CN100397686C - Double-efficient air electrode and preparation thereof - Google Patents
Double-efficient air electrode and preparation thereof Download PDFInfo
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- CN100397686C CN100397686C CNB2004100335143A CN200410033514A CN100397686C CN 100397686 C CN100397686 C CN 100397686C CN B2004100335143 A CNB2004100335143 A CN B2004100335143A CN 200410033514 A CN200410033514 A CN 200410033514A CN 100397686 C CN100397686 C CN 100397686C
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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
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Abstract
The present invention relates to the technical field of a battery, particularly to a new double effect air (oxygen) electrode for the hydrogen-air storing secondary battery and a preparation method thereof, and the double effect air electrode is in a composite structure and is used for the hydrogen-air storing secondary battery. The double effect air electrode is applied in an alkaline medium system, and the double effect air electrode comprises an electrode supporter, a gas diffusion layer, a protection layer and a double effect catalyst layer, wherein the electrode supporter is successively provided with the gas diffusion layer, the protection layer and the double effect catalyst layer, and the double effect catalyst layer is the extremely outer layer. The double effect air electrode is prepared by adopting a coating method, and the preparative electrode can effectively prevent the oxidation and the corrosion of the electrode supporter and the diffusion layer and has the good double effect performance of air (oxygen) electrode reaction. The double effect air electrode can achieve self-respiration type charge and discharge and enhance the integral performance of the hydrogen-air storing secondary battery, and the double effect air electrode also has high application value.
Description
Technical field
The present invention relates to the battery technology field, is structure and the preparation method of a kind of storage hydrogen-air secondary battery with novel economic benefits and social benefits air (oxygen) electrode.
Background technology
Small-sized MH-Ni battery has long charge and discharge circulation life, and memory-less effect particularly uses low active material, the eco-friendly advantage polluted, and promptly development is swift and violent since coming out, and by 1994, it accounted for 20% of global small-sized secondary batteries market share.In recent years, the fast development of small-sized mobile electronic equipment requires secondary cell to have higher capacity but only requires medium or lower power.The energy density that further increases secondary cell is one of emphasis of research at present to adapt to this new requirement.Fuel cell (FC) is with its zero discharge, high-energy-density, high-efficiency characteristics and the powerful competitiveness on the electric powered motor power supply thereof and become the research focus of energy field in recent years.The MH-air secondary battery is to have absorbed the characteristics of above-mentioned two kinds of batteries and advantage and a kind of novel battery of developing, is causing researcher's very big concern in recent years.In this battery, adopt the gaseous diffusion air electrode of light weight to replace heavier nickel (Ni) electrode, can make the unit mass energy density of battery improve 20%, and possess the high efficiency of fuel cell.But thing followed problem is, the gaseous diffusion air electrode generally contains carbon composite, and carbon will be oxidized in charging process.
In the previous research, adopt the method for third electrode to overcome this problem.At document Lampinen M, Viitanen M, Lamminen J and Fomino M, [P] .US:5645952,1997[1], PongT C, [P] .US:6332899B1,2001[2], Tetsuya K, Tetsuo S, NobuhiroK and Hitoshi U, [P] .JP:07272771A2,1995[4], Sakai T, Iwaki T, Ye Z and Noreus D, [J] .J Electrochem Soc, 1995,142:4040-4045[5] in, match with hydrogen storage electrode when the charging as third electrode with the wire netting that increases and to play a role.And its oxygen (air) electrode adopts the rolling depression method preparation, only carries out oxygen reduction reaction when discharge, and promptly it does not possess the effect of economic benefits and social benefits electrode.Yet the weight of the third electrode of increase has been subdued the high-energy-density advantage that air electrode brought of light weight.On the contrary, employing can be carried out the economic benefits and social benefits air electrode with stability of hydrogen reduction and oxygen evolution reaction then can eliminate third electrode, thereby obtains energy needed density.Therefore, the exploitation of economic benefits and social benefits air electrode is the research emphasis of present this kind battery.
In economic benefits and social benefits air electrode research, except the economic benefits and social benefits eelctro-catalyst of oxygen being separated out and oxygen reduction reaction all has a high catalytic activity is that the structure of electrode and technology of preparing are also most important the key factor of this electrode development.In the previous research, as document Bonnemay M, Bronoel G R, Donnet J B, Lahaye J and Alain J, [P] .US:3870565,1975[3], electrode includes only electrode layer and currect collecting net two parts, adopts the method for roll extrusion to prepare electrode.Do not have catalyst in the electrode layer, have only active carbon, electrode charcoal degraded when charging is serious, and the economic benefits and social benefits performance of electrode is bad.In document [1], [5], Gamburzev S, Zhang W, Velev O A, Srinivasan S, Appleby A J andVisintin A, [J] .Proc Electrochem Soc, 1996,96:166-173[6], MullerS, Holzer F and Haas O, [J] .Proc Electrochem Soc, 1998,98:101-110.[7], Kiros Y, Lindstrom O and Kaimakis T, [J] .J Power Sources, 1993,45:219-227[8] in, electrode generally comprises three parts, it is gas diffusion layers, Catalytic Layer and currect collecting net adopt the method for roll extrusion to prepare electrode.In the method,, mix the back as catalyst, material with carbon element and hydrophober and form paste, be rolled into certain thickness diffusion layer and Catalytic Layer then respectively repeatedly, again this two-layer roll extrusion is formed gas-diffusion electrode together different materials.Electrode and collector be connected two kinds of forms of branch, be to adopt the mode of bonding that currect collecting net and electrode are combined in document [1], it is little and effect is limited that this mode connects contact-making surface.In document [5]-[8] be again with electrode and collector repeatedly roll extrusion together so that afflux.In the preparation process, contact well with currect collecting net for obtaining practicing the good bed material of cream so that film forming reaches, the researcher adds different hydrocarbon solvent additive secondary mixing rehearsal cream after often catalyst, material with carbon element and the hydrophober that mixes being filtered, dries again, and then roll extrusion film forming, technology is complicated, and the cycle is long.
Summary of the invention
The objective of the invention is: for overcoming the deficiencies in the prior art, provide a kind of economic benefits and social benefits air electrode with double-effect oxygen electrode response function, its making is very easy.
For achieving the above object; technical solution of the present invention provides a kind of economic benefits and social benefits air electrode; be composite construction; be used to store hydrogen-air secondary battery; in the alkaline medium system, use; it comprises electrode support, gas diffusion layers, protective layer and economic benefits and social benefits Catalytic Layer four parts, is followed successively by gas diffusion layers, protective layer and economic benefits and social benefits Catalytic Layer on the electrode supporting surface, and the economic benefits and social benefits Catalytic Layer is an outermost layer.
Described economic benefits and social benefits air electrode, its described electrode support are the good carbon paper of conductivity, carbon cloth, or good nickel foam, the foam copper porous media of conductivity; Electrode support is the carrier of gas diffusion layers, protective layer and economic benefits and social benefits Catalytic Layer, plays the effect of current collector simultaneously.
Described economic benefits and social benefits air electrode, its described gas diffusion layers is made of the good acetylene black of conductivity, graphite, expanded graphite, active carbon powder and binding agent; Binding agent is polytetrafluoroethylene or Kynoar, and it is simultaneously as hydrophober; The mass ratio of powder and binding agent is between 3～0.3.
Described economic benefits and social benefits air electrode, its described protective layer is made of the dual purpose catalyst that all has high catalytic activity for hydrogen reduction and oxygen evolution reaction and binding agent and conductive additive; Dual purpose catalyst is the oxide that has the noble metal of high economic benefits and social benefits oxygen catalytic reaction activity and contain noble metal; Perofskite type oxide; Spinel oxides and burnt green stone type oxide; Binding agent is polytetrafluoroethylene or Kynoar, and it is simultaneously as hydrophober; Conductive additive is the good carbon dust of conductivity; In the protective layer content of dual purpose catalyst should be＞30%; The ratio of hydrophober and conductive agent is between 0.5～3.
Described economic benefits and social benefits air electrode, its described economic benefits and social benefits Catalytic Layer is made of dual purpose catalyst and binding agent; Dual purpose catalyst is the oxide that has the noble metal of high economic benefits and social benefits oxygen catalytic reaction activity and contain noble metal; Perofskite type oxide; Spinel oxides and burnt green stone type oxide; Binding agent is polytetrafluoroethylene or Kynoar, and it is simultaneously as hydrophober; The content of dual purpose catalyst should＞50% in the economic benefits and social benefits Catalytic Layer, binder content＜50%, thus be implemented in different catalyst and binding agent distributions in protective layer and the economic benefits and social benefits Catalytic Layer.
Described economic benefits and social benefits air electrode, the design function of the combined electrode structure that its described economic benefits and social benefits Catalytic Layer and protective layer combine are that the economic benefits and social benefits Catalytic Layer mainly carries out double-effect oxygen electrode reaction; Protective layer is when oxygen reduction reaction; expansion reaction zone as the economic benefits and social benefits Catalytic Layer; when oxygen evolution reaction; the strong oxidizing property free radical that is not combined into oxygen molecule that produces in the economic benefits and social benefits Catalytic Layer that is diffused into this layer is combined into oxygen molecule; thereby prevent the oxidized corrosion of diffusion layer and electrode support, keep electrode economic benefits and social benefits performance.
Described economic benefits and social benefits air electrode, the carbon dust that its described conductivity is good is graphite, expanded graphite, graphited acetylene black or graphited activated carbon powder.
Described economic benefits and social benefits air electrode, its described oxide that has the noble metal of high economic benefits and social benefits oxygen catalytic reaction activity and contain noble metal is platinum (Pt), silver (Ag), iridium (Ir), ruthenium (Ru), rhodium (Rh), contain platinum oxide, contain iridium oxide, contain ru oxide, the rhodium-containing oxide, one pack system wherein, the mixture of two or more components or alloy.
A kind of preparation method of economic benefits and social benefits air electrode, it adopts the rubbing method preparation, may further comprise the steps:
A) electrode support is carried out pre-treatment, comprise carbon paper, carbon cloth are carried out being used as substrate again after hydrophobisation is handled; Or, carry out pre-stampedly to nickel foam, foam copper porous media, make it have the porosity that needs and be beneficial to apply diffusion layer and Catalytic Layer;
B) the various constituents abundant mixing in solvent with diffusion layer forms emulsion;
C) with b) gained emulsion evenly is coated on the electrode support of pre-treatment and forms gas diffusion layers in the step, and be coated on the one side of supporter or be coated on the two sides of supporter; The load amount of diffusion layer is design voluntarily as required;
D) with c) electrode support roast in 280 ℃～400 ℃ scopes of having gas diffusion layers in the step after being coated with forms final gas diffusion layers;
E) adopt same b)-d) similar Step By Condition of step, order prepares protective layer and economic benefits and social benefits Catalytic Layer on gas diffusion layers; After coating protective layer, directly coat the economic benefits and social benefits Catalytic Layer after adopting hair-dryer that it is dried up, again roast together; Or coat respectively, roast prepares protective layer and the economic benefits and social benefits Catalytic Layer;
F) behind the roast, obtain an economic benefits and social benefits air electrode.
Described preparation method, it is at c) step or d) after the step coats gas diffusion layers, it can be carried out compression process, coat protective layer and economic benefits and social benefits Catalytic Layer again; Can suppress reprocessing to the protective layer and the economic benefits and social benefits Catalytic Layer that coat.
Described preparation method, in its described a) step, hydrophober is polytetrafluoroethylene or Kynoar, the mass ratio of the quality of carbon paper, carbon cloth and hydrophober should be between 0.25～4 after hydrophobisation was handled; The porosity of nickel foam, foam copper porous media should be between 50%～80%.
Described preparation method, its described b) in the step, solvent for use is deionized water and distilled water; Be organic solvent, comprise ethanol, isopropyl alcohol, ethylene glycol alcohols and acetone material; Be the mixture of organic solvent and deionized water or distilled water, the volume ratio of organic solvent and water is 1/5～5 in the mixture.
Described preparation method, it coats gas diffusion layers, protective layer or economic benefits and social benefits Catalytic Layer and suppresses reprocessing on electrode support operation is optionally adjusted.
The comparison of the present invention and correlation technique:
1. same document [1] [2] [4] [5] is compared, and the air electrode of the present invention's preparation has the double-effect oxygen electrode response function, has demonstrated fully the energy density advantage of storage hydrogen-air cell.Air electrode only carries out oxygen reduction reaction in the document [1] [2] [4] [5] when discharge, and promptly it does not possess the effect of double-effect oxygen electrode.
2. same document [3] is compared; the air electrode of the present invention's preparation comprises protective layer and economic benefits and social benefits Catalytic Layer; and adopt oxygen is reacted the Preparation of Catalyst with high economic benefits and social benefits catalytic activity; thereby make the electrode for preparing have good double-effect oxygen electrode performance, electrode performance is stable in electrode charge and discharge process.Electrode in the document [3] has only one deck electrode layer, is made of active carbon, and electrode charcoal degraded when charging is serious, and the economic benefits and social benefits performance of electrode is bad.
3. same document [1] is compared, and the effective and technology of the electrode current collecting of the present invention preparation forms naturally, and is easy and simple to handle.
4. compare in same document [5]-[8], the present invention adopts protective layer and economic benefits and social benefits catalyst layer structure, the problem of carbon in the free-radical oxidation corrosion diffusion layer of the strong oxidizing property that emphasis produces when solving oxygen evolution reaction, and the economic benefits and social benefits performance of electrode is good.
5. compare in same document [5]-[8], the present invention coats each layer in the substrate of, porous smooth at, so the thickness of electrode can be controlled effectively by the thickness of control substrate and the amount of coating, workable.
6. compare in same document [5]-[8], the consumption of raw material depended primarily on the size and the design quantity of substrate when the present invention prepared electrode, can effectively control the consumption of raw material in preparation process, avoids waste, and saves cost.
7. compare in same document [5]-[8]; the present invention can adjusting, different material rates by operation regulates and reprocessing such as compacting is optimized respectively gas diffusion layers, protective layer and economic benefits and social benefits Catalytic Layer; thereby be implemented in the different pore size distribution of formation in each layer; help realizing effect separately, improve the performance of electrode.And it is easy to implement, simple to operate.
8. comparing in same document [5]-[8], adopts nickel foam or foam copper to make electrode support, and pole strength is good, and abundant raw material, and is workable, and development space is big.
Effect of the present invention:
1. the present invention adopts the carrier of electrode support as gas diffusion layers, protective layer and economic benefits and social benefits Catalytic Layer, and it plays the effect of current collector body simultaneously, and having simplified needs electrode and currect collecting net secondary rolled technology together, and is simple and easy to do, is easy to large-scale production.
2. adopt coating process of the present invention to prepare electrode, method is easy, good reproducibility, economize in raw materials and cost, and can adopt the sizing process of scraping of comparative maturity to carry out, thereby be easy to amplify, help reducing manufacturing cost, this industrialization for storage hydrogen-air secondary battery is significant.
3. employing the technology of the present invention; adopt the method that successively coats to prepare electrode; can guarantee closely to interact between coating and substrate and the coating; at binding agent after the roasting fusion forms network structure; double-deck Catalytic Layer, protective layer and gas diffusion layers are very firm with combining of electrode support; and having strengthened pole strength, electrode stability is good.
4. employing the technology of the present invention, the thickness of electrode can be controlled effectively by the thickness of control electrode supporter and the amount of coating, and simple to operate, and is convenient.
5. adopt electrode structure of the present invention and corresponding preparation method; allow in preparation process gas diffusion layers, protective layer and economic benefits and social benefits Catalytic Layer are carried out that different material rates is regulated and processing such as compacting; thereby can be implemented in the different pore size distribution of formation in each layer; help realizing effect separately, improve electrode performance.
6. adopt the electrode of the technology of the present invention preparation, can effectively prevent electrode support and the oxidized corrosion of diffusion layer, have good economic benefits and social benefits air (oxygen) electrode reaction performance.
7. adopt the electrode of the technology of the present invention preparation, can realize that self-respiration type discharges and recharges, improved the overall performance of storage hydrogen-air secondary battery, have higher using value.
Description of drawings
Fig. 1 is an electrode structure cutaway view of the present invention (perpendicular to electrode surface);
Fig. 2 is a MH-air secondary battery performance chart;
Fig. 3 is a self-respiration type economic benefits and social benefits air electrode performance schematic diagram:
A electrode charge and discharge current potential changes with cycle-index;
In the cyclic process of b the electrode charge and discharge current potential and running time relation;
Fig. 4 is a MH-air secondary battery performance schematic diagram:
In the cyclic process of a battery charging and discharging voltage and running time relation;
B battery charging and discharging voltage changes with cycle-index.
Embodiment
The present invention is a kind of structure and preparation method who stores hydrogen-air secondary battery with novel double-effect oxygen electrode.Owing to can obtain oxygen from surrounding air (atmosphere), kind electrode can be described as the economic benefits and social benefits air electrode again.In the present invention; the economic benefits and social benefits air electrode is a composite construction, as shown in Figure 1, comprises electrode support 1, gas diffusion layers 2, protective layer 3 and economic benefits and social benefits Catalytic Layer 4 four parts; be followed successively by gas diffusion layers 2, protective layer 3 and economic benefits and social benefits Catalytic Layer 4 on electrode support 1, economic benefits and social benefits Catalytic Layer 4 is an outermost layer.Electrode support 1 is a sheet, is to adopt coating process to prepare the economic benefits and social benefits air electrode, can apply gas diffusion layers 2, protective layer 3 and economic benefits and social benefits Catalytic Layer 4 at the single or double of electrode support 1 in proper order.Adopt this kind electrode structure and method to prepare electrode, controllability is good, and conservation is easy to amplify, thereby is suitable for large-scale production.This is significant for the research and development and the industrialization that promote storage hydrogen-air secondary battery.
The diverse coating process of employing of the present invention and rolling process prepares novel economic benefits and social benefits air electrode, promptly applies gas diffusion layers 2, protective layer 3 and economic benefits and social benefits Catalytic Layer 4 on the electrode support 1 of pre-treatment, and make finished electrode after reprocessing.Adopt this kind electrode structure and method to prepare air electrode, electrode current collecting is effective, is suitable for large-scale production, and can improve diffusion layer 2 and Catalytic Layer 4 respectively, thereby improves electrode performance.Prepared air electrode has economic benefits and social benefits function preferably, can realize that self-respiration type discharges and recharges.
Adopt Kynoar (PVDF) hydrophobisation to handle carbon paper (Japan produces) as electrode support 1 substrate.Handle the Kynoar content that contains in the carbon paper of back and be about 60%.Mixing formation emulsion in deionized water evenly is coated on the one side of carbon paper substrate with 60% active carbon and 40% Kynoar, and through 300 ℃ of roastings, the formation gas diffusion layers 2 of colding pressing.Equally economic benefits and social benefits eelctro-catalyst platinum (Pt) being mixed back formation emulsion with graphited acetylene black and Kynoar in 3: 2: 3 ratios in deionized water evenly is coated on the gas diffusion layers 2; and through roasting formation protective layer 3, the load amount of platinum (Pt) catalyst is 0.6mg/cm
2(the load amount of platinum (Pt) catalyst was 0.4mg/cm in 1: 1 ratio with economic benefits and social benefits eelctro-catalyst platinum (Pt) and Kynoar (PVDF)
2) formation emulsion in mixing back evenly is coated on the protective layer 3 in deionized water, form economic benefits and social benefits Catalytic Layer 4 through roast, thereby obtain an economic benefits and social benefits air electrode.Form the MH-air secondary battery with economic benefits and social benefits air electrode and hydrogen storage electrode and carry out the constant current charge-discharge experiment in the KOH of 6M solution system, current density is 20mA/cm
2, the charging interval is 6h, and be 4h discharge time, and probe temperature is a room temperature.During charging, cell voltage (is fluctuating in error range) about 1.5V, and highly stable in the whole charging interval.During discharge, the battery performance curve as shown in Figure 2.
The nickel foam that adopts repressed pre-treatment is as electrode support 1 substrate.The porosity of handling the back nickel foam is about 70%.Mixing formation emulsion in isopropyl alcohol evenly is coated on the two sides of nickel foam substrate with 40% acetylene black and 60% polytetrafluoroethylene (PTFE), and the load amount ratio on two sides is 1: 2, forms gas diffusion layers 2 through 330 ℃ of roastings.Equally economic benefits and social benefits eelctro-catalyst-perofskite type oxide and graphited active carbon and polytetrafluoroethylene (PTFE) evenly are coated on the less substrate one side of diffusion layer 2 load amounts by the emulsion that forms homogeneous at 4: 3: 3 after the mixed; form protective layer 3 after hair-dryer dries up, the load amount of catalyst is 3mg/cm in this layer
2(the load amount of catalyst was 1.5mg/cm in 4: 1 ratios with economic benefits and social benefits eelctro-catalyst-perofskite type oxide and polytetrafluoroethylene
2) mix the emulsion that the back forms homogeneous and evenly be coated on the protective layer 3 that dries up, form economic benefits and social benefits Catalytic Layer 4 through roast, thereby obtain an economic benefits and social benefits air electrode.As the research electrode, platinum electrode is an auxiliary electrode with the economic benefits and social benefits air electrode, and the Hg/HgO electrode is that reference electrode is formed three electrode test systems carry out constant current charge-discharge loop cycle experiment, test electrode performance in the KOH of 6M solution system.Adopt 12mA/cm
2Charging and discharging currents density, 4h is one-period with charging 7.5h discharge, probe temperature is a room temperature.All under ambient pressure, nothing adds source of the gas to the economic benefits and social benefits air electrode when discharging and recharging, to realize that self-respiration type discharges and recharges.Electrode performance as shown in Figure 3.
Adopt the polytetrafluoroethylene (PTFE) hydrophobisation to handle carbon paper (Germany produces) as electrode support 1 substrate.Handle the polytetrafluoroethylene content that contains in the carbon paper of back and be about 65%.Is that mixing forms emulsion and evenly is coated on the one side of carbon paper substrate in the mixture of 1 isopropyl alcohol and first water with 35% expanded graphite and 65% polytetrafluoroethylene in volume ratio, and forms gas diffusion layers 2 through 370 ℃ of roastings.Equally economic benefits and social benefits eelctro-catalyst spinel oxides and expanded graphite and polytetrafluoroethylene were formed homogeneous emulsion by 1: 1: 1 after the mixed and evenly are coated on the gas diffusion layers 2, and through roasting, colding pressing forms protective layer 3, the load amount of catalyst is 4mg/cm
2(the load amount of catalyst was 2mg/cm in 3: 2 ratios with economic benefits and social benefits eelctro-catalyst spinel oxides and polytetrafluoroethylene
2) mix the back and form homogeneous emulsion and evenly be coated on the protective layer 3, form economic benefits and social benefits Catalytic Layer 4 through roast, thereby obtain an economic benefits and social benefits air electrode.Form the MH-air secondary battery with economic benefits and social benefits air electrode and hydrogen storage electrode and carry out the experiment of constant current charge-discharge loop cycle in the KOH of 6M solution system, charging and discharging currents density is 15mA/cm
2, 4h is one-period with charging 7.5h discharge, probe temperature is a room temperature.All under ambient pressure, nothing adds source of the gas to the economic benefits and social benefits air electrode when discharging and recharging, to realize that self-respiration type discharges and recharges.Battery performance as shown in Figure 4.
Claims (9)
1. economic benefits and social benefits air electrode, be composite construction, be used to store hydrogen-air secondary battery, in the alkaline medium system, use, it is characterized in that: comprise electrode support, gas diffusion layers, protective layer and economic benefits and social benefits Catalytic Layer four parts, be followed successively by gas diffusion layers, protective layer and economic benefits and social benefits Catalytic Layer on electrode support, the economic benefits and social benefits Catalytic Layer is an outermost layer;
Described electrode support is the good carbon paper of conductivity, carbon cloth, or the nickel foam of good conductivity, foam copper porous media one of them; Electrode support is the carrier of gas diffusion layers, protective layer and economic benefits and social benefits Catalytic Layer, plays the effect of current collector simultaneously;
Described protective layer is made of the dual purpose catalyst that all has high catalytic activity for hydrogen reduction and oxygen evolution reaction and binding agent and conductive additive; Dual purpose catalyst is oxide, perofskite type oxide, spinel oxides wherein at least a that has the noble metal of high economic benefits and social benefits oxygen catalytic reaction activity and contain noble metal; Binding agent is polytetrafluoroethylene or Kynoar, and it is simultaneously as hydrophober; Conductive additive is the good carbon dust of conductivity; In the protective layer content of dual purpose catalyst should be＞30%; The ratio of hydrophober and conductive agent is between 0.5～3;
Described economic benefits and social benefits Catalytic Layer is made of dual purpose catalyst and binding agent; Dual purpose catalyst is oxide, perofskite type oxide, spinel oxides wherein at least a that has the noble metal of high economic benefits and social benefits oxygen catalytic reaction activity and contain noble metal; Binding agent is polytetrafluoroethylene or Kynoar, and it is simultaneously as hydrophober; The content of dual purpose catalyst should＞50% in the economic benefits and social benefits Catalytic Layer, binder content＜50%, thus be implemented in different catalyst and binding agent distributions in protective layer and the economic benefits and social benefits Catalytic Layer.
2. economic benefits and social benefits air electrode as claimed in claim 1 is characterized in that: the design function of the combined electrode structure that described economic benefits and social benefits Catalytic Layer and protective layer combine is that the economic benefits and social benefits Catalytic Layer mainly carries out double-effect oxygen electrode reaction; Protective layer is when oxygen reduction reaction; expansion reaction zone as the economic benefits and social benefits Catalytic Layer; when oxygen evolution reaction; the strong oxidizing property free radical that is not combined into oxygen molecule that produces in the economic benefits and social benefits Catalytic Layer that is diffused into this layer is combined into oxygen molecule; thereby prevent the oxidized corrosion of diffusion layer and electrode support, keep electrode economic benefits and social benefits performance.
3. economic benefits and social benefits air electrode as claimed in claim 1 is characterized in that: the carbon dust that described conductivity is good, for graphite, expanded graphite, graphited acetylene black or graphited activated carbon powder one of them.
4. economic benefits and social benefits air electrode as claimed in claim 1 is characterized in that: the described oxide that has the noble metal of high economic benefits and social benefits oxygen catalytic reaction activity and contain noble metal is platinum, silver, iridium, ruthenium, rhodium, contain platinum oxide, contain iridium oxide, contain ru oxide, the rhodium-containing oxide, one pack system wherein, the mixture of two or more components or alloy.
5. the preparation method of an economic benefits and social benefits air electrode is characterized in that: adopt the rubbing method preparation, may further comprise the steps:
A) electrode support is carried out pre-treatment, comprise carbon paper, carbon cloth are carried out being used as substrate again after hydrophobisation is handled with hydrophober; Or to nickel foam, foam copper porous media one of them, carry out pre-stampedly, make it have the porosity that needs and be beneficial to apply diffusion layer and Catalytic Layer;
B) the various constituents abundant mixing in solvent with diffusion layer forms emulsion;
C) with b) gained emulsion evenly is coated on the electrode support of pre-treatment and forms gas diffusion layers in the step, and be coated on the one side of supporter or be coated on the two sides of supporter; The load amount of diffusion layer is design voluntarily as required;
D) with c) electrode support roast in 280 ℃～400 ℃ scopes of having gas diffusion layers in the step after being coated with forms final gas diffusion layers;
E) adopt same b)-d) similar Step By Condition of step, order prepares protective layer and economic benefits and social benefits Catalytic Layer on gas diffusion layers; After coating protective layer, directly coat the economic benefits and social benefits Catalytic Layer after adopting hair-dryer that it is dried up, again roast together; Or coat respectively, roast prepares protective layer and the economic benefits and social benefits Catalytic Layer;
F) behind the roast, obtain an economic benefits and social benefits air electrode.
6. preparation method as claimed in claim 5 is characterized in that: at c) or d) after the step coats gas diffusion layers, do not handle or it is carried out compression process, coat protective layer and economic benefits and social benefits Catalytic Layer again; The protective layer that coats and economic benefits and social benefits Catalytic Layer are suppressed reprocessing or do not handled.
7. preparation method as claimed in claim 5, it is characterized in that: in the described a) step, hydrophober is with after carbon paper, carbon cloth combine, prevent that greatly carbon paper, carbon cloth are by the material of water infiltration, be polytetrafluoroethylene or Kynoar, the mass ratio of the quality of carbon paper, carbon cloth and hydrophober should be between 0.25～4 after hydrophobisation was handled; The porosity of nickel foam, foam copper porous media should be between 50%～80%.
8. preparation method as claimed in claim 5 is characterized in that: described b) in the step, solvent for use is wherein at least a of deionized water, distilled water, organic solvent; Organic solvent is wherein at least a of ethanol, isopropyl alcohol, ethylene glycol alcohols and acetone material; The volume ratio of organic solvent and water is 1/5～5 in the mixture of organic solvent and deionized water or distilled water.
9. preparation method as claimed in claim 5 is characterized in that: the operation that on electrode support, coats gas diffusion layers, protective layer or economic benefits and social benefits Catalytic Layer and suppress reprocessing, optionally adjust.
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| JP5104942B2 (en) * | 2008-11-27 | 2012-12-19 | トヨタ自動車株式会社 | Air secondary battery |
| CN103165902B (en) * | 2011-12-15 | 2015-02-11 | 中国科学院大连化学物理研究所 | Cathode for metal-air battery and preparation method thereof |
| CN102867964A (en) * | 2012-09-05 | 2013-01-09 | 清华大学 | Air electrode and preparation method thereof |
| CN104716332B (en) * | 2013-12-15 | 2017-03-01 | 中国科学院大连化学物理研究所 | A kind of metal-air battery dual-catalysis layer air cathode |
| CN105161732B (en) * | 2015-07-03 | 2018-01-30 | 中国科学院宁波材料技术与工程研究所 | A kind of metal air battery cathodes material and preparation method thereof and metal-air battery |
| CN106623408A (en) * | 2016-12-27 | 2017-05-10 | 常州大学 | Electrokinetic remediation technology and method for removing heavy metal contaminated soil |
| CN106960961B (en) * | 2017-03-23 | 2019-07-23 | 北京化工大学 | Air electrode structure for zinc-air flow battery 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 |
| CN109786762B (en) * | 2019-01-17 | 2021-01-19 | 北京化工大学 | Structure of gradient hydrophilic-hydrophobic/air electrode and preparation method thereof |
| CN112993284B (en) * | 2021-02-04 | 2024-01-26 | 上海亿氢科技有限公司 | Electrolytic water catalyst layer and manufacturing method thereof |
| CN114703496B (en) * | 2022-04-12 | 2023-07-11 | 中国科学院生态环境研究中心 | Air electrode and preparation method thereof |
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| US5645952A (en) * | 1992-04-14 | 1997-07-08 | Markku Lampinen | Method and apparatus for charging and discharging electric energy |
| CN1367546A (en) * | 2001-01-21 | 2002-09-04 | 天津和平海湾电源集团有限公司 | High-energy air/hydrogen secondary cell |
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| US5645952A (en) * | 1992-04-14 | 1997-07-08 | Markku Lampinen | Method and apparatus for charging and discharging electric energy |
| CN1367546A (en) * | 2001-01-21 | 2002-09-04 | 天津和平海湾电源集团有限公司 | High-energy air/hydrogen secondary cell |
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