WO2016195087A1 - フィルム外装電池 - Google Patents
フィルム外装電池 Download PDFInfo
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- WO2016195087A1 WO2016195087A1 PCT/JP2016/066637 JP2016066637W WO2016195087A1 WO 2016195087 A1 WO2016195087 A1 WO 2016195087A1 JP 2016066637 W JP2016066637 W JP 2016066637W WO 2016195087 A1 WO2016195087 A1 WO 2016195087A1
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- 230000017525 heat dissipation Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
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- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
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Images
Classifications
-
- 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
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
-
- 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 film-clad battery, and more particularly, to a highly reliable film-clad battery that is excellent in heat-resistant safety and is not easily affected by vibration or impact.
- a film-clad battery is one in which a battery element is housed together with an electrolyte in an exterior body (also referred to as “film exterior body”) made of such a laminate film.
- Patent Document 1 various forms relating to fixing of battery elements are disclosed.
- the separator since the separator is made of a polymer film, the separator may be damaged by heat in the process of thermally fusing the fixing tape and the outer package.
- the energy of film-clad batteries has been increased, and it has become important to ensure heat-resistant safety. Accordingly, an object of the present invention is to provide a highly reliable film-clad battery that is excellent in heat-resistant safety and is not easily affected by vibration or impact.
- a battery according to an embodiment of the present invention is as follows: A battery element in which a positive electrode, a negative electrode, and a separator are laminated or wound, the battery element not melting or softening at least at 200 ° C. and having a thermal shrinkage rate of 3% or less; A film outer package that houses the battery element; A fixing tape fixed to a part of the battery element and fixed to the inner surface of the film exterior body, A film-clad battery comprising:
- -"Film-clad battery means a battery in which a battery element is housed in a film-clad body together with an electrolyte. Generally, it has a flat shape as a whole. For example, a battery for an electric vehicle is required to have a large capacity, a low internal resistance, a high heat dissipation, and the like, and a film-covered battery is advantageous in these respects.
- -“Film outer package” means an outer package made of a flexible film and containing a battery element, and the battery element is hermetically sealed by arranging two films facing each other and fusing each other. The battery element may be sealed by folding a single film and fusing the opposing surfaces. -Regarding the numerical range, when “ab” is described in the present specification, it is intended to be from a to b.
- FIG. 1 It is a perspective view which shows the basic structure of a film-clad battery. It is a disassembled perspective view which shows the basic structure of a film-clad battery. It is sectional drawing which shows the cross section of the battery of FIG. 1 typically. It is a typical top view of the film-clad battery concerning one form of the present invention. It is sectional drawing which shows a fixed tape and its peripheral structure. It is sectional drawing which shows the layer structure of a fixed tape. It is sectional drawing which shows the other example of the layer structure of a fixed tape. It is sectional drawing which shows the further another example of the layer structure of a fixed tape. It is a schematic diagram which shows the other example of the sticking position of a fixed tape.
- FIG. 1 It is a schematic diagram for demonstrating an example of the outline shape of a fixed tape. It is a figure for demonstrating another example of the outline shape of a fixed tape. It is a figure which shows the example by which the hole was provided in the fixing tape. It is a typical top view of the film-clad battery which concerns on another form of this invention. It is a figure for demonstrating another example of a fixed tape. It is a top view of the fixed tape before affixing.
- a battery according to one embodiment of the present invention includes a fixing tape that fixes a battery element.
- the battery element is described as an example of a laminated film-clad battery, but the present invention is not necessarily limited to a laminated battery but can be applied to a battery of a wound type.
- a film-clad battery 1 includes a battery element 20, a film-clad body 10 that accommodates the battery element 20 together with an electrolyte, a positive electrode tab 51 and a negative electrode tab 52 (hereinafter, these are also simply referred to as “electrode tabs”). Say).
- the battery element 20 is formed by alternately laminating a plurality of positive electrodes 30 and a plurality of negative electrodes 40 with separators 25 therebetween.
- the electrode material 32 is applied to both surfaces of the metal foil 31.
- the electrode material 42 is applied to both surfaces of the metal foil 41.
- the overall external shape of the battery element 20 is not particularly limited, in this example, it is a flat and substantially rectangular parallelepiped.
- Each of the positive electrode 30 and the negative electrode 40 has an extended portion that partially protrudes from a part of the outer periphery.
- the extension part of the positive electrode 30 and the extension part of the negative electrode 40 are alternately arranged so as not to interfere with each other when the positive electrode and the negative electrode are stacked. All the negative electrode extensions are gathered together and connected to the negative electrode tab 52. Similarly, for the positive electrode, all the positive electrode extensions are gathered together and connected to the positive electrode tab 51 (See FIGS. 2 and 3).
- the portions gathered together in the stacking direction between the extension portions in this way are also called “current collecting portions” or the like.
- resistance welding, ultrasonic welding, laser welding, caulking, adhesion with a conductive adhesive, or the like can be employed.
- the positive electrode tab 51 is aluminum or an aluminum alloy
- the negative electrode tab 52 is copper or nickel.
- the material of the negative electrode tab 52 is copper, nickel may be arranged on the surface.
- Each of the electrode tabs 51 and 52 is electrically connected to the battery element 20 and is drawn out of the film exterior body 10.
- ⁇ Separator> As the separator, for example, an aramid, polyimide, polyester, cellulose, polyolefin resin such as polyethylene or polypropylene can be used. A polyolefin resin that is crosslinked by electron beam irradiation or addition of a crosslinking agent to increase the melting point may be used. Moreover, any structure, such as a woven fabric, a nonwoven fabric, or a microporous film, may be used.
- the melting point at which the separator melts or softens and the temperature at which 3% heat shrinks is preferably not 200 ° C. or lower.
- the gap of the separator becomes small, and the ionic conductivity of the electrolytic solution can be maintained.
- the separator is completely melted, the insulation between the electrodes cannot be maintained. Further, when the separator contracts, the insulation between the electrodes cannot be maintained.
- This shrinkage is preferably 5% or less at 200 ° C., more preferably 3% or less.
- the melting point of the separator can be confirmed with a scanning calorimeter (DSC), a viscoelasticity measuring device (DMA) or the like. If the linear expansion coefficient measuring device (TMA) is used, not only the melting point but also the 3% shrinkage temperature. Can also be measured.
- the separator does not deform and shrink to a temperature that is 50 ° C. or higher, 100 ° C. or higher, or 200 ° C. or higher higher than the melting point of the heat-sealing layer of the laminate film. It is preferable not to have.
- the form of the separator may be a web or a sheet. The above items can be used alone or in combination.
- a separator made of an inorganic material such as ceramic or glass can also be used.
- a nonwoven fabric separator made of ceramic short fibers such as alumina, alumina-silica, and potassium titanate can be used.
- the separator which consists of a base material which consists of a textile fabric, a nonwoven fabric, paper, or a porous film, and a layer containing a heat resistant nitrogen-containing aromatic polymer and ceramic powder may be sufficient.
- a heat-resistant layer is provided on a part of the surface, and the heat-resistant layer is made of a porous thin film layer containing ceramic powder, a porous thin film layer of heat-resistant resin, or a composite of ceramic powder and heat-resistant resin. It may be a porous thin film layer separator. Alternatively, the separator may include a porous film layer in which secondary particles obtained by sintering or dissolving and recrystallizing a part of primary particles of a ceramic substance are bonded by a binder.
- the separator including a polymer substrate and a ceramic-containing coating layer of Al 2 O 3 , MgO, TiO 2 , Al (OH) 3 , Mg (OH) 2 , and Ti (OH) 4 formed on the polymer substrate It may be.
- the negative electrode has a negative electrode current collector formed of a metal foil and a negative electrode active material layer coated on both sides of the negative electrode current collector.
- the negative electrode active material layer is bound so as to cover the negative electrode current collector with a negative electrode binder.
- the negative electrode current collector is formed to have an extension connected to the negative electrode terminal, and the negative electrode active material is not applied to the extension.
- the negative electrode active material in the present embodiment is not particularly limited.
- a carbon material that can occlude and release lithium ions a metal that can be alloyed with lithium, a metal oxide that can occlude and release lithium ions, and the like. Is mentioned.
- Examples of the carbon material include carbon, amorphous carbon, diamond-like carbon, carbon nanotube, or a composite thereof.
- carbon with high crystallinity has high electrical conductivity, and is excellent in adhesiveness and voltage flatness with a negative electrode current collector made of a metal such as copper.
- amorphous carbon having low crystallinity has a relatively small volume expansion, it has a high effect of relaxing the volume expansion of the entire negative electrode, and deterioration due to non-uniformity such as crystal grain boundaries and defects hardly occurs.
- a negative electrode containing a metal or metal oxide is preferable in that it can improve the energy density and increase the capacity per unit weight or unit volume of the battery.
- the metal examples include Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La, and alloys of two or more thereof. Moreover, you may use these metals or alloys in mixture of 2 or more types. These metals or alloys may contain one or more non-metallic elements.
- the metal oxide examples include silicon oxide, aluminum oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, and composites thereof.
- tin oxide or silicon oxide is included as a negative electrode active material, and it is more preferable that silicon oxide is included. This is because silicon oxide is relatively stable and hardly causes a reaction with other compounds.
- one or more elements selected from nitrogen, boron and sulfur may be added to the metal oxide, for example, 0.1 to 5% by mass. By carrying out like this, the electrical conductivity of a metal oxide can be improved.
- the negative electrode active material can be used by mixing a plurality of materials without using a single material.
- the same kind of materials such as graphite and amorphous carbon may be mixed, or different kinds of materials such as graphite and silicon may be mixed.
- the binder for the negative electrode is not particularly limited.
- polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer Rubber, polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamideimide, polyacrylic acid, or the like can be used.
- polyimide or polyamideimide is preferred because of its high binding properties.
- the amount of the binder for the negative electrode used is 0.5 to 25 parts by mass with respect to 100 parts by mass of the negative electrode active material from the viewpoints of “sufficient binding force” and “high energy” which are in a trade-off relationship. Is preferred.
- the negative electrode current collector aluminum, nickel, stainless steel, chromium, copper, silver, and alloys thereof are preferable in view of electrochemical stability.
- the shape include foil, flat plate, and mesh.
- the positive electrode has a positive electrode current collector formed of a metal foil, and a positive electrode active material coated on both surfaces of the positive electrode current collector.
- the positive electrode active material is bound so as to cover the positive electrode current collector with a positive electrode binder.
- the positive electrode current collector is formed to have an extension connected to the positive electrode terminal, and the positive electrode active material is not applied to the extension.
- the positive electrode active material is not particularly limited as long as it is a material capable of occluding and releasing lithium, but it is preferable to include a high-capacity compound from the viewpoint of increasing the energy density.
- the high-capacity compound include nickel-lithium oxide (LiNiO 2 ) or lithium-nickel composite oxide obtained by substituting a part of nickel in nickel-lithium oxide with another metal element.
- the layered structure represented by the following formula (A) Lithium nickel composite oxide is preferred.
- the Ni content is high, that is, in the formula (A), x is preferably less than 0.5, and more preferably 0.4 or less.
- LiNi 0.8 Co 0.05 Mn 0.15 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2, LiNi 0.8 Co 0.1 Al can be preferably used 0.1 O 2 or the like.
- LiNi 0.4 Co 0.3 Mn 0.3 O 2 (abbreviated as NCM433), LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 (abbreviated as NCM523), LiNi 0.5 Co 0.3 Mn 0.2 O 2 (abbreviated as NCM532), etc. (however, the content of each transition metal in these compounds varies by about 10%) Can also be included).
- two or more compounds represented by the formula (A) may be used as a mixture.
- NCM532 or NCM523 and NCM433 range from 9: 1 to 1: 9 (typically 2 It is also preferable to use a mixture in 1).
- a material having a high Ni content (x is 0.4 or less) and a material having a Ni content not exceeding 0.5 (x is 0.5 or more, for example, NCM433) are mixed. As a result, a battery having a high capacity and high thermal stability can be formed.
- the positive electrode active material for example, LiMnO 2 , Li x Mn 2 O 4 (0 ⁇ x ⁇ 2), Li 2 MnO 3 , Li x Mn 1.5 Ni 0.5 O 4 (0 ⁇ x ⁇ 2) Lithium manganate having a layered structure or spinel structure such as LiCoO 2 or a part of these transition metals replaced with another metal; Li in these lithium transition metal oxides more than the stoichiometric composition And those having an olivine structure such as LiFePO 4 .
- any of the positive electrode active materials described above can be used alone or in combination of two or more.
- radical materials or the like can be used as the positive electrode active material.
- the positive electrode binder the same as the negative electrode binder can be used.
- the amount of the positive electrode binder to be used is preferably 2 to 15 parts by mass with respect to 100 parts by mass of the positive electrode active material from the viewpoints of “sufficient binding force” and “high energy” which are in a trade-off relationship. .
- the positive electrode current collector the same as the negative electrode current collector can be used.
- a conductive auxiliary material may be added to the positive electrode active material coating layer for the purpose of reducing impedance.
- the conductive auxiliary material include carbonaceous fine particles such as graphite, carbon black, and acetylene black.
- a nonaqueous electrolytic solution containing a lithium salt (supporting salt) and a nonaqueous solvent that dissolves the supporting salt can be used.
- an aprotic organic solvent such as carbonate ester (chain or cyclic carbonate), carboxylic acid ester (chain or cyclic carboxylic acid ester), and phosphate ester can be used.
- carbonate solvents examples include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and vinylene carbonate (VC); dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate. (EMC), chain carbonates such as dipropyl carbonate (DPC); and propylene carbonate derivatives.
- PC propylene carbonate
- EC ethylene carbonate
- BC butylene carbonate
- VVC vinylene carbonate
- DMC dimethyl carbonate
- DEC diethyl carbonate
- EMC ethyl methyl carbonate
- DPC dipropyl carbonate
- propylene carbonate derivatives examples include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and vinylene carbonate (VC); dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate
- carboxylic acid ester solvent examples include aliphatic carboxylic acid esters such as methyl formate, methyl acetate, and ethyl propionate; and lactones such as ⁇ -butyrolactone.
- phosphate ester examples include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, trioctyl phosphate, triphenyl phosphate, and the like.
- solvents that can be contained in the non-aqueous electrolyte include, for example, ethylene sulfite (ES), propane sultone (PS), butane sultone (BS), dioxathilane-2,2-dioxide (DD), and sulfolene.
- ES ethylene sulfite
- PS propane sultone
- BS butane sultone
- DD dioxathilane-2,2-dioxide
- sulfolene sulfolene
- the supporting salts include LiPF 6 , LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) Lithium salts that can be used for ordinary lithium ion batteries such as 2 can be used.
- the supporting salt can be used alone or in combination of two or more.
- Non-aqueous solvents can be used alone or in combination of two or more.
- a laminate film having a surface layer, a metal layer, and an inner surface layer can be used.
- the metal layer may be aluminum
- the surface layer may be nylon (registered trademark) or polyethylene terephthalate
- the inner surface layer may be a polyolefin resin such as polyethylene or polypropylene.
- the inner surface layer may be polyethylene having a melting point of 95 to 140 ° C. or polypropylene having a melting point of 160 to 165 ° C.
- the film outer package 10 may be configured by arranging two films 10-1 and 10-2 facing each other.
- a film outer package may be formed by folding a single film.
- the outline shape of the film outer package 10 is not particularly limited, but may be a quadrangle, and specifically, in this example, it is a rectangle.
- the films 10-1 and 10-2 are bonded to each other around the battery element 20 by thermal fusion, and the peripheral portion of the film outer package 10 is a thermal fusion portion 15.
- the heat fusion part 15 is formed over the entire periphery of the battery.
- the positive electrode tab 51 and the negative electrode tab 52 are drawn out from one side of the short side of the heat-sealed portion 15.
- the electrode tabs may be drawn from two or more different sides.
- the positive electrode tab 51 and the negative electrode tab 52 are preferably parallel, but the present invention is not limited to this.
- the cup portion may be formed on one film 10-1 and the cup portion may not be formed on the other film 10-2. Or it is good also as a structure (not shown) which forms a cup part in both films, and it is good also as a structure (not shown) which does not form a cup part in both.
- the film-clad battery 1 of the present embodiment is provided with a fixing tape 70 for fixing the battery element 20 and the film-clad body 10.
- the fixing tape 70 may be provided only at one place, or may be provided at a plurality of places, but in this example, four places (specifically, left and right sides) of the peripheral portion of the battery element 20 are provided. 2 places on each side).
- the fixing tape 70 is attached to the peripheral edge of the battery element 20 in a substantially U-shape. Specifically, the fixing tape 70 is fixed to the end face of the battery element 20 (or is not fixed but is simply close), and the second part is fixed to the upper surface of the battery element 20. 70b-1 and a second portion 70b-2 fixed to the lower surface. Hereinafter, the second portion may be simply indicated by reference numeral 70b.
- the state in which the first portion 70a is not “fixed” but “close” is included in one embodiment of the present invention because the following case is also assumed as an example: That is, the portions 70 b-1 and 70 b-2 on both ends of the fixing tape 70 are fixed to the battery element 20, but the first portion 70 a is not fixed to the end of the battery element 20. is there. Specifically, for example, when the electrodes are uneven on the side surface of the battery element 20 and the fixing tape is not attached to the end face of the battery element, or only the first portion 70a is not intentionally attached to the end face of the battery element. This is the case.
- the contour of the fixing tape is, for example, for the purpose of making it difficult to remove the fixing tape from between the battery element and the film. It is good also as an uneven
- the shape illustrated in FIG. 8 (schematic plan view seen from the battery upper surface side) may be used.
- the contour of the fixing tape 170 has a triangular wave-like uneven shape.
- both the side edges 170p of the fixing tape 170 (here, the edges in the direction intersecting the end surface 20e of the battery element 20) and the edge 170q of the end are formed in an uneven shape. However, at least one of them, or only the side edges 170p may be uneven.
- the uneven shape may be a rectangular wave-like uneven shape as shown in FIG. 9A, a sinusoidal wave-like uneven shape as shown in FIG. Good.
- a trapezoidal uneven shape may be made by making these shapes deformed, for example, a trapezoidal uneven shape.
- a fixing tape 171 in which one or a plurality of holes 171a are formed may be used.
- the holes 171a may be formed in the second portions 70b-1 and 70b-2 (both may be either) of the tape.
- one or a plurality of holes may be provided in a fixing tape whose contour is formed in an uneven shape.
- FIG. 10 shows an example in which the holes 171a are arranged in the length direction of the tape, a plurality of holes may be provided in the width direction.
- the shape of the hole 171a is not limited to a circle but may be an arbitrary shape such as a rectangle or a polygon.
- FIG. 5 is a sectional view of the finished product.
- the outer surface of the second portion 70b (the surface facing the film outer package) is heat-sealed to the inner surface of the film outer package 10.
- the inner surfaces (surfaces facing the film outer package) of the second portions 70b-1 and 70b-2 are joined to the upper surface and the lower surface of the battery element 20, respectively.
- 5 shows only one fixing tape 70 and its peripheral structure, the other three fixing tapes 70 can have the same configuration.
- the relationship between the size of the battery element 20 and the length of the fixing tape 20 may be as follows, for example. That is, when the length of the portion of the fixing tape 70 to be attached to the main surface of the battery element 20 is L 70 and the width is W 70 , the values of L 70 and W 70 are both 1 mm or more and 2 mm. In one form, it is preferable to set it above or about 3 mm. When the width and length of the fixing tape are too short (that is, when the value of L 70 ⁇ W 70 is too small), there is a possibility that the fixing action by the fixing tape cannot be obtained sufficiently.
- the battery element 20 and the film outer package 10 are fixed through the fixing tape 70 as described above, an impact is temporarily applied to the battery element 20 during use or transportation.
- the battery element 20 is prevented from moving in the exterior body. Therefore, damage to the electrode tab and its peripheral structure can be prevented.
- the fixing tape 70 may have a multilayer structure as shown in FIG. 6A, for example.
- a heat-resistant layer 72 serving as a base material
- a first heat-sealing layer 71 laminated on one surface thereof
- a second heat-sealing layer 73 laminated on the other surface
- a fixing tape And an adhesive layer 74 for temporarily fixing 70 to the element As another aspect, as shown in FIG. 6B, a tape in which the first heat sealing layer 71 is omitted may be used.
- the fixing tape of FIG. 6B is preferable because it has a structure without the heat-fusible layer 71, so that the battery can be made thin.
- the heat-sealing layer 71 has a heat-sealing layer on the films 10-1 and 10-2, so that the fixing tape 70 and the film 10-1 or 10-2 can be heat-sealed.
- the layer 71 is preferable because the bonding strength with the inner surface of the exterior increases.
- a heat-resistant base material is not a film, and a fixing tape made of fibers such as a nonwoven fabric or a woven fabric can be used.
- the fixing tape of FIG. 6C has a composite layer 75 and an adhesive layer 74 obtained by impregnating a fiber with a heat-sealing layer.
- the fiber can be heat-sealed with both sides by impregnating the fiber with the heat-sealing layer. Therefore, the same effect as that obtained by providing two heat-sealing layers as shown in FIG. 6A is obtained, and such a configuration is preferable because high adhesive strength can be obtained on both sides.
- the woven fabric is superior in tensile strength to the nonwoven fabric, the effect of bundling battery elements is high.
- nonwoven fabrics are preferable because they are thin and inexpensive, and are low in cost.
- thermoplastic resin material can be used, for example, PP (polypropylene), PE (polyethylene), and the like. There may be.
- the melting point (Ta) of the heat-sealing layers 71 and 73 is preferably lower than the melting point of the separator and the temperature (Ts) at which 3% heat shrinks. Thereby, it is prevented that the separator is damaged by heat at the time of heat fusion (details will be described later) with a heat press.
- the melting points (Ta) of the heat-sealing layers 71 and 73 are preferably 10 ° C. or more, 20 ° C. or more, or 30 ° C. or less lower than the melting point of the separator and the temperature (Ts) at which 3% heat shrinks.
- the melting point (Tb) of the heat-resistant layer 72 is preferably 10 ° C., 20 ° C., or 30 ° C. higher than the melting point (Ta) of the heat-sealing layers 71, 73.
- the material of the heat-resistant layer 72 is preferably a material having high adhesiveness to the heat-fusion layer 73, the heat-fusion layer 71, or the heat-fusion layer of the films 10-1 and 10-2.
- the difference in SP value is 5 (cal / cm 3 ) (1/2) or less, preferably 3 (cal / cm 3 ) (1/2) or less, more preferably 2 (cal / cm 3 ) (1/2 ) that it is preferably less.
- the heat-resistant layer is formed as a fiber layer as shown in FIG. 6C, since the melt layer impregnates the fiber layer, the difference in solubility parameter between the two may exceed 5 (cal / cm 3 ) (1/2). Since it does not peel, it is not necessary to consider this, which is preferable.
- the material of the fiber layer glass fiber, carbon fiber, or metal fiber, which is an inorganic material, may be used in addition to the above-mentioned fiber made of a crosslinked material of PP and PE and a resin such as nylon.
- the inorganic material is preferable because it has a heat resistance higher by several hundred degrees C. or more than the heat-fusible layer, and thus there is no fear of breaking when the battery element is fixed with heat.
- the adhesive layer 74 may be, for example, an acrylic adhesive layer. Although illustration is omitted, the adhesive may be applied to the entire surface of the heat-fusible layer 73, or the adhesive may be applied in a predetermined pattern such as a dot shape or a stripe shape instead of the entire surface. .
- each layer is preferably, for example, about 10 to 100 ⁇ m for the heat-sealing layers 71 and 73 and about 10 to 50 ⁇ m for the heat-resistant layer 72.
- the thickness of the adhesive layer 74 is preferably, for example, 50 ⁇ m or less, 30 ⁇ m or less, or 10 ⁇ m or less.
- a positive electrode active material layer containing a positive electrode active material is formed on a current collector, a negative electrode active material layer containing a negative electrode active material is formed on the current collector, and the positive electrode active material layer and the negative electrode active material layer are separated from each other by a separator.
- the battery elements are arranged by facing each other, and further laminated and pressed to form a battery element.
- a fixing tape is affixed to the peripheral portion of the electrode / separator laminate.
- a tape or the like is sometimes used for temporarily fixing (maintaining the shape) of the battery element.
- the laminate is finally fixed to the film outer package.
- This fixing tape can also be used as a temporary fixing tape.
- the positive electrode tab and the negative electrode tab are connected to the positive electrode and the negative electrode by a conventionally known method.
- the battery element formed in this way is placed in a film outer package in which three sides are heat-sealed to form a bag.
- the inner fixing tape 70 is heated by heat-pressing from the outside of the film outer package at a predetermined temperature, pressure, and time conditions, and the inner heat-sealing layer 73 (see FIG. 6) and the battery element 20 are heated. While fixing, the outer heat-sealing layer 71 and the inner surface of the film outer package 10 are heat-sealed.
- the temperature of the heat press can be heat-sealed in a shorter time as the temperature is higher than that of the heat-sealing layers 71 and 73, the melting point or higher, preferably 10 ° C or higher, more preferably 20 ° C higher than the melting point. This is a high temperature. In order to prevent deformation and breakage of the exterior film, it is necessary not to exceed these melting points. Further, if the fixing tape is melted and cut by the heat sealing step, the battery elements cannot be integrated, and therefore the heat press temperature is preferably lower than the melting point (Tb) of the heat-resistant layer 72.
- the melting point of the separator is preferably as high as possible, and is preferably not 200 ° C. or less.
- the upper surface or the lower surface, preferably both surfaces of the fixing tape are heated via the film outer package 10.
- the area to be heated is heated only in a range that is the same as or narrower than the area of the second portion 70b that is the joint surface between the fixing tape and the film exterior body. It is preferable.
- the outermost electrode layer is also heat-sealed using the heat-sealing layer on the inner surface of the film outer package, it is preferable to heat the portion where the fixing tape is not temporarily fixed.
- the sealing step can be performed in a reduced-pressure atmosphere (in a reduced-pressure chamber).
- a reduced-pressure chamber By returning the sealed film-covered battery to the atmospheric pressure atmosphere, the exterior film is pressed against the battery element by the atmospheric pressure, and the exterior film Can be brought into close contact with the battery element.
- the separator since the melting point of the heat sealing layers 71 and 73 of the fixing tape 70 is lower than the melting point of the separator, the separator is not damaged by heat during the heat press. Moreover, since the heat resistant layer 72 is provided on the fixing tape 70 itself, the strength of the fixing tape 70 is also ensured. In the state after the heat press, the fixing tape 70 is not temporarily fixed by the adhesive layer 74, but the heat fusion layer 73 is fused to the battery element, so that the fixing tape 70 is fixed with sufficient strength.
- the fixing tape 70 may be provided at each of the opposing sides of the battery element 20.
- one or a plurality of fixing tapes may be provided on all four sides, or one or a fixing tape may be provided on each of three sides or less.
- the fixing tape 70 is comparatively short in the form of FIG. 7A, it is fixed over the whole of the battery element 20 in the vertical direction (or horizontal direction) as shown in FIG. 7B.
- a tape 70 ' may be provided.
- the fixing tape 70 ′ may be affixed over the entire circumference of the battery element 20, or may be affixed only to a part rather than the entire circumference.
- the battery element as shown in FIG. A configuration in which only a part of 20 is fixed is preferable.
- Examples of the configuration in which one or a plurality of fixing tapes are provided on all four sides include, for example, a configuration in which fixing tapes 70 are arranged at six locations on the periphery of the battery element 20 as shown in FIG. According to such a configuration, it is preferable to fix the four sides because the central layer of the laminate cannot be moved by vibration or the like.
- the fixing tape may be heat-sealed to the inner surface of the exterior body in consideration of the impregnation property of the electrolytic solution in the pouring step.
- the fixing tape may be heat-sealed in advance after temporarily fixing the fixing tape to the battery element with the adhesive layer 74. preferable.
- a fixing tape 270 having a shape as shown in FIGS. 12 and 13 may be used.
- the fixing tape 270 includes two attaching portions 270a attached to the upper surface and the lower surface of the laminate, and an intermediate connecting portion 270b.
- the affixing portion 270a can have various shapes such as a quadrangle, a polygon, and a circle, but in this example, it is a circle.
- the width of the connecting portion 270b is formed narrower than the diameter of the pasting portion 270a.
- a fixing tape 270 it is possible to achieve both the injection property of the electrolytic solution and the bonding strength as described below. That is, if the side surface portion of the laminate is covered with a wide fixing tape, the impregnation property to the electrode interlayer portion may be deteriorated when the electrolytic solution is injected. On the contrary, if the tape width is narrowed with the fixing tape as shown in FIG. 4, the area where the electrode and the exterior body are joined decreases, and there is a possibility that sufficient adhesive force for securing the laminate to the exterior body cannot be obtained. . Therefore, it is desirable to use a tape as shown in FIG. 12 and FIG.
- a film outer package (10) containing the battery element A film-clad battery comprising: a fixing tape (70) fixed to a part of the battery element and fixed to the inner surface of the film-clad body.
- the separator is made of at least one of polyimide resin, polyamide resin, and polyphenylene sulfone resin.
- the fixing tape has a multilayer structure, A heat sealing layer (73); A heat-resistant layer (72) having a melting point higher by 10 ° C. or more than the melting point of the heat-sealing layer,
- the fixing tape has a multilayer structure including a composite layer, Composite layer (75) in which a fiber having a melting point higher by 10 ° C. or more than the melting point of the heat-seal layer is impregnated with the heat-seal layer (composite layer in which the fiber is impregnated with the heat-seal layer)
- Composite layer (75) in which a fiber having a melting point higher by 10 ° C. or more than the melting point of the heat-seal layer is impregnated with the heat-seal layer (composite layer in which the fiber is impregnated with the heat-seal layer)
- the fixing tape (70) is further The film-clad battery according to the above, comprising an adhesive layer (74) for adhering a fixing tape to the battery element before heat fusion.
- the film-clad battery according to one embodiment of the present invention can be used in, for example, all industrial fields that require a power source.
- it can be used as a power source for mobile devices such as mobile phones and laptop computers; it can be used as a power source for electric vehicles such as electric cars, hybrid cars, electric bikes, and electric assist bicycles; transport for transportation such as trains, satellites, and submarines
- electric vehicles such as electric cars, hybrid cars, electric bikes, and electric assist bicycles
- transport for transportation such as trains, satellites, and submarines
- It can be used as a power source for mediums; it can be used as a power storage system for storing electric power.
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Abstract
Description
正極、負極、およびセパレータが積層または巻回された電池要素であって、前記少なくとも200℃で、溶融または軟化せず、かつ、熱収縮率が3%以下である、電池要素と、
前記電池要素を収容するフィルム外装体と、
前記電池要素の一部に固定されるとともに、前記フィルム外装体の内面に固定された固定テープと、
を備える、フィルム外装電池。
・「フィルム外装電池」とは、電池要素を電解質とともにフィルム外装体に収容した電池のことをいう。一般的には、全体として偏平な形状をしている。例えば電動車両用の電池では、容量が大きいこと、内部抵抗が低いこと、放熱性が高いこと等が要求されるところ、フィルム外装電池はこれらの点で有利である。
・「フィルム外装体」とは、可撓性を有するフィルムで構成され電池要素を収容する外装体のことをいい、2枚のフィルムを対向配置して互いに融着することにより電池要素を密閉するものであってもよいし、1枚のフィルムを折り返して対向した面どうしを融着することにより電池要素を密閉するものであってもよい。
・数値範囲に関し、本明細書で「a~b」と記載した場合には、a以上b以下であることを意図する。
フィルム外装電池の基本的な構成について、図1~図3を参照して説明する。後述するように、本発明の一形態に係る電池は、電池要素を固定する固定テープを備えていることを特徴の1つとする。ただし、説明の都合上、図1~図3ではそれらの図示は省略している。以下では電池要素が積層型のフィルム外装電池を例に挙げて説明するが、本発明自体は、必ずしも積層型の電池に限らず捲回型などの電池にも適用しうる。
電池要素の各要素に関しては、具体的には以下のようなものを採用してもよい。
セパレータとしては、例えば、アラミド、ポリイミド、ポリエステル、セルロース、ポリエチレンやポリプロプレンなどのポリオレフィン系樹脂を用いることができる。ポリオレフィン系樹脂を電子線照射または架橋剤の添加によって架橋して融点を高めたものを用いてもよい。また、織布、不織布、または微多孔膜等のいずれの構造であっても構わない。
負極は、金属箔で形成される負極集電体と、負極集電体の両面に塗工された負極活物質層とを有する。負極活物質層は負極用結着材によって負極集電体を覆うように結着される。負極集電体は、負極端子と接続する延長部を有して形成され、この延長部には負極活物質は塗工されない。
正極は、金属箔で形成される正極集電体と、正極集電体の両面に塗工された正極活物質とを有する。正極活物質は正極用結着剤によって正極集電体を覆うように結着される。正極集電体は、正極端子と接続する延長部を有して形成され、この延長部には正極活物質は塗工されない。
(但し、0≦x<1、0<y≦1.2、MはCo、Al、Mn、Fe、Ti及びBからなる群より選ばれる少なくとも1種の元素である。)
電解質は、リチウム塩(支持塩)と、この支持塩を溶解する非水溶媒を含む非水電解液を用いることができる。
外装体のフィルムとしては、表面層、金属層、および内面層を有するラミネートフィルムを用いることができる。金属層としてアルミニウムを、表面層としてはナイロン(登録商標)やポリエチレンテレフタレートを、内面層にポリエチレンやポリプロピレンなどのポリオレフィン系樹脂を用いたものであってもよい。内面層は、融点95~140℃のポリエチレンや、融点160~165℃のポリプロピレンであってもよい。
本実施形態のフィルム外装電池1には、図4、図5に示すように、電池要素20とフィルム外装体10とを固定するための固定テープ70が設けられている。固定テープ70は、1箇所のみに設けられていてもよいし、または複数箇所に設けられていてもよいが、この例では、電池要素20の周縁部の4箇所(具体的には、左右の辺に2箇所ずつ)に設けられている。
本出願は、以下の発明を開示する:
1.正極、負極、およびセパレータが積層または巻回された電池要素(20)であって、上記セパレータは少なくとも200℃で、溶融または軟化せず、かつ、熱収縮率が3%以下である、電池要素(20)と、
上記電池要素を収容するフィルム外装体(10)と、
上記電池要素の一部に固定されるとともに、上記フィルム外装体の内面に固定された固定テープ(70)と、を備える、フィルム外装電池。
熱融着層(73)と、
上記熱融着層の融点よりも10℃以上高い融点の耐熱層(72)と、
を有する、上記記載のフィルム外装電池。
上記熱融着層の融点よりも10℃以上高い融点の繊維に熱融着層を含浸した複合体層(75)(上記繊維に熱融着層が含浸された状態となっている複合体層)を有する、上記記載のフィルム外装電池。
上記フィルム外装体の内面に固定される第1の熱融着層(71)と、
上記電池要素に固定される第1の熱融着層(73)と、
を有する、上記記載のフィルム外装電池。
熱融着前に固定テープを上記電池要素に貼着しておくための粘着層(74)を有している、上記記載のフィルム外装電池。
10 フィルム外装体
15 熱融着部
20 電池要素
25 セパレータ
30 正極
40 負極
70、70’ 固定テープ
71 熱融着層
72 耐熱層
73 熱融着層
74 粘着層
75 複合体層(耐熱繊維を含浸した熱融着層)
170、270 固定テープ
Claims (8)
- 正極、負極、およびセパレータが積層または巻回された電池要素であって、前記セパレータは少なくとも200℃で、溶融または軟化せず、かつ、熱収縮率が3%以下である、電池要素と、
前記電池要素を収容するフィルム外装体と、
前記電池要素の一部に固定されるとともに、前記フィルム外装体の内面に固定された固定テープと、
を備える、フィルム外装電池。 - 前記固定テープと前記フィルム外装体の内面とが、熱融着により固定されている、請求項1に記載のフィルム外装電池。
- 前記セパレータは、ポリイミド樹脂、ポリアミド樹脂、ポリフェニレンスルホン樹脂の少なくとも一つからなる、請求項1または2に記載のフィルム外装電池。
- 前記固定テープが多層構造であり、
熱融着層と、
前記熱融着層の融点よりも10℃以上高い融点の耐熱層と、
を有する、請求項1~3のいずれか一項に記載のフィルム外装電池。 - 前記固定テープが複合体層を含む多層構造であり、
前記熱融着層の融点よりも10℃以上高い融点の繊維に熱融着層を含浸した複合体層を有する、請求項1~3のいずれか一項に記載のフィルム外装電池。 - 前記熱融着層として、
前記フィルム外装体の内面に固定される第1の熱融着層と、
前記電池要素に固定される第1の熱融着層と、
を有する、請求項4に記載のフィルム外装電池。 - 前記熱融着層の融点が、前記セパレータの融点よりも低い、請求項4~6のいずれか一項に記載のフィルム外装電池。
- 前記固定テープが、さらに、
熱融着前に固定テープを前記電池要素に貼着しておくための粘着層を有している、請求項4~7のいずれか一項に記載のフィルム外装電池。
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