CN106654295B - A kind of air cathode based on the covalent composite material of boron nitrogen carbon ternary and preparation method thereof and zinc air secondary cell - Google Patents
A kind of air cathode based on the covalent composite material of boron nitrogen carbon ternary and preparation method thereof and zinc air secondary cell Download PDFInfo
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- CN106654295B CN106654295B CN201710034232.2A CN201710034232A CN106654295B CN 106654295 B CN106654295 B CN 106654295B CN 201710034232 A CN201710034232 A CN 201710034232A CN 106654295 B CN106654295 B CN 106654295B
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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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- H01M4/00—Electrodes
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- 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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Abstract
The invention discloses a kind of air cathodes based on the covalent composite material of boron nitrogen carbon ternary and preparation method thereof and zinc air secondary cell, the air electrode successively by collector, waterproof ventilative layer and Catalytic Layer by binder in conjunction with form, the collector is the carbon paper through hydrophobic treatment, the waterproof ventilative layer is acetylene black, and the Catalytic Layer is the covalent composite material of boron nitrogen carbon ternary that carbon black is substrate.Air cathode provided by the invention has high hydrophobicity, high conductivity, high catalytic property and high stability energy.
Description
Technical field
The present invention relates to zinc-air battery field, especially a kind of synthesis of novel catalyst material, zinc air is secondary
The the designing and producing of battery device, the optimization of gas-diffusion electrode and preparation method thereof.
Background technique
Zinc-air battery makees positive active material as one of one air cell of metal, with oxygen, electrode potential compared with
Negative metallic zinc makees cathode, and neutral or alkalinity electrolyte aqueous solution is as electrolyte.Zinc-air battery is divided into one-shot battery
With secondary cell.Compared with one-shot battery, zinc air secondary cell had not only had the characteristics that battery but also had had fuel cell, ratio
Energy is high, specific capacity is good, performance is stable, electric discharge is steady, storage time is long and it is safe small to ecological safety pollution to use, therefore
With great market prospects.
But zinc-air battery still remains wretched insufficiency, for example gas-diffusion electrode electric conductivity is poor, catalytic efficiency is low,
Being large current discharge unstable, discharge time falls short of, and seriously limits the development of zinc-air battery.Zinc air secondary cell exists
It also occur that irreversible change, leads to electrode material expansion, picking, influence it between electrode volume and structure in charge and discharge process
Service life.The key factor for determining zinc air secondary cell performance is electrode material.Currently, commonly used electrode in the market
Material is noble metal platinum and its alloy material, and platinum is at high cost, worldwide scarcity of resources, it is difficult to universal on a large scale
Using.The boron covalent composite material of nitrogen carbon ternary is suitable with business Pt/C to the catalytic current density of oxygen reduction reaction；Oxygen is precipitated
Reaction plays spike potential and limiting current density better than business Pt/C, is a kind of bifunctional catalyst of superior performance.Boron nitrogen carbon
The covalent composite material of ternary has porous structure, is capable of providing big active surface, 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, to improve the output voltage and output power of battery.
The design of zinc air secondary cell device also plays an important role to the care and maintenance in battery use process.
No leakage, quick detachable and easy replacement electrolyte and zinc metal sheet device are how made, how to prepare that good permeability, hydrophobicity are high, lead
The electrically high and high air cathode of catalytic, and how the covalent composite material of boron nitrogen carbon ternary is added to the secondary electricity of zinc air
Pond improves the problem that battery conductive is poor, catalytic efficiency is low, heavy-current discharge is unstable, is the problem to be solved in the present invention.
Summary of the invention
It is an object of the present invention to overcome the shortage of prior art, provide a kind of with high hydrophobicity, high conductivity, height
The air electrode and preparation method thereof based on the covalent composite material of boron nitrogen carbon ternary of catalytic and high stability energy.
It is also another object of the present invention to provide the zinc of a kind of good airproof performance, quick detachable and easy replacement electrolyte and zinc metal sheet is empty
Gas secondary cell.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of air electrode based on the covalent composite material of boron nitrogen carbon ternary, the air electrode is successively by collector, anti-
Water air-permeable layer and Catalytic Layer by binder in conjunction with form, the collector is the carbon paper through hydrophobic treatment, the waterproof and breathable
Layer is acetylene black, and the Catalytic Layer is using carbon black as the covalent composite material of boron nitrogen carbon ternary of substrate.
The covalent composite material of the boron nitrogen carbon ternary is diameter 210nm, the bead that wall thickness is 20nm.
The covalent composite material of the boron nitrogen carbon ternary is obtained by being prepared via a method which:
The template ball that can be stripped is synthesized, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball,
It is reacted under the pressure of 0-3MPa, it is cooling, nitrogen source is added in reaction solution, stirs 12-24h, is heated to 25 DEG C of -45 DEG C of removing water
Point, then at 600 DEG C -1100 DEG C of temperature the compound nanosphere for having boron carbon and nitrogen source mixture, obtain boron nitrogen carbon
Three element composite Nano ball materials, then be centrifuged after template is removed, washing, drying, obtain the covalent composite material of boron nitrogen carbon ternary.
The binder is ptfe emulsion.
A kind of zinc air secondary cell based on the covalent composite material of boron nitrogen carbon ternary, including zinc anode, electrolyte and sky
Pneumoelectric pole, it is characterised in that: the air electrode successively by collector, waterproof ventilative layer and Catalytic Layer by binder in conjunction with group
At the collector is the carbon paper through hydrophobic treatment, and the waterproof ventilative layer is acetylene black, and the Catalytic Layer is that carbon black is substrate
The covalent composite material of boron nitrogen carbon ternary.
Specifically, the zinc air secondary cell includes the electrolyte cavities of a cubic shaped, one is used as zinc anode
Zinc metal sheet, gasket seal, graphite flake, air electrode, cathode shell, the tops of the electrolyte cavities is top shell, is opened up in top shell
There are electrolyte injecting hole, and the strip hole passed through for zinc metal sheet；Gasket seal, graphite flake, air electrode, cathode shell are successively
Superposition, a side wall as 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 material of boron nitrogen carbon ternary, comprising the following steps:
(1) carbon paper cut is impregnated in ptfe emulsion, carries out hydrophobic treatment, it is then dry at 80 DEG C
30min is sintered 30min at 360 DEG C；
(2) by acetylene black and ptfe emulsion, dispersion mixing, ultrasound are stirred in ethanol；
(3) the mixed liquor pressure that step (2) obtains is atomized on by hydrophobic treatment using the technology mode of pressure atomization
The one side of carbon paper, dry 30min, is sintered 30min at 360 DEG C at 80 DEG C；
(4) by active carbon, the boron covalent composite material of nitrogen carbon ternary and ptfe emulsion dispersion mixing in ethanol surpass
Sound, stirring；
(5) the mixed liquor pressure that step (4) obtains is atomized on by hydrophobic treatment using the technology mode of pressure atomization
The another side of carbon paper, the dry 30min at 80 DEG C are sintered 30min at 360 DEG C to get the air electrode.
In step (1), the mass concentration of ptfe emulsion is 5wt%~60wt%, and dip time is 5~40min.
In step (2), the mass ratio of acetylene black and ptfe emulsion is 7:3~2:8, 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 mass ratio of the covalent composite material of boron nitrogen carbon ternary, active carbon and ptfe emulsion is 2:2:
0.5~2:2:5, polytetrafluoroethylene (PTFE) mass concentration are 5wt%~60wt%, and the carbon carrying capacity of the covalent composite material of boron nitrogen carbon ternary is
0.5~2.0mg/cm2。
The utility model has the advantages that
(1) zinc air secondary cell device of the invention is by based on polymethyl methacrylate materials, graphite flake is
The carrying tablet of working electrode, rubber sheet gasket are assisted consolidating the mold of leakproofness.It has good seal performance, easy to disassemble replaces
Electrolyte and zinc anode, easy to clean are changed, and is easy to observe internal-response situation.
(2) the covalent composite material of boron nitrogen carbon ternary has porous structure, is capable of providing big active surface, and 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, to improve the output voltage and output power of battery.
The boron covalent composite material of nitrogen carbon ternary is suitable with business Pt/C to the catalytic current density of oxygen reduction reaction；Oxygen evolution reaction rises
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, is realized charge and discharge cycles, is improved zinc air secondary cell
Electric conductivity, improve the catalytic performance of battery, and using without metal-doped catalyst save the cost, 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, forms fine and close, uniform microcellular structure, and the performance of liquid and gas mass transfer obtains
Improve, using optimization step by step, so that hydrophobicity, electric conductivity and stability have all obtained significantly improving.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the zinc air secondary cell of the invention based on the covalent composite material of boron nitrogen carbon ternary；
Fig. 2 is the comparison of the polarization curves of oxygen reduction figure of the catalyst and business Pt/C without metal of different doping；
Fig. 3 is the hydrogen reduction energy density profile of the catalyst and business Pt/C without metal of different doping；
Fig. 4 is the specific volume spirogram of zinc-air battery；
Fig. 5 is electric discharge figure of the covalent composite material of boron nitrogen carbon ternary from business Pt/C under different current densities；
Fig. 6 is the hydrogen reduction of the covalent composite material of boron nitrogen carbon ternary and business Pt/C and the polarization curve that oxygen is precipitated；
Fig. 7 is the charge and discharge cycles figure of zinc-air battery.
Specific embodiment
The present invention will be further explained with reference to the accompanying drawing.
It is as shown in Figure 1 a kind of zinc air secondary cell based on the covalent composite material of boron nitrogen carbon ternary, including zinc anode,
Electrolyte and air electrode, it is characterised in that: the air electrode is successively passed through by collector, waterproof ventilative layer and Catalytic Layer viscous
It ties agent and combines composition, the collector is the carbon paper through hydrophobic treatment, and the waterproof ventilative layer is acetylene black, and the Catalytic Layer is
Carbon black is the covalent composite material of boron nitrogen carbon ternary of substrate.Specifically, the electrolyte cavities 4 including a cubic shaped, one
Top as the zinc metal sheet 1 of zinc anode, gasket seal 5, graphite flake 6, air electrode 7, cathode shell 8, the electrolyte cavities 4 is
Top shell 3 offers electrolyte injecting hole 2, and the strip hole 10 passed through for zinc metal sheet 1 in top shell 3；Gasket seal 5, graphite flake
6, air electrode 7, cathode shell 8 are sequentially overlapped, and are fixed on electrolyte as a side wall of electrolyte cavities 4, and 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 cell invented is used from the zinc air secondary cell device designed and produced, is by poly- methyl-prop
Based on e pioic acid methyl ester material, graphite flake 6 is the carrying tablet of working electrode, and rubber sheet gasket 5, which is assisted consolidating leakproofness, to be made
Cathode housing is closer in conjunction with electrolyte shell, it is therefore prevented that the mold of the leakage of inside battery liquid.Top device is provided with two
Electrolyte can be taken and be injected simultaneously away new electrolyte by a electrolyte injecting hole 2, and zinc metal sheet 1 is directly by top insertion battery
Portion can quickly and easily replace it, carry out the mold of the charge and discharge of long-time stable.It is electrolysis with the KOH solution of 6M
It is secondary to test zinc air using Shanghai Chen Hua instrument company CHI660 electrochemical workstation (Chinese Shanghai) under air environment for liquid
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 optimize the hydrophobic time.
Embodiment 2
The carbon paper of 2cm*2cm is impregnated in 0wt%, 5wt%, 10wt%, the ptfe emulsion of 15wt%
10min optimizes 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, has selected 20min in this example), hydrophobic treatment is carried out, at 80 DEG C
Dry 30min, is sintered 30min at 360 DEG C；It can be by acetylene black and ptfe emulsion (acetylene black and polytetrafluoroethylene (PTFE) cream
The mass ratio of liquid is 7:3~2:8, selects 6:4 in this example；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, dry 30min, is sintered 30min at 360 DEG C at 80 DEG C；
By active carbon, the boron covalent composite material of nitrogen carbon ternary and ptfe emulsion (the covalent composite wood of boron nitrogen carbon ternary
The mass ratio of material, active carbon and ptfe emulsion is 2:2:0.5~2:2:5, has selected 2:2:1 in this example；Polytetrafluoro
Ethylene mass concentration is 5wt%~60wt%, has selected 20wt% in this example；The carbon of the covalent composite material of boron nitrogen carbon ternary carries
Amount is 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 the another side of the carbon paper of hydrophobic treatment by formula, the dry 30min at 80 DEG C, at 360 DEG C
30min is sintered to get the air diffusion electrode.
The covalent composite catalyst of above-mentioned boron nitrogen carbon ternary is obtained by being prepared via a method which: synthesis can be stripped
Template ball, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball, is reacted under the pressure of 0-3MPa,
It is cooling, nitrogen source is added in reaction solution, stirs 12-24h, is heated to 25 DEG C of -45 DEG C of removing moisture, then in 600 DEG C of temperature -
The mixture of the compound nanosphere for having boron carbon and nitrogen source at 1100 DEG C obtains three element composite Nano ball material of boron nitrogen carbon
Material, then be centrifuged after template is removed, washing, drying, obtain the covalent composite material of boron nitrogen carbon ternary.
The zinc air secondary cell 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 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, has selected 20min in this example), hydrophobic treatment is carried out, at 80 DEG C
Dry 30min, is sintered 30min at 360 DEG C；
By acetylene black and ptfe emulsion (mass ratio of acetylene black and ptfe emulsion is 7:3~2:8,
6:4 is selected in this example；Polytetrafluoroethylene (PTFE) mass concentration is 5wt%~60wt%, has selected 60wt% in this example；Acetylene black
Carbon carrying capacity is 0.7~1.5mg/cm2, 1mg/cm has been selected in this example2) in ethanol dispersion mixing adopt under a certain pressure
Above-mentioned mixed liquor pressure is atomized on to the one side of the carbon paper of hydrophobic treatment with the technology mode of pressure atomization, it is dry at 80 DEG C
30min is sintered 30min at 360 DEG C；
By active carbon, the boron covalent composite material of nitrogen carbon ternary and ptfe emulsion (the covalent composite wood of boron nitrogen carbon ternary
The mass ratio of material, active carbon and ptfe emulsion is 2:2:0.5~2:2:5, has selected 2:2:2 in this example；Polytetrafluoro
Ethylene mass concentration is 5wt%~60wt%, has selected 20wt% in this example；The carbon of the covalent composite material of boron nitrogen carbon ternary carries
Amount is 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 another side of the carbon paper of hydrophobic treatment by the technology mode of power atomization, dry at 80 DEG C
30min is sintered 30min at 360 DEG C to get the air diffusion electrode.
The covalent composite catalyst of above-mentioned boron nitrogen carbon ternary is obtained by being prepared via a method which: synthesis can be stripped
Template ball, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball, reacts in a high voltage state, it is cooling,
Nitrogen source is added in reaction solution, stirs a few hours, heats away moisture, the compound nanosphere for having boron carbon of high temperature and nitrogen source
Mixture, obtain three element composite Nano ball material of boron nitrogen carbon, then centrifugation after template is removed, washing, dry, obtain boron nitrogen
The covalent composite material of carbon ternary.
The pole piece prepared is subjected to electro-chemical test, tests chemical property again after being placed in water 2 days.
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, has selected 20min in this example), hydrophobic treatment is carried out, at 80 DEG C
Dry 30min, is sintered 30min at 360 DEG C；
By acetylene black and ptfe emulsion (mass ratio of acetylene black and ptfe emulsion is 7:3~2:8,
6:4 is selected in this example；Polytetrafluoroethylene (PTFE) mass concentration is 5wt%~60wt%, has selected 60wt% in this example；Acetylene black
Carbon carrying capacity is 0.7~1.5mg/cm2, 1mg/cm has been selected in this example2) in ethanol dispersion mixing adopt under a certain pressure
Above-mentioned mixed liquor pressure is atomized on to the one side of the carbon paper of hydrophobic treatment with the technology mode of pressure atomization, it is dry at 80 DEG C
30min is sintered 30min at 360 DEG C；
By active carbon, the boron covalent composite material of nitrogen carbon ternary and ptfe emulsion (the covalent composite wood of boron nitrogen carbon ternary
The mass ratio of material, active carbon and ptfe emulsion is 2:2:0.5~2:2:5, has selected 2:2:2 in this example；Polytetrafluoro
Ethylene mass concentration is 5wt%~60wt%, has selected 20wt% in this example；The carbon of the covalent composite material of boron nitrogen carbon ternary carries
Amount is 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 another side of the carbon paper of hydrophobic treatment by the technology mode of atomization, dry at 80 DEG C
30min is sintered 30min at 360 DEG C to get the air diffusion electrode.
The covalent composite catalyst of above-mentioned boron nitrogen carbon ternary is obtained by being prepared via a method which: synthesis can be stripped
Template ball, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball, reacts in a high voltage state, it is cooling,
Nitrogen source is added in reaction solution, stirs a few hours, heats away moisture, the compound nanosphere for having boron carbon of high temperature and nitrogen source
Mixture, obtain three element composite Nano ball material of boron nitrogen carbon, then centrifugation after template is removed, washing, dry, obtain boron nitrogen
The covalent composite material of carbon ternary.
The pole piece prepared is subjected to electro-chemical test, is placed in vacuum and tests chemical property again after 2 days.Be placed in
Pole piece in water compares, the air electrode being placed in vacuum, and 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, has selected 20min in this example), hydrophobic treatment is carried out, at 80 DEG C
Dry 30min, is sintered 30min at 360 DEG C；
By acetylene black and ptfe emulsion (mass ratio of acetylene black and ptfe emulsion is 7:3~2:8,
6:4 is selected in this example；Polytetrafluoroethylene (PTFE) mass concentration is 5wt%~60wt%, has selected 60wt% in this example；Acetylene black
Carbon carrying capacity is 0.7~1.5mg/cm2, 1mg/cm has been selected in this example2) in ethanol dispersion mixing adopt under a certain pressure
Above-mentioned mixed liquor pressure is atomized on to the one side of the carbon paper of hydrophobic treatment with the technology mode of pressure atomization, it is dry at 80 DEG C
30min is sintered 30min at 360 DEG C；
By active carbon, the boron covalent composite material of nitrogen carbon ternary and ptfe emulsion (the covalent composite wood of boron nitrogen carbon ternary
The mass ratio of material, active carbon and ptfe emulsion is 2:2:0.5~2:2:5, has selected 2:2:2 in this example；Polytetrafluoro
Ethylene mass concentration is 5wt%~60wt%, has selected 20wt% in this example；The carbon of the covalent composite material of boron nitrogen carbon ternary carries
Amount is 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 another side of the carbon paper of hydrophobic treatment by the technology mode of power atomization, dry at 80 DEG C
30min is sintered 30min at 360 DEG C to get the air diffusion electrode.
The covalent composite catalyst of above-mentioned boron nitrogen carbon ternary is obtained by being prepared via a method which: synthesis can be stripped
Template ball, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball, reacts in a high voltage state, it is cooling,
Nitrogen source is added in reaction solution, stirs a few hours, heats away moisture, the compound nanosphere for having boron carbon of high temperature and nitrogen source
Mixture, obtain three element composite Nano ball material of boron nitrogen carbon, then centrifugation after template is removed, washing, dry, obtain boron nitrogen
The covalent composite material 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, has selected 20min in this example), hydrophobic treatment is carried out, at 80 DEG C
Dry 30min, is sintered 30min at 360 DEG C；
By acetylene black and ptfe emulsion (mass ratio of acetylene black and ptfe emulsion is 7:3~2:8,
6:4 is selected in this example；Polytetrafluoroethylene (PTFE) mass concentration is 5wt%~60wt%, has selected 60wt% in this example；Acetylene black
Carbon carrying capacity is 0.7~1.5mg/cm2, 1mg/cm has been selected in this example2) in ethanol dispersion mixing adopt under a certain pressure
Above-mentioned mixed liquor pressure is atomized on to the one side of the carbon paper of hydrophobic treatment with the technology mode of pressure atomization, it is dry at 80 DEG C
30min is sintered 30min at 360 DEG C；
By active carbon, the boron covalent composite material of nitrogen carbon ternary and ptfe emulsion (the covalent composite wood of boron nitrogen carbon ternary
The mass ratio of material, active carbon and ptfe emulsion is 2:2:0.5~2:2:5, has selected 2:2:3 in this example；Polytetrafluoro
Ethylene mass concentration is 5wt%~60wt%, has selected 20wt% in this example；The carbon of the covalent composite material of boron nitrogen carbon ternary carries
Amount is 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 another side of the carbon paper of hydrophobic treatment by the technology mode of power atomization, dry at 80 DEG C
30min is sintered 30min at 360 DEG C to get the air diffusion electrode.
The covalent composite catalyst of above-mentioned boron nitrogen carbon ternary is obtained by being prepared via a method which: synthesis can be stripped
Template ball, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball, reacts in a high voltage state, it is cooling,
Nitrogen source is added in reaction solution, stirs a few hours, heats away moisture, the compound nanosphere for having boron carbon of high temperature and nitrogen source
Mixture, obtain three element composite Nano ball material of boron nitrogen carbon, then centrifugation after template is removed, washing, dry, obtain boron nitrogen
The covalent composite material 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, has selected 20min in this example), hydrophobic treatment is carried out, at 80 DEG C
Dry 30min, is sintered 30min at 360 DEG C；
By acetylene black and ptfe emulsion (mass ratio of acetylene black and ptfe emulsion is 7:3~2:8,
6:4 is selected in this example；Polytetrafluoroethylene (PTFE) mass concentration is 5wt%~60wt%, has selected 60wt% 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 to the one side of the carbon paper of hydrophobic treatment using the technology mode of pressure atomization, is done at 80 DEG C
Dry 30min is sintered 30min at 360 DEG C；
By active carbon, the boron covalent composite material of nitrogen carbon ternary and ptfe emulsion (the covalent composite wood of boron nitrogen carbon ternary
The mass ratio of material, active carbon and ptfe emulsion is 2:2:0.5~2:2:5, has selected 2:2:4 in this example；Polytetrafluoro
Ethylene mass concentration is 5wt%~60wt%, has selected 20wt% in this example；The carbon of the covalent composite material of boron nitrogen carbon ternary carries
Amount is 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 another side of the carbon paper of hydrophobic treatment by the technology mode of power atomization, dry at 80 DEG C
30min is sintered 30min at 360 DEG C to get the air diffusion electrode.
The covalent composite catalyst of above-mentioned boron nitrogen carbon ternary is obtained by being prepared via a method which: synthesis can be stripped
Template ball, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball, reacts in a high voltage state, it is cooling,
Nitrogen source is added in reaction solution, stirs a few hours, heats away moisture, the compound nanosphere for having boron carbon of high temperature and nitrogen source
Mixture, obtain three element composite Nano ball material of boron nitrogen carbon, then centrifugation after template is removed, washing, dry, obtain boron nitrogen
The covalent composite material 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, has selected 20min in this example), hydrophobic treatment is carried out, at 80 DEG C
Dry 30min, is sintered 30min at 360 DEG C；
By acetylene black and ptfe emulsion (mass ratio of acetylene black and ptfe emulsion is 7:3~2:8,
6:4 is selected in this example；Polytetrafluoroethylene (PTFE) mass concentration is 5wt%~60wt%, has selected 60wt% 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 to the one side of the carbon paper of hydrophobic treatment using the technology mode of pressure atomization, is done at 80 DEG C
Dry 30min is sintered 30min at 360 DEG C；
By active carbon, the boron covalent composite material of nitrogen carbon ternary and ptfe emulsion (the covalent composite wood of boron nitrogen carbon ternary
The mass ratio of material, active carbon and ptfe emulsion is 2:2:0.5~2:2:5, has selected 2:2:3 in this example；Polytetrafluoro
Ethylene mass concentration is 5wt%~60wt%, has selected 20wt% in this example；Boron doping hollow carbon balls, N doping hollow carbon
The carbon carrying capacity of ball, the covalent composite material 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；It 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 dry 30min, is sintered at 360 DEG C at 80 DEG C
30min is to get the air diffusion electrode.Zinc air secondary cell is assembled them into, charge and discharge electric polarization curve, constant current are carried out
Electric discharge and charge and discharge cycles test.
The covalent composite catalyst of above-mentioned boron nitrogen carbon ternary is obtained by being prepared via a method which: synthesis can be stripped
Template ball, Syringaresinol, para hydroxybenzene boric acid and aldehyde are added in the aqueous solution of template ball, reacts in a high voltage state, it is cooling,
Nitrogen source is added in reaction solution, stirs a few hours, heats away moisture, the compound nanosphere for having boron carbon of high temperature and nitrogen source
Mixture, obtain three element composite Nano ball material of boron nitrogen carbon, then centrifugation after template is removed, washing, dry, obtain boron nitrogen
The covalent composite material of carbon ternary.
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (1)
1. a kind of zinc air secondary cell based on the covalent composite material of boron nitrogen carbon ternary, including zinc anode, electrolyte and air
Electrode, it is characterised in that: the air electrode by collector, waterproof ventilative layer and Catalytic Layer by binder in conjunction with form, institute
Stating collector is the carbon paper through hydrophobic treatment, and the waterproof ventilative layer is acetylene black, and the Catalytic Layer is the boron that carbon black is substrate
The covalent composite material of nitrogen carbon ternary；
The zinc air secondary cell includes the electrolyte cavities (4) of a cubic shaped, a zinc metal sheet as zinc anode
(1), gasket seal (5), graphite flake (6), air electrode (7), cathode shell (8), the top of the electrolyte cavities (4) are top shell
(3), it is offered electrolyte injecting hole (2) in top shell (3), and the strip hole (10) passed through for zinc metal sheet (1)；Gasket seal
(5), graphite flake (6), air electrode (7), cathode shell (8) are sequentially overlapped, a side wall as electrolyte cavities (4)；Top shell
(3), electrolyte cavities (4), the material of cathode shell (8) are polymethyl methacrylate materials.
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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 |
| CN108346844B (en) * | 2018-01-16 | 2019-10-29 | 云南靖创液态金属热控技术研发有限公司 | A kind of metal fuel battery |
| CN109786762B (en) * | 2019-01-17 | 2021-01-19 | 北京化工大学 | Structure of gradient hydrophilic-hydrophobic/air electrode and preparation method thereof |
| CN110193374B (en) * | 2019-07-01 | 2021-07-27 | 山东大学 | Boron-carbon-nitrogen electrocatalytic material, preparation method thereof and application thereof in ammonia synthesis by nitrogen reduction |
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| CN201210498Y (en) * | 2008-06-06 | 2009-03-18 | 北京双威富能科技有限公司 | Air cell connection structure |
| CN102709572A (en) * | 2012-07-03 | 2012-10-03 | 北京中航长力能源科技有限公司 | Novel air electrode and preparation method thereof |
| CN105161728A (en) * | 2015-08-11 | 2015-12-16 | 东南大学 | Preparation of urea-modified boron-carbon hollow spheres and application of urea-modified boron-carbon hollow spheres in fuel cell |
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| CN201210498Y (en) * | 2008-06-06 | 2009-03-18 | 北京双威富能科技有限公司 | Air cell connection structure |
| CN102709572A (en) * | 2012-07-03 | 2012-10-03 | 北京中航长力能源科技有限公司 | Novel air electrode and preparation method thereof |
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