TW201308382A - Insulating-adhesive-layer composition, element for electricity-storage device, electricity-storage device, and manufacturing methods therefor - Google Patents
Insulating-adhesive-layer composition, element for electricity-storage device, electricity-storage device, and manufacturing methods therefor Download PDFInfo
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- TW201308382A TW201308382A TW101120549A TW101120549A TW201308382A TW 201308382 A TW201308382 A TW 201308382A TW 101120549 A TW101120549 A TW 101120549A TW 101120549 A TW101120549 A TW 101120549A TW 201308382 A TW201308382 A TW 201308382A
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- layer
- electrode layer
- insulating
- positive electrode
- negative electrode
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- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 239000010410 layer Substances 0.000 claims abstract description 446
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 63
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- 239000003990 capacitor Substances 0.000 abstract description 28
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- 239000000919 ceramic Substances 0.000 description 14
- 239000007774 positive electrode material Substances 0.000 description 12
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- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
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- 238000005470 impregnation Methods 0.000 description 3
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229920006370 Kynar Polymers 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 239000000470 constituent Substances 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
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- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 description 1
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- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
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Classifications
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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
- H01M10/058—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
- 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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/10—Multiple hybrid or EDL capacitors, e.g. arrays or modules
- H01G11/12—Stacked hybrid or EDL capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
- 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
- Y02E60/13—Energy storage using capacitors
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
Description
本發明係關於一種絕緣性接著層組合物、蓄電裝置用元件及蓄電裝置，進而關於一種蓄電裝置用元件及蓄電裝置之製造方法。 The present invention relates to an insulating adhesive layer composition, an element for a power storage device, and a power storage device, and further relates to an element for a power storage device and a method for manufacturing the power storage device.
以鋰離子蓄電池、鋰離子電容器、電雙層電容器等為代表之高能量密度之蓄電裝置例如具有蓄電要素與電解液收容於外裝體內之構造，該蓄電要素係藉由如下方式構成，即，將藉由在片狀之集電箔(鋁箔或銅箔等)上塗敷活性物質(活性碳、鋰複合氧化物、碳等)而形成之片狀電極介隔用以防止因電極間之接觸引起之短路之片狀分隔件而積層。 A power storage device having a high energy density, such as a lithium ion battery, a lithium ion capacitor, or an electric double layer capacitor, has a structure in which an electric storage element and an electrolytic solution are housed in an exterior body, and the electric storage element is configured as follows. A sheet electrode formed by coating an active material (activated carbon, lithium composite oxide, carbon, or the like) on a sheet-shaped current collector foil (aluminum foil, copper foil, or the like) is interposed to prevent contact between electrodes. The short-circuited sheet-like separator is laminated.
作為此種蓄電裝置之一，提出有如下之積層型電池：將混合電解質與多孔性陶瓷纖維且與黏合劑一併形成為膜狀之陶瓷片用作分隔件用材料，介隔上述陶瓷片積層正極層與負極層，總括積層體且經由熱壓步驟製造而成(專利文獻1)。 As one of such power storage devices, there is proposed a laminated battery in which a ceramic sheet in which a mixed electrolyte and a porous ceramic fiber are formed into a film together with a binder is used as a material for a separator, and the ceramic sheet is interposed. The positive electrode layer and the negative electrode layer are collectively produced by a hot pressing step in a laminated body (Patent Document 1).
又，作為另一蓄電裝置，提出有如下之蓄電裝置(電雙層電容器)：如圖17所示，使接著有活性碳電極110之集電金屬120對向，並且使分隔件130及電解液(未圖示)介於其等之間，進而，於集電金屬120之最外周部預先接著改性聚丙烯或改性聚乙烯等熱接著部140，對該熱接著部140進行加熱而相互接著集電金屬120，從而進行密封(專利文獻 2)。 Further, as another power storage device, a power storage device (electric double layer capacitor) has been proposed: as shown in FIG. 17, the collector metal 120 following the activated carbon electrode 110 is opposed, and the separator 130 and the electrolyte are provided. (not shown) is interposed between them, and further, a heat-receiving portion 140 such as a modified polypropylene or a modified polyethylene is applied to the outermost peripheral portion of the current collector 120, and the heat-receiving portion 140 is heated to each other. Then collect the metal 120 to seal it (Patent Literature 2).
又，作為又一蓄電裝置，提出有藉由包含具有接著性之熱塑性樹脂之墊片(gasket)而使分隔件、集電體、及分極性電極一體化之蓄電裝置(電雙層電容器)(專利文獻3)。 In addition, as another power storage device, a power storage device (electric double layer capacitor) in which a separator, a current collector, and a polarization electrode are integrated by a gasket including a thermoplastic resin having an adhesive property has been proposed ( Patent Document 3).
再者，於專利文獻3中，記載有使用具有極性官能基之熱塑性樹脂作為構成墊片之具備接著性之熱塑性樹脂之情形。 Further, Patent Document 3 describes a case where a thermoplastic resin having a polar functional group is used as a thermoplastic resin having an adhesive property constituting a gasket.
進而，作為燃料電池用墊片，提出有包含一對樹脂性膜之膜一體型燃料電池用墊片，該一對樹脂性膜係於組裝於燃料電池單元時成為外端部之樹脂製膜之外表面，分別具有由相對於該膜具有接著性之橡膠成形之山形凸狀部(專利文獻4)。 Further, as a gasket for a fuel cell, a gasket for a membrane-integrated fuel cell including a pair of resinous films, which is a resin film which is an outer end portion when assembled in a fuel cell unit, is proposed. Each of the outer surfaces has a mountain-shaped convex portion formed by rubber having an adhesive property with respect to the film (Patent Document 4).
然而，於上述專利文獻1之積層型電池之情形時，有於將混合有電解質之陶瓷片與正極層或負極層積層之步驟中，必需單獨處理陶瓷片之情形，從而對陶瓷片要求某種程度以上之強度。然而，若欲確保陶瓷片之強度，則存在分隔件之低電阻(低離子電阻)化所需之陶瓷片之薄層化或提高陶瓷粉體比率(高PVC(Pigment Volume Concentration，顏料體積濃度)化)受到制約之問題。即，若欲確保電解液、陶瓷、及黏合劑共存之陶瓷片之強度，則存在薄層化或高PVC化犧牲，而難以實現分隔件之低電阻(低離子電阻)化之問題。 However, in the case of the laminated battery of the above-mentioned Patent Document 1, in the step of laminating the ceramic sheet in which the electrolyte is mixed with the positive electrode layer or the negative electrode layer, it is necessary to separately treat the ceramic piece, thereby requiring some kind of ceramic piece. The intensity above the level. However, if the strength of the ceramic sheet is to be ensured, there is a thinning of the ceramic sheet required for the low resistance (low ionic resistance) of the separator or an increase in the ceramic powder ratio (high PVC (Pigment Volume Concentration)). The problem of being restricted. In other words, in order to secure the strength of the ceramic sheet in which the electrolytic solution, the ceramic, and the binder coexist, there is a problem of thinning or high PVC, and it is difficult to achieve a low resistance (low ionic resistance) of the separator.
又，於上述專利文獻2之蓄電裝置(電雙層電容器)之情形時，存在如下問題：改性聚丙烯或改性聚乙烯完全不具 有電解液之含浸性、滲透性，故必需於積層前預先使電解液含浸於分隔件(及視情形為電極)，從而無法應對如於積層體形成後將電解液後添加之製造方法，製造步驟變得複雜。 Moreover, in the case of the electrical storage device (electric double layer capacitor) of the above Patent Document 2, there is a problem that the modified polypropylene or the modified polyethylene does not have any Since the electrolyte is impregnated and permeable, it is necessary to impregnate the separator (and optionally the electrode) before the lamination, so that it is impossible to cope with the manufacturing method of adding the electrolyte after the formation of the laminate. The steps get complicated.
又，於上述專利文獻3之電雙層電容器之情形時，使用墊片作為接著層，但構成墊片之熱塑性樹脂不具有電解液之含液性或滲透性。因此，具有與上述專利文獻2之情形相同之問題。 Further, in the case of the electric double layer capacitor of Patent Document 3, a gasket is used as the adhesive layer, but the thermoplastic resin constituting the gasket does not have liquidity or permeability of the electrolytic solution. Therefore, it has the same problem as the case of the above-mentioned Patent Document 2.
又，於上述專利文獻4之燃料電池用墊片之情形時，與專利文獻3之情形同樣，使用墊片作為接著層，但不具有電解液之含液性或滲透性。因此，與專利文獻2或3之情形同樣，存在無法應對如於積層體形成後添加電解液之製造方法，製造步驟變得複雜之問題。 Further, in the case of the gasket for a fuel cell of Patent Document 4, as in the case of Patent Document 3, a gasket is used as the adhesive layer, but the liquidity or permeability of the electrolytic solution is not provided. Therefore, similarly to the case of Patent Document 2 or 3, there is a problem that the manufacturing method in which the electrolytic solution is added after the formation of the laminated body cannot be handled, and the manufacturing process becomes complicated.
[專利文獻1]日本專利特開平6-231796號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 6-231796
[專利文獻2]日本專利特開2002-313679號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-313679
[專利文獻3]日本專利特開2005-109293號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-109293
[專利文獻4]WO 2000/064995號說明書 [Patent Document 4] WO 2000/064995
本發明係解決上述課題者，其目的在於提供一種可對積層體賦予電解液之含浸性、滲透性之蓄電裝置用之絕緣性接著層組合物、具有包含該絕緣性接著層組合物之絕緣性 接著層之特性良好之蓄電裝置用元件、蓄電裝置、及其等之製造方法。 The present invention has been made to solve the above problems, and an object of the invention is to provide an insulating back-layer composition for an electrical storage device which is capable of imparting impregnation properties and permeability to an electrolyte solution, and having an insulating property comprising the insulating adhesive layer composition. An element for a power storage device having a good characteristic of the layer, a power storage device, and a method of manufacturing the same.
為了解決上述課題，本發明之絕緣性接著層組合物之特徵在於：其係構成包括積層體及電解液之蓄電裝置之絕緣性接著層之組合物，該積層體具有正極層與負極層介隔分隔層及上述絕緣性接著層而積層，上述正極層與上述負極層藉由上述絕緣性接著層而接合之構造；該絕緣性接著層組合物包括含有無機微粒子及熔點為160℃以下之黏合劑樹脂之複合材料，且具有使上述正極層與上述負極層接合而保持為一體之接著性及使上述電解液滲透之電解液滲透性。 In order to solve the above problems, the insulating adhesive layer composition of the present invention is characterized in that it constitutes a composition of an insulating adhesive layer of a power storage device including a laminate and an electrolytic solution, and the laminate has a positive electrode layer and a negative electrode layer interposed therebetween. a separator layer and the insulating adhesive layer are laminated, and the positive electrode layer and the negative electrode layer are joined by the insulating adhesive layer. The insulating adhesive layer composition includes an inorganic fine particle and a binder having a melting point of 160 ° C or less. The composite material of the resin has an adhesive property in which the positive electrode layer and the negative electrode layer are bonded to each other and an electrolyte permeability which permeates the electrolyte solution.
又，本發明之絕緣性接著層組合物之特徵在於：其係構成包括積層體及電解液之蓄電裝置之絕緣性接著層之組合物，該積層體具有正極層與負極層介隔分隔層及上述絕緣性接著層而積層，且上述正極層與上述負極層藉由上述絕緣性接著層而接合之構造；該絕緣性接著層組合物包括含有無機微粒子及不具有熔點而玻璃轉移溫度為110℃以下之黏合劑樹脂之複合材料，且具有使上述正極層與上述負極層接合而保持為一體之接著性及使上述電解液滲透之電解液滲透性。 Further, the insulating adhesive layer composition of the present invention is characterized in that it constitutes a composition of an insulating adhesive layer of a power storage device including a laminate and an electrolytic solution, and the laminate has a separator layer between the positive electrode layer and the negative electrode layer and The insulating layer is laminated, and the positive electrode layer and the negative electrode layer are joined by the insulating adhesive layer. The insulating adhesive layer composition includes inorganic fine particles and does not have a melting point, and the glass transition temperature is 110 ° C. The composite material of the binder resin described below has an adhesive property in which the positive electrode layer and the negative electrode layer are bonded to each other and an electrolyte permeability which permeates the electrolyte solution.
又，本發明之蓄電裝置元件之特徵在於：其包括積層體，該積層體具有正極層與負極層介隔分隔 層及絕緣性接著層而積層，上述正極層與上述負極層藉由上述絕緣性接著層而接著之構造，且與電解液一併使用而構成蓄電裝置，且於上述絕緣性接著層中使用有如技術內容1或2之絕緣性接著層組合物。 Further, the power storage device component of the present invention is characterized in that it includes a laminated body having a positive electrode layer and a negative electrode layer separated from each other. The layer and the insulating layer are laminated, and the positive electrode layer and the negative electrode layer are subsequently formed by the insulating adhesive layer, and are used together with an electrolytic solution to form a power storage device, and are used in the insulating adhesive layer. Insulating adhesive layer composition of Technical Content 1 or 2.
又，本發明之蓄電裝置之特徵在於：其包括：積層體，其具有正極層與負極層介隔分隔層及絕緣性接著層而積層，上述正極層與上述負極層藉由上述絕緣性接著層而接著之構造；電解液；及封裝體，其收納上述積層體與上述電解液；且於上述絕緣性接著層中使用有如技術內容1或2之絕緣性接著層組合物。 Further, a power storage device according to the present invention includes: a laminated body having a positive electrode layer and a negative electrode layer interposed with a separator layer and an insulating back layer, wherein the positive electrode layer and the negative electrode layer are laminated by the insulating layer And the following structure; an electrolyte; and a package for accommodating the laminate and the electrolyte; and the insulating adhesive layer composition of the first or second aspect of the invention is used for the insulating adhesive layer.
又，本發明之蓄電裝置元件之製造方法係包括積層體之蓄電裝置用元件之製造方法，該積層體具有正極層與負極層介隔分隔層及絕緣性接著層而積層，上述正極層與上述負極層藉由上述絕緣性接著層而接著之構造，且與電解液一併使用而構成蓄電裝置；該蓄電裝置元件之製造方法之特徵在於：包括如下步驟，即，藉由將成為上述正極層之正極層用材料與成為上述負極層之負極層用材料以介隔成為上述分隔層之分隔層用材料及成為上述絕緣性接著層之絕緣性接著層材料而對向之方式配置，並加熱、加壓而形成上述正極層、上述負極層、上述分隔層、及上述絕緣性接著層一體化之上述積層體；並且 作為上述絕緣性接著層材料，使用如下之絕緣性接著層材料：包含無機微粒子及熔點為160℃以下之黏合劑樹脂，且作為藉由上述步驟獲得之上述積層體之上述絕緣性接著層，形成具有使上述正極層與上述負極層接合而保持為一體之接著性及使上述電解液滲透之電解液滲透性之絕緣性接著層。 Moreover, the method for producing a power storage device device according to the present invention includes a method of manufacturing a device for a power storage device including a laminated body having a positive electrode layer and a negative electrode layer interposed with a separator and an insulating adhesive layer, wherein the positive electrode layer and the positive electrode layer are The negative electrode layer is configured by the insulating adhesive layer and is used in combination with the electrolytic solution to form a power storage device. The method for manufacturing the power storage device device includes the steps of: forming the positive electrode layer The material for the positive electrode layer and the material for the negative electrode layer serving as the negative electrode layer are disposed so as to be opposed to each other by the material for the separator which serves as the separator, and the insulating adhesive layer which is the insulating back layer, and are heated and Forming the laminated body in which the positive electrode layer, the negative electrode layer, the separator, and the insulating back layer are integrated by pressurization; As the insulating adhesive layer material, an insulating adhesive layer material containing inorganic fine particles and a binder resin having a melting point of 160 ° C or less is used as the insulating adhesive layer of the laminate obtained by the above steps. An insulating adhesive layer having an adhesive property in which the positive electrode layer and the negative electrode layer are bonded to each other and an electrolyte permeability which allows the electrolyte solution to permeate.
又，本發明之蓄電裝置元件之製造方法係包括積層體之蓄電裝置用元件之製造方法，該積層體具有正極層與負極層介隔分隔層及絕緣性接著層而積層，上述正極層與上述負極層藉由上述絕緣性接著層而接著之構造，且與電解液一併使用而構成蓄電裝置；該蓄電裝置用元件之製造方法之特徵在於：包括如下步驟，即，藉由將成為上述正極層之正極層用材料與成為上述負極層之負極層用材料以介隔成為上述分隔層之分隔層用材料及成為上述絕緣性接著層之絕緣性接著層材料而對向之方式配置，並加熱、加壓而形成上述正極層、上述負極層、上述分隔層、及上述絕緣性接著層一體化之上述積層體；並且作為上述絕緣性接著層材料，使用如下之絕緣性接著層材料：包含無機微粒子及不具有熔點而玻璃轉移溫度為110℃以下之黏合劑樹脂，且作為藉由上述步驟獲得之上述積層體之上述絕緣性接著層，形成具有使上述正極層與上述負極層接合而保持為一體之接著性及使上述電解液滲透之電解液滲透性之絕緣性接著層。 Moreover, the method for producing a power storage device device according to the present invention includes a method of manufacturing a device for a power storage device including a laminated body having a positive electrode layer and a negative electrode layer interposed with a separator and an insulating adhesive layer, wherein the positive electrode layer and the positive electrode layer are The negative electrode layer is configured by the insulating adhesive layer and is used in combination with the electrolytic solution to form a power storage device. The method for manufacturing the power storage device component includes the steps of: The material for the positive electrode layer of the layer and the material for the negative electrode layer to be the negative electrode layer are disposed so as to be opposed to each other by the material for the separation layer which serves as the separation layer, and the insulating adhesive layer material which serves as the insulating adhesive layer, and are heated. The laminated body in which the positive electrode layer, the negative electrode layer, the separator, and the insulating back layer are integrated is formed by pressurization, and as the insulating back layer material, the following insulating back layer material is used: inorganic a microparticle and a binder resin having no melting point and a glass transition temperature of 110 ° C or less, and as a step by the above Have the above-described laminate of the insulating layer is then formed so that the positive electrode having a negative electrode layer and the bonding layer is then held integrally of the electrolytic solution resistance and the insulating property of the permeability of the electrolytic solution followed by permeation layer.
又，本發明之蓄電裝置之製造方法係包括積層體、電解液、及收納上述積層體與上述電解液之封裝體之蓄電裝置之製造方法，該積層體具有正極層與負極層介隔分隔層及絕緣性接著層而積層且上述正極層與上述負極層藉由上述絕緣性接著層而接著之構造；該蓄電裝置之製造方法之特徵在於包括如下步驟：(1)藉由將成為上述正極層之正極層用材料與成為上述負極層之負極層用材料以介隔成為上述分隔層之分隔層用材料及成為上述絕緣性接著層之絕緣性接著層材料而對向之方式配置，並加熱、加壓而形成上述正極層、上述負極層、上述分隔層、及上述絕緣性接著層一體化之上述積層體，且使用如下之絕緣性接著層材料作為上述絕緣性接著層材料而形成上述積層體：包含無機微粒子及熔點為160℃以下之黏合劑樹脂，且作為構成上述積層體之上述絕緣性接著層，形成具有使上述正極層與上述負極層接合而保持為一體之接著性及使上述電解液滲透之電解液滲透性之絕緣性接著層；及(2)將上述積層體與上述電解液一併收容於上述封裝體內，使上述電解液自上述積層體之外部向內部滲透、含浸。 Moreover, the method for producing a power storage device according to the present invention includes a laminate, an electrolytic solution, and a method of manufacturing a power storage device that houses the laminate and the electrolyte solution, wherein the laminate has a separator layer between the positive electrode layer and the negative electrode layer. And the insulating layer is laminated and the positive electrode layer and the negative electrode layer are connected by the insulating adhesive layer. The method for manufacturing the power storage device includes the following steps: (1) by using the positive electrode layer The material for the positive electrode layer and the material for the negative electrode layer serving as the negative electrode layer are disposed so as to be opposed to each other by the material for the separator which serves as the separator, and the insulating adhesive layer which is the insulating back layer, and are heated and The laminated body in which the positive electrode layer, the negative electrode layer, the separator, and the insulating back layer are integrated is formed by pressurization, and the insulating backing material is used as the insulating backing material to form the laminated body. : comprising an inorganic fine particle and a binder resin having a melting point of 160 ° C or less, and as the above-mentioned insulating joint constituting the above laminated body An insulating backing layer having an adhesive property of bonding the positive electrode layer and the negative electrode layer to each other and an electrolyte permeability for permeating the electrolyte solution; and (2) forming the laminated body and the electrolyte solution And being contained in the package body, the electrolyte is permeated and impregnated from the outside of the laminate.
一種蓄電裝置之製造方法，該蓄電裝置包括積層體、電解液、及收納上述積層體與上述電解液之封裝體，該積層體具有正極層與負極層介隔分隔層及絕緣性接著層而積層，且上述正極層與上述負極層藉由上述絕緣性接著層而 接著之構造；該蓄電裝置之製造方法之特徵在於包括如下步驟：(1)藉由將成為上述正極層之正極層用材料與成為上述負極層之負極層用材料以介隔成為上述分隔層之分隔層用材料及成為上述絕緣性接著層之絕緣性接著層材料而對向之方式配置，並加熱、加壓而形成上述正極層、上述負極層、上述分隔層、及上述絕緣性接著層一體化之上述積層體，且使用如下之絕緣性接著層材料作為上述絕緣性接著層材料而形成上述積層體：包含無機微粒子及不具有熔點而玻璃轉移溫度為110℃以下之黏合劑樹脂，且作為構成上述積層體之上述絕緣性接著層，形成具有使上述正極層與上述負極層接合而保持為一體之接著性及使上述電解液滲透之電解液滲透性之絕緣性接著層；及(2)將上述積層體與上述電解液一併收容於上述封裝體內，使上述電解液自上述積層體之外部向內部滲透、含浸。 A method of manufacturing a power storage device including a laminate, an electrolytic solution, and a package accommodating the laminate and the electrolyte, wherein the laminate has a positive electrode layer and a negative electrode layer separated by a separator layer and an insulating back layer And the positive electrode layer and the negative electrode layer are provided by the insulating adhesive layer In the following, the method of manufacturing the power storage device includes the steps of: (1) separating the material for the positive electrode layer serving as the positive electrode layer and the material for the negative electrode layer serving as the negative electrode layer into the separation layer. The material for the separator layer and the insulating adhesive layer material serving as the insulating adhesive layer are disposed to face each other, and the positive electrode layer, the negative electrode layer, the separator layer, and the insulating interlayer are integrally formed by heating and pressurization. The laminated body is formed by using the insulating backing layer material as the insulating backing layer material to form the laminated body: an inorganic resin and an adhesive resin having a glass transition temperature of not more than 110 ° C and having no melting point, and The insulating adhesive layer constituting the laminated body is formed with an insulating adhesive layer having an adhesive property in which the positive electrode layer and the negative electrode layer are bonded to each other and an electrolyte permeability which permeates the electrolyte solution; and (2) The layered body and the electrolyte solution are housed in the package together, and the electrolyte solution is external to the laminate Internal penetration, impregnation.
本發明之絕緣性接著層組合物包括含有無機微粒子及熔點為160℃以下之黏合劑樹脂之複合材料(技術內容1)、或者含有無機微粒子及不具有熔點而玻璃轉移溫度為110℃以下之黏合劑樹脂之複合材料(技術內容2)，且具有使正極層與負極層接合而保持為一體之接著性及使電解液滲透之電解液滲透性。 The insulating adhesive layer composition of the present invention comprises a composite material containing inorganic fine particles and a binder resin having a melting point of 160 ° C or less (Technical Content 1), or a binder containing inorganic fine particles and having no melting point and having a glass transition temperature of 110 ° C or less. The composite material of the resin (Technical Content 2) has an adhesive property of bonding the positive electrode layer and the negative electrode layer to be integrated, and electrolyte permeability for permeating the electrolyte.
因此，藉由在構成如上所述之蓄電裝置之積層體中使用 本發明之絕緣性接著層組合物，而可獲得包括能夠使電解液自積層體之外部向內部滲透、含浸之積層體之生產性優異之蓄電裝置。 Therefore, it is used in the laminated body constituting the power storage device as described above. In the insulating adhesive layer composition of the present invention, a power storage device including a laminate capable of allowing the electrolytic solution to permeate and impregnate from the outside of the laminate to the inside can be obtained.
即，藉由使用包括含有無機微粒子及熔點為160℃以下之黏合劑樹脂之複合材料(技術內容1)、或者含有無機微粒子及不具有熔點而玻璃轉移溫度為110℃以下之黏合劑樹脂之複合材料(技術內容2)，且具有接著性及使電解液滲透之電解液滲透性之絕緣性接著層組合物，而能夠以相對低之溫度效率良好且確實地形成正極層、負極層、分隔層一體化之積層體，從而可簡化生產步驟而提高生產性。 That is, a composite material comprising a binder resin containing inorganic fine particles and a binder resin having a melting point of 160 ° C or less (Technical Content 1), or a binder resin containing inorganic fine particles and having a glass transition temperature of 110 ° C or less without melting point The material (Technical Content 2) and the insulating adhesive layer composition having the adhesiveness and the electrolyte permeability which permeates the electrolyte, and the positive electrode layer, the negative electrode layer, and the separator layer can be formed efficiently and reliably at a relatively low temperature. An integrated laminate that simplifies production steps and increases productivity.
又，無需對分隔層要求接著性等功能，因此可進行追求作為分隔層之特性或功能之設計，從而可實現作為蓄電裝置之特性之提高。 Further, since it is not necessary to require a function such as adhesion to the spacer layer, it is possible to carry out the design which is a characteristic or function of the spacer layer, and it is possible to improve the characteristics of the power storage device.
再者，於本發明中，絕緣性接著層例如能夠以包圍分隔層之整周之方式配設，亦可配設於包圍分隔層之整周之區域之一部分。然而，就確保正極層與負極層之接合穩定性、或積層體之可靠性之觀點而言，較佳為以包圍分隔層之整周之方式配設。 Further, in the present invention, the insulating adhesive layer may be disposed, for example, so as to surround the entire circumference of the partition layer, or may be disposed in a portion of the region surrounding the entire circumference of the partition layer. However, from the viewpoint of ensuring the bonding stability between the positive electrode layer and the negative electrode layer or the reliability of the laminated body, it is preferable to arrange the entire circumference of the partition layer.
再者，視情形，亦能夠以如下方式構成：以如貫通分隔層之中央部之態樣配設絕緣性接著層，藉由該絕緣性接著層將介隔分隔層而對向之正極層與負極層接合。 Further, depending on the case, it is also possible to arrange an insulating adhesive layer such as to penetrate the center portion of the spacer layer, and to align the positive electrode layer with the insulating layer through the insulating layer. The negative electrode layer is joined.
又，本發明之蓄電裝置用元件及蓄電裝置係於正極層與負極層介隔分隔層及絕緣性接著層積層而成之積層體中，在絕緣性接著層中使用上述本發明之絕緣性接著層組合 物，因此可使分隔層為最佳設計，從而可獲得離子電阻較低、高性能、且可靠性較高、生產性優異之蓄電裝置用元件及蓄電裝置。 Further, the device for power storage device and the power storage device of the present invention are used in a laminate in which a positive electrode layer and a negative electrode layer are separated by a separator layer and an insulating layer, and the insulating layer of the present invention is used for the insulating back layer. Layer combination Therefore, the separator can be optimally designed, and an element for a storage battery device and a power storage device having low ionic resistance, high performance, high reliability, and excellent productivity can be obtained.
又，本發明之蓄電裝置用元件之製造方法係於藉由將正極層用材料與負極層用材料以介隔分隔層用材料及絕緣性接著層材料而對向之方式配置，並加熱、加壓而形成正極層、負極層、分隔層、及絕緣性接著層一體化之積層體時，作為絕緣性接著層材料，使用如於已形成之積層體之階段可形成上述本發明之絕緣性接著層組合物之材料，因此可效率良好地製造高性能且可靠性較高之蓄電裝置用元件。 Moreover, the method for producing an element for a storage battery device according to the present invention is such that the material for a positive electrode layer and the material for a negative electrode layer are disposed to face each other with a material for a separator layer and an insulating back layer material, and are heated and added. When a laminate of a positive electrode layer, a negative electrode layer, a separator layer, and an insulating back layer is formed by pressure, the insulating property of the present invention can be formed as an insulating adhesive layer material at the stage of forming the laminated body. Since the material of the layer composition is used, it is possible to efficiently manufacture an element for a power storage device having high performance and high reliability.
又，本發明之蓄電裝置之製造方法係於藉由將正極層用材料與負極層用材料以介隔分隔層用材料及絕緣性接著層材料而對向之方式配置，並加熱、加壓而形成正極層、負極層、分隔層、及絕緣性接著層一體化之積層體時，作為絕緣性接著層材料，使用如於已形成之積層體之階段可形成上述本發明之絕緣性接著層組合物之材料，並且將所獲得之積層體與電解液一併收容於封裝體內，使電解液自積層體之外部向內部滲透、含浸，因此可效率良好地製造高性能且可靠性較高之蓄電裝置。 Moreover, the method for producing a power storage device according to the present invention is such that the material for the positive electrode layer and the material for the negative electrode layer are disposed to face each other with the material for the separator and the insulating backing material, and are heated and pressurized. When the positive electrode layer, the negative electrode layer, the separator layer, and the insulating back layer are laminated, the insulating back layer combination of the present invention can be formed as the insulating back layer material at the stage of forming the laminated body. The material of the material is stored in the package together with the electrolyte solution, and the electrolyte is infiltrated and impregnated from the outside of the laminate. Therefore, it is possible to efficiently produce high-performance and highly reliable power storage. Device.
再者，可使電解液自積層體之外部向內部滲透、含浸之情形係藉由如下方式實現：使用如上所述之絕緣性接著層材料(即，如可形成本發明之絕緣性接著層組合物之材料)，形成具有所需之電解液之含液性(滲透性)之絕緣性接 著層。 Furthermore, the infiltration and impregnation of the electrolyte from the outside to the inside of the laminate can be achieved by using an insulating backing material as described above (i.e., as an insulating backing layer combination of the present invention can be formed) Material of the material), forming an insulating connection with liquid (permeability) of the desired electrolyte Layer.
以下，表示本發明之實施形態，詳細地說明成為本發明之特徵之部分。 Hereinafter, embodiments of the present invention will be described in detail, and a part of the features of the present invention will be described in detail.
於積層型蓄電裝置中，要求分隔層具有低離子電阻、高接著性、電解液之高滲透性(高含液性)。然而，一般而言，PVC越高越成為低離子電阻、高含液性，而另一方面，接著性下降。 In the laminated type electricity storage device, the separator layer is required to have low ionic resistance, high adhesion, and high permeability of the electrolyte (high liquid content). However, in general, the higher the PVC, the lower the ionic resistance and the higher liquid content, and on the other hand, the adhesion decreases.
因此，於本發明中，藉由在分隔層之周邊部應用接著層(本發明之絕緣性接著層)而補充接著性、電解液之高滲透性。 Therefore, in the present invention, the adhesiveness and the high permeability of the electrolytic solution are complemented by applying an adhesive layer (the insulating adhesive layer of the present invention) to the peripheral portion of the separator.
即，於本發明中，使分隔層與絕緣性接著層介於正極層與負極層之間，藉由該絕緣性接著層，於使分隔層介於其間之狀態下，無需依存於分隔層之接著性便可接著正極層與負極層，從而不對分隔層要求接著性便可提高作為分隔層之功能(高PVC化、低離子電阻化)。 That is, in the present invention, the spacer layer and the insulating adhesive layer are interposed between the positive electrode layer and the negative electrode layer, and the insulating adhesive layer does not need to depend on the spacer layer in a state in which the spacer layer is interposed therebetween. The positive electrode layer and the negative electrode layer can be subsequently used, and the function as a separator (high PVC and low ion resistance) can be improved without requiring adhesion to the separator.
本發明所涉及之積層型蓄電裝置通常係密封於封裝體內而使用。因此，於絕緣性接著層具有電解液之含液性(滲透性)之情形時，為了使電解液能夠通過絕緣性接著層，而可使用封裝體整體所含之電解液。然而，於絕緣性接著層不具有電解液之含液性(滲透性)之情形時，例如即便電解液充滿封裝體內，處於積層體之周圍之電解液亦無法滲入至積層體內，故而無法有效地利用。與此相對，於使絕緣性接著層具有電解液之含液性(滲透性)之本發明之蓄電 裝置中，電解液之有效使用量增加，結果例如於如鋰離子蓄電池般，電解液越多越成為高電容、高速率特性、長壽命之蓄電裝置中，可效率良好地提高特性。 The build-up type power storage device according to the present invention is usually sealed and used in a package. Therefore, when the insulating adhesive layer has the liquid-containing property (permeability) of the electrolytic solution, the electrolytic solution contained in the entire package can be used in order to allow the electrolytic solution to pass through the insulating adhesive layer. However, when the insulating adhesive layer does not have the liquidity (permeability) of the electrolytic solution, for example, even if the electrolytic solution is filled in the package, the electrolyte surrounding the laminated body cannot penetrate into the laminated body, and thus cannot be effectively use. On the other hand, the storage of the present invention in which the insulating adhesive layer has liquid (permeability) of the electrolytic solution In the device, the effective use amount of the electrolytic solution is increased. As a result, for example, in a lithium ion battery, the electrolyte solution has a high capacitance, a high rate characteristic, and a long life, and the characteristics can be improved efficiently.
又，例如鋰離子蓄電池之電容下降等經時變化係因於充放電反應時，在活性物質表面產生電解液之分解反應等，結果產生電解液之枯竭(乾涸)所致。 In addition, for example, when the capacitance of the lithium ion secondary battery decreases, the time-dependent change occurs due to a decomposition reaction of the electrolytic solution on the surface of the active material during the charge-discharge reaction, and as a result, the electrolyte is depleted (dry).
與此相對，藉由對絕緣性接著層賦予電解液之含液性(滲透性)，能夠增加可利用之電解液量(有效地使用包含於封裝體與積層體間之電解液)，從而可有助於蓄電裝置之高電容化或長壽命化。 On the other hand, by providing the liquid phase (permeability) of the electrolytic solution to the insulating adhesive layer, the amount of the electrolytic solution that can be used can be increased (the electrolytic solution contained between the package and the laminated body can be effectively used). It contributes to high capacitance or long life of the power storage device.
又，對於絕緣性接著層之接著性，必需使黏合劑樹脂於熱壓接時充分地熱運動。因此，使用於黏合劑之高分子鏈必需微觀充分地運動。藉此，於不具有熔點(Tm)而僅具有玻璃轉移溫度(Tg)之非晶性高分子之情形時，必需使用玻璃轉移溫度(Tg)較低之高分子。 Further, for the adhesion of the insulating adhesive layer, it is necessary to sufficiently thermally move the adhesive resin at the time of thermocompression bonding. Therefore, the polymer chain used for the binder must be sufficiently microscopically moved. Therefore, in the case of an amorphous polymer having no glass transition temperature (Tg) without a melting point (Tm), it is necessary to use a polymer having a low glass transition temperature (Tg).
又，於具有玻璃轉移溫度(Tg)與熔點(Tm)之結晶性高分子(經結晶化之高分子鏈)之情形時，為了進行動態之熱運動而必需解開其結晶化結構，故而難以於低溫接著。於結晶性高分子之情形時，即便加溫至玻璃轉移溫度(Tg)以上之溫度，亦無法以熔點(Tm)以下之溫度實現充分之接著。即，於結晶性高分子(經結晶化之高分子鏈)之情形時，定義解開結晶結構之溫度之參數為熔點(Tm)，必需使用熔點(Tm)較低之高分子。 Further, in the case of a crystalline polymer having a glass transition temperature (Tg) and a melting point (Tm) (polymerized polymer chain), it is difficult to unravel the crystallized structure in order to perform dynamic thermal motion. Follow the low temperature. In the case of a crystalline polymer, even if it is heated to a temperature higher than the glass transition temperature (Tg), sufficient temperature cannot be achieved at a temperature equal to or lower than the melting point (Tm). That is, in the case of a crystalline polymer (polymerized polymer chain), the parameter for determining the temperature at which the crystal structure is unwrapped is the melting point (Tm), and it is necessary to use a polymer having a low melting point (Tm).
若整理以上內容，則於不具有熔點(Tm)而僅具有玻璃轉 移溫度(Tg)之非晶性高分子之情形時，較理想為使用玻璃轉移溫度(Tg)較低(Tg為110℃以下)之高分子材料，於具有玻璃轉移溫度(Tg)與熔點(Tm)之結晶性高分子之情形時，較理想為使用熔點(Tm)較低(Tm為160℃以下)之高分子材料。 If the above content is finished, it has no melting point (Tm) and only has glass transition. In the case of a temperature-shifted (Tg) amorphous polymer, it is preferred to use a polymer material having a low glass transition temperature (Tg) (Tg of 110 ° C or less) having a glass transition temperature (Tg) and a melting point ( In the case of a crystalline polymer of Tm), a polymer material having a low melting point (Tm) (Tm of 160 ° C or less) is preferably used.
適合用於發揮如上所述之效果之蓄電裝置之本發明的絕緣性接著層組合物包含如下之複合材料：於鋰離子蓄電池或電雙層電容器等之內部，化學及電化學穩定之無機微粒子藉由在鋰離子蓄電池或電雙層電容器等之內部化學及電化學穩定之黏合劑樹脂黏著而成者。 The insulating adhesive layer composition of the present invention which is suitable for use in a power storage device having the above-described effects includes a composite material which is chemically and electrochemically stabilized inside a lithium ion battery or an electric double layer capacitor. It is made of a resin that is chemically and electrochemically stable in a lithium ion battery or an electric double layer capacitor.
而且，作為構成本發明之絕緣性接著層組合物之無機微粒子，例如可列舉二氧化矽、氧化鋁、氧化鈦、鈦酸鋇等氧化物、氮化矽、氮化鋁等氮化物。 In addition, examples of the inorganic fine particles constituting the insulating adhesive layer composition of the present invention include oxides such as cerium oxide, aluminum oxide, titanium oxide, and barium titanate, and nitrides such as cerium nitride and aluminum nitride.
又，關於黏合劑樹脂，作為非晶性高分子材料，可列舉聚胺基甲酸酯、矽酮橡膠、氟橡膠等，又，作為結晶性高分子材料，可列舉聚偏二氟乙烯(PVDF，Polyvinylidene Fluoride)或聚偏二氟乙烯-六氟丙烯(PVDF-HFP，Polyvinylidene Fluoride-Hexafluoro Propylene)等。再者，PVDF或PVDF-HFP係即便非晶質部共存，亦於至少一部分包含結晶質部之高分子材料。 In addition, examples of the binder resin include a polyurethane, a fluorenone rubber, and a fluororubber. Examples of the crystalline polymer material include polyvinylidene fluoride (PVDF). , Polyvinylidene Fluoride) or polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP, Polyvinylidene Fluoride-Hexafluoro Propylene) and the like. In addition, PVDF or PVDF-HFP is a polymer material containing at least a part of a crystalline portion even if an amorphous portion coexists.
以下，表示本發明之實施例，進一步詳細地說明本發明。 Hereinafter, the present invention will be described in further detail by showing examples of the invention.
[1]包含絕緣性接著層組合物之片材之製作與評估 [1] Fabrication and evaluation of sheets comprising an insulating adhesive layer composition
作為構成絕緣性接著層組合物用之複合材料之無機微粒子，於該實施例中，準備球狀氧化鋁粉末(平均粒徑為0.3 μm)。 As the inorganic fine particles constituting the composite material for the insulating adhesive layer composition, in this example, spherical alumina powder (having an average particle diameter of 0.3 μm) was prepared.
又，作為構成複合材料之黏合劑樹脂，準備聚偏二氟乙烯(PVDF)-六氟丙烯(HFP)之黏合劑溶液(阿科瑪(ARKEMA)製造之Kynar 2801、20 wt% NMP(N-Methyl-2-Pyrrolidone，N-甲基-2-吡咯啶酮)溶液)。 Further, as a binder resin constituting the composite material, a binder solution of polyvinylidene fluoride (PVDF)-hexafluoropropylene (HFP) (Kynar 2801, 20 wt% NMP (N-made by Arkema) was prepared. Methyl-2-Pyrrolidone, N-methyl-2-pyrrolidone)).
而且，於500 ml之鍋中投入無機微粒子(球狀氧化鋁粉末)及溶劑(NMP)。進而，添加5 mmΦ之PSZ(Partially Stabilized Zirconia，部分穩定氧化鋯)製粉碎介質，使用滾動球磨機混合4小時而進行分散。此後，添加特定量之聚偏二氟乙烯(PVDF)-六氟丙烯(HFP)之黏合劑溶液，使用滾動球磨機混合2小時而調製漿料。 Further, inorganic fine particles (spherical alumina powder) and a solvent (NMP) were placed in a 500 ml pot. Further, a pulverization medium made of PSZ (Partially Stabilized Zirconia) of 5 mmΦ was added and mixed by using a rolling ball mill for 4 hours to carry out dispersion. Thereafter, a specific amount of a polyvinylidene fluoride (PVDF)-hexafluoropropylene (HFP) binder solution was added, and the slurry was prepared by mixing using a rolling ball mill for 2 hours.
於藉由刮刀法將該漿料塗敷於PET(Polyethylene Terephthalate，聚對苯二甲酸乙二酯)膜上後，進行乾燥而獲得厚度為25 μm之複合材料片材(相當於本發明之絕緣性接著層之片材)。 The slurry was applied onto a PET (Polyethylene Terephthalate) film by a doctor blade method, and then dried to obtain a composite sheet having a thickness of 25 μm (corresponding to the insulation of the present invention). a sheet of the next layer).
以下，以相同方式製作黏合劑樹脂中使用有PVDF、聚甲基丙烯酸甲酯、聚胺基甲酸酯之複合材料片材。 Hereinafter, a composite sheet in which PVDF, polymethyl methacrylate, or polyurethane was used in the binder resin was produced in the same manner.
黏合劑樹脂之玻璃轉移溫度(Tg)及/或熔點(Tm)如表1所示。 The glass transition temperature (Tg) and/or melting point (Tm) of the binder resin are shown in Table 1.
再者，各複合材料片材係以顏料體積濃度(PVC)成為40%之方式調整粉體比率。 Further, each composite sheet was adjusted in such a manner that the powder volume ratio (PVC) was 40%.
顏料體積濃度PVC(Pigment Volume Concentration)係藉由下述式(1)求出之值。 The pigment volume concentration (Pigment Volume Concentration) is a value obtained by the following formula (1).
PVC=(無機微粒子之體積)/(無機微粒子之體積+黏合劑樹脂之體積)×100(1) PVC = (volume of inorganic microparticles) / (volume of inorganic microparticles + volume of binder resin) × 100 (1)
其中，無機微粒子之體積=無機微粒子之重量/無機微粒子之密度 Wherein, the volume of the inorganic fine particles = the weight of the inorganic fine particles / the density of the inorganic fine particles
黏合劑樹脂之體積=黏合劑樹脂之重量/黏合劑樹脂之密度 Volume of binder resin = weight of binder resin / density of binder resin
其次，為了對複合材料片材(以下，亦稱為「絕緣性接著層片材」)進行評估，而調查加熱、加壓時之接著性、電解液之含液性(滲透性)。 Next, in order to evaluate a composite material sheet (hereinafter also referred to as "insulating adhesive layer sheet"), the adhesion at the time of heating and pressurization and the liquid content (permeability) of the electrolytic solution were examined.
[2]加熱、加壓時之接著性 [2] Adhesion at the time of heating and pressurization
以片材之乾燥表面成為接著面之方式設置於壓製裝置，以150℃、20 MPa加熱、加壓2分鐘而將絕緣性接著層片材彼此接合。此時之絕緣性接著層片材間之剝離力為1.0 mN/mm以上者設為接著性良好。 The insulating laminate sheets were joined to each other by being placed in a press apparatus so that the dried surface of the sheet became the adjoining surface, and heated and pressed at 150 ° C and 20 MPa for 2 minutes. At this time, the peeling force between the insulating backing sheets is 1.0. Those having a mN/mm or more are set to have good adhesion.
以此方式製作之絕緣性接著層片材中，於黏合劑樹脂中使用有PVDF-HFP、聚甲基丙烯酸甲酯、聚胺基甲酸酯之複合材料片材係如表1所示般接著性良好。 In the insulating back sheet produced in this manner, a composite sheet of PVDF-HFP, polymethyl methacrylate, and polyurethane used in the binder resin is as shown in Table 1. Good sex.
另一方面，於黏合劑樹脂中使用有熔點(Tm)為174℃之PVDF之複合材料片材之接著性不良。 On the other hand, the use of a composite sheet having a PVDF having a melting point (Tm) of 174 ° C was poor in adhesion to the binder resin.
[3]電解液之含液性(滲透性) [3] Liquid content (permeability) of electrolyte
使用乙基甲基咪唑鎓四氟硼酸鹽(EMIBF4)(關東化學製造)作為電解液而進行電解液之含液性(滲透性)試驗。 The liquid-containing (permeability) test of the electrolytic solution was carried out using ethylmethylimidazolium tetrafluoroborate (EMIBF 4 ) (manufactured by Kanto Chemical Co., Ltd.) as an electrolytic solution.
繼而，將1 cm×1 cm×30 μm(厚度)之已乾燥之絕緣性接著層片材以25℃浸漬於電解液中，測定24小時後之重量增加，藉此對電解液之含液性(滲透性)進行評估。將質量增加10%以上之分隔片設為含液性(滲透性)良好。 Then, a dried insulating backing sheet of 1 cm × 1 cm × 30 μm (thickness) was immersed in an electrolytic solution at 25 ° C, and the weight increase after 24 hours was measured, whereby the liquid content of the electrolytic solution was measured. (Permeability) is evaluated. The separator having a mass increase of 10% or more is set to have good liquidity (permeability).
其結果，如表1所示，確認出使用任一種黏合劑樹脂之情形時之電解液之含液性(滲透性)均良好。 As a result, as shown in Table 1, it was confirmed that the liquid solubility (permeability) of the electrolytic solution when any of the binder resins was used was good.
[4]關於黏合劑樹脂單體片材之接著性 [4] About the adhesion of the adhesive resin monomer sheet
以上，對包含無機微粒子與黏合劑樹脂之PVC為40%之複合材料調查了特性，但此處，準備僅包含表2所示之各黏合劑樹脂即聚偏二氟乙烯(PVDF)、聚對苯二甲酸乙二酯(PET)、聚醯胺醯亞胺(PAI，Polyamide Imide)、聚醯胺(PA，Polyamide)之黏合劑樹脂單體片材，並對其接著性進行調查。 In the above, the characteristics of the composite material containing 40% of the PVC containing the inorganic fine particles and the binder resin were investigated, but here, only the respective binder resins shown in Table 2, that is, polyvinylidene fluoride (PVDF) and poly pairs were prepared. A monomer sheet of a binder resin of ethylene phthalate (PET), polyacrylamide (PAI, Polyamide Imide), polyamine (PA, Polyamide), and its adhesion was investigated.
再者，黏合劑樹脂單體片材等於PVC為0%之絕緣性接著層。通常，PVC越增加，接著性越惡化，故而意指黏合劑樹脂單體片材(PVC為0%之片材)中未獲得良好之接著性之黏合劑樹脂不適合用於本發明之絕緣性接著層。 Further, the binder resin monomer sheet is equal to the 0% insulating backing layer of PVC. In general, the more the PVC is increased, the more deteriorated the adhesion, so that the binder resin which does not obtain good adhesion in the sheet of the binder resin monomer (the sheet of 0% of PVC) is not suitable for the insulation of the present invention. Floor.
首先，聚偏二氟乙烯(PVDF)片材係由以下方式製作。 First, a polyvinylidene fluoride (PVDF) sheet was produced in the following manner.
(1)PVDF片材 (1) PVDF sheet
於藉由刮刀法將N-甲基-2-吡咯啶酮(NMP)中溶解有聚偏二氟乙烯(PVDF)而成之黏合劑溶液塗敷於PET膜上後，進行乾燥而獲得厚度為25 μm之複合材料片材(PVDF片材)。 Applying a solution of a binder obtained by dissolving polyvinylidene fluoride (PVDF) in N-methyl-2-pyrrolidone (NMP) onto a PET film by a doctor blade method, followed by drying to obtain a thickness of 25 μm composite sheet (PVDF sheet).
(2)其他黏合劑樹脂單體片材 (2) Other adhesive resin monomer sheets
聚對苯二甲酸乙二酯(PET)、聚醯胺醯亞胺(PAI)、聚醯胺(PA)均係準備市售之膜狀者，作為黏合劑樹脂單體片材而供於試驗。 Polyethylene terephthalate (PET), polyamidimide (PAI), and polyamidamine (PA) are all prepared as commercially available film sheets, and are used as test results for adhesive resin monomer sheets. .
此處，作為黏合劑樹脂單體片材之特性，藉由以下之方法調查加熱、加壓時之接著性。 Here, as the characteristics of the binder resin monomer sheet, the adhesion at the time of heating and pressurization was investigated by the following method.
以片材之乾燥表面成為接著面之方式設置於壓製裝置，以150℃、20 MPa加熱、加壓2分鐘。繼而，將絕緣性接著層片材間之剝離力未滿1.0 mN/mm者判定為接著性不良。將其結果一併示於表2。 The drying surface of the sheet was placed on the pressing device so as to be a continuous surface, and heated at 150 ° C and 20 MPa for 2 minutes. Then, it was judged that the peeling force between the insulating backing sheets was less than 1.0 mN/mm, and the adhesion was poor. The results are shown together in Table 2.
使用有上述PVDF、PET、PAI、PA之任一者之黏合劑樹脂單體片材之接著性均不良。 The adhesive resin monomer sheet having any of the above PVDF, PET, PAI, and PA is poor in adhesion.
根據該結果，確認出該等樹脂不宜作為構成本發明之絕緣性接著層之黏合劑樹脂者。 From the results, it was confirmed that the resins are not suitable as the binder resin constituting the insulating adhesive layer of the present invention.
對照以上之結果，可使用於絕緣性接著層之熱力學參數係於該黏合劑樹脂不具有熔點時(即，為非晶性樹脂材料時)，其玻璃轉移溫度需為110℃以下，於黏合劑樹脂具有熔點時(為結晶性樹脂材料時)，其熔點需為160℃以下。 According to the above results, the thermodynamic parameters for the insulating adhesive layer can be such that when the adhesive resin does not have a melting point (that is, when it is an amorphous resin material), the glass transition temperature needs to be 110 ° C or less, in the adhesive. When the resin has a melting point (in the case of a crystalline resin material), the melting point thereof is required to be 160 ° C or lower.
圖1係表示本發明之實施例(實施例2)之蓄電裝置(電雙層電容器)之前視剖面圖，圖2係模式性地表示分隔層與絕緣性接著層之配設態樣之俯視剖面圖。 1 is a front cross-sectional view showing a power storage device (electric double layer capacitor) according to an embodiment (Example 2) of the present invention, and FIG. 2 is a plan cross-sectional view schematically showing an arrangement of a partition layer and an insulating back layer. Figure.
如圖1所示，該實施例2之電雙層電容器A包括藉由將正極集電體層21a之兩面設置有正極活性物質層21b之正極層21及負極集電體層41a之兩面設置有負極活性物質層41b之負極層41介隔分隔層11及絕緣性接著層31積層而形成之積層體1。於積層體1之第1端面2及第2端面3形成有正極外部端子電極21t、及負極外部端子電極41t。而且，該積層體1與電解液一併收容於包含蓋體70a、基底部70b之封裝體70內。又，於封裝體70，以自兩端轉入至下表面側之方式形 成有正極封裝體電極61及負極封裝體電極62。 As shown in Fig. 1, the electric double layer capacitor A of the second embodiment includes a negative electrode active body on both sides of a positive electrode layer 21 and a negative electrode current collector layer 41a on which both positive electrode active material layers 21b are provided on both surfaces of a positive electrode current collector layer 21a. The negative electrode layer 41 of the material layer 41b blocks the laminated body 1 formed by laminating the partition layer 11 and the insulating adhesive layer 31. The positive electrode external terminal electrode 21t and the negative electrode external terminal electrode 41t are formed on the first end face 2 and the second end face 3 of the laminated body 1. Further, the laminated body 1 is housed in the package 70 including the lid body 70a and the base portion 70b together with the electrolytic solution. Moreover, in the package body 70, the shape is transferred from the both ends to the lower surface side. A positive electrode package electrode 61 and a negative electrode package electrode 62 are formed.
而且，如圖1、2所示，於該實施例之電雙層電容器A中，絕緣性接著層31配設於包圍分隔層11之周圍之區域，正極層21及負極層41係介隔分隔層11及配設於包圍分隔層11之周圍之區域之絕緣性接著層31而積層。更具體而言，於該實施例中，構成正極層21之正極集電體層21a與構成負極層41之負極集電體層41a介隔絕緣性接著層31而積層，構成正極層21之正極活性物質層21b與構成負極層41之負極活性物質層41b介隔分隔層11而積層，正極活性物質層21b與負極活性物質層41b係整個區域介隔分隔層11而對向，且正極活性物質層21b、負極活性物質層41b之周圍之正極集電體層21a及負極集電體層41a係介隔絕緣性接著層31而積層。 Further, as shown in Figs. 1 and 2, in the electric double layer capacitor A of this embodiment, the insulating adhesive layer 31 is disposed in a region surrounding the periphery of the spacer layer 11, and the positive electrode layer 21 and the negative electrode layer 41 are separated by a partition. The layer 11 and the insulating adhesive layer 31 disposed in a region surrounding the partition layer 11 are laminated. More specifically, in this embodiment, the positive electrode current collector layer 21a constituting the positive electrode layer 21 and the negative electrode current collector layer 41a constituting the negative electrode layer 41 are laminated to form the edge layer 31 to form a positive electrode active material of the positive electrode layer 21. The layer 21b and the anode active material layer 41b constituting the anode layer 41 are laminated via the separator layer 11, and the cathode active material layer 21b and the anode active material layer 41b are opposed to each other via the separator layer 11, and the cathode active material layer 21b is opposed. The positive electrode current collector layer 21a and the negative electrode current collector layer 41a around the negative electrode active material layer 41b are laminated by sandwiching the edge bonding layer 31.
而且，作為絕緣性接著層31，使用包括含有作為無機微粒子之氧化鋁及作為黏合劑樹脂之PVDF-HEP之複合材料，且其PVC為40%、Λ為0.83之具備本發明之必要條件之絕緣性接著層組合物。 Further, as the insulating adhesive layer 31, a composite material comprising a composite material containing alumina as an inorganic fine particle and PVDF-HEP as a binder resin, and having a PVC of 40% and a lanthanum of 0.83, which is necessary for the present invention, is used. The adhesive layer composition.
再者，Λ係上述顏料體積濃度PVC與空隙考慮為零之最大顏料體積濃度即臨界顏料體積濃度CPVC(Critical Pigment Volume Concentration)之比，且係由下述式(2)求出之值。 Further, the ratio of the above-mentioned pigment volume concentration of PVC to the maximum pigment volume concentration of the void which is considered to be zero is the critical pigment volume concentration CPVC (Critical Pigment Volume Concentration), and is a value obtained by the following formula (2).
Λ=PVC/CPVC………(2) Λ=PVC/CPVC.........(2)
又，上述CPVC係藉由密度法測定之空隙為零之情形時之最大顏料體積濃度。 Further, the above CPVC is the maximum pigment volume concentration in the case where the void measured by the density method is zero.
於求出空隙時，首先測定沖裁為特定尺寸之試料之厚度及重量，藉由用重量除以體積而算出密度。繼而由密度之實測值及根據複合材料片材之組成而計算之理論密度，藉由下述式(3)算出空隙率。 When the void is determined, the thickness and weight of the sample which is punched into a specific size are first measured, and the density is calculated by dividing the weight by the volume. Then, the void ratio is calculated by the following formula (3) from the measured value of the density and the theoretical density calculated from the composition of the composite sheet.
空隙率={1-(密度之實測值)/(理論密度)}×100………(3) Void ratio = {1 - (measured value of density) / (theoretical density)} × 100... (3)
以下，對該電雙層電容器A之製造方法進行說明。 Hereinafter, a method of manufacturing the electric double layer capacitor A will be described.
[步驟1] [step 1]
於作為脫模層而塗佈有胺基甲酸酯之基材PET膜上，藉由蒸鍍形成厚度為0.5 μm之鋁層。其次，於所形成之鋁層之表面，藉由網版印刷而圖案塗佈蝕刻遮罩抗蝕劑並乾燥。再者，抗蝕劑係使用關西塗料製造之ALES SPR。 On the PET film of the substrate coated with the urethane as the release layer, an aluminum layer having a thickness of 0.5 μm was formed by vapor deposition. Next, an etch mask resist is pattern-coated by screen printing on the surface of the formed aluminum layer and dried. Further, the resist is ALES SPR manufactured by Kansai Paint.
此後，將該膜浸漬於40℃之氯化鐵水溶液而將鋁層圖案化。此後，於將該膜浸漬於有機溶劑中而剝離抗蝕劑後，浸漬於硫酸與氫氟酸之混合水溶液而去除鋁層表面之氧化層，藉此如圖3(a)、(b)所示，將複數個正極集電體層21a形成於基材PET膜100上。 Thereafter, the film was immersed in an aqueous solution of ferric chloride at 40 ° C to pattern the aluminum layer. Thereafter, the film is immersed in an organic solvent to remove the resist, and then immersed in a mixed aqueous solution of sulfuric acid and hydrofluoric acid to remove the oxide layer on the surface of the aluminum layer, thereby being as shown in FIGS. 3(a) and (b). A plurality of positive electrode current collector layers 21a are formed on the base material PET film 100.
[步驟2](1)活性物質層用漿料之製作 [Step 2] (1) Preparation of slurry for active material layer
稱量活性碳(BET(Brunauer(布魯尼爾)、Emmett(埃密特)、Teller(特勒))比表面積1668 m2/g、平均孔隙直徑1.83 nm、平均粒徑(D50)1.26 μm)29.0 g、及碳黑(TOKAI CARBON股份有限公司製「TOKABLACK#3855」、BET比表面積90 m2/g)2.7 g並投入至1000 ml之鍋內，進而，於投入直徑為2.0 mm之PSZ製粉碎介質及286 g之去離子水後，使用滾動球磨機以150 rpm混合4小時而進行分散。 Weighing activated carbon (BET (Brunauer, Emmett, Teller) specific surface area 1668 m 2 /g, average pore diameter 1.83 nm, average particle size (D 50 ) 1.26 μm 29.0 g, and carbon black ("TOKABLACK #3855" manufactured by TOKAI CARBON Co., Ltd., BET specific surface area: 90 m 2 /g) 2.7 g and put into a 1000 ml pot, and further, a PSZ having a diameter of 2.0 mm was introduced. After pulverizing the medium and 286 g of deionized water, the mixture was dispersed by using a rolling ball mill at 150 rpm for 4 hours.
其次，於鍋中投入3.0 g之羧甲基纖維素(DAICEL化學工業股份有限公司製造之「CMC2260」)與38.8 wt%之聚丙烯酸酯樹脂水溶液2.0 g，進而混合2小時，藉此製作活性物質層用漿料。 Next, 3.0 g of carboxymethylcellulose ("CMC2260" manufactured by DAICEL Chemical Industry Co., Ltd.) and 2.0 g of a 38.8 wt% polyacrylate resin aqueous solution were placed in a pot and mixed for 2 hours to prepare an active material. Layer slurry.
(2)活性物質層用漿料之塗敷 (2) Coating of slurry for active material layer
使用版厚為8 μm之#500絲網(mesh screen)印刷版，於圖3(a)、(b)所示之正極集電體層21a上之活性物質層塗敷部網版印刷藉由上述方法製作之活性物質層用漿料，以100℃乾燥30分鐘而形成厚度為6 μm之正極活性物質層21b，藉此如圖4(a)、(b)所示，形成包括正極集電體層21a與正極活性物質層21b之正極層21。 Using the #500 mesh screen printing plate having a plate thickness of 8 μm, the active material layer coating portion screen printing on the positive electrode current collector layer 21a shown in FIGS. 3(a) and (b) is performed by the above-mentioned The slurry for the active material layer produced by the method was dried at 100 ° C for 30 minutes to form a positive electrode active material layer 21 b having a thickness of 6 μm, thereby forming a positive electrode collector layer as shown in FIGS. 4( a ) and ( b ). 21a and the positive electrode layer 21 of the positive electrode active material layer 21b.
再者，如圖1所示，正極活性物質層21b係以於積層體1之第1端面2未直接連接於正極外部端子電極21t之方式形成於自第1端面2後退特定距離之區域。即，於印刷活性物質層用漿料時，以於下述步驟6中被切割時，自其切割面形成特定寬度之未塗敷區域之方式對活性物質層用漿料進行網版印刷。 In addition, as shown in FIG. 1 , the positive electrode active material layer 21 b is formed in a region where the first end face 2 of the laminated body 1 is not directly connected to the positive electrode external terminal electrode 21 t and is retracted by a specific distance from the first end face 2 . In other words, when the slurry for the active material layer is printed, the slurry for the active material layer is screen-printed so that the uncoated region having a specific width is formed from the cut surface when the film is cut in the following step 6.
[步驟3] [Step 3]
(1)分隔層用漿料之製作 (1) Production of slurry for separation layer
於500 ml之鍋內投入50 g二氧化矽(電化學工業(股)製造、平均粒徑(D50)為0.7 μm)、及50 g作為溶劑之甲基乙基酮。進而，投入直徑為5 mm之PSZ製粉碎介質，使用滾動球磨機以150 rpm混合16小時而進行分散。此後，作為黏合劑樹脂溶液，投入聚偏二氟乙烯(PVDF)之N-甲基-2-吡 咯啶酮(NMP)溶液(吳羽(KUREHA)製造之L#1120、分子量為28萬、12 wt%溶液)，使用滾動球磨機以150 rpm混合4小時，從而製作分隔層用漿料(分隔層用材料)。 50 g of cerium oxide (manufactured by Electrochemical Industry Co., Ltd., average particle diameter (D 50 ) of 0.7 μm) and 50 g of methyl ethyl ketone as a solvent were placed in a 500 ml pot. Further, a PSZ pulverization medium having a diameter of 5 mm was introduced and dispersed by mixing at 150 rpm for 16 hours using a rolling ball mill. Thereafter, as a binder resin solution, a solution of polyvinylidene fluoride (PVDF) in N-methyl-2-pyrrolidone (NMP) (L#1120 manufactured by Kureha, having a molecular weight of 280,000, 12) was introduced. The wt% solution) was mixed at 150 rpm for 4 hours using a rolling ball mill to prepare a separator layer (material for a separator layer).
(2)分隔層用漿料之塗敷 (2) Coating of the separator layer
使用版厚為8 μm之#500絲網印刷版，將藉由上述方法製作之分隔層用漿料塗敷於正極層21上(詳細而言，正極活性物質層21b上)，以120℃乾燥30分鐘，藉此形成厚度為3 μm之分隔層11(圖5)。 The separator for a separator prepared by the above method was applied onto the positive electrode layer 21 (specifically, the positive electrode active material layer 21b) by a #500 screen printing plate having a plate thickness of 8 μm, and dried at 120 ° C. 30 minutes, thereby forming a separator layer 11 having a thickness of 3 μm (Fig. 5).
[步驟4] [Step 4]
(1)絕緣性接著層用漿料之製作 (1) Production of an insulating back layer slurry
於500 ml之鍋中投入100 g之氧化鋁(電化學工業(股)製造，平均粒徑(D50)為0.3 μm)、及80 g作為溶劑之N-甲基-2-吡咯啶酮(NMP)。進而，投入直徑為5 mm之PSZ製粉碎介質，使用滾動球磨機以150 rpm混合4小時而進行分散。此後，投入170 g之聚偏二氟乙烯-六氟丙烯(PVDF-HFP)之黏合劑溶液(阿科瑪製造之Kynar2801、20 wt% NMP溶液)，使用滾動球磨機以150 rpm混合4小時，從而製作如乾燥後之PVC為40%、Λ為0.83之絕緣性接著層用漿料。 100 g of alumina (manufactured by Electrochemical Industry Co., Ltd., average particle size (D 50 ) of 0.3 μm) and 80 g of N-methyl-2-pyrrolidone as a solvent were placed in a 500 ml pot ( NMP). Further, a PSZ pulverization medium having a diameter of 5 mm was introduced and dispersed by mixing at 150 rpm for 4 hours using a rolling ball mill. Thereafter, 170 g of a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) binder solution (Kynar 2801, 20 wt% NMP solution manufactured by Arkema) was charged and mixed using a rolling ball mill at 150 rpm for 4 hours. A slurry for an insulating back layer such as a dried PVC of 40% and a crucible of 0.83 was produced.
(2)絕緣性接著層用漿料之塗敷 (2) Coating of the insulating adhesive layer
使用版厚為8 μm之#500絲網印刷版，將藉由上述方法製作之絕緣性接著層用漿料塗敷於包圍分隔層11之區域之正極集電體層21a上及基材PET膜100上，並以120℃乾燥30分鐘，從而形成厚度為10 μm之絕緣性接著層31。 The paste for an insulating adhesive layer produced by the above method was applied onto the positive electrode collector layer 21a surrounding the region of the separator 11 and the substrate PET film 100 using a #500 screen printing plate having a plate thickness of 8 μm. The film was dried at 120 ° C for 30 minutes to form an insulating back layer 31 having a thickness of 10 μm.
以此方式，如圖6(a)所示，於基材PET膜100上形成有包 括正極層21、分隔層11、及絕緣性接著層31之正極集合片20，該正極層21包含正極集電體層21a及形成於其表面之正極活性物質層21b。 In this manner, as shown in FIG. 6(a), a package is formed on the substrate PET film 100. The positive electrode layer 21, the separator layer 11, and the positive electrode assembly sheet 20 of the insulating adhesive layer 31 include a positive electrode current collector layer 21a and a positive electrode active material layer 21b formed on the surface thereof.
同樣地，如圖6(b)所示，於基材PET膜100上形成有包括負極層41、分隔層11、及絕緣性接著層31之負極集合片40，該負極層41包含負極集電體層41a及形成於其表面之負極活性物質層41b。 Similarly, as shown in FIG. 6(b), a negative electrode assembly 40 including a negative electrode layer 41, a separator layer 11, and an insulating adhesive layer 31 is formed on the base material PET film 100, and the negative electrode layer 41 contains a negative electrode current collector. The bulk layer 41a and the anode active material layer 41b formed on the surface thereof.
[步驟5] [Step 5]
繼而，如圖7所示，以形成有分隔層11或絕緣性接著層31之面(與基材PET膜100側為相反側之面)相互對向之方式配設正極集合片20與負極集合片40，並進行熱壓接。此時，使正極集合片20以如正極集電體層21a之位置彼此於左右方向(圖7上)偏移之態樣對向而進行熱壓接。 Then, as shown in FIG. 7, the positive electrode assembly 20 and the negative electrode assembly are disposed so as to face each other with the surface on which the separator layer 11 or the insulating adhesive layer 31 is formed (the surface opposite to the side of the base PET film 100). The sheet 40 is subjected to thermocompression bonding. At this time, the positive electrode assembly sheet 20 is thermocompression bonded in such a manner that the positions of the positive electrode current collector layer 21a are shifted from each other in the left-right direction (upward in FIG. 7).
藉此，如圖8所示，獲得正極集合片20與負極集合片40接合而成之正極負極集合片51。 Thereby, as shown in FIG. 8, the positive electrode negative electrode assembly sheet 51 obtained by joining the positive electrode assembly sheet 20 and the negative electrode assembly sheet 40 is obtained.
再者，熱壓接係分別將加壓板之溫度設為150℃，將加壓之壓力設為20 MPa，且加壓時間設為30秒。 Further, in the thermocompression bonding system, the temperature of the pressurizing plate was set to 150 ° C, the pressure of the pressurizing was set to 20 MPa, and the pressurizing time was set to 30 seconds.
繼而，如圖9所示，將2個正極負極集合片51彼此以其中一個正極負極集合片51之上下方向成為反方向之方式配置，並且剝離對向之面側之基材PET膜而使兩者接合，並進行熱壓接，由此製作如圖10所示之集合片積層體52。 Then, as shown in FIG. 9, the two positive and negative electrode assembly sheets 51 are disposed such that the upper and lower sides of the positive electrode negative electrode assembly 51 are opposite to each other, and the base PET film on the opposite side is peeled off to make two The bonding is performed and thermocompression bonding is performed, thereby producing a laminated laminated body 52 as shown in FIG.
熱壓接係分別將加壓板之溫度設為150℃，將加壓之壓力設為20 MPa，且加壓時間設為30秒。 The thermocompression bonding system set the temperature of the pressurizing plate to 150 ° C, the pressure of the pressurization to 20 MPa, and the pressurization time to 30 seconds.
其次，如圖11所示，使正極負極集合片51與集合片積層 體52對向並進行熱壓接，藉此如圖12所示，製作包含3個正極負極集合片51之複合積層體53。 Next, as shown in FIG. 11, the positive electrode negative electrode assembly 51 and the integrated laminated layer are formed. The body 52 is opposed to each other by thermocompression bonding, whereby a composite laminated body 53 including three positive electrode negative electrode sheets 51 is produced as shown in FIG.
此後，以相同方式重複正極負極集合片51之熱壓接，進行逐次壓接。藉此，獲得如圖13所示之積層集合體50，該積層集合體50係正極層21與負極層41介隔分隔層11及絕緣性接著層31積層，且正極層21與負極層41藉由絕緣性接著層31接合而成。 Thereafter, the thermocompression bonding of the positive electrode negative electrode assembly sheet 51 was repeated in the same manner, and the pressure bonding was performed successively. Thereby, the laminated body 50 shown in FIG. 13 is obtained, and the positive electrode layer 21 and the negative electrode layer 41 are laminated with the separator layer 11 and the insulating adhesive layer 31, and the positive electrode layer 21 and the negative electrode layer 41 are borrowed. It is joined by the insulating adhesive layer 31.
[步驟6] [Step 6]
繼而，藉由切塊機(dicer)沿圖14之裁斷線D1裁斷積層集合體50而使其單片化，藉此製作具有如圖15所示之構造之積層體1。 Then, the layered assembly 50 is cut and cut into pieces by the dicer along the cutting line D1 of Fig. 14, thereby producing a layered body 1 having the structure shown in Fig. 15.
該積層體1之尺寸設為長度4.7 mm，寬度3.3 mm。 The laminated body 1 has a size of 4.7 mm in length and 3.3 mm in width.
[步驟7] [Step 7]
繼而，如圖16所示，分別藉由Al濺鍍，於積層體1之第1端面2形成正極外部端子電極21t，於第2端面3形成負極外部端子電極41t。 Then, as shown in FIG. 16, the positive electrode external terminal electrode 21t is formed on the first end face 2 of the laminated body 1 by Al sputtering, and the negative electrode external terminal electrode 41t is formed on the second end face 3.
[步驟8] [Step 8]
藉由浸漬(dipping)將含有金作為導電性粒子之導電性接著劑(未圖示)塗佈於形成於第1端面2及第2端面3之正極外部端子電極21t及負極外部端子電極41t。其次，如圖1所示，以經塗佈之導電性接著劑分別連接於正極封裝體電極61及負極封裝體電極62之方式將積層體1配置於封裝體70之基底部70b，並以170℃加熱10分鐘而使導電性接著劑硬化。 A conductive adhesive (not shown) containing gold as the conductive particles is applied to the positive external terminal electrode 21t and the negative external terminal electrode 41t formed on the first end face 2 and the second end face 3 by dipping. Next, as shown in FIG. 1, the laminated body 1 is placed on the base portion 70b of the package 70 so that the applied conductive adhesive is connected to the positive electrode package electrode 61 and the negative electrode package electrode 62, respectively, and is 170. The conductive adhesive was hardened by heating at ° C for 10 minutes.
[步驟9] [Step 9]
繼而，於圖1所示之封裝體70之內部注入電解液並密封。此處，作為電解液，於減壓下注入1-乙基-3-甲基咪唑四氟硼酸鹽，於封裝體70之基底部70b上表面，與基底部70b同樣地配置液晶聚合物製之蓋體70a，並且沿封裝體70之基底部70b之框體部分照射雷射，藉此將基底部70b與蓋體70a焊接。 Then, the electrolyte is injected into the inside of the package 70 shown in FIG. 1 and sealed. Here, as the electrolytic solution, 1-ethyl-3-methylimidazolium tetrafluoroborate is injected under reduced pressure, and the upper surface of the base portion 70b of the package 70 is placed in the same manner as the base portion 70b. The cover 70a is irradiated with a laser along the frame portion of the base portion 70b of the package 70, whereby the base portion 70b is welded to the cover 70a.
藉此，獲得具有如圖1所示之構成之蓄電裝置(電雙層電容器)A。 Thereby, a power storage device (electric double layer capacitor) A having the configuration shown in FIG. 1 is obtained.
再者，於以上說明中所參照之圖1~16中，因製圖上之制約而較厚地描繪有分隔層11、正極層21、負極層41、及絕緣性接著層31等，但並非準確地放大或縮小實際尺寸。 In addition, in FIGS. 1 to 16 referred to in the above description, the partition layer 11, the positive electrode layer 21, the negative electrode layer 41, and the insulating adhesive layer 31 are thickly drawn due to the restriction on the drawing, but it is not accurate. Zoom in or out on the actual size.
又，對於說明書所隨附之其他圖式，因製圖上之制約或為容易理解，亦將大小或位置關係適當變形或誇張表示。 Moreover, for the other drawings attached to the specification, the size or positional relationship is appropriately deformed or exaggerated due to constraints on the drawing or for easy understanding.
[電雙層電容器A之電化學特性] [Electrochemical Characteristics of Electric Double Layer Capacitor A]
以此方式製作之電雙層電容器A之電化學特性係直流電容為4.37 mF。 The electrochemical double layer capacitor A produced in this manner has a DC characteristic of 4.37 mF.
再者，確認出於圖1之電雙層電容器A中，使用PVDF-HFP作為黏合劑樹脂，使用氧化鋁作為無機微粒子(絕緣微粒子)，但於使用聚甲基丙烯酸甲酯、聚胺基甲酸酯樹脂等作為黏合劑樹脂之情形時，亦可獲得相同之結果。 Further, it was confirmed that in the electric double layer capacitor A of Fig. 1, PVDF-HFP was used as the binder resin, and alumina was used as the inorganic fine particles (insulating fine particles), but polymethyl methacrylate or polyamine group was used. When an acid ester resin or the like is used as the binder resin, the same result can be obtained.
又，於圖1之電雙層電容器A中，使用氧化鋁作為無機微粒子，但亦可使用二氧化矽、氧化鈦、鈦酸鋇等氧化物、氮化矽、氮化鋁等氮化物。 Further, in the electric double layer capacitor A of Fig. 1, alumina is used as the inorganic fine particles, but an oxide such as ceria, titanium oxide or barium titanate, or a nitride such as tantalum nitride or aluminum nitride may be used.
又，於上述實施例2中，作為蓄電裝置，以電雙層電容器為例進行了說明，但本發明亦可適用於鋰離子蓄電池、鋰離子電容器等。 Further, in the second embodiment, the electric double layer capacitor has been described as an example of the power storage device. However, the present invention is also applicable to a lithium ion battery, a lithium ion capacitor, or the like.
於任一種蓄電裝置中，均具有於如下方面共通之構造：正極層與負極層介隔陶瓷層及絕緣性接著層而積層，且正極層與負極層介隔絕緣性接著層而積層，並且與電解液一併收容於外包材料內。 In any of the power storage devices, the structure is common to the following: the positive electrode layer and the negative electrode layer are laminated with a ceramic layer and an insulating adhesive layer, and the positive electrode layer and the negative electrode layer are laminated to each other to form a layer, and The electrolyte is contained in the outer covering material.
再者，例如作為鋰離子蓄電池、或者鋰離子電容器，可例示如下之構成者。 Further, for example, as a lithium ion secondary battery or a lithium ion capacitor, the following constituents can be exemplified.
於鋰離子蓄電池中，例如使用鋁箔作為正極集電體層，並將於該鋁箔上設置有包含鋰複合氧化物之混合劑層作為正極活性物質層之電極用作正極層。 In the lithium ion secondary battery, for example, an aluminum foil is used as the positive electrode current collector layer, and an electrode containing a mixture layer of a lithium composite oxide as a positive electrode active material layer on the aluminum foil is used as the positive electrode layer.
又，例如使用銅箔作為負極集電體層，並將於該銅箔上設置有包含石墨之混合劑層作為負極活性物質層之電極用作負極層。 Further, for example, a copper foil is used as the negative electrode current collector layer, and an electrode in which a mixture layer containing graphite is provided as a negative electrode active material layer on the copper foil is used as the negative electrode layer.
繼而，介隔陶瓷層及絕緣性接著層積層正極層與負極層而形成積層體，並且例如將使1 mol/l之LiPF6溶解於碳酸乙二酯與碳酸二乙酯之混合溶劑而成者用作電解液(非水電解液)，藉此可獲得鋰離子蓄電池。 Then, a ceramic layer and an insulating layer are laminated to form a laminate, and a layer of a positive electrode layer and a negative electrode layer are formed, and, for example, 1 mol/l of LiPF 6 is dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate. It is used as an electrolyte (non-aqueous electrolyte), whereby a lithium ion secondary battery can be obtained.
於鋰離子電容器中，例如使用鋁箔作為正極集電體層，並將於該鋁箔上設置有包含活性碳之混合劑層作為正極活性物質層之電極用作正極層。 In the lithium ion capacitor, for example, an aluminum foil is used as the positive electrode current collector layer, and an electrode having a mixture layer containing activated carbon on the aluminum foil as a positive electrode active material layer is used as the positive electrode layer.
又，例如使用銅箔作為負極集電體層，並將於該銅箔上設置有包含石墨之混合劑層作為負極活性物質層之電極設為負極層，對該負極層進而預摻雜鋰離子。 Further, for example, a copper foil is used as the negative electrode current collector layer, and an electrode in which a mixture layer containing graphite is provided as a negative electrode active material layer on the copper foil is used as a negative electrode layer, and the negative electrode layer is further preliminarily doped with lithium ions.
繼而，形成介隔陶瓷層及絕緣性接著層積層正極層與負極層而成之積層體，並且例如將使1 mol/l之LiPF6溶解於碳酸乙二酯與碳酸二乙酯之混合溶劑而成者用作電解液(非水電解液)，藉此可獲得鋰離子電容器。 Then, a laminate in which a ceramic layer and an insulating layer are laminated to form a positive electrode layer and a negative electrode layer are formed, and for example, 1 mol/l of LiPF 6 is dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate. The developer is used as an electrolyte (non-aqueous electrolyte), whereby a lithium ion capacitor can be obtained.
再者，本發明並不限定於上述各實施例，關於正極層或負極層、分隔層、絕緣性接著層之構成材料或形成方法、蓄電要素之具體構成(正極層、負極層、分隔層、絕緣性接著層之積層態樣或積層數量等)、電解液之種類、外包材料之構成或構造材料等，可於發明之範圍內實施各種應用、變形。 In addition, the present invention is not limited to the above-described respective embodiments, and constituent materials, forming methods, and electric storage elements of the positive electrode layer or the negative electrode layer, the separator layer, and the insulating adhesive layer have specific structures (positive electrode layer, negative electrode layer, separator layer, Various applications and deformations can be implemented within the scope of the invention, such as the laminated layer of the insulating adhesive layer or the number of laminated layers, the type of the electrolytic solution, the composition of the outer covering material, or the structural material.
1‧‧‧積層體 1‧‧ ‧ laminated body
2‧‧‧第1端面 2‧‧‧1st end face
3‧‧‧第2端面 3‧‧‧2nd end face
11‧‧‧分隔層 11‧‧‧Separation layer
20‧‧‧正極集合片 20‧‧‧ positive assembly
21‧‧‧正極層 21‧‧‧ positive layer
21a‧‧‧正極集電體層 21a‧‧‧Positive collector layer
21b‧‧‧正極活性物質層 21b‧‧‧positive active material layer
21t‧‧‧正極外部端子電極 21t‧‧‧positive external terminal electrode
31‧‧‧絕緣性接著層 31‧‧‧Insulating adhesive layer
40‧‧‧負極集合片 40‧‧‧Negative collection
41‧‧‧負極層 41‧‧‧negative layer
41a‧‧‧負極集電體層 41a‧‧‧Negative collector layer
41b‧‧‧負極活性物質層 41b‧‧‧Negative active material layer
41t‧‧‧負極外部端子電極 41t‧‧‧Negative external terminal electrode
50‧‧‧積層集合體 50‧‧‧Multilayer aggregates
51‧‧‧正極負極集合片 51‧‧‧Positive positive anode assembly
52‧‧‧集合片積層體 52‧‧‧Collected laminated body
53‧‧‧複合積層體 53‧‧‧Composite laminate
61‧‧‧正極封裝體電極 61‧‧‧ positive electrode package electrode
62‧‧‧負極封裝體電極 62‧‧‧Negative package electrode
70‧‧‧封裝體 70‧‧‧Package
70a‧‧‧蓋體 70a‧‧‧ cover
70b‧‧‧基底部 70b‧‧‧ base
100‧‧‧基材PET膜 100‧‧‧Substrate PET film
A‧‧‧電雙層電容器 A‧‧‧Electrical double layer capacitor
D1‧‧‧裁斷線 D1‧‧‧ cutting line
圖1係模式性地表示本發明之一實施例(實施例2)之蓄電裝置用(電雙層電容器用)之構成的前視剖面圖。 Fig. 1 is a front cross-sectional view schematically showing a configuration of a power storage device (for an electric double layer capacitor) according to an embodiment (Example 2) of the present invention.
圖2係模式性地表示圖1之蓄電裝置之分隔層與絕緣性接著層之配設態樣的俯視剖面圖。 Fig. 2 is a plan cross-sectional view schematically showing an arrangement of a partition layer and an insulating back layer of the electricity storage device of Fig. 1;
圖3係表示於本發明之實施例2之蓄電裝置用元件之製造方法的一步驟中，於基材膜上形成有正極集電體層之狀態之圖，(a)係俯視圖，(b)係前視剖面圖。 3 is a view showing a state in which a positive electrode current collector layer is formed on a base film in one step of a method for producing a component for a storage battery device according to a second embodiment of the present invention, wherein (a) is a plan view and (b) is a system. Front view section.
圖4係表示於圖3所示之正極集電體層上形成有正極活性物質層之狀態之圖，(a)係俯視圖，(b)係前視剖面圖。 4 is a view showing a state in which a positive electrode active material layer is formed on the positive electrode current collector layer shown in FIG. 3, wherein (a) is a plan view and (b) is a front cross-sectional view.
圖5係表示於圖4所示之正極集電體層上形成有分隔層之 狀態之圖。 Figure 5 is a view showing that a separator layer is formed on the positive electrode collector layer shown in Figure 4 State diagram.
圖6(a)係表示藉由在圖5所示之分隔層之周圍配設絕緣性接著層而形成之正極集合片的圖，(b)係表示以相同方式形成之負極集合片之圖。 Fig. 6(a) is a view showing a positive electrode assembly sheet formed by disposing an insulating adhesive layer around the separator layer shown in Fig. 5, and Fig. 6(b) is a view showing a negative electrode assembly sheet formed in the same manner.
圖7係表示使正極集合片與負極集合片相互對向配置之狀態之圖。 Fig. 7 is a view showing a state in which the positive electrode assembly piece and the negative electrode assembly piece are arranged to face each other.
圖8係表示藉由接合正極集合片與負極集合片而形成之正負極集合片之圖。 Fig. 8 is a view showing a positive and negative electrode assembly sheet formed by joining a positive electrode assembly piece and a negative electrode assembly piece.
圖9係表示使一對正負極集合片相互對向配置之狀態之圖。 Fig. 9 is a view showing a state in which a pair of positive and negative electrode pieces are arranged to face each other.
圖10係表示接合一對正負極集合片而形成之集合片積層體之圖。 Fig. 10 is a view showing a laminated laminated body formed by joining a pair of positive and negative electrode sheets.
圖11係表示使正負極集合片對向配置於圖10之集合片積層體之狀態之圖。 Fig. 11 is a view showing a state in which the positive and negative electrode assembly sheets are arranged to face each other in the collective sheet layer body of Fig. 10;
圖12係表示接合圖10之集合片積層體與正負極集合片而形成之複合積層體之圖。 Fig. 12 is a view showing a composite laminated body formed by joining the laminated laminated body of Fig. 10 and the positive and negative electrode collective sheets.
圖13係模式性地表示藉由本發明之實施例而製作之積層集合體之構成的前視剖面圖。 Fig. 13 is a front cross-sectional view schematically showing the configuration of a laminated aggregate produced by an embodiment of the present invention.
圖14係說明對圖13之積層集合體進行分割之步驟之前視剖面圖。 Fig. 14 is a front cross-sectional view showing the steps of dividing the laminated assembly of Fig. 13;
圖15係表示分割圖13之積層集合體而獲得之積層體之構成的前視剖面圖。 Fig. 15 is a front cross-sectional view showing a configuration of a laminated body obtained by dividing the laminated body of Fig. 13;
圖16係表示於圖15之積層體上形成有正負極外部端子電極之狀態之前視剖面圖。 Fig. 16 is a cross-sectional front view showing a state in which the positive and negative external terminal electrodes are formed on the laminated body of Fig. 15.
圖17係表示先前之蓄電裝置(電雙層電容器)之圖。 Fig. 17 is a view showing a conventional power storage device (electric double layer capacitor).
1‧‧‧積層體 1‧‧ ‧ laminated body
2‧‧‧第1端面 2‧‧‧1st end face
3‧‧‧第2端面 3‧‧‧2nd end face
11‧‧‧分隔層 11‧‧‧Separation layer
21‧‧‧正極層 21‧‧‧ positive layer
21a‧‧‧正極集電體層 21a‧‧‧Positive collector layer
21b‧‧‧正極活性物質層 21b‧‧‧positive active material layer
21t‧‧‧正極外部端子電極 21t‧‧‧positive external terminal electrode
31‧‧‧絕緣性接著層 31‧‧‧Insulating adhesive layer
41‧‧‧負極層 41‧‧‧negative layer
41a‧‧‧負極集電體層 41a‧‧‧Negative collector layer
41b‧‧‧負極活性物質層 41b‧‧‧Negative active material layer
41t‧‧‧負極外部端子電極 41t‧‧‧Negative external terminal electrode
61‧‧‧正極封裝體電極 61‧‧‧ positive electrode package electrode
62‧‧‧負極封裝體電極 62‧‧‧Negative package electrode
70‧‧‧封裝體 70‧‧‧Package
70a‧‧‧蓋體 70a‧‧‧ cover
70b‧‧‧基底部 70b‧‧‧ base
A‧‧‧電雙層電容器 A‧‧‧Electrical double layer capacitor
Claims (8)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011142477 | 2011-06-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW201308382A true TW201308382A (en) | 2013-02-16 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW101120549A TW201308382A (en) | 2011-06-28 | 2012-06-07 | Insulating-adhesive-layer composition, element for electricity-storage device, electricity-storage device, and manufacturing methods therefor |
Country Status (2)
| Country | Link |
|---|---|
| TW (1) | TW201308382A (en) |
| WO (1) | WO2013001962A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108475827A (en) * | 2016-01-21 | 2018-08-31 | 儒特杰德公司 | Film type battery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111868966A (en) * | 2018-03-13 | 2020-10-30 | 三洋电机株式会社 | Secondary battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4016464B2 (en) * | 1997-09-30 | 2007-12-05 | ソニー株式会社 | Gel electrolyte secondary battery |
| JPH11185773A (en) * | 1997-12-18 | 1999-07-09 | Sony Corp | Gelled electrolyte cell |
| JP3260319B2 (en) * | 1998-04-08 | 2002-02-25 | ティーディーケイ株式会社 | Manufacturing method of sheet type electrode / electrolyte structure |
-
2012
- 2012-05-28 WO PCT/JP2012/063639 patent/WO2013001962A1/en active Application Filing
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108475827A (en) * | 2016-01-21 | 2018-08-31 | 儒特杰德公司 | Film type battery |
| US10879554B2 (en) | 2016-01-21 | 2020-12-29 | Routejade Inc. | Thin film battery |
| CN108475827B (en) * | 2016-01-21 | 2021-04-13 | 儒特杰德公司 | Thin film type battery |
Also Published As
| Publication number | Publication date |
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| WO2013001962A1 (en) | 2013-01-03 |
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