WO2020235447A1 - Matériau carboné et batterie secondaire au lithium-ion l'utilisant - Google Patents

Matériau carboné et batterie secondaire au lithium-ion l'utilisant Download PDF

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WO2020235447A1
WO2020235447A1 PCT/JP2020/019292 JP2020019292W WO2020235447A1 WO 2020235447 A1 WO2020235447 A1 WO 2020235447A1 JP 2020019292 W JP2020019292 W JP 2020019292W WO 2020235447 A1 WO2020235447 A1 WO 2020235447A1
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reduced graphene
carbon material
graphene oxide
negative electrode
electrode active
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PCT/JP2020/019292
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Japanese (ja)
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前田　勝美
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日本電気株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 a carbon material and a lithium ion secondary battery.
  • Lithium-ion secondary batteries have been put into practical use as batteries for small electronic devices such as notebook computers and mobile phones due to their advantages such as high energy density, low self-discharge, and excellent long-term reliability. In recent years, the development of lithium-ion secondary batteries for electric vehicles, household storage batteries, and electric power storage has been progressing.
  • carbon materials are generally used as the negative electrode active material, and various carbon materials have been proposed to improve battery characteristics.
  • carbon materials include high crystalline carbon such as natural graphite and artificial graphite, low crystalline carbon such as easily graphitizable carbon (soft carbon) and non-graphitizable carbon (hard carbon), and amorphous carbon (amorphous carbon). Carbon) etc. are known.
  • Patent Document 1 discloses a secondary battery in which reduced graphene oxide obtained by thermally reducing graphene oxide is used as a negative electrode active material.
  • Patent Document 2 discloses a negative electrode composed of a mixture of silicon and reduced graphene oxide.
  • An object of the present invention is to provide a carbon material that improves the initial charge / discharge efficiency of a battery in view of the above-mentioned problems.
  • the first carbon material of the present invention contains two or more layers of reduced graphene oxide, and contains an arylene group between the reduced graphene oxide.
  • the first method for producing a carbon material of the present invention includes a step of reacting reduced graphene oxide with an aromatic bisdiazonium salt.
  • the first lithium ion secondary battery of the present invention includes a positive electrode containing a positive electrode active material capable of storing and releasing lithium ions, a negative electrode containing a negative electrode active material capable of storing and releasing lithium ions, and a non-aqueous electrolyte solution.
  • the negative electrode active material contains two or more layers of reduced graphene oxide, and contains a carbon material containing an arylene group between the reduced graphene oxides.
  • the carbon material of the present invention can improve the initial charge / discharge efficiency of the battery.
  • the present inventors have conducted extensive research in order to solve the above-mentioned problems. As a result, they have found that in a lithium ion secondary battery, the initial charge / discharge efficiency of the lithium ion secondary battery can be improved by using a carbon material having an arylene group between reduced graphene oxides as the negative electrode active material. completed.
  • Graphene is a sheet of sp2-bonded carbon atoms with a thickness of 1 atom.
  • graphene oxide containing oxygen functional groups such as hydroxyl groups, epoxy groups and carboxyl groups and having defects can be obtained.
  • Reduced graphene oxide is obtained by reducing graphene oxide. Oxygen functional groups such as hydroxyl groups, epoxy groups, and carboxyl groups are removed by the reduction treatment, but usually they are not completely removed and some of them remain. Therefore, reduced graphene oxide is less than graphene oxide, but also has oxygen functional groups and defects.
  • Graphene oxide can be synthesized by a conventionally known method such as the Hammers method or the Brodie method.
  • graphene oxide can be synthesized by oxidizing artificial graphite, natural graphite, or the like with an oxidizing agent such as potassium permanganate or potassium chlorate in a strong acid such as sulfuric acid or fuming nitric acid.
  • the reduced graphene oxide can be prepared by a conventionally known method such as dispersing graphene oxide in water or an organic solvent and reacting it with hydrazine, ascorbic acid or the like.
  • a plurality of reduced graphene oxides are laminated.
  • the number of layers of reduced graphene oxide is not particularly limited, and may be in the range of, for example, 2 to 20 layers or 2 to 10 layers.
  • the carbon material of the present embodiment further contains an arylene group between reduced graphene oxides.
  • the arylene group is a divalent monocyclic or polycyclic aromatic hydrocarbon.
  • the arylene group preferably has 6 to 30 carbon atoms, more preferably 10 to 18 carbon atoms. Specific examples of the arylene group include those having the following structural formulas, and among these, 4,4 "-p-terphenyldiyl is particularly preferable.
  • Such a carbon material having an arylene group between reduced graphene oxides can be prepared by reacting reduced graphene oxides with an aromatic bisdiazonium salt in a solvent.
  • the reaction is carried out by the following procedure. First, reduced graphene oxide is dispersed in an organic solvent such as N-methyl-2-pyrrolidone or N, N-dimethylformamide by ultrasonic treatment or the like.
  • Aromatic bisdiazonium salt is added to this and reacted at room temperature. It is considered that this reaction causes the reduced graphene oxide and the arylene group to be bonded via a carbon-carbon bond.
  • the aromatic bisdiazonium salt can be prepared from the aromatic diamine according to a conventionally known method for preparing a diazonium salt. Specifically, an aromatic bisdiazonium salt can be synthesized by reacting a boron trifluoride diethyl ether complex with isoamyl nitrite with an aromatic diamine.
  • the arylene group usually crosslinks the reduced graphene oxide, so that the interlayer distance of the reduced graphene oxide can be widened.
  • the arylene group is formed in a columnar shape between reduced graphene oxides. That is, the arylene group is oriented substantially perpendicular to the reduced graphene.
  • the arylene group can form an angle with the in-plane direction of reduced graphene oxide, for example, in the range of 70 ° to 90 °.
  • the interlayer distance of reduced graphene oxide is preferably 14.7 ⁇ or more, more preferably 16 ⁇ or more.
  • the interlayer distance of the reduced graphene oxide is preferably 22.0 ⁇ or less, more preferably 20 ⁇ or less.
  • the interlayer distance of reduced graphene oxide can be measured by an X-ray diffraction (XRD) apparatus.
  • the amount of the arylene group in the carbon material is not particularly limited, but may be 1 part by mass to 200 parts by mass, and more specifically, 20 parts by mass to 150 parts by mass with respect to 100 parts by mass of reduced graphene oxide. Good.
  • a negative electrode active material layer containing a negative electrode active material and a negative electrode binder may be used so as to cover the negative electrode current collector.
  • the negative electrode active material contains a carbon material having an arylene group between reduced graphene oxides, and may further contain a negative electrode active material capable of storing and releasing lithium ions.
  • Examples of the negative electrode active material include graphite materials (artificial graphite, natural graphite), carbon black (acetylene black, furnace black), coke, mesocarbon microbeads, hard carbon, carbon materials such as graphite, and silicon and silicon oxide. , Silicon-containing materials such as graphite alloys, and two types may be used in combination at any ratio.
  • the content of the carbon material of the present embodiment in the negative electrode active material is preferably 5% by mass or more, 40% by mass or more, and 100% by mass in order to increase the discharge capacity of the lithium ion secondary battery. It may be.
  • the amount of the negative electrode active material in the negative electrode active material layer is not particularly limited and may be appropriately determined.
  • the amount of the negative electrode active material in the negative electrode active material layer may be 75% by mass or more or 85% by mass or more.
  • the amount of the negative electrode active material in the negative electrode active material layer may be 99% by mass or less or 95% by mass or less.
  • the negative electrode binder is not particularly limited, but for example, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, and styrene-butadiene copolymer rubber. (SBR), polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamideimide, polyacrylic acid (including lithium salt, sodium salt, potassium salt), carboxymethyl cellulose (including lithium salt, sodium salt, potassium salt), etc. Can be used.
  • the amount of the negative electrode binder used is preferably 5 to 25 parts by mass with respect to 100 parts by mass of the negative electrode active material from the viewpoint of the binding force and the energy density, which are in a trade-off relationship.
  • the negative electrode current collector is not particularly limited, and any current collector used in a general lithium ion secondary battery can be used.
  • a metal material such as copper, nickel, or SUS can be used. Of these, copper is particularly preferable from the viewpoint of ease of processing and cost.
  • the negative electrode current collector is preferably roughened in advance. Examples of the shape of the negative electrode current collector include a foil shape, a flat plate shape, and a mesh shape. It is also possible to use a perforated type negative electrode current collector such as expanded metal or punching metal.
  • a negative electrode active material for example, a negative electrode active material, a negative electrode binder, various auxiliaries and the like, if necessary, and a solvent are kneaded to prepare a slurry, which is applied onto the negative electrode current collector, and then. It can be produced by drying and pressurizing if necessary.
  • a positive electrode active material layer containing a positive electrode active material and a positive electrode binder may be used so as to cover the positive electrode current collector.
  • a lithium transition metal composite oxide containing lithium and a transition metal such as cobalt, manganese, or nickel can be used as the positive electrode active material.
  • these lithium transition metal composite oxides include those in which Li is in excess of the stoichiometric composition.
  • a part of the lithium transition metal composite oxide may be replaced with another element.
  • a part of cobalt, manganese, and nickel may be replaced with at least one or more elements such as Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, Cu, Bi, Mo, and La.
  • a part of oxygen can be replaced with S or F, or the surface of the positive electrode can be coated with a compound containing these elements.
  • compositions of the lithium transition metal composite oxide of the present embodiment include, for example, LiMnO 2 , LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiCo 0.8 Ni 0.2 O 2 , LiNi 1/2 Mn. 3/2 O 4 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 (abbreviated as NCM111), LiNi 0.4 Co 0.3 Mn 0.3 O 2 (abbreviated as NCM433), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (abbreviated as NCM523), LiNi 0.5 Co 0.3 Mn 0.2 O 2 (abbreviated as NCM532), LiFePO 4 , LiNi 0.8 Co 0.15 Al 0.
  • NCM532 or NCM523 and NCM433 may be used in the range of 9: 1 to 1: 9 (as a typical example). 2: 1) mixture to or be used in, and NCM532 or NCM523 and LiMnO 2 or LiCoO 2, LiMn 2 O 4 9 : 1 ⁇ 1: 9 were mixed in a range of can be used.
  • the method for synthesizing the lithium transition metal composite oxide represented by the chemical formula is not particularly limited, and a conventionally known method for synthesizing an oxide can be applied.
  • a conductive auxiliary agent may be added to the positive electrode active material layer containing the positive electrode active material for the purpose of lowering the impedance.
  • the conductive auxiliary agent include graphites such as natural graphite and artificial graphite, and carbon blacks such as acetylene black, ketjen black, furnace black, channel black, and thermal black.
  • the conductive auxiliary agent a plurality of types may be appropriately mixed and used.
  • the amount of the conductive auxiliary agent is preferably 1 to 10% by mass with respect to 100% by mass of the positive electrode active material.
  • the positive electrode binder is not particularly limited, and examples thereof include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, and vinylidene fluoride-tetrafluoroethylene copolymer. Further, styrene-butadiene copolymer rubber, polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamideimide and the like may be used as the positive electrode binder. In particular, from the viewpoint of versatility and low cost, it is preferable to use polyvinylidene fluoride as a positive electrode binder.
  • the amount of the positive electrode binder used is preferably 2 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material from the viewpoint of "sufficient binding force" and "high energy" which are in a trade-off relationship.
  • the positive electrode current collector a general one can be arbitrarily used, and for example, an aluminum foil, a lath plate made of stainless steel, or the like can be used.
  • the positive electrode is a positive electrode current collector obtained by adding a solvent such as N-methylpyrrolidone to a mixture of a positive electrode active material, a conductive auxiliary agent and a positive electrode binder and kneading the mixture, and then using a doctor blade method, a die coater method, or the like. It can be produced by applying to and drying.
  • a solvent such as N-methylpyrrolidone
  • the non-aqueous electrolyte solution of a lithium ion secondary battery is mainly composed of a non-aqueous solvent and an electrolyte.
  • the non-aqueous solvent include cyclic carbonates, chain carbonates, chain esters, lactones, ethers, sulfones, nitriles, phosphate esters and the like, and cyclic carbonates and chain carbonates are included. preferable.
  • cyclic carbonates include propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, vinylethylene carbonate and the like.
  • chain carbonates include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate and the like. Further, ethyl methyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, methyl butyl carbonate and the like are also mentioned as specific examples of chain carbonates.
  • chain esters include methyl formate, methyl acetate, methyl propionate, ethyl propionate, methyl pivalate, ethyl pivalate and the like.
  • lactones include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -butyrolactone and the like.
  • ethers include tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1, 2-Dibutoxyethane and the like can be mentioned.
  • sulfones include sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane and the like.
  • nitriles include acetonitrile, propionitrile, succinonitrile, glutaronitrile, adiponitrile, and the like.
  • phosphoric acid esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate and the like.
  • non-aqueous solvent can be used alone or in combination of two or more.
  • examples of the combination of the plurality of non-aqueous solvents include a combination of cyclic carbonates and chain carbonates.
  • a non-aqueous solvent such as a fluorinated ether solvent, a fluorinated carbonate solvent, or a fluorinated phosphate ester may be further added to the combination of the cyclic carbonates and the chain carbonates.
  • fluorinated ether-based solvent examples include CF 3 OCH 3 , CF 3 OC 2 H 5 , F (CF 2 ) 2 OCH 3 , F (CF 2 ) 2 OC 2 H 5 , F (CF 2 ) 3 OCH.
  • fluorinated carbonate solvent examples include fluoroethylene carbonate, fluoromethylmethyl carbonate, 2-fluoroethylmethyl carbonate, ethyl- (2-fluoroethyl) carbonate, (2,2-difluoroethyl) ethyl carbonate, and bis (2).
  • fluoroethylene carbonate fluoromethylmethyl carbonate
  • 2-fluoroethylmethyl carbonate ethyl- (2-fluoroethyl) carbonate
  • 2,2-difluoroethyl) ethyl carbonate examples of the fluorinated carbonate solvent
  • bis (2) bis (2).
  • -Fluoroethyl) carbonate, ethyl- (2,2,2-trifluoroethyl) carbonate and the like can be mentioned.
  • fluorinated phosphate esters examples include tris phosphate (2,2,2-trifluoroethyl), tris phosphate (trifluoromethyl), tris phosphate (2,2,3,3-tetrafluoropropyl) and the like. Can be mentioned.
  • electrolyte examples include lithium hexafluorophosphate (LiPF 6 ), lithium bis (fluorosulfonyl) imide [LiN (SO 2 F) 2 ], LiBF 4 , LiClO 4 , and LiN (SO 2 CF 3 ) 2.
  • lithium salts may be used alone or in combination of two or more.
  • LiN (SO 2 F) 2 can improve the charge rate characteristic.
  • LiN (SO 2 F) 2 when LiN (SO 2 F) 2 is used alone, there is a problem that the aluminum of the positive electrode current collector is corroded. Therefore, it is preferable to use both LiPF 6 and LiN (SO 2 F) 2. At that time, by setting the concentration of LiPF 6 in the electrolytic solution to 0.3 M or more, aluminum is maintained while maintaining high charge rate characteristics. Corrosion can be suppressed.
  • the concentration of the electrolyte dissolved in the non-aqueous electrolyte solution is preferably in the range of 0.3 to 3 mol / L, and more preferably in the range of 0.5 to 2 mol / L.
  • concentration of the electrolyte is 0.3 mol / L or more, more sufficient ionic conductivity can be obtained.
  • concentration of the electrolyte is 3 mol / L or less, an increase in the viscosity of the electrolytic solution is suppressed, and more sufficient ion mobility and impregnation property can be obtained.
  • the separator is not particularly limited, but a single-layer or laminated porous film or non-woven fabric made of a resin material such as polyolefin such as polypropylene or polyethylene can be used. Further, a film obtained by coating or laminating a different material on a resin layer such as polyolefin can also be used. Examples of such a film include a polyolefin base material coated with a fluorine compound and inorganic fine particles, a polyolefin base material coated with an aramid layer, and the like.
  • the thickness of the separator is preferably 5 to 50 ⁇ m, more preferably 10 to 40 ⁇ m from the viewpoint of the energy density of the battery and the mechanical strength of the separator.
  • the form of the lithium ion secondary battery is not particularly limited, and examples thereof include a coin type battery, a button type battery, a cylindrical type battery, a square type battery, and a laminated type battery.
  • a laminated body in which positive electrodes, separators, and negative electrodes are alternately laminated is formed, metal terminals called tabs are connected to each electrode, and the battery is placed in a container made of a laminated film which is an exterior body.
  • the laminate film can be appropriately selected as long as it is stable in the electrolytic solution and has sufficient water vapor barrier properties.
  • a laminate film for example, a laminate film made of polyolefin (for example, polypropylene, polyethylene) coated with an inorganic material such as aluminum, silica, or alumina can be used.
  • an aluminum laminate film made of polyolefin coated with aluminum is preferable.
  • a typical layer structure of a laminated film is a structure in which a metal thin film layer and a thermosetting resin layer are laminated.
  • a resin film (protective layer) made of polyester such as polyethylene terephthalate or polyamide such as nylon may be further laminated on the surface of the metal thin film layer opposite to the thermosetting resin layer side.
  • the thermosetting resin layers of the two laminated films are opposed to each other so that the container made of the laminated film containing the laminated body containing the positive electrode and the negative electrode can be sealed.
  • a foil having a thickness of 10 to 100 ⁇ m, such as an Al, Ti, Ti alloy, Fe, stainless steel, or Mg alloy, is used as an Al, Ti, Ti alloy, Fe, stainless steel, or Mg alloy.
  • the resin used for the heat-sealing resin layer is not particularly limited as long as it is a resin capable of heat-sealing. , Ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ionomer resin in which ethylene-acrylic acid copolymer is intermolecularly bonded with metal ions and the like.
  • the thickness of the thermosetting resin layer is preferably 10 to 200 ⁇ m, more preferably 30 to 100 ⁇ m.
  • the obtained dispersion was centrifuged (5500 rpm, 5 minutes), and only the supernatant in which reduced graphene oxide was dispersed was taken out.
  • a solution prepared by dissolving 3 g of the p-terphenyl-4,4 ′′ -bisdiazonium salt obtained in Synthesis Example 1 in 80 ml of N-methyl-2-pyrrolidone was added dropwise thereto. The mixture was stirred at room temperature for 24 hours and polytetrafluoro. The mixture was filtered using an ethylene filter (pore size 1 ⁇ m). The recovered solid content was washed in the order of N-methyl-2-pyrrolidone and acetone, and further vacuum dried at 60 ° C. to obtain 4,4 between reduced graphene oxides. 20 mg of a carbon material having a "-p-terphenyldiyl structure" was obtained.
  • Example 1 Carbon material (8.9% by mass), graphite (80.1% by mass), carbon black (3% by mass) having a 4,4 "-p-terphenyldiyl structure between the reduced graphene oxides obtained in Synthesis Example 2. %), Carboxymethyl cellulose (5% by mass), and styrene-butadiene copolymer rubber (3% by mass) were mixed, and water was added to prepare a slurry.
  • the slurry was prepared from a negative electrode current collector made of copper foil (thickness 15 ⁇ m). It was applied on one side and dried to obtain a negative electrode.
  • Ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed at a volume ratio of 30/70 (EC / DEC), and LiPF 6 was dissolved therein so as to have a volume ratio of 1 mol / L to prepare an electrolytic solution.
  • ⁇ Preparation of test cell> The negative electrode and the Li foil produced by the above method were formed into a predetermined shape, sandwiched between porous film separators and laminated, and tabs were welded to each to obtain a power generation element.
  • This power generation element was wrapped in an exterior body made of an aluminum laminated film, and after heat-sealing the three end edges, an electrolytic solution was injected and impregnated with an appropriate degree of vacuum. Then, the remaining one end edge was sealed by heat fusion under reduced pressure to obtain a test cell.
  • Example 1 From the comparison between Example 1 and Comparative Example 1, a cell using a carbon material having a 4,4 "-p-terphenyldiyl structure between reduced graphene oxides was improved in the initial discharge capacity and charge / discharge efficiency. It turned out that there was.
  • the lithium ion secondary battery using the carbon material according to the embodiment of the present invention has a high capacity and the initial charge / discharge efficiency is improved, for example, all industrial fields requiring a power source and electricity. It can be used in the industrial field related to the transportation, storage and supply of energy. Specifically, it can be used as a power source for mobile devices such as mobile phones, laptop computers, tablet terminals, and portable game machines. It can also be used as a power source for moving / transporting media such as electric vehicles, hybrid cars, electric bikes, electrically assisted bicycles, transport carts, robots, and drones (small unmanned aerial vehicles). Further, it can be used for a household power storage system, a backup power source such as UPS, a power storage facility for storing power generated by solar power generation, wind power generation, or the like.
  • UPS backup power source

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Abstract

La présente invention concerne un matériau carboné qui améliore l'efficacité de charge/décharge initiale d'une batterie. Un matériau carboné selon la présente invention comprend deux couches d'oxyde de graphène réduit ou plus, tout en contenant un groupe arylène entre les couches d'oxyde de graphène réduit.
PCT/JP2020/019292 2019-05-17 2020-05-14 Matériau carboné et batterie secondaire au lithium-ion l'utilisant WO2020235447A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170063113A (ko) * 2015-11-30 2017-06-08 한국과학기술원 3차원 다공성 그래핀의 제조방법
KR20170090069A (ko) * 2016-01-28 2017-08-07 성균관대학교산학협력단 층 간격이 조절된 그래핀-실리콘 복합체 및 이의 제조 방법

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170063113A (ko) * 2015-11-30 2017-06-08 한국과학기술원 3차원 다공성 그래핀의 제조방법
KR20170090069A (ko) * 2016-01-28 2017-08-07 성균관대학교산학협력단 층 간격이 조절된 그래핀-실리콘 복합체 및 이의 제조 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KEUNSIK LEE, YEOHEUNG YOON, YUNHEE CHO, SAE MI LEE, YONGHUN SHIN, HANLEEM LEE, HYOYOUNG LEE: "Tunable Sub-nanopores of Graphene Flake Interlayers with Conductive Molecular Linkers for Supercapacitors", ACS NANO, vol. 10, 2016, pages 6799 - 6807, XP055762839 *

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