WO2011071106A1 - Électrode négative pour batterie secondaire et batterie secondaire équipée de cette dernière, et précurseur résineux pour liant, solution de précurseur résineux et composition de liant destinée à être utilisée dans la production d'une batterie secondaire - Google Patents

Électrode négative pour batterie secondaire et batterie secondaire équipée de cette dernière, et précurseur résineux pour liant, solution de précurseur résineux et composition de liant destinée à être utilisée dans la production d'une batterie secondaire Download PDF

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Publication number
WO2011071106A1
WO2011071106A1 PCT/JP2010/072113 JP2010072113W WO2011071106A1 WO 2011071106 A1 WO2011071106 A1 WO 2011071106A1 JP 2010072113 W JP2010072113 W JP 2010072113W WO 2011071106 A1 WO2011071106 A1 WO 2011071106A1
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Prior art keywords
secondary battery
negative electrode
active material
binder
resin precursor
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PCT/JP2010/072113
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English (en)
Japanese (ja)
Inventor
利昌 田中
和徳 小関
真二 及川
大佐 池田
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新日鐵化学株式会社
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Priority claimed from JP2010253993A external-priority patent/JP2011142068A/ja
Application filed by 新日鐵化学株式会社 filed Critical 新日鐵化学株式会社
Publication of WO2011071106A1 publication Critical patent/WO2011071106A1/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
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention provides a negative electrode for a secondary battery, a secondary battery using the same, and an electrode for a lithium secondary battery by forming an active material layer (a mixture layer) on a current collector.
  • the present invention relates to a binder resin precursor, a resin precursor solution, and a binder composition to be used.
  • Lithium secondary batteries which are one of the secondary batteries, have a higher energy density than other secondary batteries, so they can be reduced in size and weight, such as mobile phones, personal computers, and personal digital assistants (PDAs). It is widely used as a power source for mobile electronic devices such as handy video cameras, and its demand is expected to increase in the future.
  • HEVs Hybrid Electric Vehicles
  • a lithium secondary battery (lithium ion secondary battery) has a structure in which an electrolyte containing lithium ions is filled between a positive electrode and a negative electrode. Of these, for example, a negative electrode that intercalates lithium.
  • the active material is bound with a binder (binder) and includes an active material layer integrated on the current collector.
  • binder polyvinylidene fluoride (PVDF) has been mainly used so far.
  • PVDF has a problem in that the adhesive strength between the negative electrode and the positive electrode active materials or the current collector is not sufficient, the adhesiveness gradually deteriorates, and the cycle life is shortened. Further, if the battery temperature rises abnormally due to a short circuit or the like, PVDF is decomposed to generate HF, and this HF reacts violently with Li, so that the battery is damaged.
  • a negative electrode and a positive electrode using a polyimide resin as a binder have been proposed (see Patent Document 1 and Patent Document 2). Furthermore, the following improved technologies have been proposed for the negative electrode using a polyimide resin as a binder. For example, the compounding ratio of a negative electrode active material made of carbonaceous powder and a polyimide resin is specified to improve the charge / discharge capacity (see Patent Document 3), or an active material layer made of a polyimide resin and a negative electrode active material.
  • a specific acid anhydride By combining two types of polyimide resins using materials, the negative electrode active material and the binder are more reliably bonded to the current collector, and the binding force between the negative electrode active materials is increased to suppress an increase in resistance at the negative electrode.
  • Technology see Patent Document 5
  • a negative electrode active material containing silicon particles having a predetermined particle size is bound with a polyimide resin using a specific diamine to obtain a negative electrode. As withstand repeated electrodeposition, such techniques to improve the cycle characteristics (see Patent Document 6) are known.
  • Japanese Patent No. 3311402 Japanese Patent No. 3561701 JP 2008-252550 A JP 2008-84562 A Japanese Patent No. 4215532 JP 2008-34352 A
  • an object of the present invention is to provide a negative electrode capable of obtaining a secondary battery exhibiting performance such as discharge capacity, output characteristics, and cycle characteristics in a well-balanced manner.
  • Another object of the present invention is to provide a secondary battery suitable as a power source for a hybrid vehicle or an electric vehicle, using such a negative electrode.
  • Another object of the present invention is to provide a resin for a binder used for an electrode of a secondary battery that expresses performance such as discharge capacity, output characteristics, and cycle characteristics in a well-balanced manner required for a power source for a hybrid vehicle or an electric vehicle.
  • the object is to provide a precursor, a resin precursor solution, and a binder composition.
  • the present inventors were excellent in the balance of discharge capacity, output characteristics, and cycle characteristics by using a polyimide resin made from a specific acid anhydride and diamine as a raw material. It discovered that the negative electrode for secondary batteries could be obtained, and completed this invention.
  • the present invention is a negative electrode for a secondary battery including an active material layer in which a negative electrode active material is integrated with a binder, and the polyimide having a repeating unit represented by the following general formula (1) as the binder
  • a negative electrode for a secondary battery using a resin
  • Ar 1 represents a divalent aromatic diamine residue having at least two ether bonds
  • Ar 2 represents a tetravalent acid diacid represented by the following formula (2) or formula (3).
  • An anhydride residue is shown.
  • Y represents either a direct bond or —CO—.
  • the present invention is a secondary battery using the above negative electrode.
  • the present invention also relates to a resin precursor for a binder used for forming an active material layer (a mixture layer) on a current collector to form an electrode of a lithium secondary battery, the following general formula (6)
  • the resin precursor for binders is characterized by containing 50 mol% or more of a polyimide resin precursor having a repeating unit represented by: [In the formula, Ar 1 represents a divalent aromatic diamine residue having at least two ether bonds, and Ar 2 represents a tetravalent acid diacid represented by the following formula (2) or formula (3). An anhydride residue is shown. ] [In Formula (3), Y represents either a direct bond or —CO—. ]
  • the present invention is a resin precursor solution characterized by containing the binder resin precursor in an organic solvent and having a viscosity in the range of 500 to 10,000 cP.
  • the present invention is a binder composition
  • a binder composition comprising the resin precursor solution and an active material.
  • the binder composition of the present invention preferably contains 0.1 to 10% by mass of a polyimide resin precursor having a repeating unit represented by the general formula (1) with respect to the active material.
  • the active material is preferably a carbon material, and the average particle size of the active material is preferably in the range of 5 to 50 ⁇ m.
  • the negative electrode of the present invention can provide a negative electrode for a secondary battery having an excellent balance of discharge capacity, output characteristics, and cycle characteristics. Therefore, according to the negative electrode of the present invention, it is possible to obtain a secondary battery having a balance of practical characteristics required for a power source for in-vehicle use such as a hybrid vehicle or an electric vehicle.
  • a binder resin precursor, a resin precursor solution, and a binder composition suitable for forming an electrode for a secondary battery having an excellent balance of discharge capacity, output characteristics, and cycle characteristics are obtained.
  • a secondary battery having a balance of practical characteristics required for a vehicle-mounted power source such as a hybrid vehicle or an electric vehicle can be obtained.
  • the negative electrode for secondary batteries of this invention and a secondary battery using the same are first demonstrated in detail based on embodiment of the negative electrode for secondary batteries.
  • a predetermined polyimide resin is used as a binder as described below.
  • the polyimide resin is excellent in the binding force between the negative electrode active materials, and more excellent in adhesiveness to the current collector forming the negative electrode than PVDF.
  • PVDF which is a type of fluororesin
  • polyimide resin does not contain fluorine in the structure, and because it is thermally stable and has high heat resistance, the battery can be used even when the battery temperature rises abnormally. Low risk of breakage or rupture.
  • the polyimide resin used in the present invention has a repeating unit represented by the general formula (1), and Ar 1 is a divalent aromatic diamine residue having at least two ether bonds.
  • BAPP 2,2′-bis [4- (4-aminophenoxy) phenyl] propane
  • TPE-R 1,3-bis (4-amino) And phenoxy) benzene
  • APIB 1,3-bis (3-aminophenoxy) benzene
  • BAPB 4,4′-bis (4-aminophenoxy) biphenyl
  • BAPP 2,2′-bis [4- (4-aminophenoxy) phenyl] propane
  • TPE-R 1,3-bis (4-amino) And phenoxy) benzene
  • APB 1,3-bis (3-aminophenoxy) benzene
  • BAPB 4,4′-bis (4-aminophenoxy) biphenyl
  • Ar 2 shown in the general formula (1) is a tetravalent acid dianhydride residue represented by the following formula (2) or formula (3).
  • Y represents either a direct bond or —CO—.
  • Preferred acid dianhydrides that give such acid dianhydride residues are specifically pyromellitic anhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and the like.
  • the diamine and acid anhydride used as the raw material for the polyimide resin may be a mixture of two or more components, respectively, and a diamine or acid anhydride other than those represented by Ar 1 and Ar 2 may be used in combination. In that case, however, it is desirable that the ratio of the components other than those represented by Ar 1 and Ar 2 is less than 50% in terms of the molar ratio of each component.
  • Ar 1 is 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, m -Phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylethane, 4,4'- Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide,
  • Ar 2 may be used those comprising the formula (2) or (3) other than the acid dianhydride.
  • Examples of the acid anhydride in which Ar 2 gives an acid anhydride residue other than those represented by the general formulas (2) and (3) include 4,4′-oxydiphthalic dianhydride, naphthalene-2,3,6,7-tetracarboxylic Acid dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetra Carboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3 , 4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether
  • the polyimide resin of the general formula (1) When the polyimide resin of the general formula (1) is obtained, it is produced by polymerizing raw material diamine and acid anhydride in the presence of a solvent to obtain a polyimide precursor resin, followed by heat treatment and imidization. Can do.
  • a solvent When setting it as a negative electrode material binder, generally it is set as the composition for disperse-mixing with an active material, a solvent, and other required additives in the state of a polyimide precursor resin, and forming an active material layer.
  • the reaction solvent used here include dimethylacetamide, dimethylformamide, N-methylpyrrolidone, 2-butanone, diglyme, and xylene, and one or more of these may be used.
  • the polyimide precursor resin has a weight average molecular weight of 10,000 to 500, 500, from the viewpoint of the balance between the binding property / adhesiveness as a binder and the viscosity of the slurry obtained by mixing with the active material. It is preferable to be in the range of 000.
  • the negative electrode active material in this invention can be suitably selected according to the kind of secondary battery, for example, in the case of a lithium secondary battery (lithium ion secondary battery), lithium can be intercalated.
  • lithium lithium can be intercalated.
  • carbon materials such as graphite and amorphous carbon
  • lithium-transition metal compounds lithium-titanium composite oxides, metal materials, and lithium aluminum alloys
  • lithium tin An alloy lithium tin An alloy
  • a lithium alloy such as a lithium silicon alloy, or the like
  • these two or more negative electrode active materials may be used in combination.
  • carbonaceous materials are generally used, and in particular, graphite materials are excellent materials having a high energy density obtained at a high temperature of at least about 2000 ° C., usually about 2600 to 3000 ° C.
  • graphite materials are excellent materials having a high energy density obtained at a high temperature of at least about 2000 ° C., usually about 2600 to 3000 ° C.
  • a low crystalline carbon material having a low degree of graphitization is preferably used.
  • a low crystalline carbon material having a low degree of graphitization for example, a petroleum-based or coal-based heavy oil is obtained by performing a thermal decomposition / polycondensation reaction at a maximum temperature of about 400 ° C. to 800 ° C. for about 24 hours.
  • the raw coke produced and calcined coke obtained by calcining the raw coke at a maximum temperature of about 800 ° C. to 1500 ° C. may be mentioned, and these may be mixed at a predetermined ratio.
  • a material obtained by adding a boron compound, a phosphorus compound, a nitrogen compound, or the like to these carbon materials, firing, and replacing a part of carbon with a specific element can also be used.
  • the average particle diameter determined as the median diameter is preferably 5 to 50 ⁇ m, more preferably 5 to 15 ⁇ m, and the BET specific surface area is preferably 5 m 2 / g or less, more preferably. Is preferably 1 m 2 / g or less.
  • the pulverized carbon material can be used as a negative electrode active material by further firing at about 800 to 1400 ° C.
  • the polyimide resin or a precursor thereof and the negative electrode active material are mixed using a solvent such as N-methylpyrrolidone (NMP), dimethylacetamide (DMAC), dimethylformamide (DMF), water, or alcohol.
  • NMP N-methylpyrrolidone
  • DMAC dimethylacetamide
  • DMF dimethylformamide
  • water or alcohol.
  • the material of the conductive substrate used as the current collector is not particularly limited, but a metal foil such as aluminum, copper, nickel, titanium, and stainless steel can be used.
  • a metal foil such as aluminum, copper, nickel, titanium, and stainless steel
  • the form of such an electroconductive base material can be made into various forms, such as a continuous sheet, a perforated sheet, and a net-like (net-like) sheet, it is particularly preferable to use a continuous sheet.
  • the thickness of the conductive substrate is preferably 2 to 30 ⁇ m.
  • the active material layer In forming the active material layer on the current collector, a negative electrode active material and, if necessary, a conductive aid were mixed into a slurry obtained by dissolving a polyimide resin or a precursor thereof in an organic solvent such as NMP. Then, the active material layer is formed by coating the current collector with a uniform thickness by a known means such as extrusion coating, curtain coating, roll coating or gravure coating, drying to remove the organic solvent, and then heat curing. Form.
  • the content ratio of the polyimide resin with respect to the negative electrode active material is preferably in the range of 0.1 to 10% by mass, preferably 0.3 to It is good to make it the range of 8 mass%.
  • the thickness of the active material layer may be about the same as that for forming a known negative electrode for a secondary battery, and is not particularly limited, but is generally about 10 to 500 ⁇ m.
  • the negative electrode thus obtained can be suitably used as an electrode for a secondary battery such as a lithium secondary battery.
  • the opposite positive electrode includes a lithium-containing transition metal oxide LiM (1) x O 2 (where x is a numerical value in the range of 0 ⁇ x ⁇ 1).
  • M (1) represents a transition metal and is composed of at least one of Co, Ni, Mn, Ti, Cr, V, Fe, Zn, Al, Sn, and In
  • LiM (1) y M (2) 2-y O 4 wherein y is a numerical value in the range of 0 ⁇ y ⁇ 1, where M (1) and M (2) represent transition metals, Co, Ni, Mn , Ti, Cr, V, Fe, Zn, Al, Sn, In)
  • LiM (1) x PO 4 wherein x is a number in the range of 0 ⁇ x ⁇ 1, wherein M (1) represents a transition metal, Co, Ni, Mn, Ti , Cr, V
  • Examples of the electrolyte filling the space between the positive electrode and the negative electrode can be used, for example LiClO 4, LiBF 4, LiPF 6 , LiAsF 6, LiB (C 6 H 5), LiCl LiBr, Li 3 SO 3 , Li (CF 3 SO 2 ) 2 N, Li (CF 3 SO 2 ) 3 C, Li (CF 3 CH 2 OSO 2 ) 2 N, Li (CF 3 CF 2 CH 2 OSO 2 ) 2 N, Li (HCF 2 CF 2 CH 2 OSO 2 ) 2 N, Li ((CF 3 ) 2 CHOSO 2 ) 2 N, LiB [C 6 H 3 (CF 3 ) 2 ] 4 Mention may be made of mixtures of more than one species.
  • non-aqueous electrolyte examples include propylene carbonate, ethylene carbonate, butylene carbonate, chloroethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1,1-dimethoxyethane, 1,2-dimethoxyethane, 1, 2-diethoxyethane, ⁇ -butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, anisole, diethyl ether, sulfolane, methylsulfolane, acetonitrile, chloronitrile, propio Nitrile, trimethyl borate, tetramethyl silicate, nitromethane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, trimethyl orthoformate, nitrobenzene , Benzoyl chloride, benzoyl bromide, nitro
  • a predetermined polyimide resin precursor is used as described below.
  • the binder resin precursor of the present invention contains a polyimide resin precursor having a repeating unit represented by the general formula (6).
  • Ar 1 represents a divalent aromatic diamine residue having at least two ether bonds
  • Ar 2 is a tetravalent represented by Formula (2) or Formula (3).
  • An acid dianhydride residue is shown.
  • Y represents either a direct bond or —CO—.
  • Ar 1 preferably includes the following. [In Formula (4), X represents a divalent organic group having one or more aromatic rings, and preferably has a structure as shown in the following (5). ]
  • the ratio of the polyimide resin precursor having the repeating unit represented by the general formula (6) is preferably 50 mol% or more. In addition to the polyimide resin precursor having the repeating unit of the general formula (6), there is a possibility that it may be contained in less than 50 mol%.
  • Ar 1 is 4,4′-diaminodiphenyl ether.
  • a siloxane diamine having a siloxane chain having a repeating number of 1 to 20 may be used.
  • Ar 2 may be used those comprising the formula (2) or (3) other than the acid dianhydride.
  • Examples of the acid anhydride in which Ar 2 gives an acid anhydride residue other than those represented by the general formulas (2) and (3) include 4,4′-oxydiphthalic dianhydride, naphthalene-2,3,6,7-tetracarboxylic Acid dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetra Carboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3 , 4-D
  • the polyimide resin precursor having a repeating unit represented by the general formula (6) may be a resin precursor solution in a state dispersed in an organic solvent.
  • a solvent may be added separately from the solvent used during polymerization of the polyimide resin precursor.
  • Such a solvent may be the same as that used in the polymerization of the polyimide resin precursor, or may be another solvent.
  • dimethylacetamide, dimethylformamide, N-methylpyrrolidone, 2-butanone, diglyme, xylene and the like may be used, and one or more of these may be used.
  • the viscosity of the resin precursor solution is preferably in the range of 500 to 10,000 cP, more preferably in the range of 1,000 to 5,000 cP. .
  • the resin precursor solution thus obtained is mixed with an active material and other additives used as necessary to obtain a binder composition.
  • the binder composition is applied to the current collector constituting the electrode as described in detail later, and the polyimide resin precursor having the repeating unit of the general formula (6) in the composition is at this stage. It is imidized by a means such as heating to become a polyimide resin having a repeating unit represented by the following general formula (1).
  • the imidized polyimide resin having the repeating unit of the general formula (1) is obtained by imidizing the polyimide resin precursor represented by the general formula (6), and Ar 1 and Ar 2 are represented by the general formula ( This represents the same as 6). That is, Ar 1 is a divalent aromatic diamine residue having at least two ether bonds. Ar 2 shown in the general formula (4) is a tetravalent acid dianhydride residue represented by the above formula (2) or formula (3).
  • the raw material diamine and acid anhydride are polymerized in the presence of a solvent to obtain a polyimide resin precursor, and then heat treated to imidize.
  • a polyimide resin precursor is used as a binder for an electrode, as described above, a binder composition in which an active material or the like and a polyimide resin precursor are mixed is usually on a current collector. And imidized by heat treatment.
  • the solvent used for the polymerization include dimethylacetamide, dimethylformamide, N-methylpyrrolidone, 2-butanone, diglyme, xylene and the like, and one or more of these may be used.
  • the polyimide resin precursor has a weight average molecular weight in the range of 10,000 to 500,000 from the viewpoint of the balance between the binding property / adhesiveness as the binder and the viscosity of the slurry obtained by mixing with the active material. It is preferable to do so.
  • the resin precursor solution of the present invention is mixed with a positive electrode active material or a negative electrode active material depending on the application to form a binder composition.
  • the positive electrode active material and the negative electrode active material are not particularly limited, and representative examples thereof include those described above.
  • the resin precursor solution containing the polyimide resin precursor is made into a slurry using a predetermined solvent as necessary together with the positive electrode or the negative electrode active material, as exemplified above.
  • the electrode provided with the active material layer can be obtained by applying and drying on the current collector.
  • the positive electrode or negative electrode active material and, if necessary, a conductive aid are mixed with the resin precursor solution to form a slurry, and then extrusion coating, curtain coating, roll
  • the active material layer is formed by applying a uniform thickness to the current collector by a known means such as coating or gravure coating, drying and removing the organic solvent, followed by heating imidization.
  • the content ratio of the polyimide resin precursor having the repeating unit of the general formula (6) to the active material is in the range of 0.1 to 10% by mass. It is preferable to make it in the range of 0.3 to 8% by mass.
  • the thickness of the active material layer may be about the same as that for forming a known electrode for a secondary battery, and is not particularly limited, but is generally about 10 to 500 ⁇ m.
  • Binder composition production example-Example 1 First, using a refined pitch from which heavy quinoline insolubles have been removed from coal-based heavy oil, a bulk coke produced by heat treatment at a temperature of 500 ° C. for 24 hours by a delayed coking method is obtained, and finely pulverized with a jet mill. The raw coke powder having an average particle size of 9.9 ⁇ m was obtained by pulverization and sizing.
  • the bulk raw coke obtained as described above is heat-treated for 1 hour or more at a temperature from the inlet temperature of 700 ° C. to the outlet temperature of 1500 ° C. (maximum temperature reached) by a rotary kiln to obtain massive calcined coke.
  • the powder was pulverized and sized by a mill to obtain calcined coke powder having an average particle size of 9.5 ⁇ m.
  • Phosphoric acid ester (14% by mass active phosphorus solid resin: manufactured by Sanko Co., Ltd.) with respect to the total of 50 parts by mass of raw coke powder and 50 parts by mass of calcined coke powder obtained as described above (100 parts by mass of coke powder).
  • Name HCA chemical name: 9,10-dihydro-9-oxa-10-osfaphenanthrene-10-oxide) 17.9 parts by mass (phosphorus equivalent: 2.5 parts by mass), and boron carbide 3.2 parts by mass (Boron conversion: 2.5 parts by mass) was added to obtain a coke material.
  • the coke material is heated from room temperature at a rate of 600 ° C./hour, reaches 900 ° C. (maximum temperature reached), and is further held for 2 hours for carbonization treatment (firing), and a lithium secondary battery Negative electrode active material A was obtained.
  • dimethylacetamide using pyromellitic anhydride (PMDA) as the acid dianhydride and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) as the diamine is used in approximately the same mole.
  • PMDA pyromellitic anhydride
  • BAPP 2,2'-bis [4- (4-aminophenoxy) phenyl] propane
  • a precursor of polyimide resin having a weight average molecular weight of 144,000 was obtained by reacting in (DMAC) at room temperature for 4 hours.
  • the polyimide resin precursor thus obtained is used as a binder for a lithium secondary battery.
  • the negative electrode active material A obtained above and the precursor of the polyimide resin excluding the solvent (DMAC) at the time of polymerization are in a ratio of 95% by mass and 5% by mass, and dimethylacetamide (DMAC) is separately used as a solvent.
  • the mixture was added and kneaded to prepare a slurry (binder composition).
  • the composition of the obtained slurry is shown in Table 1.
  • the amount of DMAC (solvent) in the binder composition was such that the solid content concentration (polyimide resin precursor + negative electrode active material) of the slurry excluding all solvents was 50% by weight.
  • the viscosity of the polyimide resin precursor solution in Table 1 is a viscosity obtained by polymerizing raw material diamine and acid anhydride in the presence of a solvent using an E-type viscometer manufactured by TOKIMEC ( 25 ° C.).
  • the weight average molecular weight is a value in terms of polystyrene of the polyimide resin precursor.
  • Example 2 (Binder composition production example-Examples 2 to 6) Polyimide resin precursors according to Examples 2 to 6 were obtained in the same manner as in Example 1 except that the combination of acid dianhydride and diamine was changed as shown in Table 1. In addition, the polyimide resin precursors according to Examples 2 to 5 were kneaded with negative electrode active material A using dimethylacetamide (DMAC) as a solvent in the same manner as in Example 1 to obtain slurries (binder compositions). . On the other hand, about the polyimide resin precursor which concerns on Example 6, the natural graphite was used instead of the negative electrode active material A, and the slurry (binder composition) was obtained like Example 1 except it.
  • DMAC dimethylacetamide
  • BTDA 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride
  • BPDA 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride
  • TPE-R 1,3-bis (4-aminophenoxy) benzene
  • APB 1,3-bis (3-aminophenoxy) benzene
  • DSDA 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride
  • BPADA 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride
  • PDA p-Phenylenediamine DAPE: 4,4'-diaminodiphenyl ether
  • the negative electrode was produced in the following manner, and the performance as a secondary battery was evaluated. That is, the obtained binder composition was applied to a copper foil having a thickness of 10 ⁇ m so as to have a uniform thickness, and then the polyimide resin precursor was imidized by heat treatment at 350 ° C. for 30 minutes in a nitrogen atmosphere to obtain copper. An active material layer was formed on the foil. The copper foil provided with the active material layer is dried and pressed to a predetermined electrode density to produce an electrode sheet having a total thickness of 60 ⁇ m, and a negative electrode is obtained by cutting the sheet into a circle having a diameter of 15 mm ⁇ . It was.
  • a test lithium secondary battery was prepared as follows.
  • As the counter electrode metallic lithium cut out to about 15.5 mm ⁇ was used.
  • a coin cell was prepared by using a solution of LiPF 6 dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio of 1: 1) as the electrolytic solution at a concentration of 1 mol / l, and using a porous membrane of propylene as the separator. did.
  • a constant current discharge of 0.5 mA / cm 2 was initially carried out at a constant temperature of 25 ° C., with a terminal voltage lower limit voltage of 0 V and a discharge upper limit voltage of 1.5 V.
  • the discharge capacity was 313 mAh / g when the output characteristics and input characteristics at the time of carrying out constant current discharge and charging of 5 mA / cm 2 were examined by the capacity maintenance ratio, and the capacity maintenance ratio related to the output characteristics was The capacity maintenance ratio related to the input characteristics was 78.2% and 56.2%. The product of these ratios was evaluated as the input / output balance and found to be 0.44.
  • the capacity maintenance rate related to the output characteristics is obtained from the ratio of the discharge capacity during 5 mA / cm 2 constant current discharge to the initial discharge capacity, and the capacity maintenance ratio related to the input characteristics is 5 mA / cm 2 constant relative to the initial charge capacity. It calculated
  • the capacity maintenance rate after 3 cycles obtained from the ratio of the discharge capacity at the 3rd cycle to the discharge capacity at the 1st cycle by repeating the constant current discharge and the charge at 0.5 mA / cm 2 for 3 cycles is 95.2%. Met.
  • the negative electrode obtained in Comparative Example 6 for producing the negative electrode had a discharge capacity of 291 mAh / g, a capacity retention ratio of 61.2% for output characteristics, and a capacity maintenance ratio of 32.8 for input characteristics. %Met.
  • the input / output balance obtained from the product of these ratios was 0.20, and the capacity retention rate after 3 cycles obtained by repeating 3 cycles of constant current discharge and charge was 88.0%.
  • the capacity maintenance rate after 100 cycles obtained by repeating 100 cycles of constant current discharge and charge was 63.9%.
  • the bulk raw coke obtained as described above is heat-treated for 1 hour or more at a temperature from the inlet temperature of 700 ° C. to the outlet temperature of 1500 ° C. (maximum temperature reached) by a rotary kiln to obtain massive calcined coke.
  • the powder was pulverized and sized by a mill to obtain calcined coke powder having an average particle size of 9.5 ⁇ m.
  • Phosphoric acid ester (14% by mass active phosphorus solid resin: manufactured by Sanko Co., Ltd.) with respect to the total of 50 parts by mass of raw coke powder and 50 parts by mass of calcined coke powder obtained as described above (100 parts by mass of coke powder).
  • No. HCA chemical name: 9,10-dihydro-9-oxa-10-osfaphenanthrene-10-oxide
  • 17.9 parts by mass phosphorus equivalent: 2.5 parts by mass
  • the coke material is heated from room temperature at a rate of 600 ° C./hour, reaches 900 ° C. (maximum temperature reached), and is further held for 2 hours for carbonization treatment (firing), and a lithium secondary battery Negative electrode active material B was obtained.
  • a negative electrode was obtained in the same manner as in Example 7 of negative electrode production using the polyimide resin precursor used in Example 1 of binder composition production (Table 3). The obtained negative electrode was evaluated in the same manner as in Example 7. As a result, the discharge capacity was 313 mAh / g, the capacity maintenance ratio related to output characteristics was 80.1%, and the capacity maintenance ratio related to input characteristics was 57.0%. Met. The input / output balance obtained from the product of these ratios was 0.46. Further, the capacity retention rate after 3 cycles was 95.8%, and the evaluation of the cycle characteristics related to the capacity retention rate after 100 cycles was ⁇ .
  • Example 14 to 18 A negative electrode was obtained in the same manner as in Example 13 except that the binder used in Example 13 was changed to a polyimide resin precursor having the composition shown in Table 3. About the obtained negative electrode, it carried out similarly to Example 13, and evaluated discharge capacity, output characteristics, and cycling characteristics. The results are shown in Table 3. In addition, the meaning of the new abbreviation described in Table 3 is as follows, and others are as above-mentioned. Moreover, the polyimide resin was imidized by the heat processing at the time of forming an active material layer by polymerizing precursors in the same manner as in Example 1. m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl
  • the negative electrode of the present invention can provide a secondary battery with an excellent balance of discharge capacity, output characteristics, and cycle characteristics. Therefore, by using this negative electrode, it is possible to obtain a secondary battery having a balance of practical characteristics required for a power source for in-vehicle use such as a hybrid vehicle or an electric vehicle. Moreover, it is not restricted to these uses, It can utilize suitably as a power supply by which high output, a high capacity
  • the resin precursor for binder, the resin precursor solution, and the binder composition of the present invention provide an electrode useful for forming a secondary battery excellent in balance of discharge capacity, output characteristics, and cycle characteristics. Can do. Therefore, by using such an electrode, it is possible to obtain a secondary battery having a balance of practical characteristics required for a power source for use in a vehicle such as a hybrid vehicle or an electric vehicle.

Abstract

L'invention concerne une électrode négative ou analogue qui permet la production d'une batterie secondaire présentant un bon équilibre entre certaines propriétés, parmi lesquelles la capacité de décharge et les propriétés cycliques ; et un précurseur résineux pour liant ou analogue qui peut être utilisé pour la production de la batterie secondaire ou analogue. L'invention concerne plus précisément une électrode négative pour batterie secondaire, le matériau actif de l'électrode négative étant intégré à un liant constitué d'une résine de polyimide ayant un motif répétitif répondant à la formule générale (1) ; et un précurseur résineux pour liant destiné à être utilisé dans la production d'une batterie secondaire, caractérisé en ce qu'il contient 50 % en moles ou plus d'un précurseur de la résine de polyimide. [Dans la formule générale (1), Ar1 représente un résidu diamine aromatique divalent ayant au moins deux liaisons éther ; et Ar2 représente un résidu de dianhydride d'acide tétravalent répondant à la formule (2) ou (3).] [Dans la formule (3), Y représente une liaison directe ou ‑CO‑.]
PCT/JP2010/072113 2009-12-11 2010-12-09 Électrode négative pour batterie secondaire et batterie secondaire équipée de cette dernière, et précurseur résineux pour liant, solution de précurseur résineux et composition de liant destinée à être utilisée dans la production d'une batterie secondaire WO2011071106A1 (fr)

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JP2009-282097 2009-12-11
JP2009282097 2009-12-11
JP2010253993A JP2011142068A (ja) 2009-12-11 2010-11-12 バインダー用樹脂前駆体、樹脂前駆体溶液、及びバインダー組成物
JP2010253995A JP5653185B2 (ja) 2009-12-11 2010-11-12 二次電池用負極及びこれを用いた二次電池
JP2010-253995 2010-11-12
JP2010-253993 2010-11-12

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
JP2011216320A (ja) * 2010-03-31 2011-10-27 Nippon Steel Chem Co Ltd 二次電池用負極及びこれを用いた二次電池
WO2015003725A1 (fr) 2013-07-09 2015-01-15 Friedrich-Schiller-Universität Jena Polymères électroactifs, procédé de fabrication correspondant, électrode et utilisation correspondantes

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JPH10302771A (ja) * 1997-04-22 1998-11-13 Toyobo Co Ltd 二次電池用負極及びそれを用いた二次電池
JP2003193398A (ja) * 2001-12-18 2003-07-09 Ube Ind Ltd ポリイミドをバインダ−とする含浸材および積層体
JP2007012310A (ja) * 2005-06-28 2007-01-18 Jsr Corp 固体高分子電解質、プロトン伝導膜、電極電解質、電極ペーストおよび膜−電極接合体
JP2008034352A (ja) * 2006-06-30 2008-02-14 Sanyo Electric Co Ltd リチウム二次電池及びその製造方法
JP2008050611A (ja) * 2007-09-25 2008-03-06 Ube Ind Ltd バインダー樹脂
JP2009238659A (ja) * 2008-03-28 2009-10-15 Sanyo Electric Co Ltd リチウム二次電池及びその製造方法

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JPH10302771A (ja) * 1997-04-22 1998-11-13 Toyobo Co Ltd 二次電池用負極及びそれを用いた二次電池
JP2003193398A (ja) * 2001-12-18 2003-07-09 Ube Ind Ltd ポリイミドをバインダ−とする含浸材および積層体
JP2007012310A (ja) * 2005-06-28 2007-01-18 Jsr Corp 固体高分子電解質、プロトン伝導膜、電極電解質、電極ペーストおよび膜−電極接合体
JP2008034352A (ja) * 2006-06-30 2008-02-14 Sanyo Electric Co Ltd リチウム二次電池及びその製造方法
JP2008050611A (ja) * 2007-09-25 2008-03-06 Ube Ind Ltd バインダー樹脂
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011216320A (ja) * 2010-03-31 2011-10-27 Nippon Steel Chem Co Ltd 二次電池用負極及びこれを用いた二次電池
WO2015003725A1 (fr) 2013-07-09 2015-01-15 Friedrich-Schiller-Universität Jena Polymères électroactifs, procédé de fabrication correspondant, électrode et utilisation correspondantes
US10103384B2 (en) 2013-07-09 2018-10-16 Evonik Degussa Gmbh Electroactive polymers, manufacturing process thereof, electrode and use thereof

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