WO2024162139A1 - 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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WO2024162139A1
WO2024162139A1 PCT/JP2024/002053 JP2024002053W WO2024162139A1 WO 2024162139 A1 WO2024162139 A1 WO 2024162139A1 JP 2024002053 W JP2024002053 W JP 2024002053W WO 2024162139 A1 WO2024162139 A1 WO 2024162139A1
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positive electrode
composite oxide
metal composite
lithium metal
active material
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French (fr)
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貴司 大戸
晋 張
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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 CN202480009508.XA priority patent/CN120615239A/zh
Priority to EP24750089.5A priority patent/EP4661103A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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
    • 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
    • H01M4/48—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
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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
    • C01P2006/12—Surface area
    • 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 especially lithium-ion secondary batteries, have high output and high energy density, and are therefore expected to be used in small consumer applications, power storage devices, and as power sources for electric vehicles.
  • a composite oxide of lithium and a transition metal e.g., cobalt
  • cobalt transition metal
  • Patent Document 1 discloses a positive electrode active material containing a lithium transition metal composite oxide having a crystal structure belonging to the space group Fm-3m and represented by the composition formula Li1 +xNbyMezApO2 ( Me is a transition metal including Fe and/ or Mn , 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.5, 0.25 ⁇ z ⁇ 1, A is an element other than Nb and Me, and 0 ⁇ p ⁇ 0.2, excluding Li1 +pFe1 -qNbqO2 where 0.15 ⁇ p ⁇ 0.3, 0 ⁇ q ⁇ 0.3).
  • Patent Document 1 high capacity is possible by controlling the composition (i.e., adding Nb). However, the effect of improving capacity is insufficient, and there is still room for improvement.
  • one aspect of the present disclosure relates to a positive electrode active material for a secondary battery, comprising a lithium metal composite oxide having a rock-salt type crystal structure that can be assigned to the space group Fm-3m, the lithium metal composite oxide containing at least Li and Mn, and the average aspect ratio of the particles of the lithium metal composite oxide being less than 2.10.
  • 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, the positive electrode including the positive electrode active material for secondary batteries.
  • FIG. 1 is a schematic perspective view of a secondary battery according to an embodiment of the present disclosure, with a portion cut away.
  • FIG. 1 is a graph showing the relationship between the discharge capacity per mass of a lithium metal composite oxide and the average aspect ratio.
  • the embodiments of the present disclosure are described using examples, but the present disclosure is not limited to the examples described below.
  • specific numerical values and materials may be exemplified, but other numerical values and materials may be applied as long as the effects of the present disclosure are obtained.
  • the expression "numerical value A to numerical value B" includes numerical value A and numerical value B and can be read as "numerical value A or more and numerical value B or less.”
  • any of the exemplified lower limits and any of the exemplified upper limits can be arbitrarily combined as long as the lower limit is not equal to or greater than the upper limit.
  • one of the materials may be selected and used alone, or two or more of the materials may be used in combination.
  • Secondary batteries include at least lithium ion batteries, non-aqueous electrolyte secondary batteries such as lithium metal secondary batteries, and all-solid-state batteries that use solid electrolytes.
  • the positive electrode active material for secondary batteries includes a lithium metal composite oxide (hereinafter also referred to as "lithium metal composite oxide (Fm)”) having a rock-salt type crystal structure that can be assigned to the space group Fm-3m.
  • the lithium metal composite oxide (Fm) has a crystal structure based on a rock-salt structure that belongs to the space group Fm-3m, and has a crystal structure similar to the rock-salt structure represented by NaCl, for example.
  • oxygen atoms are arranged in the anion site, and Li atoms and metal atoms other than Li can be irregularly arranged in the cation site.
  • the lithium metal composite oxide (Fm) contains at least Li and Mn.
  • the lithium metal composite oxide (Fm) based on the rock salt structure Li 1+x Mn 1-x O 2 is expected to exhibit high capacity.
  • the raw material mixture contains lithium compounds and manganese compounds.
  • lithium metal composite oxide (Fm) when mass-producing lithium metal composite oxide (Fm), it is necessary to synthesize it efficiently by sintering the raw material mixture.
  • the lithium metal composite oxide (Fm) particles synthesized by sintering tend to be very hard and clumpy.
  • particles obtained by crushing hard lumps tend to have an uneven shape with sharp edges.
  • the parts that are easily receptive to charging and discharging react preferentially, and the reaction does not proceed easily in the parts that are not easily receptive to charging and discharging. It is therefore thought that the charging and discharging reaction proceeds unevenly and polarization becomes large.
  • the more uneven the particle shape the greater the degree of curvature of the electronic conduction path, and the higher the resistance tends to be.
  • lithium metal composite oxide (Fm) is more susceptible to the shape factor of the particles than conventionally used positive electrode active materials.
  • lithium metal composite oxide (Fm) shows a significant improvement in capacity when the particle shape is controlled to be more suitable for charging and discharging. The reason for this is not clear, but it is presumed to be due to a complex interrelationship between the fact that particles with a rock salt crystal structure belonging to the space group Fm-3m have relatively low electronic conductivity, that particles with high hardness are less likely to cause internal distortion, and that the surface condition of the particles is relatively smooth.
  • the capacity of the lithium metal composite oxide (Fm) synthesized by sintering is significantly improved by making the average particle aspect ratio less than 2.1.
  • the average particle aspect ratio By controlling the average particle aspect ratio to less than 2.10, the particle shape becomes uniform and the difference in acceptability between the parts that are easy to accept charge and discharge and the parts that are not easy to accept charge and discharge is reduced. As a result, the charge and discharge reaction proceeds uniformly, polarization is reduced, and it is believed that the discharge capacity is improved.
  • lithium metal composite oxide is a material with relatively low electronic conductivity.
  • the more non-uniform the particle shape the greater the degree of curvature of the electronic conduction path.
  • the average particle aspect ratio is set to less than 2.10, the distance between particles within the electrode is made uniform, and the degree of curvature of the electronic conduction path is reduced. This is thought to be a major contribution to the improvement of capacity.
  • the average particle aspect ratio should be less than 2.10, but is preferably 2.09 or less, more preferably 1.94 or less, and even more preferably 1.80 or less, or 1.70 or less.
  • the aspect ratio means the value (maximum diameter Dmax/maximum diameter dmax) obtained by dividing the maximum diameter Dmax of a particle by the maximum diameter dmax in a direction perpendicular to the maximum diameter Dmax.
  • the maximum diameter Dmax and maximum diameter dmax of the lithium metal composite oxide (Fm) may be measured using particles of the lithium metal composite oxide (Fm) as a raw material powder before becoming a positive electrode, or the maximum diameter Dmax and maximum diameter dmax in the positive electrode may be measured.
  • the lithium metal composite oxide (Fm) having a rock salt crystal structure is sturdy, so similar measurement results can be obtained by either measurement method.
  • the maximum diameter Dmax and maximum diameter dmax in the positive electrode are measured using particles of the lithium metal composite oxide (Fm) observed in a scanning electron microscope (SEM) image (hereinafter simply referred to as a "cross-sectional SEM image") of a cross section in the thickness direction of the positive electrode.
  • the particles observed in the cross-sectional SEM image of the positive electrode may be cross-sections of the particles.
  • the maximum diameter Dmax and the maximum diameter dmax of the raw material powder are measured using particles of the lithium metal composite oxide (Fm) observed in an SEM image of the raw material powder (hereinafter simply referred to as a "powder SEM image").
  • a positive electrode to be measured is prepared.
  • a positive electrode comprises a positive electrode collector and a positive electrode active material layer formed on the surface of the positive electrode collector.
  • Such a positive electrode active material layer and the positive electrode collector are cut simultaneously along the thickness direction of the positive electrode to form a cross section.
  • a thermosetting resin may be filled in the positive electrode active material layer and cured.
  • a cross section sample of the positive electrode active material layer may be obtained by a CP (cross section polisher) method, an FIB (focused ion beam) method, or the like.
  • the positive electrode to be measured is taken from a secondary battery with a depth of discharge (DOD) of 90% or more.
  • the voltage of a fully charged battery corresponds to the end of charge voltage.
  • the voltage of a fully discharged battery corresponds to the end of discharge voltage.
  • a cross-section sample of the positive electrode (positive electrode active material layer) is observed by SEM. Observation by SEM is performed, for example, at a magnification of 500 to 3000 times.
  • the cross-sectional SEM image is taken so that a region having a length of 30 ⁇ m or more (preferably 40 ⁇ m or more) in the surface direction of the positive electrode active material layer is observed.
  • image analysis software e.g., ImageJ
  • image analysis software e.g., ImageJ
  • the cross-sectional SEM image can be binarized so that the lithium metal composite oxide (Fm) particles are black (or white) and the rest are white (or black).
  • elemental analysis may be performed on the cross-sectional SEM image using EDX (energy dispersive X-ray spectroscopy) or EPMA (electron probe microanalyzer).
  • a mapping image of the lithium metal composite oxide (Fm) may then be obtained from the analysis data.
  • the "maximum diameter Dmax/maximum diameter dmax” may be measured as the aspect ratio for each of 100 or more arbitrarily selected lithium metal composite oxide (Fm) particles (particle cross sections).
  • the average particle diameter Dave (D50 (median diameter) in the cumulative particle size distribution based on the number) of the lithium metal composite oxide (Fm) can be obtained from the cumulative particle size distribution based on the number of 100 or more particles (particle cross sections) of the lithium metal composite oxide (Fm) arbitrarily selected from the cross-sectional SEM image.
  • D50 (median diameter) is the diameter of the equivalent sphere when the cumulative number becomes 50% by integrating the diameter value of the equivalent sphere from the smallest one. D50 may be selected according to the electrode design.
  • the average particle diameter D50 is, for example, greater than 0.22 ⁇ m, and may be 0.23 ⁇ m or more, or may be 0.24 ⁇ m or more.
  • the "span value" defined as (D90 - D10) / D50 can be found.
  • the span value in the cumulative particle size distribution based on the number of lithium metal composite oxide particles may, for example, satisfy 1.2 ⁇ (D90-D10)/D50, 1.4 ⁇ (D90-D10)/D50, or 1.5 ⁇ (D90-D10)/D50. There is no particular upper limit to the span value, but it may satisfy (D90-D10)/D50 ⁇ 8.4.
  • the span value may satisfy 1.6 ⁇ (D90-D10)/D50, 1.7 ⁇ (D90-D10)/D50, or 1.8 ⁇ (D90-D10)/D50.
  • D90 is greater than 0.46 ⁇ m, and may be 0.47 ⁇ m or greater, or 0.5 ⁇ m or greater.
  • Such a lithium metal composite oxide (Fm) with a relatively large particle size can be obtained by pulverizing, under appropriate conditions, a lithium metal composite oxide (Fm) with high hardness obtained by firing a raw material mixture. The presence of particles with a large particle size makes it easier to increase the electrode capacity.
  • the number-based cumulative particle size distribution obtained from 100 or more lithium metal composite oxide (Fm) particles (particle cross sections) randomly selected from a cross-sectional SEM image will be similar to the number-based cumulative particle size distribution obtained from the lithium metal composite oxide (Fm) raw material powder of an electrode or the lithium metal composite oxide (Fm) powder separated and recovered from the positive electrode by disassembling a completed battery.
  • the number-based cumulative particle size distribution of the raw material powder or the powder separated and recovered from the positive electrode can be obtained, for example, by converting the volume-based cumulative particle size distribution measured by a laser diffraction/scattering type particle size distribution measuring device.
  • the average circularity of the particles may be controlled. Specifically, when the average circularity of the particles is 0.55 or more, the capacity is significantly improved. By controlling the average circularity of the particles to 0.55 or more, the particle shape is uniformed, and the difference in acceptability between the part that is easy to accept charge and discharge and the part that is difficult to accept charge and discharge is reduced. As a result, the charge and discharge reaction proceeds uniformly, the polarization is reduced, and the discharge capacity is improved.
  • the circularity is 1. Therefore, it can be considered that the higher the circularity, the closer the particle is to a perfect sphere. If the average circularity is set to 0.55 or more, the particles will be that much closer to a perfect sphere, the distance between particles in the electrode will be more uniform, and the curvature of the electron conduction path will be reduced, further contributing to improved capacity.
  • the average circularity of the particles should be 0.55 or more, preferably 0.60 or more, more preferably 0.65 or more, and even more preferably 0.67 or more.
  • the circularity of the lithium metal composite oxide (Fm) may be measured using particles of the lithium metal composite oxide (Fm) as raw powder before it becomes a positive electrode, or may be measured in the positive electrode.
  • the lithium metal composite oxide (Fm) has a rock salt crystal structure and is robust, so similar measurement results can be obtained by either measurement method.
  • the circularity in the positive electrode is measured using particles of the lithium metal composite oxide (Fm) observed in the cross-sectional SEM image described above.
  • the particles observed in the cross-sectional SEM image of the positive electrode may be the cross-section of a particle.
  • the circularity of the raw powder is measured using particles of the lithium metal composite oxide (Fm) observed in the SEM image of the raw powder (hereinafter simply referred to as the "powder SEM image").
  • Particles of lithium metal composite oxide (Fm) may contain impurity elements.
  • impurity elements may be mixed into the particles when crushing hard agglomerated particles.
  • agitation devices capable of applying a large shear force to the object to be crushed, such as bead mills and ball mills, are used.
  • media such as balls and beads are used.
  • the impurity elements may include, for example, Al, Zr, W, Fe, Cr, Ni, etc.
  • the impurity elements are unevenly distributed on the surface layer of the particles.
  • mispurities are present at a high concentration CH from the surface of the particle to a depth of within 5% of the particle diameter, and that impurity elements are present at a low concentration CL (CH>CL) or are not present in a circular region having a radius of within 5% of the particle diameter from the center of gravity of the particle.
  • CH ⁇ 2CL or CH ⁇ 5CL may be satisfied.
  • a mapping image of impurity elements within the lithium metal composite oxide (Fm) particles may be obtained from the analysis data. Using such mapping images, an analysis may be performed on 10 or more arbitrarily selected lithium metal composite oxide (Fm) particles, and if CH>CL or CH ⁇ 2CL or CH ⁇ 5CL is satisfied in 80% or more of the particles, it may be determined that the impurity elements are unevenly distributed on the surface layer of the particles.
  • the specific surface area of the lithium metal composite oxide (Fm) is, for example, less than 21.9 m 2 /g, and may be 21 m 2 /g or less, less than 13.2 m 2 /g, 13 m 2 /g or less, 11 m 2 /g or less, or 10 m 2 /g or less.
  • the lithium metal composite oxide (Fm) synthesized in a laboratory by applying a high shear force to the raw material mixture using a stirring device such as a ball mill has a very large specific surface area.
  • the lithium metal composite oxide (Fm) synthesized by calcination does not have a history due to a high shear force that causes a solid-phase reaction to proceed, even if it is a particle or powder obtained by crushing agglomerated particles. Therefore, the specific surface area of the lithium metal composite oxide (Fm) synthesized by calcination is, for example, 0.13 m 2 /g or more and less than 21.9 m 2 /g, and may be 0.13 m 2 /g or more and less than 13.2 m 2 /g, and is likely to be 6 m 2 /g to 12 m 2 /g or 6 m 2 /g to 10 m 2 /g.
  • the specific surface area is within the above range, it is advantageous in that the filling rate of the lithium metal composite oxide (Fm) in the positive electrode can be increased and side reactions can be easily suppressed. If the specific surface area is excessively large, the surface state becomes unstable and it may be difficult to suppress side reactions.
  • the specific surface area can be measured using lithium metal composite oxide (Fm) as raw material powder before it becomes a positive electrode, or it can be measured using lithium metal composite oxide (Fm) separated from the positive electrode. Either method will give roughly similar measurement results.
  • the specific surface area of the lithium metal composite oxide (Fm) is measured after taking 0.20 g to 0.25 g of a sample of the lithium metal composite oxide (Fm), placing the sample in a measurement cell consisting of a glass tube for measuring the specific surface area, and drying and degassing the measurement cell. Drying and degassing is performed for at least one hour at a pressure of 6.67 Pa and a temperature of 250°C ⁇ 5°C. The mass of the sample in the measurement cell is then measured to the order of 0.1 mg. The amount of nitrogen adsorption of the sample at a temperature of -196°C is then measured using a specific surface area measuring device.
  • an automatic specific surface area/pore distribution measuring device "Tristar II 3020" manufactured by Shimadzu Corporation is used as the measuring device. From the measurement results of the amount of adsorption, the specific surface area of the lithium metal composite oxide (Fm) is determined by the BET multipoint method in the partial pressure (relative pressure) range of 0.001 to 0.2.
  • the lithium metal composite oxide (Fm) may contain an electropositive element M other than Li and Mn.
  • Such an element M may be any electropositive element other than hydrogen, and may be a metal element (including so-called semimetal elements).
  • the lithium metal composite oxide (Fm) may be a lithium transition metal composite oxide containing at least three types of metals.
  • the element M may be, for example, at least one element selected from the group consisting of Ti, Fe, Ge, Si, Ga, Ni, Co, Sn, Cu, Nb, Mo, Bi, V, Cr, Y, Zr, Zn, Na, K, Ca, Mg, Pt, Au, Ag, Ru, Ta, W, La, Ce, Pr, Gd, Sm, Eu, Yb, Dy, Al, and Er.
  • the lithium metal composite oxide (Fm) may contain any two or more elements selected from the above group as the element M.
  • the lithium metal composite oxide (Fm) contains the element M, it is preferable that the main component of the metal element other than Li is Mn.
  • the number of Mn atoms b in the lithium metal composite oxide (Fm) may be the largest among the number of atoms of metals other than Li in the lithium metal composite oxide (Fm).
  • the number of Mn atoms may be greater than the total number of atoms c of metal elements other than Li and Mn.
  • the ratio (b/c) of the number of Mn atoms b to the number of atoms c of metal elements other than Li and Mn in the lithium metal composite oxide (Fm) is, for example, 1 or more and 15 or less, preferably 1 or more and 12 or less, may be greater than 1 and 12 or less, or may be 2 or more and 12 or less.
  • the lithium metal composite oxide (Fm) preferably contains at least Ti as the element M.
  • the lithium metal composite oxide (Fm) containing Ti as the element M can exhibit a particularly high capacity.
  • Ti can exist in the form of Ti 4+ with an empty d orbital in the lithium metal composite oxide. In that case, it is believed that a highly symmetrical, more stable, and high-capacity rock salt type crystal structure is formed. In addition, it is believed that such a rock salt structure is less likely to become unstable even after repeated charging and discharging.
  • Mn/Ti When the lithium metal composite oxide (Fm) contains Ti, the ratio of the number of Mn atoms to the number of Ti atoms in the lithium metal composite oxide: Mn/Ti may be 4 or more, 5 or more, or 6 or more, and preferably 7 or more. In addition, Mn/Ti may be 70 or less, 30 or less, and preferably 15 or less.
  • the lithium metal composite oxide (Fm) may be an acid fluoride containing F.
  • fluorine can substitute oxygen atoms at the anion site. This stabilizes the crystal structure and provides a higher capacity even when the lithium metal composite oxide (Fm) is in a Li-excess state. Furthermore, the average discharge potential increases due to the substitution of fluorine atoms.
  • the Li-excess state refers to a state in which the number of Li atoms in the lithium metal composite oxide (Fm) is greater than the total number of atoms of metal elements other than Li.
  • Li-excess lithium metal composite oxide In Li-excess lithium metal composite oxide (Fm), the arrangement of Li in the cation sites is irregular, and the bonding state of Li is varied. Therefore, the voltage distribution associated with Li release is wide. For this reason, it may be difficult to use the tail part on the low potential side of the voltage distribution as capacitance. However, by introducing fluorine atoms, the voltage distribution associated with Li release shifts to the high potential side, making it easier to use the tail part as capacitance. This further increases the available capacity.
  • Fm Li-excess lithium metal composite oxide
  • the lithium metal composite oxide (Fm), which is an oxyfluoride, can be represented by the composition formula Li a Mn b Mc O d F e , where 1 ⁇ a ⁇ 1.4, 0.5 ⁇ b ⁇ 0.9, 0 ⁇ c ⁇ 0.4, 1.33 ⁇ d ⁇ 2, 0 ⁇ e ⁇ 0.67, and 1.7 ⁇ d+e ⁇ 2.2 are satisfied.
  • the lithium metal composite oxide (Fm) may be represented by the composition formula Li a Mn b Ti c M d O e F f .
  • 1 ⁇ a ⁇ 1.4, 0.3 ⁇ b ⁇ 0.9, 0 ⁇ c ⁇ 0.5, 0 ⁇ d ⁇ 0.25, 0 ⁇ f ⁇ 0.7, and 1.7 ⁇ e+f ⁇ 2 are satisfied.
  • 1 ⁇ a ⁇ 1.4, 0.5 ⁇ b ⁇ 0.9, 0.02 ⁇ c ⁇ 0.4, 0 ⁇ f ⁇ 0.67, and 1.7 ⁇ e+f ⁇ 2.2 are satisfied.
  • e+f is often 2 or less, and may be 1.94 or less, 1.9 or less, or 1.8 or less.
  • some of the oxygen atoms in the anion site may be replaced with fluorine atoms. This stabilizes the state in which Li is in excess (a>1), resulting in a high capacity.
  • the average discharge potential increases, further increasing the available capacity.
  • the fluorine-free lithium metal composite oxide (Fm) can be represented by a composition formula LiaMnbMcOd , where 1 ⁇ a ⁇ 1.4 , 0.5 ⁇ b ⁇ 0.75, 0 ⁇ c ⁇ 0.35 , and 1.6 ⁇ d ⁇ 2 are satisfied.
  • the content of the elements that make up the lithium metal composite oxide (Fm) can be measured using an inductively coupled plasma atomic emission spectrometer (ICP-AES), an electron probe microanalyzer (EPMA), or an energy dispersive X-ray analyzer (EDX), etc.
  • ICP-AES inductively coupled plasma atomic emission spectrometer
  • EPMA electron probe microanalyzer
  • EDX energy dispersive X-ray analyzer
  • the method for producing the lithium metal composite oxide (Fm) is not limited, but it is preferable to obtain the lithium metal composite oxide (Fm) by calcining a raw material mixture of elements that constitute the lithium metal composite oxide (Fm). Calcination promotes the growth of crystals similar to the rock salt structure belonging to the space group Fm-3m, and a lithium metal composite oxide with a large crystallite size is obtained. The crystallite size may then be controlled to a desired range by performing a pulverization process.
  • the raw materials for the elements that make up the lithium metal composite oxide may be selected from Mn compounds, compounds of element M, lithium compounds, fluorine compounds, titanium compounds, and the like.
  • the types and mixing ratios of the raw materials may be appropriately selected according to the desired composition described above.
  • Mn compounds include Mn oxides such as MnO2 and Mn2O3 , and manganese salts such as lithium manganate.
  • compounds of element M include M salts such as oxides, oxyfluorides, and hydroxides.
  • lithium compounds include lithium oxides such as Li2O , and lithium salts such as LiOH and lithium manganate ( LiMnO2 ).
  • fluorine compounds include fluorine salts such as lithium fluoride (LiF).
  • titanium compounds include titanium oxides such as TiO2 , and titanium salts such as lithium titanate.
  • the atmosphere in which the raw material mixture is fired may vary depending on the composition of the lithium metal composite oxide (Fm) to be obtained and the type of raw material, but may be, for example, an oxidizing atmosphere (e.g., in air or in the presence of oxygen). It is desirable to circulate the atmospheric gas.
  • Fm lithium metal composite oxide
  • the firing temperature of the raw material mixture may vary depending on the composition of the lithium metal composite oxide (Fm) to be obtained and the type of raw material, but may be, for example, 700°C or higher, and is preferably 900°C or higher and 1300°C or lower.
  • the aggregated particles may be pulverized to the desired aspect ratio or circularity.
  • a stirring device capable of applying a large shear force to the particles such as a ball mill or a bead mill, may be used.
  • the raw material mixture may be sintered while stirring the raw material mixture.
  • the raw material mixture may be sintered while stirring using a sintering furnace equipped with a fluidized bed.
  • particles that are nearly spherical may be used as part of the raw material.
  • a manganese compound or a manganese titanium composite compound that is nearly spherical may be used as the raw material.
  • the secondary battery includes, for example, a positive electrode, a negative electrode, an electrolyte, and a separator as described below.
  • the positive electrode comprises 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 for secondary batteries described above is used as the positive electrode.
  • 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, etc. is dispersed in a dispersion medium to the surface of the positive electrode current collector and drying it. The coating film after drying may be rolled as necessary.
  • the positive electrode mixture layer may be formed on one surface of the positive electrode current collector or on both surfaces.
  • the positive electrode mixture layer contains a positive electrode active material as an essential component, and may contain optional components such as a binder, a thickener, a conductive agent, and a positive electrode additive.
  • a binder such as a binder, a thickener, a conductive agent, and a positive electrode additive.
  • 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 (Fm) having a crystal structure similar to the rock salt structure belonging to the space group Fm-3m.
  • the lithium metal composite oxide (Fm) is, for example, a secondary particle formed by the aggregation of multiple primary particles.
  • the particle size of the primary particles is generally 0.01 ⁇ m to 1 ⁇ m.
  • the lithium metal composite oxide (Fm) may be mixed with other known lithium metal oxides to be used as the positive electrode active material.
  • other known lithium metal oxides include lithium transition metal composite oxides such as LiaCoO2 , LiaNiO2 , LiaMnO2 , LiaCobNi1 - bO2 , LiaCobM1 - bOc , LiaNi1 -bMbOc , LiaMn2O4 , LiaMn2- bMbO4 , LiMePO4 , and Li2MePO4F .
  • 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 (e.g., contains at least one selected from the group consisting of Mn, Fe, Co, and Ni), where 0 ⁇ a ⁇ 1.2, 0 ⁇ b ⁇ 0.9, and 2.0 ⁇ c ⁇ 2.3.
  • the value a which indicates the molar ratio of lithium, increases or decreases with charge and discharge.
  • the shape and thickness of the positive electrode current collector can be selected from the same shape and range as the negative electrode current collector.
  • Examples of materials for the positive electrode current collector include stainless steel, aluminum, aluminum alloy, and titanium.
  • the negative electrode may, for example, include a negative electrode current collector and include 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, etc. is dispersed in a dispersion medium to the surface of the negative electrode current collector and drying it. The coating film after drying may be rolled as necessary. That is, the negative electrode active material may be a mixture layer.
  • 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 on both surfaces.
  • the negative electrode active material layer contains a negative electrode active material as an essential component, and may contain a binder, a conductive agent, a thickener, etc. as optional components. Known materials can be used as the binder, conductive agent, and thickener.
  • Anode active materials include materials that electrochemically absorb and release lithium ions, lithium metal, and lithium alloys. Carbon materials and alloy-based materials are used as materials that electrochemically absorb and release lithium ions. Examples of carbon materials include graphite, graphitizable carbon (soft carbon), and non-graphitizable carbon (hard carbon). Among these, graphite is preferred because of its excellent charge/discharge stability and low irreversible capacity. Alloy-based materials include those that contain at least one metal that can form an alloy with lithium. For example, a lithium ion conductive phase and a composite material in which a silicon phase is dispersed in the lithium ion conductive phase may be used.
  • a non-porous conductive substrate such as metal foil
  • a porous conductive substrate such as a mesh, net, or punched sheet
  • materials for the negative electrode current collector include stainless steel, nickel, nickel alloys, copper, and copper alloys.
  • the electrolyte may be a liquid electrolyte (electrolytic solution), a gel electrolyte, or a solid electrolyte.
  • the liquid electrolyte is, for example, an electrolytic solution containing a non-aqueous solvent and a salt dissolved in the non-aqueous solvent.
  • the concentration of the salt in the electrolytic solution is, for example, 0.5 mol/L or more and 2 mol/L or less.
  • the electrolytic solution may contain a known additive.
  • the gel electrolyte contains a salt and a matrix polymer, or a salt, a non-aqueous solvent, and a matrix polymer.
  • a matrix polymer for example, a polymer material that absorbs the non-aqueous solvent and gels is used. Examples of the polymer material include fluororesin, acrylic resin, polyether resin, and polyethylene oxide.
  • solid electrolyte for example, a material known in all-solid-state lithium-ion secondary batteries (e.g., oxide-based solid electrolyte, sulfide-based solid electrolyte, halide-based solid electrolyte, etc.) is used.
  • oxide-based solid electrolyte e.g., oxide-based solid electrolyte, sulfide-based solid electrolyte, halide-based solid electrolyte, etc.
  • a liquid non-aqueous electrolyte is prepared by dissolving a salt in a non-aqueous solvent.
  • the salt is an electrolyte salt that ionizes in the electrolyte, and may include, for example, a lithium salt.
  • the electrolyte may include various additives.
  • the electrolyte is usually used in liquid form, but may also have its fluidity restricted by a gelling agent or the like.
  • non-aqueous solvents examples include cyclic carbonates, chain carbonates, cyclic carboxylates, and chain carboxylates.
  • cyclic carbonates examples include propylene carbonate (PC), ethylene carbonate (EC), and vinylene carbonate (VC).
  • chain carbonates examples include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC).
  • cyclic carboxylates include ⁇ -butyrolactone (GBL), and ⁇ -valerolactone (GVL).
  • chain carboxylates 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 of chlorine-containing acids LiClO4 , LiAlCl4 , LiB10Cl10 , etc.
  • lithium salts of fluorine-containing acids LiPF6 , LiPF2O2 , LiBF4 , LiSbF6 , LiAsF6 , LiCF3SO3 , LiCF3CO2 , etc.
  • lithium salts of fluorine-containing acid imides LiN( FSO2 ) 2 , LiN( CF3SO2 ) 2 , LiN( CF3SO2 ) ( C4F9SO2 ) , LiN( C2F5SO2 ) 2 , etc.
  • lithium halides LiCl, LiBr, LiI , etc.
  • the lithium salt may be used alone or in combination of two or more kinds.
  • the concentration of the lithium salt in the electrolyte may be 1 mol/L or more and 2 mol/L or less, or 1 mol/L or more and 1.5 mol/L or less.
  • the lithium salt concentration is not limited to the above.
  • a separator is interposed between the positive electrode and the negative electrode.
  • the separator has high ion permeability and has appropriate mechanical strength and insulation.
  • a microporous thin film, a woven fabric, a nonwoven fabric, etc. can be used.
  • polyolefin such as polypropylene and polyethylene is preferable.
  • a secondary battery is a structure in which an electrode group in which positive and negative electrodes are wound with a separator interposed therebetween, and a non-aqueous electrolyte are housed in an exterior body.
  • a wound type electrode group other types of electrode groups may be used, such as a stacked type electrode group in which positive and negative electrodes are stacked with a separator interposed therebetween.
  • the secondary battery may be in any type, such as a cylindrical type, a square type, a coin type, a button type, a laminate type, etc.
  • FIG. 1 is a schematic perspective view, with a portion cut away, of a prismatic secondary battery according to an embodiment of the present disclosure.
  • the battery includes a bottomed rectangular battery case 4, an electrode group 1 and a non-aqueous electrolyte (not shown) housed in the battery case 4.
  • the electrode group 1 includes a long strip-shaped negative electrode, a long strip-shaped positive electrode, and a separator interposed therebetween.
  • the negative electrode current collector of the negative electrode is electrically connected to a negative electrode terminal 6 provided on a sealing plate 5 via a 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 a positive electrode lead 2.
  • the positive electrode is electrically connected to the battery case 4, which also serves as a positive electrode terminal.
  • the periphery of the sealing plate 5 is fitted into the open end of the battery case 4, and the fitting portion is laser welded.
  • the sealing plate 5 has an injection hole for the non-aqueous electrolyte, which is closed by a seal plug 8 after injection.
  • the structure of the secondary battery may be cylindrical, coin, button, etc., with a metal battery case, or may be a laminated battery with a battery case made of a laminate sheet that is a laminate of a barrier layer and a resin sheet.
  • the type, shape, etc. of the secondary battery are not particularly limited.
  • the lithium metal composite oxide has a rock-salt type crystal structure that can be assigned to the space group Fm-3m,
  • the lithium metal composite oxide contains at least Li and Mn,
  • the lithium metal composite oxide particles have an average aspect ratio of less than 2.10.
  • the lithium metal composite oxide contains a positive element M different from Li and Mn
  • the positive electrode active material for a secondary battery according to the present invention includes at least one selected from the group consisting of Ti, Fe, Ge, Si, Ga, Ni, Co, Sn, Cu, Nb, Mo, Bi, V, Cr, Y, Zr, Zn, Na, K, Ca, Mg, Pt, Au, Ag, Ru, Ta, W, La, Ce, Pr, Gd, Sm, Eu, Yb, Dy, Al, and Er.
  • the lithium metal composite oxide contains at least Ti as the M.
  • the lithium metal composite oxide is represented by the composition formula Li a Mn b Mc O d Fe , 5.
  • the lithium metal composite oxide is represented by the composition formula Li a Mn b Mc O d , 6.
  • (Technique 7) The positive electrode active material for a secondary battery according to any one of the first to sixth aspects, wherein D90 in a cumulative particle size distribution based on the number of particles of the lithium metal composite oxide is greater than 0.46 ⁇ m.
  • Technique 8) The positive electrode active material for a secondary battery according to any one of techniques 1 to 7, wherein D50 in a cumulative particle size distribution based on the number of particles of the lithium metal composite oxide is 0.26 ⁇ m or less.
  • a battery comprising a positive electrode, a negative electrode, an electrolyte, and a separator interposed between the positive electrode and the negative electrode;
  • a secondary battery, wherein the positive electrode comprises the positive electrode active material for secondary batteries according to any one of claims 1 to 12.
  • the obtained lithium metal composite oxide (Fm) aggregate particles were pulverized under various conditions using a planetary ball mill to obtain lithium metal composite oxides (Fm) having various aspect ratios.
  • the lithium metal composite oxide (Fm) aggregate particles were put into a planetary ball mill (Fritsch Premium-Line P7, rotation speed: 150 to 300 rpm, container: 45 mL, ball: ⁇ 3 mm ZrO2 ball) and processed in an air atmosphere at room temperature for 12 hours or less.
  • the BET specific surface area of the lithium metal composite oxide (Fm) measured by the above-mentioned method was in the range of 7.2 m 2 /g to 8.8 m 2 /g in all cases.
  • the D50 was 0.23 ⁇ m to 0.25 ⁇ m
  • the D90 was 0.49 ⁇ m to 0.56 ⁇ m
  • the span value was 1.6 to 1.9.
  • the X-ray diffraction pattern of the crushed lithium metal composite oxide (Fm) was measured and analyzed. The number and positions of XRD peaks confirmed that the rock salt crystal structure can be assigned to the space group Fm-3m.
  • a non-aqueous electrolyte was prepared by adding LiPF6 as a lithium salt to a mixed solvent in which ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) were mixed in a predetermined volume ratio.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • Figure 2 shows that the discharge capacity is significantly improved by reducing the average aspect ratio of the lithium metal composite oxide (Fm) to less than 2.1 (especially to 1.94 or less).
  • the D50 was 0.22 ⁇ m, the D90 was 0.46 ⁇ m, the span value was 1.2, and the BET specific surface area was 13.2 m 2 /g. It is understood that the difference in physical properties from the examples arises due to the difference in the manufacturing method.

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