WO2015115243A1 - Pile secondaire à électrolyte non aqueux - Google Patents

Pile secondaire à électrolyte non aqueux Download PDF

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WO2015115243A1
WO2015115243A1 PCT/JP2015/051324 JP2015051324W WO2015115243A1 WO 2015115243 A1 WO2015115243 A1 WO 2015115243A1 JP 2015051324 W JP2015051324 W JP 2015051324W WO 2015115243 A1 WO2015115243 A1 WO 2015115243A1
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Prior art keywords
acid
negative electrode
secondary battery
electrolyte secondary
positive electrode
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PCT/JP2015/051324
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English (en)
Japanese (ja)
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弘義 武
岸井　豊
咲良 村越
植谷　慶裕
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日東電工株式会社
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte secondary battery that effectively suppresses deterioration of battery performance and has excellent cycle characteristics.
  • a secondary battery that uses a lithium-containing transition metal oxide such as lithium manganate or lithium cobaltate as an electrode active material and a carbonaceous material that can insert and desorb lithium ions as a negative electrode.
  • a lithium-containing transition metal oxide such as lithium manganate or lithium cobaltate
  • a carbonaceous material that can insert and desorb lithium ions as a negative electrode.
  • This rocking chair type secondary battery can reduce the amount of electrolyte compared to the so-called reserve type secondary battery, and can be downsized, and has a high energy density while being small. Therefore, it is widely used as an electricity storage device for the above-described electronic equipment.
  • the lithium ion secondary battery is a secondary battery that obtains electric energy by an electrochemical reaction, and has a drawback that the input / output density is low because the speed of the electrochemical reaction is low. Furthermore, since the internal resistance of the secondary battery is high, rapid discharge is difficult and rapid charge is also difficult. Moreover, since an electrode and electrolyte solution deteriorate by the electrochemical reaction accompanying charging / discharging, generally a lifetime, ie, a cycling characteristic, is not good.
  • a non-aqueous electrolyte secondary battery using a conductive polymer such as polyaniline having a dopant as a positive electrode active material is also known (Patent Document 1).
  • a secondary battery having a conductive polymer as a positive electrode active material is an anion transfer type in which an anion is doped into a positive electrode polymer during charging and the anion is dedoped from the positive electrode polymer during discharge.
  • Such a rocking chair type secondary battery cannot be constructed. Therefore, a non-aqueous electrolyte secondary battery using a conductive polymer as a positive electrode active material basically requires a large amount of electrolyte, resulting in a problem that it cannot contribute to battery size reduction.
  • a conductive polymer having a polymer anion such as polyvinyl sulfonic acid as a dopant is used for the positive electrode to be a cation transfer type so that the ion concentration in the electrolytic solution does not substantially change.
  • a secondary battery is also proposed (see Patent Document 2).
  • JP-A-3-129679 Japanese Patent Laid-Open No. 1-132052
  • Patent Document 2 still does not satisfy the cycle characteristics. Therefore, the present inventors have conducted various researches and experiments on non-aqueous electrolyte secondary batteries using a carbonaceous material capable of inserting and desorbing lithium ions from the negative electrode from the viewpoint of cycle characteristics. Therefore, efforts have been made to improve battery performance, which is a problem in the non-aqueous electrolyte secondary battery having the above structure.
  • the present invention has been made in view of such circumstances, and is a nonaqueous electrolyte secondary battery using a conductive polymer for a positive electrode, which effectively suppresses deterioration of battery performance and has excellent cycle characteristics.
  • a water electrolyte secondary battery is provided.
  • the present invention is a non-aqueous electrolyte secondary battery having an electrolyte layer, a positive electrode and a negative electrode provided opposite to each other, the positive electrode comprising a conductive polymer (a), a polycarboxylic acid And a non-aqueous electrolyte secondary battery including at least one of the metal salts (b) and the negative electrode containing lithium titanate.
  • the inventors of the present invention have made extensive studies in order to obtain an electricity storage device having no deterioration in battery performance and excellent cycle characteristics.
  • a general carbonaceous material for example, graphite
  • the present inventors have conducted intensive research in order to solve battery performance degradation in a non-aqueous electrolyte secondary battery having a positive electrode configuration containing a conductive polymer, and formed a coating film on the negative electrode to As a result of preventing side reactions, focusing on the combination of the positive electrode material and the negative electrode material, and conducting extensive research, the negative electrode containing lithium titanate is stabilized in combination with the positive electrode containing a conductive polymer. I found.
  • the non-aqueous electrolyte secondary battery of the present invention is a non-aqueous electrolyte secondary battery having an electrolyte layer and a positive electrode and a negative electrode provided to face each other, and the positive electrode is electrically conductive.
  • the conductive polymer (a) and at least one of the polycarboxylic acid and its metal salt (b) are included, and the negative electrode includes lithium titanate. Therefore, the deterioration of the battery performance is effectively suppressed and the cycle characteristics are excellent.
  • the conductive polymer (a) is at least one of polyaniline and a polyaniline derivative, battery performance such as weight energy density can be further improved.
  • polycarboxylic acid of (b) is polyacrylic acid, polymethacrylic acid, polyvinylbenzoic acid, polyallylbenzoic acid, polymethallylbenzoic acid, polymaleic acid, polyfumaric acid, polyglutamic acid, polyaspartic acid, alginic acid, carboxymethylcellulose,
  • polyacrylic acid polymethacrylic acid
  • polyvinylbenzoic acid polyallylbenzoic acid
  • polymethallylbenzoic acid polymaleic acid
  • polyfumaric acid polyglutamic acid
  • polyaspartic acid alginic acid, carboxymethylcellulose
  • each nonaqueous electrolyte secondary battery of Example 1 and Comparative Example 1 it is a graph which shows the cycle characteristic of the discharge capacity maintenance factor in 60 degreeC.
  • the vertical axis represents the discharge capacity retention rate (%) and the horizontal axis represents the number of cycles.
  • the non-aqueous electrolyte secondary battery of the present invention is a non-aqueous electrolyte secondary battery having an electrolyte layer, and a positive electrode and a negative electrode provided to face each other, and the positive electrode is made of a conductive polymer (a ) And at least one of a polycarboxylic acid and a metal salt thereof (b), and the negative electrode contains lithium titanate.
  • the positive electrode of the nonaqueous electrolyte secondary battery of the present invention contains the conductive polymer (a).
  • the conductive polymer (a) means that an ionic species is inserted into or desorbed from the polymer in order to compensate for a change in charge generated or lost by an oxidation reaction or reduction reaction of the polymer main chain.
  • a state with high conductivity is referred to as a doped state
  • a state with low conductivity is referred to as a dedope state.
  • one of the preferred conductive polymers (a) of the present invention is at least one selected from the group consisting of an inorganic acid anion, a fatty acid sulfonate anion, an aromatic sulfonate anion, a polymer sulfonate anion and a polyvinyl sulfate anion.
  • another conductive polymer preferable in the present invention is a polymer in a dedope state obtained by dedoping the conductive polymer.
  • the conductive polymer (a) include, for example, polyacetylene, polypyrrole, polyaniline, polythiophene, polyfuran, polyselenophene, polyisothianaphthene, polyphenylene sulfide, polyphenylene oxide, polyazulene, poly (3,4-ethylenediethylene). Oxythiophene) and the like and various derivatives thereof. Of these, polyaniline and polyaniline derivatives having a large electrochemical capacity are preferably used.
  • the polyaniline means a polymer obtained by electrolytic polymerization or chemical oxidative polymerization of aniline
  • the polyaniline derivative is obtained by electrolytic polymerization or chemical oxidative polymerization of an aniline derivative, for example. Refers to the polymer produced.
  • a substituent such as an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, or an alkoxyalkyl group is provided at a position other than the 4-position of aniline. What has at least one can be illustrated.
  • Preferred examples include, for example, o-substituted anilines such as o-methylaniline, o-ethylaniline, o-phenylaniline, o-methoxyaniline, o-ethoxyaniline, m-methylaniline, m-ethylaniline, m And m-substituted anilines such as -methoxyaniline, m-ethoxyaniline, m-phenylaniline and the like. These may be used alone or in combination of two or more.
  • p-phenylaminoaniline having a substituent at the 4-position can be suitably used as an aniline derivative because polyaniline is obtained by oxidative polymerization.
  • aniline or a derivative thereof may be simply referred to as “aniline”, and “at least one of polyaniline and polyaniline derivatives” may be simply referred to as “polyaniline”. Therefore, even when the polymer constituting the conductive polymer is obtained from an aniline derivative, it may be referred to as “conductive polyaniline”.
  • the positive electrode according to the nonaqueous electrolyte secondary battery of the present invention preferably further contains nitrogen in addition to the conductive polymer (a).
  • “having nitrogen” means not only when the molecular structure of the conductive polymer has an N atom, but also when adding a nitrogen source separately to the material. As described above, by containing nitrogen in the positive electrode material, the positive electrode material can more effectively adsorb acid generated in the electrolytic solution.
  • the positive electrode further has at least one (b) of polycarboxylic acid and polycarboxylic acid metal salt.
  • the component (b) will be described.
  • the polycarboxylic acid refers to a polymer having a carboxyl group in the molecule.
  • the polycarboxylic acid include polyacrylic acid, polymethacrylic acid, polyvinylbenzoic acid, polyallylbenzoic acid, polymethallylbenzoic acid, polymaleic acid, polyfumaric acid, polyglutamic acid, polyaspartic acid, alginic acid, carboxymethylcellulose, and polymers thereof.
  • a copolymer containing at least one of these repeating units is preferably used, and polyacrylic acid and polymethacrylic acid are more preferably used. These may be used alone or in combination of two or more.
  • the polycarboxylic acid metal salt is, for example, an alkali metal salt or an alkaline earth metal salt, and these may be used alone or in combination of two or more.
  • the alkali metal salt is preferably a lithium salt or a sodium salt
  • the alkaline earth metal salt is preferably a magnesium salt or a calcium salt.
  • the positive electrode according to the nonaqueous electrolyte secondary battery of the present invention is composed of a composite comprising at least the conductive polymer (a) and the component (b), and is preferably formed on a porous sheet.
  • the thickness of the positive electrode is preferably 1 to 500 ⁇ m, more preferably 10 to 300 ⁇ m.
  • the thickness of the positive electrode is obtained by measuring the positive electrode using a dial gauge (manufactured by Ozaki Mfg. Co., Ltd.) whose tip shape is a flat plate having a diameter of 5 mm, and obtaining the average of 10 measured values with respect to the surface of the electrode. .
  • a dial gauge manufactured by Ozaki Mfg. Co., Ltd.
  • the thickness of the composite is measured in the same manner as described above, the average of the measured values is obtained, and the thickness of the current collector is subtracted.
  • the thickness of the positive electrode can be obtained.
  • the positive electrode according to the nonaqueous electrolyte secondary battery of the present invention is produced, for example, as follows.
  • the component (b) is dissolved or dispersed in water, and a conductive polymer (a) powder and, if necessary, a conductive assistant such as conductive carbon black are added thereto. Disperse to prepare a paste having a solution viscosity of about 0.1 to 50 Pa ⁇ s.
  • a sheet electrode can be obtained as a porous composite having an active material-containing layer.
  • the conductive auxiliary agent is excellent in conductivity, is effective for reducing electrical resistance between battery active materials, and is a conductive material whose properties do not change depending on the potential applied during battery discharge. desirable.
  • conductive carbon black for example, acetylene black, ketjen black and the like, and fibrous carbon materials such as carbon fiber and carbon nanotube are used.
  • the component (b) is usually 1 to 100 parts by weight, preferably 2 parts per 100 parts by weight of the conductive polymer (a). It is used in the range of -70 parts by weight, most preferably in the range of 5-40 parts by weight. That is, if the amount of the component (b) relative to the conductive polymer (a) is too small, a non-aqueous electrolyte secondary battery excellent in energy density tends not to be obtained.
  • the component (b) If the amount of the material is too large, the weight of the positive electrode due to an increase in the weight of the member other than the positive electrode active material increases, so that when considering the weight of the entire battery, a high-energy density non-aqueous electrolyte secondary battery cannot be obtained. This is because there is a tendency.
  • the negative electrode according to the nonaqueous electrolyte secondary battery of the present invention is composed of a material containing lithium titanate.
  • the lithium titanate is a compound represented by the general formula Li X Ti Y O 4 , where X and Y are positive numbers.
  • Examples of such lithium titanate include Li 2.67 Ti 1.33 O 4 , LiTi 2 O 4 , Li 1.33 Ti 1.67 O 4 , Li 1.14 Ti 1.71 O 4, and the like.
  • This lithium titanate is generally in the form of particles, and in order to obtain this, a method of heating and baking a mixture of titanium oxide and a lithium compound at a temperature of 700 to 1600 ° C., producing lithium titanate hydrate in a liquid medium Thereafter, a method of firing at 200 to 1300 ° C., a method of spray-drying a slurry containing a titanate compound and a lithium compound, and a method of heating and firing are exemplified.
  • lithium titanate various commercially available products can be used in addition to those obtained by the above-mentioned production method.
  • Enamite (registered trademark) LT series manufactured by Ishihara Sangyo Co., Ltd.
  • Ishihara Sangyo Co., Ltd. can be used.
  • the particle shape is not particularly limited, such as an isotropic shape such as a spherical shape or a polyhedron shape, an anisotropic shape such as a rod shape or a plate shape, or an indefinite shape. It is preferable to aggregate the primary particles to form secondary particles because powder characteristics such as fluidity, adhesion, and filling properties are improved, and battery characteristics such as cycle characteristics are also improved.
  • the secondary particles in the present invention are in a state in which the primary particles are firmly bonded to each other, and are not easily disintegrated by industrial operations such as normal mixing, pulverization, filtration, washing, transport, weighing, bagging, and deposition. Most of them remain as secondary particles.
  • the specific surface area of the secondary particles (BET method by N 2 adsorption) is preferably in the range of 0.1 to 100 m 2 / g, and more preferably in the range of 1 to 20 m 2 / g.
  • the tap density of the secondary particles is preferably in the range of 0.5 to 2.5 g / cm 3 from the viewpoint of battery capacity, and the bulk density is in the range of 0.4 to 2.0 g / cm 3 . Preferably there is.
  • the surface of primary or secondary particles of lithium titanate is at least one coating selected from inorganic compounds such as copper, tin, carbon, silica and alumina, and organic compounds such as surfactants and coupling agents. You may have. Alternatively, different elements other than titanium and lithium can be contained in the crystal lattice by doping, etc., as long as the crystal form is not inhibited.
  • the lithium titanate is used as a negative electrode active material, and the content of lithium titanate preferably occupies 1 to 100% by weight of the negative electrode active material, more preferably 50 to 100% by weight, particularly 80 to 100% by weight. It is preferable from the viewpoint of improving the stability of the negative electrode.
  • Examples of the negative electrode active material other than the lithium titanate include materials used as the negative electrode active material of the lithium ion secondary battery, such as artificial graphite and natural graphite. These may be used alone or in combination of two or more.
  • a binder such as styrene butadiene copolymer (SBR) or polyvinylidene fluoride (PVDF), a conductive auxiliary agent such as acetylene black, carboxymethyl cellulose (CMC) Etc.
  • SBR styrene butadiene copolymer
  • PVDF polyvinylidene fluoride
  • a conductive auxiliary agent such as acetylene black, carboxymethyl cellulose (CMC) Etc.
  • the content ratio of the negative electrode active material is preferably 40 to 95% by weight of the whole negative electrode from the viewpoint of improving the stability of the negative electrode, and more preferably 50 to 90% by weight.
  • the negative electrode is prepared by adding lithium titanate particles and, if necessary, a conductive additive, a binder, etc., and dispersing in a solvent such as N-methylpyrrolidone (NMP) to collect the resulting slurry. It is obtained by applying to the body, drying, and passing through a pressing process as necessary.
  • NMP N-methylpyrrolidone
  • ⁇ Current collector> examples of the material for the current collector include metal foils such as nickel, aluminum, stainless steel, and copper, and meshes. Note that the positive electrode current collector and the negative electrode current collector may be formed of the same material or different materials.
  • the electrolytic solution is composed of an electrolyte (supporting salt) and a solvent. And in the said electrolyte solution, the negative electrode film formation agent may be contained.
  • the negative electrode film forming agent is not necessary when the negative electrode active material is composed of lithium titanate alone. What is necessary is just to consider the mixing
  • the negative electrode film-forming agent refers to a substance that acts to form a film on the surface of the negative electrode at the time of initial charging, and in particular, reacts at the time of initial charging prior to a commonly used electrolyte solvent, Those having excellent properties of the film to be formed are preferably used.
  • vinylene carbonate and fluoroethylene carbonate are preferable because they have a higher film-forming property on the negative electrode, and thus can further suppress deterioration of battery performance.
  • Examples of the electrolyte constituting the electrolytic solution include metal ions such as lithium ions and appropriate counter ions corresponding thereto, such as sulfonate ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions. , Hexafluoroarsenic ions, bis (trifluoromethanesulfonyl) imide ions, bis (pentafluoroethanesulfonyl) imide ions, halogen ions, and the like are preferably used.
  • an electrolyte examples include LiCF 3 SO 3 , LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 6 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiCl. These may be used alone or in combination of two or more.
  • the electrolytic solution contains lithium hexafluorophosphate (LiPF 6 ) as a supporting salt because deterioration of battery performance can be further suppressed.
  • the solvent constituting the electrolytic solution for example, at least one non-aqueous solvent such as carbonates, nitriles, amides, ethers, that is, an organic solvent is used.
  • organic solvents include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, acetonitrile, propionitrile, N, N'-dimethylacetamide, N-methyl-2- Examples include pyrrolidone, dimethoxyethane, diethoxyethane, and ⁇ -butyrolactone. These may be used alone or in combination of two or more.
  • the electrolyte content in the electrolyte solution a normal amount is used as the electrolyte content of the non-aqueous electrolyte secondary battery. That is, the electrolyte content in the electrolytic solution is usually used in the concentration range of 0.1 to 2.5 mol / L, preferably 0.5 to 2.0 mol / L in the electrolytic solution. . If the amount of the electrolyte is too small, there is a tendency that a non-aqueous electrolyte secondary battery having excellent weight energy density cannot be obtained. On the other hand, if the amount of the electrolyte is too large, the viscosity of the electrolyte increases and the ionic conductivity decreases. As a result, the input / output characteristics tend to be degraded.
  • the separator can prevent an electrical short circuit between the positive electrode and the negative electrode arranged to face each other, Any insulating porous sheet that is electrochemically stable, has a large ion permeability, and has a certain degree of mechanical strength may be used. Accordingly, for example, a porous film made of a resin such as paper, nonwoven fabric, polypropylene, polyethylene, or polyimide is preferably used, and these may be used alone or in combination of two or more.
  • the method for producing a non-aqueous electrolyte secondary battery of the present invention using the above material is characterized by comprising the following steps (I) to (III).
  • steps (I) to (III) this manufacturing method will be described in detail.
  • (I) A step of preparing a positive electrode and a negative electrode, arranging a separator between the two, and producing a laminate composed of the positive electrode, the separator, and the negative electrode.
  • (II) A step of accommodating at least one of the laminates in a battery container.
  • III A step of injecting an electrolytic solution into the battery container.
  • lamination is performed so that a separator is disposed between the positive electrode and the negative electrode described above, thereby producing a laminate.
  • this laminate is placed in a battery container such as an aluminum laminate package and then vacuum dried.
  • an electrolytic solution is poured into the vacuum-dried battery container.
  • the package as the battery container is sealed to complete the non-aqueous electrolyte secondary battery (laminate cell) of the present invention.
  • the non-aqueous electrolyte secondary battery of the present invention is formed into various shapes such as a film type, a sheet type, a square type, a cylindrical type, and a button type in addition to the laminate cell.
  • the reaction mixture containing the produced reaction product was further stirred for 100 minutes while cooling. Then, using a Buchner funnel and a suction bottle, the obtained solid was No. Suction filtration was performed with two filter papers (manufactured by ADVANTEC) to obtain a powder. The powder was stirred and washed in an aqueous solution of about 2 mol / L tetrafluoroboric acid using a magnetic stirrer. Then, the mixture was washed with stirring several times with acetone and filtered under reduced pressure.
  • the obtained powder was vacuum-dried at room temperature (25 ° C.) for 10 hours to obtain 12.5 g of conductive polyaniline (conductive polymer (a)) having tetrafluoroboric acid as a dopant.
  • the conductive polyaniline was a bright green powder.
  • this dedope polyaniline powder was put into a methanol solution of phenylhydrazine and subjected to reduction treatment for 30 minutes with stirring. The color of the polyaniline powder changed from brown to gray by reduction. After the reaction, it was washed with methanol, washed with acetone, filtered, and vacuum dried at room temperature to obtain polyaniline in a reduced and dedoped state.
  • aqueous solution 192.63 g 7.37 g of lithium hydroxide powder in an amount capable of lithium chlorinating the total amount of carboxyl groups of polyacrylic acid was added, and an aqueous lithium salt solution of polyacrylic acid ( 200 g of a concentration of 12% by weight was prepared and prepared.
  • the solution coating thickness was adjusted to 360 ⁇ m, and the defoaming paste was applied at a coating speed of 10 mm / second. It apply
  • this positive electrode sheet is cut into a size of 35 mm ⁇ 27 mm, a part of the active material layer is removed so that the active material layer of the positive electrode sheet has an area of 27 mm ⁇ 27 mm, and a part of the active material layer
  • the portion from which this was removed was used as a tab electrode mounting location for current extraction, and an aluminum tab was mounted by spot welding to produce a sheet-shaped flag-type positive electrode.
  • separator a nonwoven fabric (manufactured by Nippon Kogyo Paper Industries, TF40-50, thickness 50 ⁇ m, porosity 70%) was used.
  • Lithium titanate manufactured by Ishihara Sangyo Co., Ltd., Enamite (registered trademark) LT series, LT-106) 15 g, acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., Denka black granular) 3.21 g, 11.1 28.96 g of N-methyl-2-pyrrolidone solution containing 18% by weight of polyvinylidene fluoride (Kureha, KF polymer # 1100) and 18 g of N-methyl-2-pyrrolidone were weighed and stirred using a stir bar. .
  • ultrasonic treatment was performed for 4 minutes with an ultrasonic homogenizer. Thereafter, the mixture was stirred for 30 seconds at a peripheral speed of 20 m / sec using a thin film swirl type high speed mixer (manufactured by Plymix Co., Ltd., Fillmix 40-40 type) to obtain a paste having fluidity. This paste was further subjected to stirring and defoaming operation for 3 minutes using a rotation and revolution vacuum mixer (manufactured by Shinky, Awatori Nertaro ARV-310).
  • this paste was applied on an etching aluminum foil having a thickness of 30 ⁇ m to a thickness of 250 ⁇ m using an automatic coating apparatus (PI-1210 manufactured by Tester Sangyo Co., Ltd.) and a film applicator with a micrometer (manufactured by Tester Sangyo Co., Ltd.). Worked. After drying at room temperature until fluidity disappeared, a heat drying treatment was performed at 120 ° C. for 30 minutes. Next, the sheet electrode thus obtained was further vacuum-dried at 80 ° C. for 3 hours. The weight of lithium titanate per unit area on the aluminum foil was 7.1 mg / cm 2 , and the thickness of the active material layer was 100 ⁇ m.
  • the negative electrode sheet is cut into a size of 35 mm ⁇ 29 mm, and a part of the active material layer is removed so that the active material layer of the negative electrode sheet has an area of 29 mm ⁇ 29 mm.
  • the portion from which the material layer was removed was used as a tab electrode attachment location for current extraction, and an aluminum tab was attached by spot welding to produce a sheet-like flag-type negative electrode 1.
  • negative electrode 2 As the negative electrode 2 for the comparative example, a negative electrode sheet (manufactured by Piotrec Co., 0.8 mAh / cm 2 ) containing natural spherical graphite (graphite) as a negative electrode active material was used. Next, a flag-type negative electrode 2 was produced in the same manner as the flag-type negative electrode 1 except that a nickel tab was used as the current extraction tab electrode.
  • electrolyte solution i lithium hexafluorophosphate (LiPF 6 ) was dissolved at a concentration of 2 mol / L in a solvent (EC2DMC) containing ethylene carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1: 2. I prepared what I was allowed to do.
  • EC2DMC ethylene carbonate
  • DMC dimethyl carbonate
  • LiPF 6 lithium hexafluorophosphate
  • EC2DMC ethylene carbonate
  • DMC dimethyl carbonate
  • VC vinylene carbonate
  • Example 1 ⁇ Production of laminate cell> A laminate was assembled using the flag-type positive electrode, the flag-type negative electrode 1 and the separator. Specifically, the flag-type positive electrode and the separator were first vacuum-dried at 150 ° C. for 2 hours in a vacuum dryer. Next, the flag-type negative electrode 1 was vacuum-dried at 80 ° C. for 2 hours in a vacuum dryer. Next, the dried flag-type positive electrode, separator, and flag-type negative electrode 1 were placed in a glove box controlled at a dew point of ⁇ 70 ° C. or lower. Next, it laminated
  • Example 1 After putting the laminate in an aluminum laminate package, an electrolyte solution i was injected. Finally, the current extraction tab was exposed to the outside, the package was sealed, and the nonaqueous electrolyte secondary battery (laminate cell) of Example 1 was obtained.
  • Example 1 the nonaqueous electrolyte secondary battery of Comparative Example 1 was completely the same except that the upper limit voltage for charging was 3.8 V and the lower limit voltage for discharging was 2.0 V in the measurement of the initial discharge capacity at 25 ° C. described above. Similarly, the initial discharge capacity was measured. The obtained results are shown in Table 2.
  • the voltage at the upper and lower limits of charge / discharge is different from the operating potential of the negative electrode, in which lithium titanate is about 1.5 V on the lithium potential basis, whereas graphite This is because it was changed in consideration of the fact that it is around 0 V on the basis of the lithium potential.
  • 0.05 C indicates a 20 hour rate
  • the 20 hour rate means a current value that requires 20 hours to charge or discharge a battery.
  • the battery is charged to 2.3V with a current value equivalent to 1C, and after reaching 2.3V, the battery is charged with a constant voltage of 2.3V until the current value is attenuated to 20% equivalent to 1C.
  • the current value corresponding to 1 C is discharged to 55% of the initial discharge capacity at 25 ° C. to adjust the state of charge of the battery.
  • the charge value corresponding to 10% of the initial discharge capacity at 25 ° C. is the current value corresponding to 10 C.
  • Discharge capacity measurement at a current value equivalent to 0.2 C (the same method as the initial capacity measurement at the start of a 60 ° C. cycle test), and repeat the procedures (1) to (4) above.
  • the discharge capacity at a current value corresponding to 0.2 C was measured every 1000 cycles. Then, when the initial discharge capacity at the start of the 60 ° C. cycle test is 100%, the remaining ratio of these discharge capacities is defined as the discharge capacity retention rate (%), and the result is shown in FIG.
  • Example 1 using lithium titanate as the negative electrode showed the same excellent discharge capacity density, although it was slightly inferior to that of Comparative Example 1 of the graphite negative electrode. .
  • the capacity density significantly decreases with an increase in the number of cycles, and the discharge capacity retention rate decreases to about 20% after 6000 cycles.
  • the non-aqueous electrolyte secondary battery of Example 1 can suppress the decrease in capacity density even when the number of cycles increases, and the discharge capacity maintenance rate is about 80%, and has excellent cycle characteristics.
  • the use of the negative electrode film forming agent shows a large improvement tendency in the stabilization of the negative electrode in the case of the graphite negative electrode as in Comparative Example 1, but in the case of the lithium titanate negative electrode in Example 1, the negative electrode It has been found that a nonaqueous electrolyte secondary battery that effectively suppresses deterioration of battery performance and has excellent cycle characteristics can be obtained without using a film forming agent.
  • the nonaqueous electrolyte secondary battery of the present invention can be suitably used as a nonaqueous electrolyte secondary battery such as a lithium ion secondary battery.
  • the non-aqueous electrolyte secondary battery of the present invention can be used for the same applications as conventional secondary batteries.
  • portable electronic devices such as portable PCs, cellular phones, and personal digital assistants (PDAs), Widely used in driving power sources for hybrid electric vehicles, electric vehicles, fuel cell vehicles and the like.

Abstract

　Afin de fournir une pile secondaire à électrolyte non aqueux dans laquelle une quelconque dégradation de performances de la pile est efficacement supprimée et d'excellentes caractéristiques de cycles sont démontrées, la présente invention concerne une pile secondaire à électrolyte non aqueux possédant une couche d'électrolyte et une électrode positive et une électrode négative fournies de façon à se faire face mutuellement avec la couche d'électrolyte intercalé entre elles, l'électrode positive contenant (a) un polymère électroconducteur et (b) un acide polycarboxylique et/ou un sel métallique de celui-ci et l'électrode négative contenant du titanate de lithium.
PCT/JP2015/051324 2014-01-31 2015-01-20 Pile secondaire à électrolyte non aqueux WO2015115243A1 (fr)

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CN106770555B (zh) * 2016-12-29 2018-12-28 信阳师范学院 一种快速测定日落黄的电化学传感器、制备方法及在测定日落黄中的应用
JP2020004551A (ja) * 2018-06-26 2020-01-09 日東電工株式会社 正極用活物質、正極、蓄電デバイス、及び正極用活物質の製造方法
KR20220048069A (ko) * 2020-10-12 2022-04-19 주식회사 엘지에너지솔루션 리튬 이차전지용 양극 슬러리 조성물, 양극 및 이를 포함하는 리튬 이차전지

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000030692A (ja) * 1998-07-08 2000-01-28 Sanyo Electric Co Ltd 非水電解液二次電池
WO2007064043A1 (fr) * 2005-12-02 2007-06-07 Gs Yuasa Corporation Batterie electrolytique non aqueuse et son procede de production
JP2012033783A (ja) * 2010-07-30 2012-02-16 Nitto Denko Corp 電気二重層キャパシタ
WO2013002415A1 (fr) * 2011-06-29 2013-01-03 日東電工株式会社 Batterie rechargeable à électrolyte non aqueux et feuille d'électrode positive pour celle-ci
JP2013239305A (ja) * 2012-05-14 2013-11-28 Nitto Denko Corp 蓄電デバイス、それに用いる正極並びに多孔質シート、およびドープ率向上方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000030692A (ja) * 1998-07-08 2000-01-28 Sanyo Electric Co Ltd 非水電解液二次電池
WO2007064043A1 (fr) * 2005-12-02 2007-06-07 Gs Yuasa Corporation Batterie electrolytique non aqueuse et son procede de production
JP2012033783A (ja) * 2010-07-30 2012-02-16 Nitto Denko Corp 電気二重層キャパシタ
WO2013002415A1 (fr) * 2011-06-29 2013-01-03 日東電工株式会社 Batterie rechargeable à électrolyte non aqueux et feuille d'électrode positive pour celle-ci
JP2013239305A (ja) * 2012-05-14 2013-11-28 Nitto Denko Corp 蓄電デバイス、それに用いる正極並びに多孔質シート、およびドープ率向上方法

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