WO2024053110A1 - Matériau d'électrode, électrode pour dispositifs de stockage d'énergie et dispositif de stockage d'énergie - Google Patents

Matériau d'électrode, électrode pour dispositifs de stockage d'énergie et dispositif de stockage d'énergie Download PDF

Info

Publication number
WO2024053110A1
WO2024053110A1 PCT/JP2022/033953 JP2022033953W WO2024053110A1 WO 2024053110 A1 WO2024053110 A1 WO 2024053110A1 JP 2022033953 W JP2022033953 W JP 2022033953W WO 2024053110 A1 WO2024053110 A1 WO 2024053110A1
Authority
WO
WIPO (PCT)
Prior art keywords
particles
electrode
active material
energy storage
mass
Prior art date
Application number
PCT/JP2022/033953
Other languages
English (en)
Japanese (ja)
Inventor
学 平澤
Original Assignee
株式会社レゾナック
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 株式会社レゾナック filed Critical 株式会社レゾナック
Priority to PCT/JP2022/033953 priority Critical patent/WO2024053110A1/fr
Publication of WO2024053110A1 publication Critical patent/WO2024053110A1/fr

Links

Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers

Definitions

  • the present disclosure relates to electrode materials, electrodes for energy storage devices, and energy storage devices.
  • the positive and negative electrodes of such energy storage devices generally include particles of a material (active material) capable of intercalating and deintercalating alkali metal ions.
  • the volume of the active material changes as it absorbs and releases alkali metal ions, repeated charging and discharging will cause cracks in the active material and cause deterioration of the electrode. Therefore, coating the surface of the active material particles with a flexible material such as a polymer compound is considered to be an effective measure for suppressing electrode deterioration.
  • Japanese Patent Publication No. 2019-535116 describes coating active material particles with cyclized polyacrylonitrile.
  • an object of the present disclosure is to provide an electrode material, an electrode for an energy storage device, and an energy storage device that have excellent cycle characteristics.
  • Means for solving the above problems include the following embodiments.
  • An electrode comprising composite particles including particles containing a substance capable of occluding and releasing alkali metal ions, and a coating portion containing a polymeric material and a conductive agent that coats at least a portion of the surface of the particles. material.
  • the content of the conductive aid in the coating portion is 30% by mass or more.
  • the polymer material includes at least one selected from polyamideimide and polyacrylonitrile.
  • ⁇ 5> The electrode material according to ⁇ 1>, wherein the particles contain silicon.
  • ⁇ 6> The electrode material according to ⁇ 1>, wherein the conductive support agent includes particles having an aspect ratio of 10 or more.
  • ⁇ 8> An energy storage device comprising the electrode for an energy storage device according to ⁇ 7>.
  • an electrode material an electrode for an energy storage device, and an energy storage device with excellent cycle characteristics are provided.
  • Example 1 is a SEM image of composite particles produced in Example 1.
  • 1 is a cross-sectional SEM image of composite particles produced in Example 1.
  • 3 is a SEM image of composite particles produced in Example 2.
  • step includes not only a step that is independent from other steps, but also a step that cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved.
  • numerical ranges indicated using “ ⁇ ” include the numerical values written before and after " ⁇ " as minimum and maximum values, respectively.
  • the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step.
  • the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
  • each component may contain multiple types of corresponding substances.
  • each component may include a plurality of types of particles.
  • the particle diameter of each component means a value for a mixture of the plurality of types of particles present in the composition, unless otherwise specified.
  • the term "layer" includes not only the case where the layer is formed in the entire area when observing the area where the layer exists, but also the case where the layer is formed only in a part of the area. included.
  • the electrode material of the present disclosure includes particles containing a substance capable of occluding and releasing alkali metal ions (hereinafter also referred to as active material particles), a polymer material and a conductive additive that coat at least a portion of the surface of the particles.
  • An electrode material comprising: a coating portion comprising a composite particle comprising a coating portion comprising a coating portion comprising a coating portion comprising a composite particle comprising a coating portion comprising a coating portion comprising a coating portion comprising a coating portion comprising a coating portion comprising a coating portion comprising a coating portion comprising a composite particle comprising a coating portion comprising a coating portion;
  • an energy storage device fabricated using composite particles, in which at least a portion of the surface of active material particles is coated with a coating portion containing a polymeric material and a conductive agent, as an electrode material. , it was found that it exhibited excellent cycle characteristics. The reason for this is thought to be, for example, as follows.
  • the active material particles contained in the composite particles usually undergo deterioration due to repeated expansion and contraction due to occlusion and release of alkali metal ions.
  • the electrolytic solution resistance and mechanical strength of the active material particles are improved, and deterioration due to expansion and contraction of the active material particles is suppressed.
  • the conduction paths of alkali metal ions and electrons between the active material particles are blocked by the coating, causing deterioration in cycle characteristics.
  • the entire surface of the active material particles may be covered with the coating portion, or a portion of the surface may be covered with the coating portion.
  • the coverage of the surface of the active material particles by the coating portion (hereinafter also referred to as coverage of composite particles) is preferably 50% or more, more preferably 60% or more, More preferably, it is 70% or more.
  • the coverage of the composite particles may be 100% or less, 90% or less, or 80% or less.
  • the coverage may be calculated using known image processing software such as ImageJ.
  • the content of the conductive aid contained in the coating is not particularly limited. From the perspective of ensuring sufficient conduction paths for alkali metal ions and electrons between active material particles, the content of the conductive aid is preferably 30% by mass or more of the entire coating, and should be 40% by mass or more. is more preferable, and even more preferably 45% by mass or more. From the viewpoint of suppressing deterioration due to expansion and contraction of active material particles, the content of the conductive additive is preferably 80% by mass or less of the entire coating, more preferably 70% by mass or less, and 65% by mass or less. % or less is more preferable.
  • the content of the polymer material contained in the covering portion is not particularly limited. From the viewpoint of suppressing deterioration due to expansion and contraction of active material particles, the content of the polymer material is preferably 20% by mass or more of the entire coating, more preferably 30% by mass or more, and 35% by mass or more. % or more is more preferable. From the viewpoint of ensuring sufficient conduction paths for alkali metal ions and electrons on the surface of the active material particles, the content of the polymer material is preferably 70% by mass or less of the entire coating, and is 60% by mass or less. It is more preferably 55% by mass or less.
  • the covering portion may contain only the polymeric material and the conductive aid, or may contain components other than the polymeric material and the conductive aid.
  • Components other than the polymer material and the conductive aid include a silane coupling agent and the like. By including the silane coupling agent, for example, the binding force of the coating portion to the active material particles can be increased.
  • the covering part contains components other than the polymeric material and the conductive aid, the total proportion of the polymeric material and the conductive aid to the entire covering part is preferably 80% by mass or more, and should be 85% by mass or more. is more preferable, and even more preferably 90% by mass or more.
  • the proportion of the coating portion in the entire composite particle is preferably 0.1% by mass to 50% by mass, more preferably 1% by mass to 20% by mass, and 5% by mass to 10% by mass. is even more preferable.
  • the proportion of the coated portion is 0.1% by mass or more of the entire composite particle, a sufficient effect of improving cycle characteristics can be obtained.
  • the ratio of the coating portion is 50% by mass or more of the entire composite particle, a sufficient capacity of the energy storage device is ensured.
  • the ratio of the coated part to the whole composite particle is determined by, for example, the change in mass before and after the treatment when the composite particle is heat-treated at a temperature at which the coated part thermally decomposes, or the mass before and after the treatment when the coated part is dissolved in a solvent. It can be calculated from the change.
  • the composite particles may contain only one type of active material particles or two or more types of active material particles.
  • the coating portion of the composite particle may contain only one kind of polymer material and conductive aid, or two or more kinds thereof.
  • the volume average particle diameter (D50) of the composite particles measured by a laser scattering diffraction method is preferably 1 ⁇ m to 50 ⁇ m, more preferably 3 ⁇ m to 30 ⁇ m.
  • D50 volume average particle diameter of the composite particles measured by a laser scattering diffraction method.
  • the volume average particle diameter of the composite particles is 1 ⁇ m or more, it becomes easy to prepare a slurry for forming an electrode.
  • the electrode can be easily formed into a thin film, and the input/output characteristics of the energy storage device can be easily improved.
  • the volume average particle diameter of the composite particles is measured by laser scattering diffraction method. Specifically, in the volume-based particle size distribution obtained by the laser scattering diffraction method, the particle size when the accumulation from the small diameter side is 50% is defined as the volume average particle size.
  • the method for producing composite particles is not particularly limited. For example, by mixing a predetermined amount of active material particles, a polymer material, and a conductive additive with a solvent, drying the resulting mixture, subjecting it to heat treatment as necessary, and crushing it, the surface of the active material particles can be improved.
  • Composite particles can be obtained that are at least partially coated with a coating containing a polymeric material and a conductive additive.
  • the composite particles may be in a state in which individual active material particles are each covered with a coating portion, or may be in a state in which an aggregate of a plurality of active material particles is covered with a coating portion.
  • the active material particles included in the composite particles are not particularly limited as long as they contain a substance (active material) that can occlude and release alkali metal ions.
  • alkali metal ions include lithium ions, potassium ions, sodium ions, and the like. Among these, lithium ions are preferred.
  • the active materials contained in the active material particles may be one type or a combination of two or more types.
  • Examples of the active material of the positive electrode include lithium transition metal compounds such as lithium transition metal oxides and lithium transition metal phosphates.
  • Examples of lithium transition metal oxides include compounds containing one or more transition metals such as Mn, Ni, and Co, and a portion of the transition metals contained in these compounds in combination with one or more other transition metals. Examples include lithium transition metal oxides substituted with transition metals or metal elements (typical elements) such as Mg and Al.
  • Examples of the active material of the negative electrode include carbon materials, active materials containing silicon atoms, and the like. Examples of carbon materials include graphite, hard carbon, and soft carbon. Examples of active materials containing silicon atoms include Si (metallic silicon), silicon oxide represented by SiOx (0.8 ⁇ x ⁇ 1.5), and the like.
  • the silicon oxide may have a structure in which nanosilicon is dispersed in a silicon oxide matrix by a disproportionation reaction.
  • the active material containing silicon atoms may be doped with boron, phosphorus, or the like to become a
  • the active material particles may be made of a carbon material and silicon may be present on the surface of the active material particles.
  • Examples of methods for causing silicon to be present on the surface of active material particles made of a carbon material include vapor deposition, plasma CVD (Chemical Vapor Deposition), and the like.
  • the plasma CVD method may be performed by decomposing raw materials such as silane and chlorosilane.
  • active materials containing silicon atoms have a large theoretical capacity and are expected to contribute to increasing the capacity of energy storage devices, they undergo large volume changes during charging and discharging and are susceptible to deterioration. Furthermore, active materials containing silicon atoms do not themselves have electronic conductivity. In the present disclosure, electron conductivity can be imparted to the active material particles by coating the surfaces of the active material particles with a coating portion containing a conductive additive. Therefore, it is particularly suitable when the active material particles contain silicon atoms.
  • the shape of the active material particles is not particularly limited.
  • they may be spherical particles, scaly particles, lumpy particles, secondary particles composed of a plurality of primary particles, or the like.
  • the particle size of the active material particles is not particularly limited.
  • the volume average particle diameter (D50) of the active material particles is preferably 1 ⁇ m to 50 ⁇ m, more preferably 3 ⁇ m to 30 ⁇ m.
  • D50 volume average particle diameter
  • the volume average particle diameter of the active material particles is 1 ⁇ m or more, it becomes easy to prepare a slurry for forming an electrode.
  • the volume average particle diameter of the active material particles is 50 ⁇ m or less, the electrode can be easily formed into a thin film, and the input/output characteristics of the energy storage device can be easily improved.
  • the volume average particle diameter of the active material particles is measured by laser scattering diffraction method. Specifically, in the volume-based particle size distribution obtained by the laser scattering diffraction method, the particle size when the accumulation from the small diameter side is 50% is defined as the volume average particle size.
  • the volume average particle diameter is the volume average particle diameter of the secondary particles.
  • a “secondary particle” refers to a particle that is formed by agglomeration of a plurality of primary particles and is the smallest unit in normal behavior
  • a “primary particle” refers to a particle that cannot exist alone. It means the smallest possible particle.
  • the particle diameter of the primary particles constituting the secondary particles is not particularly limited.
  • the average primary particle diameter is preferably 10 nm to 50 ⁇ m. More preferably, the thickness is 30 nm to 10 ⁇ m.
  • the average primary particle diameter of the active material particles is 10 nm or more, the influence of a natural oxide film formed on the surface can be suppressed.
  • the average primary particle diameter of the active material particles is 50 ⁇ m or less, deterioration due to charging and discharging is suppressed.
  • the primary particle diameter of active material particles means the major diameter of the primary particles observed with a scanning electron microscope. Specifically, when the primary particle is spherical, it means its maximum diameter, and when the primary particle is plate-like, it means the maximum diameter or maximum diagonal length in a projected image of the particle observed from the thickness direction.
  • the "average primary particle diameter” is the arithmetic mean value of the measured values of the major diameters of 300 or more primary particles observed with a scanning electron microscope.
  • the method for adjusting the particle size of the active material particles is not particularly limited. Examples include a method of selecting raw materials, a method of adjusting grinding conditions, a method of vapor deposition, a plasma method, a method of surface treatment with silane, etc.
  • the BET specific surface area of the active material particles is preferably 0.5 m 2 /g to 100 m 2 /g, more preferably 1 m 2 /g to 30 m 2 /g.
  • the BET specific surface area of the active material particles is preferably 0.5 m 2 /g to 100 m 2 /g, more preferably 1 m 2 /g to 30 m 2 /g.
  • the BET specific surface area of the active material particles is 0.5 m 2 /g or more, sufficient discharge capacity can be easily obtained.
  • the BET specific surface area of the active material particles is 100 m 2 /g or less, handling properties during electrode production are excellent.
  • the BET specific surface area of the active material particles can be calculated from the nitrogen adsorption isotherm at -196°C.
  • the electrode material of the present disclosure may include active material particles that are in the state of composite particles and active material particles that are not in the state of composite particles.
  • the electrode material consists of active material particles that contain silicon atoms and are covered with a coating that includes a polymeric material and a conductive agent, and a carbon material that is not covered with a coating that includes a polymeric material and a conductive agent.
  • the active material particles may also be included.
  • polymer material The polymer material contained in the covering portion is not particularly limited.
  • polymeric materials include polyamideimide (PAI), polyacrylonitrile, cyclized polyacrylonitrile, polyamide, polyimide, polyacrylic acid, polymethacrylic acid, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyacrylate, and polymethacrylate.
  • PAI polyamideimide
  • PAI polyacrylonitrile
  • cyclized polyacrylonitrile polyamide
  • polyimide polyacrylic acid
  • polymethacrylic acid polystyrene
  • polyvinyl chloride polyvinylidene chloride
  • polyacrylate polymethacrylate.
  • polyamideimide polyacrylonitrile
  • cyclized polyacrylonitrile are preferable as the polymer material.
  • Cyclized polyacrylonitrile is obtained by cyclizing polyacrylonitrile as a raw material.
  • cyclizing polyacrylonitrile as a raw material it is possible to impart electronic conductivity to polyacrylonitrile.
  • Cyclized polyacrylonitrile can be said to have properties intermediate between those of carbon and polymers, and the greater the degree of ring closure of the nitrile group, the closer the cyclized polyacrylonitrile can be said to have properties to those of carbon.
  • Infrared spectroscopy may be a transmission method or a reflection method.
  • the -C ⁇ N (nitrile) group shows a peak at 2240 cm -1 to 2243 cm -1
  • -CH 2 - before becoming a double bond can be confirmed as a peak at 2939 cm -1
  • the attribution of the above peak is The influence of thermal stabilization stage on the molecular structure of polyacrylonitrile fibers prior to the carbonization stage (Fibers and Polymers 2012, Vol.13, No.3, 295-302), Structural transformation of polyacrylonitrile fibers during st abilization and low temperature carbonization (Polymer Degradation and Stability, Volume 128, June 2016, 39-45).
  • Polyacrylonitrile may be a homopolymer of acrylonitrile or a copolymer of acrylonitrile and a polymerization component other than acrylonitrile.
  • Polymerization components other than acrylonitrile include acrylic acid, vinyl acetate, styrene, vinylidene chloride, vinyl chloride, methacrylic acid, and the like.
  • polyacrylonitrile is a copolymer of acrylonitrile and a polymerization component other than acrylonitrile
  • the proportion of acrylonitrile in the total polymerization component is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. More preferably, it is at least % by mass.
  • the conductive aid contained in the covering portion is not particularly limited.
  • Specific examples of the conductive aid include carbon materials such as carbon black, carbon fiber, carbon nanotubes, fullerenes, and carbon nanohorns, oxides exhibiting conductivity, and nitrides exhibiting conductivity.
  • the coating part preferably contains particles with an aspect ratio of 10 or more as a conductive agent, more preferably contains particles with an aspect ratio of 20 or more, and preferably contains particles with an aspect ratio of 30 or more. It is even more preferable to include. If the covering part contains particles with an aspect ratio of 10 or more as a conductive agent, even if the active material particles repeatedly expand and contract, the conduction path of alkali metal ions and electrons between the active material particles formed by the conductive agent will be maintained. is less likely to be lost, and good cycle characteristics can be obtained.
  • the aspect ratio of the particles may be 500 or less, 250 or less, or 100 or less.
  • the shape of particles having an aspect ratio of 10 or more is not particularly limited, and may be fibrous, tubular, rod-like, columnar, or the like. From the viewpoint of improving cycle characteristics, the length of the long axis of particles having an aspect ratio of 10 or more is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and even more preferably 10 ⁇ m or more.
  • the proportion of the particles with an aspect ratio of 10 or more in the entire conductive aid is not particularly limited. For example, it may be within the range of 1% by mass to 50% by mass.
  • the coating portion contains particles having an aspect ratio of 10 or more and particles having an aspect ratio of less than 10 as a conductive aid.
  • the coating portion includes particles having an aspect ratio of less than 10, the adhesion of the conductive additive to the surface of the active material particles is improved.
  • particles having an aspect ratio of less than 10 include carbon black.
  • the electrode for an energy storage device includes the electrode material of the present disclosure described above. If necessary, the electrode may further contain a binder, a conductive aid, and the like.
  • the type of binder is not particularly limited, and may be selected from the polymer materials used in the electrode material of the present disclosure described above.
  • the type of the conductive aid is not particularly limited, and may be selected from the conductive aids used in the electrode material of the present disclosure described above.
  • the proportion of the conductive aid in the total of the binder and the conductive aid is not particularly limited. , for example, from the range of 1% by mass to 20% by mass.
  • the above proportion of the conductive aid may be smaller than the proportion of the conductive aid in the coating of the composite particles. That is, the electrode of the present disclosure may be in a state where more conductive aid exists near the surface of the active material particles when comparing the surface vicinity of the active material particles with the other portions. Since the electrode material of the present disclosure includes active material particles coated with a conductive aid, the electrode may not further include a conductive aid.
  • the content of the active material contained in the electrode is preferably 50% by mass or more of the entire electrode (excluding the current collector), and preferably 55% by mass or more. is more preferable, and even more preferably 60% by mass or more.
  • the content of the active material contained in the electrode is preferably 95% by mass or less of the entire electrode (excluding the current collector), and more preferably 90% by mass or less.
  • the content is preferably 80% by mass or less, and more preferably 80% by mass or less.
  • the electrode may be in a state in which a layer containing an electrode material is formed on the current collector.
  • the type of current collector is not particularly limited, and examples include metals or alloys such as aluminum, copper, nickel, titanium, and stainless steel.
  • the current collector may be carbon coated, surface roughened, or the like.
  • the energy storage device of the present disclosure comprises the electrode of the present disclosure described above.
  • the type of energy storage device is not particularly limited. Examples include devices that utilize movement of alkali metal ions between electrodes for charging and discharging, such as lithium ion batteries, sodium ion batteries, and potassium ion batteries.
  • the energy storage device of the present disclosure is comprised of a positive electrode, a negative electrode, an electrolyte, and the like.
  • the above-mentioned electrode for an energy storage device may be a positive electrode or a negative electrode, but is preferably a negative electrode.
  • an organic solvent in which an electrolyte is dissolved an ionic liquid, etc.
  • the ionic liquid include ionic liquids that are liquid at a temperature of less than 170°C, solvated ionic liquids, and the like.
  • the electrolyte salts include LiPF 6 , LiClO 4 , LiBF 4 , LiClF 4 , LiAsF 6 , LiSbF 6 , LiAlO 4 , LiAlCl 4 , LiN(FSO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , LiN( Examples include lithium salts that generate anions that are difficult to solvate, such as C 2 F 5 SO 2 ) 2 , LiC(CF 3 SO 2 ) 3 , LiCl, and LiI.
  • the electrolyte salt may be used alone or in combination of two or more.
  • the electrolyte salt concentration in the electrolytic solution is, for example, preferably 0.3 mol or more, more preferably 0.5 mol or more, and still more preferably 0.8 mol or more per liter of electrolytic solution.
  • the electrolyte salt concentration in the electrolytic solution is, for example, preferably 5 mol or less, more preferably 3 mol or less, and still more preferably 1.5 mol or less per liter of electrolytic solution.
  • the organic solvents include carbonates (propylene carbonate, ethylene carbonate, diethyl carbonate, etc.), lactones ( ⁇ -butyrolactone, etc.), chain ethers (1,2-dimethoxyethane, dimethyl ether, diethyl ether, etc.), Cyclic ethers (tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, 4-methyldioxolane, diglyme, triglyme, tetraglyme, etc.), sulfolanes (sulfolane, etc.), sulfoxides (dimethylsulfoxide, etc.), nitriles (acetonitrile, propionitrile, etc.) , benzonitrile, etc.), amides (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), and polyoxyalkylene glycols (diethylene glycol, etc.).
  • the organic solvent may be used
  • the electrolyte may contain additives.
  • the additive include fluoroethylene carbonate, propane sultone, vinylene carbonate, methanesulfonic acid, cyclohexylbenzene, tert-amylbenzene, adiponitrile, and succinonitrile.
  • the amount of the additive in the electrolytic solution is, for example, preferably 0.1% by mass to 30% by mass, and preferably 0.5% by mass to 10% by mass, based on the total electrolytic solution.
  • the energy storage device may further include commonly used members such as a separator, gasket, sealing plate, and case.
  • the separator used in the energy storage device is not particularly limited, and includes polyolefin-based porous membranes such as porous polypropylene nonwoven fabric and porous polyethylene nonwoven fabric.
  • the shape of the energy storage device can be any shape such as a cylindrical shape, a square shape, a button shape, etc.
  • the use of the energy storage device is not particularly limited.
  • it can be used as a power source or auxiliary power source for electronic devices, electric devices, automobiles, power storage devices, etc.
  • Example 1 A dispersion liquid in which carbon black (CB) was dispersed in NMP and a dispersion liquid in which VGCF was dispersed in NMP were kneaded to obtain a conductive additive slurry.
  • a conductive additive slurry was added to an SiO slurry obtained by kneading SiO particles and an NMP solution of polyamideimide (PAI), and the mixture was kneaded.
  • the resulting mixture was poured into an alumina container and dried at 120°C under air to remove the solvent. Thereafter, heat treatment was performed at 350° C. for 5 hours in a nitrogen atmosphere.
  • the obtained heat-treated product was crushed and passed through a sieve to obtain the desired composite particles.
  • FIG. 1 A SEM image of the produced composite particles is shown in FIG. As shown in FIG. 1, it was observed that carbon black and fibrous VGCF were attached to the surface of the SiO particles. The coverage of the composite particles calculated by image analysis was 50% or more.
  • FIG. 2 shows a cross-sectional SEM image of the composite particles produced. As shown by the arrow in FIG. 2, it was observed that fibrous VGCF bridged between the SiO particles.
  • a slurry for a positive electrode containing a positive electrode active material (NMC811), carbon black (CB), and polyvinylidene fluoride (PVDF) was obtained using NMP.
  • the obtained slurry was coated on the surface of the current collector using a coater and dried to obtain a positive electrode with the desired coating weight (195 g/m 2 ).
  • the density was set at 2.3 g/cm 3 using a press.
  • a laminate type battery was obtained using the produced negative and positive electrodes and a separator (polypropylene porous membrane).
  • the capacity ratio (N/P) between the negative electrode (N) and the positive electrode (P) was designed to be 1.05.
  • 1M LiPF 6 was dissolved in a mixed solvent containing EC, EMC, and DEC in a ratio of 1:1:1 (volume ratio), and further containing VC (1% by mass) and FEC (2% by mass). I used the one I made.
  • Carbon black...Acetylene black with an average primary particle size of 48 nm (DENKA BLACK Li-400, manufactured by DENKA CORPORATION)
  • VGCF...Carbon fiber with an average fiber diameter of 150 nm, an average fiber length of 15.0 ⁇ m, and a carbon content of 99.99% by mass Showa Denko K.K., VGCF-H
  • SiO particles ...SiO particles with a volume average particle diameter of 8.0 ⁇ m
  • Graphite particles ...Graphite particles with a volume average particle diameter of 10.0 ⁇ m
  • Example 2 A dispersion liquid in which carbon black (CB) was dispersed in NMP was kneaded to obtain a conductive additive slurry.
  • a conductive additive slurry was added to an SiO slurry obtained by kneading SiO particles and an NMP solution of polyamideimide (PAI), and the mixture was kneaded.
  • the resulting mixture was poured into an alumina container and dried at 120°C under air to remove the solvent. Thereafter, heat treatment was performed at 350° C. for 5 hours in a nitrogen atmosphere. The obtained heat-treated product was crushed and passed through a sieve to obtain the desired composite particles.
  • a SEM image of the prepared composite particles is shown in Figure 3. As shown in FIG. 3, carbon black was observed to be attached to the surface of the SiO particles. The coverage of the composite particles calculated by image analysis was 50% or more.
  • a battery for evaluation was produced in the same manner as in Example 1 using the obtained composite particles.
  • Example 1 A battery for evaluation was produced in the same manner as in Example 1, except that the SiO particles used as the raw material for the composite particles in Example 1 were used instead of the composite particles.
  • a battery for evaluation was produced in the same manner as in Example 1 using the obtained composite particles.
  • a battery for evaluation was produced in the same manner as in Example 1 using the obtained composite particles.
  • Discharge capacity maintenance rate (%) Discharge capacity (after 300 cycles) / Discharge capacity (after 3 cycles) x 100
  • the batteries of Examples 1 and 2 in which the active material particles are coated with a polymeric material and a conductive additive the batteries of Comparative Example 1 in which the active material particles are not coated, Compared to the batteries of Comparative Examples 2 and 3 in which the coating only contained a polymeric material, the discharge capacity retention rate after 300 cycles was large and the cycle characteristics were excellent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un matériau d'électrode contenant des particules composites comprenant : des particules comprenant une substance capable d'occlure et de libérer des ions de métal alcalin ; et une partie de revêtement recouvrant au moins une partie des surfaces des particules et comprenant un matériau polymère et un agent auxiliaire de conduction.
PCT/JP2022/033953 2022-09-09 2022-09-09 Matériau d'électrode, électrode pour dispositifs de stockage d'énergie et dispositif de stockage d'énergie WO2024053110A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2022/033953 WO2024053110A1 (fr) 2022-09-09 2022-09-09 Matériau d'électrode, électrode pour dispositifs de stockage d'énergie et dispositif de stockage d'énergie

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2022/033953 WO2024053110A1 (fr) 2022-09-09 2022-09-09 Matériau d'électrode, électrode pour dispositifs de stockage d'énergie et dispositif de stockage d'énergie

Publications (1)

Publication Number Publication Date
WO2024053110A1 true WO2024053110A1 (fr) 2024-03-14

Family

ID=90192233

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/033953 WO2024053110A1 (fr) 2022-09-09 2022-09-09 Matériau d'électrode, électrode pour dispositifs de stockage d'énergie et dispositif de stockage d'énergie

Country Status (1)

Country Link
WO (1) WO2024053110A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006339092A (ja) * 2005-06-06 2006-12-14 Matsushita Electric Ind Co Ltd 非水電解液二次電池およびその負極
JP2014139920A (ja) * 2012-12-18 2014-07-31 Shin Etsu Chem Co Ltd 非水電解質二次電池用負極及びその製造方法、ならびにリチウムイオン二次電池
JP2022032567A (ja) * 2020-08-12 2022-02-25 凸版印刷株式会社 非水系リチウムイオン二次電池用負極

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006339092A (ja) * 2005-06-06 2006-12-14 Matsushita Electric Ind Co Ltd 非水電解液二次電池およびその負極
JP2014139920A (ja) * 2012-12-18 2014-07-31 Shin Etsu Chem Co Ltd 非水電解質二次電池用負極及びその製造方法、ならびにリチウムイオン二次電池
JP2022032567A (ja) * 2020-08-12 2022-02-25 凸版印刷株式会社 非水系リチウムイオン二次電池用負極

Similar Documents

Publication Publication Date Title
CN111213262A (zh) 负极和包含所述负极的二次电池
KR20150067049A (ko) 리튬 이차 전지용 도전 조성물, 이를 포함하는 리튬 이차 전지용 양극 및 리튬 이차 전지
US11631857B2 (en) Secondary battery
US20220384790A1 (en) Negative Electrode and Secondary Battery Including the Same
WO2017159267A1 (fr) Batterie rechargeable à électrolyte non aqueux et son procédé de fabrication
KR20190095835A (ko) 양극 및 상기 양극을 포함하는 이차 전지
US20200373559A1 (en) Positive Electrode and Secondary Battery Including the Positive Electrode
JP7466982B2 (ja) 負極および前記負極を含む二次電池
KR20230010172A (ko) 리튬 이차 전지용 음극, 리튬 이차 전지용 음극의 제조 방법 및 음극을 포함하는 리튬 이차 전지
CN116670850A (zh) 负极和包含其的二次电池
KR20200047286A (ko) 입경이 상이한 흑연 및 실리콘계 소재를 포함하는 음극 및 이를 포함하는 리튬 이차전지
CN115336040A (zh) 负极和包含所述负极的二次电池
US20220216461A1 (en) Negative electrode and secondary battery including the negative electrode
US20230104135A1 (en) Negative electrode composition, negative electrode for lithium secondary battery comprising same, lithium secondary battery comprising negative electrode, and method for preparing negative electrode composition
JP7224787B2 (ja) 特定添加剤を含んだ二次電池用非水系電解質及びこれを用いた二次電池
WO2024053110A1 (fr) Matériau d'électrode, électrode pour dispositifs de stockage d'énergie et dispositif de stockage d'énergie
KR20210012801A (ko) 복합 음극 활물질, 이의 제조방법, 이를 포함하는 음극 및 이차전지
WO2024053111A1 (fr) Matériau d'électrode, électrode pour dispositifs de stockage d'énergie et dispositif de stockage d'énergie
WO2021172105A1 (fr) Particule composite pour élément électrochimique, son procédé de fabrication, électrode pour élément électrochimique et élément électrochimique
WO2021153398A1 (fr) Électrode négative de batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
CN111448689B (zh) 正极和包括该正极的二次电池
KR20220048852A (ko) 음극, 상기 음극의 제조 방법, 및 상기 음극을 포함하는 이차 전지
EP4379847A1 (fr) Électrode négative et batterie secondaire la comprenant
US20230063421A1 (en) Anode for secondary battery and secondary battery including the same
US20230125989A1 (en) Negative electrode for lithium secondary battery, lithium secondary battery comprising negative electrode, and method for preparing negative electrode for lithium secondary battery

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: 22958188

Country of ref document: EP

Kind code of ref document: A1