WO2024181461A1 - 非水電解質二次電池用の正極スラリー、非水電解質二次電池用の正極の製造方法、および、非水電解質二次電池 - Google Patents

非水電解質二次電池用の正極スラリー、非水電解質二次電池用の正極の製造方法、および、非水電解質二次電池 Download PDF

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WO2024181461A1
WO2024181461A1 PCT/JP2024/007152 JP2024007152W WO2024181461A1 WO 2024181461 A1 WO2024181461 A1 WO 2024181461A1 JP 2024007152 W JP2024007152 W JP 2024007152W WO 2024181461 A1 WO2024181461 A1 WO 2024181461A1
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positive electrode
lithium
secondary battery
electrolyte secondary
active material
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French (fr)
Japanese (ja)
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未有 田中
正憲 前川
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Panasonic Energy Co Ltd
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Panasonic Energy Co Ltd
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Priority to CN202480014900.3A priority Critical patent/CN120712657A/zh
Priority to JP2025503947A priority patent/JPWO2024181461A1/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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • 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 slurry for a non-aqueous electrolyte secondary battery, a method for producing a positive electrode for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery.
  • Non-aqueous electrolyte secondary batteries have high output and high energy density, and are therefore used in a wide range of applications, including consumer and automotive applications. In recent years, there has been a demand for even higher performance non-aqueous electrolyte secondary batteries. Various proposals have been made for non-aqueous electrolyte secondary batteries.
  • Patent Document 1 Patent No. 3540097 describes "a positive electrode mixture for non-aqueous batteries, which is prepared by adding an organic acid to a mixture consisting of a positive electrode active material made of a composite metal oxide, a conductive additive, a vinylidene fluoride polymer, and an organic solvent.”
  • One of the objectives of this disclosure is to provide a positive electrode slurry for a non-aqueous electrolyte secondary battery that exhibits minimal change over time.
  • the positive electrode slurry is a positive electrode slurry for manufacturing a positive electrode for a non-aqueous electrolyte secondary battery, and includes a lithium-containing complex oxide as a positive electrode active material, a fluorine-containing polymer as a binder, an aliphatic alcohol derivative, and a liquid medium, in which the proportion of nickel in the element Z other than lithium and oxygen in the lithium-containing complex oxide is 80 atomic % or more, and the ratio Ma/Mp of the mass Ma of the aliphatic alcohol derivative to the mass Mp of the positive electrode active material is in the range of 0.00001 to 0.001.
  • Another aspect of the present disclosure relates to a method for producing a positive electrode for a non-aqueous electrolyte secondary battery.
  • the method includes a step (i) of preparing a positive electrode slurry according to the present disclosure, and a step (ii) of forming a positive electrode mixture layer on a positive electrode current collector using the positive electrode slurry.
  • the non-aqueous electrolyte secondary battery includes a positive electrode including a positive electrode mixture layer, a negative electrode, and a non-aqueous electrolyte, and the positive electrode mixture layer includes a lithium-containing composite oxide as a positive electrode active material, a fluorine-containing polymer as a binder, and a reaction product of an aliphatic alcohol derivative and lithium hydroxide, and in the lithium-containing composite oxide, the proportion of nickel in the element Z other than lithium and oxygen is 80 atomic % or more.
  • FIG. 1 is a schematic perspective view of a nonaqueous electrolyte secondary battery according to an embodiment of the present disclosure, with a portion cut away.
  • the positive electrode slurry according to this embodiment is a positive electrode slurry for manufacturing a positive electrode for a non-aqueous electrolyte secondary battery.
  • the positive electrode slurry according to this embodiment may be referred to as "slurry (S)" or “positive electrode slurry (S)” below.
  • the slurry (S) includes a lithium-containing composite oxide as a positive electrode active material, a fluorine-containing polymer as a binder, an aliphatic alcohol derivative, and a liquid medium.
  • the proportion of nickel in the element Z other than lithium and oxygen is 80 atomic % or more.
  • the ratio Ma/Mp of the mass Ma of the aliphatic alcohol derivative to the mass Mp of the positive electrode active material is in the range of 0.00001 to 0.001.
  • the positive electrode slurry (S) according to the present disclosure changes little over time. As will be explained in the examples, by using the positive electrode slurry (S), it is possible to manufacture a nonaqueous electrolyte secondary battery with high thermal stability.
  • the proportion of nickel in the element Z other than lithium and oxygen is 80 atomic % or more, and may be 85 atomic % or more, or 90 atomic % or more. The proportion may be 100 atomic % or less, 99 atomic % or less, or 95 atomic % or less.
  • the ratio Ma/Mp of the mass Ma of the aliphatic alcohol derivative to the mass Mp of the positive electrode active material is in the range of 0.00001 to 0.001.
  • the ratio Ma/Mp may be 0.00005 or more, 0.0001 or more, or 0.0003 or more. By making the ratio Ma/Mp 0.00005 or more, an increase in the viscosity of the slurry (S) can be particularly suppressed.
  • the ratio Ma/Mp is preferably 0.0005 or less, and may be 0.00049 or less, 0.0004 or less, or 0.0003 or less.
  • the ratio Ma/Mp is in the range of 0.00001 to 0.001, and may be in the range of 0.00005 to 0.001, or in the range of 0.0003 to 0.001. Within these ranges, the upper limit may be 0.0005, 0.00049, 0.0004, or 0.0003, as long as the lower limit is not greater than or equal to the upper limit.
  • the thermal stability of the battery decreases when the ratio Ma/Mp is too high (the amount of aliphatic alcohol derivative is too large) is thought to be that when the amount of reaction product between the aliphatic alcohol derivative and lithium hydroxide becomes too large, the surface of the active material particles is coated with the reaction product, causing an increase in the internal resistance of the positive electrode.
  • the aliphatic alcohol derivative can suppress the effects of lithium hydroxide in the slurry (S) and also function as a dispersant.
  • the aliphatic alcohol derivative is a compound in which a substituent is bonded to an aliphatic alcohol.
  • An example of the substituent is an amino group.
  • An example of an aliphatic alcohol derivative is an alkanolamine.
  • An alkanolamine is a compound having an alkane skeleton and a hydroxyl group and an amino group bonded to the alkane skeleton.
  • the number of carbon atoms contained in the aliphatic alcohol derivative may be 4 or more and may be 22 or less (e.g., 10 or less or 8 or less).
  • the molecular weight of the aliphatic alcohol derivative may be 50 or more, or 80 or more, and may be 326 or less, or 150 or less. The molecular weight may be in the range of 50 to 326 (e.g., 80 to 150).
  • the aliphatic alcohol derivative is preferably a compound that dissolves in the liquid medium used in the slurry (S).
  • the number of side chains (substituents) of the aliphatic alcohol derivative may be 10 or less, and is preferably 1 to 5.
  • side chains examples include alkyl groups, aldehyde groups, amino groups, carboxyl groups, carbonyl groups, nitro groups, and hydroxy groups.
  • Preferred examples of the side chains (substituents) include amino groups and hydroxy groups.
  • the side chains (substituents) may be amino groups.
  • An example of an aliphatic alcohol derivative is a compound in which one hydrogen atom of an alkane having 4 to 10 carbon atoms (for example, 4 to 6 carbon atoms) is replaced with a hydroxyl group and one hydrogen atom is replaced with an amino group.
  • the hydroxyl group is bonded to the terminal carbon of the main chain, and the amino group is bonded to a carbon atom other than the terminal carbon.
  • the aliphatic alcohol derivative may be aminomethylpropanol, for example, 2-amino-2-methyl-1-propanol represented by the following formula.
  • 2-amino-2-methyl-1-propanol can function as a dispersant in the slurry (S).
  • the ratio Mh/Mp of the mass Mh of lithium hydroxide present in the positive electrode active material to the mass Mp of the positive electrode active material may be 0.001 or more, 0.01 or more, or 0.03 or more.
  • the ratio Mh/Mp is 0.001 or more, it is particularly important to add an aliphatic alcohol derivative.
  • the ratio Mh/Mp tends to increase as the proportion of nickel in the lithium-containing composite oxide increases.
  • the ratio Mh/Mp may be 0.05 or less.
  • the ratio Mh/Mp is determined by measuring the positive electrode active material (positive electrode active material particles) before it is added to the positive electrode slurry. Specifically, it can be determined by the following method. First, the mass Mp of the positive electrode active material is measured. Next, the mass Mh of the lithium hydroxide present in the positive electrode active material whose mass Mp has been measured is quantified. The ratio Mh/Mp can be determined from the obtained masses Mp and Mh. The mass Mh of the lithium hydroxide present in the positive electrode active material can be quantified by the method described in the examples.
  • the lithium-containing composite oxide which is the positive electrode active material, can absorb and release lithium ions.
  • the composite oxide contains at least nickel.
  • the composite oxide may have a layered structure (e.g., a rock salt crystal structure).
  • the lithium-containing composite oxide may be an oxide having a composition formula represented by Li y Ni x M (1-x) O 2- ⁇ , where 0.8 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1.2, and 0 ⁇ 0.05 are satisfied.
  • the element M in the formula includes at least one element selected from the group consisting of Co, Mn, Al, Fe, Ti, Sr, Ca, Zr, W, and B, and may be the at least one element.
  • the element M preferably contains at least one element selected from the group consisting of Co, Mn, Al, and Fe, and may be the at least one element.
  • the element M may contain Co and Al, or may be Co and Al.
  • the value of y which indicates the composition ratio of lithium in the above composition formula, increases and decreases with charging and discharging.
  • Specific examples of the composite oxide include lithium-nickel-cobalt-aluminum composite oxide (LiNi 0.9 Co 0.05 Al 0.05 O 2 , etc.).
  • x when x is 0.8 or more, the proportion of nickel in the element Z other than lithium and oxygen is 80 atomic % or more. By making x 0.8 or more, the battery capacity can be increased. On the other hand, when x is 0.8 or more, gelation of the positive electrode slurry is likely to occur, so it is particularly important to add an aliphatic alcohol derivative.
  • the lithium-containing composite oxide is usually used in the form of particles.
  • the average particle size of the lithium-containing composite oxide may be 1 ⁇ m or more, 2 ⁇ m or more, or 5 ⁇ m or more, and may be 20 ⁇ m or less, or 15 ⁇ m or less, 10 ⁇ m or less, 6 ⁇ m or less, or 5 ⁇ m or less.
  • the average particle size is the median diameter (D50) at which the cumulative volume is 50% in the volume-based particle size distribution.
  • D50 the median diameter
  • the median diameter is determined using a laser diffraction/scattering type particle size distribution measuring device.
  • the fluorine-containing polymer functions as a binder in the positive electrode mixture layer.
  • the fluorine-containing polymer contains fluorine.
  • fluorine-containing polymers include vinylidene fluoride polymers.
  • vinylidene fluoride polymers include polymers of monomers containing vinylidene fluoride.
  • the fluorine-containing polymer may be a combination of a vinylidene fluoride polymer and another fluorine-containing polymer.
  • the vinylidene fluoride polymer may be a copolymer of vinylidene fluoride and another monomer.
  • vinylidene fluoride polymers include polyvinylidene fluoride (PVDF).
  • the amount of the fluorine-containing polymer per 100 parts by mass of the positive electrode active material may be 0.1 parts by mass or more, or 0.5 parts by mass or more, and may be 2.0 parts by mass or less, or 1.2 parts by mass or less.
  • the weight average molecular weight of the fluorine-containing polymer may be 800,000 or more, 1,000,000 or more, or 1,200,000 or more, or may be 2,000,000 or less, or 1,800,000 or less. By making the weight average molecular weight 1,000,000 or more, it is possible to obtain a high effect as a binder with a small amount.
  • the positive electrode slurry (S) usually contains a conductive material.
  • the conductive material is not particularly limited, and may be a conductive material used in known positive electrode slurries, or may be a carbonaceous material having electrical conductivity. Examples of carbonaceous materials having electrical conductivity include conductive carbon particles such as carbon black, carbon nanotubes, and other conductive carbonaceous materials.
  • the liquid medium in the positive electrode slurry (S) is not particularly limited, and any liquid medium used in known positive electrode slurries may be used.
  • the liquid medium may be an organic solvent.
  • organic solvents include alcohols (such as ethanol), ethers (such as tetrahydrofuran), amides (such as dimethylformamide), and N-methyl-2-pyrrolidone (NMP).
  • An example of the positive electrode slurry (S) contains 2-amino-2-methyl-1-propanol (an aliphatic alcohol derivative), N-methyl-2-pyrrolidone (a liquid medium), and a lithium-containing composite oxide represented by the composition formula described above.
  • the positive electrode slurry (S) may contain components other than those described above, if necessary.
  • the positive electrode slurry (S) may contain a binder other than the fluorine-containing polymer.
  • An example of the positive electrode slurry (S) does not contain a cellulose ether derivative.
  • An example of the positive electrode slurry (S) does not contain diethylene glycol.
  • the positive electrode slurry (S) can be prepared by mixing the above-mentioned components.
  • the positive electrode slurry (S) contains an aliphatic alcohol derivative, which can suppress the increase in viscosity over time.
  • the method for producing a positive electrode according to this embodiment may be referred to as "production method (M)" below.
  • the production method (M) is a method for producing a positive electrode for a non-aqueous electrolyte secondary battery.
  • the production method (M) includes a step of preparing a positive electrode slurry (S) and a step of forming a positive electrode mixture layer on a positive electrode current collector using the positive electrode slurry (S).
  • the description of the positive electrode slurry (S) can be applied to the production method (M), so that overlapping descriptions may be omitted.
  • step (i) the components of the positive electrode slurry (S) are mixed to prepare the positive electrode slurry (S).
  • the mixing method is not particularly limited, and any known mixing method may be used.
  • the components and mixing ratios of the components of the positive electrode slurry (S) may be the same as those described above.
  • the positive electrode slurry (S) can be prepared by mixing a positive electrode active material, a fluorine-containing polymer, an aliphatic alcohol derivative, a liquid medium, and a conductive material.
  • step (ii) first, the positive electrode slurry (S) is applied onto a positive electrode current collector to form a coating film. Next, the formed coating film is dried by heat treatment to form a laminate including the positive electrode current collector and the coating film (positive electrode mixture layer) formed on the positive electrode current collector. Next, the laminate is rolled. In this manner, the positive electrode can be manufactured. Depending on the structure of the battery, the positive electrode mixture layer may be formed on only one side of the positive electrode current collector or on both sides of the positive electrode current collector.
  • the liquid medium is substantially removed.
  • at least a portion of the aliphatic alcohol derivative may be removed. Therefore, the ratio Ma/Mp of the mass Ma of the aliphatic alcohol derivative to the mass Mp of the positive electrode active material in the produced positive electrode may be smaller than the ratio Ma/Mp in the positive electrode slurry (S).
  • the ratio of the components contained in the positive electrode slurry (S) is, in principle, reflected in the ratio of the components in the positive electrode mixture layer. Therefore, by changing the ratio of the components contained in the positive electrode slurry (S), it is possible to change the ratio of the components in the positive electrode mixture layer.
  • the positive electrode current collector is not particularly limited, and a known positive electrode current collector may be used.
  • Examples of materials for the positive electrode current collector include stainless steel, aluminum, aluminum alloy, titanium, etc.
  • a portion of the aliphatic alcohol derivative is present in the positive electrode in the form of a reaction product with lithium hydroxide.
  • the reaction product is, for example, a reaction product that is generated by a dehydration reaction between lithium hydroxide present on the surface of the positive electrode active material particles and the hydroxyl groups of the aliphatic alcohol derivative.
  • the reaction product forms a protective film on the surface of the positive electrode active material particles, and is thought to suppress side reactions (such as gas generation) between the positive electrode active material and the electrolyte. As a result, it is thought that the thermal stability of the battery is improved.
  • the nonaqueous electrolyte secondary battery may be referred to as a "secondary battery (B)" hereinafter.
  • the secondary battery (B) includes a positive electrode including a positive electrode mixture layer, a negative electrode,
  • the positive electrode mixture layer contains a lithium-containing composite oxide as a positive electrode active material, a fluorine-containing polymer as a binder, and a reaction product of an aliphatic alcohol derivative and lithium hydroxide.
  • the ratio of nickel to the element Z other than lithium and oxygen is 80 atomic % or more.
  • the positive electrode mixture layer may contain an aliphatic alcohol derivative.
  • the positive electrode can be formed using a positive electrode slurry (S), for example, by manufacturing method (M).
  • S positive electrode slurry
  • M manufacturing method
  • the items explained about the positive electrode slurry (S) and manufacturing method (M) can be applied to the positive electrode of the secondary battery (B), so duplicated explanations may be omitted.
  • the components of the positive electrode mixture layer have been described above, so duplicated explanations will be omitted.
  • the positive electrode does not substantially contain the liquid medium described above.
  • the positive electrode mixture layer of the secondary battery (B) contains a reaction product between an aliphatic alcohol derivative and lithium hydroxide. As described above, this reaction product forms a protective film on the surface of the positive electrode active material, which is thought to improve the thermal stability of the battery.
  • the components other than the positive electrode are not particularly limited, and components used in known non-aqueous electrolyte secondary batteries may be used. Examples of components of the secondary battery (B) are described below.
  • Positive electrode As the positive electrode, the above-mentioned positive electrode is used.
  • the negative electrode typically includes a negative electrode mixture layer containing a negative electrode active material.
  • the negative electrode may include a negative electrode current collector and a negative electrode mixture layer disposed on the negative electrode current collector.
  • a negative electrode current collector on which lithium metal or a lithium alloy can be deposited is used for the negative electrode.
  • the negative electrode mixture layer contains a negative electrode active material as an essential component.
  • the negative electrode mixture layer may contain optional components such as a binder, a thickener, and a conductive material.
  • the optional components may include the components exemplified as the components of the positive electrode.
  • the negative electrode mixture layer may be formed by applying a negative electrode slurry, in which the components of the negative electrode mixture layer are dispersed in a liquid medium (dispersion medium), to the surface of the negative electrode current collector and drying it.
  • the coating film after drying may be rolled as necessary.
  • the liquid medium may be any of the liquid media exemplified for the positive electrode slurry.
  • the negative electrode active material is selected according to the type of the secondary battery (B).
  • An example of the negative electrode active material is a material capable of absorbing and releasing lithium ions. Examples of such materials include carbonaceous materials, Si-containing materials, and the like.
  • the negative electrode active material may include a Si-containing material or may be a Si-containing material. Metallic lithium, lithium alloys, and the like may be used as the negative electrode active material.
  • the negative electrode may include one type of negative electrode active material, or may include a combination of two or more types.
  • carbonaceous materials examples include graphite, easily graphitized carbon (soft carbon), and difficult-to-graphitize carbon (hard carbon).
  • the carbonaceous materials may be used alone or in combination of two or more.
  • Graphite is preferred because it has excellent charge/discharge stability and low irreversible capacity.
  • Examples of graphite include natural graphite, artificial graphite, and graphitized mesophase carbon particles.
  • Si-containing material examples include simple Si, silicon alloys, silicon compounds (such as silicon oxides), and composite materials in which a silicon phase is dispersed in a lithium ion conductive phase (matrix).
  • silicon oxides include SiO x particles. x may be, for example, 0.5 ⁇ x ⁇ 2, or 0.8 ⁇ x ⁇ 1.6.
  • the lithium ion conductive phase at least one selected from the group consisting of a SiO 2 phase, a silicate phase, and a carbon phase may be used.
  • the negative electrode current collector may be a metal foil.
  • the negative electrode current collector may be porous. Examples of materials for the negative electrode current collector include stainless steel, nickel, nickel alloys, copper, and copper alloys.
  • the non-aqueous electrolyte includes a solvent (non-aqueous solvent) and a solute dissolved in the solvent.
  • a solvent non-aqueous solvent
  • a solute dissolved in the solvent.
  • the solute include a lithium salt.
  • additives may be added to the non-aqueous electrolyte.
  • cyclic carbonate esters can be used as the solvent.
  • cyclic carbonate esters include propylene carbonate (PC), ethylene carbonate (EC), fluoroethylene carbonate (FEC), vinylene carbonate (VC), etc.
  • Chain carbonate esters include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), etc.
  • cyclic carboxylate esters include ⁇ -butyrolactone (GBL), ⁇ -valerolactone (GVL), etc.
  • chain carboxylate esters examples include non-aqueous solvents such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate (MP), and ethyl propionate (EP).
  • the non-aqueous solvents may be used alone or in combination of two or more.
  • lithium salts include lithium salts of chlorine-containing acids ( LiClO4 , LiAlCl4 , LiB10Cl10 , etc. ), lithium salts of fluorine-containing acids ( LiPF6 , LiPF2O2 , LiBF4 , LiSbF6 , LiAsF6 , LiCF3SO3 , LiCF3CO2 , etc.
  • lithium salts of fluorine-containing acid imides LiN(FSO2) 2 , LiN( CF3SO2 ) 2 , LiN( CF3SO2 ) ( C4F9SO2 ), LiN ( C2F5SO2 ) 2 , etc.
  • lithium halides LiCl , LiBr , LiI , etc.
  • the lithium salt may be used alone or in combination of two or more kinds.
  • the concentration of the lithium salt in the non-aqueous electrolyte may be 1 mol/L or more and 2 mol/L or less, or 1 mol/L or more and 1.5 mol/L or less.
  • the non-aqueous electrolyte may contain known additives.
  • additives include 1,3-propane sultone, methylbenzenesulfonate, cyclohexylbenzene, biphenyl, diphenyl ether, fluorobenzene, etc.
  • the separator is disposed between the positive electrode and the negative electrode.
  • the separator preferably has high ion permeability and appropriate mechanical strength and insulation.
  • the separator may be made of a microporous thin film, a woven fabric, a nonwoven fabric, or the like. Examples of the separator material include polyolefins (polypropylene, polyethylene, etc.) and other resins.
  • the electrode group and the non-aqueous electrolyte are housed in the exterior body (battery case).
  • the exterior body is not particularly limited, and a known exterior body may be used.
  • the electrode group is composed of a positive electrode, a negative electrode, and a separator.
  • the configuration of the electrode group is not particularly limited, and may be a wound type or a laminated type.
  • the wound type electrode group is formed by winding the positive electrode and the negative electrode with the separator interposed therebetween.
  • the laminated type electrode group is formed by stacking the positive electrode and the negative electrode with the separator interposed therebetween.
  • the shape of the non-aqueous electrolyte secondary battery is not particularly limited, and may be a cylindrical shape, a square shape, a coin shape, a button shape, a laminate shape, or the like.
  • FIG. 1 is a schematic perspective view of a secondary battery 10 according to an embodiment of the present disclosure, with a portion cut away.
  • FIG. 1 shows a rectangular non-aqueous electrolyte battery as an example.
  • the secondary battery 10 shown in FIG. 1 includes a battery case 4 in the shape of a rectangular cylinder with a bottom, and an electrode group 1 and a non-aqueous electrolyte (not shown) housed within the battery case 4.
  • the electrode group 1 includes a long strip-shaped negative electrode, a long strip-shaped positive electrode, and a separator disposed between them.
  • the positive electrode is the positive electrode described above.
  • the negative electrode current collector of the negative electrode is electrically connected to a negative electrode terminal 6 provided on a sealing plate 5 via a negative electrode lead 3.
  • the negative electrode terminal 6 is insulated from the sealing plate 5 by a resin gasket 7.
  • the positive electrode current collector of the positive electrode is electrically connected to the back surface of the sealing plate 5 via a positive electrode lead 2. That is, the positive electrode is electrically connected to the battery case 4, which also serves as a positive electrode terminal.
  • the periphery of the sealing plate 5 is fitted into the open end of the battery case 4, and the fitting portion is laser welded.
  • the sealing plate 5 has an injection hole for a non-aqueous electrolyte. The injection hole is closed by a seal plug 8 after the non-aqueous electrolyte is injected.
  • a positive electrode slurry for producing a positive electrode for a non-aqueous electrolyte secondary battery A lithium-containing composite oxide that is a positive electrode active material; a fluorine-containing polymer as a binder; An aliphatic alcohol derivative, A liquid medium,
  • the ratio of nickel to the element Z other than lithium and oxygen is 80 atomic % or more
  • a ratio Ma/Mp of a mass Ma of the aliphatic alcohol derivative to a mass Mp of the positive electrode active material is in the range of 0.00001 to 0.001.
  • the lithium-containing composite oxide is an oxide represented by a composition formula Li y Ni x M (1-x) O 2- ⁇ (wherein 0.8 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1.2, 0 ⁇ 0.05, and M contains at least one element selected from the group consisting of Co, Mn, Al, Fe, Ti, Sr, Ca, Zr, W, and B).
  • a method for producing a positive electrode for a non-aqueous electrolyte secondary battery comprising: (i) preparing a positive electrode slurry according to the first or second aspect of the present invention; and (ii) forming a positive electrode mixture layer on a positive electrode current collector using the positive electrode slurry.
  • the aliphatic alcohol derivative is 2-amino-2-methyl-1-propanol.
  • a positive electrode active material polyvinylidene fluoride (PVDF, binder), 2-amino-2-methyl-1-propanol (AMP, aliphatic alcohol derivative), acetylene black (conductive material), and N-methyl-2-pyrrolidone (NMP, liquid medium) were mixed in a predetermined mass ratio to prepare a positive electrode slurry SA1.
  • PVDF polyvinylidene fluoride
  • AMP 2-amino-2-methyl-1-propanol
  • conductive material acetylene black
  • NMP N-methyl-2-pyrrolidone
  • the ratio Mh/Mp of the positive electrode active material used was determined by the following method. First, the mass Mp of the sample of the positive electrode active material was measured. Next, the mass Mh of the lithium hydroxide present in the sample whose mass Mp was measured was quantified by the following method. First, ion-exchanged water was added to the sample of the positive electrode active material and the positive electrode active material was dissolved by shaking to obtain a solution. Next, the solution was filtered to obtain a filtrate. Next, the filtrate was titrated with hydrochloric acid (concentration: 1 mol/L) under a N2 atmosphere to obtain the mass Mh. From the masses Mp and Mh thus obtained, the ratio Mh/Mp was obtained.
  • Positive electrode slurries SA2 to SA3, SC1 to SC2 were prepared in the same manner and under the same conditions as for the preparation of positive electrode slurry SA1, except that the composition and component ratios of the positive electrode active materials were changed as shown in Table 1.
  • the ratio Mh/Mh of the positive electrode active materials used in the preparation of the positive electrode slurries was determined by the method described above.
  • Viscosity increase rate (%) 100 ⁇ ⁇ 1/ ⁇ 0
  • a battery A1 was prepared in the following manner. (1) Preparation of negative electrode A negative electrode active material, sodium carboxymethyl cellulose (CMC-Na), styrene-butadiene rubber (SBR), and water were mixed in a predetermined mass ratio to prepare a negative electrode slurry. Graphite was used as the negative electrode active material. Next, the negative electrode slurry was applied to the surface of a copper foil (negative electrode current collector) to form a laminate including the copper foil and the coating film formed on the copper foil. Next, after drying the coating film, the laminate was rolled. In this way, a negative electrode including the copper foil and the negative electrode mixture layer formed on both sides of the copper foil was formed.
  • CMC-Na sodium carboxymethyl cellulose
  • SBR styrene-butadiene rubber
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • Batteries A2 to A3, C1 to C2 were produced in the same manner and under the same conditions as those for the production of Battery A1, except that the above-mentioned positive electrode slurries SA2 to SA3, SC1 to SC2 were used instead of the positive electrode slurry SA1.
  • Battery C1 was then placed in a thermostatic chamber, and the temperature inside the chamber was raised to 135°C. The temperature of the side of battery C1 placed in the 135°C thermostatic chamber for 5 minutes (battery temperature T during the heating test) was then measured. Similar measurements were performed on the other batteries.
  • the manufacturing conditions and evaluation results of the positive electrode slurry and the battery are shown in Table 1.
  • active material: PVDF: AMP: conductive material indicates the mass ratio of these in the positive electrode slurry.
  • the viscosity increase rate and discharge capacity shown in Table 1 are values when the evaluation results of the positive electrode slurry SC1 and the battery C1 are set to 100.
  • the battery temperature T during the heating test shown in Table 1 is a relative value when the evaluation result of the battery C1 is set to 0.
  • the lower the viscosity increase rate the smaller the viscosity increase and the better the slurry.
  • the lower the battery temperature T the smaller the temperature increase when heated and the safer the battery.
  • Positive electrode slurries SA1 to SA3 are positive electrode slurries (S) according to the present disclosure, and positive electrode slurries SC1 to SC2 are comparative examples.
  • Batteries A1 to A3 are secondary batteries (B) according to the present disclosure, and batteries C1 and C2 are comparative examples.
  • the present disclosure can be utilized in a positive electrode slurry for a nonaqueous electrolyte secondary battery, a method for producing a positive electrode for a nonaqueous electrolyte secondary battery, and a nonaqueous electrolyte secondary battery.
  • Electrode group 1: Electrode group, 2: Positive electrode lead, 3: Negative electrode lead, 4: Battery case, 5: Sealing plate, 6: Negative electrode terminal, 7: Gasket, 8: Seal, 10: Secondary battery (non-aqueous electrolyte secondary battery)

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PCT/JP2024/007152 2023-02-28 2024-02-27 非水電解質二次電池用の正極スラリー、非水電解質二次電池用の正極の製造方法、および、非水電解質二次電池 Ceased WO2024181461A1 (ja)

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Publication number Priority date Publication date Assignee Title
JP2022063854A (ja) * 2020-10-12 2022-04-22 花王株式会社 蓄電デバイス電極用分散剤組成物
WO2023282246A1 (ja) * 2021-07-06 2023-01-12 日産化学株式会社 電極形成用組成物
JP2023127301A (ja) * 2022-03-01 2023-09-13 株式会社東芝 電極用スラリー、電極用スラリーの製造方法、及び、電極の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022063854A (ja) * 2020-10-12 2022-04-22 花王株式会社 蓄電デバイス電極用分散剤組成物
WO2023282246A1 (ja) * 2021-07-06 2023-01-12 日産化学株式会社 電極形成用組成物
JP2023127301A (ja) * 2022-03-01 2023-09-13 株式会社東芝 電極用スラリー、電極用スラリーの製造方法、及び、電極の製造方法

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