CN102867964A - Air electrode and preparation method thereof - Google Patents
Air electrode and preparation method thereof Download PDFInfo
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- CN102867964A CN102867964A CN2012103266188A CN201210326618A CN102867964A CN 102867964 A CN102867964 A CN 102867964A CN 2012103266188 A CN2012103266188 A CN 2012103266188A CN 201210326618 A CN201210326618 A CN 201210326618A CN 102867964 A CN102867964 A CN 102867964A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides an air electrode and a preparation method of the air electrode. The method comprises the following steps of: carrying out polytetrafluoroethylene treatment on carbon paper to form an air dispersion layer; uniformly mixing a carbon base and a catalyst; adding an adhesive and ultrasonically dispersing to form active layer slurry; spraying the active layer slurry on the air dispersion layer; and carrying out drying treatment to form an active layer. According to the air electrode and the preparation method of the air electrode, the carbon paper which is treated by polytetrafluoroethylene is used as the air dispersion layer and a good channel for dispersing oxygen is provided; the active layer is adhered on carbon paper fibers in a fiber shape, so that the air electrode is prevented from being immersed by liquid electrolyte and a good transportation channel is provided for dispersing the oxygen; a developed three-phase reaction interface is easily formed and discharging reaction can more deep into an air electrode membrane side; and more catalytic layer active points can be used for storing a discharging product so that the discharging capacity of a battery is improved.
Description
Technical field
The invention belongs to the lithium-air battery preparing technical field, be specifically related to a kind of air electrode and preparation method thereof.
Background technology
Along with the develop rapidly of modern society, resource exhaustion and problem of environmental pollution are day by day serious.People must seek a kind of effective approach alleviates this problem.A main application of fossil energy is to provide power to the vehicles; the consumption of fossil energy on the vehicles has not only caused huge energy loss; simultaneously also caused serious environmental pollution, so Development of EV is considered to a kind of feasible alleviating energy crisis and the measure of environmental pollution.Yet conventional power supply system (such as lead-acid battery, nickel-cadmium cell, lithium ion battery etc.) is difficult to support travelling at a distance of electric automobile at present, and the lithium-air battery that therefore has high theoretical specific energy has attracted to pay close attention to widely.
Lithium-air battery can be called semi-fuel cell again, is the fuel cell that consumes Li, also is that positive active material is the lithium battery of oxygen.During battery discharge, the negative pole lithium metal is oxidized to lithium ion and moves to the oxide that the anodal oxonium ion that produces with oxygen reduction forms lithium by electrolyte; During the battery charging, the oxide decomposition of lithium produces oxygen and lithium ion, and oxygen is discharged by air electrode, and the lithium ion migration is got back to the metal lithium sheet surface reduction and become lithium simple substance.Lithium-air battery has high theoretical specific energy, and its theoretical specific energy reaches 11140Wh/kg, and is approaching with the 13000Wh/kg of gasoline/oxygen system, and the actual available specific energy of the discharge specific energy that present reality can reach and gasoline system is (1700Wh/kg) quite.
Actual value and the theoretical value of lithium-air battery discharge specific energy differ huge, one of its reason is because discharging product (oxide of lithium) is not dissolved in electrolyte, to be deposited in the air electrode, stop up the oxygen transmission passage of air electrode, and cause discharge to stop in advance.The discharge specific energy of lithium-air battery is relevant with anodal porosity and pore volume.Oxygen is to carry out at the three phase boundary that electrolyte, anodal hole surface and oxygen consist of in the reduction reaction of positive pole, the gross area of three phase boundary is larger, the discharging product that can hold is just more, can improve largely discharge capacity and the continuous discharge ability of lithium-air battery.
Summary of the invention
The present invention one of is intended to solve the problems of the technologies described above at least to a certain extent or provides at least a kind of useful commerce to select.For this reason, one object of the present invention is to propose the manufacture method of the air electrode of a kind of air electrode structure that can significantly improve the lithium-air battery performance and this structure.
The invention provides a kind of preparation method of air electrode, it is characterized in that, comprising: carbon paper is carried out polytetrafluoroethylene process, to form gas diffusion layers; Carbon base body and catalyst mix is even, add binder and ultrasonic dispersion, to form the active layer slurry; Described active layer pulp spraying is coated on the described gas diffusion layers, and carries out drying and process, to form active layer.
In the preparation method's of an air electrode of the present invention preferred embodiment, described polytetrafluoroethylene is processed and is comprised: described carbon paper is dipped in the 5wt% polytetrafluoroethylsolution solution soaked 20 minutes; Take out described carbon paper and naturally dry, and 350 ℃ of lower insulations 1 hour.
In the preparation method's of an air electrode of the present invention preferred embodiment, described carbon base body is Super P Conductive Carbon Black or Ketjen Black, and described catalyst is Pt, Pt-Au, MnO
2Series, Fe
2O
3Or Co
3O
4, described binder is the 15wt% polytetrafluoroethylsolution solution, the mass ratio of described carbon base body, catalyst, adhesive is 75:15:10.
In the preparation method's of an air electrode of the present invention preferred embodiment, with described carbon base body and catalyst mix evenly after, and before described adding binder and ultrasonic dispersion, add the carbon dust dispersing agent C
34H
62O
11Solution.
In the preparation method's of an air electrode of the present invention preferred embodiment, described spraying comprises: described gas diffusion layers is placed on 350 ℃ the electric hot plate; Described active layer slurry is sprayed at equably the upper surface of described gas diffusion layers with spray gun, wherein said spray gun adopts the compressed air of 0.2MPa.
In the preparation method's of an air electrode of the present invention preferred embodiment, the carbon carrying capacity of described active layer is 1.5-7mg/cm
2, preferred 3mg/cm
2
In the preparation method's of an air electrode of the present invention preferred embodiment, described drying is treated in 60 ℃ drying box dry 12 hours.
The present invention also provides a kind of air electrode, and this air electrode is that the method according to this invention forms.
The carbon paper that the present invention processed with polytetrafluoroethylene (PTFE) is as gas diffusion layers, good passage can be provided for the diffusion of oxygen, be attached on the carbon paper fiber and make active layer be fibrous, both can avoid air electrode to be flooded by liquid electrolyte, for the diffusion of oxygen provides good transmission channel, also help to form the three-phase reaction interface of growth, make exoelectrical reaction can more be deep into air electrode barrier film side, more Catalytic Layer active site can be used to the storage of discharging product (oxide of lithium), thereby improves the discharge capacity of battery.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage are from obviously and easily understanding becoming the description of embodiment in conjunction with following accompanying drawing, wherein:
Fig. 1 is the preparation method's of air electrode of the present invention flow chart;
Fig. 2 is the structural representation of air electrode of the present invention;
Fig. 3 is the SEM figure of the carbon paper (a) processed of polytetrafluoroethylene of the present invention and the carbon paper (b) that sprayed Catalytic Layer;
Fig. 4 be the air electrode made of the air electrode made of the present invention and prior art discharge performance relatively;
Discharge performance when Fig. 5 is the different carbon carrying capacity of the air electrode made of the present invention relatively.
Embodiment
The below describes embodiments of the invention in detail, and the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or the element with identical or similar functions from start to finish.Be exemplary below by the embodiment that is described with reference to the drawings, be intended to for explaining the present invention, and can not be interpreted as limitation of the present invention.
In description of the invention, it will be appreciated that, term " " center "; " vertically "; " laterally "; " length "; " width "; " thickness ", " on ", D score, " front ", " afterwards ", " left side ", " right side ", " vertically ", " level ", " top ", " end " " interior ", " outward ", " clockwise ", orientation or the position relationship of indications such as " counterclockwise " are based on orientation shown in the drawings or position relationship, only be for convenience of description the present invention and simplified characterization, rather than device or the element of indication or hint indication must have specific orientation, with specific orientation structure and operation, therefore can not be interpreted as limitation of the present invention.
In addition, term " first ", " second " only are used for describing purpose, and can not be interpreted as indication or hint relative importance or the implicit quantity that indicates indicated technical characterictic.Thus, one or more these features can be expressed or impliedly be comprised to the feature that is limited with " first ", " second ".In description of the invention, the implication of " a plurality of " is two or more, unless clear and definite concrete restriction is arranged in addition.
In the present invention, unless clear and definite regulation and restriction are arranged in addition, broad understanding should be done in the terms such as term " installation ", " linking to each other ", " connection ", " fixing ", for example, can be to be fixedly connected with, and also can be to removably connect, or connect integratedly; Can be mechanical connection, also can be to be electrically connected; Can be directly to link to each other, also can indirectly link to each other by intermediary, can be the connection of two element internals.For the ordinary skill in the art, can understand as the case may be above-mentioned term concrete meaning in the present invention.
In the present invention, unless clear and definite regulation and restriction are arranged in addition, First Characteristic Second Characteristic it " on " or D score can comprise that the first and second features directly contact, can comprise that also the first and second features are not directly contacts but by the other feature contact between them.And, First Characteristic Second Characteristic " on ", " top " and " above " comprise First Characteristic directly over Second Characteristic and oblique upper, or only represent that the First Characteristic level height is higher than Second Characteristic.First Characteristic Second Characteristic " under ", " below " and " below " comprise First Characteristic under the Second Characteristic and tiltedly, or only represent that the First Characteristic level height is less than Second Characteristic.
Fig. 1 is the preparation method's of air electrode of the present invention flow chart.As shown in Figure 1, the method comprising the steps of:
S101. carbon paper is carried out polytetrafluoroethylene and process, to form gas diffusion layers.
Particularly, at first carbon paper is dipped in the 5wt% polytetrafluoroethylsolution solution and soaked 20 minutes; Take out subsequently carbon paper and naturally dry, and 350 ℃ of lower insulations 1 hour.
S102. carbon base body and catalyst mix is even, add binder and ultrasonic dispersion, to form the active layer slurry.
Particularly, carbon base body is Super P Conductive Carbon Black or Ketjen Black; Catalyst is Pt, Pt-Au, MnO
2Series, Fe
2O
3Or Co
3O
4Binder is the 15wt% polytetrafluoroethylsolution solution; The mass ratio of carbon base body, catalyst, adhesive is 75:15:10.Usually first that solid-state carbon base body and catalyst mix is even, add again liquid binder and ultrasonic 30min dispersion.Preferably, with carbon base body and catalyst mix evenly after, and before adding binder and ultrasonic dispersion, add an amount of carbon dust dispersing agent C
34H
62O
11Solution.
S103. the active layer pulp spraying is coated on the gas diffusion layers, and carries out drying and process, to form active layer.
Particularly, the gas diffusion layers that at first step S101 is made places on 350 ℃ the electric hot plate; Then the active layer slurry that with spray gun step S102 is made is sprayed at the upper surface of gas diffusion layers equably.In one embodiment of the invention, spray gun adopts the compressed air of 0.2MPa, at the uniform velocity sprays during spraying.Usually, control the carbon carrying capacity of active layer by the quantity for spray of control spray gun, the carbon carrying capacity of active layer is 1.5-7mg/cm
2, preferred 3mg/cm
2In one embodiment of the invention, drying is treated in 60 ℃ drying box dry 12 hours.
Fig. 2 is the structural representation of air electrode of the present invention.As shown in Figure 2, air electrode of the present invention makes by the method for above narration, has the double-decker of gas diffusion layers and active layer, and wherein gas diffusion layers contacts with air layer, and active layer contacts with electrolyte.
Fig. 3 is the SEM figure of the carbon paper (a) processed of polytetrafluoroethylene of the present invention and the carbon paper (b) that sprayed Catalytic Layer.As can be seen from Figure 3, having polytetrafluoroethylene after carbon paper is processed through polytetrafluoroethylene is attached on the carbon paper fiber.And the active layer that adopts spraying method to obtain also is to be fibrous to be attached on the carbon paper fiber.Such fibre structure can provide good transmission channel for the diffusion of oxygen, also help to form the three-phase reaction interface of growth, thereby improves the discharge capacity of battery.
Fig. 4 be the air electrode made of the air electrode made of the present invention and prior art discharge performance relatively.As seen from Figure 4, the air electrode that adopts the present invention to make is compared (be coated in active layer on the nickel foam and be sprayed on the barrier film) with the air electrode that other two kinds of prior aries obtain, and discharge capacity is larger, and voltage platform is higher.
Discharge performance when Fig. 5 is the different carbon carrying capacity of the air electrode made of the present invention relatively.As can be seen from Figure 5, when the carbon carrying capacity of active layer be 2.08 and 3.03mg/cm
2The time, larger battery capacity is all arranged, wherein, the carbon carrying capacity is 3.03mg/cm
2The time voltage platform higher, therefore the most preferred carbon carrying capacity is 3mg/cm
2
The carbon paper that air electrode of the present invention was processed with polytetrafluoroethylene is as gas diffusion layers, good passage can be provided for the diffusion of oxygen, be attached on the carbon paper fiber and make active layer be fibrous, both can avoid air electrode to be flooded by liquid electrolyte, for the diffusion of oxygen provides good transmission channel, also help to form the three-phase reaction interface of growth, make exoelectrical reaction can more be deep into air electrode barrier film side, more Catalytic Layer active site can be used to the storage of discharging product (oxide of lithium), thereby improves the discharge capacity of battery.
In the description of this specification, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or the example in conjunction with specific features, structure, material or the characteristics of this embodiment or example description.In this manual, the schematic statement of above-mentioned term not necessarily referred to identical embodiment or example.And the specific features of description, structure, material or characteristics can be with suitable mode combinations in any one or more embodiment or example.
Although the above has illustrated and has described embodiments of the invention, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, those of ordinary skill in the art is not in the situation that break away from principle of the present invention and aim can change above-described embodiment within the scope of the invention, modification, replacement and modification.
Claims (8)
1. the preparation method of an air electrode is characterized in that, comprising:
Carbon paper is carried out polytetrafluoroethylene process, to form gas diffusion layers;
Carbon base body and catalyst mix is even, add binder and ultrasonic dispersion, to form the active layer slurry;
Described active layer pulp spraying is coated on the described gas diffusion layers, and carries out drying and process, to form active layer.
2. the preparation method of air electrode as claimed in claim 1 is characterized in that, described polytetrafluoroethylene is processed and comprised:
Described carbon paper is dipped in the 5wt% polytetrafluoroethylsolution solution soaked 20 minutes;
Take out described carbon paper and naturally dry, and 350 ℃ of lower insulations 1 hour.
3. the preparation method of air electrode as claimed in claim 2 is characterized in that, described carbon base body is Super P Conductive Carbon Black or Ketjen Black, and described catalyst is Pt, Pt-Au, MnO
2Series, Fe
2O
3Or Co
3O
4, described binder is the 15wt% polytetrafluoroethylsolution solution, the mass ratio of described carbon base body, catalyst, adhesive is 75:15:10.
4. the preparation method of air electrode as claimed in claim 3 is characterized in that, with described carbon base body and catalyst mix evenly after, and before described adding binder and ultrasonic dispersion, add an amount of carbon dust dispersing agent C
34H
62O
11Solution.
5. the preparation method of air electrode as claimed in claim 4 is characterized in that, described spraying comprises:
Described gas diffusion layers placed on 350 ℃ the electric hot plate;
Described active layer slurry is sprayed at equably the upper surface of described gas diffusion layers with spray gun, wherein said spray gun adopts the compressed air of 0.2MPa.
6. the preparation method of air electrode as claimed in claim 5 is characterized in that, the carbon carrying capacity of described active layer is 1.5-7mg/cm
2, preferred 3mg/cm
2
7. the preparation method of air electrode as claimed in claim 6 is characterized in that, described drying is treated in 60 ℃ drying box dry 12 hours.
8. an air electrode is characterized in that, described air electrode is that each described method forms according to claim 1-7.
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|---|---|---|---|
| CN2012103266188A CN102867964A (en) | 2012-09-05 | 2012-09-05 | Air electrode and preparation method thereof |
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|---|---|---|---|
| CN2012103266188A CN102867964A (en) | 2012-09-05 | 2012-09-05 | Air electrode and preparation method thereof |
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| CN102867964A true CN102867964A (en) | 2013-01-09 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110165241A (en) * | 2019-05-07 | 2019-08-23 | 武汉理工大学 | Corrosion-resistant microporous layers of a kind of fuel cell based on graphitized carbon and preparation method thereof |
| CN111933954A (en) * | 2020-08-07 | 2020-11-13 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Air electrode, preparation method thereof and air battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1681148A (en) * | 2004-04-06 | 2005-10-12 | 中国科学院大连化学物理研究所 | Double-efficient air electrode and preparation thereof |
| WO2011052440A1 (en) * | 2009-10-29 | 2011-05-05 | ソニー株式会社 | Lithium-air battery |
-
2012
- 2012-09-05 CN CN2012103266188A patent/CN102867964A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1681148A (en) * | 2004-04-06 | 2005-10-12 | 中国科学院大连化学物理研究所 | Double-efficient air electrode and preparation thereof |
| WO2011052440A1 (en) * | 2009-10-29 | 2011-05-05 | ソニー株式会社 | Lithium-air battery |
Non-Patent Citations (1)
| Title |
|---|
| YONG GAO 等: "Preparation of high-capacity air electrode for lithium-air batteries", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110165241A (en) * | 2019-05-07 | 2019-08-23 | 武汉理工大学 | Corrosion-resistant microporous layers of a kind of fuel cell based on graphitized carbon and preparation method thereof |
| CN111933954A (en) * | 2020-08-07 | 2020-11-13 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Air electrode, preparation method thereof and air battery |
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Application publication date: 20130109 |