CN207781847U - A kind of metal-air battery - Google Patents
A kind of metal-air battery Download PDFInfo
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- CN207781847U CN207781847U CN201721845762.7U CN201721845762U CN207781847U CN 207781847 U CN207781847 U CN 207781847U CN 201721845762 U CN201721845762 U CN 201721845762U CN 207781847 U CN207781847 U CN 207781847U
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Abstract
The utility model provides a kind of metal-air battery, including air electrode, metal electrode and the electrolyte being arranged between the air electrode and the metal electrode, the air electrode includes matrix and the nitrogen co-doped diamond layer of boron on described matrix surface is arranged, and the nitrogen co-doped diamond layer of boron includes the flat configuration layer for being set to described matrix surface and the array bulge-structure for being set to the flat configuration layer surface.The array bulge-structure improves air electrode specific surface area, expose more active sites so that electronics is easy to transmit in particle surface, can reduce the diffusional resistance and distance of particle fraction, its reducing power is increased, so that the catalytic efficiency of metal-air battery improves.
Description
Technical field
The utility model is related to battery technology fields, more particularly to a kind of metal-air battery.
Background technology
Metal-air battery is one produced electricl energy as the oxygen generation redox reaction in fuel, with air using metal
Kind of specific fuel battery has good development and application prospect, or even is sent to great expectations to substitute current new-energy automobile main
Power battery type.It is relatively abundanter to make the available raw material of metal-air battery, has been achieved with progress at present
Metal-air battery mainly has aluminium-air cell, magnesium air battery, zinc-air battery, lithium-air battery etc..These types of type
Metal-air battery some has been provided with the condition of scale of mass production, and some also rests on laboratory stage, and some is in electricity
Good application achievements are obtained in terms of electrical automobile, and will load new energy vehicle on a large scale.
In redox reaction, hydrogen reduction can be divided into two classes by reaction path：Two electronics (O2+2H++2e-→H2O2) mistake
Journey and four electronics (O2+4H++4e-→2H2O) process.Two electron reactions have weight in environment pollution control and chemical industry synthesis field
It acts on, but in field of energy conversion, electro-catalysis when cathodic oxygen reduction is reacted by four electronic channels is more efficient, and cloudy
Four electronics oxygen reduction reaction rate of pole is a most important factor for restricting metal-air battery energy conversion efficiency slowly.Cause
This, a kind of metal-air battery of high catalytic efficiency of exploitation is highly important.
Utility model content
In view of this, the utility model provides a kind of metal-air battery, wherein air electrode includes matrix and sets
The nitrogen co-doped diamond layer of boron on described matrix surface is set, the nitrogen co-doped diamond layer of boron includes being set to described matrix
The flat configuration layer on surface and the array bulge-structure for being set to the flat configuration layer surface, the array bulge-structure improve
Specific surface area, exposes more active sites so that electronics is easy to transmit in particle surface, can reduce the expansion of particle fraction
Resistance and distance are dissipated, its reducing power is increased, so that the catalytic efficiency of metal-air battery improves.
In a first aspect, the utility model provides a kind of metal-air battery, including air electrode, metal electrode and set
The electrolyte between the air electrode and the metal electrode is set, the air electrode includes matrix and is arranged described
The nitrogen co-doped diamond layer of boron of matrix surface, the nitrogen co-doped diamond layer of boron include being set to putting down for described matrix surface
Whole structure sheaf and the array bulge-structure for being set to the flat configuration layer surface.
Optionally, the array protrusion is vertically installed on the flat configuration layer.
Optionally, the shape of the array protrusion is prism, pyramid or circular cone.
Optionally, the shape of the array protrusion is the top of pyramid or circular cone, pyramid or coniform array protrusion
End radius of curvature is 1nm-30nm.
Optionally, the draw ratio of the array bulge-structure is 20-80, tip diameter 60nm-200nm, base diameter
For 100nm-1000nm, density 104cm-2-109cm-2。
Optionally, the thickness of the flat configuration layer is 100nm-5 μm, and the height of the array protrusion is 50nm-5 μm.
Optionally, the material of described matrix includes in titanium, tantalum, niobium, molybdenum, chromium, silicon, graphite, carbon fiber and hard alloy
It is one or more.
Optionally, the material of the metal electrode includes one or more in lithium, aluminium, magnesium, zinc, copper.
Optionally, the electrolyte includes polyacrylonitrile, Kynoar, methyl difluoroacetate, bis- (fluoroform sulphonyl
Base) it is amide lithium, potassium hydroxide, sodium hydroxide, one or more in lithium hydroxide.
Optionally, the metal-air battery further includes diaphragm, and the material of the diaphragm includes porous polyethylene membrane, porous
It is one or more in polypropylene screen, glass fiber membrane, porous ceramic film.
The utility model provides a kind of metal-air battery, and the air electrode includes matrix and is arranged in the base
The nitrogen co-doped diamond layer of boron in body surface face, the nitrogen co-doped diamond layer of boron include be set to described matrix surface smooth
Structure sheaf and the array bulge-structure for being set to the flat configuration layer surface.First, the nitrogen co-doped diamond layer of boron has preferably
Potential window, be provided simultaneously with strong electro catalytic activity, high physical and chemical stability.Boron nitrogen codope can be notable
Improve the conductivity and crystal quality of diamond thin.Secondly, the protective underlayer of flat configuration matrix, prevents the body portion sudden and violent
Dew, improves the electric conductivity of air electrode；The surface layer of array bulge-structure increases the specific surface of the nitrogen co-doped diamond layer of boron
Product, to further increase active site, metal-air battery working efficiency is greatly improved.Again, array protrusion
The surface layer of structure has higher liberation of hydrogen and analysis oxygen point position, by adjusting the density and size of the bulge-structure, and then can be with
The hydrophily and hydrophobicity of the nitrogen co-doped diamond layer of boron are adjusted, the catalytic efficiency of metal-air battery is further influenced.
The advantages of the utility model, will partly illustrate in the following description, and a part is aobvious and easy according to specification
See, or can be known by the implementation of the utility model embodiment.
Description of the drawings
Fig. 1 is the structural schematic diagram of air electrode in a kind of metal-air battery that the utility model embodiment provides；
Fig. 2 is the structural representation of air electrode in a kind of metal-air battery that another embodiment of the utility model provides
Figure.
Specific implementation mode
As described below is the preferred embodiment of the utility model embodiment, it is noted that for the general of the art
For logical technical staff, under the premise of not departing from the utility model embodiment principle, several improvements and modifications can also be made,
These improvements and modifications are also considered as the protection domain of the utility model embodiment.
The utility model implementation provides a kind of metal-air battery, including air electrode, metal electrode and setting exist
Electrolyte between the air electrode and the metal electrode, the air electrode include matrix and are arranged in described matrix
The nitrogen co-doped diamond layer of boron on surface, the nitrogen co-doped diamond layer of boron include the smooth knot for being set to described matrix surface
Structure layer and the array bulge-structure for being set to the flat configuration layer surface.
It please refers to Fig.1 and Fig. 2, implements the air electrode structure in a kind of metal-air battery provided for the utility model
Schematic diagram.In the present invention, the air electrode includes that matrix 10 and the boron nitrogen being arranged on described matrix surface are co-doped with
Miscellaneous diamond layer 20, the nitrogen co-doped diamond layer 20 of boron include 21 He of flat configuration layer for being set to 10 surface of described matrix
It is set to the array bulge-structure 22 on 21 surface of flat configuration layer.In the present invention, the array protrusion 22 is vertical
It is set on the flat configuration layer 21.In the present invention, the shape of the array protrusion 22 is prism (Fig. 1), pyramid
Or circular cone (Fig. 2).In the present invention, referring to Fig. 2, the shape of the array protrusion 22 be pyramid or circular cone, pyramid or
The top radius of curvature of the coniform array protrusion 22 is 1nm-30nm.Further, pyramid or the coniform battle array
The top radius of curvature of row protrusion 22 is 3nm-27nm, 8nm-20nm or 10nm-17nm.In the present invention, the array
The draw ratio of bulge-structure is 20-80, tip diameter 60nm-200nm, base diameter 100nm-1000nm, and density is
104cm-2-109cm-2.Further, the draw ratio of the array bulge-structure be 30-60, tip diameter 100nm-150nm,
Base diameter is 300nm-500nm, density 107cm-2-109cm-2.In the present invention, the thickness of the flat configuration layer 21
Degree is 100nm-5 μm, and the height of the array protrusion 22 is 50nm-5 μm.Further, the thickness of the flat configuration layer 21
It it is 200nm-4 μm or 500nm-3 μm, the height of the array protrusion 22 is 100nm-4 μm, 500nm-3 μm or 1 μm -2 μm.
In the utility model, the material of described matrix includes one in titanium, tantalum, niobium, molybdenum, chromium, silicon, graphite, carbon fiber and hard alloy
Kind is a variety of.
In the present invention, the material of the metal electrode includes one or more in lithium, aluminium, magnesium, zinc, copper.Electricity
Solution liquid carries out metal ion conduction between air electrode and metal electrode and between air electrode and metal electrode.It is right
Be not particularly limited in electrolyte, if its can between air electrode and metal electrode conduct metal ions.Electrolysis
Liquid liquid, Electrolyte Gel, solid electrolyte, solid polymer and their mixture can be used as electrolyte.Optionally, institute
It includes polyacrylonitrile, Kynoar, methyl difluoroacetate, bis- (trifluoromethane sulfonyl group) amide lithiums, hydroxide to state electrolyte
It is one or more in potassium, sodium hydroxide, lithium hydroxide.Metal-air battery usually has for accommodating air electrode, metal
The battery case of electrode and electrolyte.The shape of battery case is not particularly limited.Specifically, can be mentioned that coin shapes, putting down
Plate shape, cylindrical shape and laminated shape.Battery case can be open atmosphere type or closed type, as long as it can feed oxygen
To air electrode.Open atmosphere type battery case has the structure that at least air electrode can come into full contact with air.Work as gold
The lamilate that air electrode, electrolyte and metal electrode are arranged with this sequence in category air cell is with multilayer form repeatedly stacking
When (such as laminate structure or winding-structure), for the angle of safety, preferably between air electrode and metal electrode
With diaphragm, the air electrode each belongs to lamilate different from each other with negative electrode.Optionally, the metal-air battery
Further include diaphragm, the material of the diaphragm includes porous polyethylene membrane, porous polypropylene film, glass fiber membrane, porous ceramics
It is one or more in film.
The utility model provides a kind of metal-air battery, and the air electrode includes matrix and is arranged in the base
The nitrogen co-doped diamond layer of boron in body surface face, the nitrogen co-doped diamond layer of boron include be set to described matrix surface smooth
Structure sheaf and the array bulge-structure for being set to the flat configuration layer surface.First, the nitrogen co-doped diamond layer of boron has preferably
Potential window, be provided simultaneously with strong electro catalytic activity, high physical and chemical stability.Boron nitrogen codope can be notable
Improve the conductivity and crystal quality of diamond thin.Secondly, the protective underlayer of flat configuration matrix, prevents the body portion sudden and violent
Dew, improves the electric conductivity of air electrode；The surface layer of array bulge-structure increases the specific surface of the nitrogen co-doped diamond layer of boron
Product, to further increase active site, metal-air battery working efficiency is greatly improved.Again, array protrusion
The surface layer of structure has higher liberation of hydrogen and analysis oxygen point position, can adjust the hydrophily of the nitrogen co-doped diamond layer of boron and hydrophobic
Property, further influence the catalytic efficiency of metal-air battery.
The above-mentioned metal-air battery of the utility model can be used under type such as and prepare：
Matrix is provided, described matrix is subjected to blasting treatment and is cleaned；Deposition is formed just in described matrix after cleaning
The nitrogen co-doped diamond layer of beginning boron；The surface layer of the nitrogen co-doped diamond layer of the initial boron is carved by inductively coupled plasma
Erosion method or electron cyclotron resonance microwave plasmas chemical vapor deposition etching method perform etching to form array bulge-structure, obtain
For the nitrogen co-doped diamond layer of boron to get to air electrode, the air electrode includes matrix and setting on described matrix surface
The nitrogen co-doped diamond layer of boron, the nitrogen co-doped diamond layer of boron includes the flat configuration layer for being set to described matrix surface
With the array bulge-structure for being set to the flat configuration layer surface；
Metal electrode and electrolyte are provided, the air electrode, the metal electrode and electrolyte are packed into battery case
Receiving space in, obtain metal-air battery.
The utility model will be further detailed with multiple specific embodiments below.
Embodiment 1
A kind of preparation method of metal-air battery, includes the following steps：
Step 1：Niobium matrix is taken, after carrying out sandblasting to niobium matrix, is respectively cleaned by ultrasonic niobium matrix in acetone and alcohol
10min.Then it is 1 niobium matrix to be placed in volume ratio:It is heated to 100 DEG C in 15 sulfuric acid and the acid solution of hydrogen peroxide, impregnates
30min.Oxide on surface is removed, and causes certain defect so as to deposition later, reuses deionized water ultrasonic cleaning
10min.Then the niobium matrix after pickling is placed in nano-diamond powder suspension and is ultrasonically treated 1 hour.
Step 2：Using the nitrogen co-doped diamond layer of niobium substrate deposit boron of hot filament CVD after cleaning,
In preparation process, the gas being passed through includes nitrogen, methane, trimethyl borine and hydrogen, and the flow of nitrogen is 24sccm, methane
Flow be 24sccm, the flow of trimethyl borine is 24sccm, and the flow of hydrogen is 728sccm.Using tantalum wire as heated filament,
The quantity of heated filament is 9, a diameter of 0.5mm of heated filament.Heated filament is 7.5mm at a distance from matrix, and depositing temperature is 2400 DEG C, is sunk
Product power is 7000W, and the temperature of niobium matrix is 850 DEG C, air pressure 4500Pa, sedimentation time 5h.Obtaining surface has boron nitrogen
The niobium matrix of co-doped diamond layer, the wherein thickness of the nitrogen co-doped diamond layer of boron are 3 μm.
Step 3：Using electron cyclotron resonance microwave plasmas chemical vapor deposition etching method to the nitrogen co-doped Buddha's warrior attendant of boron
Rock layers perform etching, in etching process.The gas being passed through includes the mixed gas of hydrogen and argon gas, and base vacuum is evacuated to
10-5Pa is hereinafter, then pass to hydrogen to 6mTorr, the flow of methane is 0.4sccm, and the flow of hydrogen is 19.6sccm.Etching
Air pressure is 5 × 10-3Torr, etching bias are -250V, and etching bias current is 80mA, etch period 2.5h.So that boron is nitrogen co-doped
Diamond layer etching is bottom and surface layer, and surface layer is made to be array bulge-structure, obtains air electrode, the wherein shape of array protrusion
Shape is coniform, is highly 1 μm, and top radius of curvature is 3nm, density 105cm-2。
Step 4：Select lithium metal as metal electrode, lithium hydroxide as electrolyte, by the air electrode, lithium metal
It is packed into lithium hydroxide in the receiving space of shell, obtains metal-air battery.
Embodiment 2
A kind of preparation method of metal-air battery, includes the following steps：
Step 1：Titanium base is taken, after carrying out sandblasting to Titanium base, is respectively cleaned by ultrasonic Titanium base in acetone and alcohol
10min.Then it is 1 Titanium base to be placed in volume ratio:1:It is heated to 80 in the alkaline solution of 5 hydrogen peroxide, ammonium hydroxide and water
DEG C, impregnate 30min.Oxide on surface is removed, and causes certain defect so as to deposition later, it is clear to reuse deionized water ultrasound
Wash 10min.Then the Titanium base after pickling is placed in nano-diamond powder suspension and is ultrasonically treated 2 hours.
Step 2：Using on the Titanium base of hot filament CVD after cleaning deposit the nitrogen co-doped diamond layer of boron,
In preparation process, the gas being passed through includes nitrogen, methane, trimethyl borine and hydrogen, and the flow of nitrogen is 124sccm, first
The flow of alkane is 124sccm, and the flow of trimethyl borine is 124sccm, and the flow of hydrogen is 628sccm.Using tantalum wire conduct
The quantity of heated filament, heated filament is 9, a diameter of 0.5mm of heated filament.Heated filament is 10mm, depositing temperature 2200 at a distance from matrix
DEG C, the temperature of deposition power 6900W, Titanium base are 800 DEG C, air pressure 4000Pa, sedimentation time 2h.Obtaining surface has
The Titanium base of the nitrogen co-doped diamond layer of boron, the wherein thickness of the nitrogen co-doped diamond layer of boron are 2 μm.
Step 3：The nitrogen co-doped diamond layer of boron is performed etching using sense coupling method, etched
Cheng Zhong, the gas being passed through include argon gas, helium, nitrogen and carbon tetrafluoride, and the flow of argon gas is 10sccm, and the flow of helium is
The flow of 10sccm, nitrogen are 5sccm, and the flow of carbon tetrafluoride is 50sccm, and etching air pressure is 0.5Pa, and power is
2200W, etching power are 160W, etch period 1h.So that the nitrogen co-doped diamond layer etching of boron is bottom and surface layer, and make
Surface layer is array bulge-structure, obtains air electrode, and the wherein shape of array protrusion is prism-shaped, is highly 50nm, density is
108cm-2。
Step 4：Select magnesium metal as metal electrode, polyacrylonitrile as electrolyte, by the air electrode, magnesium metal
It is packed into polyacrylonitrile in the receiving space of shell, obtains metal-air battery.
Above-described embodiments merely represent several embodiments of the utility model, the description thereof is more specific and detailed,
But it should not be understood as limiting the scope of the patent of the utility model.It should be pointed out that for the common of this field
For technical staff, without departing from the concept of the premise utility, various modifications and improvements can be made, these all belong to
In the scope of protection of the utility model.Therefore, the protection domain of the utility model patent should be determined by the appended claims.
Claims (10)
1. a kind of metal-air battery, which is characterized in that including air electrode, metal electrode and be arranged in the air electrode
Electrolyte between the metal electrode, the air electrode include that matrix and the boron nitrogen being arranged on described matrix surface are total
Doped diamond layer, the nitrogen co-doped diamond layer of boron include being set to the flat configuration layer on described matrix surface and being set to
The array bulge-structure of the flat configuration layer surface.
2. metal-air battery as described in claim 1, which is characterized in that the array protrusion is vertically installed in described smooth
On structure sheaf.
3. metal-air battery as described in claim 1, which is characterized in that the shape of the array protrusion is prism, pyramid
Or circular cone.
4. metal-air battery as claimed in claim 3, which is characterized in that the shape of the array protrusion is pyramid or circle
The top radius of curvature of cone, pyramid or coniform array protrusion is 1nm-30nm.
5. metal-air battery as claimed in claim 4, which is characterized in that the draw ratio of the array bulge-structure is 20-
80, tip diameter 60nm-200nm, base diameter 100nm-1000nm, density 104cm-2-109cm-2。
6. metal-air battery as described in claim 1, which is characterized in that the thickness of the flat configuration layer is 100nm-5 μ
The height of m, the array protrusion are 50nm-5 μm.
7. metal-air battery as described in claim 1, which is characterized in that the material of described matrix include titanium, tantalum, niobium, molybdenum,
It is one or more in chromium, silicon, graphite, carbon fiber and hard alloy.
8. metal-air battery as described in claim 1, which is characterized in that the material of the metal electrode include lithium, aluminium,
It is one or more in magnesium, zinc, copper.
9. metal-air battery as described in claim 1, which is characterized in that the electrolyte includes polyacrylonitrile, gathers inclined fluorine
Ethylene, methyl difluoroacetate, double trifluoromethanesulfonimide lithiums, potassium hydroxide, sodium hydroxide, one kind in lithium hydroxide or more
Kind.
10. metal-air battery as described in claim 1, which is characterized in that the metal-air battery further includes diaphragm, institute
The material for stating diaphragm include one kind in porous polyethylene membrane, porous polypropylene film, glass fiber membrane, porous ceramic film or
It is a variety of.
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| CN201721845762.7U CN207781847U (en) | 2017-12-26 | 2017-12-26 | A kind of metal-air battery |
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| CN201721845762.7U CN207781847U (en) | 2017-12-26 | 2017-12-26 | A kind of metal-air battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108054473A (en) * | 2017-12-26 | 2018-05-18 | 深圳先进技术研究院 | A kind of metal-air battery and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108054473A (en) * | 2017-12-26 | 2018-05-18 | 深圳先进技术研究院 | A kind of metal-air battery and preparation method thereof |
| CN108054473B (en) * | 2017-12-26 | 2024-04-09 | 深圳先进技术研究院 | Metal-air battery and preparation method thereof |
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