WO2015030196A1 - Solution électrolytique - Google Patents

Solution électrolytique Download PDF

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Publication number
WO2015030196A1
WO2015030196A1 PCT/JP2014/072793 JP2014072793W WO2015030196A1 WO 2015030196 A1 WO2015030196 A1 WO 2015030196A1 JP 2014072793 W JP2014072793 W JP 2014072793W WO 2015030196 A1 WO2015030196 A1 WO 2015030196A1
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Prior art keywords
aluminum
electrolytic solution
group
carbon atoms
imidazolidinone
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PCT/JP2014/072793
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English (en)
Japanese (ja)
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正男 三宅
厚志 遠藤
平藤　哲司
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国立大学法人京都大学
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Priority to JP2015534343A priority Critical patent/JPWO2015030196A1/ja
Publication of WO2015030196A1 publication Critical patent/WO2015030196A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/42—Electroplating: Baths therefor from solutions of light metals
    • C25D3/44—Aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • 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 invention relates to an electrolytic solution. More specifically, the present invention relates to an electrolytic solution for aluminum plating useful as a plating solution for aluminum plating, an electrolytic solution for aluminum secondary battery useful as an electrolytic solution for an aluminum secondary battery, and production of an aluminum material using the electrolytic solution. Regarding the method.
  • the electrolytic solution for aluminum plating of the present invention can perform electrodeposition of aluminum at a temperature near room temperature, it can be used for the production of aluminum materials and the formation of an aluminum plating film on the surface of an object to be plated. Used as a liquid.
  • the electrolytic solution for aluminum plating of the present invention is expected to be used, for example, for the manufacture of inexpensive, light and high strength structural members, electronic components, optical components and the like.
  • the electrolytic solution for an aluminum secondary battery of the present invention is easy to handle and can perform a charge / discharge reaction at a temperature near room temperature, for example, without being heated to a high temperature. Used as an electrolyte solution.
  • the electrolytic solution for an aluminum secondary battery of the present invention is expected to be used, for example, in the production of secondary batteries used in portable equipment, electric vehicles and the like.
  • an aluminum material can be efficiently produced at a temperature near room temperature, for example, without heating to a high temperature. It is expected to be used when developing inexpensive, lightweight, high-strength structural members, electronic / optical components, and the like.
  • Aluminum is expected to be used as a metal plating material in place of zinc and chromium because it has a large amount of reserves on the earth, has excellent corrosion resistance, and has a low load on humans. Since the electrodeposition potential of aluminum is significantly lower than the potential for hydrogen generation, it is difficult to deposit from an aqueous solution. Therefore, in the electrodeposition of aluminum, use of an electrolytic solution containing a non-aqueous organic solvent such as toluene as a solvent or an electrolytic solution containing a room temperature ionic liquid such as an imidazolium salt as a solvent has been studied (for example, non-patent) Reference 1). However, the electrolytic solution has many problems in terms of ease of handling and manufacturing cost.
  • an electrolytic aluminum plating solution containing dimethyl sulfone, which is a molecular organic solvent, as a solvent has been proposed (for example, see Patent Document 1).
  • the melting point of dimethyl sulfone is 110 ° C.
  • the electrolytic aluminum plating solution has a drawback that a great deal of energy is consumed when aluminum is electrodeposited.
  • the present invention has been made in view of the above prior art, is easy to handle, and can be efficiently electroplated with aluminum without being heated to a high temperature.
  • An electrolytic solution for an aluminum secondary battery that can efficiently perform a charge / discharge reaction without heating to a high temperature, and an aluminum material that can efficiently produce an aluminum material without heating to a high temperature It is an object to provide a manufacturing method.
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a nitro group, an amino group, a carboxyl group, a hydroxyl group, an optionally substituted alkyl group having 1 to 4 carbon atoms, An optionally substituted alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or 1 to 4 carbon atoms Represents an alkoxycarbonyl group of An aluminum halide is dissolved in the imidazolidinone compound represented by formula (I), and the molar ratio of the imidazolidinone compound represented by formula (I) to the aluminum halide [imidazolidinone compound / aluminum halide] is 25/75.
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a nitro group, an amino group, a carboxyl group, a hydroxyl group, an optionally substituted alkyl group having 1 to 4 carbon atoms, An optionally substituted alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or 1 to 4 carbon atoms Represents an alkoxycarbonyl group of An aluminum halide is dissolved in the imidazolidinone compound represented by formula (I), and the molar ratio of the imidazolidinone compound represented by formula (I) to the aluminum halide [imidazolidinone compound / aluminum halide] is 25/75.
  • the present invention relates to an electrolytic solution for an aluminum secondary battery that is ⁇ 50 / 50.
  • the electrolytic solution for aluminum plating of the present invention is easy to handle and has an excellent effect of being able to efficiently deposit aluminum without being heated to a high temperature.
  • the electrolytic solution for an aluminum secondary battery of the present invention is easy to handle, and exhibits an excellent effect that a charge / discharge reaction can be performed without heating to a high temperature.
  • the manufacturing method of the aluminum material of this invention even if it does not heat at high temperature, the outstanding effect that an aluminum material can be manufactured efficiently is show
  • (A) is a graph showing the results of measuring the oxidation-reduction potential of the electrolytic solution obtained in Example 1 by cyclic voltammetry
  • (B) is the result after electrodeposition using the electrolytic solution obtained in Example 1. It is a drawing substitute photograph of the cathode surface.
  • 6 is a graph showing the results of measuring the oxidation-reduction potential of the electrolytic solution obtained in Example 2 by cyclic voltammetry.
  • (A) is a graph showing the results of measuring the oxidation-reduction potential of the electrolytic solution obtained in Example 3 by cyclic voltammetry, and (B) is the result after electrodeposition using the electrolytic solution obtained in Example 3. It is a drawing substitute photograph of the cathode surface.
  • FIG. 5 is a drawing-substituting photograph of the cathode surface after electrodeposition at a current density of 0.5 mA / cm 2 using a liquid.
  • (A) is a drawing-substituting photograph of the cathode surface after electrodepositing at a current density of 0.75 mA / cm 2 using the electrolytic solution obtained in Example 6, and (B) is an electrolysis obtained in Example 7.
  • (C) is a substitute for a drawing of the cathode surface when electrodeposited at a current density of 0.5 mA / cm 2 , and the electrolyte obtained in Example 7 is used at a current density of 1 mA / cm 2.
  • (D) is a drawing substitute photograph of the cathode surface after electrodeposition using the electrolytic solution obtained in Example 3 at a current density of 0.5 mA / cm 2. is there.
  • FIG. 6 is an X-ray diffraction pattern of an aluminum plating film obtained in Experiment No. 15.
  • FIG. 6 is a drawing-substituting photograph of the cathode surface after electrodeposition using the electrolytic solution obtained in Example 8.
  • (A) is a graph showing the results of cyclic voltammetry measurement of the oxidation-reduction potential of the electrolytic solution obtained in Example 9, and (B) is the result after electrodeposition using the electrolytic solution obtained in Example 9.
  • It is a drawing substitute photograph of the cathode surface.
  • 6 is a drawing-substituting photograph of the cathode surface after electrodeposition using the electrolytic solution obtained in Example 10.
  • the present invention provides formula (I):
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a nitro group, an amino group, a carboxyl group, a hydroxyl group, an optionally substituted alkyl group having 1 to 4 carbon atoms, An optionally substituted alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or 1 to 4 carbon atoms Represents an alkoxycarbonyl group of An aluminum halide is dissolved in the imidazolidinone compound represented by formula (I), and the molar ratio of the imidazolidinone compound represented by formula (I) to the aluminum halide [imidazolidinone compound / aluminum halide] is 25/75.
  • an electrolytic solution for aluminum plating of ⁇ 50 / 50 It is an electrolytic solution for aluminum plating of ⁇ 50 / 50.
  • an aluminum halide is dissolved in the imidazolidinone compound represented by the formula (I), and the mole of the imidazolidinone compound represented by the formula (I) and the aluminum halide is An electrolytic solution for an aluminum secondary battery having a ratio [imidazolidinone compound / aluminum halide] of 25/75 to 50/50.
  • electrolytic solution for aluminum plating and the electrolytic solution for aluminum secondary battery are referred to as “electrolytic solution”.
  • an aluminum halide is dissolved in an imidazolidinone compound represented by the formula (I) [hereinafter simply referred to as an imidazolidinone compound], and an imidazolidinone compound / aluminum halide (molar ratio).
  • Is 25/75 to 50/50 for example, aluminum can be deposited (reduction of aluminum ions) and dissolved (aluminum oxidation) even at a temperature near room temperature without being heated to a high temperature. Accordingly, by using the electrolytic solution of the present invention, for example, electrodeposition of aluminum and charge / discharge reaction (oxidation-reduction reaction) can be performed even at a temperature near room temperature without heating to a high temperature.
  • the imidazolidinone compound is used as a solvent for dissolving the aluminum halide.
  • the imidazolidinone compound has a higher flash point and lower volatility than toluene, which is used as a solvent for the conventional electrolytic solution for aluminum electrodeposition, in the temperature range where the electrolytic solution is normally used. Is easy.
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a carboxyl group, a hydroxyl group, or an alkyl having 1 to 4 carbon atoms which may have a substituent.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the present invention is not limited to such examples.
  • the optionally substituted alkyl group having 1 to 4 carbon atoms has 1 or more carbon atoms, and from the viewpoint of improving the ease of handling of the electrolytic solution, 4 or less, Preferably it is 2 or less.
  • the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. It is not limited to illustration only.
  • the substituent include a halogen atom and a hydroxyl group, but the present invention is not limited to such examples.
  • the carbon number of the alkenyl group having 1 to 4 carbon atoms which may have a substituent is 2 or more, and from the viewpoint of improving the ease of handling of the electrolytic solution, 4 or less, Preferably it is 3 or less.
  • the alkenyl group having 2 to 4 carbon atoms include a vinyl group, an isopropenyl group, an allyl group, and a butenyl group, but the present invention is not limited to such examples.
  • the substituent in the alkenyl group having 1 to 4 carbon atoms which may have a substituent is the same as the substituent in the alkyl group having 1 to 4 carbon atoms which may have a substituent.
  • the alkoxy group has 1 or more carbon atoms, and is 4 or less, preferably 3 or less, from the viewpoint of improving the ease of handling of the electrolytic solution.
  • the alkoxy group having 2 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like, but the present invention is not limited to such examples.
  • the aryl group has 6 or more carbon atoms, and is 12 or less, preferably 8 or less, more preferably 7 or less, from the viewpoint of improving the ease of handling of the electrolytic solution.
  • the aryl group having 6 to 8 carbon atoms include a phenyl group and a tolyl group, but the present invention is not limited to such examples.
  • the aralkyl group has 7 or more carbon atoms, and is 13 or less, preferably 10 or less, more preferably 9 or less, from the viewpoint of improving the ease of handling of the electrolytic solution.
  • the aralkyl group having 7 to 13 carbon atoms include a phenylmethyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group.
  • the present invention is limited to such examples. It is not something.
  • the alkoxy group of the alkoxycarbonyl group has 1 or more carbon atoms, and is 4 or less, preferably 3 or less from the viewpoint of improving the ease of handling of the electrolytic solution.
  • the alkoxycarbonyl group having 1 to 4 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group.
  • the present invention is not limited to such examples.
  • an alkyl group having 1 to 4 carbon atoms is preferable, a methyl group and an ethyl group are more preferable, and methyl More preferred are groups.
  • imidazolidinone compound examples include 1,3-dimethyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3 Dialkylimidazolidinone compounds such as di (n-propyl) -2-imidazolidinone and 1,3-di (n-butyl) -2-imidazolidinone, 1,3-divinyl-2-imidazolidinone, etc.
  • 1,3-dialkenylimidazolidinone compounds 1-methyl-3-phenyl-2-imidazolidinone, 1-methyl-3-phenyl-4-imidazolidinone, 3-methyl-1-phenyl-4- Alkyl aryl imidazolidinone compounds such as imidazolidinone; 1,3-diphenyl-2-imidazolidinone, 1,3-diphenyl-4-imidazolidinone, etc.
  • diaryl imidazolidinone compounds the present invention is not limited only to those exemplified.
  • imidazolidinone compounds since both the efficiency of electrodeposition of aluminum and charge / discharge reaction and economy are satisfied, dialkylimidazolidinone compounds are preferred, and 1,3-dimethyl-2 is more preferred. -Imidazolidinone.
  • Examples of the aluminum halide include aluminum fluoride, aluminum chloride, aluminum bromide, aluminum iodide, and the like, but the present invention is not limited to such examples.
  • aluminum chloride and aluminum bromide are preferable from the viewpoint of efficiently performing aluminum electrodeposition and charge / discharge reaction, and satisfy both the efficiency and economic efficiency of aluminum electrodeposition and charge / discharge reaction.
  • Aluminum chloride is more preferred.
  • the molar ratio of the imidazolidinone compound and the aluminum halide is 25/75 or more, preferably 33/67 or more, from the viewpoint of sufficiently ensuring the ease of handling of the electrolytic solution. More preferably, it is 38/62 or more, and it is 50/50 or less, preferably 49/51 or less, more preferably 46/54 or less, from the viewpoint of efficiently performing aluminum electrodeposition and charge / discharge reaction.
  • the electrolytic solution of the present invention is used for production of an aluminum material, that is, when the electrolytic solution of the present invention is an electrolytic solution for aluminum plating, from the viewpoint of improving the smoothness of the aluminum plating film, for example, tetraethylammonium chloride, It is preferable to include an organic solvent such as ethylenetetramine, benzene, toluene, xylene in the electrolytic solution of the present invention.
  • an organic solvent such as ethylenetetramine, benzene, toluene, xylene
  • the amount of the organic solvent in the electrolytic solution of the present invention varies depending on the type of the organic solvent, the use of the electrolytic solution, etc., and thus cannot be determined unconditionally. For this reason, it is preferable to determine appropriately depending on the type of the organic solvent, the use of the electrolyte, and the like.
  • the total amount of imidazolidinone compound and aluminum halide is 100 mol.
  • the amount of per organic solvent is usually preferably 0.1 to 2 mol, more preferably 0.5 to 1.5 mol.
  • the total amount of imidazolidinone compound and aluminum halide is preferably 0.1 to 150 moles, more preferably 50 to 120 moles.
  • the electrolytic solution for aluminum plating of the present invention is easy to handle. Moreover, according to the electrolytic solution for aluminum plating of the present invention, aluminum can be deposited and dissolved efficiently even at a temperature near room temperature, for example, without heating to a high temperature. Therefore, according to the electrolytic solution for aluminum plating of the present invention, it is possible to efficiently deposit aluminum, for example, even at a temperature near room temperature, without heating to a high temperature. As described above, according to the electrolytic solution for aluminum plating of the present invention, aluminum can be efficiently electrodeposited even at a temperature near room temperature without being heated to a high temperature. It is expected to be used for forming an aluminum plating film on the surface of a plated object.
  • the electrolytic solution for an aluminum secondary battery of the present invention is easy to handle. Further, according to the electrolytic solution of the present invention, it is possible to efficiently reduce aluminum ions and oxidize aluminum even at a temperature near room temperature, for example, without heating to a high temperature. Therefore, according to the electrolytic solution of the present invention, the charge / discharge reaction (oxidation-reduction reaction) can be performed efficiently even at a temperature near room temperature, for example, without heating to a high temperature. As described above, according to the electrolytic solution of the present invention, the charge / discharge reaction can be performed efficiently even at a temperature near room temperature, for example, without being heated to a high temperature. It is expected to be used for the production of secondary batteries and the like.
  • the method for producing an aluminum material of the present invention is a method for producing an aluminum material in which an aluminum plating film is formed on the surface of an object to be plated, and the object to be plated is immersed in the electrolytic solution for aluminum plating. Aluminum is deposited on the surface of the object to be plated from the electrolytic solution for forming an aluminum plating film.
  • the operation of electrodepositing aluminum using the electrolytic solution for aluminum plating is employed. Therefore, even if it is not heated to a high temperature, for example, it is efficient even at a temperature near room temperature.
  • An aluminum plating film can be formed on the surface of the object to be plated. Therefore, according to the method for producing an aluminum material of the present invention, an aluminum material can be produced efficiently even at a temperature near room temperature, for example, without heating to a high temperature.
  • Aluminum material is a material in which an aluminum plating film is formed on the surface of an object to be plated.
  • the material constituting the object to be plated include metals other than aluminum, conductive materials such as alloys, non-conductive materials such as plastics, etc., but the present invention is limited only to such examples. It is not a thing.
  • the non-conductive material such as plastic is used as the material of the object to be plated, the non-conductive material is pre-conductive by performing electroless plating on the object to be plated made of the non-conductive material, for example. It can be used with imparting properties.
  • Aluminum electrodeposition is performed in an inert gas atmosphere.
  • the inert gas include argon gas and nitrogen gas, but the present invention is not limited to such examples.
  • an electrolytic cell When aluminum is electrodeposited, an electrolytic cell is used.
  • the size and shape of the electrolytic cell may be any suitable size and shape of the intended aluminum material, and the present invention is related to this. It is not limited by the size and shape of the electrolytic cell.
  • the electrolytic solution for aluminum plating is placed in an electrolytic cell, an anode and a cathode are inserted into the electrolytic solution for aluminum plating in the electrolytic cell, and electricity is passed between the anode and the cathode. Can be done. By performing this operation, aluminum can be electrodeposited from the electrolytic solution for aluminum plating.
  • Examples of the anode include an electrode made of aluminum and an electrode made of a base material having a surface layer made of aluminum. However, the present invention is not limited to such examples.
  • Examples of the material constituting the substrate include a conductive metal other than aluminum, a conductive material such as a conductive alloy, and a nonconductive material such as a nonconductive plastic. It is not limited only to such illustration. An object to be plated can be used for the cathode.
  • the amount of electricity applied when electrodepositing aluminum varies depending on the intended use of the aluminum material and the thickness required for the aluminum plating film, etc., it cannot be determined unconditionally, so the intended use of the aluminum material, It is preferable to determine appropriately according to the thickness required for the aluminum plating film.
  • the current density when energizing between the anode and the cathode inserted into the aluminum plating electrolyte is the temperature of the aluminum plating electrolyte when performing electrodeposition (hereinafter referred to as electrodeposition temperature), It depends on the type of imidazolidinone compound, the type of aluminum halide used in the electrolytic solution for aluminum plating, and the molar ratio of the imidazolidinone compound and aluminum halide in the electrolytic solution for aluminum plating.
  • the electrodeposition temperature is the current density, the type of imidazolidinone compound, the type of aluminum halide used in the electrolytic solution for aluminum plating, and the molar ratio of the imidazolidinone compound and aluminum halide in the electrolytic solution for aluminum plating. Since it cannot be determined in general, it depends on the current density, type of imidazolidinone compound, type of aluminum halide used in the electrolytic solution for aluminum plating, and imidazolidin in the electrolytic solution for aluminum plating. It is preferable to determine appropriately according to the molar ratio between the non-compound and the aluminum halide.
  • the electrodeposition temperature is usually from room temperature (25 ° C.) to 100 ° C. As described above, according to the method for producing an aluminum material of the present invention, aluminum can be electrodeposited from the electrolytic solution for aluminum plating at a relatively low temperature. Aluminum materials can be produced even at temperatures.
  • an aluminum material of the present invention can be produced efficiently even at a temperature near room temperature, for example, without heating to a high temperature. Therefore, the electrolytic solution of the present invention and the method for producing the aluminum material of the present invention are expected to be used, for example, in the development of an inexpensive, lightweight and high-strength structural member.
  • Example 1 In a glove box maintained in an argon gas atmosphere, an imidazolidinone compound (1,3-dimethyl-2-imidazolidinone) in which R 1 and R 2 are both methyl groups in formula (I) and aluminum halogen Compound (aluminum chloride) was mixed with 1,3-dimethyl-2-imidazolidinone / aluminum chloride (molar ratio) to be 48.8 / 51.2 to obtain an electrolytic solution.
  • imidazolidinone compound (1,3-dimethyl-2-imidazolidinone) in which R 1 and R 2 are both methyl groups in formula (I) and aluminum halogen Compound (aluminum chloride) was mixed with 1,3-dimethyl-2-imidazolidinone / aluminum chloride (molar ratio) to be 48.8 / 51.2 to obtain an electrolytic solution.
  • Example 2 Example 1 and Example 1, except that 1,3-dimethyl-2-imidazolidinone / aluminum chloride (molar ratio) was changed from 48.8 / 51.2 to 45.5 / 54.5. Similarly, an electrolytic solution was obtained.
  • Example 3 Example 1 and Example 1, except that 1,3-dimethyl-2-imidazolidinone / aluminum chloride (molar ratio) was changed from 48.8 / 51.2 to 40.0 / 60.0. Similarly, an electrolytic solution was obtained.
  • Example 4 Example 1 and Example 1, except that 1,3-dimethyl-2-imidazolidinone / aluminum chloride (molar ratio) was changed from 48.8 / 51.2 to 38.5 / 61.5. Similarly, an electrolytic solution was obtained.
  • Example 5 Example 1 and Example 1, except that 1,3-dimethyl-2-imidazolidinone / aluminum chloride (molar ratio) was changed from 48.8 / 51.2 to 33.3 / 66.7. Similarly, an electrolytic solution was obtained.
  • Example 1 Comparative Example 1 In Example 1, except that 1,3-dimethyl-2-imidazolidinone / aluminum chloride (molar ratio) was changed from 48.8 / 51.2 to 76.9 / 23.1, Similarly, an electrolytic solution was obtained.
  • a glassy carbon electrode (diameter: 3.0 mm, length: 55 mm) is polished with diamond paste, washed with distilled water and ethanol, and then cooled with cold air. A working electrode was obtained by drying.
  • Production Example 2 An aluminum plate (purity: 99% by mass, width: 20 mm, length: 30 mm, thickness: 1.0 mm) and silicon carbide polishing paper (P # 220) in a glove box maintained in an argon gas atmosphere Then, after washing with distilled water and ethanol, it was dried with cold air to obtain a counter electrode.
  • a copper plate material (purity: 99.99 mass%, width: 15 mm, length: 30 mm, thickness: 0.5 mm) was placed on a silicon carbide abrasive paper (P # 1200). No.), washed with distilled water and ethanol, and then dried with cold air. Next, the surface of the copper plate material was covered with a polytetrafluoroethylene tape so that the exposed portion of the copper plate material after drying was 1 cm 2 to obtain a cathode.
  • Test example 1 Cyclic voltammetry In a glove box kept in an argon gas atmosphere, the working electrode obtained in Production Example 1, the counter electrode obtained in Production Example 2, the reference electrode obtained in Production Example 3, Using the electrolytic solution obtained in Example 1, a three-electrode electrochemical cell (Experiment No. 1) was produced.
  • Example 1 instead of the electrolytic solution obtained in Example 1, the electrolytic solution obtained in Example 2 (Experiment No. 2), the electrolytic solution obtained in Example 3 (Experiment No. 3), and in Example 4 The same as above except that the obtained electrolytic solution (Experiment No. 4), the electrolytic solution obtained in Example 5 (Experiment No. 5) and the electrolytic solution obtained in Comparative Example 1 (Experiment No. 6) were used. By performing the above operations, a three-electrode electrochemical cell was produced.
  • the temperature of the electrolyte solution in the experiment numbers 3, 5, and 6 is different from the temperature of the electrolyte solution in the experiment numbers 1, 2, and 4.
  • the temperature of the electrolyte does not affect the appearance of current peaks caused by aluminum dissolution and precipitation, respectively. It is considered that the difference in the temperature of the electrolyte solution in Experiment Nos. 1 to 6 does not affect the presence or absence of aluminum dissolution and precipitation.
  • FIG. 1 (A) shows the results of measuring the redox potential of the electrolytic solution obtained in Example 1 by cyclic voltammetry
  • FIG. 2 shows the results measured by voltammetry
  • FIG. 3 (A) shows the results of the cyclic reduction of the redox potential of the electrolyte obtained in Example 3
  • FIG. 3A shows the oxidation of the electrolyte obtained in Example 4.
  • FIG. 4 shows the result of measuring the reduction potential by cyclic voltammetry
  • FIG. 5 shows the result of measuring the oxidation-reduction potential of the electrolytic solution obtained in Example 5
  • FIG. 5 shows the electrolytic solution obtained in Comparative Example 1.
  • the result of measuring the oxidation-reduction potential of the product by cyclic voltammetry is shown in FIG.
  • 1,3-dimethyl-2-imidazolidinone / aluminum chloride (molar ratio) was 48.8 / 51.2 (Example 1), 45.5 / 54.5 (Example 2), In the case of using electrolytic solutions of 40.0 / 60.0 (Example 3), 38.5 / 61.5 (Example 4) and 33.3 / 66.7 (Example 5), aluminum was used. Since it is possible to perform ion reduction and aluminum oxidation, it can be seen that aluminum electrodeposition and charge / discharge reactions can be performed.
  • Electrodeposition of aluminum The electrolytic solution (experiment number 7) obtained in Example 1 was put in an electrolytic cell. Thereafter, the cathode obtained in Production Example 4, the anode obtained in Production Example 5 and the reference electrode obtained in Production Example 3 were inserted into the electrolytic solution in the electrolytic cell, and the anode was subjected to the conditions shown in Table 2. Electrodeposition was carried out by energizing between the cathode and the cathode. At this time, it was confirmed that the current between the anode and the cathode was 4.3 mA / cm 2 .
  • the electrolytic solution (experiment number 8) obtained in Example 3 was placed in an electrolytic cell. Thereafter, the cathode obtained in Production Example 4 and the anode obtained in Production Example 5 were inserted into the electrolytic solution in the electrolytic cell, and electricity was passed between the anode and the cathode under the conditions shown in Table 2. Electrodeposited.
  • Test Example 1 an optical photograph of the cathode surface after electrodeposition using the electrolytic solution obtained in Example 1 was electrodeposited using the electrolytic solution obtained in FIG. An optical photograph of the cathode surface is shown in FIG. In the figure, the scale bar indicates 10 mm.
  • an electrolytic solution containing an imidazolidinone compound and an aluminum halide and having an imidazolidinone compound / aluminum halide (molar ratio) of 25/75 to 50/50 can be used to charge aluminum. It can be seen that it can be analyzed.
  • the imidazolidinone compound has a high flash point and low volatility in the temperature range in which the electrolytic solution is usually used, as compared with toluene used as a solvent for an electrolytic solution for conventional aluminum electrodeposition. Since the handling is easy, the electrolytic solution is easy to handle.
  • the electrolytic solution is a conventional electrolytic solution containing dimethylsulfone. It is considered that aluminum can be electrodeposited at a lower temperature range.
  • Test example 2 (1) Cyclic voltammetry In a glove box kept in an argon gas atmosphere, the working electrode obtained in Production Example 1, the counter electrode obtained in Production Example 2, the reference electrode obtained in Production Example 3, A three-electrode electrochemical cell was prepared using the electrolytic solution obtained in Example 3 (Experiment No. 9) or the electrolytic solution obtained in Example 4 (Experiment No. 10).
  • Example 2 the temperature of the electrolytic solution obtained in Example 3 was adjusted to 25 ° C., and the result of measuring the oxidation-reduction potential of the electrolytic solution by cyclic voltammetry was obtained in FIG.
  • FIG. 8 shows the results of adjusting the temperature of the obtained electrolyte to 25 ° C. and measuring the oxidation-reduction potential of the electrolyte by cyclic voltammetry.
  • Example 3 when the electrolytic solution obtained in Example 3 was used and the temperature of the electrolytic solution was adjusted to 25 ° C., the electrolytic solution obtained in Example 3 was used.
  • the temperature of the electrolyte is adjusted to 80 ° C. (see FIG. 3A)
  • the sweep is turned back at a potential of ⁇ 1 V or less, and when the potential is swept to the anode side, the potential is around 0 V [see FIG. 7 (A), see arrow B], the rising of the anode current is seen, indicating that the precipitated aluminum is dissolved.
  • Example 4 when the electrolytic solution obtained in Example 4 was used and the temperature of the electrolytic solution was adjusted to 25 ° C., the electrolytic solution obtained in Example 4 was used, and the electrolytic solution Similar to when the temperature of the liquid was adjusted to 60 ° C. (see FIG. 4), the sweep was turned back at a potential of ⁇ 1 V or less, and when the potential was swept to the anode side, the potential was around 0 V (see arrow B in FIG. 8). ) Shows that the anode current rises, indicating that the precipitated aluminum is dissolved.
  • Electrodeposition of aluminum After the electrolytic solution obtained in Example 3 was put in the electrolytic cell, the cathode obtained in Production Example 4 and the obtained in Production Example 5 in the electrolytic solution in the electrolytic cell Electrodeposition was performed by inserting an anode and applying current between the anode and the cathode under the conditions shown in Table 3.
  • Example 2 the temperature of the electrolytic solution obtained in Example 3 was adjusted to 25 ° C., and an optical photograph of the cathode surface after electrodeposition using the electrolytic solution is shown in FIG.
  • the temperature of the electrolyte solution obtained was adjusted to 40 ° C., and an optical photograph of the cathode surface after electrodeposition using the electrolyte solution was adjusted to 50 ° C. in FIG. 9 and the electrolyte solution obtained in Example 3
  • FIG. 10 shows an optical photograph of the cathode surface after electrodeposition using the electrolytic solution.
  • the scale bar indicates 10 mm.
  • the state of the cathode surface was evaluated based on the following evaluation criteria. The results are shown in Table 3.
  • AA An aluminum plating film having a silvery white surface and a smooth surface is formed on the cathode surface.
  • an electrolytic solution containing an imidazolidinone compound and an aluminum halide and having an imidazolidinone compound / aluminum halide (molar ratio) of 25/75 to 50/50 was used. It can be seen that aluminum can be electrodeposited when the temperature is adjusted to 25-80 ° C.
  • Test example 3 After putting the electrolytic solution obtained in Example 3 into the electrolytic cell, the cathode obtained in Production Example 4 and the anode obtained in Production Example 5 were inserted into the electrolytic solution in the electrolytic cell, Electrodeposition was performed by applying current between the anode and the cathode under the conditions shown in Table 4 (experiment numbers 14 and 12).
  • FIG. 11B shows an optical photograph of the cathode surface after electrodeposition (Experiment No. 12) using the electrolytic solution obtained in Example 3 at a current density of 0.5 mA / cm 2 .
  • the scale bar indicates 10 mm.
  • the state of the cathode surface was evaluated based on the following evaluation criteria. The results are shown in Table 4.
  • AA An aluminum plating film having a silvery white surface and a smooth surface is formed on the cathode surface.
  • Example 6 In a glove box kept in an argon gas atmosphere, an imidazolidinone compound (1,3-dimethyl-2-imidazolidinone) in which R 1 and R 2 are methyl groups in formula (I) and an aluminum halide ( Aluminum chloride) and an additive (tetraethylammonium chloride) are mixed so that 1,3-dimethyl-2-imidazolidinone / aluminum chloride / tetraethylammonium chloride (molar ratio) is 40/60/1. A liquid was obtained.
  • Example 6 is the same as Example 6 except that 1,3-dimethyl-2-imidazolidinone / aluminum chloride / tetraethylammonium chloride (molar ratio) was changed from 40/60/1 to 40/60/2 in Example 6. The electrolyte solution was obtained by performing the same operation.
  • Test example 4 Electrodeposition of aluminum The electrolytic solution obtained in Example 6 (Experiment No. 15), the electrolytic solution obtained in Example 7 (Experiment No. 16 and Experimental No. 17), or the electrolytic solution obtained in Example 3 (Experiment No. 12) was placed in the electrolytic cell, and then the cathode obtained in Production Example 4 and the anode obtained in Production Example 5 were inserted into the electrolytic solution in the electrolytic cell. Electrodeposition was performed by applying current between the anode and the cathode under conditions.
  • Example 4 using the electrolytic solution obtained in Example 6, an optical photograph of the cathode surface after electrodeposition (experiment number 15) at a current density of 0.75 mA / cm 2 is shown in FIG. Using the electrolytic solution obtained in Example 7, an optical photograph of the cathode surface after electrodeposition (experiment number 16) at a current density of 0.5 mA / cm 2 was obtained in FIG. Using the electrolytic solution, an optical photograph of the cathode surface after electrodeposition (experiment number 17) at a current density of 1 mA / cm 2 is 0.5 mA using the electrolytic solution obtained in FIG. 12 (C) and Example 3.
  • Example 6 the electrolytic solution obtained in Example 6 containing 1 mol of tetraethylammonium chloride as an additive was used for electrodeposition by adjusting the current density to 0.75 mA / cm 2 .
  • Example No. 15 when using the electrolytic solution obtained in Example 7 containing 2 mol of tetraethylammonium chloride as an additive and adjusting the current density to 0.5 mA / cm 2 for electrodeposition
  • Example No. 16 Using the electrolytic solution obtained in Example 7 containing 2 mol of tetraethylammonium chloride as an additive and adjusting the current density to 1 mA / cm 2 for electrodeposition (Experiment No.
  • Example 15 Using the electrolytic solution obtained in Example 7 containing 2 mol of tetraethylammonium chloride as an agent, the current density was adjusted to 0.5 mA / cm 2 for electrodeposition (Experiment No. 16), and tetraethylammonium as an additive
  • Example 3 containing no chloride was used for electrodeposition with the current density adjusted to 0.5 mA / cm 2 (Experiment No. 12)
  • a silver-white smooth surface was formed on the cathode surface. It can be seen that an aluminum plating film having s is formed.
  • an imidazolidinone compound and an aluminum halide contains an imidazolidinone compound and an aluminum halide, an imidazolidinone compound / aluminum halide (molar ratio) is 25/75 to 50/50, and contains tetraethylammonium chloride as an additive. According to the electrolytic solution, it can be seen that an aluminum plating film having a smoother surface can be obtained.
  • Example 8 In a glove box kept in an argon gas atmosphere, an imidazolidinone compound (1,3-dimethyl-2-imidazolidinone) in which R 1 and R 2 are methyl groups in formula (I) and an aluminum halide ( Aluminum chloride) and an additive (triethylenetetramine) are mixed so that 1,3-dimethyl-2-imidazolidinone / aluminum chloride / triethylenetetramine (molar ratio) is 40/60/1.
  • Test Example 5 The electrolytic solution obtained in Example 8 was placed in an electrolytic cell. Thereafter, the cathode obtained in Production Example 4 and the anode obtained in Production Example 5 were inserted into the electrolytic solution in the electrolytic cell, and the temperature of the electrolytic solution: 40 ° C., current density: 0.75 mA / cm. 2 and the amount of energization: Electrodeposition was performed by constant current electrolysis energized between the anode and the cathode at 10 C / cm 2 .
  • Test Example 5 an optical photograph of the cathode surface after electrodeposition using the electrolytic solution obtained in Example 8 is shown in FIG. In the figure, the scale bar indicates 10 mm.
  • an electrolytic solution containing an imidazolidinone compound and an aluminum halide, an imidazolidinone compound / aluminum halide (molar ratio) is 25/75 to 50/50, and contains triethylenetetramine as an additive. It turns out that the aluminum plating film which has a smoother surface can be obtained by using.
  • Example 9 In a glove box kept in an argon gas atmosphere, an imidazolidinone compound (1,3-dimethyl-2-imidazolidinone) in which R 1 and R 2 are methyl groups in formula (I) and an aluminum halide ( Aluminum chloride) and the additive (toluene) were mixed so that 1,3-dimethyl-2-imidazolidinone / aluminum chloride / toluene (molar ratio) was 40/60/120 to obtain an electrolytic solution. .
  • Test Example 6 Cyclic voltammetry In a glove box kept in an argon gas atmosphere, the working electrode obtained in Production Example 1, the counter electrode obtained in Production Example 2, the reference electrode obtained in Production Example 3, Using the electrolytic solution obtained in Example 9, a three-electrode electrochemical cell was produced.
  • Test Example 6 the results of measuring the redox potential of the electrolytic solution obtained in Example 9 by cyclic voltammetry are shown in FIG.
  • Electrodeposition of aluminum The electrolytic solution obtained in Example 9 was put in an electrolytic cell. Thereafter, the cathode obtained in Production Example 4 and the anode obtained in Production Example 5 were inserted into the electrolytic solution in the electrolytic cell, and the electrolyte temperature: 40 ° C., current density: 1 mA / cm 2 and Electrodeposition was carried out by constant current electrolysis in which current was applied between the anode and the cathode at an energization amount of 10 C / cm 2 .
  • Test Example 6 an optical photograph of the cathode surface after electrodeposition using the electrolytic solution obtained in Example 9 is shown in FIG. In the figure, the scale bar indicates 10 mm.
  • an electrolytic solution containing an imidazolidinone compound and an aluminum halide, an imidazolidinone compound / aluminum halide (molar ratio) of 25/75 to 50/50, and toluene as an additive. It can be seen that an aluminum plating film having a smoother surface can be obtained.
  • Example 10 In a glove box kept in an argon gas atmosphere, an imidazolidinone compound (1,3-dimethyl-2-imidazolidinone) in which R 1 and R 2 are methyl groups in formula (I) and an aluminum halide ( (Aluminum chloride) and additive (m-xylene) are mixed so that 1,3-dimethyl-2-imidazolidinone / aluminum chloride / m-xylene (molar ratio) is 40/60/100. The electrolyte solution was obtained.
  • an imidazolidinone compound (1,3-dimethyl-2-imidazolidinone) in which R 1 and R 2 are methyl groups in formula (I) and an aluminum halide (Aluminum chloride) and additive (m-xylene) are mixed so that 1,3-dimethyl-2-imidazolidinone / aluminum chloride / m-xylene (molar ratio) is 40/60/100.
  • the electrolyte solution was obtained.
  • Test Example 7 After putting the electrolytic solution obtained in Example 10 into the electrolytic cell, the cathode obtained in Production Example 4 and the anode obtained in Production Example 5 were inserted into the electrolytic solution in the electrolytic cell, Electrodeposition was performed by constant-current electrolysis in which an electric current was passed between the anode and the cathode at an electrolyte temperature of 40 ° C., a current density of 1 mA / cm 2 and an energization amount of 20 C / cm 2 .
  • Test Example 7 an optical photograph of the cathode surface after electrodeposition using the electrolytic solution obtained in Example 10 is shown in FIG. In the figure, the scale bar indicates 10 mm.
  • Electrodeposition is performed using an electrolyte containing benzene as an additive instead of using an electrolyte containing tetraethylammonium chloride, triethylenetetramine, toluene or m-xylene as an additive, Similar results are obtained when using an electrolyte containing ethylammonium chloride, triethylenetetramine, toluene or m-xylene.
  • imidazolidinone compound and aluminum halide are contained, imidazolidinone compound / aluminum halide (molar ratio) is 25 / 75-50 / 50, tetraethylammonium chloride, triethylenetetramine It can be seen that an aluminum plating film having a smoother surface can be obtained with an electrolytic solution containing a solvent such as toluene, m-xylene, or benzene.
  • Example 2 In Example 1, electrolysis was performed in the same manner as in Example 1 except that 1,3-dimethyl-2-imidazolidinone / aluminum chloride (molar ratio) was changed from 48.8 / 51.2 to 52/48. A liquid was obtained.
  • Test Example 8 (1) Cyclic voltammetry In a glove box kept in an argon gas atmosphere, the working electrode obtained in Production Example 1, the counter electrode obtained in Production Example 2, the reference electrode obtained in Production Example 3, Using the electrolytic solution obtained in Example 2 or Comparative Example 2, a three-electrode electrochemical cell was produced.
  • Test Example 8 the temperature of the electrolytic solution obtained in Example 2 or Comparative Example 2 was adjusted to 80 ° C., and the results of measuring the oxidation-reduction potential of the electrolytic solution by cyclic voltammetry are shown in FIG.
  • A is the result of measuring the redox potential of the electrolytic solution obtained in Example 2 by cyclic voltammetry
  • B is the result of measuring the redox potential of the electrolytic solution obtained in Comparative Example 2 by cyclic voltammetry. Indicates.
  • an electrolytic solution containing an imidazolidinone compound and an aluminum halide and having an imidazolidinone compound / aluminum halide (molar ratio) of 25/75 to 50/50 is easy to handle. It can be used as an electrolytic solution for aluminum secondary batteries, production of aluminum materials, formation of aluminum plating film on the surface of the object to be plated, etc. Therefore, for example, it is expected to be used for development of secondary batteries for use in portable devices, electric vehicles, and the like, development of inexpensive, high-strength structural members, and the like.

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Abstract

L'invention porte sur une solution électrolytique de placage d'aluminium et sur une solution électrolytique de batterie secondaire à l'aluminium, un halogénure d'aluminium étant dissous dans un composé imidazolidinone représenté par la formule (I) (dans laquelle R1 et R2 représentent chacun un atome d'hydrogène, un atome d'halogène, un groupe nitro, un groupe amino, un groupe carboxyle, un groupe hydroxyle, un groupe alkyle en C1-4 qui peut avoir un substituant, un groupe alcényle en C2-4 qui peut avoir un substituant, un groupe alcoxy en C1-4, un groupe aryle en C6-12, un groupe aralkyle en C7-13 ou un groupe alcoxycarbonyle en C1-4) et le rapport (rapport molaire) dudit composé imidazolidinone audit halogénure d'aluminium étant de 25/75 à 50/50. L'invention porte également sur un procédé de fabrication d'un matériau aluminium utilisant ladite solution électrolytique de placage d'aluminium.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022168755A1 (fr) * 2021-02-04 2022-08-11 セントラル硝子株式会社 Solution d'électrolyte non aqueux, batterie à électrolyte non aqueux et composé
WO2023287242A1 (fr) * 2021-07-16 2023-01-19 주식회사 엘지에너지솔루션 Solution électrolytique non aqueuse et batterie secondaire au lithium la comprenant

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004014248A (ja) * 2002-06-05 2004-01-15 Sony Corp 非水電解質電池及びその製造方法
WO2007055172A1 (fr) * 2005-11-10 2007-05-18 Matsushita Electric Industrial Co., Ltd. Solution electrolytique non aqueuse et batterie secondaire la contenant
JP2009067644A (ja) * 2007-09-14 2009-04-02 Kyoto Univ 溶融塩組成物及びその利用
JP2010257704A (ja) * 2009-04-23 2010-11-11 Sony Corp 電解質および二次電池
JP2012089410A (ja) * 2010-10-21 2012-05-10 Sony Corp 電解質および二次電池
JP2012233216A (ja) * 2011-04-28 2012-11-29 Hitachi Metals Ltd 電気アルミニウムめっき液およびアルミニウムめっき被膜の形成方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004014248A (ja) * 2002-06-05 2004-01-15 Sony Corp 非水電解質電池及びその製造方法
WO2007055172A1 (fr) * 2005-11-10 2007-05-18 Matsushita Electric Industrial Co., Ltd. Solution electrolytique non aqueuse et batterie secondaire la contenant
JP2009067644A (ja) * 2007-09-14 2009-04-02 Kyoto Univ 溶融塩組成物及びその利用
JP2010257704A (ja) * 2009-04-23 2010-11-11 Sony Corp 電解質および二次電池
JP2012089410A (ja) * 2010-10-21 2012-05-10 Sony Corp 電解質および二次電池
JP2012233216A (ja) * 2011-04-28 2012-11-29 Hitachi Metals Ltd 電気アルミニウムめっき液およびアルミニウムめっき被膜の形成方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022168755A1 (fr) * 2021-02-04 2022-08-11 セントラル硝子株式会社 Solution d'électrolyte non aqueux, batterie à électrolyte non aqueux et composé
WO2023287242A1 (fr) * 2021-07-16 2023-01-19 주식회사 엘지에너지솔루션 Solution électrolytique non aqueuse et batterie secondaire au lithium la comprenant

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