WO2023119056A1 - Procédé de production de précurseur et procédé de production de matériau actif d'électrode positive - Google Patents

Procédé de production de précurseur et procédé de production de matériau actif d'électrode positive Download PDF

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WO2023119056A1
WO2023119056A1 PCT/IB2022/062099 IB2022062099W WO2023119056A1 WO 2023119056 A1 WO2023119056 A1 WO 2023119056A1 IB 2022062099 W IB2022062099 W IB 2022062099W WO 2023119056 A1 WO2023119056 A1 WO 2023119056A1
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aqueous solution
positive electrode
temperature
coprecipitate
secondary battery
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PCT/IB2022/062099
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English (en)
Japanese (ja)
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吉谷友輔
平原誉士
宮入典子
高橋辰義
石谷哲二
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株式会社半導体エネルギー研究所
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • One aspect of the present invention relates to a method for producing a positive electrode active material and a method for producing a hydroxide.
  • the present invention also relates to an article or a manufacturing method.
  • the invention also relates to a process, machine, manufacture, or composition of matter.
  • the present invention also relates to a semiconductor device, a display device, a light-emitting device, a power storage device, a lighting device, an electronic device, or manufacturing methods thereof.
  • semiconductor device refers to all devices that can function by utilizing semiconductor characteristics, and includes electro-optical devices, semiconductor circuits, and electronic equipment.
  • a power storage device generally refers to elements and devices having a power storage function.
  • the power storage device includes a secondary battery as an element having a power storage function, and includes stationary devices such as household devices having a secondary battery as a device having a power storage function.
  • a secondary battery can use lithium ion or sodium ion as a carrier, and depending on the carrier, it is called a lithium ion battery (also referred to as a lithium ion secondary battery) or a sodium ion battery (also referred to as a sodium ion secondary battery). .
  • Patent Literature 1 discloses a precursor of a positive electrode material that provides a lithium-ion secondary battery with excellent discharge capacity and cycle characteristics, and a method for producing the same.
  • the precipitate is dried when producing the precursor. It is stated that drying at .
  • an object of the present invention is to provide a method for producing a positive electrode active material having a composite oxide containing lithium, nickel, cobalt, and manganese, and a method for producing a precursor.
  • One embodiment of the present invention has been made in view of the above problems, and provides a positive electrode active material having high discharge capacity, a method for producing a precursor thereof, and the like.
  • the present inventors have earnestly investigated the heating conditions for obtaining the precursor, and have discovered new temperature, time, atmosphere, and the like.
  • an aqueous solution in which a transition metal salt is dissolved and an alkaline aqueous solution are mixed to form a mixed solution and a coprecipitate, the mixed solution is filtered, and the coprecipitate is taken out.
  • a method for producing a precursor in which the coprecipitate is washed and then heated at a temperature of 130° C. or higher and 220° C. or lower.
  • Another aspect of the present invention is to mix an aqueous solution in which a transition metal salt is dissolved and an alkaline aqueous solution to form a mixed solution and a coprecipitate, filter the mixed solution, take out the coprecipitate, After washing the sediment, it is heated at a temperature of 130° C. or more and 220° C. or less for 3 hours or more and 15 hours or less.
  • Another aspect of the present invention includes mixing an aqueous solution in which a nickel salt, a cobalt salt, and a manganese salt are dissolved and an alkaline aqueous solution to form a mixed solution and a coprecipitate, filtering the mixed solution,
  • This is a method for producing a precursor, in which the precipitate is taken out, the coprecipitate is washed, and then heated at a temperature of 130° C. or higher and 220° C. or lower.
  • Another aspect of the present invention includes mixing an aqueous solution in which a nickel salt, a cobalt salt, and a manganese salt are dissolved and an alkaline aqueous solution to form a mixed solution and a coprecipitate, filtering the mixed solution, After taking out the precipitate and washing the coprecipitate, it is heated at a temperature of 130° C. or more and 220° C. or less for 3 hours or more and 15 hours or less.
  • the aqueous solution in which nickel salt, cobalt salt, and manganese salt are dissolved is preferably an aqueous solution in which nickel sulfate, cobalt sulfate, and manganese sulfate are dissolved in pure water.
  • the aqueous solution in which the nickel salt, cobalt salt and manganese salt are dissolved preferably contains a complexing agent.
  • the washing is a step of washing the coprecipitate obtained by filtration with water and then performing a first suction filtration, and washing with an organic solvent after the first suction filtration and then performing a second suction. It is preferable to have a step of filtering.
  • the organic solvent preferably comprises acetone or isopropyl alcohol.
  • the alkaline aqueous solution is preferably an aqueous solution in which sodium hydroxide is dissolved in pure water.
  • the pH value of the mixture it is preferable to set the pH value of the mixture to 9.0 or more and 13.0 or less.
  • Another aspect of the present invention is to mix an aqueous solution in which a transition metal salt is dissolved and an alkaline aqueous solution to form a mixed solution and a coprecipitate, filter the mixed solution, take out the coprecipitate, after washing the precipitate, heating at a temperature between 130° C. and 220° C. to form a precursor; mixing the precursor and a lithium compound to form a mixture; heating the mixture at a first temperature; A method for producing a positive electrode active material, wherein the mixture is heated to a second temperature higher than the first temperature.
  • Another aspect of the present invention is to mix an aqueous solution in which a transition metal salt is dissolved and an alkaline aqueous solution to form a mixed solution and a coprecipitate, filter the mixed solution, take out the coprecipitate, After washing the sediment, heating at a temperature of 130° C. to 220° C. for 8 hours to 15 hours to form a precursor, mixing the precursor with a lithium compound to form a mixture, and subjecting the mixture to a second step. 1, and heating the mixture at a second temperature higher than the first temperature.
  • Another aspect of the present invention includes mixing an aqueous solution in which a nickel salt, a cobalt salt, and a manganese salt are dissolved and an alkaline aqueous solution to form a mixed solution and a coprecipitate, filtering the mixed solution, After removing the precipitate and washing the coprecipitate, heating at a temperature of 130° C. or more and 220° C. or less to form a precursor, mixing the precursor and a lithium compound to form a mixture, and applying the mixture to a first and heating the mixture at a second temperature higher than the first temperature.
  • Another aspect of the present invention includes mixing an aqueous solution in which a nickel salt, a cobalt salt, and a manganese salt are dissolved and an alkaline aqueous solution to form a mixed solution and a coprecipitate, filtering the mixed solution, After removing the precipitate and washing the coprecipitate, the mixture is heated at a temperature of 130° C. or more and 220° C. or less for 8 hours or more and 15 hours or less to form a precursor, and the precursor and the lithium compound are mixed to form a mixture. forming, heating the mixture to a first temperature, and heating the mixture to a second temperature that is higher than the first temperature.
  • the first temperature range is preferably 500° C. or higher and 700° C. or lower
  • the second temperature range is preferably higher than 700° C. and 1050° C. or lower.
  • a positive electrode active material with high discharge capacity can be provided.
  • FIG. 1 is a flow chart showing a method for producing a positive electrode active material and the like.
  • FIG. 2 is a diagram showing a coprecipitation synthesis apparatus used in the precursor production method.
  • FIG. 3 is a flow chart showing a method for producing a positive electrode active material and the like.
  • FIG. 4 is a flow chart showing the manufacturing method of the positive electrode active material and the like.
  • FIG. 5 is a flow chart showing a method for producing a positive electrode active material and the like.
  • 6A is an exploded perspective view of the coin-type secondary battery
  • FIG. 6B is a perspective view of the coin-type secondary battery
  • FIG. 6C is a cross-sectional perspective view thereof.
  • FIG. 7A shows an example of a cylindrical secondary battery.
  • FIG. 7A shows an example of a cylindrical secondary battery.
  • FIG. 7B shows an example of a cylindrical secondary battery.
  • FIG. 7C shows an example of a plurality of cylindrical secondary batteries.
  • FIG. 7D shows an example of a power storage system having a plurality of cylindrical secondary batteries.
  • 8A and 8B are diagrams for explaining an example of a secondary battery, and FIG. 8C is a diagram showing the internal state of the secondary battery.
  • 9A to 9C are diagrams illustrating examples of secondary batteries.
  • 10A and 10B are diagrams showing the appearance of a secondary battery.
  • 11A to 11C are diagrams illustrating a method for manufacturing a secondary battery.
  • 12A to 12C are diagrams showing configuration examples of battery packs.
  • 13A and 13B are diagrams illustrating an example of a secondary battery.
  • 14A to 14C are diagrams illustrating examples of secondary batteries.
  • 15A and 15B are diagrams illustrating an example of a secondary battery.
  • 16A is a perspective view of a battery pack showing one embodiment of the present invention
  • FIG. 16B is a block diagram of the battery pack
  • FIG. 16C is a block diagram of a vehicle having a motor.
  • 17A to 17D are diagrams illustrating an example of a transportation vehicle.
  • 18A and 18B are diagrams illustrating a power storage device according to one embodiment of the present invention.
  • 19A is a diagram showing an electric bicycle
  • FIG. 19B is a diagram showing a secondary battery of the electric bicycle
  • FIG. 19C is a diagram explaining an electric motorcycle.
  • 20A to 20D are diagrams illustrating examples of electronic devices.
  • FIG. 21 shows SEM observation images of Samples 1 to 3 as comparative examples.
  • FIG. 21 shows SEM observation images of Samples 1 to 3 as comparative examples.
  • FIG. 21 shows SEM observation images of Samples 1 to 3 as comparative examples.
  • FIG. 21 shows SEM
  • FIG. 22 is a graph showing the crystallite sizes of samples 1 to 3 as comparative examples.
  • FIG. 23 is a graph showing the maximum discharge capacities of samples 1 to 3 as comparative examples.
  • FIG. 24 is a graph showing the charge/discharge cycle test results (discharge capacity) of samples 1 to 3.
  • FIG. 25 is a graph showing the charge/discharge cycle test results (discharge capacity retention rate) of Samples 1 to 3.
  • FIG. FIG. 26 is a graph showing the charge-discharge cycle test results (average discharge voltage) of samples 1 to 3.
  • FIG. FIG. 27 is a graph showing the charge/discharge cycle test results (discharge energy density) of samples 1 to 3.
  • Step S201 of FIG. 1 raw materials are prepared according to the type of positive electrode active material.
  • an aqueous solution in which at least a transition metal salt is dissolved is prepared.
  • An aqueous solution in which a transition metal salt is dissolved can be described as a transition metal source.
  • the pH value of the aqueous solution in which the transition metal salt is dissolved is less than 7, preferably when the pH value is 1 or more and 6 or less, the aqueous solution exhibits acidity, so the aqueous solution can be described as an acidic aqueous solution.
  • Transition metals will be explained.
  • one or a plurality of transition metals selected from manganese, cobalt, and nickel can be used.
  • the transition metal when only cobalt is used, when only nickel is used, when two kinds of cobalt and manganese are used, when two kinds of cobalt and nickel are used, or when cobalt, manganese and nickel are used Three types may be used.
  • a positive electrode active material obtained using nickel, cobalt, and manganese is sometimes referred to as NiCoMn or NCM, and has a chemical formula of LiNixCoyMnzO2 (x>0, y>0, z > 0, 0.8 ⁇ x+y+z ⁇ 1.2).
  • LiNixCoyMnzO2 for example, 0.1x ⁇ y ⁇ 8x and 0.1x ⁇ z ⁇ 8x may be satisfied .
  • the above x, y and z are sometimes referred to as the composition, compounding ratio or mixing ratio of nickel, cobalt and manganese, and when the above values of x, y and z are satisfied, a layered rock salt crystal structure can be obtained.
  • the above values can be measured by analysis by X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-mass spectroscopy (ICP-MS), or energy dispersive X-ray spectroscopy (EDX).
  • XPS X-ray photoelectron spectroscopy
  • ICP-MS inductively coupled plasma-mass spectroscopy
  • EDX energy dispersive X-ray spectroscopy
  • the analyzer for EDX is a scanning electron microscope (SEM) or an analyzer attached to a transmission electron microscope (TEM).
  • a high proportion of nickel in the transition metals is preferable because a positive electrode active material with a high capacity can be formed at a low cost.
  • the atomic ratio of nickel to the sum of the atomic numbers of nickel, cobalt, and manganese contained in the positive electrode active material is preferably 33% or more, more preferably 50% or more, and 80% or more. is more preferable.
  • the proportion of nickel is too high, chemical stability and heat resistance may decrease. Therefore, the atomic ratio of nickel to the sum of the atomic numbers of nickel, cobalt, and manganese contained in the positive electrode active material is preferably 95% or less.
  • the average discharge voltage is high, and the cobalt contributes to stabilization of the layered rock salt structure, so that the secondary battery can be highly reliable, which is preferable.
  • cobalt is more expensive and less stable than nickel and manganese, so too high a percentage of cobalt can increase production costs. Therefore, for example, the atomic ratio of cobalt to the sum of the atomic numbers of nickel, cobalt, and manganese contained in the positive electrode active material is preferably 2.5% or more and 34% or less.
  • Manganese as a transition metal is preferable because it improves heat resistance and chemical stability. However, if the proportion of manganese is too high, the discharge voltage and discharge capacity tend to decrease. Therefore, for example, the atomic ratio of manganese to the sum of the atomic numbers of nickel, cobalt, and manganese contained in the positive electrode active material is preferably 2.5% or more and 33% or less.
  • an aqueous solution in which a transition metal salt is dissolved will be described.
  • an aqueous solution in which a nickel salt is dissolved or an aqueous solution containing a water-soluble salt of nickel can be used.
  • an aqueous solution in which nickel sulfate or nickel nitrate is dissolved in water. can be used.
  • nickel ions may be present and nickel may be present as a complex.
  • an aqueous solution in which a cobalt salt is dissolved or an aqueous solution containing a water-soluble salt of cobalt can be used.
  • cobalt sulfate or cobalt nitrate is dissolved in water.
  • Aqueous solutions can be used.
  • Cobalt ions may be present in the aqueous solution, and cobalt may be present as a complex.
  • an aqueous solution in which a manganese salt is dissolved or an aqueous solution containing a water-soluble salt of manganese can be used, and an aqueous solution in which manganese sulfate, manganese nitrate, or the like is dissolved in water can be used.
  • manganese ions may be present in the aqueous solution, and manganese may be present as a complex.
  • the aqueous solution in which the transition metal salt is dissolved has a high purity, and an aqueous solution using pure water is preferable.
  • the transition metal ion concentration of the aqueous solution in which the transition metal salt is dissolved is preferably 1 mol/L or more and 5 mol/L or less, more preferably 2 mol/L or more and 3 mol/L or less.
  • the total concentration of transition metal ions preferably satisfies the above range.
  • an aqueous solution in which cobalt salt, manganese salt, and nickel salt are dissolved can be used as the aqueous solution in which transition metal salt is dissolved.
  • an aqueous solution in which nickel sulfate, cobalt sulfate and manganese sulfate are dissolved can be used as an aqueous solution in which transition metal salts are dissolved.
  • an alkaline aqueous solution (referred to as an alkaline aqueous solution) is prepared.
  • the alkaline aqueous solution refers to an aqueous solution with a pH value of more than 7, preferably an aqueous solution with a pH value of 8 or more.
  • the alkaline aqueous solution can be an aqueous solution containing sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia.
  • an aqueous solution obtained by dissolving sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia in water can be used.
  • An aqueous solution obtained by dissolving a plurality of substances selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia in water may be used. Pure water is preferably used as the water.
  • the alkali ion concentration of the alkaline aqueous solution is preferably 1 mol/L or more and 10 mol/L or less, more preferably 3 mol/L or more and 7 mol/L or less. When the aqueous solution contains a plurality of alkali ions, the total concentration of alkali ions should satisfy the above range.
  • the pure water used for the aqueous solution in which the transition metal salt is dissolved and the alkaline aqueous solution has a specific resistance of 1 M ⁇ cm or more, more preferably 10 M ⁇ cm or more, and still more preferably 15 M ⁇ cm or more. of water is preferred. Water that satisfies the specific resistance has high purity and contains very few impurities, so it is suitable for use in the production of composite oxides.
  • Step S203 of FIG. 1 the aqueous solution in which the transition metal salt is dissolved and the alkaline aqueous solution are mixed to produce a mixed aqueous solution (referred to as mixed solution or coprecipitated mixed solution).
  • the aqueous solution in which the transition metal salt is dissolved can be reacted with the alkaline aqueous solution.
  • the reaction may be referred to as neutralization reaction, acid-base reaction, or coprecipitation reaction.
  • a coprecipitate is precipitated.
  • a coprecipitate is precipitated in the mixed liquid as a reaction product.
  • a coprecipitate may precipitate in the mixed liquid and may be described as a precipitate.
  • the mixture may become a suspension.
  • the suspension refers to a liquid in which particles, which are coprecipitates, are dispersed in the liquid.
  • a hydroxide is formed as a coprecipitate.
  • the temperature of the mixed solution and the pH value of the mixed solution should be kept constant, and the mixed solution should be stirred.
  • the temperature should be 40° C. or higher and 90° C. or lower, preferably 45° C. or higher and 70° C. or lower.
  • the above pH value is 9.0 or more and 13.0 or less, preferably 10.5 or more and 11.5 or less.
  • the rotational speed of the stirring is preferably 800 rpm or more and 1200 rpm or less, preferably 900 rpm or more and 1100 rpm or less.
  • Step S205 of FIG. 1 the mixed liquid is filtered to obtain a coprecipitate from the mixed liquid. Specifically, the coprecipitate is taken out from the mixed solution. Suction filtration may be used for filtration.
  • the coprecipitate has a size of 1 ⁇ m or more and 20 ⁇ m or less (here, the length is exemplified as the size).
  • a coprecipitate obtained by filtration is sometimes referred to as filtered powder.
  • the transition metal-bearing hydroxide is obtained as a coprecipitate.
  • an aqueous solution containing a nickel salt, a cobalt salt and a manganese salt as the aqueous solution containing the transition metal results in a hydroxide containing cobalt, manganese and nickel as a coprecipitate.
  • Hydroxide obtained as a coprecipitate may become secondary particles in which primary particles are aggregated.
  • the primary particles refer to the smallest unit particles (agglomerates) that can be confirmed when observed with an SEM or the like at a magnification of, for example, 20,000.
  • the primary particles are the smallest unit particles.
  • the secondary particles refer to particles (particles independent of others) that are aggregated so that the primary particles share a part of the grain boundary (periphery of the primary particles, etc.) and are not easily separated.
  • Step S207 Washing step>
  • the coprecipitate is washed to obtain hydroxide from which impurities have been removed.
  • Cleaning using water can be applied to the cleaning in this step. Washing with water may be referred to as washing with water. Note that washing with water can be repeated once or multiple times. Impurities and the like can be removed from the coprecipitate by washing with water. Distilled water or pure water may be used as water. As for pure water, the content described in step S201 can be referred to. In this step, it is preferable to perform suction filtration after or while washing the coprecipitate with water.
  • cleaning using an organic solvent can be applied to the cleaning in the above steps.
  • washing with an organic solvent can be repeated once or multiple times.
  • the coprecipitate can be dried by washing with an organic solvent. Drying treatment includes removal of water adhering by previous washing or the like. Acetone or an alcohol such as isopropanol (typically isopropyl alcohol) may be used as the organic solvent.
  • suction filtration is preferably performed after washing the coprecipitate with an organic solvent or while washing with an organic solvent.
  • washing with water can be combined with washing using an organic solvent.
  • the preferred order is to carry out the step of suction filtration after or while washing with water, and then carry out the step of suction filtration after washing with an organic solvent or while washing with an organic solvent.
  • the above order is preferable because the water adhering to the substrate can be removed by washing with an organic solvent.
  • the number of times of washing with water is preferably set larger than the number of times of washing using an organic solvent.
  • Step S209 in FIG. 1 is a step of heating the coprecipitate, which is performed to obtain a precursor from which impurities are sufficiently removed. That is, the heating conditions in this step are not limited as long as the impurities are removed. For example, it is sufficient that this step can remove hydrogen and oxygen as water from the coprecipitate. Since removing hydrogen and oxygen as water is called dehydration, the heating process of this step may be called a dehydration process. Also, for example, this step can remove water contained in the coprecipitate. Since removing water or the like is called drying, the heating process of this step may be called a drying process. In the heating process of this step, it is also possible to gasify and remove impurities other than water. For example, the organic solvent used in step S207 can also be removed by the heating process of this step.
  • the temperature in this step will be explained.
  • the upper limit of the temperature in this step is preferably lower than the temperature at which the coprecipitate hydroxide begins to change to an oxide. That is, in this step, it is preferable to use a temperature that does not change hydroxide to oxide.
  • the temperature at which a hydroxide changes to an oxide can be determined by thermogravimetry-differential thermal analysis (TG-DTA).
  • TG-DTA thermogravimetry-differential thermal analysis
  • the curve showing the thermogravimetric analysis is in the region showing the weight loss
  • the curve showing the differential thermal analysis is typically at 220 ° C. Or it starts to fall from around there, and the maximum endothermic peak is observed at or around 260°C. From this result, 220° C. is derived as the temperature at which the hydroxide begins to decompose, dehydrate, or reduce, that is, the temperature at which the hydroxide begins to change to the oxide. can.
  • the lower limit of the temperature in this step may be at least the temperature at which the water of the hydroxide can be removed.
  • the specific temperature of the heat treatment is 130° C. to 220° C., preferably 150° C. to 220° C., more preferably 180° C. to 220° C.
  • the heat treatment time in this step is 3 hours to 15 hours, preferably 8 hours to 15 hours, preferably 10 hours to 13 hours, and more preferably 11 hours to 12 hours.
  • the atmosphere of the heat treatment in this step is preferably an oxygen-free atmosphere. That is, it can be said that the heat treatment in this step is different from so-called baking.
  • An atmosphere without oxygen is referred to as a non-oxygen atmosphere.
  • a dry atmosphere, a vacuum atmosphere, or an inert atmosphere typically, a nitrogen atmosphere or an argon atmosphere
  • the dew point in the processing container is preferably ⁇ 40° C. or less, preferably ⁇ 80° C. or less.
  • a bell jar-type vacuum apparatus having a processing container (referred to as a bell jar) whose interior can be evacuated and a vacuum pump connected to the bell jar can be used.
  • a vacuum drying furnace may be used, and the vacuum drying furnace has a vacuum pump connected to the drying furnace.
  • a dry pump, a turbomolecular pump, an oil rotary pump, a cryopump or a mechanical booster pump can be used as the vacuum pump of the bell jar type vacuum apparatus and the vacuum drying furnace.
  • the vacuum atmosphere in the bell jar-type vacuum device and the vacuum drying furnace includes an atmosphere decompressed so that the differential pressure gauge of each device is ⁇ 0.1 MPa or more and less than ⁇ 0.08 MPa.
  • a nitrogen-containing gas may be flowed into the processing container of the bell jar type vacuum apparatus and the vacuum drying furnace.
  • the heat treatment in this step may be performed multiple times. For example, it can be performed at a first temperature for a first time, and then at a second temperature for a second time. In this case, it is sufficient that the first temperature and the second temperature satisfy the above-described temperature range of this step. It can be said that the temperature range of this step should be satisfied.
  • the first temperature may be lower than the second temperature, for example, a temperature in the range of 80°C or higher and lower than 90°C.
  • the time of this step and at least the second time should satisfy the range of the heat treatment time of this step.
  • the first time may be shorter than the second time, for example, 0.5 hours or more and 1 hour or less. It is preferable to carry out the process multiple times because it facilitates removal of impurities from the precursor.
  • the method for producing a hydroxide that is one aspect of the present invention preferably includes up to this step. That is, through this step, the hydroxide that is one embodiment of the present invention can be obtained. Impurities are sufficiently reduced in the hydroxide.
  • a lithium source is provided.
  • the mixing ratio of the lithium source to the hydroxide (sum of lithium source/hydroxide transition metal) is 0.90 mol% or more and 1.05 mol% or less, preferably 0.92 mol% or more and 1.01 mol% or less. do.
  • a lithium compound can be used as the lithium source in the present invention.
  • Lithium compounds include lithium hydroxide, lithium carbonate, or lithium nitrate. A high purity lithium source is preferred. Further, it is preferable to pulverize the lithium source so that the solid-phase reaction proceeds easily.
  • Lithium hydroxide has a melting point of 462° C., which is low among lithium compounds.
  • a lithium compound with a low melting point such as lithium hydroxide, is preferably used in manufacturing a positive electrode active material, which is one embodiment of the present invention and has a high nickel content.
  • Step S211 Mixing step> Next, in step S211 of FIG. 1, the hydroxide and the lithium source are mixed to produce a mixture.
  • This mixing step may be given an ordinal number to distinguish it from the previous mixing step.
  • the mixing in this step may be dry or wet.
  • a ball mill, a bead mill, a kneader, or the like can be used as a mixing means.
  • a ball mill it is preferable to use, for example, zirconia balls as media.
  • Step S213 Heating step> Next, in step S213 of FIG. 1, the mixture is heated.
  • the heating process of this step may be given an ordinal number.
  • heating conditions in this step it is preferable to heat at a first temperature and then heat at a second temperature.
  • Heating at a first temperature may be referred to as first firing
  • heating at a second temperature may be referred to as second firing.
  • the second firing may be performed without performing the first firing. That is, this step may be performed once.
  • the second temperature is preferably higher than the first temperature.
  • heating at the first temperature may be referred to as preliminary firing, and heating at the second temperature may be referred to as final firing.
  • main firing may be performed without performing temporary firing.
  • lithium hydroxide used as the lithium source, it is preferable to perform calcination.
  • the first temperature in this step is preferably higher than the melting point of the lithium source.
  • the first temperature is preferably 500° C. or higher and 700° C. or lower.
  • the second temperature is preferably higher than 500° C. and 1050° C. or lower, and when the second temperature is higher than the first temperature, the second temperature is preferably higher than 700° C. and 1050° C. or lower.
  • the heating time at the first temperature and the heating time at the second temperature are each preferably 1 hour or more and 20 hours or less.
  • the time of heating at the first temperature may be equal, longer, or shorter than the time of heating at the second temperature.
  • each of the heating at the first temperature and the heating at the second temperature is preferably performed in an oxygen atmosphere, and particularly preferably while supplying oxygen.
  • an oxygen atmosphere for example, 2 L/min or more and 15 L/min, preferably 5 L/min and 10 L/min, per 1 L of the internal volume of the furnace.
  • the heating atmosphere at the first temperature may be the same as or different from the heating atmosphere at the second temperature.
  • an electric furnace or a rotary kiln furnace can be used for heating at the first temperature and the second temperature.
  • the calciner used for heating at the first temperature may be the same as or different from the calciner used for heating at the second temperature.
  • the mixture is preferably placed in a crucible or a sheath.
  • the crucible or sheath preferably has a material with high heat resistance such as alumina (aluminum oxide), mullite cordierite, magnesia, zirconia, or the like.
  • alumina aluminum oxide
  • mullite cordierite mullite cordierite
  • magnesia zirconia
  • aluminum oxide is preferable because it is also a material in which impurities are less likely to enter.
  • an alumina crucible or sheath with a purity of 99% or higher, preferably 99.5% or higher may be used.
  • a crucible made of aluminum oxide with a purity of 99.9% is used.
  • a lid on the crucible or sheath and heat it, in order to prevent sublimation of the materials contained in the mixture.
  • the lid may be arranged so that the inside of the crucible is isolated from the inside air of the furnace, or it may be arranged so that the inside of the crucible is partially open so that the inside of the crucible can come into contact with the inside air of the furnace.
  • the heating step at the first temperature and the heating step at the second temperature it is preferable to grind or pulverize with a mortar.
  • a sticking state of the mixtures or an agglomerated state of the mixtures can be loosened by pulverization or crushing. If the mixture adheres to each other during heating, the contact area with oxygen in the atmosphere may decrease, so pulverization or crushing as described above is recommended. Further, after pulverization or crushing, the material may be classified using a sieve.
  • the mortar is also preferably made of a material that does not easily release impurities. Specifically, it is suitable to use an alumina mortar with a purity of 90% or higher, preferably 99% or higher.
  • a positive electrode active material can be produced.
  • a nickel-cobalt-manganese composite oxide can be obtained as a positive electrode active material according to the prepared raw materials.
  • the use of the obtained nickel-cobalt-manganese composite oxide is preferable because high discharge capacity can be obtained in terms of battery characteristics.
  • a complexing agent may be added as a raw material prepared in step S201 of FIG.
  • a complexing agent is a compound capable of forming a complex with transition metal ions in an aqueous solution.
  • Complexing agents include ammonia or ammonium salts. An aqueous solution obtained by dissolving these in water such as pure water serves as a complexing agent. When ammonia is used, it can be described as an aqueous ammonia solution.
  • a chelating agent which is a complexing agent for forming a chelate compound
  • Chelating agents include glycine, oxine, 1-nitroso-2-naphthol, 2-mercaptobenzothiazole or EDTA (ethylenediaminetetraacetic acid).
  • Plural kinds selected from glycine, oxine, 1-nitroso-2-naphthol and 2-mercaptobenzothiazole may be used.
  • An aqueous solution obtained by dissolving these in water such as pure water serves as a chelating agent.
  • glycine it can be described as glycine aqueous solution.
  • the glycine concentration is preferably 0.05 mol/L or more and 0.15 mol/L or less, preferably 0.07 mol/L or more and 0.12 mol/L or less.
  • the use of a chelating agent suppresses unnecessary generation of crystal nuclei, a hydroxide having a good particle size distribution can be obtained. Further, by using a chelating agent, the acid-base reaction can be delayed, and secondary particles having a nearly spherical shape can be obtained by allowing the reaction to proceed gradually.
  • the chelating agent is more preferably a general complexing agent such as an aqueous ammonia solution.
  • a complexing agent specifically a chelating agent may be prepared.
  • the complexing agent specifically the chelating agent, should be placed in the reaction vessel.
  • the present complexing agent or chelating agent may be given an ordinal number.
  • the materials and the like that can be used for the complexing agent or chelating agent are as described above.
  • the glycine concentration in the aqueous glycine solution should be 0.05 mol/L or more and 0.15 mol/L or less, preferably 0.07 mol/L or more and 0.12 mol/L or less.
  • the glycine concentration in the glycine aqueous solution is preferably equal to the glycine concentration mixed with the aqueous solution in which the transition metal salt is dissolved.
  • steps after step S203 are performed in the same manner as in manufacturing method 1.
  • the coprecipitation synthesis apparatus 170 used in this production method 2 will be described with reference to FIG.
  • the coprecipitation synthesis apparatus 170 can be installed in a draft chamber and has at least a reaction vessel 171 .
  • a reaction container can be used as the reaction tank 171 .
  • the separable flask may be cylindrical or round. In the cylindrical type, the separable flask has a flat bottom.
  • the separable cover has a plurality of inlets, for example four inlets.
  • At least one inlet of the separable cover can be used to control the atmosphere in the reaction vessel 171 .
  • the atmosphere is preferably controlled to contain nitrogen.
  • it is preferable that the amount of air flow is necessary for discharging the gas generated by the thermal decomposition reaction.
  • nitrogen may be bubbled in the aqueous solution 103 put into the reaction tank 171 .
  • the coprecipitation synthesis apparatus 170 may be equipped with a reflux condenser connected to another inlet of the separable cover. can be returned to reaction vessel 171 .
  • aqueous solution 103 As the aqueous solution 103, the above-described chelating agent is added.
  • An aqueous solution such as the aqueous solution 103 that has been put into the reaction tank 171 from the beginning may be referred to as a charging solution.
  • the charging liquid is sometimes referred to as a conditioning liquid.
  • a charging solution and a conditioning solution refer to an aqueous solution before reaction, that is, an aqueous solution in an initial state.
  • aqueous solution in which a transition metal salt is dissolved is prepared as the aqueous solution 101 .
  • the aqueous solution 101 is kept in the tank 180 .
  • an alkaline aqueous solution is prepared as the aqueous solution 102 . Since the alkaline aqueous solution is used to keep the pH value constant, it is sometimes referred to as a pH adjusting solution.
  • Aqueous solution 102 is kept in tank 186 . Nitrogen may be bubbled through tanks 180 and 186 to remove oxygen from each aqueous solution.
  • a tank other than the tanks 180 and 186 may be prepared to contain the chelating agent described above.
  • the tank 180 has a pump 182 and a tube (also referred to as a tube) 181 connected to the pump 182.
  • the tube 181 is fixed to the inlet of the separable cover. It can be dripped.
  • the tank 186 has a pump 188 and a pipe 187 connected to the pump 188.
  • the pipe 187 is fixed to the introduction port of the separable cover, and the aqueous solution 102 is dripped into the reaction vessel 171 from the tip of the pipe 187.
  • the tip of the tube 181 and the tube 187 may be immersed in the aqueous solution 103 , and in this case also the aqueous solution 101 and the aqueous solution 102 are dripped into the reaction vessel 171 .
  • each raw material is prepared in the reaction tank 171, the tank 180, and the tank 186.
  • Step S203 Mixing step> Next, the mixing process of step S203 will be described. First, the conditions of the coprecipitation method for this step are shown.
  • the pH value of the aqueous solution 103 in the reaction tank 171 is 9.0 or more and 13.0 or less, preferably 10.5 or more and 11.5 or less.
  • the temperature of the aqueous solution 103 in the reaction tank 171 should be 40° C. or higher and 90° C. or lower, preferably 45° C. or higher and 70° C. or lower.
  • the water temperature can also be controlled according to the temperature inside the reaction tank 171 .
  • the temperature in the reaction vessel 171 may be equal to or deviate from the water temperature by less than 5°C, preferably less than 2°C. Therefore, the temperature in the reaction tank 171 is set at 35° C. or higher and 95° C. or lower, preferably 40° C.
  • the rotation speed for stirring the aqueous solution 103 in the reaction tank 171 is set to 800 rpm or more and 1200 rpm or less, preferably 900 rpm or more and 1100 rpm or less.
  • the concentration of transition metal ions in the aqueous solution 101 is 1 mol/L or more and 5 mol/L or less, preferably 2 mol/L or more and 3 mol/L or less. With multiple transition metals, the total concentration of transition metal ions satisfies the above range.
  • the dropping rate of the aqueous solution 101 is 0.05 mL/minute or more and 1.0 mL/minute or less, preferably 0.08 mL/minute or more and 0.5 mL/minute.
  • the alkali concentration of the aqueous solution 102 is 1 mol/L or more and 10 mol/L or less, preferably 3 mol/L or more and 7 mol/L or less.
  • the concentration of the chelating agent in the aqueous solution 103 is 0.05 mol/L or more and 0.15 mol/L or less, preferably 0.07 mol/L or more and 0.12 mol/L or less.
  • a stirring unit 172 is provided in the reaction tank 171 of FIG.
  • the stirring section 172 can stir the aqueous solution 103 in the reaction vessel 171 and has a stirring motor 173 as a power source for rotating the stirring section 172 .
  • the stirring unit 172 has paddle-type stirring blades (referred to as paddle blades), and the paddle blades have two or more and six or less blades, and the blades have an inclination of 40 degrees or more and 70 degrees or less. may be The blades in the stirring section 172 may be moved up and down.
  • the rotation speed of the stirring unit 172 specifically, the rotation speed of the paddle blades should be 800 rpm or more and 1200 rpm or less, preferably 900 rpm or more and 1100 rpm or less.
  • a baffle plate may be installed inside the reaction vessel 171 .
  • a thermometer 174 is provided to measure the temperature of the reaction tank 171 or the water temperature of the aqueous solution 103 .
  • the temperature of the reaction vessel 171 can be controlled using a thermoelectric element so that the temperature of the aqueous solution 103 remains constant.
  • Thermoelectric elements include, for example, Peltier elements.
  • the tip of the thermometer 174 should be immersed in the aqueous solution 103 .
  • the aqueous solution 103 may be heated to 40° C. or higher and 90° C. or lower, preferably 45° C. or higher and 70° C. or lower.
  • a thermometer 174 may be used to control the temperature of the reaction vessel 171 in order to control the water temperature of the aqueous solution 103 .
  • the coprecipitation synthesis apparatus 170 is provided with a control device 190 and the like for controlling dropping conditions or stirring conditions from each pump. Based on the information obtained from the thermometer 174, the control device 190 can control the rotational speed of the stirring section 172, the dropping amount of each aqueous solution, and the like.
  • the dropping rate of the aqueous solution 101 is set to 0.05 mL/min or more and 1.0 mL/min or less, preferably 0.08 mL/min or more and 0.5 mL/min.
  • the concentration of transition metal ions in the aqueous solution 101 is preferably 1 mol/L or more and 5 mol/L or less, preferably 2 mol/L or more and 3 mol/L or less.
  • the total concentration of each transition metal ion preferably satisfies the above range.
  • a pH meter is also arranged in the reaction tank 171 and can measure the pH of the aqueous solution 103 .
  • the above pH value is set within the range of 9.0 or more and 13.0 or less, preferably 10.5 or more and 11.5 or less.
  • the concentration of the chelating agent in the aqueous solution 103 is preferably 0.05 mol/L or more and 0.15 mol/L or less, preferably 0.07 mol/L or more and 0.12 mol/L or less.
  • the alkali concentration of the aqueous solution 102 is preferably 1 mol/L or more and 10 mol/L or less, preferably 3 mol/L or more and 7 mol/L or less.
  • reaction product precipitates in the reaction tank 171 through the mixing process of step S203.
  • the reaction product is a coprecipitate, specifically a hydroxide.
  • step S205 and subsequent steps are the same as those in manufacturing method 1, and thus description thereof is omitted.
  • a positive electrode active material can be produced.
  • a nickel-cobalt-manganese composite oxide having a good particle size distribution can be obtained as a positive electrode active material.
  • the use of the obtained nickel-cobalt-manganese composite oxide is preferable because it enhances the discharge capacity in terms of battery characteristics. Furthermore, it is preferable to use the obtained nickel-cobalt-manganese composite oxide because it suppresses variations in discharge capacity in terms of battery characteristics.
  • the NCM may contain one or more selected from calcium and aluminum at a concentration of 0.1 atm % or more and 5 atm % or less with respect to the NCM.
  • Calcium and aluminum having the above concentrations are sometimes referred to as additive elements.
  • the additive element is often located in the surface layer of the active material, and the surface layer refers to a region up to 50 nm, preferably up to 30 nm, more preferably up to 10 nm from the surface of the active material.
  • the surface layer part may be considered to be located in the same way when the active material is a primary particle or a secondary particle. More preferably, a region up to 10 nm is called a surface layer portion.
  • the surface of the primary particles or the surface of the secondary particles refers to the interface between a region where transition metals (eg, Co, Ni, Mn, Fe, etc.) that are oxidized and reduced as lithium is intercalated and desorbed exist and regions where they do not exist.
  • transition metals eg, Co, Ni, Mn, Fe, etc.
  • NCMA may be described as a lithium composite oxide containing Ni, Co, Mn, and Al.
  • NCA lithium composite oxide containing Ni and Co containing aluminum as a main component
  • NCA may be described as a lithium composite oxide containing Ni, Co, and Al.
  • step S213 the case where the above additive element source is added simultaneously with the raw material prepared in step S201 will be described with reference to FIG.
  • the manufacturing method 3 shown in FIG. 3 is the same as the manufacturing method 1 from step S203 to step S213, but newly adds step S215.
  • an additive element source is prepared.
  • an aqueous solution in which the salt of the additive element source is dissolved can be used.
  • an aqueous solution in which aluminum sulfate, aluminum chloride, aluminum nitrate, calcium oxide, calcium carbonate, calcium hydroxide, or calcium sulfate is dissolved can be used.
  • the additive element source is weighed so that the additive element is 0.1 atm % or more and 5 atm % or less of the composite oxide (for example, NCM).
  • a plurality of additive elements may be included. When a plurality of additive elements are contained, the total concentration of the additive elements should satisfy 0.1 atm % or more and 5 atm % or less of the composite oxide (for example, NCM).
  • Step S203 Mixing step>
  • the aqueous solution in which the transition metal salt is dissolved, the alkaline aqueous solution, and the aqueous solution in which the salt of the additive element source is dissolved are mixed to produce a mixed solution.
  • the mixing in this step is the same as in step S203 of manufacturing method 1.
  • step S205 and subsequent steps are the same as those in manufacturing method 1, and thus description thereof is omitted.
  • a positive electrode active material can be produced. It should be noted that, according to production method 3, a composite oxide containing an additive element can be obtained as a positive electrode active material.
  • the additive element is preferably located in the surface layer of the composite oxide.
  • Step S215 of FIG. 4 an additive element source is prepared.
  • Aluminum sulfate, aluminum chloride, aluminum nitrate, calcium oxide, calcium carbonate, calcium hydroxide, or calcium sulfate can be used as the additive element source.
  • the additive element source is weighed so that the additive element is 0.1 atm % or more and 5 atm % or less of the composite oxide (for example, NCM).
  • a plurality of additive elements may be included. When a plurality of additive elements are contained, the total concentration of the additive elements should satisfy 0.1 atm % or more and 5 atm % or less of the composite oxide (for example, NCM).
  • Step S211 Mixing step>
  • a mixture is produced by mixing a precursor, a lithium source, and an additive element source.
  • the mixing in this step is the same as step S211 of manufacturing method 1 .
  • step S213 and subsequent steps are the same as those of the manufacturing method 1, so description thereof will be omitted.
  • a positive electrode active material can be produced.
  • a composite oxide having an additive element can be obtained as a positive electrode active material.
  • the additive element is preferably located in the surface layer of the composite oxide.
  • step S213 ⁇ Manufacturing method 5>
  • the manufacturing method 5 shown in FIG. 5 is the same as the manufacturing method 1 from step S201 to step S213, but newly adds step S215.
  • the order of step S215 is different from that of manufacturing methods 3 and 4 described above.
  • Step S215 Preparation of additive element source>
  • an additive element source is prepared.
  • Aluminum sulfate, aluminum chloride, aluminum nitrate, calcium oxide, calcium carbonate, calcium hydroxide, or calcium sulfate can be used as the additive element source.
  • the additive element source is weighed so that the additive element is 0.1 atm % or more and 5 atm % or less of the composite oxide (for example, NCM).
  • a plurality of additive elements may be included. When a plurality of additive elements are contained, the total concentration of the additive elements should satisfy 0.1 atm % or more and 5 atm % or less of the composite oxide (for example, NCM).
  • Step S216 Mixing step>
  • the composite oxide and the additive element source are mixed to produce a mixture.
  • the mixing in this step is the same as step S211 of manufacturing method 1 .
  • Step S217 Heating step> In step S217 of FIG. 5, the mixture is heated. The heating in this step is the same as in step S213 of the first manufacturing method.
  • a positive electrode active material can be produced.
  • a composite oxide containing an additive element can be obtained as a positive electrode active material.
  • the additive element is preferably located in the surface layer of the composite oxide.
  • the crystallite size of the positive electrode active material can be obtained, for example, from the following Scherrer formula.
  • all diffraction peaks detected in the range of 15° to 90° 2 ⁇ can be used to calculate the crystallite size. After determining the crystallite size of each diffraction peak, it is preferable to apply a correction, and it is preferable to calculate the average value of the crystallite sizes. LiCoO 2 literature value (ICSD coll.code.172909) can be used for correction.
  • the crystallite size may be increased. However, excessive lithium may cause gelation of the binder during the production of electrodes such as positive electrodes. To avoid this demerit, it is preferable to set an upper limit for the crystallite size. For example, the above disadvantages can be avoided by setting the crystallite size calculated from the XRD diffraction pattern to 200 nm or less, preferably 150 nm or less.
  • the positive electrode active material preferably has a crystallite size of 50 nm or more, more preferably 90 nm or more, calculated from the half width of the XRD diffraction pattern. This value can be arbitrarily combined with the crystallite size described above.
  • FIG. 6A is an exploded perspective view of a coin-type (also referred to as flat-type) secondary battery
  • FIG. 6B is an external view
  • FIG. 6C is a cross-sectional view thereof.
  • Coin-type secondary batteries are mainly used in small electronic devices. In this specification and the like, coin-type batteries include button-type batteries.
  • FIG. 6A for the sake of clarity, a schematic diagram is used so that the overlapping of members (vertical relationship and positional relationship) can be understood. Therefore, FIG. 6A and FIG. 6B do not correspond to each other completely.
  • positive electrode 304, separator 310, negative electrode 307, spacer 322, and washer 312 are stacked. These are sealed with a negative electrode can 302 and a positive electrode can 301 .
  • a gasket for sealing is not shown in FIG. 6A.
  • the spacer 322 and the washer 312 are used to protect the inside or fix the position inside the can when the positive electrode can 301 and the negative electrode can 302 are crimped. Spacers 322 and washers 312 are made of stainless steel or an insulating material.
  • a positive electrode 304 has a laminated structure in which a positive electrode active material layer 306 is formed on a positive electrode current collector 305 .
  • a separator 310 and a ring-shaped insulator 313 are arranged so as to cover the side and top surfaces of the positive electrode 304, respectively.
  • the separator 310 has a larger planar area than the positive electrode 304 .
  • FIG. 6B is a perspective view of a completed coin-type secondary battery.
  • a positive electrode can 301 which also serves as a positive electrode terminal
  • a negative electrode can 302 which also serves as a negative electrode terminal
  • the positive electrode 304 is formed of a positive electrode current collector 305 and a positive electrode active material layer 306 provided so as to be in contact therewith.
  • the negative electrode 307 is formed of a negative electrode current collector 308 and a negative electrode active material layer 309 provided so as to be in contact therewith.
  • the negative electrode 307 is not limited to a laminated structure, and may be a lithium metal foil or a lithium-aluminum alloy foil.
  • the active material layers of the positive electrode 304 and the negative electrode 307 used in the coin-type secondary battery 300 may be formed only on one side.
  • the positive electrode can 301 and the negative electrode can 302 are made of metals such as nickel, aluminum, titanium, etc., which are corrosion-resistant to the liquid electrolyte, alloys thereof, and alloys of these with other metals (for example, stainless steel, etc.). can be used. In addition, it is preferable to coat with nickel, aluminum, or the like in order to prevent corrosion due to the liquid electrolyte.
  • the positive electrode can 301 and the negative electrode can 302 are electrically connected to the positive electrode 304 and the negative electrode 307, respectively.
  • negative electrode 307, positive electrode 304 and separator 310 are immersed in a liquid electrolyte, and as shown in FIG.
  • the positive electrode can 301 and the negative electrode can 302 are pressure-bonded via a gasket 303 to manufacture a coin-shaped secondary battery 300 .
  • the coin-shaped secondary battery 300 can have high capacity, high charge/discharge capacity, and excellent cycle characteristics. Note that in the case of a secondary battery having a solid electrolyte between the negative electrode 307 and the positive electrode 304, the separator 310 can be omitted.
  • a cylindrical secondary battery 616 has a positive electrode cap (battery cover) 601 on its top surface and battery cans (armor cans) 602 on its side and bottom surfaces.
  • the positive electrode cap 601 and the battery can (outer can) 602 are insulated by a gasket (insulating packing) 610 .
  • FIG. 7B is a diagram schematically showing a cross section of a cylindrical secondary battery.
  • the cylindrical secondary battery shown in FIG. 7B has a positive electrode cap (battery cover) 601 on the top surface and battery cans (armor cans) 602 on the side and bottom surfaces.
  • the positive electrode cap and the battery can (outer can) 602 are insulated by a gasket (insulating packing) 610 .
  • a battery element in which a strip-shaped positive electrode 604 and a strip-shaped negative electrode 606 are wound with a separator 605 interposed therebetween is provided inside a hollow columnar battery can 602 .
  • the battery element is wound around the central axis.
  • Battery can 602 is closed at one end and open at the other end.
  • the battery can 602 is made of metals such as nickel, aluminum, titanium, etc., which are resistant to corrosion against liquid electrolytes, alloys thereof, and alloys of these and other metals (for example, stainless steel). be able to.
  • the battery element in which the positive electrode, the negative electrode and the separator are wound is sandwiched between a pair of insulating plates 608 and 609 facing each other.
  • a non-aqueous electrolyte (not shown) is filled inside the battery can 602 in which the battery element is provided. The same non-aqueous electrolyte as used in coin-type secondary batteries can be used.
  • FIGS. 7A to 7D illustrate the secondary battery 616 in which the height of the cylinder is greater than the diameter of the cylinder, but the invention is not limited to this.
  • the diameter of the cylinder may be a secondary battery that is larger than the height of the cylinder. With such a configuration, for example, the size of the secondary battery can be reduced.
  • the cylindrical secondary battery 616 can have high capacity, high charge/discharge capacity, and excellent cycle characteristics.
  • a positive electrode terminal (positive collector lead) 603 is connected to the positive electrode 604
  • a negative electrode terminal (negative collector lead) 607 is connected to the negative electrode 606 .
  • Both the positive electrode terminal 603 and the negative electrode terminal 607 can use a metal material such as aluminum.
  • the positive electrode terminal 603 and the negative electrode terminal 607 are resistance welded to the safety valve mechanism 613 and the bottom of the battery can 602, respectively.
  • the safety valve mechanism 613 is electrically connected to the positive electrode cap 601 via a PTC (Positive Temperature Coefficient) element 611 .
  • the safety valve mechanism 613 disconnects the electrical connection between the positive electrode cap 601 and the positive electrode 604 when the increase in internal pressure of the battery exceeds a predetermined threshold.
  • the PTC element 611 is a thermal resistance element whose resistance increases when the temperature rises, and the increase in resistance limits the amount of current to prevent abnormal heat generation.
  • Barium titanate (BaTiO 3 ) semiconductor ceramics or the like can be used for the PTC element.
  • FIG. 7C shows an example of an electrical storage system 615 .
  • a power storage system 615 includes a plurality of secondary batteries 616 .
  • the positive electrode of each secondary battery contacts and is electrically connected to a conductor 624 separated by an insulator 625 .
  • Conductor 624 is electrically connected to control circuit 620 via wiring 623 .
  • a negative electrode of each secondary battery is electrically connected to the control circuit 620 through a wiring 626 .
  • a protection circuit or the like that prevents overcharge or overdischarge can be applied as the control circuit 620 .
  • FIG. 7D shows an example of an electrical storage system 615 .
  • the power storage system 615 includes a plurality of secondary batteries 616 sandwiched between the conductive plates 628 and 614 .
  • the plurality of secondary batteries 616 are electrically connected to the conductive plates 628 and 614 by wirings 627 .
  • the plurality of secondary batteries 616 may be connected in parallel, may be connected in series, or may be connected in series after being connected in parallel.
  • a plurality of secondary batteries 616 may be connected in series after being connected in parallel.
  • a temperature control device may be provided between the secondary batteries 616 .
  • the secondary battery 616 When the secondary battery 616 is overheated, it can be cooled by the temperature control device, and when the secondary battery 616 is too cold, it can be heated by the temperature control device. Therefore, the performance of power storage system 615 is less likely to be affected by the outside air temperature.
  • the power storage system 615 is electrically connected to the control circuit 620 via wiring 621 and wiring 622 .
  • the wiring 621 is electrically connected to the positive electrodes of the plurality of secondary batteries 616 through the conductive plate 628
  • the wiring 622 is electrically connected to the negative electrodes of the plurality of secondary batteries 616 through the conductive plate 614 .
  • FIG. 8 A structural example of a secondary battery will be described with reference to FIGS. 8 and 9.
  • FIG. 8 A structural example of a secondary battery will be described with reference to FIGS. 8 and 9.
  • a secondary battery 913 illustrated in FIG. 8A includes a wound body 950 provided with a terminal 951 and a terminal 952 inside a housing 930 .
  • the wound body 950 is immersed in the liquid electrolyte inside the housing 930 .
  • the terminal 952 is in contact with the housing 930, and the terminal 951 is not in contact with the housing 930 by using an insulating material.
  • the housing 930 is shown separately for the sake of convenience. exist.
  • a metal material for example, aluminum
  • a resin material can be used as the housing 930 .
  • the housing 930 shown in FIG. 8A may be made of a plurality of materials.
  • a housing 930a and a housing 930b are bonded together, and a wound body 950 is provided in a region surrounded by the housings 930a and 930b.
  • An insulating material such as an organic resin can be used for the housing 930a.
  • a material such as an organic resin for the surface on which the antenna is formed shielding of the electric field by the secondary battery 913 can be suppressed.
  • an antenna may be provided inside the housing 930a.
  • a metal material, for example, can be used as the housing 930b.
  • a wound body 950 has a negative electrode 931 , a positive electrode 932 , and a separator 933 .
  • the wound body 950 is a wound body in which the negative electrode 931 and the positive electrode 932 are laminated with the separator 933 interposed therebetween, and the laminated sheet is wound. Note that the negative electrode 931, the positive electrode 932, and the separator 933 may be stacked more than once.
  • a secondary battery 913 having a wound body 950a as shown in FIGS. 9A to 9C may be used.
  • a wound body 950 a illustrated in FIG. 9A includes a negative electrode 931 , a positive electrode 932 , and a separator 933 .
  • the negative electrode 931 has a negative electrode active material layer 931a.
  • the positive electrode 932 has a positive electrode active material layer 932a.
  • the secondary battery 913 can have high capacity, high charge/discharge capacity, and excellent cycle characteristics.
  • the separator 933 has a wider width than the negative electrode active material layer 931a and the positive electrode active material layer 932a, and is wound so as to overlap with the negative electrode active material layer 931a and the positive electrode active material layer 932a.
  • the width of the negative electrode active material layer 931a is wider than that of the positive electrode active material layer 932a.
  • the wound body 950a having such a shape is preferable because of its good safety and productivity.
  • negative electrode 931 is electrically connected to terminal 951 .
  • Terminal 951 is electrically connected to terminal 911a.
  • the positive electrode 932 is electrically connected to the terminal 952 .
  • Terminal 952 is electrically connected to terminal 911b.
  • the casing 930 covers the wound body 950 a and the liquid electrolyte to form the secondary battery 913 .
  • the housing 930 is preferably provided with a safety valve, an overcurrent protection element, and the like.
  • the safety valve is a valve that opens the interior of housing 930 at a predetermined internal pressure in order to prevent battery explosion.
  • the secondary battery 913 may have multiple wound bodies 950a. By using a plurality of wound bodies 950a, the secondary battery 913 with higher charge/discharge capacity can be obtained.
  • the description of the secondary battery 913 shown in FIGS. 8A to 8C can be referred to.
  • FIGS. 10A and 10B show an example of an external view of an example of a laminated secondary battery.
  • 10A and 10B have a positive electrode 503, a negative electrode 506, a separator 507, an outer package 509, a positive electrode lead electrode 510 and a negative electrode lead electrode 511.
  • FIG. 10A and 10B have a positive electrode 503, a negative electrode 506, a separator 507, an outer package 509, a positive electrode lead electrode 510 and a negative electrode lead electrode 511.
  • FIG. 11A shows an external view of the positive electrode 503 and the negative electrode 506.
  • the positive electrode 503 has a positive electrode current collector 501 , and the positive electrode active material layer 502 is formed on the surface of the positive electrode current collector 501 .
  • the positive electrode 503 has a region where the positive electrode current collector 501 is partially exposed (hereinafter referred to as a tab region).
  • the negative electrode 506 has a negative electrode current collector 504 , and the negative electrode active material layer 505 is formed on the surface of the negative electrode current collector 504 .
  • the negative electrode 506 has a region where the negative electrode current collector 504 is partially exposed, that is, a tab region.
  • the area and shape of the tab regions of the positive and negative electrodes are not limited to the example shown in FIG. 11A.
  • FIG. 11B shows negative electrode 506, separator 507 and positive electrode 503 stacked.
  • an example is shown in which five sets of negative electrodes and four sets of positive electrodes are used. It can also be called a laminate consisting of a negative electrode, a separator, and a positive electrode.
  • the tab regions of the positive electrode 503 are joined together, and the positive electrode lead electrode 510 is joined to the tab region of the outermost positive electrode.
  • For joining for example, ultrasonic welding or the like may be used.
  • bonding between the tab regions of the negative electrode 506 and bonding of the negative electrode lead electrode 511 to the tab region of the outermost negative electrode are performed.
  • the negative electrode 506 , the separator 507 , and the positive electrode 503 are arranged over the exterior body 509 .
  • the exterior body 509 is folded at the portion indicated by the broken line. After that, the outer peripheral portion of the exterior body 509 is joined. For example, thermocompression bonding or the like may be used for joining. At this time, a region (hereinafter referred to as an introduction port) that is not joined is provided in a part (or one side) of the exterior body 509 so that a liquid electrolyte can be introduced later.
  • an introduction port a region (hereinafter referred to as an introduction port) that is not joined is provided in a part (or one side) of the exterior body 509 so that a liquid electrolyte can be introduced later.
  • a liquid electrolyte (not shown) is introduced into the exterior body 509 through an inlet provided in the exterior body 509 . It is preferable to introduce the liquid electrolyte under a reduced pressure atmosphere or an inert atmosphere. And finally, the inlet is joined. In this manner, a laminated secondary battery 500 can be manufactured.
  • the secondary battery 500 can have high capacity, high charge/discharge capacity, and excellent cycle characteristics.
  • ⁇ Battery pack> An example of a secondary battery pack of one embodiment of the present invention that can be wirelessly charged using an antenna will be described with reference to FIGS. 12A to 12C.
  • FIG. 12A is a diagram showing the appearance of the secondary battery pack 531, which has a thin rectangular parallelepiped shape (also called a thick flat plate shape).
  • FIG. 12B is a diagram illustrating the configuration of the secondary battery pack 531. As shown in FIG.
  • the secondary battery pack 531 has a circuit board 540 and a secondary battery 513 .
  • a label 529 is attached to the secondary battery 513 .
  • Circuit board 540 is secured by seal 515 .
  • the secondary battery pack 531 has an antenna 517 .
  • the inside of the secondary battery 513 may have a structure having a wound body or a structure having a laminated body.
  • the secondary battery pack 531 has a control circuit 590 on a circuit board 540 as shown in FIG. 12B. Also, the circuit board 540 is electrically connected to the terminals 514 . In addition, the circuit board 540 is electrically connected to the antenna 517 , one of the positive and negative leads 551 and the other of the positive and negative leads 552 of the secondary battery 513 .
  • FIG. 12C it may have a circuit system 590a provided on circuit board 540 and a circuit system 590b electrically connected to circuit board 540 via terminals 514.
  • FIG. 12C it may have a circuit system 590a provided on circuit board 540 and a circuit system 590b electrically connected to circuit board 540 via terminals 514.
  • FIG. 12C it may have a circuit system 590a provided on circuit board 540 and a circuit system 590b electrically connected to circuit board 540 via terminals 514.
  • antenna 517 is not limited to a coil shape, and may have a linear shape or a plate shape, for example. Further, antennas such as planar antennas, aperture antennas, traveling wave antennas, EH antennas, magnetic field antennas, and dielectric antennas may be used. Alternatively, antenna 517 may be a planar conductor. This flat conductor can function as one of conductors for electric field coupling. That is, the antenna 517 may function as one of the two conductors of the capacitor. As a result, electric power can be exchanged not only by electromagnetic fields and magnetic fields, but also by electric fields.
  • Secondary battery pack 531 has layer 519 between antenna 517 and secondary battery 513 .
  • the layer 519 has a function of shielding an electromagnetic field generated by the secondary battery 513, for example.
  • a magnetic material for example, can be used as the layer 519 .
  • secondary battery 400 of one embodiment of the present invention includes positive electrode 410 , solid electrolyte layer 420 , and negative electrode 430 .
  • the positive electrode 410 has a positive electrode current collector 413 and a positive electrode active material layer 414 .
  • a positive electrode active material layer 414 includes a positive electrode active material 411 and a solid electrolyte 421 .
  • the positive electrode active material described in Embodiment 1 is used as the positive electrode active material 411 .
  • the positive electrode active material layer 414 may contain a conductive aid and a binder.
  • Solid electrolyte layer 420 has solid electrolyte 421 .
  • Solid electrolyte layer 420 is a region located between positive electrode 410 and negative electrode 430 and having neither positive electrode active material 411 nor negative electrode active material 431 .
  • the negative electrode 430 has a negative electrode current collector 433 and a negative electrode active material layer 434 .
  • a negative electrode active material layer 434 includes a negative electrode active material 431 and a solid electrolyte 421 . Further, the negative electrode active material layer 434 may contain a conductive aid and a binder. Note that when metal lithium is used as the negative electrode active material 431, particles do not need to be formed, and thus the negative electrode 430 without the solid electrolyte 421 can be formed as shown in FIG. 13B. Further, FIG. 13B shows an example in which the negative electrode active material 431 is formed as a film using a sputtering method. The use of metallic lithium for the negative electrode 430 is preferable because the energy density of the secondary battery 400 can be improved.
  • solid electrolyte 421 included in the solid electrolyte layer 420 for example, a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a halide-based solid electrolyte, or the like can be used.
  • Sulfide-based solid electrolytes include thiolysicone - based ( Li10GeP2S12 , Li3.25Ge0.25P0.75S4 , etc. ) , sulfide glass ( 70Li2S , 30P2S5 , 30Li2 S.26B2S3.44LiI , 63Li2S.36SiS2.1Li3PO4 , 57Li2S.38SiS2.5Li4SiO4 , 50Li2S.50GeS2 , etc. ) , sulfide crystallized glass ( Li7 P 3 S 11 , Li 3.25 P 0.95 S 4 etc.).
  • a sulfide-based solid electrolyte has advantages such as being a material with high conductivity, being able to be synthesized at a low temperature, and being relatively soft so that a conductive path is easily maintained even after charging and discharging.
  • oxide-based solid electrolytes examples include materials having a perovskite crystal structure (La2 /3- xLi3xTiO3 , etc. ) and materials having a NASICON crystal structure ( Li1- YAlYTi2 -Y ( PO4 ) 3, etc.), materials having a garnet-type crystal structure ( Li7La3Zr2O12 , etc. ), materials having a LISICON-type crystal structure ( Li14ZnGe4O16 , etc. ), LLZO ( Li7La3Zr2O 12 ), oxide glass (Li3PO4-Li4SiO4, 50Li4SiO4, 50Li3BO3 , etc. ) , oxide crystallized glass ( Li1.07Al0.69Ti1.46 ( PO4 ) 3 , Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 etc.). Oxide-based solid electrolytes have the advantage of being stable in the air.
  • Halide-based solid electrolytes include LiAlCl 4 , Li 3 InBr 6 , LiF, LiCl, LiBr, LiI, and the like. Composite materials in which pores of porous aluminum oxide or porous silica are filled with these halide-based solid electrolytes can also be used as solid electrolytes.
  • Li1 + xAlxTi2 -x ( PO4 ) 3 (0 ⁇ x ⁇ 1) (hereinafter referred to as LATP) having a NASICON-type crystal structure is aluminum and titanium in the secondary battery 400 of one embodiment of the present invention. Since it contains an element that may be contained in the positive electrode active material used in , a synergistic effect can be expected for improving cycle characteristics, which is preferable. Also, an improvement in productivity can be expected by reducing the number of processes.
  • a NASICON-type crystal structure is a compound represented by M 2 (XO 4 ) 3 (M: transition metal, X: S, P, As, Mo, W, etc.), and MO 6 It has a structure in which octahedrons and XO 4 tetrahedrons share vertices and are three-dimensionally arranged.
  • Exterior body and shape of secondary battery Various materials and shapes can be used for the exterior body of the secondary battery 400 of one embodiment of the present invention, but it preferably has a function of pressurizing the positive electrode, the solid electrolyte layer, and the negative electrode.
  • FIG. 14 is an example of a cell for evaluating materials for an all-solid-state battery.
  • FIG. 14A is a schematic cross-sectional view of the evaluation cell.
  • the evaluation cell has a lower member 761, an upper member 762, and a fixing screw or wing nut 764 for fixing them.
  • a plate 753 is pressed to secure the evaluation material.
  • An insulator 766 is provided between a lower member 761 made of stainless steel and an upper member 762 .
  • An O-ring 765 is provided between the upper member 762 and the set screw 763 for sealing.
  • the evaluation material is placed on an electrode plate 751, surrounded by an insulating tube 752, and pressed from above by an electrode plate 753. As shown in FIG. FIG. 14B is an enlarged perspective view of the periphery of this evaluation material.
  • FIG. 14C As an evaluation material, an example of lamination of a positive electrode 750a, a solid electrolyte layer 750b, and a negative electrode 750c is shown, and a cross-sectional view thereof is shown in FIG. 14C. The same symbols are used for the same portions in FIGS. 14A to 14C.
  • the electrode plate 751 and the lower member 761 electrically connected to the positive electrode 750a correspond to a positive electrode terminal. It can be said that the electrode plate 753 and the upper member 762 electrically connected to the negative electrode 750c correspond to a negative electrode terminal.
  • the electrical resistance can be measured while pressing the evaluation material through the electrode plate 751 and the electrode plate 753 .
  • a package having excellent airtightness As the exterior body of the secondary battery.
  • a ceramic package or resin package can be used.
  • sealing the exterior body it is preferable to shut off the outside air and perform the sealing in a closed atmosphere, for example, in a glove box.
  • FIG. 15A shows a perspective view of a secondary battery of one embodiment of the present invention having an exterior body and a shape different from those in FIG.
  • the secondary battery of FIG. 15A has external electrodes 771 and 772 and is sealed with an exterior body having a plurality of package members.
  • FIG. 15B shows an example of a cross section taken along the dashed line in FIG. 15A.
  • a laminate having a positive electrode 750a, a solid electrolyte layer 750b, and a negative electrode 750c includes a package member 770a in which an electrode layer 773a is provided on a flat plate, a frame-shaped package member 770b, and a package member 770c in which an electrode layer 773b is provided on a flat plate. , and has a sealed structure.
  • the package members 770a, 770b, 770c can be made of insulating materials such as resin materials and ceramics.
  • the external electrode 771 is electrically connected to the positive electrode 750a through the electrode layer 773a and functions as a positive electrode terminal.
  • the external electrode 772 is electrically connected to the negative electrode 750c through the electrode layer 773b and functions as a negative electrode terminal.
  • FIG. 16C shows an example of application to an electric vehicle (EV).
  • EV electric vehicle
  • the electric vehicle is provided with first batteries 1301a and 1301b as secondary batteries for main driving, and a second battery 1311 that supplies power to an inverter 1312 that starts the motor 1304 .
  • the second battery 1311 is also called cranking battery (also called starter battery).
  • the second battery 1311 only needs to have a high output and does not need a large capacity so much, and the capacity of the second battery 1311 is smaller than that of the first batteries 1301a and 1301b.
  • the internal structure of the first battery 1301a may be the wound type shown in FIG. 8C or 9A, or the laminated type shown in FIG. 10A or 10B. Further, the all-solid-state battery of Embodiment 5 may be used as the first battery 1301a. By using the all-solid-state battery of Embodiment 5 for the first battery 1301a, the capacity can be increased, the safety can be improved, and the size and weight can be reduced.
  • This embodiment mode shows an example in which two first batteries 1301a and 1301b are connected in parallel, but three or more batteries may be connected in parallel. Further, if the first battery 1301a can store sufficient electric power, the first battery 1301b may be omitted. A large amount of electric power can be extracted by forming a battery pack including a plurality of secondary batteries. A plurality of secondary batteries may be connected in parallel, may be connected in series, or may be connected in series after being connected in parallel. A plurality of secondary batteries is also called an assembled battery.
  • a secondary battery for vehicle has a service plug or a circuit breaker that can cut off high voltage without using a tool in order to cut off power from a plurality of secondary batteries.
  • the power of the first batteries 1301a and 1301b is mainly used to rotate the motor 1304, but is supplied to the 42V in-vehicle components (electric power steering 1307, heater 1308, defogger 1309) via the DCDC circuit 1306. supply power.
  • the first battery 1301a is also used to rotate the rear motor 1317 when the rear wheel has the rear motor 1317 .
  • the second battery 1311 supplies power to 14V in-vehicle components (audio 1313, power window 1314, lamps 1315) through the DCDC circuit 1310.
  • FIG. 14V in-vehicle components audio 1313, power window 1314, lamps 1315.
  • the first battery 1301a will be described with reference to FIG. 16A.
  • FIG. 16A shows an example in which nine prismatic secondary batteries 1300 are used as one battery pack 1415 . Also, nine square secondary batteries 1300 are connected in series, one electrode is fixed by a fixing portion 1413 made of an insulator, and the other electrode is fixed by a fixing portion 1414 made of an insulator. In this embodiment mode, an example of fixing by fixing portions 1413 and 1414 is shown; Since it is assumed that the vehicle is subject to vibration or shaking from the outside (road surface), it is preferable to fix a plurality of secondary batteries with the fixing portions 1413 and 1414 and the battery housing box. One electrode is electrically connected to the control circuit portion 1320 through a wiring 1421 . The other electrode is electrically connected to the control circuit section 1320 by wiring 1422 .
  • FIG. 16B shows an example of a block diagram of the battery pack 1415 shown in FIG. 16A.
  • the control circuit unit 1320 includes a switch unit 1324 including at least a switch for preventing overcharge and a switch for preventing overdischarge, a control circuit 1322 for controlling the switch unit 1324, a voltage measurement unit for the first battery 1301a, have
  • the control circuit unit 1320 is set with an upper limit voltage and a lower limit voltage of the secondary battery to be used, and limits the upper limit of the current from the outside and the upper limit of the output current to the outside.
  • the range from the lower limit voltage to the upper limit voltage of the secondary battery is within the voltage range recommended for use.
  • the control circuit section 1320 controls the switch section 1324 to prevent over-discharging and over-charging, it can also be called a protection circuit.
  • control circuit 1322 detects a voltage that is likely to cause overcharging
  • the switch of the switch section 1324 is turned off to cut off the current.
  • a PTC element may be provided in the charging/discharging path to provide a function of interrupting the current according to the temperature rise.
  • the control circuit section 1320 also has an external terminal 1325 (+IN) and an external terminal 1326 (-IN).
  • the switch portion 1324 can be configured by combining an n-channel transistor and a p-channel transistor.
  • the switch unit 1324 is not limited to a switch having a Si transistor using single crystal silicon. indium), SiC (silicon carbide), ZnSe (zinc selenide), GaN (gallium nitride), and GaOx (gallium oxide; x is a real number greater than 0).
  • the first batteries 1301a and 1301b mainly supply power to 42V system (high voltage system) in-vehicle equipment, and the second battery 1311 supplies power to 14V system (low voltage system) in-vehicle equipment.
  • the second battery 1311 is often adopted as a lead-acid battery because of its cost advantage.
  • Lead-acid batteries have the drawback of being more susceptible to deterioration due to a phenomenon called sulfation, which is more self-discharging than lithium-ion secondary batteries.
  • Using a lithium-ion secondary battery as the second battery 1311 has the advantage of being maintenance-free.
  • the second battery 1311 that starts the inverter becomes inoperable, the second battery 1311 is lead-free in order to prevent the motor from being unable to start even if the first batteries 1301a and 1301b have remaining capacity.
  • power is supplied from the first battery to the second battery and charged so as to always maintain a fully charged state.
  • the second battery 1311 may use a lead-acid battery, an all-solid battery, or an electric double layer capacitor.
  • the all-solid-state battery of Embodiment 3 may be used.
  • Regenerative energy generated by the rotation of tire 1316 is sent to motor 1304 via gear 1305 and charged to second battery 1311 via control circuit section 1321 from motor controller 1303 and battery controller 1302 .
  • the battery controller 1302 charges the first battery 1301 a through the control circuit unit 1320 .
  • the battery controller 1302 charges the first battery 1301 b through the control circuit unit 1320 . In order to efficiently charge the regenerated energy, it is desirable that the first batteries 1301a and 1301b be capable of rapid charging.
  • the battery controller 1302 can set the charging voltage and charging current of the first batteries 1301a, 1301b.
  • the battery controller 1302 can set charging conditions according to the charging characteristics of the secondary battery to be used and perform rapid charging.
  • the outlet of the charger or the connection cable of the charger is electrically connected to the battery controller 1302 .
  • Electric power supplied from an external charger charges the first batteries 1301 a and 1301 b via the battery controller 1302 .
  • Some chargers are provided with a control circuit and do not use the function of the battery controller 1302. In order to prevent overcharging, the first batteries 1301a and 1301b are charged via the control circuit unit 1320. is preferred.
  • the connection cable or the connection cable of the charger is provided with the control circuit.
  • the control circuit section 1320 is sometimes called an ECU (Electronic Control Unit).
  • the ECU is connected to a CAN (Controller Area Network) provided in the electric vehicle.
  • CAN is one of serial communication standards used as an in-vehicle LAN.
  • the ECU includes a microcomputer.
  • the ECU uses a CPU or a GPU.
  • External chargers installed at charging stations include 100V outlet, 200V outlet, 3-phase 200V and 50kW. Also, the battery can be charged by receiving power supply from an external charging facility by a non-contact power supply method or the like.
  • the positive electrode active material described in Embodiment 1 is used in the secondary battery of this embodiment described above. Furthermore, by using graphene as a conductive agent, even if the electrode layer is thickened and the amount supported is increased, the decrease in capacity can be suppressed and the high capacity can be maintained. realizable. To provide a vehicle which is effective especially for a secondary battery used in a vehicle and has a long cruising distance, specifically, a traveling distance of 500 km or more per charge without increasing the weight ratio of the secondary battery to the total weight of the vehicle. be able to.
  • the operating voltage of the secondary battery can be increased by using the positive electrode active material described in Embodiment 1, and as the charging voltage increases, the usable capacity increases. can be increased. Further, by using the positive electrode active material described in Embodiment 1 for the positive electrode, a secondary battery for vehicles with excellent cycle characteristics can be provided.
  • next-generation vehicles such as hybrid vehicles (HV), electric vehicles (EV), or plug-in hybrid vehicles (PHV) can be used.
  • HV hybrid vehicles
  • EV electric vehicles
  • PSV plug-in hybrid vehicles
  • a clean energy vehicle can be realized.
  • a secondary battery can also be mounted on a transport vehicle for a planetary probe or a spacecraft.
  • the secondary battery of one embodiment of the present invention can be a high-capacity secondary battery. Therefore, the secondary battery of one embodiment of the present invention is suitable for miniaturization and weight reduction, and can be suitably used for transportation vehicles.
  • a vehicle 2001 shown in FIG. 17A is an electric vehicle that uses an electric motor as a power source for running. Alternatively, it is a hybrid vehicle in which an electric motor and an engine can be appropriately selected and used as power sources for running.
  • a secondary battery is mounted in a vehicle, an example of the secondary battery described in Embodiment 4 is installed at one or more places.
  • a car 2001 shown in FIG. 17A has a battery pack 2200, and the battery pack has a secondary battery module to which a plurality of secondary batteries are connected. Furthermore, it is preferable to have a charging control device electrically connected to the secondary battery module.
  • the vehicle 2001 can be charged by receiving power from an external charging facility by a plug-in system or a non-contact power supply system to the secondary battery of the vehicle 2001 .
  • the charging method and the standard of the connector may be appropriately performed by a predetermined method such as CHAdeMO (registered trademark) or Combo.
  • the charging device may be a charging station provided in a commercial facility, or may be a household power source.
  • plug-in technology can charge a power storage device mounted on the automobile 2001 by power supply from the outside. Charging can be performed by converting AC power into DC power via a conversion device such as an ACDC converter.
  • the power receiving device can be mounted on a vehicle, and power can be supplied from a power transmission device on the ground in a non-contact manner for charging.
  • this non-contact power supply system it is possible to charge the vehicle not only while the vehicle is stopped but also while the vehicle is running by installing a power transmission device on the road or the outer wall.
  • power may be transmitted and received between two vehicles.
  • a solar battery may be provided on the exterior of the vehicle, and the secondary battery may be charged while the vehicle is stopped and while the vehicle is running.
  • An electromagnetic induction method or a magnetic resonance method can be used for such contactless power supply.
  • FIG. 17B shows a large transport vehicle 2002 with electrically controlled motors as an example of a transport vehicle.
  • the secondary battery module of the transportation vehicle 2002 has a maximum voltage of 170 V, for example, a four-cell unit of secondary batteries having a nominal voltage of 3.0 V or more and 5.0 V or less, and 48 cells connected in series. Except for the number of secondary batteries forming the secondary battery module of the battery pack 2201, the function is the same as that of FIG. 17A, so the explanation is omitted.
  • FIG. 17C shows, as an example, a large transport vehicle 2003 with electrically controlled motors.
  • the secondary battery module of the transportation vehicle 2003 has a maximum voltage of 600 V, for example, a hundred or more secondary batteries with a nominal voltage of 3.0 V or more and 5.0 V or less connected in series.
  • a secondary battery using the positive electrode active material shown in Embodiment 1 as a positive electrode it is possible to manufacture a secondary battery with excellent rate characteristics and charge/discharge cycle characteristics, and improve the performance of the transport vehicle 2003. It can contribute to longer life. 17A except that the number of secondary batteries forming the secondary battery module of the battery pack 2202 is different, the description is omitted.
  • FIG. 17D shows an aircraft 2004 having an engine that burns fuel as an example. Since the aircraft 2004 shown in FIG. 17D has wheels for takeoff and landing, it can be said to be part of a transportation vehicle. It has a battery pack 2203 including a controller.
  • the secondary battery module of the aircraft 2004 has a maximum voltage of 32V, for example, eight 4V secondary batteries connected in series. Except for the number of secondary batteries forming the secondary battery module of the battery pack 2203, the function is the same as that of FIG. 17A, so the explanation is omitted.
  • a house illustrated in FIG. 18A includes a power storage device 2612 including a secondary battery that is one embodiment of the present invention and a solar panel 2610 .
  • the power storage device 2612 is electrically connected to the solar panel 2610 through a wiring 2611 or the like. Alternatively, the power storage device 2612 and the ground-mounted charging device 2604 may be electrically connected.
  • a power storage device 2612 can be charged with power obtained from the solar panel 2610 . Electric power stored in power storage device 2612 can be used to charge a secondary battery of vehicle 2603 via charging device 2604 .
  • Power storage device 2612 is preferably installed in the underfloor space. By installing in the space under the floor, the space above the floor can be effectively used. Alternatively, power storage device 2612 may be installed on the floor.
  • the power stored in the power storage device 2612 can also supply power to other electronic devices in the house. Therefore, the use of the power storage device 2612 according to one embodiment of the present invention as an uninterruptible power supply makes it possible to use the electronic device even when power cannot be supplied from a commercial power supply due to a power failure.
  • FIG. 18B illustrates an example of a power storage device according to one embodiment of the present invention.
  • a power storage device 791 according to one embodiment of the present invention is installed in an underfloor space 796 of a building 799 .
  • the power storage device 791 can have high discharge capacity.
  • a control device 790 is installed in the power storage device 791, and the control device 790 is connected to the distribution board 703, the power storage controller 705 (also referred to as a control device), the display 706, and the router 709 by wiring. electrically connected.
  • Power is sent from commercial power supply 701 to distribution board 703 via drop wire attachment 710 .
  • Electric power is sent to the distribution board 703 from the power storage device 791 and the commercial power supply 701, and the distribution board 703 distributes the sent power to the general load via an outlet (not shown). 707 and power storage system load 708 .
  • General loads 707 are, for example, electronic devices such as televisions and personal computers
  • power storage system loads 708 are, for example, electronic devices such as microwave ovens, refrigerators, and air conditioners.
  • the power storage controller 705 has a measurement unit 711 , a prediction unit 712 and a planning unit 713 .
  • the measuring unit 711 has a function of measuring the amount of electric power consumed by the general load 707 and the power storage system load 708 during a day (for example, from 00:00 to 24:00).
  • the measurement unit 711 may also have a function of measuring the amount of power in the power storage device 791 and the amount of power supplied from the commercial power source 701 .
  • the prediction unit 712 predicts the demand to be consumed by the general load 707 and the storage system load 708 during the next day based on the amount of power consumed by the general load 707 and the storage system load 708 during the day. It has a function of predicting power consumption.
  • the planning unit 713 also has a function of planning charging and discharging of the power storage device 791 based on the amount of power demand predicted by the prediction unit 712 .
  • the amount of electric power consumed by the general load 707 and the power storage system load 708 measured by the measuring unit 711 can be checked on the display 706 .
  • the amount of power demand predicted by the prediction unit 712 for each time period (or for each hour) can be confirmed using the display 706, the electronic device, and the portable electronic terminal.
  • FIG. 19A illustrates an example of an electric bicycle using the power storage device of one embodiment of the present invention.
  • the power storage device of one embodiment of the present invention can be applied to the electric bicycle 8700 illustrated in FIG. 19A.
  • a power storage device of one embodiment of the present invention includes, for example, a plurality of storage batteries and a protection circuit.
  • Electric bicycle 8700 includes power storage device 8702 .
  • the power storage device 8702 can supply electricity to a motor that assists the driver. Also, the power storage device 8702 is portable, and is shown removed from the bicycle in FIG. 19B.
  • the power storage device 8702 includes a plurality of storage batteries 8701 included in the power storage device of one embodiment of the present invention, and the remaining battery level can be displayed on a display portion 8703 .
  • the power storage device 8702 also includes a control circuit 8704 capable of controlling charging of the secondary battery or detecting an abnormality, one example of which is shown in Embodiment 6.
  • the control circuit 8704 is electrically connected to the positive and negative electrodes of the storage battery 8701 .
  • control circuit 8704 may be provided with the small solid secondary battery shown in FIGS. 15A and 15B.
  • the small solid secondary battery shown in FIGS. 15A and 15B in the control circuit 8704, power can be supplied to hold data in the memory circuit included in the control circuit 8704 for a long time.
  • a synergistic effect of safety can be obtained by combining the secondary battery in which the positive electrode active material described in Embodiment 1 is used for the positive electrode.
  • FIG. 19C illustrates an example of a two-wheeled vehicle using the power storage device of one embodiment of the present invention.
  • a scooter 8600 shown in FIG. The power storage device 8602 can supply electricity to the turn signal lights 8603 .
  • the power storage device 8602 in which a plurality of secondary batteries in which the positive electrode active material described in Embodiment 1 is used for the positive electrode is housed can have a high capacity and can contribute to miniaturization.
  • the scooter 8600 shown in FIG. 19C can store a power storage device 8602 in the underseat storage 8604 .
  • the power storage device 8602 can be stored in the underseat storage 8604 even if the underseat storage 8604 is small.
  • FIG. 7 An example of mounting a secondary battery, which is one embodiment of the present invention, in an electronic device will be described.
  • electronic devices that implement secondary batteries include television devices (also referred to as televisions or television receivers), monitors for computers, digital cameras, digital video cameras, digital photo frames, mobile phones (mobile phones, Also referred to as a mobile phone device), a portable game machine, a personal digital assistant, a sound reproducing device, a large game machine such as a pachinko machine, and the like.
  • Portable information terminals include notebook personal computers, tablet terminals, electronic book terminals, mobile phones, and the like.
  • FIG. 20A shows an example of a mobile phone.
  • a mobile phone 2100 includes a display unit 2102 incorporated in a housing 2101, operation buttons 2103, an external connection port 2104, a speaker 2105, a microphone 2106, and the like.
  • the mobile phone 2100 has a secondary battery 2107 .
  • the secondary battery 2107 By including the secondary battery 2107 in which the positive electrode active material described in Embodiment 1 is used for the positive electrode, the capacity can be increased, and a structure that can save space due to the downsizing of the housing can be realized. can.
  • the mobile phone 2100 is capable of running a variety of applications such as mobile telephony, e-mail, text viewing and composition, music playback, Internet communication, computer games, and the like.
  • the operation button 2103 can have various functions such as time setting, power on/off operation, wireless communication on/off operation, manner mode execution/cancellation, and power saving mode execution/cancellation.
  • the operating system installed in the mobile phone 2100 can freely set the functions of the operation buttons 2103 .
  • mobile phone 2100 is capable of performing short-range wireless communication that is standardized. For example, by intercommunicating with a headset capable of wireless communication, hands-free communication is also possible.
  • the mobile phone 2100 has an external connection port 2104 and can directly exchange data with another information terminal via a connector. Also, charging can be performed via the external connection port 2104 . Note that the charging operation may be performed by wireless power supply without using the external connection port 2104 .
  • Mobile phone 2100 preferably has a sensor.
  • sensors for example, a fingerprint sensor, a pulse sensor, a human body sensor such as a body temperature sensor, a touch sensor, a pressure sensor, an acceleration sensor, etc. are preferably mounted.
  • FIG. 20B is an unmanned aerial vehicle 2300 with multiple rotors 2302 .
  • Unmanned aerial vehicle 2300 may also be referred to as a drone.
  • Unmanned aerial vehicle 2300 has a secondary battery 2301 that is one embodiment of the present invention, a camera 2303, and an antenna (not shown).
  • Unmanned aerial vehicle 2300 can be remotely operated via an antenna.
  • the secondary battery using the positive electrode active material described in Embodiment 1 for the positive electrode has a high energy density and is highly safe. It is suitable as a secondary battery for
  • FIG. 20C shows an example of a robot.
  • a robot 6400 shown in FIG. 20C includes a secondary battery 6409, an illuminance sensor 6401, a microphone 6402, an upper camera 6403, a speaker 6404, a display unit 6405, a lower camera 6406, an obstacle sensor 6407, a moving mechanism 6408, an arithmetic device, and the like.
  • a microphone 6402 has a function of detecting a user's speech, environmental sounds, and the like. Also, the speaker 6404 has a function of emitting sound. Robot 6400 can communicate with a user using microphone 6402 and speaker 6404 .
  • the display unit 6405 has a function of displaying various information.
  • the robot 6400 can display information desired by the user on the display unit 6405 .
  • the display portion 6405 may include a touch panel. Further, the display unit 6405 may be a detachable information terminal, and by installing it at a fixed position of the robot 6400, charging and data transfer are possible.
  • Upper camera 6403 and lower camera 6406 have the function of capturing images of the surroundings of robot 6400 .
  • the obstacle sensor 6407 can detect the presence or absence of an obstacle in the direction in which the robot 6400 moves forward using the movement mechanism 6408 .
  • Robot 6400 uses upper camera 6403, lower camera 6406, and obstacle sensor 6407 to recognize the surrounding environment and can move safely.
  • the robot 6400 includes a secondary battery 6409 according to one embodiment of the present invention and a semiconductor device or an electronic component in its internal region.
  • a secondary battery using the positive electrode active material described in Embodiment 1 for a positive electrode has a high energy density and is highly safe. It is suitable as the secondary battery 6409 .
  • FIG. 20D shows an example of a cleaning robot.
  • the cleaning robot 6300 has a display unit 6302 arranged on the upper surface of a housing 6301, a plurality of cameras 6303 arranged on the side surfaces, a brush 6304, an operation button 6305, a secondary battery 6306, various sensors, and the like.
  • the cleaning robot 6300 is equipped with tires, a suction port, and the like.
  • the cleaning robot 6300 can run by itself, detect dust 6310, and suck the dust from a suction port provided on the bottom surface.
  • the cleaning robot 6300 can analyze images captured by the camera 6303 and determine the presence or absence of obstacles such as walls, furniture, or steps. Further, when an object such as wiring that is likely to get entangled in the brush 6304 is detected by image analysis, the rotation of the brush 6304 can be stopped.
  • Cleaning robot 6300 includes a secondary battery 6306 according to one embodiment of the present invention and a semiconductor device or an electronic component in its internal region.
  • the secondary battery using the positive electrode active material described in Embodiment 1 for the positive electrode has a high energy density and is highly safe. It is suitable as the secondary battery 6306 to
  • a lithium composite oxide (Li 0.95 Ni 0 .8 Co 0.1 Mn 0.1 O 2 ) was formed.
  • a half cell was assembled using the above lithium composite oxide as a positive electrode active material, and battery characteristics were evaluated. Evaluation of battery characteristics using a half cell is a suitable evaluation method for verifying the characteristics of the positive electrode active material.
  • step S201 an aqueous solution A in which nickel sulfate, cobalt sulfate, manganese sulfate, and glycine are dissolved in pure water is prepared.
  • the Ni ion concentration was 2.4 mol/L
  • the Co ion concentration was 0.3 mol/L
  • the Mn ion concentration was 0.3 mol/L
  • the glycine concentration was 0.1 mol/L.
  • the neighborhood refers to a value that is 0.8 times or more and 1.2 times or less of that value.
  • step S201 sodium hydroxide was prepared and an aqueous solution B was prepared by dissolving this in pure water.
  • Aqueous solution B was prepared so that the concentration of sodium hydroxide was 5 mol/L.
  • step S201 glycine was prepared and an aqueous solution C was prepared by dissolving this in pure water.
  • concentration of glycine in aqueous solution C was adjusted to 0.1 mol/L.
  • the temperature of the reaction tank 171 was set to 50° C., the pH value of the aqueous solution C was adjusted to 11.0, and the feeding of the aqueous solution A and the like was started.
  • the aqueous solution A was supplied from the tank 180 to the reaction tank 171 so as to be 0.1 mL/min.
  • a baffle plate was installed in the reaction tank 171, and stirring was continued at 1000 rpm using a stirrer.
  • the aqueous solution B was sent to the reaction tank 171 so that the pH value of the aqueous solution in the reaction tank 171 was kept constant. Further, in order to create a nitrogen atmosphere in the reaction tank 171, nitrogen was supplied from the inlet of the flask cover at a flow rate of 1 L/min and bubbled.
  • the temperature of the reaction vessel 171 was set to 25°C. As a result, a coprecipitate was deposited in the reaction tank 171 . A coprecipitate is sometimes called a precipitate.
  • the coprecipitate obtained by filtering the mixed solution was sieved using a sieve with an opening of 100 ⁇ m. Thereafter, suction filtration was performed using a suction filtration device while washing the coprecipitate in the suction funnel with pure water. This suction filtration step was repeated three times in succession. Thereafter, suction filtration was performed using a suction filtration device while washing the coprecipitate in the suction funnel with acetone. This suction filtration step was repeated twice in succession.
  • the coprecipitate after the suction filtration step was transferred to a petri dish, the petri dish was placed in a bell jar type vacuum device, the pressure was reduced until the differential pressure gauge indicated -0.1 MPa, and heating was performed at 80°C for 1 hour.
  • the heating removed impurities from the coprecipitate, such as acetone or water.
  • the heating process is sometimes called a drying process.
  • the drying step may be performed arbitrarily.
  • the coprecipitate is transferred to a vial, the vial is placed in a vacuum drying oven, the pressure is reduced until the differential pressure gauge indicates -0.1 MPa, and the temperature is reduced under three conditions of 180 ° C., 200 ° C., and 220 ° C. for 12 hours. heated.
  • the positive electrode active materials that passed through these three conditions were designated as Samples 1 to 3, respectively.
  • a positive electrode active material that was not subjected to main heating was used as a comparative example.
  • the table below lists the heating conditions for Samples 1 to 3 and Comparative Example.
  • the weight loss rate after main heating was 1.9% for sample 1, 2.1% for sample 2, and 2.3% for sample 3.
  • the heating temperature increased, the weight loss increased, and it was possible to obtain a precursor from which impurities were sufficiently removed by the main heating step.
  • hydrogen and oxygen may have been removed from the coprecipitate as water, and the heating process can be called a dehydration process.
  • the heating process can be called a dehydration process.
  • confirmation of weight reduction before and after the main heating can be considered to indicate that the impurities have been removed.
  • hydroxide with nickel, cobalt and manganese.
  • Such hydroxides are sometimes referred to as precursors.
  • lithium hydroxide pulverized and classified at 10000 rpm for 1 hour was prepared as a lithium source. Weighed so that the ratio of lithium hydroxide was 0.95 mol% with respect to the precursors corresponding to Comparative Examples and Samples 1 to 3, and kneaded at 2000 rpm for 1.5 minutes using a kneader. A mixture was prepared by mixing with precursors corresponding to 1 to 3.
  • the mixture was placed in an alumina crucible, covered with a lid, placed in a muffle furnace, and heated at 700° C. for 10 hours.
  • Oxygen was supplied to the muffle furnace at a flow rate of 5 L/min.
  • the mixture was transferred to a mortar, pulverized, and sieved.
  • the sieved mixture was placed in an alumina crucible again, placed in a muffle furnace with a lid placed thereon, and heated at 800° C. for 10 hours.
  • Oxygen was supplied to the muffle furnace at a flow rate of 5 L/min.
  • FIG. 21 shows an SEM observation image of the NCM.
  • the SEM observation in this example was carried out using a scanning electron microscope S4800 manufactured by Hitachi High-Tech Co., Ltd., under observation conditions of an acceleration voltage of 5 kV and a magnification of 1000 times (represented as 1K in the figure) and 20,000 times (represented as 20K in the figure). .
  • an acceleration voltage of 5 kV a scanning electron microscope S4800 manufactured by Hitachi High-Tech Co., Ltd.
  • a magnification of 1000 times represented as 1K in the figure
  • 20,000 times represented as 20K in the figure
  • the lower part of FIG. 21 shows an observed image of the region enclosed by the broken line in the upper part of FIG. 21 at a magnification of 20,000 times.
  • Primary particles can be confirmed in the areas enclosed by the solid lines corresponding to the samples 1 to 3 of the comparative example. From FIG. 21, it was found that samples 1 to 3 tended to have smaller primary particle sizes than the comparative example.
  • Samples 1 to 3 which are small particles, are used as the positive electrode active material, the tap density or packing density of the positive electrode is improved.
  • XRD analysis was performed on Comparative Examples, Samples 1-3. XRD measurement was performed using the following equipment and conditions.
  • XRD device D8 ADVANCE manufactured by Bruker AXS X-ray source: CuK ⁇ ray Output: 40KV, 40mA Slit width: Div. Slit, 0.5° Detector: LynxEye Scan method: 2 ⁇ / ⁇ continuous scan Measurement range (2 ⁇ ): 15° to 90° Step width (2 ⁇ ): 0.01° setting Counting time: 1 second/step Rotation of sample table: 15 rpm
  • the obtained crystallite size (nm) is shown in FIG. From FIG. 22, it was found that Samples 1 to 3 had a smaller crystallite size than Comparative Example.
  • a crystallite refers to a region that can be regarded as a single crystal, and is different from the grain size of primary grains.
  • the crystallite size of samples 1 to 3 was smaller than 174 nm of the comparative example, and satisfied 90 nm to 120 nm. Cycle stability is considered to be improved by using Samples 1 to 3, which have small particle sizes, as the positive electrode active material.
  • a positive electrode was manufactured as follows.
  • Samples 1 to 3 were prepared as positive electrode active materials for half cells.
  • AB acetylene black
  • PVDF polyvinylidene fluoride
  • a slurry was prepared by mixing a positive electrode active material, acetylene black, and PVDF as a binder.
  • the positive electrode active material, acetylene black, and PVDF were adjusted to 95:3:2 (% by weight), and NMP (N-methyl-2-pyrrolidone) as a solvent was also added.
  • Aluminum was prepared as a positive electrode current collector. The slurry was applied to a current collector. After applying the slurry to the current collector, NMP was volatilized. Then, it was pressurized at 210 kN/m using a roll press. The supported amount was about 7 mg/cm 2 .
  • Lithium metal was prepared as the counter electrode of the half cell.
  • LiPF 6 lithium hexafluorophosphate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • VC vinylene carbonate
  • ⁇ Positive electrode can and negative electrode can> The positive and negative electrode cans of the half-cell were made of stainless steel (SUS).
  • a half-cell charge-discharge cycle test was measured using a charge-discharge measurement system (TOSCAT-3100) manufactured by Toyo System Co., Ltd. as a charge-discharge measuring instrument. The performance of the positive electrode alone can be grasped by a charge-discharge cycle test using a half-cell.
  • TOSCAT-3100 charge-discharge measurement system manufactured by Toyo System Co., Ltd.
  • the rate of the charge/discharge cycle test conditions will be described.
  • the rate during discharge is called the discharge rate, which is the relative ratio of the current during discharge to the battery capacity, expressed in units of C.
  • the current corresponding to 1C is X (A).
  • the rate at the time of charging is called the charge rate.
  • the charge rate when charging at a current of 2X (A), it is said to charge at 2C, and charging at a current of X/2 (A). It is said that the battery was charged at 0.5C.
  • a combination of the charge rate and the discharge rate is referred to as the charge/discharge rate.
  • the above charge and discharge are regarded as one cycle, and the number of cycles is repeated 100 times. was defined as the discharge capacity retention (%). That is, when the charge-discharge cycle is repeated 100 times and the discharge capacity is measured for each cycle, the value of the discharge capacity measured at the 100th cycle is the maximum value of the discharge capacity in all 100 cycles (maximum discharge capacity).
  • a higher discharge capacity retention rate is desirable as a battery characteristic because a decrease in battery capacity after repeated charging and discharging is suppressed.
  • the number of cycles mentioned above is an example.
  • the charge current and discharge current are measured by an ammeter included in the charge/discharge measuring instrument, and the integrated amount of current flowing in one charge and one discharge corresponds to the charge capacity and discharge capacity, respectively.
  • the integrated amount of the discharge current that flowed in the first cycle discharge can be called the first cycle discharge capacity
  • the integrated amount of the discharge current that flowed in the 100th cycle discharge is the 100th cycle discharge. can be called capacity.
  • the temperature of the constant temperature bath in which the half-cell was placed was set at 45°C. This temperature is sometimes called the ambient temperature or the measured temperature.
  • the charging conditions are as follows: constant current charging (CC charging) with an upper limit voltage of 4.5 V and a charging rate of 0.5 C (1 C is 200 mA/g); was 0.05C, CV charging was terminated.
  • the above charging conditions are sometimes referred to as CC/CV charging.
  • the discharge conditions were a discharge rate of 0.5 C (1 C is 200 mA/g), and constant current discharge (CC discharge) was performed to a lower limit voltage of 2.5 V.
  • a rest period may be provided between discharging and the next charging, and in this example, a rest period of 10 minutes was provided. In this charge-discharge cycle test, the charge and the discharge were repeated 100 times.
  • FIG. 23 and the table below show the maximum discharge capacity (mAh/g) in the charge-discharge cycle test.
  • maximum discharge capacity mAh/g
  • two half-cells were prepared under the same conditions, and a charge-discharge cycle test was conducted under the same conditions.
  • Samples 1 to 3 have a large maximum discharge capacity, all of which are 210 mAh/g or more, preferably 220 mAh/g or more. Furthermore, Samples 1 to 3 had little variation in maximum discharge capacity, and the difference in maximum discharge capacity between the two half-cells was within 3 mAh/g, preferably within 1 mAh/g.
  • FIG. 24 shows changes in discharge capacity in the charge-discharge cycle test.
  • sample 1 is indicated by a solid line
  • sample 2 is indicated by a broken line
  • sample 3 is indicated by a dashed line. It was found that Samples 1 to 3 had high discharge capacities and did not easily decrease even when the number of cycles increased.
  • FIG. 25 shows changes in the discharge capacity retention rate in the charge-discharge cycle test.
  • sample 1 is indicated by a solid line
  • sample 2 is indicated by a broken line
  • sample 3 is indicated by a dashed line.
  • Samples 1 to 3 had a high discharge capacity retention rate of 90% or more and less than 100%.
  • FIG. 26 shows changes in average discharge voltage in the charge/discharge cycle test.
  • sample 1 is indicated by a solid line
  • sample 2 is indicated by a broken line
  • sample 3 is indicated by a dashed line.
  • Samples 1 to 3 had a high average discharge voltage of 3.75 V or more.
  • FIG. 27 shows changes in discharge energy density in the charge-discharge cycle test.
  • sample 1 is indicated by a solid line
  • sample 2 is indicated by a broken line
  • sample 3 is indicated by a dashed line.
  • Samples 1 to 3 had a high discharge energy density of 750 mWh or more.
  • Such samples 1 to 3 exhibited excellent charge-discharge cycle characteristics, and it was confirmed that sufficient discharge capacity was obtained and the reliability of the secondary battery was improved according to the present example.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne un matériau actif d'électrode positive qui a une capacité de décharge élevée. La présente invention concerne un procédé de production d'un précurseur dans lequel : une solution aqueuse, dans laquelle un sel de nickel, un sel de cobalt et un sel de manganèse sont dissous, et une solution aqueuse alcaline sont mélangées de façon à obtenir un liquide mélangé et un produit de coprécipitation ; le liquide mélangé est filtré de façon à extraire le produit de coprécipitation ; et le produit de coprécipitation est nettoyé et ensuite chauffé à une température de 130 °C à 220 °C. De plus, la présente invention concerne un matériau actif d'électrode positive qui est obtenu en : mélangeant le précurseur avec un composé de lithium de façon à former un mélange ; chauffant le mélange à une première température ; et chauffant le mélange à une seconde température qui est supérieure à la première température.
PCT/IB2022/062099 2021-12-24 2022-12-13 Procédé de production de précurseur et procédé de production de matériau actif d'électrode positive WO2023119056A1 (fr)

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