WO2010140290A1 - アルミニウム多孔質焼結体を有するアルミニウム複合体の製造方法 - Google Patents
アルミニウム多孔質焼結体を有するアルミニウム複合体の製造方法 Download PDFInfo
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- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
- B22F3/1125—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process
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- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
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- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/002—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
- B22F7/004—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature comprising at least one non-porous part
- B22F7/006—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature comprising at least one non-porous part the porous part being obtained by foaming
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0408—Light metal alloys
- C22C1/0416—Aluminium-based alloys
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- C—CHEMISTRY; METALLURGY
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- C22C21/00—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/12—Alloys based on aluminium with copper as the next major constituent
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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
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- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/801—Sintered carriers
- H01M4/803—Sintered carriers of only powdered material
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/808—Foamed, spongy materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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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
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- 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
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention is particularly suitable for lithium ion secondary batteries and electric double layer capacitor current collectors, LED heat sink heat sinks, radiators, etc., and an aluminum porous sintered body is integrated on an aluminum foil or plate.
- the present invention relates to a method for producing a finished aluminum composite.
- the present application claims priority based on Japanese Patent Application No. 2009-135021, filed in Japan on June 4, 2009, the contents of which are incorporated herein by reference.
- a foam melting method is known.
- a thickening agent is added to molten aluminum to increase the viscosity, and then titanium hydride is added as a blowing agent, and the molten aluminum is produced using hydrogen gas generated by a thermal decomposition reaction of titanium hydride.
- the foamed aluminum obtained by this method has large closed pores of several mm.
- a foamed aluminum having a sponge skeleton by press-fitting aluminum into a mold having sponge urethane as a core and filling aluminum into a cavity formed by burning out urethane.
- a foamed aluminum having a pore diameter of 40 PPI or less that is, a pore diameter of 40 cells or less per inch (pore diameter of about 600 ⁇ m or more) is obtained.
- Patent Document 4 As a third method, aluminum alloy is pressed and infiltrated into a reinforcing material made of hollow ceramics to have closed pores having a pore diameter of 500 ⁇ m or less according to the size of the reinforcing material. There is also a method for obtaining foamed aluminum.
- Patent Document 5 as a fourth method, aluminum is foamed by decomposition of TiH 2 powder by heating and rolling a mixed powder of AlSi alloy powder and TiH 2 powder between aluminum plates. There is a way to make it.
- the foamed aluminum obtained by this method has a large pore size of several mm.
- Patent Document 6 as a fifth method, a metal whose eutectic temperature with aluminum is lower than the melting point of aluminum is mixed with aluminum, and is higher than the eutectic temperature and higher than the melting point of aluminum. There is a method of baking at a low temperature.
- the foamed aluminum obtained by this method has a small porosity of around 40% even though the pore diameter can be reduced. For this reason, the amount of the positive electrode active material and the negative electrode active material penetrating into the pores of the foamed aluminum as the current collector is small, and the desired high output and high energy density cannot be achieved.
- sponge urethane is used as a method for producing foamed aluminum having fine open pores that can achieve the purpose of high output and high energy density.
- a second method of press-fitting aluminum into the core mold can be employed.
- Patent Document 7 As a method for producing a foam metal having a high porosity having a small pore size / size open pores in which a large number of minute open pores are evenly arranged, as shown in Patent Document 7, There is a slurry foaming method in which a foamable slurry containing a foaming agent is foamed, dried and then sintered. According to this method, if a raw material powder that can be sintered is available, a high-porosity foam metal having dimensionally open pores having an arbitrary pore size ranging from about 10 PPI to about 500 PPI, that is, a pore size ranging from 2.5 mm to 50 ⁇ m. Can be easily manufactured.
- foaming is performed by containing a foaming agent, or foaming is performed by injecting gas or stirring to sinter the foamable slurry as described above in the foamed state.
- foaming is performed by containing a foaming agent, or foaming is performed by injecting gas or stirring to sinter the foamable slurry as described above in the foamed state.
- the metal powder is sintered by free sintering that is sintered without applying stress such as compression, to obtain a foam metal.
- the aluminum powder has a surface covered with a dense aluminum oxide film of several nm to several tens of nm, which inhibits sintering regardless of the solid phase or liquid phase. For this reason, it is difficult to sinter with free sintering, and therefore homogeneous foamed aluminum cannot be obtained by the slurry foaming method.
- a method of free sintering this aluminum powder a method in which a slurry foaming method is combined with the above-described fifth method can be mentioned.
- copper powder which is a metal whose eutectic temperature with aluminum is lower than the melting point of aluminum
- foaming material is mixed with aluminum together with foaming material, and then heated and fired to a temperature higher than the eutectic temperature and lower than the melting point of aluminum.
- Get aluminum aluminum.
- aluminum droplets ooze out on the surface, and the droplets solidify to form a large number of hemispherical aluminum lumps.
- the foamed aluminum is in the form of a thin plate, as shown in FIG. 9, the formation of a lump of aluminum was remarkable, and the desired homogeneous foamed aluminum could not be produced.
- the porous aluminum sintered body itself obtained by the above production method is inferior in mechanical strength and has openings formed on both surfaces when the thickness is reduced. For this reason, when used as a current collector for a lithium ion secondary battery or an electric double layer capacitor, an LED heat sink heat sink, a radiator, etc. In order to secure or block one surface, it is necessary to join and integrate a metal foil or a metal plate. As a result, the number of manufacturing steps is increased, and particularly, this type of aluminum material has a problem in that the joining method is limited and the processing requires labor.
- Japanese Patent No. 3591055 JP 2009-43536 A Japanese Patent Laid-Open No. 08-209265 JP 2007-238971 A Special table 2003-520292 Japanese Patent Publication No. 61-48566 Japanese Patent No. 3535282
- the present invention has been made in view of such circumstances, and a highly porous homogeneous aluminum porous sintered body having fine and sized open pores of 600 ⁇ m or less is integrated with an aluminum foil or an aluminum plate. It is an object of the present invention to provide a method for producing an aluminum composite that can easily and inexpensively obtain a composite.
- the inventors of the present invention sintered without forming a lump of droplets even in free sintering.
- the present inventors have found that there are conditions that can be achieved, and have completed the invention relating to the porous aluminum sintered body.
- the sintering agent powder containing titanium and / or titanium hydride etc. are mixed with aluminum powder, and the viscous composition before foaming is produced, This viscosity is produced.
- the composition is molded on an aluminum foil or an aluminum plate, foamed, and then heated and sintered in a predetermined temperature range.
- an aluminum mixed raw material powder is obtained by mixing a sintering aid powder containing either one or both of titanium and titanium hydride with aluminum powder.
- a step of adding and mixing a hydrophilic hydrocarbon-based organic solvent to form a viscous composition and a step of forming the viscous composition on an aluminum foil or an aluminum plate and foaming it to form a green body before sintering,
- the pre-sintered compact is heated and fired in a non-oxidizing atmosphere, so that a large amount of aluminum is formed on the aluminum foil or aluminum plate.
- the non-oxidizing atmosphere means an atmosphere that does not oxidize the aluminum mixed raw material powder, including an inert atmosphere or a reducing atmosphere.
- the above-described heating and firing temperature is not the temperature of the aluminum mixed raw material powder, that is, the reaction temperature of the aluminum mixed raw material powder or the like, and means the holding temperature around the aluminum mixed raw material powder.
- the average particle size of the aluminum powder may be 2 to 200 ⁇ m.
- r and W are 1 ( ⁇ m) ⁇ r ⁇ 30 ( ⁇ m), 1 ⁇ W ⁇ 20 (mass%), and 0.1 ⁇ W / r ⁇ 2 may be satisfied.
- the water-soluble resin binder may be included in the range of 0.5% to 7% of the mass of the aluminum mixed raw material powder.
- a surfactant in the range of 0.02 to 3% of the mass of the aluminum mixed raw material powder may be added to the aluminum mixed raw material powder.
- a sintering aid powder containing titanium and / or titanium hydride is mixed with aluminum powder to obtain an aluminum mixed raw material powder.
- this pre-sintered molded body is heated and fired in a predetermined temperature range in a non-oxidizing atmosphere.
- the reason for limiting the heating and firing temperature to Tm-10 (° C.) or higher is that the temperature at which the aluminum powder contained in the aluminum mixed raw material powder and the sintering aid powder containing titanium start the reaction is Tm-10 (° C. That's why.
- the melting point of aluminum is described as Tm because the pure aluminum melting point is 660 ° C., but industrially utilized aluminum contains iron and silicon as impurities, so the melting point is lower than 660 ° C. is there.
- the reason why the heating and firing temperature is limited to 685 ° C. or less is that when heated and held at a temperature higher than that temperature, a drop-shaped lump of aluminum is generated in the sintered body.
- the aluminum mixed raw material powder is mixed with a water-soluble resin binder, water, and a plasticizer to form a viscous composition, and dried in a state in which bubbles are mixed in the viscous composition, and then the sintered compact. Then, this green body before sintering is fired at the above temperature range. For this reason, since the pre-sintered molded body becomes a sponge skeleton structure (three-dimensional skeleton structure, foamed skeleton structure of open pores), the obtained sintered body has pores and sponge skeleton surrounded by the sponge skeleton. It becomes an aluminum porous body having pores having two different forms with pores formed in itself.
- the aluminum powder is so viscous that the viscous composition can be molded into a desired shape on an aluminum foil or aluminum plate, and that the pre-sintered molded body after foaming has a desired handling strength.
- the average particle diameter of the aluminum powder is 2 ⁇ m or more, thereby preventing the sintering reaction from being hindered by increasing the mass of the water-soluble resin binder. Furthermore, it is preferable to set it as 200 micrometers or less, and this ensures the intensity
- the blending ratio W of the sintering aid powder exceeds 20% by mass, the sintering aid powder has contact points in the aluminum mixed raw material powder, and the reaction heat of aluminum and titanium cannot be controlled and is desired. No porous sintered body can be obtained. For this reason, 0.1 (mass%) ⁇ W ⁇ 20 (mass%). More preferably, 1 (mass%) ⁇ W ⁇ 20 (mass%).
- the reaction heat of aluminum and titanium may become too large, In some cases, the temperature of the aluminum melted by the heat of reaction further increases, the viscosity decreases, and droplets are generated.
- the surface layer with a substantially constant thickness from the exposed surface side of the titanium particles within a range in which the calorific value can be controlled by the blending amount and particle size of titanium It was found that only the part reacted with aluminum. Thus, it was experimentally derived that it is desirable that 1 ( ⁇ m) ⁇ r ⁇ 30 ( ⁇ m) and 0.1 ⁇ W / r ⁇ 2 in order to prevent the generation of droplets.
- titanium hydride as a sintering aid powder has a titanium content of 95% by mass or more and is dehydrogenated at 470 to 530 ° C. to be titanium, so that it is thermally decomposed by the above-mentioned heating and firing. It becomes titanium. For this reason, reaction efficiency with aluminum powder can be improved by using titanium and / or titanium hydride as a sintering aid powder.
- the water-soluble binder when the water-soluble binder is contained in an amount exceeding 7% of the mass of the aluminum mixed raw material powder, the amount of carbon remaining in the pre-sintered molded body when heated and fired is increased, and the sintering reaction is caused. Easy to be disturbed. On the other hand, if it is less than 0.5%, it becomes difficult to ensure the handling strength of the green body before sintering. Therefore, it is preferably contained within the range of 0.5% to 7% of the mass of the aluminum mixed raw material powder.
- FIG. 1 It is a schematic block diagram which shows an example of the apparatus for enforcing the manufacturing method of the aluminum composite which has an aluminum porous sintered compact concerning this invention. It is a perspective view which shows the shape of the aluminum composite body which has the aluminum porous sintered compact manufactured by one Embodiment of this invention. It is a SEM photograph of the surface of the aluminum foil of FIG. It is a SEM photograph of the surface of the foam aluminum (aluminum porous sintered compact) of FIG. It is a SEM photograph of the cross section of the composite_body
- FIG. 1 shows an example of the apparatus for enforcing the manufacturing method of the aluminum composite which has an aluminum porous sintered compact concerning this invention. It is a perspective view which shows the shape of the aluminum composite body which has the aluminum porous sintered compact manufactured by one Embodiment of this invention. It
- FIG. 7 is a partially enlarged SEM photograph of FIG. 6.
- 2 is an SEM photograph of foamed aluminum of Comparative Example 1. It is the photograph of the foamed aluminum obtained by the method which combined the slurry foaming method with the 5th method in the prior art as a method of free sintering aluminum powder.
- aluminum and titanium hydride are mixed with aluminum powder to prepare an aluminum mixed raw material powder (aluminum mixed raw material powder preparation step). Then, this aluminum mixed raw material powder is mixed with a water-soluble resin binder, water, a plasticizer comprising at least one of polyhydric alcohol, ether and ester, and a water-insoluble hydrocarbon system having 5 to 8 carbon atoms. An organic solvent is added and mixed to prepare a viscous composition (viscous composition preparation step).
- the slurry of the viscous composition is stretched to a uniform predetermined thickness on an aluminum foil by a doctor blade method or the like, and dried to obtain a green body before sintering (pre-sintering step). Then, this pre-sintered compact is heated and fired at a heating and firing temperature T satisfying Tm-10 (° C.) ⁇ heating and firing temperature T ⁇ 685 (° C.) in a non-oxidizing atmosphere (sintering step).
- Tm (° C.) is a temperature at which the aluminum mixed raw material powder starts to melt.
- the aluminum mixed raw material powder preparation step aluminum powder having an average particle size of 2 to 200 ⁇ m is used. That is, when the average particle diameter is small, the viscous composition is so viscous that it can be molded into a desired shape, and in order to make the pre-sintered molded body have handling strength, It is necessary to add a large amount of the conductive resin binder. However, if a large amount of the water-soluble resin binder is added, the amount of carbon remaining in the aluminum increases when the pre-sintered molded body is heated and fired, and the sintering reaction is inhibited.
- the aluminum powder having an average particle diameter in the range of 2 to 200 ⁇ m, more preferably in the range of 7 to 40 ⁇ m is used as described above.
- the average particle diameter can be measured by a laser diffraction method.
- a sintering aid powder containing titanium and / or titanium hydride is mixed with the aluminum powder.
- a heating and firing temperature T satisfying Tm-10 (° C.) ⁇ heating and firing temperature T ⁇ 685 (° C.)
- aluminum that does not generate a lump of droplets Can be sintered at normal pressure.
- titanium hydride (TiH 2 ) has a titanium content of 47.88 (molecular weight of titanium) / (47.88 + 1 (molecular weight of hydrogen) ⁇ 2) of 95% by mass or more and 470 to 530.
- the sintering aid containing titanium preferably contains 0.1 to 20% by mass of titanium with respect to 100% by mass of aluminum and titanium in total.
- the average particle diameter of titanium and / or titanium hydride is r ( ⁇ m) and the blending ratio of titanium and / or titanium hydride is W (mass%), 1 ( ⁇ m) ⁇ r ⁇ 30 ( ⁇ m), 0.1 (mass%) ⁇ W ⁇ 20 (mass%), and preferably 0.1 ⁇ W / r ⁇ 2. More preferably, 1 (mass%) ⁇ W ⁇ 20 (mass%).
- the blending ratio W is preferably 0.4 to 8% by mass.
- the compounding ratio W is 2 to 40% by mass from the condition of 0.1 ⁇ W / 20 ⁇ 2.
- the condition of 0.1 (mass%) ⁇ W ⁇ 20 (mass%) it is preferably 2 to 20 mass%.
- the average particle diameter of titanium hydride is 0.1 ( ⁇ m) ⁇ r ⁇ 30 ( ⁇ m), preferably 1 ( ⁇ m) ⁇ r ⁇ 30 ( ⁇ m), more preferably 4 ( ⁇ m). ⁇ r ⁇ 20 ( ⁇ m). That is, if the average particle size of titanium hydride is smaller than 1 ⁇ m, there is a risk of spontaneous ignition, while if it exceeds 30 ⁇ m, the titanium particles coated with the Al—Ti compound produced by sintering are used to form an Al—Ti compound. This is because the phases are easily separated and desired strength cannot be obtained in the sintered body.
- the reaction between aluminum and titanium depends on the particle size of the sintering aid powder, even within the range of 0.1 (% by mass) ⁇ W ⁇ 20 (% by mass).
- the heat becomes too high, and the temperature of the aluminum melted by the heat of reaction further increases to lower the viscosity and generate droplets.
- the titanium particles have a substantially constant thickness from the exposed surface side. Only the surface layer was found to react with aluminum. Thus, it was experimentally derived that it is desirable that 1 ( ⁇ m) ⁇ r ⁇ 30 ( ⁇ m) and 0.1 ⁇ W / r ⁇ 2 in order to prevent the generation of droplets.
- At least one selected from the group consisting of polyvinyl alcohol, methylcellulose and ethylcellulose is added as a water-soluble resin binder to the aluminum mixed raw material powder, and as a plasticizer
- At least one selected from the group consisting of polyethylene glycol, glycerin, and di-N-butyl phthalate is added, and distilled water and alkylbetaine as a surfactant are added.
- the addition amount of the water-soluble resin binder is in the range of 0.5 to 7% by mass with respect to 100 parts by mass of the aluminum mixed raw material powder.
- the amount exceeds 7% by mass with respect to 100% by mass of the aluminum mixed raw material powder the amount of carbon remaining in the pre-sintered molded body or the like when heated and fired increases and the sintering reaction is inhibited.
- it is less than 0.5% by mass the handling strength of the green body before sintering cannot be ensured.
- alkylbetaine 0.02 to 3% by mass of alkylbetaine is added to 100% by mass of the aluminum mixed raw material powder.
- 0.02 mass% with respect to 100 mass% of aluminum mixing raw material powder a bubble will be produced
- the amount is 3% by mass or less, inhibition of the sintering reaction due to an increase in the amount of carbon remaining in the pre-sintered molded body or the like is prevented.
- the mixture is further foamed by mixing a water-insoluble hydrocarbon organic solvent having 5 to 8 carbon atoms to prepare a viscous composition in which bubbles are mixed.
- a water-insoluble hydrocarbon organic solvent having 5 to 8 carbon atoms at least one of pentane, hexane, heptane and octane can be used.
- This forming apparatus 1 includes a doctor blade 2, a hopper 4 of a viscous composition 3, a preliminary drying chamber 5, a constant temperature / high humidity tank 6, a drying tank 7, a delivery reel 9 for aluminum foil 8, a support roll 10 for aluminum foil 8, 11 and a roll 13 that guides and supports a pre-sintered compact 14 in which a porous aluminum body before sintering is applied on the aluminum foil 8.
- a strip-like 99.9% aluminum foil 8 having a thickness of 20 ⁇ m is continuously fed out from the reel 9 and the viscous composition 3 put into the hopper 4 is placed on the upper surface of the aluminum foil 8. (Applied surface) is applied with a doctor blade 2 to a thickness of 0.05 to 5 mm.
- foaming is performed from the preliminary drying chamber 5 in the constant temperature / high humidity tank 6 to size the bubbles. Subsequently, it is dried at a temperature of 70 ° C. in the drying tank 7.
- the pre-sintered molded body 14 that has been sent out from the roll 13 is cut into a predetermined shape such as a circle having a diameter of 100 mm as necessary.
- the pre-sintered compact 14 is placed on an alumina setter on which zirconia powder is spread, and in an argon atmosphere having a dew point of ⁇ 20 ° C. or lower for 1 hour at 520 ° C.
- Temporary baking is performed by heating.
- debinding for volatilizing and / or decomposing the binder solution of the water-soluble resin binder component, the plasticizer component, distilled water and the alkylbetaine of the green body 14 before sintering is performed, and hydrogen is used as the sintering aid powder.
- titanium fluoride is used, dehydrogenation is performed.
- the pre-sintered compact after preliminary firing is heated at a firing temperature T satisfying Tm-10 (° C.) ⁇ heating firing temperature T ⁇ 685 (° C.) in an argon gas atmosphere having a dew point of ⁇ 40 ° C. or less. Bake.
- Tm-10 (° C.) ⁇ heating firing temperature T ⁇ 685 (° C.) in an argon gas atmosphere having a dew point of ⁇ 40 ° C. or less.
- Tm 660
- the titanium component as a sintering aid starts to react with the aluminum powder and the aluminum foil. It is thought to do.
- aluminum powder and aluminum foil contain eutectic alloy elements such as Fe and Si as impurities, and the melting point decreases. Therefore, in practice, the reaction between aluminum and titanium starts by heating to Tm-10 (° C.), and an aluminum porous sintered body is formed. At the same time, the aluminum foil is firmly bonded.
- the melting point of aluminum is 660 ° C.
- the atomization powder having a purity of about 98% to 99.7% circulated as pure aluminum powder has a melting start temperature of around 650 ° C.
- heat-firing is performed at a temperature higher than 685 ° C., aluminum droplet-like lumps are generated in the sintered body.
- the pre-sintered molded body may be once heated and held in air at 300 ° C. to 400 ° C. for about 10 minutes to remove the binder, and then heated to a predetermined temperature in an argon atmosphere and fired. .
- the aluminum composite thus obtained has a dense aluminum foil layer on one side and a metal skeleton having a three-dimensional network structure on the other side, as seen in FIGS.
- An aluminum porous sintered body in which an Al—Ti compound is dispersed almost uniformly is provided.
- the aluminum porous sintered body has a total porosity of 70 to 90% with 20 or more pores formed per 1 cm of linear length.
- the said aluminum complex can be used suitably as a collector of a lithium ion secondary battery or an electric double layer type capacitor.
- Examples 1 to 16 an Al powder having an average particle size of 2.1 ⁇ m, 9.4 ⁇ m, 24 ⁇ m, 87 ⁇ m and 175 ⁇ m, a Ti powder having an average particle size of 9.8 ⁇ m, 24 ⁇ m and 42 ⁇ m, an average particle size of 4.2 ⁇ m, 9.1 ⁇ m and A 21 ⁇ m TiH 2 powder is prepared. Then, according to the above-mentioned embodiment, Ti powder and / or TiH 2 powder are mixed with Al powder at a ratio shown in Table 1 to prepare aluminum mixed raw material powders 1 to 10, and a binder solution with the composition shown in Table 2 1-5 were prepared. These and a water-insoluble hydrocarbon-based organic solvent were kneaded in the proportions shown in Table 3 to produce viscous compositions of Examples 1 to 16.
- these viscous compositions of Examples 1 to 16 were stretched and applied onto an aluminum foil by the doctor blade method, and the bubbles were sized by controlling the temperature and humidity to be maintained for a certain period of time. Then, it was dried at a temperature of 70 ° C. with an air dryer. Table 3 shows the application thickness of the viscous composition and the temperature, humidity and holding time. The dried viscous composition was cut into a circle having a diameter of 100 mm together with an aluminum foil to obtain pre-sintered molded bodies of Examples 1 to 16.
- the shrinkage rate and porosity of the foamed aluminum of Examples 1 to 16 obtained as described above were calculated. Further, the number of three-dimensional vacancies was measured from a stereoscopic microscope photograph, and the number of pores in the skeleton was measured from a scanning electron microscope (SEM) photograph. The obtained SEM photograph confirmed the presence or absence of droplet solidification. Furthermore, the presence of an Al—Ti compound was confirmed on the surface of the skeleton of the foamed aluminum by surface analysis using an electron beam microanalyzer (EPMA). While showing the result in Table 5, the SEM photograph of the foaming aluminum of Example 1 was shown in FIG. 6, and the one part enlarged photograph was shown in FIG.
- EPMA electron beam microanalyzer
- each of the aluminum foams of Examples 1 to 16 was subjected to a roll rolling test at a rolling reduction of 20%, and the presence or absence of cracks was visually confirmed. Then, it cut out into the rectangular shape of 20 mm x 50 mm, and measured the electrical resistance between opposing corner parts. Next, these rectangular aluminum foams were respectively wound around the outer periphery of a cylindrical body having a diameter of 5 mm, and the presence or absence of cracks was visually confirmed. The results are shown in Table 5.
- Comparative Examples 1 to 9 Next, the comparative aluminum mixed raw material powders 31 to 35 prepared by preparing the same Al powder, Ti powder and TiH 2 powder as in the examples or the aluminum mixed raw material powder 1 of the present invention were used. 5 and foamed aluminum of Comparative Examples 1 to 9 were produced in the same manner as in the Example except that the water-insoluble hydrocarbon-based organic solvent was kneaded at a ratio shown in Table 4. The results of evaluating the foamed aluminum of Comparative Examples 1 to 9 by the same method as in the example are shown in Table 5, and the SEM photograph of the foamed aluminum of Comparative Example 1 is shown in FIG.
- the foamed aluminum of Examples 1 to 16 has 2 to 4 holes per 100 ⁇ m of the skeleton length of the porous metal sintered body and 1-dimensional pores between the metal skeletons. There are 52 or more per inch, that is, 20 or more per 1 cm.
- the foamed aluminum did not form droplet-shaped lumps, had low electrical resistance, and did not crack by the winding test. Therefore, it is suitable for a positive current collector of a battery or a capacitor that requires high output and high energy density.
- LiCoO 2 lithium cobaltate
- PVdE polyvinylidene fluoride
- artificial graphite powder as a conductive material
- This positive electrode agent was mixed with N-methyl-2pyrrolidone as a solvent to prepare a positive electrode active material slurry.
- cylindrical bodies having diameters of 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, and 5 mm were prepared, and the lithium ion batteries of Examples 1 to 16 and Conventional Example 1 were prepared. No. positive electrode was wound. Then, whether or not the active material is peeled is visually observed, and the minimum diameter at which no peeling is observed is shown in Table 5.
- It can be used as a method for producing an aluminum composite in which an aluminum porous sintered body is integrated on an aluminum foil or plate, which is suitable for use as a current collector of a lithium ion secondary battery or an electric double layer capacitor.
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Abstract
Description
本願は、2009年6月4日に、日本に出願された特願2009-135021号に基づき優先権を主張し、その内容をここに援用する。
その理由について述べると、このスラリー発泡法では、金属粉末に圧縮等の応力をかけることなく焼結するフリーシンタリングによって焼結して発泡金属を得ることになる。しかし、アルミニウム粉末は表面に数nm~数10nmの緻密な酸化アルミニウム被膜で覆われていて、それが固相、液相を問わずに焼結を阻害する。そのためにフリーシンタリンングでは焼結が困難であって、そのためスラリー発泡法で均質な発泡アルミニウムが得られなかった。
本発明のアルミニウム多孔質焼結体を有するアルミニウム複合体の製造方法は、アルミニウム粉末に、チタンおよび水素化チタンのうちいずれか一方又は両方を含む焼結助剤粉末を混合してアルミニウム混合原料粉末とする工程と、次いで前記アルミニウム混合原料粉末に、水溶性樹脂結合剤と、水と、多価アルコール、エーテルおよびエステルのうちの少なくとも1種からなる可塑剤と、炭素数5~8の非水溶性炭化水素系有機溶剤とを添加・混合して粘性組成物とする工程と、前記粘性組成物をアルミニウム箔またはアルミニウム板上に成形して発泡させることにより焼結前成形体とする工程と、次いで、前記焼結前成形体を非酸化性雰囲気にて加熱焼成することにより、前記アルミニウム箔またはアルミニウム板上にアルミニウムの多孔質焼結体が一体に接合されたアルミニウム多孔質焼結体を有するアルミニウム複合体を得る工程を有し、前記アルミニウム混合原料粉末が融解を開始する温度をTm(℃)としたときに、前記加熱焼成の温度T(℃)がTm-10(℃)≦T≦685(℃)を満たす。
前記アルミニウム混合原料粉末に、前記アルミニウム混合原料粉末の質量の0.02~3%の範囲内の界面活性剤を添加してもよい。
これは、以下の理由による。焼結助剤粉末の配合比Wが20質量%を超えると、アルミニウム混合原料粉末中で焼結助剤粉末同士が接点を持つようになって、アルミニウムとチタンの反応熱を制御できなくなるとともに所望の多孔質焼結体が得られないようになる。このため、0.1(質量%)≦W≦20(質量%)とする。更に好ましくは1(質量%)≦W≦20(質量%)である。
本実施形態の製造方法を概略説明すると、先ず、アルミニウム粉末にチタンおよび/または水素化チタンを混合してアルミニウム混合原料粉末を調製する(アルミニウム混合原料粉末調製工程)。そして、このアルミニウム混合原料粉末に、水溶性樹脂結合剤と、水と、多価アルコール、エーテルおよびエステルのうちの少なくとも1種からなる可塑剤と、炭素数5~8の非水溶性炭化水素系有機溶剤とを添加して混合し、粘性組成物を調製する(粘性組成物調製工程)。
そして、この焼結前成形体を非酸化性雰囲気下において、Tm-10(℃)≦加熱焼成温度T≦685(℃)を満たす加熱焼成温度Tで加熱焼成する(焼結工程)。ここで、Tm(℃)は、アルミニウム混合原料粉末が溶解を開始する温度である。
上記アルミニウム混合原料粉末調製工程では、アルミニウム粉末として平均粒子径2~200μmのものが用いられる。すなわち、平均粒子径が小さい場合、粘性組成物が所望の形状に成形可能な程度に粘性を有し、かつ焼結前成形体がハンドリング強度を有するようにするために、アルミニウム粉末に対して水溶性樹脂結合剤を多量に加える必要が生じる。しかしながら、水溶性樹脂結合剤を多量に加えると、焼結前成形体を加熱焼成する際に、アルミニウム中に残存する炭素量が増加して、焼結反応が阻害されてしまう。他方、アルミニウム粉末の粒子径が大きすぎると、発泡アルミニウムの強度が低下してしまう。したがって、アルミニウム粉末としては、上述したように平均粒子径2~200μmの範囲内、より好ましくは7μm~40μmの範囲内のものが用いられる。なお、上記平均粒子径は、レーザー回折法によって測定することができる。
ここで、チタンおよび/または水素化チタンの平均粒子径をr(μm)、チタンおよび/または水素化チタンの配合比をW(質量%)としたときに、1(μm)≦r≦30(μm)、0.1(質量%)≦W≦20(質量%)とし、かつ0.1≦W/r≦2とすることが好ましい。更に好ましくは、1(質量%)≦W≦20(質量%)である。
この成形装置1は、ドクターブレード2、粘性組成物3のホッパ4、予備乾燥室5、恒温・高湿度槽6、乾燥槽7、アルミニウム箔8の送り出しリール9、アルミニウム箔8の支持ロール10、11およびアルミニウム箔8上に焼結前のアルミニウム多孔質体が塗布された焼結前成形体14を案内・支持するロール13を備える。
そして、上記アルミニウム多孔質焼結体は、空孔が直線長さ1cm当たりに20ヶ以上形成されて、70~90%の全体気孔率を有している。
このため、上記アルミニウム複合体は、リチウムイオン二次電池や電気二重層型キャパシタの集電体として好適に用いることができる。
次に、平均粒子径2.1μm、9.4μm、24μm、87μmおよび175μmのAl粉と、平均粒子径9.8μm、24μmおよび42μmのTi粉と、平均粒子径4.2μm、9.1μmおよび21μmのTiH2粉とを用意する。そして、上述の実施の形態に従って、表1に示す割合でAl粉にTi粉および/またはTiH2粉を混合してアルミニウム混合原料粉末1~10を調製し、表2に示す配合組成でバインダー溶液1~5を調製した。それらと非水溶性炭化水素系有機溶剤を表3に示す割合で混練して実施例1~16の粘性組成物を製造した。
次いで、実施例と同一のAl粉、Ti粉およびTiH2粉を用意して調製した比較アルミニウム混合原料粉末31~35又は本発明アルミニウム混合原料粉末1を用いて、表2に示すバインダー溶液1~5と、非水溶性炭化水素系有機溶剤を表4に示す割合で混練した以外は、実施例と同様にして比較例1~9の発泡アルミニウムを製造した。そして、比較例1~9の発泡アルミニウムを実施例と同様の方法にて評価した結果を表5に示すとともに、比較例1の発泡アルミニウムのSEM写真を図8に示した。
3 粘性組成物
8 アルミニウム箔
14 焼結前成形体
15 アルミニウム多孔質焼結体
16 アルミニウム複合体
Claims (5)
- アルミニウム粉末に、チタンおよび水素化チタンのうちいずれか一方又は両方を含む焼結助剤粉末を混合してアルミニウム混合原料粉末とする工程と、
次いで前記アルミニウム混合原料粉末に、水溶性樹脂結合剤と、水と、多価アルコール、エーテルおよびエステルのうちの少なくとも1種からなる可塑剤と、炭素数5~8の非水溶性炭化水素系有機溶剤とを添加・混合して粘性組成物とする工程と、
前記粘性組成物をアルミニウム箔またはアルミニウム板上に成形して発泡させることにより焼結前成形体とする工程と、
次いで、前記焼結前成形体を非酸化性雰囲気にて加熱焼成することにより、前記アルミニウム箔またはアルミニウム板上にアルミニウムの多孔質焼結体が一体に接合されたアルミニウム多孔質焼結体を有するアルミニウム複合体を得る工程を有し、
前記アルミニウム混合原料粉末が融解を開始する温度をTm(℃)としたときに、前記加熱焼成の温度T(℃)がTm-10(℃)≦T≦685(℃)を満たすことを特徴とするアルミニウム多孔質焼結体を有するアルミニウム複合体の製造方法。 - 前記アルミニウム粉末の平均粒子径が2~200μmであることを特徴とする請求項1に記載のアルミニウム多孔質焼結体を有するアルミニウム複合体の製造方法。
- 前記焼結助剤粉末の平均粒子径をr(μm)、前記焼結助剤粉末の配合比をW質量%としたときに、前記r及び前記Wは、1(μm)≦r≦30(μm)、1≦W≦20(質量%)、かつ0.1≦W/r≦2を満たすことを特徴とする請求項1に記載のアルミニウム多孔質焼結体を有するアルミニウム複合体の製造方法。
- 前記水溶性樹脂結合剤は、前記アルミニウム混合原料粉末の質量の0.5%~7%の範囲内で含まれていることを特徴とする請求項1に記載のアルミニウム多孔質焼結体を有するアルミニウム複合体の製造方法。
- 前記アルミニウム混合原料粉末に、前記アルミニウム混合原料粉末の質量の0.02~3%の範囲内の界面活性剤を添加することを特徴とする請求項1に記載のアルミニウム多孔質焼結体を有するアルミニウム複合体の製造方法。
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US20120135142A1 (en) | 2012-05-31 |
KR20120037399A (ko) | 2012-04-19 |
EP2439007A4 (en) | 2017-05-24 |
CN102458725A (zh) | 2012-05-16 |
EP2439007A1 (en) | 2012-04-11 |
TWI454580B (zh) | 2014-10-01 |
CN102458725B (zh) | 2013-11-13 |
KR101642539B1 (ko) | 2016-07-25 |
JP5428546B2 (ja) | 2014-02-26 |
TW201105803A (en) | 2011-02-16 |
JP2010280951A (ja) | 2010-12-16 |
US8691328B2 (en) | 2014-04-08 |
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