WO2014104005A1 - Batterie secondaire à électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux Download PDF

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WO2014104005A1
WO2014104005A1 PCT/JP2013/084466 JP2013084466W WO2014104005A1 WO 2014104005 A1 WO2014104005 A1 WO 2014104005A1 JP 2013084466 W JP2013084466 W JP 2013084466W WO 2014104005 A1 WO2014104005 A1 WO 2014104005A1
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acid
secondary battery
electrolyte secondary
positive electrode
conductive polymer
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PCT/JP2013/084466
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Japanese (ja)
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由姫 加治佐
植谷　慶裕
阿部　正男
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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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • 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, and more particularly to a non-aqueous electrolyte secondary battery that is excellent in both weight energy density and weight output density and also excellent in cycle characteristics.
  • the so-called rocking chair type lithium secondary battery in which the lithium ion concentration in the electrolytic solution does not substantially change during the charge and discharge can reduce the amount of the electrolytic solution compared to the so-called reserve type secondary battery. Since it can be miniaturized and has a high energy density, it is widely used as an electricity storage device for the electronic devices described above.
  • a lithium secondary battery is an electricity storage device that obtains electric energy by an electrochemical reaction, and because of the low rate of the electrochemical reaction, there is an important problem that the output density is low. There is also a problem that rapid charging / discharging is difficult due to high resistance. Moreover, since the specific gravity of the positive electrode active material is large, there is still room for improvement in the capacity density per unit weight. In addition, since the electrode and the electrolytic solution are deteriorated by an electrochemical reaction accompanying charging / discharging, generally the life, that is, the cycle characteristics are 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 (see 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 conductive polymer during charging and the anion is dedoped from the polymer during discharging. Therefore, when a carbon material that can insert and desorb lithium ions is used as the negative electrode active material, a cation-moving rocking chair type secondary battery in which cations move between both electrodes during charge and discharge cannot be configured. .
  • the rocking chair type secondary battery has the advantage that the amount of the electrolyte is small, but the secondary battery having the conductive polymer as the positive electrode active material cannot do so, and contributes to the miniaturization of the electricity storage device. I can't.
  • the positive electrode is composed of a conductive polymer having a polymer anion such as polyvinyl sulfonic acid as a dopant, lithium metal is used for the negative electrode, a cation transfer type, and the ion concentration in the electrolyte
  • a secondary battery in which the battery is substantially unchanged has been proposed (see Patent Document 2), the battery performance is still not sufficient.
  • An electric double layer capacitor usually uses a polarizable electrode formed of a conductive porous carbon material having a large specific surface area such as powdered activated carbon or fibrous activated carbon, and exhibits physical adsorption characteristics of supporting electrolyte ions in the electrolyte. It is a device that uses and stores electricity. For this reason, the electric double layer capacitor has a high output density, can be rapidly charged, and has a remarkably long life. However, on the other hand, the electric double layer capacitor has a very low energy density compared to the lithium ion secondary battery. For this reason, there exists a problem about putting an electric double layer capacitor into practical use as an electrical storage device for a hybrid vehicle or an electric vehicle.
  • an electric double layer capacitor has a cycle life of about 10 to 100 times and an output density of about 5 times that of a lithium ion secondary battery, but has a weight energy density of about 1/10 to 1 / 2. It is said that the volume energy density is about 1/50 to 1/20 (see Patent Document 3).
  • JP-A-3-129679 Japanese Patent Laid-Open No. 1-132052 JP 2008-16446 A
  • the present invention has been made in view of the circumstances as described above, and is excellent in weight output density and cycle characteristics like an electric double layer capacitor and far exceeds the weight energy density of a conventional electric double layer capacitor.
  • a novel non-aqueous electrolyte secondary battery having a high weight energy density is provided.
  • the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a porous film that is disposed between the positive electrode and the negative electrode and contains the electrolytic solution, the positive electrode comprising (a) a conductive polymer and (b) A non-aqueous electrolyte secondary battery comprising a polycarboxylic acid and at least one of its metal salts, wherein the negative electrode includes a material capable of inserting and releasing base metal or base metal ions, wherein the porous membrane has a permeability.
  • the gist is a non-aqueous electrolyte secondary battery of 1 to 200 sec / 100 cc.
  • the present inventors have excellent weight output density and cycle characteristics like an electric double layer capacitor, and have a high weight energy density far exceeding the weight energy density of a conventional electric double layer capacitor.
  • the present inventors use a conductive polymer (a) as a positive electrode and at least one of a polycarboxylic acid and a metal salt thereof (b), and a material capable of inserting / extracting a base metal or a base metal ion as a negative electrode.
  • the present invention comprises a positive electrode, a negative electrode, an electrolytic solution, a porous film disposed between the positive electrode and the negative electrode, and containing the electrolytic solution, the positive electrode being a conductive polymer (a).
  • a non-aqueous electrolyte secondary battery in which the negative electrode contains a material capable of inserting / extracting a base metal or a base metal ion, and at least one of a polycarboxylic acid and a metal salt thereof (b),
  • the air permeability of 1 to 200 sec / 100 cc has excellent characteristics such as an electric double layer capacitor that is excellent in weight output density and cycle characteristics.
  • the weight energy density of a conventional electric double layer capacitor is much higher. Has a high weight energy density that exceeds. That is, the non-aqueous electrolyte secondary battery of the present invention is a secondary battery having capacitor characteristics.
  • a secondary battery can be obtained in a balanced manner having an appropriate size and high weight energy density in combination with the air permeability.
  • the conductive polymer (a) is at least one of polyaniline and a polyaniline derivative, a secondary battery having an even higher weight energy density can be obtained.
  • the polycarboxylic acid is polyacrylic acid, polymethacrylic acid, polyvinyl benzoic acid, polyallyl benzoic acid, polymethallyl benzoic acid, polymaleic acid, polyfumaric acid, polyglutamic acid, polyaspartic acid, alginic acid, carboxymethylcellulose, and polymers thereof.
  • battery performance such as weight energy density can be further improved.
  • the polycarboxylic acid metal salt is at least one of a polycarboxylic acid alkali metal salt and a polycarboxylic acid alkaline earth metal salt
  • battery performance such as weight energy density can be further improved.
  • the non-aqueous electrolyte secondary battery of the present invention includes a positive electrode 2 and a negative electrode 4, and a non-porous electrolyte membrane (separator 3) disposed between the positive electrode 2 and the negative electrode 4.
  • a water electrolyte secondary battery wherein the positive electrode 2 includes a conductive polymer (a) and at least one of a polycarboxylic acid and a metal salt thereof (b), and the separator 3 has an air permeability of 1 to 200 sec. / 100 cc, a porous membrane containing a non-aqueous electrolyte.
  • the negative electrode 4 is made of a material that can insert and desorb base metal or base metal ions.
  • the film thickness of the porous film is preferably 55 to 300 ⁇ m from the viewpoint of the balance between size and weight energy density, and the upper limit of the film thickness is further 250 ⁇ m, particularly 200 ⁇ m, especially 160 ⁇ m. Is preferred.
  • the lower limit value of the film thickness is preferably 56 ⁇ m, particularly preferably 100 ⁇ m.
  • the positive electrode sheet for a non-aqueous electrolyte secondary battery forming the positive electrode 2 of the non-aqueous electrolyte secondary battery of the present invention comprises a conductive polymer (a), at least one polycarboxylic acid and a metal salt thereof (b) It consists of the composite which has the solid positive electrode active material layer containing the current collector 1 on. These materials used will be described in order.
  • the conductive polymer (a) means that an ionic species is inserted into the polymer or from the polymer in order to compensate for a change in the charge generated or lost by the oxidation reaction or reduction reaction of the polymer main chain.
  • This refers to a group of polymers (hereinafter, also referred to as “positive electrode active material”) in which the conductivity of the polymer itself is changed by desorption.
  • positive electrode active material a group of polymers
  • a state with high conductivity is referred to as a doped state, and a state in which ionic species are desorbed from the polymer and conductivity is low is referred to as a dedope state.
  • a dedope state Even if a polymer having conductivity loses conductivity due to an oxidation reaction or a reduction reaction and becomes insulative (that is, a dedope state), such a polymer is reversibly conductive again by the oxidation-reduction reaction. Therefore, the insulating polymer in the dedope state is also included in the category of the conductive polymer (a) in the present invention.
  • one of the preferred conductive polymers (a) in the present invention is at least one selected from the group consisting of inorganic acid anions, aliphatic sulfonate anions, aromatic sulfonate anions, polymer sulfonate anions and polyvinyl sulfate anions.
  • another preferable conductive polymer is a polymer in a dedope state obtained by dedoping the conductive polymer.
  • examples of the polymer constituting the conductive polymer (a) include polypyrrole, polyaniline, polythiophene, polyfuran, polyselenophene, polyisothianaphthene, polyphenylene sulfide, polyphenylene oxide, polyazulene, poly (3,4- Ethylenedioxythiophene), polyacene and the like and various derivatives thereof are used.
  • at least 1 sort (s) of polyaniline and a polyaniline derivative is used preferably.
  • the polyaniline refers to a polymer obtained by electrolytic polymerization or chemical oxidative polymerization of aniline
  • the polyaniline derivative refers to a polymer obtained by electrolytic polymerization or chemical oxidative polymerization of an aniline derivative.
  • the derivative of aniline at least 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, and an alkoxyalkyl group is present at a position other than the 4-position of aniline. What has one can be illustrated.
  • Preferable specific examples include o-substituted anilines such as o-methylaniline, o-ethylaniline, o-phenylaniline, o-methoxyaniline, o-ethoxyaniline, m-methylaniline, m-ethylaniline, m- Examples thereof include m-substituted anilines such as methoxyaniline, m-ethoxyaniline and m-phenylaniline.
  • p-phenylaminoaniline gives polyaniline by oxidative polymerization, so that it can exceptionally be suitably used as an aniline derivative.
  • aniline or a derivative thereof is simply referred to as “aniline”. Therefore, even when the polymer constituting the conductive polymer (a) is obtained from an aniline derivative, it is referred to as “conductive polyaniline”.
  • the conductive polymer (a) is obtained by electropolymerizing a monomer such as aniline or pyrrole in the presence of a protonic acid in an appropriate solvent, or using an oxidizing agent.
  • a monomer such as aniline or pyrrole
  • an oxidizing agent in the presence of a protonic acid in an appropriate solvent.
  • water is usually used, but a mixed solvent of a water-soluble organic solvent and water or a mixed solvent of water and a nonpolar organic solvent is also used.
  • a surfactant or the like may be used in combination.
  • aniline is oxidatively polymerized using the above water as a solvent. That is, chemical oxidative polymerization of aniline is performed in water using an oxidizing agent in the presence of a protonic acid.
  • the oxidizing agent used may be either water-soluble or water-insoluble.
  • oxidizing agent examples include ammonium peroxodisulfate, manganese dioxide, hydrogen peroxide, potassium dichromate, potassium permanganate, sodium chlorate, cerium ammonium nitrate, sodium iodate, and iron chloride. it can.
  • the amount of the oxidizing agent used for the oxidative polymerization of the aniline is related to the yield of the conductive polyaniline to be produced.
  • the number of moles of the aniline used (2.5 / N) It is preferable to use a mole of oxidizing agent.
  • n represents the number of electrons required when one molecule of the oxidizing agent itself is reduced. Therefore, for example, in the case of ammonium peroxodisulfate, n is 2 as understood from the following reaction formula.
  • the proton acid is doped with the produced polyaniline to make it conductive, and the aniline is salted in water and dissolved in water.
  • the pH of the polymerization reaction system is preferably 1 or less. Used to maintain strong acidity. Accordingly, in the production of the conductive polyaniline, the amount of the protonic acid used is not particularly limited as long as the above object can be achieved, but it is usually 1.1 to 5 times the number of moles of aniline. Used in a range. However, when the amount of the protonic acid used is too large, the cost for the waste liquid treatment is unnecessarily increased in the post-treatment of the aniline oxidative polymerization.
  • the protonic acid one having strong acidity is preferable, and a protonic acid having an acid dissociation constant pKa value of less than 3.0 is preferably used.
  • protic acids having an acid dissociation constant pKa value of less than 3.0 include sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, hydrofluoric acid, hydroiodic acid, and the like.
  • Inorganic acids, aromatic sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid, and aliphatic sulfonic acids (or alkanesulfonic acids) such as methanesulfonic acid and ethanesulfonic acid are preferably used.
  • a polymer having a sulfonic acid group in the molecule that is, a polymer sulfonic acid can also be used.
  • polymer sulfonic acids include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, poly (acrylamide-t-butyl sulfonic acid), phenol sulfonic acid novolak resin, and Nafion (registered trademark). Examples thereof include perfluorosulfonic acid.
  • polyvinyl sulfate can also be used as a protonic acid.
  • tetrafluoroboric acid and hexafluorophosphoric acid are the same anions as the base metal salt of the electrolyte salt of a lithium secondary battery, which is an example of a non-aqueous electrolyte secondary battery, for example.
  • the non-aqueous electrolyte secondary battery is a lithium secondary battery, it contains the same anionic species as the lithium salt of the electrolyte salt of the non-aqueous electrolyte in the lithium secondary battery. Since it is a protonic acid, it is preferably used.
  • the conductive polymer (a) may be a polymer doped with the protonic acid as described above, and the polymer doped with the protonic acid is dedoped as described above. It may be a dedoped polymer obtained by treatment. If necessary, the dedoped polymer may be further reduced.
  • Examples of the method for dedoping the conductive polymer include a method of neutralizing the conductive polymer doped with proton acid with an alkali.
  • the reduction treatment is performed by, for example, neutralizing the conductive polymer doped with the protonic acid with alkenyl and dedoping.
  • a method of reducing the obtained dedoped polymer with a reducing agent can be mentioned.
  • the conductive polymer doped with the protonic acid is neutralized with an alkali
  • the conductive polymer is charged into an alkaline aqueous solution such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, or aqueous ammonia
  • the stirring may be performed under or under heating at about 50 to 80 ° C. as necessary.
  • the dedoped polymer is reduced to hydrazine monohydrate aqueous solution, phenylhydrazine / alcohol solution, sodium dithionite aqueous solution, sodium sulfite aqueous solution or the like.
  • the solution may be poured into the agent solution and stirred at room temperature or, if necessary, at a temperature of about 50 to 80 ° C.
  • the polycarboxylic acid refers to a polymer having a carboxyl group in the molecule.
  • the polycarboxylic acid is preferably polyacrylic acid, polymethacrylic acid, polyvinylbenzoic acid, polyallylbenzoic acid, polymethallylbenzoic acid, polymaleic acid, polyfumaric acid, polyglutamic acid and polyaspartic acid, alginic acid, carboxymethylcellulose, And a copolymer containing at least two kinds of repeating units of these polymers. These may be used alone or in combination of two or more.
  • the copolymer includes a graft copolymer.
  • the metal salt of the polycarboxylic acid is at least one of an alkali metal salt and an alkaline earth metal salt of the polycarboxylic acid.
  • 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 non-aqueous electrolyte secondary battery of the present invention when at least one polycarboxylic acid and metal salt thereof (b) is used together with the conductive polymer (a), at least one polycarboxylic acid and metal salt thereof is used. Since (b) functions as a binder and also functions as a dopant for the conductive polymer (a), it has a rocking chair type mechanism, and has the characteristics of the non-aqueous electrolyte secondary battery according to the present invention. It seems to be involved in improvement. This inference is not limited by theory.
  • At least one of the polycarboxylic acid and the metal salt thereof (b) is usually 1 to 100 with respect to 100 parts by weight of the conductive polymer (a). It is used in the range of parts by weight, preferably 2 to 50 parts by weight, most preferably 5 to 30 parts by weight.
  • the conductive polymer (a), at least one kind of polycarboxylic acid and metal salt thereof (b), as well as a conductive aid, a binder other than the above (b), and the like, as appropriate. can be blended.
  • the conductive auxiliary agent is effective for reducing the electric resistance between the active materials of the battery, and may be any conductive material whose properties do not change depending on the potential applied when the non-aqueous electrolyte secondary battery is discharged.
  • conductive assistants include conductive carbon materials, metal materials, and the like. Among them, conductive carbon blacks such as acetylene black and ketjen black, carbon fibers, carbon nanotubes, carbon nanofibers, etc. A fibrous carbon material is preferably used. Particularly preferred is conductive carbon black.
  • the conductive assistant is preferably 1 to 30 parts by weight, more preferably 4 to 20 parts by weight, particularly preferably 8 to 18 parts by weight based on 100 parts by weight of the conductive polymer (a). is there.
  • the blending amount of the conductive aid is within this range, the shape and characteristics as the active material can be prepared without abnormality, and the rate characteristics can be effectively improved.
  • binder other than the above (b) examples include polyvinylidene fluoride and the like.
  • the positive electrode sheet for a non-aqueous electrolyte secondary battery in the present invention for example, at least one (b) of the polycarboxylic acid and a metal salt thereof is dissolved or dispersed in water, and the conductive polymer (a) is dissolved therein. If necessary, a conductive auxiliary agent such as conductive carbon black and a binder other than the above (b) are added and sufficiently dispersed to obtain a solution viscosity of about 0.05 to 50 Pa ⁇ s.
  • a conductive auxiliary and a binder other than the above (b)) can be obtained as a composite having a layer of a uniform mixture.
  • the thickness of the electrode is preferably 1 to 1000 ⁇ m, more preferably 10 to 700 ⁇ m.
  • the thickness of the positive electrode is obtained by measuring using a standard dial gauge (manufactured by Ozaki Mfg. Co., Ltd.), which is a flat plate with a tip shape of 5 mm in diameter, and obtaining the average of 10 measured values with respect to the surface of the electrode. .
  • a standard dial gauge manufactured by Ozaki Mfg. Co., Ltd.
  • the thickness of the composite is measured in the same manner as described above. After obtaining the average of the measured values, the thickness of the electrode is obtained by subtracting the thickness of the current collector 1.
  • At least one of the polycarboxylic acid and its metal salt (b) is present as a layer of a mixture with the conductive polymer (a), thereby fixing in the electrode. Is done. And at least 1 type (b) of the polycarboxylic acid and its metal salt fixedly arranged in the vicinity of the conductive polymer (a) in this way is also used for charge compensation during oxidation-reduction of the conductive polymer (a). Is done.
  • the non-aqueous electrolyte secondary battery according to the present invention has a rocking chair type ion transfer mechanism, so that the amount of anion in the electrolyte that acts as a dopant is small. As a result, a non-aqueous electrolyte secondary battery capable of exhibiting good characteristics even when the amount of the electrolyte used is small.
  • the porosity (%) of the electrode can be calculated by ⁇ (apparent volume of electrode ⁇ true volume of electrode) / apparent volume of electrode ⁇ ⁇ 100, preferably 35 to 80%.
  • the apparent volume of the electrode refers to “electrode area of electrode ⁇ electrode thickness”. Specifically, the volume of the electrode substance, the volume of the voids in the electrode, and the space of the uneven portions on the electrode surface The total volume of
  • the true volume of the electrode means the “volume of the electrode constituent material” excluding the current collector such as an aluminum foil. Specifically, the constituent weight ratio of the positive electrode constituent material and the true volume of each constituent material. Using the density value, the average density of the entire electrode constituent material is calculated, and the total weight of the electrode constituent material is divided by this average density.
  • the true density (true specific gravity) of each of the constituent materials for example, the true density of polyaniline, which is an example of the conductive polymer (a), is 1.2 g / cm 3 (including the dopant), and polysulfonic acid and its metal salt
  • a base metal or a material capable of inserting / extracting a base metal ion during oxidation / reduction is preferably used.
  • the base metal include alkali metals such as metal lithium, metal sodium, and metal potassium; alkaline earth metals such as metal magnesium and metal calcium; and examples of the base metal ion include ions of the base metal. be able to.
  • a preferable nonaqueous electrolyte secondary battery is a lithium secondary battery, and therefore lithium can be used as a preferable base metal and lithium ion can be used as a preferable base metal ion.
  • a carbon material is preferably used, but silicon, tin and the like can also be used.
  • “use” means not only the case where only the forming material is used, but also the case where the forming material is used in combination with another forming material. Is used at less than 50% by weight of the forming material.
  • current collectors 1 and 5 can be used in addition to the above-described positive electrode, electrolyte layer, negative electrode, and the like.
  • the current collector is not particularly limited as long as it has good conductivity and stability, but a metal foil or mesh such as nickel, aluminum, stainless steel or copper is preferably used, and a stainless steel material is preferably used.
  • the negative electrode is a metal, the negative electrode itself may also serve as a current collector.
  • the separator used in the non-aqueous electrolyte secondary battery of the present invention is disposed between the positive electrode and the negative electrode, prevents electrical short circuit between the positive electrode and the negative electrode, is electrochemically stable, and transmits ions.
  • An insulating porous film having a large property and a certain mechanical strength may be used. Therefore, as the separator, for example, a porous film made of a resin such as paper, nonwoven fabric, polypropylene, polyethylene, polyimide, epoxy resin, or aramid resin is preferably used. These may be used alone or in combination of two or more.
  • the separator has an air permeability of 1 to 200 sec / 100 cc, preferably 5 to 150 sec / 100 cc, more preferably 10 to 100 sec / 100 cc. If the air permeability is too high, the separator tends not to function. This is because if the air permeability is too low, desired input / output characteristics tend not to be obtained.
  • the separator is impregnated with an electrolytic solution.
  • the conductive polymer is reduced to an insulator when an internal short circuit occurs. , Does not fever so much. That is, it is not necessary to block the movement of base metal ions. Therefore, in the non-aqueous electrolyte secondary battery of the present invention, the range of the material selection of the separator is very wide, and it is possible to use a separator having no conventionally required strength and blocking function. For this reason, the freedom degree of separator design improves. Under such circumstances, the non-aqueous electrolyte secondary battery of the present invention can be used even with a separator having a particularly high air permeability.
  • the said electrolyte solution is comprised from the thing containing an electrolyte and a solvent.
  • the electrolyte include metal ions such as base metal ions and appropriate counter ions corresponding thereto, such as sulfonate ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions, hexafluoroarsenic ions, bismuth ions.
  • a combination of (trifluoromethanesulfonyl) imide ion, bis (pentafluoroethanesulfonyl) imide ion, halogen ion and the like is preferably used.
  • a base metal means a metal that has a higher ionization tendency than hydrogen and is easily oxidized in the air (when heated), and includes alkali metals, alkaline earth metals, aluminum, zinc, lead, and the like.
  • specific examples of such an electrolyte include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium trifluoromethanesulfonate (LiCF 3).
  • LiAsF 6 lithium hexafluoroarsenate
  • LiN (SO 2 CF 3 ) 2 lithium bis (trifluoromethanesulfonyl) imide
  • LiN (SO 2 C 2 F) 5 lithium bis (pentafluoroethanesulfonyl) imide
  • LiCl lithium chloride
  • NaPF 6 sodium hexafluorophosphate
  • NaBF 4 sodium tetrafluoroborate
  • NaClO 4 sodium trifluoromethanesulfonate
  • NaCF 3 SO 3 sodium hexafluoride arsenate (NaAsF 6), hexafluorophosphate oxide Siumu (Ca (PF 6) 2) , tetrafluoroborate calcium (Ca (BF 4) 2) , calcium perchlorate (Ca (ClO 4) 2) , trifluoromethanesulfonate
  • the solvent for example, at least one non-aqueous solvent such as carbonates, nitriles, amides, ethers, that is, an organic solvent is used.
  • an organic solvent 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 nonaqueous electrolyte secondary battery of the present invention is assembled using the above materials.
  • the battery is preferably assembled in a glove box under an inert gas atmosphere such as ultra-high purity argon gas and in a low humidity environment with a dew point of ⁇ 40 ° C. or lower.
  • the non-aqueous electrolyte secondary battery of the present invention is superior in weight output density and cycle characteristics like an electric double layer capacitor, and has a weight energy density much higher than that of a conventional electric double layer capacitor. Therefore, it can be said that the non-aqueous electrolyte secondary battery of the present invention is a capacitor secondary battery.
  • the reason why the non-aqueous electrolyte secondary battery of the present invention has such capacitor characteristics is not yet clear, but at least one of a polycarboxylic acid and a metal salt thereof combined with the conductive polymer (a) ( b) dissociates moderately in the electrolyte and has a negative charge. This negative charge facilitates the movement of base metal ions (for example, lithium ions) between the electrodes, so that a rocking chair type non-aqueous electrolyte is obtained. It is assumed that it constitutes a secondary battery.
  • the nonaqueous electrolyte secondary battery of the present invention has such a high weight capacity density is that, as described above, in the electrode formed as described above, at least one of polycarboxylic acid and metal salt thereof ( Since b) is arranged as a layer of a mixture with the conductive polymer (a), it is thereby fixed in the electrode. And at least 1 type (b) of the polycarboxylic acid and its metal salt fixedly arranged in the vicinity of the conductive polymer (a) in this way is also used for charge compensation during oxidation-reduction of the conductive polymer (a). Is done.
  • the ionic environment of at least one of the polycarboxylic acid and the metal salt thereof facilitates the movement of ions that are inserted and removed from the conductive polymer (a). Since the doping rate is improved and a rocking chair type ion transfer mechanism is provided, the amount of anions in the electrolyte solution serving as a dopant can be reduced. As a result, it is presumed that a non-aqueous electrolyte secondary battery capable of exhibiting good characteristics (such as high weight capacity density) even when the amount of electrolyte used is small.
  • a lithium secondary battery using a conductive polyaniline as the conductive polymer (a) and a positive electrode containing a polycarboxylic acid is taken as an example.
  • the doping mechanism for conductive polyaniline by carboxylic acid is shown below.
  • Conductive polyaniline doped with protonic acid is dedoped by alkali treatment and further reduced by a reducing agent. Consists of structural units.
  • a lithium secondary battery including a polyaniline whose positive electrode is composed of such an imino-p-phenylene structural unit is charged, a nitrogen atom having an unpaired electron in the polyaniline is oxidized by one electron, resulting in generation.
  • polyaniline was doped with an electrolyte anion (for example, tetrafluoroborate anion) in the electrolyte solution or an anion of polycarboxylic acid (ie, carboxylate anion) present in the electrode. It is considered that conductive polyaniline (Ib) is formed.
  • the cation radical site in the conductive polyaniline (IIb) is reduced, and the original electrically neutral group having an unshared electron pair is reduced. Return to polyaniline (IIa).
  • the anion which has interacted with Coulomb at the cation radical site is an electrolyte anion (for example, tetrafluoroborate anion)
  • the electrolyte anion moves from the vicinity of the conductive polymer (a) to the electrolyte side. To do.
  • the carboxylate anion is a polymer. Therefore, it cannot move to the electrolytic solution side like the electrolyte anion, and remains in the vicinity of the polyaniline (IIa). Therefore, in order to make the carboxylate anion electrically neutral, a lithium cation moves from the electrolytic solution to the vicinity of the conductive polymer (a), and the salt (IIIa) is used as a counter cation of the carboxylate anion. It seems to form.
  • a lithium secondary battery formed of a material containing conductive polyaniline (a) and polycarboxylic acid (b) as a positive electrode and using lithium as a negative electrode is used.
  • 2 schematically shows the behavior of lithium ions and anion ions.
  • non-aqueous electrolyte secondary batteries lithium secondary batteries
  • the following components were prepared and prepared.
  • aniline When aniline was added to the tetrafluoroboric acid aqueous solution, the aniline was dispersed as oily droplets in the tetrafluoroboric acid aqueous solution, but then dissolved in water within a few minutes, and the uniform and transparent aniline aqueous solution. Became.
  • the aniline aqueous solution thus obtained was cooled to ⁇ 4 ° C. or lower using a low temperature thermostat.
  • 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.
  • conductive polyaniline having tetrafluoroboric acid as a dopant
  • the conductive polyaniline was a bright green powder.
  • polycarboxylic acid (b) 4.4 g of polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 1,000,000) was added to 95.6 g of ion-exchanged water, and allowed to stand overnight to swell. Then, it processed for 1 minute and melt
  • polyacrylic acid manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 1,000,000
  • lithium hydroxide powder is added to 100 g of the resulting polyacrylic acid aqueous solution so that half of the amount of carboxyl groups of polyacrylic acid is lithium-chlorinated, thereby preparing a polylithic acid half-lithium salt aqueous solution. And prepared.
  • the above defoamed paste was applied to an etching aluminum foil for electric double layer capacitors (treasure) at a coating speed of 10 mm / sec using a doctor blade type applicator with a micrometer. It was applied onto Izumi Co., Ltd., 30CB). Subsequently, after leaving at room temperature (25 degreeC) for 45 minutes, it dried on the hotplate of temperature 100 degreeC, and produced the porous polyaniline sheet electrode (positive electrode). In this polyaniline sheet electrode, the porosity of the positive electrode active material composed of a half-lithium salt of polyacrylic acid, conductive polyaniline powder, and conductive carbon black was 45%.
  • separators I to IV were prepared as separator materials.
  • the film thickness per one of these porous membranes and the air permeability (sec / 100 cc) were as shown in Table 1.
  • Separator I Cellulose porous membrane (manufactured by Nippon Kogyo Paper Industries, TF4050)
  • Separator II Porous membrane made of epoxy resin (preparing an epoxy porous material described in Example 1 of International Publication WO2006 / 073173 and cutting it to obtain a sheet of epoxy porous material having a thickness of 28 ⁇ m for use as a separator )
  • Separator III polyethylene porous membrane (used in Example 1 of JP2012-052085 A) -Separator IV ... Polypropylene porous membrane (Celgard CGT2400)
  • Example 1 ⁇ Production of non-aqueous electrolyte secondary battery> A 50 ⁇ m-thick aluminum foil was connected to a positive electrode current collector (aluminum foil) with a spot welder to obtain a positive electrode tab for taking out current. In this way, the positive electrode with the tab electrode attached and the stainless mesh electrode as the negative electrode were vacuum dried at 80 ° C. together with the separator, and then the metal lithium foil was applied to the stainless mesh electrode in a glove box with a dew point of ⁇ 100 ° C. A negative electrode was formed by pressing and sinking.
  • a positive electrode current collector aluminum foil
  • Example 2 In the same manner as in Example 1, except that the three porous membranes made of cellulose (Separator I) in Example 1 were replaced with two porous membranes made of epoxy resin (Separator II), A nonaqueous electrolyte secondary battery was obtained.
  • the total film thickness and air permeability (sec / 100 cc) of the two porous porous epoxy resin membranes as separators were as shown in Table 1 below.
  • Example 1 In the same manner as in Example 1, except that the three cellulose porous membranes (Separator I) in Example 1 were replaced with two polyethylene porous membranes (Separator III), A water electrolyte secondary battery was obtained.
  • the total film thickness and air permeability (sec / 100 cc) of the two polyethylene porous membranes as the separator were as shown in Table 1 below.
  • Example 2 In the same manner as in Example 1, except that the three cellulose porous membranes (separator I) in Example 1 were replaced with two polypropylene porous membranes (separator IV). A water electrolyte secondary battery was obtained. The total film thickness and air permeability (sec / 100 cc) of the two polypropylene porous membranes as the separator were as shown in Table 1 below.
  • the non-aqueous electrolyte secondary battery produced above was put into a thermostat at 25 ° C. and connected to a charge / discharge device (TOS-CAT 3000 manufactured by Toyo System Co., Ltd.).
  • the capacity of the battery was calculated by setting the polyaniline weight of the positive electrode and the theoretical capacity density of the polyaniline to 147 mAh / g.
  • the battery capacity was first charged and discharged at 0.05 C for 5 cycles, then 0.2 C, 0.5 C Charge and discharge were performed at 1C, 2C, 5C, and 10C.
  • a non-aqueous electrolyte secondary battery having a porous membrane having an air permeability of 1 to 200 sec / 100 cc exhibits excellent rate characteristics.
  • the nonaqueous electrolyte secondary battery of the present invention can be suitably used as a secondary battery such as a lithium 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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Separators (AREA)

Abstract

L'invention a pour objet de réaliser une batterie secondaire à électrolyte non aqueux innovante qui présente une excellente densité de sortie massique et d'excellentes caractéristiques de cycle tout en présentant une densité énergétique massique élevée qui est nettement supérieure aux densités énergétiques massiques des condensateurs à double couche électriques conventionnels. La présente invention réalise à cet effet une batterie secondaire à électrolyte non aqueux qui est munie d'une électrode positive (2), d'une électrode négative (4), d'une solution d'électrolyte et d'une membrane poreuse (3) qui est disposée entre l'électrode positive et l'électrode négative et qui contient la solution d'électrolyte, et avec laquelle : l'électrode positive contient (a) un polymère conducteur et (b) au moins une substance sélectionnée parmi les acides polycarboxyliques et les sels métalliques de ceux-ci ; et l'électrode négative contient un métal de base ou un matériau qui est capable d'intercaler et de désintercaler des ions métalliques de base. La membrane poreuse présente une perméabilité à l'air de 1-200 s/100 cm3.
PCT/JP2013/084466 2012-12-27 2013-12-24 Batterie secondaire à électrolyte non aqueux WO2014104005A1 (fr)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN108682774A (zh) * 2018-06-12 2018-10-19 桑德集团有限公司 隔膜及其制备方法、锂电池
CN110100347A (zh) * 2016-12-28 2019-08-06 松下知识产权经营株式会社 非水电解质二次电池
CN114930581A (zh) * 2020-10-12 2022-08-19 株式会社Lg新能源 锂二次电池正极用浆料组合物以及包含其的正极和锂二次电池

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JPH01132052A (ja) * 1987-08-10 1989-05-24 Nitto Denko Corp 導電性有機重合体電池
WO2006123811A1 (fr) * 2005-05-17 2006-11-23 Teijin Limited Separateur pour accumulateur au lithium et accumulateur au lithium
JP2007257904A (ja) * 2006-03-22 2007-10-04 Tomoegawa Paper Co Ltd 電子部品用セパレータおよび電子部品
JP2009093880A (ja) * 2007-10-05 2009-04-30 Toyota Central R&D Labs Inc 蓄電デバイス
JP2011225736A (ja) * 2010-04-21 2011-11-10 Asahi Kasei E-Materials Corp ポリオレフィン微多孔膜、及びリチウムイオン二次電池

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Publication number Priority date Publication date Assignee Title
JPH01132052A (ja) * 1987-08-10 1989-05-24 Nitto Denko Corp 導電性有機重合体電池
WO2006123811A1 (fr) * 2005-05-17 2006-11-23 Teijin Limited Separateur pour accumulateur au lithium et accumulateur au lithium
JP2007257904A (ja) * 2006-03-22 2007-10-04 Tomoegawa Paper Co Ltd 電子部品用セパレータおよび電子部品
JP2009093880A (ja) * 2007-10-05 2009-04-30 Toyota Central R&D Labs Inc 蓄電デバイス
JP2011225736A (ja) * 2010-04-21 2011-11-10 Asahi Kasei E-Materials Corp ポリオレフィン微多孔膜、及びリチウムイオン二次電池

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110100347A (zh) * 2016-12-28 2019-08-06 松下知识产权经营株式会社 非水电解质二次电池
CN108682774A (zh) * 2018-06-12 2018-10-19 桑德集团有限公司 隔膜及其制备方法、锂电池
CN114930581A (zh) * 2020-10-12 2022-08-19 株式会社Lg新能源 锂二次电池正极用浆料组合物以及包含其的正极和锂二次电池
CN114930581B (zh) * 2020-10-12 2024-02-13 株式会社Lg新能源 锂二次电池正极用浆料组合物以及包含其的正极和锂二次电池

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