US20130224581A1 - Negative electrode of power storage device and power storage device - Google Patents

Negative electrode of power storage device and power storage device Download PDF

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US20130224581A1
US20130224581A1 US13/597,675 US201213597675A US2013224581A1 US 20130224581 A1 US20130224581 A1 US 20130224581A1 US 201213597675 A US201213597675 A US 201213597675A US 2013224581 A1 US2013224581 A1 US 2013224581A1
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negative electrode
storage device
power storage
active material
metal
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Yumiko SAITO
Rie Yokoi
Mayumi MIKAMI
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Semiconductor Energy Laboratory Co Ltd
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Semiconductor Energy Laboratory Co Ltd
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Assigned to SEMICONDUCTOR ENERGY LABORATORY CO., LTD. reassignment SEMICONDUCTOR ENERGY LABORATORY CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SAITO, YUMIKO, MIKAMI, MAYUMI, YOKOI, RIE
Publication of US20130224581A1 publication Critical patent/US20130224581A1/en
Priority to US14/937,975 priority Critical patent/US10614967B2/en
Priority to US16/840,659 priority patent/US10998141B2/en
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H01G11/32—Carbon-based
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
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    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • 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
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    • H01M4/137—Electrodes based on electro-active polymers
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    • H01M4/386—Silicon or alloys based on silicon
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
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    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a negative electrode of a power storage device and a power storage device having the negative electrode.
  • Li-ion secondary batteries which have high energy performance have attracted attention.
  • the Li-ion secondary battery which is compact but can have a large capacity, has already been mounted on a portable information terminal such as a mobile phone or a laptop personal computer, thereby contributing to miniaturization of products.
  • the power storage device basically has a structure in which an electrolyte is provided between a positive electrode and a negative electrode. It is known that each of the positive electrode and the negative electrode includes a current collector and an active material provided over the current collector. For example, in a Li-ion secondary battery, a material capable of storing and releasing Li ions is used as an active material.
  • a graphite-based carbon material which is mainly used as the negative electrode active material, has the theoretical capacity of 372 mAh/g and has already been put to practical use with a capacity close to the theoretical capacity. Thus, an active material with a higher capacity (charge capacity) is required.
  • a material containing a semimetal, a semimetal compound, a metal, or a metal compound is given as an example of a material having a higher capacity than a graphite-based carbon material when it is used as a negative electrode active material for a power storage device.
  • silicon (Si) is known to have a higher capacity than a graphite-based carbon material.
  • Patent Document 1 discloses a negative electrode of a Li-ion secondary battery in which a fiber shaped carbon material, silicon, and a silicon compound are used in addition to a graphite-based carbon material.
  • Patent Document 2 discloses a Li-ion secondary battery in which a graphite-based carbon material and a metal-carbon composite material are used.
  • An object of one embodiment of the invention is to provide a negative electrode active material with a higher capacity.
  • a mixture of amorphous polycyclic aromatic hydrocarbons (PAHs) and at least one of a carrier ion storage metal, a carrier ion storage alloy, a metal compound, Si, Sb, and SiO 2 is used as a negative electrode active material.
  • carrier ion storage metal means a metal which can store and release carrier ions in a power storage device.
  • carrier ion storage alloy means an alloy which can store and release carrier ions in a power storage device.
  • amorphous PAHs The theoretical capacity of amorphous PAHs is 1116 mAh/g and an experimental capacity thereof is 680 mAh/g, both of which greatly exceed 372 mAh/g that is the theoretical capacity of a graphite-based carbon material. Therefore, in the case where amorphous PAHs are used, a negative electrode active material can have a higher capacity than in the case where a graphite-based carbon material is used.
  • the capacity of the negative electrode active electrode can be higher than in the case where only the amorphous PAHs are used.
  • One embodiment of the invention is a negative electrode of a power storage device comprising a negative electrode active material containing amorphous PAHs and at least one of a carrier ion storage metal, a carrier ion storage alloy, a metal compound, Si, Sb, and SiO 2 ; and a current collector.
  • the carrier ion storage metal may be any one of Sn, Al, Zn, and Bi.
  • the carrier ion storage alloy may be any one of alloys expressed by a Sn-M alloy (M is Fe, Co, Mn, V, or Ti).
  • M is Fe, Co, Mn, V, or Ti.
  • a Sn compound or a metal compound used as a positive electrode material in a state where carrier ions are released (a decarrierionized state) can be used.
  • the Sn compound may be any one of SnO 2 , Sn 2 P 2 O 7 , and SnPBO 6 .
  • the metal compound used as the positive electrode material in a state where carrier ions are released (a decarrierionized state) may be any one of SnPO 4 ClCoO, NiO, MnO 2 , and FePO 4 .
  • the carrier ion may be either of a Li ion and a Na ion.
  • amorphous PAHs may have a spherical shape.
  • At least one of a metal, a metal compound, Si, Sb, and SiO 2 may be attached to the surfaces of the amorphous PAHs.
  • the amorphous PAHs may contain at least one of a metal, a metal compound, Si, Sb, and SiO 2 at greater than or equal to at 1 wt % and less than or equal to 50 wt %.
  • one embodiment of the invention is a power storage device including the negative electrode, a positive electrode, and an electrolyte solution containing an electrolyte.
  • a negative electrode active material with a higher capacity can be provided.
  • FIGS. 1A to 1C are schematic views of examples of a negative electrode active material and a negative electrode.
  • FIGS. 2A and 2B are a plan view and a cross-sectional view illustrating one embodiment of a power storage device.
  • FIG. 3 is a diagram illustrating application modes of a power storage device.
  • FIGS. 4A and 4B are scanning electron micrograph images each illustrating an example of a negative electrode active material.
  • FIGS. 5A and 5B are scanning electron micrograph images each illustrating an example of a negative electrode active material.
  • FIG. 6 shows evaluation results of an example of a negative electrode.
  • FIG. 7 shows evaluation results of an example of a negative electrode.
  • FIG. 8 shows evaluation results of an example of a negative electrode.
  • a negative electrode active material for a power storage device which is one embodiment of the invention, and a manufacturing method thereof will be described with reference to FIGS. 1A to 1C .
  • the negative electrode active material 100 includes amorphous PAHs 101 and a fine particle 102 formed of any one of a metal, a metal compound, Si, Sb, and SiO 2 .
  • the negative electrode active material 100 may include a secondary particle 103 in which a plurality of the fine particles 102 is aggregated.
  • amorphous PAHs 101 PAHs with a hydrogen/carbon atomic ratio (hereinafter referred to as a H/C ratio) of 0.05 or more and 0.5 or less are used.
  • a H/C ratio hydrogen/carbon atomic ratio
  • PAHs with a H/C ratio of 0.05 or more and 0.5 or less for example, a polyacenic material or a hard carbon-based material can be used.
  • the polyacenic material has a higher capacity (about 850 mAh/g) than the graphite-based carbon material.
  • the hard carbon-based material has a higher capacity (about 400 mAh/g to 700 mAh/g) than the graphite-based carbon material and has discharge characteristics such that voltage uniformly descends to a discharge end voltage.
  • any of these materials is preferably used for the negative electrode active material because in that case a power storage device has a high energy density.
  • the amorphous PAHs 101 When the amorphous PAHs 101 have a spherical shape, variation in the contact area with other constituent elements of the negative electrode can be reduced.
  • the amorphous PAHs preferably have a spherical shape because variation in resistance in the negative electrode active layer can be reduced; further, because there is little abrasion when it is transferred, high-density filling is easily achieved, and fluidity in the case of being mixed with other constituent elements of the negative electrode can be improved.
  • a grain diameter of the amorphous PAHs 101 is preferably 100 ⁇ m or less.
  • spherical shape does not necessarily mean an accurate spherical shape.
  • a substantially spherical shape for example, the smallest diameter is greater than or equal to 70% and less than 100% of the longest diameter
  • a deformed spherical shape for example, a spherical shape with a projection on its surface, and an elliptical spherical shape are included.
  • a spherical polyacenic material is used for the amorphous PAHs 101 .
  • a metal, a metal compound, Si, Sb, or SiO 2 is mixed to the amorphous PAHs 101 .
  • a carrier ion storage metal is used as the metal to be mixed.
  • a carrier ion storage alloy or a metal compound is used as the metal compound to be mixed.
  • alkali metal ions such as Li ions or sodium (Na) ions, alkaline earth metal ions, beryllium (Be) ions, magnesium (Mg) ions, or the like can be used.
  • Li ions as the carrier ions enables a power storage device to have a small memory effect, a high energy density, a high charge/discharge capacity, and a high output voltage, which is preferable.
  • Na ions that are abundant in resources are preferably used because the cost of manufacturing a power storage device can be reduced.
  • Li ions are used as the carrier ions.
  • carrier ion storage metal to be mixed a metal having properties of storing carrier ions, for example, Sn, Al, Zn, or Bi can be used.
  • an alloy having properties of storing carrier ions for example, an alloy represented by Sn-M (M is Fe, Co, Mn, V, or Ti) can be used.
  • a Sn compound or a metal compound used as a positive electrode material in a state where carrier ions are released can be used.
  • Sn compound for example, SnO 2 , Sn 2 P 2 O 7 , SnPBO 6 , or SnPO 4 Cl can be used.
  • the metal compound used as a positive electrode material in a state where carrier ions are released a decarrierionized state
  • a stable substance even in the absence of carrier ions among substances that can be used as a positive electrode active material, for example, CoO, NiO, MnO 2 , NiMnO 4 , or FePO 4 can be used.
  • the fine particle 102 is a particle composed of a metal, a metal compound, Si, Sb, or SiO 2 .
  • the fine particle 102 preferably has a grain diameter of, for example, 1 ⁇ m or less in order to increase the efficiency of reaction with the carrier ion.
  • the fine particle 102 composed of a metal, a metal compound, Si, Sb, or SiO 2 may be, but is not necessarily, attached to the outer surface of the amorphous PAHs 101 .
  • the secondary particle 103 may be generated from the particle 102 composed of a metal, a metal compound, Si, Sb, or SiO 2 .
  • the secondary particle 103 may be, but is not necessarily, attached to the outer surface of the amorphous PAHs 101 .
  • the amorphous PAHs 101 contain any one of a metal, a metal compound, Si, Sb, and SiO 2 at greater than or equal to 1 wt % and less than or equal to 50 wt %, preferably greater than or equal to 1 wt % and less than or equal to 30 wt %. It is not preferable that the amount of a metal, a metal compound, Si, Sb, or SiO 2 be too small, because the effect of making the power storage device having a high capacity is decreased. Also, it is not preferable that the amount of a metal, a metal compound, Si, Sb, or SiO 2 be too large, because electric conductivity of the negative electrode active material is too low. In this embodiment, the amorphous PAHs 101 contain SiO 2 at greater than or equal to 1 wt % and less than or equal to 30 wt %.
  • FIGS. 1B and 1C An example of a negative electrode 200 of a power storage device that is one embodiment of the present invention will be described with reference to FIGS. 1B and 1C .
  • the negative electrode 200 in FIG. 1B includes the negative electrode active material 100 , a conduction auxiliary agent 120 , and a binder (not shown in FIG. 1B ) over a negative electrode current collector 130 .
  • a conductive material such as copper (Cu), titanium (Ti), aluminum (Al), or stainless steel, which is processed into a foil shape, a plate shape, a net shape, or the like can be used for the negative electrode current collector 130 .
  • An electron-conductive material which does not cause chemical change in the power storage device is used for the conduction auxiliary agent 120 .
  • graphite a carbon particle; a carbon fiber; a metal material such as Cu, nickel (Ni), Al, or silver (Ag); or powder, fiver, and the like of mixtures thereof can be used.
  • acetylene black that is one of carbon particles is used.
  • the binder exists between the negative electrode active material 100 , the conduction auxiliary agent 120 , and the current collector 130 , and these substances are bonded one another by the binder.
  • the binder polysaccharides such as starch, carboxymethyl cellulose, hydroxypropyl cellulose, regenerated cellulose, and diacetyl cellulose; vinyl polymers such as polyvinyl chloride, polyethylene, polypropylene, polyvinyl alcohol, polyvinyl pyrrolidone, polytetrafluoroethylene, polyvinylidene fluoride, ethylene-propylene-diene monomer (EPDM) rubber, sulfonated EPDM rubber, styrene-butadiene rubber, butadiene rubber, and fluorine rubber; polyether such as polyethylene oxide; and the like can be given.
  • PVdF is used.
  • the negative electrode active material layer may be predoped with carrier ions.
  • carrier ions Li ions are used as the carrier ions
  • a Li layer is formed on a surface of the negative electrode active material layer by a sputtering method.
  • Li foil is provided on the surface of the negative electrode active material layer, whereby the negative electrode active material layer can be predoped with Li.
  • graphene or multilayer graphene 121 may be used instead of the conduction auxiliary agent 120 and the binder.
  • the use of graphene or multilayer graphene 121 can suppress adverse effects (pulverization of the negative electrode active material 100 and separation of the negative electrode active material layer) of expansion and contraction of the negative electrode active material 100 due to storing and releasing of carrier ions.
  • graphene or the multilayer graphene 121 stores carrier ions and functions as a negative electrode active material and thus a negative electrode with a higher capacity can be obtained.
  • materials of amorphous PAHs are prepared.
  • a polyacenic material for example, a phenol resin can be used for raw materials of the polyacenic material.
  • a baking temperature at the time of baking that is to be described later can be low; thus, productivity is improved.
  • a hard carbon-based material for example, a furfuryl alcohol resin, a saccharide such as saccharose or cellulose can be used for raw materials of the hard carbon-based material.
  • cleaning is preferably performed to remove an organic impurity attached to the amorphous PAHs 101 .
  • ultrasonic cleaning in an organic solvent may be conducted.
  • a metal, a metal compound, Si, Sb, or SiO 2 is mixed to the amorphous PAHs 101 .
  • a metal, a metal compound, Si, Sb, or SiO 2 the description of FIG. 1A can be referred to.
  • a polyacenic material is used as the amorphous PAHs 101 , and a spherical phenol resin is used for the raw materials of the polyacenic material.
  • a fine particle of SiO 2 is mixed to the spherical phenol resin.
  • a method for mixing there is no limitation on a method for mixing, and for example, a dry-mixing method can be performed.
  • a method in which the shape of the resin can be maintained is preferably employed; for example, mixing with the use of a rotatable roller is preferably employed.
  • a mixture of the material of the amorphous PAHs 101 and at least one of a metal, a metal compound, Si, Sb, and SiO 2 is baked.
  • the baking is preferably performed under an inert atmosphere, for example, a nitrogen atmosphere.
  • the temperature and time at the baking may be set under sufficient conditions for carbonization of the amorphous PAHs 101 .
  • the baking temperature can be set to greater than or equal to 600° C. and less than or equal to 800° C.
  • the negative electrode active material 100 that is one embodiment of the invention can be manufactured.
  • the negative electrode active material 100 , the conduction auxiliary agent 120 , and the binder are mixed using a solvent, so that slurry is formed.
  • a solvent for example, an organic solvent such as N-methyl-2-pyrrolidone (NMP) can be used.
  • graphene or the multilayer graphene 121 may be used instead of the conduction auxiliary agent 120 and the binder.
  • graphene refers to a one-atom-thick sheet of carbon molecules having sp 2 bonds.
  • multilayer graphene refers to a stack of 2 to 100 sheets of graphene, and may contain less than or equal to 30 at. % of an element other than carbon, such as oxygen or hydrogen. Alternatively, the multilayer graphene may contain less than or equal to 15 at. % of an element other than carbon and hydrogen.
  • an alkali metal such as Li, Na, or potassium (K) may be added to graphene or multilayer graphene.
  • the slurry is applied onto the negative electrode current collector 130 .
  • An anchor coat may be applied before the slurry is applied to the negative electrode current collector 130 so as to improve adhesion between the negative electrode current collector 130 and the negative electrode active material 100 .
  • the slurry containing the negative electrode active material 100 may be applied to one surface of the negative electrode current collector 130 as shown in FIGS. 1B and 1C or both surfaces thereof.
  • the negative electrode 200 is further dried.
  • the negative electrode 200 that is one embodiment of the invention can be manufactured.
  • FIGS. 2A and 2B an example of a power storage device that is one embodiment of the present invention will be described with reference to FIGS. 2A and 2B .
  • the power storage device that is one embodiment of the present invention includes at least a positive electrode, a negative electrode, a separator, and an electrolyte solution.
  • the negative electrode is the one described in Embodiment 1.
  • the electrolyte is a nonaqueous solution containing an electrolyte salt or a solution containing an electrolyte salt.
  • Any electrolyte salt can be used as the electrolyte salt as long as it contains carrier ions such as alkali metal ions, alkaline earth metal ions, Be ions, or Mg ions.
  • the alkali metal ions include Li ions, Na ions, and K ions.
  • the alkaline earth metal ions include calcium (Ca) ions, strontium (Sr) ions, and barium (Ba) ions.
  • the electrolyte salt is an electrolyte salt containing Li ions (hereinafter, referred to as a Li-containing electrolyte salt).
  • the power storage device can be a secondary battery or a capacitor. Further, an electric double layer capacitor can be obtained by using only a solvent for an electrolyte solution without using the electrolyte salt.
  • FIG. 2A shows a structural example of a power storage device 351 .
  • FIG. 2B is a cross-sectional view along dashed dotted line X-Y in FIG. 2A .
  • the power storage device 351 shown in FIG. 2A includes a power storage cell 355 in an exterior member 353 .
  • the power storage device 351 further includes terminal portions 357 and 359 which are connected to the power storage cell 355 .
  • a laminate film, a polymer film, a metal film, a metal case, a plastic case, or the like can be used.
  • the power storage cell 355 includes a negative electrode 363 , a positive electrode 365 , a separator 367 between the negative electrode 363 and the positive electrode 365 , and an electrolyte 369 with which the exterior member 353 is filled.
  • the negative electrode 363 is the one described in Embodiment 1.
  • the negative electrode current collector 371 is connected to the terminal portion 359 .
  • a positive electrode current collector 375 is connected to the terminal portion 357 .
  • terminal portions 357 and 359 each partly extend outside the exterior member 353 .
  • the positive electrode layer 365 is formed to include a positive electrode current collector 375 and a positive electrode active material layer 377 .
  • the positive electrode active material layer 377 is formed on one or both surfaces of the positive electrode current collector 375 .
  • the positive electrode 365 may include a binder, a conduction auxiliary agent, and the like besides the positive electrode current collector 375 and the positive electrode active material layer 377 .
  • the external shape of the power storage device 351 is not limited thereto.
  • a power storage device having any of a variety of shapes, such as a button power storage device, a cylindrical power storage device, or a rectangular power storage device can be used as the power storage device 351 .
  • the structure where the positive electrode, the negative electrode, and the separator are stacked is described in this embodiment, a structure where the positive electrode, the negative electrode, and the separator are rolled may be employed.
  • a conductive material such as Al or stainless steel which is processed into a foil shape, a plate shape, a net shape, or the like can be used.
  • a conductive layer provided by deposition separately on a substrate and then separated from the substrate can be used as the positive electrode current collector 375 .
  • the positive electrode active material layer 377 can be formed using LiFeO 2 , LiCoO 2 , LiNiO 2 , LiMnO 4 , LiFePO 4 , LiCoPO 4 , LiNiPO 4 , LiMn 2 PO 4 , V 2 O 5 , MnO 2 , or another Li compound as a material.
  • carrier ions are alkali metal ions other than Li ions, alkaline earth metal ions, Be ions, or Mg ions
  • the positive electrode active material layer 377 can be formed using, instead of Li in the above Li compounds, an alkali metal (e.g., Na or K), an alkaline earth metal (e.g., Ca, Sr, or Ba), Be, or Mg.
  • an alkali metal e.g., Na or K
  • an alkaline earth metal e.g., Ca, Sr, or Ba
  • Be or Mg.
  • carrier ions are NaNi 0.5 Mn 0.5 O 2 can be used.
  • the positive electrode active material layer 377 is formed over the positive electrode current collector 375 by a coating method or a physical vapor deposition method (e.g., a sputtering method), whereby the positive electrode 365 can be formed.
  • a coating method e.g., a sputtering method
  • the positive electrode 365 is formed in such a manner that a paste in which a conduction auxiliary agent (e.g., acetylene black), a binder (e.g., PVDF), or the like is mixed with any of the above materials for the positive electrode active material layer 377 is applied to the positive electrode current collector 375 and dried.
  • the positive electrode 365 is preferably molded by applying pressure as needed.
  • the positive electrode active material layer 377 may be formed using a paste of a mixture of the positive electrode active material and graphene or multilayer graphene instead of a conductive auxiliary agent and a binder.
  • the use of graphene or multilayer graphene instead of a conductive auxiliary agent and a binder leads to a reduction in amount of the conductive auxiliary agent and the binder in the positive electrode 365 .
  • the weight of the positive electrode 365 can be reduced; accordingly, the charge/discharge capacity of the power storage device per unit weight of the negative electrode can be increased.
  • positive electrode active material or “negative electrode active material” refers only to a material that relates to storing and releasing of ions functioning as carriers.
  • the active material layer collectively refers to the materials of the active material layer, that is, a substance that is actually an “active material”, a conductive auxiliary agent, a binder, and the like.
  • the electrolyte 369 is a nonaqueous solution containing an electrolyte salt or a solution containing an electrolyte salt.
  • a Li-containing electrolyte salt in which Li ions as carrier ions can transfer and stably exist is used.
  • the Li-containing electrolyte salt includes LiClO 4 , LiAsF 6 , LiBF 4 , LiPF 6 , and Li(C 2 F 5 SO 2 ) 2 N.
  • carrier ions are alkali metal ions other than Li ions or alkaline earth metal ions
  • alkali metal salt e.g., Na salt or K salt
  • alkaline earth metal salt e.g., Ca salt, Sr salt or Ba salt
  • Be salt Mg salt, or the like
  • Na ions are used as the carrier ions
  • NaPF 6 , NaClO 4 , or the like can be used as the solute (electrolyte salt).
  • the electrolyte 369 is preferably a nonaqueous solution containing an electrolyte salt. That is, as a solvent of the electrolyte 369 , an aprotic organic solvent is preferably used.
  • the aprotic organic solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ⁇ -butyrolactone, acetonitrile, dimethoxyethane, and tetrahydrofuran, and one or more of these materials can be used.
  • the aprotic organic solvent one ionic liquid or a plurality of ionic liquids may be used. Owing to non-flammability and non-volatility of an ionic liquid, it is possible to suppress explosion, inflammation, and the like of the power storage device 351 at the time when the internal temperature of the power storage device 351 rises, resulting in improvement in safety.
  • the electrolyte 369 When a gelled high-molecular material containing an electrolyte salt is used as the electrolyte 369 , safety against liquid leakage and the like is improved and the power storage device 351 can be thinner and more lightweight.
  • the gelled high-molecular material include a silicon gel, an acrylic gel, an acrylonitrile gel, polyethylene oxide, polypropylene oxide, and a fluorine-based polymer.
  • electrolyte 369 a solid electrolyte such as Li 3 PO 4 can be used.
  • an insulating porous material is used as the separator 367 .
  • paper; nonwoven fabric; a glass fiber; a synthetic fiber containing nylon (polyamide), vinylon (polyvinyl alcohol based fiber), polyester, acrylic, polyolefin, or polyurethane; or ceramics may be used.
  • a material which does not dissolve in the electrolyte 369 should be selected.
  • the power storage device that is one embodiment of the present invention is a Li-ion capacitor
  • a material capable of reversibly storing and releasing one of or both Li ions and anions may be used.
  • the material include active carbon, graphite, a conductive polymer, and a polyacenic material.
  • the power storage device that is one embodiment of the present invention can be used for power supplies of a variety of electric and electronic devices which are operated with power.
  • electric and electronic devices each utilizing the power storage device are as follows: display devices, lighting devices, desktop personal computers and laptop personal computers, image reproduction devices which reproduce still images and moving images stored in recording media such as digital versatile discs (DVDs), mobile phones, portable game machines, portable information terminals, tablet terminals, e-book readers, video cameras, digital still cameras, high-frequency heating appliances such as microwave ovens, electric rice cookers, electric washing machines, air-conditioning systems such as air conditioners, electric refrigerators, electric freezers, electric refrigerator-freezers, freezers for preserving DNA, and medical electrical and electronic equipment such as dialyzers.
  • moving objects driven by an electric motor using electric power from a power storage device are also included in the category of electric and electronic devices.
  • electric vehicles, hybrid vehicles which include both an internal-combustion engine and a motor, motorized bicycles including motor-assisted bicycles, and the like can be given.
  • the power storage device that is one embodiment of the present invention can be used as a power storage device for supplying enough electric power for almost the whole power consumption (such a power storage device is referred to as a main power supply).
  • the power storage device that is one embodiment of the present invention can be used as a power storage device which can supply electric power to the electric and electronic devices when the supply of power from the main power supply or a commercial power supply is stopped (such a power storage device is referred to as an uninterruptible power supply).
  • the power storage device that is one embodiment of the present invention can be used as a power storage device for supplying electric power to the electric and electronic devices at the same time as the electric power supply from the main power supply or a commercial power supply (such a power storage device is referred to as an auxiliary power supply).
  • FIG. 3 illustrates specific structures of the electric and electronic devices.
  • a display device 1000 is an example of an electronic device including a power storage device 1004 that is one embodiment of the present invention.
  • the display device 1000 corresponds to a display device for TV broadcast reception and includes a housing 1001 , a display portion 1002 , speaker portions 1003 , the power storage device 1004 , and the like.
  • the power storage device 1004 that is one embodiment of the present invention is provided in the housing 1001 .
  • the display device 1000 can receive electric power from a commercial power supply. Alternatively, the display device 1000 can use electric power stored in the power storage device 1004 .
  • the display device 1000 can be operated with use of the power storage device 1004 that is one embodiment of the present invention as an uninterruptible power supply even when electric power cannot be supplied from the commercial power supply due to power failure or the like.
  • a semiconductor display device such as a liquid crystal display device, a light-emitting device provided with a light-emitting element such as an organic EL element in each pixel, an electrophoresis display device, a digital micromirror device (DMD), a plasma display panel (PDP), a field emission display (FED), and the like can be used for the display portion 1002 .
  • a light-emitting device provided with a light-emitting element such as an organic EL element in each pixel
  • an electrophoresis display device such as an organic EL element in each pixel
  • DMD digital micromirror device
  • PDP plasma display panel
  • FED field emission display
  • the display device includes, in its category, all of information display devices for personal computers, advertisement displays, and the like other than TV broadcast reception.
  • an installation lighting device 1100 is an example of an electric device including a power storage device 1103 that is one embodiment of the present invention.
  • the lighting device 1100 includes a housing 1101 , a light source 1102 , a power storage device 1103 , and the like.
  • FIG. 3 illustrates the case where the power storage device 1103 is provided in a ceiling 1104 on which the housing 1101 and the light source 1102 are installed; alternatively, the power storage device 1103 may be provided in the housing 1101 .
  • the lighting device 1100 can receive electric power from a commercial power supply. Alternatively, the lighting device 1100 can use electric power stored in the power storage device 1103 .
  • the lighting device 1103 can be operated with the use of the power storage device 1103 that is one embodiment of the present invention as an uninterruptible power supply even when electric power cannot be supplied from the commercial power supply due to power failure or the like.
  • the power storage device that is one embodiment of the present invention can be used in an installation lighting device provided in, for example, a wall 1105 , a floor 1106 , a window 1107 , or the like other than the ceiling 1104 .
  • the power storage device can be used in a tabletop lighting device and the like.
  • an artificial light source which emits light artificially by using power can be used.
  • discharge lamps such as an incandescent lamp and a fluorescent lamp, and a light-emitting element such as an LED and an organic EL element are given as examples of the artificial light source.
  • an air conditioner including an indoor unit 1200 and an outdoor unit 1204 is an example of an electric device including a power storage device 1203 that is one embodiment of the present invention.
  • the indoor unit 1200 includes a housing 1201 , a ventilation duct 1202 , the power storage device 1203 , and the like.
  • FIG. 3 illustrates the case where the power storage device 1203 is provided in the indoor unit 1200 ; alternatively, the power storage device 1203 may be provided in the outdoor unit 1204 . Further alternatively, the power storage devices 1203 may be provided in both the indoor unit 1200 and the outdoor unit 1204 .
  • the air conditioner can receive power from the commercial power supply. Alternatively, the air conditioner can use power stored in the power storage device 1203 .
  • the air conditioner can be operated with the use of the power storage device 1203 that is one embodiment of the present invention as an uninterruptible power supply even when power cannot be supplied from a commercial power supply due to power failure or the like.
  • the power storage device that is one embodiment of the present invention can be used in an air conditioner in which the functions of an indoor unit and an outdoor unit are integrated in one housing.
  • an electric refrigerator-freezer 1300 is an example of an electric device including a power storage device 1304 that is one embodiment of the present invention.
  • the electric refrigerator-freezer 1300 includes a housing 1301 , a door for a refrigerator 1302 , a door for a freezer 1303 , and the power storage device 1304 .
  • the power storage device 1304 is provided in the housing 1301 in FIG. 3 .
  • the electric refrigerator-freezer 1300 can receive power from a commercial power supply.
  • the electric refrigerator-freezer 1300 can use power stored in the power storage device 1304 .
  • the electric refrigerator-freezer 1300 can be operated with the use of the power storage device 1304 that is one embodiment of the present invention as an uninterruptible power supply even when power cannot be supplied from a commercial power supply due to power failure or the like.
  • a high-frequency heating apparatus such as a microwave and an electric device such as an electric rice cooker require high electric power in a short time.
  • the tripping of a breaker of a commercial power supply in use of electric devices can be prevented by using the power storage device that is one embodiment of the present invention as an auxiliary power supply for supplying electric power which cannot be supplied enough by a commercial power supply.
  • power can be stored in the power storage device, whereby the usage rate of power can be reduced in a time period when the electric and electronic devices are used.
  • a proportion of the amount of power which is actually used to the total amount of power which can be supplied from a commercial power supply source such a proportion referred to as a usage rate of power
  • power can be stored in the power storage device 1304 in night time when the temperature is low and the door for a refrigerator 1302 and the door for a freezer 1303 are not often opened or closed.
  • the power storage device 1304 is used as an auxiliary power supply; thus, the usage rate of power in daytime can be reduced.
  • a tablet terminal 1400 is an example of an example of an electronic device including a power storage device 1403 that is one embodiment of the present invention.
  • the tablet terminal 1400 includes a housing 1401 , a housing 1402 , a power storage device 1403 , and the like.
  • the housings 1401 and 1402 each have a display portion having a touch panel function. By touching the display portion with a finger or the like, contents displayed on the display portion can be controlled. Further, the tablet terminal 1400 can be folded with the housings 1401 and 1402 and the display portion placed inward; thus, the tablet terminal 1400 can be compact and the display portion can be protected.
  • the power storage device 1403 that is one embodiment of the invention, the tablet terminal 1400 can be compact and used as a mobile application for a long period.
  • a negative electrode active material for a power storage device which is one embodiment of the present invention, was actually manufactured, and the results of evaluating the characteristics are described with reference to FIGS. 4A and 4B , FIGS. 5A and 5B , FIG. 6 , FIG. 7 , and FIG. 8 .
  • a spherical phenol resin (“Maririn” HF-008; Gun Ei Chemical Industry Co., Ltd.) was used as a raw material of amorphous PAHs.
  • An average grain diameter measured with a particle size analyzer was 9.6 ⁇ m.
  • SiO 2 was mixed to the raw material of the amorphous PAHs.
  • SiO 2 nanopowder manufactured by Sigma-Aldrich Corporation
  • SiO 2 nanopowder manufactured by Sigma-Aldrich Corporation
  • ultrasonic cleaning was conducted in acetone so as to remove organic impurities attached to the spherical phenol resin.
  • SiO 2 nanopowder was added to the cleaned spherical phenol resin, and dry-mixing was performed using a rotatable roller.
  • the additive amounts of SiO 2 nanopowder to 5 g of the spherical phenol resin were 0 wt % (0 g, (reference example), 1 wt % (0.05 g), 10 wt % (0.50 g), 20 wt % (1.00 g), and 30 wt % (1.50 g).
  • the mixture of the spherical phenol resin and SiO 2 nanopowder were baked so as to be a negative electrode active material.
  • the baking was performed at 700° C. using a muffle furnace under a nitrogen atmosphere (N 2 , 5 L/min) for 10 hours.
  • Table 1 shows the weight yield after the baking.
  • FIGS. 4A and 4B and FIGS. 5A and 5B each show scanning electron micrographs of the negative electrode active materials manufactured in the above manner.
  • FIG. 4A shows the negative electrode active material in which 0 wt % of SiO 2 nanopowder (reference example) was added to the spherical phenol resin
  • FIG. 4B shows the negative electrode active material in which 1 wt % of SiO 2 nanopowder was added to the spherical phenol resin
  • FIG. 5A shows the negative electrode active material in which 20 wt % of SiO 2 nanopowder was added to the spherical phenol resin
  • FIG. 4A shows the negative electrode active material in which 0 wt % of SiO 2 nanopowder (reference example) was added to the spherical phenol resin
  • FIG. 4B shows the negative electrode active material in which 1 wt % of SiO 2 nanopowder was added to the spherical phenol resin
  • FIG. 5A
  • FIG. 5B shows the negative electrode active material in which 30 wt % of SiO 2 nanopowder was added to the spherical phenol resin.
  • the state where SiO 2 nanopowder was attached to the outer surface of the spherical phenol resin was observed in each of FIG. 4B , and FIGS. 5A and 5B .
  • Negative electrodes were manufactured using the above-described negative electrode active materials.
  • acetylene black was used as a conduction auxiliary agent
  • PVdF was used as a binder
  • Cu foil was used as a current collector.
  • the combination ratio of negative electrode active material to acetylene black and PVdF was set to 82:8:10 (wt %).
  • the negative electrode active material and PVdF were mixed using a homogenizer with NMP used as a solvent; then acetylene black was added thereto to be mixed, whereby slurry was formed by adjusting the viscosity using the NMP.
  • NMP used as a solvent
  • the slurry was applied to the Cu foil current collector.
  • the Cu foil current collector and the slurry were dried at 70° C. for 15 minutes using a circulation drier. This was punched into a round hole with a diameter of 16.15 mm and baked at 170° C. for 10 hours using a vacuum furnace, whereby the negative electrode was obtained.
  • Table 2 shows the thicknesses and the densities of thus manufactured negative electrodes.
  • the negative electrodes each having a similar thickness and density were manufactured under conditions as shown in Table 2.
  • a cell was formed using thus manufactured negative electrode as a working electrode and using Li metal with a diameter of 15 mm as the opposite electrode.
  • a glass fiber filter was used as a separator, and an electrolyte in which 1 mol/L lithium hexafluorophosphate (LiPF 6 ) was dissolved in a mixed solution of ethylene carbonate (EC) and ethylmethyl carbonate (EMC) (the volume ratio was 3:7) was used.
  • LiPF 6 lithium hexafluorophosphate
  • EMC ethylmethyl carbonate
  • FIG. 6 , FIG. 7 , FIG. 8 , and Table 3 each show the results of evaluating the charge/discharge characteristics.
  • FIG. 6 shows the charge/discharge characteristics of the negative electrode using the negative electrode active material in which only the spherical phenol resin was used (0 wt % of SiO 2 addition, reference example);
  • FIG. 7 shows the charge/discharge characteristics of the negative electrode using the negative electrode active material in which 1 wt % of SiO 2 nanopowder was added to the spherical phenol resin;
  • FIG. 8 shows the charge/discharge characteristics of the negative electrode using the negative electrode active material in which 30 wt % of SiO 2 nanopowder was added to the spherical phenol resin.
  • the measurement was performed using two samples in each case. In each of the graphs, the vertical axis represents voltage and the horizontal axis represents capacity.
  • the maximum charge capacity was 1076.7 mAh/g; the maximum discharge capacity was 433.2 mAh/g; and the maximum efficiency was 40.8%
  • the maximum charge capacity was 1116.6 mAh/g; the maximum discharge capacity was 467.6 mAh/g; and the maximum efficiency was 42.3%.
  • the maximum charge capacity was 1730.0 mAh/g; the maximum discharge capacity was 633.2 mAh/g; and the maximum efficiency was 39.4%.

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140292281A1 (en) * 2013-03-29 2014-10-02 Fuji Jukogyo Kabushiki Kaisha Predoping material, electric storage device including the material, and method of producing the device
US20150318543A1 (en) * 2013-06-20 2015-11-05 Lg Chem, Ltd. High capacity electrode active material for lithium secondary battery and lithium secondary battery using the same
CN106298263A (zh) * 2016-10-31 2017-01-04 湘潭大学 一种铋/炭超级电容电池及其制备方法
CN106816361A (zh) * 2015-11-30 2017-06-09 英飞凌科技股份有限公司 用于结构化衬底的方法
US9852850B2 (en) 2014-07-18 2017-12-26 Semiconductor Energy Laboratory Co., Ltd. Electrode, power storage device, electronic device, and vehicle
US9865871B2 (en) 2014-12-26 2018-01-09 Semiconductor Energy Laboratory Co., Ltd. Silicon oxide and storage battery
US10614967B2 (en) 2011-08-31 2020-04-07 Semiconductor Energy Laboratory Co., Ltd. Negative electrode of power storage device and power storage device
US10756311B2 (en) 2015-05-06 2020-08-25 Semiconductor Energy Laboratory Co., Ltd. Secondary battery and electronic device
CN114824165A (zh) * 2022-06-30 2022-07-29 宁德新能源科技有限公司 负极极片、电化学装置及电子设备

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6453560B2 (ja) * 2014-06-03 2019-01-16 旭化成株式会社 非水系リチウム型蓄電素子用負極、及びそれを用いた非水系リチウム型蓄電素子
US10707531B1 (en) 2016-09-27 2020-07-07 New Dominion Enterprises Inc. All-inorganic solvents for electrolytes
JP2019145212A (ja) * 2018-02-15 2019-08-29 株式会社クラレ ケイ素酸化物／炭素複合体、その複合体を含む非水電解質二次電池用負極、及びその負極を含む非水電解質二次電池
CN116581386B (zh) * 2023-06-28 2024-05-28 北京民利储能技术有限公司 锂金属电池用添加剂、电解液及其锂金属电池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060057433A1 (en) * 2002-12-26 2006-03-16 Fuji Jukogyo Kabushiki Kaisha Electrical storage device and manufacturing electrical storage device
US7491467B2 (en) * 2002-12-17 2009-02-17 Mitsubishi Chemical Corporation Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the same
US20090197168A1 (en) * 2005-11-04 2009-08-06 Tetsuo Nishida Storage element

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09293507A (ja) 1996-04-26 1997-11-11 Kanebo Ltd リチウムイオン二次電池
JP3103357B1 (ja) * 1999-09-28 2000-10-30 株式会社サムスン横浜研究所 リチウム二次電池用の負極材料の製造方法
US6733922B2 (en) * 2001-03-02 2004-05-11 Samsung Sdi Co., Ltd. Carbonaceous material and lithium secondary batteries comprising same
JP2004119176A (ja) 2002-09-26 2004-04-15 Toshiba Corp 非水電解質二次電池用負極活物質及び非水電解質二次電池
WO2004049473A2 (en) 2002-11-26 2004-06-10 Showa Denko K.K. Electrode material comprising silicon and/or tin particles and production method and use thereof
JP4298988B2 (ja) 2002-12-02 2009-07-22 昭和電工株式会社 炭素材料の製造方法
JP4686974B2 (ja) 2002-12-17 2011-05-25 三菱化学株式会社 非水系電解液二次電池用負極およびそれを用いた非水系電解液二次電池
EP1575104A4 (en) 2002-12-17 2008-05-07 Mitsubishi Chem Corp CATHODE FOR A SECONDARY BATTERY WITH A WATER-FREE ELECTROLYTE AND A SECONDARY BATTERY WITH A WATER-FREE ELECTROLYTE
KR100570637B1 (ko) * 2003-05-21 2006-04-12 삼성에스디아이 주식회사 리튬 이차 전지용 음극 활물질 및 그의 제조 방법
US7662424B2 (en) * 2003-08-29 2010-02-16 Tdk Corporation Method of making composite particle for electrode, method of making electrode, method of making electrochemical device, apparatus for making composite particle for electrode, apparatus for making electrode, and apparatus for making electrochemical device
JP5058494B2 (ja) 2006-02-15 2012-10-24 株式会社クラレ 複合体およびその製造方法、並びに蓄電デバイス用電極材料
KR101386163B1 (ko) * 2007-07-19 2014-04-17 삼성에스디아이 주식회사 복합 음극활물질, 이를 채용한 음극 및 리튬 전지
KR100938059B1 (ko) 2007-10-23 2010-01-21 삼성에스디아이 주식회사 리튬 이차전지용 음극 및 이를 이용한 리튬 이차 전지
JP5369708B2 (ja) 2009-01-26 2013-12-18 旭硝子株式会社 二次電池用負極材料およびその製造方法
CN102804464B (zh) * 2009-06-25 2015-04-08 国立大学法人长崎大学 大孔多孔性石墨电极材料及其制造方法、以及锂离子二次电池
JP2011081960A (ja) * 2009-10-05 2011-04-21 Kri Inc 非水系二次電池
WO2011118350A1 (en) 2010-03-26 2011-09-29 Semiconductor Energy Laboratory Co., Ltd. Power storage device
WO2011158948A1 (en) 2010-06-18 2011-12-22 Semiconductor Energy Laboratory Co., Ltd. Method of manufacturing power storage device
JP5149364B2 (ja) * 2010-11-08 2013-02-20 国立大学法人群馬大学 炭素触媒及びその製造方法並びにこれを用いた電極及び電池
US9601228B2 (en) * 2011-05-16 2017-03-21 Envia Systems, Inc. Silicon oxide based high capacity anode materials for lithium ion batteries
US20130224581A1 (en) 2011-08-31 2013-08-29 Semiconductor Energy Laboratory Co., Ltd. Negative electrode of power storage device and power storage device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7491467B2 (en) * 2002-12-17 2009-02-17 Mitsubishi Chemical Corporation Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the same
US20060057433A1 (en) * 2002-12-26 2006-03-16 Fuji Jukogyo Kabushiki Kaisha Electrical storage device and manufacturing electrical storage device
US20090197168A1 (en) * 2005-11-04 2009-08-06 Tetsuo Nishida Storage element

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10998141B2 (en) 2011-08-31 2021-05-04 Semiconductor Energy Laboratory Co., Ltd. Negative electrode of power storage device and power storage device
US10614967B2 (en) 2011-08-31 2020-04-07 Semiconductor Energy Laboratory Co., Ltd. Negative electrode of power storage device and power storage device
US20140292281A1 (en) * 2013-03-29 2014-10-02 Fuji Jukogyo Kabushiki Kaisha Predoping material, electric storage device including the material, and method of producing the device
US9847528B2 (en) * 2013-03-29 2017-12-19 Subaru Corporation Predoping material, electric storage device including the material, and method of producing the device
US20150318543A1 (en) * 2013-06-20 2015-11-05 Lg Chem, Ltd. High capacity electrode active material for lithium secondary battery and lithium secondary battery using the same
US10593930B2 (en) * 2013-06-20 2020-03-17 Lg Chem, Ltd. High capacity electrode active material for lithium secondary battery and lithium secondary battery using the same
US9852850B2 (en) 2014-07-18 2017-12-26 Semiconductor Energy Laboratory Co., Ltd. Electrode, power storage device, electronic device, and vehicle
US9865871B2 (en) 2014-12-26 2018-01-09 Semiconductor Energy Laboratory Co., Ltd. Silicon oxide and storage battery
US10756311B2 (en) 2015-05-06 2020-08-25 Semiconductor Energy Laboratory Co., Ltd. Secondary battery and electronic device
US11916184B2 (en) 2015-05-06 2024-02-27 Semiconductor Energy Laboratory Co., Ltd. Secondary battery and electronic device
US9768023B1 (en) * 2015-11-30 2017-09-19 Infineon Technologies Ag Method for structuring a substrate
CN106816361A (zh) * 2015-11-30 2017-06-09 英飞凌科技股份有限公司 用于结构化衬底的方法
CN106298263A (zh) * 2016-10-31 2017-01-04 湘潭大学 一种铋/炭超级电容电池及其制备方法
CN114824165A (zh) * 2022-06-30 2022-07-29 宁德新能源科技有限公司 负极极片、电化学装置及电子设备

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