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WO2013145925A1 - Matière d'électrode négative pour batteries secondaires au ion-lithium, électrode négative pour batteries secondaires au ion-lithium, batterie secondaire au ion-lithium et procédé de production de matière d'électrode négative pour batteries secondaires au ion-lithium - Google Patents

Matière d'électrode négative pour batteries secondaires au ion-lithium, électrode négative pour batteries secondaires au ion-lithium, batterie secondaire au ion-lithium et procédé de production de matière d'électrode négative pour batteries secondaires au ion-lithium Download PDF

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WO2013145925A1
WO2013145925A1 PCT/JP2013/053791 JP2013053791W WO2013145925A1 WO 2013145925 A1 WO2013145925 A1 WO 2013145925A1 JP 2013053791 W JP2013053791 W JP 2013053791W WO 2013145925 A1 WO2013145925 A1 WO 2013145925A1
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negative electrode
formula
lithium ion
ion secondary
active material
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Japanese (ja)
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恵理奈 山内
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Hitachi Ltd
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Hitachi Ltd
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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 negative electrode material for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, a lithium ion secondary battery, and methods for producing them.
  • hybrid vehicles that use an engine and a motor together as a power source have been developed and commercialized.
  • a secondary battery capable of repeatedly charging and discharging electricity as an energy source of this hybrid vehicle is an essential technology.
  • the lithium ion battery is a battery having a high operating voltage and a high energy density that easily obtains a high output, and is increasingly important as a power source of a hybrid vehicle in the future.
  • Lithium ion secondary batteries have a problem in that the electrolyte is reduced and decomposed at the time of initial charge, whereby an organic film is formed on the carbon surface, which is the active material of the negative electrode, resulting in a decrease in capacity and an increase in internal resistance. there were.
  • the organic film derived from the additive is not chemically adsorbed to the carbon surface, there is a problem that the solubility in a solvent is low and the durability of the film is low.
  • the film resistance increases, making it difficult for lithium ions to move, making it difficult to use at high rates.
  • the coating is damaged without being able to follow the expansion and contraction of the carbon, and there is a problem that the newly formed active carbon surface reacts with the electrolyte and the capacity deterioration proceeds. .
  • Non-Patent Documents 1 and 2 an amorphous carbon layer is formed on the surface by heating natural graphite in a 1000 ° C. hydrocarbon gas to suppress reductive decomposition of the electrolytic solution.
  • Non-Patent Document 3 a mixture of a polymer and artificial graphite is sintered under vacuum at 100 ° C. for 10-12 hours to form a polymer coating layer on the active material, thereby suppressing the initial irreversible capacity. Yes.
  • surface treatment can be performed at low cost.
  • Patent Document 1 proposes a technique in which carbon fibers are treated with a silane coupling agent to suppress the rate of decrease in capacity maintenance rate after one charge / discharge.
  • Patent Document 2 proposes a technique for modifying the surface of a silicon oxide surface with a terminal hydrolyzable modified silicone.
  • Non-Patent Document 4 succeeds in significantly reducing the initial irreversible capacity by subjecting carbon to vapor phase oxidation in a 1000 ° C. argon atmosphere and then performing silane coupling treatment.
  • Amorphous carbon coating will not solve the problem by adding a compound such as vinylene carbonate to the electrolyte solution because an uncoated active part remains if the coating amount is small, and it must be used in combination with an additive. . Moreover, when there is much coating amount with an amorphous carbon, there exists a subject that interface resistance increases.
  • the electrolyte solution penetrates the coating layer and the coating layer swells, so that the electrolyte solution contains highly active carbon. Contact the outermost surface.
  • the present invention relates to a negative electrode material for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, a lithium ion secondary battery, and a lithium ion secondary battery that are compatible with lithium ion conductivity while suppressing capacity deterioration due to reductive decomposition of the electrolyte.
  • An object is to provide a manufacturing method.
  • a negative electrode material for a lithium ion secondary battery comprising a negative electrode active material and a coating formed on the surface of the negative electrode active material, wherein the coating is bound to the negative electrode active material,
  • the negative electrode active material contains carbon element and oxygen element, and the ratio (O / C ratio) of the carbon element concentration to the oxygen element concentration of the negative electrode active material determined by XPS measurement is
  • the negative electrode material for lithium ion secondary batteries which is 2.5 or more.
  • R 11 , R 12 , R 13 and R 14 are functional groups containing at least one of carbon, oxygen, nitrogen, silicon and phosphorus.
  • R 11 , R 12 , R 13 , At least one of R 14 is a linking group that binds to the negative electrode active material.
  • the bonding group is a negative electrode material for a lithium ion secondary battery that is any one or more of (Formula 2), (Formula 3), and (Formula 4).
  • R 21 is an alkyl group having 1 to 10 carbon atoms.
  • R 31 is a halogen element or an alkyl halide having 1 to 10 carbon atoms
  • R 41 , R 42 and R 43 are functional groups composed of at least one of carbon, oxygen, nitrogen, silicon and phosphorus elements.
  • R 11 , R 12 , R 13 , R 14 , R 41 , R 42 , R 43 are hydrogen group, alkyl group having 1 to 10 carbon atoms, hydroxyl group, phenyl group, polyalkylene oxide group, polysiloxane.
  • a negative electrode material for a lithium ion secondary battery which is one or more of a group, an alkyl group, a polyphosphazene group, or the bonding group.
  • the negative electrode material for a lithium ion secondary battery having an O / C ratio of 2.5 to 30.
  • the negative electrode material for a lithium ion secondary battery having an O / C ratio of 4.0 or more and 7.0 or less.
  • R 11 , R 12 , R 13 , R 14 , R 41 , R 42 , R 43 represent (Formula 5), (Formula 6), (Formula 7), (Formula 8), or A negative electrode material for a lithium ion secondary battery.
  • R 51 , R 52 and R 53 are hydrogen or an alkyl group having 1 to 18 carbon atoms, and n is 1 or more and 100 or less.
  • R 61 is: Hydrogen or an alkyl group having 1 to 18 carbon atoms, and m is from 1 to 100.
  • R 71 is hydrogen or an alkyl group having 1 to 18 carbon atoms, and m is 1
  • R 81 , R 82 , and R 83 are hydrogen or an alkyl group having 1 to 18 carbon atoms, and l is 1 or more and 100 or less.
  • the negative electrode active material is a negative electrode material for a lithium ion secondary battery, which is natural graphite.
  • the negative electrode active material is a negative electrode material for lithium ion secondary batteries that has been oxidized.
  • the coating agent is a negative electrode for a lithium ion secondary battery that is any one or more of (Formula 9), (Formula 10), (Formula 11), (Formula 12), (Formula 13), and (Formula 14). Wood.
  • the coating agent is any two or more of (Formula 9), (Formula 10), (Formula 11), (Formula 12), (Formula 13), and (Formula 14). Negative electrode material.
  • a lithium ion secondary battery having the above negative electrode for a lithium ion secondary battery having the above negative electrode for a lithium ion secondary battery.
  • R 11 , R 12 , R 13 and R 14 are functional groups containing at least one of carbon, oxygen, nitrogen, silicon and phosphorus.
  • R 11 , R 12 , R 13 , At least one of R 14 is a linking group that binds to the negative electrode active material.
  • a negative electrode material for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery that achieve both dissolution resistance and lithium ion conductivity while suppressing capacity deterioration due to reductive decomposition of the electrolytic solution Batteries and methods for manufacturing them can be provided. Problems, configurations, and effects other than those described above will be clarified by the following description of embodiments.
  • FIG. 3 is a schematic diagram of the bonding between the negative electrode active material and the coating agent.
  • FIG. 3 is a schematic diagram of the bonding between the negative electrode active material and the coating agent.
  • FIG. 1 is a diagram schematically showing the internal structure of a battery according to an embodiment of the present invention.
  • a battery 1 according to an embodiment of the present invention shown in FIG. 1 includes a positive electrode 10, a separator 11, a negative electrode 12, a battery can 13, a positive electrode current collecting tab 14, a negative electrode current collecting tab 15, an inner lid 16, an internal pressure release valve 17, A gasket 18, a positive temperature coefficient (PTC) resistance element 19, a battery lid 20, and an axis 21 are included.
  • the battery lid 20 is an integrated part composed of the inner lid 16, the internal pressure release valve 17, the gasket 18, and the PTC resistance element 19.
  • a positive electrode 10, a separator 11, and a negative electrode 12 are wound around the shaft center 21.
  • the separator 11 is inserted between the positive electrode 10 and the negative electrode 12 to produce an electrode group wound around the axis 21.
  • the electrode group has various shapes such as a laminate of strip electrodes, or a positive electrode 10 and a negative electrode 12 wound in an arbitrary shape such as a flat shape.
  • the shape of the battery can 13 may be selected from shapes such as a cylindrical shape, a flat oval shape, a flat oval shape, and a square shape according to the shape of the electrode group.
  • the material of the battery can 13 is selected from materials that are corrosion resistant to non-aqueous electrolytes, such as aluminum, stainless steel, and nickel-plated steel. Further, when the battery can 13 is electrically connected to the positive electrode 10 or the negative electrode 12, the material is not deteriorated due to corrosion of the battery can 13 or alloying with lithium ions in the portion in contact with the nonaqueous electrolyte. Thus, the material of the battery container 13 is selected.
  • the electrode group is housed in the battery can 13, the negative electrode current collecting tab 15 is connected to the inner wall of the battery can 13, and the positive electrode current collecting tab 14 is connected to the bottom surface of the battery lid 20.
  • the electrolyte is injected into the battery can 13 before the battery is sealed.
  • a method for injecting the electrolyte there are a method of adding directly to the electrode group in a state where the battery cover 20 is released, or a method of adding from an injection port installed in the battery cover 20.
  • the battery lid 20 is brought into close contact with the battery can 13 and the whole battery is sealed. If there is an electrolyte inlet, seal it as well.
  • a method for sealing the battery there are known techniques such as welding and caulking.
  • the lithium ion secondary battery according to an embodiment of the present invention can be manufactured by, for example, disposing the following negative electrode and positive electrode facing each other via a separator and injecting an electrolyte.
  • the structure of the lithium ion battery according to an embodiment of the present invention is not particularly limited.
  • the positive electrode and the negative electrode and the separator separating them are wound into a wound electrode group, or the positive electrode, the negative electrode, and the separator are combined.
  • a stacked electrode group can be formed by stacking.
  • the negative electrode in the present invention is formed by applying a negative electrode mixture layer comprising a negative electrode material (with a coating material formed on the surface of a negative electrode active material) and a binder onto a copper foil as a current collector. Is done. Further, a conductive agent may be further added to the negative electrode mixture layer in order to reduce electronic resistance.
  • the negative electrode active material is coated with a silane coupling agent.
  • the silane coupling reaction is a reaction between the surface of the negative electrode active material and the silane coupling agent, the amount of binding between the negative electrode active material and the coating agent, that is, the strength of the coating is the same as the state of the negative electrode surface. It is greatly influenced.
  • a sufficient coating layer cannot be formed by a silane coupling agent on a negative electrode active material having a small amount of oxygen on the surface and a negative electrode active material having a variation in the amount of oxygen.
  • an oxygen-containing functional group such as a hydroxyl group, a carboxyl group, or a lactone group is introduced into the surface of the negative electrode active material as a pretreatment for performing a reactive organosilicon compound treatment on the surface of the negative electrode active material.
  • a reactive organosilicon compound treatment By performing the oxidation treatment, the reaction between the hydrolyzable group of the reactive organosilicon compound and the surface of the active material was promoted, and the coating amount could be increased.
  • the negative electrode material that has been subjected to such an oxidation treatment and covered a part or all of the surface of the negative electrode active material can be expressed as follows, for example.
  • R 11 , R 12 , R 13 and R 14 are functional groups containing at least one of carbon, oxygen, nitrogen, silicon and phosphorus. At least one of R 11 , R 12 , R 13 , and R 14 is a linking group that binds to the negative electrode active material.
  • the coating agent represented by (Formula 1) has a bonding group capable of bonding with oxygen on the surface of the negative electrode active material.
  • the coating agent and the negative electrode active material are bonded by a coupling reaction. Since the coating agent is bonded to the negative electrode active material and the active material through a covalent bond, the coating has high solvent resistance. Since the silane coupling reaction is a reaction between oxygen on the surface of the negative electrode active material and the binding group of the coating agent, the amount of binding between the negative electrode active material and the coating agent, that is, the strength of the coating, is the state of the negative electrode surface. It is greatly influenced.
  • the binding group of the coating agent is a functional group that can bind to oxygen on the negative electrode.
  • (Expression 2), (Expression 3), (Expression 4), and the like can be used, but the present invention is not limited thereto.
  • R 21 is an alkyl group having 1 to 10 carbon atoms.
  • the number of carbon atoms is preferably as small as possible, and the number of carbon atoms is most preferably 1 or 2.
  • R 31 is a halogen element or an alkyl halide having 1 to 10 carbon atoms.
  • the number of carbon atoms is preferably as small as possible, and the number of carbon atoms is most preferably 1 or 2.
  • R 41 , R 42 , and R 43 are functional groups composed of at least one of carbon, oxygen, nitrogen, silicon, and phosphorus elements.
  • the structure of —NH—Si is important for bonding with oxygen on the surface of the negative electrode active material, and R 41 , R 42 , and R 43 are not particularly limited. From the viewpoint of lithium ion conductivity, a polyalkylene oxide group, a polysiloxane group, a polyphosphazene group, and the like are preferable.
  • R 41 , R 42 and R 43 are carbon chains
  • the number of carbon atoms is preferably large.
  • the carbon chain preferably has 1 to 18 carbon atoms, more preferably 6 to 18 carbon atoms.
  • the graphite surface can be coated with a small amount of the silane coupling agent, so that the contact between the electrolytic solution and the carbon surface can be effectively prevented.
  • the number of carbon atoms is 18 or more
  • graphite coated with a silane coupling agent tends to aggregate, and when an electrode is produced using the aggregated graphite, there is an adverse effect of damaging the copper foil when the electrode is pressed. Occur.
  • the oxygen present on the negative electrode active material is an oxygen-containing functional group such as a hydroxyl group, a carboxyl group, or a lactone group.
  • oxygen-containing functional groups are randomly present on the surface of the negative electrode active material such as carbon.
  • the amount of the oxygen-containing functional group varies greatly depending on the negative electrode active material species or the production area. For this reason, in order to form a sufficient coating layer on the surface of the negative electrode active material, it is considered that a sufficient amount of oxygen-containing functional groups is required on the surface of the negative electrode active material.
  • the method for introducing a sufficient amount of oxygen-containing functional groups onto the carbon surface includes oxidation treatment.
  • the oxidation treatment step is not particularly limited, but gas phase oxidation is performed by heating in an oxygen atmosphere, oxidation in the presence of a catalyst such as hydrogen peroxide, hydrochloric acid, sulfuric acid, nitric acid, permanganic acid, perchloric acid, or those Liquid phase oxidation that oxidizes in a solution obtained by adding a salt to the acid, and chemically bond one or more oxygen-containing functional groups such as hydroxyl group, carboxyl group, lactone group and the like with a carbon material in one molecule.
  • a catalyst such as hydrogen peroxide, hydrochloric acid, sulfuric acid, nitric acid, permanganic acid, perchloric acid, or those Liquid phase oxidation that oxidizes in a solution obtained by adding a salt to the acid, and chemically bond one or more oxygen-containing functional groups such as hydroxyl group, carb
  • a method of applying a carbon surface coating with a treating agent having a molecular structure to be obtained is applicable.
  • liquid phase oxidation is the most preferred embodiment.
  • the oxygen-containing functional group on the negative electrode active material can be measured by XPS measurement (X-ray Photoelectron Spectroscopy).
  • a sufficient amount of oxygen-containing functional group has a value of 2.5 or more in the ratio of the carbon element concentration to the oxygen element concentration (hereinafter referred to as O / C ratio) of the negative electrode active material determined by XPS measurement. It is.
  • the value is preferably 2.5 or more and 30 or less, and more preferably 4.0 or more and 7.0 or less.
  • the value of the O / C ratio is 2.5 or less, the number of bonding groups is small, and a sufficient bonding amount cannot be ensured between the negative electrode active material and the coating agent.
  • the O / C ratio when the O / C ratio is 30 or more, the amount of oxidation on the surface of the negative electrode active material is large, which may affect the structure of the negative electrode active material.
  • the O / C ratio value is preferably 4.0 or more and 7.0 or less from the balance between securing the bonding amount between the negative electrode active material and the coating agent and the structural collapse of the negative electrode active material.
  • the O / C ratio can be calculated by measuring the O1s peak and C1s peak intensity ratio (hereinafter referred to as O / C ratio) by XPS measurement and using the integrated value of the peak.
  • the state in which the negative electrode active material having an O / C ratio of 2.5 or more is coated with a coating agent is detected by measuring the carbon (aromatic ring) -oxygen-silicon bond on the negative electrode active material by XPS measurement. be able to.
  • a carbon (aromatic ring) -oxygen-silicon bond is formed by combining the carbon element of the negative electrode active material and the coating agent.
  • a peak corresponding to a carbon (aromatic ring) -oxygen-silicon bond is 531 Appears around .6 eV.
  • the ratio of the peak area of carbon (aromatic ring) -oxygen-silicon bond in the integrated value of the peak areas of 528 eV to 536 eV in the oxygen 1s orbital is a value of 1 or more and 90 or less. Further, when the amount of bonding is large and this is a preferable state, this value is 10 or more and 75 or less.
  • the material used as the negative electrode active material includes natural graphite, a composite carbonaceous material in which a film formed by a dry CVD (Chemical Vapor Deposition) method or a wet spray method is formed on natural graphite, a resin raw material such as epoxy or phenol, or Carbonaceous materials such as artificial graphite and amorphous carbon materials produced by firing from pitch-based materials obtained from petroleum or coal, or lithium and compounds formed with lithium and inserted into the crystal gaps Oxides or nitrides of Group 4 elements such as silicon and tin that can be occluded and released can be used.
  • the carbonaceous material is a material having high conductivity, and excellent in terms of low temperature characteristics and cycle stability.
  • a material having a wide carbon network surface layer (d 002 ) is excellent in rapid charge / discharge and low temperature characteristics, and is suitable.
  • d 002 is preferably 0.390 nm or less. May be called.
  • a carbonaceous material having high conductivity such as graphite, amorphous, activated carbon or the like may be mixed to constitute the electrode.
  • a material having the characteristics shown in (1) to (3) below may be used as the graphite material.
  • the R value (I D / I G ), which is the intensity ratio, is 0.20 or more and 0.40 or less.
  • the peak half-value width ⁇ value in the range of 1300 to 1400 cm ⁇ 1 measured by Raman spectroscopy is 40 cm -1 or more 100 cm -1 or less
  • the intensity ratio X values of the peak intensity of the (110) plane in X-ray diffraction (I (110)) and (004) plane peak intensity (I (004)) (I (110) / I (004) ) is 0.10 or more and 0.45 or less
  • the amount of oxygen on the negative electrode active material can be increased by oxidation treatment. For this reason, even a negative electrode active material having a large surface variation, such as natural graphite, can be uniformly coated with a sufficient coating agent.
  • groups other than the linking group are not particularly limited.
  • the group other than the linking group include a hydrogen group, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a phenyl group, a polyalkylene oxide group, a polysiloxane group, an alkyl group, and a polyphosphazene group.
  • Examples of the polysiloxane group include (Formula 5), examples of the polyalkylene oxide group include (Formula 6) and (Formula 7), and examples of the alkyl group include (Formula 8).
  • R 51 , R 52 and R 53 are hydrogen or an alkyl group having 1 to 10 carbon atoms, and n is 1 or more and 100 or less.
  • R 61 is hydrogen or an alkyl group having 1 to 10 carbon atoms, and m is 1 or more and 100 or less.
  • R 71 is hydrogen or an alkyl group having 1 to 10 carbon atoms, and m is 1 or more and 100 or less.
  • R 81 , R 82 , and R 83 are hydrogen or an alkyl group having 1 to 10 carbon atoms, and l is 1 or more and 100 or less.
  • the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20 from the viewpoint of lithium ion conductivity.
  • n, m, and l are 1 or more and 100 or less. From the viewpoint of lithium ion conductivity, 1 to 20 is preferable.
  • oxygen-containing groups such as polyalkylene oxide groups, polysiloxane groups, and polyphosphazene groups are preferred.
  • the lithium ions move to the negative electrode active material through the coating.
  • Oxygen in the polyalkylene oxide group, polysiloxane group, and polyphosphazene group draws only lithium ions from lithium ions solvated in the electrolytic solution, and retains lithium ions in the oxygen portion.
  • Lithium ions move to the adjacent oxygen in the polyalkylene oxide group, polysiloxane group, and polyphosphazene group, and are occluded by the negative electrode active material.
  • ⁇ Whether or not an appropriate amount of processing agent has been coated can be confirmed using the integrated value of the peak intensity of XPS.
  • peaks corresponding to carbon, oxygen, and silicon which are elements constituting the silane coupling agent, are observed.
  • the peaks of carbon and oxygen are superimposed with the peaks of oxygen-containing functional groups present in a trace amount on the graphite and graphite surfaces.
  • the coating amount of the silane coupling agent can be estimated from the silicon peak intensity.
  • the peak intensity can be quantified by a peak area which is an integrated value of peaks.
  • the Si / C ratio which is the ratio of the peak area of 100 eV to 104 eV of the silicon 1s orbital and the peak area of 527.5 eV to 536.5 eV of the oxygen 1s orbital, represents the concentration of the silane coupling agent relative to graphite. % To 10% is preferable, more preferably 0.2% to 5%, and particularly preferably 0.3% to 2.5%.
  • the method of treating the active material with the treatment agent is not particularly limited, but after adding a required amount of water or a mixture of water and alcohol to hydrolyze a part or the whole of the active material powder and mixing it. And a method of filtering and drying in a heating oven.
  • the reactive organosilicon compound that is the surface treating agent used in one embodiment of the present invention may be used alone or in combination of two or more.
  • a silane or siloxane represented by the average formula C h H i Si 2 O j N k (h, i, j is a positive number, k is 0 or a positive number) and (jh) is greater than 0
  • the binder is not particularly limited as long as the material constituting the negative electrode and the current collector for the negative electrode are in close contact.
  • a homopolymer or copolymer such as vinylidene fluoride, tetrafluoroethylene, acrylonitrile, ethylene oxide, styrene- Examples thereof include butadiene rubber.
  • the conductive agent is, for example, a carbon material such as carbon black, graphite, carbon fiber, and metal carbide, and each may be used alone or in combination.
  • the positive electrode is formed by applying a positive electrode mixture layer composed of a positive electrode active material, an electronic conductive material and a binder onto an aluminum foil as a current collector. Moreover, you may add a electrically conductive agent to the positive mix layer for reduction of electronic resistance.
  • M1 is Ni or Co and M2 is Co or Ni.
  • LiMn 1/3 Ni 1/3 Co 1/3 O 2 is more preferable.
  • the additive element is effective in stabilizing the cycle characteristics.
  • LiM x PO 4 Fe or Mn, 0.01 ⁇ X ⁇ 0.4
  • LiMn 1-x M x PO 4 M: divalent cation other than Mn, 0.01 ⁇
  • LiMn 1/3 Ni 1/3 Co 1/3 O 2 has high low-temperature characteristics and high cycle stability, and is suitable as a lithium battery material for hybrid vehicles (HEV).
  • the binder may be any material as long as the material constituting the positive electrode and the current collector for the positive electrode are in close contact.
  • a homopolymer or copolymer such as vinylidene fluoride, tetrafluoroethylene, acrylonitrile, ethylene oxide, styrene- Examples thereof include butadiene rubber.
  • the conductive agent is, for example, a carbon material such as carbon black, graphite, carbon fiber, and metal carbide, and each may be used alone or in combination.
  • the separator 11 is inserted between the positive electrode 10 and the negative electrode 12 produced by the above method to prevent a short circuit between the positive electrode 10 and the negative electrode 12.
  • the separator 11 can be a polyolefin polymer sheet made of polyethylene, polypropylene, or the like, or a two-layer structure in which a polyolefin polymer and a fluorine polymer sheet typified by tetrafluoropolyethylene are welded. It is.
  • a mixture of ceramics and a binder may be formed in a thin layer on the surface of the separator 11 so that the separator 11 does not shrink when the battery temperature increases. Since these separators 11 need to allow lithium ions to permeate during charging and discharging of the battery, they can generally be used for lithium ion batteries if the pore diameter is 0.01 to 10 ⁇ m and the porosity is 20 to 90%. .
  • Electrolyte solution As a representative example of an electrolyte solution that can be used in an embodiment of the present invention, a solvent obtained by mixing ethylene carbonate with dimethyl carbonate, diethyl carbonate, or ethyl methyl carbonate, lithium hexafluorophosphate (LiPF 6 ) as an electrolyte, Alternatively, there is a solution in which lithium borofluoride (LiBF 4 ) is dissolved.
  • the present invention is not limited to the type of solvent and electrolyte, and the mixing ratio of solvents, and other electrolytes can be used.
  • non-aqueous solvents examples include propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, ⁇ -butyrolactone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxyethane, -Methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, methyl propionate, ethyl propionate, phosphate triester, trimethoxymethane, dioxolane, diethyl ether, sulfolane, 3-methyl-2-
  • non-aqueous solvents such as oxazolidinone, tetrahydrofuran, 1,2-diethoxyethane, chloroethylene carbonate, or chloropropylene carbonate.
  • Other solvents may be used as long as they do not decompose on the positive electrode 10 or the negative electrode
  • examples of the electrolyte LiPF 6, LiBF 4, LiClO 4, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, or imide salts such as lithium represented by lithium trifluoromethane sulfonimide, multi
  • lithium salts A nonaqueous electrolytic solution obtained by dissolving these salts in the above-mentioned solvent can be used as a battery electrolytic solution.
  • An electrolyte other than this may be used as long as it does not decompose on the positive electrode 10 and the negative electrode 12 included in the battery according to the present embodiment.
  • ion conductive polymers such as polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polyhexafluoropropylene, and polyethylene oxide can be used for the electrolyte.
  • polyethylene oxide polyacrylonitrile
  • polyvinylidene fluoride polymethyl methacrylate
  • polyhexafluoropropylene polyethylene oxide
  • an ionic liquid can be used.
  • EMI-BF4 1-ethyl-3-methylimidazolium tetrafluoroborate
  • LiTFSI lithium salt LiN (SO 2 CF 3 ) 2
  • LiTFSI lithium salt LiN (SO 2 CF 3 ) 2
  • triglyme and tetraglyme cyclic quaternary ammonium cation
  • N-methyl -N-propylpyrrolidinium
  • an imide-based anion bis (fluorosulfonyl) imide is exemplified
  • a combination that does not decompose at the positive electrode 10 and the negative electrode 12 is selected, and according to this embodiment.
  • a lithium ion battery according to an embodiment of the present invention can be manufactured by, for example, disposing the above-described negative electrode and positive electrode facing each other via a separator and injecting an electrolyte.
  • the structure of the lithium ion battery according to an embodiment of the present invention is not particularly limited.
  • the positive electrode and the negative electrode and the separator separating them are wound into a wound electrode group, or the positive electrode, the negative electrode, and the separator are combined.
  • a stacked electrode group can be formed by stacking.
  • ⁇ Coated negative electrode active material 100 g of natural graphite as a negative electrode active material was dispersed in 500 ml of 30% hydrogen peroxide and stirred for 10 hours. The active material washed with pure water and filtered was dried in a vacuum atmosphere at 120 ° C. for 5 hours.
  • the characteristics derived from the bond between the oxygen-containing functional group present on the carbon and the reactive silicon compound were measured by measuring the transmission infrared absorption spectrum. This can be confirmed by observing typical stretching vibration. In this example, the stretching vibration of Si—O was confirmed near 1115 cm ⁇ 1 , confirming the formation of a covalent bond.
  • LiMn 1/3 Ni 1/3 Co 1/3 O 2 is used as the positive electrode active material
  • carbon black (CB1) and graphite (GF2) are used as the electronic conductive material
  • PVDF polyvinylidene fluoride
  • a positive electrode material paste was prepared using N-methylpyrrolidone).
  • the positive electrode material paste was applied to an aluminum foil to be the positive electrode current collector 1, dried at 80 ° C., pressed with a pressure roller, and dried at 120 ° C. to form a positive electrode mixture layer on the positive electrode current collector.
  • the negative electrode material paste was applied to a copper foil serving as a negative electrode current collector, dried at 80 ° C., pressed with a pressure roller, and dried at 120 ° C. to form a negative electrode mixture layer on the negative electrode current collector.
  • a separator and a lithium reference electrode were sandwiched between the prepared electrodes, and an electrolyte was injected to prepare a three-electrode battery.
  • the battery was charged at a constant current of 0.3 C to 4.1 V, charged at a constant voltage of 4.1 V until the current value reached 20 mA, and after 30 minutes of operation stop, discharged at 0.3 C to 3.0 V.
  • the initial discharge capacity relative to the initial charge capacity is defined as the initial charge / discharge efficiency, and the results are shown in Table 1. This operation was repeated 5 times.
  • O / C ratio O1s peak and C1s peak intensity ratio
  • Si / C was calculated by XPS measurement of the negative electrode active material after coating with the coating material.
  • Si / C was calculated from the ratio of the integrated value of the peak area of 100 eV to 104 eV of the silicon 1s orbital and the integrated value of the peak area of 527.5 eV to 536.5 eV of the oxygen 1s orbital measured by XPS measurement.
  • Example 1 A battery was prepared and evaluated in the same manner as in Example 1 except that the reactive organosilicon compound represented by the following (Formula 10) was used instead of (Formula 9). The results are shown in Table 1.
  • FIG. 2 shows a schematic view of the bonding between the negative electrode active material and the coating material corresponding to Example 2.
  • Example 1 A battery was produced and evaluated in the same manner as in Example 1 except that the reactive organosilicon compound represented by the following (Formula 11) was used instead of (Formula 9). The results are shown in Table 1.
  • a negative electrode active material 100 g of natural graphite was dispersed in 500 ml of hydrogen peroxide solution 30% and stirred for 10 hours. The active material washed with pure water and filtered was dried in a vacuum atmosphere at 120 ° C. for 5 hours.
  • Example 4 a battery was prepared and evaluated in the same manner as in Example 4 except that the reactive organosilicon compound represented by (Formula 10) was used instead of (Formula 9). The results are shown in Table 1.
  • FIG. 3 shows a schematic diagram of the binding between the negative electrode active material and the coating material corresponding to Example 5.
  • a first coating layer corresponding to (Equation 12) is formed on the surface of the carbon particles
  • a second coating layer corresponding to (Equation 10) is formed on the surface of the first coating layer.
  • two types of (Formula 10) and (Formula 12) are used as the coating agent.
  • Example 4 A battery was prepared and evaluated in the same manner as in Example 4 except that the reactive organosilicon compound represented by (Formula 11) was used instead of (Formula 9). The results are shown in Table 1.
  • Example 1 a battery was fabricated and evaluated in the same manner as in Example 1 except that the oxidation treatment time was 5 hours.
  • Example 1 a battery was prepared and evaluated in the same manner as in Example 1 except that the oxidation treatment time was 20 hours.
  • Example 1 A battery was produced and evaluated in the same manner as in Example 1 except that artificial graphite was used.
  • Example 1 A battery was prepared and evaluated in the same manner as in Example 1 except that (Equation 13) was used instead of (Equation 9).
  • Example 1 a battery was prepared and evaluated in the same manner as in Example 1 except that (Expression 14) was used instead of (Expression 9).
  • Example 11 a battery was produced and evaluated in the same manner as in Example 11 except that the coating material concentration was 0.08%.
  • Example 11 a battery was produced and evaluated in the same manner as in Example 11 except that the coating material concentration was 0.5%.
  • Example 11 A battery was fabricated and evaluated in the same manner as in Example 11 except that the coating material concentration was 0.8%.
  • Example 1 In Example 1, a battery was prepared and evaluated in the same manner as in Example 1 except that an active material that was not subjected to oxidation treatment or coating treatment was used. The results are shown in Table 1.
  • Example 2 the battery was fabricated and evaluated in the same manner as in Example 1 except that the oxidation treatment time of the active material was changed to 1 hour and an active material that was not subjected to coating treatment was used. The results are shown in Table 1.
  • Example 3 the battery was fabricated and evaluated in the same manner as in Example 1 except that the oxidation treatment time of the active material was changed to 5 hours and an active material that was not subjected to coating treatment was used. The results are shown in Table 1.
  • Example 4 the battery was fabricated and evaluated in the same manner as in Example 1 except that the active material oxidation treatment time was changed to 20 hours and an active material that was not subjected to coating treatment was used. The results are shown in Table 1.
  • Example 5 In Example 1, a battery was produced and evaluated in the same manner as in Example 1 except that the oxidation treatment time was 1 hour.
  • Comparative Example 6 In Comparative Example 1, a battery was prepared and evaluated in the same manner as in Comparative Example 1 except that artificial graphite was used as the negative electrode active material.
  • Comparative Example 7 In Comparative Example 5, a battery was prepared and evaluated in the same manner as in Comparative Example 5 except that artificial graphite was used as the negative electrode active material.
  • Comparative Example 5 in which the oxidation treatment was performed for one hour, the value of the O / C ratio was not sufficient at 1.23. From this, it can be seen that in the present experimental environment, the oxidation treatment is preferably performed for 2 to 3 hours or more, and the value of the O / C ratio is preferably 2.5 or more. It is considered that the time can be shortened by an efficient oxidation treatment.
  • Examples 4 to 6 in which the treatment with the reactive organosilicon compound represented by (Formula 12) and the coating treatment with (Formula 9) to (Formula 11) are performed are the best charge / discharge The characteristics are shown.
  • pretreating with (Formula 12) to form the first coating layer the reaction site with the reactive organosilicon compound increases, and the second coating layer made of the reactive organosilicon compound increases. Seem.
  • Examples 1 to 8 and Comparative Examples 1 to 5 are comparisons when natural graphite is used as the negative electrode active material, but in comparison between Example 9 and Comparative Examples 6 to 7 using artificial graphite as the negative electrode active material. Also, the same tendency as in the case of using natural graphite as the negative electrode active material was observed.
  • Examples 12 to 14 are examples in which the concentration of the coating material was changed to 0.08, 0.5, and 0.8 wt%.
  • the capacity retention rate increased by increasing the concentration of the coating material from 0.08 wt% to 0.5 wt% (Table 1). However, the capacity retention rate at 0.8 wt% was lower than that at 0.5 wt%.
  • Examples 10, 1, and 11 are examples using coating materials represented by Formula 13, Formula 9, and Formula 14, respectively.
  • the carbon number of the carbon chain bonded to the Si element is 6, 12, and 18, respectively. It was found that the capacity retention rate increased with increasing carbon number.

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WO2015033454A1 (fr) * 2013-09-09 2015-03-12 株式会社日立製作所 Matériau d'électrode négative pour batteries rechargeables lithium-ion, électrode négative pour batteries rechargeables lithium-ion, batterie rechargeable lithium-ion, méthode de production de matériau d'électrode négative pour batteries rechargeables lithium-ion, et méthode de production d'électrode négative pour batteries rechargeables lithium-ion
JP2015144050A (ja) * 2014-01-31 2015-08-06 トヨタ自動車株式会社 非水系リチウムイオン二次電池の製造方法、及び非水系リチウムイオン二次電池
WO2015170785A3 (fr) * 2014-05-08 2015-12-30 エス・イー・アイ株式会社 Batterie secondaire au lithium
JP2016081922A (ja) * 2014-10-15 2016-05-16 株式会社半導体エネルギー研究所 電極、蓄電装置、及び電子機器、並びに電極の作製方法
JP2018521495A (ja) * 2015-10-15 2018-08-02 エルジー・ケム・リミテッド 負極活物質及びこれを含む二次電池
WO2020018731A1 (fr) * 2018-07-18 2020-01-23 Nanotek Instruments, Inc. Électrodes de batterie au lithium à chargement rapide
CN112467140A (zh) * 2020-08-14 2021-03-09 珠海中科兆盈丰新材料科技有限公司 一种高安全性石墨硅碳复合材料及其制备方法
JP2023515605A (ja) * 2020-03-13 2023-04-13 エルジー エナジー ソリューション リミテッド 負極活物質、その製造方法、及び該負極活物質を備えるリチウム二次電池
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WO2014080629A1 (fr) * 2012-11-20 2014-05-30 昭和電工株式会社 Procédé de production de matériau d'électrode négative pour les batteries au lithium-ion
JP5599527B1 (ja) * 2012-11-20 2014-10-01 昭和電工株式会社 リチウムイオン電池用負極材の製造方法
WO2015033454A1 (fr) * 2013-09-09 2015-03-12 株式会社日立製作所 Matériau d'électrode négative pour batteries rechargeables lithium-ion, électrode négative pour batteries rechargeables lithium-ion, batterie rechargeable lithium-ion, méthode de production de matériau d'électrode négative pour batteries rechargeables lithium-ion, et méthode de production d'électrode négative pour batteries rechargeables lithium-ion
JP2015144050A (ja) * 2014-01-31 2015-08-06 トヨタ自動車株式会社 非水系リチウムイオン二次電池の製造方法、及び非水系リチウムイオン二次電池
WO2015170785A3 (fr) * 2014-05-08 2015-12-30 エス・イー・アイ株式会社 Batterie secondaire au lithium
JP2020102455A (ja) * 2014-10-15 2020-07-02 株式会社半導体エネルギー研究所 リチウムイオン電池
JP2016081922A (ja) * 2014-10-15 2016-05-16 株式会社半導体エネルギー研究所 電極、蓄電装置、及び電子機器、並びに電極の作製方法
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JP7104084B2 (ja) 2014-10-15 2022-07-20 株式会社半導体エネルギー研究所 リチウムイオン電池
JP2022137157A (ja) * 2014-10-15 2022-09-21 株式会社半導体エネルギー研究所 リチウムイオン電池
JP7353431B2 (ja) 2014-10-15 2023-09-29 株式会社半導体エネルギー研究所 リチウムイオン電池
JP2018521495A (ja) * 2015-10-15 2018-08-02 エルジー・ケム・リミテッド 負極活物質及びこれを含む二次電池
WO2020018731A1 (fr) * 2018-07-18 2020-01-23 Nanotek Instruments, Inc. Électrodes de batterie au lithium à chargement rapide
US11870051B2 (en) 2018-07-18 2024-01-09 Global Graphene Group, Inc. Method of improving fast-chargeability of a lithium-ion battery
JP2023515605A (ja) * 2020-03-13 2023-04-13 エルジー エナジー ソリューション リミテッド 負極活物質、その製造方法、及び該負極活物質を備えるリチウム二次電池
JP7466677B2 (ja) 2020-03-13 2024-04-12 エルジー エナジー ソリューション リミテッド 負極活物質、その製造方法、及び該負極活物質を備えるリチウム二次電池
CN112467140A (zh) * 2020-08-14 2021-03-09 珠海中科兆盈丰新材料科技有限公司 一种高安全性石墨硅碳复合材料及其制备方法

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