WO2019207964A1 - Corps poreux en aluminium, électrode, dispositif de stockage d'électricité et procédé de production d'un corps poreux en aluminium - Google Patents

Corps poreux en aluminium, électrode, dispositif de stockage d'électricité et procédé de production d'un corps poreux en aluminium Download PDF

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Publication number
WO2019207964A1
WO2019207964A1 PCT/JP2019/008555 JP2019008555W WO2019207964A1 WO 2019207964 A1 WO2019207964 A1 WO 2019207964A1 JP 2019008555 W JP2019008555 W JP 2019008555W WO 2019207964 A1 WO2019207964 A1 WO 2019207964A1
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WIPO (PCT)
Prior art keywords
aluminum
skeleton
porous body
resin
porous
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PCT/JP2019/008555
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English (en)
Japanese (ja)
Inventor
英彰 境田
健吾 後藤
細江　晃久
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住友電気工業株式会社
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Publication of WO2019207964A1 publication Critical patent/WO2019207964A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66—Current collectors
    • H01G11/68—Current collectors characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66—Current collectors
    • H01G11/70—Current collectors characterised by their structure
    • 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
    • H01M4/66—Selection of materials
    • 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
    • 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to an aluminum porous body, an electrode, an electricity storage device, and a method for producing the aluminum porous body.
  • Metal porous bodies having a skeleton having a three-dimensional network structure are used in various fields such as various filters, catalyst carriers, and battery electrodes.
  • metal porous bodies For example, aluminum cermet (registered trademark) manufactured by Sumitomo Electric Industries, Ltd., which is a metal porous body made of aluminum, is stable even in an organic electrolyte, and can be used as a positive electrode of a lithium ion battery.
  • the metal porous body having a three-dimensional network structure skeleton is characterized by a high porosity (90% or more) compared to other porous bodies such as a metal nonwoven fabric. Therefore, by filling the pores of the metal porous body with an active material and using it as an electrode of a power storage device such as a lithium ion battery, the utilization rate of the active material per unit area can be improved and the power storage with a large power storage capacity can be achieved.
  • a device can be provided.
  • Patent Document 1 As a method for producing a metal porous body made of aluminum, for example, methods described in International Publication No. 2012/111605 (Patent Document 1) and International Publication No. 2012/111665 (Patent Document 2) are known.
  • the aluminum porous body of the present disclosure is a sheet-like aluminum porous body having a skeleton having a three-dimensional network structure, the surface roughness Ra of the skeleton being 3 ⁇ m or more, and the compressive strength in the thickness direction of the aluminum porous body. Is a porous aluminum body having 1.0 MPa or more.
  • the method for producing a porous aluminum body of the present disclosure includes a conductive treatment step of forming a conductive layer on the surface of a skeleton of a resin molded body having a skeleton having a three-dimensional network structure, and aluminum on the surface of the skeleton of the resin molded body.
  • the solution contains 5.0 g / L or more and 7.5 g / L or less of 1,10-phenanthroline as an additive, and the amount of the electrolyte remaining on the surface of the skeleton of the resin structure in the resin removal step
  • cleaning is performed in a state where the apparent area of the resin structure is 35 ml / m 2 or more and 200 ml / m 2 or less, and the basis weight is 50 g / m 2 or more and 200 g / m per 1 mm thickness. It is a manufacturing method of the aluminum porous body which obtains the aluminum porous body which is 2 or less.
  • aluminum porous body whose skeleton is composed of a metal mainly composed of aluminum as a current collector in an electrode of an electricity storage device.
  • aluminum porous body whose skeleton is composed of a metal mainly composed of aluminum as a current collector in an electrode of an electricity storage device.
  • it is effective to increase the contact area between the active material filled in the pores of the skeleton of the aluminum porous body, which is a current collector, and the skeleton.
  • the concentration of phenanthroline added to the molten salt (electrolytic solution) should be low. By doing so, an aluminum porous body having a rough skeleton surface can be produced.
  • the compressive strength of the skeleton is reduced.
  • an object of the present disclosure is to provide a porous aluminum body having high strength and a rough skeleton surface.
  • an aluminum porous body having high strength and a rough skeleton surface can be provided.
  • An aluminum porous body is: A sheet-like aluminum porous body having a three-dimensional network structure skeleton, The surface roughness Ra of the skeleton is 3 ⁇ m or more, The compressive strength in the thickness direction of the aluminum porous body is 1.0 MPa or more, A porous aluminum body. According to the aspect of the invention described in (1), it is possible to provide a porous aluminum body having high strength and a rough skeleton surface.
  • the aluminum porous body according to (1) is Basis weight per a thickness of 1 mm, 50 g / m 2 or more and 200 g / m 2 or less. According to the aspect of the invention described in (2) above, it is possible to provide a porous aluminum body that is lightweight and has high strength.
  • An aluminum porous body can be provided.
  • An electrode according to one embodiment of the present disclosure is provided. It is an electrode provided with the aluminum porous body as described in any one of said (1) to said (4) as a collector. According to the aspect of the invention described in (5), it is possible to provide an electrode having a large contact area between the active material filled in the pores of the skeleton of the porous aluminum body and the skeleton and having excellent compressive strength. .
  • An electricity storage device is provided. It is an electrical storage device provided with the aluminum porous body as described in any one of said (1) to said (4) as a collector. According to the aspect of the invention described in (6), it is possible to provide an electricity storage device including an electrode having high active material utilization efficiency and high strength.
  • a method for producing a porous aluminum body includes: A conductive treatment step of forming a conductive layer on the surface of the skeleton of the resin molded body having a skeleton of a three-dimensional network structure; A plating step of obtaining a resin structure by electrodepositing aluminum on the surface of the skeleton of the resin molded body; A resin removal step of removing the resin molded body and the conductive layer from the resin structure to obtain an aluminum porous body; Including
  • the electrolytic solution used in the plating step contains 5.0 g / L or more and 7.5 g / L or less of 1,10-phenanthroline as an additive, In the resin removal step, the amount of the electrolyte remaining on the surface of the skeleton of the resin structure is 35 ml / m 2 or more and 200 ml / m 2 or less based on the apparent area of the resin structure.
  • Basis weight per a thickness of 1 mm, 50 g / m 2 or more to obtain a porous aluminum body is 200 g / m 2 or less,
  • a method for producing a porous aluminum body According to the aspect of the invention described in (7), a method for producing a porous aluminum body having high strength and a rough skeleton surface can be provided.
  • the aluminum porous body according to the embodiment of the present disclosure solves this problem, and has an unprecedented property that the surface roughness Ra of the skeleton is large and the compressive strength in the thickness direction is large. .
  • FIG. 1 shows a schematic diagram of an example of an aluminum porous body according to an embodiment of the present disclosure.
  • the porous aluminum body 10 according to an embodiment of the present disclosure has a three-dimensional network structure skeleton, and has a sheet-like appearance as a whole.
  • the pores formed by the skeleton of the three-dimensional network structure are continuous ventilation holes formed so as to continue from the surface to the inside of the porous aluminum body 10.
  • the skeleton only needs to be mainly composed of the aluminum film 11 and may contain a metal or an alloy other than aluminum intentionally or inevitably as long as the effects of the present disclosure are not impaired.
  • FIG. 2 shows an enlarged photograph showing a skeleton of a three-dimensional network structure as an example of the aluminum porous body according to the embodiment of the present disclosure.
  • the enlarged schematic diagram which expanded the cross section of the aluminum porous body shown in FIG. 2 is shown in FIG.
  • the shape of the skeleton has a three-dimensional network structure, typically, as shown in FIG. 3, the skeleton 12 of the aluminum porous body 10 is constituted by an aluminum film 11, and the inside 13 of the skeleton 12 is hollow. It has become.
  • the pore part 14 formed of the skeleton 12 is a continuous ventilation hole as described above.
  • the surface roughness Ra of the skeleton of the aluminum porous body 10 is 3 ⁇ m or more.
  • the surface roughness of the skeleton refers to the surface roughness of the surface of the aluminum film 11 forming the skeleton 12 on the side in contact with the pores 14.
  • the surface roughness Ra refers to a value obtained by measuring an area of 25 ⁇ m ⁇ 25 ⁇ m for a porous aluminum body with a laser surface roughness meter at five points and averaging the arithmetic average roughness Ra in each area.
  • the skeleton of the porous aluminum body has a three-dimensional network structure and is greatly curved depending on the location, when measuring the surface roughness Ra of the skeleton, an area of 25 ⁇ m ⁇ 25 ⁇ m is formed on the surface of the skeleton. What is necessary is just to select and measure the part as close to the plane as possible.
  • the surface roughness Ra of the skeleton is 3 ⁇ m or more, for example, when the aluminum porous body 10 is used as a current collector of an electrode of an electricity storage device, the contact area between the active material filled in the pores 14 and the skeleton Can be increased.
  • the surface roughness Ra of the skeleton of the aluminum porous body 10 is preferably 10 ⁇ m or less. From these viewpoints, the surface roughness Ra of the skeleton is preferably 3 ⁇ m or more and 10 ⁇ m or less, and more preferably 3 ⁇ m or more and 5 ⁇ m or less.
  • the porous aluminum body 10 has a compressive strength in the thickness direction of 1.0 MPa or more.
  • the compressive strength of the porous aluminum body 10 means that when a test piece is prepared by punching a sheet-like aluminum porous body to 20 mm ⁇ and a load is applied in the thickness direction of the test piece with a compression tester, The load necessary to reduce the thickness by 5% shall be said.
  • the compressive strength in the thickness direction of the aluminum porous body 10 is 1.0 MPa or more, for example, when the aluminum porous body 10 is used as a current collector of an electrode of an electricity storage device, an active material is formed in the pores 14 of the aluminum porous body 10.
  • the aluminum porous body 10 can maintain a three-dimensional network structure even if the pressure during filling is increased. That is, the pressure at the time of filling the pores 14 with the active material can be increased.
  • the compressive strength in the thickness direction of the porous aluminum body 10 is preferably as large as possible, more preferably 1.2 MPa or more, and even more preferably 1.5 MPa or more. Since the aluminum porous body 10 has a skeleton composed of the aluminum film 11 and is hollow inside, the compressive strength in the thickness direction is approximately 3.0 MPa or less.
  • Aluminum porous body 10 basis weight per a thickness of 1 mm, 50 g / m 2 or more and 200 g / m 2 or less.
  • a preferable range of the basis weight is 100 g / m 2 or more and 400 g / m 2 or less.
  • the basis weight is the apparent mass per unit area of the main surface of the sheet-like porous aluminum body.
  • the basis weight of the aluminum porous body is 200 g / m 2 or less per 1 mm thickness, an increase in manufacturing cost and an increase in weight can be suppressed.
  • the basis weight of the porous aluminum thickness 1mm per 70 g / m 2 or more, 180 g / m 2 or less is more preferably 80 g / m 2 or more, more preferably 160 g / m 2 or less.
  • the aluminum porous body 10 preferably has an average pore diameter of 300 ⁇ m or more and 3500 ⁇ m or less.
  • the average pore diameter of the aluminum porous body 10 is 300 ⁇ m or more, when the aluminum porous body 10 is used as a current collector of an electrode of an electricity storage device, the amount of active material filled in the pores 14 may be increased. it can. Further, since the average pore diameter of the aluminum porous body 10 is 3500 ⁇ m or less, when the aluminum porous body 10 is used as a current collector of an electrode of an electricity storage device, contact between the active material filled in the pores 14 and the skeleton The area can be increased and the utilization efficiency of the active material can be improved.
  • the average pore diameter of the porous aluminum body 10 is more preferably 500 ⁇ m or more and 2000 ⁇ m or less, and further preferably 550 ⁇ m or more and 900 ⁇ m or less.
  • an average pore diameter is the value calculated
  • the number of cells is a numerical value obtained by counting the number of cells on the outermost surface intersecting the line when a line of 1 inch in length is drawn on the surface (main surface) of the sheet-like porous aluminum body. Pieces / inch. However, 1 inch shall be 2.54 cm.
  • the aluminum porous body 10 preferably has a thickness of 0.6 mm or more and 10.0 mm or less.
  • the aluminum porous body 10 has a thickness of 0.6 mm or more, for example, when the aluminum porous body 10 is used as a current collector for an electrode of an electricity storage device, the current collector has a large active material retention amount. Can do.
  • the thickness of the aluminum porous body is 10.0 mm or less, an increase in manufacturing cost and an increase in weight can be suppressed. From these viewpoints, the thickness of the aluminum porous body is more preferably 0.8 mm or more and 5 mm or less, and further preferably 1 mm or more and 3 mm or less.
  • the porous aluminum body 10 preferably has a porosity of 92% or more and 98.5% or less.
  • the porosity of the aluminum porous body 10 is 92% or more, the aluminum porous body 10 can be made lightweight.
  • the aluminum porous body 10 is used as a current collector for an electrode of an electricity storage device, the amount of the active material filled in the pores 14 can be increased.
  • the porosity of the aluminum porous body 10 is 98.5% or less, the aluminum porous body 10 can have sufficient strength. From these viewpoints, the porosity of the aluminum porous body 10 is more preferably 93% or more and 97.5% or less, and further preferably 94% or more and 97% or less.
  • the electrode according to the embodiment of the present disclosure uses the porous aluminum body according to the embodiment of the present disclosure as a current collector. That is, it can be used as an electrode of an electricity storage device by filling the pores of the aluminum porous body with an active material. What is necessary is just to select an active material suitably according to the kind of electrical storage device.
  • the porous aluminum body according to the embodiment of the present disclosure has a large surface roughness Ra of 3 ⁇ m or more
  • the electrode according to the embodiment of the present disclosure is an active material filled in the pores of the aluminum porous body. The contact area between the skeleton and the skeleton is large and the utilization efficiency of the active material is excellent.
  • the electrode according to the embodiment of the present disclosure applies a large pressure when filling the pores with the active material.
  • the amount of active material filling can be increased.
  • An electricity storage device uses an aluminum porous body according to the embodiment of the present disclosure as a current collector, that is, includes an electrode according to the embodiment of the present disclosure.
  • the power storage device since the electrode according to the embodiment of the present disclosure has a large active material filling amount and is excellent in the utilization efficiency of the active material, the power storage device according to the embodiment of the present disclosure including the electrode has a storage capacity. Is a large electricity storage device.
  • the type of the electricity storage device is not particularly limited, and examples thereof include a lithium ion battery (including a lithium ion secondary battery), an electric double layer capacitor, and a lithium ion capacitor.
  • FIG. 7 the cross-sectional schematic diagram of an example of a lithium ion battery is shown.
  • a porous aluminum body with a positive electrode active material filled in pores is disposed as a positive electrode 146 in an organic electrolyte solution 143 partitioned by a separator 142, and an electrode carrying a negative electrode active material on a current collector is provided.
  • the negative electrode 147 is disposed.
  • a lead wire 148 and a lead wire 149 are connected to the positive electrode 146 and the negative electrode 147, respectively, and these are all housed in a case 145.
  • a positive electrode of a lithium ion battery including a lithium ion secondary battery
  • lithium cobaltate (LiCoO 2 ) lithium manganate (LiMn 2 ) as active materials.
  • O 4 lithium nickelate (LiNiO 2 ), or the like
  • the active material may be used in combination with a conductive additive and a binder.
  • the aluminum porous body according to the embodiment of the present disclosure can be manufactured by improving the manufacturing method of the aluminum porous body by a conventional plating method.
  • the manufacturing method of the aluminum porous body by the conventional plating method is a conductive treatment process for conducting a conductive treatment on the surface of a skeleton of a resin molded body having a skeleton having a three-dimensional network structure, and a resin subjected to the conductive treatment.
  • the conductive treatment step is a step of preparing a resin molded body having a skeleton having a three-dimensional network structure and imparting conductivity by conducting a conductive treatment on the surface of the skeleton of the resin molded body. For example, by forming a conductive layer so as to cover the surface of the skeleton of the resin molded body, conductivity can be imparted to the surface of the skeleton of the resin molded body.
  • FIG. 4 shows an enlarged schematic view of a partial cross section of an example of a state in which the conductive layer 16 is formed on the surface of the skeleton of the resin molded body 15.
  • a resin molded body having a three-dimensional network structure skeleton (hereinafter, also simply referred to as “resin molded body”) is used as a base material.
  • the resin molded body 15 has pores 14 formed by a skeleton, and further, a plurality of pores 14 are connected to form continuous ventilation holes.
  • a resin foam, a nonwoven fabric, a felt, a woven fabric, or the like can be used, and these can be used in combination as necessary.
  • the material of the resin molded body 15 may be any material that can be removed by heat treatment after aluminum is plated on the surface of the skeleton.
  • the resin molded body 15 is preferably a flexible material because the skeleton is broken when the rigidity is too high particularly in the case of a sheet-like material for handling.
  • a resin foam is preferably used as the resin molded body 15 having a three-dimensional network structure skeleton.
  • the resin foam any known or commercially available resin may be used as long as it is porous.
  • urethane foam, foamed styrene and the like can be used. Among these, urethane foam is preferable from the viewpoint of particularly high porosity.
  • FIG. 5 shows a photograph of the urethane foam resin.
  • the porosity, average pore diameter, and thickness of the aluminum porous body are the same as the porosity and average of the resin molded body 15. It becomes substantially equal to the pore diameter and thickness. For this reason, what is necessary is just to select suitably the porosity, average pore diameter, and thickness of the resin molding 15 according to the porosity, average pore diameter, and thickness of the aluminum porous body which is a manufacturing objective.
  • the porosity and average pore diameter of the resin molded body 15 are defined in the same manner as the porosity and average pore diameter of the aluminum porous body.
  • a method for conducting the surface of the skeleton of the resin molded body 15 is not particularly limited as long as the conductive layer 16 can be provided on the surface of the skeleton of the resin molded body 15.
  • the material constituting the conductive layer 16 include metals such as nickel, copper, aluminum, titanium, and stainless steel, amorphous carbon such as carbon black, and carbon powder such as graphite. Among these, carbon powder is particularly preferable, and carbon black is more preferable.
  • the conductive layer 16 is formed using amorphous carbon or carbon powder other than metal, the conductive layer 16 is also removed in a resin removal step described later.
  • the conductive treatment for example, when nickel, copper, aluminum, or the like is used, electroless plating treatment, sputtering treatment, or the like is preferable.
  • a metal such as titanium or stainless steel, or a material such as carbon black or graphite
  • a mixture obtained by adding a binder to fine powder of these materials is applied to the surface of the skeleton of the resin molded body 15. The process to perform is mentioned as a preferable method.
  • carbon black As described above, carbon black, activated carbon, graphite or the like can be used as the carbon powder. Carbon black may be used for the purpose of making the conductivity uniform, and fine graphite powder may be used for considering the strength of the conductive layer 16. Moreover, it is preferable to mix including activated carbon. You may add the thickener generally used, for example, carboxymethylcellulose (CMC) etc., when producing a slurry.
  • the surface of the skeleton of the resin molded body can be made conductive by applying this slurry to the skeleton of the resin molded body that has been cut into a plate shape or a strip shape by adjusting the thickness.
  • the resin molded body 15 may be immersed in a known electroless nickel plating bath such as a nickel sulfate aqueous solution containing sodium hypophosphite as a reducing agent. If necessary, before immersion in the plating bath, the resin molded body 15 may be immersed in an activation liquid containing a trace amount of palladium ions (a cleaning liquid manufactured by Kanigen Co., Ltd.).
  • a sputtering process using nickel, copper, aluminum, etc. for example, after the resin molded body 15 is attached to the substrate holder, the inert gas is introduced while the holder and the target (nickel, copper, aluminum, etc.) are interrogated.
  • the ionized inert gas collides with nickel, copper, aluminum or the like, and particles of nickel, copper, aluminum or the like blown off are deposited on the surface of the skeleton of the resin molded body 15. Good.
  • a porous aluminum body in which a different metal is not mixed in the skeleton can be produced.
  • the conductive layer 16 may be continuously formed so as to cover the surface of the skeleton of the resin molded body 15.
  • the basis weight of the conductive layer 16 is not limited, and is preferably 1.0 g / m 2 or more and 30 g / m 2 or less, more preferably 5.0 g / m 2 or more and 20 g / m 2 or less. 7.0 g / m 2 or more and 15 g / m 2 or less is more preferable.
  • the basis weight of the conductive layer refers to the mass of the conductive layer in an apparent unit area of the resin molded body in which the conductive layer is formed on the surface of the skeleton.
  • the plating process is a process of obtaining a resin structure by electrodepositing aluminum on the surface of the skeleton of the resin molded body by subjecting the resin molded body having a conductive layer formed on the surface of the skeleton to electrolytic treatment in an electrolytic solution. is there.
  • FIG. 6 is a schematic enlarged view of a partial cross section of an example in which the aluminum film 11 is further formed on the surface of the conductive layer 16 formed on the surface of the skeleton of the resin molded body 15.
  • molten salt containing the following component (A) and component (B) and further containing component (C) as an additive are used.
  • other components may be included intentionally in electrolyte solution.
  • the aluminum halide as the component (A) can be favorably used as long as it forms a molten salt at about 110 ° C. or less when mixed with the component (B).
  • aluminum chloride (AlCl 3 ), aluminum bromide (AlBr 3 ), aluminum iodide (AlI 3 ) and the like can be mentioned.
  • aluminum chloride is most preferable.
  • alkylimidazolium halide of the component (B) those that form a molten salt at about 110 ° C. or less when mixed with the component (A) can be used favorably.
  • imidazolium chloride having an alkyl group (1 to 5 carbon atoms) at the 1,3 position imidazolium chloride having an alkyl group (1 to 5 carbon atoms) at the 1,2,3 position, 1,3 position
  • imidazolium ioside having an alkyl group (having 1 to 5 carbon atoms).
  • EMIC 1-ethyl-3-methylimidazolium chloride
  • BMIC 1-butyl-3-methylimidazolium chloride
  • MPIC 1-methyl-3-propylimidazolium chloride
  • EMIC 1-ethyl-3-methylimidazolium chloride
  • alkylpyridinium halide of the component (B) those that form a molten salt at about 110 ° C. or less when mixed with the component (A) can be used favorably.
  • examples thereof include 1-butylpyridinium chloride (BPC), 1-ethylpyridinium chloride (EPC), 1-butyl-3-methylpyridinium chloride (BMPC), etc.
  • BPC 1-butylpyridinium chloride
  • EPC 1-ethylpyridinium chloride
  • BMPC 1-butyl-3-methylpyridinium chloride
  • 1-butylpyridinium chloride is most preferable.
  • the urea compound of the component (B) means urea and derivatives thereof, and those that form a molten salt at about 110 ° C. or less when mixed with the component (A) can be used favorably.
  • a compound represented by the following formula (1) can be preferably used.
  • R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and may be the same or different.
  • urea and dimethylurea can be particularly preferably used as the urea compound.
  • the electrolyte solution has a mixing ratio of the component (A) and the component (B) in a molar ratio of 1: 1 to 3: 1, so that the surface of the skeleton of the resin molded body An electrolytic solution (plating solution) suitable for electrodepositing aluminum is obtained.
  • An electrolytic solution (plating solution) suitable for electrodepositing aluminum is obtained.
  • the molar ratio of the component (A) is less than 1 when the component (B) is 1, no aluminum electrodeposition reaction occurs.
  • the molar ratio of the component (A) exceeds 3 when the component (B) is 1, aluminum chloride is precipitated in the electrolytic solution and is electrodeposited on the surface of the skeleton of the resin molded body. Incorporated into aluminum, the quality of aluminum is reduced.
  • the component (C) 1,10-phenanthroline is generally an additive for smoothing the surface of the aluminum film that is electrodeposited on the surface of the substrate.
  • the amount of 1,10-phenanthroline added is preferably such that, for example, the concentration in the electrolyte is 5.0 g / L or more and 7.5 g / L or less.
  • concentration of 1,10-phenanthroline in the electrolytic solution is 5.0 g / L or more, an aluminum porous body having a uniform aluminum film thickness and high compressive strength can be produced.
  • the concentration of 1,10-phenanthroline in the electrolytic solution is 7.5 g / L or less, the amount of 1,10-phenanthroline taken into the aluminum film is reduced, and the residual stress in the aluminum film becomes too large.
  • the concentration of 1,10-phenanthroline in the electrolytic solution is more preferably 5.5 g / L or more and 6.7 g / L or less, and more preferably 5.5 g / L or more and 6.1 g / L. More preferably, it is set to L or less.
  • 1,10-phenanthroline monohydrate and 1,10-phenanthrolinium chloride monohydrate can also be used.
  • the concentration in the electrolytic solution is 0.1 g / L or more and 1.0 g / L or less from the same viewpoint as described for 1,10-phenanthroline. It is preferably 0.3 g / L or more and 0.7 g / L or less, more preferably 0.3 g / L or more and 0.5 g / L or less.
  • the concentration in the electrolytic solution is preferably 0.01 g / L or more and 0.5 g / L or less, preferably 0.03 g / L. More preferably, it is L or more and 0.2 g / L or less, and further preferably 0.03 g / L or more and 0.1 g / L or less.
  • the electrolytic treatment (molten salt electrolysis) can be performed as follows.
  • the resin molded body after the conductive treatment process and aluminum are arranged facing each other in the electrolytic solution, the resin molded body is connected to the cathode side of the rectifier, aluminum is connected to the anode side, and a voltage is applied between both electrodes. Apply.
  • the current is controlled by applying a voltage so that the current density is 3.0 A / dm 2 or more and 6.0 A / dm 2 or less. It is preferable to carry out molten salt electrolysis.
  • the current density is more preferably 3.0 A / dm 2 or more and 5.0 A / dm 2 or less, and further preferably 3.5 A / dm 2 or more and 4.5 A / dm 2 or less. preferable.
  • the current density is calculated based on the apparent area of the surface of the resin molded body on which the aluminum film is formed.
  • the resin removing step is a step of obtaining a porous aluminum body by removing the resin molded body by heat-treating the resin structure obtained in the plating step.
  • the conductive layer 16 formed on the surface of the skeleton of the resin molded body 15 is amorphous carbon or carbon powder other than metal
  • the conductive layer 16 also disappears by heat treatment.
  • the resin molded body 15 and the conductive layer 16 disappear by heat treatment, and the aluminum film 11 remains.
  • skeleton of a three-dimensional network structure is obtained (refer FIG. 1).
  • the metal that has formed the conductive layer 16 diffuses into the aluminum film 11 by heat-treating the resin structure, or aluminum and It is alloyed.
  • the resin structure taken out from the electrolytic solution is first washed with pure water and then heat-treated.
  • the electrolytic solution remaining on the surface of the skeleton of the resin structure has been sufficiently removed.
  • the electrolytic solution is not sufficiently removed from the surface of the skeleton of the resin structure.
  • the electrolytic solution remaining on the surface of the skeleton of the resin structure reacts with water to corrode aluminum, forming very fine irregularities on the surface of the aluminum film 11 and forming the skeleton of the resin structure.
  • the surface roughness Ra can be increased.
  • the resin molded body is removed from the resin structure by heat treatment (about 370 ° C. or more and about 660 ° C. or less) in an oxidizing atmosphere such as an air atmosphere, and the aluminum film 11
  • an oxidizing atmosphere such as an air atmosphere
  • the amount of the electrolytic solution remaining on the surface of the skeleton of the resin structure is 35 ml / day based on the apparent area of the resin structure. It is preferable to perform the cleaning in a state of m 2 or more and 200 ml / m 2 or less.
  • the amount of the electrolyte remaining on the surface of the skeleton of the resin structure is that the thickness of the resin structure per mm.
  • the amount of electrolyte remaining on the surface of the skeleton of the resin structure is 35 ml / m 2 or more, so that the surface of the aluminum film 11 is sufficiently roughened.
  • the surface roughness Ra can be 3 ⁇ m or more.
  • the amount of electrolyte remaining on the surface of the skeleton of the resin structure is set to 200 ml / m 2 or less, so that the water that has reacted with the plating solution becomes hydrochloric acid to form the skeleton. It can suppress that the surface is corroded and the strength of the skeleton is lowered. From these viewpoints, the amount of the electrolyte remaining on the surface of the skeleton of the resin structure when washed with pure water is more preferably 40 ml / m 2 or more and 150 ml / m 2 or less, and 60 ml / m 2. 2 or more, and more preferably 100 ml / m 2 or less.
  • an electrolytic solution in which the concentration of 1,10-phenanthroline, 1,10-phenanthroline monohydrate, or 1,10-phenanthroline chloride monohydrate is a predetermined concentration or more is used.
  • a resin structure having a uniform thickness of the aluminum film 11 can be obtained.
  • the electrolyte solution remains on the surface of the skeleton as described above, so that the skeleton has a uniform film thickness and excellent strength, and the skeleton has a surface roughness Ra.
  • a large porous aluminum body can be obtained.
  • the resin structure In order to burn and remove the resin molded body from the resin structure by heat treatment, the resin structure is 370 ° C. or higher and 660 ° C. or lower, preferably 500 ° C. or higher and 620 ° C. or lower in an oxidizing atmosphere such as an air atmosphere. What is necessary is just to heat-process.
  • Example 1 ⁇ Conductive treatment process> A polyurethane sheet having a thickness of 1.0 mm was used as a resin molded body having a three-dimensional network structure. The porosity of the resin molded body was 96%, and the average pore diameter was 450 ⁇ m.
  • the conductive treatment was performed by immersing the polyurethane sheet in a carbon suspension and drying it to form a conductive layer on the surface of the skeleton of the polyurethane sheet.
  • the components of the carbon suspension included 25% graphite and carbon black, and included a resin binder, a penetrating agent, and an antifoaming agent. The particle size of carbon black was 0.5 ⁇ m.
  • ⁇ Plating process> Aluminum chloride (AlCl 3 ) is used as component (A), 1-ethyl-3-methylimidazolium chloride (EMIC) is used as component (B), and the mixing ratio of component (A) to component (B) is molar ratio.
  • the molten salt was prepared by mixing at 2: 1.
  • An electrolytic solution was obtained by adding 1,10-phenanthroline as a component (C) to the molten salt to a concentration of 5.0 g / L.
  • Molten salt electrolysis In the electrolytic solution obtained above, molten salt electrolysis was performed so that the electrically conductive polyurethane sheet was the cathode and the aluminum plate having a purity of 99.99% was the anode.
  • Example 2 In the resin removal step of Example 1, the same procedure as in Example 1 was performed, except that cleaning with pure water was performed in a state where the amount of the electrolyte remaining on the surface of the skeleton of the resin structure was 40 ml / m 2. Aluminum porous body No. 2 was obtained.
  • Example 3 In the resin removal step of Example 1, the same procedure as in Example 1 was performed, except that cleaning with pure water was performed in a state where the amount of the electrolyte remaining on the surface of the skeleton of the resin structure was 60 ml / m 2. Aluminum porous body No. 3 was obtained.
  • Example 4 In the resin removal step of Example 1, the same procedure as in Example 1 was performed, except that cleaning with pure water was performed in a state where the amount of the electrolyte remaining on the surface of the skeleton of the resin structure was 100 ml / m 2. Aluminum porous body No. 4 was obtained.
  • Example 5 In the resin removal step of Example 1, the same procedure as in Example 1 was performed, except that cleaning with pure water was performed in a state where the amount of the electrolyte remaining on the surface of the skeleton of the resin structure was 200 ml / m 2. Aluminum porous body No. 5 was obtained.
  • Example 6 In the plating step of Example 3, the porous aluminum body No. 1 was prepared in the same manner as in Example 3 except that the concentration of 1,10-phenanthroline in the electrolytic solution was 7.5 g / L. 6 was obtained.
  • Example 1 In the plating step of Example 1, the concentration of 1,10-phenanthroline in the electrolytic solution was set to 0.25 g / L, and in the resin removing step, the electrolytic solution remaining on the surface of the skeleton of the resin structure was removed. Except for washing with pure water in an amount of 14 ml / m 2 , the porous aluminum body No. 1 was prepared in the same manner as in Example 1. A was obtained.
  • Example 2 In the plating step of Example 1, the concentration of 1,10-phenanthroline in the electrolytic solution was set to 1.25 g / L, and in the resin removing step, the electrolytic solution remaining on the surface of the skeleton of the resin structure was removed. Except for washing with pure water in an amount of 13 ml / m 2 , the porous aluminum body No. 1 was prepared in the same manner as in Example 1. B was obtained.
  • Example 3 In the resin removal step of Example 1, the same procedure as in Example 1 was performed, except that cleaning with pure water was performed in a state where the amount of the electrolyte remaining on the surface of the skeleton of the resin structure was 16 ml / m 2. Aluminum porous body No. C was obtained.
  • Example 4 In the resin removal step of Example 1, the same procedure as in Example 1 was performed, except that cleaning with pure water was performed in a state where the amount of the electrolyte remaining on the surface of the skeleton of the resin structure was 30 ml / m 2. Aluminum porous body No. D was obtained.
  • Aluminum porous body No. A test piece was prepared by punching 1 into a circle having a diameter of 20 mm. A load was applied in the thickness direction of the test piece using a compression tester, and the load necessary to reduce the thickness of the test piece by 5% was measured as the compressive strength. The results are shown in Table 1. Aluminum porous body No. 2 to No. 6 and aluminum porous body no. A to No. The compressive strength was similarly measured for D.
  • porous aluminum body No. 1 As shown in Table 1, porous aluminum body No. 1 according to the embodiment of the present disclosure. 1 to No. In No. 6, the surface roughness Ra of the skeleton was 3 ⁇ m or more, and the compressive strength in the thickness direction was 1.0 MPa or more.
  • the aluminum porous body No. A and No. B has a large surface roughness but a low compressive strength.
  • C and No. D had high compressive strength but low surface roughness.
  • aluminum porous body No. The photograph which observed the cross section of 2 with the scanning electron microscope is shown in FIG. 8, and the enlarged view of the part shown with the white frame in FIG. 8 is shown in FIG.
  • an aluminum porous body No. 2 confirmed that the surface of the skeleton was very rough as compared with the conventional porous aluminum body.

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Abstract

L'invention concerne un corps poreux en aluminium de type feuille ayant un squelette de structure de type filet tridimensionnel, la rugosité de surface Ra du squelette étant de 3 µm ou plus et la résistance à la compression du corps poreux d'aluminium telle que mesurée dans la direction de l'épaisseur étant de 1,0 MPa ou plus.
PCT/JP2019/008555 2018-04-27 2019-03-05 Corps poreux en aluminium, électrode, dispositif de stockage d'électricité et procédé de production d'un corps poreux en aluminium WO2019207964A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012251210A (ja) * 2011-06-03 2012-12-20 Sumitomo Electric Ind Ltd 金属多孔体及びそれを用いた電極材料、電池
JP2016141822A (ja) * 2015-01-30 2016-08-08 日立化成株式会社 金属多孔質体
WO2018185983A1 (fr) * 2017-04-05 2018-10-11 住友電気工業株式会社 Corps en aluminium poreux et procédé de fabrication de ce dernier

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012251210A (ja) * 2011-06-03 2012-12-20 Sumitomo Electric Ind Ltd 金属多孔体及びそれを用いた電極材料、電池
JP2016141822A (ja) * 2015-01-30 2016-08-08 日立化成株式会社 金属多孔質体
WO2018185983A1 (fr) * 2017-04-05 2018-10-11 住友電気工業株式会社 Corps en aluminium poreux et procédé de fabrication de ce dernier

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