WO2006098240A1 - 高分子電解質および電池 - Google Patents
高分子電解質および電池 Download PDFInfo
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- WO2006098240A1 WO2006098240A1 PCT/JP2006/304746 JP2006304746W WO2006098240A1 WO 2006098240 A1 WO2006098240 A1 WO 2006098240A1 JP 2006304746 W JP2006304746 W JP 2006304746W WO 2006098240 A1 WO2006098240 A1 WO 2006098240A1
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a polymer electrolyte containing an electrolytic solution and a polymer compound, and a battery using the same.
- an all-solid polymer electrolyte in which an electrolyte salt is dissolved in a polymer compound or a gel-like high polymer in which an electrolyte is held in the polymer compound is used.
- Molecular electrolytes are used.
- gel-like polymer electrolytes retain electrolyte solution and thus have better contact with the active material and ionic conductivity than all solids. It is attracting attention because it has a characteristic that it is difficult to occur.
- Patent Documents 1 and 2 describe an ionic conductive solid composition using polybutyral
- Patent Document 3 describes a gel containing polyvinyl formal and an electrolytic solution.
- a ruby electrolyte is described.
- Patent Document 4 describes a gel electrolyte in which the amount of electrolytic solution is increased by adjusting the amount of hydroxyl groups contained in polyvinyl formal.
- Patent Document 5 discloses that an epoxy-based crosslinking agent or catalyst is used. A more formed gel electrolyte is described.
- Patent Document 1 JP-A-57-143355
- Patent Document 2 Japanese Patent Application Laid-Open No. 57-143356
- Patent Document 3 Japanese Patent Laid-Open No. 3-43909
- Patent Document 4 Japanese Patent Laid-Open No. 2001-200126
- Patent Document 5 US Patent No. 3985574
- the polymer electrolyte described in Patent Document 5 has a problem that discharge characteristics and the like deteriorate due to decomposition of a highly reactive crosslinking agent or the like at the electrode.
- the present invention has been made in view of significant problems, and an object of the present invention is to provide a polymer electrolyte capable of obtaining excellent discharge characteristics by improving ion conductivity, and to use the polymer electrolyte. To provide a battery.
- the first polymer electrolyte according to the present invention has a structure obtained by polymerizing an electrolyte solution containing a solvent and lithium hexafluorophosphate, and at least one member selected from the group consisting of polyvurecetal and derivatives thereof. And a polymer compound having
- the second polymer electrolyte according to the present invention has a structure obtained by polymerizing an electrolyte solution containing a solvent and lithium hexafluorophosphate, and at least one member selected from the group consisting of polybulacetal and derivatives thereof.
- the content of the polymer compound is in the range of 2 mass% to 5 mass%.
- a first battery according to the present invention includes a positive electrode and a negative electrode together with a separator and a polymer electrolyte inside an exterior member.
- the polymer electrolyte contains a solvent and lithium hexafluorophosphate. Containing electrolyte solution, polyvinylacetal and its derivatives And a polymer compound having a structure obtained by polymerizing at least one member of the group.
- a second battery according to the present invention includes a positive electrode and a negative electrode together with a separator and a polymer electrolyte inside an exterior member.
- the polymer electrolyte contains a solvent and lithium hexafluorophosphate.
- the first polymer electrolyte of the present invention since lithium hexafluorophosphate is used, polybulacetal and its derivatives can be polymerized, and the proportion of the polymer compound can be increased. Even if it is decreased, leakage can be suppressed. In addition, since the proportion of the electrolytic solution can be increased, ion conductivity can be improved. Furthermore, for example, since a low boiling point solvent can be easily contained, ion conductivity can be further improved. In addition, it is possible to suppress a decrease in discharge capacity due to a decomposition reaction in these electrodes without using a crosslinking agent or the like. Therefore, according to the first battery of the present invention using this polymer electrolyte, the discharge characteristics can be improved while suppressing leakage.
- the polyvinyl acetal and its derivative are polymerized with lithium hexafluorophosphate, and the content of the polymer compound is in the range of 2% by mass to 5% by mass. Since it is designed to be inside, it is possible to improve ion conductivity while suppressing leakage. In addition, for example, since a low boiling point solvent can be easily contained, ion conductivity can be further improved. It is not necessary to use a crosslinking agent or the like. It is also possible to suppress a decrease in discharge capacity due to a decomposition reaction in these electrodes. Therefore, according to the second battery of the present invention using this polymer electrolyte, the discharge characteristics can be improved while suppressing leakage.
- the content of the polymer compound in the polymer electrolyte is in the range of 2% by mass to 3.5% by mass, a higher effect can be obtained.
- FIG. 1 is an exploded perspective view showing a configuration of a secondary battery according to an embodiment of the present invention.
- FIG. 2 is a cross-sectional view taken along line II of the battery element shown in FIG.
- FIG. 3 is a characteristic diagram showing the relationship between the mixing amount of polyvinyl formal and the discharge capacity.
- a polymer electrolyte according to an embodiment of the present invention includes a polymer compound having a structure obtained by polymerizing at least one member selected from the group consisting of polybulucetal and derivatives thereof, and an electrolytic solution. It becomes like a gel.
- Polyvinyl acetal includes a structural unit containing an acetal group shown in Chemical Formula 1 (A), a structural unit containing a hydroxyl group shown in Chemical Formula 1 (B), and an acetyl group shown in Chemical Formula 1 (C). And a structural unit comprising a repeating unit.
- R shown in Chemical Formula 1 (A) is a hydrogen poly (vinyl formal) or R is a propyl group.
- R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- the ratio of the acetal group in the polybulucetal is preferably in the range of 60 mol% to 80 mol%. This is because the solubility in a solvent can be improved within this range, and the stability of the polymer electrolyte can be further enhanced.
- the weight average molecular weight of the polyvinyl acetal is preferably in the range of 10,000 to 500,000. This is because if the molecular weight is too low, the polymerization reaction is difficult to proceed and if the molecular weight is too high, the viscosity of the electrolyte will increase.
- the content of the polymer compound is preferably in the range of 2% by mass or more and 5% by mass or less, particularly in the range of 2% by mass or more and 3.5% by mass or less with respect to the entire polymer electrolyte. Better. If the amount is too small, the ability to hold the electrolyte may decrease. This is because the ionic conductivity decreases.
- the polymer compound may be a polymer obtained by polymerizing only polyvinyl acetal or one of its derivatives, or a polymer obtained by polymerizing two or more of these, and other than polyvinyl acetal and its derivatives. Copolymers with these monomers may also be used.
- this polymer compound is polymerized using lithium hexafluorophosphate (LiP F), which also functions as an electrolyte salt, as a catalyst, whereby the polymerization is promoted and a small amount of electricity is required.
- LiP F lithium hexafluorophosphate
- the solution can be retained.
- the electrolytic solution is obtained by dissolving an electrolyte salt in a solvent.
- the solvent include latonic solvents such as ⁇ -butyrolataton, ⁇ _noratolataton, ⁇ -valerolataton or ⁇ -force prolataton, ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate, ethylmethyl carbonate Or carbonate ester solvents such as jetyl carbonate, ether solvents such as 1,2-dimethoxyethane, 1_ethoxy-l-2-methoxyethane, 1,2-diethoxyethane, tetrahydrofuran or 2-methyltetrahydrofuran, acetonitrile, etc.
- Non-aqueous solvents such as nitrile solvents, sulfolane solvents, phosphoric acids, phosphate esters solvents, or pyrrolidones. Any one of the solvents may be used alone, or two or more may be mixed and used.
- Any electrolyte salt may be used as long as it dissolves in a solvent and generates ions.
- other electrolyte salts may be mixed and used. Good. Examples of other electrolyte salts include lithium tetrafluoroborate (LiBF) and lithium hexafluoroarsenate.
- LiAsF lithium perchlorate
- LiCIO lithium trifluoromethanesulfonate
- LiAlCl 3 lithium hexafluorosilicate
- LiSiF 3 lithium hexafluorosilicate
- This polymer electrolyte is used in a battery as follows, for example. Note that in this embodiment, a battery using lithium as an electrode reactant is described.
- FIG. 1 shows an exploded view of a secondary battery using the polymer electrolyte according to the present embodiment.
- This secondary battery includes a battery element 2 to which a positive terminal 11 and a negative terminal 12 are attached. 0 is enclosed in a film-shaped exterior member 30.
- the positive electrode terminal 11 and the negative electrode terminal 12 are led out from the inside of the exterior member 30 to the outside, for example, in the same direction.
- the positive electrode terminal 11 and the negative electrode terminal 12 are made of a metal material such as aluminum (A1), copper (Cu), nickel (Ni), or stainless steel.
- the exterior member 30 is made of, for example, a film-like material, and is made of, for example, a rectangular laminate film in which nylon vinylom, an aluminum foil, and a polyethylene film are bonded together in this order.
- the exterior member 30 is disposed, for example, so that the polyethylene film side and the battery element 20 face each other, and the outer edge portions are in close contact with each other by fusion bonding or an adhesive.
- An adhesive film 31 is inserted between the exterior member 30 and the positive electrode terminal 11 and the negative electrode terminal 12 to prevent the intrusion of outside air.
- Adhesion Finolem 31 is made of a material having adhesion to positive electrode terminal 11 and negative electrode terminal 12, for example, when positive electrode terminal 11 and negative electrode terminal 12 are made of the above-described metal materials, polyethylene, polypropylene, It is preferably composed of a polyolefin resin such as modified polyethylene or modified polypropylene.
- the exterior member 30 may be made of a laminated film having another structure, a polymer film such as polypropylene, a metal film, or the like instead of the above-described laminate film.
- FIG. 2 shows a cross-sectional structure along the line I I of the battery element 20 shown in FIG.
- the positive electrode 21 and the negative electrode 22 are positioned facing each other via the polymer electrolyte 23 and the separator 24 according to the present embodiment, and the outermost peripheral portion is protected. Protected by tape 25.
- the positive electrode 21 has, for example, a structure in which a positive electrode active material layer 21B is provided on both surfaces or one surface of a positive electrode current collector 21A having a pair of opposed surfaces.
- the positive electrode current collector 21A has an exposed portion without being provided with the positive electrode active material layer 21B at one end in the longitudinal direction, and the positive electrode terminal 11 is attached to the exposed portion.
- the positive electrode current collector 21A is made of, for example, a metal foil such as an aluminum foil, a nickel foil or a stainless steel foil.
- the positive electrode active material layer 21B for example, occludes and releases lithium as a positive electrode active material.
- One kind or two or more kinds of positive electrode materials that can be used are included, and a conductive agent and a binder may be included as necessary.
- Examples of cathode materials capable of inserting and extracting lithium include titanium sulfide (TiS), molybdenum sulfide (MoS), and selenium.
- Lithium-free chalcones such as niobium (NbSe) or vanadium oxide (V0)
- Examples thereof include a generalized compound such as a generalized compound, a lithium-containing compound containing lithium, or polyacetylene or polypyrrole.
- lithium-containing compounds are preferable because some of them can obtain a high voltage and a high energy density.
- a lithium-containing compound include a composite oxide containing lithium and a transition metal element, or a phosphate compound containing lithium and a transition metal element.
- Its chemical formula is, for example, Li MIO or Li MIIPO. Where Ml and
- Bis contains one or more transition metal elements.
- the values of X and y depend on the charge / discharge status of the battery, and are usually 0. 05 ⁇ x ⁇ l.10 and 0.05 ⁇ y ⁇ l.10.
- the composite oxide containing lithium and a transition metal element include lithium cobalt composite oxide (Li CoO), lithium nickel composite oxide (Li NiO), and lithium nickel composite oxide.
- LiMn 2 O 3 examples thereof include a manganese oxide (LiMn 2 O 3). Lithium and transition metal elements
- LiFe Mn PO (v 1) lithium iron manganese phosphate compound
- the negative electrode 22 has, for example, a structure in which a negative electrode active material layer 22B is provided on both surfaces or one surface of a negative electrode current collector 22A having a pair of opposed surfaces, similarly to the positive electrode 21.
- the negative electrode current collector 22A has an exposed portion where the negative electrode active material layer 22B is not provided at one end in the longitudinal direction, and the negative electrode terminal 12 is attached to the exposed portion.
- the negative electrode current collector 22A is made of, for example, a metal foil such as a copper foil, a nickel foil, or a stainless steel foil.
- the negative electrode active material layer 22B includes, for example, as a negative electrode active material, a negative electrode material capable of occluding and releasing lithium, or metallic lithium, and four or more kinds of displacement force.
- a conductive agent and a binder may be included as necessary.
- the negative electrode material capable of inserting and extracting lithium include carbon materials, metal oxides, and high molecular compounds.
- the carbon material include non-graphitizable carbon materials or graphite materials, and more specifically, pyrolytic carbons, coatas, graphites, glassy carbons, organic polymer compound fired bodies, There are carbon fiber and activated carbon.
- pitch coats there are pitch coats, needle coats, petroleum coats, etc.
- organic polymer compound fired bodies are made by firing a polymer material such as phenol resin or furan resin at an appropriate temperature and carbon.
- a polymer material such as phenol resin or furan resin
- the metal oxide include iron oxide, ruthenium oxide, and molybdenum oxide.
- the polymer compound include polyacetylene and polypyrrole.
- Examples of the negative electrode material capable of inserting and extracting lithium include materials containing at least one of a metal element and a metalloid element capable of forming a metal alloy with lithium as a constituent element.
- the negative electrode material may be a single element, alloy, or compound of a metal element or metalloid element, or may have at least a part of one or more of these phases.
- alloys include those containing one or more metal elements and one or more metalloid elements in addition to those composed of two or more metal elements.
- the nonmetallic element may be included.
- the structures include solid solutions, eutectics (eutectic mixtures), intermetallic compounds, or those in which two or more of them coexist.
- metal elements or metalloid elements examples include tin (Sn), lead (Pb), ano-remium, indium (In), silicon (Si), zinc (Zn), and antimony (Sb).
- group 14 metal elements or metalloid elements in the long-period type periodic table and particularly preferred is kaium or tin. This is because silicon and tin can obtain a high energy density having a large ability to occlude and release lithium.
- the second constituent element other than tin silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium (Ti), germanium, bismuth, Those containing at least one of the group consisting of antimony and chromium (Cr) It is done.
- the second constituent element other than the key is tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium. And those containing at least one member of the group.
- Examples of the tin compound or the key compound include those containing oxygen ( ⁇ ) or carbon (C), and include the second constituent element described above in addition to tin or key. May be.
- the separator 24 is a predetermined film having a high ion permeability such as a porous film made of a polyolefin-based synthetic resin such as polypropylene or polyethylene, or a porous film made of an inorganic material such as a ceramic nonwoven fabric. It is composed of an insulating thin film having mechanical strength, and may have a structure in which two or more kinds of porous films are laminated. Among these, those containing a polyolefin-based porous membrane are preferable because they are excellent in separability between the positive electrode 21 and the negative electrode 22 and can further reduce internal short-circuit and a decrease in open circuit voltage.
- the secondary battery can be manufactured, for example, as follows.
- the positive electrode 21 is produced.
- a positive electrode mixture is prepared by mixing the positive electrode active material with a conductive agent and a binder as necessary, such as N-methyl-2-pyrrolidone.
- a positive electrode mixture slurry is prepared by dispersing in a dispersion medium. After that, this positive electrode mixture slurry is applied to the positive electrode current collector 21A, dried and compression molded to form the positive electrode active material layer 21B.
- the negative electrode 22 is produced.
- a negative electrode active material is mixed with a conductive agent and a binder as necessary to prepare a negative electrode mixture, and N-methyl-2-pyrrolidone, etc.
- a negative electrode mixture slurry is prepared by dispersing in a dispersion medium. Thereafter, the negative electrode mixture slurry is applied to the negative electrode current collector 22A, dried, and compression molded to form the negative electrode active material layer 22B.
- the separator 24, the positive electrode 21, the separator 24, and the negative electrode 22 are sequentially stacked and wound to the outermost peripheral part.
- a protective tape 25 is adhered to form a wound electrode body.
- the wound electrode body is sandwiched between the exterior members 30, and the outer peripheral edge except one side is heat-sealed to form a bag shape.
- an electrolyte composition containing at least one monomer of the above-described polyvinyl acetal and derivatives thereof and an electrolytic solution containing lithium hexafluorophosphate is provided, and the exterior member 30 is prepared.
- the polymer is polymerized in the exterior member 30 by polymerizing the monomer using lithium hexafluorophosphate as a catalyst, and the secondary battery shown in FIGS. 1 and 2 is completed. Therefore, a low boiling point solvent can be easily mixed.
- this secondary battery may be manufactured as follows.
- the electrode composition is not injected after the wound electrode body is prepared, and is wound on the positive electrode 21 and the negative electrode 22, or after the electrolyte composition is applied to the separator 24, and wound inside the exterior member 30. You can enclose it.
- at least one monomer of polyvinylacetal and its derivatives is applied onto the positive electrode 21 and the negative electrode 22 or on the separator 24 and wound, and after being accommodated in the exterior member 30, lithium hexafluorophosphate It is possible to inject an electrolyte solution containing. These cases are also preferable because a low-boiling solvent can be easily mixed.
- the bondability between the polymer electrolyte 23 and the separator 24 is improved and the internal resistance can be lowered.
- the electrolyte composition is injected into the exterior member 30 to form the polymer electrolyte 23 because the polymer electrolyte 23 can be easily manufactured with less steps.
- lithium ions are released from the positive electrode active material layer 21 B and inserted into the negative electrode active material layer 22 B through the polymer electrolyte 23.
- lithium ions are released from the negative electrode active material layer 22B and inserted into the positive electrode active material layer 21B through the polymer electrolyte 23.
- the mobility of lithium ions depends on the electrolyte contained in the polymer electrolyte 23. In this embodiment, since the proportion of the electrolyte solution with a small proportion of the polymer compound is increased, the movement of lithium ions is facilitated and high ionic conductivity is obtained.
- lithium hexafluorophosphate since lithium hexafluorophosphate is used, it is possible to polymerize polybulucetal and its derivatives, thereby reducing the proportion of the polymer compound. Even so, leakage can be suppressed. Also, increase the proportion of electrolyte. Therefore, ion conductivity can be improved. Furthermore, for example, since a low boiling point solvent can be easily contained, ion conductivity can be further improved. It is also possible to suppress a reduction in discharge capacity due to a decomposition reaction in these electrodes, which does not require the use of a crosslinking agent. Therefore, it is possible to improve the discharge characteristics while suppressing leakage.
- the content of the polymer compound in the polymer electrolyte 23 is in the range of 2% by mass or more and 5% by mass or less, in particular, in the range of 2% by mass or less and 3.5% by mass or less, it is more possible. High effect can be obtained.
- FIGS. 1-10 A laminated film type secondary battery as shown in FIGS.
- a positive electrode mixture slurry was produced. Subsequently, the positive electrode mixture slurry was uniformly applied to both surfaces of a positive electrode current collector 21A made of an aluminum foil having a thickness of 20 zm and dried, followed by compression molding with a roll press to form a positive electrode active material layer 21B. Thus, the positive electrode 21 was produced. After that, the positive electrode terminal 11 was attached to the positive electrode 21.
- the pulverized graphite powder was used as a negative electrode active material, and 90 parts by mass of the graphite powder and 10 parts by mass of polyvinylidene fluoride as a binder were mixed to prepare a negative electrode mixture, and then dispersed.
- a negative electrode mixture slurry was prepared by dispersing in N_methyl_2_pyrrolidone as a medium. Subsequently, this negative electrode mixture slurry was uniformly applied to both sides of a negative electrode current collector 22 mm made of a copper foil having a thickness of 15 ⁇ m and dried, followed by compression molding to form a negative electrode active material layer 22B. Produced. After that, the negative electrode terminal 12 was attached to the negative electrode 22.
- the produced positive electrode 21 and negative electrode 22 were bonded to a microporous polyethylene film having a thickness of 25 ⁇ m.
- a wound electrode body was prepared by closely contacting with a separator 24 made of Lum, wound in the longitudinal direction, and adhering a protective tape 25 to the outermost periphery.
- the wound electrode body was sandwiched between the exterior members 30, and then the outer peripheral edge portion of the exterior member 30 was formed into a bonded bag shape except for one side.
- a moisture-proof aluminum laminating film in which a nylon film having a thickness of 25 ⁇ m, an aluminum foil having a thickness of 40 ⁇ m, and a polypropylene film having a thickness of 30 ⁇ m were laminated in order from the outermost layer was used.
- the electrolyte composition is injected from the opening of the exterior member 30, and the opening is heat-sealed and sealed under reduced pressure, and then sandwiched between glass plates to keep the battery shape constant.
- the polymer electrolyte 23 was formed by standing for a period of time, and the secondary battery shown in FIGS. 1 and 2 was produced.
- an electrolyte composition and a part of the formed polymer electrolyte 23 were extracted, and each of them was diluted 300-fold with N-methyl-2-pyrrolidone to obtain GPC (Gel Permeation Chromatography; gel permeation).
- GPC Gel Permeation Chromatography; gel permeation.
- the analysis was carried out using a dedicated system (chromatograph) (Showa Denko Co., Ltd., Shodex G PC-101).
- the weight average molecular weights f of the electrolyte composition and the polymer electrolyte 23 were 49000 and 350,000, respectively, and it was confirmed that polyvinylino lenoremanole force S was polymerized.
- Example 1-1 As Comparative Example 1-1 with respect to Example 1-1, a secondary solution was obtained in the same manner as Example 1-1 except that lithium perchlorate was used instead of lithium hexafluorophosphate. A battery was produced. Further, as Comparative Example 1-2, a secondary battery was fabricated in the same manner as in Example 1-1 except that polybula formal was not mixed.
- Liquid leakage tests were conducted on the fabricated secondary batteries of Examples 1 and 1 and Comparative Examples 1 and 1 and 1 and 1 and 2, respectively. It was performed as follows. First, 20 each of the secondary batteries of Example 11 and Comparative Examples 11 and 12 were prepared, a hole having a diameter of 0.5 mm was formed in the exterior member 30, and pressed at a pressure of 9.8 MPa. At this time, the number of batteries in which the electrolyte solution leaked was determined. The results are shown in Table 1.
- the discharge capacity was examined as follows. First, the constant current and constant voltage charge of 500mA at 23 ° C is limited to 4.2V for 2 hours, and then the constant current discharge of 100mA is performed to the final voltage of 3.0V. Asked. In addition, constant current and constant voltage charge was performed under the same conditions, 1500 mA constant current discharge was performed up to a final voltage of 3.0 V, and the discharge capacity at this time was determined. The results are shown in Table 1.
- Example 1 _ 1 in which polybulformal was polymerized using lithium hexafluorophosphate, no electrolyte leakage was observed, whereas phosphorous hexafluoride was observed.
- Comparative Example 1 — 1 using lithium perchlorate instead of lithium acid, or in Comparative Example 1 to 2 using no polybutylformal leakage of the electrolyte was observed.
- Example 1-1 in which polybulum formal was polymerized, the same discharge capacity as that of Comparative Example 1-2 was obtained using polybulal formal.
- microporous polypropylene film with a thickness of 25 ⁇ m, or thickness 25 A secondary battery was fabricated in the same manner as in Example 1-1 except that a polyethylene nonwoven fabric of / m was used.
- Example 1-1 For the fabricated secondary batteries of Examples 2-1 and 2-2, a liquid leakage test was performed in the same manner as in Example 1-1, and the discharge capacity was determined. The results are shown in Table 2 together with the results of Example 1-1-1.
- Example 2_1 As can be seen from Table 2, according to Example 2_1 using a microporous polyethylene film or microporous polypropylene film as a porous membrane, the discharge was higher than that of Example 2-2 using a non-woven fabric. A high value was shown for the capacity.
- the separator 24 preferably contains a porous film containing at least one of polyethylene and polypropylene.
- Example 1 A polymer electrolyte 23 and a secondary battery were produced in the same manner as in 1. The polybulum formal and the electrolytic solution were the same as those in Example 1-1.
- Example 3- To 3-6 and a part of the formed polymer electrolyte 23 were extracted, and in the same manner as in Example 1-1, a GPC dedicated system was used. Analysis was performed. As a result, in any case, the weight average molecular weight of the polymer electrolyte 23 is larger than the weight average molecular weight of the electrolyte composition, and the polyform formal was polymerized. It was confirmed.
- Examples 3-7 secondary batteries were fabricated such that the content of polyvinyl formal in polymer electrolyte 23 was 10% by mass. Specifically, it was produced as follows.
- the casting liquid was applied to both surfaces of the positive electrode 21 and the negative electrode 22 produced in the same manner as in Example 1-1, and the tetrahydrofuran was volatilized by drying at 50 ° C. to form the polymer electrolyte 23. did.
- the positive electrode 21 and the negative electrode 22 on which the polymer electrolyte 23 is formed are stacked and wound, and loaded between the exterior members 30 similar to Example 1-1, and the four sides are heat-sealed and sealed. Thus, a secondary battery was produced.
- Example 11 For the fabricated secondary batteries of Example 3— :! to 3-7, a liquid leakage test was performed in the same manner as in Example 11 and the discharge capacity was determined. The results are shown in Table 3 and FIG. 3 together with the results of Example 11 and Comparative Example 11.
- Example 3-4 4 0 502 439
- Example 3-5 5 0 501 435
- Example 3-6 6 0 498 378
- Example 3-7 10 0 482 313
- polyvinyl formal is polymerized using lithium hexafluorophosphate, and the content of the polymerized polymer compound is within the range of 2% by mass or more and 5% by mass or less with respect to the polymer electrolyte 23. In this way, leakage can be further suppressed. In particular, if the content of the polymer compound is in the range of 2% by mass to 3.5% by mass, the discharge characteristics can be further improved. It has been found that it can be improved.
- the present invention has been described with reference to the embodiment and examples, the present invention is not limited to the embodiment and examples, and various modifications can be made.
- the case of including the battery element 20 in which the positive electrode 21 and the negative electrode 22 are stacked and wound is described, but a flat battery element in which a pair of positive electrode and negative electrode are stacked
- the present invention can also be applied to a case where a stacked battery element in which a plurality of positive electrodes and negative electrodes are stacked is provided.
- the film-like external member 30 is used has been described.
- other shapes such as a so-called cylindrical shape, square shape, coin shape, button shape using a can as an exterior member are used.
- the same power can be applied to batteries with Furthermore, it can be applied not only to secondary batteries but also to primary batteries.
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- General Physics & Mathematics (AREA)
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/908,454 US8216724B2 (en) | 2005-03-14 | 2006-03-10 | Polymer electrolyte and battery |
KR1020077020926A KR101486577B1 (ko) | 2005-03-14 | 2006-03-10 | 고분자 전해질 및 전지 |
EP06728914A EP1860723A4 (en) | 2005-03-14 | 2006-03-10 | POLYMER ELECTROLYTE AND BATTERY |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005-071630 | 2005-03-14 | ||
JP2005071630A JP4609707B2 (ja) | 2005-03-14 | 2005-03-14 | 電池 |
JP2005-071629 | 2005-03-14 | ||
JP2005071629A JP2006253087A (ja) | 2005-03-14 | 2005-03-14 | 高分子電解質およびそれを用いた電池 |
Publications (1)
Publication Number | Publication Date |
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WO2006098240A1 true WO2006098240A1 (ja) | 2006-09-21 |
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PCT/JP2006/304746 WO2006098240A1 (ja) | 2005-03-14 | 2006-03-10 | 高分子電解質および電池 |
Country Status (5)
Country | Link |
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US (1) | US8216724B2 (ja) |
EP (1) | EP1860723A4 (ja) |
KR (1) | KR101486577B1 (ja) |
TW (1) | TW200703738A (ja) |
WO (1) | WO2006098240A1 (ja) |
Families Citing this family (3)
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CN103804892B (zh) * | 2012-11-09 | 2019-01-18 | 北京科技大学 | 一种聚合物多孔膜及其制备方法和在凝胶聚合物电解质中的应用 |
WO2016040541A1 (en) | 2014-09-12 | 2016-03-17 | Henkel IP & Holding GmbH | Cationically curable benzoxazine compositions |
CN114335698A (zh) * | 2021-12-31 | 2022-04-12 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种锂电池高压电解质的制备方法 |
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JPH0799060A (ja) * | 1993-09-29 | 1995-04-11 | Nippon Telegr & Teleph Corp <Ntt> | 固体電池 |
JPH1050141A (ja) * | 1996-07-29 | 1998-02-20 | Tdk Corp | 高分子電解質および電気化学デバイス |
JP2001200125A (ja) * | 2000-01-17 | 2001-07-24 | Toyo Ink Mfg Co Ltd | イオン伝導性組成物 |
JP2001283916A (ja) * | 2000-03-31 | 2001-10-12 | Matsushita Electric Ind Co Ltd | リチウムポリマー二次電池の製造方法 |
JP2002100406A (ja) * | 2000-09-25 | 2002-04-05 | Toshiba Battery Co Ltd | ポリマーリチウム二次電池及びその製造方法 |
JP2004079310A (ja) * | 2002-08-15 | 2004-03-11 | Toshiba Corp | ポリマーリチウム二次電池の製造方法 |
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JP2001079310A (ja) | 1999-09-10 | 2001-03-27 | Meidensha Corp | 水質制御方法及びその装置 |
JP2001200126A (ja) | 2000-01-17 | 2001-07-24 | Toyo Ink Mfg Co Ltd | イオン伝導性組成物 |
JP4606334B2 (ja) * | 2005-03-08 | 2011-01-05 | 三洋電機株式会社 | 非水電解質二次電池 |
-
2006
- 2006-03-10 WO PCT/JP2006/304746 patent/WO2006098240A1/ja active Application Filing
- 2006-03-10 KR KR1020077020926A patent/KR101486577B1/ko active IP Right Grant
- 2006-03-10 US US11/908,454 patent/US8216724B2/en active Active
- 2006-03-10 EP EP06728914A patent/EP1860723A4/en not_active Withdrawn
- 2006-03-14 TW TW095108616A patent/TW200703738A/zh unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0799060A (ja) * | 1993-09-29 | 1995-04-11 | Nippon Telegr & Teleph Corp <Ntt> | 固体電池 |
JPH1050141A (ja) * | 1996-07-29 | 1998-02-20 | Tdk Corp | 高分子電解質および電気化学デバイス |
JP2001200125A (ja) * | 2000-01-17 | 2001-07-24 | Toyo Ink Mfg Co Ltd | イオン伝導性組成物 |
JP2001283916A (ja) * | 2000-03-31 | 2001-10-12 | Matsushita Electric Ind Co Ltd | リチウムポリマー二次電池の製造方法 |
JP2002100406A (ja) * | 2000-09-25 | 2002-04-05 | Toshiba Battery Co Ltd | ポリマーリチウム二次電池及びその製造方法 |
JP2004079310A (ja) * | 2002-08-15 | 2004-03-11 | Toshiba Corp | ポリマーリチウム二次電池の製造方法 |
Non-Patent Citations (1)
Title |
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See also references of EP1860723A4 * |
Also Published As
Publication number | Publication date |
---|---|
US8216724B2 (en) | 2012-07-10 |
TW200703738A (en) | 2007-01-16 |
EP1860723A4 (en) | 2009-04-08 |
EP1860723A1 (en) | 2007-11-28 |
KR20070112171A (ko) | 2007-11-22 |
KR101486577B1 (ko) | 2015-01-26 |
US20090202918A1 (en) | 2009-08-13 |
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