WO2018190048A1 - 正極活物質 - Google Patents

正極活物質 Download PDF

Info

Publication number
WO2018190048A1
WO2018190048A1 PCT/JP2018/009219 JP2018009219W WO2018190048A1 WO 2018190048 A1 WO2018190048 A1 WO 2018190048A1 JP 2018009219 W JP2018009219 W JP 2018009219W WO 2018190048 A1 WO2018190048 A1 WO 2018190048A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
active material
electrode active
satisfies
ion secondary
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/009219
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
祐太 川本
武文 福本
博行 井関
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyota Industries Corp
Original Assignee
Toyota Industries Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyota Industries Corp filed Critical Toyota Industries Corp
Publication of WO2018190048A1 publication Critical patent/WO2018190048A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present invention relates to a positive electrode active material for a lithium ion secondary battery.
  • a lithium ion secondary battery includes a positive electrode, a negative electrode, and an electrolytic solution as main components.
  • the positive electrode includes a current collector and a positive electrode active material layer formed on the surface of the current collector and containing a positive electrode active material.
  • Patent Document 1 reports that a new composite oxide containing lithium, niobium, and iron or manganese can be used as a positive electrode active material of a lithium ion secondary battery.
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a new positive electrode active material for providing a lithium ion secondary battery having an excellent capacity retention rate.
  • the present inventor conducted research on the composite oxide described in Patent Document 1 and found that there was room for improvement in terms of capacity retention rate. As a result of intensive studies by the present inventors, it has been found that the performance of the composite oxide as a positive electrode active material is improved by doping a certain element. The present invention has been completed based on such knowledge of the present inventors.
  • the positive electrode active material of the present invention is represented by the following composition formula (1), Li 1 + x Nb y Fe a Mn b A c O 2-d F d
  • A is selected from Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Al, x satisfies 0 ⁇ x ⁇ 1, y satisfies 0 ⁇ y ⁇ 0.5, a and b satisfy 0.25 ⁇ a + b ⁇ 1, 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, c satisfies 0 ⁇ c ⁇ 0.2; d satisfies 0 ⁇ d ⁇ 0.2, However, c and d are not 0 at the same time.
  • Example 2 is an X-ray diffraction chart of positive electrode active materials of Example 1-2, Example 2-2, and Comparative Example 1.
  • the numerical range “a to b” described in this specification includes the lower limit “a” and the upper limit “b”.
  • the numerical range can be configured by arbitrarily combining these upper limit value and lower limit value and the numerical values listed in the examples. Furthermore, numerical values arbitrarily selected from these numerical ranges can be used as new upper and lower numerical values.
  • the positive electrode active material of the present invention is represented by the following composition formula (1), Li 1 + x Nb y Fe a Mn b A c O 2-d F d
  • A is selected from Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Al, x satisfies 0 ⁇ x ⁇ 1, y satisfies 0 ⁇ y ⁇ 0.5, a and b satisfy 0.25 ⁇ a + b ⁇ 1, 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, c satisfies 0 ⁇ c ⁇ 0.2; d satisfies 0 ⁇ d ⁇ 0.2, However, c and d are not 0 at the same time.
  • the positive electrode active material of the present invention preferably exhibits a crystal structure that can be assigned to the space group Fm-3m.
  • the positive electrode active material of the present invention preferably exhibits a crystal structure that can be assigned to the NaCl type crystal structure.
  • the NaCl type crystal structure belongs to the space group Fm-3m. In “Fm ⁇ 3m”, “ ⁇ 3” represents 3 with an overline.
  • the positive electrode active material of the present invention can be expressed by being divided into a positive electrode active material represented by the following composition formula (1-1) and a positive electrode active material represented by the following composition formula (1-2).
  • A is selected from Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, and Al.
  • x, y, a, b, and c are 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.5, 0.25 ⁇ a + b ⁇ 1, 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 0. .2 is satisfied.
  • X is preferably in the range of 0 ⁇ x ⁇ 0.5, more preferably in the range of 0.05 ⁇ x ⁇ 0.4, and still more preferably in the range of 0.1 ⁇ x ⁇ 0.3.
  • y is preferably in the range of 0.05 ⁇ y ⁇ 0.5, more preferably in the range of 0.1 ⁇ y ⁇ 0.4, still more preferably in the range of 0.15 ⁇ y ⁇ 0.35.
  • the range of 2 ⁇ y ⁇ 0.35 is more preferable.
  • a and b it is preferable to satisfy the relationship of 0.25 ⁇ a + b ⁇ 0.75, more preferably to satisfy the relationship of 0.3 ⁇ a + b ⁇ 0.7, and 0.35 ⁇ a + b ⁇ 0. More preferably, the relationship of .5 is satisfied.
  • y a and b, it is preferable to satisfy the relationship 0.8 ⁇ 2y + a + b ⁇ 1.2, and it is more preferable to satisfy the relationship 0.9 ⁇ 2y + a + b ⁇ 1.1.
  • the positive electrode active material represented by the composition formula (1-1) includes A selected from Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, and Al. A may be single or plural. A is considered to have an effect of stabilizing the structure of the positive electrode active material inside the positive electrode active material represented by the composition formula (1-1).
  • A is considered not to participate in or hardly participate in the oxidation-reduction reaction.
  • A is presumed to be present by substituting any one of Li, Nb, Fe and Mn.
  • A represents a space from which lithium ions are separated. It is thought to play a role as a “pillar” to hold. From the viewpoint of ease of substitution, it is preferable that A has a smaller atomic radius.
  • Be, Mg, Sc, Ti, Zr, and Al are preferable.
  • C indicating the composition ratio of A preferably satisfies 0.01 ⁇ c ⁇ 0.15, and more preferably satisfies 0.05 ⁇ c ⁇ 0.15. If c is too small, the stabilization effect of A may not be satisfactorily exhibited. On the other hand, if c is too large, the capacity of the positive electrode active material per unit mass may be small.
  • the positive electrode active material represented by the composition formula (1-2) will be described.
  • the positive electrode active material contains F.
  • F is presumed to be substituted for oxygen.
  • the composite oxide described in Patent Document 1 functions as a positive electrode active material by performing an oxidation-reduction reaction by releasing and occluding oxygen electrons contained in the composite oxide. Conceivable. However, it is considered that oxygen in a state where one electron is emitted is highly reactive because it is unstable, and can be easily separated from the positive electrode active material by being easily brought into O 2 when unstable oxygen approaches each other. .
  • F present in the positive electrode active material represented by the composition formula (1-2) physically controls the approach of unstable oxygens. Further, F has a high electron density due to its high electronegativity, and has an unshared electron pair. It is also estimated that HOMO, which is an orbit of such an unshared electron pair of F, and SOMO, which is an orbit of oxygen in a state where one electron is emitted, interact with each other, thereby stabilizing oxygen as a whole. . Furthermore, F is strongly ion-bonded with Nb, Fe, and Mn due to its high electronegativity, so it is considered that these metals suppress elution of these metals into the electrolyte. In any case, F is considered to have an effect of stabilizing the structure of the positive electrode active material inside the positive electrode active material represented by the composition formula (1-2).
  • D representing the composition ratio of F preferably satisfies 0.01 ⁇ d ⁇ 0.2, more preferably satisfies 0.03 ⁇ d ⁇ 0.15, and 0.06 ⁇ d ⁇ 0. It is more preferable to satisfy. If d is too small, the stabilization effect of F may not be satisfactorily exhibited. On the other hand, if d is too large, the capacity of the positive electrode active material per unit mass may be reduced.
  • a positive electrode active material represented by the following composition formula (1-3) can also be exemplified.
  • A is selected from Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, and Al.
  • x, y, a, b, c and d are 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.5, 0.25 ⁇ a + b ⁇ 1, 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 0.2 and 0 ⁇ d ⁇ 0.2 are satisfied.
  • the positive electrode active material represented by the composition formula (1-3) contains both A and F, it can be said that the positive electrode active material has both effects produced by A and F.
  • the explanations of the composition formula (1), the composition formula (1-1), and the composition formula (1-2) are used.
  • the manufacturing method of the positive electrode active material of this invention is demonstrated.
  • the positive electrode active material of the present invention may be synthesized by applying a solid phase method or a coprecipitation method that is employed when producing a general positive electrode active material.
  • the positive electrode active material of the present invention can be produced by mixing a lithium source, niobium source, iron source, manganese source, A source, and F source in a desired ratio and firing.
  • a hydroxide is precipitated from an aqueous solution in which niobium salt, iron salt, and manganese salt are mixed in a desired ratio to form a precipitate, and then the precipitate, lithium source, A source or
  • the positive electrode active material of this invention can be manufactured by mixing and baking with F source.
  • the firing temperature in the solid phase method and the coprecipitation method is preferably 500 to 1200 ° C, more preferably 700 to 1100 ° C, still more preferably 800 to 1000 ° C, and particularly preferably 900 to 1000 ° C. Firing is preferably performed in an inert gas atmosphere such as helium or argon.
  • lithium source examples include lithium oxide, lithium hydroxide, lithium carbonate, lithium hydrogen carbonate, and lithium fluoride.
  • examples of the niobium source or niobium salt include niobium oxide, niobium hydroxide, niobium sulfate, niobium nitrate, niobium chloride, niobium fluoride, and lithium niobate.
  • examples of the iron source or iron salt include iron oxide, iron hydroxide, iron sulfate, iron nitrate, iron chloride, and iron fluoride.
  • Examples of the manganese source or manganese salt include manganese oxide, manganese hydroxide, manganese sulfate, manganese nitrate, manganese chloride, and manganese fluoride.
  • Examples of the A source include oxidation A, hydroxide A, sulfuric acid A, nitric acid A, chloride A, and fluoride A.
  • Examples of the F source include hydrogen fluoride, lithium fluoride, niobium fluoride, iron fluoride, manganese fluoride, and fluoride A.
  • the synthesized cathode active material of the present invention is preferably subjected to a pulverization step for preparing a powder having an appropriate particle size distribution.
  • the average particle size of the positive electrode active material powder of the present invention is preferably 0.5 to 50 ⁇ m, more preferably 1 to 30 ⁇ m, and even more preferably 3 to 10 ⁇ m.
  • the average particle diameter means a 50% cumulative diameter (D 50 ) when a sample is measured with a general laser diffraction / scattering particle size distribution measuring apparatus.
  • the positive electrode for a lithium ion secondary battery comprising the positive electrode active material of the present invention is referred to as “the positive electrode of the present invention”
  • the lithium ion secondary battery comprising the positive electrode active material of the present invention is referred to as “the lithium ion secondary battery of the present invention”. It is called “second battery”.
  • the positive electrode of the present invention comprises a positive electrode active material layer containing the positive electrode active material of the present invention and a current collector.
  • the positive electrode active material layer is formed on the current collector. Examples of the proportion of the positive electrode active material of the present invention in the positive electrode active material layer include 30 to 100% by mass, 40 to 90% by mass, and 50 to 80% by mass.
  • the current collector refers to a chemically inert electronic conductor that keeps a current flowing through an electrode during discharge or charging of a lithium ion secondary battery.
  • the material of the current collector is not particularly limited as long as it is a metal that can withstand a voltage suitable for the active material to be used.
  • the current collector material is at least one selected from silver, copper, gold, aluminum, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, molybdenum, and stainless steel Examples of such a metal material can be given.
  • the current collector may be covered with a known protective layer. A current collector obtained by treating the surface of a current collector by a known method may be used as the current collector.
  • the potential of the positive electrode is 4 V or higher with respect to lithium, it is preferable to employ aluminum as the positive electrode current collector.
  • aluminum refers to pure aluminum, and aluminum having a purity of 99.0% or more is referred to as pure aluminum.
  • An alloy obtained by adding various elements to pure aluminum is referred to as an aluminum alloy. Examples of the aluminum alloy include Al—Cu, Al—Mn, Al—Fe, Al—Si, Al—Mg, Al—Mg—Si, and Al—Zn—Mg.
  • aluminum or aluminum alloy examples include A1000 series alloys (pure aluminum series) such as JIS A1085 and A1N30, A3000 series alloys (Al-Mn series) such as JIS A3003 and A3004, JIS A8079, A8021, etc. A8000-based alloy (Al-Fe-based).
  • the current collector can take the form of a foil, a sheet, a film, a linear shape, a rod shape, a mesh, or the like. Therefore, for example, a metal foil such as a copper foil, a nickel foil, an aluminum foil, and a stainless steel foil can be suitably used as the current collector.
  • a metal foil such as a copper foil, a nickel foil, an aluminum foil, and a stainless steel foil can be suitably used as the current collector.
  • the thickness is preferably in the range of 1 ⁇ m to 100 ⁇ m.
  • the positive electrode active material layer may contain a known positive electrode active material in addition to the positive electrode active material of the present invention. Further, the positive electrode active material layer preferably contains a binder and a conductive additive. As the binder and the conductive assistant contained in the positive electrode active material layer, those described in the later-described negative electrode may be appropriately employed.
  • the lithium ion secondary battery of the present invention specifically includes the positive electrode, the negative electrode, the electrolytic solution, and the separator of the present invention.
  • the negative electrode includes a current collector and a negative electrode active material layer formed on the current collector.
  • the negative electrode active material layer includes a known negative electrode active material.
  • the current collector for the negative electrode may be appropriately selected from those described for the positive electrode of the present invention.
  • the positive electrode active material and the negative electrode active material may be collectively referred to as “active material”, and the positive electrode active material layer and the negative electrode active material layer may be collectively referred to as “active material layer”. .
  • binder examples include fluorine-containing resins such as polyvinylidene fluoride, polytetrafluoroethylene, and fluororubber, thermoplastic resins such as polypropylene and polyethylene, imide resins such as polyimide and polyamideimide, alkoxysilyl group-containing resins, and carboxymethylcellulose. What is necessary is just to employ
  • Conductive aid is added to increase the conductivity of the electrode. Therefore, the conductive auxiliary agent may be added arbitrarily when the electrode conductivity is insufficient, and may not be added when the electrode conductivity is sufficiently excellent.
  • the conductive auxiliary agent may be any chemically inert electronic high conductor, such as carbon black, graphite, vapor grown carbon fiber (Vapor Grown Carbon Fiber), and various metal particles.
  • carbon black include acetylene black, ketjen black (registered trademark), furnace black, and channel black.
  • These conductive assistants can be added to the active material layer alone or in combination of two or more.
  • a current collecting method such as a roll coating method, a die coating method, a dip coating method, a doctor blade method, a spray coating method, or a curtain coating method can be used.
  • An active material may be applied to the surface of the body. Specifically, an active material, a binder, a solvent, and a conductive additive as necessary are mixed to form a slurry, and the slurry is applied to the surface of the current collector and then dried.
  • the solvent include N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone, and water.
  • the dried product may be compressed.
  • an active material layer may be formed on the surface of the current collector by preparing a mixture containing an active material, a binder, and if necessary, a conductive additive, and then bonding the mixture to the current collector. Good.
  • the separator separates the positive electrode and the negative electrode and allows lithium ions to pass while preventing a short circuit due to contact between the two electrodes.
  • a known separator may be employed, such as polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamide, polyaramid (Aromatic polymer), polyester, polyacrylonitrile, and other synthetic resins, cellulose, amylose, and other polysaccharides, fibroin. , Porous materials, nonwoven fabrics, woven fabrics, and the like using one or more natural polymers such as keratin, lignin and suberin, and ceramics and other electrically insulating materials.
  • the separator may have a multilayer structure.
  • the electrolytic solution contains a non-aqueous solvent and an electrolyte dissolved in the non-aqueous solvent.
  • cyclic carbonates examples include ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate
  • examples of the cyclic ester include gamma butyrolactone, 2-methyl-gamma butyrolactone, acetyl-gamma butyrolactone, and gamma valerolactone
  • Examples of the chain carbonate include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, and ethyl methyl carbonate.
  • chain ester examples include propionic acid alkyl ester, malonic acid dialkyl ester, and acetic acid alkyl ester.
  • ethers examples include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, and 1,2-dibutoxyethane.
  • non-aqueous solvent a compound in which part or all of hydrogen in the chemical structure of the specific solvent is substituted with fluorine may be employed.
  • Examples of the electrolyte include lithium salts such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , and LiN (CF 3 SO 2 ) 2 .
  • a lithium salt such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3
  • a non-aqueous solvent such as fluoroethylene carbonate, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate.
  • a separator is sandwiched between a positive electrode and a negative electrode to form an electrode body.
  • the electrode body may be any of a stacked type in which a positive electrode, a separator and a negative electrode are stacked, or a wound type in which a positive electrode, a separator and a negative electrode are stacked.
  • the shape of the lithium ion secondary battery of the present invention is not particularly limited, and various shapes such as a cylindrical shape, a square shape, a coin shape, and a laminate shape can be adopted.
  • the lithium ion secondary battery of the present invention may be mounted on a vehicle.
  • the vehicle may be a vehicle that uses electric energy generated by a lithium ion secondary battery for all or a part of its power source.
  • the vehicle may be an electric vehicle or a hybrid vehicle.
  • a lithium ion secondary battery is mounted on a vehicle, a plurality of lithium ion secondary batteries may be connected in series to form an assembled battery.
  • devices equipped with lithium ion secondary batteries include various home appliances driven by batteries such as personal computers and portable communication devices, office devices, and industrial devices in addition to vehicles.
  • the lithium ion secondary battery of the present invention includes wind power generation, solar power generation, hydroelectric power generation and other power system power storage devices and power smoothing devices, power supplies for ships and / or auxiliary power supply sources, aircraft, Power supply for spacecraft and / or auxiliary equipment, auxiliary power supply for vehicles that do not use electricity as a power source, power supply for mobile home robots, power supply for system backup, power supply for uninterruptible power supply, You may use for the electrical storage apparatus which stores temporarily the electric power required for charge in the charging station for electric vehicles.
  • Example 1-1 Li 2 CO 3, Nb 2 O 5, Mn 2 O 3 and Mg (NO 3) the 2 ⁇ 6H 2 O, Li: Nb: Mn: Mg is 1.225: 0.275: 0.4: 0.1 These powders were weighed at a ratio to give, and these powders were put into a ball mill. After adding 1 mass% propylene glycol with respect to the whole powder, it mixed by the ball mill, and was set as the mixture. After the mixture was molded, it was heated at 950 ° C. for 12 hours under an argon gas atmosphere to produce a fired product. The fired product was crushed to obtain a positive electrode active material of Example 1-1.
  • the theoretical composition of the positive electrode active material of Example 1-1 is Li 1.225 Nb 0.275 Mn 0.4 Mg 0.1 O 2 .
  • Example 1-1 5 parts by weight of the positive electrode active material of Example 1-1, 3 parts by weight of acetylene black as a conductive assistant, 2 parts by weight of polytetrafluoroethylene as a binder, and an appropriate amount of N-methyl-2-pyrrolidone Mix to make a slurry.
  • An aluminum foil was prepared as a current collector, and a slurry was applied to the aluminum foil and dried to obtain a positive electrode of Example 1-1.
  • Lithium foil was prepared and used as a negative electrode.
  • a polyethylene porous membrane having a thickness of 20 ⁇ m was prepared as a separator.
  • LiPF 6 was dissolved in a solvent obtained by mixing 5 parts by volume of ethylene carbonate and diethyl carbonate 5 parts by volume in a concentration of 1 mol / L electrolyte solution.
  • the separator was sandwiched between the positive electrode and the negative electrode of Example 1-1 to obtain an electrode body.
  • This electrode body was accommodated in a coin-type battery case CR2032 (Hosen Co., Ltd.), and an electrolyte was further injected to obtain a sealed coin-type battery. This was designated as the lithium ion secondary battery of Example 1-1.
  • Example 1-2 Li 2 CO 3 , Nb 2 O 5 , Mn 2 O 3 and Mg (NO 3 ) 2 .6H 2 O, Li: Nb: Mn: Mg 1.2: 0.3: 0.35: 0.1
  • a positive electrode active material, a positive electrode, and a lithium ion secondary battery of Example 1-2 were produced in the same manner as in Example 1-1, except that they were weighed at a ratio of The theoretical composition of the positive electrode active material of Example 1-2 is Li 1.2 Nb 0.3 Mn 0.35 Mg 0.1 O 2 .
  • Example 1-3 Li 2 CO 3 , Nb 2 O 5 , Mn 2 O 3 and Mg (NO 3 ) 2 .6H 2 O, Li: Nb: Mn: Mg 1.1: 0.3: 0.4: 0.1
  • a positive electrode active material, a positive electrode, and a lithium ion secondary battery of Example 1-3 were produced in the same manner as in Example 1-1, except that they were weighed at a ratio of The theoretical composition of the positive electrode active material of Example 1-3 is Li 1.1 Nb 0.3 Mn 0.4 Mg 0.1 O 2 .
  • Example 2-1 Li 2 CO 3 , Nb 2 O 5 , Mn 2 O 3 and LiF were weighed at a ratio of Li: Nb: Mn: F of 1.25: 0.3: 0.4: 0.05, and these The powder was put into a ball mill. After adding 1 mass% propylene glycol with respect to the whole powder, it mixed by the ball mill, and was set as the mixture. After the mixture was molded, it was heated at 950 ° C. for 12 hours under an argon gas atmosphere to produce a fired product. The fired product was crushed to obtain a positive electrode active material of Example 2-1. Thereafter, the positive electrode and the lithium ion secondary battery of Example 2-1 were produced in the same manner as in Example 1-1.
  • the composition of the theoretical positive electrode active material in Example 2-1 is a Li 1.25 Nb 0.3 Mn 0.4 O 1.95 F 0.05.
  • Example 2-2 Li 2 CO 3 , Nb 2 O 5 , Mn 2 O 3 and LiF were weighed and used at a ratio such that Li: Nb: Mn: F was 1.2: 0.3: 0.4: 0.1.
  • a positive electrode active material, a positive electrode, and a lithium ion secondary battery of Example 2-2 were produced in the same manner as in Example 2-1, except for the above.
  • the theoretical composition of the positive electrode active material of Example 2-2 is Li 1.2 Nb 0.3 Mn 0.4 O 1.9 F 0.1 .
  • Example 1 The positive electrode active materials of Example 1-1 and Example 2-1 were analyzed by SEM-EDX in which a scanning electron microscope (SEM) and an energy dispersive X-ray analyzer (EDX) were combined. The presence of Mg was confirmed from the positive electrode active material of Example 1-1, and the presence of F was confirmed from the positive electrode active material of Example 2-1.
  • SEM scanning electron microscope
  • EDX energy dispersive X-ray analyzer
  • Example 2 The positive electrode active materials of Example 1-2, Example 2-2, and Comparative Example 1 were analyzed with a powder X-ray diffractometer using Cu—K ⁇ rays. An X-ray diffraction chart is shown in FIG. All of the positive electrode active materials showed diffraction patterns that could be assigned to the NaCl type crystal structure.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
PCT/JP2018/009219 2017-04-10 2018-03-09 正極活物質 Ceased WO2018190048A1 (ja)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017077858A JP2018181553A (ja) 2017-04-10 2017-04-10 正極活物質
JP2017-077858 2017-04-10

Publications (1)

Publication Number Publication Date
WO2018190048A1 true WO2018190048A1 (ja) 2018-10-18

Family

ID=63793720

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/009219 Ceased WO2018190048A1 (ja) 2017-04-10 2018-03-09 正極活物質

Country Status (2)

Country Link
JP (1) JP2018181553A (https=)
WO (1) WO2018190048A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4207381A4 (en) * 2020-08-31 2024-02-28 Panasonic Intellectual Property Management Co., Ltd. ACTIVE MATERIAL OF POSITIVE ELECTRODE FOR SECONDARY BATTERIES AND SECONDARY BATTERY

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023188578A1 (ja) * 2022-03-31 2023-10-05 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用正極活物質

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000133265A (ja) * 1998-10-28 2000-05-12 Mitsubishi Materials Corp リチウム二次電池用正極活物質とその製造方法
JP2001126729A (ja) * 1999-10-28 2001-05-11 Toshiba Corp 非水電解質二次電池
JP2013100197A (ja) * 2011-11-08 2013-05-23 National Institute Of Advanced Industrial Science & Technology リチウムマンガン系複合酸化物およびその製造方法
WO2014156153A1 (ja) * 2013-03-27 2014-10-02 株式会社Ｇｓユアサ 非水電解質蓄電素子用活物質
US20180034042A1 (en) * 2016-07-28 2018-02-01 Kyler Carroll Oxides for high energy cathode materials

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000133265A (ja) * 1998-10-28 2000-05-12 Mitsubishi Materials Corp リチウム二次電池用正極活物質とその製造方法
JP2001126729A (ja) * 1999-10-28 2001-05-11 Toshiba Corp 非水電解質二次電池
JP2013100197A (ja) * 2011-11-08 2013-05-23 National Institute Of Advanced Industrial Science & Technology リチウムマンガン系複合酸化物およびその製造方法
WO2014156153A1 (ja) * 2013-03-27 2014-10-02 株式会社Ｇｓユアサ 非水電解質蓄電素子用活物質
US20180034042A1 (en) * 2016-07-28 2018-02-01 Kyler Carroll Oxides for high energy cathode materials

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4207381A4 (en) * 2020-08-31 2024-02-28 Panasonic Intellectual Property Management Co., Ltd. ACTIVE MATERIAL OF POSITIVE ELECTRODE FOR SECONDARY BATTERIES AND SECONDARY BATTERY

Also Published As

Publication number Publication date
JP2018181553A (ja) 2018-11-15

Similar Documents

Publication Publication Date Title
US10074851B2 (en) Surface modified lithium-containing composite oxide particles, positive electrode using the particles, and non-aqueous electrolyte secondary battery
JP5099168B2 (ja) リチウムイオン二次電池
KR20100105387A (ko) 비수전해액 ２차 전지
JP7446595B2 (ja) リチウム金属複合酸化物粉末の製造方法
JP2003142101A (ja) 二次電池用正極およびそれを用いた二次電池
WO2016056586A1 (ja) リチウムイオン二次電池用正極活物質、及びリチウムイオン二次電池
US20140110641A1 (en) Method for producing active material particles for lithium ion secondary battery, electrode and lithium ion secondary battery
WO2012035648A1 (ja) 非水電解液二次電池用活物質および非水電解液二次電池
CN104854035A (zh) 复合金属氧化物、复合金属氧化物的制造方法和钠二次电池
EP3627611A1 (en) Zinc salts which can be used as liquid electrolyte of zinc-ion battery
JP2018035057A (ja) リチウム金属複合酸化物粉末の製造方法及びリチウム金属複合酸化物粉末
JP2021082537A (ja) マグネシウムイオン二次電池、マグネシウムイオン二次電池用正極活物質及びマグネシウムイオン二次電池用正極
JP6962154B2 (ja) リチウムイオン二次電池
JP2019192373A (ja) 正極活物質
JP7131258B2 (ja) 複合粒子の製造方法
JP2013060319A (ja) リチウムマンガン（ｉｖ）ニッケル（ｉｉｉ）系酸化物、その酸化物を含むリチウムイオン二次電池用正極活物質、その正極活物質を用いたリチウムイオン二次電池及びそのリチウムイオン二次電池を搭載した車両
WO2018190048A1 (ja) 正極活物質
JP2019102308A (ja) 正極活物質
JP6252864B2 (ja) シリコン材料の製造方法
WO2019017199A1 (ja) 正極活物質
JP2019023990A (ja) 正極活物質
JP2019179714A (ja) 正極活物質
JP2019008990A (ja) 正極活物質
JP2019117781A (ja) 正極活物質
JP2019091580A (ja) 正極活物質

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18784797

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18784797

Country of ref document: EP

Kind code of ref document: A1