CN107195910A - One kind can discharge and recharge metal air battery cathodes and preparation method thereof - Google Patents
One kind can discharge and recharge metal air battery cathodes and preparation method thereof Download PDFInfo
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- CN107195910A CN107195910A CN201710431392.0A CN201710431392A CN107195910A CN 107195910 A CN107195910 A CN 107195910A CN 201710431392 A CN201710431392 A CN 201710431392A CN 107195910 A CN107195910 A CN 107195910A
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- Prior art keywords
- discharge
- air battery
- recharge
- base plate
- battery cathodes
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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
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
-
- 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
-
- 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
- H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
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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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- 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
- H01M4/9041—Metals or alloys
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention relates to one kind can discharge and recharge metal air battery cathodes, it includes foam base plate, the noble metal nano particles that are deposited on the foam base plate and is bonded in the Catalytic Layer of the foam base plate any surface；The thickness of the froth bed is 0.1~10mm, and its porosity is 70~98%.By its interior depositing noble metal nano-particle and bonding form Catalytic Layer, so charging when can using noble metal nano particles effect catalysis OH‑Oxygen is generated, and Catalytic Layer catalytic oxygen formation OH can be utilized in electric discharge‑, the dual-use function of discharge and recharge is realized, it is more stable；And in the absence of carbonaceous material, there is the risk aoxidized this avoid the effect of absorption oxygen.
Description
Technical field
The invention belongs to metal-air battery field, it is related to a kind of negative electrode, and in particular to one kind can discharge and recharge metal-air
Cell cathode and preparation method thereof.
Background technology
Metal-air battery not only possesses general fuel cell hair as a kind of fuel cell with special discharge mode
Electrical efficiency is high, free of contamination feature, also high with power density, the advantage of sustainable electric discharge.The work of metal-air battery is former
Reason is anode while metal is consumed, and negative electrode needs the oxygen in consumed cabin air, therefore negative electrode needs good air permeable
Rate.Existing metal-air battery is as shown in figure 1, it generally has an anode and two negative electrodes, and one of negative electrode is carried out
Charging and another negative electrode is discharged, this has resulted in that its is complicated and cost is higher；And existing has an anode
With the metal-air battery of a negative electrode then less stable.
The content of the invention
Can discharge and recharge metal air battery cathodes the invention aims to overcome the deficiencies in the prior art and provide one kind.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：One kind can discharge and recharge metal air battery cathodes, it
Including foam base plate, the noble metal nano particles being deposited on the foam base plate and it is bonded in the foam base plate either table
The Catalytic Layer in face；The thickness of the froth bed is 0.1~10mm, and its porosity is 70~98%.
Optimally, the porosity of the froth bed is 75~95%.
Optimally, it also includes forming the micropore PTFE film in the catalysis layer surface.
Optimally, the material of the foam base plate is Ni, Cu, NiCrFe, ZnCu, NiCu, NiCrW, NiFe or Ti.
Optimally, the noble metal nano particles are Pt or Ir, and its particle diameter is 5~50nm.
A further object of the present invention be provide it is a kind of it is above-mentioned can discharge and recharge metal air battery cathodes preparation method, it
Comprise the following steps：
(a) foam base plate is placed in noble metal nano particles precursor solution, is heated to boiling, is subsequently added sodium citrate
Solution keeps boiling under conditions of being stirred continuously, and obtains depositing the foam base plate of noble metal nano particles；
(b) take PTFE emulsion to be dissolved in ethanol, add metal oxide catalyst ultrasonic disperse formation slurry；
(c) slurry is coated in into deposition has the foam base plate surface of noble metal nano particles, dries formation and urges
Change layer.
Optimally, micropore PTFE film is also heated to 260~280 DEG C by it including step (d), and it is extruded with roll shaft
It is covered in the catalysis layer surface, be subsequently placed in water and carry out chilling.
Optimally, in step (a), the concentration of the noble metal nano particles precursor solution is 0.005~0.015mol/
L。
Further, in step (a), the concentration of the sodium citrate solution is 0.05~0.15mol/L.
Optimally, in the step (b), it is additionally added acetylene black while adding metal oxide catalyst so that acetylene
The black mass fraction in the slurry is 0.5~2%.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：The present invention can discharge and recharge
Metal air battery cathodes, by its interior depositing noble metal nano-particle and bonding form Catalytic Layer, so charging when energy
Enough utilize noble metal nano particles effect catalysis OH-Oxygen is generated, and can be formed in electric discharge using Catalytic Layer catalytic oxygen
OH-, the dual-use function of discharge and recharge is realized, it is more stable；And in the absence of carbonaceous material, this avoid the effect of absorption oxygen
And there is the risk aoxidized.
Brief description of the drawings
Fig. 1 is the structural representation of existing metal-air battery；
Fig. 2 for the present invention can discharge and recharge metal air battery cathodes structural representation.
Embodiment
The present invention can discharge and recharge metal air battery cathodes, it include foam base plate, be deposited on the foam base plate
Noble metal nano particles and the Catalytic Layer for being bonded in the foam base plate any surface；The thickness of the froth bed be 0.1~
10mm, its porosity is 70~98%；Preferably 75~95%.By in its interior depositing noble metal nano-particle and bonding formation
Catalytic Layer, can utilize noble metal nano particles effect catalysis OH so in charging-Oxygen is generated, and being capable of profit in electric discharge
With Catalytic Layer catalytic oxygen formation OH-, the dual-use function of discharge and recharge is realized, it is more stable；And carbonaceous material is not present, this
Sample avoids the effect of absorption oxygen and the risk aoxidized occurs.This can discharge and recharge metal air battery cathodes also include formed in institute
The micropore PTFE film (commercially available) of catalysis layer surface is stated, to reduce alkali lye side leakage.The material of foam base plate is that of routine
A bit, such as Ni, Cu, NiCrFe, ZnCu, NiCu, NiCrW, NiFe or Ti.Noble metal nano particles are preferably Pt or Ir, its particle diameter
For 5~50nm.Catalytic Layer is commercially available perovskite type metal oxide.The preparation side of above-mentioned discharge and recharge metal air battery cathodes
Method, it comprises the following steps：(a) foam base plate is placed in noble metal nano particles precursor solution, is heated to boiling, then adds
Enter sodium citrate solution and boiling is kept under conditions of being stirred continuously, obtain depositing the foam base plate of noble metal nano particles；
(b) take PTFE emulsion to be dissolved in ethanol, add metal oxide catalyst ultrasonic disperse formation slurry；(c) by the slurry
Being coated in deposition has the foam base plate surface of noble metal nano particles, and drying forms Catalytic Layer.Optimally, it also includes step
Suddenly micropore PTFE film is heated to 260~280 DEG C by (d), and carrying out extruding to it with roll shaft makes it cover in the catalysis layer surface,
It is subsequently placed in water and carries out chilling.In step (a), the concentration of the noble metal nano particles precursor solution is preferably
0.005~0.015mol/L；And the concentration of the sodium citrate solution is preferably 0.05~0.15mol/L.The step (b)
In, it is additionally added acetylene black while adding metal oxide catalyst so that PTFE emulsion and the matter of metal oxide catalyst
The mass ratio for measuring summation and acetylene black is 1~5: 1.
The present invention is further described below in conjunction with accompanying drawing embodiment.
Embodiment 1
The present embodiment provide one kind can discharge and recharge metal air battery cathodes, as shown in Fig. 2 it include foam base plate 1, it is heavy
The noble metal nano particles on foam base plate 1 are accumulated, the Catalytic Layer 2 on foam base plate surface is bonded in and is covered in Catalytic Layer 2
The micropore PTFE film 4 on surface；Its preparation method comprises the following steps：
(a) by nickel foam (commercially available, De Sike, surface density (250~450) ± 30g/m2, endwise tensile strength >=40N/
20mm, transverse tensile strength >=30N/20mm, porosity is about 90%；It is respectively washed repeatedly with ethanol, acetone using preceding) immersion
Boiling is heated in noble metal nano particles precursor solution (platinum acid chloride solution, concentration is 0.01mol/L, 10ml), continuous
(mixing speed is 1200 revs/min) adds in 10mL, 0.09mol/L sodium citrate solution and keeps boiling under conditions of stirring
15min so that deposition has nano platinum particle (20~50nm) on foam base plate；
(b) by PTFE emulsion (commercially available, Aladdin, 60wt%) and metal oxide catalyst (La0.6Ca0.4CoO3, reference
The research of Perovskite Type Catalyst for Zinc-air Battery Air Electrode) in mass ratio 1: 1 mixed, a small amount of ethanol demulsification is added,
It is ground and is mixed to form slurry；
(c) slurry is coated or is pressed in the foam base plate surface for there are noble metal nano particles in deposition, be placed in 120 DEG C of baking
Drying forms Catalytic Layer in case；
(d) micropore PTFE film (commercially available) is heated to 260~280 DEG C, extruding is carried out to it with roll shaft is covered in it to urge
Change layer surface, be subsequently placed in water (20~30 DEG C) and carry out chilling.
Embodiment 2
The present embodiment provide one kind can discharge and recharge metal air battery cathodes, its structure with it is basically identical in embodiment 1, no
Same is not cover micropore PTFE film 4 on the surface of Catalytic Layer 2.
Embodiment 3
The present embodiment provide one kind can discharge and recharge metal air battery cathodes, its structure with it is basically identical in embodiment 1, no
Same is that the precursor solution used is chloro-iridic acid.
Embodiment 4
The present embodiment provide one kind can discharge and recharge metal air battery cathodes, its structure with it is basically identical in embodiment 1, no
Be：In step (b), being additionally added acetylene black makes the mass ratio of itself and metal oxide catalyst be 1: 1.
Embodiment 5
The present embodiment provide one kind can discharge and recharge metal air battery cathodes, its structure with it is basically identical in embodiment 1, no
Be：In step (a), the platinum acid chloride solution concentration used is 0.005mol/L, and the concentration of sodium citrate solution is
0.05mol/L。
Embodiment 6
The present embodiment provide one kind can discharge and recharge metal air battery cathodes, its structure with it is basically identical in embodiment 1, no
Be：In step (a), the platinum acid chloride solution concentration used is 0.015mol/L, and the concentration of sodium citrate solution is
0.15mol/L。
Embodiment 7
The present embodiment provide one kind can discharge and recharge metal air battery cathodes, its structure with it is basically identical in embodiment 1, no
Be：In step (b), acetylene black is additionally added so that PTFE emulsion and the quality summation and acetylene of metal oxide catalyst
Black mass ratio is 1: 1.
Embodiment 8
The present embodiment provide one kind can discharge and recharge metal air battery cathodes, its structure with it is basically identical in embodiment 1, no
Be：In step (b), acetylene black is additionally added so that PTFE emulsion and the quality summation and acetylene of metal oxide catalyst
Black mass ratio is 5: 1.
Comparative example 1
This example provides a kind of metal air battery cathodes, its structure with it is basically identical in embodiment 1, unlike do not steeping
Foam substrate deposit nano platinum particle.
By obtained negative electrode in embodiment 1-8 and comparative example 1 respectively with identical calamine cream, electrolyte 6mol/L sodium hydroxides
Solution is assembled into metal-air electrode and carries out electro-chemical test, the capacity in their discharge processes be respectively 450mAh, 420mAh,
500mAh, 480mAh, 450mAh, 450mAh, 485mAh, 465mAh and 350mAh, it can be found that depositing noble metal nano-particle
Synergy is generated with Catalytic Layer afterwards, so as to improve the discharge capacity of metal-air battery, additionally it is possible to which it is carried out directly
Charging, simplifies the structure and cost of battery.But, if not covering micropore PTFE film 4, the battery in embodiment 2 is being placed
There is a small amount of electrolyte to ooze out after when one section.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention, all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (10)
1. one kind can discharge and recharge metal air battery cathodes, it is characterised in that：It includes foam base plate, is deposited on the foam-based
Noble metal nano particles on body and the Catalytic Layer for being bonded in the foam base plate any surface；The thickness of the froth bed is
0.1~10mm, its porosity is 70~98%.
2. according to claim 1 for it is described can discharge and recharge metal air battery cathodes, it is characterised in that：The hole of the froth bed
Gap rate is 75~95%.
3. according to claim 1 for it is described can discharge and recharge metal air battery cathodes, it is characterised in that：It also includes being formed
The micropore PTFE film of the catalysis layer surface.
4. according to claim 1 for it is described can discharge and recharge metal air battery cathodes, it is characterised in that：The foam base plate
Material is Ni, Cu, NiCrFe, ZnCu, NiCu, NiCrW, NiFe or Ti.
5. according to claim 1 for it is described can discharge and recharge metal air battery cathodes, it is characterised in that：The noble metal nano
Particle is Pt or Ir, and its particle diameter is 5~50nm.
6. according to any in claim 1 to 5 can discharge and recharge metal air battery cathodes preparation method, its feature exists
In it comprises the following steps：
(a) foam base plate is placed in noble metal nano particles precursor solution, is heated to boiling, is subsequently added sodium citrate solution
Boiling is kept under conditions of being stirred continuously, obtains depositing the foam base plate of noble metal nano particles；
(b) take PTFE emulsion to be dissolved in ethanol, add metal oxide catalyst ultrasonic disperse formation slurry；
(c) slurry is coated in into deposition has the foam base plate surface of noble metal nano particles, and drying forms Catalytic Layer.
7. according to claim 6 can discharge and recharge metal air battery cathodes preparation method, it is characterised in that it also includes
Micropore PTFE film is heated to 260~280 DEG C by step (d), and extruding is carried out to it with roll shaft makes it cover in the Catalytic Layer table
Face, is subsequently placed in water and carries out chilling.
8. according to claim 6 can discharge and recharge metal air battery cathodes preparation method, it is characterised in that：Step (a)
In, the concentration of the noble metal nano particles precursor solution is 0.005~0.015mol/L.
9. according to claim 8 can discharge and recharge metal air battery cathodes preparation method, it is characterised in that：Step (a)
In, the concentration of the sodium citrate solution is 0.05~0.15mol/L.
10. according to claim 6 can discharge and recharge metal air battery cathodes preparation method, it is characterised in that：The step
Suddenly in (b), it is additionally added acetylene black while adding metal oxide catalyst so that PTFE emulsion and metal oxide catalyst
Quality summation and acetylene black mass ratio be 1~5: 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710431392.0A CN107195910A (en) | 2017-06-03 | 2017-06-03 | One kind can discharge and recharge metal air battery cathodes and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710431392.0A CN107195910A (en) | 2017-06-03 | 2017-06-03 | One kind can discharge and recharge metal air battery cathodes and preparation method thereof |
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| CN107195910A true CN107195910A (en) | 2017-09-22 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101087022A (en) * | 2006-06-05 | 2007-12-12 | 上海攀业氢能源科技有限公司 | Making method for dual-function catalyzer of recycling fuel battery |
| CN103872343A (en) * | 2014-03-25 | 2014-06-18 | 哈尔滨工业大学 | Porous lithium-air battery air cathode and preparation method thereof |
| CN104393310A (en) * | 2014-10-20 | 2015-03-04 | 上海空间电源研究所 | Air electrode material of high-activity lithium air battery and preparation method of nano-composite catalyst material |
| CN105609794A (en) * | 2016-01-18 | 2016-05-25 | 湖南众麒能源科技有限责任公司 | Air electrode catalyst for zinc-air battery and preparation method of air electrode catalyst |
| CN106030899A (en) * | 2015-03-04 | 2016-10-12 | 陈忠伟 | Tri-electrode zinc-air battery with flowing electrolyte |
-
2017
- 2017-06-03 CN CN201710431392.0A patent/CN107195910A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101087022A (en) * | 2006-06-05 | 2007-12-12 | 上海攀业氢能源科技有限公司 | Making method for dual-function catalyzer of recycling fuel battery |
| CN103872343A (en) * | 2014-03-25 | 2014-06-18 | 哈尔滨工业大学 | Porous lithium-air battery air cathode and preparation method thereof |
| CN104393310A (en) * | 2014-10-20 | 2015-03-04 | 上海空间电源研究所 | Air electrode material of high-activity lithium air battery and preparation method of nano-composite catalyst material |
| CN106030899A (en) * | 2015-03-04 | 2016-10-12 | 陈忠伟 | Tri-electrode zinc-air battery with flowing electrolyte |
| CN105609794A (en) * | 2016-01-18 | 2016-05-25 | 湖南众麒能源科技有限责任公司 | Air electrode catalyst for zinc-air battery and preparation method of air electrode catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 刘时杰: "《铂族金属冶金学》", 30 June 2013, 中南大学出版社 * |
| 汪旭光，潘家柱: "《21世纪中国有色金属工业可持续发展战略》", 31 December 2001, 冶金工业出版社 * |
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Application publication date: 20170922 |