WO2011037013A1 - リチウムイオン二次電池用負極及びその製造方法 - Google Patents

リチウムイオン二次電池用負極及びその製造方法 Download PDF

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Publication number
WO2011037013A1
WO2011037013A1 PCT/JP2010/065447 JP2010065447W WO2011037013A1 WO 2011037013 A1 WO2011037013 A1 WO 2011037013A1 JP 2010065447 W JP2010065447 W JP 2010065447W WO 2011037013 A1 WO2011037013 A1 WO 2011037013A1
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Prior art keywords
active material
resin
current collector
ion secondary
negative electrode
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PCT/JP2010/065447
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English (en)
French (fr)
Japanese (ja)
Inventor
三好　学
村瀬　仁俊
林　圭一
信司 鈴木
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Toyota Industries Corp
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Toyota Industries Corp
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Priority to CN2010800420879A priority Critical patent/CN102576859A/zh
Priority to EP10818689.1A priority patent/EP2482369A4/en
Priority to US13/497,717 priority patent/US8822083B2/en
Priority to KR1020127005778A priority patent/KR101294228B1/ko
Publication of WO2011037013A1 publication Critical patent/WO2011037013A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/621—Binders
    • 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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a negative electrode for a lithium ion secondary battery and a method for producing the same.
  • a secondary battery is one that extracts chemical energy of a positive electrode active material and a negative electrode active material as electric energy to the outside by a chemical reaction via an electrolyte.
  • a secondary battery having a high energy density among the practically used secondary batteries is a lithium ion secondary battery.
  • lithium ion secondary batteries lithium-containing metal composite oxides such as lithium-cobalt composite oxide are mainly used as the active material for the positive electrode, and lithium ion insertion (interlayer between lithium ions) is used as the active material for the negative electrode.
  • a carbon material having a multilayer structure capable of forming a compound) and releasing lithium ions from the interlayer is mainly used.
  • the positive and negative electrode plates were prepared by dispersing these active materials, a binder resin, and a conductive material in a solvent to form a slurry on both surfaces of a metal foil as a current collector, and removing the solvent by drying. After forming the agent layer, it is produced by compression molding with a roll press.
  • a next-generation negative electrode active material having a charge / discharge capacity that greatly exceeds the theoretical capacity of a carbon material has been developed as a negative electrode active material of a lithium ion secondary battery.
  • a material containing a metal that can be alloyed with lithium such as Si or Sn is expected.
  • Patent Document 1 proposes an electrode for a secondary battery using an alkoxyl group-containing resin as a binder resin.
  • the negative electrode for a lithium ion secondary battery of the present invention is a negative electrode for a lithium ion secondary battery having a current collector and an active material layer fixed on the surface of the current collector, wherein the active material layer is an active material, A binder, a conductive material, and a buffer material are included, the active material includes Si and / or Sn, and the buffer material is formed of a silicone composite powder obtained by coating a silicone resin on a spherical silicone rubber powder.
  • the silicone composite powder is excellent in impact absorption. Therefore, by including the silicone composite powder as a buffer material in the active material layer, it is considered that the volume change associated with insertion / extraction of Li during charge / discharge is absorbed to suppress separation and dropping of the active material. It is done.
  • the binder preferably includes a cured polyimide resin or a cured silane-modified polyimide resin containing an alkoxyl group. Since the binder has a polyimide skeleton, the strength of the binder is strong, and the heat resistance and durability are excellent.
  • the alkoxyl group-containing silane-modified polyimide resin cured product is a hybrid of resin and silica, and has good adhesion to current collectors and active materials, conductive materials and buffer materials, which are inorganic components. Can hold firmly.
  • the buffer material is preferably contained in an amount of 1% by mass to 20% by mass.
  • FIG. 1 is a schematic diagram in which an active material 2, a buffer material 3, and a conductive material 4 are fixed on a current collector 1 through a binder 5, and an active material layer 6 is formed on the current collector 1.
  • FIG. 1 is a schematic diagram in which an active material 2, a buffer material 3, and a conductive material 4 are fixed on a current collector 1 through a binder 5, and an active material layer 6 is formed on the current collector 1.
  • FIG. 1 is a schematic diagram in which an active material 2, a buffer material 3, and a conductive material 4 are fixed on a current collector 1 through a binder 5, and an active material layer 6 is formed on the current collector 1.
  • FIG. 1 is a schematic diagram in which an active material 2, a buffer material 3, and a conductive material 4 are fixed on a current collector 1 through a binder 5, and an active material layer 6 is formed on the current collector 1.
  • FIG. 1 is a schematic diagram in which an active material 2, a buffer material 3, and a conductive material 4 are fixed on a current collector 1
  • a buffer material 3 is dispersed in the obtained active material layer 6, and the buffer material 3 absorbs a volume change associated with insertion / extraction of Li during charge / discharge, and thereby the active material 2. It is thought that exfoliation and drop-off are suppressed.
  • a binder resin comprising a polyimide resin or an alkoxyl group-containing silane-modified polyamic acid resin on the surface of the current collector, and an active material containing Si and / or Sn
  • a curing step for fixing the active material, the conductive material and the buffer material to the surface of the current collector is
  • a binder resin having a polyimide skeleton can be obtained. Since the binder has a polyimide skeleton, the binder has high strength and excellent heat resistance and durability.
  • the alkoxyl group-containing silane-modified polyamic acid resin is a hybrid of resin and silica, and has good adhesion to current collectors, active materials, conductive materials, and buffer materials, which are inorganic components. Therefore, the alkoxy group-containing silane-modified polyimide resin cured product can firmly hold an active material, a conductive material, and the like on the current collector.
  • the binder resin is cured at 150 ° C. or higher and 300 ° C. or lower. By setting it as this temperature range, binder resin can be hardened
  • the polyimide resin or the alkoxyl group-containing silane-modified polyamic acid resin as the binder resin has an amic acid group.
  • These binder resins having an amic acid group are imidized by being heated at 150 ° C. or higher. At this time, the binder resin can be cured even when the curing temperature is in a range lower than the curing temperature of 400 ° C. usually recommended for amic acid groups.
  • the silicone composite powder as a buffer material is considered to exhibit rubber elasticity in the range of -50 ° C to 300 ° C. Therefore, in the curing step, it is preferable that the temperature range is 150 ° C. or higher and 300 ° C. or lower, more preferably 200 ° C. or higher and 300 ° C. or lower in terms of improving cycle characteristics. According to such a manufacturing method, it can suppress that an active material peels and drops
  • FIG. 1 is a schematic diagram illustrating a negative electrode for a lithium ion secondary battery of the present invention.
  • FIG. 2 is a graph comparing charge and discharge efficiencies of Example 1 and Comparative Example 1 of the present invention.
  • FIG. 3 is a graph showing the cycle test results of Example 1 and Comparative Example 1 of the present invention.
  • 4A is an SEM photograph of the electrode of Example 1 of the present invention, and
  • FIG. 5 is an explanatory diagram showing the configuration of the electrode plate group of the laminate cell.
  • the negative electrode for a lithium ion secondary battery of the present invention has a current collector and an active material layer fixed to the surface of the current collector.
  • the active material layer includes an active material, a binder, a conductive material, and a buffer material.
  • the active material includes Si and / or Sn.
  • the buffer material is formed of a silicone composite powder in which a silicone resin is coated on a spherical silicone rubber powder.
  • a current collector is a chemically inert electronic high conductor that keeps current flowing through an electrode during discharging or charging.
  • the current collector is in the form of a foil, a plate or the like formed of an electronic high conductor. If it is the shape according to the objective, it will not specifically limit.
  • examples of the current collector include copper foil and aluminum foil.
  • An active material is a substance that directly contributes to electrode reactions such as charge reaction and discharge reaction.
  • the active material of the present invention is Si and / or Sn capable of inserting and extracting lithium.
  • Si and Sn are in a powder form, and are applied and fixed to the surface of the current collector via a binder resin.
  • the powder particle diameter of Si and Sn is preferably 100 ⁇ m or less.
  • the powder particle diameters of Si and Sn are more preferably 0.05 ⁇ m or more and 10 ⁇ m or less.
  • the powder particle diameter of Si and Sn is more preferably 1 ⁇ m or more and 10 ⁇ m or less, and 1 ⁇ m.
  • the theoretical capacity of carbon used for the active material of the negative electrode is 372 mAhg ⁇ 1
  • the theoretical capacity of Si is 4200 mAhg ⁇ 1
  • Sn is 994 mAhg ⁇ 1 .
  • Si and Sn have a large theoretical capacity as compared with conventionally used carbon.
  • Si and Sn have a volume change more than twice as much as insertion of lithium as compared with carbon-based materials. Specifically, in the case of Si and Sn, the volume becomes about four times the original volume due to the insertion of lithium.
  • conductive material carbon black, graphite, acetylene black, ketjen black, carbon fiber, etc., which are carbonaceous fine particles, can be added alone or in combination of two or more.
  • buffer material a silicone composite powder obtained by coating a silicone resin on a spherical silicone rubber powder is used.
  • Silicone is an organosilicon compound having a siloxane bond: —Si (R 1 R 2 ) —O— as a skeleton, and an organic group R 1 , R 2 having a methyl group, a vinyl group, a phenyl group, or the like bonded thereto. It is a general term for the polymer organopolysiloxane.
  • Silicones are classified according to their molecular weights from low molecular weight silicone oils to silicone greases, silicone rubbers, and silicone resins.
  • the spherical silicone rubber powder is a fine powder of silicone rubber having a structure in which linear dimethylpolysiloxane is crosslinked.
  • the spherical silicone rubber powder is excellent in heat resistance, cold resistance and light resistance as compared with other rubbers, and exhibits rubber elasticity in a wide temperature range of ⁇ 50 ° C. to 250 ° C.
  • Examples of the structure obtained by crosslinking linear dimethylpolysiloxane include a block of a linear polyorganosiloxane represented by the general formula: — (R 3 2 SiO) a — in the molecular structural formula.
  • R 3 represents an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl; a cycloalkyl group such as cyclopentyl, cyclohexyl, cyclooctyl; phenyl, One or two or more monovalent organic groups having 1 to 20 carbon atoms selected from aryl groups such as tolyl, etc., or a part of hydrogen atoms bonded to these carbon atoms is substituted with a halogen atom
  • the organic group is selected from valent organic groups, and 90 mol% or more of them is preferably a methyl group.
  • the silicone composite powder used in the present invention is obtained by coating the spherical silicone rubber powder with a silicone resin.
  • Silicone resins have a structure in which Si—O bonds are crosslinked in a three-dimensional network, are particularly excellent in heat resistance, hardly change in weight even at 400 ° C., do not melt by heat, and do not swell or dissolve in many organic solvents.
  • the silicone resin include polyorganosilsesquioxane resin.
  • This polyorganosilsesquioxane resin is a solid resin polymer having a siloxane unit represented by the general formula: R 4 SiO 3/2 as a structural unit.
  • R 4 is an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl; a cycloalkyl group such as cyclopentyl, cyclohexyl, cyclooctyl; phenyl, One or two or more monovalent organic groups having 1 to 20 carbon atoms selected from aryl groups such as tolyl, etc., or a part of hydrogen atoms bonded to these carbon atoms is substituted with a halogen atom Although it is selected from valent organic groups, it is preferable that 90
  • a method for producing a silicone composite powder in which a silicone resin is coated on such a spherical silicone rubber powder is, for example, a method in which an aqueous dispersion of a spherical silicone rubber powder is kept alkaline, and the silicone resin is hydrolyzed and condensed to form spherical particles.
  • a silicone resin can be coated on the surface of the silicone rubber powder.
  • Such a silicone composite powder is excellent in heat resistance, cold resistance, impact resistance, and lubricity.
  • the silicone composite powder is considered to exhibit rubber elasticity in a wide temperature range of ⁇ 50 ° C. to 300 ° C.
  • the silicone composite powder Since the surface of the silicone composite powder is coated with a silicone resin, the silicone composite powder has better dispersibility than the spherical silicone rubber powder and can be well dispersed in the active material layer. Further, since the silicone resin has higher heat resistance than the spherical silicone rubber powder, it is considered that the temperature range in which the silicone composite powder exhibits rubber elasticity is higher than that of the spherical silicone rubber powder.
  • the silicone composite powder is commercially available from Shin-Etsu Chemical Co., Ltd. as KMP-600, KMP-601, KMP-602, KMP-605, and X-52-7030 under the name of silicone composite powder.
  • the buffer material When the total amount of the active material layer is 100% by mass, the buffer material is preferably contained in an amount of 1% by mass to 20% by mass.
  • the particle size of the silicone composite powder is desirably 1 ⁇ m to 10 ⁇ m, more desirably 1 ⁇ m to 5 ⁇ m. In order to relieve the volume change of Si or Sn, the particle size of the silicone composite powder is desirably about the same as that of Si or Sn. If the particle size of the silicone composite powder is too smaller than the particle size of Si or Sn, the buffering effect is reduced. If the particle size is too large, the silicone composite powder does not reach the entire electrode and the buffering effect cannot be expected. These active material, conductive material, and buffer material are fixed to the current collector through a binder.
  • the binder is not particularly limited, but preferably contains a cured polyimide resin or a cured silane-modified polyimide resin containing an alkoxyl group.
  • a binder having a polyimide skeleton can be obtained. Since the binder has a polyimide skeleton, the binder has high strength and excellent heat resistance and durability.
  • the cured product of the alkoxyl group-containing silane-modified polyimide resin is a hybrid of resin and silica, and has good adhesion to the current collector and active material, conductive material and buffer material, which are inorganic components, and the current collector has an active material. Etc. can be held firmly.
  • the manufacturing method of the negative electrode for lithium ion secondary batteries of this invention has an application
  • a coating method As a coating method, a coating method generally used when producing an electrode for a secondary battery, such as a roll coating method, a dip coating method, a doctor blade method, a spray coating method, or a curtain coating method, can be used.
  • the binder resin is used as a binder when these active materials, conductive materials and buffer materials are applied to the current collector.
  • the binder resin is required to bind the active material or the like in as little amount as possible, and the amount is preferably 0.5 wt% to 50 wt% of the total of the active material, the conductive material, the buffer material, and the binder resin.
  • the binder resin is preferably a polyimide resin or an alkoxyl group-containing silane-modified polyamic acid resin.
  • the alkoxyl group-containing silane-modified polyamic acid resin is a hybrid of resin and silica.
  • the current collector, active material, and conductive material which are inorganic components, have good adhesion, and the current collector can hold the active material and conductive material firmly.
  • the binder resin can be synthesized by a known technique. For example, when an alkoxy group-containing silane-modified polyamic acid resin is used as the binder resin, it can be formed by reacting a polyamic acid composed of a carboxylic acid anhydride component and a diamine component as a precursor with an alkoxysilane partial condensate. it can.
  • the alkoxysilane partial condensate is obtained by partially condensing a hydrolyzable alkoxysilane monomer in the presence of an acid or base catalyst and water. At this time, the alkoxysilane partial condensate may be reacted with an epoxy compound in advance to form an epoxy group-containing alkoxysilane partial condensate and then reacted with a polyamic acid to form an alkoxy group-containing silane-modified polyamic acid resin.
  • a commercial item can be used suitably for said binder resin.
  • there is a commercial product under the trade name “COMPOCERAN H800” (Arakawa Chemical Industries, Ltd.), which is an alkoxy group-containing silane-modified polyamic acid resin.
  • the chemical formula of the basic skeleton of the above-mentioned trade name “COMPOCERAN H800” is shown below.
  • the conductive material carbon black, graphite, acetylene black, ketjen black, carbon fiber, etc., which are carbonaceous fine particles, can be added alone or in combination of two or more.
  • a binder resin, an active material, a conductive material, and a buffer material are mixed in advance, and a solvent or the like is added to form a slurry, which can be applied to the current collector.
  • the coating thickness is preferably 10 ⁇ m to 100 ⁇ m.
  • this mixing ratio has shown the upper limit and the minimum of each. For example, in the case of an active material, the upper limit is 79 wt% and the lower limit is 60 wt%.
  • the curing step is a step of curing the binder resin. At that time, the curing condition is that the binder resin is cured and the powder shape of the buffer material, which is a silicone composite powder, is maintained, and the silicone composite powder exhibits rubber elasticity.
  • the current collector coated with the active material is heated at 150 ° C. or higher and 300 ° C. or lower. By curing under this curing condition, it is considered that the composite silicone powder retains its shape and rubber elasticity and functions as a buffer material.
  • These binder resins have an amic acid group.
  • the amic acid group is imidized (dehydration polymerization) by heat treatment to form an imide group. This imidization reaction starts at about 150 ° C. and easily proceeds at 200 ° C. or higher.
  • the imidization ratio of the amic acid is desirably 70% or more.
  • the imidization is performed until the amide group has a ratio of 99: 1 to 70:30.
  • the imidation ratio becomes 70% or more at 200 ° C or higher. Therefore, if it exists in the said temperature range, it fully functions as a binder and can maintain the cycling characteristics of a negative electrode favorably.
  • a negative electrode for a lithium ion secondary battery of the present invention was prepared as follows, and a charge / discharge efficiency test and a cycle test were performed using a model battery for evaluation.
  • the test used a laminate-type lithium ion secondary battery with the negative electrode as the evaluation electrode.
  • An Si-containing powder is used as the active material, and an alkoxy-containing silane-modified polyamic acid resin having the structure shown in [Chemical Formula 2] as the binder resin (solvent composition: N, N-dimethylacetamide (DMAc), curing residue 15.1% , A viscosity of 5100 mPa ⁇ s / 25 ° C., silica in the cured residue, 2 wt%) to prepare an electrode.
  • a silicone composite powder KMP-600, Shin-Etsu Chemical Co., Ltd.
  • a carbon-based conductive additive was used as the conductive material, and specifically, a mixture of two or three types such as KB (Ketjen Black) manufactured by Ketjen Black International and graphite was used.
  • Si powder Si particles having a maximum particle diameter of 10 ⁇ m or less and an average particle diameter of 2 ⁇ m (manufactured by Fukuda Metal Foil Powder Industry) were used as they were.
  • Si: silicone composite powder: carbon-based conductive additive: binder resin (alkoxy-containing silane-modified polyamic acid resin) 60: 5: 20: 15 (wt%).
  • 60 wt% Si powder and 5 wt% silicone composite powder were added to 15 wt% of a paste in which an alkoxy-containing silane-modified polyamic acid resin was dissolved in N-methylpyrrolidone (NMP), and further 20 wt% of a carbon-based conductive additive was added.
  • NMP N-methylpyrrolidone
  • a slurry was prepared by adding and mixing.
  • Comparative Examples 1 and 2 the slurry was prepared by the same operation.
  • Example 1 and Comparative Example 1 were heated and cured at 200 ° C. for 3 hours to obtain an electrode having a thickness of about 25 ⁇ m.
  • an electrode having a thickness of about 25 ⁇ m was obtained by heat curing at 430 ° C. for 10 minutes.
  • the shape of the silicone composite powder does not change by heat treatment at 200 ° C.
  • an SEM photograph of the electrode of Example 1 and an SEM photograph of the electrode of Comparative Example 2 are shown in FIGS.
  • the imidation ratio of the alkoxy-containing silane-modified polyamic acid resin of Example 1 was about 80%.
  • the silicone composite powder remained unchanged in the 200 ° C. heat-treated product of Example 1.
  • the silicone composite powder disappeared and voids (the black round parts shown in FIG.
  • FIG. 5 is an explanatory diagram showing the configuration of the electrode plate group of the laminate cell, and the negative electrode produced by the above procedure corresponds to the electrode 11 of FIG.
  • the electrode 11 includes a sheet-shaped current collector foil 12 made of a copper foil, and a negative electrode active material layer 13 formed on the surface of the current collector foil 12.
  • the current collector foil 12 includes a rectangular (26 mm ⁇ 31 mm) composite material coating portion 12a and a tab weld portion 12b extending from a corner of the composite material coating portion 12a.
  • a negative electrode active material layer 13 is formed on one surface of the composite material coating portion 12a.
  • the negative electrode active material layer 13 includes Si powder, a carbon-based conductive additive, a binder, and a silicone composite powder.
  • a nickel tab 14 was resistance welded to the tab weld 12 b of the current collector foil 12. Furthermore, the resin film 15 was adhered to the tab weld portion 12b.
  • an electrode fixed to a 20 ⁇ m aluminum foil using LiNi 1/3 Co 1/3 Mn 1/3 O 2 as a positive electrode active material and a binder resin PVdF was prepared to obtain a positive electrode having a thickness of 90 ⁇ m or less. .
  • the above electrode was used as a negative electrode, an electrode using 85 ⁇ m thick LiNi 1/3 Co 1/3 Mn 1/3 O 2 as a positive electrode active material as a positive electrode, and 1 mol of LiPF 6 / ethylene carbonate (EC) +
  • the laminate type battery includes an electrode plate group 10 in which an electrode 11, a counter electrode 16 and a separator 19 are laminated, a laminate film (not shown) that wraps and seals the electrode plate group 10, and a non-injection that is injected into the laminate film. A water electrolyte solution.
  • the counter electrode 16 a positive electrode containing LiNi 1/3 Co 1/3 Mn 1/3 O 2 as a positive electrode active material was used.
  • an aluminum foil having a thickness of 20 ⁇ m was used as a current collector, a capacity was 3.0 mAh / cm 2 , and an electrode density was 2.3 g / cm 2 .
  • the counter electrode 16 includes a rectangular (25 mm ⁇ 30 mm) composite material coating portion 16a and a tab weld portion 16b extending from a corner of the main body portion 16a, both of which are made of aluminum foil. It became the composition which becomes.
  • a positive electrode active material layer containing LiNi 1/3 Co 1/3 Mn 1/3 O 2 was formed on one surface of the composite material coating portion 16a.
  • An aluminum tab 17 was resistance welded to the tab weld 16b. Further, a resin film 18 was attached to the tab weld 16b.
  • a plate group 10 was constructed.
  • the electrode plate group 10 was covered with a set of two laminated films, the three sides were sealed, and then a predetermined nonaqueous electrolyte was poured into the bag-like laminated film. Thereafter, the remaining one side was sealed to obtain a laminate cell in which the four sides were hermetically sealed, and the electrode plate group 10 and the non-aqueous electrolyte were sealed. Note that some of the tabs 15 and 17 on both poles extend outward for electrical connection with the outside. ⁇ Laminated battery evaluation> Evaluation of the evaluation electrode in this model battery was performed by the following method. (Charge / discharge efficiency test) Using the negative electrodes of Example 1 and Comparative Example 1 below, a charge / discharge test was performed to calculate charge / discharge efficiency (%).
  • CCCV charging constant current constant voltage charging
  • the battery was discharged at a constant current of 0.2 C up to 2.6 V (0.2 C, CC discharge (constant current discharge)).
  • the current was a constant current of 4.6 mA.
  • CCCV charge constant current constant voltage charge
  • the battery was discharged at a constant current (23 mA) of 1 C up to 2.6 V (1 C, CC discharge (constant current discharge)).
  • the charge / discharge efficiency was determined using the following equation.
  • Charging / discharging efficiency (%) discharge capacity / charge capacity ⁇ 100 At this time, the current that discharges the electric capacity in 1 hour is 1 C, and the current that discharges in 5 hours is 0.2 C. Therefore, the current value of 1C is five times the current value of 0.2C.
  • a graph comparing the charge and discharge efficiencies of the model batteries using the electrodes of Example 1 and Comparative Example 1 in the first and second cycles is shown in FIG.
  • the X axis represents the above-described current rate, and the Y axis represents charge / discharge efficiency (%).
  • the electrode of Example 1 has a charge / discharge efficiency of 99% at the first cycle (0.2C), 93% at the second cycle (1C), and about 1% at 0.2C.
  • Example 1 As compared with Comparative Example 1, the charge / discharge efficiency is about 3% at 1C. That is, it was found that the electrode of Example 1 was able to discharge the charged capacity more firmly than the electrode of Comparative Example 1. This is thought to be because the silicone composite powder worked as a buffering material and absorbed the volume change of the Si particles as the active material, thereby preventing the binder from being broken and thus preventing the active material from peeling off and falling off. In addition, compared with Comparative Example 1, Example 1 has a larger difference in charge / discharge efficiency at 1C than at 0.2C, and it can be seen that the above-described effect is particularly great during rapid charge / discharge.
  • FIG. 3 shows a graph showing the relationship between the number of cycles and the capacity retention rate (%) for the model batteries having the electrodes of Example 1 and Comparative Example 1. As is clear from FIG. 3, in the battery using the electrode of Example 1 as the evaluation electrode, the rate of decrease in capacity decreased from about the 70th cycle as compared with the battery using the electrode of Comparative Example 1 as the evaluation electrode.
  • Example 1 the capacity retention rate after 100 cycles of Comparative Example 1 was about 55%, whereas in Example 1, the capacity retention rate after 100 cycles was maintained at about 62%. That is, from the cycle test results, it was found that the electrode of Example 1 had better cycle characteristics than the electrode of Comparative Example 1. This is presumably because the silicone composite powder worked as a cushioning material and prevented the active material from peeling off and falling off. In addition, from the above-described charge / discharge efficiency test results, it is considered that the effect becomes more remarkable even in the cycle test results in the case of rapid charge / discharge (for example, discharge rate 1C). In the above Examples and Comparative Examples, an alkoxyl group-containing silane-modified polyamic acid resin was used as the binder resin, but the same effect can be obtained with a polyimide resin.

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PCT/JP2010/065447 2009-09-25 2010-09-01 リチウムイオン二次電池用負極及びその製造方法 Ceased WO2011037013A1 (ja)

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CN2010800420879A CN102576859A (zh) 2009-09-25 2010-09-01 锂离子二次电池用负极及其制造方法
EP10818689.1A EP2482369A4 (en) 2009-09-25 2010-09-01 ANODE FOR USE IN A LITHIUMION SECONDARY BATTERY AND METHOD OF MANUFACTURING THEREOF
US13/497,717 US8822083B2 (en) 2009-09-25 2010-09-01 Negative electrode for lithium-ion secondary battery and manufacturing process for the same
KR1020127005778A KR101294228B1 (ko) 2009-09-25 2010-09-01 리튬 이온 2차 전지용 부극 및 그의 제조 방법

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JP5664942B2 (ja) * 2011-05-12 2015-02-04 株式会社豊田自動織機 リチウムイオン二次電池用電極、その製造方法及びその電極を用いたリチウムイオン二次電池
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JP5525003B2 (ja) 2012-05-07 2014-06-18 古河電気工業株式会社 非水電解質二次電池用負極及びそれを用いた非水電解質二次電池
JP6267910B2 (ja) * 2012-10-05 2018-01-24 株式会社半導体エネルギー研究所 リチウムイオン二次電池用負極の製造方法
US11322745B2 (en) * 2014-10-15 2022-05-03 Semiconductor Energy Laboratory Co., Ltd. Electrode, power storage device, electronic device, and manufacturing method of electrode
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US11094933B2 (en) * 2016-07-18 2021-08-17 University Of Kentucky Research Foundation Polysiloxane binders
JP6874860B2 (ja) * 2017-01-27 2021-05-19 日本電気株式会社 シリコーンボールを含む電極及びそれを含むリチウムイオン電池
CN107732156A (zh) * 2017-11-28 2018-02-23 安徽零度新能源科技有限公司 一种提高锂电池负极低温性能的加工方法
CN107959019A (zh) * 2017-12-13 2018-04-24 南京红太阳新能源有限公司 一种石墨烯锡基硅基电池负极材料的制备
CN109860562A (zh) * 2019-02-15 2019-06-07 柔电（武汉）科技有限公司 一种电极浆料、柔性极片及其制备方法、柔性电池
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CN110649209B (zh) * 2019-09-26 2022-09-27 佛山科学技术学院 一种锂离子电池隔膜的处理方法及锂离子电池
CN111584835A (zh) * 2020-04-30 2020-08-25 汉腾新能源汽车科技有限公司 一种锂离子电池负极及其制备方法
US11532818B2 (en) 2020-05-29 2022-12-20 Uchicago Argonne, Llc Solvents and slurries comprising a poly(carboxylic acid) binder for silicon electrode manufacture

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KR101294228B1 (ko) 2013-08-07
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US8822083B2 (en) 2014-09-02
US20120177992A1 (en) 2012-07-12
JP2011070892A (ja) 2011-04-07
EP2482369A4 (en) 2014-08-06
CN102576859A (zh) 2012-07-11
KR20120039062A (ko) 2012-04-24
EP2482369A1 (en) 2012-08-01

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