WO2017187700A1 - マグネシウム二次電池用負極及びその製造方法、並びに、マグネシウム二次電池 - Google Patents
マグネシウム二次電池用負極及びその製造方法、並びに、マグネシウム二次電池 Download PDFInfo
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- WO2017187700A1 WO2017187700A1 PCT/JP2017/004046 JP2017004046W WO2017187700A1 WO 2017187700 A1 WO2017187700 A1 WO 2017187700A1 JP 2017004046 W JP2017004046 W JP 2017004046W WO 2017187700 A1 WO2017187700 A1 WO 2017187700A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
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- H—ELECTRICITY
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/466—Magnesium based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure relates to a negative electrode for a magnesium secondary battery, a manufacturing method thereof, and a magnesium secondary battery.
- Magnesium used in magnesium secondary batteries is more abundant and cheaper than lithium, and has a large amount of electricity per unit volume that can be taken out by oxidation-reduction reaction. When used in secondary batteries High safety. Therefore, the magnesium secondary battery is attracting attention as a next-generation secondary battery that replaces the lithium ion secondary battery.
- the negative electrode is often composed of a metal magnesium thin plate.
- the production of the metal magnesium thin plate requires a high-temperature rolling process, which causes a problem that the production cost is high.
- the electrode for a magnesium secondary battery disclosed in this patent publication includes a current collector and a magnesium plating layer formed on the surface of the current collector.
- the magnesium plating layer is formed by electrochemical plating.
- an object of the present disclosure is to provide a magnesium secondary battery negative electrode capable of forming a magnesium layer based on a simpler and cheaper method, a manufacturing method thereof, and a magnesium secondary battery including the magnesium secondary battery negative electrode. It is to provide.
- the method for producing a negative electrode for a magnesium secondary battery according to the first aspect of the present disclosure for achieving the above object is as follows. Prepare a current collector with an underlayer containing a metal that has a higher ionization tendency than magnesium, A negative electrode active material layer composed of a magnesium layer is formed on the current collector by chemical plating using the base layer as a material.
- a step of forming the (n + 1) th magnesium layer on the nth magnesium layer by chemical plating using the (n + 1) th underlayer as a material, n is repeated from 1 to (N-1), thereby forming a negative electrode active material layer formed by laminating magnesium layers on the current collector.
- Each step is provided.
- the negative electrode for a magnesium secondary battery of the present disclosure is A current collector, and a negative electrode active material layer made of magnesium formed on the surface of the current collector,
- the value of the BET specific surface area of the negative electrode active material layer is 1 m 2 or more, preferably 10 m 2 or more per gram of the negative electrode active material layer.
- a magnesium secondary battery of the present disclosure includes a current collector and a negative electrode active material layer made of magnesium formed on the surface of the current collector, and the BET specific surface area of the negative electrode active material layer the values, the negative electrode active material layer per gram, 1 m 2 or more, preferably a negative electrode for a magnesium secondary battery is 10 m 2 or more.
- a magnesium layer is formed on the current collector by a chemical plating method. Therefore, the magnesium layer can be formed based on a simpler and cheaper method.
- the value of the BET specific surface area of the negative electrode active material layer is defined.
- FIG. 1A is a schematic exploded view of a magnesium secondary battery of Example 1
- FIGS. 1B and 1C are schematic partial cross-sectional views of a negative electrode for a magnesium secondary battery before and after chemical plating treatment.
- FIG. 2 is a photograph before and after chemical plating treatment of a laminated foil (lithium foil side) made of copper foil / lithium foil.
- FIG. 3 is a graph showing discharge curves of the magnesium secondary battery of Example 1 and the magnesium secondary battery of Comparative Example 1.
- FIG. 4 is a schematic cross-sectional view of the magnesium secondary battery of Example 3.
- 5 is a schematic partial cross-sectional view of a wound electrode laminate in the magnesium secondary battery of Example 3.
- FIG. 6 is a schematic exploded perspective view of a laminate film type rectangular magnesium secondary battery of Example 3.
- FIG. 7A is a schematic exploded perspective view of a laminated film type magnesium secondary battery of Example 3 in a state different from that shown in FIG. 6, and FIG. 7B is a laminated film type magnesium of Example 3.
- FIG. FIG. 7B is a schematic cross-sectional view of the electrode structure in the secondary battery taken along arrows AA in FIGS. 6 and 7A.
- 8A and 8B are a schematic cross-sectional view of the electrochemical device (capacitor) of Example 4 and a conceptual diagram of the air battery of Example 4, respectively.
- FIG. 9 is a block diagram illustrating a circuit configuration example when the magnesium secondary battery according to the present disclosure described in the first to fourth embodiments is applied to a battery pack.
- FIG. 10A, 10B, and 10C respectively illustrate a block diagram illustrating a configuration of an application example (electric vehicle) of the present disclosure in the fifth embodiment, and a configuration of an application example (power storage system) of the present disclosure in the fifth embodiment. It is a block diagram showing the structure of the application example (electric tool) of this indication in Example 5 and a block diagram.
- FIG. 11 is a conceptual diagram of a magnesium secondary battery in the present disclosure.
- Example 3 Modification of Magnesium Secondary Battery of the Present Disclosure
- Example 4 Modification and Electrochemical Device of Magnesium Secondary Battery of Present Disclosure
- Example 5 Application Example of Magnesium Secondary Battery of Examples 1 to 4) 7).
- the chemical plating method in the method for manufacturing a negative electrode for a magnesium secondary battery according to the first to second aspects of the present disclosure is also referred to as a substitution method, and is further referred to as an immersion plating method.
- the (n + 1) th underlayer is formed based on an electroplating method or an electrolytic deposition method (electrodeposition method). It can be in the form.
- the metal is lithium (Li), potassium (K), calcium ( It can be in the form of at least one metal selected from the group consisting of Ca) and sodium (Na), more preferably in the form of lithium (Li).
- the value of the BET specific surface area of the negative electrode active material layer is the negative electrode active surface area.
- material layer per gram, 1 m 2 or more, preferably in the form is 10 m 2 or more.
- the measurement of the BET specific surface area of the negative electrode active material layer is performed by adsorbing gas molecules having a well-known adsorption area on the surface of the negative electrode active material layer, and measuring the specific surface area of the negative electrode active material layer from the adsorption amount of the gas molecules. It can be done based on the method.
- the method for manufacturing a negative electrode for a magnesium secondary battery according to the first to second aspects of the present disclosure including the preferred embodiments described above may be collectively referred to as “the method of the present disclosure”.
- a method of pressure bonding a base layer or the like on the current collector surface For example, a method of pressure bonding a base layer or the like on the current collector surface, a method of forming a base layer or the like on the current collector surface based on an electroplating method, a method of forming a chemical plating method, a chemical plating method and an electroplating method And a method of forming based on a combination of the above and an electrolytic deposition method (electrodeposition method).
- the thickness of the underlayer or the like is essentially arbitrary, and examples thereof include 20 ⁇ m to 50 ⁇ m.
- the value of N in the method for manufacturing a negative electrode for a magnesium secondary battery according to the second aspect of the present disclosure is essentially arbitrary, and may be determined based on the finally required magnesium layer thickness.
- the thickness of the (n + 1) th underlayer may be determined based on the finally required thickness of the magnesium layer.
- Examples of the material constituting the current collector include foil-like materials and plate-like materials such as metal foils and alloy foils (including metal plates and alloy foils) such as copper foil, nickel foil, and stainless steel foil.
- the negative electrode active material layer may be formed on one side of the current collector, or may be formed on both sides.
- the negative electrode active material layer can be formed by a batch method (batch method) or continuously (by a so-called roll-to-roll method).
- a magnesium layer is formed based on a chemical plating method (also referred to as an electroless plating method), and a magnesium salt can be used as a composition constituting a plating solution in forming the magnesium layer.
- a chemical plating method also referred to as an electroless plating method
- a magnesium salt can be used as a composition constituting a plating solution in forming the magnesium layer.
- MgX 2 where X is a halogen, preferably chlorine (Cl) or bromine (Br)
- R 2 —Mg may be mentioned, where R is an alkyl group, dialkyl boron group, diaryl boron group, alkylcarbonyl group (eg, methylcarbonyl group), trialkylsilyl group (eg, trimethylsilyl group).
- R′—Mg—X can be mentioned, where R ′ can be a linear or branched alkyl group, aryl group, or amino group having 1 to 10 carbon atoms, Specific examples include a methyl group, an ethyl group, a butyl group, a phenyl group, and an aniline group, and X is as described above.
- Mg (ClO 4 ) 2 can be cited as a composition constituting the plating solution. And these compositions can be used independently, and 2 or more types can also be mixed and used for them.
- a solvent a sulfone solvent such as ethyl-n-propylsulfone (EnPS) or an ether solvent such as triglyme or THF can be used, but the solvent is not limited thereto, and the above magnesium salt is dissolved. Any solvent can be used as long as it can precipitate magnesium (so that magnesium can be separated from the solvent).
- EnPS ethyl-n-propylsulfone
- ether solvent such as triglyme or THF
- Any solvent can be used as long as it can precipitate magnesium (so that magnesium can be separated from the solvent).
- any electrolytic solution that can deposit Li used in a lithium ion secondary battery can be used as a plating solution.
- a plating solution for example, a mixed solvent of EC (ethylene carbonate) and DMC (dimethyl carbonate) containing 1 mol / liter of LiPF 6 (mixing ratio is 1: 1 by volume).
- EC ethylene carbonate
- DMC dimethyl carbonate
- An air cell and a fuel cell can also be configured by using, as an electrode, a magnesium layer obtained by the method for manufacturing a negative electrode for a magnesium secondary battery according to the first to second aspects of the present disclosure.
- Magnesium secondary battery of the present disclosure magnesium secondary battery obtained by the method for manufacturing a negative electrode for a magnesium secondary battery according to the first to second aspects of the present disclosure, or the magnesium secondary battery of the present disclosure
- the magnesium secondary battery including the negative electrode for the battery is collectively referred to as “magnesium secondary battery and the like in the present disclosure”.
- sulfur (S), graphite fluoride ((CF) n ), various metals for example, scandium (Sc), titanium (Ti), vanadium (V), Chromium (Cr), Manganese (Mn), Iron (Fe), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Molybdenum (Mo), etc.]
- Oxides, Halides, Sulfides A positive electrode using selenide or the like as a positive electrode active material can be used, but the present invention is not limited to this.
- the positive electrode can have, for example, a structure in which a positive electrode active material layer is formed on the surface of a positive electrode current collector.
- the positive electrode may not have a positive electrode current collector and may have a structure including only a positive electrode active material layer.
- the positive electrode current collector is made of, for example, a metal foil such as an aluminum foil.
- the positive electrode active material layer may contain at least one of a conductive additive and a binder as necessary.
- Examples of the conductive assistant include carbon materials such as graphite, carbon fiber, carbon black, and carbon nanotube, and one or more of these materials can be used in combination.
- carbon fiber for example, vapor-grown carbon fiber (Vapor GrowthVCarbon Fiber: VGCF) or the like can be used.
- carbon black acetylene black, Ketjen black, etc. can be used, for example.
- carbon nanotube for example, a multi-wall carbon nanotube (MWCNT) such as a single wall carbon nanotube (SWCNT) or a double wall carbon nanotube (DWCNT) can be used.
- MWCNT multi-wall carbon nanotube
- SWCNT single wall carbon nanotube
- DWCNT double wall carbon nanotube
- a metal material such as Ni powder, a conductive polymer material, or the like can be used.
- a binder for example, a fluorine resin such as polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE), a polymer such as a polyvinyl alcohol (PVA) resin, a styrene-butadiene copolymer rubber (SBR) resin, or the like. Resin can be used.
- a conductive polymer for example, substituted or unsubstituted polyaniline, polypyrrole, polythiophene, and one or two (co) polymers selected from these can be used.
- the positive electrode and the negative electrode are separated by an inorganic separator or an organic separator that allows magnesium ions to pass while preventing a short circuit due to contact between the two electrodes.
- the separator is, for example, a porous film made of a synthetic resin such as polyolefin resin (polypropylene resin or polyethylene resin), polyimide resin, polytetrafluoroethylene resin, polyvinylidene fluoride resin, polyphenylene sulfide resin, aromatic polyamide; It is composed of non-woven fabric made of glass fiber, liquid crystal polyester fiber, aromatic polyamide fiber, cellulosic fiber, ceramic non-woven fabric, etc., among which, polypropylene and polyethylene porous films and porous membranes are short-circuited.
- a separator can also be comprised from the laminated film in which two or more types of porous films were laminated
- the thickness of the separator is preferably 5 ⁇ m or more and 50 ⁇ m or less, and more preferably 7 ⁇ m or more and 30 ⁇ m or less. If the separator is too thick, the amount of the active material filled decreases, the battery capacity decreases, and the ionic conductivity decreases and the current characteristics deteriorate. Conversely, when too thin, the mechanical strength of a separator will fall.
- the magnesium secondary battery in the present disclosure includes an electrolytic solution.
- the electrolytic solution contains sulfone and a magnesium salt dissolved in the sulfone, and the magnesium salt can be in the form of a magnesium halide.
- the magnesium halide include MgX 2 (X ⁇ Cl, Br, I), specifically, magnesium chloride (MgCl 2 ), magnesium bromide (MgBr 2 ), and magnesium iodide (MgI 2 ). .
- magnesium perchlorate Mg (ClO 4 ) 2
- magnesium tetrafluoroborate Mg (BF 4 ) 2
- magnesium hexafluorophosphate Mg (PF 6 ) 2
- hexafluoro Magnesium arsenate Mg (AsF 6 ) 2
- magnesium perfluoroalkyl sulfonate ((Mg (R f1 SO 3 ) 2 ), where R f1 is a perfluoroalkyl group)
- magnesium tetraphenylborate Mg (B (C 6 H 5 ) 4 ) 2
- magnesium perfluoroalkylsulfonyl imido acid Mg ((R f2 SO 2 ) 2 N) 2 , where R f2 is a perfluoroalkyl group).
- magnesium salt-A The magnesium salts listed from magnesium chloride to magnesium perfluoroalkylsulfonylimido are referred to as “magnesium salt-A” for convenience.
- the molar ratio of the sulfone to the magnesium salt is, for example, preferably 4 or more and 35 or less, more preferably 6 or more and 16 or less, and 7 or more and 9 or less. Is more preferable, but is not limited thereto.
- magnesium borohydride (Mg (BH 4 ) 2 ) can be given as a magnesium salt.
- the magnesium salt used is made of magnesium borohydride (Mg (BH 4 ) 2 ) and does not contain a halogen atom, it is necessary to prepare various members constituting the magnesium secondary battery from a material having high corrosion resistance. Disappears.
- Such an electrolytic solution can be produced by dissolving magnesium borohydride in sulfone.
- a magnesium salt composed of magnesium borohydride (Mg (BH 4 ) 2 ) is referred to as “magnesium salt-B” for convenience.
- Such an electrolytic solution is a magnesium ion-containing nonaqueous electrolytic solution in which a magnesium salt-B is dissolved in a solvent made of sulfone.
- the molar ratio of sulfone to magnesium salt-B in the electrolytic solution is, for example, 50 or more and 150 or less, typically 60 or more and 120 or less, preferably 65 or more and 75 or less.
- the present invention is not limited to this.
- the sulfone can be an alkyl sulfone or an alkyl sulfone derivative represented by R 1 R 2 SO 2 (where R 1 and R 2 represent an alkyl group).
- the type (carbon number and combination) of R 1 and R 2 is not particularly limited, and is selected as necessary.
- the number of carbon atoms of R 1 and R 2 is preferably 4 or less, but is not limited thereto.
- the sum of the carbon number of R 1 and the carbon number of R 2 is preferably 4 or more and 7 or less, but is not limited thereto.
- R 1 and R 2 include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, and t-butyl group.
- alkylsulfone examples include dimethylsulfone (DMS), methylethylsulfone (MES), methyl-n-propylsulfone (MnPS), methyl-i-propylsulfone (MiPS), and methyl-n-butylsulfone (MnBS).
- DMS dimethylsulfone
- MES methylethylsulfone
- MnPS methyl-n-propylsulfone
- MiPS methyl-i-propylsulfone
- MnBS methyl-n-butylsulfone
- Methyl-i-butylsulfone (MiBS), methyl-s-butylsulfone (MsBS), methyl-t-butylsulfone (MtBS), ethylmethylsulfone (EMS), diethylsulfone (DES), ethyl-n-propyl Sulfone (EnPS), ethyl-i-propylsulfone (EiPS), ethyl-n-butylsulfone (EnBS), ethyl-i-butylsulfone (EiBS), ethyl-s-butylsulfone (EsBS), ethyl-t-butyl Sulfone (EtBS), di-n-propylsulfur (DnPS), di-i-propylsulfone (DiPS), n-propyl-n-butylsulfone (nPnBS), n-butyl
- an ethyl phenyl sulfone can be mentioned as an alkyl sulfone derivative.
- EhS ethyl phenyl sulfone
- alkyl sulfone derivative at least one selected from the group consisting of EnPS, EiPS, EsBS, and DnPS is preferable.
- the electrolyte may further contain an additive as necessary.
- metal ions include aluminum (Al), beryllium (Be), boron (B), gallium (Ga), indium (In), silicon (Si), tin (Sn), titanium (Ti), Mention may be made of a salt comprising a cation of at least one atom or atomic group selected from the group consisting of chromium (Cr), iron (Fe), cobalt (Co) and lanthanum (La).
- An electrolytic solution using magnesium salt-A is, for example, After dissolving the magnesium salt-A in a low boiling point solvent in which the magnesium salt-A is soluble, Dissolving the sulfone in a solution of the magnesium salt-A dissolved in the low boiling point solvent; Removing the low boiling point solvent from the solution in which the sulfone is dissolved; It can manufacture based on each process.
- the low-boiling solvent in which the magnesium salt-A is soluble basically any solvent can be used as long as the solvent has a lower boiling point than the selected sulfone among the solvents in which the magnesium salt-A is soluble. It is often selected as necessary, but alcohol is preferably used.
- the alcohol may be a monohydric alcohol or a polyhydric alcohol, and may be a saturated alcohol or an unsaturated alcohol.
- alcohol examples include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 1-butanol, 2-butanol (sec-butanol), 2-methyl-1-propanol (isobutanol), 2- Examples thereof include, but are not limited to, methyl-2-propanol (tert-butanol) and 1-pentanol. It is preferable to use dehydrated alcohol as the alcohol.
- magnesium salt-A is dissolved in alcohol.
- an anhydrous magnesium salt can be preferably used.
- magnesium salt-A does not dissolve in sulfone but dissolves well in alcohol.
- the alcohol coordinates to the magnesium.
- the sulfone is dissolved in the alcohol in which the magnesium salt-A is dissolved.
- the alcohol is then removed by heating the solution under reduced pressure.
- the alcohol coordinated with magnesium is exchanged (or substituted) with sulfone.
- the electrolytic solution can be manufactured.
- a magnesium ion-containing non-aqueous electrolyte solution that can be used for metallic magnesium and exhibits an electrochemically reversible magnesium precipitation dissolution reaction at room temperature. it can.
- the electrolytic solution has a solvent composed of sulfone and a nonpolar solvent, and a magnesium salt-A dissolved in the solvent.
- the nonpolar solvent is selected as necessary, but is preferably a nonaqueous solvent having a dielectric constant and a donor number of 20 or less. More specifically, examples of the nonpolar solvent include at least one nonpolar solvent selected from the group consisting of aromatic hydrocarbons, ethers, ketones, esters, and chain carbonates. Examples of aromatic hydrocarbons include toluene, benzene, o-xylene, m-xylene, p-xylene, 1-methylnaphthalene and the like. Examples of ethers include diethyl ether and tetrahydrofuran. Examples of ketones include 4-methyl-2-pentanone. Examples of the ester include methyl acetate and ethyl acetate. Examples of the chain carbonate ester include dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.
- Sulfone and magnesium salt-A are as described above. Moreover, you may add the additive mentioned above to electrolyte solution as needed.
- the molar ratio of sulfone to magnesium salt-A is, for example, preferably 4 or more and 20 or less, more preferably 6 or more and 16 or less, and further preferably 7 or more and 9 or less. However, it is not limited to these.
- An electrolyte solution using magnesium salt-A and a nonpolar solvent is, for example, After dissolving the magnesium salt-A in a low boiling point solvent in which the magnesium salt-A is soluble, Dissolving the sulfone in a solution of the magnesium salt-A dissolved in the low boiling point solvent; After removing the low boiling point solvent from the solution in which the sulfone is dissolved, A nonpolar solvent is mixed with the solution from which the low-boiling solvent has been removed, It can manufacture based on each process.
- magnesium salt-A is dissolved in alcohol. This coordinates the alcohol to the magnesium.
- an anhydrous magnesium salt can be preferably used.
- the sulfone is dissolved in the alcohol in which the magnesium salt is dissolved.
- the alcohol is then removed by heating the solution under reduced pressure.
- the alcohol coordinated with magnesium is exchanged (or substituted) with sulfone.
- a nonpolar solvent is mixed with the solution from which the alcohol has been removed. As described above, the electrolytic solution can be manufactured.
- solvent examples include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, acetonitrile, dimethoxyethane, diethoxyethane, vinylene carbonate, and ⁇ -butyrolactone.
- one kind may be used alone, or two or more kinds may be mixed and used.
- ether solvent such as THF (tetrahydrofuran) can also be used.
- the electrolyte layer can be composed of an electrolytic solution and a polymer compound including a holding body that holds the electrolytic solution.
- the polymer compound may be swollen by the electrolytic solution.
- the polymer compound swollen by the electrolytic solution may be in a gel form.
- polymer compound examples include polyacrylonitrile, polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, polyphosphazene, polysiloxane, Mention may be made of polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene and polycarbonate.
- polyacrylonitrile, polyvinylidene fluoride, polyhexafluoropropylene, or polyethylene oxide is preferable from the viewpoint of electrochemical stability.
- the electrolyte layer can also be a solid electrolyte layer.
- magnesium ions move from the positive electrode to the negative electrode through the electrolyte during charging as shown in FIG.
- electric energy is converted into chemical energy and stored.
- electrical energy is generated by returning magnesium ions from the negative electrode to the positive electrode through the electrolyte.
- the electrode structure including the positive electrode, the separator, and the negative electrode may be a state in which the positive electrode, the separator, the negative electrode, and the separator are wound, or the positive electrode, the separator, the negative electrode, and the separator. May be stacked.
- the band-shaped electrode structure or the wound electrode structure can be formed in a wound state and accommodated in the electrode structure housing member, and the band-shaped electrode structure can be formed in a stacked state. It can be set as the form accommodated in the structure storage member.
- the outer shape of the electrode structure housing member may be a cylindrical shape or a square shape (flat plate type). Examples of the shape and form of the magnesium secondary battery include a coin type, a button type, a disk type, a flat plate type, a square type, a cylindrical type, and a laminate type (laminate film type).
- the electrode structure housing member constituting the cylindrical magnesium secondary battery
- iron (Fe), nickel (Ni), aluminum (Al), titanium (Ti), etc., or alloys thereof, A stainless steel (SUS) etc. can be mentioned.
- the battery can is preferably plated with, for example, nickel in order to prevent electrochemical corrosion associated with charging / discharging of the secondary battery.
- the exterior member in a laminate type (laminate film type) secondary battery has a laminated structure of a plastic material layer (fusion layer), a metal layer and a plastic material layer (surface protective layer), that is, a laminate film.
- the exterior member may be a laminate of two laminated films with an adhesive or the like.
- the fusion layer is made of an olefin resin film such as polyethylene, polypropylene, modified polyethylene, modified polypropylene, or a polymer thereof.
- a metal layer consists of aluminum foil, stainless steel foil, nickel foil, etc., for example.
- the surface protective layer is made of, for example, nylon or polyethylene terephthalate.
- the exterior member is preferably an aluminum laminated film in which a polyethylene film, an aluminum foil, and a nylon film are laminated in this order.
- the exterior member may be a laminate film having another laminated structure, a polymer film such as polypropylene, or a metal film.
- the positive electrode lead portion can be attached to the positive electrode current collector based on spot welding or ultrasonic welding.
- the positive electrode lead portion is preferably a metal foil or a mesh-like one, but may not be a metal as long as it is electrochemically and chemically stable and can conduct electricity.
- Examples of the material for the positive electrode lead portion include aluminum (Al).
- the negative electrode lead portion can be attached to the negative electrode current collector based on spot welding or ultrasonic welding.
- the negative electrode lead portion is preferably a metal foil or a mesh-like one, but may not be a metal as long as it is electrochemically and chemically stable and can conduct electricity. Examples of the material for the negative electrode lead portion include copper (Cu) and nickel (Ni).
- the magnesium secondary battery in the present disclosure includes, for example, a notebook personal computer, various display devices, a personal digital assistant including a PDA (Personal Digital Assistant), a mobile phone, a smart phone, a cordless phone parent device and a child device, a video movie (video) Cameras and camcorders), digital still cameras, electronic papers such as electronic books (electronic books) and electronic newspapers, electronic dictionaries, music players, portable music players, radios, portable radios, headphones, headphone stereos, game consoles, navigation systems, Lighting devices including memory cards, cardiac pacemakers, hearing aids, electric tools, electric shavers, refrigerators, air conditioners, television receivers, stereos, water heaters, microwave ovens, dishwashers, washing machines, dryers, room lights, etc.
- PDA Personal Digital Assistant
- mobile phone a smart phone
- digital still cameras electronic papers such as electronic books (electronic books) and electronic newspapers
- Various electrical equipment portable (Including electronic devices), toys, medical devices, robots, road conditioners, traffic lights, railway vehicles, golf carts, electric carts, electric vehicles (including hybrid vehicles), and the like. Moreover, it can mount in the electric power storage power supply etc. for buildings or electric power generation facilities including a house, or can be used in order to supply electric power to these.
- a converter that converts electric power into driving force by supplying electric power is generally a motor.
- the control device that performs information processing related to vehicle control includes a control device that displays a remaining battery level based on information related to the remaining amount of the secondary battery.
- the magnesium secondary battery can be used in a power storage device in a so-called smart grid.
- a power storage device can not only supply power but also store power by receiving power from another power source.
- power sources for example, thermal power generation, nuclear power generation, hydroelectric power generation, solar cells, wind power generation, geothermal power generation, fuel cells (including biofuel cells) and the like can be used.
- the magnesium secondary battery according to the present disclosure including the above-described various preferred forms is used as a secondary battery, a secondary battery in a battery pack having a secondary battery, a control unit that performs control related to the secondary battery, and an exterior member that encloses the secondary battery. Can be applied.
- the control means controls, for example, charge / discharge, overdischarge, or overcharge related to the secondary battery.
- the magnesium secondary battery according to the present disclosure including the above-described various preferred embodiments can be applied to a secondary battery in an electronic device that receives power supply from the secondary battery.
- a secondary battery in an electric vehicle having a conversion device that receives power supplied from a secondary battery and converts it into driving force of the vehicle, and a control device that performs information processing related to vehicle control based on information related to the secondary battery.
- the magnesium secondary battery in the present disclosure including the various preferable forms of can be applied.
- the converter typically receives power supplied from the secondary battery and drives the motor to generate a driving force. Regenerative energy can also be used to drive the motor.
- a control apparatus performs the information processing regarding vehicle control based on the battery remaining charge of a secondary battery, for example.
- This electric vehicle includes, for example, an electric vehicle, an electric motorcycle, an electric bicycle, a railway vehicle, and so-called hybrid vehicles.
- the above-described various preferred types of secondary batteries in a power storage system configured to receive power from the secondary battery and / or to supply power from the power source to the secondary battery
- the magnesium secondary battery in this indication including a form can be applied.
- the power storage system may be any power storage system as long as it uses power, and includes a simple power device.
- This power storage system includes, for example, a smart grid, a home energy management system (HEMS), a vehicle, and the like, and can also store electricity.
- HEMS home energy management system
- the magnesium secondary battery according to the present disclosure including the above-described various preferred embodiments is applied to a secondary battery in a power storage power source configured to have a secondary battery and connected to an electronic device to which power is supplied. can do.
- the power storage power source can be used for any power system or power device, regardless of the use of the power storage power source. For example, it can be used for a smart grid.
- Example 1 relates to a magnesium secondary battery according to the present disclosure, a negative electrode for a magnesium secondary battery, and a method for manufacturing a negative electrode for a magnesium secondary battery according to the first aspect of the present disclosure.
- FIG. 1A shows a schematic view of a state in which the magnesium secondary battery 10 in Example 1 is disassembled
- FIGS. 1B and 1C show schematic partial cross-sectional views of the negative electrode for a magnesium secondary battery before and after the chemical plating treatment.
- the negative electrode 25 for a magnesium secondary battery of Example 1 includes a current collector 25A and a negative electrode active material layer 25B made of magnesium formed on the surface of the current collector 25A.
- the value of the BET specific surface area of the negative electrode active material layer 25B is 1 m 2 or more, preferably 10 m 2 or more per gram of the negative electrode active material layer.
- the negative electrode active material layer 25B may be formed on one side of the current collector 25A or may be formed on both sides. In the illustrated example, the negative electrode active material layer 25B is formed on one surface of the current collector 25A.
- the magnesium secondary battery of Example 1 includes the negative electrode for a magnesium secondary battery of Example 1.
- a magnesium secondary battery negative electrode was produced by the method described below. That is, a current collector 25A having a base layer 25C containing a metal (specifically, lithium, Li) having a higher ionization tendency than magnesium is prepared. More specifically, a laminated foil in which a copper foil / lithium foil is laminated by pressing a 50 ⁇ m thick lithium foil (underlayer 25C) on one side of a 10 ⁇ m thick copper foil (current collector 25A). Prepare (see FIG. 1B). The laminated foil was punched to a diameter of 15 mm. Then, a negative electrode active material layer composed of a magnesium layer was formed on the current collector by chemical plating using the base layer as a material. Alternatively, based on the chemical plating method, magnesium is deposited by substituting the metal constituting the base layer with magnesium, thereby forming the negative electrode active material layer 25B composed of the magnesium layer on the current collector 25A (FIG. 1C).
- a metal specifically, lithium, Li
- the laminated foil is applied to a plating solution of 1.5 ml per laminated foil. Soaked.
- the laminated foil was immersed in the plating solution for 150 hours. Thereafter, the plating solution was removed from the laminated foil, the laminated foil was washed with a new plating solution, and the plating solution was further removed.
- Fig. 2 shows photographs of the laminated foil before and after chemical plating.
- a silver metallic luster (the surface of the photograph is a lithium foil) was confirmed before the chemical plating treatment. Moreover, it was confirmed that it was covered with a black deposit after the immersion treatment in the chemical plating solution. Since the discoloration occurred on the surface of the lithium foil after 2 hours from the start of immersion in the plating solution, after 2 hours, the phenomenon that magnesium is deposited by replacing lithium with magnesium proceeds, It was suggested that chemical plating could be completed in a very short time.
- Example 1 magnesium was deposited by replacing the metal (lithium) constituting the underlayer with magnesium, so that the magnesium layer was formed on the current collector. That is, magnesium was deposited by substituting the metal constituting the underlayer with magnesium, so that the magnesium layer could be formed.
- a very high-purity magnesium layer can be formed by chemical plating treatment without performing any treatment such as energization.
- the BET specific surface area was measured. As a result, a result of 41.8 m 2 per gram of the negative electrode active material layer (magnesium layer) was obtained.
- the BET specific surface area of the metal magnesium plate was 0.01 m 2 . That is, it was confirmed that a magnesium layer having a large specific surface area can be formed by chemical plating.
- Example 1 a magnesium secondary battery (coin battery CR2016 type) containing sulfur (S) in the positive electrode and magnesium in the cathode was produced. Specifically, a coin battery was manufactured using magnesium (Mg) as a negative electrode and sulfur (S) as a positive electrode.
- a schematic view of FIG. 1A shows a state where the magnesium secondary battery (specifically, the coin battery 10) of Example 1 is disassembled.
- a gasket 22 is placed on a coin battery can 21, a positive electrode 23 made of sulfur, a separator 24 made of a porous film made of polypropylene, a diameter 1.5 mm, a negative electrode 25 (Cu having a thickness of 10 ⁇ m)
- a spacer 26 made of a stainless steel plate having a thickness of 0.2 ⁇ m, and a coin battery lid 27 in this order.
- the coin battery can 21 was caulked and sealed.
- the spacer 26 was spot welded to the coin battery lid 27 in advance.
- the separator 24 contains an electrolytic solution.
- the positive electrode 23 has a structure in which a positive electrode mixture sheet is embedded in a nickel mesh (pellet positive electrode structure).
- the positive electrode mixture sheet contains 10% by mass of sulfur (S 8 ), further contains 65% by mass of ketjen black as a conductive additive, and contains 25% by mass of PTFE as a binder.
- the positive electrode mixture sheet was obtained by dispersing these materials in acetone, compression molding, and drying in a vacuum atmosphere at 70 ° C. for 12 hours.
- a negative electrode was formed from a metal magnesium plate. Specifically, a metal magnesium plate having a thickness of 0.25 mm was punched into a circle having a diameter of 15 mm, and was carefully polished with sandpaper in a glove box in an argon gas atmosphere to remove the oxide film on the surface.
- the magnesium secondary battery of Comparative Example 1 was assembled in the same manner as the magnesium secondary battery of Example 1 except for the above points and the point that the spacer 26 was not used.
- the discharge curves of the magnesium secondary battery of Example 1 and the magnesium secondary battery of Comparative Example 1 are shown in FIG.
- the discharge rate on the horizontal axis is a value normalized with the maximum discharge capacity of the magnesium secondary batteries of Example 1 and Comparative Example 1 as 100%.
- “A” indicates the result of Example 1
- “B” indicates the result of Comparative Example 1.
- the average discharge voltage of the magnesium secondary battery of Comparative Example 1 was 0.92 volts, whereas the magnesium secondary battery of Example 1 was 1.30 volts, an increase of about 0.4 volts.
- a magnesium secondary battery (specifically, a magnesium-sulfur secondary battery) having a negative electrode active material layer formed based on a chemical plating method is a magnesium using a metal magnesium plate as a negative electrode.
- the discharge voltage is greatly improved and the cycle characteristics are also improved.
- the magnesium layer formed based on the chemical plating method has a very large specific surface area compared to the metal magnesium plate, and as a result, the reaction interface between the negative electrode active material and the electrolytic solution increases, resulting in discharge. It is estimated that the overvoltage at the time was greatly suppressed.
- the cycle characteristics are improved because the load during the charge / discharge reaction is reduced and the side reactions and the like are reduced for the same reason.
- a magnesium secondary battery capable of reducing the manufacturing cost with high performance can be realized.
- the formation cost of the magnesium layer (negative electrode active material layer) based on the chemical plating method is cheaper and higher than the formation of the magnesium layer by the electroplating method or vapor deposition method as well as the production of the magnesium foil by the rolling method. It has safety.
- Example 2 relates to a method for manufacturing a negative electrode for a magnesium secondary battery according to the second aspect of the present disclosure.
- the thickness of the underlayer is generally limited to about several tens of ⁇ m.
- a step of forming the (n + 1) th magnesium layer on the nth magnesium layer by chemical plating using the (n + 1) th underlayer as a material, n is repeated from 1 to (N-1), thereby forming a negative electrode active material layer formed by laminating magnesium layers on the current collector.
- Each step is provided.
- Example 2 a current collector in which a first underlayer containing a metal having a higher ionization tendency than magnesium is formed on the surface is prepared.
- A Based on the chemical plating method, magnesium is deposited by substituting the metal constituting the first underlayer with magnesium, thereby forming the first magnesium layer on the current collector,
- magnesium is deposited by substituting the metal constituting the (n + 1) th underlayer with magnesium based on the chemical plating method, and thus the nth magnesium layer
- the step of forming the (n + 1) th magnesium layer on the top is repeated from 1 to (N-1), or the (n + 1) th magnesium layer is formed on the nth magnesium layer.
- the process is repeated for n from 1 to (N-1), whereby a negative electrode active material layer formed by laminating magnesium layers is formed on the current collector. Each step is provided.
- the (n + 1) th underlayer is formed based on an electroplating method.
- Example 1 a laminated foil in which a 50 ⁇ m thick lithium foil is laminated on a 10 ⁇ m thick copper foil is prepared. Then, similarly to Example 1, based on the chemical plating method, magnesium is deposited by substituting the metal (specifically, lithium) constituting the first underlayer with magnesium. A magnesium layer is formed on the current collector. Alternatively, the first magnesium layer is formed on the current collector by chemical plating using the first underlayer as a material.
- the metal (lithium) constituting the (n + 1) th underlayer (second) is replaced with magnesium based on the chemical plating method.
- the (n + 1) th magnesium layer is formed on the nth magnesium layer by chemical plating using the first base layer as a material.
- N 2 formation of the magnesium layer (negative electrode active material layer) is completed by the above steps.
- the (n + 1) th magnesium layer is formed on the nth magnesium layer by chemical plating using the first base layer as a material.
- a magnesium layer having a desired thickness is obtained by defining the thickness of the nth underlayer and the value of N. Obtainable.
- Example 3 a cylindrical secondary battery and a flat laminated film secondary battery will be described.
- the magnesium secondary battery 100 is composed of a cylindrical secondary battery.
- a schematic cross-sectional view of the cylindrical magnesium secondary battery 100 is shown in FIG.
- FIG. 5 shows a schematic partial sectional view along the longitudinal direction of the electrode structure constituting the secondary battery.
- FIG. 5 is a schematic partial cross-sectional view of a portion where the positive electrode lead portion and the negative electrode lead portion are not arranged, and the electrode structure is shown flat for simplification of the drawing. Since the electrode structure is wound, it is curved.
- an electrode structure 121 and a pair of insulating plates 112 and 113 are housed inside an approximately hollow cylindrical electrode structure housing member 111.
- the electrode structure 121 can be produced, for example, by stacking the positive electrode 122 and the negative electrode 124 with the separator 126 interposed therebetween to obtain an electrode structure, and then winding the electrode structure.
- the electrode structure housing member (battery can) 111 has a hollow structure with one end closed and the other end open, and is made of iron (Fe), aluminum (Al), or the like.
- the surface of the electrode structure housing member 111 may be plated with nickel (Ni) or the like.
- the pair of insulating plates 112 and 113 are arranged so as to sandwich the electrode structure 121 and extend perpendicular to the winding peripheral surface of the electrode structure 121.
- a battery lid 114, a safety valve mechanism 115, and a heat sensitive resistance element (PTC element, PositivePoTemperature Coefficient element) 116 are caulked to the open end of the electrode structure housing member 111 via a gasket 117, thereby The structure housing member 111 is sealed.
- PTC element PositivePoTemperature Coefficient element
- the battery lid 114 is made of the same material as the electrode structure housing member 111, for example.
- the safety valve mechanism 115 and the thermal resistance element 116 are provided inside the battery lid 114, and the safety valve mechanism 115 is electrically connected to the battery lid 114 via the thermal resistance element 116.
- the disk plate 115A is reversed when the internal pressure becomes a certain level or more due to an internal short circuit or external heating. As a result, the electrical connection between the battery lid 114 and the electrode structure 121 is disconnected.
- the resistance of the heat-sensitive resistor element 116 increases as the temperature rises.
- the gasket 117 is made of, for example, an insulating material. Asphalt or the like may be applied to the surface of the gasket 117.
- a center pin 118 is inserted in the winding center of the electrode structure 121. However, the center pin 118 does not have to be inserted in the winding center.
- a positive electrode lead portion 123 made of a conductive material such as aluminum is connected to the positive electrode 122. Specifically, the positive electrode lead portion 123 is attached to the positive electrode current collector 122A.
- a negative electrode lead portion 125 made of a conductive material such as copper is connected to the negative electrode 124. Specifically, the negative electrode lead portion 125 is attached to the negative electrode current collector 124A. The negative electrode lead portion 125 is welded to the electrode structure housing member 111 and is electrically connected to the electrode structure housing member 111.
- the positive electrode lead portion 123 is welded to the safety valve mechanism 115 and is electrically connected to the battery lid 114.
- the negative electrode lead portion 125 has one location (the outermost peripheral portion of the wound electrode structure), but two locations (the outermost peripheral portion and the outermost portion of the wound electrode structure). It may be provided on the inner periphery).
- the electrode structure 121 includes a positive electrode 122 having a positive electrode active material layer 122B formed on a positive electrode current collector 122A (specifically, on both surfaces of the positive electrode current collector 122A) and a negative electrode current collector 124A (specifically Specifically, the negative electrode 124 having the negative electrode active material layer 124 ⁇ / b> B formed on both surfaces of the negative electrode current collector 124 ⁇ / b> A is laminated via the separator 126.
- the positive electrode active material layer 122B is not formed in the region of the positive electrode current collector 122A to which the positive electrode lead portion 123 is attached, and the negative electrode active material layer 124B is formed in the region of the negative electrode current collector 124A to which the negative electrode lead portion 125 is attached. It has not been.
- the negative electrode active material layer 124B on the negative electrode current collector 124A is formed based on the method described in the first and second embodiments.
- Positive electrode current collector 122A Aluminum foil positive electrode active material layer 122B having a thickness of 20 ⁇ m Thickness 50 ⁇ m per side
- Positive electrode lead part 123 100 ⁇ m thick aluminum (Al) foil negative electrode current collector 124 A 20 ⁇ m thick copper foil negative electrode active material layer 124 B 50 ⁇ m thick per side
- Negative electrode lead part 125 100 ⁇ m thick nickel (Ni) foil
- the magnesium secondary battery 100 can be manufactured, for example, based on the following procedure.
- the positive electrode active material layer 122B is formed on both surfaces of the positive electrode current collector 122A, and the negative electrode active material layer 124B is formed on both surfaces of the negative electrode current collector 124A.
- the positive electrode lead portion 123 is attached to the positive electrode current collector 122A using a welding method or the like.
- the negative electrode lead portion 125 is attached to the negative electrode current collector 124A using a welding method or the like.
- the positive electrode 122 and the negative electrode 124 are laminated through a separator 126 made of a microporous polyethylene film having a thickness of 20 ⁇ m, and wound (more specifically, the positive electrode 122 / separator 126 / negative electrode 124 / separator. 126 (winding electrode structure (stacked structure) 126) and producing electrode structure 121, a protective tape (not shown) is applied to the outermost periphery.
- the center pin 118 is inserted into the center of the electrode structure 121.
- the electrode structure 121 is housed inside the electrode structure housing member (battery can) 111 while the electrode structure 121 is sandwiched between the pair of insulating plates 112 and 113.
- the distal end portion of the positive electrode lead portion 123 is attached to the safety valve mechanism 115 and the distal end portion of the negative electrode lead portion 125 is attached to the electrode structure housing member 111 using a welding method or the like.
- an organic electrolytic solution or a non-aqueous electrolytic solution is injected based on the decompression method, and the separator 126 is impregnated with the organic electrolytic solution or the non-aqueous electrolytic solution.
- the battery lid 114, the safety valve mechanism 115, and the heat sensitive resistance element 116 are caulked to the opening end portion of the electrode structure housing member 111 through the gasket 117.
- FIGS. 6 and 7A A schematic exploded perspective view of the secondary battery is shown in FIGS. 6 and 7A, and a schematic enlarged cross-sectional view (along the YZ plane) along the arrow AA of the electrode structure (laminated structure) shown in FIG. 7A.
- FIG. 7B shows a schematic enlarged sectional view).
- a schematic partial cross-sectional view (a schematic partial cross-sectional view along the XY plane) in which a part of the electrode structure shown in FIG. 7B is enlarged is the same as that shown in FIG.
- an electrode structure 221 similar to that described above is housed inside an exterior member 200 made of a laminate film.
- the electrode structure 221 can be manufactured by stacking the positive electrode 222 and the negative electrode 224 with the separator 226 and the electrolyte layer 228 interposed therebetween, and then winding the stacked structure.
- a positive electrode lead portion 223 is attached to the positive electrode 222, and a negative electrode lead portion 225 is attached to the negative electrode 224.
- the outermost periphery of the electrode structure 221 is protected by a protective tape 229.
- the positive electrode lead portion 223 and the negative electrode lead portion 225 protrude in the same direction from the inside of the exterior member 200 toward the outside.
- the positive electrode lead portion 223 is formed from a conductive material such as aluminum.
- the negative electrode lead portion 225 is formed from a conductive material such as copper, nickel, and stainless steel.
- the exterior member 200 is a single film that can be folded in the direction of the arrow R shown in FIG. 6, and a recess (emboss) for housing the electrode structure 221 is provided in a part of the exterior member 200.
- the exterior member 200 is, for example, a laminate film in which a fusion layer, a metal layer, and a surface protective layer are laminated in this order. In the manufacturing process of the secondary battery, after the exterior member 200 is folded so that the fusion layers face each other via the electrode structure 221, the outer peripheral edges of the fusion layers are fused.
- the exterior member 200 may be a laminate of two laminated films bonded with an adhesive or the like.
- the fusing layer is made of, for example, a film of polyethylene, polypropylene or the like.
- the metal layer is made of, for example, aluminum foil.
- the surface protective layer is made of, for example, nylon or polyethylene terephthalate.
- the exterior member 200 is an aluminum laminate film in which a polyethylene film, an aluminum foil, and a nylon film are laminated in this order.
- the exterior member 200 may be a laminate film having another laminated structure, a polymer film such as polypropylene, or a metal film.
- a nylon film (thickness 30 ⁇ m), an aluminum foil (thickness 40 ⁇ m), and an unstretched polypropylene film (thickness 30 ⁇ m) are laminated in this order from the outside in a moisture resistant aluminum laminate film (total thickness) 100 ⁇ m).
- an adhesion film 201 is inserted between the exterior member 200 and the positive electrode lead portion 223 and between the exterior member 200 and the negative electrode lead portion 225.
- the adhesion film 201 is made of a material having adhesion to the positive electrode lead portion 223 and the negative electrode lead portion 225, for example, a polyolefin resin, and more specifically, a polyolefin resin such as polyethylene, polypropylene, modified polyethylene, and modified polypropylene. .
- the positive electrode 222 has a positive electrode active material layer 222B on one or both surfaces of the positive electrode current collector 222A.
- the negative electrode 224 includes a negative electrode active material layer 224B on one or both surfaces of the negative electrode current collector 224A.
- the negative electrode active material layer 224B on the negative electrode current collector 224A is formed based on the method described in Examples 1 and 2.
- Example 4 is a modification of Example 1 to Example 2.
- the electrochemical device of Example 4 includes a capacitor, and a positive electrode 301 and a negative electrode 302 are arranged to face each other with a separator 303 impregnated with an electrolyte.
- Reference numerals 304 and 305 indicate current collectors, and reference numeral 306 indicates a gasket.
- the current collector and the negative electrode active material constituting the negative electrode 302 and the current collector 305 are composed of the current collector and the negative electrode active material described in Examples 1 and 2.
- the electrochemical device of Example 4 is composed of an air battery as shown in a conceptual diagram in FIG. 8B.
- This air battery includes, for example, an oxygen-selective permeable membrane 407 that hardly permeates water vapor and selectively permeates oxygen, an air electrode-side current collector 404 made of a conductive porous material, and the air electrode-side current collector 404.
- a porous diffusion layer 406 made of a conductive material and disposed between the porous positive electrode 401, a porous positive electrode 401 containing a conductive material and a catalyst material, a separator that does not easily pass water vapor, and an electrolytic solution (or an electrolytic solution)
- Oxygen 410 in the air (atmosphere) 409 is selectively permeated by the oxygen-selective permeable membrane 407, passes through the air electrode current collector 404 made of a porous material, is diffused by the diffusion layer 406, and is porous. To be supplied. The progress of oxygen that has passed through the oxygen-selective permeable membrane 407 is partially shielded by the air electrode side current collector 404, but the oxygen that has passed through the air electrode side current collector 404 is diffused and spread by the diffusion layer 406. Thus, the entire porous positive electrode 401 is efficiently distributed, and the supply of oxygen to the entire surface of the porous positive electrode 401 is not hindered by the air electrode side current collector 404.
- the permeation of water vapor is suppressed by the oxygen selective permeable membrane 407, there is little deterioration due to the influence of moisture in the air, and oxygen is efficiently supplied to the entire porous positive electrode 401, so that the battery output is increased. And can be used stably for a long time.
- Example 5 an application example of the present disclosure will be described.
- the magnesium secondary battery according to the present disclosure described in Examples 1 to 4 is a machine, device, instrument, device, which can use the secondary battery as a power source for driving / operation or a power storage source for power storage,
- the present invention can be applied to a system (an aggregate of a plurality of devices) without being particularly limited.
- a magnesium secondary battery (specifically, a magnesium-sulfur secondary battery) used as a power source may be a main power source (a power source used preferentially) or an auxiliary power source (in place of the main power source). Or a power source used by switching from the main power source).
- the main power source is not limited to the magnesium secondary battery.
- the magnesium secondary battery specifically, a magnesium-sulfur secondary battery
- a video camera, a camcorder, a digital still camera a mobile phone, a personal computer, a television receiver, Display devices, cordless telephones, headphone stereos, music players, portable radios, electronic papers such as electronic books and electronic newspapers, various electronic devices such as portable information terminals including PDAs, electrical devices (including portable electronic devices); toys; Portable household appliances such as electric shavers; lighting fixtures such as room lights; medical electronic devices such as pacemakers and hearing aids; storage devices such as memory cards; battery packs used for personal computers as removable power supplies; electric drills Electric tools such as power saws and electric saws; store power in case of emergency Power storage systems such as battery systems for gardens, home energy servers (household power storage devices), power supply systems; power storage units and backup power sources; electric vehicles such as electric cars, electric bikes, electric bicycles, Segway (registered trademark); aircraft The driving of a power driving force conversion device for a ship or a ship
- the magnesium secondary battery in the present disclosure is applied to a battery pack, an electric vehicle, an electric power storage system, an electric power supply system, an electric tool, an electronic device, an electric device, and the like.
- the battery pack is a power source using the magnesium secondary battery in the present disclosure, and is a so-called assembled battery or the like.
- the electric vehicle is a vehicle that operates (runs) using the magnesium secondary battery according to the present disclosure as a driving power source, and may be an automobile (hybrid automobile or the like) that includes a drive source other than the secondary battery.
- the power storage system (power supply system) is a system that uses the magnesium secondary battery in the present disclosure as a power storage source.
- a household power storage system power is stored in the magnesium secondary battery according to the present disclosure, which is a power storage source, so that it is possible to use household electrical products using the power. It becomes.
- An electric tool is a tool in which a movable part (for example, a drill etc.) moves, using the magnesium secondary battery in this indication as a power source for driving.
- An electronic device and an electric device are devices that exhibit various functions using the magnesium secondary battery according to the present disclosure as a power source (power supply source) for operation.
- the battery pack is a simple battery pack (so-called soft pack) using one magnesium secondary battery according to the present disclosure, and is mounted on, for example, an electronic device typified by a smartphone.
- the battery pack includes an assembled battery composed of six magnesium secondary batteries according to the present disclosure connected in two parallel three series.
- the connection form of the magnesium secondary battery may be in series, in parallel, or a mixed type of both.
- FIG. 9 is a block diagram illustrating a circuit configuration example when the magnesium secondary battery according to the present disclosure is applied to a battery pack.
- the battery pack includes a cell (assembled battery) 1001, an exterior member, a switch unit 1021, a current detection resistor 1014, a temperature detection element 1016, and a control unit 1010.
- the switch unit 1021 includes a charge control switch 1022 and a discharge control switch 1024.
- the battery pack includes a positive electrode terminal 1031 and a negative electrode terminal 1032. During charging, the positive electrode terminal 1031 and the negative electrode terminal 1032 are connected to the positive electrode terminal and the negative electrode terminal of the charger, respectively, and charging is performed. Further, when the electronic device is used, the positive electrode terminal 1031 and the negative electrode terminal 1032 are connected to the positive electrode terminal and the negative electrode terminal of the electronic device, respectively, and discharge is performed.
- the cell 1001 is configured by connecting a plurality of magnesium secondary batteries 1002 according to the present disclosure in series and / or in parallel.
- FIG. 9 shows a case where six magnesium secondary batteries 1002 are connected in two parallel three series (2P3S), but in addition p parallel q series (where p and q are integers) Any connection method may be used.
- the switch unit 1021 includes a charge control switch 1022 and a diode 1023, and a discharge control switch 1024 and a diode 1025, and is controlled by the control unit 1010.
- the diode 1023 has a reverse polarity with respect to the charging current flowing from the positive terminal 1031 toward the cell 1001 and the forward polarity with respect to the discharging current flowing from the negative terminal 1032 toward the cell 1001.
- the diode 1025 has a polarity in the forward direction with respect to the charging current and in the reverse direction with respect to the discharging current.
- the switch portion is provided on the plus (+) side, but may be provided on the minus ( ⁇ ) side.
- the charging control switch 1022 is closed when the battery voltage becomes the overcharge detection voltage, and is controlled by the control unit 1010 so that the charging current does not flow in the current path of the cell 1001. After the charging control switch 1022 is closed, only discharging is possible via the diode 1023.
- the control unit 1010 is controlled so as to be closed when a large current flows during charging and to block the charging current flowing in the current path of the cell 1001.
- the discharge control switch 1024 is closed when the battery voltage becomes the overdischarge detection voltage, and is controlled by the control unit 1010 so that the discharge current does not flow in the current path of the cell 1001. After the discharge control switch 1024 is closed, only charging is possible through the diode 1025. Further, the control unit 1010 is controlled so that the closed state is established when a large current flows during discharging and the discharge current flowing through the current path of the cell 1001 is cut off.
- the temperature detection element 1016 is formed of, for example, a thermistor, and is provided in the vicinity of the cell 1001.
- the temperature measurement unit 1015 measures the temperature of the cell 1001 using the temperature detection element 1016, and sends the measurement result to the control unit 1010.
- the voltage measurement unit 1012 measures the voltage of the cell 1001 and the voltage of each magnesium secondary battery 1002 constituting the cell 1001, A / D converts the measurement result, and sends the result to the control unit 1010.
- the current measurement unit 1013 measures the current using the current detection resistor 1014 and sends the measurement result to the control unit 1010.
- the switch control unit 1020 controls the charge control switch 1022 and the discharge control switch 1024 of the switch unit 1021 based on the voltage and current sent from the voltage measurement unit 1012 and the current measurement unit 1013.
- the switch control unit 1020 controls the switch unit 1021 when any voltage of the magnesium secondary battery 1002 becomes equal to or lower than the overcharge detection voltage or the overdischarge detection voltage, or when a large current flows rapidly. By sending a signal, overcharge, overdischarge, and overcurrent charge / discharge are prevented.
- the charge control switch 1022 and the discharge control switch 1024 can be composed of semiconductor switches such as MOSFETs, for example. In this case, diodes 1023 and 1025 are constituted by parasitic diodes of the MOSFET.
- the switch control unit 1020 supplies the control signal DO and the control signal CO to the gate units of the charge control switch 1022 and the discharge control switch 1024, respectively.
- the charge control switch 1022 and the discharge control switch 1024 are turned on by a gate potential that is lower than the source potential by a predetermined value or more. That is, in normal charging and discharging operations, the control signal CO and the control signal DO are set to a low level, and the charging control switch 1022 and the discharging control switch 1024 are turned on. For example, in the case of overcharge or overdischarge, the control signal CO and the control signal DO are set to a high level, and the charge control switch 1022 and the discharge control switch 1024 are closed.
- the memory 1011 includes, for example, an EPROM (Erasable Programmable Read Only Memory) that is a nonvolatile memory.
- EPROM Erasable Programmable Read Only Memory
- numerical values calculated by the control unit 1010, internal resistance values of magnesium secondary batteries in the initial state of each magnesium secondary battery 1002 measured in the manufacturing process, and the like are stored in advance. It is possible to rewrite as appropriate. Further, by storing the full charge capacity of the magnesium secondary battery 1002, for example, the remaining capacity can be calculated together with the control unit 1010.
- the temperature measurement unit 1015 measures the temperature using the temperature detection element 1016, performs charge / discharge control when abnormal heat is generated, and performs correction in calculating the remaining capacity.
- FIG. 10A shows a block diagram showing a configuration of an electric vehicle such as a hybrid vehicle which is an example of the electric vehicle.
- the electric vehicle includes, for example, a control unit 2001, various sensors 2002, a power supply 2003, an engine 2010, a generator 2011, inverters 2012 and 2013, a driving motor 2014, a differential device 2015, in a metal housing 2000.
- a transmission 2016 and a clutch 2017 are provided.
- the electric vehicle includes, for example, a front wheel drive shaft 2021, a front wheel 2022, a rear wheel drive shaft 2023, and a rear wheel 2024 connected to the differential device 2015 and the transmission 2016.
- the electric vehicle can travel using, for example, either the engine 2010 or the motor 2014 as a drive source.
- the engine 2010 is a main power source, such as a gasoline engine.
- the driving force (rotational force) of the engine 2010 is transmitted to the front wheel 2022 or the rear wheel 2024 via, for example, a differential device 2015, a transmission 2016, and a clutch 2017 that are driving units.
- the rotational force of the engine 2010 is also transmitted to the generator 2011, and the generator 2011 generates alternating current power using the rotational force.
- the alternating current power is converted into direct current power via the inverter 2013 and stored in the power source 2003. .
- the motor 2014 that is the conversion unit when used as a power source, power (DC power) supplied from the power supply 2003 is converted into AC power via the inverter 2012, and the motor 2014 is driven using AC power.
- the driving force (rotational force) converted from electric power by the motor 2014 is transmitted to the front wheel 2022 or the rear wheel 2024 via, for example, a differential device 2015, a transmission 2016, and a clutch 2017 that are driving units.
- the resistance force at the time of deceleration may be transmitted to the motor 2014 as a rotational force, and the motor 2014 may generate AC power using the rotational force.
- the AC power is converted into DC power via the inverter 2012, and the DC regenerative power is stored in the power supply 2003.
- the control unit 2001 controls the operation of the entire electric vehicle, and includes, for example, a CPU.
- the power supply 2003 includes one or more magnesium secondary batteries (not shown) described in the first to fourth embodiments.
- the power supply 2003 can be configured to be connected to an external power supply and accumulate power by receiving power supply from the external power supply.
- the various sensors 2002 are used, for example, to control the rotational speed of the engine 2010 and to control the opening (throttle opening) of a throttle valve (not shown).
- the various sensors 2002 include, for example, a speed sensor, an acceleration sensor, an engine speed sensor, and the like.
- the electric vehicle may be a vehicle (electric vehicle) that operates using only the power supply 2003 and the motor 2014 without using the engine 2010.
- FIG. 10B shows a block diagram showing the configuration of the power storage system (power supply system).
- the power storage system includes, for example, a control unit 3001, a power source 3002, a smart meter 3003, and a power hub 3004 in a house 3000 such as a general house or a commercial building.
- the power supply 3002 is connected to, for example, an electric device (electronic device) 3010 installed inside the house 3000 and can be connected to an electric vehicle 3011 stopped outside the house 3000.
- the power source 3002 is connected to, for example, a private power generator 3021 installed in a house 3000 via a power hub 3004 and can be connected to an external centralized power system 3022 via a smart meter 3003 and a power hub 3004. is there.
- the electric device (electronic device) 3010 includes, for example, one or more home appliances. Examples of the home appliance include a refrigerator, an air conditioner, a television receiver, and a water heater.
- the private power generator 3021 is composed of, for example, a solar power generator or a wind power generator.
- Examples of the electric vehicle 3011 include an electric vehicle, a hybrid vehicle, an electric motorcycle, an electric bicycle, and Segway (registered trademark).
- Examples of the centralized power system 3022 include a commercial power source, a power generation device, a power transmission network, and a smart grid (next generation power transmission network), and examples thereof include a thermal power plant, a nuclear power plant, a hydroelectric power plant, and a wind power plant.
- Examples of the power generation device provided in the centralized power system 3022 include various solar cells, fuel cells, wind power generation devices, micro hydropower generation devices, geothermal power generation devices, etc. It is not limited to these.
- the control unit 3001 controls the operation of the entire power storage system (including the usage state of the power supply 3002), and includes, for example, a CPU.
- the power supply 3002 includes one or more magnesium secondary batteries (not shown) described in the first to fourth embodiments.
- the smart meter 3003 is, for example, a network-compatible power meter installed in the house 3000 on the power demand side, and can communicate with the power supply side. For example, the smart meter 3003 can efficiently and stably supply energy by controlling the balance between supply and demand in the house 3000 while communicating with the outside.
- the power storage system for example, power is stored in the power source 3002 from the centralized power system 3022 that is an external power source via the smart meter 3003 and the power hub 3004, and from the private power generator 3021 that is an independent power source via the power hub 3004.
- power is stored in the power source 3002. Since the electric power stored in the power supply 3002 is supplied to the electric device (electronic device) 3010 and the electric vehicle 3011 in accordance with an instruction from the control unit 3001, the electric device (electronic device) 3010 can be operated and the electric device The vehicle 3011 can be charged.
- the power storage system is a system that enables accumulation and supply of power in the house 3000 using the power source 3002.
- the power stored in the power supply 3002 can be used arbitrarily. Therefore, for example, power can be stored in the power supply 3002 from the centralized power system 3022 at midnight when the electricity charge is low, and the power stored in the power supply 3002 can be used during the day when the electricity charge is high.
- the power storage system described above may be installed for each house (one household), or may be installed for a plurality of houses (multiple households).
- the electric tool is, for example, an electric drill, and includes a control unit 4001 and a power source 4002 inside a tool main body 4000 made of a plastic material or the like.
- a drill portion 4003 that is a movable portion is rotatably attached to the tool main body 4000.
- the control unit 4001 controls the operation of the entire power tool (including the usage state of the power source 4002), and includes, for example, a CPU.
- the power source 4002 includes one or more magnesium secondary batteries (not shown) described in the first to fourth embodiments.
- the control unit 4001 supplies power from the power source 4002 to the drill unit 4003 in response to an operation switch (not shown).
- the negative electrode for a magnesium secondary battery, the manufacturing method thereof, and the magnesium secondary battery described in the examples are examples and can be appropriately changed.
- the electrode structure may be stacked as well as wound.
- the base layer including the first base layer
- the method for forming the base layer (including the first base layer) on the surface of the current collector not only the method of pressure bonding the base layer or the like to the current collector surface described in the embodiments, but also the base layer on the surface of the current collector And the like based on the electroplating method, the method based on the chemical plating method, the method based on the combination of the chemical plating method and the electroplating method, the method based on the electrolytic deposition method (electrodeposition method) It can also be.
- this indication can also take the following structures.
- A02 ⁇ Method for Producing Secondary Battery Negative Electrode ...
- a step of forming the (n + 1) th magnesium layer on the nth magnesium layer by chemical plating using the (n + 1) th underlayer as a material, n is repeated from 1 to (N-1), thereby forming a negative electrode active material layer formed by laminating magnesium layers on the current collector.
- the manufacturing method of the negative electrode for magnesium secondary batteries provided with each process. [A03] The method for producing a negative electrode for a magnesium secondary battery according to [A02], wherein the (n + 1) th underlayer is formed based on an electroplating method or an electrolytic deposition method (electrodeposition method).
- Method. [A05] The method for producing a negative electrode for a magnesium secondary battery according to any one of [A01] to [A03], wherein the metal is lithium.
- Second Aspect Preparing a current collector on the surface of which a first underlayer containing a metal having a higher ionization tendency than magnesium is formed;
- A Based on the chemical plating method, magnesium is deposited by substituting the metal constituting the first underlayer with magnesium, thereby forming the first magnesium layer on the current collector,
- magnesium is deposited by substituting the metal constituting the (n + 1) th underlayer with magnesium based on the chemical plating method, and the nth magnesium layer is deposited on the nth magnesium layer.
- the step of forming the (n + 1) th magnesium layer is repeated from 1 to (N-1), whereby a negative electrode active material layer formed by laminating magnesium layers is formed on the current collector.
- the manufacturing method of the negative electrode for magnesium secondary batteries provided with each process. [B03] The method for producing a negative electrode for a magnesium secondary battery according to [B02], wherein the (n + 1) th underlayer is formed based on an electroplating method or an electrolytic deposition method (electrodeposition method). [B04] The method for producing a negative electrode for a magnesium secondary battery according to any one of [B01] to [B03], wherein the metal is lithium.
- Anode for secondary battery >> A current collector, and a negative electrode active material layer made of magnesium formed on the surface of the current collector,
- the value of the BET specific surface area of the negative electrode active material layer, the negative electrode active material layer per gram, 1 m 2 or more, preferably a negative electrode for a magnesium secondary battery is 10 m 2 or more.
- ⁇ secondary battery A negative electrode active material layer made of magnesium formed on the current collector and the surface of the current collector, and the value of the BET specific surface area of the negative electrode active material layer is preferably 1 m 2 or more per gram of the negative electrode active material layer Is a magnesium secondary battery comprising a negative electrode for a magnesium secondary battery that is 10 m 2 or more.
- ⁇ Battery pack A battery pack having a secondary battery, control means for controlling the secondary battery, and an exterior housing the secondary battery, The secondary battery is a battery pack comprising the magnesium secondary battery described in [D01].
- ⁇ Electronic equipment An electronic device that receives power from a secondary battery, The secondary battery is an electronic device comprising the magnesium secondary battery described in [D01].
- ⁇ Electric vehicle An electric vehicle having a conversion device that receives power supplied from a secondary battery and converts it into driving force of the vehicle, and a control device that performs information processing related to vehicle control based on information related to the secondary battery
- the secondary battery is an electric vehicle including the magnesium secondary battery described in [D01].
- ⁇ Power system A power system configured to receive power from a secondary battery and / or to supply power from a power source to the secondary battery,
- the secondary battery is a power system including the magnesium secondary battery described in [D01].
- ⁇ Power supply for power storage A power storage power source configured to have a secondary battery and connected to an electronic device to which power is supplied,
- the secondary battery is a power storage power source comprising the magnesium secondary battery described in [D01].
- positive electrode 302 ... Negative electrode, 303 ... Separator, 304, 305 ... Current collector, 306 ... Gasket, 401 ... Porous positive electrode, 402 ... Negative electrode, 403 ... Current collector on the negative electrode side Body, 404... Cathode side current collector, 05 ... Separator and electrolyte (or solid electrolyte containing electrolyte), 406 ... Diffusion layer, 407 ... Oxygen-selective permeable membrane, 408 ... Exterior body, 409 ... Air (atmosphere) ), 410 ... oxygen, 1001 ... cell (assembled battery), 1002 ... magnesium secondary battery, 1010 ... control unit, 1011 ... memory, 1012 ...
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Abstract
Description
マグネシウムよりもイオン化傾向が大きい金属を含む下地層が表面に形成された集電体を準備し、
下地層を素材として、化学メッキ法によって、マグネシウム層から成る負極活物質層を集電体上に形成する。
マグネシウムよりもイオン化傾向が大きい金属を含む第1の下地層が表面に形成された集電体を準備し、
(A)第1の下地層を素材として、化学メッキ法によって、第1番目のマグネシウム層を集電体上に形成し、次いで、
(B)第n番目(但し、n=1,2,・・・,N-1であり、Nは2以上の整数)のマグネシウム層上に、マグネシウムよりもイオン化傾向が大きい金属を含む第(n+1)番目の下地層を形成した後、第(n+1)番目の下地層を素材として、化学メッキ法によって、第n番目のマグネシウム層上に第(n+1)番目のマグネシウム層を形成する工程を、nを1から(N-1)まで繰り返し、以て、マグネシウム層が積層されて成る負極活物質層を集電体上に形成する、
各工程を備えている。
集電体、及び、集電体の表面に形成されたマグネシウムから成る負極活物質層を備えており、
負極活物質層のBET比表面積の値は、負極活物質層1グラム当たり、1m2以上、好ましくは10m2以上である。
1.本開示の第1の態様~第2の態様に係るマグネシウム二次電池用負極の製造方法、本開示のマグネシウム二次電池用負極、及び、本開示のマグネシウム二次電池、全般に関する説明
2.実施例1(本開示の第1の態様に係るマグネシウム二次電池用負極の製造方法、本開示のマグネシウム二次電池用負極、及び、本開示のマグネシウム二次電池)
3.実施例2(本開示の第2の態様に係るマグネシウム二次電池用負極の製造方法)
4.実施例3(本開示のマグネシウム二次電池の変形)
5.実施例4(本開示のマグネシウム二次電池の変形及び電気化学デバイス)
6.実施例5(実施例1~実施例4のマグネシウム二次電池の応用例)
7.その他
本開示の第1の態様~第2の態様に係るマグネシウム二次電池用負極の製造方法における化学メッキ法は、置換法とも呼ばれ、更には、浸漬メッキ法とも呼ばれる。
マグネシウム塩-Aが可溶な低沸点溶媒にマグネシウム塩-Aを溶解させた後、
低沸点溶媒にマグネシウム塩-Aを溶解させた溶液にスルホンを溶解させ、次いで、
スルホンを溶解させた溶液から低沸点溶媒を除去する、
各工程に基づき製造することができる。
マグネシウム塩-Aが可溶な低沸点溶媒にマグネシウム塩-Aを溶解させた後、
低沸点溶媒にマグネシウム塩-Aを溶解させた溶液にスルホンを溶解させ、次いで、
スルホンを溶解させた溶液から低沸点溶媒を除去した後、
低沸点溶媒を除去した溶液に非極性溶媒を混合する、
各工程に基づき製造することができる。
放電条件 :0.1ミリアンペア/カットオフ電圧0.7ボルト
充電条件 :0.1ミリアンペア/カットオフ電圧2.5ボルト
試験環境 :25゜C
サイクル劣化率
={1-(充放電4サイクル後の放電容量/初回放電容量)}×100(%)
マグネシウムよりもイオン化傾向が大きい金属を含む第1の下地層が表面に形成された集電体を準備し、
(A)第1の下地層を素材として、化学メッキ法によって、第1番目のマグネシウム層を集電体上に形成し、次いで、
(B)第n番目(但し、n=1,2,・・・,N-1であり、Nは2以上の整数)のマグネシウム層上に、マグネシウムよりもイオン化傾向が大きい金属を含む第(n+1)番目の下地層を形成した後、第(n+1)番目の下地層を素材として、化学メッキ法によって、第n番目のマグネシウム層上に第(n+1)番目のマグネシウム層を形成する工程を、nを1から(N-1)まで繰り返し、以て、マグネシウム層が積層されて成る負極活物質層を集電体上に形成する、
各工程を備えている。
(A)化学メッキ法に基づき、第1の下地層を構成する金属をマグネシウムと置換することでマグネシウムを析出させ、以て、第1番目のマグネシウム層を集電体上に形成し、次いで、
(B)第n番目(但し、n=1,2,・・・,N-1であり、Nは2以上の整数)のマグネシウム層上に、マグネシウムよりもイオン化傾向が大きい金属を含む第(n+1)番目の下地層を形成した後、化学メッキ法に基づき、第(n+1)番目の下地層を構成する金属をマグネシウムと置換することでマグネシウムを析出させ、以て、第n番目のマグネシウム層上に第(n+1)番目のマグネシウム層を形成する工程を、nを1から(N-1)まで繰り返し、あるいは又、第n番目のマグネシウム層上に第(n+1)番目のマグネシウム層を形成する工程を、nを1から(N-1)まで繰り返し、以て、マグネシウム層が積層されて成る負極活物質層を集電体上に形成する、
各工程を備えている。
正極集電体122A 厚さ20μmのアルミニウム箔
正極活物質層122B 片面当たり厚さ50μm
正極リード部123 厚さ100μmのアルミニウム(Al)箔
負極集電体124A 厚さ20μmの銅箔
負極活物質層124B 片面当たり厚さ50μm
負極リード部125 厚さ100μmのニッケル(Ni)箔
[A01]《二次電池用負極の製造方法・・・第1の態様》
マグネシウムよりもイオン化傾向が大きい金属を含む下地層が表面に形成された集電体を準備し、
下地層を素材として、化学メッキ法によって、マグネシウム層から成る負極活物質層を集電体上に形成するマグネシウム二次電池用負極の製造方法。
[A02]《二次電池用負極の製造方法・・・第2の態様》
マグネシウムよりもイオン化傾向が大きい金属を含む第1の下地層が表面に形成された集電体を準備し、
(A)第1の下地層を素材として、化学メッキ法によって、第1番目のマグネシウム層を集電体上に形成し、次いで、
(B)第n番目(但し、n=1,2,・・・,N-1であり、Nは2以上の整数)のマグネシウム層上に、マグネシウムよりもイオン化傾向が大きい金属を含む第(n+1)番目の下地層を形成した後、第(n+1)番目の下地層を素材として、化学メッキ法によって、第n番目のマグネシウム層上に第(n+1)番目のマグネシウム層を形成する工程を、nを1から(N-1)まで繰り返し、以て、マグネシウム層が積層されて成る負極活物質層を集電体上に形成する、
各工程を備えたマグネシウム二次電池用負極の製造方法。
[A03]第(n+1)番目の下地層を、電気メッキ法あるいは電解析出法(電析法)に基づき形成する[A02]に記載のマグネシウム二次電池用負極の製造方法。
[A04]金属は、リチウム、カリウム、カルシウム及びナトリウムから成る群から選択された少なくとも1種類の金属である[A01]乃至[A03]のいずれか1項に記載のマグネシウム二次電池用負極の製造方法。
[A05]金属はリチウムである[A01]乃至[A03]のいずれか1項に記載のマグネシウム二次電池用負極の製造方法。
[A06]負極活物質層のBET比表面積の値は、負極活物質層1グラム当たり、1m2以上、好ましくは10m2以上である[A01]乃至[A05]のいずれか1項に記載のマグネシウム二次電池用負極の製造方法。
[B01]マグネシウムよりもイオン化傾向が大きい金属を含む下地層が表面に形成された集電体を準備し、
化学メッキ法に基づき、下地層を構成する金属をマグネシウムと置換することでマグネシウムを析出させ、以て、マグネシウム層から成る負極活物質層を集電体上に形成するマグネシウム二次電池用負極の製造方法。
[B02]《二次電池用負極の製造方法・・・第2の態様》
マグネシウムよりもイオン化傾向が大きい金属を含む第1の下地層が表面に形成された集電体を準備し、
(A)化学メッキ法に基づき、第1の下地層を構成する金属をマグネシウムと置換することでマグネシウムを析出させ、以て、第1番目のマグネシウム層を集電体上に形成し、次いで、
(B)第n番目(但し、n=1,2,・・・,N-1であり、Nは2以上の整数)のマグネシウム層上に、マグネシウムよりもイオン化傾向が大きい金属を含む第(n+1)番目の下地層を形成した後、化学メッキ法に基づき、第(n+1)番目の下地層を構成する金属をマグネシウムと置換することでマグネシウムを析出させ、第n番目のマグネシウム層上に第(n+1)番目のマグネシウム層を形成する工程を、nを1から(N-1)まで繰り返し、以て、マグネシウム層が積層されて成る負極活物質層を集電体上に形成する、
各工程を備えたマグネシウム二次電池用負極の製造方法。
[B03]第(n+1)番目の下地層を、電気メッキ法あるいは電解析出法(電析法)に基づき形成する[B02]に記載のマグネシウム二次電池用負極の製造方法。
[B04]金属はリチウムである[B01]乃至[B03]のいずれか1項に記載のマグネシウム二次電池用負極の製造方法。
[B05]負極活物質層のBET比表面積の値は、負極活物質層1グラム当たり、1m2以上、好ましくは10m2以上である[B01]乃至[B04]のいずれか1項に記載のマグネシウム二次電池用負極の製造方法。
[C01]《二次電池用負極》
集電体、及び、集電体の表面に形成されたマグネシウムから成る負極活物質層を備えており、
負極活物質層のBET比表面積の値は、負極活物質層1グラム当たり、1m2以上、好ましくは10m2以上であるマグネシウム二次電池用負極。
[D01]《二次電池》
集電体、及び、集電体の表面に形成されたマグネシウムから成る負極活物質層を備え、負極活物質層のBET比表面積の値は、負極活物質層1グラム当たり、1m2以上、好ましくは10m2以上であるマグネシウム二次電池用負極を備えているマグネシウム二次電池。
[E01]《電池パック》
二次電池、二次電池に関する制御を行う制御手段、及び、二次電池を内包する外装を有する電池パックであって、
二次電池は、[D01]に記載のマグネシウム二次電池から成る電池パック。
[E02]《電子機器》
二次電池から電力の供給を受ける電子機器であって、
二次電池は、[D01]に記載のマグネシウム二次電池から成る電子機器。
[E03]《電動車両》
二次電池から電力の供給を受けて車両の駆動力に変換する変換装置、及び、二次電池に関する情報に基づいて車両制御に関する情報処理を行う制御装置を有する電動車両であって、
二次電池は、[D01]に記載のマグネシウム二次電池から成る電動車両。
[E04]《電力システム》
二次電池から電力の供給を受け、及び/又は、電力源から二次電池に電力を供給するように構成された電力システムであって、
二次電池は、[D01]に記載のマグネシウム二次電池から成る電力システム。
[E05]《電力貯蔵用電源》
二次電池を有し、電力が供給される電子機器が接続されるように構成された電力貯蔵用電源であって、
二次電池は、[D01]に記載のマグネシウム二次電池から成る電力貯蔵用電源。
Claims (7)
- マグネシウムよりもイオン化傾向が大きい金属を含む下地層が表面に形成された集電体を準備し、
下地層を素材として、化学メッキ法によって、マグネシウム層から成る負極活物質層を集電体上に形成するマグネシウム二次電池用負極の製造方法。 - マグネシウムよりもイオン化傾向が大きい金属を含む第1の下地層が表面に形成された集電体を準備し、
(A)第1の下地層を素材として、化学メッキ法によって、第1番目のマグネシウム層を集電体上に形成し、次いで、
(B)第n番目(但し、n=1,2,・・・,N-1であり、Nは2以上の整数)のマグネシウム層上に、マグネシウムよりもイオン化傾向が大きい金属を含む第(n+1)番目の下地層を形成した後、第(n+1)番目の下地層を素材として、化学メッキ法によって、第n番目のマグネシウム層上に第(n+1)番目のマグネシウム層を形成する工程を、nを1から(N-1)まで繰り返し、以て、マグネシウム層が積層されて成る負極活物質層を集電体上に形成する、
各工程を備えたマグネシウム二次電池用負極の製造方法。 - 第(n+1)番目の下地層を、電気メッキ法に基づき形成する請求項2に記載のマグネシウム二次電池用負極の製造方法。
- 金属はリチウムである請求項1又は請求項2に記載のマグネシウム二次電池用負極の製造方法。
- 負極活物質層のBET比表面積の値は、負極活物質層1グラム当たり、1m2以上である請求項1又は請求項2に記載のマグネシウム二次電池用負極の製造方法。
- 集電体、及び、集電体の表面に形成されたマグネシウムから成る負極活物質層を備えており、
負極活物質層のBET比表面積の値は、負極活物質層1グラム当たり、1m2以上であるマグネシウム二次電池用負極。 - 集電体、及び、集電体の表面に形成されたマグネシウムから成る負極活物質層を備え、負極活物質層のBET比表面積の値は、負極活物質層1グラム当たり、1m2以上である二次電池用負極を備えているマグネシウム二次電池。
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