent discharges, electricity
The attenuation rate in pond is 18%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of metal air battery cathodes, comprising:
A) conductive agent, binder and solvent are mixed, stirring obtains slurry；In the slurry by current collector layer dipping, drying is fired
Obtain hydrophobic layer；
B) by lubricant, conductive agent, binder and solvent mixing, precompressed, extrusion, stretching, drying, mixture is obtained；It will be described
Mixture squeezes to obtain catalytic substrate film in hydrophobic layer surface；The lubricant is selected from silicone oil, fatty acid amide, oleic acid and polyester
One or more of；The conductive agent is selected from one of active carbon, carbon black and polyethylene alkynes or a variety of；The binder choosing
From one of ptfe micropowder, ptfe emulsion, Kynoar and fluorinated ethylene propylene or a variety of；
C catalyst, binder and solvent) are mixed to get slurry, slurry thermal jet is coated on the catalytic substrate film, is urged
Change layer；
D the Catalytic Layer and hydrophobic layer) are obtained into metal air battery cathodes in hot pressing, firing.
2. preparation method according to claim 1, which is characterized in that the step A) in conductive agent be selected from active carbon, charcoal
One of black and polyethylene alkynes is a variety of；The binder is selected from ptfe micropowder, ptfe emulsion, gathers inclined fluorine
One of ethylene and fluorinated ethylene propylene are a variety of；The solvent is selected from one of terpinol, ethyl alcohol and isopropanol or more
Kind；The current collector layer raw material is selected from one or more of nickel foam, nickel screen and steel mesh；
The step B) described in solvent be selected from one of terpinol, ethyl alcohol and isopropanol or a variety of；
The step C) in catalyst be selected from MnO2、MnO、Mn3O4And Mn2O3One or more of；Binder is selected from polytetrafluoro
One of ethylene micro mist, ptfe emulsion, Kynoar and fluorinated ethylene propylene are a variety of；The solvent is selected from pine
One of oleyl alcohol, ethyl alcohol and isopropanol are a variety of.
3. preparation method according to claim 1, which is characterized in that the step A) in conductive agent, binder and solvent
Mass ratio be (0.1~5): (0.5~5): (10~300)；
The step B) in lubricant, conductive agent, binder and solvent mass ratio be (0.5~10): (0.1~3): (0.1~
10): (20~400).
4. preparation method according to claim 1, which is characterized in that the step B) in precompressed obtain the density of slurry and be
100~10000kg/cm3；Extrusion pressure is 1~30MPa；Squeezing out number is 2~20 times；Rate of extension is 0.1~10MPa/s；
Drawing numbers are 3~10 times.
5. preparation method according to claim 1, which is characterized in that the step B) in drawn material drying temperature be 80
~500 DEG C；The time of drying is 1~50h；Squeeze pressure is 1~20MPa.
6. preparation method according to claim 1, which is characterized in that the step C) in catalyst, binder and solvent
Mass ratio (1~50): (1~40): (50~1500).
7. preparation method according to claim 1, which is characterized in that the step C) in thermal spraying temperature be 100~500
℃；Pressure is 0.1~10MPa；Catalytic Layer is with a thickness of 0.01~1mm.
8. preparation method according to claim 1, which is characterized in that the step D) in hot pressing pressure be 5~
50MPa；Time is 0.5~5min；The temperature of firing is 200~1000 DEG C, and the firing time is 0.1~20h.
9. a kind of metal air battery cathodes, which is characterized in that the preparation method system as described in claim 1~8 any one
It is standby to obtain.
10. a kind of metal-air battery, which is characterized in that prepared including preparation method described in claim 1~8 any one
Obtained cathode.
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| CN107437645B (en) * | 2017-07-17 | 2020-02-14 | 潘科艳 | Method for manufacturing porous high-performance oxygen electrode of metal fuel cell |
| CN109524697A (en) * | 2018-11-05 | 2019-03-26 | 东莞市中航华讯卫星技术有限公司 | The preparation method and metal-air battery membrane electrode of metal-air battery membrane electrode |
| CN109390591A (en) * | 2018-11-19 | 2019-02-26 | 上海华普汽车有限公司 | A kind of battery electrode and its preparation method and application |
| CN109713318B (en) * | 2018-12-26 | 2021-03-19 | 宁波石墨烯创新中心有限公司 | Flexible and bendable air cathode and preparation method thereof |
| CN109980237A (en) * | 2019-04-29 | 2019-07-05 | 宁波石墨烯创新中心有限公司 | A kind of air cathode, preparation method and battery |
| CN112687897A (en) * | 2020-12-29 | 2021-04-20 | 长沙迅洋新材料科技有限公司 | Consolidation preparation method of waterproof breathable layer material for magnesium metal air battery |
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