CN107240703A - Air electrode containing graphene and/or CNT and preparation method thereof and metal-air battery - Google Patents
Air electrode containing graphene and/or CNT and preparation method thereof and metal-air battery Download PDFInfo
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- CN107240703A CN107240703A CN201710325065.7A CN201710325065A CN107240703A CN 107240703 A CN107240703 A CN 107240703A CN 201710325065 A CN201710325065 A CN 201710325065A CN 107240703 A CN107240703 A CN 107240703A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8673—Electrically conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
Abstract
The present invention relates to air cell field, disclose a kind of air electrode containing graphene and/or CNT and preparation method thereof and metal-air battery, the air electrode includes Catalytic Layer, collector and the waterproof ventilative layer stacked gradually, it is characterized in that, the Catalytic Layer, which contains conductive agent A, catalyst and binding agent A, the conductive agent A, includes graphene and/or CNT.The metal-air battery of air electrode containing the present invention has preferable electric conductivity and thermal conductivity.
Description
Technical field
The present invention relates to air cell field, and in particular to a kind of air electrode containing graphene and/or CNT
And preparation method thereof and metal-air battery.
Background technology
Metal-air battery be a kind of oxygen using in air as positive active material, with metallic zinc, aluminium, magnesium isoreactivity
Metal produces the new fuel cell of electric energy by electrochemical reaction as negative pole, alkalescence or neutral salt solution as electrolyte.
Air electrode is a kind of ventilative but liquid-tight, can film that is conductive and having catalytic activity, its Catalytic Layer in metal-air battery
Oxygen in side contacts electrolyte, waterproof ventilative layer side contacts air, air is diffused into up to gas-liquid-solid by air electrode
Three phase boundary, the reduction reaction for occurring oxygen, while oxidation reaction occurs for metal negative electrode, battery discharges electric energy.Metal-air electricity
Pond has energy density high, capacity is big, cost is low, discharge stability the characteristics of, and positive active material oxygen with it not to the utmost, environment
It is friendly, it is considered to be there is the new energy battery of development and application prospect in future very much.But, metal-air battery still Shortcomings,
Such as poorly conductive of air electrode, so as to limit the application of metal-air battery.
The content of the invention
There is above mentioned problem the invention aims to the metal-air battery for overcoming prior art there is provided one kind to contain
Air electrode of graphene and/or CNT and preparation method thereof and metal-air battery.
To achieve these goals, inventor is had found under study for action, and graphene and/or CNT are added into Catalytic Layer
In, the electric conductivity of air electrode can be improved, the discharge performance of metal-air battery is improved.
Thus, one aspect of the present invention provides a kind of air electrode containing graphene and/or CNT, the air electrode
Including the Catalytic Layer stacked gradually, collector and waterproof ventilative layer, wherein, the Catalytic Layer contains conductive agent A, catalyst and glued
Tying agent A, the conductive agent A includes graphene and/or CNT.
Second aspect of the present invention provides a kind of preparation method of the air electrode containing graphene and/or CNT, its
In, the preparation method comprises the following steps：
(1) conductive agent A, catalyst, binding agent A are mixed with absolute ethyl alcohol, and obtained mixture are pressed into diaphragm,
The diaphragm is extracted in absolute ethyl alcohol, then dries, obtains Catalytic Layer, wherein, the conductive agent A include graphene and/
Or CNT；
(2) waterproof ventilative layer is provided；
(3) Catalytic Layer, collector and the waterproof ventilative layer prepared step (1) is stacked gradually, then
It is compressing.
Third aspect present invention provides a kind of metal-air battery, and the metal-air battery includes positive pole and negative pole, wherein,
It is any in the air electrode just extremely of the present invention and the air electrode prepared by preparation method of the present invention
A kind of air electrode, the negative pole is one kind in zinc, aluminium and magnesium.
The air electrode containing graphene and/or CNT of the present invention, wherein, graphene has excellent electric conductivity
Can, CNT has unique doughnut structure, high-specific surface area, good electric conductivity, so that the air is electric
Has high conductivity so that metal-air battery has high discharge performance.Also, because graphene and CNT all have
There is good thermal conductivity, therefore, the air electrode of the invention containing graphene and/or CNT also has good heat conduction
Property, so as to avoid the problem of air cell generates heat in heavy-current discharge.
Brief description of the drawings
Fig. 1 is discharge curve of the air electrode for preparing of embodiment 1-5 and comparative example 1 in metal-air battery.
Embodiment
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of air electrode containing graphene and/or CNT, and the air electrode includes
Catalytic Layer, collector and the waterproof ventilative layer stacked gradually, wherein, the Catalytic Layer contains conductive agent A, catalyst and binding agent
A, the conductive agent A include graphene and/or CNT.
According to the present invention, in order to further improve under the electric conductivity and thermal conductivity of air electrode, preferable case, the graphite
1 μm, more preferably 0.3-0.5 μm of the particle diameter ＜ of alkene；15 μm, more preferably 3-10 μm of piece footpath ＜；Specific surface area ＞
100m2/ g, more preferably 150-300m2/g；Preferably, particle diameter≤1 μm of the CNT, more preferably
0.1-0.5μm；Carbon length of tube≤5 μm, more preferably 2-4 μm；Specific surface area ＞ 200m2/ g, more preferably 250-
400m2/g。
According to the present invention, any one of graphene and CNT, or graphene can be included in the conductive agent A
With the mixture of CNT, it is preferable that the conductive agent A includes graphene and CNT, and graphene and CNT
Weight ratio be 1-10：1.
According to the present invention, it can also include in conventional conductive compositions, such as described conductive agent A also in the conductive agent A
At least one of activated carbon, acetylene black and graphite can be included.When in the conductive agent A also include activated carbon, acetylene black and
During at least one of graphite, in order to keep air electrode to have under higher electric conductivity and thermal conductivity, preferable case, described
In conductive agent A, the content of graphene and/or CNT is 0.1-100 weight %, preferably 5-50 weight %, is more preferably
10-20 weight %.
According to the present invention, while electric conductivity and thermal conductivity in order to improve air electrode, the Catalytic Layer of air electrode is protected
Hold under higher catalytic effect, preferable case, the content of the conductive agent A is 50-80 weight %, and the content of the catalyst is
5-40 weight %, the binding agent A content are 10-30 weight %.
According to the present invention, catalyst and the binding agent A can be used in urging for air electrode for this area is existing
Under agent and binding agent, preferable case, the catalyst is nanometer MnO2, electrolysis MnO2, cobalt oxide, nickel oxide, perovskite, Ag,
One or more in Pt, more preferably nanometer MnO2And/or cobalt oxide；The binding agent A be Kynoar and/or
Polytetrafluoroethylene (PTFE).
According to the present invention, conductive agent and binding agent, also, the waterproof ventilative layer can be included in the waterproof ventilative layer
In conductive agent and binding agent can be identical or different with conductive agent A and binding agent A in Catalytic Layer, still, from cost and production
From the aspect of product are ready availability, under preferable case, the waterproof ventilative layer includes conductive agent B and binding agent B, the conductive agent B bags
At least one of activated carbon, acetylene black and graphite are included, the binding agent B is Kynoar and/or polytetrafluoroethylene (PTFE)；.
According to the present invention, the content of conductive agent B and binding agent B in the waterproof ventilative layer can be normal using prior art
Under the selection of rule, preferable case, in the waterproof ventilative layer, the content of the conductive agent B is 30-80 weight %, described viscous
The content for tying agent B is 20-70 weight %.
According to the present invention, the thickness of the Catalytic Layer and the waterproof ventilative layer can be the catalysis of existing air electrode
Under the thickness of layer and the waterproof ventilative layer, preferable case, the thickness of the Catalytic Layer is 0.05-0.25mm, further preferably
For 0.1-0.15mm；The thickness of the waterproof ventilative layer is 0.3-0.7mm, more preferably 0.45-0.6mm.
According to the present invention, the collector can for the existing air electrode that can be used for as the material of collector, it is excellent
In the case of choosing, the collector is one kind in stainless (steel) wire, copper mesh and nickel foam.
Second aspect of the present invention provides a kind of preparation method of the air electrode containing graphene and/or CNT,
Wherein, the preparation method comprises the following steps：
(1) conductive agent A, catalyst, binding agent A are mixed with absolute ethyl alcohol, and obtained mixture are pressed into diaphragm,
The diaphragm is extracted in absolute ethyl alcohol, then dries, obtains Catalytic Layer, wherein, the conductive agent A include graphene and/
Or CNT；
(2) waterproof ventilative layer is provided；
(3) Catalytic Layer, collector and the waterproof ventilative layer prepared step (1) is stacked gradually, then
It is compressing.
According to the present invention, in order to further improve under the electric conductivity and thermal conductivity of air electrode, preferable case, the graphite
1 μm, more preferably 0.3-0.5 μm of the particle diameter ＜ of alkene；15 μm, more preferably 3-10 μm of piece footpath ＜；Specific surface area ＞
100m2/ g, more preferably 150-300m2/g；Preferably, particle diameter≤1 μm of the CNT, more preferably
0.1-0.5μm；Carbon length of tube≤5 μm, more preferably 2-4 μm；Specific surface area ＞ 200m2/ g, more preferably 250-
400m2/g。
According to the present invention, in order to prevent the graphene and/or CNT from occurring during being mixed with absolute ethyl alcohol
Reunite and influence the electric conductivity and thermal conductivity of air electrode, under preferable case, in step (1), by conductive agent A and absolute ethyl alcohol
Before mixing, first the graphene and/or CNT in conductive agent A are dispersed in dispersion liquid.
According to the present invention, in order to further avoid graphene and/or CNT from being sent out during being mixed with absolute ethyl alcohol
Raw to reunite, under preferable case, the consumption of the dispersion liquid causes the solid content in dispersion liquid to be 1-10 weight %.
According to the present invention, the dispersion liquid can be used in dispersed graphite alkene and/or carbon nanometer for this area is existing
The dispersion liquid of pipe, can be commercially available, will not be repeated here.
According to the present invention, in step (1), the mode that conductive agent A, catalyst, binding agent A are mixed with absolute ethyl alcohol is preferred
For：First conductive agent A, catalyst are mixed with absolute ethyl alcohol, binding agent A is then added into obtained mixture.It is further excellent
Selection of land, after conductive agent A, catalyst are mixed with absolute ethyl alcohol, is added before binding agent A, by mixed mixture ultrasound
Decentralized processing 0.5-3h.
According to the present invention, in step (1), the process of the extraction is in order to remove the surfactant in binding agent, together
When reach under the purpose of pore-creating, preferable case, the time of the extraction is 24-48h.The condition of the drying is preferably included：Temperature
Spend for 60-100 DEG C, the time is 12-24h.
According to the present invention, any one of graphene and CNT, or graphene can be included in the conductive agent A
With the mixture of CNT, it is preferable that in step (1), the conductive agent A includes graphene and CNT, and graphene
Weight ratio with CNT is 1-10：1.
According to the present invention, conventional conductive compositions can also be included in the conductive agent A, such as described conductive agent A is also wrapped
Include at least one of activated carbon, acetylene black and graphite.
When also including at least one of activated carbon, acetylene black and graphite in the conductive agent A, in order to keep air electricity
Have under higher electric conductivity and thermal conductivity, preferable case, in the conductive agent A, graphene and/or CNT contain
Measure as 0.1-100 weight %, more preferably preferably 5-50 weight %, 10-20 weight %.
According to the present invention, while electric conductivity and thermal conductivity in order to improve air electrode, the Catalytic Layer of air electrode is protected
Hold under higher catalytic effect, preferable case, in step (1), on the basis of the gross weight of the Catalytic Layer, the conductive agent A
Consumption be 50-80 weight %, the consumption of the catalyst be that 5-40 weight %, the binding agent A consumption are that 10-30 is weighed
Measure %.
According to the present invention, catalyst and the binding agent A can be used in urging for air electrode for this area is existing
Under agent and binding agent, preferable case, the catalyst is nanometer MnO2, electrolysis MnO2, cobalt oxide, nickel oxide, perovskite, Ag,
One or more in Pt, more preferably nanometer MnO2And/or cobalt oxide；The binding agent A be Kynoar and/or
Polytetrafluoroethylene (PTFE).
According to the present invention, step is preferably included in (2) there is provided the method for waterproof ventilative layer：By conductive agent B, binding agent B with
Absolute ethyl alcohol is mixed, and obtained mixture is pressed into diaphragm, and the diaphragm is extracted in absolute ethyl alcohol, then dried,
Waterproof ventilative layer is obtained, wherein, the conductive agent B includes at least one of activated carbon, acetylene black and graphite, the binding agent
B is Kynoar and/or polytetrafluoroethylene (PTFE).
According to the present invention, in step (2), it is preferably by conductive agent B, binding agent the B mode mixed with absolute ethyl alcohol：First will
Conductive agent B is mixed with absolute ethyl alcohol, and binding agent B is then added into obtained mixture.It is further preferred that by conductive agent
After B is mixed with absolute ethyl alcohol, add before binding agent B, mixed mixture ultrasonic disperse is handled into 15-60min.
According to the present invention, in step (2), the process of the extraction is in order to remove the surfactant in binding agent, together
When reach under the purpose of pore-creating, preferable case, the time of the extraction is 24-72h.The condition of the drying is preferably included：Temperature
Spend for 60-80 DEG C, the time is 12-24h.
According to the present invention, the content of conductive agent B and binding agent B in the waterproof ventilative layer can be normal using prior art
Under the selection of rule, preferable case, in step (2), on the basis of the gross weight of the waterproof ventilative layer, the use of the conductive agent B
Measure as 30-80 weight %, the consumption of the binding agent B is 20-70 weight %.
According to the present invention, the mode of the compacting can be the existing mode for suppressing diaphragm in this area, for example, can adopt
With the mode of roll-in.
Third aspect present invention provides a kind of metal-air battery, and the metal-air battery includes positive pole and negative pole, wherein,
It is any in the air electrode just extremely of the present invention and the air electrode prepared by preparation method of the present invention
A kind of air electrode, the negative pole is one kind in zinc, aluminium and magnesium.It is electric as the air of positive pole using the air electrode of the present invention
Pond has preferable discharge performance, meanwhile, the problem of battery generates heat in heavy-current discharge can be avoided.
The present invention will be described in detail by way of examples below.In following examples, air cell is in different electric currents
Discharge performance under density is measured by the high-precision discharge testers of BTS-3008 (being purchased from the new Weir Electronics Co., Ltd. in Shenzhen)；
Dispersion liquid is taken in the fresh material Science and Technology Ltd., model SC Pas2002 purchased from letter；
Graphene is purchased from new material limited company of precious ACE Semi, and particle diameter is 0.5 μm, and piece footpath is 8 μm, and specific surface area is
200m2/g；
CNT is purchased from Nanocyl companies, model NC7000, and particle diameter is 0.15 μm, and carbon length of tube is 2 μm, compares table
Area is 250m2/g；
Collector is copper mesh, mesh 0.6*1.2mm, thickness 0.4mm.
Embodiment 1
The composition of Catalytic Layer：70 weight % conductive agents A (graphene and activated carbon, wherein, the consumption of graphene is 14 weights
% is measured, graphene is with dispersion, and solid content is 5 weight %), 10 % nanometers of weight MnO2, 20 weight % polytetrafluoroethylene (PTFE).
The composition of waterproof ventilative layer：40 weight % conductive agents B (activated carbon and acetylene black), the weight % of Kynoar 60.
(1) preparation of Catalytic Layer
According to aforementioned proportion, first by conductive agent A, nanometer MnO2It is put into beaker and mixes with absolute ethyl alcohol, stirring ultrasound
Polytetrafluoroethylene (PTFE), is then added dropwise in said mixture by 1h, continues to stir, is well mixed, then by roll-in repeatedly,
24h is extracted in diaphragm as thickness 0.15mm, immersion absolute ethyl alcohol, diaphragm is taken out, 12h is dried at 60 DEG C, is catalyzed
Layer.
(2) preparation of waterproof ventilative layer
According to aforementioned proportion, conductive agent B and absolute ethyl alcohol are put into beaker first, 30min is stirred, is then added dropwise
Kynoar, continues to stir to uniting, by roll-in repeatedly, as the diaphragm that thickness is 0.5mm, extracts in immersion absolute ethyl alcohol
48h is taken, diaphragm is taken out, 12h is dried at 60 DEG C, waterproof ventilative layer is obtained.
(3) preparation of air electrode
The waterproof ventilative layer prepared in the Catalytic Layer prepared in step (1), collector and step (2) is stacked gradually into combination
It is compressing, obtain air electrode A1.
Embodiment 2
The composition of Catalytic Layer：70 weight % conductive agents A (graphene, CNT and activated carbon, wherein, graphene and carbon
The consumption of nanotube is respectively 8 weight %, and graphene and CNT are with dispersion, and solid content is 10 weight %), 15 weights
Measure % nanometers of MnO2, 15 weight % polytetrafluoroethylene (PTFE).
The composition of waterproof ventilative layer：50 weight % conductive agents B (activated carbon and acetylene black), 50 weight % Kynoar.
(1) preparation of Catalytic Layer
According to aforementioned proportion, first by conductive agent A, nanometer MnO2It is put into absolute ethyl alcohol in beaker, stirs ultrasound 2h, so
Polytetrafluoroethylene (PTFE) is added dropwise in said mixture afterwards, continues to stir, be well mixed, then by roll-in repeatedly, turn into
48h is extracted in thickness 0.2mm diaphragm, immersion absolute ethyl alcohol, diaphragm is taken out, 18h is dried at 80 DEG C, Catalytic Layer is obtained.
(2) preparation of waterproof ventilative layer
According to aforementioned proportion, conductive agent B and absolute ethyl alcohol are put into beaker first, 40min is stirred, is then added dropwise
Kynoar, continues to stir to uniting, by roll-in repeatedly, as the diaphragm that thickness is 0.5mm, extracts in immersion absolute ethyl alcohol
48h is taken, diaphragm is taken out, 24h is dried at 80 DEG C, waterproof ventilative layer is obtained.
(3) preparation of air electrode
The waterproof ventilative layer prepared in the Catalytic Layer prepared in step (1), collector and step (2) is stacked gradually into combination
It is compressing, obtain air electrode A2.
Embodiment 3
The composition of Catalytic Layer：65 weight % conductive agents A (CNT and activated carbon, wherein, the consumption of CNT is 15
Weight %, CNT is with dispersion, and solid content is 5 weight %), 15 % nanometers of weight MnO2, 20 weight % polytetrafluoros
Ethene.
The composition of waterproof ventilative layer：60 weight % conductive agents B (activated carbon and acetylene black), the weight % of Kynoar 40.
(1) preparation of Catalytic Layer
First by conductive agent A, nanometer MnO2It is put into absolute ethyl alcohol in beaker, ultrasound 1h is stirred, then by polytetrafluoroethyl-ne
Alkene is added dropwise in said mixture, is continued to stir, is well mixed, then by roll-in repeatedly, as thickness 0.15mm's
24h is extracted in diaphragm, immersion absolute ethyl alcohol, diaphragm is taken out, 24h, Catalytic Layer is dried at 80 DEG C.
(2) preparation of waterproof ventilative layer
Conductive agent B and absolute ethyl alcohol are put into beaker first, 30min is stirred, Kynoar is then added dropwise, after
Continuous stirring is to uniting, by roll-in repeatedly, as the diaphragm that thickness is 0.5mm, extracts 48h in immersion absolute ethyl alcohol, takes out film
Piece, 18h is dried at 70 DEG C, waterproof ventilative layer is obtained.
(3) preparation of air electrode
The waterproof ventilative layer prepared in the Catalytic Layer prepared in step (1), collector and step (2) is stacked gradually into combination
It is compressing, obtain air electrode A3.
Embodiment 4
The composition of Catalytic Layer：60 weight % conductive agents A (graphene, CNT and activated carbon, wherein, graphene and carbon
The consumption of nanotube is respectively 10 weight %, and graphene and CNT are with dispersion, and solid content is 10 weight %), 20
% nanometers of MnO of weight2, 20 weight % polytetrafluoroethylene (PTFE).
The composition of waterproof ventilative layer：50 weight % conductive agents B (activated carbon and acetylene black), 50 weight % Kynoar.
(1) preparation of Catalytic Layer
According to aforementioned proportion, first by conductive agent A, nanometer MnO2It is put into absolute ethyl alcohol in beaker, stirs ultrasound 1.5h,
Then polytetrafluoroethylene (PTFE) is added dropwise in said mixture, continues to stir, is well mixed, then by roll-in repeatedly, into
For thickness 0.25mm diaphragm, immerse and 48h is extracted in absolute ethyl alcohol, take out diaphragm, 12h is dried at 70 DEG C, Catalytic Layer is obtained.
(2) preparation of waterproof ventilative layer
According to aforementioned proportion, conductive agent B and absolute ethyl alcohol are put into beaker first, 20min is stirred, is then added dropwise
Kynoar, continues to stir to uniting, by roll-in repeatedly, as the diaphragm that thickness is 0.6mm, extracts in immersion absolute ethyl alcohol
48h is taken, diaphragm is taken out, 16h is dried at 70 DEG C, waterproof ventilative layer is obtained.
(3) preparation of air electrode
The waterproof ventilative layer prepared in the Catalytic Layer prepared in step (1), collector and step (2) is stacked gradually into combination
It is compressing, obtain air electrode A4.
Embodiment 5
The composition of Catalytic Layer：50 weight % conductive agents A (graphene and activated carbon, wherein, the consumption of graphene is 10 weights
% is measured, graphene is with dispersion, and solid content is 5 weight %), 30 % nanometers of weight MnO2, 20 weight % polytetrafluoroethylene (PTFE).
The composition of waterproof ventilative layer：60 weight % conductive agents B (activated carbon and acetylene black), the weight % of Kynoar 40.
(1) preparation of Catalytic Layer
According to aforementioned proportion, first by conductive agent A, nanometer MnO2It is put into absolute ethyl alcohol in beaker, stirs ultrasound 1h, so
Polytetrafluoroethylene (PTFE) is added dropwise in said mixture afterwards, continues to stir, be well mixed, then by roll-in repeatedly, turn into
24h is extracted in thickness 0.15mm diaphragm, immersion absolute ethyl alcohol, diaphragm is taken out, 12h is dried at 80 DEG C, Catalytic Layer is obtained.
(2) preparation of waterproof ventilative layer
According to aforementioned proportion, conductive agent B and absolute ethyl alcohol are put into beaker first, 30min is stirred, is then added dropwise
Binding agent Kynoar, continues to stir to uniting, by roll-in repeatedly, as the diaphragm that thickness is 0.55mm, immerses anhydrous
48h is extracted in ethanol, diaphragm is taken out, 12h is dried at 80 DEG C, waterproof ventilative layer is obtained.
(3) preparation of air electrode
The gas diffusion layers prepared in the Catalytic Layer prepared in step (1), collector and step (2) are stacked gradually into combination
It is compressing, obtain air electrode A5.
Embodiment 6
Method according to embodiment 1 prepares air electrode, unlike use the graphene b of identical weight (particle diameter is 5 μ
M, piece footpath is 20 μm, and specific surface area is 20m2/ g) instead of the graphene in embodiment 1.Obtain air electrode A6.
Embodiment 7
Method according to embodiment 3 prepares air electrode, unlike, use identical weight CNT b (particle diameter for
1 μm, carbon length of tube is 15 μm, and specific surface area is 200m2/ g) instead of the CNT in embodiment 3.Obtain air electrode A7.
Embodiment 8
Method according to embodiment 1 prepares air electrode, unlike, graphene is added not in the form of dispersion liquid.
To air electrode A8.
Comparative example 1
Method according to embodiment 1 prepares air electrode, unlike, do not contain graphite in the conductive agent A in Catalytic Layer
Alkene, namely conductive agent A are activated carbon.Obtain air electrode D1.
Test case 1
Using metallic zinc as metal-air battery negative pole, air electrode A1 is used as electrolysis as positive pole, 30%KOH solution
Liquid, carries out the discharge test under different current densities.As a result as shown in figure 1 and table 1.
Test case 2-8
According to test case 1 method determine air cell discharge performance, unlike, be respectively adopted A2, A3, A4, A5,
A6, A7 and A8 replace A1.A2, A3, A4, A5 test result as shown in figure 1 and table 1, A6, A7 and A8 test result such as table 1
It is shown.
Contrast test example 1
The discharge performance of air cell is determined according to the method for test case 1, unlike, A1 is replaced using D1.Test knot
Fruit is as shown in figure 1 and table 1.
Table 1
Can be seen that by the result of table 1 is had using the air electrode of the present invention as the metal-air battery of positive pole
Preferable discharge performance.
The preferred embodiment of the present invention described in detail above, still, the present invention is not limited thereto.In the skill of the present invention
In art concept, technical scheme can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and these simple variants and combination should equally be considered as content disclosed in this invention, belong to
Protection scope of the present invention.
Claims (10)
1. a kind of air electrode containing graphene and/or CNT, the air electrode includes Catalytic Layer, the collection stacked gradually
Fluid and waterproof ventilative layer, it is characterised in that the Catalytic Layer contains conductive agent A, catalyst and binding agent A, the conductive agent A
Including graphene and/or CNT.
2. air electrode according to claim 1, wherein, 1 μm of the particle diameter ＜ of the graphene, 15 μm of piece footpath ＜ compare table
Area ＞ 100m2/g；
Preferably, particle diameter≤1 μm of the CNT, carbon length of tube≤5 μm, specific surface area ＞ 200m2/g。
3. air electrode according to claim 1 or 2, wherein, the conductive agent A includes graphene and CNT, and
The weight ratio of graphene and CNT is 1-10：1；
Preferably, the conductive agent A also includes at least one of activated carbon, acetylene black and graphite.
It is further preferred that in the conductive agent A, the content of graphene and/or CNT is 0.1-100 weight %, excellent
Elect 5-50 weight %, more preferably 10-20 weight % as.
4. air electrode according to claim 1 or 2, wherein, in the Catalytic Layer, the content of the conductive agent A is
50-80 weight %, the content of the catalyst is that 5-40 weight %, the binding agent A content are 10-30 weight %；
Preferably, the catalyst is nanometer MnO2, electrolysis MnO2, cobalt oxide, nickel oxide, perovskite, one kind in Ag, Pt or
It is a variety of；The binding agent A is Kynoar and/or polytetrafluoroethylene (PTFE)；
Preferably, the waterproof ventilative layer includes conductive agent B and binding agent B, the conductive agent B include activated carbon, acetylene black and
At least one of graphite, the binding agent B is Kynoar and/or polytetrafluoroethylene (PTFE)；
Preferably, in the waterproof ventilative layer, the content of the conductive agent B is 30-80 weight %, and the binding agent B's contains
Measure as 20-70 weight %.
5. a kind of preparation method of the air electrode containing graphene and/or CNT, it is characterised in that the preparation method bag
Include following steps：
(1) conductive agent A, catalyst, binding agent A are mixed with absolute ethyl alcohol, and obtained mixture is pressed into diaphragm, by institute
State diaphragm to extract in absolute ethyl alcohol, then dry, obtain Catalytic Layer, wherein, the conductive agent A includes graphene and/or carbon
Nanotube；
(2) waterproof ventilative layer is provided；
(3) Catalytic Layer, collector and the waterproof ventilative layer prepared step (1) is stacked gradually, and is then suppressed
Shaping.
6. preparation method according to claim 5, wherein, the particle diameter of the graphene<1 μm, piece footpath<15 μm, compare surface
Product ＞ 100m2/g；
Preferably, particle diameter≤1 μm of the CNT, carbon length of tube≤5 μm, specific surface area ＞ 200m2/g。
7. the preparation method according to claim 5 or 6, wherein, in step (1), mixed by conductive agent A with absolute ethyl alcohol
Before, first the graphene and/or CNT in conductive agent A are dispersed in dispersion liquid；
Preferably, the consumption of the dispersion liquid causes the solid content in dispersion liquid to be 1-10 weight %.
8. the preparation method according to claim 5 or 6, wherein, in step (1), the conductive agent A includes graphene and carbon
The weight ratio of the consumption of nanotube, graphene and CNT is 1-10：1；
Preferably, the conductive agent A also includes at least one of activated carbon, acetylene black and graphite；
It is further preferred that in the conductive agent A, the content of graphene and/or CNT is 0.1-100 weight %, excellent
Elect 5-50 weight %, more preferably 10-20 weight % as.
9. the preparation method according to claim 5 or 6, wherein, in step (1), using the gross weight of the Catalytic Layer as base
Standard, the consumption of the conductive agent A is 50-80 weight %, and the consumption of the catalyst is 5-40 weight %, the binding agent A's
Consumption is 10-30 weight %；
Preferably, the catalyst is nanometer MnO2, electrolysis MnO2, cobalt oxide, nickel oxide, perovskite, one kind in Ag, Pt or
It is a variety of；The binding agent A is Kynoar and/or polytetrafluoroethylene (PTFE)；
Preferably, include in step (2) there is provided the method for waterproof ventilative layer：Conductive agent B, binding agent B and absolute ethyl alcohol are mixed
Close, and obtained mixture is pressed into diaphragm, the diaphragm is extracted in absolute ethyl alcohol, then dries, obtains waterproof saturating
Gas-bearing formation, wherein, the conductive agent B includes at least one of activated carbon, acetylene black and graphite, and the binding agent B is to gather inclined fluorine
Ethene and/or polytetrafluoroethylene (PTFE)；
It is further preferred that in step (2), on the basis of the gross weight of the waterproof ventilative layer, the consumption of the conductive agent B is
30-80 weight %, the binding agent B consumption are 20-70 weight %.
10. a kind of metal-air battery, the metal-air battery includes positive pole and negative pole, it is characterised in that described just extremely to weigh
Profit requires air electrode in 1-4 described in any one and prepared as the preparation method described in any one in claim 5-9
Air electrode in any one air electrode, the negative pole be zinc, aluminium and magnesium in one kind.
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| CN109149020A (en) * | 2018-09-10 | 2019-01-04 | 江西克莱威纳米碳材料有限公司 | Carbon nanotube-graphene-aramid fiber conductive material, lithium air battery positive electrode material and lithium-air battery |
| CN109980323A (en) * | 2019-04-23 | 2019-07-05 | 陈让珠 | Graphene aluminium air fuel cell production method |
| WO2020121337A1 (en) * | 2018-12-15 | 2020-06-18 | Log 9 Materials Scientific Private Limited | System and method for extending a range of an electric vehicle |
| CN112687899A (en) * | 2020-12-29 | 2021-04-20 | 长沙迅洋新材料科技有限公司 | Positive electrode catalyst of magnesium alloy air battery and forming method thereof |
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| CN113725447A (en) * | 2021-09-02 | 2021-11-30 | 中国地质大学（北京） | Magnesium-air battery with graphene oxide coated copper mesh current collector |
| CN114388825A (en) * | 2021-01-14 | 2022-04-22 | 安徽朔代科技有限公司 | Metal-air battery catalyst, catalyst layer and air electrode |
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