WO2024262183A1 - 被覆活物質、正極材料、および電池 - Google Patents

被覆活物質、正極材料、および電池 Download PDF

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Publication number
WO2024262183A1
WO2024262183A1 PCT/JP2024/017532 JP2024017532W WO2024262183A1 WO 2024262183 A1 WO2024262183 A1 WO 2024262183A1 JP 2024017532 W JP2024017532 W JP 2024017532W WO 2024262183 A1 WO2024262183 A1 WO 2024262183A1
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Prior art keywords
active material
coated active
positive electrode
solid electrolyte
battery
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PCT/JP2024/017532
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English (en)
French (fr)
Japanese (ja)
Inventor
敬太 水野
裕太 杉本
和弥 橋本
出 佐々木
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Toyota Motor Corp
Panasonic Holdings Corp
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Toyota Motor Corp
Panasonic Holdings Corp
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Priority to EP24825592.9A priority Critical patent/EP4734172A1/en
Priority to CN202480034953.1A priority patent/CN121263879A/zh
Priority to JP2025527558A priority patent/JPWO2024262183A1/ja
Publication of WO2024262183A1 publication Critical patent/WO2024262183A1/ja
Anticipated expiration legal-status Critical
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This disclosure relates to coated active materials, positive electrode materials, and batteries.
  • Patent Document 1 discloses a positive electrode material including a positive electrode active material and a first solid electrolyte material that covers at least a portion of the surface of the positive electrode active material.
  • the first solid electrolyte material includes Li, Ti, M1, and F, and M1 is at least one element selected from the group consisting of Ca, Mg, Al, Y, and Zr.
  • Non-Patent Document 1 describes that when a layered positive electrode material is heated, moisture generated from the positive electrode material can exist in various forms, such as adsorbed water on the surface of the positive electrode material, adsorbed water, and a reaction product between CO2 and the positive electrode material.
  • the coated active material of the present disclosure is A positive electrode active material; a coating material including a first solid electrolyte and coating at least a portion of a surface of the positive electrode active material;
  • a coated active material comprising:
  • the first solid electrolyte comprises Li, M, and X;
  • M is at least one element selected from the group consisting of metal elements other than Li and metalloid elements;
  • X is a halogen element;
  • FIG. 1 is a cross-sectional view showing a schematic configuration of a coated active material according to a first embodiment.
  • FIG. 2 is a cross-sectional view showing a schematic configuration of a positive electrode material according to the second embodiment.
  • FIG. 3 is a cross-sectional view showing a schematic configuration of a battery according to the third embodiment.
  • the solid electrolyte when the positive electrode active material and the solid electrolyte are in contact with each other at the positive electrode, the solid electrolyte may be oxidized and decomposed during charging of the battery. Oxidative decomposition tends to occur easily when a solid electrolyte with poor oxidation stability, such as a sulfide solid electrolyte, is used. To address this issue, it has been proposed to coat the surface of the positive electrode active material with a coating material containing a solid electrolyte with excellent oxidation stability, such as a halide solid electrolyte.
  • the inventors have discovered that even if the composition of the solid electrolyte contained in the coating material is the same, there are differences in the durability of the battery, more specifically, the degree of increase in the resistance of the battery after a durability test. As a result of extensive research, the inventors have found that there is a correlation between the amount of moisture released when a positive electrode active material whose surface is coated with a coating material containing a solid electrolyte is heated and the degree of increase in the resistance of the battery after a durability test, which led to the invention of the disclosed technology.
  • Coated active material 1 is a cross-sectional view showing a schematic configuration of a coated active material in embodiment 1.
  • Coated active material 100 in embodiment 1 includes a positive electrode active material 11 and a coating material 12.
  • Coating material 12 includes a first solid electrolyte, and coats at least a portion of the surface of positive electrode active material 11.
  • MC 180 is defined as the value obtained by dividing the integrated amount of moisture released from the coated active material 100 when the coated active material 100 is heated from 120° C. to 180° C. by the total mass of the coated active material 100. In this case, the moisture amount MC 180 satisfies 0 ppm ⁇ MC 180 ⁇ 600 ppm.
  • ppm means mass fraction, i.e., wtppm (mass/mass).
  • the coated active material 100 may contain moisture physically adsorbed on the surface of the coated active material 100 and moisture chemically bonded to the coated active material 100.
  • the moisture chemically bonded to the coated active material 100 may be, for example, crystal water, an intermediate-like compound formed by the reaction of Li, CO 2 , and H 2 O near the surface of the positive electrode active material 11 and/or the coating material 12, etc. Details of what form of moisture is contained in the moisture released from the coated active material 100 when the coated active material 100 is heated from 120° C. to 180° C. are not necessarily clear. However, considering that the moisture is desorbed from the coated active material 100 in a relatively high temperature range exceeding 120° C., it is presumed that the moisture is mainly moisture chemically bonded to the coated active material 100.
  • water of crystallization when water of crystallization is present in the crystals of the compound constituting the positive electrode active material 11 and/or the coating material 12, it is considered that the water of crystallization is bound to the coated active material 100 with a stronger binding energy than physically adsorbed water, and is bound to the coated active material 100 with a weaker binding energy than a covalent bond or an ionic bond.
  • the amount of moisture contained in the coated active material is as small as possible. This is because it was thought that a part of the coating layer is altered by the reaction between the moisture contained in the coated active material and the lithium - containing fluoride such as Li2.7Ti0.3Al0.7F6 contained in the coating layer, and the altered part functions as a resistance layer at the interface between the positive electrode active material and the coating layer.
  • the present inventors have newly found that it is rather desirable for the coated active material to contain a very small amount of water.
  • the coated active material 100 When the moisture content MC180 satisfies 0 ppm ⁇ MC180 ⁇ 600 ppm, the coated active material 100 has a sufficient amount of moisture chemically bonded thereto so that a reaction layer having an appropriate thickness is formed at the interface between the two during the initial charging of a battery containing a positive electrode material prepared by mixing the coated active material 100 and a second solid electrolyte described later. If the moisture content MC 180 is greater than 60 ppm, the thickness of the reaction layer formed will increase, resulting in a larger side surface as the above-mentioned resistance layer, which is not preferable as it leads to a significant increase in the resistance of the battery.
  • the reaction layer is formed by the reaction of moisture with the second solid electrolyte.
  • a reaction layer having a suitable thickness can suppress deterioration of the positive electrode including the coated active material 100 and the second solid electrolyte, for example, a thermodynamic reaction caused by contact between the coated active material 100 and the second solid electrolyte, and oxidative decomposition of the second solid electrolyte caused by exposure to a high potential. Therefore, the coated active material 100 can suppress an increase in the resistance of the battery.
  • the amount of moisture released from the coated active material 100 increases rapidly. This is presumably because intermediate-like compounds formed by the reaction of Li, CO 2 , and H 2 O, which are present in the coated active material 100 near the surface of the positive electrode active material 11, begin to decompose and release moisture.
  • the water content MC 180 can be measured, for example, by the Karl Fischer method.
  • the water content MC 180 can be determined as follows using a Karl Fischer device (Karl Fischer moisture meter).
  • coated active material 100 which is the measurement sample
  • the introduction section of the coated active material 100 is pre-baked at 300°C to stabilize the device.
  • Coated active material 100 which is the measurement sample” refers to a particle group of coated active material 100.
  • the temperature of the inlet After the device has stabilized, set the temperature of the inlet to 180°C. When the temperature of the inlet reaches 180°C, measure the background amount of water released ( ⁇ g/sec).
  • the temperature of the introduction part is set to 25°C.
  • the measurement sample is introduced into the introduction part.
  • the measurement sample is heated from 25°C to 120°C at a temperature increase rate of 10°C per minute to vaporize the moisture contained in the measurement sample.
  • the measurement sample is heated from 120°C to 180°C at a temperature increase rate of 10°C per minute to vaporize the moisture contained in the measurement sample.
  • the vaporized moisture is quantified by coulometric titration until it reaches a value equal to or less than the background moisture release amount, and then integrated to obtain the integrated value of the moisture amount released from the measurement sample.
  • the integrated value of the moisture amount is divided by the total mass of the measurement sample to obtain the moisture amount MC 180 .
  • the degree of increase in the resistance of the battery is expressed by the index "( R2 / R1 ) x 100 (%)".
  • ( R2 / R1 ) is the value obtained by dividing the resistance R2 after the durability test by the resistance R1 before the durability test.
  • the durability test is, for example, a test in which the battery is stored in a high-temperature environment for a certain period of time.
  • the resistances R1 and R2 can be obtained by the following method. A battery made using a positive electrode material containing the coated active material 100 is placed in a thermostatic chamber at 25°C and charged and discharged. Next, charging and discharging are performed to a predetermined voltage. Then, constant current discharge is performed at a predetermined current value for a range of 1 second to 10 seconds.
  • the voltage drop at this time that is, the difference between the open circuit voltage before discharge and the open circuit voltage at the end of discharge is divided by the discharge current value to obtain the resistance R1 before the durability test.
  • a durability test is performed under appropriate conditions. After the durability test, the charging and discharging process is performed in the same manner as described above. Next, charging and discharging are performed to a predetermined voltage. Then, a constant current discharge is performed at a predetermined current value for 1 to 10 seconds. The voltage drop at this time is divided by the discharge current value to obtain the resistance R2 after the durability test.
  • the moisture content MC 180 may satisfy MC 180 ⁇ 400 ppm.
  • the water content MC 180 may satisfy MC 180 ⁇ 390 ppm, MC 180 ⁇ 380 ppm, MC 180 ⁇ 370 ppm, MC 180 ⁇ 360 ppm, MC 180 ⁇ 350 ppm, or even MC 180 ⁇ 343 ppm. According to such a configuration, as a result, an increase in resistance in the initial stage of the battery can be further suppressed.
  • the moisture content MC 180 may satisfy 1 ppm ⁇ MC 180 , 2 ppm ⁇ MC 180 , 3 ppm ⁇ MC 180 , or even 4 ppm ⁇ MC 180.
  • the water content MC 180 may satisfy 5 ppm ⁇ MC 180 , 10 ppm ⁇ MC 180 , 20 ppm ⁇ MC 180 , 30 ppm ⁇ MC 180 , or further may satisfy 35 ppm ⁇ MC 180. With such a configuration, an increase in the resistance of the battery can be further suppressed.
  • the water content MC 180 may satisfy 50 ppm ⁇ MC 180 , and may further satisfy 58 ppm ⁇ MC 180. With this configuration, an increase in the resistance of the battery can be further suppressed.
  • the water content MC 180 may satisfy 70 ppm ⁇ MC 180 , 80 ppm ⁇ MC 180 , 90 ppm ⁇ MC 180 , or even 100 ppm ⁇ MC 180. With this configuration, an increase in the resistance of the battery can be further suppressed.
  • the coating material 12 is in direct contact with the positive electrode active material 11.
  • the coating material 12 includes a first solid electrolyte.
  • the first solid electrolyte has ion conductivity.
  • the ion conductivity is typically lithium ion conductivity.
  • the first solid electrolyte contains Li, M, and X.
  • M is at least one element selected from the group consisting of metal elements other than Li and metalloid elements.
  • X is a halogen element.
  • the first solid electrolyte having such a composition has excellent oxidation resistance. Therefore, it is possible to suppress oxidation of the second solid electrolyte in contact with the positive electrode active material 11. This makes it possible to suppress an increase in the resistance of the battery.
  • metal elements include B, Si, Ge, As, Sb, and Te.
  • Metal elements include all elements in groups 1 to 12 of the periodic table except hydrogen, and all elements in groups 13 to 16 except B, Si, Ge, As, Sb, Te, C, N, P, O, S, and Se.
  • metal elements are a group of elements that can become cations when forming an inorganic compound with a halogen element.
  • the first solid electrolyte contains a halogen element.
  • a solid electrolyte containing a halogen element is also called a halide solid electrolyte.
  • a halide solid electrolyte has excellent oxidation resistance.
  • X may be F.
  • a halide solid electrolyte containing F has excellent oxidation resistance due to the high electronegativity of F. Therefore, by covering at least a portion of the surface of the positive electrode active material 11 with the coating material 12 containing the first solid electrolyte, oxidation of the second solid electrolyte in contact with the positive electrode active material 11 can be further suppressed. This can further suppress an increase in the resistance of the battery.
  • M may include M1 and M2.
  • M1 may be at least one selected from the group consisting of Ti and Zr
  • M2 may be at least one selected from the group consisting of Al, Y, Mg, and Ca.
  • a cationic framework structure suitable for ion conduction may be formed in the crystal lattice. Therefore, the first solid electrolyte exhibits high ion conductivity.
  • the high ion conductivity is, for example, 1.0 ⁇ 10 ⁇ 8 S/cm or more. That is, the first solid electrolyte may have, for example, an ion conductivity of 1.0 ⁇ 10 ⁇ 8 S/cm or more.
  • M2 may be Al.
  • a first solid electrolyte having such a composition exhibits even higher ionic conductivity.
  • M1 may be Ti.
  • a first solid electrolyte having such a composition exhibits even higher ionic conductivity.
  • the first solid electrolyte may consist essentially of Li, Ti, Al, and F.
  • the first solid electrolyte consists essentially of Li, Ti, Al, and F
  • the molar ratio (i.e., molar fraction) of the total amount of substance of Li, Ti, Al, and F to the total amount of substance of all elements constituting the first solid electrolyte is 90% or more.
  • the molar ratio (i.e., molar fraction) may be 95% or more.
  • the first solid electrolyte may consist only of Li, Ti, Al, and F.
  • the first solid electrolyte may be represented by the following composition formula (1):
  • M3 is at least one selected from the group consisting of Zr, Ni, Fe, and Cr
  • m is the valence of M3, and satisfies 0.1 ⁇ x ⁇ 0.9, 0 ⁇ y ⁇ 0.1, 0 ⁇ z ⁇ 0.1, and 0.8 ⁇ b ⁇ 1.2.
  • a first solid electrolyte having such a composition has high ionic conductivity and can be produced by a method with high industrial productivity.
  • a first solid electrolyte having such a composition has a higher ionic conductivity.
  • composition formula (1) 0.1 ⁇ x ⁇ 0.7 may be satisfied.
  • the upper and lower limits of the range of x in composition formula (1) can be defined by any combination selected from the following values: 0.1, 0.3, 0.4, 0.5, 0.6, 0.65, 0.67, 0.7, 0.8, and 0.9.
  • composition formula (1) can be defined by any combination selected from the numerical values of 0.8, 0.9, 0.94, 1.0, 1.06, 1.1, and 1.2.
  • the first solid electrolyte may be crystalline or amorphous.
  • the shape of the first solid electrolyte is not particularly limited.
  • the shape of the first solid electrolyte is, for example, needle-like, spherical, or elliptical.
  • the shape of the first solid electrolyte may be particulate.
  • the first solid electrolyte When the shape of the first solid electrolyte is, for example, particulate (e.g., spherical), the first solid electrolyte may have a median diameter of 0.01 ⁇ m or more and 100 ⁇ m or less.
  • volume size refers to the particle size when the cumulative volume in the volume-based particle size distribution is equal to 50%.
  • the volume-based particle size distribution is measured, for example, by a laser diffraction measuring device or an image analyzer.
  • the coating material 12 may contain the first solid electrolyte as a main component, or may contain only the first solid electrolyte.
  • main component means the component that is contained in the largest amount by mass ratio.
  • Constaining only the first solid electrolyte means that, except for unavoidable impurities, materials other than the first solid electrolyte are not intentionally added. For example, the raw materials of the first solid electrolyte and by-products generated when producing the first solid electrolyte are included in the unavoidable impurities.
  • the mass ratio of the unavoidable impurities to the total mass of the coating material 12 may be 5% or less, 3% or less, 1% or less, or 0.5% or less.
  • the coating material 12 does not have to contain sulfur.
  • the coating material 12 may uniformly coat the positive electrode active material 11.
  • the coating material 12 may cover only a portion of the surface of the positive electrode active material 11. In this case, the particles of the positive electrode active material 11 come into direct contact with each other through the portion not covered by the coating material 12, improving the electronic conductivity between the particles of the positive electrode active material 11. As a result, high-power operation of the battery is possible.
  • the shape of the coating material 12 itself is not particularly limited.
  • a thin film formed by the accumulation of fine particles of the coating material 12, such as a plate-like, needle-like, spherical, or elliptical sphere, may cover at least a portion of the surface of the positive electrode active material 11.
  • the thickness of the thin film of the coating material 12 is, for example, 1 nm or more and 500 nm or less. If the thickness of the thin film of the coating material 12 is appropriately adjusted, contact between the positive electrode active material 11 and the second solid electrolyte can be sufficiently suppressed.
  • the thickness of the thin film of the coating material 12 can be determined, for example, by observing the cross section of a particle of the coated active material 100 with a scanning electron microscope (SEM). The average value of the thicknesses of the thin film of the coating material 12 measured at any multiple positions (for example, five points) can be regarded as the thickness of the thin film of the coating material 12.
  • the positive electrode active material 11 includes a material having a property of absorbing and releasing metal ions (e.g., lithium ions).
  • a lithium-containing transition metal oxide, a transition metal fluoride, a polyanion material, a fluorinated polyanion material, a transition metal sulfide, a transition metal oxysulfide, a transition metal oxynitride, or the like can be used.
  • the manufacturing cost of the battery can be reduced and the average discharge voltage of the battery can be improved.
  • the lithium-containing transition metal oxide include Li(Ni,Co,Al) O2 , Li(Ni,Co,Mn) O2 , and LiCoO2 .
  • the positive electrode active material 11 has, for example, a particle shape.
  • the particle shape of the positive electrode active material 11 is not particularly limited.
  • the particle shape of the positive electrode active material 11 can be spherical, oval spherical, scaly, or fibrous.
  • the median diameter of the positive electrode active material 11 may be 0.1 ⁇ m or more and 100 ⁇ m or less.
  • the coated active material 100 and the second solid electrolyte can form a good dispersion state. As a result, the charge and discharge characteristics of the battery are improved.
  • the median diameter of the positive electrode active material 11 is 100 ⁇ m or less, the diffusion speed of lithium inside the positive electrode active material 11 is sufficiently ensured. Therefore, the battery can operate at high output.
  • the positive electrode active material 11 may contain lithium nickel cobalt aluminum oxide.
  • the dilithium nickel cobalt aluminum oxide may be Li(Ni,Co,Al)O 2. With this configuration, the energy density of the battery can be increased.
  • Li(Ni,Co,Al) O2 includes those containing at least one additional element in addition to Li, Ni, Co, and Al.
  • the additional element may be at least one or more elements selected from boron (B), sodium (Na), magnesium (Mg), silicon (Si), phosphorus (P), sulfur (S), potassium (K), calcium (Ca), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), zirconium (Zr), niobium (Nb), molybdenum (Mo), indium (In), tin (Sn), tungsten (W), lanthanum (La), and cerium (Ce).
  • the first solid electrolyte contained in the coating material 12 can be produced, for example, by the following method.
  • Two or more kinds of raw material powders are prepared so as to have a desired composition.
  • the raw material powders may be mixed in a molar ratio previously adjusted to offset composition changes that may occur in the synthesis process.
  • the raw powders are mixed, they are reacted with each other using a mechanochemical milling method in a mixing device such as a planetary ball mill to obtain a reactant.
  • the resulting reactant may then be fired in an inert gas atmosphere or in vacuum.
  • the mixture of raw material powders may be fired in an inert gas atmosphere to react with each other to obtain reactants.
  • inert gases are helium, nitrogen, or argon.
  • the firing may be performed in a vacuum.
  • the mixture of raw material powders may be placed in a container and fired in a heating furnace.
  • the container may be, for example, a crucible, a sealed container, or a vacuum sealed tube.
  • composition of the first solid electrolyte can be determined, for example, by inductively coupled plasma atomic emission spectroscopy, ion chromatography, or the like.
  • the coated active material 100 in the first embodiment can be produced, for example, by the following method.
  • a powder of the positive electrode active material 11 and a powder of the coating material 12 containing the first solid electrolyte are prepared in a predetermined mass ratio.
  • a powder of Li(Ni,Co,Al) O2 is prepared as the positive electrode active material 11
  • a powder of Li2.7Al0.7Ti0.3F6 which is the first solid electrolyte
  • the coating material 12 is prepared as the coating material 12.
  • the two materials may be placed in a container, and a shear force may be applied to the two materials using a rotating blade.
  • the two materials may be placed in a container, and the two materials may be collided by a jet stream.
  • the powder of the positive electrode active material 11 and the powder of the coating material 12 are mixed in an appropriate ratio.
  • the mixture Before mechanical energy is applied to the mixture of the powder of the positive electrode active material 11 and the powder of the coating material 12, the mixture may be milled.
  • a mixing device such as a ball mill may be used for the milling process.
  • the milling process may be performed in a dry atmosphere or an inert atmosphere.
  • the coated active material 100 may be manufactured by a dry particle compounding method.
  • the process by the dry particle compounding method includes applying at least one mechanical energy selected from the group consisting of impact, compression, and shear to a mixture of the powder of the positive electrode active material 11 and the powder of the coating material 12.
  • the apparatus used in the manufacture of the coated active material 100 is not particularly limited.
  • the apparatus can be an apparatus capable of applying mechanical energy such as impact, compression, and shear to a mixture of the powder of the positive electrode active material 11 and the powder of the coating material 12.
  • apparatus capable of applying mechanical energy include a ball mill, a jet mill, compression shear processing apparatus (particle composite apparatus) such as "Mechanofusion” (manufactured by Hosokawa Micron Corporation) and "Nobilta” (manufactured by Hosokawa Micron Corporation), "Hybridization System (high-velocity air current impact apparatus)” (manufactured by Nara Machinery Works), and “Balance Gran” (manufactured by Freund Turbo Corporation).
  • Mechanisms is a particle compounding device that uses dry mechanical compounding technology by applying strong mechanical energy to particles of multiple different materials.
  • mechanofusion the powdered raw materials are fed between a rotating container and a press head, and mechanical energy such as compression, shear, and friction is applied to them, causing the particles to compound.
  • Nobilta is a particle compounding device that uses dry mechanical compounding technology, an advanced form of particle compounding technology, to compound nanoparticles as raw materials. Nobilta produces composite particles by applying mechanical energy in the form of impact, compression, and shear to multiple raw material powders.
  • a rotor that is positioned so as to have a specified gap between itself and the inner wall of a horizontal cylindrical mixing vessel rotates at high speed, and the raw material powder is forced to pass through the gap, a process that is repeated multiple times. This applies impact, compression, and shear forces to the mixture, making it possible to produce composite particles of positive electrode active material 11 and coating material 12. Conditions such as the rotor rotation speed, processing time, and feed amount can be adjusted as appropriate.
  • the Balance Gran is equipped with a chopper that stirs the powder in a spiral shape from the outer periphery to the inner periphery, promoting convection, and an agitator scraper that rotates in the opposite direction to the chopper.
  • the action of the chopper and agitator scraper disperses the mixture evenly, making it possible to produce composite particles of the positive electrode active material 11 and the coating material 12.
  • the coated active material 100 may be produced by mixing the powder of the positive electrode active material 11 with the powder of the coating material 12 using a mortar, mixer, or the like.
  • the coating material 12 may be deposited on the surface of the positive electrode active material 11 by various methods such as a spray method, a spray dry coating method, an electrodeposition method, an immersion method, or a mechanical mixing method using a disperser.
  • the moisture content MC180 can be adjusted to the above range (0 ppm ⁇ MC180 ⁇ 600 ppm) by performing the manufacturing process of the coated active material 100 in an environment with low environmental moisture.
  • the manufacturing process of the coated active material 100 may be performed in a dry air environment with a dew point of ⁇ 30° C. or lower.
  • the manufacturing process of the coated active material 100 may be performed in a dry air environment with a dew point of ⁇ 50° C. or lower.
  • the positive electrode active material 11 may be temporarily stored in an environment with low environmental moisture to adjust the moisture content MC 180 to the above range (0 ppm ⁇ MC 180 ⁇ 600 ppm).
  • the positive electrode active material 11 may be stored in a sealed container in a dry air environment with a dew point of ⁇ 30° C. or lower.
  • the positive electrode active material 11 may be stored in a sealed container in a dry air environment with a dew point of ⁇ 50° C. or lower.
  • FIG. 2 is a cross-sectional view showing a schematic configuration of a positive electrode material 200 according to the second embodiment.
  • the positive electrode material 200 includes the coated active material 100 in the first embodiment and the second solid electrolyte 21. Because the positive electrode material 200 includes the coated active material 100, it is suitable for suppressing an increase in the resistance of the battery.
  • the positive electrode active material 11 of the coated active material 100 is separated from the second solid electrolyte 21 by the coating material 12.
  • the positive electrode active material 11 does not need to be in direct contact with the second solid electrolyte 21. This is because the coating material 12 has ion conductivity.
  • the second solid electrolyte 21 may have a different composition from the first solid electrolyte contained in the coating material 12 of the coated active material 100, or may have the same composition.
  • the second solid electrolyte 21 may include at least one selected from the group consisting of a halide solid electrolyte, a sulfide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, and a complex hydride solid electrolyte.
  • the second solid electrolyte 21 may include a sulfide solid electrolyte.
  • the second solid electrolyte 21 can achieve high ionic conductivity in the positive electrode material 200.
  • halide solid electrolytes examples include Li3REX6, Li3(Al,Ga,In)X6, Li2MgX4, Li2FeX4 , Li ( Al , Ga , In) X4 , and LiI, where X is at least one selected from the group consisting of Cl, Br, and I, and RE is at least one selected from the group consisting of rare earth elements.
  • LiX, Li2O , MOq , and LipMOq may be added to these.
  • the element X in “ LiX” is at least one element selected from the group consisting of F, Cl, Br, and I.
  • the element M in “ MOq " and “ LipMOq " is at least one element selected from the group consisting of P, Si , Ge, B, Al, Ga, In, Fe, and Zn. In “MO q " and " Lip MO q ", p and q are each independent natural numbers.
  • oxide solid electrolytes examples include NASICON-type solid electrolytes such as LiTi2 ( PO4 ) 3 and its elemental substitution products, (LaLi) TiO3 -based perovskite - type solid electrolytes, LISICON-type solid electrolytes such as Li14ZnGe4O16 , Li4SiO4 , LiGeO4 and their elemental substitution products, garnet-type solid electrolytes such as Li7La3Zr2O12 and its elemental substitution products, Li3N and its H- substitution products, Li3PO4 and its N -substitution products, and glasses or glass ceramics based on Li-B- O compounds such as LiBO2 and Li3BO3 to which materials such as Li2SO4 and Li2CO3 have been added.
  • NASICON-type solid electrolytes such as LiTi2 ( PO4 ) 3 and its elemental substitution products
  • LaLi) TiO3 -based perovskite - type solid electrolytes LISICON-type solid
  • the polymer solid electrolyte for example, a compound of a polymer compound and a lithium salt can be used.
  • the polymer compound may have an ethylene oxide structure. By having an ethylene oxide structure, the polymer compound can contain a large amount of lithium salt. Therefore, the ion conductivity can be further increased.
  • the lithium salt for example, LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiSO 3 CF 3 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), LiC (SO 2 CF 3 ) 3 , etc.
  • the lithium salt one lithium salt selected from these may be used alone, or a mixture of two or more lithium salts selected from these may be used.
  • LiBH 4 --LiI LiBH 4 --P 2 S 5, etc.
  • LiBH 4 --LiI LiBH 4 --P 2 S 5, etc.
  • the second solid electrolyte 21 may contain two or more materials selected from the materials listed as solid electrolytes.
  • the second solid electrolyte 21 may contain, for example, a halide solid electrolyte and a sulfide solid electrolyte.
  • the second solid electrolyte 21 may contain unavoidable impurities such as starting materials, by-products, and decomposition products used in synthesizing the solid electrolyte.
  • the shape of the second solid electrolyte 21 is not particularly limited and may be needle-like, spherical, elliptical, or the like.
  • the shape of the second solid electrolyte 21 may be particulate.
  • the solid electrolyte 21 When the second solid electrolyte 21 has a particulate (e.g., spherical) shape, the solid electrolyte may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less. When the solid electrolyte has a median diameter in this range, the coated active material 100 and the second solid electrolyte 21 are well dispersed in the positive electrode material 200.
  • a particulate e.g., spherical
  • the median diameter of the second solid electrolyte 21 may be 10 ⁇ m or less. In this case, the dispersion state of the coated active material 100 and the second solid electrolyte 21 in the positive electrode material 200 becomes better.
  • the median diameter of the second solid electrolyte 21 may be smaller than the median diameter of the coated active material 100. In this case, the dispersion state of the coated active material 100 and the second solid electrolyte 21 in the positive electrode material 200 becomes better.
  • the coated active material 100 and the second solid electrolyte 21 may be in contact with each other.
  • the coating material 12 and the second solid electrolyte 21 are in contact with each other.
  • the positive electrode material 200 may contain a plurality of particles of the second solid electrolyte 21 and a plurality of particles of the coated active material 100.
  • the positive electrode material 200 may be a mixture of a powder of the coated active material 100 and a powder of the second solid electrolyte 21.
  • the content of the coated active material 100 and the content of the second solid electrolyte 21 may be the same or different.
  • the positive electrode material 200 may contain a binder for the purpose of improving adhesion between particles.
  • the binder is used to improve the binding of the material that constitutes the positive electrode.
  • binders include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, polyacrylic acid hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polycarbonate, polyethersulfone, polyetherketone, polyetheretherketone, polyphenylene sulfide, hexafluoropolypropylene, styren
  • the binder may be an elastomer because of its excellent binding properties.
  • An elastomer is a polymer that has rubber elasticity.
  • the elastomer used as the binder may be a thermoplastic elastomer or a thermosetting elastomer.
  • the binder may contain a thermoplastic elastomer.
  • thermoplastic elastomers examples include styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene (SEPS), styrene-ethylene-ethylene-propylene-styrene (SEEPS), butylene rubber (BR), isoprene rubber (IR), chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), styrene-butylene rubber (SBR), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), hydrogenated isoprene rubber (HIR), hydrogenated butyl rubber (HIIR), hydrogenated nitrile rubber (HNBR), hydrogenated styrene-butylene rubber (HSBR), polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), etc.
  • the positive electrode material 200 may contain a conductive additive for the purpose of increasing electronic conductivity.
  • conductive additives include graphites such as natural graphite or artificial graphite, carbon blacks such as acetylene black and ketjen black, conductive fibers such as carbon fiber or metal fiber, metal powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide or potassium titanate, conductive metal oxides such as titanium oxide, and conductive polymer compounds such as polyaniline, polypyrrole, and polythiophene.
  • the above-mentioned conductive additive may be contained in the coating material 12 of the coated active material 100.
  • the positive electrode material 200 is obtained by mixing the coated active material 100 and the second solid electrolyte 21.
  • the method of mixing the coated active material 100 and the second solid electrolyte 21 is not particularly limited.
  • the coated active material 100 and the second solid electrolyte 21 may be mixed using a tool such as a mortar, or the coated active material 100 and the second solid electrolyte 21 may be mixed using a mixing device such as a ball mill.
  • the battery in embodiment 3 includes a positive electrode, a separator section, and a negative electrode.
  • the separator section is located between the positive electrode and the negative electrode.
  • the positive electrode includes the positive electrode material 200 in embodiment 2. With this configuration, an increase in the resistance of the battery is suppressed, improving the durability of the battery.
  • the separator portion may be an electrolyte layer containing a solid electrolyte, or a separator impregnated with an electrolyte solution.
  • FIG. 3 is a cross-sectional view showing the schematic configuration of battery 300 in embodiment 3.
  • the battery 300 includes a positive electrode 31, an electrolyte layer 32, and a negative electrode 33.
  • the electrolyte layer 32 is disposed between the positive electrode 31 and the negative electrode 33.
  • the separator portion is the electrolyte layer 32.
  • the positive electrode 31 includes the positive electrode material 200 in the second embodiment. With this configuration, an increase in the resistance of the battery 300 is suppressed, and thus the durability of the battery 300 is improved.
  • the thickness of each of the positive electrode 31 and the negative electrode 33 may be 10 ⁇ m or more and 500 ⁇ m or less. If the thickness of the positive electrode 31 and the negative electrode 33 is 10 ⁇ m or more, a sufficient energy density of the battery 300 can be ensured. If the thickness of the positive electrode 31 and the negative electrode 33 is 500 ⁇ m or less, high-output operation of the battery 300 can be achieved.
  • the electrolyte layer 32 is a layer containing an electrolyte material.
  • the electrolyte layer 32 may contain at least one solid electrolyte selected from the group consisting of a sulfide solid electrolyte, an oxide solid electrolyte, a halide solid electrolyte, a polymer solid electrolyte, and a complex hydride solid electrolyte. Details of each solid electrolyte are as described in the second embodiment.
  • the thickness of the electrolyte layer 32 may be 1 ⁇ m or more and 300 ⁇ m or less. When the thickness of the electrolyte layer 32 is 1 ⁇ m or more, the positive electrode 31 and the negative electrode 33 can be more reliably separated. When the thickness of the electrolyte layer 32 is 300 ⁇ m or less, the battery 300 can be operated at high output.
  • the negative electrode 33 contains a material as the negative electrode active material that has the property of absorbing and releasing metal ions (e.g., lithium ions).
  • metal ions e.g., lithium ions
  • metal materials, carbon materials, oxides, nitrides, tin compounds, silicon compounds, etc. can be used as the negative electrode active material.
  • the metal material may be a single metal.
  • the metal material may be an alloy.
  • Examples of the metal material include lithium metal and lithium alloys.
  • Examples of the carbon material include natural graphite, coke, partially graphitized carbon, carbon fiber, spherical carbon, artificial graphite, and amorphous carbon. From the viewpoint of capacity density, silicon (Si), tin (Sn), silicon compounds, tin compounds, etc. can be preferably used.
  • the median diameter of the particles of the negative electrode active material may be 0.1 ⁇ m or more and 100 ⁇ m or less.
  • the negative electrode 33 may contain other materials, such as a solid electrolyte.
  • the material described in embodiment 2 can be used as the solid electrolyte.
  • the battery 300 can be configured as a battery of various shapes, such as a coin type, a cylindrical type, a square type, a sheet type, a button type, a flat type, a laminated type, etc.
  • a positive electrode active material comprising:
  • the first solid electrolyte comprises Li, M, and X;
  • M is at least one element selected from the group consisting of metal elements other than Li and metalloid elements;
  • X is a halogen element;
  • the coated active material of Technology 1 can suppress the increase in battery resistance.
  • the first solid electrolyte is represented by the following composition formula (1): Li 6-(4-x-4y+my)b (Ti 1-xy Al x M3 y ) b F 6-2z O z ...(1)
  • M3 is at least one selected from the group consisting of Zr, Ni, Fe, and Cr, and m is the valence of M3; 0.1 ⁇ x ⁇ 0.9, 0 ⁇ y ⁇ 0.1, 0 ⁇ z ⁇ 0.1, and 0.8 ⁇ b ⁇ 1.2, 10.
  • the coated active material according to any one of claims 1 to 9, which satisfies the above. According to this configuration, the first solid electrolyte has high ionic conductivity and can be produced by a method with high industrial productivity.
  • the coated active material according to any one of techniques 1 to 11, A second solid electrolyte having a different composition from the first solid electrolyte;
  • the positive electrode material comprises:
  • the positive electrode material of Technology 12 contains a coated active material, making it suitable for suppressing an increase in battery resistance.
  • the battery of Technology 14 suppresses the increase in battery resistance, improving the durability of the battery.
  • a positive electrode comprising the positive electrode material according to technology 12; A negative electrode; an electrolyte layer disposed between the positive electrode and the negative electrode; Equipped with a battery.
  • the battery of Technology 15 suppresses the increase in battery resistance, improving the durability of the battery.
  • Example 1 Li(NiCoAl)O 2 (hereinafter, abbreviated as NCA) having a median diameter of 5 ⁇ m was used.
  • NCA Li(NiCoAl)O 2
  • NCA as a positive electrode active material
  • LTAF a coating material
  • a thin film of LTAF was formed by compression shear processing using a particle composite device (NOB-MINI, manufactured by Hosokawa Micron Corporation). Specifically, NCA and LTAF were weighed to have a weight ratio of 97.3:2.7, and processed under the conditions of blade clearance: 2 mm, rotation speed: 6000 rpm, and processing time: 50 minutes. As a result, a thin film was formed by coating LTAF on the surface of NCA. Thereafter, the amount of moisture contained in the coated active material was adjusted by leaving it to stand for 48 hours in a draft chamber at a temperature of about 20°C and a humidity of about 20%. As a result, the coated active material of Example 1 was obtained.
  • LPS Li 2 S-P 2 S 5
  • the obtained LPS was used as the second solid electrolyte of Example 1.
  • Example 2 After coating the surface of the NCA with LTAF, the coated active material was left to stand for 5 minutes in a dry air environment with a temperature of about 20° C. and a dew point of about ⁇ 30° C. to adjust the moisture content of the coated active material. Except for this, the coated active material of Example 2 was obtained in the same manner as in Example 1. The positive electrode material of Example 2 was produced in the same manner as in Example 1 using the coated active material of Example 2.
  • Example 3 After coating the surface of the NCA with LTAF, the coated active material was left to stand for 1 hour in a dry air environment with a temperature of about 20° C. and a dew point of about ⁇ 30° C., thereby adjusting the moisture content of the coated active material. Except for this, the coated active material of Example 3 was obtained in the same manner as in Example 1. The positive electrode material of Example 3 was produced in the same manner as in Example 1 using the coated active material of Example 3.
  • Example 4 After coating the surface of the NCA with LTAF, the coated active material was left to stand for 6 hours in a dry air environment with a temperature of about 20° C. and a dew point of about ⁇ 30° C., thereby adjusting the moisture content of the coated active material. Except for this, the coated active material of Example 4 was obtained in the same manner as in Example 1. The positive electrode material of Example 4 was produced in the same manner as in Example 1 using the coated active material of Example 4.
  • Example 5 After coating the surface of the NCA with LTAF, the coated active material was left to stand for 12 hours in a dry air environment with a temperature of about 20° C. and a dew point of about ⁇ 30° C., thereby adjusting the moisture content of the coated active material. Except for this, the coated active material of Example 5 was obtained in the same manner as in Example 1. The positive electrode material of Example 5 was produced in the same manner as in Example 1 using the coated active material of Example 5.
  • Example 6 After coating the surface of the NCA with LTAF, the coated active material was left to stand for 24 hours in a draft chamber at a temperature of about 20° C. and a humidity of about 20%, to adjust the moisture content of the coated active material. Except for this, the coated active material of Example 6 was obtained in the same manner as in Example 1. The positive electrode material of Example 6 was produced in the same manner as in Example 1 using the coated active material of Example 6.
  • Example 7 After coating the surface of the NCA with LTAF, the coated active material was left to stand for 10 minutes in a dry air environment with a temperature of about 20° C. and a dew point of about ⁇ 20° C. to adjust the moisture content of the coated active material. Except for this, the coated active material of Example 7 was obtained in the same manner as in Example 1. The positive electrode material of Example 7 was produced in the same manner as in Example 1 using the coated active material of Example 7.
  • Example 8 After coating the surface of the NCA with LTAF, the coated active material was left to stand for 20 minutes in a dry air environment with a temperature of about 20° C. and a dew point of about ⁇ 20° C. to adjust the moisture content of the coated active material. Except for this, the coated active material of Example 8 was obtained in the same manner as in Example 1. The positive electrode material of Example 8 was produced in the same manner as in Example 1 using the coated active material of Example 8.
  • Example 9 After coating the surface of the NCA with LTAF, the coated active material was left to stand for 5 minutes in a dry air environment with a temperature of about 20° C. and a dew point of about ⁇ 50° C. to adjust the moisture content of the coated active material. Except for this, the coated active material of Example 9 was obtained in the same manner as in Example 1. The positive electrode material of Example 9 was produced in the same manner as in Example 1 using the coated active material of Example 9.
  • Example 10 After coating the surface of the NCA with LTAF, the coated active material was left to stand for 10 minutes in a dry air environment with a temperature of about 20° C. and a dew point of about ⁇ 50° C. to adjust the moisture content of the coated active material. Except for this, the coated active material of Example 10 was obtained in the same manner as in Example 1. The positive electrode material of Example 10 was produced in the same manner as in Example 1 using the coated active material of Example 10.
  • Example 11 After coating the surface of the NCA with LTAF, the coated active material was left to stand for 12 hours in a dry air environment with a temperature of about 20° C. and a dew point of about ⁇ 30° C., and then dried for 14 days in a vacuum drying oven at a temperature of 140° C., thereby adjusting the moisture content of the coated active material. Except for this, the coated active material of Example 11 was obtained in the same manner as in Example 1. The positive electrode material of Example 11 was produced in the same manner as in Example 1 using the coated active material of Example 11.
  • Comparative Example 1 The material in which LTAF was coated on the surface of NCA was used as the coated active material of Comparative Example 1. That is, in Comparative Example 1, after the surface of NCA was coated with LTAF, the moisture content was not adjusted.
  • the positive electrode material of Comparative Example 1 was produced using the coated active material of Comparative Example 1 in the same manner as in Example 1.
  • the moisture content MC180 was determined by the Karl Fischer method described in embodiment 1.
  • a Karl Fischer moisture meter (HIRANUMA Corporation, EV-2010) was used to measure the moisture content of the coated active materials. The results are shown in Table 1.
  • MC 120 was obtained by dividing the integrated value of the amount of moisture released from the coated active material when the coated active material was heated from 25 ° C. to 120 ° C. by the total mass of the coated active material. The results are shown in Table 1.
  • the moisture amount MC 120 was obtained by the following method. In the Karl Fischer method described in the first embodiment, the measurement sample was heated from 25 ° C. to 120 ° C. at a heating rate of 10 ° C. per minute to vaporize the moisture contained in the measurement sample.
  • the vaporized moisture was quantified by coulometric titration until it reached a value equal to or less than the background moisture release amount, and the integrated value of the amount of moisture released from the coated active material was obtained, and the integrated value of the amount of moisture was divided by the total mass of the coated active material. It is presumed that the moisture released from the coated active material when the coated active material is heated from 25 ° C. to 120 ° C. is mainly moisture physically adsorbed on the surface of the coated active material.
  • the moisture content MC 180 and the moisture content MC 120 of the coated active material of Comparative Example 1 were both 0 ppm. This indicates that the moisture content of the coated active material of Comparative Example 1 was below the detection limit of the Karl Fischer moisture meter.
  • the positive electrode material was weighed so that it contained 5 mg of NCA.
  • the LPS and the positive electrode material were laminated in this order inside an insulating outer cylinder.
  • the resulting laminate was pressure-molded at a pressure of 720 MPa.
  • metallic lithium was placed so as to be in contact with the LPS layer, and pressure-molded again at a pressure of 40 MPa.
  • stainless steel current collectors were placed above and below the laminate. Current collector leads were attached to each current collector.
  • the outer cylinder was sealed using an insulating ferrule to isolate the inside of the outer cylinder from the outside atmosphere.
  • the battery was placed in a thermostatic chamber at 25°C.
  • the battery was charged at a constant current of 50 ⁇ A, which corresponds to a 0.05C rate (20 hour rate) relative to the theoretical capacity of the battery, until the voltage reached 4.25V.
  • the battery was then discharged at a constant current of 50 ⁇ A, which corresponds to a 0.05C rate (20 hour rate) relative to the theoretical capacity of the battery, until the voltage reached 3.75V.
  • the battery was then discharged at a constant current of 46.4mA, which corresponds to a 46.4C rate relative to the theoretical capacity of the battery, for 2 seconds.
  • the voltage drop at this time was divided by the discharge current value to determine the resistance R1 before the durability test.
  • the temperature of the thermostatic chamber was changed to 25°C, and the battery was charged at a constant current of 50 ⁇ A, which is a 0.05 C rate (20 hour rate) relative to the theoretical capacity of the battery, until the voltage reached 4.25 V.
  • the battery was then discharged at a constant current of 50 ⁇ A, which is a 0.05 C rate (20 hour rate) relative to the theoretical capacity of the battery, until the voltage reached 3.75 V.
  • a constant current discharge was performed for 2 seconds at a current value of 46.4 mA, which is a 46.4 C rate relative to the theoretical capacity of the battery.
  • the resistance R2 after the durability test was calculated by dividing the voltage drop at this time by the discharge current value.
  • the resistance R2 after the durability test was divided by the resistance R1 before the durability test, ie, ( R2 / R1 ) x 100 (%), is shown in Table 1.
  • Example 9 Comparative Example 1
  • an increase in the resistance of the battery is suppressed when the moisture content MC180 is 1 ppm or more. This is presumably because the homogeneity of the reaction layer formed on the surface of the coated active material is improved when the coated active material and the second solid electrolyte are mixed.
  • Example 7 Comparing Example 7 with Example 2 and Comparative Example 1, it is understood that when the moisture content MC180 is 30 ppm or more, the increase in the resistance of the battery is further suppressed. This is presumably because the homogeneity of the reaction layer formed on the surface of the coated active material is further improved when the coated active material and the second solid electrolyte are mixed.
  • Example 5 Comparing Example 5 with Examples 2 to 4 and Comparative Example 1, it is understood that when the moisture content MC180 is 120 ppm or more, the increase in the resistance of the battery is further suppressed. This is presumably because the thickness of the reaction layer formed on the surface of the coated active material becomes relatively thick when the coated active material and the second solid electrolyte are mixed.
  • the moisture content MC180 is the amount of moisture desorbed from the coated active material 100 in a relatively high temperature range exceeding 120° C. It is presumed that the moisture is mainly moisture chemically bonded to the coated active material 100. Therefore, it is presumed that the same tendency as the result of this example will be observed even when, for example, Li(NiCoMn)O 2 or LiCoO 2 other than NCA is used as the positive electrode active material.
  • Examples 1 to 8 and 11 it is understood from a comparison of Examples 1 to 8 and 11 with Examples 9 to 10 that even if the moisture content MC 120 is 0 ppm, as long as the moisture content MC 180 satisfies 0 ppm ⁇ MC 180 ⁇ 600 ppm, the effect of suppressing an increase in battery resistance can be obtained.
  • (MC 120 +MC 180 ) may satisfy 1 ppm ⁇ MC 120 +MC 180 ⁇ 1000 ppm, 1 ppm ⁇ MC 120 +MC 180 ⁇ 900 ppm, or 1 ppm ⁇ MC 120 +MC 180 ⁇ 810 ppm.
  • the technology disclosed herein is useful, for example, in lithium secondary batteries.

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