WO2016084909A1 - Noir de carbone revêtu de silice, composition d'électrode dans laquelle celui-ci est utilisé, électrode pour batterie rechargeable et batterie rechargeable - Google Patents

Noir de carbone revêtu de silice, composition d'électrode dans laquelle celui-ci est utilisé, électrode pour batterie rechargeable et batterie rechargeable Download PDF

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WO2016084909A1
WO2016084909A1 PCT/JP2015/083267 JP2015083267W WO2016084909A1 WO 2016084909 A1 WO2016084909 A1 WO 2016084909A1 JP 2015083267 W JP2015083267 W JP 2015083267W WO 2016084909 A1 WO2016084909 A1 WO 2016084909A1
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carbon black
silica
coated carbon
dbp absorption
electrode
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PCT/JP2015/083267
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Japanese (ja)
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裕輝 名古
みか 西川
哲哉 伊藤
横田　博
崇人 今井
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デンカ株式会社
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Priority to JP2016561949A priority Critical patent/JP6604965B2/ja
Priority to CN201580074376.XA priority patent/CN107207876B/zh
Publication of WO2016084909A1 publication Critical patent/WO2016084909A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • 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 present invention relates to silica-coated carbon black, an electrode composition using the same, a secondary battery electrode, and a secondary battery.
  • the lithium ion secondary battery in which the negative electrode is formed using a material capable of occluding and releasing lithium ions can suppress the deposition of dendride compared to the lithium battery in which the negative electrode is formed using metallic lithium. Therefore, there is an advantage that a battery having a high capacity and a high energy density can be provided while safety is improved by preventing a short circuit of the battery.
  • Patent Document 1 discloses a positive electrode material for a lithium ion secondary battery in which a halide is coated on the surface of the positive electrode material.
  • Patent Document 2 discloses a positive electrode mixture in which the surface of the positive electrode current collector is coated with a fluorine compound.
  • Patent Document 3 discloses a BET specific surface area, DBP absorption amount, electric resistivity, sulfur content, and volatile component content as carbon black for non-aqueous secondary batteries excellent in conductivity and dispersibility. Carbon blacks each in a predetermined range are disclosed. Patent Document 4 discloses a carbon black slurry having good slurry stability.
  • Carbon black has been conventionally used as a conductive agent for secondary batteries.
  • a positive electrode active material having a high potential is used as described above, the carbon black that is a conductive agent has a large contact area with the electrolytic solution, which is a factor that easily causes oxidative decomposition and gas generation of the electrolytic solution. ing.
  • Patent Documents 1 and 2 None of the methods described in Patent Documents 1 and 2 has improved carbon black, and the effect of suppressing gas generation due to oxidative decomposition of the electrolyte is insufficient.
  • carbon black has a structure in which primary particles close to a spherical shape are connected on a bead as a common structure, and such a structure is called a structure.
  • a structure In general, the longer the structure is connected, the greater the distance that can be conducted without contact resistance, so that the electron conductivity is improved.
  • the length of the structure is indirectly evaluated using a DBP absorption amount generally measured in accordance with JIS K6217-4.
  • carbon black having a long structure is excellent in conductivity, but has an aspect that the interaction between particles becomes large, so that it is difficult to disintegrate and easily aggregates.
  • the present invention is a silica-coated carbon black that suppresses decomposition and gas generation of an electrolyte in a high-potential secondary battery, particularly a lithium ion secondary battery, and has excellent conductivity and dispersibility.
  • An object of the present invention is to provide a secondary battery electrode and a secondary battery having excellent durability using the same.
  • the present invention employs the following means in order to solve the above problems.
  • It includes carbon black and silica that covers the surface of the carbon black, and a ratio of DBP absorption to compression DBP absorption of the carbon black (DBP absorption / compression DBP absorption) is 2.2 or less.
  • n represents an integer of 1 or more and 5 or less.
  • the silica is obtained by hydrolysis and condensation of the tetraalkoxysilane having a mass ratio of 20 to 250 with respect to the ammonium salt in the presence of the ammonium salt represented by the formula (2).
  • the silica-coated carbon black described in 1. In the formula, X represents Cl, Br or I, and m represents an integer of 3 to 30.
  • a coating amount of the silica is 10% by mass to 30% by mass with respect to a total amount of the silica and the carbon black.
  • the carbon black is acetylene black.
  • the silica-coated carbon black according to any one of (1) to (9), a positive electrode active material capable of occluding and releasing cations, and a negative electrode active capable of occluding and releasing cations An electrode composition comprising at least one selected from the group consisting of substances and a binder.
  • An electrode for a secondary battery comprising a metal foil and a coating film of the electrode composition according to claim 10 provided on the metal foil.
  • a secondary battery comprising the secondary battery electrode according to (11) on at least one of a positive electrode and a negative electrode.
  • the tetraalkoxysilane represented by the formula (1) is hydrolyzed and condensed, and the surface of the carbon black is silica containing the hydrolyzed condensate of the tetraalkoxysilane.
  • a method for producing silica-coated carbon black comprising a step of coating, wherein a ratio of DBP absorption to compression DBP absorption of carbon black (DBP absorption / compression DBP absorption) is 2.2 or less.
  • n represents an integer of 1 to 5, inclusive.
  • the dispersion further contains an ammonium salt represented by the formula (2), and a mass ratio of the tetraalkoxysilane to the ammonium salt is 20 to 250.
  • X represents Cl, Br or I, and m represents an integer of 3 to 30.
  • the present inventors have found that the silica-coated carbon black of the present invention can suppress decomposition of the electrolyte and gas generation in the secondary battery.
  • the silica-coated carbon black of the present invention has excellent dispersibility and good conductivity.
  • the secondary electrode and the secondary battery using the silica-coated carbon black of the present invention have a feature that they have a long life.
  • FIG. 1 is a scanning electron micrograph of silica-coated carbon black of Example 1.
  • FIG. FIG. 2 is a scanning electron micrograph of carbon black of Comparative Example 1.
  • the silica-coated carbon black of the present embodiment includes carbon black and silica that coats the surface of the carbon black, and the ratio of DBP absorption amount to the compressed DBP absorption amount of the carbon black (DBP absorption amount / compressed DBP absorption amount). 2.2 or less, and the silica contains a hydrolyzed condensate of tetraalkoxysilane represented by the formula (1).
  • the coating in this specification means a state where silica is adsorbed or adhered to at least a part or all of the surface of the carbon black particles as shown in FIG. (In the formula, n represents an integer of 1 or more and 5 or less.)
  • the silica-coated carbon black of the present embodiment is a silica-coated carbon black obtained by coating the surface of carbon black with silica, and the ratio of the DBP absorption amount to the compressed DBP absorption amount of the carbon black (DBP absorption amount / compressed DBP absorption amount). Is 2.2 or less, and it can be said that the silica-coated carbon black is a hydrolysis-condensation product of tetraalkoxysilane represented by the formula (1).
  • the carbon black in the present embodiment is selected from acetylene black, furnace black, channel black, and the like, like carbon black as a general battery conductive agent. Among these, acetylene black having excellent crystallinity and purity is more preferable.
  • the DBP absorption amount of carbon black in the present embodiment is a value measured according to JIS K6217-4.
  • the compressed DBP absorption amount is a value measured by the same method as the DBP absorption amount for a compressed sample produced according to JIS K6217-4 Annex A.
  • the ratio of the DBP absorption amount to the compressed DBP absorption amount of carbon black in this embodiment is 2.2 or less, and more preferably 1.4 to 2.1.
  • a large DBP absorption value compared to the compressed DBP absorption amount means that the amount of agglomerated particles that are destroyed when producing a compressed sample is large, and that more energy is required to break them up. . Therefore, by setting the ratio of the DBP absorption amount to the compressed DBP absorption amount to 2.2 or less, the energy necessary for crushing the agglomerated particles can be suppressed, and the dispersibility becomes good.
  • the DBP absorption amount of carbon black in the present embodiment is preferably 280 mL / 100 g or less, and more preferably 200 mL / 100 g or less. By setting the DBP absorption amount to 280 mL / 100 g or less, aggregation due to entanglement between structures is suppressed, and dispersibility is improved.
  • the DBP absorption amount of carbon black in the present embodiment may be 90 mL / 100 g or more, or 150 mL / 100 g or more.
  • Silica in the present embodiment is a hydrolyzed condensate of tetraalkoxysilane.
  • the hydrolysis reaction and the condensation reaction are preferably performed in the presence of an ammonium salt represented by the formula (2) (also referred to as a halogenated alkyltrimethylammonium salt). Since the hydrolysis reaction of tetraalkoxysilane goes through an anionic intermediate, in the presence of alkyltrimethylammonium halide, which is a cationic surfactant, on the carbon black surface where the alkyltrimethylammonium halide molecule is adsorbed. A hydrolysis reaction and a condensation reaction proceed selectively.
  • silica obtained as a hydrolysis condensate in the presence of alkyltrimethylammonium halide of tetraalkoxysilane is easy to take a shape that coats the surface of carbon black in a shell shape, so the effect of preventing oxidative decomposition of the electrolyte is even better. It becomes.
  • X represents Cl, Br or I
  • m represents an integer of 3 to 30.
  • halogenated alkyltrimethylammonium halide one having an arbitrary halogen atom and alkyl group can be selected within the range in which the above-described effects can be obtained.
  • halogen atom represented by X chlorine is preferable.
  • the alkyl group preferably has 3 to 30 carbon atoms (that is, m), more preferably 10 to 20 carbon atoms. Among these, hexadecyltrimethylammonium chloride and dodecyltrimethylammonium chloride are preferable.
  • the mass ratio of tetraalkoxysilane to alkyltrimethylammonium halide is preferably 20 to 250.
  • the mass ratio the mass of tetraalkoxysilane / the mass of alkyltrimethylammonium halide
  • the amount of the cation relative to the anionic intermediate is sufficiently large, so that the hydrolysis reaction and the condensation reaction are more carbon. It progresses selectively on the black surface, and the silica coverage increases.
  • mass ratio mass of tetraalkoxysilane / mass of halogenated alkyltrimethylammonium
  • the carbon number of the alkyl group of tetraalkoxysilane is 5 or less, and preferably 3 or less. Since the hydrolysis reaction of tetraalkoxysilane proceeds faster as the carbon number of the alkyl group is smaller, the yield of silica is increased by setting the carbon number to 5 or less even if the reaction time is short.
  • the coating amount of silica is preferably 10% by mass to 30% by mass with respect to the total amount of silica and carbon black.
  • the coating amount is preferably 10% by mass to 30% by mass with respect to the total amount of silica and carbon black.
  • Free silica it is preferable in terms of conductivity to be removed from the produced silica-coated carbon black.
  • Free silica can be filtered to the filtrate side after synthesis of silica-coated carbon black, for example, with a filter having a mesh diameter of 1 to 9 ⁇ m.
  • the volume resistivity of silica-coated carbon black is a value obtained by measuring a powder sample compressed in a disk shape at a pressure of 24 MPa in an environment of 25 ° C. and a relative humidity of 50% by a four-terminal four-probe method.
  • the volume resistivity of the silica-coated carbon black is preferably 1 ⁇ 10 6 ⁇ ⁇ cm or less, and more preferably 1 ⁇ 10 3 ⁇ ⁇ cm or less.
  • the method for producing the silica-coated carbon black of the present embodiment is not particularly limited.
  • Langmuir 2012, 28, 7055-7062 A known method as described in 1) can be used. Specifically, prepare a dispersion in which the original carbon black is dispersed in ethanol and a solution in which tetraethoxysilane is dissolved in ethanol. After mixing both, add aqueous ammonia to make it alkaline. By doing so, a method of hydrolyzing tetraethoxysilane can be used.
  • the silica-coated carbon black can be dispersed in a medium together with a positive electrode active material or a negative electrode active material and a binder and used as an electrode composition.
  • the positive electrode active material may be any positive electrode active material that can occlude and release cations.
  • composite oxides having a layered rock salt structure such as lithium cobaltate, lithium nickelate, nickel cobalt lithium manganate, nickel cobalt lithium aluminum oxide, and spinel structures such as lithium manganate and lithium nickel manganate
  • composite oxides having an olivine structure such as lithium iron phosphate, lithium manganese phosphate, and lithium iron manganese phosphate.
  • the negative electrode active material may be any negative electrode active material that can occlude and release cations.
  • Examples of the negative electrode active material include carbon-based materials such as artificial graphite, natural graphite, soft carbon, and hard carbon, metal-based materials alloyed with alkali metals such as silicon and tin, and metal composite oxides such as lithium titanate. .
  • binder examples include polymers such as polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene copolymer, polyvinyl alcohol, acrylonitrile-butadiene copolymer, and carboxylic acid-modified (meth) acrylic acid ester copolymer. It is done. Among these, polyvinylidene fluoride is preferable from the viewpoint of oxidation resistance when used for the positive electrode, and polyvinylidene fluoride or styrene-butadiene copolymer is preferable from the viewpoint of adhesion when used for the negative electrode.
  • polymers such as polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene copolymer, polyvinyl alcohol, acrylonitrile-butadiene copolymer, and carboxylic acid-modified (meth) acrylic acid ester copolymer. It is done. Among these,
  • Examples of the dispersion medium for the electrode composition include water, N-methyl-2-pyrrolidone, cyclohexane, methyl ethyl ketone, and methyl isobutyl ketone.
  • N-methyl-2-pyrrolidone is preferable from the viewpoint of solubility, and when using a styrene-butadiene copolymer, water is preferable.
  • a mixing machine such as a rachi machine, a universal mixer, a Henschel mixer or a ribbon blender, or a medium stirring type mixer such as a bead mill, a vibration mill or a ball mill is used.
  • the manufactured electrode coating liquid is preferably subjected to vacuum defoaming at a stage before coating in order to ensure smoothness without causing defects in the coating film. If air bubbles are present in the coating solution, the coating film will be defective when applied to the electrode, which may impair smoothness.
  • the electrode composition can contain components other than silica-coated carbon black, a positive electrode active material, a negative electrode active material, and a binder as long as the above-described effects are obtained.
  • a positive electrode active material a positive electrode active material
  • a negative electrode active material a binder
  • carbon nanotubes, carbon nanofibers, graphite, graphene, carbon fibers, elemental carbon, glassy carbon, metal particles, and the like may be included in addition to silica-coated carbon black for the purpose of further improving conductivity.
  • polyvinyl pyrrolidone polyvinyl imidazole, polyethylene glycol, polyvinyl alcohol, polyvinyl butyral, carboxymethyl cellulose, acetyl cellulose, a carboxylic acid-modified (meth) acrylic acid ester copolymer and the like may be included.
  • the present invention may relate to an electrode composition containing the silica-coated carbon black described above.
  • the electrode composition may include the silica-coated carbon black, at least one selected from the group consisting of a positive electrode active material and a negative electrode active material, and a binder.
  • the present invention may also relate to a secondary battery electrode comprising a metal foil and a coating film of the electrode composition provided on the metal foil.
  • the metal foil may be, for example, an aluminum foil when used as a positive electrode. Moreover, when using as a negative electrode, copper foil etc. may be sufficient, for example.
  • the shape of the metal foil is not particularly limited. From the viewpoint of facilitating workability, the thickness of the metal foil is preferably 5 to 30 ⁇ m.
  • the coating film of the electrode composition is, for example, a slot die method, a lip method, a reverse roll method, a direct roll method, a blade method, a knife method, an extrusion method, a curtain method, a gravure method, a bar method, a dip method, and a squeeze. It may be formed by applying a composition for an electrode on a metal foil by a method such as a method. Of these, the slot die method, the lip method, and the reverse roll method are preferable. The coating method may be appropriately selected according to the solution physical properties, drying properties, etc. of the binder. The coating film of the electrode composition may be formed on one side of the metal foil or on both sides.
  • the electrode composition When the coating film of the electrode composition is formed on both surfaces of the metal foil, the electrode composition may be sequentially applied to the metal foil one side at a time or may be simultaneously applied to both surfaces of the metal foil.
  • the application mode of the electrode composition may be continuous, intermittent, or striped.
  • the thickness, length and width of the coating film of the electrode composition may be appropriately determined according to the size of the battery.
  • the thickness of the coating film may be in the range of 10 ⁇ m to 500 ⁇ m.
  • the coating film of the electrode composition may be formed by applying and drying the electrode composition.
  • the electrode composition can be dried using, for example, means such as hot air, vacuum, infrared rays, far infrared rays, electron beams, and low-temperature air, alone or in combination.
  • the secondary battery electrode may be pressed as necessary.
  • a generally adopted method may be used, and for example, a die pressing method, a calendar pressing method (cold or hot roll) and the like are preferable.
  • the pressing pressure in the calender pressing method is not limited, but is preferably 0.02 to 3 ton / cm, for example.
  • the present invention may also relate to a secondary battery provided with the secondary battery electrode on at least one of a positive electrode and a negative electrode.
  • the secondary battery may be, for example, a lithium ion secondary battery, a sodium ion secondary battery, a magnesium ion secondary battery, a nickel hydride secondary battery, or an electric double layer capacitor.
  • the present invention may also relate to a method for producing silica-coated carbon black.
  • the method for producing a silica-coated carbon black comprises hydrolyzing and condensing the tetraalkoxysilane in a dispersion containing the carbon black, so that the surface of the carbon black is made of the tetraalkoxysilane. It may include a step of coating with silica containing a hydrolysis condensate.
  • the dispersion may further contain the alkyltrimethylammonium halide.
  • the mass ratio of the tetraalkoxysilane to the ammonium salt may be 20 to 250.
  • the present invention may also relate to a conductive agent for a secondary battery containing the silica-coated carbon black, and may relate to the use of the silica-coated carbon black as a conductive agent for a secondary battery.
  • the present invention may also relate to the use of the silica-coated carbon black for the production of a secondary battery electrode, and may relate to the use of the silica-coated carbon black for the production of a secondary battery. .
  • silica-coated carbon black according to the present invention will be described in detail with reference to Examples and Comparative Examples.
  • the present invention is not limited to the following examples unless it exceeds the gist.
  • Example 1 (Carbon black)
  • acetylene black (HS100, manufactured by Denki Kagaku Kogyo K.K.) having a DBP absorption of 171 mL / 100 g and a compressed DBP absorption of 83 mL / 100 g was used as carbon black.
  • the DBP absorption amount and compression DBP absorption amount of carbon black were measured by the following methods.
  • DBP absorption and compressed DBP absorption DBP absorption was measured by a method according to JIS K6217-4. Further, the compressed DBP absorption amount was measured by the same method as the DBP absorption amount for a compressed sample prepared by compressing four times at 165 MPa according to JIS K6217-4 Annex A.
  • Electrode composition and electrode 90 parts by mass of spinel-type lithium nickel manganate (manufactured by Hosen Co., Ltd.) as an active material, 5 parts by mass of silica-coated carbon black, and a polyvinylidene fluoride solution (manufactured by Kureha Chemical Co., Ltd., “KF Polymer (registered trademark) 1120” as a binder
  • This electrode composition was applied to a 20 ⁇ m thick aluminum foil using a Baker-type applicator, dried, then pressed and cut to obtain a positive electrode for a lithium secondary battery.
  • Electrode composition evaluation of dispersibility (electrode composition)
  • the dispersibility of the silica-coated carbon black in the electrode composition was evaluated by a method using a crush gauge described in JIS K5600-2-5. Specifically, a scraper was used to apply the coating solution, and the graduations were measured at locations where three or more linear traces of 10 mm or more continuous on the sample surface were arranged in one groove. The lower the numerical value, the better the dispersibility.
  • the dispersibility of the silica-coated carbon black in the secondary battery electrode was judged by the appearance of the positive electrode for the lithium secondary battery. Specifically, five 100 mm square electrodes were prepared and evaluated according to the following scale. A: No streak of coating marks and aggregates were observed on the electrode surfaces of all five sheets. B: Streaky coating marks or aggregates less than 1 mm were observed on one or more electrode surfaces. C: Agglomerates of 1 mm or more were observed on one or more electrode surfaces.
  • a positive electrode for a secondary battery produced using the electrode composition as a positive electrode was cut into 40 mm length and 40 mm width, and a negative electrode for the secondary battery cut into 44 mm length and 44 mm width was used as a negative electrode. Then, a non-woven fabric made of olefin fiber was used as a separator for electrically isolating them, and an aluminum laminate film was used as an exterior to make a laminated battery.
  • EC ethylene carbonate, manufactured by Aldrich
  • DEC diethyl carbonate, manufactured by Aldrich
  • LiPF6 lithium hexafluorophosphate
  • the secondary battery produced above was evaluated as follows. The results are shown in Table 1. Unless otherwise specified, the evaluation value is an arithmetic average value of the evaluation values of the three batteries.
  • a positive electrode active material amount (g) present on the positive electrode was determined from the mass of the positive electrode, and a value (mA) obtained by dividing this by 140 was defined as a current value “1C”.
  • a constant current / constant voltage charge is performed with a current of 1 C and an upper limit voltage of 5.0 V, and a constant current discharge is performed with a current of 1 C and a lower limit voltage of 3.0 V.
  • the charge capacity per 1 g of the positive electrode active material The ratio (%) of the discharge capacity (mAh / g) per gram of the positive electrode active material to the mAh / g) was defined as the Coulomb efficiency.
  • the volume change (mL) of the battery before and after the cycle characteristic test was measured as a gas generation amount.
  • the volume of the battery was measured in a constant temperature room at 25 ⁇ 1 ° C. using a specific gravity measuring device (AUW220D manufactured by Shimadzu Corporation).
  • AUW220D specific gravity measuring device manufactured by Shimadzu Corporation
  • Examples 2 to 8> A silica-coated carbon black and an electrode composition were prepared in the same manner as in Example 1 except that the addition amounts of hexadecyltrimethylammonium chloride and tetraethoxysilane in Example 1 were changed to the mass ratio shown in Table 1. A secondary battery electrode and a secondary battery were prepared and evaluated. The results are shown in Table 1.
  • Example 9 Except for changing the carbon black of Example 1 to furnace black (SuperPLi, manufactured by Timcal Graphite and Carbon, Inc.) having a DBP absorption of 234 mL / 100 g and a compressed DBP absorption of 115 mL / 100 g, the same as in Example 1
  • the silica-coated carbon black, the electrode composition, the secondary battery electrode and the secondary battery were prepared by various methods, and each evaluation was performed. The results are shown in Table 2.
  • Example 10 The same method as in Example 1 except that the carbon black in Example 1 was changed to acetylene black (AB powder, manufactured by Denki Kagaku Kogyo Co., Ltd.) having a DBP absorption of 228 mL / 100 g and a compressed DBP absorption of 125 mL / 100 g.
  • acetylene black ABS powder, manufactured by Denki Kagaku Kogyo Co., Ltd.
  • the silica-coated carbon black, the electrode composition, the secondary battery electrode and the secondary battery were prepared and evaluated. The results are shown in Table 2.
  • Example 11 In the same manner as in Example 1, except that the carbon black of Example 1 was changed to acetylene black (SAB, manufactured by Denki Kagaku Kogyo Co., Ltd.) having a DBP absorption of 338 mL / 100 g and a compressed DBP absorption of 240 mL / 100 g. Coated carbon black, an electrode composition, an electrode for a secondary battery, and a secondary battery were prepared and evaluated. The results are shown in Table 2.
  • SAB acetylene black
  • Example 12 The tetraethoxysilane of Example 1 was changed to tetrabutoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the addition amounts of tetrabutoxysilane and hexadecyltrimethylammonium chloride were changed so that the mass ratio shown in Table 2 was obtained.
  • Example 13 The tetraethoxysilane in Example 1 was changed to tetrapropoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the addition amount of tetrabutoxysilane and hexadecyltrimethylammonium chloride was changed to the mass ratio shown in Table 2.
  • tetraethoxysilane in Example 1 was changed to tetrapropoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the addition amount of tetrabutoxysilane and hexadecyltrimethylammonium chloride was changed to the mass ratio shown in Table 2.
  • Example 14 Except that hexadecyltrimethylammonium chloride of Example 1 was changed to dodecyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), silica-coated carbon black, electrode composition, secondary battery electrode were obtained in the same manner as in Example 1. And the secondary battery was produced and each evaluation was implemented. The results are shown in Table 2.
  • Example 1 Except that the amount of tetraethoxysilane added in Example 1 was changed to 0, silica-coated carbon black, an electrode composition, a secondary battery electrode, and a secondary battery were prepared in the same manner as in Example 1, Evaluation was performed. The results are shown in Table 3. In the secondary battery of Comparative Example 1, the discharge capacity was zero in less than 200 cycles in the measurement of cycle characteristics.
  • FIG. 2 is a scanning electron micrograph of carbon black of Comparative Example 1.
  • Example 2 The carbon black of Example 1 was changed to Furnace Black (SuperC65 manufactured by Timcal Graphite and Carbon) having a DBP absorption of 254 mL / 100 g and a compressed DBP absorption of 104 mL / 100 g.
  • Silica-coated carbon black, an electrode composition, a secondary battery electrode, and a secondary battery were prepared by the method, and each evaluation was performed. The results are shown in Table 3.
  • the secondary battery electrode of Comparative Example 2 was inferior in electrode appearance. Further, the secondary battery of Comparative Example 2 had a low cycle characteristic.
  • an electrode composition and a secondary battery electrode excellent in conductivity and dispersibility can be obtained. Thereby, a long-life secondary battery in which decomposition of the electrolyte and generation of gas can be suppressed can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (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)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

Selon l'invention, le rapport d'absorption de DBP à l'absorption de DBP comprimé de noir de carbone (absorption de DBP/absorption de DBP comprimé) est de 2,2 ou moins et du noir de carbone revêtu de silice, dans lequel la silice est un produit de condensation hydrolysé d'un tétraalcoxysilane présentant une structure spécifique, est utilisé pour obtenir une plus longue durée de vie d'une batterie, ainsi que de bonnes caractéristiques électroconductrices et une bonne dispersibilité.
PCT/JP2015/083267 2014-11-26 2015-11-26 Noir de carbone revêtu de silice, composition d'électrode dans laquelle celui-ci est utilisé, électrode pour batterie rechargeable et batterie rechargeable WO2016084909A1 (fr)

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CN201580074376.XA CN107207876B (zh) 2014-11-26 2015-11-26 二氧化硅覆盖碳黑及使用其的电极用组合物、二次电池用电极以及二次电池

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WO2016186065A1 (fr) * 2015-05-19 2016-11-24 デンカ株式会社 Noir de carbone revêtu de silice, composition d'électrode l'utilisant, électrode de batterie secondaire, et batterie secondaire
CN110676445A (zh) * 2019-09-19 2020-01-10 安徽清泉新能源科技集团有限责任公司 一种溶胶包覆锂电池材料及其制备方法
JP2020149794A (ja) * 2019-03-11 2020-09-17 トヨタ自動車株式会社 非水系リチウムイオン二次電池
WO2023176099A1 (fr) * 2022-03-15 2023-09-21 株式会社村田製作所 Batterie secondaire

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CN117343096B (zh) * 2023-12-04 2024-04-02 瑞浦兰钧能源股份有限公司 一种离子化导电剂及其制备方法和应用

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JPH0668869A (ja) * 1992-08-21 1994-03-11 Central Res Inst Of Electric Power Ind リチウム二次電池
JPH09296072A (ja) * 1996-04-30 1997-11-18 Yokohama Rubber Co Ltd:The 高電気抵抗性カーボンブラック含有成形品
JP2006210007A (ja) * 2005-01-25 2006-08-10 Mitsubishi Chemicals Corp 電気化学素子用電極およびそれを用いたリチウム二次電池

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WO1996037547A2 (fr) * 1995-05-22 1996-11-28 Cabot Corporation Composes elastomeres incorporant des noirs de carbone traites au silicium
JP5624361B2 (ja) * 2009-08-07 2014-11-12 パナソニック株式会社 メソポーラスシリカ微粒子の製造方法、メソポーラスシリカ微粒子、メソポーラスシリカ微粒子分散液、メソポーラスシリカ微粒子含有組成物、及びメソポーラスシリカ微粒子含有成型物
FR2992230B1 (fr) * 2012-06-21 2014-07-25 Michelin & Cie Procede de preparation d'une espece carbonee recouverte de silice

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JPH0668869A (ja) * 1992-08-21 1994-03-11 Central Res Inst Of Electric Power Ind リチウム二次電池
JPH09296072A (ja) * 1996-04-30 1997-11-18 Yokohama Rubber Co Ltd:The 高電気抵抗性カーボンブラック含有成形品
JP2006210007A (ja) * 2005-01-25 2006-08-10 Mitsubishi Chemicals Corp 電気化学素子用電極およびそれを用いたリチウム二次電池

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016186065A1 (fr) * 2015-05-19 2016-11-24 デンカ株式会社 Noir de carbone revêtu de silice, composition d'électrode l'utilisant, électrode de batterie secondaire, et batterie secondaire
JPWO2016186065A1 (ja) * 2015-05-19 2018-04-12 デンカ株式会社 シリカ被覆カーボンブラック、それを用いた電極用組成物、二次電池用電極および二次電池
JP2020149794A (ja) * 2019-03-11 2020-09-17 トヨタ自動車株式会社 非水系リチウムイオン二次電池
JP7071701B2 (ja) 2019-03-11 2022-05-19 トヨタ自動車株式会社 非水系リチウムイオン二次電池
CN110676445A (zh) * 2019-09-19 2020-01-10 安徽清泉新能源科技集团有限责任公司 一种溶胶包覆锂电池材料及其制备方法
WO2023176099A1 (fr) * 2022-03-15 2023-09-21 株式会社村田製作所 Batterie secondaire

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