WO2017119428A1 - Élément de carbone pour électrode négative de pile rechargeable, substance active pour électrode négative de pile rechargeable, électrode négative de pile rechargeable et pile rechargeable - Google Patents

Élément de carbone pour électrode négative de pile rechargeable, substance active pour électrode négative de pile rechargeable, électrode négative de pile rechargeable et pile rechargeable Download PDF

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WO2017119428A1
WO2017119428A1 PCT/JP2017/000091 JP2017000091W WO2017119428A1 WO 2017119428 A1 WO2017119428 A1 WO 2017119428A1 JP 2017000091 W JP2017000091 W JP 2017000091W WO 2017119428 A1 WO2017119428 A1 WO 2017119428A1
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Prior art keywords
negative electrode
secondary battery
battery negative
secondary cell
carbon
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PCT/JP2017/000091
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English (en)
Japanese (ja)
Inventor
峻 園田
達也 永井
哲哉 伊藤
裕輝 名古
横田　博
渡邉　毅
佐々木　龍朗
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デンカ株式会社
住友ベークライト株式会社
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Publication of WO2017119428A1 publication Critical patent/WO2017119428A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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 a carbon material for a secondary battery negative electrode, an active material for a secondary battery negative electrode, a secondary battery negative electrode, and a secondary battery.
  • secondary batteries In recent years, the use of secondary batteries has been studied in various technical fields ranging from small electrical products such as mobile phones to large machine products such as automobiles.
  • various types such as a non-aqueous electrolyte secondary battery using an organic electrolyte as an electrolyte and a solid battery using a solid electrolyte have been studied.
  • charging and discharging are repeated as a chemical species such as lithium ion serving as a charge carrier moves between the positive electrode active material layer and the negative electrode active material layer.
  • the negative electrode has an electrode active material layer, and a carbon material is widely used as an electrode active material constituting the electrode active material layer.
  • the electrode active material layer allows the secondary battery to be charged and discharged by occluding chemical species between layers of the carbon material having a layer structure and releasing the chemical species stored from the interlayer.
  • Patent Document 1 as a negative electrode active material layer in a secondary battery, carbon black satisfying a predetermined condition, a composite metal oxide such as LiFePO 4 , and a binder resin such as polyvinylidene fluoride are mixed. It is described that it is used.
  • the present invention has been made in view of the above problems, and provides a carbon material for a secondary battery negative electrode that can ensure battery performance with excellent cycle characteristics during charge and discharge even when the secondary battery is used in a low temperature environment. To do.
  • the present invention also provides an active material for a secondary battery negative electrode produced by including the carbon material for a secondary battery negative electrode, a secondary battery negative electrode configured using the active material for a secondary battery negative electrode, and the secondary battery negative electrode.
  • a secondary battery including a secondary battery negative electrode is provided.
  • the carbon material for secondary battery negative electrode of the present invention includes a carbonaceous material having a (002) plane average layer spacing d 002 of 0.340 nm or more obtained by X-ray diffraction using CuK ⁇ rays as a radiation source, and DBP And carbon black having an absorption amount of 240 mL / 100 g or more.
  • the active material for secondary battery negative electrode of the present invention contains the carbon material for secondary battery negative electrode described above.
  • the secondary battery negative electrode of the present invention has a secondary battery negative electrode active material layer containing the above-mentioned secondary battery negative electrode active material and the secondary battery negative electrode active material layer laminated on at least a part of the surface. And a negative electrode current collector.
  • the secondary battery of the present invention comprises the above secondary battery negative electrode, electrolyte layer, separator and positive electrode.
  • the carbon material for secondary battery negative electrodes which can make the cycling characteristics at the time of charging / discharging of a secondary battery favorable in a low temperature environment, the active material for secondary battery negative electrodes, and a secondary battery negative electrode are provided.
  • a secondary battery having good cycle characteristics during charging and discharging even in a low temperature environment is provided.
  • the present inventors have found that the conventional secondary battery negative electrode has an electrolyte supplied to the negative electrode active material at the time of charging as compared to a normal temperature environment. It was speculated that the battery characteristics could be deteriorated due to shortage. That is, in a secondary battery negative electrode used in a low temperature environment such as below freezing point, particularly -10 ° C or lower, particularly -20 ° C or lower, the viscosity of the electrolyte solution increases and the fluidity decreases, and the negative electrode is supplied to the negative electrode active material. Insufficient amount of electrolyte is produced.
  • the present inventors have come to the idea that by improving the supply of the electrolyte to the negative electrode active material, it is possible to occlude and release chemical species in a low temperature environment. More specifically, the present inventors blend carbon black having a predetermined characteristic having liquid retention properties with respect to hard carbon in which finer pores are developed than the graphite material. Thus, the present invention has been completed based on the technical idea that the above problem can be solved.
  • a secondary battery negative electrode carbon material hereinafter also referred to as a carbon material
  • a secondary battery negative electrode active material hereinafter also referred to as a negative electrode active material
  • a negative electrode hereinafter sometimes referred to as a negative electrode
  • a secondary battery will be described.
  • the carbon material of the present embodiment is a carbonaceous negative electrode material used for an alkali metal ion secondary battery such as a lithium ion battery or a sodium ion battery.
  • the carbon material of the present embodiment has an average layer surface spacing d 002 (hereinafter, sometimes referred to as an average layer surface spacing d 002 ) of (002) plane obtained by X-ray diffraction using CuK ⁇ rays as a radiation source is 0.340 nm.
  • the carbonaceous material which is the above and carbon black whose DBP absorption amount is 240 mL / 100g or more are included.
  • the carbon material contains carbon as a main material, and may further contain components other than carbon as necessary.
  • carbon is a main material” means that carbon is contained in an amount of 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more when the carbon material is 100% by mass.
  • the carbonaceous material which comprises the carbon material of this embodiment is demonstrated.
  • the d 002 of the carbonaceous material obtained by the X-ray diffraction method using CuK ⁇ rays as a radiation source is 0.340 nm or more, preferably 0.350 nm or more, and more preferably 0.365 nm or more.
  • the average layer surface distance d 002 is equal to or greater than the above lower limit value, destruction of the crystal structure due to repeated occlusion and release of alkali metal ions such as lithium can be suppressed, and charge / discharge cycle characteristics of the negative electrode can be improved.
  • the upper limit of the average layer surface distance d 002 is not particularly limited, but is 0.400 nm or less, preferably 0.395 nm or less, more preferably 0.390 nm or less.
  • a carbonaceous material having such an average layer spacing d 002 is generally called hard carbon or non-graphitizable carbon.
  • the water content may be measured by the Karl Fischer coulometric titration method as follows. Specifically, the carbonaceous material of the present embodiment is held for 120 hours under conditions of a temperature of 40 ° C. and a relative humidity of 90% RH, and then the carbonaceous material is heated for 1 hour under conditions of a temperature of 130 ° C. and a nitrogen atmosphere. Hold and pre-dry. Next, moisture generated by holding the carbonaceous material after the preliminary drying at 200 ° C. for 30 minutes is measured by the Karl Fischer coulometric titration method.
  • the amount of water generated from the carbonaceous material after the preliminary drying is preferably 0.20% by mass or less, more preferably 0.15% with respect to 100% by mass of the carbonaceous material after the preliminary drying.
  • the content is not more than mass%, particularly preferably not more than 0.10 mass%. Even when the carbonaceous material according to the present embodiment is stored in the atmosphere for a long period of time when the water content is not more than the above upper limit, deterioration of the carbonaceous material can be further suppressed.
  • the minimum of said moisture content is not specifically limited, 0.01 mass% or more is preferable.
  • the carbonaceous material according to the present embodiment preferably has a crystallite size in the c-axis direction obtained by X-ray diffraction (hereinafter sometimes referred to as Lc (002)) of 0.8 nm or more and 5 nm or less. Yes, more preferably 3 nm or less, still more preferably 2 nm or less.
  • the carbonaceous material of this embodiment preferably has a 50% cumulative particle size D 50 (hereinafter sometimes referred to as an average particle size) in a volume-based cumulative distribution of 1 ⁇ m or more and 50 ⁇ m or less, preferably 2 ⁇ m or more, More preferably, it is 30 ⁇ m or less. Thereby, a high-density negative electrode can be produced.
  • D 50 cumulative particle size
  • Lc (002) is calculated as follows. That is, it can be determined from the half width of the 002 plane peak and the diffraction angle in the spectrum obtained from the X-ray diffraction measurement using the following Scherrer equation.
  • Lc 0.94 ⁇ / ( ⁇ cos ⁇ ) (Scherrer equation) Where Lc is the size of the crystallite, ⁇ is the wavelength of the characteristic X-ray K ⁇ 1 output from the cathode, ⁇ is the half width (radian) of the peak, and ⁇ is the reflection angle of the spectrum.
  • the X-ray diffraction spectrum in the carbonaceous material can be measured by an X-ray diffractometer such as XRD-7000 manufactured by Shimadzu Corporation.
  • the measuring method of said average layer surface spacing in a carbonaceous material (hard carbon) is as follows. That is, from the spectrum calculated
  • ⁇ the wavelength of the characteristic X-ray K ⁇ 1 output from the cathode
  • ⁇ the reflection angle of the spectrum
  • the carbonaceous material of the present embodiment preferably has a specific surface area of 0.5 m 2 / g or more and 15 m 2 / g or less, preferably 1 m 2 / g or more and 8 m 2 / g or less, according to the BET three-point method in nitrogen adsorption. Is more preferable.
  • the specific surface area by the BET three-point method in nitrogen adsorption is not more than the above upper limit value, irreversible reaction between the carbonaceous material and the electrolytic solution can be suppressed.
  • the specific surface area by the BET three-point method in nitrogen adsorption is not less than the above lower limit value, appropriate permeability of the electrolytic solution to the carbonaceous material can be obtained.
  • the specific surface area of the carbonaceous material can be calculated as follows. That is, the monolayer adsorption amount Wm is calculated by the following equation (1), the total surface area Total is calculated by the following equation (2), and the specific surface area S is obtained by the following equation (3).
  • Formula (2) Total (Wm ⁇ N ⁇ Acs) M
  • N is the Avogadro number
  • M is the molecular weight
  • Acs is the adsorption cross section.
  • Formula (3) S Total / w
  • w is a sample weight (g).
  • the raw material of the carbonaceous material (hard carbon) of the present embodiment is not particularly limited, and examples thereof include a resin material such as a thermosetting resin or a thermoplastic resin.
  • the above raw materials are obtained by petroleum-based tar or pitch by-produced during ethylene production, coal tar produced during coal dry distillation, heavy components or pitch obtained by distilling off low-boiling components of coal tar, and coal liquefaction. Examples thereof include petroleum-based or coal-based materials such as tar or pitch, and those obtained by crosslinking the aforementioned petroleum-based or coal-based materials.
  • the hard carbon raw materials described above can be used alone or in combination of two or more. Also, plant materials such as coconut shells can be used as raw materials for hard carbon.
  • thermosetting resin is not particularly limited.
  • phenolic resins such as novolac type phenolic resin and resol type phenolic resin, epoxy resins such as bisphenol type epoxy resin and novolac type epoxy resin, melamine resin, urea resin, aniline resin, Examples include cyanate resin, furan resin, ketone resin, unsaturated polyester resin, and urethane resin.
  • the carbon material may be a modified product obtained by modifying these materials with various components.
  • curing agent can be used together.
  • curing agent is not specifically limited, A well-known hardening
  • novolac type phenol resin hexamethylenetetramine, resol type phenol resin, polyacetal, or paraform can be used as a curing agent.
  • epoxy resins use polyamine compounds such as aliphatic polyamines and aromatic polyamines, acid anhydrides, imidazole compounds, dicyandiamide, novolac-type phenol resins, bisphenol-type phenol resins, or resole-type phenol resins as curing agents. Can do.
  • thermoplastic resin is not particularly limited.
  • polyethylene polystyrene, polyacrylonitrile, acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin, polypropylene, vinyl chloride, methacrylic resin, polyethylene terephthalate, polyamide
  • AS acrylonitrile-styrene
  • ABS acrylonitrile-butadiene-styrene
  • polypropylene vinyl chloride
  • methacrylic resin polyethylene terephthalate
  • polyamide examples include polycarbonate, polyacetal, polyphenylene ether, polybutylene terephthalate, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyetherimide, polyamideimide, polyimide, and polyphthalamide.
  • the composition or a cured product of the composition may be carbonized.
  • the temperature is raised from room temperature to 1 ° C./hour or more and 200 ° C./hour or less, 800 ° C. or more and 1500 ° C. or less, 0.01 Pa or more and 101 kPa (1 atm) or less, and 0.1 hour. This can be carried out for 50 hours or less, preferably 0.5 hours or more and 10 hours or less.
  • the carbonaceous material of the present embodiment under an inert atmosphere such as nitrogen or helium gas, under a substantially inert atmosphere where a trace amount of oxygen is present in the inert gas, or under a reducing gas atmosphere It is preferable to perform carbonization treatment. By doing in this way, thermal decomposition (oxidative decomposition) of the resin material which is a raw material of a carbonaceous material can be suppressed, and a desired negative electrode material can be obtained.
  • an inert atmosphere such as nitrogen or helium gas
  • a substantially inert atmosphere where a trace amount of oxygen is present in the inert gas or under a reducing gas atmosphere
  • carbonization treatment By doing in this way, thermal decomposition (oxidative decomposition) of the resin material which is a raw material of a carbonaceous material can be suppressed, and a desired negative electrode material can be obtained.
  • a pre-carbonization treatment may be performed before the carbonization treatment.
  • the pre-carbonization treatment for example, it can be performed at 200 ° C. or more and 1000 ° C. or less for 1 hour or more and 10 hours or less.
  • the resin composition Before the pre-carbonization treatment, the resin composition may be cured.
  • a hardening processing method For example, it can carry out by the method of giving the heat quantity which can perform hardening reaction to a resin composition, the method of thermosetting, the method of using a thermosetting resin and a hardening
  • a metal, a pigment, a lubricant, an antistatic agent, an antioxidant, or the like may be added to the resin composition to impart desired characteristics to the negative electrode material.
  • the carbon black which comprises the carbon material of this embodiment with said carbonaceous material (hard carbon) is demonstrated.
  • the carbon black of the present embodiment is considered to play a role of holding an electrolytic solution as well as lowering electric resistance as a conductive auxiliary.
  • the carbon black CB has a three-dimensional network structure, and it is considered that the electrolyte ES is taken in and retained therein.
  • the carbon material CM is composed of a carbonaceous material HC and carbon black CB.
  • the carbon black CB is dispersed and compounded around the carbonaceous material HC, so that an electrolyte such as lithium ion (Li + ) existing around the carbon black CB is contained in the secondary battery.
  • an electrolyte such as lithium ion (Li + ) existing around the carbon black CB is contained in the secondary battery.
  • the carbonaceous material HC takes in the carbon black CB having a large liquid retention amount. For this reason, it is considered that the decrease of the electrolyte concentration on the surface of the carbonaceous material HC during charging is suppressed even at a low temperature.
  • the DBP absorption amount of the carbon black of this embodiment is 240 mL / 100 g or more, preferably 300 mL / 100 g or more.
  • the DBP absorption amount of carbon black can be obtained by measuring the oil absorption amount under the conditions relating to the uncompressed sample according to JIS K 6217-4.
  • the carbon black sample is measured as 20 g. It has been clarified by the present inventors that the carbon black has a DBP absorption amount equal to or higher than the above lower limit value, so that stable conductive performance is imparted to the carbonaceous material.
  • the average particle diameter of the primary particles of carbon black is preferably 25 nm or less, and more preferably 20 nm or less.
  • the average particle diameter of the primary particles of carbon black is measured using an image photographed with a transmission electron microscope (TEM) at a magnification of, for example, 10,000 times, and a large number (for example, 100) of primary particles are measured. It can be determined as an average value of the particle diameter.
  • TEM transmission electron microscope
  • the average particle diameter of the primary particle of carbon black is preferably 2.5% or less, and more preferably 1% or less, of the particle diameter D 50 (average particle diameter) of the carbonaceous material described above.
  • the carbon black CB By setting the carbon black CB to a value not more than the upper limit, the carbon black CB having a sufficiently small diameter forms a fine network structure with respect to the carbonaceous material HC and takes in the electrolyte ES well. It is thought that it disperses and adheres to the surface (see FIG. 1).
  • the bulk density of carbon black is preferably 0.04 or less, and more preferably 0.03 g / cm 3 or less.
  • the bulk density of carbon black can be measured according to JIS K 6219.
  • the volatile content of carbon black is preferably 0.20% or less.
  • the ratio of volatile components of carbon black can be measured according to JIS K 6221.
  • the carbon black of this embodiment is exemplified by thermal black, furnace black, lamp black, channel black, acetylene black, and the like.
  • a method for producing carbon black can be produced by incompletely burning acetylene gas and oxygen gas. If necessary, other gases may be added to cause incomplete combustion.
  • the mixing ratio of the carbonaceous material and carbon black in the carbon material of the present embodiment is not particularly limited, but the mass of the carbonaceous material is 100 and the mass of the carbon black is 0.1 or more, preferably 1 or more. The same mass can be 5 or less, preferably 3 or less. By setting it as the said range, the low temperature cycling characteristic in a secondary battery becomes favorable so that it may mention later.
  • the carbonaceous material (hard carbon) may be preliminarily fired and pulverized and then mixed with carbon black.
  • a kneading apparatus such as a kneading roll, a rotating / revolving mixer, a uniaxial or biaxial kneader can be used.
  • the negative electrode active material of the present invention including the carbon material of the present invention
  • the secondary battery negative electrode of the present invention including the negative electrode active material layer including the negative electrode active material
  • the present invention including the secondary battery negative electrode.
  • the secondary battery will be described.
  • the secondary battery negative electrode active material of this embodiment contains the carbon material (carbon material) for the secondary battery negative electrode described above. By containing the carbon material described above, the negative electrode active material of the present embodiment exhibits excellent cycle characteristics under the low temperature environment of the negative electrode.
  • the negative electrode active material refers to a material capable of occluding and releasing chemical species that serve as charge carriers in the secondary battery negative electrode. Examples of the chemical species include lithium ions or sodium ions in an alkali metal ion secondary battery.
  • the negative electrode active material may be substantially composed of only the carbon material of the present embodiment, but may further include a material different from the carbon material. Examples of such materials include materials generally known as negative electrode materials such as silicon, silicon monoxide, and other graphite materials.
  • the secondary battery negative electrode of the present embodiment has at least the surface of the secondary battery negative electrode active material layer including the secondary battery negative electrode active material of the present embodiment described above and the secondary battery negative electrode active material layer. And a negative electrode current collector disposed in the portion.
  • the secondary battery of the present embodiment includes the above-described secondary battery negative electrode, an electrolyte layer, and a secondary battery positive electrode.
  • the secondary battery including the negative electrode of the present embodiment reflects the above effect of the negative electrode active material, and exhibits excellent cycle characteristics even in a low temperature environment.
  • the secondary battery examples include, but are not limited to, an alkali metal secondary battery such as a lithium ion secondary battery or a sodium ion secondary battery.
  • the secondary battery includes various types using different electrolytes such as a non-aqueous electrolyte secondary battery and a solid secondary battery.
  • a lithium ion secondary battery will be described as an example of a secondary battery.
  • FIG. 2 is a schematic diagram showing an example of a lithium ion secondary battery 100 including the carbon material of the present embodiment.
  • the lithium ion secondary battery 100 includes a negative electrode 10, a positive electrode 20, a separator 30, and an electrolyte solution layer 40.
  • the negative electrode 10 includes a negative electrode active material layer 12 and a negative electrode current collector 14 as shown in FIG.
  • the negative electrode active material layer 12 is laminated and disposed on at least part of the surface of the negative electrode current collector 14.
  • the negative electrode active material layer 12 contains the carbon material described above.
  • the negative electrode current collector 14 is not particularly limited, and a current collector that can be used for the negative electrode can be appropriately selected and used. For example, a copper foil or a nickel foil can be used.
  • the negative electrode 10 can be manufactured as follows, for example. A known organic polymer binder and an appropriate amount of a viscosity adjusting solvent or water are added to the negative electrode active material and kneaded to prepare a negative electrode slurry. The obtained slurry can be formed into a sheet shape, a pellet shape, or the like by compression molding, roll molding, or the like, and the negative electrode active material layer 12 can be obtained. The negative electrode 10 can be obtained by laminating the negative electrode active material layer 12 and the negative electrode current collector 14 thus obtained. Moreover, the negative electrode 10 can also be manufactured by apply
  • the electrolyte layer 40 fills between the positive electrode 20 and the negative electrode 10, and is a layer in which lithium ions move by charge / discharge.
  • the electrolyte solution layer 40 can be configured by filling a known electrolyte.
  • a known electrolyte for example, a nonaqueous electrolytic solution in which a lithium salt serving as an electrolyte is dissolved in a nonaqueous solvent is used.
  • a known substance can be used.
  • a lithium metal salt such as LiClO 4 or LiPF 6 can be used.
  • the electrolyte layer 40 has an aspect having a gel polymer electrolyte containing a polymer material such as polyethylene oxide or polyacrylonitrile, or zirconia.
  • a polymer material such as polyethylene oxide or polyacrylonitrile, or zirconia.
  • the aspect which has a solid electrolyte is mentioned.
  • the separator 30 is not particularly limited, and can be a member that is permeable to chemical species such as lithium ions, and a known separator can be used.
  • a porous film, a nonwoven fabric, or the like configured using polyethylene or polypropylene is used. Can be mentioned.
  • the positive electrode 20 includes a positive electrode active material layer 22 and a positive electrode current collector 24.
  • the positive electrode active material layer 22 can be formed of a known positive electrode active material.
  • the positive electrode active material include lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), lithium manganese oxide (LiMn 2 O 4 ), and ternary Li (Ni 1/3 Mn 1/3).
  • a composite oxide such as Co 1/3 ) O 2 ; a conductive polymer such as polyaniline and polypyrrole; and the like can be used.
  • the positive electrode active material contains an organic polymer binder and a conductive material in the same manner as the negative electrode active material described above.
  • the blending amounts of the organic polymer binder and the conductive material in the positive electrode active material are not particularly limited, and may be the same as the negative electrode active material or may be blended in an amount different from the negative electrode active material.
  • a known positive electrode current collector can be used.
  • an aluminum foil, a stainless steel foil, a titanium foil, a nickel foil, a copper foil, or the like can be used.
  • the carbon material of the present embodiment can also be used for a secondary battery using alkali ions other than lithium ions as chemical species, such as sodium ions.
  • the carbonaceous material of the present embodiment is preferable in the first cycle of the charge / discharge cycle when the secondary battery produced under the conditions described below is charged / discharged at the low temperature cycle characteristics evaluation described below. Is 30 mAh / g or more, more preferably 35 mAh / g or more. In the present specification, “mAh / g” indicates a capacity per 1 g of the positive electrode active material.
  • the discharge capacity at the 50th cycle of the charge / discharge cycle is preferably 24 mAh / g or more, more preferably 28 mAh / g or more, and further preferably 32 mAh.
  • the maintenance rate of the discharge capacity at the 50th cycle relative to the discharge capacity at the 1st cycle of the charge / discharge cycle is preferably 80% or more, more preferably 83% or more, and still more preferably 90% or more.
  • thermosetting resin 510 g was allowed to stand in a heat treatment furnace. Thereafter, without reducing gas replacement, inert gas replacement, reducing gas flow, and inert gas flow, the temperature was raised from room temperature to 500 ° C. at 100 ° C./hour.
  • B Next, reducing gas replacement, inert gas replacement, reducing gas flow, and inert gas flow were not performed, and after degreasing at 500 ° C. for 2 hours, cooling was performed.
  • C The obtained powder was finely pulverized with a vibration ball mill.
  • D Thereafter, 204 g of the obtained powder was allowed to stand in a heat treatment furnace. Subsequently, the temperature was raised from room temperature to 1200 ° C.
  • Example 1 Acetylene gas is mixed at 12 m 3 / hour, oxygen gas is 9 m 3 / hour, and hydrogen gas is mixed at 0.5 m 3 / hour.
  • the carbon black concerning sample 1 was manufactured by spraying from the installed nozzle and utilizing thermal decomposition and combustion reaction of acetylene.
  • the average particle size of the primary particles of the carbon black of Sample 1 is increased by 150% using a transmission electron microscope (TEM) without changing the aspect ratio of the 10000 times photograph, and becomes the maximum at the diameter of 100 particles. The value was measured and the average value was obtained.
  • TEM transmission electron microscope
  • the average particle diameter of primary particles of the carbon black of Sample 1 was 18 nm.
  • the volatile content measured according to JIS K 6217-4 was 0.18%.
  • Example 2 After carbon black according to Sample 1 is used as a raw material, water is contained for 0.5 hour in a constant temperature and humidity device under conditions of a temperature of 25 ° C. and a humidity of 80%, and then placed in an electric furnace heated to 750 ° C. While maintaining the pressure in the furnace at 0.1 kPa, air was introduced at 25 L / hour and oxidation treatment was performed for 1 hour to obtain carbon black according to sample 2.
  • the average particle size of the carbon black primary particles of Sample 2 was 18 nm, the specific surface area was 863 m 2 / g, and the volatile content was 1.10%.
  • Example 3 As the carbon black of Sample 3, Denka Black FS-35, which is acetylene black manufactured by Denka Corporation (Electrochemical Industry Co., Ltd.), was used.
  • the carbon black of Sample 3 was a press product obtained by pressing the following powder product, and the average particle size of the primary particles was 23 nm and the specific surface area was 133 m 2 / g.
  • Example 4 As the carbon black of Sample 4, Denka Black AB, which is acetylene black manufactured by Denka Corporation (Electrochemical Industry Co., Ltd.), was used.
  • the carbon black of Comparative Example 1 was a powdery product as produced in the cracking furnace, and the primary particles had an average particle size of 35 nm and a specific surface area of 68 m 2 / g.
  • the negative electrode mixture (sample 1 to sample 5) was applied to one side of a 14 ⁇ m thick copper foil (Furukawa Electric Co., Ltd., NC-WS), and then pre-dried in air at 60 ° C. for 2 hours. Next, it was vacuum-dried at 120 ° C. for 15 hours. After vacuum drying, the electrode was pressure-formed by a roll press. This was cut into a disk shape having a diameter of 13 mm to produce a negative electrode. The thickness of the negative electrode material layer was 50 ⁇ m.
  • Li (Ni 1/3 Mn 1/3 Co 1/3 ) O 2 as an active material and applied on a current collector
  • a sheet formed into a disk shape having a diameter of 12 mm was used.
  • a polyolefin porous film manufactured by Celgard, trade name: Celgard 2400
  • the full cell type lithium ion secondary batteries prepared from the negative electrode mixture (sample 1) using the negative electrode mixture (sample 3) are referred to as the full cell secondary batteries of Examples 1 to 3, respectively, and the negative electrode mixture (sample 4).
  • a negative electrode mixture (sample 5) are referred to as full cell secondary batteries of Comparative Example 1 and Comparative Example 2, respectively.
  • each lithium ion secondary battery is charged to 4.2 V with a constant current of 0.2 C in a temperature environment of 25 ° C., and then the current value is attenuated to 0.02 C with a constant voltage of 4.2 V.
  • the battery was charged and rested for 5 minutes.
  • the battery was discharged at a constant current of 0.2 C to 2.5 V and rested for 5 minutes.
  • Such charging / discharging was performed 5 cycles.
  • “1C” means a current density at which discharge is completed in one hour.
  • the following charge / discharge cycles were performed at least 50 cycles.
  • each full cell type lithium ion secondary battery is charged to 4.2 V at a constant current of 1 C in a temperature environment of minus 20 ° C., and then charged at a constant voltage until the current reaches 0.1 C. 5 Then, the battery was discharged at a constant current of 1 C to 2.5 V and then rested for 5 minutes.
  • the maintenance rate (%) of the discharge capacity at the 50th cycle relative to the discharge capacity at the first cycle of the charge / discharge cycle was calculated as a low temperature life characteristic.
  • Table 1 shows the full-cell lithium ion secondary batteries according to Examples 1 to 3 and Comparative Examples 1 and 2 in the first cycle, the tenth cycle, and the 50th cycle of the charge / discharge cycle of the pretreatment in the low-temperature environment test. The discharge capacity is shown.
  • Table 1 in addition to the discharge capacity [mAh / g] at each cycle, the ratio [%] of the discharge capacity at the 10th cycle and the 50th cycle when the discharge capacity at the first cycle is taken as 100% is also shown. it's shown.
  • Example 1 a surprising result was obtained in which the discharge capacities at the first, tenth and fifty cycles were substantially equal to each other.
  • Comparative Examples 1 and 2 a significant decrease in the discharge capacity was confirmed from the 1st cycle to the 10th cycle and from the 10th cycle to the 50th cycle. From the above results, according to the carbon material, the negative electrode active material, the secondary battery negative electrode, and the secondary battery according to Examples 1 to 3 of the present invention, the cycle characteristics during charging and discharging are well maintained even in a severe low temperature environment. I found it possible.
  • the carbonaceous material is 1 ⁇ m or more particle diameter D 50 at 50% accumulation in a cumulative distribution on a volume basis, the secondary battery negative electrode carbon material of the above (1) is 50 ⁇ m or less.
  • a carbon material for a secondary battery negative electrode used for a secondary battery negative electrode wherein the low-temperature life characteristic shown in the following low-temperature cycle characteristic evaluation is 80% or more, and any one of (1) to (4) Carbon material for secondary battery negative electrode;
  • the low temperature cycle characteristic evaluation is A secondary battery negative electrode containing the carbon material for a secondary battery negative electrode, a positive electrode using Li (Ni 1/3 Mn 1/3 Co 1/3 ) O 2 as an active material, and an electrolyte solution containing a dissolved electrolyte, A lithium ion secondary battery comprising a separator, After charging to 4.2V with a constant current of 1C in a temperature environment of minus 20 ° C, the battery is charged for a constant voltage until the current reaches 0.1C, and rests for 5 minutes, and then 2.5V with a constant current of 1C.
  • a charge / discharge cycle in which discharge is performed and paused for 5 minutes is repeated, and a maintenance ratio of the discharge capacity at the 50th cycle to the discharge capacity at the first cycle of the charge / discharge cycle is calculated as the low-temperature life characteristic.
  • a secondary battery comprising the secondary battery negative electrode, electrolyte layer, separator and positive electrode of (7) above.

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Abstract

La présente invention porte sur, entre autres, un élément de carbone pour électrode négative de pile rechargeable qui peut assurer une performance de pile qui est excellente en termes de caractéristiques de cycle durant la charge et la décharge, même lorsque la pile rechargeable est utilisée dans des environnements à basse température. Ledit élément de carbone pour électrode négative de pile rechargeable (élément carbone CM) contient une matière carbonée HC dont l'intervalle de surface de couche moyen d002 du plan (002) déterminé par diffraction de rayons X impliquant l'utilisation de rayons CuKα comme source de rayonnement est d'au moins 0,340 nm, et du noir de carbone CB pour lequel l'absorption DBP est d'au moins 240 mL/100 g. D'autre part, ladite substance active pour électrode négative de pile rechargeable contient l'élément de carbone pour une électrode négative de pile rechargeable, et ladite électrode négative de pile rechargeable présente un collecteur pour électrode négative et une couche de substance active pour électrode négative de pile rechargeable contenant la substance active pour une électrode négative de pile rechargeable. Ladite pile rechargeable est pourvue de l'électrode négative de pile rechargeable, d'une couche de solution électrolytique, d'un séparateur et d'une électrode positive.
PCT/JP2017/000091 2016-01-06 2017-01-05 Élément de carbone pour électrode négative de pile rechargeable, substance active pour électrode négative de pile rechargeable, électrode négative de pile rechargeable et pile rechargeable WO2017119428A1 (fr)

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CN111755741A (zh) * 2019-03-29 2020-10-09 三星电子株式会社 全固态锂二次电池、其制造方法、其使用方法、和其充电方法
US12126005B2 (en) 2019-03-29 2024-10-22 Samsung Electronics Co., Ltd. All-solid lithium secondary battery, manufacturing method thereof, method of use thereof, and charging method thereof

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JPWO2022196745A1 (fr) * 2021-03-19 2022-09-22

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JP2002313320A (ja) * 2001-04-09 2002-10-25 Asahi Kasei Corp 非水系二次電池
JP2011023342A (ja) * 2009-06-16 2011-02-03 Sumitomo Chemical Co Ltd 非水電解液二次電池用負極材料およびそれを備える非水電解液二次電池
JP2011023221A (ja) * 2009-07-16 2011-02-03 Nec Energy Devices Ltd リチウムイオン二次電池
JP2013134896A (ja) * 2011-12-26 2013-07-08 Sumitomo Bakelite Co Ltd 負極用合剤、リチウムイオン二次電池用負極、およびリチウムイオン二次電池
JP2015030777A (ja) * 2013-08-01 2015-02-16 東洋インキＳｃホールディングス株式会社 カーボンブラック分散液およびその利用
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JP2002313320A (ja) * 2001-04-09 2002-10-25 Asahi Kasei Corp 非水系二次電池
JP2011023342A (ja) * 2009-06-16 2011-02-03 Sumitomo Chemical Co Ltd 非水電解液二次電池用負極材料およびそれを備える非水電解液二次電池
JP2011023221A (ja) * 2009-07-16 2011-02-03 Nec Energy Devices Ltd リチウムイオン二次電池
JP2013134896A (ja) * 2011-12-26 2013-07-08 Sumitomo Bakelite Co Ltd 負極用合剤、リチウムイオン二次電池用負極、およびリチウムイオン二次電池
JP2015030777A (ja) * 2013-08-01 2015-02-16 東洋インキＳｃホールディングス株式会社 カーボンブラック分散液およびその利用
JP2015138695A (ja) * 2014-01-23 2015-07-30 三井化学株式会社 リチウムイオン二次電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111755741A (zh) * 2019-03-29 2020-10-09 三星电子株式会社 全固态锂二次电池、其制造方法、其使用方法、和其充电方法
US12126005B2 (en) 2019-03-29 2024-10-22 Samsung Electronics Co., Ltd. All-solid lithium secondary battery, manufacturing method thereof, method of use thereof, and charging method thereof

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