CN108054473B - Metal-air battery and preparation method thereof - Google Patents
Metal-air battery and preparation method thereof Download PDFInfo
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- CN108054473B CN108054473B CN201711430202.XA CN201711430202A CN108054473B CN 108054473 B CN108054473 B CN 108054473B CN 201711430202 A CN201711430202 A CN 201711430202A CN 108054473 B CN108054473 B CN 108054473B
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- 229910003460 diamond Inorganic materials 0.000 claims abstract description 60
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- 239000010955 niobium Substances 0.000 claims description 11
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
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- 238000006243 chemical reaction Methods 0.000 description 6
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 6
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000002113 nanodiamond Substances 0.000 description 4
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 4
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
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- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 2
- 229960000909 sulfur hexafluoride Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
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- 230000002378 acidificating effect Effects 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a metal-air battery, which comprises an air electrode, a metal electrode and electrolyte arranged between the air electrode and the metal electrode, wherein the air electrode comprises a matrix and a boron-nitrogen co-doped diamond layer arranged on the surface of the matrix, and the boron-nitrogen co-doped diamond layer comprises a flat structure layer arranged on the surface of the matrix and an array protruding structure arranged on the surface of the flat structure layer. The array bulge structure improves the specific surface area of the air electrode, exposes more active sites, ensures that electrons are easy to transport on the surface of particles, can reduce the diffusion resistance and distance of particle components, and increases the reduction capacity of the particle components, thereby improving the catalytic efficiency of the metal-air battery.
Description
Technical Field
The invention relates to the field of metal-air batteries, in particular to a metal-air battery and a preparation method thereof.
Background
The metal-air battery is a special fuel battery which takes metal as fuel and generates electric energy through oxidation-reduction reaction with oxygen in the air, has good development and application prospect, and is even expected to replace the main power battery type of the current new energy automobile. The metal-air battery is made of a relatively rich raw material, and the metal-air battery which has been researched and developed at present mainly comprises an aluminum-air battery, a magnesium-air battery, a zinc-air battery, a lithium-air battery and the like. Some of these types of metal-air batteries already have large-scale mass production conditions, some remain in the laboratory stage, and some have achieved good application results in electric vehicles, and are about to be loaded with new energy vehicles on a large scale.
In oxygenIn the chemical reduction reaction, oxygen reduction can be classified into two types according to reaction pathways: two electrons (O) 2 +2H + +2e - →H 2 O 2 ) Process and four electrons (O) 2 +4H + +4e - →2H 2 O) process. Two-electron reactions play an important role in the fields of environmental pollution control and chemical synthesis, but in the field of energy conversion, the electrocatalytic efficiency of cathodic oxygen reduction through a four-electron pathway reaction is higher, and the slow rate of cathodic four-electron oxygen reduction is one of the most important factors limiting the energy conversion efficiency of metal-air batteries. Therefore, it is important to develop a metal-air battery with high catalytic efficiency.
Disclosure of Invention
In view of the above, the present invention provides a metal-air battery, in which an air electrode includes a substrate and a boron-nitrogen co-doped diamond layer disposed on a surface of the substrate, the boron-nitrogen co-doped diamond layer including a flat structure layer disposed on a surface of the substrate and an array protrusion structure disposed on a surface of the flat structure layer, the array protrusion structure increasing a specific surface area and exposing more active sites, so that electrons are easily transported on a particle surface, diffusion resistance and distance of particle components can be reduced, and reduction capability thereof is increased, thereby improving catalytic efficiency of the metal-air battery.
In a first aspect, the invention provides a metal-air battery, comprising an air electrode, a metal electrode and an electrolyte arranged between the air electrode and the metal electrode, wherein the air electrode comprises a substrate and a boron-nitrogen co-doped diamond layer arranged on the surface of the substrate, and the boron-nitrogen co-doped diamond layer comprises a flat structure layer arranged on the surface of the substrate and an array protruding structure arranged on the surface of the flat structure layer.
Optionally, the array protrusion is vertically disposed on the flat structural layer.
Optionally, the array protrusion is prismatic, pyramidal or conical in shape.
Optionally, the shape of the array protrusion is a pyramid or a cone, and the curvature radius of the top end of the pyramid or the cone-shaped array protrusion is 1nm-30nm.
Optionally, the length-diameter ratio of the array convex structure is 20-80, the diameter of the tip is 60-200 nm, the diameter of the bottom is 100-1000 nm, and the density is 10 4 cm -2 -10 9 cm -2 。
Optionally, the thickness of the flat structure layer is 100nm-5 μm, and the height of the array protrusion is 50nm-5 μm.
Optionally, the material of the substrate includes one or more of titanium, tantalum, niobium, molybdenum, chromium, silicon, graphite, carbon fiber and cemented carbide.
The metal-air battery provided by the first aspect of the invention comprises a substrate and a boron-nitrogen co-doped diamond layer arranged on the surface of the substrate, wherein the boron-nitrogen co-doped diamond layer comprises a flat structure layer arranged on the surface of the substrate and an array protruding structure arranged on the surface of the flat structure layer. Firstly, the boron-nitrogen co-doped diamond layer has a better potential window, and simultaneously has strong electrocatalytic activity and high physicochemical stability. The co-doping of boron and nitrogen elements can obviously improve the conductivity and the crystal quality of the diamond film. Secondly, the bottom layer of the flat structure protects the matrix, prevents the matrix from being partially exposed, and improves the conductivity of the air electrode; the surface layer of the array bulge structure increases the specific surface area of the boron-nitrogen co-doped diamond layer, so that the active site is further increased, and the working efficiency of the metal-air battery is greatly improved. And thirdly, the surface layer of the array bulge structure has higher hydrogen evolution and oxygen evolution points, and the hydrophilicity and the hydrophobicity of the boron-nitrogen co-doped diamond layer can be further adjusted by adjusting the density and the size of the bulge structure, so that the catalytic efficiency of the metal-air battery is further influenced.
In a second aspect, the present invention provides a method for preparing a metal-air battery, comprising the steps of:
providing a substrate, carrying out sand blasting treatment on the substrate, and cleaning;
depositing an initial boron-nitrogen co-doped diamond layer on the cleaned substrate;
etching the surface layer of the initial boron-nitrogen co-doped diamond layer to form an array protruding structure, and obtaining a boron-nitrogen co-doped diamond layer to obtain an air electrode, wherein the air electrode comprises a substrate and the boron-nitrogen co-doped diamond layer arranged on the surface of the substrate, and the boron-nitrogen co-doped diamond layer comprises a flat structure layer arranged on the surface of the substrate and an array protruding structure arranged on the surface of the flat structure layer;
and providing a metal electrode and electrolyte, and filling the air electrode, the metal electrode and the electrolyte into a containing space of a battery shell to obtain the metal-air battery.
Optionally, the boron-nitrogen co-doped diamond layer is etched by adopting an inductively coupled plasma etching method, wherein in the etching process, the flow of etching gas is 10sccm-400sccm, the etching air pressure is 0.5Pa-10Pa, the power supply power is 600W-3500W, the etching power is 50W-350W, and the etching time is 0.5h-10h.
Optionally, the etching gas includes at least one of argon, oxygen, hydrogen, helium, nitrogen, a gaseous carbon source, carbon tetrafluoride, and sulfur hexafluoride.
Optionally, etching the boron-nitrogen co-doped diamond layer by adopting an electron cyclotron resonance microwave plasma chemical vapor deposition etching method, wherein in the etching process, the introduced gas comprises at least one of hydrogen, argon and gaseous carbon source, and the etching pressure is (5-10) multiplied by 10 -3 The Torr, the etching bias voltage is 50V-250V, the etching bias current is 50mA-150mA, and the etching time is 0.5h-10h.
The preparation method of the metal-air battery provided by the second aspect of the invention has the advantages of simple process and low cost, and can be used for preparing the metal-air battery with excellent electrocatalytic reduction oxygen performance, and the service life of the metal-air battery is longer in a severe environment.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the embodiments of the invention.
Drawings
FIG. 1 is a flow chart of a method for manufacturing a metal-air battery according to an embodiment of the present invention;
fig. 2 is a schematic diagram of step S101 in a method for manufacturing a metal-air battery according to an embodiment of the present invention;
fig. 3 is a schematic diagram of step S102 in the method for manufacturing a metal-air battery according to the embodiment of the present invention;
fig. 4 is a schematic structural diagram of an air electrode in a metal-air battery according to an embodiment of the present invention;
fig. 5 is a schematic structural diagram of an air electrode in a metal-air battery according to another embodiment of the present invention.
Detailed Description
The following description is of the preferred embodiments of the present invention, and it should be noted that, for those skilled in the art, it is possible to make several improvements and modifications without departing from the principle of the embodiments of the present invention, and these improvements and modifications are also considered as the protection scope of the embodiments of the present invention.
Referring to fig. 1, the method for preparing a metal-air battery according to the embodiment of the present invention includes:
step S101: providing a substrate, carrying out sand blasting treatment on the substrate, and cleaning.
In step S101, referring to fig. 2, the material of the substrate 10 includes one or more of titanium, tantalum, niobium, molybdenum, chromium, silicon, graphite, carbon fiber, and cemented carbide. The cleaning comprises acid washing or alkali washing. The specific operation of cleaning is as follows: heating the substrate 10 to 80-100deg.C in acidic or alkaline solution, and soaking for 10-30 min. Optionally, when the cleaning is acid cleaning, the acid cleaning solution comprises sulfuric acid and hydrogen peroxide, wherein the volume ratio of the sulfuric acid to the hydrogen peroxide is 1:10-15. Optionally, when the cleaning is alkaline cleaning, the alkaline solution for alkaline cleaning comprises hydrogen peroxide, ammonium hydroxide and water, wherein the volume ratio of the hydrogen peroxide to the ammonium hydroxide to the water is 1:1 (5-10).
Step S102: and depositing an initial boron-nitrogen co-doped diamond layer on the cleaned substrate.
Before step S102, the substrate 10 is subjected to crystal growing operation, and the cleaned substrate 10 is placed in the nano-diamond suspension for ultrasonic treatment for 1-3 hours. Wherein the grain diameter of the nano diamond powder is 4nm-50nm, and the Zeta potential is about + -30 mV- + -50 mV. Referring to fig. 3, in a preferred embodiment of the present invention, a hot filament chemical vapor deposition method is used to prepare the boron-nitrogen co-doped diamond layer 20 on the substrate 10, wherein in the preparation process, the introduced gas includes nitrogen, methane, trimethylborane and hydrogen, the flow rate of the nitrogen is 24sccm-124sccm, the flow rate of the methane is 24sccm-124sccm, the flow rate of the trimethylborane is 24sccm-124sccm, and the flow rate of the hydrogen is 628sccm-728sccm. Tantalum wires are adopted as hot wires, the number of the hot wires is 9-13, and the diameter of the hot wires is 0.5-1 mm. The distance between the hot wire and the substrate 10 is 5mm-20mm, the deposition temperature is 2200-2400 ℃, the deposition power is 5000-7000W, the temperature of the substrate 10 is 650-900 ℃, the air pressure is 2000-5000 Pa, and the deposition time is 0.5-10 h. Optionally, the boron nitrogen co-doped diamond layer 20 deposited on the substrate 10 has a thickness of 500nm-10 μm. In a preferred embodiment of the present invention, the boron nitrogen co-doped diamond layer 20 may be disposed on one side or on opposite sides of the substrate 10. The boron nitrogen co-doped diamond layer 20 is provided on opposite sides of the substrate 10 to further enhance the ability to electrocatalytically reduce oxygen.
Step S103: and etching the surface layer of the initial boron-nitrogen co-doped diamond layer to form an array protruding structure to obtain a boron-nitrogen co-doped diamond layer, so as to obtain the air electrode, wherein the air electrode comprises a matrix and the boron-nitrogen co-doped diamond layer arranged on the surface of the matrix, and the boron-nitrogen co-doped diamond layer comprises a flat structure layer arranged on the surface of the matrix and an array protruding structure arranged on the surface of the flat structure layer.
In step S103, in the preferred embodiment of the invention, the boron-nitrogen co-doped diamond layer is etched by adopting an inductively coupled plasma etching method, wherein in the etching process, the flow of etching gas is 10sccm-400sccm, the etching gas pressure is 0.5Pa-10Pa, the power supply power is 600W-3500W, the etching power is 50W-350W, and the etching time is 0.5h-10h. In an embodiment of the present invention, the etching gas includes at least one of argon, oxygen, hydrogen, helium, nitrogen, a gaseous carbon source, carbon tetrafluoride, and sulfur hexafluoride.
In the preferred embodiment of the present inventionEtching the boron-nitrogen co-doped diamond layer by adopting an electron cyclotron resonance microwave plasma chemical vapor deposition etching method, wherein in the etching process, the introduced gas comprises at least one of hydrogen, argon and gaseous carbon source, and the etching pressure is (5-10) multiplied by 10 -3 The Torr, the etching bias voltage is 50V-250V, the etching bias current is 50mA-150mA, and the etching time is 0.5h-10h. Referring to fig. 4 and 5, after etching, a flat structure layer 21 disposed on the surface of the substrate 10 and an array of bump structures 22 disposed on the surface of the flat structure layer 21 are obtained. In a preferred embodiment of the present invention, the array protrusions 22 are vertically disposed on the flat structure layer 21, and the array protrusions 22 are spaced apart from each other. The array of protrusions 22 perpendicular to the underlayer 21 allows electrons to be transported easily at the particle surface, reduces the diffusion resistance and distance of the particle components, and increases its electrocatalytic oxygen reduction capacity. The array protrusions 22 arranged at intervals further increase the specific surface area of the boron-nitrogen co-doped diamond layer, and the electrocatalytic oxygen reduction capability is further improved. In a preferred embodiment of the present invention, the array of protrusions 22 are in the shape of prisms (fig. 4), pyramids, or cones (fig. 5). Preferably, the array of projections 22 are pyramid or cone shaped. The array protrusion with the tip can play a role of converging electrons, so that the electron transmission and circulation are easier. In the preferred embodiment of the present invention, when the shape of the array protrusion 22 is a pyramid or a cone, the tip of the pyramid or cone (the end of the array protrusion 22 away from the flat structure layer 21) is not a point, but has a certain radius of curvature, and the tip benefit and electric field enhancement generated by the tip have a beneficial effect on the catalytic performance of the air electrode. Preferably, the radius of curvature of the tip of the pyramid or cone-shaped array protrusion 22 is 1nm to 30nm, and further, the radius of curvature of the tip of the pyramid or cone-shaped array protrusion 22 is 3nm to 27nm,8nm to 20nm, or 10nm to 17nm. The length-diameter ratio of the array convex structure is 20-80, the diameter of the tip is 60-200 nm, the diameter of the bottom is 100-1000 nm, and the density is 10 4 cm -2 -10 9 cm -2 Further, the length-diameter ratio of the array convex structure is 30-60, the diameter of the tip is 100-150 nm, the diameter of the bottom is 300-500 nm, and the density is 10 7 cm -2 -10 9 cm -2 . Preferably, the tip is of single crystal diamond construction, allowing a wider electrochemical window and lower hydrogen evolution potential for the air electrode.
In a preferred embodiment of the present invention, the thickness of the planarization structure layer 21 is 100nm to 5 μm and the height of the array protrusions 22 is 50nm to 5 μm. Further, the thickness of the planarizing structure layer 21 is 200nm-4 μm or 500nm-3 μm, and the height of the array bump 22 is 100nm-4 μm, 500nm-3 μm or 1 μm-2 μm.
Step S104: and providing a metal electrode and electrolyte, and filling the air electrode, the metal electrode and the electrolyte into a containing space of a battery shell to obtain the metal-air battery.
In step S104, the electrolyte is interposed between the air electrode and the metal electrode and metal ion conduction is performed between the air electrode and the metal electrode. The electrolyte is not particularly limited as long as it can conduct metal ions between the air electrode and the metal electrode. Electrolyte liquids, electrolyte gels, solid electrolytes, solid polymers, and mixtures thereof may be used as the electrolyte. The metal electrode is made of one or more of lithium, aluminum, magnesium, zinc and copper. Metal-air batteries typically have a battery housing for containing an air electrode, a metal electrode, and an electrolyte. The shape of the battery case is not particularly limited. In particular, a coin shape, a flat plate shape, a cylindrical shape, and a laminate shape can be mentioned. The battery case may be of an open atmosphere type or a sealed type as long as it can feed oxygen to the air electrode. The open-cell battery case has a structure in which at least the air electrode can be sufficiently contacted with the atmosphere. When the laminated body in which the air electrode, the electrolyte, and the metal electrode are arranged in this order in the metal-air battery are repeatedly stacked in a multi-layer form (for example, a laminated body structure or a wound structure), it is preferable from the viewpoint of safety to have a separator between the air electrode and the metal electrode, each of which belongs to a laminated body different from each other. As such a separator, a porous film of polyethylene or polypropylene may be mentioned; and nonwoven fabrics such as resin nonwoven fabrics or glass fiber nonwoven fabrics.
The preparation method of the metal-air battery provided by the invention has the advantages that the process is simple, the cost is low, the metal-air battery with excellent electrocatalytic reduction oxygen performance can be prepared, the service life of the metal-air battery in a severe environment is longer, the air electrode in the prepared metal-air battery comprises a matrix and a boron-nitrogen co-doped diamond layer arranged on the surface of the matrix, and the boron-nitrogen co-doped diamond layer comprises a flat structure layer arranged on the surface of the matrix and an array protruding structure arranged on the surface of the flat structure layer. Firstly, the boron-nitrogen co-doped diamond layer has a wider potential window than the traditional electrode material, and simultaneously has strong electrocatalytic activity and high physicochemical stability. The co-doping of boron and nitrogen elements can obviously improve the conductivity and the crystal quality of the diamond film. Secondly, the bottom layer of the flat structure protects the matrix, prevents the matrix from being partially exposed, and improves the conductivity of the air electrode; the surface layer of the array bulge structure increases the specific surface area of the boron-nitrogen co-doped diamond layer, so that the active site is further increased, and the working efficiency of the metal-air battery is greatly improved. And thirdly, the surface layer of the array bulge structure has higher hydrogen evolution and oxygen evolution points, and the hydrophilicity and the hydrophobicity of the boron-nitrogen co-doped diamond layer can be further adjusted by adjusting the density and the size of the bulge structure, so that the catalytic efficiency of the metal-air battery is further influenced.
The following examples are provided to further illustrate embodiments of the invention.
Example 1
A method of making a metal-air battery comprising the steps of:
step 1: and taking a niobium substrate, performing sand blasting on the niobium substrate, and respectively ultrasonically cleaning the niobium substrate in acetone and alcohol for 10min. Then placing the niobium matrix in an acidic solution of sulfuric acid and hydrogen peroxide with the volume ratio of 1:15, heating to 100 ℃, and soaking for 30min. Removing surface oxide and causing certain defects for subsequent deposition, and ultrasonically cleaning for 10min by using deionized water. The pickled niobium substrate was then placed in a nano-diamond powder suspension for 1 hour of ultrasonic treatment.
Step 2: and depositing a boron-nitrogen co-doped diamond layer on the cleaned niobium substrate by adopting a hot wire chemical vapor deposition method, wherein in the preparation process, the introduced gas comprises nitrogen, methane, trimethylborane and hydrogen, the flow rate of the nitrogen is 24sccm, the flow rate of the methane is 24sccm, the flow rate of the trimethylborane is 24sccm, and the flow rate of the hydrogen is 728sccm. Tantalum wires are adopted as hot wires, the number of the hot wires is 9, and the diameter of the hot wires is 0.5mm. The distance between the hot wire and the substrate is 7.5mm, the deposition temperature is 2400 ℃, the deposition power is 7000W, the temperature of the niobium substrate is 850 ℃, the air pressure is 4500Pa, and the deposition time is 5h. A niobium substrate having a boron-nitrogen co-doped diamond layer on the surface thereof was obtained, wherein the thickness of the boron-nitrogen co-doped diamond layer was 3 μm.
Step 3: and etching the boron-nitrogen co-doped diamond layer by adopting an electron cyclotron resonance microwave plasma chemical vapor deposition etching method, wherein the boron-nitrogen co-doped diamond layer is etched in the etching process. Introducing gas comprising mixed gas of hydrogen and argon, and vacuumizing to 10 -5 Under Pa, then hydrogen gas was introduced to 6mTorr, the flow rate of methane was 0.4sccm, and the flow rate of hydrogen gas was 19.6sccm. Etching gas pressure of 5×10 -3 Torr, etching bias voltage of 250V, etching bias current of 80mA and etching time of 2.5h. The boron-nitrogen co-doped diamond layer is etched to form a bottom layer and a surface layer, and the surface layer is in an array bulge structure to obtain the air electrode, wherein the array bulge is conical, the height is 1 mu m, the top end curvature radius is 3nm, and the density is 10 5 cm -2 。
Step 4: and (3) selecting metal lithium as a metal electrode and lithium chloride as electrolyte, and filling the air electrode, the metal lithium and the lithium chloride into the accommodating space of the shell to obtain the metal-air battery.
Example 2
A method of making a metal-air battery comprising the steps of:
step 1: taking a titanium substrate, performing sand blasting on the titanium substrate, and respectively ultrasonically cleaning the titanium substrate in acetone and alcohol for 10min. Then the titanium matrix is placed in alkaline solution of hydrogen peroxide, ammonium hydroxide and water with the volume ratio of 1:1:5, heated to 80 ℃, and soaked for 30min. Removing surface oxide and causing certain defects for subsequent deposition, and ultrasonically cleaning for 10min by using deionized water. The pickled titanium substrate was then placed in a nanodiamond powder suspension for 2 hours of ultrasonic treatment.
Step 2: and depositing a boron-nitrogen co-doped diamond layer on the cleaned titanium substrate by adopting a hot wire chemical vapor deposition method, wherein in the preparation process, the introduced gas comprises nitrogen, methane, trimethylborane and hydrogen, the flow rate of the nitrogen is 124sccm, the flow rate of the methane is 124sccm, the flow rate of the trimethylborane is 124sccm, and the flow rate of the hydrogen is 628sccm. Tantalum wires are adopted as hot wires, the number of the hot wires is 9, and the diameter of the hot wires is 0.5mm. The distance between the hot wire and the substrate is 10mm, the deposition temperature is 2200 ℃, the deposition power is 6900W, the temperature of the titanium substrate is 800 ℃, the air pressure is 4000Pa, and the deposition time is 2h. A titanium substrate having a boron-nitrogen co-doped diamond layer on the surface thereof was obtained, wherein the thickness of the boron-nitrogen co-doped diamond layer was 2 μm.
Step 3: and etching the boron-nitrogen co-doped diamond layer by adopting an inductively coupled plasma etching method, wherein in the etching process, the introduced gas comprises argon, helium, nitrogen and carbon tetrafluoride, the flow of the argon is 10sccm, the flow of the helium is 10sccm, the flow of the nitrogen is 5sccm, the flow of the carbon tetrafluoride is 50sccm, the etching air pressure is 0.5Pa, the power supply power is 2200W, the etching power is 160W, and the etching time is 1h. Etching the boron-nitrogen co-doped diamond layer as a bottom layer and a surface layer, and making the surface layer be in an array convex structure to obtain the air electrode, wherein the array convex is prismatic, the height is 50nm, and the density is 10 8 cm -2 。
Step 4: and (3) selecting metal magnesium as a metal electrode and polyacrylonitrile as electrolyte, and filling the air electrode, the metal magnesium and the polyacrylonitrile into the accommodating space of the shell to obtain the metal-air battery.
The preparation method of the metal-air battery provided by the invention has the advantages of simple process and low cost, and can be used for preparing the metal-air battery with excellent electrocatalytic reduction oxygen performance, and the service life of the metal-air battery is longer in a severe environment.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (6)
1. The utility model provides a metal-air battery, its characterized in that includes air electrode, metal electrode and set up air electrode with electrolyte between the metal electrode, air electrode includes the base member and sets up the boron nitrogen codoped diamond layer on base member surface, boron nitrogen codoped diamond layer including set up in the smooth structural layer on base member surface with set up in the array protruding structure on smooth structural layer surface, the shape of array protruding structure is pyramid or circular cone, the top radius of curvature of array protruding structure is 1nm-30nm, the top of array protruding structure is single crystal diamond structure.
2. The metal-air cell of claim 1, wherein the array of raised structures is disposed vertically on the planar structural layer.
3. The metal-air cell of claim 1, wherein the array of raised structures has an aspect ratio of 20-80, a tip diameter of 60-200 nm, a base diameter of 100-1000 nm, and a density of 10 4 cm -2 -10 9 cm -2 。
4. The metal-air cell of claim 1, wherein the planar structural layer has a thickness of 100nm to 5 μm and the array of raised structures has a height of 50nm to 5 μm.
5. The metal-air cell of claim 1, wherein the substrate comprises one or more of titanium, tantalum, niobium, molybdenum, chromium, silicon, graphite, carbon fiber, and cemented carbide.
6. A method of making a metal-air battery comprising the steps of:
providing a substrate, carrying out sand blasting treatment on the substrate, and cleaning;
depositing an initial boron-nitrogen co-doped diamond layer on the cleaned substrate by adopting a hot wire chemical vapor deposition method, wherein the deposition temperature is 2200-2400 ℃, the deposition power is 5000-7000W, the deposition air pressure is 2000-5000 Pa, and the deposition time is 0.5-10 h;
etching the surface layer of the initial boron-nitrogen co-doped diamond layer to form an array protruding structure, so as to obtain a boron-nitrogen co-doped diamond layer, namely an air electrode, wherein the air electrode comprises a substrate and the boron-nitrogen co-doped diamond layer arranged on the surface of the substrate, the boron-nitrogen co-doped diamond layer comprises a flat structure layer arranged on the surface of the substrate and an array protruding structure arranged on the surface of the flat structure layer, the shape of the array protruding structure is a pyramid or cone, the curvature radius of the top end of the array protruding structure is 1nm-30nm, the top end of the array protruding structure is a single crystal diamond structure, the boron-nitrogen co-doped diamond layer is etched by adopting an inductive coupling plasma etching method, in the etching process, the flow rate of etching gas is 10sccm-400sccm, the etching pressure is 0.5Pa-10Pa, the power is 600W-3500W, the etching power is 50W-350W, and the etching time is 0.5h-10h; or adopting an electron cyclotron resonance microwave plasma chemical vapor deposition etching method to etch the boron-nitrogen co-doped diamond layer, wherein in the etching process, the introduced gas comprises at least one of hydrogen, argon and gaseous carbon source, and the etching pressure is (5-10) multiplied by 10 -3 Torr, etching bias voltage is 50V-250V, etching bias current is 50mA-150mA, and etching time is 0.5h-10h;
and providing a metal electrode and electrolyte, and filling the air electrode, the metal electrode and the electrolyte into a containing space of a battery shell to obtain the metal-air battery.
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