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WO2025153936A1 - Particule de matériau actif d'électrode positive et procédé de production de particule de matériau actif d'électrode positive - Google Patents

Particule de matériau actif d'électrode positive et procédé de production de particule de matériau actif d'électrode positive

Info

Publication number
WO2025153936A1
WO2025153936A1 PCT/IB2025/050346 IB2025050346W WO2025153936A1 WO 2025153936 A1 WO2025153936 A1 WO 2025153936A1 IB 2025050346 W IB2025050346 W IB 2025050346W WO 2025153936 A1 WO2025153936 A1 WO 2025153936A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
active material
electrode active
lithium
material particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/IB2025/050346
Other languages
English (en)
Japanese (ja)
Inventor
高橋正弘
三上真弓
落合輝明
佐々木宏輔
平原誉士
中村聡宏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Semiconductor Energy Laboratory Co Ltd
Original Assignee
Semiconductor Energy Laboratory Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Semiconductor Energy Laboratory Co Ltd filed Critical Semiconductor Energy Laboratory Co Ltd
Publication of WO2025153936A1 publication Critical patent/WO2025153936A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • 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
    • H01M4/50—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
    • 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
    • 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

  • One aspect of the present invention relates to an object, a method, or a manufacturing method. Alternatively, the present invention relates to a process, a machine, a manufacture, or a composition of matter.
  • One aspect of the present invention relates to a power storage device including a secondary battery, a semiconductor device, a display device, a light-emitting device, a lighting device, an electronic device, or a manufacturing method thereof.
  • lithium-excess positive electrode active materials have issues such as a large drop in the initial discharge capacity compared to the initial charge capacity, poor rate characteristics, and a large drop in voltage and/or discharge capacity in charge/discharge cycle tests. This is thought to be because when lithium is released from lithium-excess positive electrode active material particles, a change in the crystal structure and/or release of oxygen occurs.
  • one aspect of the present invention has an objective to provide a lithium-excess positive electrode active material particle or composite oxide in which a decrease in the initial discharge capacity relative to the initial charge capacity is suppressed.
  • an objective to provide a lithium-excess positive electrode active material particle or composite oxide in which a change in crystal structure during charging is suppressed.
  • Another aspect of the present invention is to provide novel positive electrode active material particles, composite oxides, energy storage devices, or methods for manufacturing the same.
  • the positive electrode active material particles have a core-shell structure, and the shell contains a large amount of additive elements, including magnesium.
  • a fluoride salt that functions as a flux is used to effectively dope the shell with the additive elements.
  • the shell contains more of one or more of the following elements selected from titanium, aluminum, nickel, zirconium, vanadium, iron, manganese, chromium, niobium, arsenic, zinc, silicon, sulfur, phosphorus, boron, bromine, and beryllium than the core.
  • the core has a layered rock salt type or an irregular rock salt type crystal structure.
  • the shell has a rock salt type or spinel type crystal structure.
  • Another embodiment of the present invention is a method for producing positive electrode active material particles, comprising the steps of: mixing a composite oxide represented by LixM2 -xO2 ( M is one or more selected from Mn, Ni, Co, Cr, Mo, Nb, V, Fe, Ti, and Ru, and 1 ⁇ x ⁇ 2) with an additive element source to produce a mixture; and heating the mixture at 700°C or higher and 900°C or lower, where the additive element source is a fluorine source and a magnesium source.
  • M is one or more selected from Mn, Ni, Co, Cr, Mo, Nb, V, Fe, Ti, and Ru, and 1 ⁇ x ⁇ 2
  • the fluorine source is lithium fluoride and the magnesium source is magnesium fluoride.
  • a lithium-excess positive electrode active material particle or composite oxide in which the decrease in the initial discharge capacity relative to the initial charge capacity is suppressed. Or, it is possible to provide a lithium-excess positive electrode active material particle or composite oxide with good rate characteristics. Or, it is possible to provide a lithium-excess positive electrode active material particle or composite oxide in which the decrease in voltage or discharge capacity during charge/discharge cycles is suppressed. Or, it is possible to provide a lithium-excess positive electrode active material particle or composite oxide in which the change in crystal structure during charging is suppressed. Or, it is possible to provide a lithium-excess positive electrode active material particle or composite oxide in which the release of oxygen is suppressed. Or, it is possible to provide a positive electrode active material particle or composite oxide with a high discharge capacity. Or, it is possible to provide a secondary battery with high charge/discharge capacity, safety, or reliability.
  • 8A to 8D are diagrams illustrating a lithium-ion battery and a power storage system of one embodiment of the present invention.
  • 9A to 9C are diagrams illustrating a lithium-ion battery of one embodiment of the present invention.
  • 10A to 10C illustrate a lithium-ion battery of one embodiment of the present invention.
  • 11A to 11C are diagrams illustrating an electric vehicle according to one embodiment of the present invention.
  • 12A to 12D are diagrams illustrating a transportation vehicle according to one embodiment of the present invention.
  • 13A to 13C are diagrams illustrating a two-wheeled vehicle etc. according to one embodiment of the present invention.
  • 14A to 14D are diagrams illustrating electronic devices and the like according to one embodiment of the present invention.
  • 15A to 15D are diagrams showing an example of space equipment.
  • the space group is expressed using short notation of the international notation (or Hermann-Mauguin notation).
  • the crystal plane and crystal direction are expressed using Miller indices.
  • the space group, crystal plane, and crystal direction are expressed by adding a superscript bar to the numbers, but in this specification, due to format restrictions, instead of adding a bar above the numbers, a - (minus sign) may be added before the numbers.
  • Individual directions that indicate directions within a crystal are expressed with [ ]
  • collective directions that indicate all equivalent directions are expressed with ⁇ >
  • individual faces that indicate crystal faces are expressed with ( )
  • collective faces with equivalent symmetry are expressed with ⁇ ⁇ .
  • particles are not limited to those having a spherical shape (a circular cross-sectional shape), but may have an elliptical, rectangular, trapezoidal, triangular, rectangular with rounded corners, asymmetrical shape, etc., cross-sectional shape of each particle may be irregular.
  • this includes primary particles and secondary particles.
  • the characteristics of the positive electrode active material particles it is not necessary that all particles have that characteristic. For example, if 50% or more, preferably 70% or more, and more preferably 90% or more of three or more randomly selected positive electrode active material particles have the preferred characteristics described below, it can be said that there is a sufficient effect of improving the characteristics of a secondary battery having the positive electrode active material particles.
  • the distribution of a certain element refers to the region in which the element is continuously detected in a non-noise range using a certain continuous analytical method.
  • a region in which the element is continuously detected in a non-noise range can also be defined as a region in which the element is always detected when the analysis is performed multiple times.
  • the space group of a crystal structure is identified by XRD, electron diffraction, neutron diffraction, etc. Therefore, in this specification, etc., "belonging to a certain space group,” “belonging to a certain space group,” or “being a certain space group” can be rephrased as "identified with a certain space group.”
  • a rock salt type crystal structure refers to a cubic crystal structure in which cations and anions are arranged alternately. It can also be said to be a crystal structure in which anions are arranged in a cubic close-packed manner, with cations occupying all of the octahedral positions. There may be one type of cation and one type of anion, or multiple types. There may be a deficiency of cations or anions.
  • the layered rock salt type crystal structure is a crystal structure that is common to the rock salt type in that anions are arranged in a cubic close-packed manner, and cations and anions at octahedral positions are arranged alternately, and in addition, it is clear that there are multiple types of cations, and the arrangement of at least one type of cation forms a two-dimensional plane.
  • Such a lithium-excess oxide and lithium-excess positive electrode structure can also be called a layered type.
  • a disordered rock salt type crystal structure refers to a crystal structure that has a cubic crystal structure, anions are arranged in a cubic close-packed manner, and cations and anions at octahedral positions are arranged alternately, which is common to the rock salt type, and in addition, it is clear that there are multiple types of cations, and the arrangement of these cations is irregular.
  • the arrangement of cations is irregular means that the ratio of the frequency of appearance of each cation type at each cation site is almost fixed, and no significant difference is observed between the cation sites. For example, this means that there is no significant difference in the contrast of the cation sites in HAADF-STEM (High-angle Annular Dark Field Scanning TEM) images. Defects such as missing cations or anions may be present.
  • the positive electrode active material particles of one embodiment of the present invention have a stable crystal structure even at high voltages. Because the crystal structure of the positive electrode active material particles is stable in the charged state, it is possible to suppress the decrease in charge/discharge capacity that accompanies repeated charging and discharging.
  • lithium-rich positive electrode active material particles include layered rock-salt type composite oxides and irregular rock-salt type composite oxides.
  • the positive electrode active material particle 100 has a core 102 and a shell 101 outside the core.
  • the shell 101 contains a larger amount of the additive element than the core 102.
  • the shell 101 has a higher concentration and/or detectable amount of the additive element than the core 102. It is also preferable that the concentration and/or detectable amount of the additive element is higher on the outer side of the shell 101.
  • the atomic ratio of Mg/M (M is the sum of one or more elements selected from Mn, Ni, Co, Cr, Mo, Nb, V, Fe, Ti, and Ru) when XPS analysis of the positive electrode active material particles 100 is performed at a take-off angle of 45° is preferably 3% or more, more preferably 4% or more, and even more preferably 5% or more.
  • the atomic ratio of Mg/M is preferably 3% or more, more preferably 5% or more, and even more preferably 7% or more.
  • the atomic ratio F/M when XPS analysis of the positive electrode active material particles 100 is performed at a take-off angle of 45° is preferably 15% or more, more preferably 20% or more, and even more preferably 30% or more.
  • the atomic ratio F/M is preferably 15% or more, more preferably 25% or more, and even more preferably 35% or more.
  • the shell 101 which is the region including the surface of the positive electrode active material particle 100 or the region close to the surface, has a rock salt or spinel crystal structure that contains a large amount of added elements, which is expected to have the effect of suppressing side reactions with the electrolyte and/or electrolyte.
  • the orientations of the two crystal structures are approximately the same.
  • the approximately same orientation can provide a stable shell 101, and therefore, the release of oxygen from the core 102, the elution of cations, and the like can be more effectively suppressed.
  • the fact that the crystal orientations of the two regions roughly match can be determined from TEM (Transmission Electron Microscope) images, STEM (Scanning Transmission Electron Microscope) images, HAADF-STEM images, ABF-STEM (Annular Bright-Field Scanning Transmission Electron Microscope) images, electron diffraction patterns, etc. It can also be determined from the FFT patterns of TEM images and FFT patterns of STEM images, etc. Furthermore, XRD (X-ray Diffraction), neutron diffraction, etc. can also be used to make the determination.
  • TEM images, STEM images, etc. provide images that reflect the crystal structure. Furthermore, electron diffraction patterns can provide information on the crystal orientation for each location. To obtain information on the crystal orientation of a particularly small area, it is useful to use nanobeam electron diffraction as the electron diffraction method.
  • the coincidence of the crystal planes can be observed by high-resolution STEM images, electron diffraction patterns, etc. It is preferable to use different electron diffraction methods, such as selected area diffraction and nanobeam diffraction, depending on the particle size and/or the range of the rock salt structure of the shell 101.
  • these reciprocal lattice points are spot-like, that is, that they are not concentric rings that are continuous with other reciprocal lattice points.
  • the ⁇ 111> directions of both may roughly match.
  • the ⁇ 111> directions of both may roughly match.
  • the orientations of the layered rock-salt type and the spinel type roughly match, the ⁇ 111> directions of both may roughly match.
  • the layered rock salt type positive electrode active material particles of space group R-3m are likely to have the (001) plane and its equivalent plane, as well as the (104) plane and its equivalent plane as crystal planes. Therefore, when observing the (001) plane with a TEM or the like, it is preferable to first select a positive electrode active material particle in which a crystal plane expected to be the (001) plane is observed with a SEM or the like, and then to process the positive electrode active material particle into a thin slice with a FIB (Focused Ion Beam) or the like so that the (001) plane can be observed with an electron beam incident at [120] in the TEM or the like.
  • FIB Fluorused Ion Beam
  • the crystal structures of the shell 101 and the core 102 roughly match, so that the shell 101, which contains a large amount of the additive element, functions as a pillar that supports the crystal structure of the positive electrode active material particle 100.
  • the additive elements magnesium is particularly preferred because it has a strong bond with oxygen and is expected to function well as a pillar of the positive electrode active material particle 100.
  • the presence of the additive element stabilizes the crystal structure of the surface and/or bulk of the positive electrode active material particle 100. This makes it possible to suppress changes in the crystal structure and/or the release of oxygen when the positive electrode active material particle 100 is charged.
  • positive electrode active material particles 100 in which the decrease in the initial discharge capacity relative to the initial charge capacity is suppressed, or positive electrode active material particles 100 with good rate characteristics, or positive electrode active material particles 100 in which the decrease in voltage or discharge capacity during charge/discharge cycles is suppressed.
  • the metal-metal distance here is the average distance between the nearest metal atoms in the same layer.
  • the interlayer distance is the average distance between the two metal layers.
  • the metal layer refers to the plane on which the metal atoms are arranged, and in the case of a rock salt structure and an irregular rock salt structure (Fm-3m), it refers to the (111) plane.
  • a layered rock salt structure it refers to the (001) plane for R-3m, the (001) plane for C/2m, and the (001) plane for P2/m.
  • a spinel structure Fd-3m
  • the plane on which the same type of metal is most frequently arranged may be called the metal layer.
  • the crystal structures can be roughly identical.
  • the core 102 has the crystal structure and composition of layered rock salt type lithium-rich positive electrode active material particles, and the shell 101 has a rock salt type crystal structure.
  • the layered rock salt type lithium-rich positive electrode active material particles are a material obtained by mixing and synthesizing Li2MnO3 and LiMO2 (M is one or more selected from Mn, Ni, Co, Cr, Mo, Nb, V, Fe, Ti, and Ru) at a certain ratio, it is considered that the metal-metal distance and interlayer distance of the core 102 are somewhere between Li2MnO3 and LiMO2 .
  • Table 1 shows experimental values of the metal-metal distance and interlayer distance of the known Li2MnO3 .
  • the upper part of Figure 2A shows the (001) plane of the crystal structure of Li 2 MnO 3 , which has the space group C2/m, and the lower part shows a schematic diagram of a plane perpendicular to the (001) plane.
  • the (001) plane of the crystal structure of Li 2 MnO 3 is a plane on which metals are arranged in layers.
  • the (001) plane in the upper part of Figure 2A shows an excerpt of one metal layer and oxygen layers above and below it.
  • the plane perpendicular to these in the lower part shows only bonds between one metal layer and oxygen layers above and below it.
  • the concentration and/or detectable amount of the added element is higher in the shell 101 than in the core 102, it is believed that the metal-metal distance and interlayer distance of the shell 101 will be somewhere between the values of the rock-salt oxide of the added element and the crystal structure of the core 102.
  • magnesium, cobalt, nickel, and manganese are taken as examples of added elements, and Table 1 shows the experimental values of the metal-metal distance and interlayer distance of the known MgO, CoO, NiO, and MnO. In all cases, the interlayer distance is 2.412 ⁇ to 2.567 ⁇ , and the metal-metal distance is 2.954 ⁇ to 3.144 ⁇ , with four significant digits.
  • the core 102 has the crystal structure and composition of an irregular rock-salt type lithium-rich positive electrode active material particle
  • the shell 101 has a rock-salt type crystal structure. Since the irregular rock-salt type crystal structure of the core 102 is the same as the rock-salt type crystal structure of the shell, the two can be compared in terms of lattice constant.
  • the core 102 or the shell 101 has a spinel crystal structure.
  • the oxygen layers of the rock-salt type are also cubic close-packed, with ABCABC... stacking in the ⁇ 111> direction.
  • the oxygen layers of the layered rock-salt type R-3m are also cubic close-packed, with ABCABC... stacking in the [001] direction.
  • the oxygen layers of the layered rock-salt type C/2m are also cubic close-packed, with ABCABC... stacking in the direction roughly perpendicular to the c-plane.
  • the metal-metal distance is the same as the oxygen-oxygen distance.
  • the interlayer distance of the metal layer is the same as the interlayer distance of the oxygen layer.
  • the metal-metal distance is the same as the oxygen-oxygen distance.
  • oxygen and metal are arranged alternately, and the average interlayer distance of the metal layer is the same as the average interlayer distance of the oxygen layer.
  • the oxygen positions on the (111) plane of LiMn2O4 are shifted from the positions of the triangular lattices. Therefore, the distance between the triangular lattices when the oxygen is arranged to be the positions of the triangular lattices on the same plane is assumed to be the oxygen-oxygen distance.
  • the oxygen-oxygen distance calculated under this assumption is 2.908 ⁇ , and the relative value to the oxygen-oxygen distance of MgO is 0.98.
  • the oxygen position of LiMn 2 O 4 is shifted from the (111) plane, the average of the oxygen positions on the (111) plane is similarly taken as the oxygen position on the (111) plane, and the distance of the oxygen layer in the [111] direction calculated using the oxygen position on the (111) plane is assumed to be the interlayer distance of the oxygen layer.
  • the interlayer distance of the oxygen layer calculated under this assumption is 2.375 ⁇ , and the relative value to the interlayer distance of the oxygen layer of MgO is 0.98. In this way, the relative values of the oxygen-oxygen distance and the interlayer distance of the oxygen layer of LiMn 2 O 4 to MgO are in the range of 0.94 to 1.06.
  • the crystal orientation may be approximately the same as that of the Mg-containing rock-salt shell 101.
  • the crystal orientation may be approximately the same as that of the core 102 having a layered rock-salt and/or disordered rock-salt crystal structure.
  • the particle diameter of the positive electrode active material particles 100 is preferably 500 nm or less, more preferably 250 nm or less, and even more preferably about 100 nm, in order to suppress the diffusion resistance of lithium within the particles. On the other hand, if the particle diameter is too small, disadvantages such as a tendency for aggregation to occur may arise. Therefore, the diameter is preferably 25 nm or more, and more preferably 50 nm or more.
  • the positive electrode active material particles 100 may have secondary particles formed by agglomeration, adhesion and/or sintering of multiple primary particles. If secondary particles are present, the particle size becomes larger, which is preferable as it makes it easier to apply the particles to a current collector, etc.
  • a shell 101 may be formed for each primary particle that the secondary particle has. Also, the shell 101 may be formed for the secondary particles as a single particle. In other words, there may be a primary particle inside the secondary particle that does not have a shell 101. Also, an additive element may be used as a sintering aid when granulating the primary particles into secondary particles.
  • shell 101 has a rock salt or spinel crystal structure, but it is not necessary that only shell 101 has a rock salt or spinel crystal structure.
  • a part of core 102 may have a rock salt or spinel crystal structure.
  • the shell 101 does not necessarily have to cover the entire surface of the positive electrode active material particle 100. However, in order to function as a pillar, it is preferable that the shell 101 is present on 50% or more of the surface of the positive electrode active material particle 100, preferably 70% or more, and more preferably 90% or more.
  • the shell 101 does not have to be entirely of a rock-salt or spinel crystal structure.
  • a portion of it may be amorphous, or it may have another crystal structure.
  • the core 102 does not have to be entirely of a layered rock-salt or irregular rock-salt crystal structure.
  • a portion of it may be amorphous, or it may have another crystal structure.
  • composition of the positive electrode active material particle 100 is preferably evaluated by combining a plurality of analyses.
  • the ratios of the main components lithium, transition metal M, and oxygen are preferably determined by ICP-MS (inductively coupled plasma mass spectrometry) or the like.
  • the ratios of the additive elements are preferably determined by an analysis with high detection sensitivity for trace elements, such as GD-MS (glow discharge mass spectrometry).
  • the distribution of the added element in the positive electrode active material particle 100 according to one embodiment of the present invention is preferably evaluated, for example, by a cross-sectional analysis of the positive electrode active material particle 100 .
  • cross-sectional STEM-EDX is preferable because of its high spatial resolution.
  • the diameter of the electron beam also called the beam diameter, probe diameter, or probe diameter
  • the beam diameter in STEM-EDX ray analysis is preferably 0.3 nm or less, more preferably 0.2 nm or less, and even more preferably 0.1 nm or less.
  • the first image is binarized using image processing software and particle analysis is performed.
  • Image processing software that can be used is, for example, ImageJ.
  • the binarization process is explained below.
  • a first image shown in a 256-value grayscale is used as a frequency graph excluding black (value 0) and white (value 255), and the low value side (HWHM_L) and high value side (HWHM_H) are obtained as the half-width at half maximum (HWHM) of the maximum peak in the frequency graph.
  • HWHM_L low value side
  • HWHM_H high value side
  • the minimum value a of the range that is twice the width of HWHM_L on the low value side from the value that is the peak top (maximum frequency) of the maximum peak and the maximum value b of the range that is twice the width of HWHM_H on the high value side are determined.
  • the particle size distribution of each particle can be calculated from the cross-sectional SEM image.
  • Performing the above analysis is called performing particle size distribution analysis using a cross-sectional SEM image of the positive electrode.
  • a lithium (Li) source and an M source are prepared.
  • lithium carbonate (Li2CO3 ) , lithium hydroxide (LiOH) and/or lithium oxide ( Li2O ) can be used as the lithium source.
  • Li2O lithium oxide
  • M source an oxide, hydroxide, carbonate, etc. of a transition metal M can be used.
  • step S12 the lithium source and the M source are mixed to prepare a mixture 901 (step S13). Grinding during the mixing process is useful for reducing the particle size. It is preferable to use a bead mill and/or a ball mill for grinding. A planetary ball mill can be used as the ball mill. The bead mill and/or ball mill may be either a dry type or a wet type. If heat is generated during mixing and grinding, it is preferable to cool the mixture.
  • step S14 the first mixture 901 prepared above is heated.
  • the higher the heating temperature the shorter the heating time, and therefore the higher the productivity.
  • the heating temperature is too high, the particle size of the primary particles may become large, and the charge/discharge capacity may decrease.
  • the transition metal may be easily reduced, and for example, Mn may be reduced from tetravalent to trivalent, and a composite oxide of the intended composition may not be synthesized.
  • a shorter heating time is preferable because it is more productive, but if the heating time is too short, the reaction may be insufficient. Therefore, the heating temperature is preferably, for example, 700°C or more and 1200°C or less, and more preferably, 800°C or more and 1050°C or less.
  • the heating time is, for example, preferably 15 minutes or more and 100 hours or less, and more preferably, 2 hours or more and 20 hours or less.
  • the heating time here refers to the time during which the heating temperature is maintained, and does not include the time during which the temperature is increased or decreased.
  • Heating when preparing layered rock salt type and disordered rock salt type LixM2 -xO2 may be performed in an oxidizing atmosphere containing oxygen, or in an inert atmosphere such as argon or nitrogen.
  • an oxidizing atmosphere containing oxygen or in an inert atmosphere such as argon or nitrogen.
  • the heating step if the amount of first mixture 901 per heating container is too large, the first mixture 901 may not be in sufficient contact with the atmosphere, and the reaction may be partially insufficient. Therefore, it is preferable to heat the mixture in multiple heating containers as necessary. When heating the mixture in multiple heating containers, these are mixed after heating. For this mixing, a bead mill, a ball mill, a mortar, a mix rotor, and/or a mixer can be used.
  • a source of the additive element (A) is prepared.
  • the additive element is synonymous with a mixture or a part of a raw material.
  • the additive element source a single additive element or a compound of the additive element can be used.
  • magnesium oxide (MgO) and/or magnesium fluoride (MgF 2 ) can be used as the magnesium source.
  • fluorine is used as the additive element, the fluorine source is preferably a fluoride of a typical metal element, and lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF) and/or magnesium fluoride (MgF 2 ) can be used. Considering the use in lithium ion batteries, it is particularly preferable to use lithium fluoride as the fluorine source.
  • the fluorides of these typical metal elements function as fluxes in the subsequent heating step, and can promote the diffusion and doping of the additive elements in the shell 101.
  • Mixtures containing fluorides are preferred because they may have a melting point lower than the decomposition temperature of the composite oxide represented by LixM2 - xO2 and are also safe.
  • a mixture of a combination having a eutectic point of 1000°C, preferably 900°C or less in an oxygen-containing atmosphere is preferred because it is a mixture that easily becomes liquid at a relatively low temperature.
  • fluorine may be lost due to volatilization or the like, so even if fluorine is added as an additive element, there are cases in which fluorine is not detected in the positive electrode active material particles 100 after production.
  • an additive element is added in a process of preparing a composite oxide represented by Li x M 2-x O 2 (M is one or more selected from Mn, Ni, Co, Cr, Mo, Nb, V, Fe, Ti, and Ru, 1 ⁇ x ⁇ 2). That is, in step S11, a lithium source, an M source, and an additive element source are mixed and heated to synthesize. Even in the case of such a preparation process, it is possible to make the shell 101 contain a large amount of the additive element by changing the additive element and heating conditions. For example, by using an additive element having a low solid solubility limit in the composite oxide represented by Li x M 2-x O 2 , a shell 101 containing a large amount of the additive element can be formed.
  • the above-mentioned organic solvent has almost no peaks due to impurities that can be confirmed by NMR measurement or the like.
  • "Almost no peaks can be confirmed” includes that the ratio of the integrated area of the peak due to the impurity to the integrated area of the peak due to the main component (simply called integral ratio) is 0.005 or less, preferably 0.002 or less.
  • integral ratio the ratio of the integrated area of the peak due to the impurity to the integrated area of the peak due to the main component
  • integral ratio 0.005 or less, preferably 0.002 or less.
  • the central peak can be 1.94 ppm.
  • a solid electrolyte containing inorganic materials such as sulfides or oxides, or a solid electrolyte containing polymeric materials such as PEO (polyethylene oxide) can be used.
  • PEO polyethylene oxide
  • the safety of the lithium-ion battery can be maintained even if the overall thickness of the separator is thin, allowing the capacity per volume of the lithium-ion battery to be increased.
  • FIG. 7A is a schematic diagram that shows the overlapping of parts (vertical relationship and positional relationship). Therefore, Fig. 7A and Fig. 7B are not completely corresponding drawings.
  • FIG. 7A shows the state in which the positive electrode 304, negative electrode 307, spacer 342, and washer 332 are stacked and sealed with the negative electrode can 302 and positive electrode can 301. Note that FIG. 7A does not show the electrolyte and separator described in the above embodiment.
  • the spacer 342 and washer 332 are used to protect the inside or to fix the position inside the can when the positive electrode can 301 and the negative electrode can 302 are crimped together.
  • the spacer 342 or washer 332 is made of stainless steel or an insulating material.
  • the positive electrode 304 is a laminated structure in which a positive electrode active material layer 306 is formed on a positive electrode current collector 305.
  • FIG. 7B is an oblique view of the completed coin-type lithium-ion battery 300.
  • the positive electrode can 301 which also serves as the positive electrode terminal
  • the negative electrode can 302 which also serves as the negative electrode terminal
  • the positive electrode 304 is formed of a positive electrode current collector 305 and a positive electrode active material layer 306 provided in contact with it.
  • the negative electrode 307 is formed of a negative electrode current collector 308 and a negative electrode active material layer 309 provided in contact with it.
  • the positive electrode can 301 is electrically connected to the positive electrode 304
  • the negative electrode can 302 is electrically connected to the negative electrode 307.
  • the positive electrode 304 and the negative electrode 307 used in the coin-type lithium-ion battery 300 each have an active material layer formed on only one side.
  • the positive electrode can 301 is placed at the bottom, and the positive electrode 304, negative electrode 307, and negative electrode can 302 are stacked in this order, and the positive electrode can 301 and the negative electrode can 302 are crimped together via a gasket 303 to produce a coin-shaped lithium-ion battery 300.
  • a cylindrical lithium ion battery 616 has a positive electrode cap (battery lid) 601 on the top surface, and a battery can (external can) 602 on the side and bottom surfaces.
  • the positive electrode cap 601 and the battery can (external can) 602 are insulated by a gasket (insulating packing) 610.
  • FIG. 8B is a schematic diagram showing a cross section of a cylindrical lithium-ion battery.
  • the cylindrical lithium-ion battery shown in FIG. 8B has a positive electrode cap (battery lid) 601 on the top surface, and a battery can (external can) 602 on the side and bottom surfaces.
  • the positive electrode cap and battery can (external can) 602 are insulated by a gasket (insulating packing) 610.
  • a battery element is provided inside a hollow cylindrical battery can 602, in which a strip-shaped positive electrode 604 and negative electrode 606 are wound with an electrolyte layer 605 sandwiched between them.
  • the battery element is wound around a central axis. One end of the battery can 602 is closed and the other end is open.
  • the battery element, in which the positive electrode, negative electrode, and separator are wound is sandwiched between a pair of opposing insulating plates 608 and 609.
  • An electrolyte (not shown) is injected into the inside of the battery can 602 in which the battery element is provided.
  • the positive and negative electrodes used in a cylindrical storage battery are wound, it is preferable to form active material on both sides of the current collector.
  • a lithium ion battery 616 in which the height of the cylinder is greater than the diameter is illustrated in Figures 8A to 8D, this is not limited to this.
  • a lithium ion battery in which the diameter of the cylinder is greater than the height of the cylinder may also be used. With this configuration, for example, it is possible to miniaturize the lithium ion battery.
  • the power storage system 615 is electrically connected to the control circuit 620 via wiring 621 and wiring 622.
  • Wiring 621 is electrically connected to the positive electrodes of the multiple lithium ion batteries 616 via conductive plate 628
  • wiring 622 is electrically connected to the negative electrodes of the multiple lithium ion batteries 616 via conductive plate 614.
  • the lithium ion battery 913 shown in FIG. 9A has a wound body 950 with terminals 951 and 952 provided inside the housing 930.
  • the wound body 950 is impregnated with an electrolyte inside the housing 930.
  • the terminal 952 is in contact with the housing 930, and the terminal 951 is not in contact with the housing 930 due to the use of an insulating material or the like.
  • the housing 930 is shown separated for convenience, but in reality, the wound body 950 is covered by the housing 930, and the terminals 951 and 952 extend outside the housing 930.
  • the housing 930 can be made of a metal material (such as aluminum), a composite material of metal and resin, or the like.
  • the housing 930 shown in FIG. 9A may be formed from a plurality of materials.
  • the lithium ion battery 913 shown in FIG. 9B has housings 930a and 930b bonded together, and a wound body 950 is provided in the area surrounded by housings 930a and 930b.
  • the internal structure of the first battery 1301a may be a wound type or a layered type.
  • the second battery 1311 also supplies power to 14V in-vehicle components (audio 1313, power windows 1314, lamps 1315, etc.) via the DCDC circuit 1310.
  • the control circuit unit 1320 uses a transistor using an oxide semiconductor.
  • the control circuit unit 1320 may be formed using a unipolar transistor.
  • a transistor using an oxide semiconductor in the semiconductor layer has a wider operating ambient temperature range than single-crystal Si, from -40°C to 150°C, and the change in characteristics is smaller than that of single crystal even when the lithium-ion battery is heated.
  • the off-current of a transistor using an oxide semiconductor is below the lower measurement limit regardless of temperature, even at 150°C, but the off-current characteristics of a single-crystal Si transistor are highly temperature-dependent. For example, at 150°C, the off-current of a single-crystal Si transistor increases, and the current on/off ratio does not become sufficiently large.
  • the control circuit unit 1320 can improve safety.
  • the control circuit section 1320 which uses a memory circuit including transistors using oxide semiconductors, can also function as an automatic control device for lithium-ion batteries against 10 causes of instability, such as micro-shorts.
  • Functions that eliminate the 10 causes of instability include overcharging prevention, overcurrent prevention, overheating control during charging, cell balancing in the battery pack, over-discharging prevention, a remaining capacity meter, automatic control of charging voltage and current according to temperature, control of charging current according to degree of deterioration, detection of abnormal behavior of micro-shorts, and prediction of abnormalities related to micro-shorts, and at least one of these functions is provided by the control circuit section 1320. It is also possible to ultra-miniaturize the automatic control device for lithium-ion batteries.
  • Micro-short circuits refer to tiny short circuits inside lithium-ion batteries.
  • One of the causes of micro-short circuits is said to be localized current concentration in parts of the positive electrode and negative electrode due to uneven distribution of positive electrode active material particles caused by multiple charge and discharge cycles, or the generation of by-products due to side reactions, resulting in micro-short circuits.
  • control circuit section 1320 can also be said to detect the terminal voltage of the lithium-ion battery and manage the charge/discharge state of the lithium-ion battery. For example, to prevent overcharging, it can turn off both the output transistor and the cutoff switch of the charging circuit almost simultaneously.
  • FIG. 11C An example of a block diagram of the battery pack 1415 shown in FIG. 11B is shown in FIG. 11C.
  • the control circuit unit 1320 has at least a switch unit 1324 including a switch for preventing overcharging and a switch for preventing overdischarging, a control circuit 1322 for controlling the switch unit 1324, and a voltage measurement unit for the first battery 1301a.
  • the control circuit unit 1320 is set with an upper limit voltage and a lower limit voltage for the lithium ion battery to be used, and limits the upper limit of the current from the outside and the upper limit of the output current to the outside.
  • the range between the lower limit voltage and the upper limit voltage of the lithium ion battery is within the voltage range recommended for use, and when it is outside this range, the switch unit 1324 operates and functions as a protection circuit.
  • the control circuit unit 1320 can also be called a protection circuit because it controls the switch unit 1324 to prevent overcharging and overdischarging. For example, when the control circuit 1322 detects a voltage that is likely to cause overcharging, it turns off the switch unit 1324 to cut off the current. Furthermore, a PTC element may be provided in the charge/discharge path to provide a function for cutting off the current in response to an increase in temperature. In addition, the control circuit section 1320 has an external terminal 1325 (+IN) and an external terminal 1326 (-IN).
  • the first batteries 1301a and 1301b mainly supply power to 42V (high voltage) in-vehicle devices, and the second battery 1311 supplies power to 14V (low voltage) in-vehicle devices.
  • Lead-acid batteries are often used as the second battery 1311 because of their cost advantage.
  • the advantage of using a lithium-ion battery as the second battery 1311 is that it is maintenance-free, but if it is used for a long period of time, for example, more than three years, there is a risk of abnormalities occurring that cannot be detected at the time of manufacture.
  • the second battery 1311 that starts the inverter becomes inoperable, even if the first batteries 1301a and 1301b have remaining capacity, in order to prevent the motor from being unable to start, if the second battery 1311 is a lead-acid battery, power is supplied from the first battery to the second battery, and the battery is charged to always maintain a fully charged state.
  • the second battery 1311 may be a lead acid battery, an all-solid-state battery, or an electric double layer capacitor.
  • the regenerative energy produced by the rotation of the tire 1316 is sent to the motor 1304 via the gear 1305, and is then charged from the motor controller 1303 and the battery controller 1302 via the control circuit unit 1321 to the second battery 1311.
  • the first battery 1301a is charged from the battery controller 1302 via the control circuit unit 1320.
  • the first battery 1301b is charged from the battery controller 1302 via the control circuit unit 1320.
  • the first batteries 1301a and 1301b are capable of being rapidly charged.
  • the battery controller 1302 can set the charging voltage and charging current of the first batteries 1301a and 1301b.
  • the battery controller 1302 can set charging conditions according to the charging characteristics of the lithium ion battery used, and can perform rapid charging.
  • the charger outlet or the charger connection cable is electrically connected to the battery controller 1302.
  • the power supplied from the external charger is charged to the first batteries 1301a and 1301b via the battery controller 1302.
  • some chargers are provided with a control circuit, and although the function of the battery controller 1302 may not be used, it is preferable to charge the first batteries 1301a and 1301b via the control circuit section 1320 to prevent overcharging.
  • the connection cable or the charger connection cable may be provided with a control circuit.
  • the control circuit section 1320 may also be called an ECU (Electronic Control Unit).
  • the ECU is connected to a CAN (Controller Area Network) provided in the electric vehicle.
  • the CAN is one of the serial communication standards used as an in-vehicle LAN.
  • the ECU includes a microcomputer.
  • the ECU also uses a CPU or GPU.
  • External chargers installed at charging stations and the like come in a variety of types, including 100V outlets, 200V outlets, and 3-phase 200V and 50kW outlets.
  • charging can also be performed by receiving power from external charging equipment using a contactless power supply system, etc.
  • Lithium-ion batteries can also be installed in transportation vehicles such as agricultural machinery, mopeds including electrically assisted bicycles, motorcycles, electric wheelchairs, electric carts, small or large ships, submarines, aircraft such as fixed-wing aircraft and rotary-wing aircraft, rockets, artificial satellites, space probes, planetary probes, and spacecraft.
  • transportation vehicles such as agricultural machinery, mopeds including electrically assisted bicycles, motorcycles, electric wheelchairs, electric carts, small or large ships, submarines, aircraft such as fixed-wing aircraft and rotary-wing aircraft, rockets, artificial satellites, space probes, planetary probes, and spacecraft.
  • the automobile 2001 shown in FIG. 12A has a battery pack 2200, which has a battery module to which multiple lithium ion batteries are connected. It is further preferable that the battery pack 2200 has a charge control device electrically connected to the battery module.
  • automobile 2001 can charge its lithium ion battery by receiving power from an external charging facility using a plug-in method, a contactless power supply method, or the like.
  • the charging method and connector standards can be appropriately determined using a predetermined method such as CHAdeMO (registered trademark) or Combo.
  • CHAdeMO registered trademark
  • Combo a predetermined method
  • the external charging facility a charging station installed in a commercial facility, a home power source, or the like can be used.
  • a power storage device installed in automobile 2001 can be charged by an external power supply using plug-in technology. Charging can be performed by converting AC power to DC power via a conversion device such as an AC-DC converter.
  • FIG. 12B shows a large transport vehicle 2002 having an electrically controlled motor as an example of a transport vehicle.
  • the battery module of the transport vehicle 2002 is, for example, a four-cell unit of lithium ion batteries with a nominal voltage of 3.0V to 5.0V, with 48 cells connected in series to achieve a maximum voltage of 170V.
  • the battery pack 2201 it has the same functions as FIG. 11B, so a description will be omitted.
  • FIG. 12C shows, as an example, a large transport vehicle 2003 having an electrically controlled motor.
  • the battery module of the transport vehicle 2003 has, for example, 100 or more lithium ion batteries with a nominal voltage of 3.0 V to 5.0 V connected in series to produce a maximum voltage of 600 V. Furthermore, apart from the difference in the number of lithium ion batteries that make up the battery module of the battery pack 2202, it has the same functions as FIG. 11B, so a description thereof will be omitted.
  • the positive electrode active material particles of the present invention in the lithium ion batteries of the module it is possible to produce a secondary battery with high capacity, high discharge capacity, and excellent cycle characteristics.
  • FIG. 14B shows an unmanned aerial vehicle 2300 having multiple rotors 2302.
  • the unmanned aerial vehicle 2300 is sometimes called a drone.
  • the unmanned aerial vehicle 2300 has a lithium ion battery 2301, which is one embodiment of the present invention, a camera 2303, and an antenna (not shown).
  • the unmanned aerial vehicle 2300 can be remotely controlled via the antenna.
  • FIG. 14C shows an example of a robot.
  • the robot 6400 shown in FIG. 14C includes a lithium ion battery 6409, an illuminance sensor 6401, a microphone 6402, an upper camera 6403, a speaker 6404, a display unit 6405, a lower camera 6406, an obstacle sensor 6407, a movement mechanism 6408, a computing device, etc.
  • the microphone 6402 has a function of detecting the user's voice and environmental sounds.
  • the speaker 6404 has a function of emitting sound.
  • the robot 6400 can communicate with the user using the microphone 6402 and the speaker 6404.
  • the display unit 6405 has a function of displaying various information.
  • the robot 6400 can display information desired by the user on the display unit 6405.
  • the display unit 6405 may be equipped with a touch panel.
  • the display unit 6405 may also be a removable information terminal, and by installing it in a fixed position on the robot 6400, charging and data transfer are possible.
  • the upper camera 6403 and the lower camera 6406 have the function of capturing images of the surroundings of the robot 6400.
  • the obstacle sensor 6407 can detect the presence or absence of obstacles in the direction of travel when the robot 6400 moves forward using the moving mechanism 6408.
  • the robot 6400 can recognize the surrounding environment and move safely using the upper camera 6403, the lower camera 6406, and the obstacle sensor 6407.
  • the robot 6400 includes a lithium ion battery 6409 according to one embodiment of the present invention and a semiconductor device or electronic component in its internal area.
  • a lithium ion battery 6409 according to one embodiment of the present invention
  • a semiconductor device or electronic component in its internal area.
  • FIG 14D shows an example of a cleaning robot.
  • the cleaning robot 6300 has a display unit 6302 arranged on the top surface of a housing 6301, multiple cameras 6303 arranged on the side, brushes 6304, operation buttons 6305, a lithium ion battery 6306, various sensors, and the like.
  • the cleaning robot 6300 is equipped with tires, a suction port, and the like.
  • the cleaning robot 6300 can move by itself, detect dirt 6310, and suck up the dirt from a suction port arranged on the bottom surface.
  • the cleaning robot 6300 can analyze an image captured by the camera 6303 and determine whether or not there is an obstacle such as a wall, furniture, or a step. Furthermore, if an object that may become entangled in the brush 6304, such as a wire, is detected by image analysis, the rotation of the brush 6304 can be stopped.
  • the cleaning robot 6300 includes a lithium ion battery 6306 according to one embodiment of the present invention and a semiconductor device or electronic component in its internal area. By using the positive electrode active material particles of the present invention in the lithium ion battery, a secondary battery with high capacity, high discharge capacity, and excellent cycle characteristics can be obtained.
  • FIG. 15A shows an artificial satellite 6800 as an example of space equipment.
  • the artificial satellite 6800 has a body 6801, a solar panel 6802, an antenna 6803, and a lithium-ion battery 6805.
  • the solar panel may be called a solar cell module.
  • the power required for the operation of the satellite 6800 is generated.
  • the amount of power generated is small. Therefore, there is a possibility that the power required for the operation of the satellite 6800 will not be generated.
  • Satellite 6800 can generate a signal.
  • the signal is transmitted via antenna 6803, and can be received, for example, by a receiver located on the ground or by another satellite.
  • a receiver located on the ground or by another satellite.
  • the position of the receiver that received the signal can be measured.
  • satellite 6800 can constitute, for example, a satellite positioning system.
  • the artificial satellite 6800 can be configured to have a sensor.
  • the artificial satellite 6800 can have the function of detecting sunlight reflected off an object located on the ground.
  • the artificial satellite 6800 can have the function of detecting thermal infrared rays emitted from the earth's surface. From the above, the artificial satellite 6800 can have the function of, for example, an earth observation satellite.
  • FIG. 15B shows a probe 6900 with a solar sail (also called a sun sail) as an example of space equipment.
  • the probe 6900 has a body 6901, a solar sail 6902, and a lithium ion battery 6905.
  • a secondary battery with high capacity, high discharge capacity, and excellent cycle characteristics can be obtained.
  • the surface of the solar sail 6902 has a thin film with high reflectivity, and it is further preferable that it faces the sun.
  • the solar sail 6902 may also be designed to be folded up small until it leaves the atmosphere, and then deployed into a large sheet shape outside the Earth's atmosphere (outer space) as shown in Figure 15B.
  • FIG. 15C shows a spacecraft 6910 as an example of space equipment.
  • the spacecraft 6910 has a body 6911, a solar panel 6912, and a lithium ion battery 6913.
  • the body 6911 can have, for example, a pressurized compartment and a non-pressurized compartment.
  • the pressurized compartment may be designed to accommodate a crew member. Electricity generated by irradiating the solar panel 6912 with sunlight can be charged into the lithium ion battery 6913.
  • FIG. 15D shows a rover 6920 as an example of space equipment.
  • the rover 6920 has a body 6921 and a lithium ion battery 6923.
  • the rover 6920 may also have a solar panel 6922.
  • lithium carbonate was prepared as the Li source in step S11
  • manganese carbonate was prepared as the Mn source
  • nickel carbonate was prepared as the Ni source.
  • step S12 for mixing in step S12, a ball mill was used, and dehydrated acetone was used as the solvent, and wet mixing was performed while cooling. Zirconia balls with a diameter of 3 mm were used as the ball mill media, and mixing was performed for 2 hours. After that, the dehydrated acetone was dried in a drying oven at 55°C, and the mixed media was removed with a sieve to obtain the first mixture.
  • step S14 for the first heating in step S14, a muffle furnace was used, and heating was performed while flowing dry air.
  • the heating conditions were 1000°C and 10 hours.
  • the temperature increase rate was 200°C/hour.
  • the temperature decrease rate was 200°C/hour or less.
  • the atomic ratio of F/(Mn+Ni) in sample 3 in XPS was 46.6 at% when the take-off angle was 45°, and 58.1 at% when the take-off angle was 15°.
  • the atomic ratio of F/(Mn+Ni) in sample 4 was 37.4 at% when the take-off angle was 45°, and 46.6 at% when the take-off angle was 15°. In both cases, the shallower the take-off angle, the higher the fluorine concentration, which made it clear that the closer to the surface the fluorine concentration is.
  • a coin-shaped half cell (also called a coin cell) was fabricated using each of the above positive electrodes, lithium metal foil, a separator, an electrolyte, a coin cell positive electrode can, and a coin cell negative electrode can.
  • the shape of the coin-shaped half cell was CR2032 type (diameter 20 mm, height 3.2 mm).
  • a porous polypropylene film was used as the separator.
  • the charge/discharge curves for the first cycle of the half cells containing Samples 1 and 2 are shown in Figure 19A, and the charge/discharge curves for the second cycle are shown in Figure 19B.
  • the cycle characteristics of the discharge capacity per weight of the positive electrode active material particles for the half cells containing Samples 1 and 2 are shown in Figure 20A, the discharge capacity retention rate in Figure 20B, and the discharge energy density in Figure 20C.
  • the discharge capacity retention rate was calculated assuming the maximum discharge capacity in the charge/discharge cycle test to be 100%.
  • Sample 1 which was heated with the addition of an additive element source, had better cycle characteristics than Sample 2, which was heated without the addition of an additive element source.
  • the initial discharge capacity of Sample 1 was 233.7 mAh/g, and the 30th discharge capacity was 211.7 mAh/g.
  • Samples 3 and 4 in which the second heating time was 800°C and 900°C, respectively, showed good discharge capacity and cycle characteristics. Sample 4 had better cycle characteristics than Sample 3.
  • lithium-rich positive electrode active material particles that contain magnesium and fluorine as added elements and have high magnesium and fluorine concentrations in the shell exhibit good discharge capacity and cycle characteristics.

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Abstract

L'invention concerne des particules de matériau actif d'électrode positive à excès de lithium ayant une structure cristalline stabilisée, et une batterie secondaire comprenant lesdites particules. Les particules de matériau actif d'électrode positive contiennent du lithium, un métal de transition M (M représente un ou plusieurs éléments choisis parmi Mn, Ni, Co, Cr, Mo, Nb, V, Fe, Ti et Ru), de l'oxygène, du magnésium et du fluor, le rapport Li/M (rapport atomique) des particules de matériau actif d'électrode positive étant supérieur à 1, les particules de matériau actif d'électrode positive ayant un cœur et une écorce à l'extérieur du cœur, le magnésium et le fluor étant détectés en quantités supérieures dans l'écorce que dans le cœur, et les orientations cristallines du cœur et de l'écorce coïncidant grossièrement.
PCT/IB2025/050346 2024-01-19 2025-01-13 Particule de matériau actif d'électrode positive et procédé de production de particule de matériau actif d'électrode positive Pending WO2025153936A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018195581A (ja) * 2017-05-19 2018-12-06 株式会社半導体エネルギー研究所 正極活物質、正極活物質の作製方法、および二次電池
JP2018206747A (ja) * 2016-07-05 2018-12-27 株式会社半導体エネルギー研究所 正極活物質、正極活物質の作製方法、および二次電池
JP2023180233A (ja) * 2022-06-08 2023-12-20 株式会社半導体エネルギー研究所 電池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018206747A (ja) * 2016-07-05 2018-12-27 株式会社半導体エネルギー研究所 正極活物質、正極活物質の作製方法、および二次電池
JP2018195581A (ja) * 2017-05-19 2018-12-06 株式会社半導体エネルギー研究所 正極活物質、正極活物質の作製方法、および二次電池
JP2023180233A (ja) * 2022-06-08 2023-12-20 株式会社半導体エネルギー研究所 電池

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