WO2023248047A1 - 正極活物質およびその作製方法および二次電池 - Google Patents

正極活物質およびその作製方法および二次電池 Download PDF

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Publication number
WO2023248047A1
WO2023248047A1 PCT/IB2023/056016 IB2023056016W WO2023248047A1 WO 2023248047 A1 WO2023248047 A1 WO 2023248047A1 IB 2023056016 W IB2023056016 W IB 2023056016W WO 2023248047 A1 WO2023248047 A1 WO 2023248047A1
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Prior art keywords
positive electrode
active material
electrode active
secondary battery
battery
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English (en)
French (fr)
Japanese (ja)
Inventor
宮入典子
吉谷友輔
平原誉士
石谷哲二
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Semiconductor Energy Laboratory Co Ltd
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Semiconductor Energy Laboratory Co Ltd
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Priority to US18/871,300 priority Critical patent/US20250349834A1/en
Priority to JP2024527890A priority patent/JPWO2023248047A1/ja
Publication of WO2023248047A1 publication Critical patent/WO2023248047A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 product, a method, or a manufacturing method. Alternatively, the invention relates to a process, machine, manufacture, or composition of matter.
  • One embodiment of the present invention relates to a power storage device including a secondary battery, a semiconductor device, a display device, a light emitting device, a lighting device, an electronic device, or a manufacturing method thereof.
  • lithium ion secondary batteries lithium ion capacitors
  • air batteries air batteries
  • all-solid-state batteries lithium ion secondary batteries
  • demand for high-output, high-capacity lithium-ion secondary batteries is rapidly expanding along with the development of the semiconductor industry, and they have become indispensable in today's information society as a source of rechargeable energy. .
  • NCM in which a large amount of nickel is used has a problem in that oxygen is easily desorbed and deterioration is likely to occur.
  • Another problem is that a phenomenon called cation mixing, in which transition metals such as nickel and manganese enter sites where lithium ions are inserted or desorbed during charging and discharging, tends to occur.
  • NCM NCM
  • Charging or discharging causes occlusion or desorption of lithium ions, causing the primary particles to expand or contract. Volume changes occur as the primary particles expand or contract, and secondary particles crack or become finer as the primary particles disaggregate.
  • One of the causes of cracking or refinement is that the a-axis or c-axis of the NCM crystal changes due to repeated charging or discharging, and the voids between primary particles become larger. Note that although the term "voids between primary particles" is used, it is not used in the sense of space; in the case of a secondary battery, an electrolytic solution is present at the position of the voids. However, in the case of an all-solid-state battery, it is a void.
  • heating is performed at a second temperature higher than the first temperature, and the mixing state of the mixture is improved by performing the heat treatment twice in total. Therefore, when a secondary battery is produced, voids in the secondary particles can be reduced. Further, crystallinity can be improved by performing the heat treatment a total of two times.
  • the range of the first heating temperature is 400°C or more and 750°C or less.
  • the range of the second heating temperature and the third heating temperature is higher than 750°C and lower than 1050°C.
  • an aqueous manganese sulfate solution or an aqueous manganese nitrate solution can be used.
  • the pH of the mixed liquid inside the reaction tank is preferably 9.0 or more and 12.0 or less, more preferably 10.0 or more and 11.5 or less.
  • a chelate aqueous solution it makes it easier to control the pH of the liquid mixture present inside the reaction tank when obtaining the cobalt compound. Further, it is preferable to use a chelate aqueous solution because it can suppress unnecessary generation of crystal nuclei and promote growth. When the generation of unnecessary nuclei is suppressed, the generation of fine particles is suppressed, so that a composite oxide with a good particle size distribution can be obtained. In addition, by using an aqueous chelate solution, the acid-base reaction can be delayed, and the reaction proceeds gradually, making it possible to obtain nearly spherical secondary particles.
  • Glycine has the effect of keeping the pH constant at a pH of 9.0 to 10.0 and around it, and by using a glycine aqueous solution as the chelate aqueous solution, the pH of the reaction tank when obtaining the above cobalt compound can be adjusted. is preferable because it becomes easier to control.
  • the glycine concentration of the glycine aqueous solution is preferably 0.05 mol/L or more and 0.09 mol/L or less in the aqueous solution.
  • the positive electrode active material obtained by the above method has secondary particles, and the secondary particles have a plurality of primary particles.
  • the positive electrode active material obtained by the above method has a crystal with a hexagonal layered structure, and the crystal is not limited to a single crystal (also called a crystallite), but in the case of a polycrystal, several crystallites are gathered together.
  • Form primary particles refers to a particle that is recognized as a single particle during SEM observation.
  • secondary particles refer to aggregates of primary particles.
  • the bonding force acting between a plurality of primary particles does not matter. It may be a covalent bond, an ionic bond, a hydrophobic interaction, a van der Waals force, or any other intermolecular interaction, or a plurality of bonding forces may be at work.
  • secondary particles When using a coprecipitation method, secondary particles may be formed.
  • the crystal having a hexagonal layered structure has one or more selected from a first transition metal, a second transition metal, and a third transition metal.
  • the first transition metal is nickel
  • the second transition metal is cobalt
  • the third transition metal is manganese
  • LiNix Co y Mn z O 2 (x>0, y> 0, z>0, 0.8 ⁇ x+y+z ⁇ 1.2)
  • NiCoMn system (also referred to as NCM)
  • the positive electrode active material has secondary particles, the secondary particles have a plurality of primary particles, and a layer containing magnesium on the surface layer of at least one primary particle among the plurality of primary particles,
  • the thickness of the layer containing magnesium is 1 nm or more and 10 nm or less.
  • a secondary battery using the above positive electrode active material is also one of the configurations disclosed in this specification.
  • a secondary battery has a positive electrode having a positive electrode active material and a negative electrode having a negative electrode active material. Furthermore, a separator is provided between the positive electrode and the negative electrode. The separator is used to prevent short circuits, and can provide a highly safe or reliable secondary battery.
  • the mixing state of the mixture is improved, and when a secondary battery is manufactured, the number of voids in the secondary particles can be reduced.
  • crystallinity can be improved by performing heat treatment three times in total: twice before addition of magnesium and once after addition. Therefore, a relatively stable positive electrode active material can be provided even after repeated charging and discharging. Alternatively, a highly safe or reliable secondary battery can be provided.
  • FIG. 1A is a schematic diagram showing the appearance of secondary particles
  • FIG. 1B is a schematic diagram showing an example of a cross section of the secondary particles
  • FIG. 2A is a diagram showing an example of a cross section of a secondary particle
  • FIG. 2B is a schematic diagram showing an example of a cross section of a secondary particle.
  • FIG. 3 is an example of a flow diagram of a manufacturing process illustrating one embodiment of the present invention.
  • FIG. 4 is an example of a flow diagram of a manufacturing process illustrating one embodiment of the present invention.
  • FIG. 5A is an exploded perspective view of a coin-type secondary battery
  • FIG. 5B is a perspective view of the coin-type secondary battery
  • FIG. 5C is a cross-sectional perspective view thereof.
  • FIG. 5A is an exploded perspective view of a coin-type secondary battery
  • FIG. 5B is a perspective view of the coin-type secondary battery
  • FIG. 5C is a cross-sectional perspective view thereof.
  • FIG. 6A shows an example of a cylindrical secondary battery.
  • FIG. 6B shows an example of a cylindrical secondary battery.
  • FIG. 6C shows an example of a plurality of cylindrical secondary batteries.
  • FIG. 6D shows an example of a power storage system including a plurality of cylindrical secondary batteries.
  • 7A and 7B are diagrams illustrating an example of a secondary battery
  • FIG. 7C is a diagram illustrating the inside of the secondary battery.
  • FIGS. 8A to 8C are diagrams illustrating examples of secondary batteries.
  • 9A and 9B are diagrams showing the appearance of the secondary battery.
  • FIGS. 10A to 10C are diagrams illustrating a method for manufacturing a secondary battery.
  • FIG. 11A is a perspective view of a battery pack showing one embodiment of the present invention, FIG.
  • FIG. 11B is a block diagram of the battery pack
  • FIG. 11C is a block diagram of a vehicle having the battery pack.
  • 12A to 12D are diagrams illustrating an example of a transportation vehicle.
  • FIG. 12E is a diagram illustrating an example of an artificial satellite.
  • FIG. 13A is a diagram showing an electric bicycle
  • FIG. 13B is a diagram showing a secondary battery of the electric bicycle
  • FIG. 13C is a diagram explaining a scooter.
  • 14A to 14D are diagrams illustrating an example of an electronic device.
  • FIG. 15 is a planar SEM photograph of the positive electrode active material of this example.
  • FIG. 16A is a diagram showing the results of a cycle test with the vertical axis representing the discharge capacity
  • FIG. 16B is a diagram showing the results of the cycle test with the vertical axis representing the capacity retention rate.
  • particles is not limited to only spherical shapes (circular cross-sectional shapes), but also includes individual particles whose cross-sectional shapes are elliptical, rectangular, trapezoidal, pyramidal, square with rounded corners, and asymmetrical. Further, individual particles may have an amorphous shape.
  • a positive electrode active material to which an additive element is added may be expressed as a composite oxide, a positive electrode material, a positive electrode material, a positive electrode material for a secondary battery, or the like.
  • the positive electrode active material of one embodiment of the present invention preferably contains a compound.
  • the positive electrode active material of one embodiment of the present invention preferably has a composition.
  • the positive electrode active material of one embodiment of the present invention preferably has a composite.
  • the characteristics of individual particles of the positive electrode active material in the following embodiments and the like, not all particles necessarily have the characteristics. For example, if 50% or more, preferably 70% or more, more preferably 90% or more of three or more randomly selected positive electrode active material particles have the characteristic, it is sufficient to have the positive electrode active material and the same. It can be said that this has the effect of improving the characteristics of the secondary battery.
  • a short circuit in the secondary battery not only causes problems in the charging and/or discharging operation of the secondary battery, but also may cause heat generation and ignition.
  • short current is suppressed even at high charging voltage. Therefore, it is possible to obtain a secondary battery that has both high discharge capacity and safety.
  • a decrease in discharge capacity due to aging treatment (which may also be called burn-in treatment) in the secondary battery manufacturing stage is not called deterioration.
  • a lithium ion secondary cell or a lithium secondary assembled battery hereinafter referred to as a lithium ion secondary battery
  • the rated capacity is based on JIS C 8711:2019 for lithium ion secondary batteries for portable devices. In the case of other lithium ion secondary batteries, they comply with not only the JIS standards mentioned above but also JIS and IEC standards for electric vehicle propulsion, industrial use, etc.
  • the state of the materials of the secondary battery before deterioration is called the initial product or initial state
  • the state after deterioration (the state when the secondary battery has a discharge capacity of less than 97% of its rated capacity) is called the initial product or initial state.
  • the positive electrode active material of a lithium ion secondary battery needs to contain a transition metal capable of redox in order to maintain charge neutrality even when lithium ions are inserted or removed.
  • the positive electrode active material 101 according to one embodiment of the present invention includes nickel, manganese, and cobalt as the transition metal M responsible for the redox reaction.
  • FIG. 1B shows an example of a schematic cross-sectional view of the positive electrode active material 101.
  • FIG. 1B illustrates several variations in the case where a layer containing magnesium is provided on the primary particles constituting the secondary particles. Some primary particles and their surface layer portions drawn out by arrows are shown in multiple locations in FIG. 1B.
  • the layer 100m containing magnesium is provided on the entire surface of the primary particles 100, and in other cases, the primary particles 100 are not provided with a layer containing magnesium. Further, layers 100m1 and 100m2 containing magnesium may be provided at both ends of the primary particles 100, respectively. Further, even if the primary particle is located in the center of the secondary particle, the layer 100m containing magnesium may be provided on the entire surface of the primary particle 100. Further, 100 m3 of a layer containing magnesium may be provided only on one surface. Moreover, 100 m4 of layers containing magnesium common to the two primary particles may be provided.
  • FIG. 2B also shows an example of a schematic cross-sectional view of the positive electrode active material 101b.
  • FIG. 2B shows an example in which a layer 100m6 containing magnesium is provided on the surface layer of the positive electrode active material 101b.
  • FIG. 2B it can be said that the surface layer portion of the positive electrode active material 101b and the layer 100m6 containing magnesium coincide with each other.
  • transition metal M sources that is, a nickel source (Ni source), a cobalt source (Co source), and a manganese source (Mn source) are prepared. It is preferable that the mixing ratio of nickel, cobalt, and manganese be such that a layered rock salt type crystal structure can be formed.
  • the raw material may be cheaper than when the positive electrode active material 101 contains a large amount of cobalt, and the charge/discharge capacity per weight may increase, which is preferable.
  • nickel preferably accounts for more than 25 atom %, more preferably 60 atom % or more, and even more preferably 80 atom % or more.
  • the content of nickel in the transition metal M is 95 atomic % or less.
  • cobalt as the transition metal M, since the average discharge voltage is high and cobalt contributes to stabilizing the layered rock-salt structure, resulting in a highly reliable secondary battery.
  • the transition metal M source is prepared as an aqueous solution containing transition metal M.
  • an aqueous solution of nickel salt can be used.
  • nickel salt for example, nickel sulfate, nickel chloride, nickel nitrate, or hydrates thereof can be used.
  • organic acid salts of nickel such as nickel acetate, or hydrates thereof can also be used.
  • an aqueous solution of nickel alkoxide or an organic nickel complex can be used as the nickel source.
  • an organic acid salt refers to a compound of an organic acid such as acetic acid, citric acid, oxalic acid, formic acid, butyric acid, and a metal.
  • an aqueous solution of cobalt salt can be used as the cobalt source.
  • cobalt salt for example, cobalt sulfate, cobalt chloride, cobalt nitrate, or hydrates thereof can be used.
  • organic acid salts of cobalt such as cobalt acetate, or hydrates thereof can also be used.
  • an aqueous solution of a cobalt alkoxide or an organic cobalt complex can be used as the cobalt source.
  • an aqueous solution of manganese salt can be used as the manganese source.
  • the manganese salt for example, manganese sulfate, manganese chloride, manganese nitrate, or an aqueous solution of a hydrate thereof can be used.
  • organic acid salts of manganese such as manganese acetate, or hydrates thereof can also be used.
  • an aqueous solution of manganese alkoxide or an organic manganese complex can be used as the manganese source.
  • an aqueous solution in which nickel sulfate, cobalt sulfate, and manganese sulfate are dissolved in pure water is prepared as a transition metal M source.
  • the aqueous solution exhibits acidity.
  • a chelating agent may be prepared.
  • Chelating agents include, for example, glycine, oxine, 1-nitroso-2-naphthol, 2-mercaptobenzothiazole, or EDTA (ethylenediaminetetraacetic acid).
  • you may use multiple types selected from glycine, oxine, 1-nitroso-2-naphthol, and 2-mercaptobenzothiazole. At least one of these is dissolved in pure water and used as a chelate aqueous solution.
  • Chelating agents are complexing agents that create chelate compounds and are preferred over common complexing agents.
  • a complexing agent may be used instead of a chelating agent, and aqueous ammonia can be used as the complexing agent.
  • a chelate aqueous solution because it can suppress unnecessary generation of crystal nuclei and promote growth. When the generation of unnecessary nuclei is suppressed, the generation of fine particles is suppressed, so that a composite hydroxide with a good particle size distribution can be obtained.
  • an aqueous chelate solution the acid-base reaction can be delayed, and the reaction proceeds gradually, making it possible to obtain nearly spherical secondary particles.
  • Glycine has the effect of keeping the pH value constant at a pH of 9 or more and 10 or less, and by using a glycine aqueous solution as the chelate aqueous solution, the pH of the reaction tank when obtaining the above composite hydroxide 98 can be adjusted. This is preferable because it is easier to control.
  • an alkaline solution is prepared.
  • an aqueous solution containing sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonia can be used.
  • An aqueous solution in which these are dissolved using pure water can be used.
  • it may be an aqueous solution in which multiple types selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia are dissolved in pure water.
  • the pure water preferably used for the transition metal M source and alkaline solution is water with a specific resistance of 1 M ⁇ cm or more, more preferably water with a specific resistance of 10 M ⁇ cm or more, and even more preferably 15 M ⁇ cm or more. water. Water that satisfies the specific resistance has high purity and contains very few impurities.
  • Step S122 Further, as shown in step S122 in FIG. 3, it is preferable to prepare water in the reaction tank.
  • This water may be an aqueous solution of a chelating agent, but is more preferably pure water. By using pure water, nucleation is promoted and a composite hydroxide with a small particle size can be produced.
  • the water prepared in this reaction tank can be called a filling liquid or adjustment liquid for the reaction tank.
  • the description in step S13 can be taken into consideration.
  • step S131 in FIG. 3 the acid solution and the alkaline solution are mixed and reacted.
  • the reaction can be referred to as a coprecipitation reaction, a neutralization reaction, or an acid-base reaction.
  • the pH of the reaction system is preferably set to 9.0 or more and 11.5 or less.
  • the reaction tank has a reaction container and the like.
  • the stirring means includes a stirrer or stirring blades. Two or more stirring blades and six or less stirring blades can be provided. For example, when four stirring blades are provided, they are preferably arranged in a cross shape when viewed from above.
  • the rotation speed of the stirring means is preferably 800 rpm or more and 1200 rpm or less.
  • a baffle plate may be provided in the reaction tank to change the stirring direction and flow rate. By providing a baffle plate, mixing efficiency is improved and more uniform composite hydroxide particles can be synthesized.
  • the temperature of the reaction tank it is preferable to adjust the temperature of the reaction tank to 50°C or more and 90°C or less. It is preferable to start dropping the alkaline solution or acid solution after the reaction tank has reached the desired temperature.
  • the inert atmosphere in this case can be nitrogen or argon.
  • nitrogen gas is preferably introduced at a flow rate of 0.5 L/min or more and 2 L/min or less.
  • a reflux condenser allows nitrogen gas to be vented from the reactor and water vapor to be returned to the reactor.
  • composite hydroxide 98 containing transition metal M can be obtained.
  • the composite hydroxide 98 refers to hydroxides of multiple types of metals.
  • the composite hydroxide 98 can be said to be a precursor of the positive electrode active material 101.
  • step S142 in FIG. 4 the composite hydroxide 98 and a lithium source are mixed.
  • Mixing can be done dry or wet.
  • a ball mill, a bead mill, etc. can be used for mixing.
  • zirconia balls it is preferable to use zirconia balls as the media, for example.
  • the peripheral speed is preferably 100 mm/sec to 2000 mm/sec in order to suppress contamination from media or materials.
  • the cobalt compound and the lithium compound may be crushed.
  • Step S143 Next, the mixture of the composite hydroxide 98 and the lithium source is heated. To distinguish from other heating steps, in FIG. 4, step S143 may be referred to as first heating, step S145 as second heating, and step S153 as third heating.
  • step S144 it is preferable to include a crushing step after heating. Disintegration can be carried out, for example, in a mortar. Furthermore, it may be classified using a sieve.
  • the temperature of the heating in step S145 is preferably higher than 750°C and lower than 1050°C. Further, the heating time in step S145 is preferably 1 hour or more and 30 hours or less, more preferably 2 hours or more and 20 hours or less.
  • the temperature is preferably 850°C or higher, more preferably 900°C or higher, and even more preferably 1000°C or lower.
  • the heating temperature in step S153 is too high, the same disadvantages as described above may occur, so it is preferably 1050° C. or lower.
  • the description in step S145 can be referred to.
  • This embodiment mode can be freely combined with other embodiment modes.
  • FIG. 5A is a schematic diagram so that the overlapping (vertical relationship and positional relationship) of members can be seen. Therefore, FIGS. 5A and 5B are not completely corresponding diagrams.
  • a positive electrode 304, a separator 310, a negative electrode 307, a spacer 322, and a washer 312 are stacked. These are sealed with a negative electrode can 302 and a positive electrode can 301 with a gasket. Note that in FIG. 5A, a gasket for sealing is not shown.
  • 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 together.
  • the spacer 322 and washer 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 slurry containing the positive electrode active material 101 is applied onto the current collector and dried to form the positive electrode active material layer 306. Pressing may be performed after forming the positive electrode active material layer 306.
  • the slurry includes a conductive material and a solvent in addition to the positive electrode active material 101. Note that a carbon material such as graphite or carbon fiber is used as the conductive material.
  • FIG. 5B is a perspective view of the completed coin-shaped secondary battery.
  • a positive electrode can 301 that also serves as a positive electrode terminal and a negative electrode can 302 that also serves as a negative electrode terminal are insulated and sealed with a gasket 303 made of polypropylene or the like.
  • the positive electrode 304 is formed by a positive electrode current collector 305 and a positive electrode active material layer 306 provided in contact with the positive electrode current collector 305 .
  • the negative electrode 307 is formed of a negative electrode current collector 308 and a negative electrode active material layer 309 provided in contact with the negative electrode current collector 308. Further, the negative electrode 307 is not limited to a laminated structure, and lithium metal foil or lithium-aluminum alloy foil may be used.
  • the positive electrode 304 and the negative electrode 307 used in the coin-shaped secondary battery 300 may each have an active material layer formed only on one side.
  • the positive electrode can 301 and the negative electrode can 302 metals such as nickel, aluminum, titanium, etc., which are corrosion resistant to electrolyte, or alloys thereof, or alloys of these and other metals (for example, stainless steel, etc.) can be used. can. Further, in order to prevent corrosion due to electrolyte and the like, it is preferable to coat with nickel, aluminum, or the like.
  • the positive electrode can 301 is electrically connected to the positive electrode 304
  • the negative electrode can 302 is electrically connected to the negative electrode 307.
  • negative electrode 307, positive electrode 304, and separator 310 are immersed in an electrolytic solution, and the positive electrode can 304, separator 310, negative electrode 307, and negative electrode can 302 are stacked in this order with the positive electrode can 301 facing down, as shown in FIG. 301 and a negative electrode can 302 are crimped together via a gasket 303 to produce a coin-shaped secondary battery 300.
  • the cylindrical secondary battery 616 has a positive electrode cap (battery lid) 601 on the top surface and a battery can (exterior can) 602 on the side and bottom surfaces. These positive electrode cap 601 and battery can (exterior can) 602 are insulated by a gasket (insulating packing) 610.
  • FIG. 6B is a diagram schematically showing a cross section of a cylindrical secondary battery.
  • the cylindrical secondary battery shown in FIG. 6B has a positive electrode cap (battery lid) 601 on the top surface and a battery can (exterior can) 602 on the side and bottom surfaces.
  • These positive electrode caps and the battery can (exterior can) 602 are insulated by a gasket (insulating packing) 610.
  • a band-shaped positive electrode 604 and a negative electrode 606 are wound with a separator 605 in between.
  • a wound body in which a band-shaped positive electrode 604 and a negative electrode 606 are wound with a separator 605 in between is wound around a central axis.
  • the battery can 602 has one end closed and the other end open.
  • metals such as nickel, aluminum, titanium, etc., which are corrosion resistant to electrolyte, or alloys thereof, or alloys of these and other metals (for example, stainless steel, etc.) can be used. .
  • the battery can 602 in order to prevent corrosion caused by the electrolyte, it is preferable to coat the battery can 602 with nickel, aluminum, or the like. Inside the battery can 602, a wound body in which a positive electrode, a negative electrode, and a separator are wound is sandwiched between a pair of opposing insulating plates 608 and 609. Furthermore, a non-aqueous electrolyte (not shown) is injected into the inside of the battery can 602 provided with the wound body. As the non-aqueous electrolyte, the same one as a coin-type secondary battery can be used.
  • the positive electrode and negative electrode used in a cylindrical storage battery are wound, it is preferable to form an active material on both sides of the current collector.
  • the PTC element 611 is a heat-sensitive 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 )-based semiconductor ceramics or the like can be used for the PTC element.
  • FIG. 6C shows an example of the power storage system 615.
  • Power storage system 615 includes a plurality of secondary batteries 616.
  • the positive electrode of each secondary battery contacts a conductor 624 separated by an insulator 625 and is electrically connected.
  • the conductor 624 is electrically connected to the control circuit 620 via the wiring 623.
  • the negative electrode of each secondary battery is electrically connected to the control circuit 620 via a wiring 626.
  • As the control circuit 620 a charging/discharging control circuit that performs charging and discharging, or a protection circuit that prevents overcharging and/or overdischarging can be applied.
  • FIG. 6D shows an example of the power storage system 615.
  • the power storage system 615 includes a plurality of secondary batteries 616, and the plurality of secondary batteries 616 are sandwiched between a conductive plate 628 and a conductive plate 614.
  • the plurality of secondary batteries 616 are electrically connected to a conductive plate 628 and a conductive plate 614 by wiring 627.
  • the plurality of secondary batteries 616 may be connected in parallel, connected in series, or connected in parallel and then further connected in series.
  • the set may be further connected in series.
  • a temperature control device may be provided between the plurality of 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 affected by outside temperature.
  • the housing 930 shown in FIG. 7A may be formed of a plurality of materials.
  • a housing 930a and a housing 930b are bonded together, and a wound body 950 is provided in an area surrounded by the housing 930a and the housing 930b.
  • an insulating material such as organic resin can be used.
  • a material such as an organic resin on the surface where 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 can be used as the housing 930b.
  • the wound body 950 includes a negative electrode 931, a positive electrode 932, and a separator 933.
  • the wound body 950 is a wound body in which a negative electrode 931 and a positive electrode 932 are stacked on top of each other with a separator 933 in between, and the laminated sheet is wound. Note that a plurality of layers of the negative electrode 931, the positive electrode 932, and the separator 933 may be stacked.
  • a secondary battery 913 having a wound body 950a as shown in FIG. 8 may be used.
  • a wound body 950a shown in FIG. 8A 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 separator 933 has a width wider 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. Further, from the viewpoint of safety, it is preferable that the width of the negative electrode active material layer 931a is wider than that of the positive electrode active material layer 932a. Further, the wound body 950a having such a shape is preferable because it has good safety and productivity.
  • FIGS. 9A and 9B an example of an external view of an example of a laminate type secondary battery is shown in FIGS. 9A and 9B.
  • 9A and 9B have a positive electrode 503, a negative electrode 506, a separator 507, an exterior body 509, a positive lead electrode 510, and a negative lead electrode 511.
  • FIG. 10A 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 . Further, the positive electrode 503 has a region (hereinafter referred to as a tab region) where the positive electrode current collector 501 is partially exposed.
  • 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 . Further, the negative electrode 506 has a region where the negative electrode current collector 504 is partially exposed, that is, a tab region. Note that the area or shape of the tab regions of the positive electrode and the negative electrode is not limited to the example shown in FIG. 10A.
  • a negative electrode 506, a separator 507, and a positive electrode 503 are placed on the exterior body 509.
  • the exterior body 509 is bent 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 inlet) that is not joined is provided in a part (or one side) of the exterior body 509 so that the electrolyte can be introduced later.
  • an inlet a region (hereinafter referred to as an inlet) that is not joined is provided in a part (or one side) of the exterior body 509 so that the electrolyte can be introduced later.
  • the electrolytic solution is introduced into the interior of the exterior body 509 through an inlet provided in the exterior body 509 .
  • the electrolytic solution is preferably introduced under a reduced pressure atmosphere or an inert atmosphere. Finally, connect the inlet. In this way, a laminate type secondary battery 500 can be manufactured.
  • a secondary battery can typically be applied to an automobile.
  • automobiles include next-generation clean energy vehicles such as hybrid vehicles (HV), electric vehicles (EV), and plug-in hybrid vehicles (PHEV or PHV).
  • a secondary battery can be applied.
  • Vehicles are not limited to automobiles.
  • vehicles include trains, monorails, ships, submersibles (deep sea exploration vehicles, unmanned submarines), flying vehicles (helicopters, unmanned aerial vehicles (drones), airplanes, rockets, artificial satellites), electric bicycles, electric motorcycles, etc.
  • the secondary battery of one embodiment of the present invention can be applied to these vehicles.
  • first batteries 1301a and 1301b are connected in parallel, but three or more may be connected in parallel. Furthermore, if the first battery 1301a can store sufficient power, the first battery 1301b may not be necessary.
  • a battery pack that includes a plurality of secondary batteries, a large amount of electric power can be extracted.
  • a plurality of secondary batteries may be connected in parallel, may be connected in series, or may be connected in parallel and then further connected in series.
  • a plurality of secondary batteries is also called an assembled battery.
  • the first battery 1301a has a service plug or circuit breaker that can cut off high voltage without using tools. provided.
  • the electric power of the first batteries 1301a and 1301b is mainly used to rotate the motor 1304, but it is also used to power 42V-based in-vehicle components (electric power steering 1307, heater 1308, defogger 1309, etc.) via a DCDC circuit 1306. ). Even when the rear motor 1317 is provided on the rear wheel, the first battery 1301a is used to rotate the rear motor 1317.
  • the second battery 1311 supplies power to 14V vehicle components (audio 1313, power window 1314, lamps 1315, etc.) via the DCDC circuit 1310.
  • FIG. 11A shows an example in which nine square secondary batteries 1300 are used as one battery pack 1415. Further, nine prismatic secondary batteries 1300 are connected in series, one electrode is fixed by a fixing part 1413 made of an insulator, and the other electrode is fixed by a fixing part 1414 made of an insulator.
  • this embodiment shows an example in which the battery is fixed using the fixing parts 1413 and 1414, it may also be configured to be housed in a battery housing box (also referred to as a housing). Since it is assumed that the vehicle is subjected to vibrations or shaking from the outside (road surface, etc.), it is preferable to fix the plurality of secondary batteries using fixing parts 1413, 1414, a battery housing box, or the like.
  • one electrode is electrically connected to the control circuit section 1320 by a wiring 1421.
  • the other electrode is electrically connected to the control circuit section 1320 by a wiring 1422.
  • the control circuit section 1320 includes a switch section 1324 including at least a switch for preventing overcharging and a switch for preventing overdischarge, a control circuit 1322 for controlling the switch section 1324, and a voltage measuring section for the first battery 1301a. has.
  • the control circuit section 1320 has an upper limit voltage and a lower limit voltage set for the secondary battery to be used, and limits the upper limit of the current from the outside or the upper limit of the output current to the outside.
  • the range of the secondary battery's lower limit voltage to upper limit voltage is within the recommended voltage range, and when the voltage is outside of that range, the switch section 1324 is activated and functions as a protection circuit.
  • control circuit section 1320 can also be called a protection circuit because it controls the switch section 1324 to prevent over-discharging and/or over-charging. For example, when the control circuit 1322 detects a voltage that is likely to cause overcharging, the switch section 1324 is turned off to cut off the current. Furthermore, a PTC element may be provided in the charging/discharging path to provide a function of cutting off the current in response to a rise in temperature. Further, the control circuit section 1320 has an external terminal 1325 (+IN) and an external terminal 1326 (-IN).
  • FIG. 11C An example of applying a lithium ion battery to an electric vehicle (EV) is shown using FIG. 11C.
  • 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 a lead-acid battery is often used because it is advantageous in terms of cost.
  • the second battery 1311 may be a lead-acid battery, an all-solid-state battery, or an electric double layer capacitor.
  • the battery controller 1302 can set the charging voltage, charging current, etc. of the first batteries 1301a and 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.
  • Power supplied from an external charger charges the first batteries 1301a and 1301b via the battery controller 1302.
  • a control circuit is provided and the function of the battery controller 1302 is not used in some cases, but in order to prevent overcharging, the first batteries 1301a and 1301b are charged via the control circuit section 1320. It is preferable.
  • the connecting cable or the connecting cable of the charger is provided with a 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 the serial communication standards used as an in-vehicle LAN.
  • the ECU includes a microcomputer. Further, the ECU uses a CPU or a GPU.
  • External chargers installed at charging stations and the like include 100V outlet-200V outlet, or 3-phase 200V and 50kW. It is also possible to charge the battery by receiving power from an external charging facility using a non-contact power supply method or the like.
  • the capacity decrease is suppressed even when the electrode layer is made thicker and the loading amount is increased, and the synergistic effect of maintaining high capacity has resulted in a secondary battery with significantly improved electrical characteristics.
  • It is particularly effective for secondary batteries used in vehicles, and provides a vehicle with a long cruising range, specifically a cruising range of 500 km or more on one charge, without increasing the weight ratio of the secondary battery to the total vehicle weight. be able to.
  • the secondary battery of this embodiment described above can have a high operating voltage by using the positive electrode active material 101 described in Embodiment 1, and can be used as the charging voltage increases. Capacity can be increased. Further, by using the positive electrode active material 101 described in Embodiment 1 for the positive electrode, a secondary battery for a vehicle with excellent safety can be provided.
  • next-generation clean energy such as a hybrid vehicle (HV), electric vehicle (EV), or plug-in hybrid vehicle (PHV) can be realized.
  • HV hybrid vehicle
  • EV electric vehicle
  • PSV plug-in hybrid vehicle
  • a car can be realized.
  • secondary batteries in agricultural machinery, motorized bicycles including electric assist bicycles, motorcycles, electric wheelchairs, electric carts, ships, submarines, aircraft, rockets, artificial satellites, space probes, planetary probes, or spacecraft. It can also be installed.
  • 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 reduction in size and weight, and can be suitably used for transportation vehicles.
  • a car 2001 shown in FIG. 12A is an electric car that uses an electric motor as a power source for driving. Alternatively, it is a hybrid vehicle that can appropriately select and use an electric motor and an engine as a power source for driving.
  • a secondary battery is mounted on a vehicle, the example of the secondary battery shown in Embodiment 5 is installed at one or multiple locations.
  • a car 2001 shown in FIG. 12A includes a battery pack 2200, and the battery pack includes a secondary battery module to which a plurality of secondary batteries are connected. Furthermore, it is preferable to include a charging control device electrically connected to the secondary battery module.
  • the automobile 2001 can be charged by receiving power from an external charging facility using a plug-in method, a non-contact power supply method, or the like to a secondary battery of the automobile 2001.
  • a predetermined charging method or connector standard such as CHAdeMO (registered trademark) or combo may be used as appropriate.
  • the charging equipment may be a charging station provided at a commercial facility or may be a home power source.
  • plug-in technology it is possible to charge the power storage device mounted on the vehicle 2001 by supplying power from the outside. Charging can be performed by converting AC power into DC power via a conversion device such as an ACDC converter.
  • a power receiving device can be mounted on a vehicle and electrical power can be supplied from a ground power transmitting device in a non-contact manner for charging.
  • this non-contact power supply method by incorporating a power transmission device into the road or outside wall, charging can be performed not only while the vehicle is stopped but also while the vehicle is running. Further, electric power may be transmitted and received between two vehicles using this contactless power supply method.
  • a solar cell may be provided on the exterior of the vehicle, and the secondary battery may be charged when the vehicle is stopped or traveling.
  • an electromagnetic induction method or a magnetic resonance method can be used.
  • FIG. 12B shows a large transport vehicle 2002 having an electrically controlled motor as an example of a transport vehicle.
  • the secondary battery module of the transport vehicle 2002 has a maximum voltage of 170V, for example, in which four secondary batteries with a nominal voltage of 3.0 V or more and 5.0 V or less are connected in series, and 48 cells are connected in series. Except for the difference in the number of secondary batteries constituting the secondary battery module of the battery pack 2201, it has the same functions as those in FIG. 12A, so a description thereof will be omitted.
  • FIG. 12C shows, by way of example, a large transport vehicle 2003 with an electrically controlled motor.
  • the secondary battery module of the transportation vehicle 2003 has a maximum voltage of 600 V, for example, by connecting in series one hundred or more secondary batteries with a nominal voltage of 3.0 V or more and 5.0 V or less. Therefore, a secondary battery with small variations in characteristics is required.
  • a secondary battery in which the positive electrode active material 101 described in Embodiments 1 to 3 is used as a positive electrode a secondary battery with stable battery characteristics can be manufactured, and from the viewpoint of yield, it is possible to manufacture a secondary battery that has stable battery characteristics. Mass production is possible at low cost.
  • it since it has the same functions as those in FIG. 14A except for the difference in the number of secondary batteries constituting the secondary battery module of the battery pack 2202, a description thereof will be omitted.
  • FIG. 12E shows an artificial satellite 2005 equipped with a secondary battery 2204 as an example. Since the artificial satellite 2005 is used in outer space, it is desired that there be no failure due to ignition, and it is preferable to include the secondary battery 2204, which is an aspect of the present invention and has excellent safety. Furthermore, it is more preferable that the secondary battery 2204 is mounted inside the artificial satellite 2005 while being covered with a heat insulating member.
  • FIG. 13A is 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 an electric bicycle 8700 illustrated in FIG. 13A.
  • a power storage device according to one embodiment of the present invention includes, for example, a plurality of storage batteries and a protection circuit.
  • Electric bicycle 8700 includes a power storage device 8702.
  • the power storage device 8702 can supply electricity to a motor that assists the driver. Further, the power storage device 8702 is portable, and FIG. 13B shows a state in which it is removed from the bicycle. Further, the power storage device 8702 has a plurality of built-in storage batteries 8701 included in the power storage device of one embodiment of the present invention, and can display the remaining battery level and the like on a display portion 8703.
  • Power storage device 8702 also includes a control circuit 8704 that can control charging or detect abnormality of a secondary battery, an 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.
  • the positive electrode active material 101 obtained in Embodiment 1 with a secondary battery using the positive electrode as the positive electrode, a synergistic effect regarding safety can be obtained.
  • the secondary battery and control circuit 8704 using the positive electrode active material 101 obtained in Embodiment 1 as a positive electrode are highly safe and can greatly contribute to eliminating accidents such as fires caused by secondary batteries.
  • the mobile phone 2100 can run various applications such as mobile telephony, e-mail, text viewing and creation, music playback, Internet communication, computer games, and so on.
  • the upper camera 6403 and the lower camera 6406 have a function of capturing images around the robot 6400. Further, the obstacle sensor 6407 can detect the presence or absence of an obstacle in the direction of movement of the robot 6400 when the robot 6400 moves forward using the moving mechanism 6408.
  • the robot 6400 uses an upper camera 6403, a lower camera 6406, and an obstacle sensor 6407 to recognize the surrounding environment and can move safely.
  • FIG. 14D shows an example of a cleaning robot.
  • the cleaning robot 6300 includes a display portion 6302 placed on the top surface of a housing 6301, a plurality of cameras 6303 placed on the side, 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 is self-propelled, can detect dirt 6310, and can suck the dirt from a suction port provided on the bottom surface.
  • the cleaning robot 6300 can analyze the image taken by the camera 6303 and determine the presence or absence of obstacles such as walls, furniture, or steps. Furthermore, if an object such as wiring that is likely to become entangled with the brush 6304 is detected through image analysis, the rotation of the brush 6304 can be stopped.
  • the 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 area.
  • a secondary battery using the positive electrode active material 101 obtained in Embodiment 1 as a positive electrode has a high energy density and is highly safe, so it can be used safely for a long time and is suitable for the cleaning robot 6300. This is suitable as the secondary battery 6306 to be mounted.
  • a positive electrode active material according to one embodiment of the present invention was manufactured, and its shape was evaluated.
  • a composite hydroxide (Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 ) was formed.
  • the obtained composite hydroxide and lithium hydroxide were mixed, heated, crushed, and further heated to obtain a composite oxide.
  • the heating conditions after mixing (S143) were 700°C for 10 hours, and the subsequent heating conditions (S145) were 800°C for 10 hours.
  • the obtained composite oxide can be expressed as Li 1.01 Ni 0.8 Co 0.1 Mn 0.1 O 2 .
  • a half cell was assembled using the above 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 a positive electrode active material.
  • a coin-shaped half cell was used, and cycle characteristics were evaluated as battery characteristics for the half cell.
  • Acetylene black was used as a conductive additive for the positive electrode.
  • positive electrode active materials positive electrode active materials corresponding to the sample, Comparative Example 1, and Comparative Example 2 were prepared, and mixed with acetylene black, a binder (PVDF), and a solvent (NMP) to prepare a slurry, and the slurry was mixed with aluminum. It was applied to a current collector (thickness: 20 ⁇ m). After applying the slurry to the current collector, the solvent used for mixing was evaporated. Thereafter, pressure was applied at 210 kN/m using a roll press machine. The temperature of the roll was 120°C. Through the above steps, a positive electrode was obtained.
  • a CR2032 type (diameter 20 mm, height 3.2 mm) half cell (coin-shaped battery cell) was produced.
  • Lithium metal was used as the counter electrode of the half cell.
  • the positive electrode can and negative electrode can of the half cell were made of stainless steel (SUS).
  • the charging voltage was 4.5 V, and the temperature of the thermostat in which the half cells were placed was 45°C.
  • Charging was performed at a constant current (CC)/constant voltage (CV) rate of 0.5C (1C is 200mA/g), and charging was completed when the rate reached 0.05C.
  • Discharge was completed at constant current (CC), rate of 0.5C (1C: 200mA/g), and voltage of 2.5V.
  • a rest time may be provided between discharging and the next charge, and in this example, a 10 minute rest time was provided.
  • the above charging and discharging were repeated 100 times.
  • FIGS. 16A and 16B show the cycle test results of the sample, Comparative Example 1, and Comparative Example 2.
  • samples are shown as solid lines
  • Comparative Example 1 is shown as a dashed line
  • Comparative Example 2 is shown as a broken line.
  • the vertical axis shows the discharge capacity and the horizontal axis shows the number of cycles
  • the vertical axis shows the discharge capacity maintenance rate and the horizontal axis shows the number of cycles.
  • the sample of this example showed the best cycle characteristics compared to Comparative Example 1 and Comparative Example 2.
  • the cycle characteristics resulted in a small decrease in discharge capacity even when the number of cycles was large. Therefore, cycle characteristics can be improved by mixing magnesium carbonate with NCM, but rather than mixing lithium hydroxide and magnesium carbonate and heating, heating is performed after mixing lithium hydroxide, and then carbonate is heated. It has been found that a process of mixing and heating magnesium is effective.

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006031987A (ja) * 2004-07-13 2006-02-02 Matsushita Electric Ind Co Ltd 非水電解液二次電池用正極活物質の製造方法
JP2007257890A (ja) * 2006-03-20 2007-10-04 Nissan Motor Co Ltd 非水電解質リチウムイオン電池用正極材料およびこれを用いた電池
WO2020027158A1 (ja) * 2018-07-31 2020-02-06 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質、リチウムイオン二次電池用正極活物質の製造方法、リチウムイオン二次電池
JP2020031071A (ja) * 2016-10-12 2020-02-27 株式会社半導体エネルギー研究所 リチウムイオン二次電池、電子機器、携帯情報端末、自動車、家屋、及びビル

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006031987A (ja) * 2004-07-13 2006-02-02 Matsushita Electric Ind Co Ltd 非水電解液二次電池用正極活物質の製造方法
JP2007257890A (ja) * 2006-03-20 2007-10-04 Nissan Motor Co Ltd 非水電解質リチウムイオン電池用正極材料およびこれを用いた電池
JP2020031071A (ja) * 2016-10-12 2020-02-27 株式会社半導体エネルギー研究所 リチウムイオン二次電池、電子機器、携帯情報端末、自動車、家屋、及びビル
WO2020027158A1 (ja) * 2018-07-31 2020-02-06 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質、リチウムイオン二次電池用正極活物質の製造方法、リチウムイオン二次電池

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