WO2022070893A1 - 二次電池用正極活物質および二次電池 - Google Patents

二次電池用正極活物質および二次電池 Download PDF

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WO2022070893A1
WO2022070893A1 PCT/JP2021/033788 JP2021033788W WO2022070893A1 WO 2022070893 A1 WO2022070893 A1 WO 2022070893A1 JP 2021033788 W JP2021033788 W JP 2021033788W WO 2022070893 A1 WO2022070893 A1 WO 2022070893A1
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positive electrode
composite oxide
metal composite
lithium metal
active material
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French (fr)
Japanese (ja)
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晋 張
一成 池内
光宏 日比野
健祐 名倉
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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 US18/028,999 priority Critical patent/US20230369579A1/en
Priority to JP2022553785A priority patent/JPWO2022070893A1/ja
Priority to EP21875195.6A priority patent/EP4224576A4/en
Priority to CN202180066934.3A priority patent/CN116325227B/zh
Publication of WO2022070893A1 publication Critical patent/WO2022070893A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/24—Oxygen compounds of fluorine
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C01G45/1228—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/1315—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This disclosure relates to a positive electrode active material for a secondary battery and a secondary battery.
  • Secondary batteries are expected as power sources for small consumer applications, power storage devices and electric vehicles because they have high output and high energy density.
  • a composite oxide of lithium and a transition metal for example, cobalt
  • cobalt transition metal
  • Li excess type lithium metal composite oxides based on Li 1 + x Mn 1-x O 2 having a rock salt structure have been attracting attention.
  • Patent Document 1 has a crystal structure belonging to the space group Fm-3m and has a composition formula Li 1 + x Nby Me z App O 2 (Me is a transition metal containing Fe and / or Mn, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.5, 0.25 ⁇ z ⁇ 1, A is an element other than Nb and Me, 0 ⁇ p ⁇ 0.2, where Li 1 + p Fe 1-q Nb q O 2 and 0.
  • a positive electrode active material containing a lithium transition metal composite oxide represented by (15 ⁇ p ⁇ 0.3, 0 ⁇ q ⁇ 0.3) is disclosed.
  • Patent Document 1 high capacity is possible by controlling the composition (that is, adding Nb). However, the effect of improving the capacity is insufficient, and there is still room for improvement.
  • one aspect of the present disclosure includes a lithium metal composite oxide having a crystal structure based on a rock salt structure belonging to the space group Fm-3m, and the lithium metal composite oxide is derived from Ca, Al and Si.
  • the present invention relates to a positive electrode active material for a secondary battery, which comprises at least one element A 1 selected from the group.
  • Another aspect of the present disclosure relates to a secondary battery comprising a positive electrode, a negative electrode, an electrolyte and a separator interposed between the positive electrode and the negative electrode, wherein the positive electrode contains the positive electrode active material for the secondary battery.
  • a secondary battery having a high energy density can be realized.
  • FIG. 1 is a schematic perspective view in which a part of the secondary battery according to the embodiment of the present disclosure is cut out.
  • the positive electrode active material for a secondary battery according to the embodiment of the present disclosure includes a lithium metal composite oxide having a crystal structure based on a rock salt structure belonging to the space group Fm-3m. That is, this lithium metal composite oxide has a crystal structure similar to the rock salt structure belonging to the space group Fm-3m.
  • This lithium metal composite oxide contains at least one element A 1 selected from the group consisting of Ca, Al and Si.
  • the total content of Ca, Al and Si (element A1) contained in the lithium metal composite oxide may be 10 to 1000 ppm with respect to the total amount of the lithium metal composite oxide on a mass basis.
  • the capacity is improved by containing a small amount of element A1.
  • the formation of a dielectric layer composed of the oxide of element A1 on at least a part of the surface of the positive electrode active material causes the surface of the active material to change due to the change in the electric field distribution. It is considered that one of the causes is that the electron orbital energy of the electron changes and the tunnel transfer of electrons (charge transfer reaction) accompanying the transfer of lithium ions between the electrolyte and the active material is promoted.
  • the above lithium metal composite oxide has a crystal structure based on a rock salt structure represented by NaCl, for example, an oxygen atom is arranged at an anion site, and Li atom and a metal atom other than Li are arranged at a cation site. It may have a structure in which (including element A 1 ) is irregularly arranged.
  • the lithium metal composite oxide preferably contains Mn as a transition metal element.
  • the molar ratio of Mn in the lithium metal composite oxide may be larger than the total molar ratio of the transition metal elements excluding Mn. That is, the lithium metal composite oxide may be based on the composite oxide of Li and Mn. Examples of such a composite oxide of Li and Mn include Li 1 + x Mn 1-x O 2 .
  • the cation site may have pores in which Li atoms and metal atoms are not arranged.
  • having pores means that in the positive electrode active material immediately after production or by disassembling and taking out a secondary battery in a discharged state, pores that are not filled with Li atoms or metal atoms are present in the lithium metal composite oxide.
  • the proportion of pores can be 0.5% or more, preferably 1% or more, more preferably 2% or more of the sites in which lithium or metal atoms can be arranged in the crystal structure.
  • the lithium metal composite oxide may contain fluorine (F). Fluorine can replace the oxygen atom of the anion site in the crystal structure. As a result, the state of excess Li is stabilized and a high capacity can be obtained. In addition, the average discharge potential rises due to the substitution of fluorine atoms.
  • the state of excess Li refers to a state in which the number of Li atoms in the composite oxide is larger than the number of transition metal atoms.
  • the arrangement of Li at the cation site is irregular and the bonding state of Li is various, so that the range of voltage distribution associated with Li emission is wide. Therefore, it may be difficult to use the hem portion on the low potential side of the voltage distribution as a capacitance.
  • the voltage distribution associated with Li emission moves to the high potential side, so that the hem portion can be easily used as a capacitance. This further increases the available capacity.
  • lithium metal composite oxide examples include the composition formula Li a Mn b M c O 2-d F d (where 0 ⁇ a ⁇ 1.35, 0.4 ⁇ b ⁇ 0.9, 0 ⁇ c ⁇ 0). .2, 0 ⁇ d ⁇ 0.66, 1.75 ⁇ a + b + c ⁇ 2).
  • M contains at least one metal element other than Li and Mn, and contains at least the element A1.
  • the molar ratio x of the pores is 0 ⁇ x ⁇ 0.25.
  • the molar ratio x of the pores is preferably x ⁇ 0.02, more preferably x ⁇ 0.05, and even more preferably x ⁇ 0.1.
  • a + b + c ⁇ 1.98 is preferable
  • a + b + c ⁇ 1.95 is more preferable
  • a + b + c ⁇ 1.9 is even more preferable.
  • the molar ratio x of the pores is more preferably x ⁇ 0.15 (a + b + c ⁇ 1.85).
  • the vacancies and the content ratio of vacancies can be derived based on the crystal structure and composition of the lithium metal composite oxide.
  • the crystal structure of the lithium metal composite oxide is identified from the X-ray diffraction pattern measured using a powder X-ray diffractometer (for example, desktop X-ray diffractometer MiniFlex manufactured by Rigaku Co., Ltd., X-ray source: CuK ⁇ ). To.
  • the composition of the lithium metal composite oxide can be measured using an ICP emission spectrophotometer (iCAP6300 manufactured by Thermo Fisher Scientific).
  • the vacancies and the content ratio of vacancies may be evaluated by a method utilizing positron annihilation.
  • a part of the oxygen atom in the anion site may be replaced with a fluorine atom.
  • the state of excess Li (a> 1) is stabilized, and a high capacity can be obtained.
  • the average discharge potential increases and the available capacity further increases.
  • the substitution ratio d of the fluorine atom in the composition formula of the lithium metal composite oxide may be 0.1 ⁇ d ⁇ 0.58, and 0.1 ⁇ d. It may be ⁇ 0.5, or 0.2 ⁇ d ⁇ 0.5.
  • the lithium metal composite oxide may contain a metal element M other than Li and Mn in addition to the element A1.
  • the lithium metal composite oxide has Ni, Co, Sn, Cu, Nb, Mo, Bi, V, Cr, Y, Zr, Zn, Na, K, Mg, Pt, Au, Ag, Ru, as the metal element M. It may contain at least one selected from the group consisting of Ta, W, La, Ce, Pr, Sm, Eu, Dy, and Er.
  • the lithium metal composite oxide preferably contains, as the metal element M, at least one selected from the group consisting of Ni, Sn, Mo, W, Ta, and Zn.
  • the lithium metal composite oxide is prepared by mixing, for example, lithium fluoride (LiF), lithium manganate (LiMnO 2 ), and an oxide of element A1 in an inert gas atmosphere such as Ar by a planetary ball mill. It can be synthesized by doing. Li 2 O and Mn 2 O 3 may be used as raw materials. Further, by adding lithium peroxide (Li 2 O 2 ) in addition to the above raw materials and performing a mixing treatment, a lithium metal composite oxide having pores can be synthesized. Instead of the planetary ball mill, a mixer capable of applying the same stirring shear force to the powder may be used, or the powder may be heated during the mixing process. The composition of the composite oxide and the like can be adjusted to a target range by changing, for example, the mixing ratio of LiF and LiMnO 2 and the mixing conditions (rotation speed, treatment time, treatment temperature, etc.).
  • the lithium metal composite oxide synthesized by the above method may contain Ca derived from the Li raw material used in the synthesis.
  • Al or Si derived from the material constituting the processing container at the time of mixing processing may be contained. If the amount of Ca, Al and / or Si that can be contained in the composite oxide is small, it contributes to the capacity improvement as described above.
  • CaO, Al 2 O 3 , and SiO 2 may be added to LiF and LiMnO 2 in predetermined amounts to perform a mixing treatment.
  • the secondary battery includes, for example, the following positive electrode, negative electrode, electrolyte and separator.
  • the positive electrode includes a positive electrode current collector and a positive electrode mixture layer formed on the surface of the positive electrode current collector and containing a positive electrode active material.
  • the positive electrode the above-mentioned positive electrode for a secondary battery is used.
  • the positive electrode mixture layer can be formed, for example, by applying a positive electrode slurry in which a positive electrode mixture containing a positive electrode active material, a binder and the like is dispersed in a dispersion medium to the surface of a positive electrode current collector and drying it. The dried coating film may be rolled if necessary.
  • the positive electrode mixture layer may be formed on one surface of the positive electrode current collector, or may be formed on both surfaces.
  • the positive electrode mixture layer contains a positive electrode active material as an essential component, and may contain a binder, a thickener, a conductive agent, a positive electrode additive, etc. as optional components.
  • a binder a binder, a thickener, a conductive agent, a positive electrode additive, etc.
  • Known materials can be used as the binder, thickener, and conductive agent.
  • the positive electrode active material includes the above-mentioned lithium metal composite oxide having a crystal structure similar to the rock salt structure belonging to the space group Fm-3m.
  • the composite oxide is, for example, a secondary particle formed by aggregating a plurality of primary particles.
  • the particle size of the primary particles is generally 0.05 ⁇ m to 1 ⁇ m.
  • the average particle size of the composite oxide is, for example, 3 ⁇ m to 30 ⁇ m, preferably 5 ⁇ m to 25 ⁇ m.
  • the average particle size of the composite oxide means the median diameter (D50) at which the cumulative frequency is 50% in the volume-based particle size distribution, and is measured by a laser diffraction type particle size distribution measuring device.
  • the content of the elements constituting the composite oxide is measured by an inductively coupled plasma emission spectrophotometer (ICP-AES), an electron probe microanalyzer (EPMA), an energy dispersive X-ray analyzer (EDX), or the like. be able to.
  • ICP-AES inductively coupled plasma emission spectrophotometer
  • EPMA electron probe microanalyzer
  • EDX energy dispersive X-ray analyzer
  • the above-mentioned lithium metal composite oxide having a crystal structure similar to the above-mentioned rock salt structure may be mixed with another known lithium metal oxide other than the above-mentioned lithium metal composite oxide.
  • other lithium metal oxides include Li a CoO 2 , Li a NiO 2 , Li a MnO 2 , Li a Co b Ni 1-b O 2 , Li a Co b M 1-b O c , and Li a .
  • lithium transition metal composite oxides such as Ni 1-b M b O c , Li a Mn 2 O 4 , Li a Mn 2-b M b O 4, LiMePO 4, and Li 2 MePO 4 F.
  • M is at least one selected from the group consisting of Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B.
  • Me contains at least a transition element (eg, includes at least one selected from the group consisting of Mn, Fe, Co, Ni).
  • the a value indicating the molar ratio of lithium increases or decreases depending on charging and discharging.
  • the shape and thickness of the positive electrode current collector can be selected from the shape and range according to the negative electrode current collector.
  • Examples of the material of the positive electrode current collector include stainless steel, aluminum, aluminum alloy, and titanium.
  • the negative electrode includes, for example, a negative electrode current collector and a negative electrode active material layer formed on the surface of the negative electrode current collector.
  • the negative electrode active material layer can be formed, for example, by applying a negative electrode slurry in which a negative electrode mixture containing a negative electrode active material, a binder and the like is dispersed in a dispersion medium to the surface of a negative electrode current collector and drying it. The dried coating film may be rolled if necessary. That is, the negative electrode active material may be a mixture layer. Further, a lithium metal foil or a lithium alloy foil may be attached to the negative electrode current collector.
  • the negative electrode active material layer may be formed on one surface of the negative electrode current collector, or may be formed on both surfaces.
  • the negative electrode active material layer contains a negative electrode active material as an essential component, and can contain a binder, a conductive agent, a thickener, and the like as optional components. Known materials can be used as the binder, the conductive agent, and the thickener.
  • the negative electrode active material includes a material that electrochemically stores and releases lithium ions, a lithium metal, and / or a lithium alloy.
  • a material that electrochemically occludes and releases lithium ions a carbon material, an alloy-based material, or the like is used.
  • the carbon material include graphite, easily graphitized carbon (soft carbon), and non-graphitized carbon (hard carbon). Of these, graphite, which has excellent charge / discharge stability and has a small irreversible capacity, is preferable.
  • the alloy-based material include those containing at least one kind of metal capable of forming an alloy with lithium, and examples thereof include silicon, tin, silicon alloys, tin alloys, and silicon compounds. Silicon oxide, tin oxide, or the like in which these are combined with oxygen may be used.
  • a lithium ion conductive phase and a silicon composite material in which silicon particles are dispersed in the lithium ion conductive phase can be used.
  • the lithium ion conductive phase for example, a silicon oxide phase, a silicate phase and / or a carbon phase can be used.
  • the main component of the silicon oxide phase eg, 95-100% by weight
  • a composite material composed of a silicate phase and silicon particles dispersed in the silicate phase is preferable in that it has a high capacity and a small irreversible capacity.
  • the silicate phase may include, for example, at least one selected from the group consisting of Group 1 elements and Group 2 elements in the long periodic table.
  • Examples of the Group 1 element of the long-periodic table and the Group 2 element of the long-periodic table include lithium (Li), potassium (K), sodium (Na), magnesium (Mg), and calcium (Ca).
  • Strontium (Sr), barium (Ba) and the like can be used.
  • Other elements may include aluminum (Al), boron (B), lanthanum (La), phosphorus (P), zirconium (Zr), titanium (Ti) and the like.
  • a silicate phase containing lithium hereinafter, also referred to as a lithium silicate phase
  • a silicate phase containing lithium is preferable because the irreversible capacity is small and the initial charge / discharge efficiency is high.
  • the lithium silicate phase may be an oxide phase containing lithium (Li), silicon (Si), and oxygen (O), and may contain other elements.
  • Atomic ratio of O to Si in 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.
  • Atomic ratio of Li to Si in lithium silicate phase: Li / Si is, for example, greater than 0 and less than 4.
  • Elements other than Li, Si and O that can be contained in the lithium silicate phase include, for example, iron (Fe), chromium (Cr), nickel (Ni), manganese (Mn), copper (Cu), molybdenum (Mo), and the like. Examples thereof include zinc (Zn) and aluminum (Al).
  • the carbon phase may be composed of, for example, amorphous carbon having low crystallinity (that is, amorphous carbon).
  • amorphous carbon may be, for example, hard carbon, soft carbon, or other carbon.
  • the negative electrode current collector As the negative electrode current collector, a non-perforated conductive substrate (metal foil, etc.) and a porous conductive substrate (mesh body, net body, punching sheet, etc.) are used. Examples of the material of the negative electrode current collector include stainless steel, nickel, nickel alloy, copper, and copper alloy.
  • the electrolyte contains a solvent and a solute dissolved in the solvent.
  • the solute is an electrolyte salt that ionically dissociates in the electrolyte.
  • the solute may include, for example, a lithium salt.
  • the components of the electrolyte other than the solvent and solute are additives.
  • the electrolyte may contain various additives.
  • the electrolyte is usually used in a liquid state, but the fluidity may be restricted by a gelling agent or the like.
  • an aqueous solvent or a non-aqueous solvent is used.
  • a non-aqueous solvent for example, a cyclic carbonate ester, a chain carbonate ester, a cyclic carboxylic acid ester, a chain carboxylic acid ester and the like are used.
  • the cyclic carbonic acid ester include propylene carbonate (PC), ethylene carbonate (EC), vinylene carbonate (VC) and the like.
  • Examples of the chain carbonate ester include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC) and the like.
  • Examples of the cyclic carboxylic acid ester include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
  • Examples of the chain carboxylic acid ester include methyl acetate, ethyl acetate, propyl acetate, methyl propionate (MP), ethyl propionate (EP) and the like.
  • As the non-aqueous solvent one type may be used alone, or two or more types may be used in combination.
  • non-aqueous solvent examples include cyclic ethers, chain ethers, nitriles such as acetonitrile, and amides such as dimethylformamide.
  • cyclic ethers are 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,4-.
  • examples thereof include dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineole, crown ether and the like.
  • chain ethers examples include 1,2-dimethoxyethane, dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether and butyl phenyl ether.
  • Pentyl phenyl ether methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, o-dimethoxybenzene, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, Examples thereof include 1,1-dimethoxymethane, 1,1-diethoxyethane, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
  • These solvents may be fluorinated solvents in which a part of hydrogen atoms is replaced with fluorine atoms.
  • fluorination solvent fluoroethylene carbonate (FEC) may be used.
  • lithium salt examples include a lithium salt of a chlorine-containing acid (LiClO 4 , LiAlCl 4 , LiB 10 Cl 10 , etc.) and a lithium salt of a fluorine-containing acid (LiPF 6 , LiPF 2 O 2 , LiBF 4 , LiSbF 6 , LiAsF 6 ).
  • 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.
  • the lithium salt one kind may be used alone, or two or more kinds may be used in combination.
  • the concentration of the lithium salt in the 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.
  • the lithium salt concentration is not limited to the above.
  • the electrolyte may contain other known additives.
  • the additive include 1,3-propanesarton, methylbenzenesulfonate, cyclohexylbenzene, biphenyl, diphenyl ether, fluorobenzene and the like.
  • a separator is interposed between the positive electrode and the negative electrode.
  • the separator has high ion permeability and has moderate mechanical strength and insulation.
  • a microporous thin film, a woven fabric, a non-woven fabric, or the like can be used.
  • polyolefins such as polypropylene and polyethylene are preferable.
  • the structure of the secondary battery there is a structure in which an electrode group in which a positive electrode and a negative electrode are wound via a separator and a non-aqueous electrolyte are housed in an exterior body.
  • an electrode group in which a positive electrode and a negative electrode are wound via a separator and a non-aqueous electrolyte are housed in an exterior body.
  • another form of electrode group such as a laminated type electrode group in which a positive electrode and a negative electrode are laminated via a separator may be applied.
  • the secondary battery may be in any form such as a cylindrical type, a square type, a coin type, a button type, and a laminated type.
  • FIG. 1 is a schematic perspective view in which a part of a square secondary battery according to an embodiment of the present disclosure is cut out.
  • the battery includes a bottomed square battery case 4, an electrode group 1 housed in the battery case 4, and a non-aqueous electrolyte.
  • the electrode group 1 has a long strip-shaped negative electrode, a long strip-shaped positive electrode, and a separator interposed between them.
  • the negative electrode current collector of the negative electrode is electrically connected to the negative electrode terminal 6 provided on the sealing plate 5 via the negative electrode lead 3.
  • the negative electrode terminal 6 is insulated from the sealing plate 5 by a resin gasket 7.
  • the positive electrode current collector of the positive electrode is electrically connected to the back surface of the sealing plate 5 via the positive electrode lead 2. That is, the positive electrode is electrically connected to the battery case 4 that also serves as the positive electrode terminal.
  • the peripheral edge of the sealing plate 5 is fitted to the open end portion of the battery case 4, and the fitting portion is laser welded.
  • the sealing plate 5 has an injection hole for a non-aqueous electrolyte, and is closed by the sealing 8 after injection.
  • the structure of the secondary battery may be cylindrical, coin-shaped, button-shaped or the like provided with a metal battery case, and may be laminated with a laminated sheet battery case which is a laminate of a barrier layer and a resin sheet. It may be a type battery. In the present disclosure, the type, shape, etc. of the secondary battery are not particularly limited.
  • Lithium fluoride (LiF), lithium manganate (LiMnO 2 ), calcium oxide (CaO), aluminum oxide (Al 2 O 3 ), and silicon oxide (SiO 2 ) were mixed in a predetermined mass ratio.
  • the mixed powder was put into a planetary ball mill (Premium-Line P7 manufactured by Fritzch, rotation speed: 600 rpm, container: 45 mL, ball: Zr ball of ⁇ 5 mm), and operated at room temperature for 35 hours (1 hour operation) in an Ar atmosphere. After that, a cycle of resting for 10 minutes was performed 35 times) to obtain a lithium metal composite oxide having a predetermined composition.
  • the obtained lithium metal composite oxide, acetylene black, and polyvinylidene fluoride were mixed at a solid content mass ratio of 7: 2: 1, and N-methyl-2-pyrrolidone (NMP) was used as a dispersion medium.
  • NMP N-methyl-2-pyrrolidone
  • Positive mixture mixture slurry was prepared.
  • a positive electrode mixture slurry was applied onto a positive electrode core made of aluminum foil, the coating film was dried and compressed, and then cut to a predetermined electrode size to obtain a positive electrode.
  • LiPF 6 as a lithium salt was added to a mixed solvent in which ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) were mixed at a predetermined volume ratio to prepare a non-aqueous electrolyte.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • test cell A test cell was prepared using the above positive electrode and the negative electrode counter electrode made of lithium metal foil.
  • the positive electrode and the negative electrode counter electrode were arranged so as to face each other via a separator to form an electrode body, and the electrode body was housed in a coin-shaped outer can. After injecting the electrolyte into the outer can, the outer can was sealed to obtain a coin-shaped secondary battery for testing.
  • the secondary batteries A2 used as the active material were prepared respectively.
  • the secondary battery A1 corresponds to the first embodiment
  • the secondary battery A2 corresponds to the second embodiment.
  • the composition of the composite oxide was identified by ICP emission spectrometry.
  • the composition of the lithium metal composite oxide X1 was evaluated to be approximately Li 1.29 Mn 0.71 O 1.42 F 0.58 , and on a mass basis, 40 ppm Ca, 30 ppm Al, and 100 ppm Si, respectively. It was included.
  • the composition of the lithium metal composite oxide X2 is evaluated to be approximately Li 1.29 Mn 0.71 O 1.42 F 0.58 , with 100 ppm Ca, 60 ppm Al and 250 ppm Si on a mass basis. Each was included.
  • lithium fluoride (LiF), lithium manganate (LiMnO 2 ), calcium oxide (CaO), aluminum oxide (Al 2 O 3 ), and silicon oxide (SiO 2 ) are mixed in a predetermined mass ratio.
  • the mixed powder was put into a planetary ball mill in the same manner as in Example 1 and treated at room temperature in an Ar atmosphere to obtain a lithium metal composite oxide having a predetermined composition.
  • a positive electrode was prepared in the same manner as in Example 1 to obtain a secondary battery for testing.
  • the secondary batteries B2 used as the active material were prepared respectively.
  • the secondary battery B1 corresponds to Comparative Example 1
  • the secondary battery B2 corresponds to Comparative Example 2.
  • the composition of the composite oxide was identified by ICP emission spectrometry.
  • the composition of the lithium metal composite oxide Y1 was evaluated to be approximately Li 1.28 Mn 0.62 Al 0.1 O 1.7 F 0.3 , and on a mass basis, 40 ppm Ca, 34300 ppm Al, 200 ppm. Si was contained in each.
  • the composition of the lithium metal composite oxide X2 is evaluated to be approximately Li 1.25 Mn 0.65 Si 0.1 O 1.7 F 0.3 , and on a mass basis, 30 ppm Ca, 30 ppm Al, Each contained 35,400 ppm of Si.
  • the X-ray diffraction patterns of the composite oxide were measured and analyzed by a powder X-ray diffractometer, respectively. It was confirmed that the oxide has a crystal structure based on the rock salt type belonging to the space group Fm-3m.
  • Table 1 shows the evaluation results of the initial discharge capacity C 0 together with the composition of the lithium metal composite oxide used as the positive electrode active material in each battery and the Ca, Al, and Si contents.
  • the initial discharge capacity was improved by containing a small amount of Ca, Al and Si in the range of 10 to 1000 ppm in total.
  • the initial discharge capacity was lowered by containing a large amount of Ca, Al and Si exceeding 1000 ppm in total.
  • the secondary battery according to the present disclosure it is possible to provide a secondary battery having a high capacity and excellent cycle characteristics.
  • the secondary battery according to the present disclosure is useful as a main power source for mobile communication devices, portable electronic devices, and the like.
  • Electrode group 2 Positive electrode lead 3 Negative lead 4 Battery case 5 Seal plate 6 Negative terminal 7 Gasket 8 Seal

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