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WO2012132387A1 - Matière d'électrode, son procédé de fabrication, électrode, batterie secondaire et véhicule - Google Patents

Matière d'électrode, son procédé de fabrication, électrode, batterie secondaire et véhicule Download PDF

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Publication number
WO2012132387A1
WO2012132387A1 PCT/JP2012/002074 JP2012002074W WO2012132387A1 WO 2012132387 A1 WO2012132387 A1 WO 2012132387A1 JP 2012002074 W JP2012002074 W JP 2012002074W WO 2012132387 A1 WO2012132387 A1 WO 2012132387A1
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Prior art keywords
active material
carbon
electrode
sample
negative electrode
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PCT/JP2012/002074
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English (en)
Japanese (ja)
Inventor
森口　勇
山田　博俊
幸幾 瓜田
宏隆 曽根
佑介 杉山
村瀬　仁俊
直人 安田
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Toyota Industries Corp
Nagasaki University NUC
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Toyota Industries Corp
Nagasaki University NUC
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Priority to JP2013507168A priority Critical patent/JPWO2012132387A1/ja
Publication of WO2012132387A1 publication Critical patent/WO2012132387A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/36—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 suitable electrode material for a negative electrode and a positive electrode provided with a surface-coated active material, a manufacturing method thereof, an electrode having these electrode materials, a secondary battery, and a vehicle using the same.
  • lithium (secondary) ion secondary batteries have been widely used as a power source for small electronic devices such as mobile phones and notebook computers with high energy density. Aiming for applications such as power sources for electric vehicles and storage battery systems for natural energy load leveling, it is desired to increase the output and capacity of Li-ion secondary batteries. In particular, in order to apply to a power source for electric vehicles, further increase in capacity of the Li ion secondary battery is desired.
  • the Li ion secondary battery generally includes a negative electrode made of a negative electrode material and a negative electrode current collector, a positive electrode made of a positive electrode material and a positive electrode current collector, a separator, and an electrolyte.
  • a negative electrode active material is used as the negative electrode material. Since the negative electrode active material generally has low electronic conductivity, carbon particles such as acetylene black are mixed as a conductive additive.
  • a negative electrode active material such as graphite, a conductive agent such as acetylene black, and a binder such as polytetofluoroethine (PTFE) and polyvinylidene fluoride resin (PVDF) are used as appropriate solvents.
  • the slurry is made into a slurry, and this slurry is applied to a negative electrode current collector such as a copper foil having a predetermined thickness and dried.
  • a positive electrode active material for example, a positive electrode active material, a conductive agent such as acetylene black, and a binder such as PTFE and PVDF are slurried with an appropriate solvent, and the slurry is made of an aluminum foil having a predetermined thickness. It is applied to a positive electrode current collector such as, and dried.
  • a positive electrode active material for example, a positive electrode active material, a conductive agent such as acetylene black, and a binder such as PTFE and PVDF are slurried with an appropriate solvent, and the slurry is made of an aluminum foil having a predetermined thickness. It is applied to a positive electrode current collector such as, and dried.
  • the negative electrode and the positive electrode are disposed so as to face each other in a battery can, for example.
  • An electrolyte is provided between the positive electrode and the negative electrode.
  • a separator is provided in the approximate center of the electrolyte. It uses for a separator as needed.
  • As the separator polyethylene (PE) or polypropylene (PP) formed into a microporous shape is used.
  • a predetermined electrolytic solution is used as the electrolyte.
  • the carbothermal method is a method in which carbon and positive electrode active material are mixed by ball milling and then heat-treated to generate carbon on the particle surface of the positive electrode active material.
  • carbon (C) adhere to the active material and carbonizing the electrode material as much as possible, it is easy to make electronic contact between the active materials. Thereby, it is possible to reduce the amount of conductive aid while ensuring a certain degree of conductivity.
  • Japanese Patent Application Publication No. 2010-528967 discloses a method for producing nanoparticles coated with carbon and coated with a transition metal oxide.
  • the method for producing nanoparticles includes preparing a liquid mixture containing, as a precursor, an alkoxide of one transition metal, an alcohol, and an excess amount of acetic acid with respect to the transition metal, and the prepared liquid mixture A step of diluting with water to form an aqueous solution, a step of freeze-drying the aqueous solution, and a step of thermally decomposing the lyophilized product obtained in the freeze-drying step under a vacuum or an inert atmosphere to obtain nanoparticles.
  • Nanoparticles contain transition metal elements, carbon elements, and oxygen elements in stoichiometric ratios.
  • Nanoparticles made of an oxide of a transition element selected from (Zn) and coated with amorphous carbon can be produced.
  • group 14 silicon (Si) in the Periodic Table of Elements has a theoretical charge / discharge capacity of 4200 mAh / g, and more than 10 times the graphite (theoretical capacity 372 mAh / g) currently used as a negative electrode material. However, it is expected as a large capacity negative electrode active material.
  • the Li ion secondary battery according to the conventional example has the following problems. i.
  • the active material since the active material has low electron conductivity, the amount of materials other than the active material should be reduced as much as possible in the electrode material. This is because the capacity per electrode and cell increases as the amount of materials other than the active material is reduced.
  • the Li ion diffusion length is shortened, Li ions can efficiently react with the active material in a short time, so that the refinement of the active material particles is effective in improving the charge / discharge characteristics.
  • a large amount of a binder and a conductive aid are required, and as a result, the capacity per electrode and the capacity per cell are reduced.
  • the fine particles easily aggregate, it is difficult to uniformly mix with the conductive additive, and it is difficult to secure an electron transfer path from the current collector to the active material. Therefore, in order to use the fine particle active material, a device for reducing the amount of materials other than the active material is necessary.
  • Si has a theoretical capacity about 10 times that of graphite (theoretical capacity: 370 mAh / g) used as a negative electrode material.
  • Si-based materials are highly expected as negative electrode materials for next-generation Li ion secondary batteries.
  • the Si-based material has a large volume change due to alloying / dealloying with Li.
  • the Li ion secondary battery using Si-type material as an electrode material has a problem that it does not show a stable charge / discharge cycle.
  • the present invention solves the above-described problems, and devise an electrode formation method to make it possible to manufacture a large capacity secondary battery, its manufacturing method, electrode, and lithium ion secondary battery.
  • the purpose is to provide.
  • the electrode material of the present invention comprises an active material and a carbon-based material that covers the entire surface of the active material or a part of the surface, and the carbon-based material is added to an aromatic organic solvent to which the active material is added. It is generated by performing a vibration process.
  • the method for producing an electrode material of the present invention is a carbon-based material generated from the aromatic organic solvent by subjecting the aromatic organic solvent to which the active material has been added, to the entire surface of the active material or It has the process of covering the one part surface, It is characterized by the above-mentioned.
  • the electrode of the present invention is an electrode comprising a current collector and an electrode material provided on the current collector, the electrode material comprising an active material and the entire surface of the active material or a partial surface thereof
  • the carbonaceous material is formed by subjecting the aromatic organic solvent to which the active material is added to vibration treatment.
  • the secondary battery of the present invention includes a positive electrode and a negative electrode, and an electrolyte provided between the positive electrode and the negative electrode.
  • the positive electrode or / and the negative electrode are on a current collector and the current collector.
  • the electrode material comprises an active material and an active material and a carbon-based material covering the entire surface of the active material or a part of the active material, and the carbon-based material includes the active material. It is produced by subjecting an aromatic organic solvent to which a substance is added to vibration treatment.
  • the vehicle of the present invention is equipped with the secondary battery.
  • the present invention since the entire surface or a part of the surface of the active material is covered with the carbon-based material, it is possible to provide an electrode material and an electrode having excellent conductivity and stability.
  • a secondary battery using such an electrode material and electrode can have a high capacity.
  • the vehicle carrying the said secondary battery can exhibit a high output.
  • FIG. 6 is a graph showing a Raman spectrum of a C—Si (X) Y [h] Z [W] ⁇ 600 [° C.] heat-treated sample.
  • FIG. 4 is a photograph taken by TEM of unmodified Si nanoparticles 4 and C—Si (100) 9 [h] 300 [W] samples. It is a particle size distribution figure which shows the comparative example of the average particle diameter of the sample before and behind surface coating.
  • FIG. 6 is a photograph taken by a TEM in the vicinity of a particle gap of a C—Si (100) 9 [h] 300 [W] sample.
  • FIG. 6 is a photograph taken by TEM of a C—Si (100) 9 [h] 300 [W] —H sample.
  • FIG. 4 is a photograph taken by TEM of unmodified Si nanoparticles 4 and C—Si (100) 9 [h] 300 [W] samples. It is a particle size distribution figure which shows the comparative example of the average particle diameter of the sample before and behind surface coating.
  • FIG. 6 is a photograph taken by a TEM in the vicinity of a particle gap of a C—Si (100) 9 [h] 300 [
  • FIG. 6 is a photograph taken by TEM of C—Si (100) 9 [h] 200 [W] and C—Si (100) 9 [h] 200 [W] —H samples. It is the photograph taken by TEM of the C-Si (100) 3 [h] 300 [W] sample. It is a graph which shows a X-ray photoelectron spectroscopy (XPS) analysis result. It is process drawing which shows the formation method of the negative electrode 11 as 2nd Embodiment. 3 is a configuration diagram illustrating an electrochemical measurement method for a negative electrode 11.
  • XPS X-ray photoelectron spectroscopy
  • FIG. 5 is a photograph taken by TEM of a C-LMO-LNMCO (300-12) sample. It is a graph which shows the XRD pattern of a C-LMO-LNMCO type
  • FIG. 2 is a configuration diagram illustrating an electrochemical measurement method for a positive electrode material 12.
  • FIG. It is a graph which shows the constant current charging / discharging characteristic of a LMO-LNMCO and a C-LMO-LNMCO (300-12) sample. It is a graph which shows the rate characteristic of a C-LMO-LNMCO type
  • an electrode material, a manufacturing method thereof, an electrode, and a lithium ion secondary battery according to an embodiment of the present invention will be described with reference to the drawings.
  • the inventors of the present invention by applying surface coating of Si nanoparticles with a carbon-based material with a thickness of nanometer order using ultrasonic waves, suppresses structural collapse due to volume expansion and contraction during alloying / dealloying processes. By providing conductivity, we succeeded in stabilizing the charge / discharge cycle while maintaining a high Si capacity to some extent.
  • the inventors of the present invention ultrasonically disperse an active material selected from silicon and a compound containing silicon, which is actually expected as a negative electrode material with a large capacity, in an aromatic organic solvent, and further, several ultrasonic waves are continuously generated.
  • an active material selected from silicon and a compound containing silicon which is actually expected as a negative electrode material with a large capacity, in an aromatic organic solvent, and further, several ultrasonic waves are continuously generated.
  • the entire surface of the active material or a partial surface (at least a part of the surface) of the active material was successfully coated with a carbon-based material having a thickness of several nm to several tens nm.
  • the electrode material includes an active material constituting the electrode and a carbon-based material covered on the entire surface or a part of the surface of the active material.
  • the carbon-based material is added to an aromatic organic solvent to which the active material is added. It is generated by performing the vibration process.
  • An electrode material having excellent conductivity can be provided by infiltrating (depositing) the carbon-based material into every corner of the active material crystal.
  • the active material expands and contracts with the Li ion insertion / desorption reaction.
  • By coating the active material with a carbon-based material structural collapse due to expansion and contraction of the active material can be suppressed, and a stable electrode material can be provided. Thereby, an active material is covered to every corner with a carbonaceous material, and a high capacity
  • the active material is preferably in the form of particles, and the carbon-based material is preferably formed on the surface of the particulate active material.
  • the thickness of the carbon-based material is preferably 1.0 nm or more and 50 nm or less, more preferably 2.5 nm or more and 25 nm or less, and preferably 5.0 nm or more and 10 nm or less. When the thickness of the carbon-based material is too small, there is a possibility that the influence on the improvement of the conductivity of the electrode material is reduced. When the thickness of the carbon-based material is excessive, the mass of the active material used in the electrode is relatively reduced, and the battery capacity may be reduced.
  • the carbon-based material may be further formed in the gaps between the particulate active materials. That is, the carbon-based material may be formed not only on the surface of the particulate active material but also on the gap between the active materials.
  • the carbonaceous material is amorphous, the occlusion rate of Li may be improved. Further, when the carbon-based material contains graphite, the conductivity is improved. In the Raman shift, it is preferable that the relative intensity of the peak (G band) near 1580 [cm ⁇ 1 ] with respect to the peak (D band) near 1360 [cm ⁇ 1 ] is high. Since a large amount of graphite is contained, conductivity is further increased.
  • the active material may be a negative electrode active material capable of inserting / extracting lithium ions or a positive electrode active material capable of inserting / extracting lithium ions.
  • the active material may be composed of a negative electrode active material that can occlude and release lithium ions, or a positive electrode active material that can occlude and release lithium ions.
  • the positive electrode active material may be an active material containing lithium.
  • the positive electrode active material may be made of, for example, a lithium manganese composite oxide such as a Li 2 MnO 3 active material.
  • the electrode material is formed by coating the surface of the Li 2 MnO 3 based active material a carbon-based material, and Li 2 MnO 3 based active material / carbon composite.
  • the electrode material has higher capacity and higher rate characteristics than the Li 2 MnO 3 -based active material.
  • the negative electrode active material may be an active material selected from silicon and a compound containing silicon.
  • the theoretical capacity of graphite currently used as a negative electrode material is 372 [mAh / g].
  • the theoretical capacity of the Si negative electrode active material is 4200 [mAh / g], and has a capacity 10 times or more that of graphite. For this reason, a large capacity electrode material can be provided.
  • the negative electrode active material is a lithium-containing silicon oxide
  • the lithium-containing silicon oxide is represented by a composition formula LixSiOy
  • the lithium content x and the oxygen content y are preferably 0 ⁇ x and 0 ⁇ y ⁇ 2, respectively.
  • the negative electrode active material may be Li 2 SiO 3 .
  • the electrode may include an electrode material for a negative electrode including a negative electrode active material whose entire surface or a part of the surface thereof is covered with a carbon-based material.
  • the negative electrode is preferably formed by providing an electrode material for a negative electrode on a negative electrode current collector. In this case, it greatly contributes to the stabilization of the alloy-based negative electrode active material.
  • the electrode is an electrode composed of a current collector and an electrode material provided on the current collector, and the electrode material is carbon that covers the active material and the entire surface of the active material or a part of the surface thereof. It is preferable that the carbon material is generated by subjecting the aromatic material to an aromatic organic solvent to which the active material is added.
  • the electrode may have a positive electrode material in which the entire surface or a part of the surface of the positive electrode active material containing lithium is covered with a carbon-based material.
  • the positive electrode material made of a positive electrode active material covered with a carbon-based material may be a positive electrode provided on a positive electrode current collector. In this case, it greatly contributes to the stabilization of the positive electrode active material.
  • the method for producing an electrode material includes a step of subjecting an active organic material to a surface treatment with a carbon-based material generated from the aromatic organic solvent by oscillating the aromatic organic solvent to which the active material is added. Have. When the aromatic organic solvent to which the active material is added is subjected to vibration treatment, ultrasonic waves having a predetermined frequency and a predetermined output may be irradiated for a predetermined time in the aromatic organic solvent to which the active material is added.
  • the frequency f When the frequency of the ultrasonic wave is f, the frequency f may be selected from a frequency range of 20 [kHz] ⁇ f ⁇ 800 [kHz]. For example, the frequency f may be set to 40 [kHz]. .
  • the output Z may be selected from an output range of 100 [W] ⁇ Z ⁇ 800 [W].
  • the output Z may be set to 300 [W]. .
  • a carbon-based material can be infiltrated into every corner of the crystal of the active material, providing an electrode material with excellent conductivity, and an active material associated with Li ion insertion / desorption reaction It is possible to provide a stable electrode material in which structural collapse due to expansion / contraction of the material is suppressed. Thereby, an active material is covered to every corner with a carbonaceous material, and a high capacity
  • the method for producing the electrode material may further include a step of heat-treating the surface-treated active material in which the entire surface or a part of the surface thereof is covered with the carbon-based material.
  • the temperature H is preferably selected from a heat treatment temperature range of 200 [° C.] ⁇ H ⁇ 600 [° C.].
  • the heat treatment is preferably performed in an inert atmosphere such as a halogen atmosphere such as Ar, an oxygen-free atmosphere, or a reduced oxygen atmosphere.
  • Electrode material can be provided.
  • Aromatic organic solvents have benzene halides including chloride, bromide and iodide, halogenated aromatic derivatives, vinyl groups, acetylene groups, hydroxyl groups, amino groups, nitro groups, carboxyl groups, and sulfone groups.
  • a liquid containing at least one aromatic compound selected from an aromatic derivative, a 5-membered ring aromatic compound, and a 6-membered ring aromatic compound; a solution in which the aromatic compound is dissolved may be used.
  • Organic solvent molecules can be polymerized and carbonized under local high temperature and high pressure conditions by cavitation under ultrasonic irradiation, and the surface of the active material particles can be preferentially covered with the carbon-based material.
  • dispersibility can be improved by releasing aggregation of active materials such as Si nanoparticles (C is difficult to enter the gap) under ultrasonic irradiation.
  • the carbon-based material can be made to enter the gaps between the nanoparticles as thin as possible and have conductivity, and the carbon-based material can be uniformly coated with a thickness of nanometer order. it can.
  • the secondary battery of the present invention includes a positive electrode and a negative electrode, and an electrolyte provided between the positive electrode and the negative electrode.
  • the positive electrode or / and the negative electrode are on a current collector and the current collector.
  • the electrode material comprises an active material and an active material and a carbon-based material covering the entire surface of the active material or a part of the active material, and the carbon-based material includes the active material. It may be generated by subjecting an aromatic organic solvent to which a substance has been added to vibration treatment.
  • the secondary battery of the present invention can be applied to a secondary battery such as a sodium ion secondary battery in addition to the lithium ion secondary battery described below.
  • a lithium ion secondary battery includes a positive electrode in which an electrode material made of a positive electrode active material containing lithium is provided on a positive electrode current collector, and an electrode made of a negative electrode active material in which the entire surface or a part of the surface is covered with a carbon-based material
  • the material may include a negative electrode provided on a negative electrode current collector and an electrolyte provided between the positive electrode and the negative electrode.
  • the entire surface or a part of the surface of the positive electrode active material containing lithium is covered with a carbon-based material, and an electrode material made of the positive electrode active material covered with the carbon-based material is disposed on the positive electrode current collector.
  • the positive electrode provided on the negative electrode, the negative electrode provided with the negative electrode active material on the negative electrode current collector, and the electrolyte provided between the positive electrode and the negative electrode may be provided.
  • conductivity is imparted to the positive electrode by the carbon nano-coating on the entire surface or a part of the surface of the positive electrode active material, and the positive electrode active material is stabilized. Stability can be improved. Thereby, a high capacity
  • the entire surface or a part of the surface of the positive electrode active material containing lithium is covered with a carbon-based material, and an electrode material made of the positive electrode active material covered with the carbon-based material is disposed on the positive electrode current collector.
  • conductivity is imparted to the negative electrode and the positive electrode by the carbon nano-coating on the entire surface of each of the negative electrode active material and the positive electrode active material or a part of the surface, and an alloy-based negative electrode active material
  • the positive electrode active material can be stabilized, and the stability of the charge / discharge cycle can be improved. Thereby, a high capacity
  • the electrode material may include an active material and a carbon-based material that covers the entire surface or a part of the surface of the active material.
  • the electrode material has an active material and a carbon-based material that covers the entire surface of the active material or a part of the active material, and the carbon-based material is further formed in a gap between the particulate active materials. Also good.
  • the average particle diameter of the particulate active material is preferably 3 nm or more and 500 nm or less. In X-ray photoelectron spectroscopy (XPS), a peak derived from a C ⁇ C bond may be expressed.
  • the above non-aqueous electrolyte secondary battery may be mounted on a vehicle. By driving the driving motor with the non-aqueous electrolyte secondary battery, it can be used for a long time with a large capacity and a large output.
  • the vehicle may be a vehicle that uses electric energy generated by a non-aqueous electrolyte secondary battery for all or a part of its power source.
  • the vehicle may be an electric vehicle or a hybrid vehicle.
  • Examples of non-aqueous electrolyte secondary batteries include various home electric appliances, office equipment, and industrial equipment driven by batteries, such as personal computers and portable communication devices, in addition to vehicles.
  • FIG. 1 is a diagram schematically showing the structure of the electrode material 10.
  • the electrode material 10 includes an active material 1 and a carbon-based material (hereinafter referred to as carbon-based material 2).
  • the active material 1 is a part that accumulates electricity in the battery, and is a substance that directly participates in the transfer of electrons. In general, the active material has low resistance.
  • the active material 1 constitutes a negative electrode material (electrode material for negative electrode) and a positive electrode material (electrode material for positive electrode) of the battery.
  • the negative electrode material is made of, for example, a silicon-based material.
  • the silicon-based material refers to one or more selected from Si, SiOx (0 ⁇ x ⁇ 2), and SiO 2 or a compound thereof.
  • SiO 2 is electrochemically inactive and cannot directly become the active material 1, but has a function of preventing the active material 1 from collapsing with the active material 1 together with Si and SiOx. In the examples described below, SiO 2 is present on the Si surface.
  • the surface of the active material 1 is covered with a carbon-based material 2 having a thickness of nanometer order (surface carbon coating).
  • the carbon-based material 2 is generated by, for example, subjecting the aromatic organic solvent to free radical reaction (radical reaction) by irradiating the aromatic organic solvent with a predetermined frequency and a predetermined output ultrasonic wave for a predetermined time. It is thought that.
  • the frequency range of ultrasonic waves is a frequency range that is inaudible to the human ear, for example, exceeds 20 kHz and reaches several GHz.
  • the preferable frequency range of the ultrasonic wave irradiated to the aromatic organic solvent differs depending on the Si-based active material 1, the Li 2 MnO 3 -based active material 1, the aromatic organic solvent, and the like.
  • the frequency f may be selected from a frequency range of 20 [kHz] ⁇ f ⁇ 800 [kHz].
  • the ultrasonic frequency f may be set to 40 [kHz].
  • the preferable output range of ultrasonic waves irradiated to the aromatic organic solvent varies depending on the active material 1, the aromatic organic solvent, and the like.
  • the output Z may be selected from an output range of 100 [W] ⁇ Z ⁇ 800 [W].
  • the ultrasonic output Z may be set to 200 [W] to 300 [W].
  • the range of the preferable irradiation time of the ultrasonic wave irradiated to the aromatic organic solvent varies depending on the active material 1, the aromatic organic solvent, and the like.
  • the irradiation time Y is preferably selected from an irradiation time range of 0 [h] ⁇ Y ⁇ 16 [h].
  • the ultrasonic irradiation time Y may be set to 2 [h] to 9 [h]. The reason for setting the upper limit value 16 [h] of the irradiation time Y will be described with reference to FIG.
  • the electrode material 10 when forming an electrode material for a negative electrode of a lithium (hereinafter referred to as Li) ion secondary battery, includes an active material selected from silicon and a compound containing silicon, and carbon (hereinafter referred to as Si-based / C). It is good that it is composed of a complex.
  • the compound containing silicon includes SiOx (0 ⁇ x ⁇ 2) and the like.
  • a negative electrode material containing only Si is unstable and breaks immediately.
  • the purpose of coating the active material selected from silicon and a compound containing silicon with the carbon-based material 2 is to protect Si and to impart conductivity to the Si.
  • aromatic organic solvents include halogenated benzenes including chloride, bromide and iodide, for example, dichlorobenzene (monochlorobenzene confirms only carbonization of the solvent), aromatics such as halogenated benzene and naphthalene.
  • An ultrasonic wave which is an example of a vibration treatment, is applied to a solution in which at least one aromatic compound is dissolved.
  • organic solvent molecules can be polymerized and carbonized in a local high temperature / high pressure state by cavitation, and the carbon-based material 2 is preferentially applied to the particle surface of the active material 1.
  • the dispersibility can be improved by solving the aggregation of the active material 1 such as the Si nanoparticles 4 (C is difficult to enter the gap).
  • the carbon-based material 2 can be made to enter the gap between the Si nanoparticles 4 in the thinnest possible state so as to have conductivity, and the carbon-based material 2 can be evenly distributed with a thickness of nanometer order.
  • Coating can be performed.
  • the vibration treatment is not limited to ultrasonic irradiation, but a container obtained by adding an active material to an aromatic organic solvent is placed on the vibrating body of the vibration device, and the container is subjected to vibration treatment in an Ar atmosphere.
  • the active material may be surface-treated with the carbon-based material generated by doing so.
  • Si nanoparticles in o-dichlorobenzene by adding Si nanoparticles in o-dichlorobenzene and irradiating with ultrasonic waves, the surface of the Si nanoparticles is coated with a carbon-based material 2 having a thickness on the order of nanometers to obtain a Si / C composite.
  • the modification state of the Si nanoparticle surface is TEM (transmission electron microscope), XPS (X-ray photoelectron spectroscopy), Raman spectroscopy, XRD (X-ray diffraction), elemental analysis, TG (thermogravimetric analysis), EDX (energy) (Dispersive X-ray analysis).
  • TEM transmission electron microscope
  • XPS X-ray photoelectron spectroscopy
  • Raman spectroscopy Raman spectroscopy
  • XRD X-ray diffraction
  • elemental analysis TG (thermogravimetric analysis)
  • EDX energy
  • the modification amount of the carbon-based material 2 in the above depends on the ultrasonic irradiation conditions (Si dispersion amount, output, time, etc.).
  • the temperature H is preferably selected from a heat treatment temperature range of 100 [° C.] ⁇ H ⁇ 1200 [° C.]. .
  • the lower limit temperature of 100 ° C. in the above heat treatment temperature range is the drying treatment temperature of the Si / C composite obtained by coating Si nanoparticles with the carbon-based material 2.
  • SiO 2 reacts with carbon at 1200 ° C. or more, and SiC which is undesirable in the present invention is generated.
  • the temperature is not more than this upper limit temperature.
  • the heat treatment temperature described above varies depending on the active material 1, the aromatic organic solvent, and the like. For this reason, what is necessary is just to heat-process the active material after surface carbon coating by setting optimal temperature according to the active material 1, an aromatic organic solvent, etc.
  • the heat treatment temperature is preferably less than 400 ° C.
  • the highest possible temperature is preferable in the temperature range where SiC is not generated. The reason is that carbonization proceeds with higher reproducibility at higher temperatures.
  • the heat treatment temperature is 600 ° C., for example, the chlorine component liberated from dichlorobenzene is reduced (eliminated) as described in the examples (see Table 1). Therefore, the heat treatment temperature is preferably 600 ° C. for the purpose of carbonizing the Si nanoparticles 4.
  • sample after surface carbon coating is heat-treated at a high temperature, thermal agglomeration occurs, so the sample after surface carbon coating is not only at the point of carbonization but also at the optimum temperature based on the condition of uniform surface carbon coating. May be heat-treated.
  • the structural example of the manufacturing apparatus 60 for manufacturing the electrode material 10 is demonstrated.
  • a case where the negative electrode material is formed and a composite made of silicon and carbon (Si / C) is manufactured for the negative electrode material 10 will be described as an example.
  • the manufacturing apparatus 60 shown in FIG. 2 is an apparatus that realizes a surface modification method for the carbon-based material 2 using ultrasonic waves.
  • the manufacturing apparatus 60 includes an ultrasonic adjustment device 61, a quartz cell 62, and a cooling device 63.
  • An ultrasonic vibrator 64 is attached to the quartz cell 62.
  • the ultrasonic transducer 64 is connected to the ultrasonic adjustment device 61.
  • the ultrasonic adjustment device 61 adjusts and sets the ultrasonic frequency, its output, and its irradiation time.
  • the frequency, output, and irradiation time are set by, for example, an adjustment volume provided in the ultrasonic adjustment device 61.
  • the quartz cell 62 is provided with a stirring bar 65 in addition to the ultrasonic vibrator 64.
  • reference numeral 3 denotes an aromatic organic solvent.
  • transparent colorless o-dichlorobenzene hereinafter also referred to as o-DCB3
  • the active material 1 constitutes an electrode material.
  • Si nanoparticles 4 are employed as an example of the active material 1 that is a target for surface coating.
  • the target active material 1 is not limited to the Si nanoparticles 4.
  • the active material 1 is a material that forms an alloy with Li such as Sn, an oxide such as SiOx (0 ⁇ x ⁇ 2), Nb, Fe, Ti, or the like.
  • Metal oxides, metal nitrides, and metal sulfides may be used.
  • the cooling device 63 has an upper open container 66 and a heat exchanger 67. Water 5 is placed in the upper open container 66. A lower portion of the quartz cell 62 is disposed inside the upper open container 66, and the lower portion of the quartz cell 62 is cooled. A heat exchanger 67 is provided in the upper open container 66. A cooling medium, for example, cooling water 6 is introduced (circulated) into the heat exchanger 67.
  • the ultrasonic vibrator 64 continues to irradiate ultrasonic waves in the quartz cell 62, the solution temperature in the quartz cell 62 rises. Therefore, in order to prevent deterioration of the ultrasonic transducer 64, for example, the temperature of the water 5 is maintained at 5 ° C.
  • the manufacturing apparatus 60 which implement
  • Si nanoparticle is added as the active material 1 in o-dichlorobenzene, and the surface of the Si nanoparticle is nanometer by irradiating with ultrasonic waves.
  • An Si / C composite is obtained by coating with a carbon-based material 2 having an order thickness. This Si / C composite is a sample composed of a Si nanoparticle / carbon composite.
  • powder of 100 to 150 [mg] Si nanoparticles (30 to 50 [nm]) was mixed with 200 [mL] o-DCB3. Then, in an argon (Ar) atmosphere, ultrasonic waves were irradiated under stirring under the following irradiation conditions.
  • the irradiation conditions were an ultrasonic output of 200 to 300 [W], a frequency of 40 kHz, and an irradiation time of 0 to 9 hours (hereinafter referred to as [h]).
  • Si nano-particle powder was added (mixed) to replace the atmosphere with Ar.
  • the mixed atmosphere is replaced with an Ar atmosphere.
  • SAMPLE a sample in which Si nanoparticles 4 were charged in o-DCB3 was used.
  • the sample was sonicated in step # 2.
  • the irradiation time was set to 3 [h] to 9 [h] for two types of ultrasonic output, 200 [W] and 300 [W]. It has long been known that when an aromatic organic solvent is irradiated with ultrasonic waves, it becomes black. Si nanoparticles 4 were dispersed in o-DCB3 and ultrasonic irradiation was started. After 30 minutes from the start of ultrasonic irradiation, the colorless and transparent o-DCB3 turned yellow.
  • o-DCB3 turned yellow and then turned black after several hours.
  • the organic solvent molecules were polymerized and carbonized by the radical reaction of o-DCB3, and the resulting carbon-based material 2 surface-treated the Si nanoparticles 4 (active material 1).
  • carbon C could be detected from the surface of the Si nanoparticles 4.
  • a black-colored solution containing the Si nanoparticles 4 was obtained.
  • the sample was centrifuged using a centrifuge in step # 3. Separation conditions were set such that the rotational speed of the centrifuge was set to 10,000 [rpm] and the separation time was 1 hour.
  • the black solution containing the Si nanoparticles 4 was centrifuged at 10,000 [rpm] for 1 hour to collect the precipitate.
  • the previously collected sample was dried at a temperature of 100 [° C.]. By this drying treatment, a black sample containing Si nanoparticles 4 before heat treatment at a high temperature (for example, 200 [° C.] to 600 [° C.]) was obtained.
  • Step # 6 the process was branched depending on whether the heat treatment was performed in Step # 5 or not.
  • the process proceeds to step # 6, and a notation process is performed in which a notation is given to the sample before the heat treatment.
  • C is added to the head (head)
  • the charged amount of the Si nanoparticles 4 is X [mg]
  • the ultrasonic irradiation time is Y [h].
  • the ultrasonic output is Z [W]
  • equation (1) that is, C-Si (X) Y [h] Z [W] (1)
  • the process proceeds to step # 7, and the Si nanoparticles 4 (active material 1) surface-treated with the carbon-based material 2 are heat-treated.
  • the heat treatment conditions were an electric tubular furnace, a heating rate of 10 ° C./min, a temperature of 600 [° C.], a heat treatment time of 4 hours, and an Ar atmosphere.
  • the Si nanoparticles 4 after the heat treatment showed higher capacity and higher rate characteristics than the Si nanoparticles 4 before the heat treatment.
  • the present inventors analyzed the modified state of the carbon-based material 2 by TEM observation, XPS, Raman spectroscopic analysis, XRD, elemental analysis, TG measurement, and EDX. While maintaining the Si crystal structure, the surface modification by the carbon-based material 2 and the modification to the particle gap were confirmed.
  • an XRD pattern of a C-Si (X) Y [h] Z [W] sample or the like will be described.
  • an XRD (X-ray diffraction) pattern of a C—Si (X) Y [h] Z [W] sample or the like was obtained in order to examine whether or not the Si nanoparticles 4 were present in the sample.
  • an X-ray diffractometer (Rigaku RINT-2200 (source: CuK ⁇ )) was used.
  • the XRD analysis conditions were as follows: counter cathode: CuK ⁇ , scan speed: 2.0 [degree / min], tube voltage: 40 [kV], tube current: 40 [mA], sampling interval: 0.010 [degree].
  • the vertical axis represents the X-ray diffraction intensity (Intensity)
  • the horizontal axis represents the X-ray incident angle [2 ⁇ / degree (CuK ⁇ )].
  • Comparative Example 1 is an XRD pattern of Si nanoparticles 4 without coating treatment (unmodified).
  • Example 1 is an XRD pattern of C—Si (100) 9 [h] 200 [W] only by coating treatment.
  • Example 2 is an XRD pattern of C—Si (150) 9 [h] 300 [W] only by coating treatment.
  • Example 3 is an XRD pattern of C—Si (100) 9 [h] 300 [W] only by coating treatment.
  • Example 4 is an XRD pattern of C—Si (100) 3 [h] 300 [W] only by coating treatment.
  • Comparative Example 2 is an XRD pattern of Si nanoparticles 4 without coating treatment (unmodified) + heat treatment 600 [° C.].
  • Example 5 is an XRD pattern of a C—Si (100) 9 [h] 200 [W] —H sample subjected to a coating treatment and a heat treatment of 600 [° C.].
  • Example 6 is an XRD pattern of a C—Si (150) 9 [h] 300 [W] —H sample subjected to a coating treatment and a heat treatment of 600 [° C.].
  • Example 7 is an XRD pattern of a C—Si (100) 9 [h] 300 [W] —H sample subjected to coating treatment + heat treatment 600 [° C.].
  • Example 8 is an XRD pattern of a C—Si (100) 3 [h] 300 [W] —H sample subjected to coating treatment + heat treatment 600 [° C.].
  • a Raman spectrum of a C—Si (X) Y [h] Z [W] sample or the like was acquired in order to examine whether or not the carbon-based material 2 was satisfactorily coated.
  • a Raman spectrum apparatus JASCO JASCO RMP-210 (laser light wavelength: 532 [nm]) was used. The acquisition conditions were an exposure time of 10 sec (seconds), an integration count of 20 times, and a wave number of 100 to 2000 [cm ⁇ 1 ].
  • the vertical axis represents intensity (Intensity: [Arb. Unit]), and the horizontal axis represents Raman shift ([cm ⁇ 1 ]).
  • the right figure of FIG. 5 shows an enlarged Raman spectrum of 1300 to 1800 [cm ⁇ 1 ] region.
  • Comparative Example 3 is a Raman spectrum of the Si nanoparticles 4 without coating treatment (unmodified).
  • Example 9 is a Raman spectrum of C—Si (100) 9 [h] 200 [W] only by coating treatment.
  • Example 10 is a Raman spectrum of C—Si (150) 9 [h] 300 [W] only by coating treatment.
  • Example 11 is a Raman spectrum of C—Si (100) 9 [h] 300 [W] only by coating treatment.
  • Example 12 is a Raman spectrum of C—Si (100) 3 [h] 300 [W] only by coating treatment.
  • Comparative Example 3 is a Raman spectrum of the Si nanoparticles 4 without coating treatment (unmodified). In Comparative Example 3, the carbon-based material 2 is not confirmed.
  • Example 9 is a Raman spectrum of C—Si (100) 9 [h] 200 [W] only by coating treatment.
  • Example 10 is a Raman spectrum of C—Si (150) 9 [h] 300 [W] only by coating treatment.
  • Example 11 is a Raman spectrum of C—Si (100) 9 [h] 300 [W] only by coating treatment.
  • Example 12 is a Raman spectrum of C—Si (100) 3 [h] 300 [W] only by coating treatment.
  • the peak (G band) in the vicinity of the Raman shift 1580 [cm ⁇ 1 ] in Examples 9 to 12 is graphitic carbon.
  • the peak (D band) near the Raman shift of 1360 cm ⁇ 1 is a peak derived from amorphous carbon. That is, it was found that in Examples 9 to 12, the carbon-based material 2 remained.
  • Raman such as a C—Si (X) Y [h] Z [W] —H sample is used to examine whether the carbon-based material 2 after heat treatment at 600 [° C.] remains excellent. A spectrum was acquired.
  • the Raman spectrum apparatus and acquisition conditions at that time are as described above.
  • Comparative Example 4 is a Raman spectrum of Si nanoparticles 4 without coating treatment (unmodified) + heat treatment 600 [° C.].
  • Example 13 is a Raman spectrum of a C—Si (100) 9 [h] 200 [W] —H sample subjected to a coating treatment and a heat treatment of 600 [° C.].
  • Example 14 is a Raman spectrum of a C—Si (150) 9 [h] 300 [W] —H sample subjected to a coating treatment and a heat treatment of 600 [° C.].
  • Example 15 is a Raman spectrum of a C—Si (100) 9 [h] 300 [W] —H sample subjected to a coating treatment and a heat treatment of 600 [° C.].
  • Example 16 is a Raman spectrum of a C—Si (100) 3 [h] 300 [W] —H sample subjected to coating treatment + heat treatment 600 [° C.].
  • Comparative Example 4 is a Raman spectrum of the Si nanoparticles 4 without coating treatment (unmodified) + heat treatment 600 [° C.]. In Comparative Example 4, the carbon-based material 2 was not confirmed.
  • Example 13 is a Raman spectrum of a C—Si (100) 9 [h] 200 [W] —H sample subjected to a coating treatment and a heat treatment of 600 [° C.].
  • Example 14 is a Raman spectrum of a C—Si (150) 9 [h] 300 [W] —H sample subjected to a coating treatment and a heat treatment of 600 [° C.].
  • Example 15 is a Raman spectrum of a C—Si (100) 9 [h] 300 [W] —H sample subjected to a coating treatment and a heat treatment of 600 [° C.].
  • Example 16 is a Raman spectrum of a C—Si (100) 3 [h] 300 [W] —H sample subjected to coating treatment + heat treatment 600 [° C.].
  • the amount of modification of the carbon-based material 2 described above depends on the ultrasonic irradiation conditions (Si dispersion amount, output, time, etc.). Then, with reference to FIG. 7, the relationship between ultrasonic irradiation conditions and a surface modification amount is demonstrated.
  • thermogravimetric analysis (TG) analysis in air is used to measure the weight change of the sample while changing the temperature or at a constant temperature, and estimate it from the weight change due to the decomposition of the organic matter part.
  • the amount of modification of the carbon-based material 2 was determined. From this result, as shown in the left and right diagrams of FIG. 7, the relationship between the modification amount [wt%] of the carbon-based material 2 and the ultrasonic irradiation time [hour] was created.
  • the vertical axis represents the modification amount [wt%] of the carbon-based material 2.
  • the horizontal axis represents the ultrasonic irradiation time [hour].
  • TG thermogravimetric
  • Example 17 is a white square mark and C—Si (100) 3 [h] 300 [ W].
  • Example 18 is the case of C—Si (100) 9 [h] 300 [W] with white circles.
  • Example 19 is a case of C-Si (150) 9 [h] 300 [W] with white triangle marks.
  • Example 20 is a case where C—Si (100) 9 [h] 200 [W] is indicated by white diamond marks.
  • the ultrasonic irradiation time was 3 [h]
  • the modification amount of the carbon-based material 2 was 12 [wt%].
  • the ultrasonic irradiation time is 9 [h].
  • the modification amount of the carbon-based material 2 was about 40 [wt%] in Example 18, about 5 [wt%] in Example 19, and about 12 [wt%] in Example 20.
  • Example 21 is a black square mark and C—Si (100) 3 [h] 300. This is the case of [W] -H sample.
  • Example 22 is a case of a C—Si (100) 9 [h] 300 [W] —H sample indicated by black circles.
  • Example 23 is a case of a C—Si (150) 9 [h] 300 [W] —H sample with black triangle marks.
  • Example 24 is the case of a C—Si (100) 9 [h] 200 [W] —H sample with black rhombus marks.
  • the ultrasonic irradiation time was 3 [h]
  • the modification amount of the carbon-based material 2 was 10 [wt%].
  • the ultrasonic irradiation time is 9 [h].
  • the modification amount of the carbon-based material 2 was about 30 [wt%] in Example 22, and about 8 [wt%] in both Example 23 and Example 24.
  • the modification compositions of the C-Si (100) 9 [h] 300 [W] sample and the C-Si (100) 9 [h] 300 [W] -H sample were compared.
  • the composition of the modification was analyzed by examining the relative number of moles of Si and Cl by EDX analysis (fluorescence X-ray analysis method).
  • Table 1 shows the EDX analysis results of the C—Si (100) 9 [h] 300 [W] sample and the C—Si (100) 9 [h] 300 [W] —H sample.
  • Table 2 shows organic element analysis results of the C—Si (100) 9 [h] 300 [W] sample and the C—Si (100) 9 [h] 300 [W] —H sample.
  • the meaning of carbonization means that the ratio of C in the carbon-based material is increased.
  • the ratio of H decreases, and the normal carbonization forms a graphene structure linked to the benzene skeleton, so this figure is used as a guide for carbonization .
  • the H / C weight ratio in the coating (without heat treatment) sample was 0.020, whereas the H / C ratio decreased to 0.008 after coating + heat treatment. It was found that carbonization was progressing. A carbon component was deposited on the Si nanoparticles 4 by the coating treatment of the carbon-based material 2. Even after the coating treatment, the Si crystal phase was retained. It was found that the carbonization was further advanced by the heat treatment.
  • TEM transmission electron microscope observation of the unmodified Si nanoparticles 4 and the C—Si (100) 9 [h] 300 [W] sample will be described.
  • the Si nanoparticles 4 used as the electrode material 10 had an average particle diameter of 30-50 nm.
  • a lattice image showing that the Si nanoparticles 4 had a crystal structure was observed.
  • a SiO 2 layer having a thickness of about 1 to 2 nm was observed on the surface of the Si crystal phase (lattice crystal) before the coating treatment.
  • An enlarged view of the SiO 2 layer is also shown in the photograph shown on the left side of FIG.
  • the surface of the Si crystal phase (Si nanoparticles) is covered with an amorphous layer having a thickness of about 5 nm. It was. It was found that the carbon-based material 2 has a thickness of about 5 nm and coats the surface of the Si crystal phase.
  • An enlarged view of the carbon-based material 2 is shown in the right diagram of FIG. According to this sample, an SiO 2 layer was also observed by XPS analysis.
  • the particle diameter of about 15 to 20 nm in thickness was increased. From this, it is considered that a coating layer having an average thickness of about 5 to 10 nm is formed. Thus, the carbonaceous material 2 having a thickness of nanometer order could be uniformly formed on the surface of the Si nanoparticles 4.
  • the vertical axis represents the ratio [%] of the sample (Si nanoparticle 4) showing the particle diameter
  • the horizontal axis represents the average particle diameter [nm] of the sample.
  • the ratio of the average particle diameter of the sample before surface coating shown in the upper diagram of FIG. 9, the ratio of the sample having an average particle diameter of 10 to 20 [nm] is 8 [%], and the average particle diameter of 20 to 30 [ nm] is 35 [%], the average particle size is 30 to 40 [nm], the sample is 35 [%], and the average particle size is 40 to 50 [nm]. [%], The ratio of samples having an average particle diameter of 50 to 60 [nm] was 5 [%], and the ratio of samples having an average particle diameter of 60 to 70 [nm] was also 3 [%].
  • the ratio of the average particle diameter of the sample after surface coating shown in the lower part of FIG. 9, the ratio of the sample having an average particle diameter of 20 to 30 [nm] is 1 [%], and the average particle diameter of 30 to 40 [nm] ] Is also 5 [%], the ratio of samples having an average particle diameter of 40 to 50 [nm] is 13 [%], and the ratio of samples having an average particle diameter of 50 to 60 [nm] is 33 [%]. %], The ratio of samples having an average particle diameter of 60 to 70 [nm] is 25 [%], the ratio of samples having an average particle diameter of 70 to 80 [nm] is 16 [%], and the average particle diameter is The ratio of the sample of 80 to 90 [nm] was also 5 [%].
  • the ratio of the average particle diameter of the sample before the surface coating shown in the upper part of FIG. 9 was compared with the ratio of the average particle diameter of the sample after the surface coating shown in the lower part of FIG. It was found that the average particle diameter of the sample after the surface coating shown in the lower diagram of FIG. 9 is shifted to the right as compared with the sample before the surface coating shown in the upper diagram of FIG. That is, it was found that the average particle size of the sample after the surface coating was larger than that of the sample before the surface coating.
  • the surface of the Si crystal phase (Si nanoparticles) is an amorphous layer of about 5 to 7 nm. It was found that amorphous was formed in the particle gaps of the Si nanoparticles 4 while being uniformly covered.
  • the surface coating method according to the present invention not only coats the surface of the Si nanoparticles 4 with the carbon-based material 2, but also shows that the carbon-based material 2 can be generated in the normally difficult nanoparticle gaps. As described above, the carbon-based material 2 can be formed also between the Si nanoparticles 4.
  • FIG. 11 is a TEM photograph of the C-Si (100) 9 [h] 300 [W] -H sample. According to the TEM observation example of the C—Si (100) 9 [h] 300 [W] —H sample shown in the right diagram of FIG. 11, the carbon-based material 2 could be confirmed even after the heat treatment.
  • FIG. 11 is an enlarged view near the boundary between the Si crystal phase and the carbon-based material 2.
  • the carbon-based material 2 is a portion surrounding the black Si nanoparticles of about 30-50 [nm] with a light gray color.
  • the lower left diagram in FIG. 11 is an enlarged view of the Si nanoparticles 4 and the surroundings.
  • Si nanoparticles 4 having a thickness of about 30-50 [nm] are observed, and the amorphous part around the Si nanoparticles 4 where the lattice image is confirmed is the carbon-based material 2.
  • the carbonization of the Si nanoparticles 4 can be further advanced, and the conductivity can be increased.
  • the surface of the Si nanoparticles 4 is covered with the carbon-based material 2.
  • carbonization further proceeds due to the heat treatment of the carbon-based material 2, and thermal agglomeration occurs to make it nonuniform.
  • the ultrasonic power 200 [W] +600 [° C.] even after heat treatment Si nano-particles 4 having the above were observed, and the carbon-based material 2 was also confirmed.
  • the round part is the Si nanoparticle 4
  • the surrounding amorphous part is the carbon-based material 2.
  • amorphous particles were also generated in the particle gaps.
  • the amorphous portion is the carbon-based material 2. Since the heat treatment time was as short as 3 hours, the amount of the carbon-based material 2 modified was small, but there were few completely adhered portions. As described above, when the ultrasonic wave irradiation time was short, the surface of the Si crystal phase was only partially coated, and the thickness was thin. Except for the haze on the surface of the Si crystal phase in the oblique lattice portion, it is considered that the SiO 2 layer is not coated with the carbon-based material 2.
  • XPS X-ray photoelectron spectroscopy
  • Example 25 According to the sample of C—Si (100) 9 [h] 300 [W] as Example 25 shown in the left middle diagram of FIG. 14, two peaks are observed even in the Si nanoparticle 4 only with the coating treatment. It was. The left peak is the Si crystal phase and the lower right peak is the SiO 2 layer. Further, according to the sample of Example 25 shown in the upper right diagram of FIG. 14, a C1s signal composed of several peaks due to the coating of the carbon-based material 2 was observed.
  • the peak near the binding energy of 287 eV is derived from the C—Cl bond, and the broad peak near 289 eV is derived from the C ⁇ C bond, indicating that the carbon-based material 2 contains components such as chlorine and C ⁇ C. ing.
  • the C ⁇ C bond is considered to form part of the structure of o-dichlorobenzene, which is an aromatic organic solvent. That is, the surface of the Si nanoparticle 4 is covered with the carbon-based material 2. This is because, in XPS analysis, the signal is larger at the outermost surface and becomes exponentially smaller with respect to the distance in the depth direction.
  • the active material 1 constituting the electrode for example, a material in which the carbon-based material 2 is covered on the surface of the Si nanoparticles 4 is used.
  • the carbon-based material 2 penetrates (deposits) to every corner of the crystal of the Si nanoparticle 4 and is excellent in electrical conductivity.
  • the structure collapses due to expansion / contraction of the active material accompanying Li ion insertion / desorption reaction. It is now possible to provide a stable Si nanoparticle electrode material that suppresses the above.
  • the Si / carbon composite is formed by dispersing the Si nanoparticles 4 in the organic solvent by strong ultrasonic irradiation and simultaneously polymerizing and carbonizing the organic solvent molecules. I was able to synthesize. That is, carbon having a thickness on the order of nanometers can be formed on the surface of the Si nanoparticles 4.
  • the organic solvent used for the surface modification of the Si nanoparticles 4 with the carbon-based material 2 is not limited to dichlorobenzene, and may be other aromatic compounds.
  • the surface modification method using the carbon-based material 2 is a simple method in which Si nanoparticles 4 are added to a non-polymerizable organic solvent (dichlorobenzene) and irradiated with ultrasonic waves. It is an available method.
  • the amount of carbon produced can be changed depending on the ultrasonic output, the ultrasonic irradiation time, the concentration of the active material 1, and the like.
  • the active material 1 is the Si nanoparticles 4 has been described.
  • the present invention is not limited to this, and the active material 1 is selected from compounds containing Si. SiOx (0 ⁇ x ⁇ 2 Or the like.
  • Li2SiO3 particles (particle size 1 to 10 [ ⁇ m]) were also subjected to experiments under the same conditions as in the method for producing the electrode material 10 in the Si nanoparticles 4 described above. Carbon of the order thickness could be formed. That is, a Li2SiO3 particle / carbon composite could be synthesized by dispersing Li2SiO3 particles in an organic solvent by strong ultrasonic irradiation and simultaneously polymerizing and carbonizing organic solvent molecules. From this, the present invention can also be applied to a lithium-containing silicon oxide represented by the composition formula LixSiOy and having a lithium content x and an oxygen content y of 0 ⁇ x and 0 ⁇ y ⁇ 2, respectively.
  • the formation method of the negative electrode 11 as 2nd Embodiment is demonstrated.
  • the negative electrode 11 is formed of a C—Si (X) Y [h] Z [W] sample.
  • the electrode material 10 is an electrode material for a negative electrode, that is, a negative electrode material, and is composed of Si nanoparticles 4 (negative electrode active material) whose entire surface or a part of the surface thereof is covered with the carbon-based material 2.
  • the electrode material 10 the C—Si (X) Y [h] Z [W] sample described in FIGS. 1 to 14 is used.
  • the negative electrode 11 is formed by providing an electrode material 10 on a negative electrode current collector.
  • the negative electrode 11 is formed from a (C—Si (100) 9 [h] 300 [W]) sample
  • the C ⁇ (100) 9 [h] 300 [W]) sample and the conductive auxiliary material acetylene black (AB) and a binder such as polyvinylidene fluoride resin (PVDF) or polytetrafloor styrene (PTFE) were mechanically mixed and kneaded to form a mixed paste.
  • the mixed paste was applied or pressure-bonded to the Ni mesh 7 shown in the lower part of FIG. Further, the mixed paste on the Ni mesh 7 was dried in an electric tubular furnace at a temperature of 150 [° C.], a drying time of 2 [h], and an Ar atmosphere. Thereafter, in a cold trap, the mixed paste on the Ni mesh 7 was further vacuum-dried at a temperature of 150 [° C.] and a drying time of 2 [h]. Thereby, the negative electrode 11 in which the (C—Si (100) 9 [h] 300 [W]) sample was deposited on the Ni mesh 7 was completed.
  • the entire surface or a part of the surface thereof includes the negative electrode active material covered with the carbon-based material 2, which greatly contributes to the stabilization of the alloy-based negative electrode active material.
  • the electrode material 10 has a large capacity Si negative electrode active material having a theoretical charge / discharge capacity of 4200 [mAh / g], 10 of graphite having a theoretical capacity of 372 [mAh / g] which is currently used as a negative electrode material.
  • the negative electrode 11 having a double or more capacity can be provided.
  • a tripolar cell 20 shown in FIG. 16 performs electrochemical measurement of the negative electrode 11 shown in FIG.
  • the tripolar cell 20 forms the charge / discharge principle of a Li ion secondary battery.
  • a charge / discharge measuring device 21 is used for electrochemical measurement of the negative electrode 11 (working electrode).
  • the triode cell 20 includes a clip 13, a cell container 22, a lid 23 for drawing out an electrode, an electrolyte solution 24 (Electrolyte), a counter electrode 25 (Counter electrode), a reference electrode 26 (Reference electrode), and a Lugin tube 27. ing.
  • the clip 13 sandwiched the lead wire of the negative electrode 11.
  • the clip 13 was connected to the charge / discharge measuring device 21 via a predetermined lead wire.
  • the counter electrode 25 and the reference electrode 26 were connected to a predetermined lead wire and connected to the charge / discharge measuring device 21 via the electrode lead-out lid 23.
  • metal Li bonded to Ni mesh Lion Ni mesh
  • the negative electrode 11, the counter electrode 25 and the reference electrode 26 were immersed in the electrolytic solution 24.
  • 1M LiPF 6 / [EC: DMC (1: 1)] was used as the electrolytic solution 24.
  • the weight ratio of ethylene carbonate (EC) to dimethyl carbonate (DMC) is 50:50.
  • the cell preparation was performed in an Ar atmosphere in a glove box.
  • the reference electrode 26 was brought as close as possible to the negative electrode 11 through the Lugin tube 27. Electrochemical measurement of the negative electrode 11 was performed in the triode cell 20 in an argon atmosphere. The measurement voltage range of the C—Si (100) 9 [h] 300 [W] sample constituting the negative electrode 11 is 3 to 0.01 [V]. The voltage measurement voltage range of the other sample electrodes is 2 to 0.01 [V].
  • the charge / discharge measuring device 21 For the charge / discharge measuring device 21, an electrochemical analyzer (HJ-SM8) manufactured by Hokuto Denko was used, and the measurement was performed in a constant current electricity measurement (CC) mode.
  • the charge / discharge measuring device 21 has a potentiostat or galvanostat function, and can measure at a constant potential or a constant current.
  • the current density based on the weight of Si is 210 [mA / g] and 420 [mA / g], the potential range is 0.01 [V] to 3.0 [V] vs Li / Li +, and room temperature conditions
  • the constant current charge / discharge measurement was performed. According to the constant current charge / discharge measurement, the current is made constant by the galvanostat of the charge / discharge measuring device 21, and a constant current is passed from the charge / discharge measuring device 21 to the tripolar cell 20. A method of monitoring the change in coulomb amount with the charge / discharge measuring device 21 was adopted.
  • CC mode a constant current was passed through the triode cell 20 and the amount of electricity was measured.
  • CC-CV mode in the CC mode, after a current is passed to a certain potential, the measurement is continued in the CC mode after a quantity of electricity that is held at a constant potential and not fully charged / discharged is passed.
  • Si-based electrode was subjected to electrochemical measurement in the CC mode.
  • the present inventors confirmed that the surface coating of the carbon-based material 2 improves both the charge / discharge capacity and the cycle stability as compared with the case of using only the Si negative electrode active material. Further, it was confirmed that the charge / discharge capacity of the sample subjected to the heat treatment was further increased.
  • FIG. 17 shows a charge / discharge curve (curve) of each sample under a current density condition of 420 [mA / g].
  • three electrodes of an unmodified Si nanoparticle-based sample, a C—Si (100) 9 [h] 300 [W] sample, and a C—Si (100) 9 [h] 300 [W] —H sample Material was used.
  • these charge / discharge operations were performed once to four times, and the charge / discharge characteristics were compared (considered).
  • the counter electrode 25 and the reference electrode 26 are metal Li bonded to a Ni mesh.
  • the measurement voltage range is 3 to 0.01 [V].
  • the charging current density is 420 [mA / g]. Electrochemical measurements were performed in CC mode.
  • the vertical axis represents the potential of the triode cell 20 (Potential / [V vs Li / Li + ].
  • the horizontal axis shown in the left diagram of FIG. 17 represents the Si weight of the Si nanoparticles 4.
  • the horizontal axis shown in the middle and right diagrams of Fig. 17 is the discharge capacity [mAh / g] per unit weight of the Si + -modified carbon-based material 2. It is.
  • the left diagram in FIG. 17 shows the charge / discharge characteristics of the Si nanoparticle sample.
  • numerals (1), (2), (3), (4) in the figure indicate the order of the charge / discharge cycles.
  • (1) is an initial charge / discharge curve of the Si nanoparticle sample.
  • (2) is a second charge / discharge curve of the Si nanoparticle sample.
  • (3) is the third charge / discharge curve of the Si nanoparticle sample.
  • (4) is a fourth charge / discharge curve of the Si nanoparticle sample.
  • the charge curve of the Si nanoparticle sample shown in the left diagram of FIG. It is shifted to the left as compared with the charge / discharge curve.
  • (1) is the initial charge / discharge curve of the C—Si (100) 9 [h] 300 [W] sample.
  • (2) is the second charge / discharge curve of the C—Si (100) 9 [h] 300 [W] sample.
  • (3) is the third charge / discharge curve of the C—Si (100) 9 [h] 300 [W] sample.
  • (4) is the fourth charge / discharge curve of the C—Si (100) 9 [h] 300 [W] sample.
  • the charge curve is the charge / discharge curve of the Si nanoparticle-based sample shown in the left diagram of FIG. It is shifted to the right compared to In the right diagram of FIG. 17, (1) is the initial charge / discharge curve of the C—Si (100) 9 [h] 300W—H sample. (2) is the second charge / discharge curve of the C—Si (100) 9 [h] 300W—H sample. (3) is the third charge / discharge curve of the C—Si (100) 9 [h] 300 [W] —H sample. (4) is the fourth charge / discharge curve of the C—Si (100) 9 [h] 300W—H sample.
  • the charging curve of the negative electrode 11 is due to an alloy reaction (Si + xLi ⁇ LixSi) in which the Si nanoparticles 4 occlude Li.
  • the initial charge curve also includes the capacity of the interfacial film (SEI) formation caused by electrolyte decomposition.
  • the alloy reaction (Si + xLi ⁇ LixSi) between the Si nanoparticle 4 and Li usually occurs at 0.3 [V] or less at a potential based on Li.
  • the leveling characteristics (capacity increase) of 0.3 [V] or less in the charging curves shown in each diagram of FIG. 17 indicate that this reaction occurs.
  • the characteristic that increases in capacity as the electric potential increases is a curve at the time of discharge (discharge curve).
  • the discharge curve of the negative electrode 11 is due to a dealloying reaction (LixSi ⁇ Si + xLi) that releases Li. Since the weight of the negative electrode 11 serving as a reference is different in the charge / discharge characteristics of a composite such as a Si nanoparticle 4 and a C—Si (X) Y [h] Z [W] sample, in FIG. Both figures were compared and considered.
  • the discharge characteristics of the Si-based sample will be described with reference to FIG.
  • the discharge cycle characteristics of two Si-based samples at a charging current density of 420 [mA / g] were obtained and compared. That is, the discharge cycle characteristic of each sample was determined from the charge / discharge curve (curve) of each sample measured under a current density condition of 420 [mA / g].
  • the change with the charge / discharge cycle of the discharge capacity (capacity per Si weight) of the Si nanoparticles obtained here was compared with the discharge capacity per weight of the complex of the Si + -modified carbon-based material 2.
  • the sample is C—Si (100) 9 [h] 300 [W].
  • the left figure of FIG. 18 is a discharge characteristic diagram showing the discharge capacity (SOC (charge rate): 0 to 100%) per weight of the composite (Si / C) of the Si-based sample in measurement of 1 to 10 charge / discharge cycles. It is.
  • the vertical axis represents the discharge capacity (Capacity) [mAh (g-Si) ⁇ 1 ], and the horizontal axis represents the number of cycles (Cycle Number).
  • Comparative Example 10 is a sample containing only Si (no coating), the discharge capacity per unit weight of Si is shown.
  • Comparative Example 10 indicated by a square mark is the discharge cycle characteristics of the Si nanoparticles 4 as they are.
  • the characteristic of shifting from the middle stage to the lower stage was a capacity of 100 mAh / g or less in the tenth discharge cycle.
  • Example 35 indicated by a triangle mark shows the characteristics after the coating treatment, and the capacity is low at the initial number of times, but is reversed from the characteristics of the Si nanoparticles 4 after the fourth time.
  • the discharge capacity was maintained at 200 [mAh / g] or more at the 10th time.
  • Example 36 indicated by an ellipse is a characteristic after coating treatment + heat treatment, and maintained a discharge capacity of 300 [mAh / g] or more for 10 times.
  • the right figure of FIG. 18 is a discharge characteristic diagram showing the discharge capacity (SOC: 0 to 100%) per Si weight for extracting and comparing discharge characteristics between Si.
  • the vertical axis represents the discharge capacity (Capacity) [mAh (g-Si) ⁇ 1 ], and the horizontal axis represents the number of cycles (Cycle Number).
  • Comparative Example 10 indicated by a square mark is a discharge cycle characteristic in the case of Si nanoparticles 4. According to this discharge cycle characteristic, the discharge capacity was high at 1200 [mAh / g] for the first time, but the discharge capacity rapidly decreased to 100 [mAh / g] or less at the 10th time.
  • Example 37 indicated by a triangle mark is a discharge cycle characteristic after the coating treatment.
  • the discharge capacity was high at 1250 [mAh / g] at the first time, and the discharge capacity was 400 [mAh / g] at the 10th time.
  • Example 38 indicated by a circle on the solid line shows the discharge cycle characteristics after coating and heat treatment. According to this discharge cycle characteristic, 400 [mAh / g] was maintained at the discharge capacity of the 10th time.
  • the discharge capacity rapidly decreased with an increase in the number of cycles, and almost no capacity was obtained after 10 cycles.
  • Li for example, Li 4.4 Si expands the volume four times.
  • the Si nanoparticles 4 are dealloyed, the volume shrinks to 1/4 compared to Li 4.4 Si. Due to this large volume change, pulverization occurs, resulting in a loss from the current collector and in-electrode electron conductivity due to poor contact.
  • the C—Si (100) 9 [h] 300 [W] sample shown in Example 35 on the left side of FIG. 18 had a small discharge capacity at the beginning of the cycle, but the capacity decrease with the passage of the cycle was small. After 5 cycles, rather, the discharge capacity was larger than the discharge cycle characteristics of the Si nanoparticles 4. It is considered that the surface coating with the carbon-based material 2 suppresses the structural breakdown accompanying the alloy / dealloying reaction of the Si nanoparticles 4 and enables stable charge / discharge.
  • the right diagram in FIG. 18 shows the cycle characteristics per Si weight in Comparative Example 10 in order to compare the discharge cycle characteristics on the same weight basis.
  • the Si in the C—Si (100) 9 [h] 300 [W] sample of Example 37 initially shows the same discharge capacity as that of the unmodified Si nanoparticles 4, but the cycle progresses. The capacity drop was small. That is, the cycle stability was improved by the coating of the carbon-based material 2.
  • the conductivity of the C—Si (100) 9 [h] 300 [W] —H sample of Example 38 was improved by heat treatment. As a result, it was found that the initial capacity was greatly increased.
  • the charge / discharge characteristics of the Si-based sample will be described with reference to FIG.
  • the present inventors generally increase the polarization in the electrode, thereby reducing the charge / discharge capacity.
  • the higher the charging current density the faster the alloy and dealloying reaction. Therefore, it was considered that the volume change rate is large and the structure collapse is likely to occur. Therefore, measurement was performed at a lower current density.
  • the discharge cycle characteristics of two Si-based samples at a charging current density of 210 [mA / g] were obtained, and the discharge cycle characteristics of the Si-based samples were compared. That is, the discharge cycle characteristics were determined from the charge / discharge curves of each sample measured under a current density condition of 210 [mA / g].
  • the vertical axis represents potential (Potential / [VvsLi / Li + ] and the horizontal axis represents discharge capacity (mAh / (g-Si)].
  • the unmodified Si nanoparticles 4 and the C-Si (100) 9 [h] 300 [W] sample shown in the figure and the middle figure were compared with the current density set at 210 mA / g.
  • the charging and discharging curves in the first cycle to the tenth cycle are sequentially performed from the right curve.
  • the charging curve of the negative electrode 11 with the Si nanoparticles 4 remains is due to an alloy reaction (Si + xLi ⁇ LixSi) in which the Si nanoparticles 4 occlude Li.
  • the initial charge curve also includes the capacity of the interfacial film (SEI) formation caused by electrolyte decomposition.
  • the downward-sloping characteristic in which the capacity increases as the electric potential decreases is a curve (charge curve) during charging.
  • the charging curve of the negative electrode 11 is due to an alloy reaction (Si + xLi ⁇ LixSi) between the Si nanoparticles 4 and Li.
  • the alloy reaction usually occurs at a potential based on Li of 0.3 [V] or less, and a leveling portion (capacity increase) of 0.3 [V] or less in the charging curve shown in each diagram of FIG. Indicates that a reaction is taking place.
  • a curve that rises to the right and increases in capacity as the potential increases is a curve during discharge (discharge curve).
  • the discharge curve of the negative electrode 11 is due to a dealloying reaction (LixSi ⁇ Si + xLi) that releases Li.
  • FIG. 19 is a charge / discharge curve of the negative electrode 11 after coating treatment (before heat treatment), measured under a current density condition of 210 [mA / g].
  • the charge / discharge curve shown in the right diagram of FIG. 19 is shifted to the right as compared to the charge / discharge curve shown in the left diagram of FIG.
  • the vertical axis represents discharge capacity per Si weight (Capacity) [mAh / (g-Si)], and the horizontal axis represents the number of charge / discharge cycles (Cycle Number).
  • the comparative example 12 of the round mark shown in FIG. 20 is a cycling characteristic in case the negative electrode 11 is only Si nanoparticle 4.
  • FIG. According to this cycle characteristic even at a low current density, the discharge capacity of the Si nanoparticles 4 suddenly decreased with the cycle. That is, the discharge capacity was as high as 2000 [mAh / (g-Si)] for the first time, but rapidly decreased to 100 [mAh / g] or less after the 15th time. 30 times showed almost no capacity.
  • the negative electrode 11 is a C—Si (100) 9 [h] 300 [W] sample, and the cycle characteristics of the Si nanoparticles after the coating treatment.
  • the discharge capacity was as high as 3250 [mAh / (g-Si)] at the first time, and the discharge capacity was maintained at 1000 [mAh / (g-Si)] or more at the 15th time. After 35 times, the discharge capacity was almost constant and after 60 times the discharge capacity 700 [mAh / (g-Si)] was maintained.
  • the existing graphite negative electrode material has a discharge capacity of 372 to 350 [mAh / g].
  • the electrode material in which the carbon-based material 2 is covered on the entire surface or a part of the surface of the Si nanoparticles 4 as the active material 1 is used.
  • the carbon-based material 2 is irradiated with o-DCB3 under the conditions of an ultrasonic frequency of 40 kHz, an output of 200 to 300 [W], and an irradiation time of 3 [h] to 9 [h]. It is produced by the radical reaction.
  • the carbon-based material 2 penetrates (deposits) into every corner of the crystal of the Si nanoparticle 4, so that the crystal structure of the Si nanoparticle 4 is protected from alloying and dealloying reactions, and
  • the negative electrode 11 excellent in conductivity can be provided.
  • the Si / carbon composite is synthesized by dispersing the Si nanoparticles 4 in the organic solvent by strong ultrasonic irradiation and simultaneously polymerizing and carbonizing the organic solvent molecules. That is, carbon having a thickness of nanometer order can be formed on the surface of the Si nanoparticles 4.
  • the organic solvent used for the surface modification of the Si nanoparticles 4 with the carbon-based material 2 is not limited to dichlorobenzene, and may be other aromatic compounds.
  • the surface modification method using the carbon-based material 2 is a simple method in which Si nanoparticles 4 are added to a non-polymerizable organic solvent (dichlorobenzene) and irradiated with ultrasonic waves. It is an available method.
  • the amount of carbon produced can be changed depending on the ultrasonic output, the ultrasonic irradiation time, the concentration of the active material 1, and the like.
  • the surface modification method using the carbon-based material 2 is a technology that has a high impact in practical use as a surface nano-coating method for the active material 1 of the battery.
  • a flow-type device such as a circulation device
  • the negative electrode 11 is formed. Can be produced in large quantities.
  • conductivity is imparted by the surface nano-coating of the active material 1, and stability of charge / discharge cycle characteristics can be improved.
  • the surface modification method for the carbon-based material 2 according to the present invention is also effective for stabilizing the alloy-based negative electrode active material and the negative electrode.
  • the collapse of the Si crystal structure of the negative electrode 11 can be suppressed, and the reversible characteristics of alloying and dealloying are favorably performed.
  • the negative electrode having Si nanoparticles 4 covered and protected in every corner by the carbon-based material 2 greatly contributes to the increase in capacity of Li-ion secondary batteries and the production of high-capacity Li-ion secondary batteries. .
  • the formation method of the electrode material for positive electrodes as 3rd Embodiment is demonstrated.
  • carbonization of the LMO-LNMCO particles can be further advanced by the positive electrode active material + ultrasonic carbon coating method, and the conductivity of the electrode material for the positive electrode can be increased.
  • This example is an electrode material for a positive electrode as an example of the electrode material 10, that is, a positive electrode material.
  • the positive electrode material the entire surface or a part of the surface of the positive electrode active material which is the active material 1 is covered with the carbon-based material 2.
  • the positive electrode 12 is obtained by providing a positive electrode material 10 on a positive electrode current collector.
  • Li 2 MnO 3 -based active material 1 is used as the positive electrode active material.
  • a positive electrode active material composed of a Li 2 MnO 3 based active material is covered with a carbon based material 2 to form a positive electrode material. Therefore in comparison with the active material of Li 2 MnO 3 system can provide a cathode material 12 including a high-rate characteristic Li 2 MnO 3 is obtained based active material / carbon composites with showing a higher capacity.
  • the positive electrode material according to the present invention the entire surface or a part of the surface thereof is made of the positive electrode active material covered with the carbon-based material 2, which greatly contributes to the stabilization of the positive electrode active material.
  • the method for forming a positive electrode material according to the present invention is a method for surface modification of a Li 2 MnO 3 -based active material with a carbon-based material 2.
  • a Li 2 MnO 3 -based active material with a carbon-based material 2.
  • o- dichlorobenzene by irradiating for example ultrasound after addition of Li 2 MnO 3 -based grain body as the active material 1, with ultrasonically dispersed Li 2 MnO 3 system particles of Li 2 MnO 3 system particles all The surface or a part of the surface is coated with a carbon-based material 2 having a thickness on the order of nanometers to obtain a Li 2 MnO 3 -based active material / C composite (preparation of a sample composed of Li 2 MnO 3 particles / carbon composite) .
  • o-DCB3 500 [mL] of o-DCB3 (hereinafter, o-DCB3 is also simply referred to as C) is charged as 1 [g] of 0.5Li 2 MnO 3 -0.5Li 2 Ni 1/3 Co.
  • a powder of 1/3 O 2 (hereinafter referred to as LMO-LNMCO) was mixed.
  • LMO-LNMCO 1/3 O 2
  • the irradiation conditions were an ultrasonic output of 300 [W], a frequency of 40 [kHz], and an irradiation time of 9 [h].
  • a sample in which LMO-LNMCO particles are charged in o-DCB3 is referred to as a sample (SAMPLE).
  • the sample was sonicated in step # 12.
  • the frequency f was set to 40 [kHz]
  • the output was set to 300 [W]
  • the irradiation time was set to 9 [h].
  • the color of the o-DCB3 changed to yellow and then changed to black after several hours.
  • organic solvent molecules were polymerized and carbonized by the radical reaction of o-DCB3.
  • the resulting carbon-based material 2 surface-treated the LMO-LNMCO particles (active material 1), and carbon C could be detected from the surface of the LMO-LNMCO particles as described later.
  • a black-colored solution containing LMO-LNMCO particles was obtained.
  • the sample was centrifuged using a centrifuge in step # 13. Separation conditions were set such that the rotational speed of the centrifuge was set to 10,000 [rpm] and the separation time was set to 1 hour. The solution which turned to black containing LMO-LNMCO particles was centrifuged at 10,000 [rpm] for 1 hour to collect the precipitate.
  • step # 14 the previously collected sample was dried at a temperature of 120 [° C.].
  • a black sample containing C-LMO-LNMCO particles before heat treatment at a high temperature for example, 300 [° C.] to 500 [° C.] was obtained.
  • step # 15 the process was branched depending on whether the heat treatment was performed in step # 15 or not.
  • the process proceeds to step # 16, and a notation process is performed in which a notation is given to the sample before the heat treatment.
  • C the sample not subjected to the heat treatment is expressed by the equation (3), that is, C-LMO-LNMCO (3)
  • electrochemical analysis was performed.
  • Step # 17 When performing heat treatment of the sample, the process proceeds to Step # 17, and the C-LMO-LNMCO particles (active material 1) surface-treated with the carbon-based material 2 are heat-treated.
  • the heat treatment conditions were as follows: the temperature was 300 to 500 [° C.] in an electric tubular furnace, the heat treatment time was maintained for 3 to 12 hours, and the sample was fired in an Ar atmosphere. It was possible to provide a positive electrode material that showed higher capacity and higher rate characteristics than C-LMO-LNMCO particles before heat treatment.
  • the LMO-LNMCO particles used as the active material 1 had an average particle diameter of about 30-50 [nm]. .
  • the amorphous phase is composed of the carbon-based material 2 when considered together with the results of Raman spectrum measurement and composition analysis.
  • formation of an amorphous phase was also observed in the particle gap, and carbon coating by ultrasonic treatment was confirmed also in the electrode material for the positive electrode.
  • the carbonaceous material 2 having a thickness of nanometer order could be uniformly formed on the surface of the LMO-LNMCO particles.
  • the XRD pattern of the C-LMO-LNMCO (300-12) sample or the like will be described with reference to FIG.
  • an XRD pattern of a C-LMO-LNMCO (HY) sample or the like was acquired in order to examine whether or not LMO-LNMCO particles were present in the sample.
  • the acquisition conditions are the counter cathode: CuK ⁇ , scan speed: 2.0 [degree / min], tube voltage: 40 [kV], tube current: 40 [mA], and sampling interval: 0.010 [degree].
  • the vertical axis represents the X-ray diffraction intensity (Intensity), and the horizontal axis represents the X-ray incident angle [2 ⁇ / degree (CuK ⁇ )].
  • Example 23 is an XRD pattern of LMO-LNMCO particles without coating treatment (unmodified).
  • Example 41 is an XRD pattern of C-LMO-LNMCO with only coating treatment.
  • Example 42 is an XRD pattern of a C + LMO-LNMCO (300-12) sample with coating + heat treatment.
  • Example 43 is an XRD pattern of a C + LMO-LNMCO (400-12) sample with coating plus heat treatment.
  • Example 44 is an XRD pattern of a C + LMO-LNMCO (500-12) sample with coating plus heat treatment.
  • the Raman spectrum of the C-LMO-LNMCO sample (300 [° C.]) will be described with reference to FIG.
  • a Raman spectrum of a C-LMO-LNMCO sample (300 [° C.]) was obtained in order to check whether or not the carbon-based material 2 was satisfactorily coated.
  • a Raman spectrum apparatus (JASCO Corp. JASCORMP-210 (laser beam wavelength: 532 [nm])) was used.
  • the acquisition conditions were an exposure time of 10 sec, an integration count of 20, and a wave number of 100 to 2000 [cm ⁇ 1 ].
  • the vertical axis is intensity (Intensity: [Arb. Unit]), and the horizontal axis is Raman shift (Raman shift: [cm ⁇ 1 ]. Note that FIG. 24 shows 1200 to 2000 [cm ⁇ 1 ] region. 24 is a Raman spectrum of LMO-LNMCO particles without coating treatment (unmodified), and no peak derived from the carbonaceous material 2 is confirmed in Comparative Example 14.
  • Example 45 is a Raman spectrum of C-LMO-LNMCO particles that are only coated.
  • Example 46 is the Raman spectrum of a C + LMO-LNMCO (300-3) sample with coating + heat treatment.
  • Example 47 is the Raman spectrum of a C + LMO-LNMCO (300-6) sample with coating + heat treatment.
  • Example 48 is the Raman spectrum of a C + LMO-LNMCO (300-12) sample with coating plus heat treatment.
  • the modified composition of the C-LMO-LNMCO sample will be described.
  • the composition of the carbon-based material 2 was examined by organic element analysis.
  • the content of the carbon (C), hydrogen (H), and nitrogen (N) contained in the sample was examined [wt%], and the composition of the modification was analyzed.
  • Samples of C-LMO-LNMCO before heat treatment, samples of C-LMO-LNMCO (300-3), C-LMO-LNMCO (300-6), and C-LMO-LNMCO (300-12) after heat treatment The results of organic element analysis are shown in Table 3.
  • the element content of C is 2.7 [wt%] and the element content of H is 0.0 [wt%].
  • the element content of N was 0.0 [wt%].
  • the element content of C is 2.6 [wt%] and the element content of H is 0.8 [wt%].
  • the elemental content of N was 0.0 [wt%].
  • the element content of C is 2.2 [wt%] and the element content of H is 0.8 [wt%].
  • the elemental content of N was 0.0 [wt%].
  • the element content of C is 2.4 [wt%] and the element content of H is 0.8 [wt%]. Yes, the elemental content of N was 0.0 [wt%].
  • C-LMO-LNMCO and C-LMO-LNMCO (300-Y) samples confirmed C and H elements not present in the unmodified LMO-LNMCO, and carbon-based material 2 was produced. I found out.
  • EDX analysis results of C-LMO-LNMCO sample before heat treatment C-LMO-LNMCO (300-3), C-LMO-LNMCO (300-6), and C-LMO-LNMCO (300-12) after heat treatment are shown in Table 4.
  • the Mn content is 40.33 [wt%]
  • the Co content is 12.61 [wt%]
  • the Ni content was 15.72 [wt%]
  • the Cl content was 29.29 [wt%].
  • the Mn content is 48.61 [wt%]
  • the Co content is 15.67 [wt%]
  • the Ni content was 15.72 [wt%]
  • the Cl content was 19.62 [wt%].
  • the Mn content is 50.21 [wt%]
  • the Co content is 16.21 [wt%]
  • the Ni content was 16.22 [wt%]
  • the Cl content was 14.33 [wt%].
  • C-LMO-LNMCO and C-LMO-LNMCO (300-Y) samples confirmed C and H elements not present in the unmodified LMO-LNMCO, and the carbon-based substance 2 It was found that it was generated. Further, the presence of Cl element was confirmed, and it was found that it decreased with the heat treatment time of 300 [° C.].
  • the specific surface area was 8.87 [m 2 / g].
  • the specific surface area was 15.03 [m 2 / g].
  • the specific surface area was 15.23 [m 2 / g]
  • C-LMO-LNMCO (300-6) after coating and heat treatment According to the sample, the specific surface area is 15.04 [m 2 / g]
  • the specific surface area is 15.18 [m 2 / g].
  • the electrochemical measurement of the positive electrode 12 using a positive electrode material is demonstrated.
  • the positive electrode material 12 is formed using a C—LMO-LNMCO (300-Y) sample obtained by subjecting a Li 2 MnO 3 based active material to ultrasonic carbon coating and heat treatment will be described as an example.
  • a tripolar cell 20 shown in FIG. 25 performs electrochemical measurement of the positive electrode 12 instead of the negative electrode 11 shown in FIG. Since the same reference numerals and the same names have the same functions, the description thereof is omitted.
  • the positive electrode 12 (Working electrode), the counter electrode 25 (Counter electrode), and the reference electrode 26 (Reference electrode) were connected to the charge / discharge measuring device 21 via a predetermined lead wire.
  • metal Li bonded to Ni mesh (Lion Ni mesh) was used.
  • the positive electrode material 12, the counter electrode 25, and the reference electrode 26 were immersed in the electrolytic solution 24.
  • the positive electrode 12 was subjected to electrochemical measurement in the CC-CV mode, and was charged up to 4.7 [V] only for the first time for activation.
  • the measurement was continued in the CC mode after a quantity of electricity that was held at a constant potential and was not fully charged / discharged was passed.
  • the reference electrode 26 was brought as close as possible to the positive electrode material 12 through the Lugin tube 27. Electrochemical measurement of the positive electrode 12 was performed in the triode cell 20 in an argon atmosphere.
  • C rate based on LMO-LNMCO weight is 0.2 to 5C (converted to 200 [mAh / g]), and potential range is 2.0 [V] to 4.5 [V] vs Li / Li + ,
  • Constant current charge / discharge measurement was performed under conditions of room temperature (25 ° C.). According to the constant current charge / discharge measurement, the current is made constant by the galvanostat of the charge / discharge measuring device 21, and a constant current is passed from the charge / discharge measuring device 21 to the tripolar cell 20. A method of monitoring the change in coulomb amount with the charge / discharge measuring device 21 was adopted.
  • the constant current charge / discharge characteristics of the C-LMO-LNMCO sample will be described with reference to FIG.
  • the charge / discharge capacity of the unmodified LMO-LNMCO sample (capacity per LMO-LNMCO weight) with the charge / discharge cycle and the discharge capacity of the LMO-LNMCO + modified carbon-based material 2 (LMO-LNMCO weight) (Capacity per unit) was compared with the change accompanying the charge / discharge cycle.
  • the positive electrode 12 of C-LMO-LNMCO (300-12) shown in FIG. 25 was used.
  • the vertical axis represents potential (Potential / [V vs Li / Li + ], and the horizontal axis represents discharge capacity (mAh / g), which is a capacity per LMO-LNMCO weight.
  • the curve in which the capacity increases as the potential decreases is the discharge curve, and the curve in which the capacity increases as the potential increases is the charge curve. Is the opposite.
  • the C rates are 0.2, 0.5C, 1C, 2C, and 5C in order from the curve on the right side.
  • the difference in the start potential is due to the voltage drop (IR).
  • the C-LMO-LNMCO (300-12) of Example 49 shown on the right side of FIG. 26 has both charge and discharge curves compared to the unmodified LMO-LNMCO of Comparative Example 15 shown on the left side of FIG. Shifted to the right.
  • the discharge capacity of C-LMO-LNMCO (300-12) was significantly increased as compared with unmodified LMO-LNMCO by heat treatment at 300 [° C.].
  • the voltage drop (IR drop) at the start of discharge has a small value at a high C rate in the C-LMO-LNMCO sample, indicating that polarization is suppressed. That is, it can be said that the surface modification of the carbon-based material 2 by the ultrasonic carbon coating method according to the present invention is effective for increasing the capacity by improving the conductivity. When polarization occurs, the electrode reaction cannot catch up. Further, as described in the rate characteristics shown in FIG. 27, the capacity drop at a high rate is small.
  • Example 50 is a C-LMO-LNMCO sample before heat treatment
  • Example 51 is a C-LMO-LNMCO (300-12) sample after heat treatment.
  • the rate characteristics are shown.
  • the vertical axis represents the discharge capacity (Capacity) [mAh / g] per LMO-LNMCO weight
  • the horizontal axis represents the current density [mA / g].
  • the discharge capacity of the LMO-LNMCO sample decreased with the current density. That is, the discharge capacity was as high as 215 [mAh / g] under the condition of a current density of 40 [mA / g], but the discharge capacity rapidly decreased to 100 [mAh / g] at a current density of 400 [mA / g]. . At a current density of 1000 [mA / g], the discharge capacity decreased to about 50 [mAh / g].
  • Example 50 indicated by the square marks shows the rate characteristics of the sample obtained by coating the positive electrode material 12 with the C-LMO-LNMCO sample before the heat treatment.
  • the discharge capacity is higher than that of the untreated LMO-LNMCO sample (Comparative Example 15) at 250 [mAh / g] at a current density of 40 [mA / g], and the untreated LMO-LNMCO sample (Comparative Example) even at a higher current density. 15) Higher discharge capacity was shown.
  • Example 51 indicated by triangles shows the rate characteristics of the sample after the coating and heat treatment in which the positive electrode material 12 is a C-LMO-LNMCO (300-12) sample after heat treatment.
  • the initial capacity was high and the rate characteristics were improved. That is, according to the rate characteristics after coating and heat treatment, the discharge capacity is as high as 250 [mAh / g] at a current density of 40 [mA / g] and about 150 [mAh / g] at a current density of 400 [mA / g].
  • the discharge capacity was greatly improved. Even at a current density of 1000 [mA / g], the discharge capacity was significantly improved as compared with Comparative Example 15 at about 125 [mAh / g].
  • the carbon-based material 2 is covered on the entire surface or a part of the surface of the LMO-LNMCO particles as the active material 1. Is generated by the radical reaction of o-DCB3 by irradiating the o-DCB3 with ultrasonic waves having an ultrasonic frequency of 40 kHz and an ultrasonic output of 200 to 300 [W] for an irradiation time of 9 [h].
  • the carbon-based material 2 penetrates (deposits) into every corner of the crystal of the LMO-LNMCO particles, so that the crystal structure of the LMO-LNMCO particles is protected from alloying and dealloying reactions, and An electrode material for a positive electrode having excellent conductivity can be provided.
  • a C-LMO-LNMCO composite is obtained by dispersing LMO-LNMCO particles in an organic solvent by strong ultrasonic irradiation and polymerizing / carbonizing the organic solvent molecules.
  • the organic solvent used for the surface modification with the carbonaceous material 2 is not limited to dichlorobenzene, and may be other aromatic compounds.
  • the surface modification method using the carbon-based material 2 is a simple method in which LMO-LNMCO particles are added to a non-polymerizable organic solvent (dichlorobenzene) and irradiated with ultrasonic waves. It is an available method.
  • the amount of carbon produced can be changed depending on the ultrasonic output, the ultrasonic irradiation time, the concentration of the active material 1, and the like.
  • the surface modification method using the carbon-based material 2 is a technology that has a high impact in practice as a surface nano-coating method for the active material 1 of the battery.
  • a circulation type device such as a circulation device, the positive electrode material 12 can be produced in large quantities.
  • the surface nano-coating of the active material 1 can provide conductivity and improve the stability of charge / discharge cycle characteristics. It was confirmed that the surface modification method for the carbon-based material 2 according to the present invention is effective in improving the charge / discharge characteristics of the positive electrode material.
  • the surface nano-coating of the positive electrode active material exhibits higher capacity and improves rate characteristics. This greatly contributes to increasing the capacity of a Li-ion secondary battery equipped with a positive electrode of LMO-LNMCO particles covered and protected by the carbon-based material 2 and manufacturing a high-capacity Li-ion secondary battery. .
  • a configuration example of the lithium ion secondary battery 40 as the fourth embodiment will be described with reference to FIG. 28 includes a negative electrode material 41, a positive electrode material 42, a negative electrode current collector 43, a positive electrode current collector 44, a separator 45, an electrolyte member 46, a main body housing member 47, a negative electrode.
  • a terminal 48 and a positive electrode terminal 49 are included (partially cut out).
  • the negative electrode of the Li ion secondary battery 40 has a negative electrode material 41, a negative electrode current collector 43, and a negative electrode terminal 48.
  • a negative electrode active material whose surface is covered with the carbon-based material 2 is provided on the negative electrode current collector 43.
  • the negative electrode material 41 for example, the electrode material 10 for negative electrode described in the first and second embodiments is used.
  • O-DCB3 is irradiated and generated by radical reaction of the o-DCB3.
  • a negative electrode active material such as Si nanoparticle 4 after ultrasonic carbon coating and heat treatment, a conductive agent such as acetylene black, a binder such as PVdf, Is applied to the negative electrode current collector 43 and dried.
  • a copper foil or the like band electrode having a thickness of about several tens of ⁇ m is used (see FIG. 15).
  • a foil plate such as Ni (nickel) or SUS (stainless steel) may be used in addition to the copper foil.
  • a negative electrode terminal 48 is connected to the negative electrode current collector 43.
  • the positive electrode of the Li ion secondary battery 40 has a positive electrode material 42, a positive electrode current collector 44, and a positive electrode terminal 49.
  • the positive electrode is configured by providing a positive electrode material 42 having a positive electrode active material containing lithium on a positive electrode current collector 44.
  • the positive electrode material 10 described in the third embodiment is used as the positive electrode material 42.
  • a positive electrode active material such as a C-LMO-LNMCO composite after ultrasonic carbon coating and heat treatment, a conductive agent such as acetylene black, PVdf, etc.
  • a positive electrode current collector 44 is applied to a positive electrode current collector 44 which is made into a slurry with an appropriate solvent and dried.
  • the positive electrode current collector 44 is made of an aluminum foil (band electrode) having a thickness of about several tens of ⁇ m, and a positive electrode terminal 49 is connected to the positive electrode current collector 44.
  • the positive electrode material 42 combined with the negative electrode material 41 is not limited to the positive electrode material 12 described in the third embodiment.
  • an active material such as LiCoO 2 , a conductive agent such as acetylene black, and a binder such as PVdf are slurried in an appropriate solvent. You may apply what was made to aluminum foil etc., and may dry it.
  • the positive electrode active material at that time includes, for example, a composite metal oxide containing Li, a polyanionic material such as a metal phosphate or metal silicate containing Li, a metal sulfide containing Li, or an organic polymer containing Li Substances are used.
  • the negative electrode active material used for the negative electrode material 41 includes, for example, Si particles and thin films, particles and thin films of alloy materials such as Sn, and oxides such as SiOx (0 ⁇ x ⁇ 2) in addition to the Si nanoparticles 4.
  • Si particles and thin films particles and thin films of alloy materials such as Sn, and oxides such as SiOx (0 ⁇ x ⁇ 2) in addition to the Si nanoparticles 4.
  • Lithium metal, graphite, carbon-based materials, metal oxides such as Nb, Fe, and Ti, metal nitrides, metal sulfides, and organic polymer materials may also be used.
  • the negative electrode active material may be composed of an element capable of occluding and releasing lithium ions and capable of being alloyed with lithium or / and an element compound capable of being alloyed with lithium.
  • Elements capable of alloying with lithium include Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi are mentioned.
  • the main body housing member 47 is arranged so that the negative electrode material 41 and the positive electrode material 42 face each other.
  • An electrolyte 46 is provided between the positive electrode and the negative electrode.
  • a separator 45 is provided at substantially the center of the electrolyte 46.
  • the separator 45 porous membrane
  • PE polyethylene
  • PP polypropylene
  • the electrolyte 46 includes a mixed solvent with a chain carbonate or an ether compound (aprotic organic solvent), a lithium salt composed of an anion having a large ionic radius, LiClO 4 , LiPF.
  • a non-aqueous solution in which 6 etc. is dissolved is used.
  • the electrolyte 46 includes an ionic liquid electrolyte in which a Li salt is dissolved in an ionic liquid composed of a cation such as 1-ethyl-3-methylimidazolium (EMI) and an anion such as (CF 3 SO 2 ) 2 N.
  • EMI 1-ethyl-3-methylimidazolium
  • the electrolyte 46 may be selected depending on the active material 1.
  • the body housing member 47 constitutes a battery can.
  • the battery can may have a cylindrical shape, a casing shape, or a flat shape.
  • a body member formed of a negative electrode material 41, a positive electrode material 42, a negative electrode current collector 43, a positive electrode current collector 44, a separator 45, and an electrolyte 46 is stored.
  • the above-mentioned main body member formed in a folded shape is stored.
  • the negative electrode material 41, the positive electrode material 42, and the like may be shared within the main body housing member 47.
  • a battery may be formed by forming a common electrode current collector coated with the negative electrode material 41 or the positive electrode material 42 and sandwiching the common electrode current collector between two electrode current collectors of the same polarity.
  • the electrolyte 46 and the separator 45 are interposed. Suitable for cylindrical battery cans.
  • different negative electrode materials 41 or positive electrode materials 42 may be arranged for one electrode current collector, and electrodes may be arranged in series to form a battery.
  • a battery having a high output voltage can be formed while being suitable for a battery-shaped battery can.
  • the negative electrode material is made of C—Si (X) y [h] Z [W] or the like, and the Si nanoparticles 4 The entire surface of the (negative electrode active material) or a part of the surface is covered with the carbon-based material 2.
  • the surface carbon nano-coating of the Si nanoparticles 4 imparts conductivity to the negative electrode, stabilizes the alloy-based negative electrode active material, and improves the stability of the charge / discharge cycle. Thereby, the high capacity
  • the positive electrode material is covered with the carbon-based material 2 on the entire surface or a part of the surface of the C-CMO-LNMCO-based CMO-LNMCO particles (positive electrode active material). ing.
  • the surface carbon nanocoating of CMO-LNMCO particles imparts conductivity to the positive electrode, stabilizes the positive electrode active material, and improves the stability of the charge / discharge cycle. Thereby, the high capacity
  • the third Li ion secondary battery includes a negative electrode and an electrolyte 46 provided between the positive electrode and the negative electrode.
  • the positive electrode material is formed by covering the entire surface or a part of the surface of C-CMO-LNMCO-based CMO-LNMCO particles (positive electrode active material) containing lithium with the carbon-based material 2.
  • the positive electrode material is provided on the positive electrode current collector 44.
  • the negative electrode material is composed of Si nanoparticles 4 whose entire surface or a part of the surface thereof is covered with the carbonaceous material 2.
  • the negative electrode is formed by providing a negative electrode material on the negative electrode current collector 43.
  • the surface carbon nano-coating of each of the Si nanoparticles 4 (negative electrode active material) and CMO-LNMCO particles (positive electrode active material) imparts conductivity to the negative electrode and the positive electrode, and the alloy-based negative electrode active material and the positive electrode active material. Stabilization is achieved, and the stability of the charge / discharge cycle can be improved. Thereby, the high capacity
  • the additive-free state refers to a state in which no active material 1 is added to o-dichlorobenzene.
  • the left diagram of FIG. 29 is an explanatory diagram showing a change in the color of o-dichlorobenzene and its ultraviolet-visible absorption spectrum during ultrasonic irradiation.
  • the vertical axis represents absorbance [arb.unit]
  • the horizontal axis represents wavelength [nm].
  • the photograph in the figure shows the ultrasonic wave of an o-dichlorobenzene-only liquid in the non-added state from the left side to the right side during six irradiation times of 20, 90, 180, 360, 540, and 1080 [min].
  • a time change of the color of the sample subjected to ultrasonic treatment is shown at an output of 300 [W] and a frequency of 40 [kHz].
  • the color of the sample in the ultrasonic treatment changed as transparent (color) ⁇ yellow ⁇ ocher ⁇ dark brown ⁇ gray ⁇ black etc. as the time of ultrasonic irradiation elapsed (black and white display: gray scale) (White ⁇ gray ⁇ black).
  • black and white display: gray scale gray scale
  • FIG. 29 is a graph showing an example of the relationship between the absorbance at each wavelength and the ultrasonic irradiation time.
  • the vertical axis represents absorbance [arb.unit]
  • the horizontal axis represents ultrasonic irradiation time [min].
  • the sample was extracted from the long wavelength side of the UV-visible absorption spectrum shown in FIG. 29A with a wavelength of 500 nm or more in which the absorbance [arb.unit] decreased and the carbon-based material 2 increased.
  • four samples having wavelengths of 500 [nm], 600 [nm], 700 [nm], and 800 [nm] are listed.
  • the upper limit of the ultrasonic irradiation time Y will be considered from this relationship graph.
  • the wavelengths are 500 [nm], 600 [nm], and 700 [nm] associated with the polymerization and the generation of the carbon-based material 2.
  • 800 [nm] it was confirmed by experiment that the ultrasonic wave irradiation time was about 16 to 18 hours and was almost saturated from the change with time of the absorption on the long wavelength side of the four samples.
  • the upper limit value Y 16 [h] (960 [min]) of the ultrasonic irradiation time is selected from the change in absorption time on the long wavelength side.
  • the upper limit value of the ultrasonic irradiation time depends on the type of the aromatic organic solvent and the frequency and output of the ultrasonic wave to be irradiated, and is not limited to this.
  • the type of active material 1 added to the aromatic organic solvent also affects.
  • the carbon-based material 2 is generated in a shorter time.
  • the range of ultrasonic irradiation conditions, the optimum conditions, and the like vary depending on the active material 1 and the aromatic organic solvent.
  • the present invention is applied to a novel surface coating method of an active material, a negative electrode material and a positive electrode material provided with a surface-coated active material, and further applied to a secondary battery including these negative electrode material and positive electrode material. Is preferred.

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Abstract

La présente invention vise à proposer une batterie secondaire ayant une capacité élevée par invention d'un procédé de formation d'une matière d'électrode. Cette matière d'électrode comprend à la fois une matière active qui constitue une matière d'électrode négative ou positive ou similaire, et une substance carbonée qui recouvre la surface de la matière active, la substance carbonée étant une substance formée par irradiation d'un solvant organique aromatique, tel que le o-dichlorobenzène, par une onde ultrasonore à une fréquence de 40 kHz et une émission de 200 à 300 W avec un temps d'irradiation de 2 à 9h, puis réalisation de la réaction radicalaire du solvant organique aromatique. Par cette configuration, la substance carbonée peut pénétrer n'importe où entre les cristaux de la matière active pour y adhérer. Ainsi, une matière d'électrode ayant une excellente conductivité électrique peut être fournie. En outre, des matières d'électrode négative et positive stables dans lesquelles l'affaissement structural d'une matière active est réduit au minimum peuvent être fournies. Incidemment, l'affaissement structural d'une matière active est provoqué par la dilatation et le rétrécissement de celle-ci qui sont associés à l'introduction/extraction d'ions Li.
PCT/JP2012/002074 2011-03-28 2012-03-26 Matière d'électrode, son procédé de fabrication, électrode, batterie secondaire et véhicule Ceased WO2012132387A1 (fr)

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JP2014099368A (ja) * 2012-11-15 2014-05-29 Sumitomo Metal Mining Co Ltd 非水電解質二次電池用正極活物質およびその製造方法
KR101839000B1 (ko) * 2013-03-15 2018-04-26 나노 원 머티리얼즈 코포레이션. 배터리 제품에 이용되는 층상 리튬혼합금속 산화물의 미세분말, 초미세분말, 및 나노분말의 산업생산화를 위한 착화합물 전구체 제제 방법
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