CN101683613A - Catalytic agent for air electrode and novel air electrode manufactured by catalytic agent and manufacturing method of air electrode - Google Patents
Catalytic agent for air electrode and novel air electrode manufactured by catalytic agent and manufacturing method of air electrode Download PDFInfo
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- CN101683613A CN101683613A CN200810222690A CN200810222690A CN101683613A CN 101683613 A CN101683613 A CN 101683613A CN 200810222690 A CN200810222690 A CN 200810222690A CN 200810222690 A CN200810222690 A CN 200810222690A CN 101683613 A CN101683613 A CN 101683613A
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- 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
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Abstract
The invention discloses a catalytic agent for an air electrode and a novel air electrode manufactured by the catalytic agent and a manufacturing method of the air electrode; the catalytic agent for the air electrode is formed by compounding a main catalytic agent and at least one auxiliary catalytic agent; the main catalytic agent is metal salts containing manganese, and the auxiliary catalytic agent is rare earth compound or rare metal compound; the weight of the main catalytic agent accounts for 60-85 percent of total weight of the catalytic agent, and the remaining is the auxiliary catalytic agent. The novel air electrode is formed by pressing a catalytic membrane, a current collector and a water-proofing breathable film sequentially. In order to manufacture the novel air electrode, thecatalytic membrane and the water-proofing breathable film are firstly manufactured, and then are pressed together or pressed together with a meshed current collector, and then the air electrode is prepared after removing organic solvents.
Description
Technical field
The present invention relates to a kind of air electrode with catalyst and with the novel air electrode and the preparation method of its making.
Background technology
Zinc-air battery has that capacity is big, specific energy is high, stable operating voltage, safe in utilization, cheap, advantages of environment protection, receives the concern of domestic and international research unit and enterprise always.Development along with Modern Manufacturing Technology, its potentiality show gradually, its application and enlarging gradually, not only continue extensive use in traditional field such as portable communicator, medical device, rivers navigation light, electronic watch, calculator, and the present power supply of just developing multiple advanced portable type electronic products such as being applicable to mobile phone, notebook computer, and be used to develop the electric vehicle electrical source of power.
Oxygen electrode is a kind of gas-diffusion electrode, is widely used in fuel cell and the metal-air battery.The one side of oxygen electrode contacts with electrolyte, and another side contacts with oxygen.Oxygen electrode is as negative electrode in battery discharge procedure, and oxygen diffuses into electrode interior along electrode surface, and the reduction reaction takes place under the effect of catalyst.For chargeable battery, oxygen electrode in charging process as anode, at electrode surface generation oxygen evolution reaction.If the oxygen in the direct consumed cabin air of battery, corresponding electrode just is called air electrode, and its basic operation principle is identical with oxygen electrode.
The development of fuel cell and metal-air battery mainly comes from the continual renovation of oxygen electrode catalyst, so the research of catalyst material receives much concern always.Searching is cheap, catalyst has become the key that improves oxygen electrode performance efficiently.This development of technology will promote the development of metal-air battery and fuel cell.
For a long time, the research of catalyst mainly launches round following several series: platinum and platinum alloy, silver, metallo-chelate, metal oxide (as Mn oxide, spinel oxides, burnt green stone type oxide, perovskite type oxide) etc.As shown in Figure 1.
Noble metal platinum and platinum alloy are good catalyst, have very high catalytic activity and stability, but are difficult to commercialization because of it costs an arm and a leg.Electrolysis MnO
2Advantages of being cheap is arranged but its catalytic activity is lower.Rare-earth transition metal perovskite composite oxide (ABO
3Type) hydrogen reduction there is good catalytic activity, has advantages of higher stability concurrently and become the focus of research.But present The experimental results shows that it is optimized, the best catalytic performance of screening also is at 100～180mA/cm
2About, do not reach the needs of present zinc air and fuel cell development, therefore need novel, efficient, the cheap catalyst material of development.
The power output capacity of metal-air battery depends mainly on the performance of air electrode.Preparation high activity, thin layer air electrode are the keys that improves the zinc-air battery performance, comprising the gas-diffusion electrode of highly active oxygen reduction catalyst, stability and high efficiency and current collection mode etc.
Summary of the invention
The purpose of this invention is to provide a kind of air electrode catalyst, this catalyst hydrogen reduction is active high, can be in order to prepare high performance air (oxygen) electrode.
Another purpose of the present invention provides the novel air electrode that the above-mentioned catalyst of a kind of usefulness is made, and the catalytic performance of air (oxygen) electrode that this catalyst is made is extremely superior and have a chemical property of stability and high efficiency.
A further object of the present invention provides a kind of preparation method of above-mentioned novel air electrode.
For achieving the above object, the present invention takes following design:
A kind of air electrode catalyst, it adds at least a auxiliary catalyst by the major event catalyst and is composited; Described major event catalyst is for containing the manganese metallic salt; Described auxiliary catalyst is rare earth compound and scarce metallic compound.
Described major event catalyst accounts for the 60-85% of total catalyst weight, and all the other are an auxiliary catalyst.
Described major event catalyst can be MnSO
4Or Mn (NO
3)
2, KMnO
4Scarce metallic compound in described auxiliary the catalyst can be lanthana La
2O
3, cerium oxide Ce
2O
3, praseodymium oxide Pr
2O
3, neodymia Nd
2O
3, titanium dioxide TiO
2, brown lead oxide PdO
2, manganese dioxide MnO
2
A kind of novel air electrode, it is arranged compacting in proper order by catalytic membrane, collector and waterproof ventilated membrane at least and synthesizes; Described catalytic membrane is finalized the design after by aforesaid catalyst and material with carbon element, ptfe emulsion mixing mill tablet forming and is formed, and wherein the percentage that accounts for gross weight of ptfe emulsion is: 10～25%; The percentage that material with carbon element accounts for gross weight is: 45～75%, and the percentage that catalyst accounts for gross weight is 5～35%.Described waterproof ventilated membrane is with acetylene black and pore creating material (sodium sulphate Na
2SO
4, or carbonic hydroammonium NH
4HCO
3), be the film that bonding agent prepares after roll-in with the polytetrafluoroethylene (PTFE), wherein: polytetrafluoroethylene content 20～55%; Acetylene black 40～65%; Sodium sulphate Na
2SO
4, or bicarbonate NH
4HCO
3: 0～20%.Described collector adopts nickel screen or copper mesh.
A kind of preparation method of novel air electrode, method step is as follows:
1. the ratio in described each component of catalytic membrane takes by weighing the material of making catalytic membrane;
2. the above-mentioned material that takes by weighing is mixed;
3. make material water after manganese sulfate being used deionized water dissolving, add in the said mixture, the addition of material water is 5 times of said mixture weight, and ultrasonic wave stirs and became the muddy mixture in 40 minutes;
4. said mixture is placed water bath with thermostatic control, stirring concentrates under 60～90 ℃ of temperature, and branch evaporates into water content and is lower than 5%.
5. in above-mentioned powder, add absolute ethyl alcohol, constantly stir the adding ptfe emulsion.
6. above-mentioned material on the roller film machine folding roll 10-20 time after, be pressed into desired thickness 0.5-1.5mm; For catalytic membrane stand-by;
7. prepare the material of producing waterproof ventilated membrane again by following proportioning:
Acetylene black: 30～75%; Polytetrafluoroethylene (PTFE) (Gu material) 25～70%
Repeat 5. above-mentioned～6. step, prepare waterproof ventilated membrane.
8. two kinds of films of above-mentioned catalytic membrane and waterproof ventilated membrane are under 40～80 ℃ of temperature, at 1-20kg/cm
2Pressure is compressed together by setting arrangement mode down, and drying is removed organic solvent then, is air electrode.
Air electrode after described synthesizing should be heat-treated in 230-450 ℃ of scope through 0-3 hour again.
8. middle catalytic membrane of described step and waterproof ventilated membrane and reticulated collectors are compressed together by setting arrangement mode, that is: the arrangement mode of the arrangement mode of catalytic membrane+collector+waterproof ventilated membrane or catalytic membrane+waterproof ventilated membrane+collector+waterproof ventilated membrane.
The catalytic performance of the novel air electrode of being made by catalyst of the present invention is greater than 260mA/cm
2, can be applied to fields such as hydrogen-oxygen fuel cell, metallic hydrogen air-fuel battery, metal-air battery (comprising the electrochmical power source that is constituted such as all metals such as zinc, aluminium, magnesium and air (oxygen)) electro-chemistry oxygen-producing.
Advantage of the present invention is:
1, air electrode of the present invention employed all catalysis materials of catalyst, be cheap metallic salt, rare earth compound scarce metallic compound, and do not use such as noble metal catalysts such as platinum, silver, cobalts, reduced the cost of making air electrode.
2, adopt air electrode catalyst of the present invention, have very strong catalytic capability, the discharge current density of the feasible air electrode of making can reach 260mA/cm
2, performance is unsurpassed in excellence.
3, the outstanding advantage that has in the preparation method of air electrode of the present invention is, when the preparation of other carbon supported catalyst, as carbon-supported metal Pt or Ag, the dispersion of metal distributes, and the reunion of avoiding metal, reduce links such as noble metal dosage, be the difficult key link that breaks through; The present invention makes this link obtain breaking through and has solved fully and disperse difficult problem owing to adopt this water-soluble metal salt to tire out catalyst first.Therefore the electrode performance of preparing is superior.
Description of drawings
Fig. 1 is the air electrode catalytic performance resolution chart of the present invention's preparation
Fig. 2 is the classification schematic diagram of prior art development catalyst
Below in conjunction with drawings and the specific embodiments the present invention is described in further details:
The specific embodiment
Air electrode of the present invention is selected for use exactly with catalyst and is contained the manganese metallic salt and make the major event catalyst, add at least a auxiliary catalyst and add a small amount of rare earth compound or scarce metallic compound modification, develop the compound catalyze material of the metal air fuel cell of novel high-performance.
For major event selection of catalysts and requirement: that adopt in the preferred embodiment of the present invention is MnSO
4, KMnO
4Or Mn (NO
3)
2, purity is greater than 99.9%.
For assisting a selection of catalysts and requirement: can select cerium oxide Ce for use
2O
3, praseodymium oxide Pr
2O
3, neodymia Nd
2O
3,And titanium dioxide TiO
2,Brown lead oxide PdO
2,Manganese dioxide MnO
2, select the lanthana La of white powder for use
2O
3Better.
Novel air electrode of the present invention can be by waterproof ventilated membrane (claim not only hydrophobic breathable layer), collector (claim not only afflux conductive mesh) and catalytic membrane (but also claiming the porous catalytic layer) (1～20kg/cm under the certain pressure condition
2) and nickel screen formation compressed together.
The concrete preparation method of novel air electrode of the present invention is:
1, at first makes catalytic membrane: the compound of in accordance with regulations percentage by weight configuration catalyst of the present invention: ptfe emulsion PTFE:10～25% wherein; Material with carbon element (as acetylene black, carbon black): 45～75%, MnSO
4Perhaps Mn (NO
3)
2: 8～28%; Rare earth oxide such as La
2O
3, Nd
2O
3): 4～25%.Compound is mixed the back add absolute ethyl alcohol, under agitation add ptfe emulsion, use tablet press machine roll-in fibrillatable to desired thickness (0.05-1.5mm).
2, make waterproof ventilated membrane: described waterproof ventilated membrane can be to mix stirring with ultrasonic wave after several materials of the following percentage of employing add absolute ethyl alcohols, 60% the ptfe emulsion that adds certain mass, through rolling repeatedly, make it abundant fibrillatable, it is stand-by to be pressed into appointed thickness 0.05～1.5mm at last; Wherein: polytetrafluoroethylene content 20～55%; Acetylene black 40～80%; Na
2SO
4, or NH
4HCO
3: 0～20%.
3, with catalytic membrane, waterproof ventilated membrane, collector according to needed pattern: adopt the arrangement mode of Catalytic Layer+collector+waterproof ventilative layer or the arrangement mode of Catalytic Layer+waterproof ventilative layer+collector+waterproof ventilative layer to make air electrode, process conditions are: under 40～80 ℃ of the temperature, and pressure 1-20kg/cm
2, final drying is gone out organic solvent, and obtains air electrode.
Above-mentioned material with carbon element can be active carbon, graphite, acetylene black etc.; In general, the specific area of carbon base body is big more, and the electrode performance of making is good more; Therefore it is better to do the matrix material of air electrode with carbon black, because carbon black has higher specific surface area and the better hydrophobic energy is arranged.For example: carbon black product Vulcan XC-72R, the XC-500 of Cabot company, average specific surface area is＞200m
2/ g.
Polytetrafluoroethylene (PTFE) has the hydrophobicity, hear resistance of height and to the corrosion resistance of highly basic, is the more satisfactory binding material of each air electrode of system.The PTFE aqueous dispersions of employing 60% is good as binding agent.
With adopting the air electrode of the inventive method preparation, be placed in the hole of regulation area, as auxiliary electrode, carry out electro-chemical test with the Zn battery, the voltage of test air electrode under certain current density, the result is as shown in Figure 1.Show that air electrode of the present invention has the performance that is unsurpassed in excellence, discharge current density can reach 260mA/cm
2
Novel air electrode of the present invention can adopt the arrangement mode of Catalytic Layer+collector+waterproof ventilative layer or the arrangement mode of Catalytic Layer+waterproof ventilative layer+collector+waterproof ventilative layer to make air electrode.Also can not select collector for use, directly adopt Catalytic Layer+waterproof ventilative layer; Waterproof ventilated membrane, the waterproof ventilative material that can adopt low-pressure polyethylene material or polytetrafluoroethylmaterial material to make.
In such scheme, air electrode of the present invention can nickel screen as the collector of air electrode; Also can be that copper mesh is as collector.
The present invention designs the efficient gas electrode according to " gas-diffusion electrode " theory.The condition that must satisfy during preparation efficient gas electrode is to exist a large amount of gases to arrive easily in the electrode and the thin liquid film that can better be communicated with whole solution.Electrode must form good three phase boundary, not only had enough " pore " that gas is delivered in the electrode everywhere easily in electrode interior: but have cover the catalyst table in a large number and on thin liquid film: these thin liquid films also must be beneficial to the migration of liquid phase reactor and product particle by " liquid hole " and the mutually unobstructed connection of solution outside the electrode.
Hydrophobic breathable layer claims waterproof ventilative layer again, general porous Teflon or the polyethylene with very strong hydrophobicity used makes, wherein be formed with a large amount of pores, when it contacts with electrolyte solution, because hydrophobicity, liquid level in the pore is falcate, produces the additional pressure of a directional liquid inside thus, and this pressure has guaranteed the hydrophobic and permeability of electrode.If the material of selecting for use is certain, if the diameter of pore is too big, the hydrophobicity of electrode will descend, and can cause electrode to be submerged or leakage, if the diameter of pore is too little, can influence the diffusion velocity of gas, thereby influences the discharge performance of electrode; In hydrophobic breathable layer, form loose structure by polytetrafluoroethylene (PTFE), allow gas to enter into electrode interior and stop electrolyte to leak out from hydrophobic breathable layer.
Catalytic membrane of the present invention is the Catalytic Layer of porous, form by carbon and polytetrafluoroethylene (PTFE) and catalyst, carbon wherein and catalyst are hydrophilic substances, and hydrophobic polytetrafluoroethylene (PTFE) bonds them together, and make and form a large amount of thin liquid film layer and three phase boundary in the micropore of porous catalytic layer.The zone that has mainly comprised two kinds of structures in the porous catalytic layer, a kind of is " doing the district ", has the pore of hydrophobic substance and structure thereof to constitute, a kind of is " wet district ", is made of electrolyte and wetted catalyst granule and carbon micropore.What these micropores had is full of by liquid, and what have then is wetted, and the micropore in this two district is staggered to form the network of interconnection each other, and the reduction reaction of oxygen then is to carry out being coated with on the micro-pore wall of thin liquid film.
It is as follows that the present invention prepares the specific embodiment of air electrode:
Embodiment 1
1. take by weighing material in following ratio;
Acetylene black: activated carbon: polytetrafluoroethylene (PTFE) (Gu material): manganese sulfate: lanthana: neodymia
6∶56∶19∶11∶5∶3
2. acetylene black, activated carbon, lanthana, neodymia are fully mixed;
3. after manganese sulfate being used deionized water dissolving, add in the said mixture, add 5 times of above-mentioned material water, ultrasonic wave stirs and became the muddy mixture in 40 minutes.
4. said mixture is placed water bath with thermostatic control, 80 ℃ of concentrated moisture of stirring evaporate into moisture and are lower than 5%.
5. in above-mentioned powder, add absolute ethyl alcohol, constantly stir the adding ptfe emulsion.
6. above-mentioned material on the roller film machine folding roll 10-20 time after, be pressed into desired thickness 0.5-1.5mm.For catalytic membrane stand-by.
7. by following proportioning preparation material:
Acetylene black: 30～75%; Polytetrafluoroethylene (PTFE) (Gu material) 25～70%
Repeat 5. above-mentioned～6. step, prepare waterproof ventilated membrane.
8. above-mentioned two kinds of films are under 40～80 ℃ of temperature, at 1～20kg/cm
2Pressure is following and nickel screen is compressed together, and drying is removed organic solvent then, is air electrode.
9. in order to strengthen its intensity and resistance to corrosion, the air electrode after synthetic was heat-treated in 230-450 ℃ of scope through 0-3 hour.
The various embodiments described above can not depart from the scope of the present invention down in addition some variations, thus more than explanation comprise and accompanying drawing shown in structure should be considered as exemplary, but not in order to limit claim of the present invention.
Claims (10)
1, a kind of air electrode catalyst is characterized in that:
It adds at least a auxiliary catalyst by the major event catalyst and is composited;
Described major event catalyst is for containing the manganese metallic salt;
Described auxiliary catalyst is rare earth compound and scarce metallic compound; Described major event catalyst accounts for the 60-85% of total catalyst weight, and all the other are an auxiliary catalyst.
2, air electrode catalyst according to claim 1 is characterized in that: described major event catalyst is MnSO
4Or KMnO
4, Mn (NO
3)
2Described auxiliary catalyst is lanthana La
2O
3Or cerium oxide Ce
2O
3, praseodymium oxide Pr
2O
3, neodymia Nd
2O
3And titanium dioxide TiO
2,Brown lead oxide PdO
2,Manganese dioxide MnO
2
3, air electrode catalyst according to claim 2 is characterized in that: described MnSO
4Or KMnO
4, Mn (NO
3)
2Purity is greater than 99%.
4, a kind of novel air electrode, its at least by catalytic membrane, and waterproof ventilated membrane to arrange compacting in proper order synthetic; It is characterized in that:
Described catalytic membrane is finalized the design after by the described catalyst of claim 1 and material with carbon element, ptfe emulsion mixing mill tablet forming and is formed, and wherein the percentage that accounts for gross weight of ptfe emulsion is: 10～25%; The percentage that material with carbon element accounts for gross weight is: 45～75%, and the percentage that catalyst accounts for gross weight is MnSO
4Perhaps Mn (NO
3)
2: 8～28%; Rare earth oxide such as La
2O
3: 4～25%;
Described waterproof ventilated membrane is with material with carbon element, pore creating material (Na
2SO
4, or NH
4HCO
3) be major ingredient, ptfe emulsion is a bonding agent, through mixing the film for preparing after the roll-in, wherein: polytetrafluoroethylene content 20～55%; Acetylene black 35-80%; Pore creating material (Na
2SO
4, or NH
4HCO
3Upper title): 0～20%.
5, novel air electrode according to claim 4 is characterized in that: described material with carbon element is acetylene black or carbon black; Described pore creating material (Na
2SO
4, or NH
4HCO
3Upper title) be Na
2SO
4, or NH
4HCO
3, described collector adopts nickel screen or copper mesh; Described ptfe emulsion is the aqueous dispersions of concentration 60%.
6, novel air electrode according to claim 4 is characterized in that: described material with carbon element is carbon black product Vulcan XC-72R, the XC-500 of acetylene black, activated carbon, Cabot company.
7, a kind of method of making the described novel air electrode of claim 4 is characterized in that described method step is as follows:
1. the ratio in each component of catalytic membrane described in the claim 4 takes by weighing the material of making catalytic membrane;
2. the above-mentioned material that takes by weighing is mixed;
3. make material water after will containing manganese metallic salt use deionized water dissolving, add in the said mixture, the addition of material water is 5 times of said mixture weight, and ultrasonic wave stirs and became the muddy mixture in 40 minutes;
4. said mixture is placed water bath with thermostatic control, stirring concentrates under 60～90 ℃ of temperature, evaporates into moisture and is lower than 5%;
5. in above-mentioned powder, add absolute ethyl alcohol, constantly stir adding polytetrafluoroethylene (PTFE) breast;
6. above-mentioned material on the roller film machine folding roll 10～20 times after, be pressed into desired thickness 0.05～1.5mm; Be catalytic membrane;
7. prepare the material of producing waterproof ventilated membrane again by following proportioning:
Acetylene black: 30～75%; Polytetrafluoroethylene (PTFE) (Gu material) 25～70%
Repeat 5. above-mentioned～6. step, prepare waterproof ventilated membrane;
8. two kinds of films of above-mentioned catalytic membrane and waterproof ventilated membrane are under 40～80 ℃ of temperature, at 1～20kg/cm
2Pressure is compressed together by setting arrangement mode down, and drying is removed organic solvent then, is air electrode.
8, the method for novel air electrode according to claim 7 is characterized in that the air electrode after described synthesizing was heat-treated in 230～450 ℃ of scopes through 0～3 hour.
9, the method for novel air electrode according to claim 7 is characterized in that: 8. middle catalytic membrane of described step and waterproof ventilated membrane and reticulated collectors are compressed together by setting arrangement mode.
10, the method for novel air electrode according to claim 9 is characterized in that two kinds of films of described catalytic membrane and waterproof ventilated membrane and reticulated collectors setting arrangement mode compressed together is: the arrangement mode of the arrangement mode of catalytic membrane+collector+waterproof ventilated membrane or catalytic membrane+waterproof ventilated membrane+collector+waterproof ventilated membrane.
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