CN107069046A - A kind of metal air battery cathodes and preparation method thereof, metal-air battery - Google Patents
A kind of metal air battery cathodes and preparation method thereof, metal-air battery Download PDFInfo
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- CN107069046A CN107069046A CN201710286894.9A CN201710286894A CN107069046A CN 107069046 A CN107069046 A CN 107069046A CN 201710286894 A CN201710286894 A CN 201710286894A CN 107069046 A CN107069046 A CN 107069046A
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- Prior art keywords
- metal
- hydrophobic
- catalyst
- diaphragm
- air battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8673—Electrically conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8896—Pressing, rolling, calendering
Abstract
The invention provides a kind of metal air battery cathodes, including metal collector, the hydrophobic layer of the metal collector side is compounded in；It is compounded in the catalyst layer on the hydrophobic layer；The catalyst layer includes fiber nickel.In the metal air battery cathodes that the present invention is provided, fiber nickel is with the addition of as conductive filler, effectively alleviates the cracking caused by the volumetric expansion contraction of negative electrode different materials in preparation process and comes off.
Description
Technical field
The present invention relates to air cell technical field, it is related to a kind of metal air battery cathodes and preparation method thereof, metal
Air cell.
Background technology
Air cell is one kind of chemical cell, and aufbauprinciple is similar to dry cell, different simply its oxidants
The oxygen in air is derived from, metal-air battery is a kind of room temperature fuel cell, generally with magnesium, aluminium, the metal such as zinc is used as fuel sun
Pole, using alkali lye or neutral solution as electrolyte, during electric discharge, metal M is oxidized to corresponding metal ions M during electric dischargen+, air
In oxygen be catalyzed into OH- in cathode side.Such as zinc-air battery, be exactly using zinc as negative electrode, using sodium hydroxide as electrolyte, and
Anode is porous activated carbon, therefore can adsorb the oxygen in air to replace the oxidant (manganese dioxide) in general dry cell.
Existing air cell main still zinc-air battery, aluminium-air cell and magnesium air cell, wherein, zinc air electricity
Pond (zinc air battery), with the oxygen or pure oxygen in charcoal absorption air as positive active material, using zinc as negative pole,
Using ammonium chloride or caustic solution as a kind of galvanic cell of electrolyte, also known as zinc-oxygen battery.Existing zinc-air battery mainly has 4
Type, neutral zinc-air battery, button-shaped zinc-air battery, the zinc air wet cell and high power zinc of the big carrying capacity of low-power
Air cell.Aluminium-air cell, it is pollution-free, long-acting and reliable and stable, it is a to environment very friendly battery, with than energy
Amount is big, light weight and nontoxic non-hazardous feature, and the structure of battery and the raw material that use can be according to different practical rings
Border changes with requiring, with very big adaptability, can be used for land can be used for deep-sea, can both do electrokinetic cell, and energy
Make the signal battery of long-life high specific energy, there is very wide application prospect, in recent years, the progress of aluminium-air cell is very fast
Speed, its application on EV has obtained good result, is a kind of rising air cell.
In various metal-air batteries, its negative electrode is needed with following effect：One be with certain permeability,
The oxygen in air is allowed to pass through, two be to have higher oxygen reduction catalytic activity, and three be, with certain hydrophobicity, to prevent electricity
Solution liquid floods cathode side.But current air cathode is during preparation, due to the constituent physical property difference of negative electrode
It is larger, cracking, the problems such as coming off, and existing cathode material are also easy to produce in drying and sintering process and also results in air electricity
The output performance in pond is relatively low.
Therefore, the metal air battery cathodes with better performance how are designed and prepare, while prepared by solution
Problem present in journey, it has also become numerous forward position scientific research personnel widely one of focus of attention in field.
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 metal air battery cathodes and its preparation side
It is stable in method, metal-air battery, present invention design and the metal air battery cathodes prepared, preparation process, and using this
Inventing the metal-air battery of the metal air battery cathodes provided has more preferable electrochemistry.
The invention provides a kind of metal air battery cathodes, including metal collector；
It is compounded in the hydrophobic layer of the metal collector side；
It is compounded in the catalyst layer on the hydrophobic layer；
The catalyst layer includes fiber nickel.
It is preferred that, the hydrophobic layer includes conductive carbon material and hydrophobic material；
In the hydrophobic layer, the mass ratio of the conductive carbon material and the hydrophobic material is (0.1~1)：(0.1~1).
It is preferred that, catalyst material and hydrophobic material are also included in the catalyst layer；
The catalyst material includes Mn oxide, noble metal catalyst, spinel oxides and Ca-Ti ore type oxidation
One or more in thing, the mixture with conductive carbon material；
The hydrophobic material include polytetrafluoroethylene (PTFE), one kind in poly- inclined tetrafluoroethene, makrolon and polyphenylene sulfide or
It is a variety of；
The fiber nickel also includes the fiber nickel for being compounded with graphene quantum dot.
It is preferred that, the mass ratio of the catalyst material and the fiber nickel for being compounded with graphene quantum dot for (0.5~
2)：(0.2~1)；
In the catalyst layer, the mass ratio of the catalyst material and hydrophobic material is (0.5~2)：(0.1~1)；
The Mn oxide includes MnO2、Mn3O4, MnO (OH) and Mn2O3In one or more；
The noble metal catalyst includes silver or platinum；
The conductive carbon material include VX-72, BP2000, KB EC-300J, PT XE2-B, Super-P, CNT and
One or more in graphite；
A diameter of 30~100 μm of the fiber nickel；The length of the fiber nickel is 100~500 μm.
The invention provides a kind of preparation method of metal air battery cathodes, comprise the following steps：
1) hydrophobic diaphragm is placed in metal collector, then the catalyst diaphragm containing fiber nickel is placed in hydrophobic diaphragm
On, roll-in is carried out, cathode assembly is obtained；
2) after the cathode assembly that above-mentioned steps are obtained is sintered, metal air battery cathodes are obtained.
It is preferred that, the hydrophobic diaphragm by following steps prepare after obtain：
By conductive carbon material, hydrophobic material and solvent after roll-in, hydrophobic diaphragm is obtained；
The mass ratio of the hydrophobic material and the solvent is (0.1~1)：(3~8)；The thickness of the hydrophobic diaphragm is
0.1~0.3mm；
The catalyst diaphragm by following steps prepare after obtain：
A) catalyst material, hydrophobic material, fiber nickel and solvent are obtained into tablet after roll is pressed and mixed；It is described to urge
The mass ratio of agent material and the solvent is (0.5~2)：(1~10)；
B) multiple tablets superposition obtained above-mentioned steps is carried out after roll-in, obtains fine and close diaphragm；
C) the fine and close diaphragm for obtaining above-mentioned steps is carried out after roll-in again, obtains catalyst diaphragm.
It is preferred that, the step c) is specially：
The fine and close diaphragm that above-mentioned steps are obtained, by the way of thickness is gradually reduced, after multiple roll-in, is urged
Agent diaphragm；The multiple number of times is 3~5 times；
The thickness of the fine and close diaphragm is 0.02~0.08mm；
The thickness of the catalyst diaphragm is 0.1~1.0mm.
It is preferred that, the metal collector includes foil-like collector and/or reticulated collectors；
The metal includes the one or more in nickel foam, stainless steel, gold, silver and copper；
The solvent includes the mixture of polyvinyl alcohol, alcohols solvent and water；
The temperature of the sintering is 100~500 DEG C；The time of the sintering is 0.5~2 hour；
The thickness of the metal air battery cathodes is 0.1~0.6cm.
It is preferred that, the fiber nickel is also included by the pretreated fiber nickel for being compounded with graphene quantum dot；
The pre-treatment step is：
Fiber nickel is placed in graphene quantum dot solution, takes out after drying, obtains being compounded with the fibre of graphene quantum dot
Tie up nickel；
The metal collector is also included by the pretreated metal collector for being compounded with graphene quantum dot；
The pre-treatment step is：
Metal collector is placed in graphene quantum dot solution, takes out after drying, obtains being compounded with graphene quantum dot
Metal collector.
The invention provides a kind of metal-air battery, including the metal-air electricity described in above-mentioned technical proposal any one
Metal air battery cathodes prepared by pool cathode or above-mentioned technical proposal any one.
The invention provides a kind of metal air battery cathodes, including metal collector, the metal collector is compounded in
The hydrophobic layer of side；It is compounded in the catalyst layer on the hydrophobic layer；The catalyst layer includes fiber nickel.With prior art
Compare, the present invention is directed to existing metal air battery cathodes, exist during drying, sintering and use and be also easy to produce out
Split, the problem of coming off.In the metal air battery cathodes that the present invention is provided, fiber nickel is with the addition of as conductive filler, can be with
Alleviate the cracking caused by the volumetric expansion contraction of negative electrode different materials in preparation process and come off.
Test result indicates that, aluminium-air electricity of the metal air battery cathodes of the addition fiber nickel provided using the present invention
Exemplified by pond, the peak power output of battery is by being not added with the 200mWcm of fiber nickel-2250mWcm is brought up to-2, with the addition of
The fiber nickel of graphene quantum dot processing, battery performance is improved to 300mWcm-2.The long-term of battery for being not added with fiber nickel is declined
Lapse rate is 19%/100h, and the long-term rate of decay for adding the battery of fiber nickel is reduced to 10%/100h, with the addition of graphene
The performance steady in a long-term that the long-term rate of decay of the battery of the nickel foam of quantum dot processing is reduced to 2%/100h batteries is obtained
Very big lifting.
Brief description of the drawings
Fig. 1 is the discharge performance curve map of metal-air battery prepared by the embodiment of the present invention 1；
Fig. 2 is the long-term constant-current discharge curve map of metal-air battery prepared by the embodiment of the present invention 1.
Embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described with reference to embodiment, but
It is it should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention rather than to patent requirements of the present invention
Limitation.
All raw materials of the present invention, originate to it and are not particularly limited, commercially buying or according to people in the art
Known to member prepared by conventional method.
During the present invention is raw materials used, it is related to the product of the specific trade mark, its mode of originating is not particularly limited, with this area
Commercially available commodity of the conventional manufacturer of the trade mark known to technical staff.
All raw materials of the present invention, its purity is not particularly limited, and present invention preferably employs analyze pure or air cell material
The conventional purity in material field.
The invention provides a kind of metal air battery cathodes, including metal collector；
It is compounded in the hydrophobic layer of the metal collector side；
It is compounded in the catalyst layer on the hydrophobic layer；
The catalyst layer includes fiber nickel.
Definition of the present invention to the metal-air battery is not particularly limited, with metal well known to those skilled in the art
The definition of air cell, those skilled in the art can be right according to practical situations, raw material condition and product requirement
The species of metal-air battery is selected and adjusted.
Metal air battery cathodes of the present invention include metal collector, property of the present invention to the metal collector
It is not particularly limited, with the shape well known to those skilled in the art for being used to prepare the collector of metal-air battery, sheet
Art personnel can be selected and be adjusted according to practical situations, raw material condition and product requirement, and the present invention is
The more preferable chemical property of realization, the shape of the collector preferably includes foil-like and/or netted, more preferably foil-like or net
Shape, it is most preferably netted, it is specifically as follows with the netted of some strength.
The specific material of the metal is not particularly limited the present invention, is used for air with well known to those skilled in the art
The metal material of the collector of battery, those skilled in the art can be according to practical situations, raw material condition and production
Product requirement is selected and adjusted, and metal material of the present invention preferably includes one in nickel foam, stainless steel, gold, silver and copper
Plant or a variety of, more preferably nickel foam, stainless steel, gold, silver or copper.
The present invention is ensures metal collector, and fusion performance in the cathode further improves the property of metal-air battery
Energy.Particularly, the metal collector preferably also includes the metal collector for being compounded with graphene quantum dot, i.e., by graphene
The pretreated metal collector of quanta point material.
The present invention is compounded with the metal collector of graphene quantum dot to described, and compound form is not particularly limited,
With conventional complex form well known to those skilled in the art, those skilled in the art can be according to practical situations, original
Material situation and product requirement are selected and adjusted, of the present invention compound to preferably include to spray, smear brush, doping, growth, sink
One or more in product, embedded, bonding, cladding and load, more preferably spray, smear brush, doping, growth, deposition, insertion,
Bonding, cladding are loaded, and are most preferably loaded.
The compound load capacity is not particularly limited the present invention, with conventional load amount well known to those skilled in the art
, those skilled in the art can be selected and be adjusted according to practical situations, raw material condition and product requirement, this
Invent compound (load) amount preferably 0.005~0.05wt% of the graphene quantum dot, more preferably 0.01~
0.04wt%, most preferably 0.02~0.03wt%.
Metal air battery cathodes of the present invention include the hydrophobic layer for being compounded in the metal collector side.
The direction of the side is not particularly limited the present invention, with any of collector well known to those skilled in the art
Side, those skilled in the art can be selected and be adjusted according to practical situations, raw material condition and product requirement
It is whole.
The compound definition is not particularly limited the present invention, is with compound concept well known to those skilled in the art
Can, those skilled in the art can be selected and be adjusted, this hair according to practical situations, raw material condition and product requirement
The bright compound one or more preferably bond, coat, smearing in brush, insertion or cladding, are more preferably embedded in.The present invention is
The practicality and stability of metal air battery cathodes are improved, described in actual use wire netting or piece are to load or adhere to
The hydrophobic layer, forms supporting role, and sheet metal or gold can be filled, be embedded in, adhere to or be coated in hydrophobic layer of the present invention
Category is online.
The composition of the hydrophobic layer is not particularly limited the present invention, is used for air electricity with well known to those skilled in the art
The hydrophobic layer of the collector in pond, those skilled in the art can want according to practical situations, raw material condition and product
Ask and selected and adjusted, hydrophobic layer of the present invention preferably includes conductive carbon material and hydrophobic material.
The conductive carbon material is not particularly limited the present invention, is with conductive carbon material well known to those skilled in the art
Can, those skilled in the art can be selected and be adjusted, this hair according to practical situations, raw material condition and product requirement
The bright conductive carbon material preferably includes VX-72, BP2000, KB EC-300J, PT XE2-B, Super-P, CNT and stone
One or more in ink, more preferably VX-72, BP2000, KB EC-300J, PT XE2-B, Super-P, CNT or
Graphite, most preferably VX-72, KB EC-300J, Super-P, CNT or graphite.
VX-72 of the present invention is preferably the product that Shanghai Cabot (cabot) company produces and sells；It is described
BP2000 is preferably the product that Shanghai Cabot (cabot) company produces and sells；The KB EC-300J are preferably Japan
The product that lion princes and dukes department produces and sells；The PT XE2-B are preferably the production that Evonik Degussa Corp. produces and sells
Product；The Super-P is preferably the product that Switzerland Te meter Gao (TIMCAL) company produces and sells.
The hydrophobic material is not particularly limited the present invention, with well known to those skilled in the art for battery electrode
Hydrophobic material, those skilled in the art can be selected according to practical situations, raw material condition and product requirement
And adjustment, hydrophobic material of the present invention preferably included in polytetrafluoroethylene (PTFE), poly- inclined tetrafluoroethene, makrolon and polyphenylene sulfide
One or more, more preferably polytetrafluoroethylene (PTFE), poly- inclined tetrafluoroethene, makrolon or polyphenylene sulfide, most preferably poly- four
PVF, makrolon or polyphenylene sulfide.
The ratio of the conductive carbon material and hydrophobic material is not particularly limited the present invention, and those skilled in the art can be with
Selected and adjusted according to practical situations, raw material condition and product requirement, it is described to lead in hydrophobic layer of the present invention
The mass ratio of electrical carbon material and the hydrophobic material is preferably (0.1~1)：(0.1~1), more preferably (0.3~0.8)：(0.1
~1), more preferably (0.5~0.6)：(0.1~1), more preferably (0.1~1)：(0.3~0.8), more preferably (0.1~
1)：(0.5~0.6).
Metal air battery cathodes of the present invention include the catalyst layer being compounded on the hydrophobic layer, the catalyst
Layer includes fiber nickel.
Metal air battery cathodes of the present invention possess metal collector, hydrophobic layer and catalyst layer and are combined setting successively
Structure.
The compound definition is not particularly limited the present invention, is with compound concept well known to those skilled in the art
Can, those skilled in the art can be selected and be adjusted, this hair according to practical situations, raw material condition and product requirement
The bright compound one or more preferably bond, coat, smearing in brush, insertion or cladding, are more preferably coated.
The source of the fiber nickel is not particularly limited the present invention, with coming for fiber nickel well known to those skilled in the art
Source, those skilled in the art can be prepared according to the conventional method or commercially available purchase is selected and adjusted, institute of the present invention
It is preferably prepared by conventional commercial product or conventional method to state fiber nickel, is particularly preferred as Shanghai and causes what adopted new material produced and sold
The product or《Power technology》In, Xia Baojia, Zhang Quansheng, Yin Geping solve sparkling and crystal-clear, Wang Suqin is disclosed in 2 (1994) 4-8
It is prepared by the method disclosed in " electrochemical impregnations of fibrous nickel electrodes " text.
The parameter of the fiber nickel is not particularly limited the present invention, with the normal of fiber nickel well known to those skilled in the art
Advise parameter, those skilled in the art can be selected according to practical situations, raw material condition and product requirement and
Adjustment, the diameter of fiber nickel of the present invention is preferably 30~100 μm, more preferably 40~90 μm, more preferably 50~80 μm；
The length of fiber nickel of the present invention is preferably 100~500 μm, more preferably 200~400 μm, most preferably 250~350 μm.
Other compositions of the catalyst layer are not particularly limited the present invention, and those skilled in the art can be according to reality
Applicable cases, raw material condition and product requirement are selected and adjusted, and preferably also include urging in catalyst layer of the present invention
Agent material and hydrophobic material.
The catalyst material is not particularly limited the present invention, is with catalyst material well known to those skilled in the art
Can, those skilled in the art can be selected and be adjusted, this hair according to practical situations, raw material condition and product requirement
The bright catalyst material preferably includes Mn oxide, noble metal catalyst, spinel oxides and perofskite type oxide
In one or more, the mixture with conductive carbon material, more preferably Mn oxide, noble metal catalyst, spinel-type oxygen
The mixture of any one in compound and perofskite type oxide with conductive carbon material, most preferably Mn oxide and conductive carbon
The mixture of material, the mixture or spinel oxides of noble metal catalyst and conductive carbon material and conductive carbon material it is mixed
Compound.
The specifically chosen of the Mn oxide is not particularly limited the present invention, is used for well known to those skilled in the art
The Mn oxide of catalyst material, those skilled in the art can be according to practical situations, raw material condition and product
It is required that being selected and being adjusted, Mn oxide of the present invention preferably includes MnO2、Mn3O4, MnO (OH) and Mn2O3In one
Plant or a variety of, more preferably MnO2、Mn3O4, MnO (OH) or Mn2O3。
The specifically chosen of the noble metal catalyst is not particularly limited the present invention, with well known to those skilled in the art
For the noble metal catalyst of catalyst material, those skilled in the art can be according to practical situations, raw material condition
And product requirement is selected and adjusted, noble metal catalyst of the present invention preferably includes silver or platinum.
The spinel oxides and the specifically chosen of perofskite type oxide are not particularly limited the present invention, with this
It is used for the spinel oxides and perofskite type oxide of catalyst material, this area skill known to art personnel
Art personnel can be selected and be adjusted according to practical situations, raw material condition and product requirement.
The conductive carbon material is not particularly limited the present invention, is with conductive carbon material well known to those skilled in the art
Can, those skilled in the art can be selected and be adjusted, this hair according to practical situations, raw material condition and product requirement
The bright conductive carbon material preferably includes VX-72, BP2000, KB EC-300J, PT XE2-B, Super-P, CNT and stone
One or more in ink, more preferably VX-72, BP2000, KB EC-300J, PT XE2-B, Super-P, CNT or
Graphite, most preferably VX-72, KB EC-300J, Super-P, CNT or graphite.The conduction of the above-mentioned trade mark of the present invention
The source optimum principle of carbon material is consistent with the source optimum principle of the conductive carbon material conductive carbon material in foregoing hydrophobic layer,
This is no longer going to repeat them.
The hydrophobic material is not particularly limited the present invention, with well known to those skilled in the art for battery electrode
Hydrophobic material, those skilled in the art can be selected according to practical situations, raw material condition and product requirement
And adjustment, hydrophobic material of the present invention preferably included in polytetrafluoroethylene (PTFE), poly- inclined tetrafluoroethene, makrolon and polyphenylene sulfide
One or more, more preferably polytetrafluoroethylene (PTFE), poly- inclined tetrafluoroethene, makrolon or polyphenylene sulfide, most preferably poly- four
PVF, makrolon or polyphenylene sulfide.
The additional proportion of the fiber nickel is not particularly limited the present invention, and those skilled in the art can answer according to actual
Selected and adjusted with situation, raw material condition and product requirement, catalyst material of the present invention and the fiber nickel
Mass ratio is preferably (0.5~2)：(0.2~1), more preferably (0.75~1.75)：(0.2~1), more preferably (1.0~
1.5)：(0.2~1), more preferably (0.5~2)：(0.4~0.8), more preferably (0.5~2)：(0.5~0.7).
The present invention is further improves fusion performance of the fiber nickel in catalyst layer, and particularly, the fiber nickel is preferred
Also include the fiber nickel for being compounded with graphene quantum dot, i.e., by the pretreated fiber nickel of graphene quantum dot material.This hair
The bright additional proportion to the fiber nickel for being compounded with graphene quantum dot is not particularly limited, and those skilled in the art can root
Selected and adjusted according to practical situations, raw material condition and product requirement, catalyst material of the present invention and described
The mass ratio for being compounded with the fiber nickel of graphene quantum dot is preferably (0.5~2)：(0.2~1), more preferably (0.75~
1.75)：(0.2~1), more preferably (1.0~1.5)：(0.2~1), more preferably (0.5~2)：(0.4~0.8), more preferably
For (0.5~2)：(0.5~0.7).
The compound form is not particularly limited the present invention, with conventional complex form well known to those skilled in the art
, those skilled in the art can be selected and be adjusted according to practical situations, raw material condition and product requirement, this
The described compound one kind or many for preferably including to spray, smear in brush, doping, growth, deposition, insertion, bonding, cladding and load of invention
Kind, more preferably spray, smear brush, doping, growth, deposition, insertion, bonding, cladding or load, most preferably load.
The compound load capacity is not particularly limited the present invention, with conventional load amount well known to those skilled in the art
, those skilled in the art can be selected and be adjusted according to practical situations, raw material condition and product requirement, this
Invent compound (load) amount preferably 0.005~0.05wt% of the graphene quantum dot, more preferably 0.01~
0.04wt%, most preferably 0.02~0.03wt%.
The additional proportion of the hydrophobic material is not particularly limited the present invention, and those skilled in the art can be according to reality
Applicable cases, raw material condition and product requirement are selected and adjusted, catalyst material of the present invention and the hydrophobic material
The mass ratio of material is preferably (0.5~2)：(0.1~1), more preferably (0.75~1.75)：(0.1~1), more preferably (1.0
~1.5)：(0.1~1), more preferably (0.5~2)：(0.3~0.8), more preferably (0.5~2)：(0.5~0.6).
The invention provides a kind of preparation method of metal air battery cathodes, comprise the following steps：
1) hydrophobic diaphragm is placed in metal collector, then catalyst diaphragm is placed on hydrophobic diaphragm, carried out roll-in, obtain
To cathode assembly；
2) after the cathode assembly that above-mentioned steps are obtained is sintered, metal air battery cathodes are obtained.
In the above-mentioned preparation method of the present invention, the selection of the material and its preferred scope are cloudy with aforementioned metal air cell
The selection of material in extremely and its preferred scope are consistent, and this is no longer going to repeat them.
Hydrophobic diaphragm is placed in metal collector by the present invention first, then catalyst diaphragm is placed on hydrophobic diaphragm, is entered
Row roll-in, obtains cathode assembly.After being sequentially placed metal collector, hydrophobic diaphragm and catalyst diaphragm, roll-in is carried out, is obtained
To cathode assembly.
The parameter and process of the roll-in are not particularly limited the present invention, with roll-in well known to those skilled in the art
Conventional parameter and process, those skilled in the art can enter according to practical condition, raw material condition and product requirement
Row selection and adjustment.
The present invention is to the thickness of the cathode assembly, i.e. the thickness of metal air battery cathodes is not particularly limited, with this
The thickness of metal air battery cathodes known to art personnel, those skilled in the art can be according to actual production feelings
Condition, raw material condition and product requirement are selected and adjusted, and the thickness of metal air battery cathodes of the present invention is preferably
0.1~0.6cm, more preferably 0.2~0.5cm, most preferably 0.3~0.4cm.
The specific material of the metal is not particularly limited the present invention, is used for air with well known to those skilled in the art
The metal material of the collector of battery, those skilled in the art can be according to practical situations, raw material condition and production
Product requirement is selected and adjusted, and metal material of the present invention preferably includes one in nickel foam, stainless steel, gold, silver and copper
Plant or a variety of, more preferably nickel foam, stainless steel, gold, silver or copper.
The present invention is metal collector, and fusion performance in the cathode further improves the performance of metal-air battery.It is special
Other, the metal collector preferably also includes passing through the pretreated metal collector of graphene quantum dot material, that is, is combined
There is the metal collector of graphene quantum dot.
The process of the pretreatment is not particularly limited the present invention, with such pretreatment well known to those skilled in the art
Method, those skilled in the art can be selected according to practical condition, raw material condition and product requirement and
Adjust, pre-treatment step of the present invention is preferably：
Metal collector is placed in graphene quantum dot solution, takes out after drying, obtains being compounded with graphene quantum dot
Metal collector.
The source of the graphene quantum dot is not particularly limited the present invention, with graphite well known to those skilled in the art
The source of alkene quantum dot, those skilled in the art can enter according to practical condition, raw material condition and product requirement
Row selection and adjustment, can buy from commercially available, can also conventionally prepare.The present invention is to the graphene quantum dot
Parameter be not particularly limited, with the parameter of ordinary graphite alkene quantum dot well known to those skilled in the art, this area skill
Art personnel can be selected and be adjusted according to practical condition, raw material condition and product requirement, graphite of the present invention
The carbon spot diameter of alkene quantum dot is preferably 1~10nm, more preferably 3~8nm, most preferably 5~6nm.
The graphene quantum dot solution is not particularly limited the present invention, with graphene well known to those skilled in the art
Quantum dot solution, those skilled in the art can be selected according to practical condition, raw material condition and product requirement
Select and adjust, graphene quantum dot solution of the present invention is preferably the graphene quantum dot aqueous solution.The present invention is to the graphite
The concentration of alkene quantum dot solution is not particularly limited, and the concentration with graphene quantum dot solution well known to those skilled in the art is
Can, those skilled in the art can be selected and be adjusted, this hair according to practical condition, raw material condition and product requirement
The concentration of the bright graphene quantum dot solution is preferably 0.01~0.1mg/mL, and more preferably 0.03~0.08mg/mL is optimal
Elect 0.05~0.06mg/mL as.
The mode being placed in is not particularly limited the present invention, and mode is placed in routine well known to those skilled in the art
, those skilled in the art can be selected and be adjusted according to practical condition, raw material condition and product requirement, this
The one or more for preferably including to spray, smear in brush, bonding, dipping and submergence are placed in described in invention, more preferably sprays, smear
Brush, bond, dip in or impregnate, most preferably impregnate.
The time being placed in is not particularly limited the present invention, and the time is placed in routine well known to those skilled in the art
, those skilled in the art can be selected and be adjusted according to practical condition, raw material condition and product requirement, this
The time being placed in described in invention is preferably greater than to be equal to 30 minutes, more preferably greater than equal to 40 minutes, is most preferably more than or equal to
60 minutes.
The mode of the drying is not particularly limited the present invention, in conventional drying mode well known to those skilled in the art
, those skilled in the art can be selected and be adjusted according to practical condition, raw material condition and product requirement, this
Invent the drying preferably to dry in atmosphere, more preferably dry in the shade, be particularly preferred as at room temperature in air in atmosphere
In dry in the shade.
The present invention is improves the integrality and operability of integrated artistic, and the preparation process of the cathode assembly specifically can be with
For：
(1) metal collector, hydrophobic diaphragm and catalyst diaphragm are subjected to roll-in, because collector used preferably has one
Fixed intensity and hole, it is ensured that can be rolled down to diaphragm in metal current collector layer in nipping process, being formed has certain thickness
The cathode assembly spent and combined closely.
(2) cathode assembly is cut or remolded, you can obtain cathode assembly of different shapes.
The preparation process of the hydrophobic diaphragm is not particularly limited the present invention, with well known to those skilled in the art such
The preparation method of hydrophobic membrane or hydrophobic layer, those skilled in the art can according to practical condition, raw material condition and
Product requirement is selected and adjusted, and the present invention is being prepared and used to improve metal air battery cathodes and metal-air battery
During stability, the hydrophobic diaphragm preferably by following steps prepare after obtain：
By conductive carbon material, hydrophobic material and solvent after roll-in, hydrophobic diaphragm is obtained.
Selection of the present invention to the solvent is not particularly limited, and is with such solvent well known to those skilled in the art
Can, those skilled in the art can be selected and be adjusted, this hair according to practical condition, raw material condition and product requirement
The bright solvent is preferably double solvents, more preferably includes the mixture of polyvinyl alcohol, alcohols solvent and water, most preferably poly- second
The mixture of enol, absolute ethyl alcohol and water.
The specific proportioning of the double solvents is not particularly limited the present invention, with well known to those skilled in the art such
The specific proportioning of solvent, those skilled in the art can enter according to practical condition, raw material condition and product requirement
Row selection and adjustment, the mass ratio of polyvinyl alcohol of the present invention, water and absolute ethyl alcohol is preferably (1~5)：(60~90)：
(5~10), more preferably (1.5~4.5)：(60~90)：(5~10), more preferably (2~4)：(60~90)：(5~10),
More preferably (1~5)：(65~85)：(5~10), more preferably (1~5)：(70~80)：(5~10), more preferably (1~
5)：(60~90)：(6~9), more preferably (1~5)：(60~90)：(7~8).
The additional proportion of the solvent is not particularly limited the present invention, with conventional ratio well known to those skilled in the art
, those skilled in the art can be selected and be adjusted according to practical condition, raw material condition and product requirement, this
The mass ratio for inventing the hydrophobic material and the solvent is preferably (0.1~1)：(3~8), more preferably (0.3~0.8)：(3
~8), more preferably (0.5~0.6)：(3~8), more preferably (0.1~1)：(4~7), more preferably (0.1~1)：(5~
6)。
The parameter and process of the roll-in are not particularly limited the present invention, with conventional ginseng well known to those skilled in the art
Number and process, those skilled in the art can be selected according to practical condition, raw material condition and product requirement
And adjustment, the thickness of roll-in of the present invention, i.e., the thickness of hydrophobic diaphragm is preferably 0.1~0.3mm, more preferably 0.13~
0.27mm, most preferably 0.16~0.24mm.
The present invention is improves the integrality and operability of integrated artistic, and the preparation process of the hydrophobic diaphragm specifically can be with
For：
(1) conductive carbon material, hydrophobic material and organic solvent are well mixed according to a certain ratio；
(2) hydrophobic layer material after will be well mixed, which is placed on roll squeezer, to be rolled, and is highly 0.1 between regulation roller
~0.3mm；
(3) hydrophobic layer rolled is cut and remolded, obtain hydrophobic layer of different shapes (hydrophobic diaphragm) component.
The preparation process of the catalyst diaphragm is not particularly limited the present invention, with it is well known to those skilled in the art this
The preparation method of class catalyst film or catalyst layer, those skilled in the art can be according to practical condition, raw material feelings
Condition and product requirement are selected and adjusted, and the present invention is being prepared to improve metal air battery cathodes and metal-air battery
With the stability during use, the catalyst diaphragm preferably by following steps prepare after obtain：
A) catalyst material, hydrophobic material, fiber nickel and solvent are obtained into tablet after roll is pressed and mixed；It is described to urge
The mass ratio of agent material and the solvent is (0.5~2)：(1~10)；
B) multiple tablets superposition obtained above-mentioned steps is carried out after roll-in, obtains fine and close diaphragm；
C) the fine and close diaphragm for obtaining above-mentioned steps is carried out after roll-in again, obtains catalyst diaphragm.
The present invention after roll is pressed and mixed, obtains sheet first by catalyst material, hydrophobic material, fiber nickel and solvent
Thing.
Selection of the present invention to the solvent is not particularly limited, and is with such solvent well known to those skilled in the art
Can, those skilled in the art can be selected and be adjusted, this hair according to practical condition, raw material condition and product requirement
The bright solvent is preferably double solvents, more preferably includes the mixture of polyvinyl alcohol, alcohols solvent and water, most preferably poly- second
The mixture of enol, absolute ethyl alcohol and water.
The specific proportioning of the double solvents is not particularly limited the present invention, with well known to those skilled in the art such
The specific proportioning of solvent, those skilled in the art can enter according to practical condition, raw material condition and product requirement
Row selection and adjustment, the mass ratio of polyvinyl alcohol of the present invention, water and absolute ethyl alcohol is preferably (1~5)：(60~90)：
(5~10), more preferably (1.5~4.5)：(60~90)：(5~10), more preferably (2~4)：(60~90)：(5~10),
More preferably (1~5)：(65~85)：(5~10), more preferably (1~5)：(70~80)：(5~10), more preferably (1~
5)：(60~90)：(6~9), more preferably (1~5)：(60~90)：(7~8).
The additional proportion of the solvent is not particularly limited the present invention, with conventional ratio well known to those skilled in the art
, those skilled in the art can be selected and be adjusted according to practical condition, raw material condition and product requirement, this
The mass ratio for inventing the catalyst material and the solvent is (0.5~2)：(1~10), more preferably (0.7~1.8)：(1
~10), more preferably (1.0~1.5)：(1~10), more preferably (0.5~2)：(3~8), more preferably (0.5~2)：(5
~6).
The present invention presses the parameter mixed and process to be not particularly limited on the roll, with roller well known to those skilled in the art
The conventional parameter and process of pressure, those skilled in the art can want according to practical condition, raw material condition and product
Ask and selected and adjusted.
The present invention and then multiple tablets superposition for obtaining above-mentioned steps are carried out after roll-in, obtain fine and close diaphragm.
The particular number of multiple tablets is not particularly limited the present invention, and those skilled in the art can be according to reality
Border applicable cases, raw material condition and product requirement are selected and adjusted.The present invention does not have to the parameter and process of the roll-in
There is special limitation, with the conventional parameter and process of roll-in well known to those skilled in the art, those skilled in the art can be with
Selected and adjusted according to practical condition, raw material condition and product requirement.Thickness of the present invention to the fine and close diaphragm
Degree is not particularly limited, and with general thickness well known to those skilled in the art, those skilled in the art can be according to reality
Applicable cases, raw material condition and product requirement are selected and adjusted, and the thickness of fine and close diaphragm of the present invention is preferably
0.02~0.08mm, more preferably 0.03~0.07mm, most preferably 0.04~0.06mm.
The last fine and close diaphragm for obtaining above-mentioned steps of the invention is carried out after roll-in again, obtains catalyst diaphragm.
The parameter and process of the roll-in are not particularly limited the present invention, with roll-in well known to those skilled in the art
Conventional parameter and process, those skilled in the art can enter according to practical condition, raw material condition and product requirement
Row selection and adjustment.
The present invention improves the stability and chemical property of final products to improve the compactness of catalyst diaphragm, above-mentioned
Step, i.e. step c) is particularly preferred as：
The fine and close diaphragm that above-mentioned steps are obtained, by the way of thickness is gradually reduced, after multiple roll-in, is urged
Agent diaphragm
The specific number of times of the multiple roll-in is not particularly limited the present invention, and those skilled in the art can be according to reality
Applicable cases, raw material condition and product requirement are selected and adjusted, and multiple number of times of the present invention is preferably 3~5 times,
More preferably 4 times.
The parameter for the mode that the present invention is gradually reduced to the thickness is not particularly limited, and is known with those skilled in the art
This generic operation parameter, those skilled in the art can be according to practical situations, raw material condition and product requirement
Selected and adjusted, the thickness range that thickness of the present invention is gradually reduced is preferably 1.0~0.1mm, more preferably 0.8~
0.2mm, most preferably 0.5~0.3mm.
The thickness of the catalyst diaphragm is not particularly limited the present invention, with well known to those skilled in the art conventional thick
Degree, those skilled in the art can be selected and be adjusted according to practical situations, raw material condition and product requirement,
The thickness of catalyst diaphragm of the present invention is preferably 0.1~1.0mm, more preferably 0.3~0.8mm, most preferably 0.5~
0.6mm。
The present invention is improves the integrality and operability of integrated artistic, and the preparation process of the catalyst diaphragm specifically may be used
Think：
(1) catalyst, hydrophobic material, fiber nickel, organic solvent are well mixed, obtain mixture；During mixing, using rolling
Roller mode, when the roll rotation rolled in opposite directions, mixture is by continuously extruded, and catalyst and hydrophobic material can be well mixed,
And uniformly coated by organic solvent.
(2) in nipping process, a part of organic solvent is extruded, when mixture can form uniform, continuous rolling
After diaphragm, multiple stacking rolling is carried out, the diaphragm of densification is formed it into；
(3) progressively the height between film roller is rolled in regulation, and diaphragm thickness is altered in steps, the Catalytic Layer of thickness needed for obtaining
(catalyst diaphragm) component.
The present invention further improves metal-air battery to ensure fusion performance of the fiber nickel in catalyst layer and negative electrode
Performance.Particularly, the fiber nickel preferably also includes passing through the pretreated fiber nickel of graphene quantum dot material, that is, is combined
There is the fiber nickel of graphene quantum dot.
The process of the pretreatment is not particularly limited the present invention, with such pretreatment well known to those skilled in the art
Method, those skilled in the art can be selected according to practical condition, raw material condition and product requirement and
Adjust, pre-treatment step of the present invention is preferably：
Fiber nickel is placed in graphene quantum dot solution, takes out after drying, obtains being compounded with the fibre of graphene quantum dot
Tie up nickel.
The source of the graphene quantum dot is not particularly limited the present invention, with graphite well known to those skilled in the art
The source of alkene quantum dot, those skilled in the art can enter according to practical condition, raw material condition and product requirement
Row selection and adjustment, can buy from commercially available, can also conventionally prepare.The present invention is to the graphene quantum dot
Parameter be not particularly limited, with the parameter of ordinary graphite alkene quantum dot well known to those skilled in the art, this area skill
Art personnel can be selected and be adjusted according to practical condition, raw material condition and product requirement, graphite of the present invention
The carbon spot diameter of alkene quantum dot is preferably 1~10nm, more preferably 3~8nm, most preferably 5~6nm.
The graphene quantum dot solution is not particularly limited the present invention, with graphene well known to those skilled in the art
Quantum dot solution, those skilled in the art can be selected according to practical condition, raw material condition and product requirement
Select and adjust, graphene quantum dot solution of the present invention is preferably the graphene quantum dot aqueous solution.The present invention is to the graphite
The concentration of alkene quantum dot solution is not particularly limited, and the concentration with graphene quantum dot solution well known to those skilled in the art is
Can, those skilled in the art can be selected and be adjusted, this hair according to practical condition, raw material condition and product requirement
The concentration of the bright graphene quantum dot solution is preferably 0.01~0.1mg/mL, and more preferably 0.03~0.08mg/mL is optimal
Elect 0.05~0.06mg/mL as.
The mode being placed in is not particularly limited the present invention, and mode is placed in routine well known to those skilled in the art
, those skilled in the art can be selected and be adjusted according to practical condition, raw material condition and product requirement, this
The one or more for preferably including to spray, smear in brush, bonding, dipping and submergence are placed in described in invention, more preferably sprays, smear
Brush, bond, dip in or impregnate, most preferably impregnate.
The time being placed in is not particularly limited the present invention, and the time is placed in routine well known to those skilled in the art
, those skilled in the art can be selected and be adjusted according to practical condition, raw material condition and product requirement, this
The time being placed in described in invention is preferably greater than to be equal to 30 minutes, more preferably greater than equal to 40 minutes, is most preferably more than or equal to
60 minutes.
The mode of the drying is not particularly limited the present invention, in conventional drying mode well known to those skilled in the art
, those skilled in the art can be selected and be adjusted according to practical condition, raw material condition and product requirement, this
Invent the drying preferably to dry in atmosphere, more preferably dry in the shade, be particularly preferred as at room temperature in air in atmosphere
In dry in the shade.
The additional proportion of the fiber nickel for being compounded with graphene quantum dot is not particularly limited the present invention, this area skill
Art personnel can be selected and be adjusted according to practical situations, raw material condition and product requirement, catalysis of the present invention
Agent material and the mass ratio of the fiber nickel for being compounded with graphene quantum dot are preferably (0.5~2): (0.2~1), more preferably
For (0.75~1.75): (0.2~1), more preferably (1.0~1.5): (0.2~1), more preferably (0.5~2): (0.4~
0.8), more preferably (0.5~2): (0.5~0.7).
Above-mentioned steps of the present invention have carried out further pretreatment to fiber nickel and metal collector, in its area load stone
Black alkene quantum dot, improves the fusion performance of fiber nickel and metal collector in catalyst layer and in negative electrode, and with the addition of
After the fiber nickel of graphene quantum dot processing, due to the high conductivity and specific surface area of graphene, the electricity of Catalytic Layer can be increased
The contact area of sub- conduction velocity and catalyst material and air, so as to further lift the power output of battery, and is reduced
The rate of decay of battery.
The parameter and process of the sintering are not particularly limited the present invention, with similar material well known to those skilled in the art
The conventional parameter and process of the sintering of material, those skilled in the art can according to practical condition, raw material condition and
Product requirement is selected and adjusted, and the temperature of sintering of the present invention is preferably 100~500 DEG C, more preferably 150~450
DEG C, more preferably 200~400 DEG C, most preferably 250~350 DEG C.The time of sintering of the present invention is preferably 0.5~2 small
When, more preferably 0.8~1.7 hour, most preferably 1.0~1.5 hours.
Above-mentioned steps of the present invention provide the preparation method of metal air battery cathodes, and the present invention is for cathode performance restriction
The factor of air cell performance, after the influence of catalyst is excluded, it is believed that the gas permeability of cathode construction and hydrophobic quality are right
The performance impact of metal-air battery is very big.The present invention by it is special proportioning and technique be prepared for hydrophobic layer (hydrophobic diaphragm) and
Catalyst layer (catalyst diaphragm), regulates and controls the proportioning of film mixture to be rolled, diaphragm is prepared by progressively roll mode, by secondary
Roll is formd with preferable gas permeability and hydrophobic air cathode hydrophobic layer with collector set, effectively raises gold
Belong to the output performance of air cell.
Present invention also offers a kind of metal-air battery, including the metal-air described in above-mentioned technical proposal any one
Metal air battery cathodes prepared by cell cathode or above-mentioned technical proposal any one.
Definition of the present invention to the metal-air battery is not particularly limited, with metal well known to those skilled in the art
The definition of air cell, those skilled in the art can be right according to practical situations, raw material condition and product requirement
The species of metal-air battery is selected and adjusted.The present invention is not limited especially the other assemblies of the metal-air battery
System, with the component of metal-air battery well known to those skilled in the art, those skilled in the art can answer according to actual
Selected and adjusted with situation, raw material condition and product requirement.Preparation process of the present invention to the metal-air battery
It is not particularly limited, with the preparation process of metal-air battery well known to those skilled in the art, those skilled in the art
It can be selected and be adjusted according to practical situations, raw material condition and product requirement.
The invention provides a kind of metal air battery cathodes and preparation method thereof, metal-air battery.The present invention is provided
Metal air battery cathodes in, with the addition of fiber nickel as conductive filler, negative electrode can be alleviated different in preparation process
The volumetric expansion of material shrink caused by cracking and come off；But also by it is special proportioning and technique be prepared for hydrophobic diaphragm and
Catalyst diaphragm, regulates and controls the proportioning of film mixture to be rolled, prepares diaphragm by progressively roll mode, pass through secondary roll and afflux
Body set is formd with preferable gas permeability and hydrophobic air cathode hydrophobic layer, effectively raises metal-air battery
Output performance.
And the present invention has carried out further pretreatment to fiber nickel and metal collector again, in its area load graphite
Alkene quantum dot, improves the fusion performance of fiber nickel and metal collector in catalyst layer and in negative electrode, and with the addition of stone
After the fiber nickel of black alkene quantum dot processing, due to the high conductivity and specific surface area of graphene, the electronics of Catalytic Layer can be increased
The contact area of conduction velocity and catalyst material and air, so as to further lift the power output of battery, and reduces electricity
The rate of decay in pond.
In addition, the preparation method technique of the present invention is simple, mild condition is suitable for industrialized production.
Test result indicates that, aluminium-air electricity of the metal air battery cathodes of the addition fiber nickel provided using the present invention
Exemplified by pond, the peak power output of battery is by being not added with the 200mWcm of fiber nickel-2250mWcm is brought up to-2, with the addition of
The fiber nickel of graphene quantum dot processing, battery performance is improved to 300mWcm-2More than.It is not added with the length of the battery of fiber nickel
Phase attenuation rate is 19%/100h, and the long-term rate of decay for adding the battery of fiber nickel is reduced to 10%/100h, with the addition of stone
The long-term rate of decay of the battery of the nickel foam of black alkene quantum dot processing is reduced to 2%/below 100h, battery it is steady in a long-term
Performance is greatly improved.
In order to further illustrate the present invention, a kind of metal air battery cathodes provided with reference to embodiments the present invention
And preparation method thereof, metal-air battery is described in detail, but it is to be understood that these embodiments are with the technology of the present invention
It is lower premised on scheme to be implemented, detailed embodiment and specific operating process are given, simply to further illustrate this
The feature and advantage of invention, rather than limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following
Embodiment.
Embodiment 1
The proportioning of hydrophobic layer：Conductive Carbon Materials VX-72：Hydrophobic material polytetrafluoroethylene (PTFE)：Organic solvent weight ratio is 0.5：
0.5：5.
The preparation of hydrophobic diaphragm：
(1) Carbon Materials, hydrophobic material and organic solvent are well mixed according to said ratio；
(2) hydrophobic layer material after will be well mixed, which is placed on roll squeezer, to be rolled, and is highly between regulation roller
0.2mm；
(3) hydrophobic layer rolled is cut and remolded, obtain hydrophobic layer assembly.
The proportioning of catalyst layer：Fiber nickel after catalyst material, hydrophobic material, graphene quantum dot processing is (or common
Fiber nickel) and weight of solvent ratio be 0.5：1：0.5：8.
The preparation of catalyst diaphragm：
(1) catalyst, hydrophobic material, fiber nickel, organic solvent are well mixed, obtain mixture；During mixing, using rolling
Roller mode.
(2) in nipping process, a part of organic solvent is extruded, when mixture can form uniform, continuous rolling
After diaphragm, 3 superposition rollings are carried out, the diaphragm of densification is formed it into；
(3) height rolled between film roller is progressively adjusted from 0.8mm to 0.2mm, diaphragm thickness is altered in steps, needed for obtaining
The diaphragm of thickness.
The preparation of negative electrode：
(1) hydrophobic layer and Catalytic Layer are sequentially placed into metal collector -- graphene quantum dot processing after nickel foam (or
Nickel foam) side, carry out roll-in, by adjust roll-in height, prepare cathode sets of the thickness between 0.2cm~0.25cm
Part；
(2) cathode assembly is sintered 1.0 hours in 350 DEG C of air.
The metal air battery cathodes that the present invention is provided do not occur in preparation process during drying, sintering etc.
The phenomenon for ftractureing and coming off.
Metal air battery cathodes prepared by the embodiment of the present invention 1 are assembled.
The negative electrode of preparation is cut to suitable size and is placed in homemade test fixture, using 4M KOH solutions as electrolyte,
Using high-purity Al as anode, cell discharge performance and the test of constant current stability are carried out.
Metal-air battery is prepared to the embodiment of the present invention 1 to detect.
Referring to Fig. 1, Fig. 1 is the discharge performance curve map of metal-air battery prepared by the embodiment of the present invention 1.It is left in Fig. 1
The curve that side arrow is indicated gradually reduces for cell voltage with the increase of current density, correspond to the ordinate on the left side；It is right
Curve indicated by the arrow of side is the product of voltage and current density, as power density, correspond to the ordinate on the right.Work as electricity
When pressure and current density reach particular value, the power density for now having maximum occurs, i.e. the peak of arc curve, represents
The maximum power density that the type battery can be released.Referring to Fig. 2, Fig. 2 is metal-air battery prepared by the embodiment of the present invention 1
Long-term constant-current discharge curve map.When being discharged under a certain fixed current density, voltage can be with the increase of discharge time
Gradually decay.Different cathode constructions, it is different to battery voltage decay performance impact.
From Fig. 1 and Fig. 2, the present invention is using the fiber nickel after fiber nickel or graphene quantum dot processing, compared to tradition
Metal-air battery, the peak power output of battery is significantly improved, and the long-term attenuation rate of battery also has obvious reduction.This
Invention is again using the nickel foam after nickel foam or graphene quantum dot processing, compared to conventional metals air cell, the maximum of battery
Power output is also significantly improved, and the long-term attenuation rate of battery also has obvious reduction.The peak power output of battery is
300mW·cm-2, the rate of decay of battery is 1.5%/200h.
Embodiment 2
The proportioning of hydrophobic layer：Conductive Carbon Materials VX-72：Hydrophobic material polytetrafluoroethylene (PTFE)：Organic solvent weight ratio is 0.5：
0.4：8.
The preparation of hydrophobic diaphragm：
(1) Carbon Materials, hydrophobic material and organic solvent are well mixed according to said ratio；
(2) hydrophobic layer material after will be well mixed, which is placed on roll squeezer, to be rolled, and is highly between regulation roller
0.3mm；
(3) hydrophobic layer rolled is cut and remolded, obtain hydrophobic layer assembly.
The proportioning of catalyst layer：Catalyst material, hydrophobic material, the fiber nickel of graphene quantum dot processing and weight of solvent
Than for 1：1：1：5.
The preparation of catalyst diaphragm：
(1) catalyst, hydrophobic material, fiber nickel, organic solvent are well mixed, obtain mixture；During mixing, using rolling
Roller mode.
(2) in nipping process, a part of organic solvent is extruded, when mixture can form uniform, continuous rolling
After diaphragm, 4 superposition rollings are carried out, the diaphragm of densification is formed it into；
(3) height rolled between film roller is progressively adjusted from 0.7mm to 0.1mm, diaphragm thickness is altered in steps, needed for obtaining
The diaphragm of thickness.
The preparation of negative electrode：
(1) hydrophobic layer and Catalytic Layer are sequentially placed into the side of the metal collector after graphene quantum dot processing, carried out
Roll-in, by adjusting roll-in height, prepares cathode assembly of the thickness between 0.2cm~0.3cm；
(2) cathode assembly is sintered 0.5 hour in 400 DEG C of air.
The metal air battery cathodes that the present invention is provided do not occur in preparation process during drying, sintering etc.
The phenomenon for ftractureing and coming off.
Metal air battery cathodes prepared by the embodiment of the present invention 2 are assembled.
The negative electrode of preparation is cut to suitable size and is placed in homemade test fixture, using 4M KOH solutions as electrolyte,
Using high-purity Al as anode, cell discharge performance and the test of constant current stability are carried out.
Metal-air battery is prepared to the embodiment of the present invention 2 to detect, the peak power output of battery is 312mW
cm-2, the rate of decay of battery is 2.0%/200h.
Embodiment 3
The proportioning of hydrophobic layer：Conductive Carbon Materials VX-72：Hydrophobic material polytetrafluoroethylene (PTFE)：Organic solvent weight ratio is 0.5：
0.5：6.
The preparation of hydrophobic diaphragm：
(1) Carbon Materials, hydrophobic material and organic solvent are well mixed according to said ratio；
(2) hydrophobic layer material after will be well mixed, which is placed on roll squeezer, to be rolled, and is highly between regulation roller
0.4mm；
(3) hydrophobic layer rolled is cut and remolded, obtain hydrophobic layer assembly.
The proportioning of catalyst layer：Catalyst material, hydrophobic material, the fiber nickel of graphene quantum dot processing and weight of solvent
Than for 0.8：0.6：1：8.
The preparation of catalyst diaphragm：
(1) catalyst, hydrophobic material, fiber nickel, organic solvent are well mixed, obtain mixture；During mixing, using rolling
Roller mode.
(2) in nipping process, a part of organic solvent is extruded, when mixture can form uniform, continuous rolling
After diaphragm, 2 superposition rollings are carried out, the diaphragm of densification is formed it into；
(3) height rolled between film roller is progressively adjusted from 0.8mm to 0.4mm, diaphragm thickness is altered in steps, needed for obtaining
The diaphragm of thickness.
The preparation of negative electrode：
(1) hydrophobic layer and Catalytic Layer are sequentially placed into the side of the metal collector after graphene quantum dot processing, carried out
Roll-in, by adjusting roll-in height, prepares cathode assembly of the thickness between 0.4cm~0.5cm；
(2) cathode assembly is sintered 0.5 hour in 380 DEG C of air.
The metal air battery cathodes that the present invention is provided do not occur in preparation process during drying, sintering etc.
The phenomenon for ftractureing and coming off.
Metal air battery cathodes prepared by the embodiment of the present invention 3 are assembled.
The negative electrode of preparation is cut to suitable size and is placed in homemade test fixture, using 4M KOH solutions as electrolyte,
Using high-purity Al as anode, cell discharge performance and the test of constant current stability are carried out.
Metal-air battery is prepared to the embodiment of the present invention 3 to detect, the peak power output of battery is 315mW
cm-2, the rate of decay of battery is 1.8%/200h.
Metal air battery cathodes provided above the present invention and preparation method thereof, metal-air battery have been carried out in detail
Introduction, specific case used herein is set forth to the principle and embodiment of the present invention, and above example is said
The bright method and its core concept for being only intended to help to understand the present invention, including best mode, and also cause appointing for this area
What technical staff can put into practice the present invention, including manufacture and the method using any device or system, and any combination of implementation.
It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also be right
The present invention carries out some improvement and modification, and these are improved and modification is also fallen into the protection domain of the claims in the present invention.This hair
The scope of bright patent protection is defined by the claims, and may include those skilled in the art it is conceivable that other implementation
Example.If these other embodiments have the structural element for being not different from claim character express, or if they are wrapped
Include equivalent structural elements of the character express without essence difference with claim, then these other embodiments should also be included in power
In the range of profit is required.
Claims (10)
1. a kind of metal air battery cathodes, it is characterised in that including metal collector；
It is compounded in the hydrophobic layer of the metal collector side；
It is compounded in the catalyst layer on the hydrophobic layer；
The catalyst layer includes fiber nickel.
2. metal air battery cathodes according to claim 1, it is characterised in that the hydrophobic layer includes conductive carbon material
And hydrophobic material；
In the hydrophobic layer, the mass ratio of the conductive carbon material and the hydrophobic material is (0.1~1)：(0.1~1).
3. metal air battery cathodes according to claim 2, it is characterised in that also include catalysis in the catalyst layer
Agent material and hydrophobic material；
The catalyst material is included in Mn oxide, noble metal catalyst, spinel oxides and perofskite type oxide
One or more, the mixture with conductive carbon material；
The hydrophobic material includes the one or more in polytetrafluoroethylene (PTFE), poly- inclined tetrafluoroethene, makrolon and polyphenylene sulfide；
The fiber nickel also includes the fiber nickel for being compounded with graphene quantum dot.
4. metal air battery cathodes according to claim 3, it is characterised in that the catalyst material and described compound
The mass ratio for having the fiber nickel of graphene quantum dot is (0.5~2)：(0.2~1)；
In the catalyst layer, the mass ratio of the catalyst material and hydrophobic material is (0.5~2)：(0.1~1)；
The Mn oxide includes MnO2、Mn3O4, MnO (OH) and Mn2O3In one or more；
The noble metal catalyst includes silver or platinum；
The conductive carbon material includes VX-72, BP2000, KB EC-300J, PT XE2-B, Super-P, CNT and graphite
In one or more；
A diameter of 30~100 μm of the fiber nickel；The length of the fiber nickel is 100~500 μm.
5. a kind of preparation method of metal air battery cathodes, it is characterised in that comprise the following steps：
1) hydrophobic diaphragm is placed in metal collector, then the catalyst diaphragm containing fiber nickel is placed on hydrophobic diaphragm, entered
Row roll-in, obtains cathode assembly；
2) after the cathode assembly that above-mentioned steps are obtained is sintered, metal air battery cathodes are obtained.
6. preparation method according to claim 5, it is characterised in that the hydrophobic diaphragm by following steps prepare after
Arrive：
By conductive carbon material, hydrophobic material and solvent after roll-in, hydrophobic diaphragm is obtained；
The mass ratio of the hydrophobic material and the solvent is (0.1~1)：(3~8)；The thickness of the hydrophobic diaphragm be 0.1~
0.3mm；
The catalyst diaphragm by following steps prepare after obtain：
A) catalyst material, hydrophobic material, fiber nickel and solvent are obtained into tablet after roll is pressed and mixed；The catalyst
The mass ratio of material and the solvent is (0.5~2)：(1~10)；
B) multiple tablets superposition obtained above-mentioned steps is carried out after roll-in, obtains fine and close diaphragm；
C) the fine and close diaphragm for obtaining above-mentioned steps is carried out after roll-in again, obtains catalyst diaphragm.
7. preparation method according to claim 6, it is characterised in that the step c) is specially：
The fine and close diaphragm that above-mentioned steps are obtained, by the way of thickness is gradually reduced, after multiple roll-in, obtains catalyst
Diaphragm；The multiple number of times is 3~5 times；
The thickness of the fine and close diaphragm is 0.02~0.08mm；
The thickness of the catalyst diaphragm is 0.1~1.0mm.
8. preparation method according to claim 6, it is characterised in that the metal collector include foil-like collector and/
Or reticulated collectors；
The metal includes the one or more in nickel foam, stainless steel, gold, silver and copper；
The solvent includes the mixture of polyvinyl alcohol, alcohols solvent and water；
The temperature of the sintering is 100~500 DEG C；The time of the sintering is 0.5~2 hour；
The thickness of the metal air battery cathodes is 0.1~0.6cm.
9. preparation method according to claim 8, it is characterised in that the fiber nickel is also included by pretreated multiple
Close the fiber nickel for having graphene quantum dot；
The pre-treatment step is：
Fiber nickel is placed in graphene quantum dot solution, takes out after drying, obtains being compounded with the fiber nickel of graphene quantum dot；
The metal collector is also included by the pretreated metal collector for being compounded with graphene quantum dot；
The pre-treatment step is：
Metal collector is placed in graphene quantum dot solution, takes out after drying, obtains being compounded with the gold of graphene quantum dot
Belong to collector.
10. a kind of metal-air battery, it is characterised in that including the metal-air battery described in Claims 1 to 4 any one
Metal air battery cathodes prepared by negative electrode or claim 5~9 any one.
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