WO2015015598A1 - Matériau de revêtement de matériaux actifs d'électrode négative de batteries secondaires au lithium-ion, matériau actif d'électrode négative de batteries secondaires au lithium-ion revêtu dudit matériau de revêtement et batterie secondaire au lithium-ion utilisant ledit matériau actif d'électrode négative dans l'électrode négative - Google Patents

Matériau de revêtement de matériaux actifs d'électrode négative de batteries secondaires au lithium-ion, matériau actif d'électrode négative de batteries secondaires au lithium-ion revêtu dudit matériau de revêtement et batterie secondaire au lithium-ion utilisant ledit matériau actif d'électrode négative dans l'électrode négative Download PDF

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WO2015015598A1
WO2015015598A1 PCT/JP2013/070763 JP2013070763W WO2015015598A1 WO 2015015598 A1 WO2015015598 A1 WO 2015015598A1 JP 2013070763 W JP2013070763 W JP 2013070763W WO 2015015598 A1 WO2015015598 A1 WO 2015015598A1
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negative electrode
electrode active
lithium ion
ion secondary
active material
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PCT/JP2013/070763
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English (en)
Japanese (ja)
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紀雄 岩安
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株式会社日立製作所
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Priority to PCT/JP2013/070763 priority Critical patent/WO2015015598A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • 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 coating material for a negative electrode active material for a lithium ion secondary battery, a negative electrode active material for a lithium ion secondary battery coated with the coating material, and a lithium ion secondary battery using the negative electrode active material as a negative electrode.
  • Patent Document 1 discloses a polymer electrolyte containing, as a matrix, a copolymer containing a polymer unit based on vinylidene fluoride and a polymer unit having —CF 2 COOLi or —CF 2 SO 3 Li in the side chain, and containing an organic solvent.
  • a lithium battery is disclosed.
  • Patent Document 2 discloses a lithium ion secondary battery in which a liquid containing lithium bis (oxalate) borate is in contact with the surface of an electrode.
  • An object of the present invention is to provide a novel coating material for a negative electrode active material of a lithium ion secondary battery that can reduce the irreversible capacity and reduce the battery resistance.
  • the covering material for a negative electrode active material for a lithium ion secondary battery is composed of a polymer represented by the chemical formula 1, wherein Z has a structure represented by the chemical formula 2, R 1 , R 2 , and R 3 each represent any of an alkyl group, a halogen group, and a hydrogen group; m 1 , n 1 , and n 2 each represent the number of repeating structural units; , A and B each represent a functional group containing a halogen element or hydrogen, at least one of A and B is a functional group containing a halogen element, and X is hydrogen, an alkali metal, and an alkaline earth metal. Represents either.
  • the covering material for a negative electrode active material for a lithium ion secondary battery includes a first monomer corresponding to a structural unit of a polymer represented by Chemical Formula 1, and a second monomer represented by Chemical Formulas 3-7.
  • At least one selected from the group consisting of a copolymer obtained by copolymerization wherein in Formula 1, Z has a structure represented by Formula 2, and R 1 , R 2 , and R 3 are each an alkyl group , A halogen group, and a hydrogen group, m 1 , n 1 , and n 2 each represent the number of repeating structural units, and in Chemical Formula 2, A and B are each a functional group containing a halogen element or Represents hydrogen, at least one of A and B is a functional group containing a halogen element, X represents any one of hydrogen, an alkali metal, and an alkaline earth metal; Y represents an alkali metal or hydrogen.
  • a coating material for a lithium ion secondary battery negative electrode active material capable of reducing irreversible capacity and battery resistance, and a lithium ion secondary battery negative electrode active material coated with the coating material can provide. Further, by using the negative electrode active material for the negative electrode, it is possible to provide a lithium ion secondary battery having a small irreversible capacity, a high capacity, a low battery resistance, and excellent output characteristics.
  • FIG. 1 is a cross-sectional view schematically showing a cross-sectional structure of a lithium ion secondary battery.
  • FIG. 2 is a diagram illustrating the synthesis of the monomer according to the embodiment of the present invention.
  • FIG. 3 is a table showing the composition of the coating material, the irreversible capacity of the negative electrode, and the direct current resistance of the battery in Examples and Comparative Examples of the present invention.
  • FIG. 1 is a diagram schematically showing the internal structure of a lithium ion battery.
  • a lithium ion battery 1 shown in FIG. 1 includes a positive electrode 10, a separator 11, a negative electrode 12, a battery container (battery can) 13, a positive electrode current collector tab 14, a negative electrode current collector tab 15, an inner lid 16, an internal pressure release valve 17, and a gasket 18. , A positive temperature coefficient (PTC) resistance element 19, a battery lid 20, and an axis 21.
  • the battery lid 20 is configured integrally with the inner lid 16, the internal pressure release valve 17, the gasket 18, and the PTC resistance element 19.
  • An electrode group composed of the separator 11 inserted between the positive electrode 10 and the negative electrode 12 is configured to be wound around an axis 21.
  • the electrode group may have various shapes such as a laminate of strip electrodes, a positive electrode 10 and a negative electrode 12 wound in an arbitrary shape such as a flat shape. it can.
  • the shape of the battery case 13 can be selected from shapes such as a cylindrical shape, a flat oval shape, a flat oval shape, and a square shape according to the shape of the electrode group.
  • the material of the battery container 13 is selected from materials that are corrosion resistant to the nonaqueous electrolyte, such as aluminum, stainless steel, and nickel-plated steel. Further, when the battery container 13 is electrically connected to the positive electrode 10 or the negative electrode 12, the material is not deteriorated due to corrosion of the battery container 13 or alloying with lithium ions in the portion in contact with the nonaqueous electrolyte. Thus, the material of the battery container 13 is selected.
  • the electrode group is housed in the battery container 13, the negative electrode current collecting tab 15 is connected to the inner wall of the battery container 13, and the positive electrode current collecting tab 14 is connected to the bottom surface of the battery lid 20.
  • the electrolytic solution is injected into the battery container interior 13. There are two methods for injecting the electrolytic solution: a method in which the battery lid 20 is opened and a direct injection into the electrode group, or a method in which injection is performed from an injection port installed in the battery lid 20. After injecting the electrolyte, the battery lid 20 is brought into close contact with the battery container 13 to seal the entire battery. If there is an electrolyte inlet, seal the inlet.
  • Known methods such as welding and caulking can be applied to the method of sealing the battery.
  • the positive electrode 10 is produced by applying a positive electrode mixture containing a positive electrode active material, a conductive agent, and a binder to the surface of the positive electrode current collector to form a positive electrode mixture layer.
  • Typical examples of the positive electrode active material include LiCoO 2 , LiNiO 2 , and LiMn 2 O 4 .
  • the size of the positive electrode active material particles is set to be equal to or less than the thickness of the positive electrode mixture layer formed by the positive electrode active material, the conductive agent, and the binder. When there are particles larger than the thickness of the positive electrode mixture layer in the positive electrode active material powder, it is preferable to remove the large particles in advance by sieving classification or wind classification.
  • the purpose of using the conductive agent is to supplement the electrical conductivity because the positive electrode active material is generally an oxide having a high electrical resistance.
  • a conductive agent carbon powder is generally used.
  • the positive electrode active material and the conductive agent are generally powders, and these powders can be attached to the surface of the positive electrode current collector in a bound state by mixing a binder.
  • an aluminum foil having a thickness of 10 to 100 ⁇ m, an aluminum perforated foil in which a large number of holes having a diameter of 0.1 to 10 mm are formed on an aluminum foil having a thickness of 10 to 100 ⁇ m, an expanded metal, a foam metal plate, or the like is used. be able to.
  • materials such as stainless steel and titanium are also applicable, and various materials, shapes, and manufacturing methods are applicable.
  • the positive electrode is formed by applying a positive electrode mixture slurry prepared by mixing a positive electrode active material, a conductive agent, and a binder in an organic solvent to the positive electrode current collector, then evaporating the organic solvent, and then press-molding by a roll press. Can be produced. Application methods such as a doctor blade method, a dipping method, and a spray method can be applied to the application of the positive electrode mixture slurry. It is also possible to stack the positive electrode mixture layer on the positive electrode current collector by performing the steps from application of the positive electrode mixture slurry to drying in a plurality of times.
  • the negative electrode is produced by applying a negative electrode mixture containing a negative electrode active material and a binder to the surface of the negative electrode current collector to form a negative electrode mixture layer.
  • a negative electrode active material an easily graphitized material obtained from natural graphite, petroleum coke, coal pitch coke, etc. is heat-treated at a high temperature of 2500 ° C. or higher, and mesophase carbon, amorphous carbon, carbon fiber, and lithium are alloyed.
  • Metal a material having a metal supported on the carbon particle surface, and the like are applicable.
  • the metal a single material selected from lithium, silver, aluminum, tin, silicon, indium, gallium, and magnesium, or an alloy material of these metals can be used.
  • lithium titanate can also be used.
  • the negative electrode active material is coated with a negative electrode active material coating material.
  • the coating amount with the negative electrode active material coating material is 0.01% by mass or more and 10% by mass or less, preferably 0.1% by mass or more and 5% by mass or less, more preferably, with respect to the mass of the negative electrode active material. It is 0.3 mass% or more and 3 mass% or less.
  • the covering material for a negative electrode active material according to the present invention is a polymer having a structural formula represented by Chemical Formula 1.
  • m 1 is the number of repeating structural units (the structural portion shown in parentheses in Chemical Formula 1).
  • Z is a site containing halogen and a site due to an ionic functional group such as a sulfo group (—SO 3 X), a carboxyl group (—COOX), a phosphate group (—O—PO (OX) 2 ), etc. It consists of.
  • a sulfo group is preferable from the viewpoint of reducing the resistance of the battery.
  • R 1 , R 2 , and R 3 each represent an alkyl group, a halogen group, or hydrogen.
  • n 1 and n 2 are the number of repeating structural units, respectively.
  • the structural unit having the repeating number n 1 is composed of a methylene group.
  • n 1 is preferably an integer of 0 or more and 20 or less.
  • a and B are each composed of a functional group containing hydrogen or hydrogen, and at least one of A and B is configured to contain halogen.
  • halogen fluorine or chlorine is preferable, and fluorine is more preferable.
  • the functional group containing fluorine as a halogen fluorine and CF 3 are preferable.
  • the functional group containing halogen is preferably adjacent to the sulfo group. That is, in Chemical Formula 2, it is preferable that B contains a functional group containing a halogen. From the viewpoint of reducing battery resistance, in Chemical Formula 2, n 2 is preferably an integer of 1 or more and 20 or less, and more preferably 1 or more and 10 or less.
  • the explanation regarding the halogen-containing functional group and the sulfo group is similarly applied to the case where the ionic functional group includes a carboxyl group or a phosphate group instead of the sulfo group in Chemical Formula 2.
  • Chemical Formula 8 to Chemical Formula 10 are shown.
  • the structure shown in Chemical Formula 8 has the best solubility in a solvent, and the workability when preparing the coating material is considered to be the best.
  • the structure represented by Chemical Formula 10 is not as soluble in the solvent as the structure represented by Chemical Formula 8, but has a large polarity because CF 3 is disposed adjacent to the sulfo group (ionic functional group). Since it is easy to move ions, the effect of reducing the resistance of the battery is considered to be greater.
  • the solubility in a solvent and the ease of ion transfer are considered to be intermediate.
  • the structural formulas of chemical formulas 8 to 10 show structures in which the values of n 1 and n 2 are both 1. However, if these values are within the above ranges, the same effect can be obtained.
  • a polymer having the structure of Chemical Formula 1 is produced by polymerizing a monomer as the structural unit.
  • the synthesis of the monomer will be described with reference to FIG. 2, taking as an example the case where the Z portion in Chemical Formula 1 has the structure shown in Chemical Formula 8.
  • the negative electrode active material coating material according to the present invention is produced by polymerizing the above monomers.
  • the polymerization may be any of conventionally known bulk polymerization, solution polymerization, and emulsion polymerization.
  • the polymerization method is not particularly limited, but radical polymerization is preferred.
  • a polymerization initiator may or may not be used, but a radical polymerization initiator is preferably used from the viewpoint of ease of work. In polymerization using a radical polymerization initiator, there is no problem in the normal temperature range and polymerization time.
  • the blending amount of the polymerization initiator is preferably in the range of 0.1% by mass to 20% by mass with respect to the mass of the compound to be polymerized, and in the range of 0.3% by mass to 5% by mass. More preferably.
  • the coating material for negative electrode active material according to the present invention may be composed of a copolymer obtained by copolymerizing a monomer (main monomer) corresponding to the polymer represented by Chemical Formula 1 and another monomer (copolymerization monomer). Good.
  • a monomer having a structure represented by Chemical Formula 3 to Chemical Formula 7 is preferable.
  • Y represents an alkali metal or hydrogen, and is preferably an alkali metal from the viewpoint of electrochemical stability.
  • An improvement in irreversible capacity can be expected by using a negative electrode coating material made of a copolymer. Possible reasons for this are as follows. There is a possibility that the coating material with the polymer represented by Chemical Formula 1 may not necessarily have sufficient wettability with respect to the negative electrode active material. In such a case, there is a portion where the surface of the negative electrode active material cannot be covered with the coating material. It is considered a thing. In a portion that cannot be covered, it is conceivable that the negative electrode active material and the electrolytic solution are in direct contact with each other and the electrolytic solution is decomposed.
  • the wettability to the negative electrode active material is improved, and more part of the surface of the negative electrode active material is coated with the coating material Can be considered.
  • the effect of reducing the irreversible capacity by suppressing the decomposition of the electrolytic solution can be expected.
  • the monomers represented by the chemical formulas 3 to 7 the effect of improving the wettability with respect to the negative electrode active material is relatively large for the monomers represented by the chemical formulas 3 and 4, and the effects for the monomers represented by the chemical formulas 6 and 7 are relatively small. it is conceivable that.
  • the monomer represented by Formula 5 is considered to have an intermediate effect.
  • the present invention includes a mixture of a polymer represented by Chemical Formula 1 and at least one polymer obtained by polymerizing monomers represented by Chemical Formulas 3 to 7 as a negative electrode active material coating material.
  • the polymer structure may be any of a linear structure, a branched structure, a crosslinked structure, and a dendrimer structure. From the viewpoint of workability when coating the negative electrode active material, a polymer having a linear structure is preferable.
  • the polymerization mode for copolymerization is not particularly limited, and examples thereof include random copolymerization, alternating copolymerization, block copolymerization, and graft copolymerization.
  • the number average molecular weight of the polymer used as the negative electrode active material coating material according to the present invention is 1,000 or more and 5,000,000 or less, preferably 1,000 or more and 1,000,000 or less. By adjusting the number average molecular weight, aggregation of the negative electrode active material, which tends to occur when the negative electrode active material is coated, can be suppressed.
  • the “polymer” mentioned here includes a copolymer.
  • the composition ratio of the monomer (main monomer), which is the structural unit of the polymer represented by Chemical Formula 1, to the monomer (copolymerization monomer) to be copolymerized is x for the number of moles of the main monomer, and When y, 0 ⁇ x / (x + y) ⁇ 1, preferably 0.1 ⁇ x / (x + y) ⁇ 1, more preferably 0.25 ⁇ x / (x + y) ⁇ 0.75. is there.
  • a coating material for a negative electrode active material that has a smaller irreversible capacity and a low battery resistance can be provided.
  • the method for coating the negative electrode active material with the coating material is not particularly limited.
  • a negative electrode active material surface is prepared by preparing a solution in which a negative electrode active material coating material is dissolved in a solvent, mixing the negative electrode active material in the solution, and then evaporating the solvent. It is preferable to coat with.
  • the solvent is not particularly limited as long as the polymer dissolves well. Protic solvents such as water and ethanol, aprotic solvents such as N-methylpyrrolidone, nonpolar solvents such as toluene and hexane, and the like can be used.
  • the separator 11 is inserted between the positive electrode 10 and the negative electrode 12 to prevent the positive electrode 10 and the negative electrode 12 from being short-circuited.
  • a sheet made of a polyolefin polymer such as polyethylene or polypropylene, or a sheet having a two-layer structure in which a fluorine polymer sheet made of polyolefin polymer and tetrafluoropolyethylene is laminated is used. It is possible.
  • a sheet having a thin layer formed of a mixture of ceramic and binder on the surface may be used. Since the separator 11 needs to allow lithium ions to pass therethrough during charge / discharge of the battery, generally, a large number of fine pores having a diameter of 0.01 to 10 ⁇ m are provided so as to have a porosity of 20 to 90%. .
  • Electrode> As an electrolytic solution, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or the like mixed with ethylene carbonate is used as a solvent, and lithium hexafluorophosphate (LiPF 6 ) or lithium borofluoride (LiBF 4 ) is used as an electrolyte in this solvent. ) Is generally used. However, there are no particular restrictions on the type of solvent or electrolyte, and the mixing ratio thereof, and electrolytes other than those described above can also be used.
  • non-aqueous solvents examples include propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, ⁇ -butyrolactone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxyethane, 2-methyl Tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, methyl propionate, ethyl propionate, phosphate triester, trimethoxymethane, dioxolane, diethyl ether, sulfolane, 3-methyl-2-oxazolidinone, Tetrahydrofuran, 1,2-diethoxyethane, chloroethylene carbonate, fluoroethylene carbonate, chloropropylene carbonate, etc. . Solvents other than those described above may be used as long as they do not decompose in the positive electrode 10 or the negative electrode 12.
  • Nonaqueous electrolytes in which these lithium salts are dissolved in the above various nonaqueous solvents can be used.
  • An electrolyte other than the above may be used as long as it does not decompose in the positive electrode 10 or the negative electrode 12.
  • solid polymer electrolyte polymer electrolyte
  • ion conductive polymers such as polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polyhexafluoropropylene, and polyethylene oxide can be used.
  • these solid polymer electrolytes there is an advantage that the separator 11 can be omitted.
  • An ionic liquid can also be used as the electrolyte.
  • the ionic liquid include 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF4), a mixed salt of lithium salt LiN (SO 2 CF 3 ) 2 (LiTFSI), triglyme and tetraglyme, and a cyclic quaternary ammonium type.
  • EMI-BF4 1-ethyl-3-methylimidazolium tetrafluoroborate
  • LiTFSI lithium salt LiN (SO 2 CF 3 ) 2
  • triglyme and tetraglyme tetraglyme
  • a cyclic quaternary ammonium type LiN (SO 2 CF 3 ) 2
  • a combination that does not decompose in the positive electrode 10 or the negative electrode 12 can be selected from a cation (for example, N-methyl-N-propylpyrrolidinium) and an imide anion (for
  • Example 1 Preparation of coating material for negative electrode active material>
  • monomer A represented by Chemical Formula 11 and Tetrohydrofuran as a reaction solvent were added, AIBN (azoisobutylnitrile) was further added as a polymerization initiator, and heated at a temperature of 60 ° C. for 3 hours.
  • Polymer A was polymerized where the Z moiety had the structure of Formula 8.
  • the part of X in Chemical formula 8 was Li (lithium).
  • the concentration of the polymerization initiator was 4% by mass with respect to the mass of the monomer.
  • the polymer A corresponds to the coating material for a negative electrode active material according to the present invention.
  • the produced negative electrode was punched into a circle having a diameter of 15 mm to produce an evaluation electrode.
  • a separator was sandwiched between the evaluation electrode and the Li metal electrode, and the sample was inserted into the container, and an electrolytic solution was injected to prepare an evaluation cell.
  • the evaluation cell was charged at a current density of 0.72 mA / cm 2 to a preset lower limit voltage, and then discharged at a current density of 0.72 mA / cm 2 to a preset upper limit voltage.
  • the lower limit voltage was 0.01V, and the upper limit voltage was 1.5V.
  • the irreversible capacity was determined from the difference between the charge capacity and the discharge capacity obtained during charge / discharge.
  • the same electrode as the above evaluation electrode was produced.
  • a separator was sandwiched between the evaluation electrode as the negative electrode and the positive electrode and the battery was inserted into the battery container, and an electrolytic solution was injected into the battery container to produce an evaluation battery.
  • the positive electrode was produced by the following procedure.
  • LiCoO 2 as a positive electrode active material, graphite (SP270: manufactured by Nippon Graphite Industries) as a conductive agent, and polyvinylidene fluoride as a binder are mixed so as to have a mass ratio of 85: 7.5: 7.5.
  • N-methyl-2-pyrrolidone was added to adjust the viscosity to prepare a positive electrode mixture slurry.
  • This positive electrode mixture slurry was applied to the surface of an aluminum foil having a thickness of 20 ⁇ m by a doctor blade method, and then the solvent was evaporated and further pressed to produce a positive electrode.
  • the coating amount of the positive electrode mixture was 200 g / m 2 .
  • the battery for evaluation was charged at a current density of 0.72 mA / cm 2 to a preset upper limit voltage, and then discharged at a current density of 0.72 mA / cm 2 to a preset lower limit voltage.
  • the upper limit voltage was 4.2V
  • the lower limit voltage was 3.0V.
  • the discharge capacity obtained during discharge was taken as the initial capacity of the battery.
  • the battery was charged to 50% of the initial capacity, and the DC resistance at that time was measured.
  • Example 2 A coating material for a negative electrode active material was prepared by the following procedure. That is, the monomer B represented by the chemical formula 12 was polymerized by the same procedure as in Example 1 to polymerize the polymer B in which the Z portion in the chemical formula 1 has the structure of the chemical formula 9. Note that X in Chemical Formula 9 was Li. The coating amount of the coating material with respect to the mass of the negative electrode active material was 0.5 wt%. The irreversible capacity and DC resistance were measured by the same procedure as in Example 1 except that the above-described negative electrode active material coating material was used. Polymer B corresponds to the negative electrode active material coating material according to the present invention.
  • Example 3 A coating material for a negative electrode active material was prepared by the following procedure. That is, the monomer C represented by the chemical formula 13 was polymerized by the same procedure as in Example 1 to polymerize the polymer C in which the Z portion in the chemical formula 1 has the structure of the chemical formula 10. Note that X in Chemical Formula 10 was Li. The coating amount of the coating material with respect to the mass of the negative electrode active material was 0.5 wt%. The irreversible capacity and DC resistance were measured by the same procedure as in Example 1 except that the above-described negative electrode active material coating material was used. The polymer C corresponds to the negative electrode active material coating material according to the present invention.
  • Example 4 A coating material for a negative electrode active material was prepared by the following procedure. That is, the monomer A (main monomer) and the monomer shown in Chemical Formula 5 (copolymerization monomer) are mixed so as to have a molar ratio of 75:25, and then polymerized to copolymerize as a coating material for the negative electrode active material. Polymer D was synthesized. Note that the Y portion in Chemical Formula 5 was Li. The coating amount of the coating material with respect to the mass of the negative electrode active material was 0.5 wt%. The irreversible capacity and DC resistance were measured by the same procedure as in Example 1 except that the above-described negative electrode active material coating material was used.
  • Example 5 The irreversible capacity and direct current were the same as in Example 4 except that the copolymer A was prepared by setting the molar ratio of the monomer A (main monomer) and the monomer (copolymerized monomer) shown in Chemical Formula 5 to 50:50. Resistance was measured.
  • Example 6 The irreversible capacity and direct current were the same as in Example 4 except that the copolymer A was prepared by setting the molar ratio of the monomer A (main monomer) and the monomer (copolymerized monomer) shown in Chemical Formula 5 to 25:75. Resistance was measured.
  • the irreversible capacity is 25.4 mAhg ⁇ 1 in the comparative example, whereas in Examples 1 to 6, all are lower than 25 mAhg ⁇ 1 . From this, it can be seen that the irreversible capacity could be reduced by producing the negative electrode using the negative electrode active material whose surface was coated with the negative electrode active material coating material according to the present invention. In Examples 4 to 6, a low value lower than 24 mAhg ⁇ 1 was obtained. From this, it can be seen that the irreversible capacity could be further reduced by using the coating material made of a copolymer.
  • the direct current resistance was 11.5 ⁇ in the comparative example, whereas all of Examples 1 to 6 were less than 11 ⁇ , and the negative electrode active material whose surface was coated with the coating material for negative electrode active material according to the present invention. It can be seen that the battery resistance can be lowered by producing the negative electrode using the substance.
  • X in the chemical formulas 8 to 10 is Li in all examples, but the same effect can be obtained even when X is hydrogen or an alkali metal or alkaline earth metal other than Li. Is obtained.
  • the portion indicated by Y in the structures shown in the chemical formulas 3 to 7 is Li in any of the examples, but the same effect can be obtained even when Y is hydrogen or an alkali metal other than Li. can get.
  • a coating material for a negative electrode active material for a lithium ion secondary battery capable of reducing the irreversible capacity and the battery resistance, and a lithium ion secondary coated with the coating material can be provided.

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Abstract

La présente invention concerne un matériau de revêtement de matériaux actifs d'électrode négative de batteries secondaires au lithium-ion composé d'un polymère représenté par la formule chimique (1). Dans la formule (1), Z a une structure représentée par la formule chimique (2); R1, R2 et R3 représentent individuellement un groupe alkyle, un groupe halogène ou un groupe hydrogène; et m1, n1 et n2 représentent individuellement le nombre de répétitions de chaque unité structurale. Dans la formule chimique (2), A et B représentent individuellement un groupe fonctionnel contenant un élément halogène ou un atome d'hydrogène; A et/ou B représentent un groupe fonctionnel contenant un élément halogène; et X représente un atome d'hydrogène, un atome de métal alcalin ou un atome de métal alcalino-terreux.
PCT/JP2013/070763 2013-07-31 2013-07-31 Matériau de revêtement de matériaux actifs d'électrode négative de batteries secondaires au lithium-ion, matériau actif d'électrode négative de batteries secondaires au lithium-ion revêtu dudit matériau de revêtement et batterie secondaire au lithium-ion utilisant ledit matériau actif d'électrode négative dans l'électrode négative WO2015015598A1 (fr)

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PCT/JP2013/070763 WO2015015598A1 (fr) 2013-07-31 2013-07-31 Matériau de revêtement de matériaux actifs d'électrode négative de batteries secondaires au lithium-ion, matériau actif d'électrode négative de batteries secondaires au lithium-ion revêtu dudit matériau de revêtement et batterie secondaire au lithium-ion utilisant ledit matériau actif d'électrode négative dans l'électrode négative

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PCT/JP2013/070763 WO2015015598A1 (fr) 2013-07-31 2013-07-31 Matériau de revêtement de matériaux actifs d'électrode négative de batteries secondaires au lithium-ion, matériau actif d'électrode négative de batteries secondaires au lithium-ion revêtu dudit matériau de revêtement et batterie secondaire au lithium-ion utilisant ledit matériau actif d'électrode négative dans l'électrode négative

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160017068A1 (en) * 2014-07-18 2016-01-21 Shin-Etsu Chemical Co., Ltd. Polymer compound for a conductive polymer and method for producing same
US20170058066A1 (en) * 2015-08-24 2017-03-02 Shin-Etsu Chemical Co., Ltd. Polymer compound for a conductive polymer and method for producing same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007072948A1 (fr) * 2005-12-22 2007-06-28 Jsr Corporation Composition de liant et bouillie pour une electrode de batterie secondaire et electrode de batterie secondaire
WO2011024789A1 (fr) * 2009-08-24 2011-03-03 Jsr株式会社 Composition pour former une électrode, bouillie pour former une électrode, électrode et dispositif électrochimique
JP2012084420A (ja) * 2010-10-13 2012-04-26 Hitachi Maxell Energy Ltd リチウム二次電池
JP2013114945A (ja) * 2011-11-30 2013-06-10 Hitachi Ltd リチウム二次電池正極活物質用被覆材、リチウム二次電池正極活物質、リチウム二次電池、および、それらの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007072948A1 (fr) * 2005-12-22 2007-06-28 Jsr Corporation Composition de liant et bouillie pour une electrode de batterie secondaire et electrode de batterie secondaire
WO2011024789A1 (fr) * 2009-08-24 2011-03-03 Jsr株式会社 Composition pour former une électrode, bouillie pour former une électrode, électrode et dispositif électrochimique
JP2012084420A (ja) * 2010-10-13 2012-04-26 Hitachi Maxell Energy Ltd リチウム二次電池
JP2013114945A (ja) * 2011-11-30 2013-06-10 Hitachi Ltd リチウム二次電池正極活物質用被覆材、リチウム二次電池正極活物質、リチウム二次電池、および、それらの製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160017068A1 (en) * 2014-07-18 2016-01-21 Shin-Etsu Chemical Co., Ltd. Polymer compound for a conductive polymer and method for producing same
US9663593B2 (en) * 2014-07-18 2017-05-30 Shin-Etsu Chemical Co., Ltd. Polymer compound for a conductive polymer and method for producing same
US20170058066A1 (en) * 2015-08-24 2017-03-02 Shin-Etsu Chemical Co., Ltd. Polymer compound for a conductive polymer and method for producing same
US9777093B2 (en) * 2015-08-24 2017-10-03 Shin-Etsu Chemical Co., Ltd. Polymer compound for a conductive polymer and method for producing same

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