WO2022054415A1 - リチウムイオン二次電池 - Google Patents

リチウムイオン二次電池 Download PDF

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WO2022054415A1
WO2022054415A1 PCT/JP2021/027133 JP2021027133W WO2022054415A1 WO 2022054415 A1 WO2022054415 A1 WO 2022054415A1 JP 2021027133 W JP2021027133 W JP 2021027133W WO 2022054415 A1 WO2022054415 A1 WO 2022054415A1
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negative electrode
lithium
active material
ion secondary
secondary battery
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French (fr)
Japanese (ja)
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巧 日浅
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to JP2022547425A priority Critical patent/JP7524956B2/ja
Priority to CN202180062042.6A priority patent/CN116114077B/zh
Publication of WO2022054415A1 publication Critical patent/WO2022054415A1/ja
Priority to US18/118,465 priority patent/US20230246179A1/en
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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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
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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
    • H01M10/24—Alkaline accumulators
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

  • This technology relates to lithium-ion secondary batteries.
  • lithium-ion secondary batteries Due to the widespread use of various electronic devices such as mobile phones, the development of lithium-ion secondary batteries is underway as a power source that is compact and lightweight and can obtain high energy density.
  • a lithium ion secondary battery provided with an electrolytic solution containing an aqueous solvent (so-called aqueous electrolytic solution) has been developed, and various studies have been conducted on the configuration of the lithium ion secondary battery. It has been done.
  • an aqueous electrolyte containing lithium ion, an imide anion and a metal cation and having a PH of 3 to 12 is used ().
  • Patent Document 1 In order to realize a self-supporting electrode that does not include a binder and a current collector, a composite material containing electrode active material particles in a three-dimensional crosslinked network structure of carbon nanotubes is used, and a battery is used in the main body containing the composite material. The tab is fixed (see, for example, Patent Document 2).
  • a negative electrode active material containing a Ti-containing composite oxide is used, and Hg or the like is present on the surface of the negative electrode containing the negative electrode active material (for example, Patent Document). See 3.).
  • a non-woven fabric formed of a fibrous active electrode material is used as an electrode (see, for example, Patent Document 4).
  • a carbon coat layer is provided on the surface of the negative electrode active material containing titanium oxide (see, for example, Patent Document 5).
  • Lithium titanate having macropores is used as an electrode active material for a power storage device in order to obtain excellent rate characteristics (see, for example, Patent Document 6).
  • the lithium ion secondary battery of one embodiment of the present technology includes a positive electrode that occludes and releases lithium ions, a negative electrode that contains a negative electrode active material that occludes and releases the lithium ions, and an electrolytic solution that contains an aqueous solvent.
  • the negative electrode active material contains a titanium-containing compound, and the electrolytic solution has a pH of 11 or more.
  • another lithium ion secondary battery of one embodiment of the present technology is arranged between the positive electrode space and the negative electrode space, and is arranged inside a partition wall that allows lithium ions to pass through and the positive electrode space thereof, and exhibits lithium ions.
  • a positive electrode that is stored and discharged a negative electrode that is arranged inside the negative electrode space and contains a negative electrode active material that stores and releases lithium ions, a positive electrode electrolyte that is housed inside the positive electrode space and contains an aqueous solvent, and a negative electrode space thereof. It is housed inside the above and is provided with a negative electrode electrolytic solution containing an aqueous solvent.
  • the negative electrode active material contains a titanium-containing compound, the positive electrode electrolyte has a pH of less than 11, and the negative electrode electrolyte has a pH of 11 or more.
  • the ratio of the sum of the detected amounts of lithium, titanium, tin, zirconium and bismuth and indium to the sum of the detected amounts of all metal elements was 99. Atomic% or more.
  • all metal elements are all metal elements that can be analyzed (detected) by using the X-ray photoelectron spectroscopic analysis method, and more specifically, the first of the long periodic table. All metallic elements (including lithium) belonging to Group 1 to Group 17.
  • the ratio is the average value of the 10 ratios calculated at each of the above 10 locations.
  • the negative electrode active material of the negative electrode contains a titanium-containing compound
  • the electrolytic solution containing an aqueous solvent has a pH of 11 or more
  • an X-ray photoelectron spectroscopic analysis method is performed. Since the ratio when the surface of the negative electrode is analyzed using the above range is in the above range, excellent charge / discharge characteristics can be obtained.
  • the negative electrode active material of the negative electrode contains a titanium-containing compound
  • the positive electrode electrolytic solution containing an aqueous solvent has a pH of less than 11, and is aqueous. Since the negative electrode electrolytic solution containing the solvent has a pH of 11 or more and the ratio when the surface of the negative electrode is analyzed using the X-ray photoelectron spectroscopic analysis method is in the above range, excellent charge / discharge characteristics can be obtained. Can be done.
  • the effect of the present technology is not necessarily limited to the effect described here, and may be any effect of a series of effects related to the present technology described later.
  • the lithium ion secondary battery described here is a secondary battery that utilizes the storage and release of lithium ions, and includes an electrolytic solution (aqueous electrolyte solution) that is a liquid electrolyte containing an aqueous solvent together with a positive electrode and a negative electrode. ..
  • an electrolytic solution aqueous electrolyte solution
  • the charge / discharge reaction proceeds by utilizing the storage / discharge of lithium ions, so that the battery capacity can be obtained.
  • FIG. 1 shows a cross-sectional configuration of the lithium ion secondary battery of the first embodiment.
  • this lithium ion secondary battery includes an exterior member 11, a positive electrode 12, a negative electrode 13, and an electrolytic solution 14.
  • the electrolytic solution 14 is lightly shaded.
  • the upper side in FIG. 1 is the upper side of the lithium ion secondary battery
  • the lower side in FIG. 1 is the lower side of the lithium ion secondary battery.
  • the exterior member 11 is a substantially box-shaped member having an internal space S for accommodating the positive electrode 12, the negative electrode 13, the electrolytic solution 14, and the like.
  • the exterior member 11 contains any one or more of metal materials, glass materials, polymer compounds, and the like.
  • the exterior member 11 may be a rigid metal can, a glass case, a plastic case, or the like, or may be a flexible (or flexible) metal foil, a polymer film, or the like.
  • the positive electrode 12 is arranged in the internal space S and occludes and discharges lithium ions.
  • the positive electrode 12 includes a positive electrode current collector 12A having a pair of surfaces and a positive electrode active material layer 12B formed on both surfaces of the positive electrode current collector 12A.
  • the positive electrode active material layer 12B may be formed on only one side of the positive electrode current collector 12A on the side where the positive electrode 12 faces the negative electrode 13.
  • the positive electrode current collector 12A may be omitted. Therefore, the positive electrode 12 may be only the positive electrode active material layer 12B.
  • the positive electrode current collector 12A supports the positive electrode active material layer 12B, and contains any one or more of conductive materials such as a metal material, a carbon material, and a conductive ceramic material.
  • conductive materials such as a metal material, a carbon material, and a conductive ceramic material.
  • metallic materials include titanium, aluminum and their alloys.
  • conductive ceramic material are indium tin oxide (ITO) and the like.
  • ITO indium tin oxide
  • the material for forming the positive electrode current collector 12A has insolubility, poor solubility and corrosion resistance with respect to the electrolytic solution 14, and also has low reactivity with the positive electrode active material. Therefore, the positive electrode current collector 12A preferably contains the above-mentioned metal material, that is, titanium, aluminum, an alloy thereof, and the like. This is because the positive electrode current collector 12A is less likely to deteriorate even if a lithium ion secondary battery is used.
  • the positive electrode current collector 12A may be a conductor plated so that any one or more of the above-mentioned metal materials, carbon materials, and conductive ceramic materials cover the surface.
  • the material of the conductor is not particularly limited as long as it has conductivity.
  • the positive electrode active material layer 12B contains any one or more of the positive electrode active materials that occlude and release lithium ions. However, the positive electrode active material layer 12B may further contain a positive electrode binder, a positive electrode conductive agent, and the like.
  • the positive electrode active material contains a lithium-containing compound and the like.
  • the type of the lithium-containing compound is not particularly limited, and specific examples thereof include a lithium composite oxide and a lithium phosphoric acid compound.
  • the lithium composite oxide is an oxide containing lithium and one or more kinds of transition metal elements as constituent elements, and the lithium phosphate compound contains lithium and one or more kinds of transition metal elements. It is a phosphoric acid compound contained as a constituent element.
  • the type of the transition metal element is not particularly limited, but specifically, nickel, cobalt, manganese, iron and the like.
  • lithium composite oxide having a layered rock salt type crystal structure LiNiO 2 , LiCoO 2 , LiCo 0.98 Al 0.01 Mg 0.01 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiNi 0.33 Co 0.33 Mn 0.33 O 2 , Li 1.2 Mn 0.52 Co 0.175 Ni 0.1 O 2 and Li 1.15 (Mn 0.65 Ni 0.22 Co 0.13 ) O 2 .
  • lithium composite oxide having a spinel-type crystal structure include LiMn 2 O 4 .
  • lithium phosphoric acid compound having an olivine type crystal structure examples include LiFePO 4 , LiMnPO 4 , LiMn 0.5 Fe 0.5 PO 4 , LiMn 0.7 Fe 0.3 PO 4 and LiMn 0.75 Fe 0.25 PO 4 .
  • the positive electrode binder contains any one or more of synthetic rubber and polymer compounds.
  • synthetic rubber are styrene-butadiene rubber and the like.
  • polymer compound include polyvinylidene fluoride and polyimide.
  • the positive electrode conductive agent contains any one or more of conductive materials such as carbon materials, and specific examples of the carbon materials are graphite, carbon black, acetylene black, ketjen black and the like. ..
  • the conductive material may be a metal material, a conductive ceramic material, a conductive polymer, or the like.
  • the negative electrode 13 is arranged in the internal space S so as to be separated from the positive electrode 12, and stores and discharges lithium ions.
  • the negative electrode 13 includes a negative electrode current collector 13A having a pair of surfaces and a negative electrode active material layer 13B formed on both surfaces of the negative electrode current collector 13A.
  • the negative electrode active material layer 13B may be formed on only one side of the negative electrode current collector 13A on the side where the negative electrode 13 faces the positive electrode 12.
  • the negative electrode 13 Since one or both of the negative electrode current collector 13A and the negative electrode active material layer 13B constituting the negative electrode 13 have a specific metal material on the surface, the negative electrode 13 is a strongly alkaline electrolytic solution described later. It exhibits properties that are difficult to react with and dissolve in 14.
  • This specific metal material is a material containing a specific kind of metal element as a constituent element, and more specifically, any one kind or two or more kinds of titanium, tin, zirconium, bismuth and indium are constituent elements. It is a material contained as.
  • the type of the specific metal material may be only one type or two or more types.
  • the specific metal material may be a simple substance (single metal), an alloy, an oxide (metal oxide which is a conductor), or two or more of them.
  • Specific examples of the oxide are oxides containing any one or more of the above-mentioned metal elements such as titanium as constituent elements, and more specifically, titanium oxide and the like.
  • the negative electrode current collector 13A and the negative electrode active material layer 13B constituting the negative electrode 13 have a non-specific metal material on the surface
  • the negative electrode 13 is strongly alkaline. It exhibits the property of being easily reacted and dissolved in the electrolytic solution 14 of the above.
  • This non-specific metal material is a material containing a metal element other than the above-mentioned specific metal element as a constituent element, and more specifically, any of aluminum, copper, lead, zinc, magnesium, iron and the like. It is a material containing one kind or two or more kinds as constituent elements.
  • One or both of the negative electrode current collector 13A and the negative electrode active material layer 13B have a specific metal material on the surface, if the appropriate conditions regarding the element ratio A described later are satisfied, strong alkaline electrolysis is performed. This is because the negative electrode 13 is less likely to react and dissolve in the liquid 14, so that the constituent atoms of the negative electrode 13 are less likely to be eluted in the electrolytic solution 14. As a result, the electrolytic solution 14 is less likely to deteriorate and decompose, so that the charge / discharge characteristics of the lithium ion secondary battery are less likely to deteriorate. The details of the element ratio A will be described later.
  • one or both of the negative electrode current collector 13A and the negative electrode active material layer 13B have a material containing titanium as a constituent element as a specific metal material on the surface. This is because the negative electrode 13 is difficult to sufficiently react and dissolve with the strongly alkaline electrolytic solution 14, so that the electrolytic solution 14 is sufficiently difficult to deteriorate and decompose.
  • both the negative electrode current collector 13A and the negative electrode active material layer 13B preferably have a specific metal material on the surface, and more preferably have a material containing titanium as a constituent element on the surface. This is because the negative electrode 13 is less likely to react and dissolve with respect to the strongly alkaline electrolytic solution 14, so that the electrolytic solution 14 is less likely to deteriorate and decompose.
  • the negative electrode current collector 13A when only one of the negative electrode current collector 13A and the negative electrode active material layer 13B has a specific metal material on the surface, the negative electrode current collector 13A has the specific metal material on the surface. It is more preferable to have a material containing titanium as a constituent element on the surface. Since the negative electrode current collector 13A has a high affinity for the negative electrode active material (titanium-containing compound described later), the negative electrode active material layer 13B easily adheres stably to the negative electrode current collector 13A and its negative electrode. This is because the charge / discharge reaction tends to proceed stably in the active material layer 13B.
  • the surface of one or both of the negative electrode current collector 13A and the negative electrode active material layer 13B may be coated with a specific metal material.
  • the surfaces of one or both of the negative electrode current collector 13A and the negative electrode active material layer 13B may be plated with a specific metal material.
  • one or both of the negative electrode current collector 13A and the negative electrode active material layer 13B may further contain a non-specific metal material as long as it has a specific metal material on the surface, or the non-specific metal material thereof may be further contained. It may contain materials other than metallic materials.
  • the negative electrode current collector 13A supports the negative electrode active material layer 13B, and contains any one or more of the conductive materials.
  • the conductive material is a metal material, a carbon material, a conductive ceramic material, etc., and specific examples of the metal material include stainless steel (SUS), titanium, zinc, tin, lead, and two or more kinds of alloys thereof. Is.
  • connection terminal portion 13AT is not formed on a part of the negative electrode current collector 13A (connection terminal portion 13AT), and the connection terminal portion 13AT is led out to the outside of the exterior member 11.
  • the lead-out direction of the connection terminal portion 13AT is not particularly limited, but specifically, it is the same as the lead-out direction of the connection terminal portion 12AT.
  • the negative electrode active material layer 13B contains any one or more of the negative electrode active materials that occlude and release lithium ions. However, the negative electrode active material layer 13B may further contain a negative electrode binder, a negative electrode conductive agent, and the like.
  • the details regarding the negative electrode binder are the same as the details regarding the positive electrode binder, and the details regarding the negative electrode conductive agent are the same as the details regarding the positive electrode conductive agent.
  • the negative electrode conductive agent is a metal material, it is preferable that the metal material has the above-mentioned specific metal material on the surface.
  • the negative electrode active material contains any one or more of the titanium-containing compounds. This is because even when the strongly alkaline electrolytic solution 14 is used, the charge / discharge reaction can easily proceed smoothly and stably. It is preferable that the negative electrode active material has the above-mentioned specific metal material on the surface.
  • This titanium-containing compound is a general term for compounds containing titanium as a constituent element, and specifically, it is a titanium oxide, a lithium titanium composite oxide, a titanium phosphorus oxide, a lithium titanium phosphoric acid compound, a hydrogen titanium compound, or the like. ..
  • Titanium oxide is a compound represented by the formula (1) (so-called titanium oxide), that is, bronze-type titanium oxide or the like.
  • This titanium oxide is one or more of anatase-type, rutile-type and brookite-type titanium oxide (TiO 2 ).
  • the titanium oxide may be a composite oxide containing one or more of phosphorus, vanadium, tin, copper, nickel, iron, cobalt and the like as constituent elements together with titanium.
  • Specific examples of this composite oxide include TIM 2 -P 2 O 5 , TiO 2 -V 2 O 5 , TiO 2 -P 2 O 5 -SnO 2 , and TIM 2 -P 2 O 5 -MeO.
  • Me is any one or more of Cu, Ni, Fe, Co and the like.
  • the titanium oxide is preferably anatase-type titanium oxide. This is because the anatase-type titanium oxide is stable with respect to the strongly alkaline electrolytic solution 14, so that the lithium ion secondary battery operates (charges / discharges) stably.
  • the lithium titanium composite oxide is any one or more of the compounds represented by the formulas (2) to (4), that is, rams delight type lithium titanate and the like.
  • M1 represented by the formula (2) is a metal element that can be a divalent ion.
  • M2 represented by the formula (3) is a metal element that can be a trivalent ion.
  • M3 represented by the formula (4) is a metal element that can be a tetravalent ion.
  • M1 is at least one of Mg, Ca, Cu, Zn and Sr. X satisfies 0 ⁇ x ⁇ 1/3.
  • Specific examples of the compound represented by the formula (2) are Li 3.75 Ti 4.875 Mg 0.375 O 12 and the like.
  • Specific examples of the compound represented by the formula (3) are LiCrTiO 4 and the like.
  • Specific examples of the compound represented by the formula (4) are Li 4 Ti 5 O 12 and Li 4 Ti 4.95 Nb 0.05 O 12 .
  • titanium phosphate oxide are titanium phosphate (TiP 2 O 7 ) and the like.
  • lithium-titanium phosphoric acid compound include LiTi 2 (PO 4 ) 3 .
  • titanium hydrogen hydrogen compound include H 2 Ti 3 O 7 (3TIO 2.1H 2 O), H 6 Ti 12 O 27 (3TIO 2 ⁇ 0.75H 2 O), and H 2 Ti 6 O 13 ( 3TIO 2 ⁇ ). 0.5H 2 O), H 2 Ti 7 O 15 (3TIO 2 ⁇ 0.43H 2 O) and H 2 Ti 12 O 25 (3Tio 2 ⁇ 0.25H 2 O).
  • the titanium-containing compound is preferably one or both of a titanium oxide and a lithium titanium composite oxide, and more preferably a titanium oxide. This is because the charge / discharge reaction proceeds sufficiently even when the strongly alkaline electrolytic solution 14 is used.
  • the negative electrode active material may further contain any one or more of the other compounds that do not contain titanium as a constituent element, in addition to the above-mentioned titanium-containing compound.
  • the types of other compounds are not particularly limited, but alkali metal titanium composite oxides (however, excluding the above-mentioned lithium titanium composite oxides) and alkali metal titanium phosphate compounds (however, the above-mentioned lithium titanium composite oxides are used. Excludes), niobium-containing compounds, vanadium-containing compounds, iron-containing compounds, molybdenum-containing compounds, etc.
  • the niobium-containing compound is a lithium niobium composite oxide, a hydrogen niobium compound, a titanium niobium composite oxide, or the like.
  • the material corresponding to the niobium-containing compound is excluded from the titanium-containing compound.
  • Specific examples of the lithium niobium composite oxide include LiNbO 2 .
  • Specific examples of the hydrogen niobium compound are H 4 Nb 6 O 17 and the like.
  • Specific examples of the titanium niobium composite oxide include TiNb 2 O 7 and Ti 2 Nb 10 O 29 .
  • lithium may be intercalated in the titanium-niobium composite oxide.
  • Vanadium-containing compounds include vanadium oxides and alkali metal vanadium composite oxides. However, the material corresponding to the vanadium-containing compound is excluded from each of the titanium-containing compound and the niobium-containing compound. Specific examples of vanadium oxide are vanadium dioxide (VO 2 ) and the like. Specific examples of the lithium vanadium composite oxide, which is an alkali metal vanadium composite oxide, are LiV 2 O 4 and LiV 3 O 8 .
  • the iron-containing compound is iron hydroxide or the like. However, the material corresponding to the iron-containing compound is excluded from each of the titanium-containing compound, the niobium-containing compound and the vanadium-containing compound.
  • Specific examples of iron hydroxide are iron oxyhydroxide (FeOOH) and the like.
  • the iron oxyhydroxide may be ⁇ -iron oxyhydroxide, ⁇ -iron oxyhydroxide, ⁇ -iron oxyhydroxide, ⁇ -iron oxyhydroxide, or any of them. Any two or more of them may be used.
  • Molybdenum-containing compounds include molybdenum oxides and cobalt molybdenum composite oxides. However, the material corresponding to the molybdenum-containing compound is excluded from each of the titanium-containing compound, niobium-containing compound, vanadium-containing compound and iron-containing compound. Specific examples of the molybdenum oxide are molybdenum dioxide (MoO 2 ) and the like. Specific examples of the cobalt molybdenum composite oxide are CoMoO 4 and the like.
  • the negative electrode 13 may or may not contain a carbon material.
  • the case where the negative electrode 13 described here contains a carbon material means that the negative electrode current collector 13A contains carbon as a constituent element, the negative electrode current collector 13A contains a carbon coating layer, and the negative electrode activity.
  • the carbon coating layer may cover the entire surface of the negative electrode current collector 13A, or may cover only a part of the surface of the negative electrode current collector 13A. In the latter case, a plurality of carbon coating layers separated from each other may cover the surface of the negative electrode current collector 13A.
  • the details regarding the coverage range of the carbon coating layer described here are related to the case where the carbon coating layer covers the surface of the negative electrode active material layer 13B and the case where the carbon coating layer covers the surface of the negative electrode active material layer. Is the same.
  • the negative electrode 13 does not contain a carbon material. This is because the hydrogen overvoltage of the carbon material is low, and if the negative electrode 13 contains the carbon material, the aqueous solvent in the electrolytic solution 14 is likely to be decomposed on the surface of the negative electrode 13. Therefore, in order to suppress the decomposition reaction of the aqueous solvent, it is preferable that the negative electrode 13 does not contain a carbon material.
  • the content of the carbon material in the negative electrode 13 is preferably as small as possible.
  • the ratio of the weight of the carbon material to the weight of the negative electrode 13 is preferably less than 0.1% by weight. This is because the aqueous solvent is less likely to decompose on the surface of the negative electrode 13.
  • the value of the carbon ratio C is a value rounded off to the second decimal place.
  • the electrolytic solution 14 is housed in the internal space S, and is an aqueous electrolytic solution containing an aqueous solvent as described above. That is, the electrolytic solution 14 is a solution in which an ionizable substance that can be ionized is dissolved or dispersed in an aqueous solvent.
  • the electrolytic solution 14 contains one or more of the ionic substances that can be ionized in the aqueous solvent together with the aqueous solvent. More specifically, the electrolytic solution 14 contains lithium ions that are occluded and released in each of the positive electrode 12 and the negative electrode 13.
  • the type of the aqueous solvent is not particularly limited, but specifically, pure water or the like.
  • the type of the ionic substance is not particularly limited, but specifically, any one or two or more of acids, bases, electrolyte salts and the like.
  • Specific examples of the acid include carbonic acid, oxalic acid, nitric acid, sulfuric acid, hydrochloric acid, acetic acid and citric acid.
  • the electrolyte salt is a salt containing cations and anions, and more specifically, any one or more of lithium salts.
  • the lithium salt include lithium carbonate, lithium oxalate, lithium nitrate, lithium sulfate, lithium chloride, lithium acetate, lithium citrate, lithium hydroxide and imide salt.
  • the imide salt includes bis (fluorosulfonyl) imide lithium and bis (trifluoromethanesulfonyl) imide lithium.
  • the electrolytic solution 14 has a pH of 11 or more as described above, and therefore has a strong alkalinity. This is because the lithium ions easily move in the electrolytic solution 14, so that the charge / discharge reaction easily proceeds.
  • This pH value is a value rounded off to the first decimal place, and the definition of the pH value described here is the same thereafter.
  • the electrolyte salt is lithium hydroxide or the like. This is because the pH of the electrolytic solution 14 tends to be 11 or higher, so that the strongly alkaline electrolytic solution 14 can be easily and stably realized.
  • the content of the ionic substance, that is, the concentration (mol / kg) of the electrolytic solution 14 is not particularly limited and can be set arbitrarily. Specifically, the concentration of the electrolytic solution 14 is preferably 0.2 mol / kg to 4 mol / kg. This is because the strongly alkaline electrolytic solution 14 is easily and stably realized.
  • the electrolyte salt may further contain any one or more of the other metal salts in addition to the above-mentioned lithium salt.
  • the types of other metal salts are not particularly limited, and specific examples thereof include alkali metal salts (excluding lithium salts), alkaline earth metal salts, and transition metal salts. Specific examples of alkali metal salts include sodium salts and potassium salts. Specific examples of alkaline earth metal salts include calcium salts and magnesium salts.
  • the electrolytic solution 14 is a saturated solution of the electrolyte salt. This is because lithium ions are likely to be stably stored and discharged during charging / discharging, so that the charging / discharging reaction is likely to proceed stably.
  • the electrolytic solution 14 is a saturated solution of the electrolyte salt
  • the internal space S is the surface of the positive electrode 12 and the inner wall surface of the exterior member 11 in the electrolytic solution 14. Since the electrolyte salt is precipitated, when the electrolyte solution 14 (liquid) and the electrolyte salt precipitate (solid) coexist in the internal space S, the electrolyte solution 14 is a saturated solution of the electrolyte salt. it is conceivable that.
  • a surface analysis method such as X-ray photoelectron spectroscopy (XPS) can be used, and a composition analysis method such as inductively coupled plasma (ICP) emission spectroscopy can be used. be able to.
  • XPS X-ray photoelectron spectroscopy
  • ICP inductively coupled plasma
  • [Element ratio A] Specifically, when the surfaces of the negative electrode active material layer 13B and the negative electrode current collector 13A were analyzed using XPS, the ratio of the detected amount of the second element group to the detected amount of the first element group (element ratio A). (Atomic%)) is 99 atomic% or more.
  • the first element group is a series of metal elements that can be constituent elements of the negative electrode current collector 13A and the negative electrode active material layer 13B, and more specifically, as described above, has a long periodic period. All metal elements (including lithium) belonging to Group 1 to Group 17 in the table. Therefore, the detected amount of the first element group is the sum of the detected amounts of all the metal elements.
  • the second element group includes a series of metal elements constituting the above-mentioned specific metal material and lithium among a series of elements that can be constituent elements of the negative electrode current collector 13A and the negative electrode active material layer 13B.
  • this series of metal elements is one or more of titanium, tin, zirconium, bismuth and indium.
  • the detected amount of the second element group is the sum of the detected amounts of any one or more of titanium, tin, zirconium, bismuth and indium, and the detected amount of lithium.
  • the value of the element ratio A is a value rounded off to the first decimal place.
  • lithium is contained in both the first element group and the second element group because lithium ions are stored in the negative electrode 13 in the lithium ion secondary battery, so XPS is used in the negative electrode active material layer 13B. This is because lithium can be detected when the surface is analyzed, and lithium can be detected when the surface of the negative electrode current collector 13A is analyzed using XPS.
  • the element ratio A is an average value calculated based on the surface analysis result of the negative electrode 13 using XPS as described above.
  • the element ratio A is the average value of the 10 element ratios A calculated at each of the above 10 locations.
  • the negative electrode 13 includes the negative electrode current collector 13A and the negative electrode active material layer 13B.
  • the element ratio A is calculated by the procedure described below.
  • any nine points on the surface of the negative electrode active material layer 13B are analyzed.
  • Any one point on the surface of the negative electrode current collector 13A is analyzed.
  • Arbitrary 9 locations on the surface of the negative electrode active material layer 13B are 9 locations sufficiently separated from each other on the surface of the negative electrode active material layer 13B. Further, any one place on the surface of the negative electrode current collector 13A is a portion of the negative electrode current collector 13A where the negative electrode active material layer 13B is not formed (connection terminal portion 13AT or the like).
  • the element ratio A is 9 element ratios A calculated at 9 points in the negative electrode active material layer 13B and 1 element ratio A calculated at 1 place in the negative electrode current collector 13A. It is an average value of 10 element ratios A in total.
  • the element ratio A of 99 atomic% or more is the abundance of metal elements constituting the specific metal material with respect to the constituent materials (constituent elements) on the surface of the negative electrode 13 (negative electrode current collector 13A and negative electrode active material layer 13B). Is sufficiently large with respect to the abundance of metal elements constituting the non-characteristic metal material.
  • the constituent atoms of the negative electrode 13 are less likely to elute into the strongly alkaline electrolytic solution 14, so that the electrolytic solution 14 is less likely to deteriorate and decompose. Therefore, even if the strongly alkaline electrolytic solution 14 is used, the charge / discharge reaction is likely to proceed stably, and the discharge capacity is less likely to decrease even if the charge / discharge is repeated.
  • analysis software When calculating the element ratio A based on the surface analysis results of the negative electrode active material layer 13B and the negative electrode current collector 13A using XPS, commercially available analysis software may be used.
  • the type of analysis software is not particularly limited, but specifically, there is a SpecSurf manufactured by JEOL Ltd., which calculates the atomic fraction based on the peak area of the XPS spectrum for each constituent element.
  • the third element group is titanium and lithium among a series of metal elements constituting the above-mentioned specific metal material. Therefore, the detected amount of the third element group is the sum of the detected amount of titanium and the detected amount of lithium.
  • the value of the element ratio B is a value rounded off to the first decimal place.
  • the element ratio B is an average value calculated based on the surface analysis results of the negative electrode 13 (negative electrode current collector 13A and negative electrode active material layer 13B) using XPS, similarly to the element ratio A described above.
  • the reason why the element ratio B is 99 atomic% or more is that the constituent atoms of the negative electrode 13 are less likely to be eluted by the strongly alkaline electrolytic solution 14, so that the electrolytic solution 14 is less likely to be deteriorated and decomposed. Therefore, even if the strongly alkaline electrolytic solution 14 is used, the charge / discharge reaction can proceed more stably, and even if the charge / discharge is repeated, the discharge capacity is less likely to decrease.
  • the procedure is the same as the above-mentioned procedure for calculating the element ratio A.
  • each of the positive electrode 12 and the negative electrode 13 is prepared and the electrolytic solution 14 is prepared, and then the lithium ion secondary battery is manufactured.
  • the positive electrode active material, the positive electrode binder and the positive electrode conductive agent are mixed with each other to obtain a positive electrode mixture.
  • the positive electrode mixture is added to the solvent to prepare a paste-like positive electrode mixture slurry.
  • This solvent may be an aqueous solvent or an organic solvent.
  • the positive electrode mixture slurry is applied to both sides of the positive electrode current collector 12A (excluding the connection terminal portion 12AT), and then the positive electrode mixture slurry is dried to form the positive electrode active material layer 12B.
  • the positive electrode active material layer 12B may be compression-molded using a roll press machine or the like. In this case, the positive electrode active material layer 12B may be heated, or compression molding may be repeated a plurality of times. As a result, the positive electrode 12 is manufactured.
  • the negative electrode active material layers 13B are formed on both sides of the negative electrode current collector 13A by the same procedure as the procedure for manufacturing the positive electrode 12 described above. Specifically, the negative electrode binder and the negative electrode conductive agent are mixed with the negative electrode active material containing the titanium-containing compound to form a negative electrode mixture, and then the negative electrode mixture is added to the solvent to form a paste. Prepare a negative electrode mixture slurry. Subsequently, the negative electrode mixture slurry is applied to both sides of the negative electrode current collector 13A (excluding the connection terminal portion 13AT), and then the negative electrode mixture slurry is dried to form the negative electrode active material layer 13B. After that, the negative electrode active material layer 13B may be compression-molded. As a result, the negative electrode 13 is manufactured.
  • the positive electrode 12 and the negative electrode 13 are housed in the internal space S of the exterior member 11.
  • the connection terminal portions 12AT and 13AT are led out to the outside of the exterior member 11.
  • the electrolytic solution 14 is supplied to the internal space S from the injection hole (not shown) communicated with the internal space S. As a result, the electrolytic solution 14 is filled in the internal space S. After that, the injection hole is sealed.
  • electrolytic solution 14 is housed in the internal space S in which each of the positive electrode 12 and the negative electrode 13 is housed, a lithium ion secondary battery using one type of aqueous electrolytic solution (electrolyte solution 14) is completed.
  • the negative electrode active material of the negative electrode 13 contains a titanium-containing compound
  • the electrolytic solution 14 containing an aqueous solvent has a pH of 11 or more
  • the element ratio A is 99 atoms. % Or more.
  • the constituent atoms of the negative electrode 13 are less likely to elute into the strongly alkaline electrolytic solution 14, so that the electrolytic solution 14 deteriorates and decomposes. It becomes difficult to do.
  • the strongly alkaline electrolytic solution 14 is used together with the negative electrode 13 containing the titanium-containing compound, the charge / discharge reaction is likely to proceed stably, and the discharge capacity is less likely to decrease even if the charge / discharge is repeated. Therefore, excellent charge / discharge characteristics can be obtained.
  • the constituent atoms of the negative electrode 13 are less likely to be eluted by the strongly alkaline electrolytic solution 14, so that a higher effect can be obtained.
  • the electrolytic solution 14 is less likely to be deteriorated and decomposed, so that a higher effect can be obtained.
  • the concentration of the electrolytic solution 14 is 0.2 mol / kg to 4 mol / kg, the strongly alkaline electrolytic solution 14 is easily and stably realized, so that a higher effect can be obtained.
  • the titanium-containing compound contains one or both of the titanium oxide and the lithium-titanium composite oxide, the charge / discharge reaction proceeds sufficiently even if the strongly alkaline electrolytic solution 14 is used, so that the effect is higher. Can be obtained.
  • the titanium oxide contains anatase-type titanium oxide, a high voltage can be obtained, so that a higher effect can be obtained.
  • the negative electrode 13 contains the negative electrode active material layer 13B and the surface of the negative electrode active material layer 13B is analyzed using XPS, the constituent atoms of the negative electrode active material layer 13B become the strongly alkaline electrolytic solution 14. Since it is difficult to sufficiently elute, a higher effect can be obtained.
  • the negative electrode 13 further contains the negative electrode current collector 13A and the surfaces of the negative electrode active material layer 13B and the negative electrode current collector 13A are analyzed using XPS, the negative electrode active material layer is analyzed. Since not only the constituent atoms of 13B but also the constituent atoms of the negative electrode current collector 13A are less likely to be eluted in the strongly alkaline electrolytic solution 14, a higher effect can be obtained.
  • FIG. 2 shows a cross-sectional configuration of the lithium ion secondary battery of the second embodiment.
  • the lithium ion secondary battery of the second embodiment has the same configuration as the above-mentioned configuration of the lithium ion secondary battery of the first embodiment (FIG. 1), except as described below.
  • this lithium ion secondary battery is newly provided with a partition wall 15, and is provided with a positive electrode electrolytic solution 16 and a negative electrode electrolytic solution 17 instead of the electrolytic solution 14.
  • the positive electrode electrolytic solution 16 is lightly shaded, and the negative electrode electrolytic solution 17 is darkly shaded.
  • the exterior member 11 has two spaces (positive electrode chamber S1 which is a positive electrode space and negative electrode chamber S2 which is a negative electrode space) separated by a partition wall 15.
  • the partition wall 15 is arranged between the positive electrode 12 and the negative electrode 13, and the internal space of the exterior member 11 is separated into the positive electrode chamber S1 and the negative electrode chamber S2. As a result, the positive electrode 12 and the negative electrode 13 are separated from each other via the partition wall 15 and face each other via the partition wall 15.
  • the partition wall 15 is a substance (excluding anions) such as lithium ions (cations) that are occluded and released in each of the positive electrode 12 and the negative electrode 13 without allowing anions to permeate between the positive electrode chamber S1 and the negative electrode chamber S2. To be transparent. This is because the mixing of the positive electrode electrolytic solution 16 and the negative electrode electrolytic solution 17 is prevented. That is, the partition wall 15 allows lithium ions to permeate from the positive electrode chamber S1 toward the negative electrode chamber S2, and also allows lithium ions to permeate from the negative electrode chamber S2 toward the positive electrode chamber S1.
  • the partition wall 15 contains one or both of an ion exchange membrane and a solid electrolyte membrane.
  • the ion exchange membrane is a porous membrane (cation exchange membrane) capable of transmitting lithium ions.
  • the solid electrolyte membrane has the conductivity of lithium ions. This is because the permeability of lithium ions is improved in the partition wall 15.
  • the partition wall 15 contains an ion exchange membrane rather than a solid electrolyte membrane. This is because each of the aqueous solvent in the positive electrode electrolytic solution 16 and the aqueous solvent in the negative electrode electrolytic solution 17 easily permeates the inside of the partition wall 15, so that the lithium ion conductivity is improved inside the partition wall 15.
  • the positive electrode 12 is arranged inside the positive electrode chamber S1 to occlude and release lithium ions
  • the negative electrode 13 is arranged inside the negative electrode chamber S2 to occlude and release lithium ions.
  • the negative electrode 13 contains a titanium-containing compound as the negative electrode active material.
  • Each of the positive electrode electrolytic solution 16 and the negative electrode electrolytic solution 17 is an aqueous electrolytic solution containing an aqueous solvent.
  • the positive electrode electrolyte 16 is housed inside the positive electrode chamber S1
  • the negative electrode electrolyte 17 is housed inside the negative electrode chamber S2. Therefore, the positive electrode electrolytic solution 16 and the negative electrode electrolytic solution 17 are separated from each other via the partition wall 15 so as not to be mixed with each other.
  • the positive electrode electrolyte 16 is housed inside the positive electrode chamber S1, it is in contact with the positive electrode 12 without being in contact with the negative electrode 13.
  • the negative electrode electrolytic solution 17 is housed inside the negative electrode chamber S2, it is in contact with the negative electrode 13 without being in contact with the positive electrode 12.
  • the pH of the positive electrode electrolyte 16 and the pH of the negative electrode electrolyte 17 are different from each other.
  • the negative electrode electrolytic solution 17 in contact with the negative electrode 13 has a pH of 11 or more, similar to the electrolytic solution 14 in the first embodiment.
  • the positive electrode electrolytic solution 16 in contact with the positive electrode 12 has a pH of less than 11.
  • the composition of each of the positive electrode electrolytic solution 16 and the negative electrode electrolytic solution 17 (type of aqueous solvent, type and concentration of ionic substance, etc.) can be arbitrarily set.
  • the positive electrode electrolyte 16 has a pH of less than 11, and the negative electrode electrolyte 17 has a pH of 11 or more, as compared with the case where the pH of both is equal to each other. This is because the decomposition potential of the aqueous solvent shifts due to the difference in pH. As a result, the potential window of the aqueous solvent is expanded while the decomposition reaction of the aqueous solvent is thermodynamically suppressed during charging and discharging. Therefore, while a high voltage is obtained, the charge / discharge reaction utilizing the occlusion / discharge of lithium ions proceeds sufficiently and stably.
  • composition formula (type of electrolyte salt) of the negative electrode electrolyte 17 is different from the composition formula (type of electrolyte salt) of the positive electrode electrolyte 16. This is because the above-mentioned magnitude relationship regarding pH is easily satisfied.
  • the pH values of the positive electrode electrolyte 16 and the negative electrode electrolyte 17 are not particularly limited.
  • the pH of the negative electrode electrolyte 17 is preferably 12 or more, and more preferably 13 or more. This is because the pH of the negative electrode electrolytic solution 17 becomes sufficiently high, so that the above-mentioned magnitude relationship regarding pH can be easily satisfied. Further, since the difference between the pH of the positive electrode electrolytic solution 16 and the pH of the negative electrode electrolytic solution 17 becomes sufficiently large, it becomes easy to maintain the magnitude relationship between the pH of both.
  • the pH of the positive electrode electrolyte 16 is preferably 3 to 8, more preferably 4 to 8, and even more preferably 4 to 6. This is because the difference between the pH of the positive electrode electrolyte 16 and the pH of the negative electrode electrolyte 17 becomes sufficiently large, so that the magnitude relationship between the pH of both can be easily maintained. Further, since the exterior member 11 is less likely to be corroded and the battery components such as the positive electrode current collector 12A and the negative electrode current collector 13A are less likely to be corroded, the electrochemical durability (stability) of the lithium ion secondary battery is increased. Is improved.
  • one or both of the positive electrode electrolyte 16 and the negative electrode electrolyte 17 is preferably a saturated solution of the electrolyte salt (lithium salt), as in the electrolyte 14 of the first embodiment.
  • the charge / discharge reaction lithium ion occlusion / discharge reaction
  • the method of confirming whether or not each of the positive electrode electrolytic solution 16 and the negative electrode electrolytic solution 17 is a saturated solution of a lithium salt is the same as the method of confirming whether or not the electrolytic solution 14 is a saturated solution of a lithium salt. ..
  • the physical properties of the negative electrode 13 are optimized in order to obtain excellent charge / discharge characteristics, as in the case of the lithium ion secondary battery of the first embodiment described above. That is, the element ratio A when the surfaces of the negative electrode active material layer 13B and the negative electrode current collector 13A are analyzed using XPS is 99 atomic% or more. In this case, the element ratio B is preferably 99 atomic% or more.
  • the procedure for manufacturing the lithium ion secondary battery is the same as the procedure for manufacturing the lithium ion secondary battery in the first embodiment described above, except that the procedure will be described below.
  • the pH of the positive electrode electrolyte 16 is set to less than 11 and the pH of the negative electrode electrolyte 17 is set to 11 or more by adjusting conditions such as the type and concentration (mol / kg) of the ionic substance. ..
  • an exterior member 11 (positive electrode chamber S1 and negative electrode chamber S2) to which a partition wall 15 is attached is prepared in advance.
  • the positive electrode 12 is housed inside the positive electrode chamber S1 and the connection terminal portion 12AT is led out to the outside of the positive electrode chamber S1.
  • the negative electrode 13 is housed inside the negative electrode chamber S2, and the connection terminal portion 13AT is led out to the outside of the negative electrode chamber S2.
  • the positive electrode electrolytic solution 16 is supplied to the inside of the positive electrode chamber S1 from the positive electrode injection hole (not shown) communicated with the positive electrode chamber S1, and the negative electrode injection hole (not shown) communicated with the negative electrode chamber S2.
  • the negative electrode electrolytic solution 17 is supplied to the inside of the negative electrode chamber S2. After that, each of the positive electrode injection hole and the negative electrode injection hole is sealed. As a result, the positive electrode electrolytic solution 16 is housed inside the positive electrode chamber S1 in which the positive electrode 12 is arranged, and the negative electrode electrolytic solution 17 is housed inside the negative electrode chamber S2 in which the negative electrode 13 is arranged. Therefore, a lithium ion secondary battery using two types of aqueous electrolytic solutions (positive electrode electrolytic solution 16 and negative electrode electrolytic solution 17) is completed.
  • the negative electrode active material of the negative electrode 13 contains a titanium-containing compound
  • the positive electrode electrolytic solution 16 containing an aqueous solvent has a pH of less than 11
  • the negative electrode containing an aqueous solvent has a pH of less than 11
  • the negative electrode containing an aqueous solvent has a pH of 11 or more
  • the element ratio A is 99 atomic% or more. Therefore, excellent charge / discharge characteristics can be obtained for the same reason as that of the lithium ion secondary battery of the first embodiment described above.
  • the other actions and effects of the lithium ion secondary battery are the same as the other actions and effects of the lithium ion secondary battery in the first embodiment.
  • the negative electrode 13 includes the negative electrode current collector 13A together with the negative electrode active material layer 13B.
  • the negative electrode 13 does not include the negative electrode current collector 13A (excluding the connection terminal portion 13AT), it may include only the negative electrode active material layer 13B.
  • the element ratio A is calculated by analyzing any 10 points on the surface of the negative electrode active material layer 13B.
  • the negative electrode active material layer 13B is formed by using the coating method. That is, in the step of forming the negative electrode active material layer 13B, a paste-like negative electrode mixture slurry containing a negative electrode binder and a negative electrode conductive agent together with a negative electrode active material containing a titanium-containing compound is applied to both surfaces of the negative electrode current collector 13A. , The negative electrode mixture slurry is dried.
  • the negative electrode active material layer 13B may be formed by using a sintering method instead of the coating method. That is, in the step of forming the negative electrode active material layer 13B, the negative electrode mixture slurry may be applied, the negative electrode mixture slurry may be dried, and then the negative electrode mixture slurry may be fired at a high temperature. As a result, the negative electrode active material in the negative electrode mixture slurry is sintered, so that the negative electrode active material layer 13B is formed.
  • a negative electrode active material containing a titanium-containing compound and polyethylene oxide which is a negative electrode binder
  • a negative electrode mixture is added to the solvent to form a paste.
  • the negative electrode mixture slurry is calcined in an oxygen atmosphere.
  • the firing temperature is not particularly limited, but specifically, it is 500 ° C. to 1200 ° C. Since the firing time is not particularly limited, it can be set arbitrarily.
  • the negative electrode active material in the negative electrode mixture slurry is sintered, and the negative electrode active material is fixed to the surface of the negative electrode current collector 13A, so that the negative electrode active material layer 13B is formed.
  • the negative electrode active material layer 13B is formed by the sintering method, it is not necessary to contain one or both of the negative electrode binder and the negative electrode conductive agent in the negative electrode mixture slurry.
  • the negative electrode active material is sintered, so that the negative electrode active material is fixed to the negative electrode current collector 13A without using the negative electrode binder, and the negative electrode conductive material is not used. This is because the electrical conductivity of the negative electrode active material layer 13B is ensured.
  • the lithium ion secondary battery further includes a separator 20, which is interposed between the electrolyte layers 18 and 19.
  • the electrolyte layer 18 is arranged between the positive electrode 12 and the separator 20, and the electrolyte layer 19 is arranged between the negative electrode 13 and the separator 20. That is, the electrolyte layer 18 is adjacent to each of the positive electrode 12 and the separator 20, and the electrolyte layer 19 is adjacent to each of the negative electrode 13 and the separator 20.
  • each of the electrolyte layers 18 and 19 contains a polymer compound together with the electrolytic solution 14, and the electrolytic solution 14 is held by the polymer compound.
  • the type of the polymer compound is not particularly limited, but specifically, any one or more of polyvinylidene fluoride, polyethylene oxide and the like.
  • each of the electrolyte layers 18 and 19 is lightly shaded.
  • the separator 20 is an insulating porous film that allows lithium ions to permeate while separating the electrolyte layers 18 and 19 from each other, and contains a polymer compound such as polyethylene.
  • a sol-like precursor solution is prepared by mixing the solvent together with the electrolyte solution 14 and the polymer compound, and then the precursor solution is applied to the surface of the positive electrode 12.
  • the procedure for forming the electrolyte layer 19 is the same as the procedure for forming the electrolyte layer 18 except that the precursor solution is applied to the surface of the negative electrode 13.
  • the electrolyte layer 21 is arranged between the positive electrode 12 and the partition wall 15, and the electrolyte layer 22 is arranged between the negative electrode 13 and the partition wall 15. That is, the electrolyte layer 21 is adjacent to each of the positive electrode 12 and the partition wall 15, and the electrolyte layer 22 is adjacent to each of the negative electrode 13 and the partition wall 15.
  • the electrolyte layer 21 contains a polymer compound together with the positive electrode electrolytic solution 16, and the positive electrode electrolytic solution 16 is held by the polymer compound.
  • the electrolyte layer 22 contains a polymer compound together with the negative electrode electrolyte 17, and the negative electrode electrolyte 17 is held by the polymer compound. Details regarding the types of polymer compounds are as described above. In FIG. 4, the electrolyte layer 21 containing the positive electrode electrolyte 16 is lightly shaded, and the electrolyte layer 22 containing the negative electrode electrolyte 17 is heavily shaded.
  • a sol-like precursor solution is prepared by mixing the solvent together with the positive electrode electrolyte 16 and the polymer compound, and then the precursor solution is applied to the surface of the positive electrode 12.
  • a sol-like precursor solution is prepared by mixing the solvent together with the negative electrode electrolyte 17 and the polymer compound, and then the precursor solution is applied to the surface of the negative electrode 13.
  • the application (application example) of the lithium ion secondary battery is not particularly limited.
  • the lithium ion secondary battery used as a power source may be a main power source for electronic devices and electric vehicles, or may be an auxiliary power source.
  • the main power source is a power source that is preferentially used regardless of the presence or absence of another power source.
  • the auxiliary power supply is a power supply used in place of the main power supply or a power supply that can be switched from the main power supply.
  • lithium-ion secondary batteries Specific examples of applications for lithium-ion secondary batteries are as follows. Electronic devices such as video cameras, digital still cameras, mobile phones, laptop computers, headphone stereos, portable radios and portable information terminals. A storage device such as a backup power supply and a memory card. Power tools such as electric drills and saws. It is a battery pack installed in electronic devices. Medical electronic devices such as pacemakers and hearing aids. It is an electric vehicle such as an electric vehicle (including a hybrid vehicle). It is a power storage system such as a household or industrial battery system that stores power in case of an emergency. In these applications, one lithium ion secondary battery may be used, or a plurality of lithium ion secondary batteries may be used.
  • the battery pack may use a single battery or an assembled battery.
  • the electric vehicle is a vehicle that operates (runs) using a lithium ion secondary battery as a driving power source, and may be a hybrid vehicle that also has a drive source other than the lithium ion secondary battery.
  • household electric products and the like can be used by using the power stored in a lithium ion secondary battery which is a power storage source.
  • the use of the lithium ion secondary battery may be other than the series of uses exemplified here.
  • a lithium ion secondary battery using one kind of water-based electrolytic solution (electrolyte solution 14) shown in FIG. 1 was manufactured by the following procedure.
  • the negative electrode active material layer 13B was formed by using the coating method.
  • 89 parts by mass of the negative electrode active material (titanium-containing compound) and 11 parts by mass of the negative electrode binder (polyvinylidene fluoride) were mixed with each other to obtain a negative electrode mixture.
  • 89 parts by mass of the negative electrode active material (titanium-containing compound), 10 parts by mass of the negative electrode binder (polyvinylidene fluoride), and 1 part by mass of the negative electrode conductive agent (carbon black (CB) which is a carbon material) are mixed with each other. The mixture was made into a negative electrode mixture.
  • Titanium-containing compounds include anatase-type titanium oxide (TIM 2 ), which is a titanium oxide, lithium-titanium composite oxide (Li 4 Ti 5 O 12 (LTO)), and a carbon layer (carbon), which is a carbon material.
  • TIM 2 anatase-type titanium oxide
  • Li 4 Ti 5 O 12 LTO
  • carbon carbon
  • a negative electrode mixture was added to a solvent (N-methyl-2-pyrrolidone which is an organic solvent), and then the solvent was stirred to prepare a paste-like negative electrode mixture slurry.
  • the negative electrode active material layer 13B was formed. As a result, the negative electrode 13 was manufactured.
  • Example 6 the negative electrode active material layer 13B was formed by using the sintering method.
  • the negative electrode active material anatase-type titanium oxide which is a titanium-containing compound
  • 11 parts by mass of the negative electrode binder polyethylene oxide
  • a surfactant was added to the solvent (pure water which is an aqueous solvent) together with the negative electrode mixture, and then the solvent was stirred to prepare a paste-like negative electrode mixture slurry.
  • the carbon ratio C (% by weight) with respect to the negative electrode 13 is as shown in Table 1. Further, after surface analysis of the negative electrode 13 (negative electrode current collector 13A and negative electrode active material layer 13B) using XPS, the element ratios A and B (atomic%) are determined based on the surface analysis results using the above analysis software. As a result of calculation, the results shown in Table 1 were obtained.
  • An ionic substance was added to an aqueous solvent (pure water), and then the aqueous solvent was stirred to prepare an electrolytic solution 14.
  • the types of ionic substances and the concentration (mol / kg) and pH of the electrolytic solution 14 are as shown in Table 1. In this case, the pH of the electrolytic solution 14 was set to 11 or higher.
  • the ionic substance lithium hydroxide (LiOH) and lithium carbonate (Li 2 CO 3 ), which are electrolyte salts (lithium salts), were used.
  • each of the positive electrode 12 and the negative electrode 13 was housed in the internal space S of the exterior member 11 (glass beaker) made of glass.
  • the connection terminal portions 12AT and 13AT were led out to the outside of the exterior member 11.
  • a reference electrode silver-silver chloride electrode
  • the electrolytic solution 14 was supplied to the internal space S. As a result, the electrolytic solution 14 was accommodated in the internal space S, so that the lithium ion secondary battery was completed.
  • a lithium ion secondary battery was manufactured by the same procedure except that an aluminum (Al) foil and a copper (Cu) foil were used as the negative electrode current collector 13A. Further, by using lithium nitrate (LiNO 3 ) as an ionic substance, a lithium ion secondary battery was manufactured by the same procedure except that the pH of the electrolytic solution 14 was set to less than 11. The types of ionic substances and the concentration (mol / kg) and pH of the electrolytic solution 14 are as shown in Table 1.
  • charge / discharge efficiency (%) (discharge capacity / charge capacity) ⁇ 100.
  • the voltage is constantly charged until the voltage reaches ⁇ 1.3 V at a current of 1 C, and the voltage reaches ⁇ 1.0 V at a current of 1 C. After the constant current was discharged to, the constant voltage was discharged until the current reached 0.1 C at the voltage of ⁇ 1.0 V.
  • 1C is a current value that can completely discharge the battery capacity (theoretical capacity) in 1 hour
  • 0.1C is a current value that can completely discharge the battery capacity in 10 hours.
  • the voltage is constantly charged until the voltage reaches -1.65V with a current of 1C, and the voltage reaches -1.35V with a current of 1C. After the constant current was discharged until the current reached 0.1 C, the constant voltage was discharged at the voltage of ⁇ 1.35 V.
  • the pH of the electrolytic solution 14 is 11 or more, it is caused by using a metal material composed of metal elements (Al, Cu) constituting the non-specific metal material as the forming material of the negative electrode current collector 13A.
  • a metal material composed of metal elements (Al, Cu) constituting the non-specific metal material As the forming material of the negative electrode current collector 13A.
  • the element ratio A is less than 99 atomic% (Comparative Examples 1 and 2), the lithium ion secondary battery cannot be charged or discharged, or the lithium ion secondary battery can be charged or discharged. Even so, the charge / discharge efficiency was significantly reduced.
  • the element ratio A is 99 atomic% or more due to the fact that a metal material composed of a metal element (Ti) constituting the specific metal material is used as the forming material of the negative electrode current collector 13A, but the electrolytic solution 14 has an element ratio A of 99 atomic% or more.
  • the pH was less than 11 (Comparative Example 3)
  • the lithium ion secondary battery could not be charged and discharged.
  • the element ratio A is 99 atomic% or more and electrolysis due to the fact that a metal material composed of a metal element (Ti) constituting the specific metal material is used as the forming material of the negative electrode current collector 13A.
  • a metal material composed of a metal element (Ti) constituting the specific metal material is used as the forming material of the negative electrode current collector 13A.
  • the tendency explained below was obtained.
  • the negative electrode active material of the negative electrode 13 contains a titanium-containing compound
  • the electrolytic solution 14 containing an aqueous solvent has a pH of 11 or more
  • the element ratio A is 99 atomic% or more.
  • the lithium ion secondary battery could be charged and discharged, and high charge / discharge efficiency was also obtained. Therefore, excellent charge / discharge characteristics were obtained in the lithium ion secondary battery.
  • the configuration of the lithium ion secondary battery of the present technology has been described above with reference to one embodiment and examples. However, the configuration of the lithium ion secondary battery of the present technology is not limited to the configuration described in one embodiment and the embodiment, and can be variously modified.

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JP2009094034A (ja) * 2007-10-12 2009-04-30 Gs Yuasa Corporation:Kk 水系リチウム二次電池
WO2013137273A1 (ja) * 2012-03-15 2013-09-19 株式会社 東芝 非水電解質二次電池および電池パック
WO2017135323A1 (ja) * 2016-02-01 2017-08-10 株式会社 東芝 二次電池、組電池、電池パック、及び車両
JP6383038B1 (ja) * 2017-03-22 2018-08-29 株式会社東芝 二次電池、電池パック及び車両
JP2019057373A (ja) * 2017-09-20 2019-04-11 株式会社東芝 二次電池、電池パック及び車両

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JP2012123952A (ja) * 2010-12-06 2012-06-28 Iwate Univ 不定比チタン化合物、不定比チタン化合物の金属酸化物被覆複合体、それら化合物の製造方法、及びリチウムイオン二次電池用負極活物質、並びにリチウムイオン二次電池
JP6455807B2 (ja) * 2014-05-19 2019-01-23 Tdk株式会社 リチウムイオン二次電池

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009094034A (ja) * 2007-10-12 2009-04-30 Gs Yuasa Corporation:Kk 水系リチウム二次電池
WO2013137273A1 (ja) * 2012-03-15 2013-09-19 株式会社 東芝 非水電解質二次電池および電池パック
WO2017135323A1 (ja) * 2016-02-01 2017-08-10 株式会社 東芝 二次電池、組電池、電池パック、及び車両
JP6383038B1 (ja) * 2017-03-22 2018-08-29 株式会社東芝 二次電池、電池パック及び車両
JP2019057373A (ja) * 2017-09-20 2019-04-11 株式会社東芝 二次電池、電池パック及び車両

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