CN106785241A - Metal air battery cathodes and preparation method thereof - Google Patents
Metal air battery cathodes and preparation method thereof Download PDFInfo
- Publication number
- CN106785241A CN106785241A CN201611169826.6A CN201611169826A CN106785241A CN 106785241 A CN106785241 A CN 106785241A CN 201611169826 A CN201611169826 A CN 201611169826A CN 106785241 A CN106785241 A CN 106785241A
- Authority
- CN
- China
- Prior art keywords
- slurry
- binding agent
- solvent
- preparation
- layer
- 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.)
- Granted
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
- H01M12/04—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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a kind of preparation method of metal air battery cathodes, including：A) conductive agent, binding agent and solvent are mixed, stirring obtains slurry；By current collector layer raw material dipping in the slurry, firing obtains hydrophobic layer；B) lubricant, conductive agent, binding agent and solvent are mixed, slurry is obtained；Slurry extrusion, stretching, drying are obtained into mixture；The mixture is squeezed into film in hydrophobic layer surface；C catalyst, binding agent and solvent) are mixed to get slurry, slurry is sprayed on the film, obtain Catalytic Layer；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 used as the carrier of catalyst, the component of film, with preferable structural strength, is then sprayed catalyst by thermal spraying by extruding and being drawn into fibrosis distribution, can be stronger be fixed on hydrophobic layer.Catalytic Layer of the invention has excellent battery performance and stability.
Description
Technical field
The present invention relates to cell art, more particularly, to a kind of metal air battery cathodes and preparation method thereof.
Background technology
The energy is developing national economy and the important substance basis uplifted the people's living standard, and is also to directly affect economic hair
One key factor of exhibition.Since 21 century, facing mankind the significant challenge for realizing economy and social sustainable development,
How to keep rapid development of economy to have become global focus under the dual restriction that resource-constrained and environmental protection are strict with to ask
Topic.And will more be protruded the problems such as shortage of resources, environmental pollution, greenhouse effects that traditional energy utilization patterns are brought, because
The need for this traditional energy structure and its Land use systems are increasingly difficult in adapt to survival and development of mankind.In order to efficiently, reasonably make
With non-renewable energy resources and holding environment and the ecological balance, Basic Ways are exactly fuel electricity of the exploitation with these resources as fuel
Pool technology.
Metal-air battery is a kind of between galvanic cell and fuel cell " half fuel " battery, has galvanic cell and fuel concurrently
The characteristics of battery, with capacity it is big, specific energy is high, low cost and other advantages, it is considered to be there are very much development and application prospect in future
Novel battery material.Metal-air battery is typically made up of air cathode, electrolyte and metal anode, and metal anode is business
Rafifinal and aluminium alloy, therefore, cell cathode directly determines battery performance.Negative electrode includes current collector layer, hydrophobic layer and catalysis
There is redox reaction in layer, battery, three-phase reaction interface is that the place of above-mentioned reaction, phase reaction circle occur in Catalytic Layer
Face area has large effect to the performance of air electrode.
The Chinese patent of Application No. 201310282853.4 is disclosed catalyst, activated carbon, acetylene black and binding agent
Ptfe emulsion is well mixed according to certain ratio, with absolute ethyl alcohol as solvent, after 20~50min of ultrasonic disperse, turns
Move to and obtain rubber pureed mixture after removing ethanol in 70~90 DEG C of water-baths, be rolled into the catalytic membrane after 0.2~0.5mm, this
It is the Catalytic Layer of battery.Hydrophobic layer uses same method, and with activated carbon, acetylene black, prepared by polyfluortetraethylene of binding element emulsion
Form, be then hot pressed into the negative electrode of air cell according to the order of waterproof membrane, collector, catalytic membrane.Negative electrode prepared by the method
Catalytic Layer easily absorbs water cracking in test process, therefore the long-time stability of battery are poor, by 200mA/cm2Constant-current discharge
Pattern is tested 40 hours, and in 1.24V, output energy density is only 1.902kWh/ (Kg, Al).Additionally, the method preparation technology
Complexity, is unfavorable for the amplification and commercialized popularization of product.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation side of metal air battery cathodes
Method, the metal air battery cathodes good stability that the present invention is prepared.
The invention provides a kind of preparation method of metal air battery cathodes, including：
A) conductive agent, binding agent and solvent are mixed, stirring obtains slurry；By current collector layer dipping in the slurry, dry,
Firing obtains hydrophobic layer；
B) by the mixing of lubricant, conductive agent, binding agent and solvent, precompressed, extrusion, stretching, drying, mixture is obtained；Will
The mixture obtains catalytic substrate film in the extruding of hydrophobic layer surface；
C catalyst, binding agent and solvent) are mixed to get slurry, slurry thermal jet is coated onto on the catalytic substrate film, 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 activated carbon, carbon black and polyethylene alkynes in one or more；It is described
Binding agent is selected from the one kind or many in ptfe micropowder, ptfe emulsion, Kynoar and PEP
Kind；The solvent is selected from one or more in terpinol, ethanol and isopropanol；The current collector layer raw material is selected from nickel foam, nickel
One or more in net and steel mesh；
The step B) in lubricant be selected from silicone oil, fatty acid amide, oleic acid and polyester in one or more；It is described to lead
Electric agent is selected from one or more in activated carbon, carbon black and polyethylene alkynes；The binding agent is selected from ptfe micropowder, poly- four
One or more in PVF emulsion, Kynoar and PEP；The solvent is selected from terpinol, ethanol and different
One or more in propyl alcohol；
The step C) in catalyst be selected from MnO2、MnO、Mn3O4And Mn2O3In one or more；Binding agent is selected from poly-
One or more in tetrafluoroethene micro mist, ptfe emulsion, Kynoar and PEP；The solvent choosing
One or more from terpinol, ethanol and isopropanol.
Preferably, the step A) in the mass ratio of conductive agent, binding agent and solvent be preferably (0.1~5)：(0.5~
5)：(10~300)；
The step B) in lubricant, conductive agent, binding agent 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；Extrusion number of times is 2~20 times；Rate of extension is 0.1~10MPa/s；Drawing numbers is 3~10 times.
Preferably, the step B) in drawn material drying temperature be 80~500 DEG C；The time of drying is 1~50h；Squeeze
Pressure pressure is 1~20MPa.
Preferably, the step C) in catalyst, binding agent 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
It is 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 invention provides a kind of metal air battery cathodes, the preparation method as described in above-mentioned technical proposal is prepared into
Arrive.
The invention provides a kind of metal-air battery, including preparation method described in above-mentioned technical proposal is prepared
Negative electrode.
Compared with prior art, the invention provides a kind of preparation method of metal air battery cathodes, including：A) will lead
Electric agent, binding agent and solvent mixing, stirring obtain slurry；By current collector layer dipping in the slurry, drying, firing obtains hydrophobic layer；
B) by the mixing of lubricant, conductive agent, binding agent and solvent, precompressed, extrusion, stretching, drying, mixture is obtained；By the mixing
Thing obtains catalytic substrate film in the extruding of hydrophobic layer surface；C catalyst, binding agent and solvent) are mixed to get slurry, by slurry heat
Spray on the catalytic substrate film, obtain Catalytic Layer；D the Catalytic Layer and hydrophobic layer) are obtained into metal sky in hot pressing, firing
Pneumoelectric pool cathode.The metal-air battery that the present invention is provided first prepares a tunic in hydrophobic layer surface, as the carrier of catalyst,
The component of film is by extrusion and is drawn into fibrosis distribution, can be stronger be fixed on hydrophobic layer, with preferable structural strength,
Catalyst is sprayed by thermal spraying then.The Catalytic Layer that the method for the present invention is prepared has more three phase boundary, and
And be firmly combined with hydrophobic layer, therefore with excellent battery performance and stability, test result indicate that, electricity prepared by the present invention
Pond long-term intermittent discharges 24 times, and attenuation rate is only 6%.
Brief description of the drawings
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 invention provides a kind of preparation method of metal air battery cathodes, including：
A) conductive agent, binding agent and solvent are mixed, stirring obtains slurry；By current collector layer dipping in the slurry, dry,
Firing obtains hydrophobic layer；
B) by the mixing of lubricant, conductive agent, binding agent and solvent, precompressed, extrusion, stretching, drying, mixture is obtained；Will
The mixture obtains catalytic substrate film in the extruding of hydrophobic layer surface；
C catalyst, binding agent and solvent) are mixed to get slurry, slurry thermal jet is coated onto on the catalytic substrate film, 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 the metal air battery cathodes that the present invention is provided first mixes conductive agent, binding agent 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 in nickel foam, nickel screen and steel mesh.The conductive agent is excellent
Choosing is selected from one or more in activated carbon, carbon black and polyethylene alkynes；The binding agent is preferably selected from ptfe micropowder, gathers
One or more in tetrafluoroethene emulsion, Kynoar and PEP；The solvent is preferably selected from terpinol, second
One or more in alcohol and isopropanol.The mass ratio of the conductive agent, binding agent 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 is not defined for the concrete mode of the mixing, 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 in 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
Elect 1~3h as.
After obtaining hydrophobic layer, the mixing of lubricant, conductive agent, binding agent and solvent, precompressed, extrusion, stretching, drying are obtained
To mixture；The mixture is obtained into catalytic substrate film in the extruding of hydrophobic layer surface.
Catalytic substrate film of the present invention is preferably prepared by following methods：
Lubricant, conductive agent, binding agent and solvent are mixed, slurry is obtained.It is preferred that be specially by lubricant, conductive agent,
Binding agent is added to solvent mixing, and heating makes it flocculate, obtains powdery lotion；Lotion obtains slurry through precompressed.
In the present invention, the temperature of the heating flocculation is preferably 40~120 DEG C；More preferably 60~100 DEG C；Most preferably
It is 80~90 DEG C；The present invention is not defined for the precompressed, precompressed mode well known to those skilled in the art, preferably
The precompressed in cylindrical obturation tubular die.The density of the precompressed disposed slurry is preferably 100~10000kg/cm3, more preferably
It is 500~8000kg/cm3, most preferably 2000~6000kg/cm3。
In the present invention, the lubricant is preferably selected from the one kind or several in silicone oil, fatty acid amide, oleic acid and polyester
Kind；It is more preferably selected from one or more in silicone oil, fatty acid amide and oleic acid；The conductive agent is preferably selected from activated carbon, charcoal
One or more in black and polyethylene alkynes；The binding agent is preferably selected from ptfe micropowder, ptfe emulsion, gathers
One or more in vinylidene and PEP；The solvent is preferably selected from terpinol, ethanol and isopropanol
One or more.
In the present invention, the mass ratio of the lubricant, conductive agent, binding agent 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, by slurry extrusion, stretching, drying obtains mixture.
The slurry to be extruded in an extruder, repeated processing is circulated under certain speed, extrusion pressure is preferably 1~
30MPa；More preferably 5~20MPa；Most preferably 10~15MPa；Extrusion number of times is preferably 2~20 times, more preferably 5~15
It is secondary；Most preferably 9~12 times；In extrusion, there is fibrosis in binding agent particle, many in the presence of compression and shearing force
Secondary extrusion can significantly improve the degree of fibrosis.
Extrusion after-drawing, the rate of extension of the stretching is preferably 0.1~10MPa/s, more preferably 1~8MPa/s；Most
Preferably 3~5MPa；Drawing numbers is preferably 3~10 times；More preferably 4~8 times；Most preferably 5~7 times.
Stretching causes that microfibre is further elongated, and cleaves, and forms space.
By drawn material drying, 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
Elect 20~30h as.
After drying, lubricant is volatilized, and is conducive to the preparation of film.
The mixture is squeezed into film in hydrophobic layer surface, catalytic substrate film is now formd, the film compactness is high, but
Still there is more hole, isolation electrolyte is played a part of while gas permeability is ensured and is oozed out；The pressure of the extruding is preferably 1
~20MPa；More preferably 5~15MPa；Most preferably 7~10MPa.
Catalyst, binding agent and solvent are mixed to get slurry, slurry is sprayed on the catalytic substrate film, urged
Change layer.
In the present invention, the catalyst is selected from MnO2、MnO、Mn3O4And Mn2O3In one or more；Binding agent is selected from
One or more in ptfe micropowder, ptfe emulsion, Kynoar and PEP；The solvent
Selected from one or more in terpinol, ethanol and isopropanol.
In the present invention, the mass ratio of the catalyst, binding agent 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 causes that the binding agent particle in the binding agent particle and catalytic substrate film in hydrophobic layer is mutual
Connection, can play a part of fixed catalyst, increased 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 binding agent particle enter into it is mesoporous in, increased spatial depth
The content of upper catalyst, this is the second tunic of Catalytic Layer, and voidage is high, can improve the contact surface of electrolyte and catalyst
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 invention provides a kind of metal air battery cathodes, the preparation method as described in above-mentioned technical proposal is prepared into
Arrive.
The invention provides a kind of metal-air battery, including preparation method described in above-mentioned technical proposal is prepared
Negative electrode.
The invention provides a kind of preparation method of metal air battery cathodes, including：A) by conductive agent, binding agent and molten
Agent mixes, stirring, obtains slurry；By current collector layer dipping in the slurry, drying, firing obtains hydrophobic layer；B) by lubricant, conduction
The mixing of agent, binding agent and solvent, precompressed, extrusion, stretching, drying, obtain mixture；The mixture is squeezed in hydrophobic layer surface
Pressure obtains catalytic substrate film；C catalyst, binding agent 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, used as the carrier of catalyst, the group of film
Lease making crosses extrusion and is drawn into fibrosis distribution, and can be stronger be fixed on hydrophobic layer, with preferable structural strength, is then led to
Thermal spraying is crossed to spray catalyst.The Catalytic Layer that the method for the present invention is prepared has a more three phase boundary, and with
Hydrophobic layer is firmly combined with, therefore with excellent battery performance and stability.
Performance measurement is carried out present invention preferably employs the metal air battery cathodes that following manner is prepared to the present invention：
Stability Determination：Using test one day, then electrolyte is poured out, allow Catalytic Layer and air contact one day.
In order to further illustrate the present invention, the metal air battery cathodes that the present invention is provided are carried out with reference to embodiments
Describe in detail.
Embodiment 1
According to 1：2：100 ratio weighs polyethylene alkynes, and binding agent PTFE powder, etoh solvent is well mixed, and obtains hydrophobic
Layer slurry.Nickel foam is impregnated in the slurry 3 times, be dried to after drying, it is that can obtain hydrophobic layer that 3h is fired at 350 DEG C.
According to 4：1：3：150 mass ratio weighs lubricant fatty acid amide, and nano carbon black, PTFE micro mists and ethanol mix
Uniformly, 80 DEG C are heated to and bring it about flocculation, obtain powdery lotion, lotion carried out in cylindrical obturation tubular die pre-
Pressure, the density for obtaining slurry is 2000kg/cm3；Raw material is transferred to extruder, is extruded 12 times under 10MPa pressure, Ran Hou
Stretched 7 times under 3MPa pulling force, microfibre is further elongated, and cleaved, form space；The product of stretching is placed on
30h is dried in baking oven at 200 DEG C, it is then pressed into film in hydrophobic layer surface under room temperature 7MPa；
According to 4：3：20 mass ratio weighs catalyst MnO2, binding agent PTFE micro mists and etoh solvent, then clipping the ball
Mill obtains Catalytic Layer spray liniment, and at 300 DEG C, thermal jet is coated onto on Catalytic Layer basilar memebrane under 2MPa, obtains thickness for 0.3mm is catalyzed
Film, then the hot pressing 3min under 20MPa, fires 5h, you can obtain metal by the Catalytic Layer and hydrophobic layer after hot pressing at 340 DEG C
The negative electrode of air cell.
The negative electrode prepared using the embodiment of the present invention is applied to metal aluminium-air cell, and anode is commercially available using in the market
The quaternary aluminium alloy bought, and be measured using method of the present invention, performance is as shown in figure 1, Fig. 1 is the embodiment of the present invention
1~4 battery performance figure for preparing, as seen from Figure 1, when voltage is 1.0V, the electricity of the battery prepared to embodiment 1
Current density is 255mA/cm2, power density is 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%, illustrates to use the method
The cell catalyst layer of preparation improves a lot with hydrophobic layer firmness, even if to expose also be not easy in atmosphere after electric discharge taking off
Fall.
Embodiment 2
According to 3：3：200 ratio weighs polyethylene alkynes, and binding agent PTFE powder, etoh solvent is well mixed, and obtains hydrophobic
Layer slurry.Nickel foam is impregnated in the slurry 5 times, be dried to after drying, it is that can obtain hydrophobic layer that 1h is fired at 450 DEG C.
According to 6：2：5：300 mass ratio weighs lubricant fatty acid amide, and nano carbon black, PTFE micro mists and ethanol mix
Uniformly, 90 DEG C are heated to and bring it about flocculation, obtain powdery lotion, lotion carried out in cylindrical obturation tubular die pre-
Pressure, the density for obtaining slurry is 6000kg/cm3；Raw material is transferred to extruder, is extruded 9 times under 15MPa pressure, Ran Hou
Stretched 5 times under 5MPa pulling force, microfibre is further elongated, and cleaved, form space；The product of stretching is placed on
20h is dried in baking oven at 300 DEG C, it is then pressed into film in hydrophobic layer surface under room temperature 10MPa；
According to 6：5：200 mass ratio weighs catalyst MnO2, binding agent PTFE micro mists and etoh solvent, then clipping the ball
Mill obtains Catalytic Layer spray liniment, and at 500 DEG C, thermal jet is coated onto on Catalytic Layer basilar memebrane under 5MPa, obtains thickness for 0.5mm is catalyzed
Film, then the hot pressing 2min under 30MPa, fires 0.5h, you can obtain gold by the Catalytic Layer and hydrophobic layer after hot pressing at 500 DEG C
Belong to the negative electrode of air cell.
The negative electrode prepared using the embodiment of the present invention is applied to metal aluminium-air cell, and anode is commercially available using in the market
The quaternary aluminium alloy bought, and be measured using method of the present invention, performance is as shown in figure 1, Fig. 1 is the embodiment of the present invention
1~4 battery performance figure for preparing, as seen from Figure 1, when voltage is 1.0V, the electricity of the battery prepared to embodiment 2
Current density is 243mA/cm2, power density is 250mW/cm2。
The battery that will be prepared carries out long-term intermittent discharge performance test, when battery carries out 24 intermittent discharges, electricity
The attenuation rate in pond is 8%, illustrates that the cell catalyst layer prepared using the method is improved a lot with hydrophobic layer firmness, even if
Exposed after electric discharge and also do not allow in atmosphere easy to fall off.
Embodiment 3
According to 0.5：1：50 ratio weighs polyethylene alkynes, and binding agent PTFE powder, etoh solvent is well mixed, and obtains hydrophobic
Layer slurry.Nickel foam is impregnated in the slurry 2 times, be dried to after drying, it is that can obtain hydrophobic layer that 4h is fired at 300 DEG C.
According to 3：0.5：2：100 mass ratio weighs lubricant fatty acid amide, and nano carbon black, PTFE micro mists and ethanol are mixed
Close uniform, be heated to 60 DEG C and bring it about flocculation, obtain powdery lotion, lotion is carried out in cylindrical obturation tubular die pre-
Pressure, the density for obtaining slurry is 500kg/cm3；Raw material is transferred to extruder, is extruded 15 times under 5MPa pressure, then in 1MPa
Stretched 8 times under pulling force, microfibre is further elongated, and cleaved, form space；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 under room temperature 5MPa；
According to 10：10：150 mass ratio weighs catalyst MnO2, binding agent PTFE micro mists and etoh solvent, then at a high speed
Ball milling obtains Catalytic Layer spray liniment, and at 200 DEG C, thermal jet is coated onto on Catalytic Layer basilar memebrane under 8MPa, obtains thickness for 0.1mm is catalyzed
Film, then the hot pressing 4min under 10MPa, fires 10h, you can obtain gold by the Catalytic Layer and hydrophobic layer after hot pressing at 300 DEG C
Belong to the negative electrode of air cell.
The negative electrode prepared using the embodiment of the present invention is applied to metal aluminium-air cell, and anode is commercially available using in the market
The quaternary aluminium alloy bought, and be measured using method of the present invention, performance is as shown in figure 1, Fig. 1 is the embodiment of the present invention
1~4 battery performance figure for preparing, as seen from Figure 1, when voltage is 1.0V, the electricity of the battery prepared to embodiment 3
Current density is 230mA/cm2, power density is 245mW/cm2。
The battery that will be prepared carries out long-term intermittent discharge performance test, when battery carries out 24 intermittent discharges, electricity
The attenuation rate in pond is 10%, illustrates that the cell catalyst layer prepared using the method is improved a lot with hydrophobic layer firmness, i.e.,
Make to expose after electric discharge also do not allow in atmosphere easy to fall off.
Embodiment 4
According to 4：4：250 ratio weighs polyethylene alkynes, and binding agent PTFE powder, etoh solvent is well mixed, and obtains hydrophobic
Layer slurry.Nickel foam is impregnated in the slurry 8 times, be dried to after drying, it is that can obtain hydrophobic layer that 0.5h is fired at 500 DEG C.
According to 8：2.5：8：350 mass ratio weighs lubricant fatty acid amide, and nano carbon black, PTFE micro mists and ethanol are mixed
Close uniform, be heated to 100 DEG C and bring it about flocculation, obtain powdery lotion, lotion is carried out in cylindrical obturation tubular die
Precompressed, the density for obtaining slurry is 8000kg/cm3；Raw material is transferred to extruder, is extruded 5 times under 20MPa pressure, Ran Hou
Stretched 4 times under 8MPa pulling force, microfibre is further elongated, and cleaved, form space；The product of stretching is placed on
10h is dried in baking oven at 400 DEG C, it is then pressed into film in hydrophobic layer surface under room temperature 15MPa；
According to 40：30：1200 mass ratio weighs catalyst MnO2, binding agent PTFE micro mists and etoh solvent, Ran Hougao
Fast ball milling obtains Catalytic Layer spray liniment, and at 600 DEG C, thermal jet is coated onto on Catalytic Layer basilar memebrane under 1MPa, obtains thickness for 0.7mm is urged
Change film, then the hot pressing 1min under 40MPa, fires 0.2h, you can obtain by the Catalytic Layer and hydrophobic layer after hot pressing at 800 DEG C
The negative electrode of metal-air battery.
The negative electrode prepared using the embodiment of the present invention is applied to metal aluminium-air cell, and anode is commercially available using in the market
The quaternary aluminium alloy bought, and be measured using method of the present invention, performance is as shown in figure 1, Fig. 1 is the embodiment of the present invention
1~4 battery performance figure for preparing, as seen from Figure 1, when voltage is 1.0V, the electricity of the battery prepared to embodiment 4
Current density is 220mA/cm2, power density is 230mW/cm2。
The battery that will be prepared carries out long-term intermittent discharge performance test, when battery carries out 24 intermittent discharges, electricity
The attenuation rate in pond is 9%, illustrates that the cell catalyst layer prepared using the method is improved a lot with hydrophobic layer firmness, even if
Exposed after electric discharge and also do not allow in atmosphere easy to fall off.
Comparative example 1
According to 1：2：100 ratio weighs polyethylene alkynes, and binding agent PTFE powder, etoh solvent is well mixed, and obtains hydrophobic
Layer slurry.Nickel foam is impregnated in the slurry 3 times, be dried to after drying, it is that can obtain hydrophobic layer that 3h is fired at 350 DEG C.
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, contrasts the change of its battery performance, detailed process is：According to 4：
1：3：4：150 mass ratio weighs lubricant fatty acid amide, nano carbon black, PTFE micro mists, MnO2It is well mixed with ethanol, plus
Hot to 80 DEG C bring it about flocculation, obtain powdery lotion, and lotion is carried out into precompressed in cylindrical obturation tubular die, are starched
The density of material is 2000kg/cm3；Slurry is placed and dries 30h at 200 DEG C in an oven, then under room temperature 7MPa by its
Hydrophobic layer surface is pressed into film, and now negative electrode forms Catalytic Layer, then under 20MPa hot pressing 3min, by hot pressing after urge
Change layer and hydrophobic layer fires 5h at 340 DEG C, you can obtain the negative electrode of metal-air battery.
The negative electrode prepared using the embodiment of the present invention is applied to metal aluminium-air cell, and anode is commercially available using 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 for preparing of comparative example 1, as seen from Figure 3, when voltage is 1.0V, the electricity prepared to embodiment 1
The current density in pond is 255mA/cm2, power density is 260mW/cm2, the current density of battery prepared by comparative example 1 is
175mA/cm2, power density is 185mW/cm2。
The battery that will be prepared carries out long-term intermittent discharge performance test, when battery carries out 24 intermittent discharges, electricity
The attenuation rate in pond is 18%.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of metal air battery cathodes, including：
A) conductive agent, binding agent and solvent are mixed, stirring obtains slurry；By current collector layer dipping in the slurry, drying, firing
Obtain hydrophobic layer；
B) by the mixing of lubricant, conductive agent, binding agent and solvent, precompressed, extrusion, stretching, drying, mixture is obtained；Will be described
Mixture obtains catalytic substrate film in the extruding of hydrophobic layer surface；
C catalyst, binding agent and solvent) are mixed to get slurry, slurry thermal jet is coated onto on the catalytic substrate film, 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, it is characterised in that the step A) in conductive agent be selected from activated carbon, charcoal
One or more in black and polyethylene alkynes；The binding agent is selected from ptfe micropowder, ptfe emulsion, gathers inclined fluorine
One or more in ethene and PEP；The solvent is selected from the one kind or many in terpinol, ethanol and isopropanol
Kind；The current collector layer raw material is selected from one or more in nickel foam, nickel screen and steel mesh；
The step B) in lubricant be selected from silicone oil, fatty acid amide, oleic acid and polyester in one or more；The conductive agent
Selected from one or more in activated carbon, carbon black and polyethylene alkynes；The binding agent is selected from ptfe micropowder, polytetrafluoroethyl-ne
One or more in alkene emulsion, Kynoar and PEP；The solvent is selected from terpinol, ethanol and isopropanol
In one or more；
The step C) in catalyst be selected from MnO2、MnO、Mn3O4And Mn2O3In one or more；Binding agent is selected from polytetrafluoro
One or more in ethene micro mist, ptfe emulsion, Kynoar and PEP；The solvent is selected from pine
One or more in oleyl alcohol, ethanol and isopropanol.
3. preparation method according to claim 1, it is characterised in that the step A) in conductive agent, binding agent and solvent
Mass ratio be preferably (0.1~5)：(0.5~5)：(10~300)；
The step B) in lubricant, conductive agent, binding agent and solvent mass ratio be (0.5~10)：(0.1~3)：(0.1~
10)：(20~400).
4. preparation method according to claim 1, it is characterised in that the step B) in precompressed obtain the density of slurry and be
100~10000kg/cm3；Extrusion pressure is 1~30MPa；Extrusion number of times is 2~20 times；Rate of extension is 0.1~10MPa/s；
Drawing numbers is 3~10 times.
5. preparation method according to claim 1, it is characterised 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, it is characterised in that the step C) in catalyst, binding agent and solvent
Mass ratio (1~50)：(1~40)：(50~1500).
7. preparation method according to claim 1, it is characterised in that the step C) in thermal spraying temperature be 100~500
℃；Pressure is 0.1~10MPa；Catalytic Layer thickness is 0.01~1mm.
8. preparation method according to claim 1, it is characterised in that the step D) in hot pressing pressure for 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, it is characterised 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, it is characterised in that prepared including the preparation method described in claim 1~8 any one
The negative electrode for obtaining.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611169826.6A CN106785241B (en) | 2016-12-16 | 2016-12-16 | Metal air battery cathodes and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611169826.6A CN106785241B (en) | 2016-12-16 | 2016-12-16 | Metal air battery cathodes and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106785241A true CN106785241A (en) | 2017-05-31 |
| CN106785241B CN106785241B (en) | 2019-04-12 |
Family
ID=58893210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611169826.6A Active CN106785241B (en) | 2016-12-16 | 2016-12-16 | Metal air battery cathodes and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106785241B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107437645A (en) * | 2017-07-17 | 2017-12-05 | 潘科艳 | A kind of porous high performance metal fuel battery oxygen electrode preparation method |
| 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 |
| 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 |
| CN109713318A (en) * | 2018-12-26 | 2019-05-03 | 宁波石墨烯创新中心有限公司 | A kind of air cathode of flexible 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0917434A (en) * | 1995-06-28 | 1997-01-17 | Matsushita Electric Ind Co Ltd | Manufacture of catalytic layer for air-zinc battery |
| CN1388997A (en) * | 2000-03-23 | 2003-01-01 | 吉莱特公司 | Battery |
| CN101015796A (en) * | 2006-02-07 | 2007-08-15 | 三星Sdi株式会社 | Method of preparing metal catalyst and electrode including the same |
| CN103326039A (en) * | 2013-06-17 | 2013-09-25 | 重庆稳能能源科技有限公司 | Catalyst for air electrode, catalytic layer spraying agent, air electrode and preparation methods of catalyst and air electrode |
| CN105932301A (en) * | 2016-07-06 | 2016-09-07 | 中国科学院宁波材料技术与工程研究所 | Method for preparing cathode of metal-air battery, and metal-air battery |
-
2016
- 2016-12-16 CN CN201611169826.6A patent/CN106785241B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0917434A (en) * | 1995-06-28 | 1997-01-17 | Matsushita Electric Ind Co Ltd | Manufacture of catalytic layer for air-zinc battery |
| CN1388997A (en) * | 2000-03-23 | 2003-01-01 | 吉莱特公司 | Battery |
| CN101015796A (en) * | 2006-02-07 | 2007-08-15 | 三星Sdi株式会社 | Method of preparing metal catalyst and electrode including the same |
| CN103326039A (en) * | 2013-06-17 | 2013-09-25 | 重庆稳能能源科技有限公司 | Catalyst for air electrode, catalytic layer spraying agent, air electrode and preparation methods of catalyst and air electrode |
| CN105932301A (en) * | 2016-07-06 | 2016-09-07 | 中国科学院宁波材料技术与工程研究所 | Method for preparing cathode of metal-air battery, and metal-air battery |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107437645A (en) * | 2017-07-17 | 2017-12-05 | 潘科艳 | A kind of porous high performance metal fuel battery oxygen electrode preparation method |
| 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 |
| CN109713318A (en) * | 2018-12-26 | 2019-05-03 | 宁波石墨烯创新中心有限公司 | A kind of air cathode of flexible and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106785241B (en) | 2019-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106785241B (en) | Metal air battery cathodes and preparation method thereof | |
| CN110148759B (en) | Preparation method of high-current-density-oriented proton exchange membrane fuel cell gas diffusion layer | |
| JP4745330B2 (en) | Gas diffusion electrode and membrane electrode assembly for proton exchange membrane fuel cell | |
| CN106784943A (en) | A kind of membrane electrode of fuel batter with proton exchange film of high power density and preparation method thereof | |
| CN110504472A (en) | A kind of direct methanol fuel cell membrane electrode and preparation method thereof improving catalyst utilization | |
| CN103943877A (en) | Membrane electrode of direct alcohol type fuel battery and preparation method thereof | |
| CN110380063A (en) | A kind of used in proton exchange membrane fuel cell gas diffusion layers and preparation method thereof and Proton Exchange Membrane Fuel Cells | |
| CN103022509A (en) | Micro direct methanol fuel cell membrane electrode and preparation method thereof | |
| CN106356537B (en) | A kind of preparation method of N doping porous carbon foam material and its application in metal-air battery | |
| CN101752570B (en) | Preparation method of proton exchange membrane fuel cell electrode | |
| CN104538646A (en) | Method for manufacturing air electrode of aluminum-air cell | |
| CN105932301B (en) | The preparation method and metal-air battery of metal air battery cathodes | |
| CN107369838A (en) | It is a kind of to exempt from hot pressing combination electrode and preparation method thereof for DMFC | |
| CN102769141A (en) | Membrane electrode assembly of proton exchange membrane fuel cell and manufacturing method of membrane electrode assembly | |
| CN104733691A (en) | Preparation method of high-capacity lithium battery positive plate | |
| CN102522570A (en) | Method for preparing enhanced membrane electrode (MEA) of proton exchange membrane fuel cell (PEMFC) | |
| CN109904469A (en) | A kind of method for preparing membrane electrode optimizing cathode catalysis layer structure | |
| CN102074715A (en) | Double-effect membrane electrode for integrated regenerative fuel cell and preparation method thereof | |
| CN109786795A (en) | It is a kind of based on stronitum stannate/lanthanum-strontium ferro-cobalt composite material low-temperature solid oxide fuel cell | |
| CN105161729A (en) | Miniature direct methanol fuel cell membrane electrode and preparation method thereof | |
| CN103474683B (en) | Improve membrane electrode assembly of integral type regenerative fuel cell performance and preparation method thereof | |
| KR20080105255A (en) | Method for manufacturing 5-layer mea | |
| CN100524913C (en) | Method for preparing membrane electrode of direct methanol fuel cell | |
| CN102503531A (en) | Method for preparing SOFC (Solid Oxide Fuel Cell) anode by adopting spherical and fibrous composite pore forming agent | |
| CN104347884A (en) | Method for preparing electrode for fuel cell |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220831 Address after: No. 1818, Zhongguan West Road, Zhuangshi street, Zhenhai District, Ningbo City, Zhejiang Province, 315000 Patentee after: NINGBO GRAPHENE INNOVATION CENTER Co.,Ltd. Address before: 315201, No. 519, Zhuang Avenue, Zhenhai District, Zhejiang, Ningbo Patentee before: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES |