WO2024004709A1 - 非水電解質二次電池用正極活物質及び非水電解質二次電池 - Google Patents

非水電解質二次電池用正極活物質及び非水電解質二次電池 Download PDF

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WO2024004709A1
WO2024004709A1 PCT/JP2023/022391 JP2023022391W WO2024004709A1 WO 2024004709 A1 WO2024004709 A1 WO 2024004709A1 JP 2023022391 W JP2023022391 W JP 2023022391W WO 2024004709 A1 WO2024004709 A1 WO 2024004709A1
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positive electrode
active material
electrode active
aqueous electrolyte
secondary battery
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English (en)
French (fr)
Japanese (ja)
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元治 斉藤
毅 小笠原
光宏 日比野
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to EP23831155.9A priority Critical patent/EP4550465A4/en
Priority to CN202380047076.7A priority patent/CN119366001A/zh
Priority to US18/877,872 priority patent/US20250385256A1/en
Priority to JP2024530698A priority patent/JPWO2024004709A1/ja
Publication of WO2024004709A1 publication Critical patent/WO2024004709A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • 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

  • the present disclosure relates to a positive electrode active material for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery.
  • Patent Document 1 describes an NCM-based lithium transition metal composite oxide ( Single particles with a Ni content of 0.3 ⁇ Ni ⁇ 0.6 are disclosed.
  • Patent Document 2 describes an NCM-based lithium transition metal composite oxide (Ni content: 0.3 ⁇ Ni ⁇ 0.6) with an average particle size of 3 ⁇ m to 8 ⁇ m and a crystallite size of 1100 ⁇ to 2000 ⁇ . Single particles are disclosed.
  • Patent Documents 1 and 2 do not consider achieving both high capacity and high durability, and there is still room for improvement.
  • An object of the present disclosure is to provide a positive electrode active material for a non-aqueous electrolyte secondary battery that can improve the capacity and durability of the non-aqueous electrolyte secondary battery.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery that is an embodiment of the present disclosure includes a lithium transition metal composite oxide containing 70 mol% or more of Ni and Mn with respect to the total molar amount of metal elements excluding Li.
  • the lithium transition metal composite oxide is characterized by being composed of single particles, the average particle size of the single particles being 0.65 ⁇ m to 4 ⁇ m, and the crystallite size of the single particles being 380 ⁇ to 750 ⁇ .
  • a non-aqueous electrolyte secondary battery that is one aspect of the present disclosure is characterized by comprising a positive electrode containing the above-described positive electrode active material, a negative electrode, and a non-aqueous electrolyte.
  • a non-aqueous electrolyte secondary battery with high capacity and improved durability can be provided.
  • FIG. 1 is an axial cross-sectional view of a non-aqueous electrolyte secondary battery that is an example of an embodiment.
  • FIG. 2 is a schematic cross-sectional view of test cells produced in Examples and Comparative Examples.
  • FIG. 3 is a SEM image of the positive electrode active material according to Example C1 before and after crushing.
  • FIG. 7 is a SEM image of the positive electrode active material according to Example C2 before and after crushing.
  • FIG. 7 is a SEM image of the positive electrode active material according to Example C3 before and after crushing.
  • FIG. FIG. 7 is a SEM image of the positive electrode active material according to Comparative Example C4 before and after crushing.
  • FIG. FIG. 7 is a SEM image of the positive electrode active material according to Comparative Example C5 before and after crushing.
  • the positive electrode active material is preferably one containing relatively inexpensive Ni and Mn as main components.
  • the present inventors found that single particles of a lithium transition metal composite oxide containing Ni and Mn as main components have a predetermined average particle diameter and crystallite size. We have discovered that it is possible to achieve both high capacity and high durability.
  • a cylindrical battery in which a wound type electrode body is housed in a cylindrical exterior body is illustrated, but the electrode body is not limited to the wound type, and a plurality of positive electrodes and a plurality of negative electrodes are housed in a separator. It may also be of a laminated type in which the sheets are alternately laminated one by one.
  • the exterior body is not limited to a cylindrical shape, and may be, for example, square, coin-shaped, or the like. Further, the exterior body may be a pouch type made of a laminate sheet including a metal layer and a resin layer.
  • the expression "numerical value (A) to numerical value (B)” means greater than or equal to numerical value (A) and less than or equal to numerical value (B).
  • FIG. 1 is an axial cross-sectional view of a cylindrical secondary battery 10 that is an example of an embodiment.
  • an electrode body 14 and a non-aqueous electrolyte (not shown) are housed in an exterior body 15.
  • the electrode body 14 has a wound structure in which a positive electrode 11 and a negative electrode 12 are wound with a separator 13 in between.
  • the sealing body 16 side will be referred to as "upper” and the bottom side of exterior body 15 will be referred to as "lower”.
  • the inside of the secondary battery 10 is sealed. Insulating plates 17 and 18 are provided above and below the electrode body 14, respectively.
  • the positive electrode lead 19 extends upward through the through hole of the insulating plate 17 and is welded to the lower surface of the filter 22, which is the bottom plate of the sealing body 16.
  • the cap 26, which is the top plate of the sealing body 16 electrically connected to the filter 22, serves as a positive terminal.
  • the negative electrode lead 20 passes through the through hole of the insulating plate 18 , extends to the bottom side of the exterior body 15 , and is welded to the bottom inner surface of the exterior body 15 .
  • the exterior body 15 serves as a negative terminal. Note that when the negative electrode lead 20 is installed at the outer end of the winding, the negative electrode lead 20 passes through the outside of the insulating plate 18, extends to the bottom side of the exterior body 15, and is welded to the bottom inner surface of the exterior body 15. .
  • the exterior body 15 is, for example, a cylindrical metal exterior can with a bottom.
  • a gasket 27 is provided between the exterior body 15 and the sealing body 16 to ensure airtightness inside the secondary battery 10.
  • the exterior body 15 has a grooved portion 21 that supports the sealing body 16 and is formed by, for example, pressing a side surface from the outside.
  • the grooved portion 21 is preferably formed in an annular shape along the circumferential direction of the exterior body 15, and supports the sealing body 16 via the gasket 27 on its upper surface.
  • the sealing body 16 includes a filter 22, a lower valve body 23, an insulating member 24, an upper valve body 25, and a cap 26, which are laminated in order from the electrode body 14 side.
  • Each member constituting the sealing body 16 has, for example, a disk shape or a ring shape, and each member except the insulating member 24 is electrically connected to each other.
  • the lower valve body 23 and the upper valve body 25 are connected to each other at their central portions, and an insulating member 24 is interposed between their peripheral edges.
  • the positive electrode 11, negative electrode 12, separator 13, and non-aqueous electrolyte that constitute the electrode body 14 will be explained in detail, especially the positive electrode 11.
  • the positive electrode 11 includes a positive electrode current collector and a positive electrode mixture layer formed on the surface of the positive electrode current collector.
  • the positive electrode mixture layer is preferably formed on both sides of the positive electrode current collector.
  • a foil made of a metal such as aluminum or an aluminum alloy that is stable in the potential range of the positive electrode 11, a film in which the metal is disposed on the surface, or the like can be used.
  • the positive electrode mixture layer includes, for example, a positive electrode active material, a conductive agent, a binder, and the like.
  • the thickness of the positive electrode mixture layer is, for example, 10 ⁇ m to 150 ⁇ m on one side of the positive electrode current collector.
  • the positive electrode 11 is made by applying a positive electrode mixture slurry containing a positive electrode active material, a conductive agent, and a binder to the surface of a positive electrode current collector, drying the coating film, and then rolling it to form a positive electrode mixture layer. It is produced by forming on both sides of a positive electrode current collector.
  • Examples of the conductive agent contained in the positive electrode mixture layer include carbon-based particles such as carbon black (CB), acetylene black (AB), Ketjen black, carbon nanotubes (CNT), graphene, and graphite. These may be used alone or in combination of two or more.
  • the content of the conductive agent is, for example, 0.1% by mass to 5.0% by mass based on 100 parts by mass of the positive electrode active material.
  • binder included in the positive electrode mixture layer examples include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide, acrylic resin, and polyolefin. These resins may be used in combination with cellulose derivatives such as carboxymethyl cellulose (CMC) or its salts, polyethylene oxide (PEO), and the like.
  • the content of the binder is, for example, 0.1% by mass to 5.0% by mass based on 100 parts by mass of the positive electrode active material.
  • the positive electrode active material contained in the positive electrode mixture layer contains a lithium transition metal composite oxide.
  • the lithium transition metal composite oxide is composed of single particles.
  • the positive electrode active material may also include secondary particles formed by agglomeration of single particles. This increases the charging density of the positive electrode active material in the positive electrode mixture layer, so that the capacity of the secondary battery 10 can be increased.
  • the secondary particles formed by agglomeration of single particles are, for example, formed by aggregation of 2 to 1000 single particles. Further, it may include general primary particles that are not single particles, and secondary particles formed by agglomeration of these primary particles.
  • the positive electrode active material may contain LiF, Li 2 S, etc. in addition to the lithium transition metal composite oxide.
  • the proportion of single particles in the positive electrode active material is preferably 10% or more, more preferably 80% or more, particularly preferably 90% or more, and may be substantially 100%.
  • the lithium transition metal composite oxide may contain secondary particles formed by agglomerating more than 100 primary particles.
  • the average particle size of single particles is 0.65 ⁇ m to 4 ⁇ m.
  • the average particle size means the volume-based median diameter (D50).
  • D50 means a particle size at which the cumulative frequency is 50% from the smallest particle size in the volume-based particle size distribution, and is also called the median diameter.
  • the particle size distribution of the positive electrode active material can be measured using a laser diffraction type particle size distribution measuring device (for example, MT3000II manufactured by Microtrac Bell Co., Ltd.) using water as a dispersion medium. If the particle size of the single particles is too large, the battery capacity will decrease or the charging/discharging efficiency will deteriorate. If the particle size of the single particles is too small, secondary aggregation occurs, which causes battery deterioration.
  • the BET specific surface area of a single particle is, for example, 0.5 m 2 /g to 4 m 2 /g. Secondary particles have voids within them, so even if the particle size is large, the specific surface area is relatively large. On the other hand, since single particles have no voids within the particles, the larger the particle size, the smaller the BET specific surface area.
  • the particle shapes of the secondary particles and single particles vary depending on the production conditions, so the BET specific surface area changes.
  • the BET specific surface area can be measured using Tristar II3020 (manufactured by Shimadzu Corporation) under the following conditions.
  • the product AB of A and B is 1 It is preferable to satisfy .5 ⁇ AB ⁇ 6.
  • the battery capacity and durability of the secondary battery 10 are significantly improved.
  • Secondary particles that are agglomerated single particles with small particle sizes may have cracked grain boundaries, resulting in a decrease in charge/discharge cycle characteristics.
  • Single particles with a large particle size may reduce battery capacity.
  • the BET specific surface area of the single particles is small, the contact area with the non-aqueous electrolyte is small, which may lead to a decrease in battery capacity and deterioration of load characteristics.
  • the crystallite size of a single particle is 380 ⁇ to 750 ⁇ .
  • the crystallite size is calculated from the half-value width of the diffraction peak of the (104) plane of the X-ray diffraction pattern obtained by X-ray diffraction using the Scherrer equation expressed by the following equation.
  • s is the crystallite size
  • ⁇ is the wavelength of the X-ray
  • B is the half-width of the diffraction peak of the (104) plane
  • ⁇ is the diffraction angle (rad)
  • K is the Scherrer constant.
  • the lithium transition metal composite oxide contains Ni and Mn in an amount of 70 mol% or more based on the total molar amount of metal elements excluding Li. This makes it possible to obtain a lithium transition metal composite oxide that is relatively inexpensive and has a high capacity. Note that the lithium transition metal composite oxide may be composed only of Ni and Mn.
  • Ni is preferably contained in the largest amount among the metal elements other than Li that constitute the lithium-transition metal composite oxide.
  • the Ni content in the lithium transition metal composite oxide is preferably 50 mol% or more, more preferably 70 mol% or more, based on the total molar amount of metal elements excluding Li.
  • the upper limit of the Ni content may be 95 mol%, but is preferably 90 mol%.
  • Mn is preferably contained in the second largest amount next to Ni among the metal elements other than Li that constitute the lithium-transition metal composite oxide. Mn can stabilize the crystal structure of the lithium transition metal composite oxide.
  • the Mn content in the lithium-transition metal composite oxide is, for example, 5 mol% to 50 mol% with respect to the total molar amount of metal elements excluding Li.
  • lithium transition metal composite oxides with a Ni content of 80% or less and a high Mn content can obtain high capacity by increasing the charging potential, so single particles with high potential resistance can be used. is necessary.
  • a surface modification layer containing a boron compound may be formed on the surface of the single particle. This improves charging and discharging efficiency. It is presumed that the boron compound suppresses the decomposition of the electrolytic solution and promotes the exchange of Li ions between the nonaqueous electrolyte and the positive electrode active material on the surface of the lithium transition metal composite oxide.
  • a boron compound is a compound containing B (boron). Examples of boron compounds include boron oxide, boron fluoride, boron chloride, and boron sulfide. Preferably, the boron compound is a boron oxide.
  • boron oxides examples include boric acid (H 3 BO 3 ), boron oxide (B 2 O 3 ), and lithium borate (LiBO 2 , LiB 3 O 5 , Li 2 B 4 O 7 ).
  • the boron compound present on the surface of the lithium-transition metal composite oxide can be confirmed by low-acceleration SEM, TEM-EDX, or the like.
  • the thickness of the surface modification layer is, for example, 1 nm to 100 nm.
  • the amount of the boron compound in the surface modification layer is, for example, 0.1 mol% to 7 mol% with respect to the total molar amount of metal elements excluding Li in the single particle.
  • the atomic concentration of each element can be measured by X-ray photoelectron spectroscopy (XPS).
  • the lithium transition metal composite oxide may further contain at least one metal element selected from the group consisting of Ca, Sr, W, and S. These metal elements may be contained in the lithium transition metal composite oxide, but are preferably present on the surface of the lithium transition metal composite oxide. Thereby, side reactions between the lithium transition metal composite oxide and the electrolytic solution can be suppressed, and battery deterioration can be suppressed. These metal elements may be contained together with B in the surface modification layer.
  • the positive electrode active material may contain, for example, 0.01 mol% to 5 mol% of these metal elements based on the total amount of Ni and Mn.
  • the method for producing a positive electrode active material includes, for example, a synthesis step, a washing step, a drying step, and a crushing step.
  • a metal hydroxide containing 70 mol% or more of Ni and Mn and a Li compound are mixed and fired to obtain a lithium transition metal composite oxide.
  • the metal hydroxide can be prepared by adding an alkaline solution such as sodium hydroxide dropwise to a solution of a metal salt containing Ni, Mn, and any metal element (Fe, etc.) while stirring, and adjusting the pH to the alkaline side (for example, 8. 5 to 12.5) and precipitate (co-precipitate).
  • a metal oxide obtained by heat-treating the metal hydroxide may be used instead of the metal hydroxide.
  • the particle size of the metal hydroxide is preferably 7 ⁇ m or less because the smaller the particle size, the easier the primary particles will grow.
  • Li compound examples include Li 2 CO 3 , LiOH, Li 2 O 2 , Li 2 O, LiNO 3 , LiNO 2 , Li 2 SO 4 , LiOH ⁇ H 2 O, LiH, LiF, and the like.
  • the mixing ratio of the metal hydroxide and the Li compound is such that the above-mentioned parameters can be easily adjusted within the above-defined ranges.
  • the molar ratio of metal elements other than Li:Li is 1:0.
  • the ratio is preferably in the range of 98 to 1:1.1.
  • a Ca compound, a Sr compound, a W compound, etc. may be added.
  • the Ca compound include CaO, Ca(OH) 2 and CaCO 3 .
  • Sr compound examples include SrO, Sr(OH) 2 and SrCO 3 .
  • W compound examples include WO 3 , Li 2 WO 4 , Li 4 WO 5 , and Li 6 W 2 O 9 .
  • the mixture of metal hydroxide, Li compound, etc. is fired, for example, in an oxygen atmosphere (flowing gas with an oxygen concentration of 80% or more).
  • the firing conditions are such that the temperature increase rate is in the range of more than 1.0°C/min and less than 5.5°C/min at 450°C or more and 680°C or less, and the maximum temperature is in the range of 850°C or more and 1100°C or less. There may be.
  • the temperature increase rate from over 680°C to the maximum temperature may be, for example, 0.1°C/min to 3.5°C/min. Further, the maximum temperature may be maintained for 1 hour or more and 30 hours or less.
  • this firing step may be a multi-stage firing, and a plurality of first temperature increase rates and second temperature increase rates may be set for each temperature range as long as they are within the ranges defined above.
  • the particle size of the single particles can be adjusted. For example, by increasing the maximum temperature, the particle size of single particles can be increased.
  • the lithium transition metal composite oxide obtained in the synthesis step is washed with water and dehydrated to obtain a cake-like composition. Washing with water and dehydration can be performed using known methods and conditions. This may be carried out within a range where lithium is not eluted from the lithium-transition metal composite oxide and the battery characteristics are not deteriorated. Note that a Ca compound, Sr compound, W compound, S compound, P compound, etc. may be added to the cake-like composition.
  • the cake-like composition obtained in the washing step is dried to obtain a powder-like composition.
  • the drying step may be performed under a vacuum atmosphere. Drying conditions are, for example, 150° C. to 400° C. for 0.5 hours to 15 hours.
  • Single particles can be obtained by crushing the powder composition obtained in the drying step.
  • a jet mill or the like can be used for crushing.
  • Crushing with a jet mill can be carried out using, for example, PJM-80 (manufactured by Nippon Pneumatic) under the following conditions.
  • a surface modification layer containing a boron compound is formed on the surface of the single particles.
  • the amount of the boron-containing compound added is, for example, 0.1 mol% to 7 mol% with respect to the total molar amount of metal elements other than Li in the lithium-transition metal composite oxide.
  • the negative electrode 12 includes a negative electrode current collector and a negative electrode mixture layer formed on the surface of the negative electrode current collector.
  • the negative electrode mixture layer is preferably formed on both sides of the negative electrode current collector.
  • a metal foil such as copper that is stable in the potential range of the negative electrode 12, a film with the metal disposed on the surface, or the like can be used.
  • the negative electrode mixture layer contains, for example, a negative electrode active material, a binder, and the like.
  • the negative electrode 12 is produced, for example, by coating a negative electrode mixture slurry containing a negative electrode active material and a binder on the surface of a negative electrode current collector, drying the coating film, and then rolling the negative electrode mixture layer to form a negative electrode current collector. It is produced by forming it on both sides of.
  • the negative electrode 12 may contain boron. A part of boron present on the surface of the positive electrode active material may move from the positive electrode 11 to the negative electrode 12. Even if a metal element such as Ni is precipitated on the surface of the negative electrode, deterioration of the battery can be suppressed by coexisting with B.
  • the amount of boron contained in the negative electrode is preferably 50 ⁇ g or more, more preferably 400 ⁇ g or more and 1200 ⁇ g or less per 1 g of positive electrode active material. For example, 35% or more of boron added to the positive electrode is deposited on the negative electrode, and 55% or less remains on the positive electrode.
  • the negative electrode active material contained in the negative electrode mixture layer includes, for example, a carbon-based active material that reversibly occludes and releases lithium ions.
  • Suitable carbon-based active materials include natural graphite such as flaky graphite, lumpy graphite, and earthy graphite, and graphite such as artificial graphite such as massive artificial graphite (MAG) and graphitized mesophase carbon microbeads (MCMB).
  • a Si-based active material composed of at least one of Si and a Si-containing compound may be used, or a carbon-based active material and a Si-based active material may be used in combination.
  • the binder contained in the negative electrode mixture layer fluororesin, PAN, polyimide, acrylic resin, polyolefin, etc. can be used as in the case of the positive electrode 11, but styrene-butadiene rubber (SBR) is used. It is preferable. Moreover, it is preferable that the negative electrode mixture layer further contains CMC or a salt thereof, polyacrylic acid (PAA) or a salt thereof, polyvinyl alcohol (PVA), or the like. Among these, it is preferable to use SBR, CMC or a salt thereof, and PAA or a salt thereof in combination. Note that the negative electrode mixture layer may contain a conductive agent.
  • a porous sheet having ion permeability and insulation properties is used.
  • porous sheets include microporous thin films, woven fabrics, and nonwoven fabrics.
  • Suitable materials for the separator 13 include polyolefins such as polyethylene and polypropylene, cellulose, and the like.
  • the separator 13 may have a single layer structure or a laminated structure. Further, the surface of the separator 13 may be provided with a resin layer having high heat resistance such as an aramid resin, and a filler layer containing an inorganic compound filler.
  • the non-aqueous electrolyte includes a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • non-aqueous solvents examples include esters, ethers, nitriles such as acetonitrile, amides such as dimethylformamide, and mixed solvents of two or more of these.
  • the non-aqueous solvent may contain a halogen-substituted product in which at least some of the hydrogen atoms of these solvents are replaced with halogen atoms such as fluorine.
  • halogen-substituted product examples include fluorinated cyclic carbonate esters such as fluoroethylene carbonate (FEC), fluorinated chain carbonate esters, fluorinated chain carboxylic acid esters such as methyl fluoropropionate (FMP), and the like.
  • FEC fluoroethylene carbonate
  • FMP fluorinated chain carboxylic acid esters
  • esters examples include cyclic carbonate esters such as ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate, dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), and methylpropyl carbonate.
  • chain carbonate esters such as ethylpropyl carbonate and methyl isopropyl carbonate
  • cyclic carboxylic acid esters such as ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL), methyl acetate, ethyl acetate, propyl acetate, and methyl propionate (MP).
  • chain carboxylic acid esters such as ethyl propionate, and the like.
  • ethers examples include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,4 - Cyclic ethers such as dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineole, crown ether, 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether , dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butylphenyl ether, pentylphenyl ether, methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl
  • the electrolyte salt is a lithium salt.
  • lithium salts include LiBF4 , LiClO4 , LiPF6 , LiAsF6 , LiSbF6 , LiAlCl4 , LiSCN, LiCF3SO3 , LiCF3CO2 , Li(P( C2O4 ) F4 ) , LiPF 6-x (C n F 2n+1 ) x (1 ⁇ x ⁇ 6, n is 1 or 2), LiB 10 Cl 10 , LiCl, LiBr, LiI, chloroborane lithium, lower aliphatic carboxylic acid lithium, Li 2 B 4 O 7 , borates such as Li(B(C 2 O 4 )F 2 ), LiN(SO 2 CF 3 ) 2 , LiN(C 1 F 2l+1 SO 2 )(C m F 2m+1 SO 2 ) ⁇ l , m is an integer of 0 or more ⁇ .
  • the lithium salts may be used alone or in combination.
  • LiPF 6 is preferably used from the viewpoint of ionic conductivity, electrochemical stability, etc.
  • the concentration of the lithium salt is preferably 0.8 mol to 1.8 mol per liter of nonaqueous solvent, for example.
  • This mixture was fired from room temperature to 650°C for 5 hours under an oxygen stream with an oxygen concentration of 90% or more (flow rate of 0.15 to 0.2 L/min per 1 L of furnace volume), and then fired at 1000°C. C. for 2 hours and held for 9 hours to obtain a lithium transition metal composite oxide. Excess lithium of this lithium-transition metal composite oxide was removed by washing with water and dried to obtain secondary particles in which single particles were aggregated. Furthermore, this secondary particle was crushed with a jet mill to obtain positive electrode active material A1.
  • Positive electrode active materials A2 to 5 were obtained in the same manner as positive electrode active material A1, except that the maximum temperature reached was changed as shown in Tables 1 and 3.
  • ⁇ Positive electrode active material B1-4> The same procedure as positive electrode active material A1 was used except that the composition of the hydroxide to be mixed was changed to Ni 0.6 Mn 0.4 (OH) 2 and the maximum temperature was changed as shown in Tables 1 and 3. Thus, positive electrode active materials B1 to B4 were obtained.
  • ⁇ Cathode active material C1-5> In the preparation of the positive electrode active material, the composition of the hydroxide to be mixed was changed to Ni 0.7 Mn 0.3 (OH) 2 , and the maximum temperature reached was changed as shown in Tables 1 and 3. Positive electrode active materials C1 to C5 were obtained in the same manner as positive electrode active material A1. SEM images of positive electrode active materials before and after crushing of positive electrode active materials C1 to C5 are shown in FIGS. 3 to 7. Before crushing in Figures 3, 4, and 6, the primary particles were in the form of aggregated secondary particles, but after crushing in Figures 3 and 4, the shape of single particles was confirmed. On the other hand, after the crushing shown in FIG. 6, the shape of the single particles cannot be confirmed.
  • the average particle size of the single particles is 0.65 ⁇ m to 4 ⁇ m, and the crystallite size of the single particles is If it is 380 ⁇ to 750 ⁇ , the effect as a single particle will be exhibited.
  • particles that are hardly crushed as shown in FIG. 6 are not single particles and do not exhibit the effect as a single particle.
  • FIGS. 5 and 7 some particles are in the form of single particles even before being crushed. However, as in the example shown in FIG. 7, if the average particle diameter or crystallite size of the particles is outside the above range, the characteristics of the battery will not be sufficiently improved.
  • ⁇ Positive electrode active material D1-3> In preparing the positive electrode active material, the composition of the hydroxide to be mixed was changed to Ni 0.75 Mn 0.25 (OH) 2 and the maximum temperature reached was changed as shown in Tables 1 and 3. Positive electrode active materials D1 to D3 were obtained in the same manner as positive electrode active material A1.
  • the amount of boric acid added was 2 mol % with respect to the total molar amount of metal elements other than Li in the single particles.
  • Positive electrode active materials E2 to 4 were obtained in the same manner as positive electrode active material E1, except that the maximum temperature reached was changed as shown in Tables 2 and 4.
  • ⁇ Positive electrode active material F1-4> The same procedure as positive electrode active material E1 was used except that the composition of the hydroxide to be mixed was changed to Ni 0.6 Mn 0.4 (OH) 2 and the maximum temperature was changed as shown in Tables 2 and 4. Thus, positive electrode active materials F1 to F4 were obtained.
  • ⁇ Cathode active material G1-4> In the preparation of the positive electrode active material, the composition of the hydroxide to be mixed was changed to Ni 0.7 Mn 0.3 (OH) 2 , and the maximum temperature reached was changed as shown in Tables 2 and 4. Positive electrode active materials G1 to G4 were obtained in the same manner as positive electrode active material E1.
  • ⁇ Positive electrode active material H1, 2> In preparing the positive electrode active material, the composition of the hydroxide to be mixed was changed to Ni 0.75 Mn 0.25 (OH) 2 and the maximum temperature reached was changed as shown in Tables 2 and 4. Positive electrode active materials H1 and 2 were obtained in the same manner as positive electrode active material E1.
  • test cell The test cell shown in FIG. 2 was produced by the following procedure. First, the above positive electrode active material, acetylene black (conductive material), and polyvinylidene fluoride (binder) were mixed in a weight ratio of 80:10:10, and N-methyl-2-pyrrolidone was used. It was made into a slurry. Next, this slurry was applied onto an aluminum foil current collector serving as a positive electrode current collector, and vacuum dried at 110° C. to produce a working electrode 30 (positive electrode).
  • acetylene black conductive material
  • binder polyvinylidene fluoride
  • test cells A1 to H4 corresponding to each of the positive electrode active materials A1 to H4 were obtained. Details of each component are as follows.
  • Counter electrode Lithium metal Reference electrode: Lithium metal Separator: Polyethylene separator
  • Non-aqueous electrolyte Non-aqueous electrolyte obtained by mixing ethylene carbonate (EC) and ethyl methyl carbonate (EMC) at a volume ratio of 3:7.
  • LiPF 6 as an electrolyte salt is dissolved in an aqueous solvent to a concentration of 1.0 mol/l.
  • Tables 1 and 2 show the evaluation results of Examples and Comparative Examples.
  • Table 1 shows the results for test cells A1 to D2
  • Table 2 shows the results for test cells E1 to H2.
  • the results of test cells containing single particles with an average particle diameter of 0.65 ⁇ m to 4 ⁇ m and a crystallite size of 380 ⁇ to 750 ⁇ were used as examples, and the results of test cells other than those described above were used as comparative examples.
  • the results of test cell F1 were designated as Example F1-1.
  • Tables 3 and 4 show the evaluation results of Examples and Comparative Examples.
  • Table 3 shows the results for test cells A1 to D3, and Table 4 shows the results for test cells E1 to H2.
  • the results of test cells containing single particles with an average particle diameter of 0.65 ⁇ m to 4 ⁇ m and a crystallite size of 380 ⁇ to 750 ⁇ were used as examples, and the results of test cells other than those described above were used as comparative examples.
  • the results of test cell E1 were designated as Example E1-2.
  • test cells of the examples achieved both charging capacity and capacity retention rate.
  • test cells of the comparative examples were inferior to the examples in either charging capacity or capacity retention rate. Therefore, it can be seen that when the single particles have a predetermined average particle diameter and crystallite size, both high capacity and high durability can be achieved.
  • the single particles themselves can improve battery characteristics, the protection of the positive electrode surface by the boron compound further improves battery capacity, charge/discharge efficiency, and capacity retention rate. In addition, it has the effect of suppressing generated gas.
  • Configuration 1 Contains a lithium transition metal composite oxide containing 70 mol% or more of Ni and Mn with respect to the total molar amount of metal elements excluding Li,
  • the lithium transition metal composite oxide is composed of single particles, The average particle size of the single particles is 0.65 ⁇ m to 4 ⁇ m,
  • Configuration 2 When the BET specific surface area of the lithium transition metal composite oxide is A (m 2 /g), and the average particle size of the lithium transition metal composite oxide is B ( ⁇ m), The positive electrode active material for a non-aqueous electrolyte secondary battery according to Configuration 1, wherein the product AB of A and B satisfies 1.5 ⁇ AB ⁇ 6.
  • Configuration 3 The positive electrode active material for a non-aqueous electrolyte secondary battery according to configuration 1 or 2, wherein a surface modification layer containing a boron compound is formed on the surface of the single particle.
  • Configuration 4 The lithium transition metal composite oxide further contains at least one metal element selected from the group consisting of Ca, Sr, W, S, and P.
  • Positive electrode active material for water electrolyte secondary batteries The positive electrode active material for a non-aqueous electrolyte secondary battery according to any one of configurations 1 to 4, which includes, in addition to the single particles, secondary particles formed by agglomerating the single particles.
  • Configuration 6 For a non-aqueous electrolyte secondary battery according to any one of configurations 1 to 5, the single particle is contained in an amount of 10% by mass or more based on the total amount of the positive electrode active material for a non-aqueous electrolyte secondary battery. Cathode active material.
  • Configuration 7 A nonaqueous electrolyte secondary battery comprising a positive electrode containing the positive electrode active material for a nonaqueous electrolyte secondary battery according to any one of Configurations 1 to 6, a negative electrode, and a nonaqueous electrolyte.

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PCT/JP2023/022391 2022-06-30 2023-06-16 非水電解質二次電池用正極活物質及び非水電解質二次電池 Ceased WO2024004709A1 (ja)

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CN202380047076.7A CN119366001A (zh) 2022-06-30 2023-06-16 非水电解质二次电池用正极活性物质和非水电解质二次电池
US18/877,872 US20250385256A1 (en) 2022-06-30 2023-06-16 Positive electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
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WO2025164411A1 (ja) * 2024-02-02 2025-08-07 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および非水電解質二次電池
WO2025164382A1 (ja) * 2024-02-02 2025-08-07 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および非水電解質二次電池
WO2025164374A1 (ja) * 2024-02-02 2025-08-07 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および非水電解質二次電池
WO2026070858A1 (ja) * 2024-09-30 2026-04-02 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、非水電解質二次電池、および非水電解質二次電池用正極活物質の製造方法

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WO2025164382A1 (ja) * 2024-02-02 2025-08-07 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および非水電解質二次電池
WO2025164374A1 (ja) * 2024-02-02 2025-08-07 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および非水電解質二次電池
WO2026070858A1 (ja) * 2024-09-30 2026-04-02 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、非水電解質二次電池、および非水電解質二次電池用正極活物質の製造方法

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