WO2016114321A1 - Batterie secondaire - Google Patents

Batterie secondaire Download PDF

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Publication number
WO2016114321A1
WO2016114321A1 PCT/JP2016/050879 JP2016050879W WO2016114321A1 WO 2016114321 A1 WO2016114321 A1 WO 2016114321A1 JP 2016050879 W JP2016050879 W JP 2016050879W WO 2016114321 A1 WO2016114321 A1 WO 2016114321A1
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Prior art keywords
electrode
secondary battery
battery according
transmission member
lithium
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PCT/JP2016/050879
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English (en)
Japanese (ja)
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中島　潤二
祥雅 藤原
章理 出川
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中島　潤二
祥雅 藤原
章理 出川
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Application filed by 中島　潤二, 祥雅 藤原, 章理 出川 filed Critical 中島　潤二
Priority to JP2016569490A priority Critical patent/JP6527174B2/ja
Publication of WO2016114321A1 publication Critical patent/WO2016114321A1/fr

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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • 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
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • 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
    • H01M4/40—Alloys based on alkali metals
    • 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
    • H01M4/42—Alloys based on zinc
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a secondary battery.
  • the battery converts the chemical energy of the chemical substance contained in the battery into electrical energy through an electrochemical redox reaction.
  • batteries are widely used around the world, mainly in portable electronic devices such as electronics, communication, and computers. Further, in the future, practical use as a large-sized device such as a moving body such as an electric vehicle and a stationary battery such as a power load leveling system is desired, and the battery is becoming an increasingly important key device.
  • a typical lithium ion secondary battery includes a positive electrode using a lithium-containing transition metal composite oxide as an active material and a material capable of inserting and extracting lithium ions (for example, lithium metal, lithium alloy, metal oxide or A negative electrode using carbon) as an active material, a non-aqueous electrolyte, and a separator are provided (for example, refer to JPH05-242911A).
  • JP2015-2167A discloses a secondary battery having characteristics of both a chemical battery and a semiconductor battery.
  • JP2015-2167A discloses a secondary battery capable of obtaining a high capacity and a high output that could not be obtained by a conventional lithium ion secondary battery. It is expected to further improve performance.
  • the secondary battery disclosed in JP2015-2167A can be confirmed to have a life of about 3000 cycles, but it is expected that the life performance will be further improved for the spread of electric vehicles and smart grids.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a novel secondary battery that has a long life and can realize both high input / output and high capacity.
  • a secondary battery includes a first electrode, a second electrode, an ion transmission member that contacts the first electrode and the second electrode, and a contact with the first electrode and the second electrode. Or a hole transmission member that is in contact via a solid electrolyte, and the second electrode contains at least graphene and silicon.
  • the first electrode includes a composite oxide, and the composite oxide contains an alkali metal or an alkaline earth metal.
  • the composite oxide includes a p-type composite oxide that is a p-type semiconductor.
  • the p-type composite oxide contains lithium and nickel doped with at least one selected from the group consisting of antimony, lead, phosphorus, boron, aluminum, and gallium.
  • the composite oxide is Li 1 + x (Fe 0.2 Ni 0.2 ) Mn 0.6 O 3 , where 0 ⁇ x ⁇ 3, and M is antimony, lead, phosphorus, boron, aluminum, and It is at least one selected from the group consisting of gallium.
  • the composite oxide contains fluorine.
  • the ion transmission member is one of a liquid, a gel body, and a solid. It contains at least fluorinated ethylene carbonate and phenazine methosulfate.
  • the hole transmission member contains at least a ceramic material and a polymer resin.
  • the hole transmission member has a nonwoven fabric carrying a ceramic material.
  • At least one of the first electrode and the second electrode is bonded to a porous film layer containing an inorganic oxide filler.
  • the inorganic oxide filler contains ⁇ -Al 2 O 3 as a main component.
  • the porous membrane layer further contains ZrO 2 —P 2 O 5 .
  • the porous film layer contains at least one element selected from the group consisting of antimony, sodium, lithium, magnesium, and aluminum.
  • the second electrode contains graphene and a silicon-containing material.
  • the graphene contains carbon nanotubes.
  • the second electrode contains graphene, carbon nanotubes, or a mixture of graphene and carbon nanotubes, and a silicon-containing material, and is doped with lithium.
  • the lithium is doped by heating the organic lithium contained in the second electrode.
  • lithium metal is attached to the second electrode.
  • the second electrode has a halogen.
  • the halogen includes fluorine.
  • the halogen includes iodine.
  • the second electrode includes an alkali metal.
  • the alkali metal includes sodium.
  • the alkali metal includes potassium
  • the second electrode contains titanium.
  • the second electrode contains zinc.
  • At least one of the first electrode and the second electrode has an acrylic resin layer.
  • the acrylic resin layer has a rubbery polymer containing polyacrylic acid as a basic unit.
  • the acrylic resin layer has polymers having different molecular weights as the rubbery polymer.
  • the secondary battery further includes a first current collector in contact with the first electrode and a second current collector in contact with the second electrode, wherein the first current collector and the first current collector Each of the two current collectors is formed from stainless steel.
  • FIG. 1 shows a schematic diagram of the secondary battery 100 of the present embodiment.
  • the secondary battery 100 includes an electrode 10, an electrode 20, an ion transmission member 30, and a hole transmission member 40.
  • the electrode 10 faces the electrode 20 via the ion transmission member 30 and the hole transmission member 40, and the electrode 10 does not physically contact the electrode 20 by at least one of the ion transmission member 30 and the hole transmission member 40.
  • the electrode (first electrode) 10 functions as a positive electrode
  • the electrode (second electrode) 20 functions as a negative electrode.
  • the potential of the electrode 10 is higher than the potential of the electrode 20, and current flows from the electrode 10 to the electrode 20 via an external load (not shown).
  • a high potential terminal of an external power source (not shown) is electrically connected to the electrode 10
  • a low potential terminal of an external power source (not shown) is electrically connected to the electrode 20.
  • the electrode 10 is in contact with the current collector (first current collector) 110 to form a positive electrode
  • the electrode 20 is in contact with the current collector (second current collector) 120 to form the negative electrode. Forming.
  • the ion transmission member 30 is in contact with the electrode 10 and the electrode 20.
  • FIG. 1 schematically shows a case where the ion transmission member 30 is located in a hole provided in the hole transmission member 40 so as to connect the electrode 10 and the electrode 20.
  • an ion conductive membrane such as NASICON without holes may be used.
  • the ion transmission member 30 located in the hole is, for example, a liquid (specifically, an electrolytic solution).
  • the ion transmission member 30 may be a solid or a gel body.
  • ions (cations) generated in the electrode 20 move to the electrode 10 via the ion transmission member 30.
  • ions generated at the electrode 10 move to the electrode 20 via the ion transmission member 30.
  • the electrode 20 is electronically inserted to generate holes in the electrode 10 due to excessive cations, the holes are directed toward the electrode 20, and the ion transfer member 30 and the hole transfer member 40.
  • the hole generated from the electrode 10 collides with the material containing the polyvalent cation contained in the portion including the hole transmission member 40 or the ion transmission member 30 and transports the polyvalent cation to the electrode 20.
  • Multivalent cations collide and cause holes.
  • the holes in the electrode 20 travel in a direction perpendicular to the direction of the electric field at the electrode 10 and electrons are accumulated in the direction opposite to the holes.
  • the electrode 10 is a semiconductor material made p-type by doping
  • the electrode 20 is a semiconductor material made n-type of contained silicon.
  • NASICON is the following structural material. Li 1 + x + y Alx (Ti, Ge) 2-x Si y P 3-y O 12
  • the difference between the phenomenon of the electrode 10 and the electrode 20 is a battery having a bipolar structure in which two batteries exist. As a result, it has been found that an unprecedented high safety, long life, high input / output, and high capacity battery can be obtained.
  • the ions are alkali metal or alkaline earth metal ions.
  • the electrode 10 contains a compound containing an alkali metal or an alkaline earth metal.
  • the electrode 20 can occlude and release alkali metal ions or alkaline earth metal ions.
  • alkali metal ions or alkaline earth metal ions are released from the electrode 20 and move to the electrode 10 through the ion transmission member 30.
  • ions of alkali metal or alkaline earth metal move from the electrode 10 to the electrode 20 through the ion transmission member 30 and are occluded by the electrode 20.
  • the ions transmitted through the ion transmission member 30 may be both alkali metal ions and alkaline earth metal ions.
  • the electrode 10 has a p-type semiconductor. In each case of charging and discharging, the hole moves through the electrode 10.
  • the hole transmission member 40 is in contact with the electrode 10 and the electrode 20. During discharge, the hole of the electrode 10 moves to the electrode 20 via an external load (not shown), and the electrode 10 receives the hole via the hole transmission member 40. On the other hand, at the time of charging, the hole of the electrode 10 moves to the electrode 20 through the hole transmitting member 40, and the electrode 10 receives the hole from an external power source (not shown).
  • ions generated at the electrode 20 not only move to the electrode 10 via the ion transfer member 30, but also due to the potential difference between the electrode 10 and the electrode 20, 10, the external load (not shown), the electrode 20, and the hole transmission member 40 are circulated in this order.
  • ions generated in the electrode 10 not only move to the electrode 20 via the ion transmission member 30 but also the holes are formed in the electrode 10, the hole transmission member 40, the electrode 20, an external power source (not shown) ) Can be assumed to circulate in this order, but this time, the following phenomenon was found under the conditions shown in the claims.
  • the holes existing in the electrode 20 collide with the multivalent cations of the ion transfer member 30 and those that reach the hole transfer member 40. There are those in which cations return to each metal-containing material.
  • the in-electrode quantum balance with the electrons in the electrode 10 is balanced. That is, an electron accumulation in the electrode 20 is caused by high input / output and capacity, and a bipolar structure having a mechanism with the electrode 10 as a trigger function of the operation is obtained. Since the material of the electrode 20 is an inclusion of graphene and silicon, more holes can be secured than in the conventional ion battery, so that more electrons can be stored than in the conventional ion battery. As a result, the present invention effect could be obtained.
  • the ions generated at the electrode 10 or the electrode 20 move between the electrode 10 and the electrode 20 via the ion transmission member 30. Since the ions move between the electrode 10 and the electrode 20, the secondary battery 100 can realize a high capacity. Further, in the secondary battery 100 of the present embodiment, the hole moves between the electrode 10 and the electrode 20 via the hole transmission member 40. Since the hole is smaller than the ion and has high mobility, the secondary battery 100 can achieve high output.
  • the hole transmission member 40 and the ion transmission member 30 have also found out a role of replacing ions and holes. As a result, high safety and long life, high capacity and high output were achieved.
  • FIG. 2 is a graph showing the weight energy density of the secondary battery 100 of this embodiment and a general lithium ion battery. As can be understood from FIG. 2, according to the secondary battery 100 of the present embodiment, the output characteristics can be greatly improved.
  • the secondary battery 100 of the present embodiment achieves high capacity and high output.
  • the secondary battery 100 of this embodiment includes a chemical battery that transmits ions through the ion transfer member 30 and a semiconductor battery that transmits holes from the electrode 10 that is a p-type semiconductor through the hole transfer member 40.
  • the secondary battery 100 can be said to be a hybrid battery of a chemical battery and a physical battery (semiconductor battery).
  • the electrode 20 is a semiconductor battery
  • the electrode 10 is a bipolar battery that triggers the semiconductor battery.
  • the secondary battery 100 of this embodiment since the amount of the electrolyte solution as the ion transfer member 30 can be reduced, even if the electrode 10 and the electrode 20 come into contact with each other and the inside is short-circuited, the secondary battery 100 The rise in temperature can be suppressed.
  • the secondary battery 100 of the present embodiment is excellent in cycle characteristics with little decrease in capacity due to rapid discharge.
  • the effects of the present invention can be easily obtained, and the capacity and output characteristics of the secondary battery 100 can be further improved.
  • the electrode 10 and the electrode 20 are a p-type semiconductor and an n-type semiconductor can be determined by measuring a Hall effect. Due to the Hall effect, when a magnetic field is applied while a current is flowing, a voltage is generated in a direction in which the current flows and in a direction perpendicular to the direction in which the magnetic field is applied. Whether the semiconductor is a p-type semiconductor or an n-type semiconductor can be determined based on the direction of the voltage.
  • the ion transmission member 30 is typically located in the hole provided in the hole transmission member 40, but the present invention is not limited to this.
  • the ion transmission member 30 may be located at a location away from the hole transmission member 40.
  • ions and holes are transmitted through the ion transmission member 30 and the hole transmission member 40 during charging and discharging, respectively, but ion transmission is performed during one of charging and discharging. Ions or holes may be transmitted through one of the member 30 and the hole transmitting member 40.
  • the ion transmission member (for example, electrolyte) 30 may not be present, and only holes may be transmitted.
  • the hole transmission member 40 may not be provided, and ions may be transmitted from the electrode 10 to the electrode 20 via the ion transmission member 30.
  • the hole transmission member 40 may be formed integrally with the ion transmission member 30. That is, the same member may transmit both ions and holes.
  • the ion transmission member 30 contains fluorinated ethylene carbonate and phenazine methosulfate, which greatly improves the life and input / output performance.
  • the effect of phenazine methosulfate on reducing the reduction reaction at the interface between graphene and electrolyte has been confirmed, and the effect of reducing the resistance of electron and hole movement between the graphene layers has also been confirmed this time. It is thought that there is.
  • fluorinated ethylene carbonate suppresses silicon from being attacked by hydrofluoric acid in the electrolytic solution, and has also confirmed the effect of lowering the barrier for hole incorporation into silicon. As a result, this effect is considered to be obtained.
  • the electrode 10 has a composite oxide containing an alkali metal or an alkaline earth metal.
  • the alkali metal is at least one of lithium and sodium
  • the alkaline earth metal is magnesium.
  • the composite oxide functions as a positive electrode active material of the secondary battery 100.
  • the electrode 10 is formed from a positive electrode material obtained by mixing a composite oxide and a positive electrode binder. Further, a conductive material may be further mixed with the positive electrode material.
  • the composite oxide is not limited to one type, and may be a plurality of types.
  • the complex oxide includes a p-type complex oxide that is a p-type semiconductor.
  • the p-type composite oxide has lithium and nickel doped with at least one selected from the group consisting of antimony, lead, phosphorus, boron, aluminum, and gallium.
  • This composite oxide is expressed as Li x Ni y Mz O ⁇ .
  • M is an element for functioning as a p-type semiconductor, and M is at least one selected from the group consisting of antimony, lead, phosphorus, boron, aluminum, and gallium. Due to the doping, structural defects are generated in the p-type composite oxide, thereby forming holes.
  • the p-type complex oxide preferably contains lithium nickelate doped with a metal element.
  • the p-type composite oxide is antimony-doped lithium nickelate.
  • the complex oxide preferably includes a solid solution complex oxide that forms a solid solution with the p-type complex oxide.
  • the solid solution is formed from a p-type complex oxide and a solid solution complex oxide.
  • the solid solution composite oxide easily forms a layered solid solution with nickel acid, and the solid solution has a structure in which holes are easily moved.
  • the solid solution composite oxide is lithium manganese oxide (Li 2 MnO 3 ). In this case, the valence of lithium is 2.
  • the composite oxide preferably further contains an olivine structure composite oxide having an olivine structure. Due to the olivine structure, deformation of the electrode 10 is suppressed even when the p-type complex oxide forms holes.
  • the olivine structure composite oxide has lithium and manganese, and the valence of lithium is preferably larger than 1. In this case, lithium ions easily move and holes are easily formed.
  • the olivine structure composite oxide is LiMnPO 4 .
  • the composite oxide may include a p-type composite oxide, a solid solution composite oxide, and an olivine structure composite oxide.
  • the composite oxide may contain Li x Ni y M z O ⁇ , Li 2 MnO 3 , and Li ⁇ MnPO 4 .
  • 0 ⁇ x ⁇ 3, y + z 1, 1 ⁇ ⁇ 4, and ⁇ > 1.0.
  • the composite oxide may contain Li x Ni y M z O ⁇ , Li 2 MnO 3 , and Li ⁇ MnSiO 4 .
  • 0 ⁇ x ⁇ 3, y + z 1, 1 ⁇ ⁇ 4, ⁇ > 1.0.
  • the composite oxide may contain Li 1 + x (Fe 0.2 Ni 0.2 ) Mn 0.6 O 3 , Li 2 MnO 3 , and Li ⁇ MnPO 4 .
  • modified products thereof antimony, aluminum, magnesium, etc.
  • the composite oxide may contain fluorine.
  • LiMnPO 4 F may be used as the composite oxide.
  • the electrode 10 is formed from a positive electrode material in which a composite oxide, a positive electrode binder, and a conductive material are mixed.
  • the positive electrode binder contains an acrylic resin, and an acrylic resin layer is formed on the electrode 10.
  • the positive electrode binder contains a rubbery polymer containing polyacrylic acid units.
  • a polymer having a relatively high molecular weight and a polymer having a relatively low molecular weight are mixed as the rubbery polymer.
  • the mixture of polymers having different molecular weights is resistant to hydrofluoric acid and inhibits the movement of holes.
  • the positive electrode binder is a modified acrylonitrile rubber particle binder (such as BM-520B manufactured by Nippon Zeon Co., Ltd.), carboxymethylcellulose (CMC) having a thickening effect, and soluble modified acrylonitrile rubber (BM manufactured by Nippon Zeon Co., Ltd.). -720H and the like). It is preferable to use a binder (SX9172 manufactured by Nippon Zeon Co., Ltd.) made of a polyacrylic acid monomer having an acrylic group as the positive electrode binder.
  • acetylene black, ketjen black, and various graphites, graphenes, carbon nanotubes, and carbon nanofibers may be used alone or in combination.
  • the electrode 10 is hardly cracked, and the yield can be maintained high. Further, by using a material having an acrylic group as the positive electrode binder, the internal resistance is lowered, and inhibition of the properties of the p-type semiconductor of the electrode 10 can be suppressed.
  • the positive electrode binder which has an acrylic group.
  • the positive electrode binder does not become a resistor, electrons are not easily trapped, and heat generation of the electrode 10 is suppressed.
  • the presence of graphene, phosphorus element, or ion conductive glass in the positive electrode binder having an acrylic group promotes lithium dissociation and diffusion in the case of a lithium ion battery.
  • the acrylic resin layer can cover the active material, and the generation of gas due to the reaction between the active material and the electrolytic solution can be suppressed. Further, even in the case of this battery, since the internal resistance of the battery is kept low, the result that the operation with the electrode 20 can be performed efficiently is brought about.
  • the electrode 20 can occlude and emit ions, holes, and electrons generated in the electrode 10.
  • the active material of the electrode 20 has at least graphene and a silicon-containing material, and in addition, various natural graphites, artificial graphite, silicon-based composite materials (silicides), silicon oxide-based materials, titanium alloy-based materials, and various alloy composition materials Can be used alone or in combination.
  • the electrode 20 contains a mixture of graphene and silicon. Further, in this case, the electrode 20 becomes an n-type semiconductor by adding and dispersing phosphorus oxide or sulfur oxide with a thin-film swirl type high-speed mixer (for example, Filmix (registered trademark) manufactured by Primics Co., Ltd.).
  • graphene is a nano-level layer having 10 or fewer layers.
  • the graphene may contain carbon nanotube (CNT).
  • the electrode 20 preferably contains a mixture of graphene and silicon or silicon oxide.
  • the occlusion efficiency of ions (cations) and holes of the electrode 20 can be improved, and at the same time, an electron storage layer can be provided.
  • graphene and silicon oxide are unlikely to function as heating elements, the safety and lifetime of the secondary battery 100 can be improved.
  • the electrode 20 is preferably an n-type semiconductor.
  • the electrode 20 includes a material containing graphene and silicon.
  • the substance containing silicon is, for example, SiOxa (xa ⁇ 2). Further, by using graphene and / or silicon for the electrode 20, even when an internal short circuit of the secondary battery 100 occurs, it is difficult to generate heat and the secondary battery 100 can be prevented from bursting.
  • the electrode 20 may be doped with a donor.
  • the electrode 20 is doped with a metal element as a donor.
  • the metal element is, for example, an alkali metal or a transition metal.
  • an alkali metal for example, any of copper, lithium, sodium, and potassium may be doped.
  • titanium or zinc may be doped as a transition metal.
  • phosphorus oxide or sulfur oxide may be used.
  • the electrode 20 may have graphene doped with lithium.
  • lithium may be doped by heating the material of the electrode 20 containing organolithium, or by using the heat of impact of a substance under high dispersion conditions using the above-described thin film swirl type high speed mixer.
  • lithium doping may be performed by attaching lithium metal to the electrode 20.
  • the electrode 20 contains graphene and silicon doped with lithium.
  • the thin-film swirl type high-speed mixer has a rotor (turbine) at the center of the container.
  • the coating material is pressed against the container wall surface by centrifugal force.
  • a thin film coating layer is formed, and emulsified droplet dispersion is performed in this thin film coating layer in a balance between rotational force and centrifugal force. Since the dispersion treatment is performed using a thin film, the zeta potential between the material particles of nano-level fine particles can be lowered to make the dispersion uniform.
  • the electrode 20 may contain halogen and the life is further improved.
  • halogen includes fluorine.
  • the electrode 20 may contain SiOxaF.
  • the halogen includes iodine.
  • the electrode 20 is formed from a negative electrode material obtained by mixing a negative electrode active material and a negative electrode binder.
  • a negative electrode binder the same material as the positive electrode binder can be used. Note that a conductive material may be further mixed into the negative electrode material.
  • the ion transmission member 30 is either a liquid, a gel body, or a solid.
  • a liquid electrolytic solution
  • the electrolytic solution preferably contains at least fluorinated ethylene carbonate and phenazine methosulfate.
  • LiPF 6 as a salt, LiBF 4, LiClO 4, LiSbF 6, LiAsF 6, LiCF 3 SO 3, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F 5) 2, LiC (SO 2 CF 3) 3 LiN (SO 3 CF 3 ) 2 , LiC 4 F 9 SO 3 , LiAlO 4 , LiAlCl 4 , LiCl, LiI, lithium bis (pentafluoroethanesulfonyl) imide (LiN (SO 2 C 2 Fb) 2 : Lithium Bis ( Pentafluoro-ethane-sulfonyl) Imide: LiBETI) and a mixture of one or more selected from the group consisting of lithium bis (trifluoromethanesulfonyl) imide (Lithium Bis (Trifluoromethanesulfonyl) Imide: LiTFS) Object is used.
  • ethylene carbonate Ethylene Carbonate: EC
  • fluorinated Ethyl Carbonate FEC
  • dimethyl carbonate DMC
  • diethyl carbonate Diethyl Carbonate: DEC
  • methyl ethyl carbonate A mixture obtained by mixing one or two or more selected from the group consisting of Methyl Ethyl Carbonate (MEC) is used.
  • the electrolyte solution includes vinylene carbonate (VC), cyclohexylbenzene (CHB), propane sultone (PS), propylene sulfite (Propylene). Sulfite (PRS), ethylene sulfite (ES) and the like, and modified products thereof may be added.
  • VC vinylene carbonate
  • CHB cyclohexylbenzene
  • PS propane sultone
  • Propylene propylene sulfite
  • Sulfite (PRS) ethylene sulfite (ES) and the like, and modified products thereof may be added.
  • the hole transmission member 40 is a solid or a gel body.
  • the hole transmission member 40 is bonded to at least one of the electrode 10 and the electrode 20. Alternatively, they are bonded via an electrolyte.
  • the hole transmission member 40 preferably has a porous layer.
  • the electrolytic solution communicates between the electrode 10 and the electrode 20 through the pores of the porous layer.
  • the hole transmission member 40 includes a ceramic material.
  • the hole transmission member 40 has a porous film layer containing an inorganic oxide filler.
  • the inorganic oxide filler is preferably composed mainly of alumina ( ⁇ -Al 2 O 3 ), and the holes move on the surface of the alumina.
  • the porous film layer may further contain ZrO 2 —P 2 O 5 .
  • titanium oxide or silica may be used as the hole transmission member 40, or Li 1 + x + y Alx (Ti, Ge) 2-x Si y P 3-y O 12 is mixed with titanium oxide or silica. You may use what you did.
  • the hole transmission member 40 does not easily shrink regardless of the temperature change.
  • the resistance of the hole transmission member 40 is preferably low.
  • a nonwoven fabric carrying a ceramic material is used as the hole transmission member 40. Nonwoven fabrics are difficult to shrink regardless of temperature changes. Moreover, a nonwoven fabric shows voltage resistance and oxidation resistance, and shows low resistance. For this reason, a nonwoven fabric is used suitably as a material of the hole transmission member 40.
  • the hole transmission member 40 preferably functions as a so-called separator.
  • the hole transmission member 40 has a composition that can withstand the usage range of the secondary battery 100 and is not particularly limited as long as the semiconductor function in the secondary battery 100 is not lost.
  • As the hole transmission member 40 it is preferable to use a non-woven fabric carrying alumina ( ⁇ -Al 2 O 3 ).
  • the thickness of the hole transmission member 40 is not particularly limited, but is preferably designed to be 6 ⁇ m to 25 ⁇ m so as to be within a film thickness that can provide a design capacity. More preferably, alumina is mixed with ZrO 2 —P 2 O 5 .
  • the hole transmission member 40 preferably has a mixture in which an additive is mixed with a ceramic material.
  • the additive includes at least one of a compound containing at least one of antimony, aluminum, and magnesium, a compound containing at least one of antimony, aluminum, and magnesium, or a complex containing at least one of antimony, aluminum, and magnesium. preferable. In this case, as a result, the holes can be more easily transmitted.
  • the hole transmission member 40 preferably contains at least a ceramic material and a polymer resin. It is conceivable that the hole transmission part deposits a ceramic material or a metal by vapor deposition or the like. However, a metal is short-circuited as a battery. In addition, the process cost increases in vapor deposition. Therefore, as a means of obtaining this feature in the process of conventional lithium batteries in productivity, by using a ceramic and resin coated film, it prevents tact and process increase and suppresses increase in process cost. Can do.
  • the first current collector 110 and the second current collector 120 are made of stainless steel. Thereby, the potential width can be expanded at low cost.
  • artificial graphite a styrene-butadiene copolymer rubber particle binder BM-400B (solid content 40 parts by weight) manufactured by Nippon Zeon Co., Ltd., and carboxymethylcellulose (CMC) in a weight ratio of 100: 2.5.
  • CMC carboxymethylcellulose
  • the mixture was stirred with a double-arm kneader together with an appropriate amount of water to prepare a negative electrode material.
  • a negative electrode material was applied to a copper foil having a thickness of 10 ⁇ m and dried, and then rolled to a total thickness of 180 ⁇ m, and then cut into a specific size to form a negative electrode.
  • a polypropylene microporous film having a thickness of 20 ⁇ m was sandwiched between the positive electrode and the negative electrode as a separator, laminated, cut into a predetermined size, and inserted into a battery case.
  • An electrolytic solution obtained by dissolving 1 M of LiPF 6 in a mixed solvent in which ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (MEC) are mixed in a dry air environment. After injecting into a can and leaving for a certain period of time, it was precharged for about 20 minutes at a current corresponding to 0.1 C, and then sealed to produce a stacked lithium ion secondary battery. After that, it was left to age for a certain period in a room temperature environment.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • MEC methyl ethyl carbonate
  • Example 1 Polyacrylic acid monomer having acetylene black, which is a conductive member, and a material obtained by adding 0.4% by weight of antimony (Sb) (manufactured by High Purity Science) to lithium nickelate (manufactured by JFE Mineral Co., Ltd.) and an acrylic group A binder consisting of SX9172 manufactured by ZEON Co., Ltd. in a solid weight ratio of 92: 3: 5 is stirred and dispersed with N-methylpyrrolidone (NMP) in a film mix which is a thin film swirl type high-speed mixer manufactured by Primix Co., Ltd. Thus, a positive electrode material was produced.
  • SB antimony
  • NMP N-methylpyrrolidone
  • the positive electrode material was applied to a SUS current collector foil (manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) having a thickness of 13 ⁇ m, dried, and then rolled to an area density of 26.7 mg / cm 2 . Then, it cut
  • silicon-containing graphene material (“xGnP Graphene Nanoplatelets H type + Si” manufactured by XG Sciences, Inc.), 0.2 wt% of sulfur oxide with respect to the silicon-containing graphene material, and a polyacrylic acid monomer having an acrylic group A negative electrode binder (SX 9172 manufactured by Nippon Zeon Co., Ltd.) was stirred at a solid content ratio of 95: 5 together with N-methylpyrrolidone (NMP) in a film mix to prepare a negative electrode material.
  • NMP N-methylpyrrolidone
  • a negative electrode material was applied to a SUS current collector foil (manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) having a thickness of 13 ⁇ m, dried, and then rolled to a surface density of 5.2 mg / cm 2 . Then, it cut
  • SUS current collector foil manufactured by Nippon Steel & Sumikin Materials Co., Ltd.
  • a laminated structure is formed by sandwiching a sheet (“Nano X” manufactured by Mitsubishi Paper Industries Co., Ltd.) between the electrode 10 and the electrode 20 with ⁇ -alumina supported on a non-woven fabric having a thickness of 20 ⁇ m.
  • the laminated structure has a predetermined size. It cut
  • a mixed solvent in which EC (ethylene carbonate), DMC (dimethyl carbonate), and EMC (ethyl methyl carbonate) are mixed at a volume ratio of 1/1/1 is prepared, and 1M of LiPF 6 is dissolved in this mixed solvent. Furthermore, (vinylene carbonate (VC) 1.5 wt%, fluorinated ethylene carbonate (FEC) 2.0 wt%, phenazine methosulfate (PMS) 0.5 wt% and propane An electrolyte was prepared by adding 1% by weight of sultone (1,3-Propanesultone: PS), and was treated so that the electrolyte was immersed in the non-woven sheet carrying the ⁇ -alumina in a dry environment.
  • VC ethylene carbonate
  • FEC fluorinated ethylene carbonate
  • PMS phenazine methosulfate
  • Example 2 In Example 2, the positive electrode acetylene black of Example 1 was replaced with graphene (“xGnP Graphene Nanoplatelets H type” manufactured by XG Sciences, Inc.) to produce a secondary battery.
  • graphene xGnP Graphene Nanoplatelets H type manufactured by XG Sciences, Inc.
  • Example 3 In Example 3, a solid electrolyte, here LiNbO 3 , between the hole transfer member 40 and the ion transfer member 30 and the electrode 10 of Example 1, and between the hole transfer member 40 and the ion transfer member 30 and the electrode 20, is used. / Li 3 PS 4 was provided, and an electrolyte was dropped only on the surface of the solid electrolyte to produce a secondary battery.
  • a solid electrolyte here LiNbO 3
  • Example 4 the hole transmission member 40 and the ion transmission member 30 of Example 3 are an integral ion conductive film Li 1 + x + y Alx (Ti, Ge) 2 ⁇ x Si y P 3 ⁇ y O 12 , A secondary battery having a surface made of polyethylene oxide (PEO) containing the above electrolyte solution and made into an appropriate paste was prepared.
  • PEO polyethylene oxide
  • Example 5 a secondary battery in which the hole transmission member 40 of Example 1 includes a substance containing antimony, aluminum, and magnesium was manufactured.
  • Example 6 carbon nanotubes manufactured by Cano Technology Limited were added to the graphene of Example 1 so as to have a volume ratio of 3: 1 to produce a secondary battery.
  • Example 7 a secondary battery was fabricated by attaching a lithium metal foil having an area of 1/7 of the electrode 20 to the electrode 20 in Example 1.
  • Example 8 when producing the negative electrode material of Example 1, a secondary battery was produced by adding 0.06% by weight of lithium powder in a moisture content environment of 10 ppm or less.
  • Example 9 when the negative electrode material of Example 1 was produced, a secondary battery was produced by adding 0.06% by weight of sodium powder.
  • Example 10 when producing the negative electrode material of Example 1, a secondary battery was produced by adding 0.06% by weight of potassium powder.
  • Example 11 In Example 11, when the negative electrode material of Example 1 was produced, a secondary battery was produced by adding 0.06% by weight of zinc powder.
  • Example 12 In Example 12, a secondary battery was manufactured by adding ZrO 2 —P 2 O 5 to the nonwoven fabric of Example 1 at a volume ratio of 250 ppm.
  • Example 13 when producing the negative electrode material of Example 1, a secondary battery was produced by adding 0.8% by weight of lithium octylate.
  • Example 14 In Example 1, a secondary battery was manufactured by mixing materials with a double arm stirrer without using a fill mix.
  • Example 15 Lithium nickel oxide (manufactured by Sumitomo Metal Mining Co., Ltd.) doped with 0.7% by weight of antimony (Sb), Li 1.2 MnPO 4 (Lithated Metal Phosphate II manufactured by Dow Chemical Company), and Li 2 MnO 3 (Zhenhua) ZHFL-01 manufactured by E-Chem Co., Ltd. was mixed at a weight ratio of 54.7% by weight, 18.2% by weight and 18.2% by weight, respectively, and AMS-LAB manufactured by Hosokawa Micron Corporation ( The active material of the electrode 10 was produced by performing a treatment for 3 minutes at a rotation speed of 1500 rpm in Mechanofusion (registered trademark).
  • a binder (SX9172 manufactured by Nippon Zeon Co., Ltd.) composed of an active material, acetylene black as a conductive member, and a polyacrylic acid monomer having an acrylic group at a solid weight ratio of 92: 3: 5, N—
  • NMP methylpyrrolidone
  • the positive electrode material was applied to a SUS current collector foil (manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) having a thickness of 13 ⁇ m, dried, and then rolled to an area density of 26.7 mg / cm 2 . Then, it cut
  • a graphene material (“xGnP Graphene Nanoplatelets H type” manufactured by XG Sciences, Inc.) and silicon oxide SiO xa (“SiOx” manufactured by Shanghai Sugisugi Technology Co., Ltd.) have a weight ratio of 56.4: 37.6.
  • the mixture was treated with NOB-130 (Nobilta (registered trademark)) manufactured by Hosokawa Micron Corporation for 3 minutes at a rotational speed of 800 rpm to prepare a negative electrode active material.
  • a negative electrode binder composed of a negative electrode active material and a polyacrylic acid monomer having an acryl group (SX 9172 manufactured by Nippon Zeon Co., Ltd.) at a solid content weight ratio of 95: 5 is combined with N-methylpyrrolidone (NMP). The mixture was stirred with an arm kneader to produce a negative electrode material.
  • NMP N-methylpyrrolidone
  • a negative electrode material was applied to a SUS current collector foil (manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) having a thickness of 13 ⁇ m, dried, and then rolled to a surface density of 5.2 mg / cm 2 . Then, it cut
  • SUS current collector foil manufactured by Nippon Steel & Sumikin Materials Co., Ltd.
  • a laminated structure is formed by sandwiching a sheet (“Nano X” manufactured by Mitsubishi Paper Industries Co., Ltd.) between the electrode 10 and the electrode 20 with ⁇ -alumina supported on a non-woven fabric having a thickness of 20 ⁇ m.
  • the laminated structure has a predetermined size. It cut
  • “Novolyte EEL-003” (Vinylene Carbonate (VC)) and lithium bis (oxalato) borate (LiBOB) of Novolite technologies are used for the nonwoven sheet carrying ⁇ -alumina. 2% by weight and 1% by weight added) were soaked.
  • a mixed solvent in which EC (ethylene carbonate), DMC (dimethyl carbonate), EMC (ethyl methyl carbonate), and PC (propylene carbonate) are mixed at a volume ratio of 1: 1: 1: 1 is prepared.
  • An electrolytic solution in which 1M LiPF 6 was dissolved in the mixed solvent was formed. Then, after injecting the electrolyte into the battery container in a dry air environment and leaving it for a certain period of time, it is precharged for about 20 minutes at a current corresponding to 0.1 C, and then sealed and aged for a certain period of time in a room temperature environment. A secondary battery was produced by allowing it to stand.
  • the capacity comparison performance of each secondary battery was evaluated by setting the 1C discharge capacity in the specification potential range of 2V-4.3V of Comparative Example 1 to 100.
  • the capacity evaluation was performed on the capacity comparison performance of each secondary battery even in the potential range of 2V-4.6V.
  • the discharge capacity ratio of 10C / 1C was measured.
  • the output performance is evaluated.
  • the 10C / 1C charge capacity ratio was measured. This evaluates input performance and quick chargeability.
  • Table 1 shows the results of the evaluation described above.
  • the secondary battery of Comparative Example 1 is a so-called general lithium ion secondary battery.
  • overheating was remarkable after 1 second regardless of the nail penetration speed, whereas in the secondary battery of Example 1, there was almost no increase in temperature after the nail penetration. Was suppressed.
  • the separator was melted over a wide range, but in the secondary battery of Example 1, the ceramic-containing non-woven fabric had its original shape. I kept it.
  • the ceramic-containing non-woven fabric was able to prevent significant overheating because the structure was not destroyed even in the case of heat generation due to a short circuit that occurred after nail penetration, and the expansion of the short circuit area could be suppressed.
  • the battery operated as a battery when the nail was removed after nail penetration.
  • Comparative Example 1 there was no battery operation. This is presumably because the battery of the present invention is not an ion battery but a battery having a semiconductor mechanism utilizing hole movement.
  • the mechanism of the semiconductor can be operated even if a part is destroyed, and it becomes a battery with good impact resistance that could not be obtained with conventional ion batteries, and this time, by finding this feature, it is highly safe A high-capacity, high-output battery could be obtained.
  • the positive electrode binder is examined.
  • PVDF was used as the positive electrode binder, and overheating could not be suppressed when the nail penetration speed was reduced.
  • the active material was dropped from the aluminum foil (current collector). The reason is considered as follows.
  • Example 1 When the nail pierces the secondary battery of Comparative Example 1 and an internal short circuit occurs, Joule heat is generated by the short circuit, and the positive electrode is deformed by melting PVDF (crystal melting point 174 ° C.). When the active material fell off, the resistance decreased and the current flowed more easily, and overheating was promoted and deformed. In contrast, in Example 1, SX9172 manufactured by Nippon Zeon Co., Ltd. was used as the negative electrode binder, and deformation was suppressed even when the current was temporarily concentrated and overheated.
  • PVDF crystal melting point 174 ° C.
  • Example 1 shows a direction in which high input performance, that is, the possibility of rapid charging can be obtained. Furthermore, it has been found that the lifetime is also greatly improved. This is because graphene, silicon, and nanoparticles of dopant can be uniformly dispersed to make a semiconductor uniformly, and the portion that does not become a semiconductor only generates ion migration, so there is a portion where the features of the present invention do not occur.
  • the portion that is not made into a semiconductor is mainly composed of a chemical reaction, it becomes a state close to that of a conventional ion battery, it is difficult to rapidly charge, and chemical deterioration occurs, so that it is considered difficult to obtain a long life effect.
  • FIG. 3 shows the 1C discharge capacity in Examples 1, 5 and Comparative Example 1. From FIG. 3, it can be understood that the secondary battery of this example exhibits a high capacity.
  • Example 1 at 4.6 V charging, the distribution of electrons in the electrode 20 was divided into blocks and evaluated by measuring current and resistance. As a result, distribution bias was observed in one direction perpendicular to the electric field. I understand. At the same time, Hall measurement was performed. As a result, there was a bias in the direction opposite to the electron distribution and almost perpendicular to the electric field direction. From this, it was also possible to find a phenomenon in which electrons and holes move in the electrode 20 in directions opposite to each other and substantially perpendicular to the electric field. It has also been found that an electron storage layer is provided in the electrode 20 during charging.
  • the secondary battery of the present invention can achieve high output and high capacity, and is suitably used as a highly safe large-sized storage battery or the like.
  • the secondary battery of the present invention is suitably used as a storage battery for a power generation mechanism with unstable power generation, such as geothermal power generation, wind power generation, solar power generation, hydroelectric power generation, and wave power generation.
  • the secondary battery of the present invention is also suitably used for mobile objects such as electric vehicles. Furthermore, since it is highly safe, it can be used for card batteries, mobile phones and mobile terminals.

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Abstract

L'invention concerne une batterie secondaire qui est pourvue d'une première électrode, d'une seconde électrode, d'un élément de transfert d'ions qui est en contact avec la première électrode et la seconde électrode, et d'un élément de transfert de trous qui est en contact avec la première électrode et la seconde électrode directement ou avec un électrolyte solide intercalé entre celles-ci, et laquelle seconde électrode contient au moins du graphène et du silicium.
PCT/JP2016/050879 2015-01-15 2016-01-13 Batterie secondaire WO2016114321A1 (fr)

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CN109855768A (zh) * 2019-02-22 2019-06-07 清华大学 一种基于石墨烯的传感装置及其制备方法、使用方法
WO2020137912A1 (fr) * 2018-12-28 2020-07-02 株式会社パワーフォー Batterie secondaire
JP2020109735A (ja) * 2018-12-28 2020-07-16 株式会社パワーフォー 二次電池

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