WO2019031349A1 - Electrode for lithium secondary batteries and method for producing same - Google Patents

Electrode for lithium secondary batteries and method for producing same Download PDF

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Publication number
WO2019031349A1
WO2019031349A1 PCT/JP2018/028838 JP2018028838W WO2019031349A1 WO 2019031349 A1 WO2019031349 A1 WO 2019031349A1 JP 2018028838 W JP2018028838 W JP 2018028838W WO 2019031349 A1 WO2019031349 A1 WO 2019031349A1
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Prior art keywords
electrode
layer
pai
porous
solvent
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PCT/JP2018/028838
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French (fr)
Japanese (ja)
Inventor
健太 柴田
耕 竹内
山田　宗紀
朗 繁田
良彰 越後
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ユニチカ株式会社
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Priority to JP2019535139A priority Critical patent/JP7113527B2/en
Priority to CN201880050976.6A priority patent/CN111033817A/en
Priority to KR1020207003143A priority patent/KR102579616B1/en
Publication of WO2019031349A1 publication Critical patent/WO2019031349A1/en

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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
    • 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
    • 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
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • 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 an electrode for a lithium secondary battery which is excellent in safety, high in capacity, and excellent in charge and discharge cycle characteristics, and a method of manufacturing the same.
  • the electrical insulating properties of the separator in contact with the electrode may be destroyed due to scratches or irregularities on the surface of the electrode. As a result, an electrical internal short circuit may occur.
  • Patent Document 1 applies a solution in which a heat resistant polymer such as polyamideimide (PAI) is dissolved on the positive electrode surface, and immerses the positive electrode in a coagulating solution containing a poor solvent for PAI.
  • a method of manufacturing a positive electrode for a lithium secondary battery in which the porous PAI layer and the positive electrode are integrated is proposed by depositing PAI or the like and drying.
  • the ion permeability of the porous layer made of PAI or the like manufactured using such a method is not sufficient, the internal resistance of the electrode becomes high, and as a result, there is a problem that good charge / discharge characteristics can not be obtained. there were.
  • the method of obtaining the porous layer using the above-mentioned coagulation liquid also has a problem as a manufacturing method from the viewpoint of environmental compatibility.
  • Patent Document 2 discloses that a uniform solution containing a good solvent and a poor solvent for a heat resistant polymer such as PAI is applied to the electrode surface and dried. Methods have been proposed for forming a texture layer.
  • the ion permeability is not sufficient to be an electrode for a lithium secondary battery that can be charged and discharged in a short time, and the ion permeability is further improved, It was necessary to provide a porous PAI layer with further reduced internal resistance.
  • this invention solves the said subject, and it aims at providing the electrode for lithium secondary batteries which was excellent in safety
  • the present inventors have solved the above problems by an electrode in which a porous PAI layer obtained from a PAI solution is specified by specifying the chemical structure of PAI and specifying the solvent composition of the PAI solution for application as a specific one.
  • the present invention has been completed.
  • the present invention is as follows.
  • An electrode for a lithium secondary battery in which the porous PAI layer is integrally laminated on the surface of the electrode active material layer, and the porous PAI layer has the following features. 1) The ion conductivity of the porous PAI layer is 0.6 mS / cm or more. 2) The thickness of the porous PAI layer is more than 1 ⁇ m and less than 30 ⁇ m. ⁇ 2> A dispersion containing a binder, active material fine particles, and a solvent is applied to the surface of a metal foil that is a current collector of an electrode for lithium secondary batteries, and dried to form an electrode active material layer on the metal foil.
  • a coating solution containing PAI and a solvent is applied to the surface of the electrode active material layer to form a coating film, and then the solvent in the coating film is removed to separate the phases in the coating film.
  • PAI is used as a diamine component.
  • DADE 4,4′-diaminodiphenyl ether
  • TG tetraglyme
  • the electrode for a lithium secondary battery of the present invention is excellent in ion permeability, so the internal resistance of the electrode is low and the safety is excellent. Therefore, it can be suitably used as an electrode for a lithium secondary battery that can be charged and discharged in a short time. Further, in the production method of the present invention, the electrode of the present invention can be easily produced by a simple process.
  • the electrode for a lithium secondary battery of the present invention is one in which a porous PAI layer is laminated and integrated on the surface of an electrode active material layer.
  • the lithium secondary battery electrode is an electrode constituting a lithium secondary battery, and a positive electrode in which a positive electrode active material layer is bonded to a positive electrode current collector, or a negative electrode active material layer is bonded to a negative electrode current collector Refers to the negative electrode.
  • the electrode active material layer is a generic term for a positive electrode active material layer and a negative electrode active material layer.
  • metal foils such as copper foil, stainless steel foil, nickel foil, and aluminum foil can be used.
  • Aluminum foil is preferably used for the positive electrode, and copper foil is preferably used for the negative electrode.
  • the thickness of these metal foils is preferably 5 to 50 ⁇ m, more preferably 9 to 18 ⁇ m.
  • the surface of these metal foils may be roughened or rustproofed to improve the adhesion to the active material layer.
  • the positive electrode active material layer is a layer obtained by binding positive electrode active material particles with a binder.
  • a material used as a positive electrode active material particle what can occlude and preserve lithium ion is preferable, and a material generally used as a positive electrode active material of a lithium secondary battery can be mentioned.
  • oxide systems LiCoO 2 , LiNiO 2 , LiMn 2 O 4 etc.
  • complex oxide systems LiCo 1/3 Ni 1/3 Mn 1/3 O 2 etc.
  • iron phosphate systems LiFePO 4 , Li etc.
  • Active material particles such as FePO 4 F, etc., and high molecular weight compounds (polyaniline, polythiophene, etc.) can be mentioned.
  • LiCoO 2 , LiNiO 2 and LiFePO 4 are preferable.
  • conductive particles such as carbon (graphite, carbon black, etc.) particles and metal (silver, copper, nickel, etc.) particles are blended in an amount of about 1 to 30 mass% in order to reduce the internal resistance. It may be
  • the negative electrode active material layer is a layer obtained by binding negative electrode active material particles with a binder.
  • a material used as negative electrode active material particles those which can occlude and store lithium ions are preferable, and materials generally used as a negative electrode active material of a lithium secondary battery can be mentioned.
  • active material particles of graphite, amorphous carbon, silicon, tin and the like can be mentioned.
  • graphite particles and silicon particles are preferable.
  • Examples of silicon-based particles include particles of simple silicon, silicon alloys, silicon-silicon dioxide composites, and the like. Among these silicon-based particles, particles of simple silicon (hereinafter sometimes abbreviated as “silicon particles”) are preferable.
  • Silicon alone refers to crystalline or amorphous silicon having a purity of 95% by mass or more.
  • conductive particles such as carbon (graphite, carbon black, etc.) particles and metal (silver, copper, nickel, etc.) particles are blended in an amount of about 1 to 30 mass% in order to reduce the internal resistance. It may be
  • the particle diameter of each of the active material particles and the conductive particles is preferably 50 ⁇ m or less, and more preferably 10 ⁇ m or less for both of the positive electrode and the negative electrode.
  • the particle diameter is usually 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, because the binding by the binder becomes difficult if the particle diameter is too small.
  • the porosity of the electrode active material layer is preferably 5 to 50% by volume, and more preferably 10 to 40% by volume, for both the positive electrode and the negative electrode.
  • the thickness of the electrode active material layer is usually about 20 to 200 ⁇ m.
  • binder for binding the active material particles examples include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene / butadiene copolymer rubber, poly Examples thereof include tetrafluoroethylene, polypropylene, polyethylene and imide polymers. Among these, polyvinylidene fluoride, styrene-butadiene copolymer rubber, and imide polymers are preferable.
  • the active material layer of a positive electrode or a negative electrode can apply
  • porous PAI having high ion permeability is laminated and integrated on the surface of the electrode active material layer.
  • PAI constituting the porous PAI layer is a polymer obtained by performing a polycondensation reaction of a tricarboxylic acid component as a raw material and a diamine component.
  • the tricarboxylic acid component of PAI is an organic compound having three carboxyl groups (including its derivatives) and one or more aromatic rings per molecule, and at least two of the three carboxyl groups have carboxyl groups. The group is placed at a position that can form an acid anhydride form.
  • aromatic tricarboxylic acid component a benzene tricarboxylic acid component and a naphthalene tricarboxylic acid component can be mentioned, for example.
  • benzenetricarboxylic acid component examples include, for example, trimellitic acid, hemimellitic acid, and their anhydrides and their monochlorides.
  • naphthalene tricarboxylic acid component examples include, for example, 1,2,3-naphthalene tricarboxylic acid, 1,6,7-naphthalene tricarboxylic acid, 1,4,5-naphthalene tricarboxylic acid, and anhydrides thereof and monochlorides thereof Can be mentioned.
  • trimellitic anhydride and trimellitic anhydride chloride are preferred.
  • the tricarboxylic acid component may be used alone or in combination of two or more.
  • the tricarboxylic acid component is partially composed of terephthalic acid, isophthalic acid, pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid Or the like may be used.
  • the diamine component of PAI is an organic compound having two primary amino groups (including its derivatives) per molecule.
  • the diamine component of PAI forming the porous PAI layer of the present invention preferably contains DADE.
  • the DADE is more preferably 30 to 100 mol%, further preferably 40 to 100 mol%, particularly preferably 50 to 100 mol%, based on the total diamine component of PAI.
  • DADE is more preferably 30 to 100 mol%, further preferably 40 to 100 mol%, particularly preferably 50 to 100 mol%, based on the total diamine component of PAI.
  • diamine components copolymerized with DADE include m-phenylenediamine (MDA), p-phenylenediamine, 4,4'-diphenylmethanediamine (DMA), 4,4'-diphenyletherdiamine, diphenylsulfone- Mention 4,4'-diamine, diphenyl-4,4'-diamine, o-tolidine, 2,4-tolylenediamine, 2,6-tolylenediamine, xylylenediamine, naphthalenediamines, and their diisocyanate derivatives Can.
  • MDA m-phenylenediamine
  • DMA 4,4'-diphenylmethanediamine
  • DMA 4,4'-diphenyletherdiamine
  • diphenylsulfone- Mention 4'-diamine, diphenyl-4,4'-diamine o-tolidine
  • 2,4-tolylenediamine 2,6-tolylenedi
  • MDA is preferred.
  • the diamine component used by copolymerizing with said DADE may be used independently, and may be used combining 2 or more types.
  • PAI usually has a glass transition temperature of 200 ° C. or higher.
  • the glass transition temperature uses the value measured by DSC (differential thermal analysis).
  • the PAI used in the present invention can be obtained using known methods. That is, for example, it is possible to use PAI isolated as a powder from a solution obtained by blending the tricarboxylic acid component as the raw material and the diamine component in approximately equimolar amounts and polymerizing them in the mixed solvent. Can.
  • the porous PAI layer of the present invention needs to have an ion conductivity of 0.6 mS / cm or more.
  • the ion conductivity is preferably 0.7 mS / cm or more, more preferably 0.8 mS / cm or more, and still more preferably 0.9 mS / cm or more.
  • a porous layer exhibiting such high conductivity is not conventionally known, and the porous PAI of the present invention With a layer, it is a down arrow.
  • C represents the electrode area (cm 2 )
  • B represents the thickness ( ⁇ m) of the porous PAI layer.
  • this ion conductivity is a value evaluated as a lamination
  • the porous PAI of the present invention needs to have a thickness of more than 1 ⁇ m and less than 30 ⁇ m, and preferably more than 5 ⁇ m and less than 25 ⁇ m. More preferably, the thickness is more than 5 ⁇ m and less than 20 m. If the thickness is 1 ⁇ m or less, the insulating property of the porous PAI layer may be insufficient, and the safety as an electrode may not be secured. In addition, when the thickness is 30 ⁇ m or more, the ion permeability is impaired, and when the electrode is formed, the internal resistance is increased.
  • the thickness of the porous PAI indicates a value calculated by acquiring an SEM image obtained by observing an electrode cross section in which the porous PAI is laminated and integrated and observing a 500 ⁇ magnification electron microscope.
  • a coating solution containing, for example, PAI and a solvent is applied to the surface of the electrode active material layer to form a coating film, and then the solvent in the coating film is removed to form a phase in the coating film. Separation can occur to form a porous PAI layer.
  • This coating solution can be obtained by dissolving the aforementioned PAI powder in a solvent.
  • a solvent used here, it is preferable to use a mixed solvent composed of an amide-based solvent which is a good solvent for PAI and TG (boiling point: 275 ° C.) which is a poor solvent for PAI.
  • Specific examples of amide solvents include N-methyl-2-pyrrolidone (NMP boiling point: 202 ° C.), N, N-dimethylformamide (boiling point: 153 ° C.), N, N-dimethylacetamide (DMAc boiling point: 166 ° C.) Can be mentioned. These amide solvents may be used alone or in combination of two or more. Among these, NMP is preferable.
  • a good solvent means a solvent having a solubility of 1% by mass or more at 25 ° C. in PAI.
  • the poor solvent refers to a solvent having a solubility in PAI of less than 1% by mass at 25 ° C.
  • the mixed solvent is preferably a mixed solvent composed of 5 parts by mass or more and 20 parts by mass or less of an amide solvent and 95 parts by mass or less and 80 parts by mass or more of TG, and is 10 parts by mass or more and 20 parts by mass or less It is more preferable to set it as the mixed solvent which consists of 90 mass parts or less and 80 mass parts or more of TG of this.
  • the mixed solvent is a mixture of an amide solvent and a TG solvent so that the total amount thereof is 100 parts by mass.
  • additives such as various surfactants and organic silane coupling agents may be added to the PAI coating solution as long as the effects of the present invention are not impaired.
  • polymers other than PAI may be added to the PAI coating solution as long as the effects of the present invention are not impaired.
  • fillers such as alumina, silica, boehmite and kaolin may be added.
  • a PAI coating solution is applied to the surface of the electrode active material layer, dried at 100 to 150 ° C., and optionally heat-treated at 250 to 350 ° C. to form porous PAI having good ion permeability. be able to.
  • the porosity of the formed porous PAI can be 30 to 90% by volume.
  • the average pore diameter of the imide porous layer can be 0.1 to 10 ⁇ m. By setting the porosity and the average pore diameter in such a range, good ion permeability is ensured.
  • the porosity and the average pore diameter can be adjusted by selecting the type of amide solvent in the PAI coating solution and the blending amount of TG.
  • the porosity can also be adjusted by selecting the drying conditions.
  • a method of applying continuously by roll-to-roll or a method of applying a sheet can be adopted, and any method may be used.
  • a coating apparatus a die coater, a multilayer die coater, a gravure coater, a comma coater, a reverse roll coater, a doctor blade coater or the like can be used.
  • the electrode of the present invention is formed by applying the above-mentioned coating solution on a substrate having releasability such as polyester film, aluminum foil and the like to form a porous PAI film, which is then coated on the electrode active material. It can also be obtained by laminating and integrating, and then peeling off the substrate having releasability.
  • the electrode (a positive electrode and a negative electrode) of the present invention can constitute a cell by laminating a common lithium secondary battery separator made of porous polyolefin or the like between the electrodes.
  • the electrode of the present invention can also be used as an electrode for constituting a so-called "separatorless" cell without using such a separator.
  • the electrode (negative electrode) active material layer used in the following Examples and Comparative Examples was obtained as follows.
  • N-methyl-2-pyrrolidone 88 parts by mass of graphite particles (average particle diameter: 8 ⁇ m) which is a negative electrode active material, 5 parts by mass of carbon black (acetylene black) which is a conductive additive, and 7 parts by mass of PVDF which is a binder resin
  • the mixture was uniformly dispersed therein to obtain an anode active material dispersion having a solid content concentration of 25% by mass.
  • This dispersion is applied to a copper foil having a thickness of 18 ⁇ m, which is a negative electrode current collector, and the resulting coated film is dried at 150 ° C. for 20 minutes and then heat pressed to form a 100 ⁇ m thick film formed on the copper foil.
  • An electrode (N-1) provided with a negative electrode active material layer was obtained.
  • the ionic conductivity of the electrodes obtained in the following Examples and Comparative Examples was evaluated by the following method.
  • An electrode in which a porous PAI layer is integrally laminated on the surface of N-1 is punched into a circle having a diameter of 1.6 cm to form a symmetric cell consisting of an electrode / a separator (thickness 20 ⁇ m) consisting of a polyethylene porous membrane / an electrode
  • An electrolytic solution (solvent: mixed solvent of ethylene carbonate and dimethyl carbonate mixed at a volume ratio of 1: 1, electrolyte: 1 M LiPF 6 ) is injected, and stored in a flat cell made of stainless steel (manufactured by Takumi Giken)
  • a cell (C-1) for evaluation was obtained.
  • C-2 a cell (C-2) for evaluation was obtained using N-1 (unlaminated electrode).
  • the impedance of C-1 and C-2 was measured using an AC impedance measuring device (Celltest System 1470E manufactured by Solartron Analysis). The measurement conditions were as follows.
  • Example 1 In a dry nitrogen gas atmosphere, DADE (0.07 mol) and MDA (0.03 mol) are added to a glass reaction vessel, NMP and 0.1 mol of triethylamine are added to this, and the NMP solution with a solid content concentration of 15% by mass is stirred. I got Thereafter, while the solution was kept at 10 ° C. or less, a solution of 0.1 mol of TAC in NMP (solid content concentration: 20% by mass) was slowly dropped under stirring. After the addition was completed, the solution was returned to room temperature and stirring was continued for 2 hours. The resulting solution is poured into a large amount of water to precipitate PAI, which is filtered and washed to obtain a yellow solid, which is then heated at 200 ° C.
  • PAI powder (AP) was obtained by carrying out.
  • the Tg of the AP by DSC was 285 ° C.
  • AP was dissolved in a mixed solvent of NMP and TG to obtain a PAI coating solution (L-1) having a solid content concentration of 9% by mass.
  • the mixing ratio of NMP and TG was such that the amount of TG was 85% by mass with respect to the mass of the mixed solvent.
  • L-1 was applied to the surface of the electrode (N-1) and dried at 150 ° C. for 20 minutes to obtain an electrode (P-1) on which a porous PAI layer having a thickness of 10 ⁇ m was formed.
  • the evaluation results of this porous PAI layer are shown in Table 1.
  • Example 2 An electrode (P-2) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that 0.1 mol of DADE alone was used as the diamine and the thickness of the porous PAI layer was 8 ⁇ m. The evaluation results of this porous PAI layer are shown in Table 1.
  • Example 3 An electrode (P-3) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that “a mixture of 0.05 mol of DADE and 0.05 mol of MDA” was used as the diamine. The evaluation results of this porous PAI layer are shown in Table 1.
  • Example 4 An electrode (P-4) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that “a mixture of 0.03 mol of DADE and 0.07 mol of MDA” was used as the diamine. The evaluation results of this porous PAI layer are shown in Table 1.
  • Example 5 An electrode (P-4) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that DMAc was used as an amide solvent and the thickness of the porous PAI layer was 6 ⁇ m. The evaluation results of this porous PAI layer are shown in Table 1.
  • Example 6 An electrode (P-6) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that “a mixture of 0.05 mol of DADE and 0.05 mol of DMA” was used as the diamine. The evaluation results of this porous PAI layer are shown in Table 1.
  • Example 7 An electrode (P-7) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that the thickness of the porous PAI was 15 ⁇ m. The evaluation results of this porous PAI layer are shown in Table 1.
  • Example 8 An electrode (P-8) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that the TG amount of the mixed solvent was set to 82 mass% with respect to the mass of the mixed solvent. The evaluation results of this porous PAI layer are shown in Table 1.
  • Example 9 An electrode (P-9) on which a porous PAI layer was formed in the same manner as in Example 1 except that the TG amount of the mixed solvent was 82 mass% with respect to the mass of the mixed solvent and the thickness of the porous PAI layer was 15 ⁇ m Got). The evaluation results of this porous PAI layer are shown in Table 1.
  • Example 10 An electrode (P-10) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that the amount of TG of the mixed solvent was set to 87 mass% with respect to the mass of the mixed solvent. The evaluation results of this porous PAI layer are shown in Table 1.
  • Comparative Example 1 An electrode (R-1) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that “a mixture of 0.01 mol of DADE and 0.09 mol of MDA” was used as the diamine. The evaluation results of this porous PAI layer are shown in Table 1.
  • Comparative Example 2 An electrode (R-2) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that “a mixture of 0.01 mol of DADE and 0.09 mol of DMA” was used as the diamine. The evaluation results of this porous PAI layer are shown in Table 1.
  • Comparative Example 3 An electrode in which a porous PAI layer was formed in the same manner as in Example 1 except that “a mixture of 0.01 mol of DADE and 0.09 mol of MDA” was used as the diamine and the thickness of the porous PAI layer was 6 ⁇ m I got R-3). The evaluation results of this porous PAI layer are shown in Table 1.
  • Comparative Example 4 An electrode (R-4) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that the amount of TG of the mixed solvent was set to 75% by mass with respect to the mass of the mixed solvent. The evaluation results of this porous PAI layer are shown in Table 1.
  • Comparative Example 5 An electrode (R-5) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that the amount of TG of the mixed solvent was 65 mass% with respect to the mass of the mixed solvent. The evaluation results of this porous PAI layer are shown in Table 1.
  • Comparative Example 6 An electrode (R-6) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that the thickness of the porous PAI layer was 35 ⁇ m. The evaluation results of this porous PAI layer are shown in Table 1.
  • Comparative Example 7 An electrode (R-7) in which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that 0.1 mol of DADE alone was used as the diamine and the thickness of the porous PAI layer was 35 ⁇ m. The evaluation results of this porous PAI layer are shown in Table 1.
  • Comparative Example 8 An electrode (R-8) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that only 0.1 mol of DMA was used as a diamine. The evaluation results of this porous PAI layer are shown in Table 1.
  • Comparative Example 9 An electrode (R-9) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that only 0.1 mol of MDA was used as a diamine. The evaluation results of this porous PAI layer are shown in Table 1.
  • Comparative Example 10 An electrode (R-10) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that the mixed solvent TG was changed to triethylene glycol dimethyl ether (TRG). The evaluation results of this porous PAI layer are shown in Table 1.
  • Comparative Example 11 An electrode (R-11) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that diethylene glycol dimethyl ether (DG) was used as the mixed solvent TG. The evaluation results of this porous PAI layer are shown in Table 1.
  • DG diethylene glycol dimethyl ether
  • Comparative Example 12 An electrode (R-12) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that only NMP was used as the solvent for dissolving AP obtained in Example 1. The evaluation results of this porous PAI layer are shown in Table 1.
  • Comparative Example 13 An electrode (R-13) in which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that “a mixture of 0.02 mol of DADE and 0.08 mol of MDA” was used as the diamine. The evaluation results of this porous PAI layer are shown in Table 1.
  • Comparative Example 14 An electrode (R-14) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that “a mixture of 0.02 mol of DADE and 0.08 mol of DMA” was used as the diamine. The evaluation results of this porous PAI layer are shown in Table 1.
  • the porous PAI layer of the present invention having a specific ion conductivity and thickness has a sufficiently lowered resistance, so an electrode obtained by laminating and integrating the same Can be suitably used as a lithium secondary battery electrode with enhanced safety. Further, it can be understood that good cycle characteristics can be obtained by this effect. Further, according to the manufacturing method of the present invention, it is possible to manufacture an electrode with excellent safety by a simple process with high environmental compatibility.
  • the electrode for a lithium secondary battery of the present invention can be suitably used as an electrode for a lithium secondary battery which can be charged and discharged in a short time and has high safety because its internal resistance is sufficiently low. According to the production method of the present invention, it is possible to produce an electrode with excellent safety by a simple process with high environmental compatibility.

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Abstract

The purpose of the present invention is to provide: an electrode for lithium secondary batteries, which has a sufficiently decreased internal resistance, while exhibiting excellent safety; and a method for producing this electrode for lithium secondary batteries. [1] An electrode for lithium secondary batteries, which is obtained by laminating and integrating a porous polyamide-imide (PAI) layer onto the surface of an electrode active material layer, and which is characterized in that the porous PAI layer has the following features. (1) The ion conductivity of the porous PAI layer is 0.6 mS/cm or more. (2) The thickness of the porous PAI layer is more than 1 μm but less than 30 μm. [2] A method for producing an electrode for lithium secondary batteries, wherein: a dispersion which contains a binder, active material fine particles and a solvent is applied onto the surface of a metal foil that serves as a collector of an electrode for lithium secondary batteries, and then the applied dispersion is dried, thereby forming an electrode active material layer on the metal foil; and after that, a coating liquid which contains a PAI and a solvent is applied to the surface of the electrode active material layer so as to form a coating film, and phase separation is subsequently caused within the coating film by removing the solvent from the coating film so as to form an ion-permeable porous layer, while laminating and integrating the electrode active material layer and the ion-permeable porous layer with each other. This method for producing an electrode for lithium secondary batteries is characterized in that: the PAI contains, as a diamine component, 4, 4'-diaminodiphenyl ether; and the solvent is a mixed solvent that is composed of from 5 parts by mass to 20 parts by mass (inclusive) of an amide solvent and from 80 parts by mass to 95 parts by mass (inclusive) of tetraglyme (TG) (provided that the total of the amide solvent and TG is 100 parts by mass).

Description

リチウム二次電池用電極およびその製造方法Electrode for lithium secondary battery and method of manufacturing the same
　本発明は、安全性に優れ、かつ高容量で充放電サイクル特性の良好な、リチウム二次電池用電極およびその製造方法に関する。 The present invention relates to an electrode for a lithium secondary battery which is excellent in safety, high in capacity, and excellent in charge and discharge cycle characteristics, and a method of manufacturing the same.
　リチウム二次電池において、電極表面の傷や凹凸が原因となって、電極に接しているセパレータの電気絶縁性を破壊することがある。その結果、電気的な内部短絡が発生することがある。 In a lithium secondary battery, the electrical insulating properties of the separator in contact with the electrode may be destroyed due to scratches or irregularities on the surface of the electrode. As a result, an electrical internal short circuit may occur.
　この内部短絡を防止するため、特許文献１には、ポリアミドイミド（ＰＡＩ）等の耐熱性高分子が溶解した溶液を正極面上に塗布し、ＰＡＩに対する貧溶媒を含む凝固液にこの正極を浸漬して、ＰＡＩ等を析出させ、乾燥することにより、多孔質ＰＡＩ層と正極とが一体化したリチウム二次電池用正極を製造する方法が提案されている。しかしながら、このような方法を用いて製造されたＰＡＩ等からなる多孔質層のイオン透過性は十分ではないため、電極の内部抵抗高くなり、結果として良好な充放電特性が得られないという問題があった。さらに、前記した凝固液を用いて、多孔質層を得る方法は、凝固浴から貧溶媒を含む廃液が発生するので、環境適合性の観点から、製造法としても問題があった。 In order to prevent this internal short circuit, Patent Document 1 applies a solution in which a heat resistant polymer such as polyamideimide (PAI) is dissolved on the positive electrode surface, and immerses the positive electrode in a coagulating solution containing a poor solvent for PAI. A method of manufacturing a positive electrode for a lithium secondary battery in which the porous PAI layer and the positive electrode are integrated is proposed by depositing PAI or the like and drying. However, since the ion permeability of the porous layer made of PAI or the like manufactured using such a method is not sufficient, the internal resistance of the electrode becomes high, and as a result, there is a problem that good charge / discharge characteristics can not be obtained. there were. Furthermore, since the waste liquid containing a poor solvent is generated from the coagulation bath, the method of obtaining the porous layer using the above-mentioned coagulation liquid also has a problem as a manufacturing method from the viewpoint of environmental compatibility.
　このような凝固液を用いる方法の問題を解決する方法として、特許文献２には、ＰＡＩ等の耐熱性高分子に対する良溶媒と貧溶媒を含む均一溶液を電極表面に塗布、乾燥することにより多孔質層を形成させるための方法が提案されている。 As a method of solving the problem of the method using such a coagulating solution, Patent Document 2 discloses that a uniform solution containing a good solvent and a poor solvent for a heat resistant polymer such as PAI is applied to the electrode surface and dried. Methods have been proposed for forming a texture layer.
特開平１１－１８５７３１号公報Japanese Patent Application Laid-Open No. 11-185731 国際公開２０１４／１０６９５４号公報International Publication 2014/106954
　しかしながら、この方法で得られた電極においても、短時間で充放電可能なリチウム二次電池用の電極とするには、イオン透過性が十分なものではなく、イオン透過性をさらに向上させて、内部抵抗がさらに低下した多孔質ＰＡＩ層とする必要があった。 However, even in the electrode obtained by this method, the ion permeability is not sufficient to be an electrode for a lithium secondary battery that can be charged and discharged in a short time, and the ion permeability is further improved, It was necessary to provide a porous PAI layer with further reduced internal resistance.
　そこで本発明は、前記課題を解決するものであって、安全性に優れ、内部抵抗が十分に低下したリチウム二次電池用電極とその製造方法を提供することを目的とする。 Then, this invention solves the said subject, and it aims at providing the electrode for lithium secondary batteries which was excellent in safety | security, and internal resistance reduced sufficiently, and its manufacturing method.
　本発明者らは、ＰＡＩの化学構造を特定し、かつ塗布用のＰＡＩ溶液の溶媒組成を特定のものとしたＰＡＩ溶液から得られる多孔質ＰＡＩ層を積層一体化した電極により前記課題が解決されることを見出し、本発明の完成に至った。 The present inventors have solved the above problems by an electrode in which a porous PAI layer obtained from a PAI solution is specified by specifying the chemical structure of PAI and specifying the solvent composition of the PAI solution for application as a specific one. The present invention has been completed.
　本発明は以下を趣旨とするものである。 The present invention is as follows.
＜１＞　電極活物質層の表面に、多孔質ＰＡI層が積層一体化したリチウム二次電池用電極であって、多孔質ＰＡＩ層が以下の特徴を有するリチウム二次電池用電極。
１）多孔質ＰＡＩ層のイオン伝導度が０．６ｍＳ／ｃｍ以上である。
２）多孔質ＰＡＩ層の厚みが１μｍ超、３０μｍ未満である。
＜２＞　リチウム二次電池用電極の集電体である金属箔の表面に、バインダと活物質微粒子と溶媒とを含む分散体を塗布し乾燥して金属箔上に電極活物質層を形成させ、その後、この電極活物質層の表面にＰＡＩと溶媒とを含む塗液を塗布して塗膜を形成し、しかる後、前記塗膜中の溶媒を除去することにより、塗膜内で相分離を起こさせてイオン透過性多孔質層を形成せしめるとともに、前記電極活物質層と前記イオン透過性多孔質層とを積層一体化するリチウム二次電池用電極の製造方法において、ＰＡＩがジアミン成分として４，４′－ジアミノジフェニルエーテル（ＤＡＤＥ）を含み、溶媒が５質量部以上、２０質量部以下のアミド系溶媒と、９５質量部以下、８０質量部以上のテトラグライム（ＴＧ）とからなる混合溶媒（ただし、前記アミド系溶媒とＴＧの合計量が１００質量部）であることを特徴とする前記リチウム二次電池用電極の製造方法。
＜３＞　ＤＡＤＥの含有量が、全ジアミン成分に対し、３０～１００モル％である前記リチウム二次電池用電極の製造方法。 <1> An electrode for a lithium secondary battery in which the porous PAI layer is integrally laminated on the surface of the electrode active material layer, and the porous PAI layer has the following features.
1) The ion conductivity of the porous PAI layer is 0.6 mS / cm or more.
2) The thickness of the porous PAI layer is more than 1 μm and less than 30 μm.
<2> A dispersion containing a binder, active material fine particles, and a solvent is applied to the surface of a metal foil that is a current collector of an electrode for lithium secondary batteries, and dried to form an electrode active material layer on the metal foil. Then, a coating solution containing PAI and a solvent is applied to the surface of the electrode active material layer to form a coating film, and then the solvent in the coating film is removed to separate the phases in the coating film. In the method for producing an electrode for a lithium secondary battery, in which the ion active porous layer is formed while the ion active porous layer is laminated and integrated, PAI is used as a diamine component. A mixed solvent containing 4,4′-diaminodiphenyl ether (DADE), an amide solvent having a solvent content of 5 to 20 parts by mass, and 95 parts by mass or less and 80 parts by mass or more of tetraglyme (TG) (However, The total amount of the amide-based solvent and TG is 100 parts by mass), and the method for producing an electrode for a lithium secondary battery described above.
<3> The method for producing an electrode for a lithium secondary battery, wherein the content of DADE is 30 to 100 mol% with respect to all diamine components.
　本発明のリチウム二次電池用電極は、イオン透過性に優れるので、電極の内部抵抗が低く、安全性に優れる。
　従い、短時間で充放電可能なリチウム二次電池用の電極として好適に用いることができる。また、本発明の製造方法においては、本発明の電極を、簡単なプロセスで容易に製造することができる。 The electrode for a lithium secondary battery of the present invention is excellent in ion permeability, so the internal resistance of the electrode is low and the safety is excellent.
Therefore, it can be suitably used as an electrode for a lithium secondary battery that can be charged and discharged in a short time. Further, in the production method of the present invention, the electrode of the present invention can be easily produced by a simple process.
　本発明のリチウム二次電池用電極は、電極活物質層の表面に、多孔質ＰＡＩ層が積層一体化されたものである。リチウム二次電池用電極とは、リチウム二次電池を構成する電極であって、正極活物質層が正極集電体に接合された正極、もしくは、負極活物質層が負極集電体に接合された負極をいう。電極活物質層は、正極活物質層と負極活物質層の総称である。 The electrode for a lithium secondary battery of the present invention is one in which a porous PAI layer is laminated and integrated on the surface of an electrode active material layer. The lithium secondary battery electrode is an electrode constituting a lithium secondary battery, and a positive electrode in which a positive electrode active material layer is bonded to a positive electrode current collector, or a negative electrode active material layer is bonded to a negative electrode current collector Refers to the negative electrode. The electrode active material layer is a generic term for a positive electrode active material layer and a negative electrode active material layer.
　集電体としては、銅箔、ステンレス箔、ニッケル箔、アルミ箔等の金属箔を使用することができる。正極にはアルミ箔が、負極には銅箔が好ましく用いられる。これらの金属箔の厚みは５～５０μｍが好ましく、９～１８μｍがより好ましい。これらの金属箔の表面は、活物質層との接着性を向上させるための粗面化処理や防錆処理がされていてもよい。 As the current collector, metal foils such as copper foil, stainless steel foil, nickel foil, and aluminum foil can be used. Aluminum foil is preferably used for the positive electrode, and copper foil is preferably used for the negative electrode. The thickness of these metal foils is preferably 5 to 50 μm, more preferably 9 to 18 μm. The surface of these metal foils may be roughened or rustproofed to improve the adhesion to the active material layer.
　正極活物質層は、正極活物質粒子をバインダで結着して得られる層である。正極活物質粒子として用いられる材料としては、リチウムイオンを吸蔵保存できるものが好ましく、リチウム二次電池の正極活物質として一般に用いられるものを挙げることができる。例えば、酸化物系（ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＭｎ２Ｏ４等）、複合酸化物系（ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２等）、リン酸鉄系（ＬｉＦｅＰＯ４、Ｌｉ２ＦｅＰＯ４Ｆ等）、高分子化合物系（ポリアニリン、ポリチオフェン等）等の活物質粒子を挙げることができる。この中でも、ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＦｅＰＯ４が好ましい。正極活物質層には、その内部抵抗を低下させるため、カーボン（黒鉛、カーボンブラック等）粒子や金属（銀、銅、ニッケル等）粒子等の導電性粒子が、１～３０質量％程度配合されていてもよい。 The positive electrode active material layer is a layer obtained by binding positive electrode active material particles with a binder. As a material used as a positive electrode active material particle, what can occlude and preserve lithium ion is preferable, and a material generally used as a positive electrode active material of a lithium secondary battery can be mentioned. For example, oxide systems (LiCoO 2 , LiNiO 2 , LiMn 2 O 4 etc.), complex oxide systems (LiCo 1/3 Ni 1/3 Mn 1/3 O 2 etc.), iron phosphate systems (LiFePO 4 , Li etc.) 2 Active material particles, such as FePO 4 F, etc., and high molecular weight compounds (polyaniline, polythiophene, etc.) can be mentioned. Among these, LiCoO 2 , LiNiO 2 and LiFePO 4 are preferable. In the positive electrode active material layer, conductive particles such as carbon (graphite, carbon black, etc.) particles and metal (silver, copper, nickel, etc.) particles are blended in an amount of about 1 to 30 mass% in order to reduce the internal resistance. It may be
　負極活物質層は、負極活物質粒子をバインダで結着して得られる層である。負極活物質粒子として用いられる材料としては、リチウムイオンを吸蔵保存できるものが好ましく、リチウム二次電池の負極活物質として一般に用いられるものを挙げることができる。例えばグラファイト、アモルファスカーボン、シリコン系、錫系等の活物質粒子を挙げることができる。この中でもグラファイト粒子、シリコン系粒子が好ましい。シリコン系粒子としては、例えば、シリコン単体、シリコン合金、シリコン・二酸化珪素複合体等の粒子を挙げることができる。これらシリコン系粒子の中でも、シリコン単体の粒子（以下、「シリコン粒子」と略記することがある）が好ましい。シリコン単体とは、純度が９５質量％以上の結晶質もしくは非晶質のシリコンをいう。負極活物質層には、その内部抵抗を低下させるため、カーボン（黒鉛、カーボンブラック等）粒子や金属（銀、銅、ニッケル等）粒子等の導電性粒子が、１～３０質量％程度配合されていてもよい。 The negative electrode active material layer is a layer obtained by binding negative electrode active material particles with a binder. As a material used as negative electrode active material particles, those which can occlude and store lithium ions are preferable, and materials generally used as a negative electrode active material of a lithium secondary battery can be mentioned. For example, active material particles of graphite, amorphous carbon, silicon, tin and the like can be mentioned. Among these, graphite particles and silicon particles are preferable. Examples of silicon-based particles include particles of simple silicon, silicon alloys, silicon-silicon dioxide composites, and the like. Among these silicon-based particles, particles of simple silicon (hereinafter sometimes abbreviated as “silicon particles”) are preferable. Silicon alone refers to crystalline or amorphous silicon having a purity of 95% by mass or more. In the negative electrode active material layer, conductive particles such as carbon (graphite, carbon black, etc.) particles and metal (silver, copper, nickel, etc.) particles are blended in an amount of about 1 to 30 mass% in order to reduce the internal resistance. It may be
　活物質粒子や導電性粒子の粒子径は、正極、負極いずれも５０μｍ以下が好ましく、１０μｍ以下がさらに好ましい。粒子径は、反対に小さすぎてもバインダによる結着が難しくなるので、通常０．１μｍ以上、好ましくは０．５μｍ以上である。 The particle diameter of each of the active material particles and the conductive particles is preferably 50 μm or less, and more preferably 10 μm or less for both of the positive electrode and the negative electrode. The particle diameter is usually 0.1 μm or more, preferably 0.5 μm or more, because the binding by the binder becomes difficult if the particle diameter is too small.
　電極活物質層の気孔率は、正極、負極いずれも５～５０体積％が好ましく、１０～４０体積％がより好ましい。 The porosity of the electrode active material layer is preferably 5 to 50% by volume, and more preferably 10 to 40% by volume, for both the positive electrode and the negative electrode.
　電極活物質層の厚みは、通常２０～２００μｍ程度である。 The thickness of the electrode active material layer is usually about 20 to 200 μm.
　前記活物質粒子を結着させるためのバインダとしては、例えば、ポリフッ化ビニリデン、ビニリデンフロライド－ヘキサフルオロプロピレン共重合体、ビニリデンフロライド－テトラフルオロエチレン共重合体、スチレン・ブタジエン共重合ゴム、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレン、イミド系高分子等を挙げることができる。この中でもポリフッ化ビニリデン、スチレン・ブタジエン共重合ゴム、イミド系高分子が好ましい。 Examples of the binder for binding the active material particles include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene / butadiene copolymer rubber, poly Examples thereof include tetrafluoroethylene, polypropylene, polyethylene and imide polymers. Among these, polyvinylidene fluoride, styrene-butadiene copolymer rubber, and imide polymers are preferable.
　正極または負極の活物質層は、バインダと活物質微粒子と溶媒とを含む分散体を塗布し乾燥して金属箔上に電極活物質層を形成させることができる。 The active material layer of a positive electrode or a negative electrode can apply | coat and dry the dispersion containing a binder, active material microparticles, and a solvent, and can form an electrode active material layer on metal foil.
　本発明の電極においては、電極活物質層の表面に高いイオン透過性を有する多孔質ＰＡＩが積層一体化されている。 In the electrode of the present invention, porous PAI having high ion permeability is laminated and integrated on the surface of the electrode active material layer.
　多孔質ＰＡＩ層を構成するＰＡＩは、原料であるトリカルボン酸成分とジアミン成分との重縮合反応を行うことにより得られる高分子である。 PAI constituting the porous PAI layer is a polymer obtained by performing a polycondensation reaction of a tricarboxylic acid component as a raw material and a diamine component.
　ＰＡＩのトリカルボン酸成分は、１分子あたり３個のカルボキシル基（その誘導体を含む）および１個以上の芳香環を有する有機化合物であって、当該３個のカルボキシル基のうち、少なくとも２個のカルボキシル基が酸無水物形態を形成し得る位置に配置されたものである。 The tricarboxylic acid component of PAI is an organic compound having three carboxyl groups (including its derivatives) and one or more aromatic rings per molecule, and at least two of the three carboxyl groups have carboxyl groups. The group is placed at a position that can form an acid anhydride form.
　芳香族トリカルボン酸成分として、例えば、ベンゼントリカルボン酸成分、ナフタレントリカルボン酸成分を挙げることができる。 As an aromatic tricarboxylic acid component, a benzene tricarboxylic acid component and a naphthalene tricarboxylic acid component can be mentioned, for example.
　ベンゼントリカルボン酸成分の具体例として、例えば、トリメリット酸、ヘミメリット酸、ならびにこれらの無水物およびそのモノクロライドを挙げることができる。 Specific examples of the benzenetricarboxylic acid component include, for example, trimellitic acid, hemimellitic acid, and their anhydrides and their monochlorides.
　ナフタレントリカルボン酸成分の具体例として、例えば、１，２，３－ナフタレントリカルボン酸、１，６，７－ナフタレントリカルボン酸、１，４，５－ナフタレントリカルボン酸、ならびにこれらの無水物およびそのモノクロライドを挙げることができる。 Specific examples of the naphthalene tricarboxylic acid component include, for example, 1,2,3-naphthalene tricarboxylic acid, 1,6,7-naphthalene tricarboxylic acid, 1,4,5-naphthalene tricarboxylic acid, and anhydrides thereof and monochlorides thereof Can be mentioned.
　芳香族トリカルボン酸成分の中では、無水トリメリット酸および無水トリメリット酸クロライド（ＴＡＣ）が好ましい。 Among the aromatic tricarboxylic acid components, trimellitic anhydride and trimellitic anhydride chloride (TAC) are preferred.
　トリカルボン酸成分は、単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The tricarboxylic acid component may be used alone or in combination of two or more.
　また、トリカルボン酸成分は、その一部がテレフタル酸、イソフタル酸、ピロメリット酸、３，３′，４，４′－ビフェニルテトラカルボン酸、３，３′，４，４′－ベンゾフェノンテトラカルボン酸等の成分で置換されたものを用いてもよい。 Moreover, the tricarboxylic acid component is partially composed of terephthalic acid, isophthalic acid, pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid Or the like may be used.
　ＰＡＩのジアミン成分は、１分子あたり２個の１級アミノ基（その誘導体を含む）を有する有機化合物である。 The diamine component of PAI is an organic compound having two primary amino groups (including its derivatives) per molecule.
　本発明の多孔質ＰＡＩ層形成するＰＡＩのジアミン成分には、ＤＡＤＥを含むことが好ましい。
ＤＡＤＥはＰＡＩの全ジアミン成分に対し、３０～１００モル％とすることがより好ましく、４０～１００モル％がさらに好ましく、５０～１００モル％とすることが特に好ましい。このようにジアミン成分としてＤＡＤＥを用いることにより、多孔質ＰＡＩ層形成した際、良好なイオン透過性を確保することができる。このようなＤＡＤＥを含有させることによる効果のメカニズムについては、定かではないが、ＤＡＤＥのエーテル結合と、後述するＰＡＩの貧溶媒であるＴＧのエーテル結合とが、何らかの相互作用をするため、均質な多孔質構造を形成し、良好なイオン透過性が発現するものと考えられる。 The diamine component of PAI forming the porous PAI layer of the present invention preferably contains DADE.
The DADE is more preferably 30 to 100 mol%, further preferably 40 to 100 mol%, particularly preferably 50 to 100 mol%, based on the total diamine component of PAI. As described above, by using DADE as the diamine component, when the porous PAI layer is formed, good ion permeability can be secured. Although it is not clear about the mechanism of the effect by containing such DADE, since the ether bond of DADE and the ether bond of TG which is a poor solvent of PAI mentioned later have some interaction, they are homogeneous. It is considered that a porous structure is formed and good ion permeability is exhibited.
　ＤＡＤＥと共重合して用いられるジアミン成分の具体例として、ｍ－フェニレンジアミン（ＭＤＡ）、ｐ－フェニレンジアミン、４，４′－ジフェニルメタンジアミン（ＤＭＡ）、４，４′－ジフェニルエーテルジアミン、ジフェニルスルホン－４，４′－ジアミン、ジフェニルー４，４′－ジアミン、ｏ－トリジン、２，４－トリレンジアミン、２，６－トリレンジアミン、キシリレンジアミン、ナフタレンジアミン、ならびにこれらのジイソシアネート誘導体を挙げることができる。 Specific examples of diamine components copolymerized with DADE include m-phenylenediamine (MDA), p-phenylenediamine, 4,4'-diphenylmethanediamine (DMA), 4,4'-diphenyletherdiamine, diphenylsulfone- Mention 4,4'-diamine, diphenyl-4,4'-diamine, o-tolidine, 2,4-tolylenediamine, 2,6-tolylenediamine, xylylenediamine, naphthalenediamines, and their diisocyanate derivatives Can.
　これらジアミン成分の中では、ＭＤＡが好ましい。 Among these diamine components, MDA is preferred.
　前記ＤＡＤＥと共重合して用いられるジアミン成分は、単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The diamine component used by copolymerizing with said DADE may be used independently, and may be used combining 2 or more types.
　ＰＡＩは、通常、２００℃以上のガラス転移温度を有する。ガラス転移温度は、ＤＳＣ（示差熱分析）により測定された値を用いている。 PAI usually has a glass transition temperature of 200 ° C. or higher. The glass transition temperature uses the value measured by DSC (differential thermal analysis).
　本発明で用いられるＰＡＩは、公知の方法を用いて得ることができる。すなわち、例えば、原料である前記トリカルボン酸成分および前記ジアミン成分を略等モルで　配合し、それを前記混合溶媒中で重合反応させて得られる溶液からＰＡＩを粉体として単離したものを用いることができる。 The PAI used in the present invention can be obtained using known methods. That is, for example, it is possible to use PAI isolated as a powder from a solution obtained by blending the tricarboxylic acid component as the raw material and the diamine component in approximately equimolar amounts and polymerizing them in the mixed solvent. Can.
　本発明の多孔質ＰＡＩ層は、そのイオン伝導度が０．６ｍＳ／ｃｍ以上であることが必要である。イオン伝導度は、０．７ｍＳ／ｃｍ以上とするが好ましく、０．８ｍＳ／ｃｍ以上とすることがより好ましく、０．９ｍＳ／ｃｍ以上とすることがさらに好ましい。ポリアミドイミド（ＰＡＩ）等の耐熱性高分子からなる多孔質層が積層一体化された電極において、このような高い伝導度を示す多孔質層は従来知られておらず、本発明の多孔質ＰＡＩ層をもって、嚆矢とするものである。 The porous PAI layer of the present invention needs to have an ion conductivity of 0.6 mS / cm or more. The ion conductivity is preferably 0.7 mS / cm or more, more preferably 0.8 mS / cm or more, and still more preferably 0.9 mS / cm or more. In an electrode in which a porous layer made of a heat resistant polymer such as polyamide imide (PAI) is laminated and integrated, a porous layer exhibiting such high conductivity is not conventionally known, and the porous PAI of the present invention With a layer, it is a down arrow.
　多孔質ＰＡＩ層のイオン伝導度は、公知の評価法である交流インピーダンス法によって求めることができる。具体的には電解液が含浸された積層電極からなるセルおよび未積層電極からなるセルのインピーダンス測定を行い、両セルのナイキストプロットにおけるリアルパートの抵抗値（Ω）を求め、積層電極の抵抗値から未積層電極の抵抗値を減じた値「Ａ」（Ω）から以下の計算式を用いて算出することができる。
　イオン伝導度（ｍＳ／ｃｍ）　　＝　０．１＊Ｂ／（Ａ＊Ｃ）　
ここで、Ｃは電極面積（ｃｍ２）、Ｂは多孔質ＰＡＩ層の厚み（μｍ）を表す。なお、このイオン伝導度は、電解液中の積層電極として評価した値であり、通常の高分子材料のバルク状態のイオン伝導度とは必ずしも同一の値ではない。 The ion conductivity of the porous PAI layer can be determined by an alternating current impedance method which is a known evaluation method. Specifically, the impedance of a cell consisting of a laminated electrode impregnated with an electrolytic solution and a cell consisting of a non-laminated electrode is measured, and the resistance (Ω) of the real part in the Nyquist plot of both cells is determined. It can calculate using the following formula from value "A" ((ohm)) which deducted the resistance value of the unlaminated electrode from these.
Ion conductivity (mS / cm) = 0.1 * B / (A * C)
Here, C represents the electrode area (cm 2 ), and B represents the thickness (μm) of the porous PAI layer. In addition, this ion conductivity is a value evaluated as a lamination | stacking electrode in electrolyte solution, and the ion conductivity of the bulk state of a normal polymeric material is not necessarily the same value.
　本発明の多孔質ＰＡＩは、その厚みを１μｍ超、３０μｍ未満とすることが必要であり、５μｍ超、２５μｍ未満とすることが好ましい。５μｍ超、２０ｍ未満とすることがより好ましい。厚みが１μｍ以下では、多孔質ＰＡＩ層の絶縁性が不足し、電極としての安全性が確保されないことがある。また、厚みが３０μｍ以上では、イオン透過性が損なわれ、電極とした際、内部抵抗が増加してしまう。
　多孔質ＰＡＩの厚みは、多孔質ＰＡＩが積層一体化された電極断面を、倍率５００倍の電子顕微鏡を観察することにより得られるＳＥＭ像を取得することにより算出された値を示している。 The porous PAI of the present invention needs to have a thickness of more than 1 μm and less than 30 μm, and preferably more than 5 μm and less than 25 μm. More preferably, the thickness is more than 5 μm and less than 20 m. If the thickness is 1 μm or less, the insulating property of the porous PAI layer may be insufficient, and the safety as an electrode may not be secured. In addition, when the thickness is 30 μm or more, the ion permeability is impaired, and when the electrode is formed, the internal resistance is increased.
The thickness of the porous PAI indicates a value calculated by acquiring an SEM image obtained by observing an electrode cross section in which the porous PAI is laminated and integrated and observing a 500 × magnification electron microscope.
　前記した電極活物質層の表面に、例えば、ＰＡＩと溶媒とを含む塗液を塗布して塗膜を形成し、しかる後、前記塗膜中の溶媒を除去することにより、塗膜内で相分離を起こさせて多孔質ＰＡＩ層を形成させることができる。 A coating solution containing, for example, PAI and a solvent is applied to the surface of the electrode active material layer to form a coating film, and then the solvent in the coating film is removed to form a phase in the coating film. Separation can occur to form a porous PAI layer.
　この塗液は、前記したＰＡＩ粉体を溶媒に溶解させることにより得ることができる。ここで用いられる溶媒としては、ＰＡＩに対する良溶媒であるアミド系溶媒と、ＰＡＩに対する貧溶媒であるＴＧ（沸点：２７５℃）とからなる混合溶媒を用いることが好ましい。アミド系溶媒の具体例としては、Ｎ－メチル－２－ピロリドン（ＮＭＰ　沸点：２０２℃）、Ｎ，Ｎ－ジメチルホルムアミド（沸点：１５３℃）、Ｎ，Ｎ－ジメチルアセトアミド（ＤＭＡｃ　沸点：１６６℃）を挙げることができる。アミド系溶媒は、これらを単独で用いてもよく、２種以上を組み合わせて用いてもよい。これらの中でも、ＮＭＰが好ましい。ここで、良溶媒とは、２５℃において、ＰＡＩに対する溶解度が１質量％以上の溶媒をいう。貧溶媒とは、２５℃において、ＰＡＩに対する溶解度が１質量％未満の溶媒をいう。 This coating solution can be obtained by dissolving the aforementioned PAI powder in a solvent. As the solvent used here, it is preferable to use a mixed solvent composed of an amide-based solvent which is a good solvent for PAI and TG (boiling point: 275 ° C.) which is a poor solvent for PAI. Specific examples of amide solvents include N-methyl-2-pyrrolidone (NMP boiling point: 202 ° C.), N, N-dimethylformamide (boiling point: 153 ° C.), N, N-dimethylacetamide (DMAc boiling point: 166 ° C.) Can be mentioned. These amide solvents may be used alone or in combination of two or more. Among these, NMP is preferable. Here, a good solvent means a solvent having a solubility of 1% by mass or more at 25 ° C. in PAI. The poor solvent refers to a solvent having a solubility in PAI of less than 1% by mass at 25 ° C.
　混合溶媒は、５質量部以上、２０質量部以下のアミド系溶媒と、９５質量部以下、８０質量部以上のＴＧとからなる混合溶媒とすることが好ましく、１０質量部以上、２０質量部以下のアミド系溶媒と、９０質量部以下、８０質量部以上のＴＧとからなる混合溶媒とすることがより好ましい。ただし、混合溶媒は、アミド系溶媒とＴＧの両溶媒を、その合計量が１００質量部となるように、混合してなるものとする。このような混合溶媒を用いることにより、前記塗膜中を乾燥して除去する際、塗膜内で、混合溶媒を構成する溶媒の沸点差による相分離が効率良く起こり、高いイオン透過性を有する多孔質層を形成せしめるとともに、電極活物質層と多孔質ＰＡＩとを積層一体化することができる。 The mixed solvent is preferably a mixed solvent composed of 5 parts by mass or more and 20 parts by mass or less of an amide solvent and 95 parts by mass or less and 80 parts by mass or more of TG, and is 10 parts by mass or more and 20 parts by mass or less It is more preferable to set it as the mixed solvent which consists of 90 mass parts or less and 80 mass parts or more of TG of this. However, the mixed solvent is a mixture of an amide solvent and a TG solvent so that the total amount thereof is 100 parts by mass. By using such a mixed solvent, when the inside of the coating film is dried and removed, phase separation occurs efficiently in the coating film due to the difference in boiling point of the solvent constituting the mixed solvent, and has high ion permeability. While forming the porous layer, the electrode active material layer and the porous PAI can be laminated and integrated.
　ＰＡＩ塗液には、各種界面活性剤や有機シランカップリング剤のような公知の添加物を、本発明の効果を損なわない範囲で添加してもよい。また、ＰＡＩ塗液に、ＰＡＩ以外のポリマーを、本発明の効果を損なわない範囲で添加してもよい。さらに、必要に応じて、アルミナ、シリカ、ベーマイト、カオリン等のフィラを添加してもよい。 Known additives such as various surfactants and organic silane coupling agents may be added to the PAI coating solution as long as the effects of the present invention are not impaired. In addition, polymers other than PAI may be added to the PAI coating solution as long as the effects of the present invention are not impaired. Furthermore, if necessary, fillers such as alumina, silica, boehmite and kaolin may be added.
　ＰＡＩ塗液を、電極活物質層の表面に塗布し、１００～１５０℃で乾燥後、必要に応じ、２５０～３５０℃で熱処理を行うことにより、イオン透過性が良好な多孔質ＰＡＩを形成することができる。形成された多孔質ＰＡＩの気孔率は３０～９０体積％とすることができる。また、イミド多孔質層の平均気孔径は、０．１～１０μｍとすることができる。気孔率や平均気孔径をこのような範囲とすることにより、良好なイオン透過性が確保される。気孔率や平均気孔径は、ＰＡＩ塗液中のアミド系溶媒の種類、ＴＧの配合量を選ぶことによって、調整することができる。また、乾燥条件を選ぶことによっても気孔率を調整することができる。
　なお、気孔率（体積％）は、イミド多孔質層の見掛け密度がＡ（ｇ／ｃｍ３）、ＰＡＩの真密度がＢ（ｇ／ｃｍ３）の場合、以下の計算式を用いて算出することができる。
気孔率（体積％）＝１００－Ａ＊（１００／Ｂ） A PAI coating solution is applied to the surface of the electrode active material layer, dried at 100 to 150 ° C., and optionally heat-treated at 250 to 350 ° C. to form porous PAI having good ion permeability. be able to. The porosity of the formed porous PAI can be 30 to 90% by volume. The average pore diameter of the imide porous layer can be 0.1 to 10 μm. By setting the porosity and the average pore diameter in such a range, good ion permeability is ensured. The porosity and the average pore diameter can be adjusted by selecting the type of amide solvent in the PAI coating solution and the blending amount of TG. The porosity can also be adjusted by selecting the drying conditions.
When the apparent density of the imide porous layer is A (g / cm 3 ) and the true density of PAI is B (g / cm 3 ), the porosity (volume%) is calculated using the following formula. be able to.
Porosity (volume%) = 100-A * (100 / B)
　ＰＡＩ塗液を、電極表面に塗布するに際しては、ロールツーロールにより連続的に塗布する方法、枚様で塗布する方法が採用でき、いずれの方法でもよい。塗布装置としては、ダイコータ、多層ダイコータ、グラビアコータ、コンマコータ、リバースロールコータ、ドクタブレードコータ等が使用できる。 When the PAI coating solution is applied to the electrode surface, a method of applying continuously by roll-to-roll or a method of applying a sheet can be adopted, and any method may be used. As a coating apparatus, a die coater, a multilayer die coater, a gravure coater, a comma coater, a reverse roll coater, a doctor blade coater or the like can be used.
　本発明の電極は、前記した塗液をポリエステルフィルム、アルミ箔等の離形性を有する基材上に塗布、乾燥することにより、多孔質ＰＡＩ被膜を形成させたのち、これを電極活物質上に積層一体化し、しかる後、離形性を有する基材を剥離することにより得ることもできる。 The electrode of the present invention is formed by applying the above-mentioned coating solution on a substrate having releasability such as polyester film, aluminum foil and the like to form a porous PAI film, which is then coated on the electrode active material. It can also be obtained by laminating and integrating, and then peeling off the substrate having releasability.
　本発明の電極（正極および負極）は、この電極の間に、多孔質ポリオレフィン等からなる通常のリチウム二次電池用セパレータを積層してセルを構成することができる。また、本発明の電極は、このようなセパレータを使用せずに、いわゆる「セパレータレス」のセルを構成するための電極として用いることもできる。 The electrode (a positive electrode and a negative electrode) of the present invention can constitute a cell by laminating a common lithium secondary battery separator made of porous polyolefin or the like between the electrodes. The electrode of the present invention can also be used as an electrode for constituting a so-called "separatorless" cell without using such a separator.
　以下に、実施例を挙げて、本発明をさらに詳細に説明する。なお本発明は実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited by the examples.
　以下の実施例及び比較例で使用した電極（負極）活物質層を以下のようにして得た。 The electrode (negative electrode) active material layer used in the following Examples and Comparative Examples was obtained as follows.
　負極活物質である黒鉛粒子（平均粒子径８μｍ）８８質量部と、導電助剤のカーボンブラック（アセチレンブラック）５質量部と、バインダ樹脂であるＰＶＤＦ７質量部とを、Ｎ－メチル－２－ピロリドン中に均一に分散して、固形分濃度２５質量％の負極活物質分散体を得た。この分散体を負極集電体である厚さ１８μｍの銅箔に塗布し、得られた塗膜を１５０℃で２０分乾燥後、熱プレスして、銅箔上に形成された厚みが１００μｍの負極活物質層を設けた電極（Ｎ－１）を得た。 N-methyl-2-pyrrolidone: 88 parts by mass of graphite particles (average particle diameter: 8 μm) which is a negative electrode active material, 5 parts by mass of carbon black (acetylene black) which is a conductive additive, and 7 parts by mass of PVDF which is a binder resin The mixture was uniformly dispersed therein to obtain an anode active material dispersion having a solid content concentration of 25% by mass. This dispersion is applied to a copper foil having a thickness of 18 μm, which is a negative electrode current collector, and the resulting coated film is dried at 150 ° C. for 20 minutes and then heat pressed to form a 100 μm thick film formed on the copper foil. An electrode (N-1) provided with a negative electrode active material layer was obtained.
　以下の実施例及び比較例において得られた電極のイオン伝導度は、以下の方法で評価した。 The ionic conductivity of the electrodes obtained in the following Examples and Comparative Examples was evaluated by the following method.
　Ｎ－１の表面に多孔質ＰＡＩ層を積層一体化した電極を直径１．６ｃｍの円形に打ち抜き、電極／ポリエチレン多孔質膜からなるセパレータ（厚み２０μｍ）／電極からなる対称セルを構成し、これに電解液（溶媒：エチレンカーボネートとジメチルカーボネートとを体積比で１：１の割合で混合した混合溶媒、電解質：１ＭＬｉＰＦ６）を注入して、ステンレス製のフラットセル（タクミ技研製）に収納して評価用のセル（Ｃ－１）を得た。一方、前記と同様にして、Ｎ－１（未積層電極）を用い、評価用のセル（Ｃ－２）を得た。
　Ｃ－１およびＣ－２のインピーダンスを交流インピーダンス測定装置（Ｓｏｌａｒｔｒｏｎ　Ａｎａｌｙｓｉｓ社製Ｃｅｌｌｔｅｓｔ　Ｓｙｓｔｅｍ　１４７０Ｅ）を用いて測定した。測定条件は、以下の通りであった。
＜測定条件＞
　測定温度：２５℃
　周波数範囲：１００ｍＨｚ～１ＭＨｚ
　振幅：±１０ｍＶ
　この交流インピーダンス測定により得られたナイキストプロットにおけるリアルパートの抵抗値（Ω）を求め、Ｃ－１の抵抗値（Ｒ－１）からＣ－２の抵抗値（Ｒ－２）を減じ、これを２で割った値（Ａ）を、多孔質ＰＡＩ層の抵抗値（Ω）とし、以下の計算式を用いて、多孔質ＰＡＩ層のイオン伝導度を算出した。
イオン伝導度（ｍＳ／ｃｍ）　　＝　０．０３９１＊Ｂ／Ａ
ここでＢは多孔質ＰＡＩ層の厚み（μｍ）を表す。 An electrode in which a porous PAI layer is integrally laminated on the surface of N-1 is punched into a circle having a diameter of 1.6 cm to form a symmetric cell consisting of an electrode / a separator (thickness 20 μm) consisting of a polyethylene porous membrane / an electrode An electrolytic solution (solvent: mixed solvent of ethylene carbonate and dimethyl carbonate mixed at a volume ratio of 1: 1, electrolyte: 1 M LiPF 6 ) is injected, and stored in a flat cell made of stainless steel (manufactured by Takumi Giken) Thus, a cell (C-1) for evaluation was obtained. On the other hand, in the same manner as described above, a cell (C-2) for evaluation was obtained using N-1 (unlaminated electrode).
The impedance of C-1 and C-2 was measured using an AC impedance measuring device (Celltest System 1470E manufactured by Solartron Analysis). The measurement conditions were as follows.
<Measurement conditions>
Measurement temperature: 25 ° C
Frequency range: 100mHz to 1MHz
Amplitude: ± 10mV
The resistance value (Ω) of the real part in the Nyquist plot obtained by this AC impedance measurement is determined, and the resistance value (R-2) of C-2 is subtracted from the resistance value (R-1) of C-1 The value (A) divided by 2 was used as the resistance value (Ω) of the porous PAI layer, and the ionic conductivity of the porous PAI layer was calculated using the following formula.
Ion conductivity (mS / cm) = 0.0391 * B / A
Here, B represents the thickness (μm) of the porous PAI layer.
［実施例１］
　乾燥窒素ガス雰囲気下、ガラス製反応容器に、ＤＡＤＥ０．０７モル、ＭＤＡ０．０３モルを入れ、これにＮＭＰとトリエチルアミン０．１モルを加え、撹拌することにより固形分濃度が１５質量％のＮＭＰ溶液を得た。その後、この溶液を１０℃以下に保ちつつ、ＴＡＣ０．１モルのＮＭＰ溶液（固形分濃度：２０質量％）を、撹拌下、ゆっくりと滴下した。滴下終了後、溶液を室温に戻し、２時間攪拌を続けた。得られた溶液を、大量の水に投入して、ＰＡＩの沈殿を生じせしめ、これを濾過、洗浄することにより、黄色の固体を得た後、２００℃で加熱して、乾燥とイミド化を行うことによりＰＡＩ粉体（ＡＰ）を得た。ＡＰのＤＳＣによるＴｇは２８５℃であった。次に、ＡＰをＮＭＰとＴＧとの混合溶媒に溶解し、固形分濃度が９質量％のＰＡＩ塗液（Ｌ－１）を得た。ここでＮＭＰとＴＧの混合比率は、ＴＧ量を混合溶媒質量に対し８５質量％とした。Ｌ－１を、電極（Ｎ－１）表面に塗布し、１５０℃で２０分乾燥することにより、厚みが１０μｍの多孔質ＰＡＩ層が形成された電極（Ｐ－１）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Example 1
In a dry nitrogen gas atmosphere, DADE (0.07 mol) and MDA (0.03 mol) are added to a glass reaction vessel, NMP and 0.1 mol of triethylamine are added to this, and the NMP solution with a solid content concentration of 15% by mass is stirred. I got Thereafter, while the solution was kept at 10 ° C. or less, a solution of 0.1 mol of TAC in NMP (solid content concentration: 20% by mass) was slowly dropped under stirring. After the addition was completed, the solution was returned to room temperature and stirring was continued for 2 hours. The resulting solution is poured into a large amount of water to precipitate PAI, which is filtered and washed to obtain a yellow solid, which is then heated at 200 ° C. for drying and imidization. PAI powder (AP) was obtained by carrying out. The Tg of the AP by DSC was 285 ° C. Next, AP was dissolved in a mixed solvent of NMP and TG to obtain a PAI coating solution (L-1) having a solid content concentration of 9% by mass. Here, the mixing ratio of NMP and TG was such that the amount of TG was 85% by mass with respect to the mass of the mixed solvent. L-1 was applied to the surface of the electrode (N-1) and dried at 150 ° C. for 20 minutes to obtain an electrode (P-1) on which a porous PAI layer having a thickness of 10 μm was formed. The evaluation results of this porous PAI layer are shown in Table 1.
［実施例２］
　ジアミンとしてＤＡＤＥ０．１モルのみを用い、多孔質ＰＡＩ層の厚みを８μｍとしたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｐ－２）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Example 2
An electrode (P-2) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that 0.1 mol of DADE alone was used as the diamine and the thickness of the porous PAI layer was 8 μm. The evaluation results of this porous PAI layer are shown in Table 1.
［実施例３］
　ジアミンとして「ＤＡＤＥ０．０５モルとＭＤＡ０．０５モルの混合物」を用いたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｐ－３）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 [Example 3]
An electrode (P-3) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that “a mixture of 0.05 mol of DADE and 0.05 mol of MDA” was used as the diamine. The evaluation results of this porous PAI layer are shown in Table 1.
［実施例４］
　ジアミンとして「ＤＡＤＥ０．０３モルとＭＤＡ０．０７モルとの混合物」を用いたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｐ－４）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Example 4
An electrode (P-4) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that “a mixture of 0.03 mol of DADE and 0.07 mol of MDA” was used as the diamine. The evaluation results of this porous PAI layer are shown in Table 1.
［実施例５］
　アミド系溶媒としてＤＭＡｃを用い、多孔質ＰＡＩ層の厚みを６μｍとしたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｐ－４）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 [Example 5]
An electrode (P-4) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that DMAc was used as an amide solvent and the thickness of the porous PAI layer was 6 μm. The evaluation results of this porous PAI layer are shown in Table 1.
［実施例６］
　ジアミンとして「ＤＡＤＥ０．０５モルとＤＭＡ０．０５モルの混合物」を用いたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｐ－６）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 [Example 6]
An electrode (P-6) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that “a mixture of 0.05 mol of DADE and 0.05 mol of DMA” was used as the diamine. The evaluation results of this porous PAI layer are shown in Table 1.
［実施例７］
　多孔質ＰＡＩの厚みを１５μｍとしたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｐ－７）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 [Example 7]
An electrode (P-7) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that the thickness of the porous PAI was 15 μm. The evaluation results of this porous PAI layer are shown in Table 1.
［実施例８］
　混合溶媒のＴＧ量を混合溶媒質量に対し８２質量％としたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｐ－８）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 [Example 8]
An electrode (P-8) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that the TG amount of the mixed solvent was set to 82 mass% with respect to the mass of the mixed solvent. The evaluation results of this porous PAI layer are shown in Table 1.
［実施例９］
　混合溶媒のＴＧ量を混合溶媒質量に対し８２質量％とし、多孔質ＰＡＩ層の厚みを１５μｍとしたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｐ－９）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 [Example 9]
An electrode (P-9) on which a porous PAI layer was formed in the same manner as in Example 1 except that the TG amount of the mixed solvent was 82 mass% with respect to the mass of the mixed solvent and the thickness of the porous PAI layer was 15 μm Got). The evaluation results of this porous PAI layer are shown in Table 1.
［実施例１０］
　混合溶媒のＴＧ量を混合溶媒質量に対し８７質量％としたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｐ－１０）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 [Example 10]
An electrode (P-10) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that the amount of TG of the mixed solvent was set to 87 mass% with respect to the mass of the mixed solvent. The evaluation results of this porous PAI layer are shown in Table 1.
［比較例１］
　ジアミンとして「ＤＡＤＥ０．０１モルとＭＤＡ０．０９モルとの混合物」を用いたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｒ－１）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Comparative Example 1
An electrode (R-1) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that “a mixture of 0.01 mol of DADE and 0.09 mol of MDA” was used as the diamine. The evaluation results of this porous PAI layer are shown in Table 1.
［比較例２］
　ジアミンとして「ＤＡＤＥ０．０１モルとＤＭＡ０．０９モルとの混合物」を用いたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｒ－２）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Comparative Example 2
An electrode (R-2) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that “a mixture of 0.01 mol of DADE and 0.09 mol of DMA” was used as the diamine. The evaluation results of this porous PAI layer are shown in Table 1.
［比較例３］
　ジアミンとして「ＤＡＤＥ０．０１モルとＭＤＡ０．０９モルとの混合物」を用い、多孔質ＰＡＩ層の厚みを６μｍとしたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｒ－３）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Comparative Example 3
An electrode in which a porous PAI layer was formed in the same manner as in Example 1 except that “a mixture of 0.01 mol of DADE and 0.09 mol of MDA” was used as the diamine and the thickness of the porous PAI layer was 6 μm I got R-3). The evaluation results of this porous PAI layer are shown in Table 1.
［比較例４］
　混合溶媒のＴＧ量を混合溶媒質量に対し７５質量％としたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｒ－４）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Comparative Example 4
An electrode (R-4) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that the amount of TG of the mixed solvent was set to 75% by mass with respect to the mass of the mixed solvent. The evaluation results of this porous PAI layer are shown in Table 1.
［比較例５］
　混合溶媒のＴＧ量を混合溶媒質量に対し６５質量％としたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｒ－５）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Comparative Example 5
An electrode (R-5) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that the amount of TG of the mixed solvent was 65 mass% with respect to the mass of the mixed solvent. The evaluation results of this porous PAI layer are shown in Table 1.
［比較例６］
　多孔質ＰＡＩ層の厚みを３５μｍとしたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｒ－６）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Comparative Example 6
An electrode (R-6) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that the thickness of the porous PAI layer was 35 μm. The evaluation results of this porous PAI layer are shown in Table 1.
［比較例７］
　ジアミンとしてＤＡＤＥ０．１モルのみを用い、多孔質ＰＡＩ層の厚みを３５μｍとしたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｒ－７）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Comparative Example 7
An electrode (R-7) in which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that 0.1 mol of DADE alone was used as the diamine and the thickness of the porous PAI layer was 35 μm. The evaluation results of this porous PAI layer are shown in Table 1.
［比較例８］
　ジアミンとしてＤＭＡ０．１モルのみを用いたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｒ－８）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Comparative Example 8
An electrode (R-8) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that only 0.1 mol of DMA was used as a diamine. The evaluation results of this porous PAI layer are shown in Table 1.
［比較例９］
　ジアミンとしてＭＤＡ０．１モルのみを用いたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｒ－９）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Comparative Example 9
An electrode (R-9) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that only 0.1 mol of MDA was used as a diamine. The evaluation results of this porous PAI layer are shown in Table 1.
［比較例１０］
　混合溶媒のＴＧをトリエチレングリコールジメチルエーテル（ＴＲＧ）としたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｒ－１０）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Comparative Example 10
An electrode (R-10) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that the mixed solvent TG was changed to triethylene glycol dimethyl ether (TRG). The evaluation results of this porous PAI layer are shown in Table 1.
［比較例１１］
　混合溶媒のＴＧをジエチレングリコールジメチルエーテル（ＤＧ）としたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｒ－１１）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Comparative Example 11
An electrode (R-11) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that diethylene glycol dimethyl ether (DG) was used as the mixed solvent TG. The evaluation results of this porous PAI layer are shown in Table 1.
［比較例１２］
　実施例１で得られたＡＰを溶解させるための溶媒をＮＭＰのみとしたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｒ－１２）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Comparative Example 12
An electrode (R-12) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that only NMP was used as the solvent for dissolving AP obtained in Example 1. The evaluation results of this porous PAI layer are shown in Table 1.
［比較例１３］
　ジアミンとして「ＤＡＤＥ０．０２モルとＭＤＡ０．０８モルとの混合物」を用いたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｒ－１３）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Comparative Example 13
An electrode (R-13) in which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that “a mixture of 0.02 mol of DADE and 0.08 mol of MDA” was used as the diamine. The evaluation results of this porous PAI layer are shown in Table 1.
［比較例１４］
　ジアミンとして「ＤＡＤＥ０．０２モルとＤＭＡ０．０８モルとの混合物」を用いたこと以外は、実施例１と同様にして多孔質ＰＡＩ層が形成された電極（Ｒ－１４）を得た。この多孔質ＰＡＩ層の評価結果を表１に示す。 Comparative Example 14
An electrode (R-14) on which a porous PAI layer was formed was obtained in the same manner as in Example 1 except that “a mixture of 0.02 mol of DADE and 0.08 mol of DMA” was used as the diamine. The evaluation results of this porous PAI layer are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　以上、実施例、比較例で示したように、特定のイオン伝導度と厚みとを有する本発明の多孔質ＰＡＩ層は、その抵抗が十分に低下しているので、これを積層一体化した電極は、安全性が高められたリチウム二次電池用電極として好適に用いることができる。また、この効果により良好なサイクル特性を得られることが判る。また、本発明の製造方法によれば、環境適合性の高い、簡単なプロセスで、安全性に優れた電極を製造することができる。 As described above, as shown in the examples and comparative examples, the porous PAI layer of the present invention having a specific ion conductivity and thickness has a sufficiently lowered resistance, so an electrode obtained by laminating and integrating the same Can be suitably used as a lithium secondary battery electrode with enhanced safety. Further, it can be understood that good cycle characteristics can be obtained by this effect. Further, according to the manufacturing method of the present invention, it is possible to manufacture an electrode with excellent safety by a simple process with high environmental compatibility.
　本発明のリチウム二次電池用電極は、その内部抵抗が十分に低いので、短時間で充放電可能で、かつ安全性の高いリチウム二次電池用の電極として好適に用いることができる。　本発明の製造方法によれば、環境適合性の高い、簡単なプロセスで、安全性に優れた電極を製造することができる。 The electrode for a lithium secondary battery of the present invention can be suitably used as an electrode for a lithium secondary battery which can be charged and discharged in a short time and has high safety because its internal resistance is sufficiently low. According to the production method of the present invention, it is possible to produce an electrode with excellent safety by a simple process with high environmental compatibility.

Claims (3)

  1. 　電極活物質層の表面に、多孔質ポリアミドイミド（ＰＡＩ）層が積層一体化したリチウム二次電池用電極であって、多孔質ＰＡＩ層が以下の特徴を有するリチウム二次電池用電極。
    １）多孔質ＰＡＩ層のイオン伝導度が０．６ｍＳ／ｃｍ以上である。
    ２）多孔質ＰＡＩ層の厚みが１μｍ超、３０μｍ未満である。     An electrode for a lithium secondary battery in which a porous polyamideimide (PAI) layer is integrally laminated on the surface of the electrode active material layer, wherein the porous PAI layer has the following features.
    1) The ion conductivity of the porous PAI layer is 0.6 mS / cm or more.
    2) The thickness of the porous PAI layer is more than 1 μm and less than 30 μm.
  2. 　リチウム二次電池用電極の集電体である金属箔の表面に、バインダと活物質微粒子と溶媒とを含む分散体を塗布し乾燥して金属箔上に電極活物質層を形成させ、その後、この電極活物質層の表面にＰＡＩと溶媒とを含む塗液を塗布して塗膜を形成し、しかる後、前記塗膜中の溶媒を除去することにより、塗膜内で相分離を起こさせてイオン透過性多孔質層を形成せしめるとともに、前記電極活物質層と前記イオン透過性多孔質層とを積層一体化するリチウム二次電池用電極の製造方法において、ＰＡＩがジアミン成分として４，４′－ジアミノジフェニルエーテル（ＤＡＤＥ）を含み、溶媒が５質量部以上、２０質量部以下のアミド系溶媒と、９５質量部以下、８０質量部以上のテトラグライム（ＴＧ）とからなる混合溶媒（ただし、前記アミド系溶媒とＴＧの合計量が１００質量部）であることを特徴とする請求項１記載のリチウム二次電池用電極の製造方法。 A dispersion containing a binder, fine particles of active material, and a solvent is applied to the surface of a metal foil that is a current collector of an electrode for lithium secondary batteries and dried to form an electrode active material layer on the metal foil, and A coating solution containing PAI and a solvent is applied to the surface of the electrode active material layer to form a coating, and then the solvent in the coating is removed to cause phase separation in the coating. In the method of manufacturing an electrode for a lithium secondary battery, in which the ion active porous layer is formed and the electrode active material layer and the ion permeable porous layer are laminated and integrated, PAI is used as the diamine component 4,4. A mixed solvent comprising an amide-based solvent containing 5 or more and 20 or less parts by weight of a solvent containing '-diaminodiphenyl ether (DADE), and 80 or more parts of tetraglyme (TG) or less Said Method for producing a lithium secondary battery electrode of claim 1, wherein the total amount of bromide-based solvent and TG is 100 parts by weight).
  3. 　ＤＡＤＥの含有量が、全ジアミン成分に対し、３０～１００モル％である請求項２記載のリチウム二次電池用電極の製造方法。 The method for producing an electrode for a lithium secondary battery according to claim 2, wherein the content of DADE is 30 to 100 mol% with respect to the total diamine component.
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