CN104538652A - Air electrode for metal air battery and metal air battery - Google Patents
Air electrode for metal air battery and metal air battery Download PDFInfo
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- CN104538652A CN104538652A CN201410778420.2A CN201410778420A CN104538652A CN 104538652 A CN104538652 A CN 104538652A CN 201410778420 A CN201410778420 A CN 201410778420A CN 104538652 A CN104538652 A CN 104538652A
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- air 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
- 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
- H01M4/8605—Porous electrodes
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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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Hybrid Cells (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides an air electrode for a metal air battery and the metal air battery. The air electrode is made of a fibrous conductive material with a porous structure, a relatively good air electrode with a relatively stable mechanical performance is provided for the metal air battery, and a chemically stable and relatively conductive supporting structure is also provided for a catalyst; metal catalyst particles are deposited in the porous structure of the air electrode, so that the oxygen reduction reaction rate of the battery can be increased. The invention provides the metal air battery. The metal air battery comprises the improved air electrode, wherein an oxygen selectivity membrane is arranged at one side of the air electrode, and oxygen is selectively filtered from air, so that the oxidization reduction reaction rate can be increased by multiple times; compared with an existing metal air battery, the metal air battery is higher in output power and longer in charging-discharging cycle life and can be used as a battery of an electric car.
Description
Technical field
The present invention relates to metal-air cell field, particularly relate to and a kind ofly there is high power factor and a large amount of charge and discharge cycles and be designed for the air electrode improved in the metal-air cell of electric automobile and this metal-air cell.
Background technology
The harm that side effect-environmental pollution that the mankind stay in process of industrialization brings be familiar with by countries in the world, and due to the exhaustive exploitation of primary energy, global energy supply is increasingly deficient.Since the nineties in 20th century, be studied a series of high-performance, novel pollution-free green energy resource both at home and abroad, it creates far-reaching influence to the change of world industry structure.
Metal-air cell is the fuel cell of a kind of new ideas replacing hydrogen energy source with metal fuel and formed, and is expected to become the new generation of green energy.It has played the many merits of fuel cell, the metal such as zinc, aluminium is provided to as hydrogen the response location in battery, a continuous print electric energy generation device is formed together with oxygen, there is nontoxic, pollution-free, discharging voltage balance, high-energy-density, the advantage such as internal resistance is little, storage life is long, price is relatively low, process specifications is lower, high-specific-power, existing abundant low-cost resource, again can regeneration, and simpler than hydrogen fuel cell structure, be the new forms of energy having very much development and application prospect.
Compared with existing battery, although the price of zinc-manganese dioxide dry cell is cheap, capacity is too low; Compared with Ni-Cd battery, metal-air cell can provide the electric power of large about 10 times, and considerably reduces the charging interval; Especially in energy efficiency, more high than internal combustion engine homenergic conversion equipment.In today that the energy is day by day in short supply, more highlight its important function.
Metal-air cell is compared with lithium ion battery, and it has larger energy density and lower cycle life; Although lithium ion battery is the first-selection of batteries of electric automobile, metal-air cell can have the power density higher than lithium ion battery, and the energy density of metal-air cell is 10 times of existing lithium ion battery; Metal-air cell also possesses long shelf-life (kept dry) simultaneously, the advantages such as low cost, and in working range, do not rely on the ability of load and temperature, but metal-air cell also has limited charge and discharge circulation life, limited power ratio, limited power stage and limited operating temperature range, and the shortcoming such as metal anode is perishable.These bad characteristics seriously limit the application of metal-air cell.
Summary of the invention
The object of the present invention is to provide a kind of air electrode for metal-air cell, the material of described air electrode is the electric conducting material of the fibre morphology with loose structure, for metal-air cell provides an air electrode that better machinery is more stable, simultaneously for catalyst provides a chemically stable and the supporting construction of more conducting electricity; Depositing Metal Catalyst particle in the loose structure of described air electrode, thus the oxygen reduction reaction speed improving battery.
The present invention also aims to provide a kind of metal-air cell, except comprising the air electrode of the present invention's improvement, also comprise the oxygen selective film being arranged at described air electrode side, optionally from air, filter out oxygen thus make redox reaction speed be increased to original several times, compared with existing metal-air cell, metal-air cell of the present invention has higher power stage and longer charge and discharge circulation life, can be used as the battery of electric automobile.
For achieving the above object, the invention provides a kind of air electrode for metal-air cell, the electrolyte that described metal-air cell comprises described air electrode, negative electrode and is provided between described air electrode and described negative electrode, wherein, the material of described air electrode is the electric conducting material of the fibre morphology with loose structure.
The material of described air electrode has the loose structure of micron or sub-micrometer sized pores.
The material of described air electrode is carbon nano-tube.
Metal catalyst particles is deposited in the loose structure of described air electrode.
Described metallic catalyst is the metal-based catalyst with nanocrystalline structure.
Described metallic catalyst is platinum base nanometer crystal body.
The present invention also provides a kind of metal-air cell, comprises:
According to arbitrary air electrode as above;
Negative electrode; With
Be provided in the electrolyte solution between described air electrode and described negative electrode.
Also comprise the oxygen selective film being arranged at described air electrode side.
Described negative electrode is made up of active metal zinc, aluminium or nickel.
Described electrolyte solution is sodium hydroxide solution.
Beneficial effect of the present invention: a kind of air electrode for metal-air cell provided by the invention, compared with prior art, there is following improvement: 1) adopt the electric conducting material with the fibre morphology of loose structure as the material of air electrode, be not only metal-air cell and provide a gas electrode that better machinery is more stable, simultaneously for catalyst provides a chemically stable and the supporting construction of more conducting electricity; 2) Depositing Metal Catalyst particle in the loose structure of described air electrode, thus the oxygen reduction reaction speed improving battery.A kind of metal-air cell provided by the invention, except comprising the air electrode of the present invention's improvement, also comprise the oxygen selective film being arranged at described air electrode side, optionally from air, filter out oxygen thus make redox reaction speed be increased to original several times, compared with existing metal-air cell, metal-air cell of the present invention has higher power stage and longer charge and discharge circulation life, can be used as the battery of electric automobile.
In order to further understand feature of the present invention and technology contents, refer to following detailed description for the present invention and accompanying drawing, but accompanying drawing only provides reference and explanation use, is not used for being limited the present invention.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, by the specific embodiment of the present invention describe in detail, will make technical scheme of the present invention and other beneficial effect apparent.
In accompanying drawing,
Fig. 1 is the structural representation of metal-air cell of the present invention.
Embodiment
For further setting forth the technological means and effect thereof that the present invention takes, be described in detail below in conjunction with the preferred embodiments of the present invention and accompanying drawing thereof.
In general, in metal-air cell, negative pole is active metal sacrificial electrode, just very air diffusion electrode, and electrolyte is neutral salt solution or alkaline solution, and positive pole reaction is the electrode reaction of oxygen reduction:
O
2+2H
2O+4e＝4OH
-(E＝+0.401V)。
The theoretical energy density of metal-air cell only depends on negative pole, i.e. fuel electrode, and this is the sole active agent transmitted in battery, and oxygen is then quoted in discharge process from air.Used metal, electrolyte and other factors are depended in exoelectrical reaction on metal electrode, and the general general formula of exoelectrical reaction is:
M＝M
n++ne
-；
Battery discharge overall reaction is: 4M+nO
2+ 2nH
2o=4M (OH)
n;
Wherein, M is metal, and n is the variation of valence value in burning process.
Refer to Fig. 1, the invention provides a kind of metal-air cell, it barrier film comprising negative pole, positive pole and be arranged between negative pole and positive pole.Described barrier film is by electrolyte solution impregnation.Described positive pole is air electrode.
The material of described negative pole is the active metals such as zinc, aluminium or nickel.
Described electrolyte solution is sodium hydroxide solution.
The present invention relates generally to the improvement carried out the air electrode of metal-air cell, and compared with prior art, described air electrode has the following technical characteristic improved, and comprising:
1) material of described air electrode is the electric conducting material of the fibre morphology with loose structure, as the carbon based fibers of carbon nano-tube and so on.
The air electrode of the present invention by adopting the electric conducting material with the fibre morphology of loose structure to be used as in metal-air cell, for metal-air cell provides the better more stable air electrode of machinery and a chemically stable and the catalyst supporting structure more conducted electricity.Described loose structure is used to the contact area of the metal ion increasing oxygen and be attracted to electrode surface; The material of described air electrode has stronger mechanical strength as catalyst carrier, for catalyst granules forms a stable supporting construction.
Concrete, the material of described air electrode can be a kind of network of connection opening of the three-dimensional based on loose structure.The air electrode material with the loose structure of micron or sub-micrometer sized pores becomes the first-selection in the O_2 transport of metal-air cell due to its good dynamics.
2) deposit metal catalyst particles in the loose structure of described air electrode, described metallic catalyst is the metal-based catalyst with nanocrystalline structure, as platinum base nanometer crystal body.
Due to air electrode diffusion slowly and other restriction, when being subject to serious polarization, the cathode voltage of described metal-air cell declines suddenly with the increase of electric current.This polarization causes metal-air cell to be limited in low power applications.But in the application of automobile, we need high-power and high efficiency battery as automobile power source.For improving the power of metal-air cell, we advise using a kind of metal-based catalyst to improve the oxygen reduction reaction speed of battery.A good example of described metal-based catalyst is platinum base nanometer crystal body, and it can reduce the polarization of oxygen reduction reaction (ORR).
When the diameter of platinum base nanometer crystal body is between 2-100 nanometer, effect is best, preferred 10nm.
Deposit in case at platinum base nanometer crystal body catalyst, described redox reaction, by catalyzed, to realize high rate of reduction, gives the more power of metal-air cell and speed output.We advise that metal-based catalyst adopts nanocrystalline structure to increase the catalyst area in redox reaction.Described catalyst can reduce activation energy, and redox reaction speed is accelerated.
Prepare the typical lab process of described Pt nanocrystal body: the mixture using one water/surfactant according to the method being similar to previously report, NaBH
4(sodium borohydride) reduces H
2ptCl
6(chloroplatinic acid) produces nano platinum particle (Pt NPs).
Because do not relate to kinetic steps in reduction reaction, above-mentioned reaction has replicability, can be used for industrial mass production Pt nanoparticle.
Except Pt nanocrystal body catalyst, the antigravity system of other Metal Substrate can also be attempted.They are nickel (Ni), palladium (Pd), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn) or their alloy.Their binary, ternary, or multicomponent alloy can show even better catalytic performance in redox reaction.
Except air electrode, negative pole, be arranged on barrier film between air electrode and negative pole, be provided between air electrode and negative pole electrolyte solution except, metal-air cell of the present invention also comprises the oxygen selective film (OSM, oxygen selective membrane) being arranged at described air electrode side.
Because oxygen selective film (OSM) can allow oxygen enter battery, use this film optionally from air, to filter out oxygen, pure oxygen is injected metal-air cell to improve battery operated efficiency.Although the air of routine has the oxygen of 20%, 100% pure oxygen will make redox reaction speed bring up to original 5 times.
The above, for the person of ordinary skill of the art, can make other various corresponding change and distortion according to technical scheme of the present invention and technical conceive, and all these change and be out of shape the protection range that all should belong to the claims in the present invention.
Claims (10)
1. the air electrode for metal-air cell, the electrolyte that described metal-air cell comprises described air electrode, negative electrode and is provided between described air electrode and described negative electrode, it is characterized in that, the material of described air electrode is the electric conducting material of the fibre morphology with loose structure.
2. air electrode as claimed in claim 1, it is characterized in that, the material of described air electrode has the loose structure of micron or sub-micrometer sized pores.
3. air electrode as claimed in claim 1, it is characterized in that, the material of described air electrode is carbon nano-tube.
4. air electrode as claimed in claim 1, is characterized in that, deposit metal catalyst particles in the loose structure of described air electrode.
5. air electrode as claimed in claim 4, it is characterized in that, described metallic catalyst is the metal-based catalyst with nanocrystalline structure.
6. air electrode as claimed in claim 5, it is characterized in that, described metallic catalyst is platinum base nanometer crystal body.
7. a metal-air cell, comprises:
Air electrode according to any one of claim 1 to 6;
Negative electrode; With
Be provided in the electrolyte solution between described air electrode and described negative electrode.
8. metal-air cell as claimed in claim 7, is characterized in that, also comprise the oxygen selective film being arranged at described air electrode side.
9. metal-air cell as claimed in claim 7, it is characterized in that, described negative electrode is made up of active metal zinc, aluminium or nickel.
10. metal-air cell as claimed in claim 7, it is characterized in that, described electrolyte solution is sodium hydroxide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410778420.2A CN104538652A (en) | 2014-12-15 | 2014-12-15 | Air electrode for metal air battery and metal air battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410778420.2A CN104538652A (en) | 2014-12-15 | 2014-12-15 | Air electrode for metal air battery and metal air battery |
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| CN104538652A true CN104538652A (en) | 2015-04-22 |
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| CN201410778420.2A Pending CN104538652A (en) | 2014-12-15 | 2014-12-15 | Air electrode for metal air battery and metal air battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110199411A (en) * | 2016-12-15 | 2019-09-03 | 斐源有限公司 | System and method for initializing and running metal-air battery |
| CN111033827A (en) * | 2017-07-10 | 2020-04-17 | 法国电力公司 | Method for managing the electric power transferred through a metal-air battery cell and associated cell |
| CN111537900A (en) * | 2020-04-07 | 2020-08-14 | 清华大学 | Comprehensive test and evaluation method for durability of metal-air fuel cell |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102308414A (en) * | 2009-02-06 | 2012-01-04 | 吉列公司 | Thin metal-air batteries |
| CN102637879A (en) * | 2012-04-09 | 2012-08-15 | 中南大学 | Micro-nano-structure anode material for Li-air battery and preparation method of micro-nano-structure anode material |
| CN102983380A (en) * | 2012-11-07 | 2013-03-20 | 华中科技大学 | Lithium air battery based on three-dimensional carbon nanotube structure and preparation method thereof |
| CN103125047A (en) * | 2010-10-07 | 2013-05-29 | 住友化学株式会社 | Air battery |
| CN103337641A (en) * | 2013-03-12 | 2013-10-02 | 上海中聚佳华电池科技有限公司 | Oxygen electrode composite catalyst used for lithium-air batteries and preparation method of the oxygen electrode composite catalyst |
-
2014
- 2014-12-15 CN CN201410778420.2A patent/CN104538652A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102308414A (en) * | 2009-02-06 | 2012-01-04 | 吉列公司 | Thin metal-air batteries |
| CN103125047A (en) * | 2010-10-07 | 2013-05-29 | 住友化学株式会社 | Air battery |
| CN102637879A (en) * | 2012-04-09 | 2012-08-15 | 中南大学 | Micro-nano-structure anode material for Li-air battery and preparation method of micro-nano-structure anode material |
| CN102983380A (en) * | 2012-11-07 | 2013-03-20 | 华中科技大学 | Lithium air battery based on three-dimensional carbon nanotube structure and preparation method thereof |
| CN103337641A (en) * | 2013-03-12 | 2013-10-02 | 上海中聚佳华电池科技有限公司 | Oxygen electrode composite catalyst used for lithium-air batteries and preparation method of the oxygen electrode composite catalyst |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110199411A (en) * | 2016-12-15 | 2019-09-03 | 斐源有限公司 | System and method for initializing and running metal-air battery |
| US11228067B2 (en) | 2016-12-15 | 2022-01-18 | Phinergy Ltd. | System and method for initializing and operating metal-air cell |
| CN110199411B (en) * | 2016-12-15 | 2022-03-29 | 斐源有限公司 | System and method for initializing and operating a metal-air battery |
| US11616264B2 (en) | 2016-12-15 | 2023-03-28 | Phinergy Ltd. | System and method for initializing and operating metal-air cell |
| CN111033827A (en) * | 2017-07-10 | 2020-04-17 | 法国电力公司 | Method for managing the electric power transferred through a metal-air battery cell and associated cell |
| CN111537900A (en) * | 2020-04-07 | 2020-08-14 | 清华大学 | Comprehensive test and evaluation method for durability of metal-air fuel cell |
| CN111537900B (en) * | 2020-04-07 | 2021-03-16 | 清华大学 | Comprehensive test and evaluation method for durability of metal-air fuel cell |
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Application publication date: 20150422 |
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