WO2024042919A1 - 非水電解質二次電池 - Google Patents

非水電解質二次電池 Download PDF

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Publication number
WO2024042919A1
WO2024042919A1 PCT/JP2023/026230 JP2023026230W WO2024042919A1 WO 2024042919 A1 WO2024042919 A1 WO 2024042919A1 JP 2023026230 W JP2023026230 W JP 2023026230W WO 2024042919 A1 WO2024042919 A1 WO 2024042919A1
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lithium
secondary battery
aqueous electrolyte
electrolyte secondary
positive electrode
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French (fr)
Japanese (ja)
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菜々美 竹田
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to EP23857035.2A priority Critical patent/EP4579851A1/en
Priority to JP2024542648A priority patent/JPWO2024042919A1/ja
Priority to CN202380060664.4A priority patent/CN119744466A/zh
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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
    • 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
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a non-aqueous electrolyte secondary battery.
  • non-aqueous electrolyte secondary batteries have expanded to include power sources for electric vehicles and power storage devices for utilizing natural energy.
  • the characteristics required of the positive electrode active material used in non-aqueous electrolyte secondary batteries also vary depending on the application.
  • Patent Document 1 discloses a lithium titanate powder containing Li 4 Ti 5 O 12 as a main component, which has an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms on at least a part of the particle surface.
  • a lithium titanate powder for electrodes of power storage devices which is characterized by having a surface layer containing a sulfonic acid lithium salt compound having a group.
  • Patent Document 1 aims to suppress resistance changes before and after long-term high-temperature charging and storage of an electricity storage device. However, there is much room for improvement in terms of increasing the capacity of non-aqueous electrolyte secondary batteries and improving charge-discharge cycle characteristics.
  • One aspect of the present invention includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein the positive electrode includes a positive electrode active material, and the positive electrode active material includes a lithium-containing composite oxide and a lithium-containing composite oxide. sulfonic acid compound present on the surface, and the nonaqueous electrolyte contains a sulfur-containing compound.
  • FIG. 1 is a longitudinal cross-sectional view of a non-aqueous electrolyte secondary battery according to an embodiment of the present disclosure.
  • the term “contains” or “includes” is an expression that includes “contains (or includes),” “substantially consists of,” and “consists of.” It is.
  • Secondary batteries include at least nonaqueous electrolyte secondary batteries such as lithium ion batteries and lithium metal secondary batteries.
  • the non-aqueous electrolyte secondary battery includes a positive electrode, a negative electrode, and a non-aqueous electrolyte.
  • the positive electrode includes a positive electrode active material, and the positive electrode active material includes a lithium-containing composite oxide and a sulfonic acid compound present on the surface of the lithium-containing composite oxide.
  • the surface of the lithium-containing composite oxide may be the surface of the secondary particles of the lithium-containing composite oxide, the surface of the primary particles, or the interface where the primary particles are in contact with each other.
  • Lithium-containing composite oxides usually include secondary particles formed by agglomeration of primary particles. That is, the sulfonic acid compound exists on at least one of the surfaces of the secondary particles of the lithium-containing composite oxide, the surfaces of the primary particles, or the interfaces where the primary particles contact each other.
  • At least a portion of the sulfonic acid compound is not dissolved in the nonaqueous electrolyte and remains in a solid state on the surface of the lithium-containing composite oxide.
  • the sulfonic acid compound protects the surface of the lithium-containing composite oxide and has a barrier effect of suppressing side reactions involving the lithium-containing composite oxide and the nonaqueous electrolyte.
  • the sulfonic acid compound can also suppress an increase in reaction resistance on the surface of the lithium-containing composite oxide.
  • the non-aqueous electrolyte contains a sulfur-containing compound. At least a portion (usually all) of the sulfur-containing compound in the non-aqueous electrolyte is dissolved in the non-aqueous electrolyte, so it can always act on the surface of the lithium-containing composite oxide. Not only the presence of sulfonic acid compounds on the surface of the lithium-containing composite oxide, but also the presence of sulfur-containing compounds in the nonaqueous electrolyte form a good surface condition on the lithium-containing composite oxide that suppresses side reactions. it is conceivable that.
  • the sulfur-containing compound may act between the surface of the lithium-containing composite oxide and the sulfonic acid compound, or may act on a region not covered with scattered particulate sulfonic acid compounds.
  • the surface state of the lithium-containing composite oxide is similar to that in which a dense protective film with low resistance is formed.
  • the non-aqueous electrolyte contains a sulfur-containing compound, it is difficult to obtain the effect of suppressing side reactions if a sulfonic acid compound is not present on the surface of the lithium-containing composite oxide. This is considered to be because the sulfur-containing compound does not act sufficiently on the surface of the lithium-containing composite oxide.
  • the sulfur-containing compound in the non-aqueous electrolyte has the effect of enhancing the protective action of the lithium-containing composite oxide by the sulfonic acid compound.
  • the sulfonic acid compound only needs to be in contact with the surface of the particles of the lithium-containing composite oxide.
  • the sulfonic acid compound may cover at least a portion of the surface of the particles of the lithium-containing composite oxide.
  • the sulfonic acid compound may be attached to or precipitated on the surface of the particles of the lithium-containing composite oxide.
  • the sulfonic acid compound may form particles smaller than the particles of the lithium-containing composite oxide, and may form an island-like film that covers at least a portion of the surface of the particles of the lithium-containing composite oxide. .
  • the positive electrode includes a positive electrode current collector and a positive electrode mixture layer provided on the surface of the positive electrode current collector.
  • the positive electrode current collector is made of a sheet-like conductive material.
  • the positive electrode mixture layer is supported on one or both surfaces of the positive electrode current collector.
  • the positive electrode mixture layer is usually a layer or film composed of a positive electrode mixture.
  • the thickness of the positive electrode mixture layer is, for example, 10 ⁇ m to 150 ⁇ m per side of the positive electrode current collector.
  • the positive electrode mixture contains a positive electrode active material as an essential component.
  • the positive electrode active material includes a lithium-containing composite oxide and a sulfonic acid compound present on the surface of the lithium-containing composite oxide.
  • the positive electrode mixture layer may include a conductive agent as an optional component.
  • a conductive agent include carbon-based materials such as carbon black (CB), acetylene black (AB), Ketjen black, carbon nanotubes (CNT), graphene, and graphite. These may be used alone or in combination of two or more.
  • the positive electrode mixture layer may contain a binder.
  • binder include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, and polyolefin resins. These may be used alone or in combination of two or more.
  • the positive electrode current collector a non-porous conductive substrate (metal foil, etc.) or a porous conductive substrate (mesh body, net body, punched sheet, etc.) is used.
  • the material of the positive electrode current collector include aluminum, aluminum alloy, titanium, and titanium alloy.
  • the sulfonic acid compound is an organic compound having a sulfonic acid group (SO 3 H) or an organic compound having a salt of a sulfonic acid group.
  • the sulfonic acid compound may be a monosulfonic acid compound having only one sulfonic acid group (SO 3 H), a disulfonic acid compound having two sulfonic acid groups, or a polysulfonic acid compound having three or more sulfonic acid groups.
  • the valence of the cation of the salt of the sulfonic acid group may be monovalent or divalent or more.
  • the sulfonic acid compounds may be used alone or in combination of two or more.
  • the sulfonic acid compound has, for example, general formula (I): It is expressed as
  • A is a Group 1 element or a Group 2 element.
  • A is preferably a Group 1 element, and more preferably Li.
  • R is a hydrocarbon group, preferably an alkyl group.
  • R may be an alkyl group having 5 or less carbon atoms or an alkyl group having 3 or less carbon atoms, but is preferably a methyl group.
  • a portion of the hydrogen bonded to carbon may be substituted with fluorine.
  • all of the hydrogens bonded to carbons are not replaced with fluorine. The smaller the molecular weight of R, the lower the reaction resistance.
  • the sulfonic acid compound examples include lithium methanesulfonate, lithium ethanesulfonate, lithium propanesulfonate, sodium methanesulfonate, magnesium methanesulfonate, lithium fluoromethanesulfonate, and the like.
  • the amount of the sulfonic acid compound present on the surface of the lithium-containing composite oxide may be, for example, 0.1% by mass or more and 1% by mass or less, and 0.3% by mass or more and 0.0% by mass or less, based on the mass of the lithium-containing composite oxide. It may be .8% by mass or less.
  • the presence of the sulfonic acid compound on the surface of the lithium-containing composite oxide can be confirmed by Fourier transform infrared spectroscopy (FT-IR).
  • FT-IR Fourier transform infrared spectroscopy
  • the positive electrode active material may have an absorption peak at at least one location near 1238 cm -1 , 1175 cm -1 , 1065 cm -1 , and 785 cm -1 .
  • a positive electrode active material containing lithium methanesulfonate has absorption peaks around 1238 cm -1 , 1175 cm -1 , 1065 cm -1 , and 785 cm -1 .
  • the peaks around 1238 cm -1 , 1175 cm -1 , and 1065 cm -1 are absorption peaks resulting from SO stretching vibrations derived from lithium methanesulfonate.
  • the peak near 785 cm ⁇ 1 is an absorption peak resulting from CS stretching vibration derived from lithium methanesulfonate.
  • an absorption peak derived from the sulfonic acid compound contained in the positive electrode active material can be identified, as in the case of a positive electrode active material containing lithium methanesulfonate.
  • the presence of the sulfonic acid compound on the surface of the lithium-containing composite oxide can also be confirmed by ICP, atomic absorption spectrometry, X-ray photoelectron spectroscopy (XPS), synchrotron radiation XRD measurement, TOF-SIMS, etc.
  • the average particle diameter of the particulate sulfonic acid compound is, for example, 100 ⁇ m or less, may be 50 ⁇ m or less, may be 30 ⁇ m or less, or may be 15 ⁇ m or less. In this case, the sulfonic acid compound can be more uniformly adhered to the entire positive electrode active material powder, and the effects of the sulfonic acid compound can be more significantly exhibited.
  • the lower limit of the average particle diameter of the sulfonic acid compound is, for example, 1 ⁇ m.
  • the average particle diameter of the sulfonic acid compound can be determined by observing the sulfonic acid compound present on the surface of the lithium-containing composite oxide using a SEM. Specifically, after specifying the outer shape of 50 randomly selected particles, the major axis (longest axis) of each of the 50 particles is determined, and the average value thereof is taken as the average particle diameter of the sulfonic acid compound.
  • the particle size of the primary particles constituting the secondary particles of the lithium-containing composite oxide is, for example, 0.02 ⁇ m to 20 ⁇ m.
  • the particle size of a primary particle is measured as the diameter of a circumscribed circle in a particle image observed by a scanning electron microscope (SEM).
  • the average particle diameter of the secondary particles of the lithium-containing composite oxide is, for example, 20 ⁇ m to 300 ⁇ m.
  • the average particle diameter means the volume-based median diameter (D50).
  • D50 means a particle size at which the cumulative volume from the small particle size side is 50% in the volume-based particle size distribution.
  • the particle size distribution of the secondary particles of the lithium-containing composite oxide can be measured using a laser diffraction type particle size distribution measuring device (for example, MT3000II manufactured by Microtrac Bell Co., Ltd.) using water as a dispersion medium.
  • the lithium-containing composite oxide may have a layered rock salt structure.
  • the layered rock salt structure may belong to space group R-3m, space group C2/m, etc., for example. Among these, a layered rock salt structure belonging to space group R-3m is preferred because of its high capacity and high stability of crystal structure.
  • the layered rock salt structure of the lithium-containing composite oxide may include a transition metal layer, a Li layer, and an oxygen layer.
  • the proportion of Ni (Ni content) in the metal elements other than Li contained in the lithium-containing composite oxide may be set to 50 atomic % or more, 80 atomic % or more, or 90 atomic %. It may be more than that.
  • the proportion of Co (Co content) in the metal elements other than Li contained in the lithium-containing composite oxide is set to 0 atomic %. It may be more than 1.5 atomic % or more. Further, the Co content may be 20 atomic % or less, 16 atomic % or less, or 10 atomic % or less.
  • the proportion of Al (Al content) in the metal elements other than Li contained in the lithium-containing composite oxide is reduced to 0. It may be at least 3.5 at %, or at least 4 at %. Further, the Al content may be set to 18.5 at % or less, or 10 at % or less.
  • the proportion of Mn in the metal elements other than Li contained in the lithium-containing composite oxide may be set to 0 atomic % or more, or may be set to 5 atomic % or more. Further, the Mn content may be set to 50 at % or less, or 30 at % or less.
  • the content of each metal element contained in the lithium-containing composite oxide is measured, for example, by inductively coupled plasma (ICP) emission spectrometry.
  • ICP inductively coupled plasma
  • M1 is Mn, Fe, Ti, Si, It may be a composite oxide represented by at least one element selected from Nb, Zr, Mo, and Zn. In this case, M1 is preferably Mn.
  • the method for producing a positive electrode active material includes, for example, a synthesis step, a washing step, a drying step, and an addition step.
  • a transition metal oxide and a Li compound are mixed and fired to obtain a lithium-containing composite oxide.
  • Transition metal oxides can be prepared by, for example, adding an alkaline solution such as sodium hydroxide dropwise to a solution of a metal salt containing a metal element such as Ni, Co, Al, or Mn while stirring to adjust the pH to an alkaline side (for example, 8.5). ⁇ 12.5), the composite hydroxide can be precipitated (co-precipitated), and the composite hydroxide can be obtained by heat treatment.
  • the heat treatment temperature is not particularly limited, but is, for example, in the range of 300°C to 600°C.
  • Li compound examples include Li 2 CO 3 , LiOH, Li 2 O 2 , Li 2 O, LiNO 3 , LiNO 2 , Li 2 SO 4 , LiOH ⁇ H 2 O, LiH, and LiF.
  • the mixing ratio of the metal oxide and the Li compound is preferably such that, for example, the molar ratio of metal elements other than Li to Li is in the range of 1:0.98 to 1:1.1.
  • other metal raw materials may be added as necessary.
  • other metal raw materials include oxides containing metal elements other than the metal elements constituting the transition metal oxide.
  • the mixture of the transition metal oxide and the Li compound is fired, for example, in an oxygen atmosphere.
  • the firing conditions are such that the temperature increase rate is in the range of more than 1.0°C/min and less than 5.5°C/min at 450°C or more and 680°C or less, and the maximum temperature reached is in the range of 700°C or more and 850°C or less. There may be.
  • the temperature increase rate from over 680°C to the maximum temperature reached may be, for example, 0.1°C/min to 3.5°C/min. Further, the maximum temperature reached may be maintained for 1 hour or more and 10 hours or less.
  • this firing step may be a multi-stage firing, and a plurality of first temperature increase rates and second temperature increase rates may be set for each temperature range as long as they are within the ranges defined above.
  • the lithium-containing composite oxide obtained in the synthesis step is washed with water and dehydrated to obtain a cake-like composition. Washing with water and dehydration can be performed using known methods and conditions. This may be carried out within a range where lithium is not eluted from the lithium-containing composite oxide and the battery characteristics are not deteriorated. Note that since the positive electrode active material according to this embodiment is washed with water, there is little remaining alkaline component.
  • the cake-like composition obtained in the washing step is dried.
  • the drying step may be performed under a vacuum atmosphere. Drying conditions are, for example, 150° C. to 400° C. for 0.5 hours to 15 hours.
  • a sulfonic acid compound and a sulfonic acid solution eg, an aqueous solution
  • the sulfonic acid compound can be attached to the surface of the lithium-containing composite oxide.
  • at least one of a sulfonic acid compound and a sulfonic acid solution is added to the cake-like composition. Li compounds remain in the cake-like composition, and this residual Li compound is dissolved in the water contained in the cake-like composition, so even when a sulfonic acid solution is added, the sulfonic acid containing Li remains. A compound is formed.
  • the amount of the sulfonic acid compound added is preferably 0.1% by mass to 1% by mass, more preferably 0.3% by mass to 0.8% by mass, based on the mass of the lithium-containing composite oxide. preferable.
  • the concentration of the sulfonic acid solution is, for example, 0.5% by weight to 40% by weight.
  • the raw material for the nonmetallic compound may be added, for example, during the synthesis process, after the synthesis process, during the washing process, after the washing process, during the drying process, after the drying process, or during the addition process.
  • a nonmetallic compound containing the element can be attached to the surface of the lithium-containing composite oxide.
  • Examples of the Sr raw material include Sr(OH) 2 , Sr(OH) 2.8H2O , SrO, SrCo3 , SrSO4 , Sr( NO3 ) 2 , SrCl2 , SrAlO4, and the like.
  • Examples of the Ca raw material include Ca(OH) 2 , CaO, CaCO 3 , CaSO 4 , Ca(NO 3 ) 2 , CaCl 2 , and CaAlO 4 .
  • Examples of the Zr raw material include Zr(OH) 4 , ZrO 2 , Zr(CO 3 ) 2 , Zr (SO 4 ) 2.4H 2 O, and the like.
  • rare earth raw materials include rare earth oxides, hydroxides, carbonates, and the like.
  • the W raw material include tungsten oxide (WO 3 ), lithium tungstate (Li 2 WO 4 , Li 4 WO 5 , Li 6 W 2 O 9 ), and the like. Note that a solution containing W may be used as the W raw material.
  • Al raw material Al2O3 , Al(OH)3, Al2 ( SO4 ) 3, etc. may be used, but Al derived from a lithium-containing composite oxide may also be used.
  • the P raw material include Li 3-x H x PO 4 (0 ⁇ x ⁇ 3).
  • the B raw material include H 3 BO 3 , Li 3 BO 3 , Li 2 B 4 O 7 and the like.
  • the negative electrode includes at least a negative electrode current collector, and may have a negative electrode mixture layer provided on the surface of the negative electrode current collector.
  • the negative electrode current collector is made of a sheet-like conductive material.
  • the negative electrode mixture layer is supported on one or both surfaces of the negative electrode current collector.
  • the negative electrode mixture layer is usually a layer or film composed of a negative electrode mixture.
  • the thickness of the negative electrode mixture layer is, for example, 10 ⁇ m to 150 ⁇ m per side of the negative electrode current collector.
  • the negative electrode mixture contains a negative electrode active material as an essential component, and can also contain a binder, a conductive agent, a thickener, etc. as optional components. Known materials can be used as the binder, conductive agent, and thickener.
  • the negative electrode active material includes materials that electrochemically absorb and release lithium ions, lithium metal, lithium alloys, and the like.
  • Carbon materials, alloy materials, and the like are used as materials that electrochemically absorb and release lithium ions.
  • Examples of the carbon material include graphite, graphitizable carbon (soft carbon), and non-graphitizable carbon (hard carbon). Among these, graphite is preferable because it has excellent charging/discharging stability and low irreversible capacity.
  • the alloy material is a material containing at least one metal that can form an alloy with lithium. Such materials include silicon, tin, silicon alloys, tin alloys, silicon compounds, and the like. Silicon oxide, tin oxide, etc. may also be used.
  • silicon-containing alloy material for example, a silicon-containing material containing a lithium ion conductive phase and a silicon phase dispersed in the lithium ion conductive phase can be preferably used.
  • the lithium ion conductive phase for example, a silicon oxide phase, a silicate phase, a carbon phase, etc. can be used.
  • the main component (eg 95-100% by weight) of the silicon oxide phase can be silicon dioxide.
  • a silicate phase is preferable because it has a small irreversible capacity.
  • a silicate phase containing lithium hereinafter also referred to as lithium silicate phase
  • the lithium silicate phase may be an oxide phase containing lithium (Li), silicon (Si), and oxygen (O), and may also contain other elements.
  • the atomic ratio of O to Si in the lithium silicate phase: O/Si is, for example, greater than 2 and less than 4.
  • O/Si is greater than 2 and less than 3.
  • the atomic ratio of Li to Si in the lithium silicate phase: Li/Si is, for example, greater than 0 and less than 4.
  • the lithium silicate phase may have a composition represented by the formula: Li 2z SiO 2+z (0 ⁇ z ⁇ 2).
  • Examples of elements other than Li, Si and O that may be included in the lithium silicate phase include iron (Fe), chromium (Cr), nickel (Ni), manganese (Mn), copper (Cu), molybdenum (Mo), Examples include zinc (Zn) and aluminum (Al).
  • the carbon phase may be composed of, for example, amorphous carbon with low crystallinity (that is, amorphous carbon).
  • amorphous carbon may be, for example, hard carbon, soft carbon, or other materials.
  • a silicon-containing material and a carbon material may be used together as the negative electrode active material.
  • the silicon-containing material expands and contracts in volume as it is charged and discharged, so if its proportion in the negative electrode active material becomes large, poor contact between the negative electrode active material and the negative electrode current collector is likely to occur as the silicon-containing material is charged and discharged.
  • a silicon-containing material and a carbon material together, it is possible to achieve excellent cycle characteristics while imparting high capacity to the negative electrode.
  • the proportion of the silicon-containing material in the total of the silicon-containing material and the carbon material is, for example, preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass. This makes it easier to achieve both higher capacity and improved cycle characteristics.
  • a non-porous conductive substrate metal foil, etc.
  • a porous conductive substrate meh body, net body, punched sheet, etc.
  • the material of the negative electrode current collector include stainless steel, nickel, nickel alloy, copper, and copper alloy.
  • the non-aqueous electrolyte includes a non-aqueous solvent and a solute dissolved in the non-aqueous solvent.
  • the solute includes, for example, a lithium salt.
  • Components of the nonaqueous electrolyte other than the nonaqueous solvent and solute are additives.
  • the non-aqueous electrolyte may contain various additives.
  • a sulfur-containing compound is particularly used as an essential component.
  • the non-aqueous electrolyte may contain one type of sulfur-containing compound, or may contain a combination of two or more types.
  • the sulfur-containing compound may include a fluorosulfonic acid or a fluorosulfonate. Among the fluorosulfonates, lithium fluorosulfonate is preferred.
  • sulfur-containing compound at least one selected from the group consisting of sulfuric esters, sulfite esters, sulfonic acid esters, and sulfonylimide compounds may be used.
  • the sulfuric acid ester may be cyclic or chain-like, or may constitute a salt.
  • C 2-4 alkyl sulfate is preferred. Specific examples include ethylene sulfate, propylene sulfate, trimethylene sulfate, butylene sulfate, vinylene sulfate, ethyl sulfate, methyl sulfate, and the like.
  • the sulfite ester may be cyclic or chain-like, or may constitute a salt.
  • C 2-4 alkylene sulfite is preferred. Specific examples include ethylene sulfite (ES), propylene sulfite, trimethylene sulfite, butylene sulfite, and vinylene sulfite.
  • the sulfonic acid ester may be cyclic or chain-like, or may constitute a salt.
  • As the sulfonic acid ester at least one selected from the group consisting of C 3-5 alkanesultone and C 3-5 alkene sultone is preferable.
  • cyclic sulfonic acid esters are preferred. Specific examples include 1,3-propane sultone, 1,4-butane sultone, and 1,3-propene sultone.
  • an imide salt can be used as the sulfonylimide compound.
  • imide salts include lithium bisfluorosulfonylimide (LiN(FSO 2 ) 2 ), lithium bistrifluoromethanesulfonate imide (LiN(CF 3 SO 2 ) 2 ), and lithium trifluoromethanesulfonate nonafluorobutanesulfonate imide (LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 )), lithium bispentafluoroethanesulfonic acid imide (LiN(C 2 F 5 SO 2 ) 2 ), and the like.
  • the non-aqueous electrolyte may contain one type of imide salt, or may contain a combination of two or more types.
  • one or more hydrogen atoms of the compounds exemplified above may be substituted with a substituent.
  • substituents include an alkyl group, a hydroxyalkyl group, a hydroxy group, an alkoxy group, and a halogen atom.
  • the substituent may have 1 to 4 carbon atoms or 1 to 3 carbon atoms.
  • the halogen atom include a chlorine atom and a fluorine atom.
  • the content of the sulfur-containing compound contained in the non-aqueous electrolyte is, for example, 0.01% by mass or more and 10% by mass or less.
  • the content of the sulfur-containing compound in the nonaqueous electrolyte may be 5% by mass or less, 3% by mass or less, or 2% by mass or less.
  • the content of the sulfur-containing compound in the nonaqueous electrolyte may be 0.1% by mass or more, or 0.5% by mass or more.
  • the content rate of the sulfur-containing compound in the non-aqueous electrolyte changes during the storage period or during the charge/discharge cycle. Therefore, it is sufficient that the sulfur-containing compound remains in the non-aqueous electrolyte collected from the non-aqueous electrolyte secondary battery at a concentration higher than the detection limit.
  • the non-aqueous electrolyte may also contain other additives.
  • additives include vinyl ethylene carbonate and cyclohexylbenzene.
  • cyclic carbonate for example, cyclic carbonate, chain carbonate, cyclic carboxylic acid ester, chain carboxylic ester, etc. are used.
  • cyclic carbonate examples include propylene carbonate (PC), ethylene carbonate (EC), vinylene carbonate (VC), and the like.
  • chain carbonate esters examples include diethyl carbonate (DEC), ethylmethyl carbonate (EMC), and dimethyl carbonate (DMC).
  • examples of the cyclic carboxylic acid ester include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
  • chain carboxylic acid esters examples include methyl acetate, ethyl acetate, propyl acetate, methyl propionate (MP), and ethyl propionate (EP).
  • the non-aqueous solvents may be used alone or in combination of two or more.
  • lithium salts include lithium salts of chlorine-containing acids (LiClO 4 , LiAlCl 4 , LiB 10 Cl 10 , etc.), lithium salts of fluorine-containing acids (LiPF 6 , LiPF 2 O 2 , LiBF 4 , LiSbF 6 , LiAsF 6 ).
  • lithium salts of fluorine-containing acid imides LiN(FSO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , LiN(CF 3 SO 2 )(C 4 F 9 SO 2 ), LiN (C 2 F 5 SO 2 ) 2 , etc.
  • lithium halide LiCl, LiBr, LiI, etc.
  • One type of lithium salt may be used alone, or two or more types may be used in combination.
  • the concentration of the lithium salt in the non-aqueous electrolyte may be 1 mol/liter or more and 2 mol/liter or less, or 1 mol/liter or more and 1.5 mol/liter or less.
  • an electrolytic solution having excellent ionic conductivity and appropriate viscosity can be obtained.
  • the lithium salt concentration is not limited to the above.
  • the separator has high ion permeability, appropriate mechanical strength, and insulation properties.
  • a microporous thin film, woven fabric, nonwoven fabric, etc. can be used.
  • polyolefins such as polypropylene and polyethylene are preferred.
  • Nonaqueous electrolyte secondary battery An example of the structure of a non-aqueous electrolyte secondary battery is a structure in which an electrode group including a positive electrode and a negative electrode wound together with a separator interposed therebetween is housed in an exterior body together with a non-aqueous electrolyte.
  • the present invention is not limited to this, and other forms of electrode groups may be applied.
  • a stacked electrode group in which a positive electrode and a negative electrode are stacked with a separator interposed therebetween may be used.
  • the shape of the secondary battery is not limited either, and may be, for example, cylindrical, square, coin-shaped, button-shaped, laminated, or the like.
  • FIG. 1 is a longitudinal cross-sectional view of a cylindrical secondary battery 10 that is an example of this embodiment.
  • the present disclosure is not limited to the following configuration.
  • the secondary battery 10 includes an electrode group 18, an electrolyte (not shown), and a bottomed cylindrical battery can 22 that accommodates these.
  • the sealing body 11 is caulked and fixed to the opening of the battery can 22 with a gasket 21 interposed therebetween. This seals the inside of the battery.
  • the sealing body 11 includes a valve body 12, a metal plate 13, and an annular insulating member 14 interposed between the valve body 12 and the metal plate 13.
  • the valve body 12 and the metal plate 13 are connected to each other at their respective centers.
  • a positive electrode lead 15a led out from the positive electrode 15 is connected to the metal plate 13. Therefore, the valve body 12 functions as a positive external terminal.
  • a negative electrode lead 16a led out from the negative electrode 16 is connected to the bottom inner surface of the battery can 22.
  • An annular groove 22a is formed near the open end of the battery can 22.
  • a first insulating plate 23 is arranged between one end surface of the electrode group 18 and the annular groove 22a.
  • a second insulating plate 24 is arranged between the other end surface of the electrode group 18 and the bottom of the battery can 22.
  • the electrode group 18 is formed by winding a positive electrode 15 and a negative electrode 16 with a separator 17 in between.
  • Examples 1 to 4> The composite hydroxide represented by [Ni 0.90 Co 0.05 Al 0.05 ](OH) 2 obtained by the coprecipitation method was calcined at 500°C for 8 hours to form a metal oxide (Ni 0.90 Co 0.05 Al 0.05 O 2 ). Obtained. Next, LiOH and the metal oxide were mixed such that the molar ratio of Li to the total amount of Ni, Co, and Al was 1.03:1 to obtain a mixture. After firing the mixture from room temperature to 650 °C at a heating rate of 2.0 °C / min under an oxygen stream with an oxygen concentration of 95% (flow rate of 2 mL / min per 10 cm 3 and 5 L / min per 1 kg of mixture). A lithium-containing composite oxide was obtained by firing from 650°C to 780°C at a temperature increase rate of 0.5°C/min (synthesis step).
  • Particulate lithium methanesulfonate having an average particle diameter of 30 ⁇ m was added to the cake-like composition (addition step).
  • the amount of lithium methanesulfonate added was 0.5% by mass based on the mass of the lithium-containing composite oxide.
  • a drying step was performed at 180° C. for 2 hours in a vacuum atmosphere to obtain the positive electrode active material of Example 1.
  • [Positive electrode] 98 parts by mass of a positive electrode active material having lithium methanesulfonate on the surface, 1 part by mass of acetylene black as a conductive material, 1 part by mass of polyvinylidene fluoride as a binder, and N-methyl-2-pyrrolidone. (NMP) was mixed as a dispersion medium to prepare a positive electrode slurry. After applying the positive electrode slurry to both sides of a positive electrode current collector made of thick aluminum foil and drying the coating film, the coating film is rolled with a rolling roller and cut into a predetermined electrode size, and a positive electrode mixture layer is applied to both sides. A positive electrode was obtained. An exposed portion where the surface of the positive electrode current collector was exposed was provided in a part of the positive electrode.
  • the negative electrode active material a mixture of a silicon-containing material and artificial graphite in a mass ratio of 10:90 was used.
  • a negative electrode slurry was prepared by blending 100 parts by mass of the negative electrode active material, 1 part by mass of carboxymethyl cellulose sodium (CMC-Na), and 1 part by mass of styrene-butadiene rubber (SBR), and mixing with water as a dispersion medium.
  • CMC-Na carboxymethyl cellulose sodium
  • SBR styrene-butadiene rubber
  • a negative electrode having the following properties was obtained. An exposed portion where the surface of the negative electrode current collector was exposed was provided in a part of the negative electrode.
  • Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) were mixed at a volume ratio of 3:3:4.
  • a nonaqueous electrolyte was prepared by dissolving lithium hexafluorophosphate (LiPF 6 ) in the mixed solvent to a concentration of 1.2 mol/liter.
  • LiPF 6 lithium hexafluorophosphate
  • One of the following sulfur-containing compounds was dissolved in the non-aqueous electrolyte at a content of 0.5% by mass.
  • a positive electrode lead is attached to the exposed part of the positive electrode, and a negative electrode lead is attached to the negative electrode, and the positive and negative electrodes are spirally wound through a polyolefin separator, and then press-formed in the radial direction to form a flat wound electrode.
  • a group was created. The electrode group was housed in an exterior body made of an aluminum laminate sheet, and after the nonaqueous electrolyte was injected, the opening of the exterior body was sealed to obtain test cells (batteries A1 to A4).
  • Table 1 shows the discharge capacities of batteries A1 to A4, when the discharge capacity of battery B2 of Comparative Example 2, which will be described later, is 100%. The larger the value in Table 1, the better the charge/discharge cycle characteristics.
  • Battery B1 of Comparative Example 1 was prepared in the same manner as in Example 1, except that lithium methanesulfonate was not added to the positive electrode active material and lithium fluorosulfonate was not included in the nonaqueous electrolyte. evaluated.
  • Battery B2 of Comparative Example 2 was produced in the same manner as in Example 1, except that lithium fluorosulfonate was not included in the non-aqueous electrolyte, and evaluated in the same manner.
  • Batteries B3 to B6 of Comparative Examples 3 to 6 were produced in the same manner as Examples 1 to 4, except that lithium methanesulfonate was not added to the positive electrode active material, and evaluated in the same manner.
  • Table 1 shows that when lithium methanesulfonate was not added to the positive electrode active material, the sulfur-containing compound contained in the non-aqueous electrolyte had no effect on improving the capacity retention rate.
  • the present disclosure includes the embodiments described below.
  • the positive electrode includes a positive electrode active material
  • the positive electrode active material includes a lithium-containing composite oxide and a sulfonic acid compound present on the surface of the lithium-containing composite oxide
  • a non-aqueous electrolyte secondary battery wherein the non-aqueous electrolyte contains a sulfur-containing compound.
  • the sulfonic acid compound has the general formula (I): It is expressed as In the general formula (1), A is a group 1 element or a group 2 element, R is a hydrocarbon group, The non-aqueous electrolyte secondary battery according to (1) above, wherein n is 1 or 2. (3) The nonaqueous electrolyte secondary battery according to (1) or (2) above, wherein the A is a Group 1 element. (4) The nonaqueous electrolyte secondary battery according to any one of (1) to (3) above, wherein the A is Li. (5) The nonaqueous electrolyte secondary battery according to any one of (1) to (4) above, wherein R is an alkyl group.
  • the proportion of Ni in the metal elements other than Li contained in the lithium-containing composite oxide is 50 atomic % or more, the proportion of Co is 0 atomic % or more and 20 atomic % or less, and the proportion of Al is 0.
  • the negative electrode includes a negative electrode active material, The non-aqueous electrolyte secondary battery according to any one of (1) to (13) above, wherein the negative electrode active material includes a carbon material and a silicon-containing material.
  • the nonaqueous electrolyte secondary battery according to the present disclosure is useful as a main power source for mobile communication devices, electric vehicles, hybrid vehicles, portable electronic devices, and the like.

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PCT/JP2023/026230 2022-08-23 2023-07-18 非水電解質二次電池 Ceased WO2024042919A1 (ja)

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Citations (7)

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JPH0513068A (ja) * 1991-07-04 1993-01-22 Sanyo Electric Co Ltd 非水電解液二次電池
JP2003173782A (ja) * 2001-09-26 2003-06-20 Mitsubishi Chemicals Corp リチウム二次電池及び正極
JP2016091724A (ja) * 2014-10-31 2016-05-23 トヨタ自動車株式会社 リチウム二次電池およびその製造方法
WO2016136210A1 (ja) * 2015-02-25 2016-09-01 三洋電機株式会社 非水電解質二次電池
JP2018006164A (ja) 2016-07-01 2018-01-11 宇部興産株式会社 蓄電デバイスの電極用チタン酸リチウム粉末および活物質材料、並びにそれを用いた蓄電デバイス
JP2021044137A (ja) * 2019-09-10 2021-03-18 トヨタ自動車株式会社 非水電解液二次電池
JP2021520023A (ja) * 2019-03-18 2021-08-12 寧徳新能源科技有限公司Ｎｉｎｇｄｅ Ａｍｐｅｒｅｘ Ｔｅｃｈｎｏｌｏｇｙ Ｌｉｍｉｔｅｄ 電気化学機器及びそれを備えた電子機器

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0513068A (ja) * 1991-07-04 1993-01-22 Sanyo Electric Co Ltd 非水電解液二次電池
JP2003173782A (ja) * 2001-09-26 2003-06-20 Mitsubishi Chemicals Corp リチウム二次電池及び正極
JP2016091724A (ja) * 2014-10-31 2016-05-23 トヨタ自動車株式会社 リチウム二次電池およびその製造方法
WO2016136210A1 (ja) * 2015-02-25 2016-09-01 三洋電機株式会社 非水電解質二次電池
JP2018006164A (ja) 2016-07-01 2018-01-11 宇部興産株式会社 蓄電デバイスの電極用チタン酸リチウム粉末および活物質材料、並びにそれを用いた蓄電デバイス
JP2021520023A (ja) * 2019-03-18 2021-08-12 寧徳新能源科技有限公司Ｎｉｎｇｄｅ Ａｍｐｅｒｅｘ Ｔｅｃｈｎｏｌｏｇｙ Ｌｉｍｉｔｅｄ 電気化学機器及びそれを備えた電子機器
JP2021044137A (ja) * 2019-09-10 2021-03-18 トヨタ自動車株式会社 非水電解液二次電池

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