CN106654295A - Air cathode based on boron-nitrogen-carbon ternary covalent composite material, preparation method for air cathode, and zinc air secondary battery - Google Patents
Air cathode based on boron-nitrogen-carbon ternary covalent composite material, preparation method for air cathode, and zinc air secondary battery Download PDFInfo
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- CN106654295A CN106654295A CN201710034232.2A CN201710034232A CN106654295A CN 106654295 A CN106654295 A CN 106654295A CN 201710034232 A CN201710034232 A CN 201710034232A CN 106654295 A CN106654295 A CN 106654295A
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- H—ELECTRICITY
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- 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
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
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- 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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- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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- H01M4/90—Selection of catalytic material
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Abstract
The invention discloses an air cathode based on a boron-nitrogen-carbon ternary covalent composite material, a preparation method for the air cathode, and a zinc air secondary battery. The air cathode is formed by bonding a current collector, a waterproof ventilation layer and a catalytic layer in sequence through a bonder; the current collector is carbon paper subjected to hydrophobic treatment; the waterproof ventilation layer is acetylene black; and the catalytic layer is the boron-nitrogen-carbon ternary covalent composite material taking carbon black as a substrate. The air cathode provided by the invention has high hydrophobicity, high conductivity, good catalytic property and high stability.
Description
Technical field
The present invention relates to zinc-air battery field, especially a kind of synthesis of novel catalyst material, zinc air secondary
The the designing and producing of battery device, the optimization of gas-diffusion electrode and preparation method thereof.
Background technology
Zinc-air battery makees positive active material as the one kind in the air cell of metal one with oxygen, electrode potential compared with
Negative metallic zinc makees negative pole, and the electrolyte aqueous solution of neutral or alkalescence is used as electrolyte.Zinc-air battery is divided into one-shot battery
With secondary cell.Compared with one-shot battery, the characteristics of not only there is zinc air secondary battery battery to have fuel cell again, it compares
Energy height, good specific capacity, stable performance, electric discharge steady, storage time length and little is polluted to ecological safety using safety, therefore
With great market prospects.
But still there is wretched insufficiency in zinc-air battery, such as gas-diffusion electrode electric conductivity is poor, catalytic efficiency is low,
Heavy-current discharge is unstable, discharge time falls short of, and seriously limits the development of zinc-air battery.Zinc air secondary battery exists
Irreversible change is also occurred that in charge and discharge process between electrode volume and structure, causes electrode material expansion, dry linting, affect it
Service life.The key factor for determining zinc air secondary battery performance is electrode material.At present, electrode commonly used on market
Material is noble metal platinum and its alloy material, platinum high cost, worldwide scarcity of resources, it is difficult to popularization on a large scale
Using.The covalent composite of boron nitrogen carbon ternary is suitable with business Pt/C to the catalytic current density of oxygen reduction reaction；Oxygen is separated out
A spike potential of reaction and limiting current density are better than business Pt/C, are a kind of bifunctional catalysts of superior performance.Boron nitrogen carbon
The covalent composite of ternary has loose structure, using the teaching of the invention it is possible to provide big active surface, its electron transfer number shows oxygen close to four
Gas reduction process is mainly four electron paths, and oxygen is directly reduced into OH-, improve electron transmission during oxygen reduction
Efficiency, reduces polarization of electrode, so as to improve the output voltage and power output of battery.
The design of zinc air secondary battery device also plays an important role to the care and maintenance during battery use.
No leakage, the quick detachable and easy device for replacing electrolyte and zinc metal sheet are how made, good permeability, hydrophobicity height how is prepared, is led
The electrical high and high air cathode of catalytic, and how the covalent composite of boron nitrogen carbon ternary is added into zinc air secondary electricity
Pond, improves that battery conductive is poor, catalytic efficiency is low, the problem that heavy-current discharge is unstable, is the problem to be solved in the present invention.
The content of the invention
It is an object of the present invention to overcome prior art not enough, there is provided one kind has high hydrophobicity, high conductivity, height
Air electrode based on the covalent composite of boron nitrogen carbon ternary of catalytic and high stability energy and preparation method thereof.
It is also another object of the present invention to provide a kind of good airproof performance, the quick detachable and easy zinc sky for replacing electrolyte and zinc metal sheet
Gas secondary cell.
For achieving the above object, the technical solution used in the present invention is：
A kind of air electrode based on the covalent composite of boron nitrogen carbon ternary, the air electrode is successively by collector, anti-
Water air-permeable layer and Catalytic Layer are combined composition by binding agent, the collector for Jing hydrophobic treatments carbon paper, the waterproof and breathable
Layer is acetylene black, and the Catalytic Layer is the covalent composite of boron nitrogen carbon ternary with carbon black as substrate.
The covalent composite of the boron nitrogen carbon ternary be diameter 210nm, wall thickness for 20nm bead.
The covalent composite of the boron nitrogen carbon ternary be prepared via a method which obtained by:
The template ball that synthesis can be stripped, adds Syringaresinol, para hydroxybenzene boric acid and aldehyde in the aqueous solution of template ball,
React under the pressure of 0-3MPa, cooling adds nitrogen source in reactant liquor, stirs 12-24h, be heated to 25 DEG C of -45 DEG C of removing water
Point, then it is combined at 600 DEG C -1100 DEG C of temperature and has the nanosphere of boron carbon and the mixture of nitrogen source, obtain boron nitrogen carbon
Three element composite Nano ball materials, then be centrifuged after template is peeled off, wash, be dried, obtain the covalent composite of boron nitrogen carbon ternary.
The binding agent is ptfe emulsion.
A kind of zinc air secondary battery based on the covalent composite of boron nitrogen carbon ternary, including zinc anode, electrolyte and sky
Pneumoelectric pole, it is characterised in that：The air electrode is combined group with Catalytic Layer by collector, waterproof ventilative layer by binding agent successively
Into the collector is the carbon paper of Jing hydrophobic treatments, and the waterproof ventilative layer is acetylene black, and it is substrate that the Catalytic Layer is carbon black
The covalent composite of boron nitrogen carbon ternary.
Specifically, the zinc air secondary battery includes the electrolyte cavities of a cubic shaped, and one used as zinc anode
Zinc metal sheet, gasket seal, graphite flake, air electrode, cathode shell, the top of the electrolyte cavities is top shell, is opened up in top shell
There is an electrolyte injecting hole, and be available for the strip hole that zinc metal sheet passes through；Gasket seal, graphite flake, air electrode, cathode shell are successively
Superposition, as a side wall of electrolyte cavities；Top shell, electrolyte cavities, the material of cathode shell are polymethyl methacrylate material
Material.
A kind of preparation method of the air electrode based on the covalent composite of boron nitrogen carbon ternary, comprises the following steps：
(1) carbon paper for cutting is impregnated in ptfe emulsion, carries out hydrophobic treatment, be then dried at 80 DEG C
30min, at 360 DEG C 30min is sintered；
(2) by acetylene black and ptfe emulsion dispersion mixing in ethanol, ultrasound, stirring；
(3) the mixed liquor pressure that step (2) is obtained is atomized on by hydrophobic treatment using the technology mode of pressure atomization
The one side of carbon paper, at 80 DEG C 30min is dried, and at 360 DEG C 30min is sintered；
(4) by activated carbon, the covalent composite of boron nitrogen carbon ternary and ptfe emulsion dispersion mixing in ethanol surpasses
Sound, stirring；
(5) the mixed liquor pressure that step (4) is obtained is atomized on by hydrophobic treatment using the technology mode of pressure atomization
The another side of carbon paper, at 80 DEG C 30min is dried, and at 360 DEG C 30min is sintered, and obtains final product the air electrode.
In step (1), the mass concentration of ptfe emulsion is 5wt%～60wt%, and dip time is 5～40min.
In step (2), acetylene black is 7 with the mass ratio of ptfe emulsion:3～2:8, the matter of ptfe emulsion
Amount concentration is 5wt%～60wt%, and the carbon carrying capacity of acetylene black is 0.5～1.5mg/cm2。
In step (4), the covalent composite of boron nitrogen carbon ternary, activated carbon is 2 with the mass ratio of ptfe emulsion:2:
0.5～2:2:5, polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, and the carbon carrying capacity of the covalent composite of boron nitrogen carbon ternary is
0.5～2.0mg/cm2。
Beneficial effect：
(1) zinc air secondary battery device of the invention, it by polymethyl methacrylate materials is main body to be, graphite flake is
The carrying tablet of working electrode, rubber sheet gasket is aided in consolidating the mould of sealing.It has good seal performance, facilitates dismounting to replace
Electrolyte and zinc anode, convenient cleaning are changed, and is easy to observe internal-response situation.
(2) the covalent composite of boron nitrogen carbon ternary, with loose structure, using the teaching of the invention it is possible to provide big active surface, its electronics turns
Number is moved close to four, shows that oxygen reduction process is mainly four electron paths, oxygen is directly reduced into OH-, improve oxygen
The efficiency of electron transmission, reduces polarization of electrode in reduction process, so as to improve the output voltage and power output of battery.
The covalent composite of boron nitrogen carbon ternary is suitable with business Pt/C to the catalytic current density of oxygen reduction reaction；Oxygen evolution reaction rise
Spike potential and limiting current density are better than business Pt/C, are a kind of bifunctional catalysts of superior performance.The present invention by by this
Bifunctional catalyst is added in the air electrode of zinc-air battery, realizes charge and discharge cycles, improves zinc air secondary battery
Electric conductivity, improve the catalytic performance of battery, and using cost-effective without metal-doped catalyst, reduce to environment
Pollution.
(3) under a certain pressure, waterproof ventilative layer and Catalytic Layer are prepared using the technology mode pressure atomization of pressure atomization,
The air electrode prepared in this manner, defines densification, uniform microcellular structure, and the performance of liquid and gas mass transfer is obtained
Improve, then through optimization step by step so that hydrophobicity, electric conductivity and stability is obtained for and significantly improves.
Description of the drawings
Fig. 1 is the structural representation of the zinc air secondary battery based on the covalent composite of boron nitrogen carbon ternary of the present invention；
Fig. 2 is the contrast of the catalyst without metal with the polarization curves of oxygen reduction figure of business Pt/C of different doping；
Fig. 3 is the hydrogen reduction energy density profile of the catalyst without metal with business Pt/C of different doping；
Fig. 4 is the specific volume spirogram of zinc-air battery；
Fig. 5 is electric discharge figure of the covalent composite of boron nitrogen carbon ternary from business Pt/C under different current densities；
Fig. 6 is the polarization curve that the covalent composite of boron nitrogen carbon ternary is separated out with the hydrogen reduction of business Pt/C with oxygen；
Fig. 7 is the charge and discharge cycles figure of zinc-air battery.
Specific embodiment
The present invention is further described below in conjunction with the accompanying drawings.
It is illustrated in figure 1 a kind of zinc air secondary battery based on the covalent composite of boron nitrogen carbon ternary, including zinc anode,
Electrolyte and air electrode, it is characterised in that：The air electrode is successively by collector, waterproof ventilative layer and Catalytic Layer by viscous
Knot agent combines composition, and the collector is the carbon paper of Jing hydrophobic treatments, and the waterproof ventilative layer is acetylene black, and the Catalytic Layer is
Carbon black is the covalent composite of boron nitrogen carbon ternary of substrate.Specifically, including a cubic shaped electrolyte cavities 4, one
Used as the zinc metal sheet 1 of zinc anode, gasket seal 5, graphite flake 6, air electrode 7, cathode shell 8, the top of the electrolyte cavities 4 is
Top shell 3, offers electrolyte injecting hole 2 in top shell 3, and is available for the strip hole 10 that zinc metal sheet 1 passes through；Gasket seal 5, graphite flake
6th, air electrode 7, cathode shell 8 are sequentially overlapped, and as a side wall of electrolyte cavities 4, and are fixed on electrolyte by screw 9
On chamber 4；Top shell 3, electrolyte cavities 4, the material of cathode shell 8 are polymethyl methacrylate materials.
The zinc air secondary battery invented, using from the zinc air secondary battery device for designing and producing, is by poly- methyl-prop
E pioic acid methyl ester material is main body, graphite flake 6 for working electrode carrying tablet, rubber sheet gasket 5 is aided in consolidating sealing to be caused
Positive pole housing is combined tightr with electrolyte housing, it is therefore prevented that the mould of the seepage of inside battery liquid.Top device is provided with two
Individual electrolyte injecting hole 2, electrolyte can be taken away and while inject new electrolyte, zinc metal sheet 1 is directly by top insertion battery
Portion, can quickly and easily be replaced to it, carry out the mould of the discharge and recharge of long-time stable.With the KOH solution of 6M as electrolysis
Liquid, using Shanghai Chen Hua instrument companies CHI660 electrochemical workstations (Chinese Shanghai) zinc air secondary is tested under air ambient
The chemical property of battery.
Embodiment 1
The carbon paper of 2cm*2cm is impregnated into 5min, 10min, 15min, 20min in the ptfe emulsion of 15wt%,
25min, 30min, 40min, are optimized to the hydrophobic time.
Embodiment 2
The carbon paper of 2cm*2cm is impregnated in 0wt%, the ptfe emulsion of 5wt%, 10wt%, 15wt%
10min, is optimized to hydrophobe concentration.
Embodiment 3
By carbon paper, in ptfe emulsion, (polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, is selected in this example
10wt%) in dipping (dip time is 5～40min, and 20min has been selected in this example), carry out hydrophobic treatment, at 80 DEG C
30min is dried, at 360 DEG C 30min is sintered；Can be by acetylene black and ptfe emulsion (acetylene black and polytetrafluoroethylene (PTFE) breast
The mass ratio of liquid is 7:3～2:8, in this example from 6:4；Polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, in this example
In selected 60wt%；The carbon carrying capacity of acetylene black is 0.5～1.5mg/cm2, 1mg/cm has been selected in this example2) divide in ethanol
Mixing is dissipated, under a certain pressure, above-mentioned mixed liquor pressure is atomized on by hydrophobic treatment using the technology mode of pressure atomization
The one side of carbon paper, at 80 DEG C 30min is dried, and at 360 DEG C 30min is sintered；
By activated carbon, the covalent composite of boron nitrogen carbon ternary and ptfe emulsion (the covalent composite wood of boron nitrogen carbon ternary
Material, activated carbon is 2 with the mass ratio of ptfe emulsion:2:0.5～2:2:5,2 have been selected in this example:2:1；Polytetrafluoro
Ethylene mass concentration is 5wt%～60wt%, and 20wt% has been selected in this example；The carbon of the covalent composite of boron nitrogen carbon ternary is carried
Measure as 0.5～2.0mg/cm2, 1mg/cm has been selected in this example2) dispersion mixing in ethanol；Using the technique side of pressure atomization
Above-mentioned mixed liquor pressure is atomized on formula the another side of the carbon paper of hydrophobic treatment, and at 80 DEG C 30min is dried, at 360 DEG C
Sintering 30min, obtains final product the air diffusion electrode.
The covalent composite catalyst of above-mentioned boron nitrogen carbon ternary be prepared via a method which obtained by:Synthesis can be stripped
Template ball, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball, react under the pressure of 0-3MPa,
Cooling, adds nitrogen source in reactant liquor, stirs 12-24h, is heated to 25 DEG C of -45 DEG C of removing moisture, then 600 DEG C of temperature -
It is combined at 1100 DEG C and has the nanosphere of boron carbon and the mixture of nitrogen source, obtains the element composite Nano ball material of boron nitrogen carbon three
Material, then be centrifuged after template is peeled off, wash, be dried, obtain the covalent composite of boron nitrogen carbon ternary.
The zinc air secondary battery air electrode that the present embodiment is prepared is sequentially disposed in waterproof ventilative layer, collector, urges
Change layer, according to air electrode prepared by this order of placement, hydrophobic performance, electric conductivity, catalytic performance are of a relatively high, and battery dissipates
Thermal effect is also splendid.
Embodiment 4
By carbon paper, in ptfe emulsion, (polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, is selected in this example
10wt%) in dipping (dip time is 5～40min, and 20min has been selected in this example), carry out hydrophobic treatment, at 80 DEG C
30min is dried, at 360 DEG C 30min is sintered；
By acetylene black and ptfe emulsion, (acetylene black is 7 with the mass ratio of ptfe emulsion:3～2:8,
6 are selected in this example:4；Polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, and 60wt% has been selected in this example；Acetylene black
Carbon carrying capacity is 0.7～1.5mg/cm2, 1mg/cm has been selected in this example2) dispersion mixing in ethanol, under a certain pressure, adopt
Above-mentioned mixed liquor pressure is atomized on the one side of the carbon paper of hydrophobic treatment with the technology mode of pressure atomization, is dried at 80 DEG C
30min, at 360 DEG C 30min is sintered；
By activated carbon, the covalent composite of boron nitrogen carbon ternary and ptfe emulsion (the covalent composite wood of boron nitrogen carbon ternary
Material, activated carbon is 2 with the mass ratio of ptfe emulsion:2:0.5～2:2:5,2 have been selected in this example:2:2；Polytetrafluoro
Ethylene mass concentration is 5wt%～60wt%, and 20wt% has been selected in this example；The carbon of the covalent composite of boron nitrogen carbon ternary is carried
Measure as 0.5～2.0mg/cm2, 1mg/cm has been selected in this example2) dispersion mixing in ethanol；Under a certain pressure, using pressure
Above-mentioned mixed liquor pressure is atomized on the technology mode of power atomization the another side of the carbon paper of hydrophobic treatment, is dried at 80 DEG C
30min, at 360 DEG C 30min is sintered, and obtains final product the air diffusion electrode.
The covalent composite catalyst of above-mentioned boron nitrogen carbon ternary be prepared via a method which obtained by:Synthesis can be stripped
Template ball, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball, react in a high voltage state, cool down,
Nitrogen source is added in reactant liquor, a few hours are stirred, moisture is heated away, high temperature is combined the nanosphere and nitrogen source for having boron carbon
Mixture, obtain the element composite Nano ball material of boron nitrogen carbon three, then centrifugation, washing after template is peeled off, be dried, obtain boron nitrogen
The covalent composite of carbon ternary.
The pole piece for preparing is carried out into electro-chemical test, chemical property is tested after being placed in water 2 days again.
Embodiment 5
By carbon paper, in ptfe emulsion, (polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, is selected in this example
10wt%) in dipping (dip time is 5～40min, and 20min has been selected in this example), carry out hydrophobic treatment, at 80 DEG C
30min is dried, at 360 DEG C 30min is sintered；
By acetylene black and ptfe emulsion, (acetylene black is 7 with the mass ratio of ptfe emulsion:3～2:8,
6 are selected in this example:4；Polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, and 60wt% has been selected in this example；Acetylene black
Carbon carrying capacity is 0.7～1.5mg/cm2, 1mg/cm has been selected in this example2) dispersion mixing in ethanol, under a certain pressure, adopt
Above-mentioned mixed liquor pressure is atomized on the one side of the carbon paper of hydrophobic treatment with the technology mode of pressure atomization, is dried at 80 DEG C
30min, at 360 DEG C 30min is sintered；
By activated carbon, the covalent composite of boron nitrogen carbon ternary and ptfe emulsion (the covalent composite wood of boron nitrogen carbon ternary
Material, activated carbon is 2 with the mass ratio of ptfe emulsion:2:0.5～2:2:5,2 have been selected in this example:2:2；Polytetrafluoro
Ethylene mass concentration is 5wt%～60wt%, and 20wt% has been selected in this example；The carbon of the covalent composite of boron nitrogen carbon ternary is carried
Measure as 0.5～2.0mg/cm2, 1mg/cm has been selected in this example2) in ethanol dispersion mixing under a certain pressure, using pressure
Above-mentioned mixed liquor pressure is atomized on the technology mode of atomization the another side of the carbon paper of hydrophobic treatment, is dried at 80 DEG C
30min, at 360 DEG C 30min is sintered, and obtains final product the air diffusion electrode.
The covalent composite catalyst of above-mentioned boron nitrogen carbon ternary be prepared via a method which obtained by:Synthesis can be stripped
Template ball, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball, react in a high voltage state, cool down,
Nitrogen source is added in reactant liquor, a few hours are stirred, moisture is heated away, high temperature is combined the nanosphere and nitrogen source for having boron carbon
Mixture, obtain the element composite Nano ball material of boron nitrogen carbon three, then centrifugation, washing after template is peeled off, be dried, obtain boron nitrogen
The covalent composite of carbon ternary.
The pole piece for preparing is carried out into electro-chemical test, is placed in vacuum after 2 days and is tested chemical property again.Be placed in
Pole piece in water compares, and the air electrode being placed in vacuum, chemical property is more stable.
Embodiment 6
By carbon paper, in ptfe emulsion, (polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, is selected in this example
10wt%) in dipping (dip time is 5～40min, and 20min has been selected in this example), carry out hydrophobic treatment, at 80 DEG C
30min is dried, at 360 DEG C 30min is sintered；
By acetylene black and ptfe emulsion, (acetylene black is 7 with the mass ratio of ptfe emulsion:3～2:8,
6 are selected in this example:4；Polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, and 60wt% has been selected in this example；Acetylene black
Carbon carrying capacity is 0.7～1.5mg/cm2, 1mg/cm has been selected in this example2) dispersion mixing in ethanol, under a certain pressure, adopt
Above-mentioned mixed liquor pressure is atomized on the one side of the carbon paper of hydrophobic treatment with the technology mode of pressure atomization, is dried at 80 DEG C
30min, at 360 DEG C 30min is sintered；
By activated carbon, the covalent composite of boron nitrogen carbon ternary and ptfe emulsion (the covalent composite wood of boron nitrogen carbon ternary
Material, activated carbon is 2 with the mass ratio of ptfe emulsion:2:0.5～2:2:5,2 have been selected in this example:2:2；Polytetrafluoro
Ethylene mass concentration is 5wt%～60wt%, and 20wt% has been selected in this example；The carbon of the covalent composite of boron nitrogen carbon ternary is carried
Measure as 0.5～2.0mg/cm2, 1mg/cm has been selected in this example2) dispersion mixing in ethanol；Under a certain pressure, using pressure
Above-mentioned mixed liquor pressure is atomized on the technology mode of power atomization the another side of the carbon paper of hydrophobic treatment, is dried at 80 DEG C
30min, at 360 DEG C 30min is sintered, and obtains final product the air diffusion electrode.
The covalent composite catalyst of above-mentioned boron nitrogen carbon ternary be prepared via a method which obtained by:Synthesis can be stripped
Template ball, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball, react in a high voltage state, cool down,
Nitrogen source is added in reactant liquor, a few hours are stirred, moisture is heated away, high temperature is combined the nanosphere and nitrogen source for having boron carbon
Mixture, obtain the element composite Nano ball material of boron nitrogen carbon three, then centrifugation, washing after template is peeled off, be dried, obtain boron nitrogen
The covalent composite of carbon ternary.
Embodiment 7
By carbon paper, in ptfe emulsion, (polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, is selected in this example
10wt%) in dipping (dip time is 5～40min, and 20min has been selected in this example), carry out hydrophobic treatment, at 80 DEG C
30min is dried, at 360 DEG C 30min is sintered；
By acetylene black and ptfe emulsion, (acetylene black is 7 with the mass ratio of ptfe emulsion:3～2:8,
6 are selected in this example:4；Polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, and 60wt% has been selected in this example；Acetylene black
Carbon carrying capacity is 0.7～1.5mg/cm2, 1mg/cm has been selected in this example2) dispersion mixing in ethanol, under a certain pressure, adopt
Above-mentioned mixed liquor pressure is atomized on the one side of the carbon paper of hydrophobic treatment with the technology mode of pressure atomization, is dried at 80 DEG C
30min, at 360 DEG C 30min is sintered；
By activated carbon, the covalent composite of boron nitrogen carbon ternary and ptfe emulsion (the covalent composite wood of boron nitrogen carbon ternary
Material, activated carbon is 2 with the mass ratio of ptfe emulsion:2:0.5～2:2:5,2 have been selected in this example:2:3；Polytetrafluoro
Ethylene mass concentration is 5wt%～60wt%, and 20wt% has been selected in this example；The carbon of the covalent composite of boron nitrogen carbon ternary is carried
Measure as 0.5～2.0mg/cm2, 1mg/cm has been selected in this example2) dispersion mixing in ethanol；Under a certain pressure, using pressure
Above-mentioned mixed liquor pressure is atomized on the technology mode of power atomization the another side of the carbon paper of hydrophobic treatment, is dried at 80 DEG C
30min, at 360 DEG C 30min is sintered, and obtains final product the air diffusion electrode.
The covalent composite catalyst of above-mentioned boron nitrogen carbon ternary be prepared via a method which obtained by:Synthesis can be stripped
Template ball, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball, react in a high voltage state, cool down,
Nitrogen source is added in reactant liquor, a few hours are stirred, moisture is heated away, high temperature is combined the nanosphere and nitrogen source for having boron carbon
Mixture, obtain the element composite Nano ball material of boron nitrogen carbon three, then centrifugation, washing after template is peeled off, be dried, obtain boron nitrogen
The covalent composite of carbon ternary.
Embodiment 8
By carbon paper, in ptfe emulsion, (polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, is selected in this example
10wt%) in dipping (dip time is 5～40min, and 20min has been selected in this example), carry out hydrophobic treatment, at 80 DEG C
30min is dried, at 360 DEG C 30min is sintered；
By acetylene black and ptfe emulsion, (acetylene black is 7 with the mass ratio of ptfe emulsion:3～2:8,
6 are selected in this example:4；Polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, and 60wt% has been selected in this example；Acetylene black
Carbon carrying capacity is 0.7～1.5mg/cm2, 0.5mg/cm has been selected in this example2) dispersion mixing in ethanol, under a certain pressure,
Above-mentioned mixed liquor pressure is atomized on using the technology mode of pressure atomization for the one side of the carbon paper of hydrophobic treatment, is done at 80 DEG C
Dry 30min, at 360 DEG C 30min is sintered；
By activated carbon, the covalent composite of boron nitrogen carbon ternary and ptfe emulsion (the covalent composite wood of boron nitrogen carbon ternary
Material, activated carbon is 2 with the mass ratio of ptfe emulsion:2:0.5～2:2:5,2 have been selected in this example:2:4；Polytetrafluoro
Ethylene mass concentration is 5wt%～60wt%, and 20wt% has been selected in this example；The carbon of the covalent composite of boron nitrogen carbon ternary is carried
Measure as 0.5～2.0mg/cm2, 1mg/cm has been selected in this example2) dispersion mixing in ethanol；Under a certain pressure, using pressure
Above-mentioned mixed liquor pressure is atomized on the technology mode of power atomization the another side of the carbon paper of hydrophobic treatment, is dried at 80 DEG C
30min, at 360 DEG C 30min is sintered, and obtains final product the air diffusion electrode.
The covalent composite catalyst of above-mentioned boron nitrogen carbon ternary be prepared via a method which obtained by:Synthesis can be stripped
Template ball, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball, react in a high voltage state, cool down,
Nitrogen source is added in reactant liquor, a few hours are stirred, moisture is heated away, high temperature is combined the nanosphere and nitrogen source for having boron carbon
Mixture, obtain the element composite Nano ball material of boron nitrogen carbon three, then centrifugation, washing after template is peeled off, be dried, obtain boron nitrogen
The covalent composite of carbon ternary.
Embodiment 9
By carbon paper, in ptfe emulsion, (polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, is selected in this example
10wt%) in dipping (dip time is 5～40min, and 20min has been selected in this example), carry out hydrophobic treatment, at 80 DEG C
30min is dried, at 360 DEG C 30min is sintered；
By acetylene black and ptfe emulsion, (acetylene black is 7 with the mass ratio of ptfe emulsion:3～2:8,
6 are selected in this example:4；Polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, and 60wt% has been selected in this example；Acetylene black
Carbon carrying capacity is 0.7～1.5mg/cm2, 0.8mg/cm has been selected in this example2) dispersion mixing in ethanol, under a certain pressure,
Above-mentioned mixed liquor pressure is atomized on using the technology mode of pressure atomization for the one side of the carbon paper of hydrophobic treatment, is done at 80 DEG C
Dry 30min, at 360 DEG C 30min is sintered；
By activated carbon, the covalent composite of boron nitrogen carbon ternary and ptfe emulsion (the covalent composite wood of boron nitrogen carbon ternary
Material, activated carbon is 2 with the mass ratio of ptfe emulsion:2:0.5～2:2:5,2 have been selected in this example:2:3；Polytetrafluoro
Ethylene mass concentration is 5wt%～60wt%, and 20wt% has been selected in this example；Boron doping hollow carbon balls, N doping hollow carbon
The carbon carrying capacity of ball, the covalent composite of boron nitrogen carbon ternary and commercially available 40wt%Pt/C is 0.5～2.0mg/cm2, in this example
In selected 1.0mg/cm2) dispersion mixing in ethanol；Under a certain pressure, will be above-mentioned using the technology mode of pressure atomization
Mixed liquor pressure is atomized on the another side of the carbon paper of hydrophobic treatment, and at 80 DEG C 30min is dried, and sinters at 360 DEG C
30min, obtains final product the air diffusion electrode.Zinc air secondary battery is assembled them into, charge and discharge electric polarization curve, constant current is carried out
Electric discharge and charge and discharge cycles test.
The covalent composite catalyst of above-mentioned boron nitrogen carbon ternary be prepared via a method which obtained by:Synthesis can be stripped
Template ball, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball, react in a high voltage state, cool down,
Nitrogen source is added in reactant liquor, a few hours are stirred, moisture is heated away, high temperature is combined the nanosphere and nitrogen source for having boron carbon
Mixture, obtain the element composite Nano ball material of boron nitrogen carbon three, then centrifugation, washing after template is peeled off, be dried, obtain boron nitrogen
The covalent composite of carbon ternary.
The above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of air electrode based on the covalent composite of boron nitrogen carbon ternary, it is characterised in that：The air electrode successively by
Collector, waterproof ventilative layer are combined composition with Catalytic Layer by binding agent, and the collector is the carbon paper of Jing hydrophobic treatments, described
Waterproof ventilative layer is acetylene black, and the Catalytic Layer is the covalent composite of boron nitrogen carbon ternary with carbon black as substrate.
2. the air electrode based on the covalent composite of boron nitrogen carbon ternary according to claim 1, it is characterised in that：It is described
The bead that the covalent composite of boron nitrogen carbon ternary is diameter 210nm, wall thickness is 20nm.
3. the air electrode based on the covalent composite of boron nitrogen carbon ternary according to claim 1 and 2, it is characterised in that：
The covalent composite of the boron nitrogen carbon ternary be prepared via a method which obtained by:
The template ball that synthesis can be stripped, adds Syringaresinol, para hydroxybenzene boric acid and aldehyde, in 0- in the aqueous solution of template ball
React under the pressure of 3MPa, cooling adds nitrogen source in reactant liquor, stirs 12-24h, be heated to 25 DEG C of -45 DEG C of removing moisture,
Then it is combined at 600 DEG C -1100 DEG C of temperature and has the nanosphere of boron carbon and the mixture of nitrogen source, obtains boron nitrogen carbon ternary
Plain composite Nano ball material, then be centrifuged after template is peeled off, wash, be dried, obtain the covalent composite of boron nitrogen carbon ternary.
4. the air electrode based on the covalent composite of boron nitrogen carbon ternary according to claim 1, it is characterised in that：It is described
Binding agent is ptfe emulsion.
5. a kind of zinc air secondary battery based on the covalent composite of boron nitrogen carbon ternary, including zinc anode, electrolyte and air
Electrode, it is characterised in that：The air electrode is combined group with Catalytic Layer by collector, waterproof ventilative layer by binding agent successively
Into the collector is the carbon paper of Jing hydrophobic treatments, and the waterproof ventilative layer is acetylene black, and it is substrate that the Catalytic Layer is carbon black
The covalent composite of boron nitrogen carbon ternary.
6. the zinc air secondary battery based on the covalent composite of boron nitrogen carbon ternary according to claim 5, its feature exists
In：Including the electrolyte cavities (4) of a cubic shaped, a zinc metal sheet (1) as zinc anode, gasket seal (5), graphite flake
(6), air electrode (7), cathode shell (8), the top of the electrolyte cavities (4) is top shell (3), and top shell offers electricity on (3)
Solution liquid hand-hole (2), and it is available for the strip hole (10) that zinc metal sheet (1) passes through；Gasket seal (5), graphite flake (6), air electrode
(7), cathode shell (8) is sequentially overlapped, used as a side wall of electrolyte cavities (4)；Outside top shell (3), electrolyte cavities (4), negative electrode
The material of shell (8) is polymethyl methacrylate materials.
7. a kind of preparation method of the air electrode based on the covalent composite of boron nitrogen carbon ternary, it is characterised in that：Including following
Step：
(1) carbon paper for cutting is impregnated in ptfe emulsion, carries out hydrophobic treatment, be then dried at 80 DEG C
30min, at 360 DEG C 30min is sintered；
(2) by acetylene black and ptfe emulsion dispersion mixing in ethanol, ultrasound, stirring；
(3) the mixed liquor pressure that step (2) is obtained is atomized on using the technology mode of pressure atomization for the carbon paper of hydrophobic treatment
One side, be dried 30min at 80 DEG C, sinter 30min at 360 DEG C；
(4) by activated carbon, the covalent composite of boron nitrogen carbon ternary and ptfe emulsion dispersion mixing in ethanol, ultrasound,
Stirring；
(5) the mixed liquor pressure that step (4) is obtained is atomized on using the technology mode of pressure atomization for the carbon paper of hydrophobic treatment
Another side, be dried 30min at 80 DEG C, sinter 30min at 360 DEG C, obtain final product the air electrode.
8. the preparation method of the air electrode of the covalent composite of boron nitrogen carbon ternary, its feature are based on as claimed in claim 7
It is：In step (1), the mass concentration of ptfe emulsion is 5wt%～60wt%, and dip time is 5～40min.
9. the preparation method of the air electrode of the covalent composite of boron nitrogen carbon ternary, its feature are based on as claimed in claim 7
It is：In step (2), acetylene black is 7 with the mass ratio of ptfe emulsion:3～2:8, the quality of ptfe emulsion
Concentration is 5wt%～60wt%, and the carbon carrying capacity of acetylene black is 0.5～1.5mg/cm2。
10. the preparation method of the air electrode of the covalent composite of boron nitrogen carbon ternary, its feature are based on as claimed in claim 7
It is：In step (4), the covalent composite of boron nitrogen carbon ternary, activated carbon is 2 with the mass ratio of ptfe emulsion:2:0.5
～2:2:5, polytetrafluoroethylene (PTFE) mass concentration is 5wt%～60wt%, and the carbon carrying capacity of the covalent composite of boron nitrogen carbon ternary is 0.5
～2.0mg/cm2。
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| CN109962321A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | A kind of test device in oxygen reduction cathode service life |
| CN109975706A (en) * | 2017-12-14 | 2019-07-05 | 中国科学院大连化学物理研究所 | A kind of test method in oxygen reduction cathode service life |
| CN110193374A (en) * | 2019-07-01 | 2019-09-03 | 山东大学 | Boron carbon nitrogen electrocatalysis material and preparation method thereof and the application in nitrogen reduction synthesis ammonia |
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