CN107039657A - A kind of aluminium-air cell air electrode structure - Google Patents
A kind of aluminium-air cell air electrode structure Download PDFInfo
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- CN107039657A CN107039657A CN201710265206.0A CN201710265206A CN107039657A CN 107039657 A CN107039657 A CN 107039657A CN 201710265206 A CN201710265206 A CN 201710265206A CN 107039657 A CN107039657 A CN 107039657A
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- aluminium
- layer
- air electrode
- anion exchange
- electrode structure
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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
- H01M4/8647—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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- 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
Abstract
The present invention provides a kind of aluminium-air cell air electrode structure, including Catalytic Layer, collector, gas diffusion layers and waterproof ventilative layer, and high molecular polymer anion exchange resin layer is covered with outside electrolyte side in described Catalytic Layer.Described high molecular polymer anion exchange resin thickness degree is 0.1~50 micron.The high molecular polymer anion exchange resin layer on the air electrode surface of the present invention effectively to the diffusion inside air electrode, can significantly improve the life-span of aluminium-air cell by barrier discharge product.By adding a certain amount of anion exchange component in air-electrode catalyst layer, OH can be effectively facilitated‑Transmission, can reduce to greatest extent avtive spot be discharged product covering probability.Due to using the less anion exchange component of thickness, it can't significantly hinder the diffusion of electrolyte, Wet Out of the reduction electrolyte on air electrode surface so that electrode reaction can continue to carry out.
Description
Technical field
The invention belongs to electrochmical power source preparing technical field, and in particular to a kind of aluminium-air cell air electrode structure.
Background technology
Aluminium-air cell be using oxygen as positive active material, aluminium as negative pole, using neutral or alkaline solution as
Electrolyte, its specific energy may be up to 8100Wh/kg in theory, far above the electrochmical power source of other species.Aluminium-air cell discharges
Product is aluminium hydroxide, and it can be to positive pole and negative terminal surface diffusional deposition, and then causes electrode that passivation occurs to early.Particularly with
For air electrode, on the one hand the deposition of aluminium hydroxide product can cause active site to be capped, and on the other hand can cause
The change of air electrode microporous structure, makes life of air electrode sharp-decay.In order to solve the above problems, many researchers carry
Some corresponding schemes are gone out：For example increase electrolyte circulated filter system, in time dispose product.But in practical application mistake
Cheng Zhong, many times due to that discharging product can not be precipitated and filtered out in time, can still result in discharging product in air electricity
The diffusion accumulation of pole surface and inside, causes air electrode performance degradation.In addition, also researcher proposes others side
Case, such as patent document 1 (CN103329342A) propose alkaline anion-exchange membrane being placed between aluminium-air cell both positive and negative polarity,
Migration of the discharging product to positive pole can actually be suppressed to a certain extent.But because anion-exchange membrane water flux used is special
It is not small, electrolyte can only be injected separately into both positive and negative polarity both sides, battery is artificially divided into two electrolyte liquor chambers, and two electrolyte liquor chambers
There can not be connected pore channel, otherwise just not have the effect for suppressing product diffusion, battery structure is become increasingly complex.
The content of the invention
In view of the above-mentioned problems, present invention aims at a kind of aluminium-air cell air electrode structure is provided, it can be effective
Suppress adverse effect of the aluminium electrode discharging product to air electrode, and then improve aluminium-air cell service life；On the other hand, make
It is easy to simplify design with the aluminium-air cell of this kind of structure, further reduces cost.
In order to achieve the above object, technical scheme is as follows：A kind of aluminium-air cell air electrode structure, including
Catalytic Layer, collector, gas diffusion layers and waterproof ventilative layer, height is covered with described Catalytic Layer outside electrolyte side
Molecularly Imprinted Polymer anion exchange resin layer.
The present invention also has following technical characteristic：
1st, high molecular polymer anion exchange resin thickness degree as described above is 0.1~50 micron.
2nd, described high molecular polymer anion exchange resin thickness degree is 2~10 microns.
3rd, the mass percent that as above high molecular polymer anion exchange resin accounts for Catalytic Layer is 1.0~40.0%.
4th, a kind of preparation method of aluminium-air cell air electrode structure as described above, as follows：Using spraying, brush,
Then it is heating and curing in catalysis layer surface one floor height Molecularly Imprinted Polymer anion-exchange resin membrane of formation, the temperature that is heating and curing is
30-150 DEG C, the time is 3-12 hours.
5th, as above each Rotating fields are arranged in the following order：Catalytic Layer/collector/gas diffusion layers/waterproof ventilative layer；Catalysis
Layer/gas diffusion layers/collector/waterproof ventilative layer；Or collector/Catalytic Layer/gas diffusion layers/waterproof ventilative layer.
6th, the SiO containing mass percent 0.1~10.0% in Catalytic Layer as described above2Or Al2O3Nano particle.
7th, catalyst layer as described above also contains conductive agent, catalyst and polytetrafluoroethylene (PTFE) binding agent, wherein described
Conductive agent is activated carbon and Ketjen black, and weight/mass percentage composition is 30%~70%；Catalyst is silver or manganese dioxide, quality percentage
Content is 10%~50%；Polytetrafluoroethylene (PTFE) binding agent, weight/mass percentage composition is 10%~40%.
8th, high molecular polymer anion exchange resin as described above be from styrene resin, benzyl ethylene resin,
Acrylic resin, polyamide-based resin, polysulfones resinoid, polyolefin resin, polyethers resinoid, polyketone resinoid, poly- carbon
The quaternary ammoniated modified resin of acid esters or polyesters, and above-mentioned species mixture
Or add the derivatives resin that other functional groups make it have ion-exchange performance.
9th, nano particle diameter as described above is 0.01~20 micron.
Compared with prior art, its advantage is the present invention：
(1) the high molecular polymer anion exchange resin layer on air electrode surface can effectively barrier discharge product to sky
The diffusion of gas electrode interior, significantly improves the life-span of aluminium-air cell.
(2) by adding a certain amount of anion exchange component in air-electrode catalyst layer, OH can be effectively facilitated-Biography
It is defeated, because anion exchange component is equably covered in catalyst surface, avtive spot can be reduced to greatest extent and be discharged product
The probability of covering.
(3) due to using the less anion exchange component of thickness, it can't significantly hinder the diffusion of electrolyte,
Reduce Wet Out of the electrolyte on air electrode surface so that electrode reaction can continue to carry out.
Brief description of the drawings
Fig. 1 is aluminium-air cell monomer voltage-time plot.
Embodiment
Technical scheme is further described with reference to embodiment, but is not so limited, it is every right
Technical solution of the present invention is modified or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, all should be contained
Cover in protection scope of the present invention.
Embodiment 1
1-METHYLPYRROLIDONE (NMP) solution of the quaternized polyarylether of configuration quality fraction 10%, then according to the institute of table 1
State mass ratio and weigh corresponding material, it is then fully dispersed in nmp solvent to obtain dispersed catalyst pulp.Then
Catalyst pulp blade coating in gas diffusion layer surface, then successively with porous nickel screen, the polytetrafluoroethylene (PTFE) that thickness is 300 microns
Waterproof ventilated membrane is hot-pressed onto together at 200 DEG C in 10MPa pressure, obtains air electrode.Afterwards by the N- of quaternized polyarylether
Methyl pyrrolidone (NMP) homogeneous dispersion is sprayed on catalysis layer surface, is 10 microns to final thickness.Then it is true at 50 DEG C
Sky dries 6h, that is, obtains final air electrode.
The catalyst layer each group distribution ratio of table 1
| Polyarylether | Ag catalyst | Acetylene black | Activated carbon | Polytetrafluoroethylene (PTFE) | |
| Mass fraction | 25% | 30% | 5% | 25% | 20% |
Embodiment 2
N-N dimethyl acetamides (DMF) solution of the quaternized polystyrene of configuration quality fraction 15%, is then pressed first
Corresponding material is weighed according to mass ratio described in table 2, it is then fully dispersed in DMF solvent to obtain dispersed catalyst slurry
Material.Then it is then poly- for 200 microns with porous nickel screen, thickness successively catalyst pulp blade coating in gas diffusion layer surface
Tetrafluoroethene waterproof ventilated membrane is hot-pressed onto together at 210 DEG C in 8MPa pressure, obtains air electrode.Afterwards will be quaternized poly-
The DMF homogeneous dispersions of styrene are sprayed on catalysis layer surface, are 8 microns to final thickness.Then it is dried in vacuo at 60 DEG C
8h, that is, obtain respective air electrode.
The catalyst layer each group distribution ratio of table 2
Embodiment 3
N-N dimethyl acetamides (DMAc) solution of the aminated polyethers sulfone of configuration quality fraction 8% first, then according to table
Mass ratio described in 3 weighs corresponding material, is then dispersed in DMAc solvents and obtains catalyst pulp.Then catalyst slurry
Material spray gun spraying reaches 5mg/cm in gas diffusion layer surface to catalyst loading2, then successively with porous nickel screen, polytetrafluoroethyl-ne
Alkene waterproof ventilated membrane is hot-pressed onto together at 200 DEG C in 12MPa pressure, obtains air electrode.And then aminated polyethers sulfone
N-N dimethyl acetamides (DMAc) homogeneous dispersion is sprayed on catalysis layer surface, forms the amberplex that thickness is 6 microns
Layer.4h is dried in vacuo at 50 DEG C afterwards, fully the air electrode is obtained after solidification.
The catalyst layer each group distribution ratio of table 3
Embodiment 4：
N-N dimethyl acetamides (DMAc) solution of the amination polyarylsulfone (PAS) of configuration quality fraction 15% first, then according to
Mass ratio described in table 4 weighs respective substance and is dispersed in DMAc solvents, and abundant ultrasonic disperse obtains certain density catalyst slurry
Material.Then catalyst pulp even application is reached 4mg/cm in gas diffusion layer surface to catalyst loading2, then by it successively
It is hot-pressed onto together with porous silver-plated nickel screen, polytetrafluoroethylene (PTFE) waterproof ventilated membrane.Then it is mass fraction is poly- fragrant for 15% amination
N-N dimethyl acetamides (DMAc) the solution even application of sulfone forms the ion exchange that thickness is 10 microns in catalysis layer surface
Film layer.6h is dried in vacuo at 45 DEG C afterwards, treats that solvent fully volatilizees, corresponding air electrode is obtained after solidification.By gained
Air electrode and aluminum alloy anode are assembled into aluminium-air cell monomer, electrolyte used for 4mol/L sodium hydroxide and
0.05mol/L sodium stannate mixed solution, in 120mA/cm2Current density under carry out constant-current discharge test, record aluminium air
Battery cell voltage-time curve, as a result as shown in Figure 1.
Comparative example：
Ion exchange resin component is added without in Catalytic Layer and not in its surface Coating Ions exchanger resin component, and make
For corresponding air electrode, then it is compared with the present embodiment, as a result as shown in Figure 1.It can be seen that the present embodiment
Have greatly improved relative to comparative example air electrode performance, polarization substantially reduction, life.
The catalyst layer each group distribution ratio of table 4
| Amination polyarylsulfone (PAS) | Ag catalyst | Ketjen black | Activated carbon | Polytetrafluoroethylene (PTFE) | |
| Mass fraction | 25% | 25% | 5% | 20% | 25% |
Embodiment 5
A kind of aluminium-air cell air electrode structure, containing Catalytic Layer, collector, gas diffusion layers and waterproof ventilative layer,
High molecular polymer anion exchange resin layer is covered with outside electrolyte side in Catalytic Layer.Described high molecular polymerization
Thing anion exchange resin thickness degree is 0.1 micron.Each layer is arranged in the following order：Catalytic Layer/collector/gas diffusion layers/
Waterproof ventilative layer.Weight/mass percentage composition of the high molecular polymer anion exchange resin in Catalytic Layer is 1.0%.Utilize spray
Apply, brush, be then heating and curing in catalysis layer surface one floor height Molecularly Imprinted Polymer anion-exchange resin membrane of formation, be heating and curing
Temperature is 30 DEG C, and the time is 12 hours.
Embodiment 6
A kind of aluminium-air cell air electrode structure, containing Catalytic Layer, collector, gas diffusion layers and waterproof ventilative layer,
High molecular polymer anion exchange resin layer is covered with outside electrolyte side in Catalytic Layer.Described high molecular polymerization
Thing anion exchange resin thickness degree is 50 microns.Each layer is arranged in the following order：Catalytic Layer/gas diffusion layers/collector/anti-
Water air-permeable layer.Weight/mass percentage composition of the high molecular polymer anion exchange resin in Catalytic Layer is 40.0%.Using spraying,
Brush, be then heating and curing in catalysis layer surface one floor height Molecularly Imprinted Polymer anion-exchange resin membrane of formation, be heating and curing temperature
Spend for 150 DEG C, the time is 12 hours.
Embodiment 7
A kind of aluminium-air cell air electrode structure, containing Catalytic Layer, collector, gas diffusion layers and waterproof ventilative layer,
High molecular polymer anion exchange resin layer is covered with outside electrolyte side in Catalytic Layer.Described high molecular polymerization
Thing anion exchange resin thickness degree is 2 microns.Each layer is arranged in the following order：Collector/Catalytic Layer/gas diffusion layers/anti-
Water air-permeable layer.Weight/mass percentage composition of the high molecular polymer anion exchange resin in Catalytic Layer is 20%.Utilize spraying, brush
Apply, be then heating and curing in catalysis layer surface one floor height Molecularly Imprinted Polymer anion-exchange resin membrane of formation, be heating and curing temperature
For 150 DEG C, the time is 3 hours.
Embodiment 8
This implementation is same as Example 6, and its difference is the SiO containing mass fraction 0.1% in described Catalytic Layer2
Or Al2O3Nano particle, particle diameter is 0.01 micron.Described high molecular polymer anion exchange resin thickness degree is 50 microns.
Described catalyst layer also includes conductive agent, catalyst and polytetrafluoroethylene (PTFE) binding agent, wherein the catalyst is silver amount hundred
It is 30.9% to divide content；Polytetrafluoroethylene (PTFE) binding agent, weight/mass percentage composition is 20%；Conductive agent is answering for activated carbon and Ketjen black
Condensation material (both mass ratioes 2:1), weight/mass percentage composition is 49%.
Embodiment 9
This implementation is same as Example 6, and its difference is the SiO containing mass fraction 10% in described Catalytic Layer2
Or Al2O3Nano particle, particle diameter is 20 microns.Described catalyst layer is also bonded comprising conductive agent, catalyst and polytetrafluoroethylene (PTFE)
Agent, wherein the catalyst is manganese dioxide, weight/mass percentage composition is 25%；Polytetrafluoroethylene (PTFE) binding agent, weight/mass percentage composition
For 15%；Conductive agent is activated carbon and Ketjen black (both mass ratioes 4:1), weight/mass percentage composition is 50%.
Embodiment 10
This implementation is identical with embodiment 6-7, and its difference is that described high molecular polymer anion exchange resin is
From the quaternary amine of phenylethylene, benzyl ethylene, acrylic compounds, polyamide-based, TPO, polyketone class, makrolon or polyesters
Change modifier, and the mixture of above-mentioned species or the other functional groups of addition make it have the derivative of anion exchange performance.
Claims (10)
1. a kind of aluminium-air cell air electrode structure, including Catalytic Layer, collector, gas diffusion layers and waterproof ventilative layer, its
It is characterised by：High molecular polymer anion exchange resin layer is covered with outside electrolyte side in described Catalytic Layer.
2. a kind of aluminium-air cell air electrode structure according to claim 1, it is characterised in that：Described polyphosphazene polymer
Compound anion exchange resin thickness degree is 0.1~50 micron.
3. a kind of aluminium-air cell air electrode structure according to claim 1, it is characterised in that：Described polyphosphazene polymer
Compound anion exchange resin thickness degree is 2~10 microns.
4. a kind of aluminium-air cell air electrode structure according to claim 1, it is characterised in that：Described polyphosphazene polymer
Weight/mass percentage composition of the compound anion exchange resin in Catalytic Layer is 1.0~40.0%.
5. a kind of preparation method of aluminium-air cell air electrode structure according to claim 1, it is characterised in that：Utilize
Spraying, brushing, are then heating and curing in catalysis layer surface one floor height Molecularly Imprinted Polymer anion-exchange resin membrane of formation, heating is solid
It is 30-150 DEG C to change temperature, and the time is 3-12 hours.
6. a kind of aluminium-air cell air electrode structure according to claim 1, it is characterised in that：Each Rotating fields are by following
Order is arranged：Catalytic Layer/collector/gas diffusion layers/waterproof ventilative layer；Catalytic Layer/gas diffusion layers/collector/waterproof is saturating
Gas-bearing formation；Or collector/Catalytic Layer/gas diffusion layers/waterproof ventilative layer.
7. a kind of aluminium-air cell air electrode structure according to claim 1, it is characterised in that：In described Catalytic Layer
SiO containing mass percent 0.1~10.0%2Or Al2O3Nano particle.
8. a kind of aluminium-air cell air electrode structure according to claim 1, it is characterised in that：Described catalyst layer
Conductive agent, catalyst and polytetrafluoroethylene (PTFE) binding agent are also included, wherein the catalyst is silver or manganese dioxide, quality percentage contains
Measure as 10%~50%；Polytetrafluoroethylene (PTFE) binding agent, weight/mass percentage composition is 10%~40%；Conductive agent is activated carbon and Ke Qin
Black, weight/mass percentage composition is 30%~70%.
9. a kind of aluminium-air cell air electrode structure according to claim 1, it is characterised in that：Described polyphosphazene polymer
Compound anion exchange resin is from styrene resin, benzyl ethylene resin, acrylic resin, polyamide-based resin, poly-
Sulfone resinoid, polyolefin resin, polyethers resinoid, polyketone resinoid, the quaternary ammoniated modifier tree of makrolon or polyesters
Fat, and the mixture of above-mentioned species or the other functional groups of addition make it have the derivatives resin of ion-exchange performance.
10. a kind of aluminium-air cell air electrode structure according to claim 7, it is characterised in that：Described nanometer
Grain particle diameter is 0.01~20 micron.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108736019A (en) * | 2018-04-10 | 2018-11-02 | 云南铝业股份有限公司 | Metal fuel battery air electrode and preparation method thereof |
| CN109411768A (en) * | 2018-10-17 | 2019-03-01 | 东莞市中航华讯卫星技术有限公司 | The preparation method of air electrode |
| CN110336042A (en) * | 2019-07-05 | 2019-10-15 | 中国科学院重庆绿色智能技术研究院 | A kind of gas diffusion cathode and the preparation method and application thereof |
| CN112825356A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院大连化学物理研究所 | Composite gas diffusion electrode and battery |
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| US20100323249A1 (en) * | 2008-02-18 | 2010-12-23 | National Institute Of Advanced Industrial Science And Technology | Air electrode |
| CN105932300A (en) * | 2016-05-30 | 2016-09-07 | 昆明纳太科技有限公司 | Gas diffusion electrode and preparation method thereof |
| CN106104909A (en) * | 2014-03-28 | 2016-11-09 | 日本碍子株式会社 | Metal-air battery air pole |
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2017
- 2017-04-21 CN CN201710265206.0A patent/CN107039657A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100323249A1 (en) * | 2008-02-18 | 2010-12-23 | National Institute Of Advanced Industrial Science And Technology | Air electrode |
| CN106104909A (en) * | 2014-03-28 | 2016-11-09 | 日本碍子株式会社 | Metal-air battery air pole |
| CN105932300A (en) * | 2016-05-30 | 2016-09-07 | 昆明纳太科技有限公司 | Gas diffusion electrode and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108736019A (en) * | 2018-04-10 | 2018-11-02 | 云南铝业股份有限公司 | Metal fuel battery air electrode and preparation method thereof |
| CN109411768A (en) * | 2018-10-17 | 2019-03-01 | 东莞市中航华讯卫星技术有限公司 | The preparation method of air electrode |
| CN110336042A (en) * | 2019-07-05 | 2019-10-15 | 中国科学院重庆绿色智能技术研究院 | A kind of gas diffusion cathode and the preparation method and application thereof |
| CN112825356A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院大连化学物理研究所 | Composite gas diffusion electrode and battery |
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Application publication date: 20170811 |