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WO2018190374A1 - Matériau actif d'électrode positive et son procédé de fabrication, électrode positive, batterie, bloc-batterie, appareil électronique, véhicule électrique, dispositif de stockage d'électricité et système d'alimentation électrique - Google Patents

Matériau actif d'électrode positive et son procédé de fabrication, électrode positive, batterie, bloc-batterie, appareil électronique, véhicule électrique, dispositif de stockage d'électricité et système d'alimentation électrique Download PDF

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Publication number
WO2018190374A1
WO2018190374A1 PCT/JP2018/015243 JP2018015243W WO2018190374A1 WO 2018190374 A1 WO2018190374 A1 WO 2018190374A1 JP 2018015243 W JP2018015243 W JP 2018015243W WO 2018190374 A1 WO2018190374 A1 WO 2018190374A1
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Prior art keywords
positive electrode
active material
electrode active
battery
coating layer
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PCT/JP2018/015243
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English (en)
Japanese (ja)
Inventor
宮崎　武志
佐藤　晋
松田　賢治
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株式会社村田製作所
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Publication of WO2018190374A1 publication Critical patent/WO2018190374A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/52—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

  • the present technology relates to a positive electrode active material and a manufacturing method thereof, a positive electrode, a battery, a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system.
  • Patent Document 1 proposes a technique for forming an extremely thin uniform coating layer on the surface of the positive electrode active material particles by an ALD (Atomic Layer Deposition) process as a method for forming the coating layer.
  • ALD Atomic Layer Deposition
  • An object of the present technology is to provide a positive electrode active material capable of suppressing gas generation, a manufacturing method thereof, a positive electrode, a battery, a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system.
  • a positive electrode active material of the present technology includes particles containing a lithium-containing compound and a coating layer that covers at least a part of the surface of the particles, and temperature programmed desorption gas analysis (TDS)
  • TDS temperature programmed desorption gas analysis
  • the method for producing a positive electrode active material of the present technology includes producing a coated particle by forming a coating layer on the surface of a particle containing a lithium-containing compound, and heat-treating the coated particle, and the average thickness of the coating layer is
  • TDS temperature-programmed desorption gas analysis
  • the amount of gas attributed to the gas desorption peak is 0.2 wt% or less with respect to the weight of the positive electrode active material.
  • the positive electrode of the present technology includes the positive electrode active material described above.
  • the battery of the present technology includes a positive electrode, a negative electrode, and an electrolyte, and the positive electrode includes the positive electrode active material described above.
  • the battery pack, electronic device, electric vehicle, power storage device, and power system of the present technology include the above-described battery.
  • gas generation can be suppressed.
  • the effects described here are not necessarily limited, and may be any of the effects described in the present disclosure or effects different from those.
  • FIG. 1A is a cross-sectional view showing an example of the configuration of the positive electrode active material according to the first embodiment of the present technology.
  • FIG. 1B is a cross-sectional view illustrating another example of the configuration of the positive electrode active material according to the first embodiment of the present technology.
  • FIG. 2 is a schematic diagram illustrating an example of the configuration of the coating layer.
  • FIG. 3A is a cross-sectional view illustrating an example of a configuration of a positive electrode active material according to a modification of the first embodiment of the present technology.
  • FIG. 3B is a cross-sectional view illustrating another example of the configuration of the positive electrode active material according to the modification of the first embodiment of the present technology.
  • FIG. 1A is a cross-sectional view showing an example of the configuration of the positive electrode active material according to the first embodiment of the present technology.
  • FIG. 1B is a cross-sectional view illustrating another example of the configuration of the positive electrode active material according to the first embodiment of the present technology.
  • FIG. 4 is an exploded perspective view showing an example of the configuration of the nonaqueous electrolyte secondary battery according to the second embodiment of the present technology.
  • FIG. 5 is a sectional view taken along line VV in FIG.
  • FIG. 6 is a block diagram illustrating an example of a configuration of an electronic device as an application example.
  • FIG. 7 is a schematic diagram illustrating an example of a configuration of a power storage system in a vehicle as an application example.
  • FIG. 8 is a schematic diagram illustrating an example of a configuration of a power storage system in a house as an application example.
  • FIG. 9B is a graph showing a fitting result of the actual measurement curve of FIG. 9A.
  • FIG. 9C is a graph showing a peak separation result of the actual measurement curve of FIG. 9A.
  • a positive electrode active material capable of suppressing gas generation can be realized if the amount of residual organic substances derived from ALD processing is suppressed to a specified value or less.
  • the positive electrode active material is a so-called positive electrode active material for a lithium ion secondary battery, and includes a powder of surface-coated positive electrode active material particles 1.
  • the surface-covered positive electrode active material particle 1 includes a core particle 2 and a coating layer 3 that covers at least a part of the surface of the core particle 2.
  • the positive electrode active material according to the first embodiment is suitable for application to a battery having a high charge voltage (for example, a battery having a positive electrode potential of 4.50 V (vsLi / Li + ) or more in a fully charged state). .
  • a part of the surface of the core particle 2 may be exposed from the coating layer 3. More specifically, for example, the coating layer 3 may have one or more openings 4, and the surfaces of the core particles 2 may be exposed from the openings 4.
  • the coating layer 3 may have an island shape or the like and may be scattered on the surface of the core particle 2.
  • the exposed portion exposed from the surface of the core particle 2 includes an exposed portion formed in the coating treatment step of the coating layer 3 and cracks in the surface-covered positive electrode active material particles 1 in the battery manufacturing step after the coating treatment step.
  • the exposed part formed by the above may be included.
  • non-coated particles the charge transfer resistance equivalent to that of the positive electrode active material particles whose surfaces are not covered with the coating layer 3 (hereinafter referred to as “non-coated particles”) is maintained.
  • non-coated particles a decrease in the initial battery capacity due to an increase in resistance is suppressed.
  • the shape of the opening 4 provided in the coating layer 3 include a substantially circular shape, a substantially elliptical shape, and an indefinite shape, but are not particularly limited to these shapes.
  • FIG. 1A shows an example in which a part of the surface of the core particle 2 is exposed from the coating layer 3, but the configuration of the surface-coated positive electrode active material particle 1 is not limited to this example. Absent.
  • FIG. 1B a configuration in which the entire surface of the core particle 2 is completely covered with the coating layer 3 may be adopted.
  • a state in which the entire surface of the core particle 2 is completely covered with the coating layer 3 is referred to as a “completely coated state”
  • a state in which the entire surface of the core particle 2 is partially covered with the coating layer 3 is referred to as “unavailable”. It is called “completely covered state”.
  • the positive electrode active material if necessary, in addition to the surface-coated positive electrode active material particles (first particles) 1, the positive electrode active material particles in which the coating layer 3 is not provided on the surface and the entire surface is exposed. (Second particle) may further be included.
  • the positive electrode active material may contain two or more kinds of surface-covered positive electrode active material particles 1 as necessary. Examples of the two or more types of surface-coated positive electrode active material particles 1 include surface-coated positive electrode active material particles 1 having different average thicknesses of the coating layer 3 and surface-coated type having different coating states of the coating layer 3.
  • the positive electrode active material particle 1 examples include a surface-coated positive electrode active material particle 1 having a different constituent material, and a surface-coated positive electrode active material particle 1 having a different particle size distribution.
  • the surface-coated positive electrode active material particles 1 having different coating states of the coating layer 3 for example, the surface-coated positive electrode active material particles 1 in which the coating state of the coating layer 3 is a completely coated state and an incompletely coated state.
  • the core particle 2 is, for example, a primary particle or a secondary particle in which primary particles are aggregated.
  • Examples of the shape of the core particle 2 include a spherical shape, an ellipsoidal shape, a needle shape, a plate shape, a scale shape, a tube shape, a wire shape, a rod shape (rod shape), and an indefinite shape. It is not something. Two or more kinds of particles having the above shapes may be used in combination.
  • the spherical shape includes not only a true spherical shape but also a shape in which the true spherical shape is slightly flattened or distorted, a shape in which irregularities are formed on the true spherical surface, or a shape in which these shapes are combined.
  • the ellipsoidal shape is not only a strict ellipsoidal shape, but a strict ellipsoidal shape that is slightly flattened or distorted, a shape in which irregularities are formed on a strict ellipsoidal surface, or a combination of these shapes. The shape is also included.
  • the core particle 2 contains one or more lithium-containing compounds capable of inserting and extracting lithium (Li).
  • a lithium-containing compound for example, lithium oxide, lithium phosphorus oxide, lithium sulfide, or an intercalation compound containing lithium is suitable, and a mixture of two or more of these may be used.
  • a lithium-containing compound containing lithium, a transition metal element, and oxygen (O) is preferable.
  • Examples of such a lithium-containing compound include a lithium composite oxide having a layered rock salt structure shown in Formula (A) and a lithium composite phosphate having an olivine structure shown in Formula (B). Can be mentioned.
  • the lithium-containing compound includes at least one member selected from the group consisting of cobalt (Co), nickel (Ni), manganese (Mn), and iron (Fe) as a transition metal element.
  • a lithium-containing compound include a lithium composite oxide having a layered rock salt type structure represented by the formula (C), formula (D), or formula (E), and a spinel type compound represented by the formula (F).
  • LiNi 0.50 Co 0.20 Mn 0.30 O 2 Li a CoO 2 (A ⁇ 1), Li b NiO 2 (b ⁇ 1), Li c1 Ni c2 Co 1-c2 O 2 (c1 ⁇ 1, 0 ⁇ c2 ⁇ 1), Li d Mn 2 O 4 (d ⁇ 1) or Li e FePO 4 (e ⁇ 1).
  • M1 represents at least one element selected from Group 2 to Group 15 excluding nickel (Ni) and manganese (Mn).
  • X represents Group 16 other than oxygen (O)) It represents at least one of elements and elements of group 17.
  • p, q, y, and z are 0 ⁇ p ⁇ 1.5, 0 ⁇ q ⁇ 1.0, 0 ⁇ r ⁇ 1.0, ⁇ 0.10 ⁇ y ⁇ 0.20 and 0 ⁇ z ⁇ 0.2.
  • M2 represents at least one element selected from Group 2 to Group 15.
  • a and b are 0 ⁇ a ⁇ 2.0 and 0.5 ⁇ b ⁇ 2.0. It is a value within the range.
  • M3 is cobalt (Co), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe ), Copper (Cu), zinc (Zn), zirconium (Zr), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr) and tungsten (W) F
  • g, h, j and k are 0.8 ⁇ f ⁇ 1.2, 0 ⁇ g ⁇ 0.5, 0 ⁇ h ⁇ 0.5, g + h ⁇ 1, ⁇ 0.1 ⁇ j. ⁇ 0.2, 0 ⁇ k ⁇ 0.1
  • the composition of lithium varies depending on the state of charge and discharge, and the value of f represents the value in the complete discharge state.
  • M4 is cobalt (Co), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr ), Iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W).
  • M, n, p and q are 0.8 ⁇ m ⁇ 1.2, 0.005 ⁇ n ⁇ 0.5, ⁇ 0.1 ⁇ p ⁇ 0.2, 0 ⁇ q ⁇ 0.1.
  • M5 is nickel (Ni), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr ), Iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W).
  • R, s, t, and u are in a range of 0.8 ⁇ r ⁇ 1.2, 0 ⁇ s ⁇ 0.5, ⁇ 0.1 ⁇ t ⁇ 0.2, and 0 ⁇ u ⁇ 0.1. (Note that the composition of lithium varies depending on the state of charge and discharge, and the value of r represents a value in a fully discharged state.)
  • M6 is cobalt (Co), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr ), Iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W).
  • V, w, x, and y are in the range of 0.9 ⁇ v ⁇ 1.1, 0 ⁇ w ⁇ 0.6, 3.7 ⁇ x ⁇ 4.1, and 0 ⁇ y ⁇ 0.1. (Note that the composition of lithium varies depending on the state of charge and discharge, and the value of v represents the value in a fully discharged state.)
  • Li z M7PO 4 (However, in formula (G), M7 is cobalt (Co), manganese (Mn), iron (Fe), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti ), Vanadium (V), niobium (Nb), copper (Cu), zinc (Zn), molybdenum (Mo), calcium (Ca), strontium (Sr), tungsten (W) and zirconium (Zr) Z represents a value in a range of 0.9 ⁇ z ⁇ 1.1, wherein the composition of lithium varies depending on the state of charge and discharge, and the value of z is a value in a fully discharged state. Represents.)
  • examples of the positive electrode active material capable of inserting and extracting lithium include inorganic compounds not containing lithium, such as MnO 2 , V 2 O 5 , V 6 O 13 , NiS, and MoS.
  • the coating layer 3 is an ALD film obtained by an ALD process and has a crystal structure.
  • the coating layer 3 contains residual organic substances derived from the ALD process as impurities.
  • the covering layer 3 is a metal oxide layer containing a metal oxide as a main component.
  • the metal oxide include aluminum (Al), titanium (Ti), silicon (Si), vanadium (V), zirconium (Zr), niobium (Nb), tantalum (Ta), magnesium (Mg), and boron (B ), Zinc (Zn), tungsten (W), tin (Sn), hafnium (Hf), lanthanum (La), yttrium (Y), cerium (Ce), scandium (Sc), erbium (Er), indium (In) ), Lithium (Li), barium (Ba), and strontium (Sr).
  • the metal includes a semi-metal.
  • the metal oxide includes aluminum oxide (alumina), titanium oxide (titania), silicon oxide (silica), vanadium oxide, zirconium oxide (zirconia), niobium oxide, tantalum oxide, magnesium oxide, boron oxide, At least one selected from the group consisting of zinc oxide, tungsten oxide, tin oxide, hafnium oxide, lanthanum oxide, yttrium oxide, cerium oxide, scandium oxide, erbium oxide, indium oxide, lithium titanate, barium titanate and strontium titanate Of metal oxides.
  • composition analysis method for the coating layer 3 examples include ICP emission spectroscopy (Inductively Coupled Plasma Atomic Emission Spectroscopy: ICP-AES), time-of-flight secondary ion mass spectrometer: TOF-SIMS) can be used.
  • ICP emission spectroscopy Inductively Coupled Plasma Atomic Emission Spectroscopy: ICP-AES
  • TOF-SIMS time-of-flight secondary ion mass spectrometer
  • the content of residual organic matter in the coating layer 3 is reduced below a specified value.
  • TDS temperature-programmed desorption gas analysis
  • the amount of gas attributed to the gas desorption peak having an apex in the temperature region is reduced to a specified value or less so as to be 0.2 wt% or less with respect to the weight of the positive electrode active material.
  • the amount of the gas is preferably 0.05 wt% or less, more preferably less than 0.012 wt%, still more preferably 0.006 wt% or less, particularly preferably based on the weight of the positive electrode active material. Is 0.002 wt% or less.
  • the residual organic matter derived from the ALD treatment includes, for example, an alkyl group.
  • the number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 7 or less, still more preferably 1 or more and 4 or less, and particularly preferably 1 or more and 2 or less.
  • the alkyl group may have a substituent, may have a cyclic structure, may have a branched structure, has a substituent, and has a cyclic structure. Or may have a substituent and a branched structure, may have a branched structure and a cyclic structure, may have a substituent and may have a branched structure and a cyclic structure. You may have.
  • the coating layer 3 contains a compound having a methyl group as a residual organic substance derived from the ALD process.
  • the amount of the gas is preferably less than 0.012 wt%, more preferably 0.006 wt% or less, still more preferably 0.002 wt% with respect to the weight of the positive electrode active material, from the viewpoint of further improving battery characteristics. % Or less, particularly preferably 0.001 wt% or less.
  • the coating layer 3 contains a compound having a butyl group as a residual organic substance derived from the ALD process.
  • the amount of the gas is preferably less than 0.067 wt%, more preferably 0.063 wt% or less, still more preferably 0.051 wt%, based on the weight of the positive electrode active material, from the viewpoint of further improving battery characteristics. % Or less, particularly preferably 0.021 wt% or less.
  • the average thickness D of the coating layer 3 is preferably 0.2 nm or more and 5 nm or less, more preferably 0.2 nm or more and 2 nm or less, still more preferably 0.2 nm or more and 1 nm or less, particularly preferably 0.2 nm or more and 0.8 nm. Hereinafter, it is most preferably in the range of 0.2 nm to 0.5 nm. If the average thickness is less than 0.2 nm, the effect of surface modification by the coating layer 3 (more specifically, the effect of improving the capacity retention rate) may be significantly reduced. On the other hand, if the average thickness exceeds 5 nm, the initial battery capacity may be reduced.
  • the average thickness D of the coating layer 3 can be determined as follows. Ten surface-coated positive electrode active material particles 1 are selected at random from the powder of the positive electrode active material, and a cross-sectional TEM (Transmission Electron Microscope) image of each of the surface-coated positive electrode active material particles 1 is obtained. D 1 , d 2 ,..., D 10 are obtained. Next, the obtained thicknesses d 1 , d 2 ,..., D 10 are simply averaged (arithmetic average) to obtain the average thickness D of the coating layer 3.
  • the gas amount is preferably less than 0.012 wt% with respect to the weight of the positive electrode active material, from the viewpoint of further improving battery characteristics. More preferably, it is 0.006 wt% or less, More preferably, it is 0.002 wt% or less, Most preferably, it is 0.001 wt% or less.
  • the gas amount is preferably less than 0.05 wt%, more preferably, based on the weight of the positive electrode active material, from the viewpoint of further improving battery characteristics. Is 0.049 wt% or less, still more preferably 0.023 wt% or less, and particularly preferably 0.01 wt% or less.
  • the amount of the gas is preferably 0.197 wt% or less, more preferably based on the weight of the positive electrode active material, from the viewpoint of further improving battery characteristics. Is 0.083 wt% or less, still more preferably 0.021 wt% or less, and particularly preferably 0.002 wt% or less.
  • FIG. 2 is a schematic diagram illustrating an example of the configuration of the coating layer 3.
  • the covering layer 3 is preferably composed of a deposited monolayer ML.
  • the monolayer ML is a monomolecular layer. This is because the surface of the core particle 2 can be covered with the coating layer 3 having high film thickness uniformity.
  • FIG. 2 shows an example in which the coating layer 3 is a metal oxide layer made of aluminum oxide. Whether or not the coating layer 3 is composed of the deposited monolayer ML can be confirmed by acquiring a cross-sectional TEM image of the surface-coated positive electrode active material particles 1.
  • the average deposition number of the monolayer ML is preferably 2 or more and 50 or less, more preferably 2 or more and 20 or less, still more preferably 2 or more and 10 or less, particularly preferably 2 or more and 8 or less, most preferably Is in the range of 2 to 5 layers. If the average number of deposited layers is less than two layers, the effect of surface modification by the coating layer 3 (more specifically, the effect of improving the capacity retention rate) may be significantly reduced. On the other hand, if the average deposition number exceeds 50 layers, the initial battery capacity may be reduced.
  • the monolayer ML means a monomolecular layer of an inorganic oxide, not a monomolecular layer of an inorganic substance (for example, metal) or oxygen.
  • the inorganic oxide is, for example, MO x (where M is Al, Ti, Si, V, Zr, Nb, Ta, Mg, B, Zn, W, Sn, Hf, La, Y, Ce, Sc) , Er, In, Li, Ba, and Sr represent at least one metal element, and X is a value in the range of 1 ⁇ X ⁇ 3. .
  • the monolayer ML means a monomolecular layer of aluminum oxide (AlO x ), not a monomolecular layer of aluminum or oxygen, as shown in FIG.
  • the average deposition number of the monolayer ML is obtained as follows. First, the composition of the coating layer 3 is analyzed. Next, the thickness of one monolayer ML is specified from the composition of the analysis result. For example, when it is determined as a result of analysis that the coating layer 3 is made of aluminum oxide (alumina), the thickness of one monolayer ML can be specified to be about 0.1 nm. For example, ICP-AES, TOF-SIMS or the like can be used as a method for composition analysis of the coating layer 3. Next, the average thickness of the coating layer 3 is obtained as described above. Next, the average thickness of the monolayer ML is obtained by dividing the average thickness of the coating layer 3 by the thickness of one monolayer ML.
  • the average coverage of the surface-coated positive electrode active material particles 1 is preferably in the range of 30% to 100%, more preferably 30% to 96%. If the average coverage is less than 30%, the capacity retention rate may decrease. On the other hand, if the average coverage exceeds 96%, the initial capacity may be lowered although the capacity retention ratio is high.
  • the average coverage of the surface-covered positive electrode active material particles 1 is obtained by the following equation.
  • the actual weight x of the coating layer 3 is obtained as follows. First, the mass M of the positive electrode active material powder is weighed. Next, the positive electrode active material powder is dissolved in an acid solution, the solution is analyzed by ICP-AES, and the mass ratio A: B [mass%] between the core particles 2 and the coating layer 3 is quantified.
  • the specific surface area of the core particle 2 is determined by the BET method (Brunauer-Emmett-Teller method). When the average thickness of the coating layer 3 is very thin, for example, about 0.2 nm to 5 nm, the specific surface area between the core particles 2 and the surface-coated positive electrode active material particles 1 determined by the BET method is It is considered to be almost equal.
  • the average thickness n of the coating layer 3 is obtained in the same manner as the average thickness D of the coating layer 3 described above.
  • the density ⁇ of the coating layer 3 is obtained as follows using XRR. First, X-rays are incident on the surface of the coating layer 3 at an extremely shallow angle, and the X-ray intensity profile reflected in the incident angle versus the mirror surface direction is measured. Next, the density of the coating layer 3 is determined by comparing the profile obtained by this measurement with the simulation result and optimizing the simulation parameters.
  • the coating layer 3 is formed by repeatedly depositing the monolayer ML of the inorganic oxide on the surface of the core particle 2.
  • ALD atomic layer deposition
  • the first reactant contains oxygen (O) that is a constituent element of the coating layer 3.
  • oxygen oxygen
  • water H 2 O
  • an inert gas (purge gas) is supplied to the film forming chamber of the ALD film forming apparatus, and excess first reactant and by-product substances are exhausted.
  • the inert gas for example, N 2 gas, Ar gas, or the like can be used.
  • the vapor of the second reactant (second precursor) is supplied to the film formation chamber of the ALD film formation apparatus, and reacted with the first reactant adsorbed on the surface of the core particle 2.
  • the second reactant includes an inorganic material such as a metal that is a constituent element of the coating layer 3.
  • Examples of the second reactant include trimethylaluminum, triisobutylaluminum, titanium tetrachloride, tetrakis (ethylmethylamino) titanium (IV), tetrakis (dimethylamido) titanium (IV), silicon tetrachloride, methylsilane, hexamethyldisilane , Dodecamethylcyclohexasilane, tetramethylsilane, tetraethylsilane, bis (cyclopentadienyl) vanadium (II), tetrakis (ethylmethylamido) zirconium (IV), tetrakis (dimethylamido) zirconium (IV), bis (cyclo Pentadienyl) niobium (IV) dichloride, pentakis (dimethylamino) tantalum (V), bis (cyclopentadienyl) magnesium (II), tris (
  • an inert gas (purge gas) is supplied to the film forming chamber of the ALD film forming apparatus, and excess second reactant and by-product substances are exhausted.
  • the inert gas for example, N 2 gas, Ar gas, or the like can be used.
  • the monolayer ML can be repeatedly deposited by repeating this ALD cycle by setting the above-described first to fourth steps as one cycle (hereinafter, this cycle is referred to as “ALD cycle”). Therefore, the coating layer 3 having a desired thickness can be formed by adjusting the number of ALD cycles.
  • the number of cycles is preferably 2 or more and 50 or less, more preferably 2 or more and 20 or less, still more preferably 2 or more and 10 or less, particularly preferably 2 or more and 8 or less, and most preferably 2 or more and 5 or less.
  • a monomolecular layer formed in one ALD cycle corresponds to the above-described one monolayer ML. Thus, a positive electrode active material is obtained.
  • the average coverage of the surface-coated positive electrode active material particles 1 can be set in a desired range by adjusting the coordination number of the core particles 2 in the powder.
  • the coordination number is the number of contact points and / or the number of bonded portions present on the surface of the contacted and / or bonded core particle 2. Since the contact portion and / or the bonding portion of the core particle 2 are not exposed to the vapors of the first reactant and the second reactant, the monolayer ML is not deposited on the contact portion and / or the bonding portion. .
  • the contact portions and / or bonding portions of these particles become the openings 4 of the coating layer 3 and the like.
  • the surface of the core particle 2 is exposed through the above.
  • a method for adjusting the coordination number of the positive electrode active material particles for example, a method for adjusting the amount of the core particles 2 accommodated in the film forming chamber of the ALD film forming apparatus, or the adhesion state or aggregation between the positive electrode active material particles. There is a method of adjusting the state. Note that the coordination number of the core particles 2 in the powder tends to increase as the amount of the core particles 2 accommodated in the film forming chamber of the ALD film forming apparatus is increased.
  • the temperature of the heat treatment is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, even more preferably 300 ° C. or higher, particularly preferably 350 ° C. or higher. It is.
  • the upper limit of the temperature of heat processing is not specifically limited, Preferably it is 600 degrees C or less, More preferably, it is 500 degrees C or less, More preferably, it is 400 degrees C or less.
  • the temperature of the heat treatment is the temperature of the surface of the positive electrode active material.
  • the heat treatment time is preferably 30 min or more, more preferably 1 h or more, and even more preferably 2 h or more.
  • the upper limit of the heat treatment time is not particularly limited, but is preferably 10 h or less, more preferably 5 h or less.
  • the positive electrode active material according to the first embodiment includes a core particle 2 containing a lithium-containing compound and a coating layer 3 that covers at least a part of the surface of the core particle 2.
  • the average thickness of the coating layer 3 is in a range of 0.2 nm or more and 5 nm or less.
  • the amount of gas attributed to a gas desorption peak having an apex in the temperature range of 350 ° C. or lower is 0.2 wt% or less with respect to the weight of the positive electrode active material.
  • the ALD method Since the ALD method has high film thickness controllability, a uniform coating layer 3 can be formed on the surface of the core particle 2 as much as necessary. For this reason, the following effects are acquired. A decrease in the energy density of the battery due to the provision of the coating layer 3 on the surface of the core particle 2 can be suppressed. An increase in Li ion reaction resistance due to the coating layer 3 can be suppressed. The change in particle size distribution due to the provision of the coating layer 3 on the surface of the core particle 2 can be suppressed. The absolute amount of the coating layer 3 can be reduced. Therefore, the surface-coated positive electrode active material particles 1 can be reduced in price. When the coated state of the surface-coated positive electrode active material particles 1 is set to the incompletely coated state, both the cycle characteristics and the initial battery capacity can be achieved.
  • atomic layers can be stacked one layer at a time by alternately repeating the step of supplying precursor gas to the powder contained in a vacuum vessel and the step of removing surplus molecules by purging. Since the self-stop mechanism of the surface chemical reaction acts in the film forming process, uniform layer control at the monoatomic layer level becomes possible, and the coating layer 3 having excellent film quality can be formed.
  • the surface-coated positive electrode active material particles 1 When the surface-coated positive electrode active material particles 1 are in an incompletely coated state, the lithium ions are not inhibited by the coating layer 3 through the exposed portions of the core particles 2 and the core particles 2 and the electrolyte Can move between. Therefore, even the surface-coated positive electrode active material particles 1 can maintain the charge transfer resistance equivalent to that of the non-coated particles, and can suppress the decrease in the initial battery capacity due to the increase in resistance. On the other hand, when the surface-coated positive electrode active material particles 1 are in a completely coated state, the cycle characteristics can be improved, but lithium ions pass through the coating layer and are absorbed and desorbed in the positive electrode active material. There is a possibility that the resistance increases and the initial battery capacity decreases.
  • FIG. 3A is a cross-sectional view showing an example of the configuration of the positive electrode active material according to the first modification.
  • the positive electrode active material according to the first modified example is different from the first embodiment in that the first coating layer 3 a and the second coating layer 3 b are laminated on the surface of the core particle 2.
  • the number of coating layers 3 is not limited to this example, and three or more coating layers 3 may be stacked on the surface of the core particle 2.
  • the first coating layer 3a and the second coating layer 3b are made of different inorganic oxides, for example.
  • the first coating layer 3a is made of a first metal oxide such as aluminum oxide
  • the second coating layer 3b is made of a second metal oxide such as silicon oxide.
  • the first coating layer 3a and the second coating layer 3b may be layers formed by different forming methods. More specifically, one of the first coating layer 3a and the second coating layer 3b is a layer formed by the ALD method, and the other is a layer formed by the sol-gel method or the mechanochemical method. Also good. When the layer formed in this way is employed, the first covering layer 3a and the second covering layer 3b may be made of the same material.
  • FIG. 3A shows an example in which a part of the surface of the core particle 2 is exposed from the laminated first coating layer 3a and second coating layer 3b.
  • the configuration of the particles 1 is not limited to this example.
  • FIG. 3B a configuration in which the entire surface of the core particle 2 is completely covered by the laminated first covering layer 3a and second covering layer 3b may be adopted.
  • One of the laminated first covering layer 3a and second covering layer 3b may be in a completely covered state, and the other may be in an incompletely covered state.
  • the covering layer 3 may be a metal nitride layer, a metal sulfide layer, a metal carbide layer, a metal fluoride layer, or the like.
  • the method of reducing the amount of residual organic matter by heat-treating the ALD-treated positive electrode active material has been described, but the method of reducing the amount of residual organic matter is not limited to this.
  • the amount of residual organic matter may be reduced by selecting the type of the second precursor during the ALD process. Further, the type of the second precursor at the time of ALD treatment may be selected, and heat treatment may be performed on the positive electrode active material that has been ALD treated.
  • a nonaqueous electrolyte secondary battery (hereinafter simply referred to as “battery”) 10 is a so-called laminate film type battery, and includes a positive electrode lead 11 and a negative electrode lead 12.
  • the flat wound electrode body 20 to which is attached is housed inside the film-shaped exterior member 30 and can be reduced in size, weight, and thickness.
  • the positive electrode lead 11 and the negative electrode lead 12 are led out from the inside of the exterior member 30 to the outside, for example, in the same direction.
  • the positive electrode lead 11 and the negative electrode lead 12 are made of a metal material such as aluminum (Al), copper (Cu), nickel (Ni), or stainless steel, respectively, and each have a thin plate shape or a mesh shape.
  • the exterior member 30 is made of, for example, a flexible laminate film.
  • the exterior member 30 has a configuration in which, for example, a heat sealing resin layer, a metal layer, and a surface protective layer are sequentially laminated.
  • the surface on the heat sealing resin layer side is a surface on the side where the wound electrode body 20 is accommodated.
  • the material for the heat-sealing resin layer include polypropylene (PP) and polyethylene (PE).
  • the material for the metal layer include aluminum.
  • Examples of the material for the surface protective layer include nylon (Ny).
  • the exterior member 30 is made of, for example, a rectangular aluminum laminated film in which a nylon film, an aluminum foil, and a polyethylene film are bonded together in this order.
  • the exterior member 30 is disposed, for example, so that the heat-sealing resin layer side and the wound electrode body 20 face each other, and the outer edge portions are in close contact with each other by fusion or an adhesive.
  • An adhesion film 31 is inserted between the exterior member 30 and the positive electrode lead 11 and the negative electrode lead 12 to prevent intrusion of outside air.
  • the adhesion film 31 is made of a material having adhesion to the positive electrode lead 11 and the negative electrode lead 12, for example, a polyolefin resin such as polyethylene, polypropylene, modified polyethylene, or modified polypropylene.
  • the exterior member 30 may be made of a laminated film having another structure, a polymer film such as polypropylene, or a metal film instead of the above-described laminated film.
  • a laminate film in which an aluminum film is used as a core and a polymer film is laminated on one or both sides thereof may be used.
  • a coloring material is included in the thing further provided with a colored layer and / or at least 1 type of layer chosen from a heat-fusion resin layer and a surface protective layer.
  • a thing may be used.
  • the adhesive layer may include a coloring material.
  • the wound electrode body 20 as a battery element is formed by laminating a positive electrode 21 and a negative electrode 22 having a long shape through a separator 23 having a long shape and an electrolyte layer 24.
  • the outermost peripheral part is protected by a protective tape 25.
  • the positive electrode 21, the negative electrode 22, the separator 23, and the electrolyte layer 24 constituting the battery will be described in order.
  • the positive electrode 21 has a structure in which a positive electrode active material layer 21B is provided on both surfaces of a positive electrode current collector 21A. Although not shown, the positive electrode active material layer 21B may be provided only on one surface of the positive electrode current collector 21A.
  • the positive electrode current collector 21A is made of, for example, a metal foil such as an aluminum foil, a nickel foil, or a stainless steel foil.
  • the positive electrode active material layer 21B contains a positive electrode active material.
  • the positive electrode active material layer 21B may further include at least one of a conductive agent and a binder as necessary.
  • the positive electrode active material is a positive electrode active material according to the first embodiment or a modification thereof.
  • binder examples include resin materials such as polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), styrene butadiene rubber (SBR), and carboxymethyl cellulose (CMC), and resins thereof. At least one selected from copolymers mainly composed of materials is used.
  • PVdF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PAN polyacrylonitrile
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • the conductive agent examples include carbon materials such as graphite, carbon fiber, carbon black, ketjen black, and carbon nanotube. One of these may be used alone, or two or more may be mixed. May be used. In addition to the carbon material, a metal material or a conductive polymer material may be used as long as it is a conductive material.
  • the negative electrode 22 has, for example, a structure in which a negative electrode active material layer 22B is provided on both surfaces of a negative electrode current collector 22A. Although not shown, the negative electrode active material layer 22B may be provided only on one surface of the negative electrode current collector 22A.
  • the negative electrode current collector 22A is made of, for example, a metal foil such as a copper foil, a nickel foil, or a stainless steel foil.
  • the negative electrode active material layer 22B contains one or more negative electrode active materials capable of inserting and extracting lithium.
  • the negative electrode active material layer 22B may further include at least one of a conductive agent and a binder as necessary.
  • the electrochemical equivalent of the negative electrode 22 or the negative electrode active material is larger than the electrochemical equivalent of the positive electrode 21, so that theoretically lithium metal does not deposit on the negative electrode 22 during charging. It is preferable that
  • Negative electrode active material examples of the negative electrode active material include carbon materials such as non-graphitizable carbon, graphitizable carbon, graphite, pyrolytic carbons, cokes, glassy carbons, organic polymer compound fired bodies, carbon fibers, and activated carbon. Is mentioned. Among these, examples of coke include pitch coke, needle coke, and petroleum coke.
  • An organic polymer compound fired body refers to a carbonized material obtained by firing a polymer material such as phenol resin or furan resin at an appropriate temperature, and part of it is non-graphitizable carbon or graphitizable carbon.
  • These carbon materials are preferable because the change in crystal structure that occurs during charge and discharge is very small, a high charge and discharge capacity can be obtained, and good cycle characteristics can be obtained.
  • graphite is preferable because it has a high electrochemical equivalent and can provide a high energy density.
  • non-graphitizable carbon is preferable because excellent cycle characteristics can be obtained.
  • those having a low charge / discharge potential, specifically, those having a charge / discharge potential close to that of lithium metal are preferable because a high energy density of the battery can be easily realized.
  • a material containing at least one of a metal element and a metalloid element as a constituent element for example, an alloy, a compound, or a mixture
  • a material containing at least one of a metal element and a metalloid element as a constituent element for example, an alloy, a compound, or a mixture
  • the alloy includes an alloy including one or more metal elements and one or more metalloid elements in addition to an alloy composed of two or more metal elements.
  • the nonmetallic element may be included.
  • Examples of such a negative electrode active material include a metal element or a metalloid element capable of forming an alloy with lithium.
  • a metal element or a metalloid element capable of forming an alloy with lithium.
  • magnesium, boron, aluminum, titanium, gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin, lead (Pb), bismuth (Bi), cadmium (Cd), Silver (Ag), zinc, hafnium (Hf), zirconium, yttrium (Y), palladium (Pd), or platinum (Pt) can be used. These may be crystalline or amorphous.
  • the negative electrode active material those containing a 4B group metal element or semi-metal element in the short-period type periodic table as a constituent element are preferable, and more preferable are those containing at least one of silicon and tin as a constituent element. This is because silicon and tin have a large ability to occlude and release lithium, and a high energy density can be obtained.
  • Examples of such a negative electrode active material include a simple substance, an alloy or a compound of silicon, a simple substance, an alloy or a compound of tin, or a material having one or more phases thereof at least in part.
  • Examples of the silicon alloy include, as the second constituent element other than silicon, tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony (Sb), and chromium.
  • the thing containing at least 1 sort (s) of a group is mentioned.
  • As an alloy of tin for example, as a second constituent element other than tin, among the group consisting of silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium The thing containing at least 1 sort (s) of these is mentioned.
  • tin compound or silicon compound examples include those containing oxygen or carbon, and may contain the second constituent element described above in addition to tin or silicon.
  • the Sn-based negative electrode active material cobalt, tin, and carbon are included as constituent elements, the carbon content is 9.9 mass% or more and 29.7 mass% or less, and tin and cobalt A SnCoC-containing material in which the proportion of cobalt with respect to the total is 30% by mass to 70% by mass is preferable. This is because a high energy density can be obtained in such a composition range, and excellent cycle characteristics can be obtained.
  • This SnCoC-containing material may further contain other constituent elements as necessary.
  • other constituent elements for example, silicon, iron, nickel, chromium, indium, niobium, germanium, titanium, molybdenum, aluminum, phosphorus (P), gallium, or bismuth are preferable, and two or more kinds may be included. This is because the capacity or cycle characteristics can be further improved.
  • This SnCoC-containing material has a phase containing tin, cobalt, and carbon, and this phase preferably has a low crystallinity or an amorphous structure.
  • this SnCoC-containing material it is preferable that at least a part of carbon that is a constituent element is bonded to a metal element or a metalloid element that is another constituent element.
  • the decrease in cycle characteristics is thought to be due to the aggregation or crystallization of tin or the like, but this is because such aggregation or crystallization can be suppressed by combining carbon with other elements. .
  • XPS X-ray photoelectron spectroscopy
  • the peak of the carbon 1s orbital (C1s) appears at 284.5 eV in an energy calibrated apparatus so that the peak of the gold atom 4f orbital (Au4f) is obtained at 84.0 eV if it is graphite. .
  • Au4f gold atom 4f orbital
  • it will appear at 284.8 eV.
  • the charge density of the carbon element increases, for example, when carbon is bonded to a metal element or a metalloid element, the C1s peak appears in a region lower than 284.5 eV.
  • the peak of the synthetic wave of C1s obtained for the SnCoC-containing material appears in a region lower than 284.5 eV
  • at least a part of the carbon contained in the SnCoC-containing material is a metal element or a half of other constituent elements. Combined with metal elements.
  • the C1s peak is used to correct the energy axis of the spectrum.
  • the C1s peak of the surface-contaminated carbon is set to 284.8 eV, which is used as an energy standard.
  • the waveform of the C1s peak is obtained as a shape including the surface contamination carbon peak and the carbon peak in the SnCoC-containing material. Therefore, by analyzing using, for example, commercially available software, the surface contamination The carbon peak and the carbon peak in the SnCoC-containing material are separated. In the waveform analysis, the position of the main peak existing on the lowest bound energy side is used as the energy reference (284.8 eV).
  • Examples of other negative electrode active materials include metal oxides or polymer compounds that can occlude and release lithium.
  • Examples of the metal oxide include lithium titanium oxide containing titanium and lithium, such as lithium titanate (Li 4 Ti 5 O 12 ), iron oxide, ruthenium oxide, or molybdenum oxide.
  • Examples of the polymer compound include polyacetylene, polyaniline, and polypyrrole.
  • binder examples include at least one selected from resin materials such as polyvinylidene fluoride, polytetrafluoroethylene, polyacrylonitrile, styrene butadiene rubber and carboxymethyl cellulose, and copolymers mainly composed of these resin materials. Is used.
  • the same material as that of the positive electrode active material layer 21B can be used.
  • the separator 23 separates the positive electrode 21 and the negative electrode 22 and allows lithium ions to pass through while preventing a short circuit of current due to contact between the two electrodes.
  • the separator 23 is made of, for example, a porous film made of a resin such as polytetrafluoroethylene, polypropylene, or polyethylene, and may have a structure in which two or more kinds of these porous films are laminated.
  • a porous film made of polyolefin is preferable because it is excellent in the effect of preventing short circuit and can improve the safety of the battery due to the shutdown effect.
  • polyethylene is preferable as a material constituting the separator 23 because it can obtain a shutdown effect within a range of 100 ° C.
  • the porous film may have a structure of three or more layers in which a polypropylene layer, a polyethylene layer, and a polypropylene layer are sequentially laminated.
  • the separator 23 may have a configuration including a base material and a surface layer provided on one or both surfaces of the base material.
  • the surface layer includes inorganic particles having electrical insulating properties and a resin material that binds the inorganic particles to the surface of the base material and binds the inorganic particles to each other.
  • This resin material may have, for example, a three-dimensional network structure in which the fibers are fibrillated and the fibrils are continuously connected to each other.
  • the inorganic particles can be maintained in a dispersed state without being connected to each other by being supported on the resin material having the three-dimensional network structure.
  • the resin material may be bound to the surface of the base material or the inorganic particles without being fibrillated. In this case, higher binding properties can be obtained.
  • the base material is a porous layer having porosity. More specifically, the base material is a porous film composed of an insulating film having a large ion permeability and a predetermined mechanical strength, and the electrolytic solution is held in the pores of the base material. It is preferable that the base material has a predetermined mechanical strength as a main part of the separator, while having a high resistance to an electrolytic solution, a low reactivity, and a property of being difficult to expand.
  • a polyolefin resin such as polypropylene or polyethylene, an acrylic resin, a styrene resin, a polyester resin, or a nylon resin.
  • polyethylenes such as low density polyethylene, high density polyethylene, linear polyethylene, or their low molecular weight wax, or polyolefin resins such as polypropylene are suitable because they have an appropriate melting temperature and are easily available.
  • a material including a porous film made of a polyolefin resin is excellent in separability between the positive electrode 21 and the negative electrode 22 and can further reduce a decrease in internal short circuit.
  • a non-woven fabric may be used as the base material.
  • fibers constituting the nonwoven fabric aramid fibers, glass fibers, polyolefin fibers, polyethylene terephthalate (PET) fibers, nylon fibers, or the like can be used. Moreover, it is good also as a nonwoven fabric by mixing these 2 or more types of fibers.
  • the inorganic particles contain at least one of metal oxide, metal nitride, metal carbide, metal sulfide and the like.
  • the metal oxide include aluminum oxide (alumina, Al 2 O 3 ), boehmite (hydrated aluminum oxide), magnesium oxide (magnesia, MgO), titanium oxide (titania, TiO 2 ), zirconium oxide (zirconia, ZrO 2). ), Silicon oxide (silica, SiO 2 ), yttrium oxide (yttria, Y 2 O 3 ) or the like can be suitably used.
  • silicon nitride Si 3 N 4
  • aluminum nitride AlN
  • boron nitride BN
  • titanium nitride TiN
  • metal carbide silicon carbide (SiC) or boron carbide (B4C)
  • metal sulfide barium sulfate (BaSO 4 ) or the like can be preferably used.
  • zeolite M 2 / n O ⁇ Al 2 O 3 ⁇ xSiO 2 ⁇ yH 2 O, M represents a metal element, x ⁇ 2, y ⁇ 0 ) porous aluminosilicates such as layered silicates, titanates Minerals such as barium (BaTiO 3 ) or strontium titanate (SrTiO 3 ) may be used.
  • alumina titania (particularly those having a rutile structure), silica or magnesia, and more preferably alumina.
  • the inorganic particles have oxidation resistance and heat resistance, and the surface layer on the side facing the positive electrode containing the inorganic particles has strong resistance to an oxidizing environment in the vicinity of the positive electrode during charging.
  • the shape of the inorganic particles is not particularly limited, and any of a spherical shape, a plate shape, a fiber shape, a cubic shape, a random shape, and the like can be used.
  • Resin materials constituting the surface layer include fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene, fluorine-containing rubbers such as vinylidene fluoride-tetrafluoroethylene copolymer and ethylene-tetrafluoroethylene copolymer, styrene -Butadiene copolymer or hydride thereof, acrylonitrile-butadiene copolymer or hydride thereof, acrylonitrile-butadiene-styrene copolymer or hydride thereof, methacrylic acid ester-acrylic acid ester copolymer, styrene-acrylic acid ester Copolymer, acrylonitrile-acrylic ester copolymer, rubber such as ethylene propylene rubber, polyvinyl alcohol, polyvinyl acetate, ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, carbo Cellulose derivatives such as
  • resin materials may be used alone or in combination of two or more.
  • fluorine resins such as polyvinylidene fluoride are preferable from the viewpoint of oxidation resistance and flexibility, and aramid or polyamideimide is preferably included from the viewpoint of heat resistance.
  • the particle size of the inorganic particles is preferably in the range of 1 nm to 10 ⁇ m. If it is smaller than 1 nm, it is difficult to obtain, and even if it can be obtained, it is not worth the cost. On the other hand, if it is larger than 10 ⁇ m, the distance between the electrodes becomes large, and a sufficient amount of active material cannot be obtained in a limited space, resulting in a low battery capacity.
  • a slurry composed of a matrix resin, a solvent and an inorganic substance is applied on a base material (porous membrane), and is passed through a poor solvent of the matrix resin and a solvate bath of the above solvent.
  • a method of separating and then drying can be used.
  • the inorganic particles described above may be contained in a porous film as a base material. Further, the surface layer may not be composed of inorganic particles and may be composed only of a resin material.
  • the electrolyte layer 24 includes a non-aqueous electrolyte and a polymer compound serving as a holding body that holds the non-aqueous electrolyte, and the polymer compound is swollen by the non-aqueous electrolyte.
  • the electrolyte layer 24 is preferably a gel electrolyte layer. This is because when the electrolyte layer 24 is a gel electrolyte layer, high ion conductivity can be obtained, and leakage of the battery 10 can be particularly suppressed.
  • the nonaqueous electrolytic solution includes a nonaqueous solvent and an electrolyte salt dissolved in the nonaqueous solvent.
  • the non-aqueous electrolyte may contain a known additive in order to improve battery characteristics.
  • cyclic carbonates such as ethylene carbonate or propylene carbonate can be used, and it is preferable to use one of ethylene carbonate and propylene carbonate, particularly a mixture of both. This is because the cycle characteristics can be improved.
  • non-aqueous solvent in addition to these cyclic carbonates, it is preferable to use a mixture of chain carbonates such as diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate or methylpropyl carbonate. This is because high ionic conductivity can be obtained.
  • the non-aqueous solvent preferably further contains 2,4-difluoroanisole or vinylene carbonate. This is because 2,4-difluoroanisole can improve discharge capacity, and vinylene carbonate can improve cycle characteristics. Therefore, it is preferable to use a mixture of these because the discharge capacity and cycle characteristics can be improved.
  • non-aqueous solvents include butylene carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1, 3-dioxolane, methyl acetate, methyl propionate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropironitrile, N, N-dimethylformamide, N-methylpyrrolidinone, N-methyloxazolidinone, N, N -Dimethylimidazolidinone, nitromethane, nitroethane, sulfolane, dimethyl sulfoxide or trimethyl phosphate.
  • a compound obtained by substituting at least a part of hydrogen in these non-aqueous solvents with fluorine may be preferable because the reversibility of the electrode reaction may be improved depending on the type of electrode to be combined.
  • lithium salt As electrolyte salt, lithium salt is mentioned, for example, 1 type may be used independently, and 2 or more types may be mixed and used for it.
  • Lithium salts include LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB (C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 CF 3 ) 3 , LiAlCl 4 , LiSiF 6 , LiCl, difluoro [oxolato-O, O ′] lithium borate, lithium bisoxalate borate, or LiBr.
  • LiPF 6 is preferable because it can obtain high ion conductivity and can improve cycle characteristics.
  • polymer compound examples include polyacrylonitrile, polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, polyphosphazene, and polysiloxane.
  • polyacrylonitrile, polyvinylidene fluoride, polyhexafluoropropylene, or polyethylene oxide is preferable from the viewpoint of electrochemical stability.
  • the electrolyte layer 24 may contain inorganic particles. This is because the heat resistance can be further improved.
  • the inorganic particles the same inorganic particles as those contained in the surface layer of the separator 23 can be used. Further, an electrolytic solution may be used instead of the electrolyte layer 24.
  • the positive electrode potential (vsLi / Li + ) in the fully charged state is preferably 4.30 V or more, more preferably 4.40 V or more, still more preferably 4.50 V or more, and particularly preferably 4.60 V or more.
  • the positive electrode potential (vsLi / Li + ) in the fully charged state may be less than 4.30 V (for example, 4.20 V or 4.25 V).
  • the upper limit value of the positive electrode potential (vsLi / Li + ) in the fully charged state is not particularly limited, but is preferably 6.00 V or less, more preferably 5.00 V or less, even more preferably 4.80 V or less, Especially preferably, it is 4.70V or less.
  • the positive electrode 21 is produced as follows. First, for example, a positive electrode active material, a conductive agent, and a binder are mixed to prepare a positive electrode mixture, and this positive electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone (NMP). A paste-like positive electrode mixture slurry is prepared. Next, this positive electrode mixture slurry is applied to the positive electrode current collector 21 ⁇ / b> A, the solvent is dried, and the positive electrode active material layer 21 ⁇ / b> B is formed by compression molding with a roll press or the like, thereby forming the positive electrode 21.
  • NMP N-methyl-2-pyrrolidone
  • the negative electrode 22 is produced as follows. First, for example, a negative electrode active material and a binder are mixed to prepare a negative electrode mixture, and this negative electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to obtain a paste-like negative electrode mixture slurry Is made. Next, the negative electrode mixture slurry is applied to the negative electrode current collector 22A, the solvent is dried, and the negative electrode active material layer 22B is formed by compression molding using a roll press or the like, and the negative electrode 22 is manufactured.
  • a solvent such as N-methyl-2-pyrrolidone
  • the electrolyte layer 24 is produced as follows. First, an electrolyte solution containing a matrix polymer, a nonaqueous electrolytic solution, and a dilution solvent is prepared. Next, this electrolyte solution is uniformly applied and impregnated on each of the positive electrode 21 and the negative electrode 22 obtained as described above. Thereafter, the electrolyte layer 24 is formed by evaporating and removing the diluted solvent.
  • the wound electrode body 20 is manufactured as follows. First, the positive electrode lead 11 is attached to the end of the positive electrode current collector 21A by welding, and the negative electrode lead 12 is attached to the end of the negative electrode current collector 22A by welding. Next, the positive electrode 21 and the negative electrode 22 on which the electrolyte layer 24 is formed are laminated through a separator 23 to form a laminated body, and then the laminated body is wound in the longitudinal direction, and the protective tape 25 is attached to the outermost peripheral portion.
  • the wound electrode body 20 is formed by bonding.
  • the wound electrode body 20 is sealed by the exterior member 30 as follows. First, for example, the wound electrode body 20 is sandwiched between flexible exterior members 30, and the outer edge portions of the exterior member 30 are brought into close contact with each other by thermal fusion or the like and sealed. At that time, the adhesion film 31 is inserted between the positive electrode lead 11 and the negative electrode lead 12 and the exterior member 30. The adhesion film 31 may be attached in advance to each of the positive electrode lead 11 and the negative electrode lead 12. Further, the exterior member 30 may be embossed in advance to form a concave portion as an accommodation space for accommodating the wound electrode body 20. Thus, the battery 10 in which the wound electrode body 20 is accommodated by the exterior member 30 is obtained.
  • the battery 10 is molded by heat pressing as necessary. More specifically, the battery 10 is heated at a temperature higher than normal temperature while being pressurized. Next, if necessary, a pressure plate or the like is pressed against the main surface of the battery 10 to press the battery 10 uniaxially.
  • a battery 10 according to the second embodiment includes a positive electrode 21 including a positive electrode active material according to the first embodiment or a modification thereof.
  • a battery having excellent charge / discharge cycle characteristics and excellent gas reliability, in which gas generation, that is, battery swelling, is suppressed can be obtained.
  • the manifestation of this effect is particularly prominent in the case of a battery having a high charge voltage (for example, a battery having a positive electrode potential of 4.50 V (vsLi / Li + ) or more in a fully charged state).
  • the battery 10 according to the second embodiment is a battery with a high charge voltage
  • the effective discharge capacity of the positive electrode 21 can be increased. Therefore, the battery 10 maintaining the reliability while improving the capacity and energy density can be obtained.
  • the positive electrode lead 11 and the negative electrode lead 12 are attached to the positive electrode 21 and the negative electrode 22.
  • the positive electrode 21 and the negative electrode 22 are laminated and wound via the separator 23, and the protective tape 25 is bonded to the outermost peripheral portion to form a wound body.
  • the wound body is sandwiched between the exterior members 30, and the outer peripheral edge portion excluding one side is heat-sealed to form a bag shape, and is stored inside the exterior member 30.
  • the opening of the exterior member 30 is heat-sealed in a vacuum atmosphere and sealed.
  • the electrolyte layer 24 is formed by applying heat to polymerize the monomer to obtain a polymer compound.
  • the target battery 10 is obtained.
  • the present technology can be applied to a secondary battery such as a cylindrical type, a square type, or a coin type, and a flexible battery mounted on a wearable terminal such as a smart watch, a head mounted display, or iGlass (registered trademark). It is also possible to apply the present technology to, for example.
  • a secondary battery such as a cylindrical type, a square type, or a coin type
  • a flexible battery mounted on a wearable terminal such as a smart watch, a head mounted display, or iGlass (registered trademark). It is also possible to apply the present technology to, for example.
  • the structure of the battery is not limited to this, and for example, a stack type battery (positive electrode and The present technology can also be applied to a battery having a structure in which a positive electrode, a negative electrode, and a separator are stacked so that the separator is sandwiched between the negative electrode and a battery having a structure in which the positive electrode and the negative electrode are folded.
  • the configuration in which the electrode includes the current collector and the active material layer has been described as an example.
  • the configuration of the electrode is not limited to this.
  • the electrode may be composed of only the active material layer.
  • the electronic device 400 includes an electronic circuit 401 of the electronic device body and a battery pack 300.
  • the battery pack 300 is electrically connected to the electronic circuit 401 via the positive terminal 331a and the negative terminal 331b.
  • the electronic device 400 has a configuration in which the battery pack 300 is detachable by a user.
  • the configuration of the electronic device 400 is not limited to this, and the battery pack 300 is built in the electronic device 400 so that the user cannot remove the battery pack 300 from the electronic device 400. May be.
  • the positive terminal 331a and the negative terminal 331b of the battery pack 300 are connected to the positive terminal and the negative terminal of a charger (not shown), respectively.
  • the positive terminal 331a and the negative terminal 331b of the battery pack 300 are connected to the positive terminal and the negative terminal of the electronic circuit 401, respectively.
  • the electronic device 400 for example, a notebook personal computer, a tablet computer, a mobile phone (for example, a smartphone), a portable information terminal (Personal Digital Assistant: PDA), a display device (LCD, EL display, electronic paper, etc.), imaging Devices (eg digital still cameras, digital video cameras, etc.), audio equipment (eg portable audio players), game machines, cordless phones, e-books, electronic dictionaries, radio, headphones, navigation systems, memory cards, pacemakers, hearing aids, Electric tools, electric shavers, refrigerators, air conditioners, TVs, stereos, water heaters, microwave ovens, dishwashers, washing machines, dryers, lighting equipment, toys, medical equipment, robots, road conditioners, traffic lights, etc. It is, but not such limited thereto.
  • the electronic circuit 401 includes, for example, a CPU, a peripheral logic unit, an interface unit, a storage unit, and the like, and controls the entire electronic device 400.
  • the battery pack 300 includes an assembled battery 301 and a charge / discharge circuit 302.
  • the assembled battery 301 is configured by connecting a plurality of secondary batteries 301a in series and / or in parallel.
  • the plurality of secondary batteries 301a are connected, for example, in n parallel m series (n and m are positive integers).
  • FIG. 6 shows an example in which six secondary batteries 301a are connected in two parallel three series (2P3S).
  • the secondary battery 301a the battery according to the second embodiment or its modification is used.
  • the battery pack 300 includes the assembled battery 301 including a plurality of secondary batteries 301 a
  • the battery pack 300 includes a single secondary battery 301 a instead of the assembled battery 301. It may be adopted.
  • the charging / discharging circuit 302 is a control unit that controls charging / discharging of the assembled battery 301. Specifically, during charging, the charging / discharging circuit 302 controls charging of the assembled battery 301. On the other hand, at the time of discharging (that is, when the electronic device 400 is used), the charging / discharging circuit 302 controls the discharging of the electronic device 400.
  • FIG. 7 schematically illustrates an example of a configuration of a hybrid vehicle that employs a series hybrid system to which the present disclosure is applied.
  • a series hybrid system is a car that runs on an electric power driving force conversion device using electric power generated by a generator driven by an engine or electric power once stored in a battery.
  • the hybrid vehicle 7200 includes an engine 7201, a generator 7202, a power driving force conversion device 7203, a driving wheel 7204a, a driving wheel 7204b, a wheel 7205a, a wheel 7205b, a battery 7208, a vehicle control device 7209, various sensors 7210, and a charging port 7211. Is installed.
  • the above-described power storage device of the present disclosure is applied to the battery 7208.
  • Hybrid vehicle 7200 travels using power driving force conversion device 7203 as a power source.
  • An example of the power driving force conversion device 7203 is a motor.
  • the electric power / driving force conversion device 7203 is operated by the electric power of the battery 7208, and the rotational force of the electric power / driving force conversion device 7203 is transmitted to the driving wheels 7204a and 7204b.
  • the power driving force conversion device 7203 can be applied to either an AC motor or a DC motor by using DC-AC (DC-AC) or reverse conversion (AC-DC conversion) where necessary.
  • Various sensors 7210 control the engine speed through the vehicle control device 7209, and control the opening (throttle opening) of a throttle valve (not shown).
  • Various sensors 7210 include a speed sensor, an acceleration sensor, an engine speed sensor, and the like.
  • the rotational force of the engine 7201 is transmitted to the generator 7202, and the electric power generated by the generator 7202 by the rotational force can be stored in the battery 7208.
  • the resistance force at the time of deceleration is applied as a rotational force to the power driving force conversion device 7203, and the regenerative power generated by the power driving force conversion device 7203 by this rotational force is applied to the battery 7208. Accumulated.
  • the battery 7208 is connected to an external power source of the hybrid vehicle, so that the battery 7208 can receive power from the external power source using the charging port 211 as an input port and store the received power.
  • an information processing apparatus that performs information processing related to vehicle control based on information related to the secondary battery may be provided.
  • an information processing apparatus for example, there is an information processing apparatus that displays a remaining battery level based on information on the remaining battery level.
  • a series hybrid vehicle that runs on a motor using electric power generated by a generator driven by an engine or electric power stored once in a battery has been described as an example.
  • the present disclosure is also effective for a parallel hybrid vehicle that uses both the engine and motor outputs as the drive source, and switches between the three modes of running with the engine alone, running with the motor alone, and engine and motor running as appropriate. Applicable.
  • the present disclosure can be effectively applied to a so-called electric vehicle that travels only by a drive motor without using an engine.
  • the house 9001 is provided with a power generation device 9004, a power consumption device 9005, a power storage device 9003, a control device 9010 that controls each device, a smart meter 9007, and a sensor 9011 that acquires various types of information.
  • Each device is connected by a power network 9009 and an information network 9012.
  • a solar cell, a fuel cell, or the like is used, and the generated power is supplied to the power consumption device 9005 and / or the power storage device 9003.
  • the power consuming apparatus 9005 is a refrigerator 9005a, an air conditioner 9005b, a television receiver 9005c, a bath 9005d, or the like.
  • the electric power consumption device 9005 includes an electric vehicle 9006.
  • the electric vehicle 9006 is an electric vehicle 9006a, a hybrid car 9006b, and an electric motorcycle 9006c.
  • the battery unit of the present disclosure described above is applied to the power storage device 9003.
  • the power storage device 9003 is composed of a secondary battery or a capacitor.
  • a lithium ion battery is used.
  • the lithium ion battery may be a stationary type or used in the electric vehicle 9006.
  • the smart meter 9007 has a function of measuring the usage amount of commercial power and transmitting the measured usage amount to an electric power company.
  • the power network 9009 may be any one or a combination of DC power supply, AC power supply, and non-contact power supply.
  • the various sensors 9011 are, for example, human sensors, illuminance sensors, object detection sensors, power consumption sensors, vibration sensors, contact sensors, temperature sensors, infrared sensors, and the like. Information acquired by the various sensors 9011 is transmitted to the control device 9010. Based on the information from the sensor 9011, the weather condition, the condition of the person, and the like can be grasped, and the power consumption device 9005 can be automatically controlled to minimize the energy consumption. Furthermore, the control device 9010 can transmit information on the house 9001 to an external power company or the like via the Internet.
  • the power hub 9008 performs processing such as branching of power lines and DC / AC conversion.
  • a communication method of the information network 9012 connected to the control device 9010 a method using a communication interface such as UART (Universal Asynchronous Receiver-Transmitter), Bluetooth (registered trademark), ZigBee (registered trademark), or the like.
  • a sensor network based on a wireless communication standard such as Wi-Fi.
  • the Bluetooth (registered trademark) system is applied to multimedia communication and can perform one-to-many connection communication.
  • ZigBee (registered trademark) uses a physical layer of IEEE (Institute of Electrical and Electronics Electronics) (802.15.4). IEEE 802.15.4 is the name of a short-range wireless network standard called PAN (Personal Area Network) or W (Wireless) PAN.
  • the control device 9010 is connected to an external server 9013.
  • the server 9013 may be managed by any one of the house 9001, the electric power company, and the service provider.
  • Information transmitted / received by the server 9013 is, for example, information on power consumption information, life pattern information, power charges, weather information, natural disaster information, and power transactions. These pieces of information may be transmitted / received from a power consuming device (for example, a television receiver) in the home, or may be transmitted / received from a device outside the home (for example, a mobile phone). Such information may be displayed on a device having a display function, for example, a television receiver, a mobile phone, a PDA (Personal Digital Assistant) or the like.
  • a control device 9010 that controls each unit is configured by a CPU (Central Processing Unit), a RAM (Random Access Memory), a ROM (Read Only Memory), and the like, and is stored in the power storage device 9003 in this example.
  • the control device 9010 is connected to the power storage device 9003, the home power generation device 9004, the power consumption device 9005, various sensors 9011, the server 9013 and the information network 9012, for example, a function of adjusting the amount of commercial power used and the amount of power generation have. In addition, you may provide the function etc. which carry out an electric power transaction in an electric power market.
  • electric power can be stored not only in the centralized power system 9002 such as the thermal power 9002a, the nuclear power 9002b, and the hydropower 9002c but also in the power storage device 9003 in the power generation device 9004 (solar power generation, wind power generation). it can. Therefore, even if the generated power of the home power generation apparatus 9004 fluctuates, it is possible to perform control such that the amount of power to be sent to the outside is constant or discharge is performed as necessary.
  • the power obtained by solar power generation is stored in the power storage device 9003, and midnight power with a low charge is stored in the power storage device 9003 at night, and the power stored by the power storage device 9003 is discharged during a high daytime charge. You can also use it.
  • control device 9010 is stored in the power storage device 9003.
  • control device 9010 may be stored in the smart meter 9007, or may be configured independently.
  • the power storage system 9100 may be used for a plurality of homes in an apartment house, or may be used for a plurality of detached houses.
  • a positive electrode active material subjected to ALD coating treatment was prepared as follows. First, LiCoO 2 particle powder (manufactured by Nippon Chemical Industry Co., Ltd., trade name: Cellseed C-10N) was prepared as the core particle powder. Next, the prepared powder was accommodated in a film forming chamber of an ALD film forming apparatus. Thereafter, the ALD process was repeated twice to form an Al 2 O 3 layer composed of two monolayers on the surface of the LiCoO 2 particles, whereby a positive electrode active material composed of powder of surface-coated LiCoO 2 particles was obtained.
  • LiCoO 2 particle powder manufactured by Nippon Chemical Industry Co., Ltd., trade name: Cellseed C-10N
  • the average coverage of the surface-coated LiCoO 2 particles was adjusted to 92% by changing the degree of aggregation of the LiCoO 2 particle powder in the ALD process.
  • the average coverage of the surface-covered LiCoO 2 particles is a value determined by the average coverage measurement method described in the first embodiment.
  • Example 1-2 After the ALD process, a positive electrode active material was obtained in the same manner as in Example 1-1 except that 150 ° C. vacuum heat treatment was further applied to the powder of the surface-coated LiCoO 2 particles for 1 h.
  • Example 1-3 After the ALD process, a positive electrode active material was obtained in the same manner as in Example 1-1, except that a 200 ° C. vacuum heat treatment was further applied to the surface-coated LiCoO 2 particles for 1 h.
  • Example 1-4 After the ALD process, a positive electrode active material was obtained in the same manner as in Example 1-1, except that a 250 ° C. vacuum heat treatment was further applied to the powder of the surface-coated LiCoO 2 particles for 1 h.
  • Example 1-5 After the ALD process, a positive electrode active material was obtained in the same manner as in Example 1-1, except that a 300 ° C. vacuum heat treatment was further applied to the powder of the surface-coated LiCoO 2 particles for 1 h.
  • Example 1-6 After the ALD process, a positive electrode active material was obtained in the same manner as in Example 1-1, except that a surface heat treatment type LiCoO 2 particle powder was further subjected to a vacuum heat treatment at 350 ° C. for 1 h.
  • Examples 2-1 to 2-6 A positive electrode active material was obtained in the same manner as in Examples 1-1 to 1-6 except that triisobutylaluminum (TIBA) gas was used as the metal source (second precursor) gas.
  • TIBA triisobutylaluminum
  • Examples 3-1 to 3-6 A positive electrode active material was obtained in the same manner as in Examples 1-1 to 1-6 except that an Al 2 O 3 layer composed of 20 monolayers was formed on the surface of the LiCoO 2 particles.
  • a positive electrode active material was obtained in the same manner as in Examples 1-1 to 1-6 except that an Al 2 O 3 layer composed of 50 monolayers was formed on the surface of the LiCoO 2 particles.
  • the average thickness of the Al 2 O 3 layer of the positive electrode active material subjected to the ALD coating treatment was measured by the method for measuring the average thickness of the coating layer described in the first embodiment.
  • Thermal desorption gas analysis was performed on the positive electrode active material subjected to ALD coating treatment.
  • a gas desorption peak having a vertex in a temperature range of 250 ° C. or higher and 350 ° C. or lower in a gas detection amount curve of m / z 44 acquired with respect to the temperature of the positive electrode active material, with a temperature increase rate of 60 ° C./min.
  • the amount of gas attributed to was quantified.
  • fitting analysis by a nonlinear least square method was performed using a curve expressed by adding a normal distribution function to a TDS curve.
  • Table 1 shows the treatment conditions of the positive electrode active material and the quantified gas amount.
  • TMA Trimethylaluminum
  • TIBA Triisobutylaluminum
  • Gas amount (wt%) is a sample for measuring the amount of desorbed gas estimated from the gas desorption peak area and the instrument sensitivity constant. Weight percentage obtained by dividing by weight (LiCoO 2 weight)
  • NMP N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • LiPF 6 lithium hexafluorophosphate
  • a laminate film type lithium ion secondary battery was produced as follows. First, the positive electrode and the negative electrode lead were welded to the positive electrode and the negative electrode obtained as described above, respectively, and then the positive electrode and the negative electrode were alternately stacked via a separator made of a polyethylene microporous film to obtain an electrode body.
  • this electrode body was loaded between the exterior members, and three sides of the exterior member were heat-sealed, and one side was not heat-sealed so as to have an opening.
  • a moisture-proof aluminum laminate film in which a 25 ⁇ m-thick nylon film, a 40 ⁇ m-thick aluminum foil, and a 30 ⁇ m-thick polypropylene film were laminated in order from the outermost layer was used.
  • a non-aqueous electrolyte was injected from the opening of the exterior member, and the remaining one side of the exterior member was heat-sealed under reduced pressure to seal the electrode body.
  • the laminate film type battery is designed so that the amount of the positive electrode active material and the amount of the negative electrode active material are adjusted, and the open circuit voltage (that is, the battery voltage) at the time of full charge is 4.50V.
  • Table 2 shows the amount of TDS detection gas and the evaluation results.
  • TDS m / z 44
  • the cycle characteristics and the rate characteristics are greatly reduced, and the battery swells greatly.
  • the large decrease in the cycle characteristics and the rate characteristics is caused by loosening of the electrode body due to a large amount of gas generated and an increase in the distance between the electrodes.
  • TDS m / z 44
  • the gas amount is in the range of more than 0.05 wt% and not more than 0.2 wt%
  • TDS m / z 44
  • TDS m / z 44
  • both cycle characteristics and rate characteristics are good, and battery swelling is suppressed.
  • the method of changing the second precursor during ALD treatment and the method of performing heat treatment on the positive electrode active material subjected to ALD treatment were used as methods for adjusting the amount of residual organic matter.
  • the method of adjusting is not limited to this.
  • the present technology can also employ the following configurations.
  • Particles comprising a lithium-containing compound;
  • a coating layer covering at least a part of the surface of the particle,
  • TDS temperature-programmed desorption gas analysis
  • the amount of gas attributed to a gas desorption peak having an apex in the temperature range of 250 ° C. or higher and 350 ° C. or lower is
  • the positive electrode active material which is 0.2 wt% or less with respect to the weight of the positive electrode active material.
  • the average thickness of the said coating layer is a positive electrode active material as described in (1) which exists in the range of 0.2 nm or more and 5 nm or less.
  • the said coating layer is a positive electrode active material in any one of (1) to (3) comprised by the deposited monomolecular layer.
  • the said coating layer is a positive electrode active material in any one of (1) to (5) containing a metal oxide.
  • the metal oxide is aluminum (Al), titanium (Ti), silicon (Si), vanadium (V), zirconium (Zr), niobium (Nb), tantalum (Ta), magnesium (Mg), boron (B).
  • the positive electrode active material according to (6) comprising at least one member selected from the group consisting of lithium (Li), barium (Ba), and strontium (Sr).
  • the said coating layer is a positive electrode active material in any one of (1) to (7) containing the organic substance derived from ALD process.
  • the coating layer includes a methyl group, The positive electrode active material according to any one of (1) to (8), wherein the gas amount is less than 0.012 wt% with respect to the weight of the positive electrode active material.
  • the coating layer includes a butyl group, The positive electrode active material according to any one of (1) to (8), wherein the gas amount is less than 0.067 wt% with respect to the weight of the positive electrode active material.
  • a coated particle is produced by forming a coating layer on the surface of the particle containing the lithium-containing compound, Heat treating the coated particles, The average thickness of the coating layer is in the range of 0.2 nm to 5 nm,
  • TDS temperature-programmed desorption gas analysis
  • the amount of gas attributed to a gas desorption peak having an apex in the temperature range of 250 ° C. or higher and 350 ° C. or lower is The manufacturing method of the positive electrode active material which is 0.2 wt% or less with respect to the weight of a positive electrode active material.
  • (12) (1) The positive electrode containing the positive electrode active material in any one of (10).
  • a battery pack comprising: (17) (13) The battery according to any one of (15) is provided, An electronic device that receives power from the battery.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un matériau actif d'électrode positive comprenant des particules comprenant un composé contenant du lithium, et une couche de revêtement revêtant au moins une partie de la surface des particules, en termes de comportement de désorption de gaz à m/z = 44 tel que détecté par spectroscopie de désorption thermique (TDS), la quantité de gaz attribuée à un pic de désorption de gaz ayant un pic dans une plage de température supérieure ou égale à 250 °C et inférieure ou égale à 350 °C est inférieure ou égal à 0,2 % en poids par rapport au poids du matériau actif d'électrode positive.
PCT/JP2018/015243 2017-04-12 2018-04-11 Matériau actif d'électrode positive et son procédé de fabrication, électrode positive, batterie, bloc-batterie, appareil électronique, véhicule électrique, dispositif de stockage d'électricité et système d'alimentation électrique WO2018190374A1 (fr)

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