WO2023233520A1 - Batterie et bloc-batterie - Google Patents

Batterie et bloc-batterie Download PDF

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Publication number
WO2023233520A1
WO2023233520A1 PCT/JP2022/022123 JP2022022123W WO2023233520A1 WO 2023233520 A1 WO2023233520 A1 WO 2023233520A1 JP 2022022123 W JP2022022123 W JP 2022022123W WO 2023233520 A1 WO2023233520 A1 WO 2023233520A1
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Prior art keywords
positive electrode
battery
active material
electrode active
negative electrode
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PCT/JP2022/022123
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English (en)
Japanese (ja)
Inventor
卓哉 長谷川
孝徳 荻原
夏希 大谷
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株式会社 東芝
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Priority to PCT/JP2022/022123 priority Critical patent/WO2023233520A1/fr
Publication of WO2023233520A1 publication Critical patent/WO2023233520A1/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
    • 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
    • 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
    • H01M4/48—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

Definitions

  • Embodiments of the present invention relate to batteries and battery packs.
  • the problem to be solved by the present invention is to provide a battery and a battery pack that can achieve practical energy density and improve thermal stability.
  • a battery that includes a positive electrode and a negative electrode.
  • the positive electrode is Li a Ni (1-bcd) Co b Mn c M d O 2 (here, 1 ⁇ a ⁇ 1.2, 0 ⁇ b ⁇ 0.4, 0 ⁇ c ⁇ 0.4, 0 ⁇ d ⁇ 0.1, M contains one or more elements selected from the group consisting of Fe, Cu, Ti, Mg, Al, W, Y, B, Mo, Nb, Zn, Sn, Zr, Ga, and V ) and includes a plurality of positive electrode active materials having different Ni molar ratios (1-b-c-d).
  • the negative electrode contains a Ti-based oxide containing at least Ti as a negative electrode active material.
  • the first positive electrode active material having the highest Ni molar ratio among the plurality of positive electrode active materials is in the form of a single particle.
  • the battery satisfies the following formula (1). 2.5g/Ah ⁇ y/x ⁇ 3.5g/Ah (1)
  • x is the nominal capacity (Ah) of the battery
  • y is the amount (g) of the first positive electrode active material.
  • a battery pack is provided.
  • the battery pack includes the battery according to the embodiment.
  • FIG. 1 is an exploded perspective view of an example of a non-aqueous electrolyte battery according to an embodiment.
  • 2 is a partially developed perspective view of an electrode group used in the nonaqueous electrolyte battery shown in FIG. 1.
  • FIG. FIG. 1 is a block diagram showing an example of an electric circuit of a battery pack according to an embodiment.
  • LNCM Composite oxides containing Li, Ni, Co, and Mn
  • LNCM Composite oxides containing Li, Ni, Co, and Mn
  • LNCM secondary particles have been proposed to use multiple types of LNCM secondary particles as a positive electrode material for lithium ion secondary batteries.
  • attempts have been made to make the Ni content of one LNCM the same as or lower than that of the other LNCM.
  • the secondary particles of LNCM with a high Ni content cracks occur at the particle boundaries of the secondary particles during the pressing process when manufacturing the positive electrode.
  • a film is formed on the cracked surface due to a side reaction between the electrolyte and secondary particles during charge/discharge cycles.
  • LNCM which is a single-crystal type that can take the form of a single particle (primary particle) and has a high Ni molar ratio, has a lower calorific value and higher energy density than a polycrystalline type. I found it.
  • the battery of the first embodiment includes a positive electrode and a negative electrode.
  • the positive electrode includes a plurality of positive electrode active materials represented by the following formula (A) and having different Ni molar ratios (1-b-c-d).
  • M is Fe, Cu, Ti, Mg, Al, W, Y , B, Mo, Nb, Zn, Sn, Zr, Ga, and V.
  • the negative electrode contains a Ti-based oxide containing at least Ti as a negative electrode active material.
  • the first positive electrode active material having the highest Ni molar ratio among the plurality of positive electrode active materials is in the form of a single particle.
  • the battery of the embodiment satisfies the following formula (1). 2.5g/Ah ⁇ y/x ⁇ 3.5g/Ah (1)
  • x is the nominal capacity (Ah) of the battery
  • y is the total amount (g) of the first positive electrode active material contained in the battery.
  • y/x is set to the above range. Although a smaller y/x is advantageous for improving safety, if y/x is less than 2.5 g/Ah, a practical energy density cannot be obtained. Moreover, if y/x exceeds 3.5 g/Ah, it may become difficult to suppress heat generation or smoke generation of the battery when an internal short circuit or the like occurs. By satisfying formula (1), it is possible to realize a highly safe battery that has a practical energy density and can prevent bursting and ignition in the event of an internal short circuit. A preferable range of y/x is 2.5 g/Ah or more and 3.4 g/Ah or less.
  • the battery of the embodiment satisfies the following formula (2).
  • p is the capacity per unit area of the positive electrode (mAh/cm 2 )
  • n is the capacity per unit area of the negative electrode (mAh/cm 2 ).
  • p/n is less than 1
  • the battery capacity is regulated by the negative electrode capacity rather than the positive electrode capacity, which is what is called negative electrode regulation.
  • p/n is less than 0.8
  • the positive electrode is used to a high potential during charging and discharging, so there is a risk that the life of the charging/discharging cycle and calender (storage, preservation) will be shortened due to deterioration of the positive electrode.
  • the positive electrode includes a current collector and an active material-containing layer formed on at least one surface of the current collector.
  • the active material-containing layer may be supported on at least one main surface of the current collector.
  • the active material-containing layer is represented by formula (A) and includes a plurality of positive electrode active materials having different Ni molar ratios (1-b-c-d).
  • the first positive electrode active material having the highest Ni molar ratio among the plurality of positive electrode active materials is in the form of a single particle.
  • the active material-containing layer may contain substances other than the active material, such as a conductive agent and a binder.
  • the number of types of positive electrode active materials having different Ni molar ratios (1-b-c-d) can be two or three or more.
  • the Ni molar ratio (1-bc-d) of the first positive electrode active material having the highest Ni molar ratio is desirably 0.8 or more. Thereby, the energy density of the first positive electrode active material can be increased.
  • the Ni molar ratio of the first positive electrode active material can be at most 1.
  • a second positive electrode active material having a smaller Ni molar ratio than the first positive electrode active material can be included.
  • the Ni molar ratio of the second positive electrode active material can be less than 0.8. This makes it possible to improve the thermal stability of the second positive electrode active material, especially at high voltages.
  • the Ni molar ratio of the second positive electrode active material is desirably 0.5 or more and less than 0.8. There may be a plurality of types of the second positive electrode active material.
  • the first positive electrode active material with the highest Ni molar ratio is in the form of a single particle.
  • a single particle does not contain grain boundaries inside. Therefore, single particles have a small specific surface area and are less likely to crack due to expansion and contraction of the particles. Moreover, this single particle can reduce the amount of heat generated when the positive electrode generates heat due to factors such as internal short circuits.
  • the average particle diameter (D50) of the single particles can be in the range of 1 ⁇ m or more and 8 ⁇ m or less. If the average particle diameter is less than 1 ⁇ m, handling of the particles may become difficult. On the other hand, if the average particle diameter exceeds 8 ⁇ m, the input/output performance of the electrode may deteriorate.
  • the content of the first positive electrode active material in the positive electrode active material be equal to or less than the content of the second positive electrode active material in the positive electrode active material. This is useful for improving the thermal stability of the battery.
  • the content of the first positive electrode active material in the positive electrode active material is preferably 20% by mass or more and 50% by mass or less.
  • the composition formula (A) of the plurality of positive electrode active materials will be explained.
  • the lithium-containing metal oxide represented by the formula (A) can obtain a large capacity when used up to a positive electrode potential of 4.2 V (vs. Li/Li + ) or higher.
  • the molar ratio a in formula (A) can vary as the positive electrode intercalates and releases lithium ions. A more preferable range is 1 ⁇ a ⁇ 1.15.
  • the lithium-containing metal oxide can contain Co and Mn in addition to Ni as transition metals. , the capacity per unit mass increases. More preferable ranges for the molar ratio b and c are 0.05 ⁇ b ⁇ 0.3 and 0.05 ⁇ c ⁇ 0.3.
  • a more preferable range of the molar ratio d of element M in formula (A) is 0.01 ⁇ d ⁇ 0.05.
  • M may consist of one or more elements selected from the group consisting of Fe, Cu, Ti, Mg, Al, W, Y, B, Mo, Nb, Zn, Sn, Zr, Ga and V; It may also contain other elements (for example, unavoidable impurities).
  • a conductive agent can improve current collection performance and suppress contact resistance between the active material and the current collector.
  • the conductive agent preferably contains a carbon material. Examples of the carbon material include acetylene black, Ketjen black, furnace black, graphite, carbon nanotubes, and carbon nanofibers.
  • the active material-containing layer can contain one or more of the above carbon materials.
  • the conductive agent has, for example, a particle or fiber shape.
  • the average particle diameter of the conductive agent particles is preferably 20 nm or more and 100 nm or less.
  • the proportion occupied by the conductive agent is preferably 3% by mass or more and 20% by mass or less, for example.
  • binder examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), or fluororubber.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • fluororubber fluororubber.
  • the type of binder used can be one type or two or more types.
  • the proportion occupied by the binder is preferably 1% by mass or more and 1.8% by mass or less.
  • the density of the positive electrode active material-containing layer is preferably 3.2 g/cm 3 or more and 3.8 g/cm 3 or less.
  • metal foil or alloy foil can be used as the positive electrode current collector.
  • metal foil include aluminum foil, stainless steel foil, and nickel foil.
  • alloy foils include aluminum alloys, copper alloys, and nickel alloys.
  • the thickness of the positive electrode can be 64 ⁇ m or more and 99 ⁇ m or less.
  • the positive electrode is produced, for example, by the following method.
  • a slurry (also referred to as paste) is prepared by kneading an active material, a conductive agent, and a binder with a solvent (eg, N-methylpyrrolidone (NMP)).
  • NMP N-methylpyrrolidone
  • the obtained slurry is applied to a current collector, dried, and then pressed to obtain an electrode. If necessary, a step of cutting to a predetermined width may be performed before or after pressing.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material-containing layer formed on the negative electrode current collector. Further, the negative electrode active material-containing layer can contain a conductive agent and a binder in addition to the negative electrode active material.
  • the negative electrode active material includes a Ti-based oxide containing at least Ti. It may contain metal elements other than Ti, and examples of the metal elements include at least one element selected from the group consisting of Li, Nb, P, V, Sn, Cu, Ni, and Fe.
  • Ti-based oxides include lithium titanium composite oxide and niobium titanium composite oxide, but titanium dioxide such as TiO 2 is not included.
  • lithium titanium composite oxides include lithium titanium composite oxides having a spinel-type crystal structure (for example, Li 4+a Ti 5 O 12 , where the molar ratio a is within the range of 0 ⁇ a ⁇ 3).
  • Lithium titanium composite oxide for example, Li 2+x Ti 3 O 7 , where x changes in the range of -1 ⁇ x ⁇ 3 due to charge/discharge reactions) having a ramsteride-type crystal structure Can be mentioned.
  • niobium titanium composite oxides include the general formula Li m Ti 1-n M3 n Nb 2-l M4 l O 7+ ⁇ (M3 is selected from the group consisting of Zr, Si, Sn, Fe, Co, Mn, and Ni). M4 is at least one element selected from the group consisting of V, Nb, Ta, Mo, W and Bi, 0 ⁇ m ⁇ 5, 0 ⁇ n ⁇ 1, 0 ⁇ l ⁇ 2, -0.3 ⁇ 0.3) and a niobium titanium composite oxide having a monoclinic crystal structure, Ti 2 Nb 10 O 19 , etc. Can be mentioned.
  • the particles of the negative electrode active material may include primary particles and secondary particles of Ti-based oxide. Secondary particles are aggregates of primary particles.
  • Examples of conductive agents include carbonaceous materials such as acetylene black, carbon black, and graphite.
  • binders examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine rubber, and styrene-butadiene rubber.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • fluorine rubber fluorine rubber
  • styrene-butadiene rubber examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine rubber, and styrene-butadiene rubber.
  • the negative electrode active material is a material that can store and release lithium ions
  • a material that is electrochemically stable at the lithium ion storage and release potentials of the negative electrode active material can be used as the negative electrode current collector.
  • the negative electrode current collector is a metal foil made of at least one selected from nickel, stainless steel, and aluminum, or contains at least one element selected from Mg, Ti, Zn, Mn, Fe, Cu, and Si. Preferably it is an alloy foil made from an aluminum alloy. Various shapes of the negative electrode current collector can be used depending on the use of the battery.
  • the negative electrode can be produced, for example, by the following method. First, a negative electrode active material, a binder, and, if necessary, a conductive agent are suspended in a commonly used solvent, such as N-methylpyrrolidone, to prepare a negative electrode manufacturing slurry (also referred to as a negative electrode manufacturing paste). do. The obtained slurry is applied onto a negative electrode current collector. By drying the applied slurry and pressing the dried coating film, a negative electrode including a negative electrode current collector and a negative electrode active material-containing layer formed on the negative electrode current collector can be obtained. If necessary, a step of cutting to a predetermined width may be performed before or after pressing.
  • a commonly used solvent such as N-methylpyrrolidone
  • the battery of the embodiment can include a nonaqueous electrolyte and a separator located between the positive electrode and the negative electrode.
  • the positive electrode, negative electrode, and separator can constitute an electrode group.
  • the positive electrode can include a positive current collection tab electrically connected to the electrode group.
  • the negative electrode can include a negative electrode current collection tab electrically connected to the electrode group.
  • the battery according to the embodiment can further include an exterior member.
  • the electrode group can be housed within this exterior member.
  • the exterior member can further contain a non-aqueous electrolyte.
  • the non-aqueous electrolyte may be impregnated into the electrode group housed within the exterior member.
  • the battery according to the embodiment may further include a positive terminal and a negative terminal electrically connected to the exterior member.
  • the positive terminal may be electrically connected to the positive current collecting tab of the positive electrode.
  • the negative terminal may be electrically connected to the negative current collecting tab of the negative electrode.
  • the separator nonaqueous electrolyte, exterior member, and electrode group will be described in detail below.
  • the separator is not particularly limited as long as it has insulation properties, but porous films or nonwoven fabrics made of polymers such as polyolefin, cellulose, polyethylene terephthalate, and vinylon can be used.
  • the separator may be made of one type of material or a combination of two or more types.
  • the thickness of the separator can be 5 ⁇ m or more and 20 ⁇ m or less.
  • the non-aqueous electrolyte includes a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • Examples of non-aqueous electrolytes include non-aqueous electrolytes and gelled non-aqueous electrolytes.
  • electrolyte salt examples include LiPF 6 , LiBF 4 , Li(CF 3 SO 2 ) 2 N (lithium bistrifluoromethanesulfonylamide; commonly known as LiTFSI), LiCF 3 SO 3 (commonly known as LiTFS), Li(C 2 F 5 SO 2 ) 2 N (lithium bispentafluoroethanesulfonylamide; commonly known as LiBETI), LiClO 4 , LiAsF 6 , LiSbF 6 , lithium bisoxalatoborate ⁇ LiB(C 2 O 4 ) 2 , commonly known as LiBOB ⁇ , difluoro(trifluoro- A lithium salt such as 2-oxide-2-trifluoro-methylpropionato(2-)-0,0) lithium borate ⁇ LiBF 2 OCOOC(CF 3 ) 2 , commonly known as LiBF 2 (HHIB) ⁇ is used.
  • These electrolyte salts may be used alone or in combination of two or more.
  • the electrolyte salt concentration in the nonaqueous electrolyte is preferably within the range of 1 mol/L or more and 3 mol/L or less.
  • concentration of the electrolyte salt is within this range, it becomes possible to further improve the performance when a high load current is passed while suppressing the influence of viscosity increase due to an increase in the electrolyte salt concentration in a non-aqueous electrolyte.
  • Non-aqueous solvent is not particularly limited.
  • Non-aqueous solvents include, for example, cyclic carbonates such as propylene carbonate (PC) and ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), and dipropyl carbonate (DPC).
  • Chain carbonate 1,2-dimethoxyethane (DME), ⁇ -butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeHF), 1,3-dioxolane, sulfolane, or acetonitrile (AN) Use.
  • PC propylene carbonate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • MEC methyl ethyl carbonate
  • DPC dipropyl carbonate
  • Chain carbonate 1,2-dimethoxyethane (DME), ⁇ -
  • nonaqueous solvent a nonaqueous solvent containing a cyclic carbonate and/or a chain carbonate is preferable.
  • a laminate film or a metal container is used as the exterior member.
  • the thickness of the laminate film and the thickness of the metal container can each be 0.5 mm or less.
  • a resin container made of polyolefin resin, polyvinyl chloride resin, polystyrene resin, acrylic resin, phenol resin, polyphenylene resin, fluorine resin, etc. may be used as the exterior member.
  • the shape of the exterior member that is, the shape of the battery, includes flat (thin), square, cylindrical, coin, button, etc. Further, the battery can be applied to both small-sized applications such as being loaded into portable electronic devices and large-sized applications such as being loaded into two-wheel to four-wheeled automobiles.
  • laminate films include multilayer films that include a resin layer and a metal layer interposed between the resin layers.
  • the metal layer is preferably aluminum foil or aluminum alloy foil for weight reduction.
  • a polymer material such as polypropylene (PP), polyethylene (PE), nylon, or polyethylene terephthalate (PET) can be used, for example.
  • PP polypropylene
  • PE polyethylene
  • PET polyethylene terephthalate
  • the laminate film can be sealed by heat fusion and formed into the shape of the exterior member.
  • the metal container is made from aluminum or an aluminum alloy or the like.
  • the aluminum alloy an alloy containing elements such as magnesium, zinc, and silicon is preferable.
  • the alloy contains transition metals such as iron, copper, nickel, and chromium, the amount thereof is preferably 100 ppm or less.
  • the electrode group may have a wound structure in which a positive electrode, a separator, and a negative electrode are laminated, or a stacked structure in which a plurality of positive electrodes and a plurality of negative electrodes are alternately stacked with separators interposed between them. or may have other structures.
  • the number of electrode groups included in one battery may be one or more.
  • the (y/x) value of the battery of the embodiment is, for example, the amount of positive electrode slurry (also referred to as positive electrode paste or positive electrode coating liquid) applied to the current collector, the so-called basis weight of the positive electrode slurry (mass per unit area, g/ cm 2 ), the density of the positive electrode active material containing layer, the density of the negative electrode active material containing layer, the p/n ratio, the number of stacked positive and negative electrodes, the number of windings, etc.
  • the basis weight of the positive electrode slurry may be reduced to reduce the p/n ratio.
  • the positive electrode becomes thinner, so that the electrode group can be more densely packed in the exterior member, and the number of laminations or the number of windings of the positive and negative electrodes increases.
  • the positive electrode becomes thinner by increasing the density of the positive electrode, the number of layers or number of windings increases.
  • the basis weight of the positive electrode slurry may be increased to increase the p/n ratio.
  • the positive electrode becomes thicker, so it is necessary to reduce the number of stacked positive and negative electrodes or the number of times they are wound.
  • the positive electrode becomes thicker, so the number of layers or number of windings decreases.
  • the amount y of the first positive electrode active material increases or decreases, the nominal capacity x may change.
  • the (y/x) value includes at least the basis weight of the cathode slurry, the density of the cathode active material-containing layer, the p/n ratio, and the content of the first cathode active material in the cathode active material. It can be set within a predetermined range by adjusting the number of layers or the number of turns.
  • FIG. 1 is an exploded perspective view of an example of a non-aqueous electrolyte battery according to an embodiment.
  • the battery shown in FIG. 1 is a sealed prismatic nonaqueous electrolyte battery.
  • the nonaqueous electrolyte battery shown in FIG. 1 includes an outer can 1, a lid 2, a positive external terminal 3, a negative external terminal 4, and an electrode group 5.
  • the exterior can 1 and the lid 2 constitute an exterior member.
  • the outer can 1 has a rectangular cylinder shape with a bottom, and is made of metal such as aluminum, aluminum alloy, iron, or stainless steel.
  • FIG. 2 is a partially exploded perspective view of an electrode group used in the non-aqueous electrolyte battery shown in FIG. 1.
  • the flat electrode group 5 has a positive electrode 6 and a negative electrode 7 wound into a flat shape with a separator 8 interposed therebetween.
  • the positive electrode 6 includes a band-shaped positive electrode current collector made of, for example, metal foil, a positive electrode current collecting tab 6a consisting of one end parallel to the long side of the positive electrode current collector, and a positive electrode except for at least a portion of the positive electrode current collecting tab 6a.
  • the positive electrode material layer (positive electrode active material-containing layer) 6b formed on the current collector.
  • the negative electrode 7 includes a band-shaped negative electrode current collector made of, for example, metal foil, a negative electrode current collecting tab 7a consisting of one end parallel to the long side of the negative electrode current collector, and at least a portion of the negative electrode current collecting tab 7a. and a negative electrode material layer (negative electrode active material-containing layer) 7b formed on the negative electrode current collector.
  • the positive electrode current collecting tab 6a projects from the separator 8 in the direction of the winding axis of the electrode group, and the negative electrode current collecting tab 7a projects from the separator 8 in the opposite direction.
  • the positive electrode 6 and the negative electrode 7 are wound with their positions shifted. Due to this winding, the electrode group 5 has a spirally wound positive electrode current collecting tab 6a protruding from one end surface and a spirally wound positive electrode current collecting tab 6a from the other end surface, as shown in FIG. A negative electrode current collecting tab 7a protrudes.
  • the electrode group 5 is impregnated with a non-aqueous electrolyte (not shown).
  • the positive electrode current collector tab 6a and the negative electrode current collector tab 7a are each divided into two bundles with a border near the winding center of the electrode group.
  • the conductive clamping member 9 includes first and second clamping parts 9a and 9b that are substantially U-shaped, and a connecting part that electrically connects the first clamping part 9a and the second clamping part 9b. 9c.
  • One bundle of the positive and negative electrode current collecting tabs 6a and 7a is held by a first holding part 9a, and the other bundle is held by a second holding part 9b.
  • the positive electrode lead 10 includes a substantially rectangular support plate 10a, a through hole 10b opened in the support plate 10a, and strip-shaped current collectors 10c and 10d that branch into two from the support plate 10a and extend downward.
  • the negative electrode lead 11 includes a substantially rectangular support plate 11a, a through hole 11b opened in the support plate 11a, a strip-shaped current collector portion 11c that branches into two from the support plate 11a, and extends downward. 11d.
  • the positive electrode lead 10 sandwiches the holding member 9 between the current collecting parts 10c and 10d.
  • the current collector 10c is arranged at the first clamping part 9a of the clamping member 9.
  • the current collector 10d is arranged on the second holding part 9b.
  • the current collecting parts 10c and 10d, the first and second holding parts 9a and 9b, and the positive electrode current collecting tab 6a are joined by, for example, ultrasonic welding. Thereby, the positive electrode 6 of the electrode group 5 and the positive electrode lead 10 are electrically connected via the positive electrode current collecting tab 6a.
  • the negative electrode lead 11 sandwiches the holding member 9 between the current collecting parts 11c and 11d.
  • the current collector 11c is arranged at the first clamping part 9a of the clamping member 9.
  • the current collecting section 11d is arranged on the second holding section 9b.
  • the current collecting parts 11c and 11d, the first and second holding parts 9a and 9b, and the negative electrode current collecting tab 7a are joined by, for example, ultrasonic welding. Thereby, the negative electrode 7 of the electrode group 5 and the negative electrode lead 11 are electrically connected via the negative electrode current collecting tab 7a.
  • the materials of the positive and negative electrode leads 10 and 11 and the clamping member 9 are not particularly specified, it is desirable that they be made of the same material as the positive and negative electrode external terminals 3 and 4.
  • aluminum or an aluminum alloy is used for the positive external terminal 3
  • aluminum, aluminum alloy, copper, nickel, or nickel-plated iron is used for the negative external terminal 4.
  • the lead is preferably made of aluminum or an aluminum alloy.
  • the material of the lead be copper or the like.
  • the rectangular plate-shaped lid 2 is seam-welded to the opening of the outer can 1 using, for example, a laser.
  • the lid 2 is made of metal such as aluminum, aluminum alloy, iron, or stainless steel. It is desirable that the lid 2 and the outer can 1 be formed from the same type of metal.
  • the positive external terminal 3 is electrically connected to the support plate 10a of the positive lead 10
  • the negative external terminal 4 is electrically connected to the support plate 11a of the negative lead 11.
  • the insulating gasket 12 is disposed between the positive and negative external terminals 3 and 4 and the lid 2, and electrically insulates the positive and negative external terminals 3 and 4 from the lid 2. It is desirable that the insulating gasket 12 is a resin molded product.
  • the battery is charged with a constant current at a rate of 0.2C to the maximum voltage used in an environment of 25°C.
  • the battery is further charged while maintaining the maximum voltage used until the current value reaches 0.05C.
  • the battery is discharged at a rate of 0.2C to the final voltage to obtain the discharge capacity.
  • the obtained discharge capacity is the nominal capacity.
  • maximum operating voltage is the maximum voltage at which the battery can be used without danger or defects, and is a value unique to each battery.
  • the maximum voltage used is, for example, the voltage described as “charging voltage” and “maximum security voltage” in the specifications of the battery.
  • final voltage is the lowest operating voltage at which a battery can be used while suppressing overdischarge of both the positive and negative electrodes, i.e., suppressing battery deterioration, and is a value unique to each battery. . (capacity ratio p/n) A method for measuring the capacitance ratio p/n will be explained below.
  • a battery having a discharge capacity of 80% or more of the rated capacity is prepared as a battery to be tested.
  • the method for measuring rated capacity is as follows. The battery is charged at a constant current of 1 C in a constant temperature bath maintained at 25° C. until the voltage reaches 2.75 V. Next, the battery is charged in the same thermostatic chamber at a constant voltage of 2.75V until the current value reaches 0.05C. The battery is then left open circuit for 30 minutes. The battery is then discharged at a constant current of 0.2C until the voltage reaches 1.5V. Repeat the above charge-leave-discharge cycle three times. The capacity obtained during the third cycle of discharge is defined as the rated capacity.
  • the battery is placed in an inert gas atmosphere, such as in a glove box with an argon gas atmosphere. Then, in such a glove box, open the battery. Remove the electrode group from the cut-out battery. If the electrode group taken out includes a positive electrode lead and a negative electrode lead, cut the positive electrode lead and the negative electrode lead while being careful not to short-circuit the positive and negative electrodes.
  • an inert gas atmosphere such as in a glove box with an argon gas atmosphere.
  • the electrode group taken out is disassembled into a positive electrode, a negative electrode, and a separator.
  • the portion of the positive electrode active material containing layer that was facing the negative electrode active material containing layer is cut out to form a positive electrode piece.
  • the positive electrode piece may include a positive electrode current collector supporting a cut-out portion of the positive electrode active material-containing layer.
  • the portion of the negative electrode active material containing layer that was facing the positive electrode active material containing layer is cut out and used as a negative electrode piece.
  • the negative electrode piece may include a negative electrode current collector supporting a cut-out portion of the negative electrode active material-containing layer. Thereafter, the positive electrode piece and the negative electrode piece are washed with a solvent.
  • chain carbonate dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, etc.
  • acetonitrile can be used as the solvent.
  • the positive electrode piece and the negative electrode piece are transferred to a vacuum chamber filled with an inert gas atmosphere without being exposed to the atmosphere, and the pressure inside the vacuum chamber is reduced.
  • the positive electrode piece and the negative electrode piece are dried in this reduced pressure chamber. Drying can be performed, for example, under vacuum at 50° C. for 10 hours.
  • the masses of the positive electrode piece and the negative electrode piece are measured. Thereafter, a positive electrode sample including, for example, a 3 cm square positive electrode active material-containing layer is cut from the positive electrode piece.
  • a negative electrode sample containing, for example, a 3 cm square negative electrode active material-containing layer is cut from the negative electrode piece.
  • a bipolar or three-polar electrochemical measurement cell is fabricated using the positive electrode sample as a working electrode and lithium metal foil as a counter electrode and a reference electrode.
  • the produced electrochemical measurement cell is charged until the potential of the working electrode reaches the upper limit potential of 4.25 V (vs. Li/Li + ).
  • the current value at this time is 0.1 mA/cm 2 .
  • discharging is performed at the same current value as charging until the potential of the working electrode reaches the lower limit potential of 3.0 V (vs. Li/Li + ).
  • the above charging and discharging is performed for a total of three cycles, and the discharge capacity obtained during the third cycle of discharging is recorded.
  • the mass of the negative electrode sample cut out earlier is measured.
  • a two-electrode or three-electrode electrochemical measurement cell is fabricated using the negative electrode sample as a working electrode and lithium metal foil as a counter electrode and a reference electrode.
  • the fabricated electrochemical measurement cell had a lower limit potential of 1.0 V (vs. Li/Li + ) and an upper limit potential of 3.0 V (vs. Li/Li + ).
  • the cell is subjected to a total of three charging and discharging cycles similar to the charging and discharging performed on the measurement cell. The discharge capacity obtained during the third cycle of discharge is recorded.
  • the capacity ratio p/n is calculated by dividing the capacity p per unit area of the positive electrode obtained as described above by the capacity n per unit area of the negative electrode.
  • composition of positive electrode active material and negative electrode active material The composition of the active material can be analyzed using, for example, inductively coupled plasma (ICP) emission spectroscopy. At this time, the abundance ratio (molar ratio) of each element depends on the sensitivity of the analyzer used. Therefore, the measured molar ratio may deviate from the actual molar ratio by the error of the measuring device. However, even if the numerical value deviates within the error range of the analyzer, the performance of the active material can be fully demonstrated.
  • the battery to be measured shall have a discharge capacity of 80% or more of the rated capacity. In other words, batteries with excessive deterioration are not measured.
  • the method for measuring the discharge capacity of 80% or more of the rated capacity is as explained in the method for measuring the nominal capacity.
  • the prepared battery is discharged until the open circuit voltage reaches 2.0 to 2.2V.
  • the discharged battery is then transferred into an argon-filled glove box where the internal atmosphere has a dew point of -70°C. Open the battery, such as in a glove box. Remove the electrode group from the cut-out battery. If the electrode group taken out includes a positive electrode lead and a negative electrode lead, cut the positive electrode lead and the negative electrode lead while being careful not to short-circuit the positive electrode and the negative electrode.
  • the electrode group is disassembled into a positive electrode, a negative electrode, and a separator.
  • the positive electrode and negative electrode thus obtained are washed using diethyl carbonate as a solvent. In this cleaning, the parts obtained by disassembly are completely immersed in diethyl carbonate solvent and left in that state for 60 minutes.
  • the positive and negative electrodes are each subjected to vacuum drying.
  • the pressure is reduced from atmospheric pressure to -97 kpa or higher in a 25°C environment, and this state is maintained for 10 minutes.
  • composition of positive electrode active material The crystal structure of the active material is identified by powder X-ray diffraction (XRD) measurement on a powder sample. The measurement is performed using CuK ⁇ radiation as a radiation source in a measurement range where 2 ⁇ is 10° or more and 90° or less. Through this measurement, an X-ray diffraction pattern of the compound contained in the selected particles can be obtained.
  • XRD powder X-ray diffraction
  • X-ray source Cu target Output: 45kV, 200mA Solar slit: 5° for both incident and receiving light Step width: 0.02deg Scan speed: 20deg/min Semiconductor detector: D/teX Ultra 250 Sample plate holder: flat glass sample plate holder (thickness 0.5mm) Measurement range: 10° ⁇ 2 ⁇ 90°.
  • the sample containing the active material is observed using a scanning electron microscope (SEM). Even during SEM observation, it is desirable to prevent the sample from coming into contact with the atmosphere and to perform the observation in an inert atmosphere such as argon or nitrogen.
  • SEM scanning electron microscope
  • some particles having the form of primary particles or secondary particles that are confirmed within the field of view are selected. From the difference in shape, it can be assumed that the single crystal primary particles are the first positive electrode active material and the polycrystalline secondary particles are the second positive electrode active material. At this time, the particles are selected so that the particle size distribution of the selected particles is as wide as possible.
  • EDX Electron Dispersive X-ray Spectroscopy
  • analysis of the observed active material particles identifies the types and composition of the constituent elements of the active material. Thereby, the type and amount of elements other than Li among the elements contained in each selected particle can be specified. The same operation is performed for each of the plurality of active material particles to determine the mixed state of the active material particles.
  • the powdered sample collected from the active material-containing layer is washed with acetone and dried.
  • the resulting powder is dissolved in hydrochloric acid, the conductive agent is removed by filtration, and then diluted with ion-exchanged water to prepare a measurement sample.
  • the metal content ratio in the measurement sample is calculated by inductively coupled plasma atomic emission spectroscopy (ICP-AES) analysis method.
  • the mass ratio is estimated from the content ratio of elements specific to each active material.
  • the ratio between the specific element and the mass of the active material is determined from the composition of the constituent elements determined by EDX analysis.
  • a measurement sample obtained from the active material-containing layer may contain multiple types of positive electrode active materials.
  • the chemical formula and formula weight of each positive electrode active material are calculated from the determined metal ratio, and the mass ratio of each positive electrode active material contained in a predetermined mass of the collected active material-containing layer is determined. y is calculated by multiplying the mass of the measurement sample calculated from the metal content ratio by the mass ratio of the first active material.
  • composition of negative electrode active material The negative electrode is taken out from the battery in the same manner as for the positive electrode active material, and the negative electrode is washed to obtain a powdered sample.
  • the obtained powdered sample is heated in the atmosphere for a short time (for example, at 500° C. for about 1 hour) to burn off unnecessary components such as binder components and carbon.
  • a liquid sample containing the active material can be created.
  • the acid hydrochloric acid, nitric acid, sulfuric acid, hydrogen fluoride, etc. can be used.
  • the composition of the active material can be determined.
  • the target electrode is taken out from the battery and washed in the same manner as explained in the method for confirming the composition of the active material. Peel off the active material-containing layer from the cleaned electrode using, for example, a spatula, crush it ultrasonically, and use a particle size distribution measuring device (for example, a laser diffraction particle size distribution measuring device SALD-2300 (manufactured by Shimadzu Corporation)). Measure.
  • a particle size distribution measuring device for example, a laser diffraction particle size distribution measuring device SALD-2300 (manufactured by Shimadzu Corporation)
  • the battery according to the first embodiment described above includes a positive electrode that is represented by the formula (A) and includes a plurality of positive electrode active materials having different Ni molar ratios (1-b-c-d), and includes at least Ti. and a negative electrode containing a Ti-based oxide as a negative electrode active material. Further, the battery satisfies equation (1). Furthermore, the first positive electrode active material having the highest Ni molar ratio among the plurality of positive electrode active materials is in the form of a single particle. According to the battery of the embodiment, it is possible to realize a battery that has a practical energy density and can prevent the battery from bursting or catching fire due to an internal short circuit.
  • a battery pack including a battery is provided.
  • the battery according to the first embodiment is used as the battery.
  • the number of cells included in the battery pack can be one or more.
  • a plurality of batteries can be electrically connected in series, in parallel, or in a combination of series and parallel to form a battery pack.
  • the battery pack may include a plurality of assembled batteries.
  • the battery pack can further include a protection circuit.
  • the protection circuit has a function of controlling charging and discharging of the battery.
  • a circuit included in a device for example, an electronic device, an automobile, etc.
  • a battery pack as a power source can be used as a protection circuit for the battery pack.
  • the battery pack may further include an external terminal for power supply.
  • the external terminal for energization is used to output current from the battery to the outside and to input current to the battery.
  • current is supplied to the outside through the external terminal for energization.
  • charging current including regenerated energy from the motor vehicle is supplied to the battery pack through an external terminal for energization.
  • FIG. 3 is a block diagram showing an example of the electric circuit of the battery pack according to the embodiment.
  • the battery pack shown in FIG. 3 includes a plurality of flat batteries 100 having the structure shown in FIGS. 1 and 2. These unit cells 100 are electrically connected to each other in series as shown in FIG.
  • a positive lead 28 is connected to the positive external terminal of the unit cell 100 of the assembled battery, and the positive lead 28 is electrically connected to the positive connector 29 of the printed wiring board.
  • a negative lead 30 is connected to the negative external terminal of another unit cell 100 of the assembled battery, and the negative lead 30 is electrically connected to a negative connector 31 of the printed wiring board. These connectors 29 and 31 are electrically connected to the protection circuit 26 by wires 32 and 33 formed on the printed wiring board.
  • the thermistor 25 detects the temperature of each cell 100 and sends the detection signal to the protection circuit 26.
  • the protection circuit 26 can cut off the positive wiring 34a and the negative wiring 34b between the protection circuit 26 and the terminal 27 for supplying electricity to an external device under predetermined conditions.
  • An example of the predetermined condition is, for example, when a signal is received from the thermistor 25 indicating that the temperature of the unit cell 100 is equal to or higher than a predetermined temperature.
  • Another example of the predetermined condition is when overcharging, overdischarging, overcurrent, etc. of the cell 100 is detected. This detection of overcharging and the like is performed for each unit cell 100 or the unit battery 100 as a whole.
  • the battery voltage When detecting each unit cell 100, the battery voltage may be detected, or the positive electrode potential or the negative electrode potential may be detected. In the latter case, a lithium electrode used as a reference electrode is inserted into each cell 100.
  • wiring 35 for voltage detection is connected to each cell 100, and a detection signal is transmitted to the protection circuit 26 through these wirings 35.
  • the battery pack shown in FIG. 3 has a configuration in which a plurality of single cells 100 are connected in series, but the battery pack according to the second embodiment has a plurality of single cells 100 connected in parallel to increase battery capacity. You may. Alternatively, the battery pack according to the second embodiment may include a plurality of unit cells 100 connected in a combination of series connection and parallel connection. The assembled battery packs can also be further connected in series or in parallel.
  • the battery pack shown in FIG. 3 includes a plurality of single cells 100
  • the battery pack according to the second embodiment may include one single battery 100.
  • the aspect of the battery pack may be changed as appropriate depending on the use.
  • cycle characteristics with large current characteristics are desired.
  • examples thereof include power supplies for digital cameras, and in-vehicle applications such as two-wheel to four-wheel hybrid electric vehicles, two-wheel to four-wheel electric vehicles, and assisted bicycles. In particular, it is suitable for use in vehicles.
  • the battery pack is, for example, one that recovers regenerated energy from the power of the vehicle.
  • the battery pack of the second embodiment detailed above includes the battery of the first embodiment. Therefore, the battery pack has a practical energy density and is highly safe as it can prevent bursting and ignition in the event of an internal short circuit.
  • NMP N-methylpyrrolidone
  • the paste-like dispersion liquid was used as a positive electrode coating liquid and was uniformly applied to both the front and back sides of a current collector made of a band-shaped aluminum foil.
  • the coating film of the positive electrode coating liquid was dried to form a positive electrode active material-containing layer.
  • the dried strip was press-molded, and the rolled positive electrode was cut into predetermined dimensions.
  • a current collector tab was welded thereto to obtain a positive electrode.
  • the density of the positive electrode active material-containing layer was 3.27 g/cm 3 .
  • a negative electrode active material lithium titanium oxide particles having a spinel crystal structure represented by Li 4 Ti 5 O 12 were prepared.
  • graphite was prepared as a conductive agent and polyvinylidene fluoride was prepared as a binder.
  • a paste was prepared by dissolving and mixing these negative electrode active material, conductive agent, and binder in NMP at a mass ratio of 94:4:2. This paste was used as a negative electrode coating liquid and was uniformly applied to both the front and back surfaces of a negative electrode current collector made of a strip-shaped aluminum foil.
  • the negative electrode coating liquid was dried to form a negative electrode active material-containing layer. After the dried strip was press-molded, the strip was cut into predetermined dimensions.
  • a current collector tab was welded thereto to obtain a negative electrode.
  • the density of the negative electrode active material-containing layer was 2.20 g/cm 3 .
  • Two sheets of cellulose nonwoven fabric were prepared as separators. The thickness of each separator was 8 ⁇ m. Next, one separator, the positive electrode, the other separator, and the negative electrode were stacked in this order to form a wound body. This was performed continuously, and the separator was positioned at the outermost periphery of the thus obtained wound body. Next, the obtained coil of the wound body was pressed while being heated. In this way, a wound electrode group was produced.
  • a mixed solvent of propylene carbonate and diethyl carbonate mixed at a volume ratio of 1:2 was prepared as a non-aqueous solvent.
  • a non-aqueous electrolyte was prepared by dissolving LiPF 6 as an electrolyte salt in this mixed solvent at a concentration of 1.0 mol/L.
  • Electrode terminals were electrically connected to the positive and negative electrodes of the wound electrode group obtained as described above, respectively. The electrode group was placed in an aluminum square container.
  • Example 7 Polycrystalline particles (secondary particles) of LiNi 0.5 Co 0.3 Mn 0.2 O 2 were used as the second positive electrode active material. Further, the p/n ratio and the number of turns of the electrode group were adjusted so that the values of the nominal capacity x, the amount of first positive electrode active material y, and (y/x) became the values shown in Table 1.
  • Example 9 A non-aqueous electrolyte battery was manufactured in the same manner as in Example 1 except for the above. (Example 9, 10) Single particles of LiNi 0.9 Co 0.05 Mn 0.05 O 2 were used as the first positive electrode active material.
  • the p/n ratio and the number of turns of the electrode group were adjusted so that the values of the nominal capacity x, the amount of first positive electrode active material y, and (y/x) became the values shown in Table 1. Note that the value of the p/n ratio was adjusted by the amount of the positive electrode coating liquid applied to the positive electrode current collector per unit area. Further, the number of windings of the electrode group was increased or decreased depending on the p/n ratio, and the thickness of the electrode group was set to 21 mm (with respect to the thickness D of 22 mm, the inner dimension was 21 mm). A non-aqueous electrolyte battery was manufactured in the same manner as in Example 1 except for the above.
  • Niobium titanium oxide particles having a monoclinic structure represented by TiNb 2 O 7 were used as the negative electrode active material. Further, the p/n ratio and the number of turns of the electrode group were adjusted so that the values of the nominal capacity x, the amount of first positive electrode active material y, and (y/x) became the values shown in Table 1. Note that the value of the p/n ratio was adjusted by the amount of the positive electrode coating liquid applied to the positive electrode current collector per unit area. Further, the number of windings of the electrode group was increased or decreased depending on the p/n ratio, and the thickness of the electrode group was set to 21 mm (with respect to the thickness D of 22 mm, the inner dimension was 21 mm).
  • a non-aqueous electrolyte battery was manufactured in the same manner as in Example 1 except for the above.
  • the p/n ratio and the number of turns of the electrode group were adjusted so that the values of the nominal capacity x, the amount of first positive electrode active material y, and (y/x) became the values shown in Table 1. Note that the value of the p/n ratio was adjusted by the amount of the positive electrode coating liquid applied to the positive electrode current collector per unit area. Further, the number of windings of the electrode group was increased or decreased depending on the p/n ratio, and the thickness of the electrode group was set to 21 mm (with respect to the thickness D of 22 mm, the inner dimension was 21 mm).
  • a non-aqueous electrolyte battery was manufactured in the same manner as in Example 1 except for the above.
  • (Comparative example 2) Graphite was used as the negative electrode active material, and strip-shaped copper foil was used as the negative electrode current collector. Further, the p/n ratio and the number of turns of the electrode group were adjusted so that the values of the nominal capacity x, the amount of first positive electrode active material y, and (y/x) became the values shown in Table 1. Note that the value of the p/n ratio was adjusted by the amount of the positive electrode coating liquid applied to the positive electrode current collector per unit area.
  • a non-aqueous electrolyte battery was manufactured in the same manner as in Example 1 except for the above.
  • the nominal capacity x, the amount of first positive electrode active material y, and the p/n ratio were measured by the method described above, and the results and the value of y/x are shown in Table 1.
  • Table 1 shows the volumetric energy density (Wh/L) of the batteries of each Example and each Comparative Example, and the nail insertion test results of ⁇ 5.
  • the ⁇ 5 nail insertion test was conducted by inserting a nail with a diameter of 5 mm into the battery at a descending speed of 5.5 mm/sec. The condition of the battery during the nail insertion test was judged based on the hazard level of EUCAR hazard level description, and the judgment results are shown in Table 1 as the nail insertion test results.
  • Table 2 shows the composition of the first positive electrode active material, the second positive electrode active material, and the negative electrode active material of the batteries of each Example and each Comparative Example.
  • the battery of Example 1 did not emit smoke, explode, or catch fire.
  • the batteries of Examples 2 to 12 produced smoke, they did not explode or catch fire, and their volumetric energy densities were higher than those of Example 1.
  • the battery of Comparative Example 1 in which y/x exceeds 3.5, had a higher volumetric energy density than Example 1, but exploded and caused ignition.
  • the y/x was 2.5
  • the battery of Comparative Example 2 using graphite for the negative electrode burst and ignited although the volumetric energy density was higher than that of Example 1-12. Therefore, the batteries of Examples 1 to 12 have practical volumetric energy densities and can prevent bursting and ignition due to internal short circuits.
  • Li a Ni (1-bcd) Co b Mn c M d O 2 where 1 ⁇ a ⁇ 1.2, 0 ⁇ b ⁇ 0.4, 0 ⁇ c ⁇ 0.4, 0 ⁇ d ⁇ 0.1, M selected from the group consisting of Fe, Cu, Ti, Mg, Al, W, Y, B, Mo, Nb, Zn, Sn, Zr, Ga, and V
  • a battery is provided, comprising a negative electrode containing as a substance.
  • the first positive electrode active material having the highest Ni molar ratio among the plurality of positive electrode active materials is in the form of a single particle. Further, the battery satisfies the following formula (1). 2.5g/Ah ⁇ y/x ⁇ 3.5g/Ah (1) Here, x is the nominal capacity (Ah) of the battery, and y is the amount (g) of the first positive electrode active material.
  • Li a Ni (1-bcd) Co b Mn c M d O 2 (here, 1 ⁇ a ⁇ 1.2, 0 ⁇ b ⁇ 0.4, 0 ⁇ c ⁇ 0.4, 0 ⁇ d ⁇ 0.1, M contains one or more elements selected from the group consisting of Fe, Cu, Ti, Mg, Al, W, Y, B, Mo, Nb, Zn, Sn, Zr, Ga, and V ) and containing a plurality of positive electrode active materials having different Ni molar ratios (1-b-c-d);
  • a battery comprising a negative electrode containing a Ti-based oxide containing at least Ti as a negative electrode active material,
  • the first positive electrode active material having the highest Ni molar ratio among the plurality of positive electrode active materials is in the form of a single particle, A battery that satisfies formula (1) below.
  • x is the nominal capacity (Ah) of the battery
  • y is the amount (g) of the first positive electrode active material.
  • x is the nominal capacity (Ah) of the battery
  • y is the amount (g) of the first positive electrode active material.
  • the plurality of positive electrode active materials further include a second positive electrode active material in which the Ni molar ratio is less than 0.8.
  • the Ni molar ratio of the second positive electrode active material is 0.5 or more and less than 0.8.
  • [5] The battery according to any one of [1] to [4], which satisfies the following formula (2).
  • p is the capacity per unit area of the positive electrode (mAh/cm 2 )
  • n is the capacity per unit area of the negative electrode (mAh/cm 2 ).
  • SYMBOLS 1... Exterior can, 2... Lid, 3... Positive electrode external terminal, 4... Negative electrode external terminal, 5... Electrode group, 6... Positive electrode, 6a... Positive electrode current collection tab, 6b... Positive electrode material layer (positive electrode active material containing layer), 7... Negative electrode, 7a... Negative electrode current collecting tab, 7b... Negative electrode material layer (negative electrode active material containing layer), 8... Separator, 9... Sandwiching member, 9a... First clamping part, 9b...
  • Second clamping part, 9c ...Connection part, 10...Positive electrode lead, 10a...Support plate, 10b...Through hole, 10c...Current collector, 10d...Current collector, 11...Negative electrode lead, 11a...Support plate, 11b...Through hole, 11c...Current collector Part, 11d... Current collecting part, 12... Insulating gasket, 25... Thermistor, 26... Protection circuit, 27... Current carrying terminal, 28... Positive electrode side lead, 29... Positive electrode side connector, 30... Negative electrode side lead, 31... Negative electrode side Connector, 32...Wiring, 33...Wiring, 34a...Positive side wiring, 34b...Minus side wiring, 35...Wiring, 100...Single battery.

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Abstract

Selon un mode de réalisation, l'invention concerne une batterie ayant une électrode positive et une électrode négative. L'électrode positive est représentée par LiaNi(1-b-c-d)CobMncMdO2 et comprend de multiples substances actives d'électrode positive qui ont des rapports molaires de Ni différents (1-b-c-d). L'électrode négative comprend une substance active d'électrode négative qui est un oxyde à base de Ti contenant au moins du Ti. La première substance active d'électrode positive, qui a le rapport molaire de Ni le plus élevé des multiples substances actives d'électrode positive, est sous la forme de particules individuelles. De plus, la batterie satisfait la formule (1). Formule (1) : 2,5 g/Ah ≤ y/x ≤ 3,5 g/Ah. x est la capacité nominale (Ah) de la batterie et y est la quantité (g) de la première substance active d'électrode positive.
PCT/JP2022/022123 2022-05-31 2022-05-31 Batterie et bloc-batterie WO2023233520A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002237333A (ja) * 2001-02-09 2002-08-23 Toshiba Corp 非水電解質二次電池
WO2014156011A1 (fr) * 2013-03-27 2014-10-02 三洋電機株式会社 Batterie secondaire à électrolyte non aqueux
WO2017094237A1 (fr) * 2015-11-30 2017-06-08 パナソニックＩｐマネジメント株式会社 Batterie rechargeable à électrolyte non aqueux
WO2020003642A1 (fr) * 2018-06-29 2020-01-02 パナソニックＩｐマネジメント株式会社 Substance active d'électrode positive pour cellule secondaire à électrolyte non aqueux, et cellule secondaire à électrolyte non aqueux
WO2020122284A1 (fr) * 2018-12-13 2020-06-18 주식회사 포스코 Matériau actif de cathode pour batterie secondaire au lithium, et batterie secondaire au lithium le comprenant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002237333A (ja) * 2001-02-09 2002-08-23 Toshiba Corp 非水電解質二次電池
WO2014156011A1 (fr) * 2013-03-27 2014-10-02 三洋電機株式会社 Batterie secondaire à électrolyte non aqueux
WO2017094237A1 (fr) * 2015-11-30 2017-06-08 パナソニックＩｐマネジメント株式会社 Batterie rechargeable à électrolyte non aqueux
WO2020003642A1 (fr) * 2018-06-29 2020-01-02 パナソニックＩｐマネジメント株式会社 Substance active d'électrode positive pour cellule secondaire à électrolyte non aqueux, et cellule secondaire à électrolyte non aqueux
WO2020122284A1 (fr) * 2018-12-13 2020-06-18 주식회사 포스코 Matériau actif de cathode pour batterie secondaire au lithium, et batterie secondaire au lithium le comprenant

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