WO2023037555A1 - Électrode de dispositif de stockage d'énergie, dispositif de stockage d'énergie, procédé de production d'électrode de dispositif de stockage d'énergie et matériau pour former une électrode - Google Patents

Électrode de dispositif de stockage d'énergie, dispositif de stockage d'énergie, procédé de production d'électrode de dispositif de stockage d'énergie et matériau pour former une électrode Download PDF

Info

Publication number
WO2023037555A1
WO2023037555A1 PCT/JP2021/033590 JP2021033590W WO2023037555A1 WO 2023037555 A1 WO2023037555 A1 WO 2023037555A1 JP 2021033590 W JP2021033590 W JP 2021033590W WO 2023037555 A1 WO2023037555 A1 WO 2023037555A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
energy storage
storage device
active material
polyacrylonitrile
Prior art date
Application number
PCT/JP2021/033590
Other languages
English (en)
Japanese (ja)
Inventor
真代 堀川
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 JP2023546722A priority Critical patent/JPWO2023037555A1/ja
Priority to PCT/JP2021/033590 priority patent/WO2023037555A1/fr
Publication of WO2023037555A1 publication Critical patent/WO2023037555A1/fr

Links

Images

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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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 absorbance ratio A is preferably 0.01 or more, more preferably 0.02 or more, and even more preferably 0.03 or more.
  • cyclized polyacrylonitrile has an acridone structure
  • pyrolysis GC/MS analysis Panolysis Gas Chromatography Mass Spectrometry
  • known techniques for X-ray photoelectron spectrum analysis The presence of the acridone structure can be confirmed by a fragment of mass 177 in pyrolysis GC/MS analysis and by a peak around 532 eV in X-ray photoelectron spectroscopy.
  • the molecular weight of the polyacrylonitrile that is the precursor of the cyclized polyacrylonitrile is not particularly limited, but the weight-average molecular weight is preferably 5,000 to 3,000,000, more preferably 10,000 to 1,000,000. When the weight average molecular weight of polyacrylonitrile is 5,000 or more, a good binder can be obtained. .
  • a carboxy group in the present disclosure is a monovalent group represented by —COOH.
  • the ratio of the polymer components other than acrylonitrile in the acrylonitrile copolymer to the total polymer components is preferably 20% by mass or less, and is 15% by mass or less. is more preferable, and 10% by mass or less is even more preferable.
  • Binders other than cyclized polyacrylonitrile include polyacrylic acid, polyvinyl acetate, polystyrene, polyvinylidene chloride, polyvinyl chloride, and polymethacrylic acid.
  • the content of the binder contained in the electrode is preferably 10% by mass or more, more preferably 20% by mass or more, of the entire electrode (excluding the current collector). More preferably, it is 30% by mass or more.
  • the content of the binder contained in the electrode is preferably 50% by mass or less, more preferably 45% by mass or less, and 40% by mass or less of the entire electrode (excluding the current collector). is more preferred.
  • the electrodes of the present disclosure contain a silane coupling agent.
  • a silane coupling agent refers to a silane compound having a functional group that can chemically bond with an inorganic material and a functional group that can chemically bond with an organic material.
  • the state in which all or part of the functional groups possessed by the silane coupling agent in the electrode are chemically bonded to the functional groups possessed by the active material particles and the binder is also “the electrode contains the silane coupling agent”. included in the case.
  • the active material particles contained in the electrode of the present disclosure are not particularly limited as long as they contain a material (active material) that can occlude and release alkali metal ions.
  • the active material particles contained in the electrode may be of one type or a combination of two or more types.
  • positive electrode active materials include lithium transition metal compounds such as lithium transition metal oxides and lithium transition metal phosphates.
  • Carbon materials include graphite, hard carbon, and soft carbon.
  • active materials containing silicon atoms include Si (metallic silicon) and silicon oxides represented by SiOx (0.8 ⁇ x ⁇ 1.5).
  • the silicon oxide may have a structure in which nano-silicon 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 make it a semiconductor.
  • the active material particles may include active material particles made of a carbon material and having silicon present on the surface thereof.
  • Active materials containing silicon atoms have a large theoretical capacity and are expected to contribute to increasing the capacity of energy storage devices. In addition, active materials containing silicon atoms themselves are not electronically conductive.
  • the cyclized polyacrylonitrile used as a binder in the electrode of the present disclosure has both sufficient flexibility and electronic conductivity to accommodate changes in the volume of the active material. Therefore, it can be particularly suitably used as a binder for active material particles containing silicon atoms.
  • the shape of the active material particles is not particularly limited.
  • it may be spherical, wire-shaped, scaly, massive, composite particles composed of a plurality of particles, or the like.
  • the volume average particle size of the active material particles is measured by a laser scattering diffraction method.
  • the volume-average particle diameter is defined as the particle diameter when the accumulation from the small diameter side is 50% in the volume-based particle diameter distribution obtained by the laser scattering diffraction method.
  • the volume average particle size is the volume average particle size of the secondary particles.
  • secondary particle means a particle that is the smallest unit of normal behavior formed by agglomeration of a plurality of primary particles
  • primary particle means that it can exist alone. It means the smallest unit particle that can be made.
  • the particle size of the primary particles that make up the secondary particles is not particularly limited.
  • the average primary particle size is preferably 10 nm to 50 ⁇ m. More preferably, it is 30 nm to 10 ⁇ m.
  • the average primary particle size of the active material particles is 10 nm or more, the influence of the natural oxide film formed on the surface can be suppressed.
  • the average primary particle size of the active material particles is 50 ⁇ m or less, deterioration due to charging and discharging is suppressed.
  • the primary particle diameter of the active material means the major diameter of the primary particles observed with a scanning electron microscope. Specifically, when the primary particles are spherical, it means the maximum diameter, and when the primary particles are tabular, it means the maximum diameter or maximum diagonal length in the projected image of the particles observed from the thickness direction. "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 active material particles are wire-shaped, there is no particular limit to their length. For example, it is preferably 10 nm to 10 ⁇ m. When the length of the wire-shaped active material particles is 10 nm or more, the handleability is improved, and when the length is 10 ⁇ m or less, stress during expansion of the active material particles tends to be easily dispersed.
  • the diameter of wire-like particles is preferably 1 nm to 5 ⁇ m.
  • the wire-shaped active material particles may contain a catalyst component for forming the wire-shaped active material particles. Specific examples of the wire-shaped active material particles include metallic silicon particles.
  • the method for adjusting the particle size of the active material particles is not particularly limited. Examples thereof include a method of selecting raw materials, a method of adjusting pulverization conditions, a vapor deposition method, a plasma method, and a method of surface treatment with silane or the like.
  • 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, the handling property during electrode production is excellent.
  • the BET specific surface area of the active material particles can be calculated from the nitrogen adsorption isotherm at -196°C.
  • the active material particles may have a coating on their surfaces.
  • the active material particles may have a coating (carbon coating) made of a carbon material.
  • a coating carbon coating
  • electronic conductivity can be imparted to active material particles that do not have electrical conductivity.
  • the material of the carbon material is not particularly limited, and may be graphite or amorphous carbon.
  • the carbon material contained in the coating may be obtained by carbonizing an organic compound.
  • organic compounds include tar, pitch, and organic polymer compounds.
  • organic polymer compounds include polyacrylonitrile, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, starch, and cellulose.
  • An embodiment of the electrode may include active material particles containing silicon and active material particles made of a carbon material.
  • the ratio of the active material particles containing silicon and the active material particles made of a carbon material is not particularly limited, but the ratio of the active material particles containing silicon is 5% by mass to 90% by mass of the total active material particles. is preferred, and 10% by mass to 70% by mass is more preferred.
  • the capacity of the energy storage device can be sufficiently increased.
  • the ratio of the active material particles containing silicon is 90% by mass or less of the entire active material particles, it is possible to sufficiently suppress the deterioration of the electrode due to the volume change of the active material.
  • the content of the active material particles contained in the electrode is preferably 50% by mass or more of the entire electrode (excluding the current collector), and is 55% by mass or more. is more preferable, and 60% by mass or more is even more preferable.
  • the content of the active material particles contained in the electrode is preferably 95% by mass or less of the entire electrode (excluding the current collector), and 90% by mass or less. and more preferably 80% by mass or less.
  • the electrodes may contain a conductive aid.
  • conductive aids include carbon materials such as carbon black, carbon nanotubes, carbon nanofibers, fullerenes and carbon nanohorns, conductive oxides, and conductive nitrides.
  • the content is not particularly limited, and may be 1% by mass to 20% by mass of the entire electrode (excluding the current collector).
  • the electrode may be in a state in which a layer containing active material particles, a binder, and optionally a conductive aid is formed on a current collector.
  • the type of current collector is not particularly limited, and metals or alloys such as aluminum, copper, nickel, titanium, and stainless steel can be used.
  • the current collector may be carbon-coated, surface-roughened, or the like.
  • the electrode 10 shown in FIG. 1 is in a state in which a layer containing active material particles 2 and a binder 3 is formed on a current collector 1 .
  • the electrode 11 shown in FIG. 2 is a modification of the electrode 10 shown in FIG. is in a state.
  • Electrode 12 shown in FIG. 3 is a modification of electrode 10 shown in FIG. 1, and active material particles 2 have carbon coating 5 .
  • the energy storage device of the present disclosure comprises the electrodes of the present disclosure as described above.
  • the type of energy storage device is not particularly limited. Examples thereof include devices such as lithium-ion batteries, sodium-ion batteries, and potassium-ion batteries, which utilize movement of alkali metal ions between electrodes for charging and discharging.
  • the energy storage device of the present disclosure is composed of a positive electrode, a negative electrode, an electrolytic solution, and the like.
  • the energy storage device electrode described above may be a positive electrode or a negative electrode, but is preferably a negative electrode.
  • organic solvents, ionic liquids, etc. in which electrolyte salts are dissolved can be used.
  • the ionic liquid include ionic liquids that are liquid at a temperature of less than 170° C., solvated ionic liquids, and the like.
  • 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( Lithium salts that generate poorly solvated anions such as C 2 F 5 SO 2 ) 2 , LiC(CF 3 SO 2 ) 3 , LiCl, and LiI are included.
  • electrolyte salt Only one electrolyte salt may be used, or two or more electrolyte salts may be used.
  • 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 even more preferably 0.8 mol or more per 1 L of the 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 even more preferably 1.5 mol or less per 1 L of the electrolytic solution.
  • 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.), polyoxyalkylene glycols (diethylene glycol, etc.), and other aprotic solvents (t
  • Only one type of organic solvent may be used, or two or more types may be used.
  • the cation part that constitutes the ionic liquid may be either an organic cation or an inorganic cation, but is preferably an organic cation.
  • organic cations that make up the ionic liquid include imidazolium cations, pyridinium cations, pyrrolidinium cations, phosphonium cations, ammonium cations, and sulfonium cations.
  • the anion part constituting the ionic liquid may be either an organic anion or an inorganic anion.
  • organic anions constituting the ionic liquid include alkyl sulfate anions such as methyl sulfate anion (CH 3 SO 4 ⁇ ) and ethyl sulfate anion (C 2 H 5 SO 4 ⁇ ); tosylate anion (CH 3 C 6 H 4 SO 3 ⁇ ); alkanesulfonate anions such as methanesulfonate anion (CH 3 SO 3 ⁇ ), ethanesulfonate anion (C 2 H 5 SO 3 ⁇ ), butanesulfonate anion (C 4 H 9 SO 3 ⁇ ); romethanesulfonate anion (CF 3 SO 3 ⁇ ), pentafluoroethanesulfonate anion (C 2 F 5 SO 3 ⁇ ), heptafluoropropanesulfonate anion (C 3 H 7 SO 3 ⁇ ), nonafluorobutanesulfonate anion (C 4 H 9 SO 3
  • Specific inorganic anions constituting the ionic liquid include bis(fluorosulfonyl)imide anion (N(SO 2 F) 2 ⁇ ); bis(trifluorosulfonyl)imide anion (N(SO 2 CF 3 ) 2 ⁇ ).
  • hexafluorophosphate anion PF 6 ⁇
  • tetrafluoroborate anion BF 4 ⁇
  • halide anions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), iodide ion (I ⁇ ); tetrachloro aluminate anion (AlCl 4 ⁇ ); thiocyanate anion (SCN ⁇ ); and the like.
  • ionic liquids include those composed of a combination of any of the above cation moieties and any of the above anion moieties.
  • the ionic liquid whose cation moiety is an imidazolium cation include 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-methyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium chloride, 1-butyl-3 -methylimidazolium chloride, 1-ethyl-3-methylimidazolium methanesulfonate, 1-butyl-3-methylimidazolium methanesulfonate, 1,2,3-trimethylimidazolium methylsulfate, methylimidazolium chloride, methylimid
  • ionic liquids in which the cation portion is a pyrrolidinium cation include 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) ) imide and the like.
  • solvated ionic liquids examples include glyme-lithium salt complexes.
  • lithium salt in the glyme-lithium salt complex examples include lithium bis(fluorosulfonyl)imide (LiN(SO 2 F) 2 , sometimes abbreviated as “LiFSI” in the present disclosure), lithium bis(trifluoro romethanesulfonyl)imide (LiN(SO 2 CF 3 ) 2 , sometimes abbreviated as “LiTFSI” in the present disclosure), and the like.
  • glyme in the glyme-lithium salt complex examples include triethylene glycol dimethyl ether (CH 3 (OCH 2 CH 2 ) 3 OCH 3 , triglyme), tetraethylene glycol dimethyl ether (CH 3 (OCH 2 CH 2 ) 4 OCH 3 , tetraglyme) and the like.
  • a glyme-lithium salt complex can be prepared, for example, by mixing a lithium salt and glyme so that the lithium salt:glyme (molar ratio) is preferably 10:90 to 90:10.
  • the electrolyte may contain additives.
  • additives include fluoroethylene carbonate, propanesultone, 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, preferably 0.5% by mass to 10% by mass, based on the total amount of the electrolytic solution.
  • the energy storage device may further comprise commonly used members such as separators, gaskets, sealing plates, and cases in addition to the electrodes and electrolyte.
  • the separator used in the energy storage device is not particularly limited, and examples include polyolefin-based porous membranes such as porous polypropylene nonwoven fabrics and porous polyethylene nonwoven fabrics.
  • the shape of the energy storage device can be any shape, such as cylindrical, square, and button.
  • a method for producing an electrode for an energy storage device heat-treats a composition containing particles (active material particles) containing a substance capable of absorbing and releasing alkali metal ions, polyacrylonitrile, and a silane coupling agent.
  • the details and preferred aspects of the active material particles, polyacrylonitrile, and silane coupling agent are the same as the details and preferred aspects of the active material particles, polyacrylonitrile, and silane coupling agent used in the electrode described above.
  • the method for preparing the composition is not particularly limited.
  • the following methods (1) to (4) can be mentioned.
  • (1) a method of collectively mixing the active material particles, the polyacrylonitrile, and the silane coupling agent is preferable from the viewpoint of production efficiency.
  • the heat treatment in the above method is performed under conditions (for example, 278°C to 600°C) that cause a cyclization reaction of polyacrylonitrile.
  • the temperature at which the cyclization treatment is performed is 278°C or higher, preferably 280°C or higher, more preferably 290°C or higher, and even more preferably 300°C or higher.
  • the temperature at which the cyclization treatment is performed is 600°C or lower, preferably 500°C or lower, more preferably 450°C or lower, and even more preferably 400°C or lower.
  • the oxygen concentration during the cyclization treatment is preferably 4 ppm or higher, more preferably 7.5 ppm or higher, even more preferably 10 ppm or higher, and particularly preferably 15 ppm or higher.
  • the oxygen concentration when performing the cyclization treatment is 100 ppm or less, preferably 80 ppm or less, more preferably 60 ppm or less, and 40 ppm or less. More preferred.
  • the components other than oxygen in the atmosphere in which the cyclization treatment is performed are not particularly limited, and may be nitrogen, an inert gas such as argon, or a mixture thereof.
  • the time for performing the cyclization treatment is not particularly limited, and can be selected, for example, from 3 hours to 15 hours.
  • the time for performing the cyclization treatment in the present disclosure means the time during which the temperature of the composition is 278°C to 600°C.
  • the method of the present disclosure may include a step of heat-treating the composition at a temperature of 150°C or more and less than 278°C (hereinafter also referred to as pretreatment) before the cyclization treatment.
  • polyacrylonitrile shows a large exothermic peak at 278°C.
  • the yield of the cyclization reaction of polyacrylonitrile can be increased. This is because the polyacrylonitrile undergoes a rapid reaction and the main chain of polyacrylonitrile is cleaved, thereby suppressing the production of low-molecular-weight components, as compared with the case where the cyclization treatment is performed without pretreatment.
  • the time for performing pretreatment is not particularly limited, and can be selected, for example, from 3 hours to 15 hours.
  • the time during which the pretreatment is performed in the present disclosure means the time during which the temperature of the composition is 150°C or higher and lower than 278°C.
  • the atmosphere during the pretreatment is not particularly limited, and may be an inert atmosphere that does not contain oxygen or an atmosphere that contains oxygen (such as air). From the viewpoint of cycle characteristics, the atmosphere preferably contains 5% to 30% by volume of oxygen.
  • the pretreatment and the cyclization treatment may or may not be performed consecutively.
  • a step of cooling the composition may be performed between the pretreatment and the cyclization treatment.
  • the composition may contain a conductive aid, solvent, etc.
  • Solvents include those capable of dissolving polyacrylonitrile, such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, and dimethylsulfoxide.
  • the polyacrylonitrile contained in the composition may be in the form of a polymer or in the form of a raw material monomer.
  • the composition may be pressurized. By pressurizing the composition, a cyclization reaction occurs in a state where the polyacrylonitrile molecules are oriented, and the molecules stack to increase the crystallinity. When polyacrylonitrile is highly crystallized, the strength of the obtained cyclized polyacrylonitrile tends to improve, and the electron conductivity also tends to improve.
  • the method of applying pressure to the composition is not particularly limited.
  • a method of sandwiching between members and applying surface pressure (for example, 0.1 MPa to 10 MPa) can be used.
  • the pressure treatment may be performed before the cyclization treatment, during the cyclization treatment, or after the cyclization treatment.
  • the composition for the cyclization treatment may be in a layered state on the current collector.
  • Electrode forming material is a material for forming an electrode of an energy storage device, and contains particles containing a substance capable of absorbing and releasing alkali metal ions, polyacrylonitrile, and a silane coupling agent. It is an electrode forming material.
  • Electrodes and energy storage devices formed using the above materials exhibit excellent characteristics.
  • the state in which all or part of the functional groups of the silane coupling agent in the electrode-forming material are chemically bonded to the functional groups of the active material particles and the binder is included when it includes a coupling agent.
  • Example 1 Polyacrylonitrile (PAN) was added to N-methyl-2-pyrrolidone (NMP) and mixed at room temperature to dissolve PAN to prepare a PAN/NMP solution (PAN content: 13.3% by mass).
  • PAN Polyacrylonitrile
  • NMP N-methyl-2-pyrrolidone
  • polyacrylonitrile a copolymer containing sodium methallylsulfonate (0.3% by mass) and methyl acrylate (5.8% by mass) as polymerization components other than acrylonitrile and having a weight average molecular weight of 80,000 is used. board.
  • Si particles (average secondary particle diameter: about 5 ⁇ m) and a PAN/NMP solution as an active material, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane as a silane coupling agent having an amino group, Si, PAN, and the silane coupling agent were mixed in a mass ratio (Si:PAN:silane coupling agent) of 69.5:29.8:0.7 to obtain a slurry.
  • the slurry was applied to a copper foil as a current collector and dried to obtain a laminate of the electrode and the current collector (electrode density: 0.4 g/cm 3 , mass per area: 7 g/m 2 ).
  • Example 2 An electrode was produced in the same manner as in Example 1, except that the silane coupling agent was changed to a polyfunctional silane coupling agent having an amino group (Shin-Etsu Chemical Co., Ltd.).
  • ⁇ Comparative Example 1 Si particles (average secondary particle diameter: about 5 ⁇ m) as an active material and a PAN/NMP solution were mixed so that the mass ratio of Si and PAN (Si:PAN) was 70:30 to obtain a slurry.
  • An electrode was produced in the same manner as in Example 1, except that the temperature of the cyclization treatment was changed to 440°C.
  • ⁇ Production of battery LiCo 1/3 Ni 1/3 Mn 1/3 O 2 as a positive electrode active material, acetylene black as a conductive agent, and polyvinylidene fluoride as a binder at a ratio of 94:3:3 (active material: conductive agent: binding agent).
  • composition layer was 2.9 mAh/cm 2 in terms of capacity (calculated based on the capacity of LiCo 1/3 Ni 1/3 Mn 1/3 O 2 being 152 mAh/g).
  • the positive electrode was pressed with a roll press to an electrode density of 2.8 g/cm 3 .
  • a 2032-type coin cell was prepared as an evaluation battery using the electrode prepared above as the negative electrode and the positive electrode.
  • a polypropylene porous membrane is used as the separator, and 1M LiPF6 as the electrolyte is EC (ethylene carbonate), EMC (ethyl methyl carbonate) and DEC (diethyl carbonate) in a ratio of 1:1:1 (volume ratio).
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • Table 1 shows the results.
  • Capacity retention rate (%) (10th cycle discharge capacity (mAh) / 1st cycle discharge capacity (mAh)) x 100 (Charging conditions) Charging mode: constant current - low voltage mode, charging current: 1/10 (CA), cutoff voltage: 50 (mV), cutoff current: 1/50 (CA) (discharge conditions) Discharge mode: constant current mode, discharge voltage: 1.5 (V), discharge current: 1/10 (CA) ⁇ Electrode strength> As an index of the electrode strength, when the prepared electrode is divided into three equal parts in the thickness direction, the electrode is divided into the layers in the order of the layer farthest from the current collector (upper layer), the middle layer (middle layer), and the layer closest to the current collector (lower layer). A SAICAS (Surface And Interfacial Cutting Analysis System) test for measuring the peel strength when scraping off was performed. Measurement conditions are as follows. Table 1 shows the results.
  • Measurement mode Low speed mode Blade width: 1.0mm Horizontal speed: 5 ⁇ m/s Vertical velocity: 0.5 ⁇ m/s Number of tests: 2 Test environment: temperature 24.3°C to 25.7°C, relative humidity 20% to 21%
  • the examples in which the electrodes contain a silane coupling agent are superior in battery cycle characteristics to the comparative examples in which the electrodes do not contain a silane coupling agent. Furthermore, the electrodes of the examples are superior in electrode strength to the electrodes of the comparative examples.

Landscapes

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

Abstract

L'électrode de dispositif de stockage d'énergie comprend : des particules qui contiennent une substance capable d'absorber et de libérer des ions de métal alcalin ; un matériau liant qui contient un polyacrylonitrile cyclisé ; et un agent de couplage au silane.
PCT/JP2021/033590 2021-09-13 2021-09-13 Électrode de dispositif de stockage d'énergie, dispositif de stockage d'énergie, procédé de production d'électrode de dispositif de stockage d'énergie et matériau pour former une électrode WO2023037555A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2023546722A JPWO2023037555A1 (fr) 2021-09-13 2021-09-13
PCT/JP2021/033590 WO2023037555A1 (fr) 2021-09-13 2021-09-13 Électrode de dispositif de stockage d'énergie, dispositif de stockage d'énergie, procédé de production d'électrode de dispositif de stockage d'énergie et matériau pour former une électrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2021/033590 WO2023037555A1 (fr) 2021-09-13 2021-09-13 Électrode de dispositif de stockage d'énergie, dispositif de stockage d'énergie, procédé de production d'électrode de dispositif de stockage d'énergie et matériau pour former une électrode

Publications (1)

Publication Number Publication Date
WO2023037555A1 true WO2023037555A1 (fr) 2023-03-16

Family

ID=85506279

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/033590 WO2023037555A1 (fr) 2021-09-13 2021-09-13 Électrode de dispositif de stockage d'énergie, dispositif de stockage d'énergie, procédé de production d'électrode de dispositif de stockage d'énergie et matériau pour former une électrode

Country Status (2)

Country Link
JP (1) JPWO2023037555A1 (fr)
WO (1) WO2023037555A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007109549A (ja) * 2005-10-14 2007-04-26 Toyota Central Res & Dev Lab Inc 水系リチウム二次電池
JP2015519001A (ja) * 2012-06-08 2015-07-06 ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングＲｏｂｅｒｔ Ｂｏｓｃｈ Ｇｍｂｈ ポリアクリロニトリル−硫黄複合材料の製造方法
WO2017061323A1 (fr) * 2015-10-05 2017-04-13 東レ株式会社 Électrode positive pour batterie secondaire au lithium-ion, particules composites de matière active d'électrode positive/graphène, et leurs procédés de fabrication, et pâte d'électrode positive pour batterie secondaire au lithium-ion
JP2018504762A (ja) * 2015-02-06 2018-02-15 チェン，ジョングウェイ リチウム電池用負極の作製方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007109549A (ja) * 2005-10-14 2007-04-26 Toyota Central Res & Dev Lab Inc 水系リチウム二次電池
JP2015519001A (ja) * 2012-06-08 2015-07-06 ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングＲｏｂｅｒｔ Ｂｏｓｃｈ Ｇｍｂｈ ポリアクリロニトリル−硫黄複合材料の製造方法
JP2018504762A (ja) * 2015-02-06 2018-02-15 チェン，ジョングウェイ リチウム電池用負極の作製方法
WO2017061323A1 (fr) * 2015-10-05 2017-04-13 東レ株式会社 Électrode positive pour batterie secondaire au lithium-ion, particules composites de matière active d'électrode positive/graphène, et leurs procédés de fabrication, et pâte d'électrode positive pour batterie secondaire au lithium-ion

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MIYUKI, TAKAHIRO; KOJIMA, TOSHIKATSU; OKUYAMA, YASUE; SAKAI, TETSUO: "Development of Olganosulfur Cathodes Using Nanofiber Nonwoven Precursor and Their Electrode Performance for the Rechargeable Lithium Battery", JOURNAL OF THE SOCIETY OF FIBER SCIENCE AND TECHNOLOGY, vol. 68, no. 7, 1 January 2012 (2012-01-01), pages 179 - 183, XP009544293, ISSN: 0037-9875, DOI: 10.2115/fiber.68.179 *
NURPEISSOVA ARAILYM, MUKANOVA ALIYA, KALIMULDINA GULNUR, UMIROV NURZHAN, KIM SUNG-SOO, BAKENOV ZHUMABAY: "Onion-Structured Si Anode Constructed with Coating by Li4Ti5O12 and Cyclized-Polyacrylonitrile for Lithium-Ion Batteries", NANOMATERIALS, vol. 10, no. 10, pages 1995, XP093044022, DOI: 10.3390/nano10101995 *

Also Published As

Publication number Publication date
JPWO2023037555A1 (fr) 2023-03-16

Similar Documents

Publication Publication Date Title
US12009515B2 (en) Negative electrode active material for lithium secondary battery and preparation method thereof
KR20180028814A (ko) 리튬 이차전지용 전극 및 이를 포함하는 리튬 이차전지
JP2022536290A (ja) リチウムイオン電池用のその場重合されたポリマー電解質
KR20210106923A (ko) 리튬 이차 전지용 비수 전해액 및 이를 포함하는 리튬 이차전지
JP2022547501A (ja) 二次電池の製造方法
KR20210059233A (ko) 비수 전해액 및 이를 포함하는 리튬 이차 전지
JP7134555B2 (ja) 非水電解液添加剤、これを含むリチウム二次電池用非水電解液及びリチウム二次電池
WO2022244885A1 (fr) Matériau actif revêtu pour dispositif de stockage d'énergie, dispositif de stockage d'énergie, procédé de fabrication de matériau actif revêtu pour dispositif de stockage d'énergie, et matériau de revêtement
KR20220109699A (ko) 이차전지의 제조방법
KR102501252B1 (ko) 리튬 이차 전지용 비수 전해질 및 이를 포함하는 리튬 이차 전지
JP6970890B2 (ja) 非水二次電池用負極活物質、及び、非水二次電池
JP7417790B2 (ja) 新規な化合物、それを含む二次電池用電解液およびそれを含む二次電池
WO2023037555A1 (fr) Électrode de dispositif de stockage d'énergie, dispositif de stockage d'énergie, procédé de production d'électrode de dispositif de stockage d'énergie et matériau pour former une électrode
WO2023037556A1 (fr) Électrode pour dispositifs de stockage d'énergie, dispositif de stockage d'énergie, procédé de production d'électrode pour dispositifs de stockage d'énergie, et matériau pour former une électrode
EP3975305A1 (fr) Procédé de fabrication de batterie secondaire
JP2023524703A (ja) 二次電池用電解液添加剤、それを含むリチウム二次電池用非水電解液およびリチウム二次電池
JP2018125219A (ja) リチウムイオン二次電池用の電解液
WO2022244884A1 (fr) Électrode pour dispositifs de stockage d'énergie, dispositif de stockage d'énergie, procédé de production d'électrode pour dispositifs de stockage d'énergie, et matériau de liant
KR20220105397A (ko) 리튬 이차 전지
KR20210059232A (ko) 비수 전해액 및 이를 포함하는 리튬 이차 전지
US12074324B2 (en) Negative electrode active material, negative electrode including the negative electrode active material, secondary battery including the negative electrode, and method of preparing the negative electrode active material
JP7341592B2 (ja) リチウム二次電池用非水電解質およびこれを含むリチウム二次電池
EP4261911A2 (fr) Cathode pour batterie secondaire au lithium, batterie secondaire au lithium la comprenant et procédé de fabrication de batterie secondaire au lithium
EP4345944A2 (fr) Matériau actif d'anode pour batterie secondaire au lithium, son procédé de préparation et batterie secondaire au lithium le comprenant
US20240088378A1 (en) 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: 21956850

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023546722

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21956850

Country of ref document: EP

Kind code of ref document: A1