TW201302971A - 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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- TW201302971A TW201302971A TW101117640A TW101117640A TW201302971A TW 201302971 A TW201302971 A TW 201302971A TW 101117640 A TW101117640 A TW 101117640A TW 101117640 A TW101117640 A TW 101117640A TW 201302971 A TW201302971 A TW 201302971A
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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)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (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, a power storage device, an element for a power storage device, and a method for manufacturing the power storage device.
以鋰離子二次電池、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於外裝體內收容有以如下方式構成之蓄電要素與電解液之構造：將藉由於片狀之集電箔(鋁箔或銅箔等)上塗佈活性物質(活性碳、鋰複合氧化物、碳等)而形成的片狀之電極介隔用以防止電極間之接觸所引起之短路的片狀之分隔件進行積層。 A high-energy-density power storage device typified by a lithium ion secondary battery, a lithium ion capacitor, an electric double layer capacitor, or the like, for example, has a structure in which an electric storage element and an electrolytic solution configured as follows are housed in an exterior body: A sheet-shaped electrode formed by coating an active material (activated carbon, lithium composite oxide, carbon, or the like) on a current collector foil (such as aluminum foil or copper foil) is used to prevent short circuit caused by contact between electrodes. The sheet-like separator is laminated.
作為此種蓄電裝置之一，提出有經過如下步驟而製造之積層型電池：將混合電解質與多孔性陶瓷且與黏合劑一併形成為膜狀之陶瓷片材用作分隔件用材料，將正極層與負極層介隔上述陶瓷片材而積層，且對積層體總括地進行熱壓(專利文獻1)。 As one of the above-described power storage devices, a laminated battery manufactured by the following steps is proposed: a ceramic sheet in which a mixed electrolyte and a porous ceramic are formed into a film together with a binder is used as a material for a separator, and a positive electrode is used. The layer and the negative electrode layer are laminated via the ceramic sheet, and the laminated body is collectively hot-pressed (Patent Document 1).
又，作為另一蓄電裝置，提出有以如下方式形成之蓄電裝置(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相對向，並且使分隔件130及電解液(未圖示)介於該等之間，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，加熱該熱接著部140而使集電金屬120相互接著且密封(專利文獻2)。 Further, as another power storage device, there is proposed a power storage device (electric double layer capacitor) formed as follows: as shown in FIG. 17, the collector metal 120 followed by the activated carbon electrode 110 is opposed to each other, and the spacer 130 is provided. Further, an electrolyte solution (not shown) is interposed between the two, 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 collector metal 120 to heat the heat-receiving portion 140. The collector metals 120 are bonded to each other and sealed (Patent Document 2).
又，作為又一蓄電裝置，提出有將分隔件、集電體、及 極化電極藉由包含具有接著性之熱塑性樹脂之墊片而一體化之蓄電裝置(電雙層電容器)(專利文獻3)。 Further, as another power storage device, a separator, a current collector, and The polarized electrode is an electric storage device (electric double layer capacitor) which is integrated by a gasket containing a thermoplastic resin having an adhesive property (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有接著性之熱塑性樹脂。 Further, Patent Document 3 describes a thermoplastic resin having a polar functional group as a thermoplastic resin having a bonding property constituting a gasket.
然而，於上述專利文獻1之積層型電池之情形時，有在將混合有電解質之陶瓷片材與正極層或負極層進行積層之步驟中，需要單獨處理陶瓷片材之情形，從而要求陶瓷片材具有某種程度以上之強度。然而，有如下問題點：若欲確保陶瓷片材之強度，則為使分隔件低電阻(低離子電阻)化而要求之陶瓷片材之薄層化、或陶瓷粉體比率之提高(高PVC(Pigment Volume Concentration，顏料體積濃度)化)受到制約。即，有若欲確保電解液、陶瓷、及黏合劑共存之陶瓷片材之強度，則要犧牲薄層化或高PVC化而難以實現分隔件之低電阻(低離子電阻)化之問題點。 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 sheet, thereby requiring the ceramic sheet. The material has a certain degree of strength. However, there is a problem in that if the strength of the ceramic sheet is to be ensured, the thinning of the ceramic sheet required for the low resistance (low ionic resistance) of the separator or the increase of the ceramic powder ratio (high PVC) (Pigment Volume Concentration) is restricted. In other words, in order to secure the strength of the ceramic sheet in which the electrolyte, the ceramic, and the binder coexist, it is difficult to achieve the problem of low resistance (low ionic resistance) of the separator by sacrificing thinning or high PVC.
又，於上述專利文獻2之蓄電裝置(電雙層電容器)之情形時，由於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，故而需要於積層之前預先使電解液含浸於分隔件(及根據情況之電極)中，而存在無法應對如於積層體形成後添加電解液之製造方法，且製造步驟變得複雜之問題點。 Further, in the case of the electric storage device (electric double layer capacitor) of Patent Document 2, since the modified polypropylene or the modified polyethylene does not have the impregnation property and the permeability of the electrolyte at all, it is necessary to preliminarily electrolyze before the lamination. The liquid is impregnated into the separator (and, as the case may be), and there is a problem that the manufacturing method of adding the electrolyte after the formation of the laminate is not possible, and the manufacturing steps become complicated.
又，於上述專利文獻3之電雙層電容器之情形時，係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，存在與上述專利文獻2之情形相同之問題點。 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 liquid solubility or permeability of the electrolytic solution. Therefore, there is a problem similar to the case of the above-mentioned Patent Document 2.
[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
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滲透性或含浸性之蓄電裝置用絕緣性接著層組合物、包含由該絕緣性接著層組合物形成之絕緣性接著層且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 in view of the above-mentioned problems, and an object of the invention is to provide an insulating back-layer composition for an electrical storage device which can impart permeability or impregnation property to an electrolyte solution, and an insulating layer formed of the insulating adhesive layer composition. An element for a power storage device having a good layer and a characteristic, a power storage device, and the like.
為解決上述課題，本發明之絕緣性接著層組合物之特徵在於：其係構成蓄電裝置之下述絕緣性接著層者，該蓄電裝置包含具有使正極層與負極層介隔分隔層及絕緣性接著層予以積層、且上述正極層與上述負極層藉由上述絕緣性接著層接著之構造的積層體；該絕緣性接著層組合物包含含有無機微粒子與有機黏合劑之複合材料；且上述複合材料之由下述式(1)：PVC=(無機微粒子之體積)/(無機微粒子之體積+有機黏合劑之體積)×100………(1) In order to solve the above problems, the insulating adhesive layer composition of the present invention is characterized in that it constitutes an insulating back layer of a power storage device including a separator layer and an insulating layer between a positive electrode layer and a negative electrode layer. a layered body in which the positive electrode layer and the negative electrode layer are connected by the insulating adhesive layer; the insulating adhesive layer composition comprising a composite material containing inorganic fine particles and an organic binder; and the composite material It is represented by the following formula (1): PVC = (volume of inorganic fine particles) / (volume of inorganic fine particles + volume of organic binder) × 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，有機黏合劑之體積=有機黏合劑之重量/有機黏合劑之密度) (wherein the volume of inorganic fine particles = the weight of inorganic fine particles / the density of inorganic fine particles, the volume of organic binder = the weight of organic binder / the density of organic binder)
所表示之顏料體積濃度PVC、與認為空隙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Λ滿足下述式(2)：0.7≦Λ≦1.15………(2) The ratio of the indicated pigment volume concentration of PVC to the maximum pigment volume concentration of CPVC (Critical Pigment Volume Concentration) which is considered to be zero voids satisfies the following formula (2): 0.7≦Λ≦1.15...( 2)
(其中，Λ=PVC/CPVC)之必要條件。 (Where, Λ = PVC / CPVC) necessary conditions.
又，本發明之蓄電裝置用元件之特徵在於：其係包含具有使正極層與負極層介隔分隔層及絕緣性接著層予以積層、且上述正極層與上述負極層藉由上述絕緣性接著層接著之構造的積層體者；於上述絕緣性接著層，使用有技術方案1之絕緣性接著層組合物。 Further, the device for an electrical storage device according to the present invention is characterized in that the positive electrode layer and the negative electrode layer are separated by a separator layer and an insulating back layer, and the positive electrode layer and the negative electrode layer are laminated by the insulating layer. In the laminated body of the subsequent structure, the insulating adhesive layer composition of the first aspect is used for the insulating adhesive layer.
又，本發明之蓄電裝置之特徵在於：其係包含積層體、電解液、及收納上述積層體與上述電解液之封裝體者，該積層體具有使正極層與負極層介隔分隔層及絕緣性接著層予以積層、且上述正極層與上述負極層藉由上述絕緣性接著層接著之構造；於上述絕緣性接著層，使用有技術方案1之絕緣性接著層組合物。 Further, the power storage device according to the present invention is characterized in that it includes a laminate, an electrolytic solution, and a package in which the laminate and the electrolyte are accommodated, and the laminate has a separator layer and insulation between the cathode layer and the anode layer. The positive electrode layer is laminated, and the positive electrode layer and the negative electrode layer are connected by the insulating adhesive layer. The insulating adhesive layer of the first embodiment is used for the insulating adhesive layer.
又，本發明之蓄電裝置用元件之製造方法中，該蓄電裝置用元件包含具有使正極層與負極層介隔分隔 層及絕緣性接著層予以積層、且上述正極層與上述負極層藉由上述絕緣性接著層接著之構造的積層體，該製造方法之特徵在於：包括如下步驟：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相對向之方式配置，並進行加熱、加壓，藉此形成上述正極層、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：經由形成上述積層體之步驟所得之上述積層體之上述絕緣性接著層包含含有無機微粒子與有機黏合劑之複合材料，且上述複合材料之由下述式(1)：PVC=(無機微粒子之體積)/(無機微粒子之體積+有機黏合劑之體積)×100………(1) Further, in the method of manufacturing an element for a storage battery device according to the present invention, the element for the electricity storage device includes a separator for separating the positive electrode layer from the negative electrode layer. A layered body and an insulating backing layer are laminated, and the positive electrode layer and the negative electrode layer are laminated by the insulating adhesive layer. The manufacturing method includes the following steps: forming a positive electrode layer of the positive electrode layer The material and the material for the negative electrode layer to be the negative electrode layer are disposed so as to separate the material for the partition layer which serves as the partition layer, and the insulating back layer material which serves as the insulating adhesive layer, and are heated and pressurized. Thereby, the laminated body in which the positive electrode layer, the negative electrode layer, the separator, and the insulating back layer are integrated is formed, and an insulating back layer material is used as the insulating back layer material: by forming the above-mentioned laminated layer The above-mentioned insulating adhesive layer of the above-mentioned laminated body obtained by the step of the body comprises a composite material containing inorganic fine particles and an organic binder, and the composite material is represented by the following formula (1): PVC = (volume of inorganic fine particles) / (inorganic Volume of microparticles + volume of organic binder) × 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，有機黏合劑之體積=有機黏合劑之重量/有機黏合劑之密度) (wherein the volume of inorganic fine particles = the weight of inorganic fine particles / the density of inorganic fine particles, the volume of organic binder = the weight of organic binder / the density of organic binder)
所表示之顏料體積濃度PVC、與認為空隙為零之最大顏料體積濃度即臨界顏料體積濃度CPVC之比Λ滿足下述式(2)：0.7≦Λ≦1.15………(2) The ratio of the indicated pigment volume concentration of PVC to the maximum pigment volume concentration which is considered to be zero void, that is, the critical pigment volume concentration CPVC, satisfies the following formula (2): 0.7≦Λ≦1.15...(2)
(其中，Λ=PVC/CPVC)之必要條件。 (Where, Λ = PVC / CPVC) necessary conditions.
又，本發明之蓄電裝置之製造方法中， 該蓄電裝置包含積層體、電解液、及收納上述積層體與上述電解液之封裝體，該積層體具有使正極層與負極層介隔分隔層及絕緣性接著層予以積層、且上述正極層與上述負極層藉由上述絕緣性接著層接著之構造，該製造方法之特徵在於包括以下步驟：(1)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相對向之方式配置，並進行加熱、加壓，藉此形成上述正極層、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：經由形成上述積層體之步驟所得之上述積層體之上述絕緣性接著層包含含有無機微粒子與有機黏合劑之複合材料，且上述複合材料之由下述式(1)：PVC=(無機微粒子之體積)/(無機微粒子之體積+有機黏合劑之體積)×100………(1) Moreover, in the method of manufacturing the electrical storage device of the present invention, The power storage device includes a laminate, an electrolytic solution, and a package containing 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 positive electrode layer are The negative electrode layer is formed by the insulating adhesive layer, and the manufacturing method is characterized in that the method includes the following steps: (1) separating the material for the positive electrode layer serving as the positive electrode layer from the material for the negative electrode layer serving as the negative electrode layer The material for the spacer layer of the spacer layer and the insulating back layer material serving as the insulating adhesive layer are disposed to face each other, and are heated and pressurized to form the positive electrode layer, the negative electrode layer, and the separation layer. And the laminated body in which the insulating backing layer is integrated, and the insulating backing layer material is used as the insulating backing layer material to form the laminated body: the laminated body obtained by the step of forming the laminated body The insulating adhesive layer comprises a composite material containing inorganic fine particles and an organic binder, and the above composite material is Formula (1): PVC = (volume of inorganic fine particles) / (volume of inorganic fine particles + volume of an organic binder) × 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，有機黏合劑之體積=有機黏合劑之重量/有機黏合劑之密度) (wherein the volume of inorganic fine particles = the weight of inorganic fine particles / the density of inorganic fine particles, the volume of organic binder = the weight of organic binder / the density of organic binder)
所表示之顏料體積濃度PVC、與認為空隙為零之最大顏料體積濃度即臨界顏料體積濃度CPVC之比Λ滿足下述式(2)：0.7≦Λ≦1.15………(2) The ratio of the indicated pigment volume concentration of PVC to the maximum pigment volume concentration which is considered to be zero void, that is, the critical pigment volume concentration CPVC, satisfies the following formula (2): 0.7≦Λ≦1.15...(2)
(其中，Λ=PVC/CPVC) 之必要條件；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，並使上述電解液自上述積層體之外部向內部滲透、含浸。 (where Λ=PVC/CPVC) And (2) the laminate is housed in the package together with the electrolyte, and the electrolyte is permeated and impregnated from the outside of the laminate.
本發明之絕緣性接著層組合物係構成蓄電裝置之上述絕緣性接著層者，該蓄電裝置包含具有使正極層與負極層介隔分隔層及絕緣性接著層予以積層、且正極層與負極層藉由絕緣性接著層接著之構造的積層體，該絕緣性接著層組合物構成為包含含有無機微粒子與有機黏合劑之複合材料，且複合材料之顏料體積濃度PVC與臨界顏料體積濃度CPVC之比Λ(=PVC/CPVC)滿足0.7≦Λ≦1.15之必要條件，從而具有接著性且具有所需之電解液之滲透性或含液性。因此，藉由於構成此種蓄電裝置之積層體中使用本發明之絕緣性接著層組合物，可獲得包含可使電解液自積層體之外部向內部滲透、含浸之積層體且生產性優異之蓄電裝置。 The insulating adhesive layer composition of the present invention comprises the insulating interlayer of the electricity storage device, comprising: a positive electrode layer and a negative electrode layer interposed with a separator layer and an insulating back layer, and a positive electrode layer and a negative electrode layer; The insulating adhesive layer composition is composed of a composite material containing inorganic fine particles and an organic binder, and the ratio of the pigment volume concentration of the composite material to the critical pigment volume concentration CPVC is formed by an insulating and subsequent layered structure. Niobium (=PVC/CPVC) satisfies the requirements of 0.7≦Λ≦1.15, thereby having an adhesiveness and having the required electrolyte permeability or liquidity. Therefore, by using the insulating adhesive layer composition of the present invention in the laminated body constituting the above-described electrical storage device, it is possible to obtain a storage material including a laminate which allows the electrolytic solution to permeate and impregnate from the outside of the laminated body to the inside and which is excellent in productivity. Device.
即，由於包含如滿足0.7≦Λ≦1.15之必要條件之複合材料之絕緣性接著層具有所需之接著性，故而可確實地形成正極層、負極層、及分隔層一體化而成之積層體，且可使生產步驟簡化，而提高生產性。 That is, since the insulating adhesive layer containing the composite material satisfying the requirements of 0.7≦Λ≦1.15 has the desired adhesiveness, the positive electrode layer, the negative electrode layer, and the laminated body in which the separator layers are integrated can be surely formed. And the production steps can be simplified to improve productivity.
又，由於不必要求分隔層具有接著性等功能，故而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 the partition layer to have functions such as adhesion, it is possible to pursue the design as a function or function of the partition 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全周之方式配設，亦可配設於包圍分隔層之全周之區域之一部分。其中，自確保正極層與負極層之接合穩定性、及積層體之可靠性之觀點而言，較佳為以包圍分隔層之全周之方式配設。 Furthermore, in the present invention, the insulating adhesive layer may be disposed, for example, so as to surround the entire circumference of the separation layer, or may be disposed in a portion of the region surrounding the entire circumference of the separation layer. Among them, from the viewpoint of ensuring the bonding stability between the positive electrode layer and the negative electrode layer and the reliability of the laminated body, it is preferable to arrange the entire circumference of the partition layer.
再者，根據情況亦可構成為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相對向之正極層與負極層接合。 Further, depending on the case, the insulating adhesive layer may be disposed so as to penetrate the center portion of the separator, and the insulating layer may be bonded to the positive electrode layer and the negative electrode layer via the separator layer.
又，本發明之蓄電裝置用元件及蓄電裝置係於使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，在絕緣性接著層使用上述本發明之絕緣性接著層組合物，因此可將分隔層設為最佳之設計，從而可獲得離子電阻較低、性能較高、可靠性較高、且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. Since the layer composition is optimal, the separator layer 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中，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相對向之方式配置，並進行加熱、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係使用會於所形成之積層體之階段中形成上述本發明之絕緣性接著層組合物的材料，因此可效率良好地製造性能較高且可靠性較高之蓄電裝置用元件。 Further, in the method for producing a device for a power storage device of the present invention, 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 layer and the insulating backing material, and are heated. When the laminated body in which the positive electrode layer, the negative electrode layer, the separator layer, and the insulating adhesive layer are integrated is formed by pressurization, the above-described present invention is formed at the stage of forming the laminated body as the insulating adhesive layer material. Since the material of the insulating adhesive layer composition is excellent, 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中，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 層材料而相對向之方式配置，並進行加熱、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，係使用會形成本發明之絕緣性接著層組合物之材料作為絕緣性接著層材料，並且將所得之積層體與電解液一併收容於封裝體內，並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性能較高且可靠性較高之蓄電裝置。 Further, in the method for producing a power storage device according to the present invention, the material for the positive electrode layer and the material for the negative electrode layer are separated by a material for the partition layer and insulation. When the layer material is disposed to face and is heated and pressurized to form a laminated body in which the positive electrode layer, the negative electrode layer, the separator layer, and the insulating back layer are integrated, the insulating adhesive layer of the present invention is formed. The material of the composition is used as an insulating adhesive layer material, and the obtained laminated body is housed in the package together with the electrolytic solution, and the electrolytic solution is infiltrated and impregnated from the outside of the laminated body, so that the manufacturing performance can be efficiently performed. High and reliable power storage device.
再者，可使電解液自積層體之外部向內部滲透、含浸之原因在於，使用如上所述之絕緣性接著層材料(即，會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含液性之絕緣性接著層。 Further, the electrolyte may be allowed to permeate and impregnate from the outside of the laminate to the inside by using the insulating backing layer material as described above (i.e., the material forming the insulating adhesive layer composition of the present invention). The required electrolyte contains a liquid insulating underlayer.
以下，示出本發明之實施形態並詳細說明本發明之特徵之處。 Hereinafter, embodiments of the present invention will be described and 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、及高含液性。然而，通常PVC越高，雖越為低離子電阻、高含液性，但接著性越是降低。 In the multilayer type electricity storage device, the separator layer is required to have low ionic resistance, high adhesion, and high liquid content. However, generally, the higher the PVC, the lower the ionic resistance and the higher liquid content, but the lower the adhesion.
因此，於本發明中，藉由於分隔層之周邊部導入接著層(本發明中之絕緣性接著層)而彌補接著性。 Therefore, in the present invention, the adhesion is compensated for by the introduction of the adhesive layer (the insulating adhesive layer in the present invention) in 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，可於分隔層介於之間的狀態下不依賴分隔層之接著性而將正極層與負極層接著，從而不要求分隔層具有接著性，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 can be used without depending on the spacer layer in a state in which the spacer layer is interposed therebetween. The positive electrode layer and the negative electrode layer are bonded to each other, so that the separator is not required to have an adhesive property, and the function as a separator (high PVC and low ion resistance) can be improved.
又，本發明之特徵在於使絕緣性接著層具有含液性。通常，將樹脂單體用作接著劑，但於該情形時，實際情況為雖實現較高之接著性，但幾乎無法期待含液性。因此，於本發明中，藉由使用於有機黏合劑中混合有無機微粒子(絕緣性微粒子)之樹脂，而使絕緣性接著層具有含液性。 Further, the present invention is characterized in that the insulating adhesive layer has liquid-containing properties. Usually, a resin monomer is used as an adhesive, but in this case, in actuality, although high adhesiveness is achieved, liquid repellency is hardly expected. Therefore, in the present invention, the insulating adhesive layer has liquid-containing properties by using a resin in which inorganic fine particles (insulating fine particles) are mixed in the organic binder.
然而，含液性與接著性處於折衷之關係，而需要選擇適當之PVC。由於PVC越低(即，絕緣性粒子(例如氧化鋁(Al2O3)粒子或二氧化矽(SiO2)粒子等)之比率越少)，可自由移動之高分子鏈越增加，故而接著性提高，但因高分子鏈之柔軟性而填埋空隙，使含液性降低。又，若PVC變高，則接著性降低，含液性增大。相對於此，於本發明中，藉由適當地調節自由移動之高分子鏈與空隙之平衡，而同時實現較高之接著性與含液性。 However, liquidity and adhesion are in a trade-off relationship, and it is necessary to select an appropriate PVC. Since the lower the PVC (that is, the smaller the ratio of insulating particles (for example, alumina (Al 2 O 3 ) particles or cerium oxide (SiO 2 ) particles), the more freely movable polymer chains are increased, and then The property is improved, but the voids are filled due to the flexibility of the polymer chain to lower the liquid content. Further, when the PVC becomes high, the adhesion is lowered and the liquid content is increased. On the other hand, in the present invention, high adhesion and liquid content are simultaneously achieved by appropriately adjusting the balance between the freely moving polymer chain and the void.
本發明相關之積層型之蓄電裝置通常係由封裝體密封而使用。因此，於絕緣性接著層具有含液性之情形時，由於電解液可通過絕緣性接著層，故而可使用封裝體整體中所含之電解液。然而，於絕緣性接著層不具有含液性之情形時，即便封裝體內充滿電解液，位於積層體之周圍之電解液亦無法滲入積層體內，故而無法有效地利用。與此相對，於使絕緣性接著層具有含液性之本發明之蓄電裝置中，電解液之有效使用量增加，結果於例如鋰離子二次電池般認為電解液越多則越為高容量、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 by a package. Therefore, when the insulating adhesive layer has liquid-containing properties, since the electrolytic solution can be laminated by an insulating layer, the electrolytic solution contained in the entire package can be used. However, when the insulating adhesive layer does not have liquid-containing properties, even if the electrolyte is filled in the package, the electrolyte located around the laminate cannot penetrate into the laminate, and thus cannot be effectively utilized. On the other hand, in the power storage device of the present invention in which the insulating adhesive layer is liquid-containing, the effective use amount of the electrolytic solution is increased. As a result, for example, in the case of a lithium ion secondary battery, the higher the electrolyte, the higher the capacity. In the power storage device having high rate characteristics and long life, the characteristics can be improved efficiently.
又，例如鋰離子二次電池之容量降低等經時變化係因充 放電反應時於活性物質表面發生電解液之分解反應等，結果發生電解液之枯竭(dry up)而引起。 Further, for example, a change in capacity of a lithium ion secondary battery, such as a decrease in capacity, is caused by charging In the discharge reaction, a decomposition reaction of the electrolytic solution or the like occurs on the surface of the active material, and as a result, the electrolyte is dried up.
相對於此，亦藉由對絕緣性接著層賦予含液性，可增加能夠利用之電解液量(有效地使用封裝體與積層體之間所含之電解液)，從而可有助於蓄電裝置之高容量化及長壽命化。 On the other hand, by imparting liquid-containing property 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), which contributes to the electrical storage device. High capacity and long life.
又，由於預先含浸有電解液之分隔片材之強度會降低，因此於製造上較理想為於積層後注液電解液之方法，藉由如本發明般對絕緣性接著層賦予含液性，即便於採用以包圍分隔層之方式配設有絕緣性接著層之構造之情形時，亦可進行積層後之電解液之注液。其結果為可使用更薄、PVC更高且離子電阻較先前更低之分隔層，從而可獲得高特性之蓄電裝置。 Further, since the strength of the separator sheet in which the electrolytic solution is impregnated in advance is lowered, it is preferable to apply a liquid electrolyte solution to the insulating adhesive layer as in the present invention by a method of producing a liquid electrolyte after lamination. In other words, when it is convenient to use a structure in which an insulating backing layer is disposed so as to surround the separator, it is also possible to perform liquid filling of the electrolyte after lamination. As a result, it is possible to use a partition layer which is thinner, has a higher PVC, and has a lower ion resistance than before, so that a high-characteristic power storage device can be obtained.
即，藉由將絕緣性接著層之Λ(=PVC/CPVC)設為0.7≦Λ≦1.15之範圍，而於以例如利用逐次壓接之方法進行積層壓接而製作積層體之情形時，可實現間歇時間之短時間化，並且可實現蓄電裝置之高容量化、長壽命化。又，可提高生產性，以低成本製造積層型之蓄電裝置。 In other words, when the layer of the insulating adhesive layer (=PVC/CPVC) is set to be in the range of 0.7 to 1.15, and the laminate is formed by, for example, sequential pressure bonding, the laminate can be produced. The short time of the intermittent time is achieved, and the capacity of the power storage device can be increased and the life can be extended. Further, productivity can be improved, and a build-up type power storage device can be manufactured at low cost.
適合用於發揮如上所述之效果之蓄電裝置的本發明之絕緣性接著層組合物包含如下之複合材料：利用於鋰離子二次電池或電雙層電容器等之內部化學性及電化學性穩定之有機黏合劑，將於鋰離子二次電池或電雙層電容器等之內部化學性及電化學性穩定之無機微粒子黏合而成。 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 used for internal chemical and electrochemical stability of a lithium ion secondary battery or an electric double layer capacitor. The organic binder is bonded to inorganic chemistry and electrochemically stable inorganic fine particles such as a lithium ion secondary battery or an electric double layer capacitor.
並且，作為構成本發明之絕緣性接著層組合物之無機微 粒子，可列舉例如二氧化矽、氧化鋁、氧化鈦、鈦酸鋇等氧化物，氮化矽、氮化鋁等氮化物。 Further, as inorganic fines constituting the insulating adhesive layer composition of the present invention Examples of the particles include oxides such as cerium oxide, aluminum oxide, titanium oxide, and barium titanate, and nitrides such as cerium nitride and aluminum nitride.
又，作為有機黏合劑，可列舉聚偏二氟乙烯(PVDF，Polyvinylidene Fluoride)、聚偏二氟乙烯與六氟丙烯之共聚物(PVDF-HFP，Polyvinylidene Fluoride-Hexafluoropropylene)等。 Further, examples of the organic binder include polyvinylidene fluoride (PVDF), a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVDF-HFP, and polyvinylidene fluoride-Hexafluoropropylene).
又，作為複合材料，使用由式(1)：PVC=(無機微粒子之體積)/(無機微粒子之體積+有機黏合劑之體積)×100………(1) Further, as the composite material, the formula (1): PVC = (volume of inorganic fine particles) / (volume of inorganic fine particles + volume of organic binder) × 100 (...) is used.
(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，有機黏合劑之體積=有機黏合劑之重量/有機黏合劑之密度) (wherein the volume of inorganic fine particles = the weight of inorganic fine particles / the density of inorganic fine particles, the volume of organic binder = the weight of organic binder / the density of organic binder)
所表示之顏料體積濃度PVC(Pigment Volume Concentration)、與認為空隙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Λ滿足下述式(2)：0.7≦Λ≦1.15………(2)之必要條件者。 The ratio of the pigment volume concentration of PVC (Pigment Volume Concentration) to the maximum pigment volume concentration of CPVC (Critical Pigment Volume Concentration) which is considered to be zero voids satisfies the following formula (2): 0.7≦Λ≦ 1.15.........(2) The necessary conditions.
再者，Λ係指「Reduced Pigment Volume Concentration(對比顏料體積濃度)」，且由下述式(3)所表示。 In addition, Λ means "Reduced Pigment Volume Concentration" and is represented by the following formula (3).
Λ=PVC/CPVC………(3) Λ=PVC/CPVC.........(3)
又，上述空隙係如以下般藉由密度法進行評價。 Further, the above voids were evaluated by a density method as follows.
測定沖裁為特定尺寸之試樣之厚度及重量，藉由將重量除以體積而算出密度。繼而，由密度之實測值與根據複合 材料片材之組成所算出之理論密度，藉由下式計算出空隙率。 The thickness and weight of the sample punched into a specific size were measured, and the density was calculated by dividing the weight by the volume. Then, by the measured value of the density and the composite The theoretical density calculated from the composition of the material sheet was calculated from the following formula.
(空隙率)={1-(密度之實測值)/(理論密度)}×100 (void ratio) = {1 - (measured value of density) / (theoretical density)} × 100
再者，複合材料係藉由使用例如球磨機等將無機微粒子、有機黏合劑、及溶劑製備成漿料，以刮刀法等使該漿料於基材上流延，並進行乾燥而獲得。 In addition, the composite material is obtained by preparing inorganic fine particles, an organic binder, and a solvent into a slurry using, for example, a ball mill, and casting the slurry onto a substrate by a doctor blade method or the like, followed by drying.
以下，示出本發明之實施例並進而詳細地說明本發明。 Hereinafter, embodiments of the invention will be described and the invention will be described in detail.
[包含絕緣性接著層組合物之片材之製作與評價] [Production and Evaluation of Sheets Containing Insulating Adhesive Composition]
準備球狀氧化鋁粉末(平均粒徑0.3 μm)作為構成絕緣性接著層組合物用複合材料之無機微粒子。 Spherical alumina powder (average particle diameter: 0.3 μm) was prepared as the inorganic fine particles constituting the composite material for the insulating adhesive layer composition.
又，準備聚偏二氟乙烯(PVDF)作為構成複合材料之有機黏合劑。 Further, polyvinylidene fluoride (PVDF) was prepared as an organic binder constituting the composite material.
繼而，藉由以下說明之方法，製作乾燥後之絕緣性接著層之PVC成為20、25、30、32、34、36、40、46、48、50、55、60、65、70、75%之複合材料片材。 Then, the PVC of the insulating backing layer after drying is made into 20, 25, 30, 32, 34, 36, 40, 46, 48, 50, 55, 60, 65, 70, 75% by the method described below. Composite sheet.
於500 ml之罐中投入無機微粒子與作為溶劑之N-甲基-2-吡咯啶酮(NMP，N-methyl-2-pyrrolidone)。進而，放入5 mmΦ之PSZ(Partially Stabilized Zirconia，部分穩定氧化鋯)製粉碎介質，使用滾動球磨機進行4小時混合並進行分散。其後，添加特定量之PVDF(聚偏二氟乙烯)之NMP(N-甲基-2-吡咯啶酮)溶液，使用滾動球磨機進行2小時混合而製備漿料。 Inorganic microparticles and N-methyl-2-pyrrolidone (NMP, NMP) were placed in a 500 ml jar. Further, a pulverization medium made of 5 mm Φ PSZ (Partially Stabilized Zirconia) was placed and mixed by a rolling ball mill for 4 hours to be dispersed. Thereafter, a specific amount of PVDF (polyvinylidene fluoride) NMP (N-methyl-2-pyrrolidone) solution was added, and the mixture was mixed for 2 hours using a rolling ball mill to prepare a slurry.
利用刮刀法將該漿料塗佈於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 to PET (Polyethylene Terephthalate) by a doctor blade method. After the polyethylene terephthalate film was dried, it was dried to obtain a composite sheet having a thickness of 25 μm (corresponding to the sheet of the insulating adhesive layer of the present invention).
之後，為評價複合材料片材(以下稱為「絕緣性接著層片材」)，調查臨界顏料體積濃度CPVC、加熱加壓時之接著性、及電解液之含液性。 Thereafter, in order to evaluate the composite sheet (hereinafter referred to as "insulating adhesive sheet"), the critical pigment volume concentration CPVC, the adhesion at the time of heating and pressurization, and the liquid content of the electrolytic solution were examined.
(1)臨界顏料體積濃度CPVC(密度法) (1) Critical pigment volume concentration CPVC (density method)
對於以上述方式製作之絕緣性接著層片材，藉由密度法測定之CPVC為48%。 For the insulating back sheet produced in the above manner, the CPVC measured by the density method was 48%.
(2)加熱加壓時之接著性 (2) Adhesion when heated and pressurized
以片材之乾燥表面成為接著面之方式設置於壓製裝置中，於150℃、20 MPa下進行2分鐘加熱加壓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之間之剝離力為1.0 mN/mm以上者設為接著性良好。 The dry surface of the sheet was placed in a press apparatus so as to be a continuous surface, and the insulating backsheet sheets were joined to each other by heating and pressing at 150 ° C and 20 MPa for 2 minutes. In the case where the peeling force between the insulating backing sheets at this time is 1.0 mN/mm or more, the adhesion is good.
以上述方式製作之絕緣性接著層片材中，PVC為55%(Λ=1.15)以下之絕緣性接著層片材為接著性良好，PVC為55%(Λ=1.25)以上者為接著性不良。 In the insulating back sheet produced in the above manner, the insulating back sheet having a PVC of 55% (Λ=1.15) or less has good adhesion, and the PVC is 55% (Λ=1.25) or more. .
(3)電解液之含液性 (3) Liquid content of electrolyte
製備以下者作為電解液並用於含液性試驗。 The following were prepared as an electrolyte solution and used for the liquidity test.
作為非水系溶劑，使用將作為環狀碳酸酯之碳酸伸乙酯(EC，Ethylene Carbonate)與碳酸二乙酯(DEC，Diethyl Carbonate)以3：7之體積比混合而成之混合溶劑，使電解質之LiPF6以成為1 mol‧1-1之濃度之方式溶解於該混合溶 劑中，而製作非水電解液。 As a nonaqueous solvent, a mixed solvent obtained by mixing a cyclic carbonate (EC, Ethylene Carbonate) and diethyl carbonate (DEC, Diethyl Carbonate) in a volume ratio of 3:7 is used to make an electrolyte. LiPF 6 was dissolved in the mixed solvent so as to have a concentration of 1 mol ‧1 -1 to prepare a nonaqueous electrolytic solution.
繼而，將1 cm×1 cm×25 μm(厚度)之經乾燥之絕緣性接著層片材於25℃下浸漬於電解液中，測定24小時後之重量增加，藉此評價含液性。將質量增加10%以上之分隔片材設為含液性良好。 Then, the dried insulating back sheet of 1 cm × 1 cm × 25 μm (thickness) was immersed in an electrolytic solution at 25 ° C, and the weight increase after 24 hours was measured, thereby evaluating the liquid content. The separator sheet having a mass increase of 10% or more is preferably liquid-containing.
PVC為34%(Λ=0.70)以上者為含液性良好，PVC為32%(Λ=0.67)以下者為含液性不良。 When the PVC is 34% (Λ=0.70) or more, the liquid content is good, and the PVC is 32% (Λ=0.67) or less, and the liquid content is poor.
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平面剖面圖。 1 is a front cross-sectional view showing a power storage device (electric double layer capacitor) of an embodiment (Example 2) of the present invention, and FIG. 2 is a plan cross-sectional view schematically showing a configuration 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包含積層體1，該積層體1係藉由將於正極集電體層21a之兩面設置有正極活性物質21b之正極層21、與於負極集電體層41a之兩面設置有負極活性物質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。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。並且，該積層體1係與電解液一併收容於包含蓋體70a、基座部70b之封裝體70中。又，於封裝體70，以自兩端向下表面側折入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 laminated body 1 which is provided with a positive electrode layer 21 provided with a positive electrode active material 21b on both surfaces of a positive electrode current collector layer 21a. The negative electrode layer 41 provided with the negative electrode active material 41b on both surfaces of the negative electrode current collector layer 41a is formed by laminating the separator 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. Further, in the package 70, the positive electrode package electrode 61 and the negative electrode package electrode 62 are formed so as to be folded from the both ends to the lower surface side.
並且，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係配設於包圍分隔層11之周圍之區域，正極層21及負極層41係介隔分隔層11、與配設於包圍 分隔層11之周圍之區域之絕緣性接著層31而積層。 Further, as shown in Figs. 1 and 2, in the electric double layer capacitor A of the 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. Separation layer 11 and surrounding The insulating region of the region around the spacer layer 11 is laminated with the layer 31.
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係介隔絕緣性接著層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係介隔分隔層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而相對向，且正極活性物質層21b與負極活性物質層41b之周圍之正極集電體層21a與負極集電體層41a係介隔絕緣性接著層31而積層。 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 bonding layer 31, and the positive electrode active layer 21 is formed. The material layer 21b and the negative electrode active material layer 41b constituting the negative electrode layer 41 are laminated via the separator layer 11, and the positive electrode active material layer 21b and the negative electrode active material layer 41b are opposed to each other via the separator layer 11 and the positive electrode active material is opposed thereto. The layer 21b and the cathode current collector layer 21a and the anode current collector layer 41a around the anode active material layer 41b are laminated to form the edge layer 31.
並且，作為絕緣性接著層31，使用有如下絕緣性接著層組合物：包含含有作為無機微粒子之氧化鋁(0.3 μm)與有機黏合劑之複合材料，且其PVC為40%、CPVC為48%、Λ為0.83之具備本發明之必要條件。 Further, as the insulating adhesive layer 31, an insulating adhesive layer composition containing alumina containing inorganic fine particles is used ( A composite material of 0.3 μm) and an organic binder, and having a PVC of 40%, a CPVC of 48%, and a enthalpy of 0.83 are essential for the present invention.
以下，說明該電雙層電容器A之製造方法。 Hereinafter, a method of manufacturing the electric double layer capacitor A will be described.
[步驟1(集電體之製作)] [Step 1 (Production of Current Collector)]
於塗佈有胺基甲酸酯作為脫模層之基材PET膜上，藉由蒸鍍形成厚度為0.5 μm之鋁層。其後，於所形成之鋁層之表面，藉由絲網印刷而圖案塗佈蝕刻遮罩抗蝕劑，並進行乾燥。再者，抗蝕劑係使用KANSAI PAINT製造之ALES SPR。 On the base PET film coated with the urethane as the release layer, an aluminum layer having a thickness of 0.5 μm was formed by evaporation. Thereafter, an etch mask resist is pattern-coated on the surface of the formed aluminum layer by screen printing, and dried. Further, the resist was an ALES SPR manufactured by KANSAI PAINT.
其後，將該膜浸漬於40℃之氯化鐵水溶液中，將鋁層圖案化。其後，將該膜浸漬於有機溶劑中剝離抗蝕劑後，浸漬於硫酸與氫氟酸之混合水溶液中除去鋁層表面之氧化層，藉此如圖3(a)、(b)所示，於基材PET膜100上形成複數 個正極集電體層21a。 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 3(b). Forming a plurality on the substrate PET film 100 A cathode current collector layer 21a.
[步驟2] [Step 2]
(1)活性物質層用漿料之製作 (1) Preparation of slurry for active material layer
稱量活性碳(BET(布厄特，Brunauer-Emmett-Teller)比表面積為1668 m2/g、平均孔隙直徑為1.83 nm、平均粒徑(D50)為1.26 μm)29.0 g、及碳黑(Tokai Carbon股份有限公司製造之「tokablack #3855」，BET比表面積為90 m2/g)2.7 g，投入至1000 ml之罐中，進而投入直徑為2.0 mm之PSZ製粉碎介質及286 g之去離子水之後，使用滾動球磨機以150 rpm進行4小時混合並進行分散。 Weighing activated carbon (BET (Brunauer-Emmett-Teller) specific surface area of 1668 m 2 /g, average pore diameter of 1.83 nm, average particle size (D 50 ) of 1.26 μm) 29.0 g, and carbon black (Tokablack #3855, manufactured by Tokai Carbon Co., Ltd., BET specific surface area of 90 m 2 /g) 2.7 g, put into a 1000 ml tank, and then put into a PSZ crushing medium with a diameter of 2.0 mm and 286 g. After deionized water, it was mixed and dispersed at 150 rpm for 4 hours using a rolling ball mill.
其後，於罐中投入3.0 g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，進而進行2小時混合，藉此製作活性物質層用漿料。 Thereafter, 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 can, and further mixed for 2 hours to prepare an activity. A slurry for the material layer.
(2)活性物質層用漿料之塗佈 (2) Coating of slurry for active material layer
使用版厚為8 μm之#500目絲網印刷版，於圖3(a)、(b)所示之正極集電體層21a上之活性物質層塗佈部，絲網印刷以上述方法製作之活性物質層用漿料，並於100℃下進行30分鐘乾燥，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，形成包含正極集電體層21a與正極活性物質層21b之正極層21。 Using a #500 mesh screen printing plate having a plate thickness of 8 μm, the active material layer coating portion on the positive electrode current collector layer 21a shown in Figs. 3(a) and (b), screen printing was produced by the above method. The slurry for the active material layer 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 current collector layer as shown in FIGS. 4( a ) and 4 ( 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處不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中被切斷時自該切斷面起形成有特定寬度之未塗佈區域之方式絲網印刷活性物質層用漿料。 In addition, as shown in FIG. 1, the positive electrode active material layer 21b 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 21t, and is formed at a predetermined distance from the first end face 2. That is, in printing activity In the case of the slurry for the material layer, 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之罐中投入二氧化矽(電化學工業股份有限公司製造，平均粒徑(D50)為0.7 μm)50 g、與作為溶劑之甲基乙基酮50 g。進而放入直徑為5 mm之PSZ製粉碎介質，使用滾動球磨機以150 rpm進行16小時混合並進行分散。其後，投入作為有機黏合劑溶液之聚偏二氟乙烯(PVDF)之NMP(N-甲基-2-吡咯啶酮)溶液(KUREHA製造之L#1120，分子量28萬，12 wt%溶液)，使用滾動球磨機以150 rpm進行4小時混合，而製作分隔層用漿料(分隔層用材料)。 Into a 500 ml tank, cerium oxide (manufactured by Electrochemical Industry Co., Ltd., average particle diameter (D 50 ): 0.7 μm) 50 g and 50 g of methyl ethyl ketone as a solvent were charged. Further, a PSZ pulverization medium having a diameter of 5 mm was placed, and mixed and dispersed at 150 rpm for 16 hours using a rolling ball mill. Thereafter, a solution of NMP (N-methyl-2-pyrrolidone) of polyvinylidene fluoride (PVDF) as an organic binder solution (L#1120 manufactured by KUREHA, molecular weight: 280,000, 12 wt% solution) was introduced. The mixture was mixed for 4 hours at 150 rpm using a rolling ball mill to prepare a separator for the separator (material for the separator).
(2)分隔層用漿料之塗佈 (2) Coating of the separator layer
使用版厚為8 μm之#500目絲網印刷版，將以上述方法製作之分隔層用漿料塗佈於正極層21上(更詳細而言為正極活性物質層21b上)，並於120℃下進行30分鐘乾燥，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 (more specifically, the positive electrode active material layer 21b) using a #500 mesh screen printing plate having a plate thickness of 8 μm, and was used at 120 Drying was carried out for 30 minutes at ° C, 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之罐中投入氧化鋁(電化學工業股份有限公司製造，平均粒徑(D50)為0.3 μm)100 g、與作為溶劑之N-甲基-2-吡咯啶酮(NMP)80 g。進而放入直徑為5 mm之PSZ製粉碎介質，使用滾動球磨機以150 rpm進行16小時混合並進 行分散。其後，投入PVDF(聚偏二氟乙烯)-HDP(六氟丙烯)之黏合劑溶液(Arkema製造之Kynar2801，20 wt% NMP溶液)170 g，使用滾動球磨機以150 rpm進行4小時混合，製作乾燥後之PVC成為40%、Λ成為0.83之絕緣性接著層用漿料。 Alumina (manufactured by Electrochemical Industry Co., Ltd., average particle diameter (D 50 ) of 0.3 μm) 100 g, and N-methyl-2-pyrrolidone (NMP) 80 as a solvent were placed in a 500 ml tank. g. Further, a PSZ pulverization medium having a diameter of 5 mm was placed, and mixed and dispersed at 150 rpm for 16 hours using a rolling ball mill. Thereafter, 170 g of a PVDF (polyvinylidene fluoride)-HDP (hexafluoropropylene) binder solution (Kynar 2801, 20 wt% NMP solution manufactured by Arkema) was placed, and mixed at 150 rpm for 4 hours using a rolling ball mill. The PVC after drying was 40%, and the crucible became a slurry for an insulating back layer of 0.83.
(2)絕緣性接著層用漿料之塗佈 (2) Coating of the insulating adhesive layer
使用版厚為8 μm之#500目絲網印刷版，將以上述方法製作之絕緣性接著層用漿料塗佈於包圍分隔層11之區域之正極集電體層21a及基材PET膜100上，於120℃下進行30分鐘乾燥，形成厚度為10 μm之絕緣性接著層31。 The slurry for an insulating adhesive layer produced by the above method was applied onto the positive electrode collector layer 21a and the base PET film 100 in the region surrounding the separator 11 by using a #500 mesh screen printing plate having a plate thickness of 8 μm. It was dried at 120 ° C for 30 minutes to form an insulating back layer 31 having a thickness of 10 μm.
如此，如圖6(a)所示，於基材PET膜100上形成具備包含正極集電體層21a及形成於其表面之正極活性物質層21b之正極層21、分隔層11、及絕緣性接著層31之正極集合片材20。 As shown in FIG. 6(a), the positive electrode layer 21 including the positive electrode current collector layer 21a and the positive electrode active material layer 21b formed on the surface thereof, the separator layer 11, and the insulating property are formed on the base material PET film 100. The positive electrode assembly sheet 20 of layer 31.
同樣地，如圖6(b)所示，於基材PET膜100上形成具備包含負極集電體層41a及形成於其表面之負極活性物質層41b之負極層41、分隔層11、及絕緣性接著層31之負極集合片材40。 Similarly, as shown in FIG. 6(b), the negative electrode layer 41 including the negative electrode current collector layer 41a and the negative electrode active material layer 41b formed on the surface thereof, the separator layer 11, and the insulating property are formed on the base material PET film 100. Next, the negative electrode assembly sheet 40 of layer 31.
[步驟5] [Step 5]
繼而，如圖7所示，將正極集合片材20與負極集合片材40以形成有分隔層11及絕緣性接著層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，並進行熱壓接。此時，使正極集合片材20以正極集電體21a之位置相互於左右方向(圖7上)偏移之態樣對向，並進行熱壓接。 Then, as shown in FIG. 7, the positive electrode assembly sheet 20 and the negative electrode assembly sheet 40 are opposed to each other on the surface on which the separator layer 11 and the insulating adhesive layer 31 are formed (the surface opposite to the substrate PET film 100 side). It is equipped in a way and is thermocompression bonded. At this time, the positive electrode assembly sheet 20 is opposed to each other in such a manner that the positions of the positive electrode current collectors 21a are shifted from each other in the left-right direction (upward in FIG. 7), and thermocompression bonding is performed.
藉此，如圖8所示，獲得正極集合片材20與負極集合片材40接合而成之正極負極集合片材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，熱壓接係將加壓板之溫度設為150℃、加壓之壓力設為20 MPa、加壓時間設為30秒。 Further, 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9所示，對於2個正極負極集合片材51彼此，將一正極負極集合片材51以上下方向成為反向之方式配置，並且剝離相對向之面側之基材PET膜，使兩者接合並進行熱壓接，藉此製作如圖10所示之集合片材積層體52。 Then, as shown in FIG. 9, the positive electrode negative electrode assembly sheet 51 is disposed such that the upper and lower sides of the positive electrode negative electrode assembly sheet 51 are reversed, and the base material PET film is peeled off from the surface side. The both are joined and thermocompression bonded, whereby the aggregate sheet laminate 52 as shown in Fig. 10 is produced.
熱壓接係將加壓板之溫度設為150℃、加壓之壓力設為20 MPa、加壓時間設為30秒。 The thermocompression bonding system set the temperature of the pressure plate to 150 ° C, the pressure of the pressurization to 20 MPa, and the pressurization time to 30 seconds.
其後，如圖11所示，使正極負極集合片材51與集合片材積層體52相對向並進行熱壓接，藉此，如圖12所示，製作包含3個正極負極集合片材51之複合積層體53。 Then, as shown in FIG. 11, the positive electrode negative electrode assembly sheet 51 and the aggregate sheet laminated body 52 are opposed to each other and thermocompression bonded, whereby three positive electrode negative electrode assembly sheets 51 are produced as shown in FIG. The composite laminate body 53.
其後，同樣地重複進行正極負極集合片材51之熱壓接，進行逐次壓接。藉此，獲得如圖13所示之正極層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接合而成之積層集合體50。 Thereafter, the thermocompression bonding of the positive electrode negative electrode assembly sheet 51 is repeated in the same manner, and the pressure bonding is performed successively. Thereby, a laminate in which the positive electrode layer 21 and the negative electrode layer 41 are laminated with the separator layer 11 and the insulating adhesive layer 31 as shown in FIG. 13 and the positive electrode layer 21 and the negative electrode layer 41 are joined by the insulating adhesive layer 31 is obtained. Aggregate 50.
[步驟6] [Step 6]
其次，藉由切塊機將積層集合體50沿圖14之裁斷線D1裁斷，進行單片化，藉此製作具有如圖15所示之構造之積層體1。 Next, the laminated aggregate 50 is cut by the cutting machine along the cutting line D1 of Fig. 14 to be singulated, whereby the laminated body 1 having the structure shown in Fig. 15 is produced.
該積層體1之尺寸係設為長度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]
其次，如圖16所示，藉由Al濺鍍分別於積層體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。 Next, as shown in FIG. 16, the first end of the laminated body 1 is respectively sputtered by Al sputtering. The surface 2 forms the positive electrode external terminal electrode 21t, and the second end surface 3 forms the negative electrode external terminal electrode 41t.
[步驟8] [Step 8]
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上，藉由浸漬法塗佈含有金作為導電性粒子之導電性接著劑(未圖示)。繼而，如圖1所示，以所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之基座部70b，並於170℃下加熱10分鐘，使導電性接著劑硬化。 On the positive electrode external terminal electrode 21t and the negative electrode external terminal electrode 41t formed on the first end face 2 and the second end face 3, a conductive adhesive (not shown) containing gold as the conductive particles is applied by a dipping method. Then, 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. The conductive adhesive was hardened by heating at 170 ° C for 10 minutes.
[步驟9] [Step 9]
繼而，於圖1所示之封裝體70之內部注液電解液並進行密封。此處，於減壓下注液1-乙基-3-甲基咪唑鎓四氟硼酸鹽作為電解液，於封裝體70之基座部70b上表面，配置與基座部70b同為液晶聚合物製之蓋體70a，藉由沿封裝體70之基座部70b之框體部分進行雷射照射，而熔接基座部70b與蓋體70a。 Then, the electrolyte is injected into the inside of the package 70 shown in FIG. 1 and sealed. Here, 1-ethyl-3-methylimidazolium tetrafluoroborate is injected as an electrolytic solution under reduced pressure, and is disposed on the upper surface of the base portion 70b of the package 70, and is disposed in the same manner as the base portion 70b. The lid body 70a of the material is irradiated with laser light along the frame portion of the base portion 70b of the package body 70 to weld the base portion 70b and the lid body 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，於以上之說明中所參照之圖1~16中，因作圖上之制約而將分隔層11、正極層21、負極層41、及絕緣性接著層31等繪製得較厚，其並非將實際尺寸準確地放大或縮小者。 Further, in FIGS. 1 to 16 referred to in the above description, the spacer layer 11, the positive electrode layer 21, the negative electrode layer 41, and the insulating adhesive layer 31 are drawn thickly due to the restriction on the drawing. It is not the exact size of the actual size is enlarged or reduced.
又，關於說明書中隨附之其他圖式，亦因作圖上之制約 或為便於理解而將大小或位置關係適當變形或誇張地表示。 Also, regarding the other drawings attached to the manual, it is also restricted by the drawing. Or the size or positional relationship is appropriately deformed or exaggerated for ease of understanding.
[電雙層電容器A之電化學特性] [Electrochemical Characteristics of Electric Double Layer Capacitor A]
以上述方式製作之電雙層電容器A之電化學特性係直流容量為4.37 mF。 The electrochemical characteristics of the electric double layer capacitor A produced in the above manner were DC current of 4.37 mF.
再者，於具有如圖1所示之構成之該實施例2之電雙層電容器A中，包圍分隔層之絕緣性接著層構成為包含含有無機微粒子與有機黏合劑之複合材料，且複合材料之顏料體積濃度PVC與臨界顏料體積濃度CPVC之比Λ(=PVC/CPVC)滿足0.7≦Λ≦1.15之必要條件，從而具有接著性且具有所需之電解液之滲透性或含液性，故而可形成能夠使電解液自積層體之外部向內部滲透、含浸之積層體。因此，可獲得生產性優異之電雙層電容器。 Further, in the electric double layer capacitor A of the second embodiment having the configuration shown in FIG. 1, the insulating adhesive layer surrounding the separator is composed of a composite material containing inorganic fine particles and an organic binder, and the composite material The ratio of the pigment volume concentration of PVC to the critical pigment volume concentration CPVC (=PVC/CPVC) satisfies the requirements of 0.7≦Λ≦1.15, and thus has the adhesiveness and the required electrolyte permeability or liquid content. A laminate capable of allowing the electrolyte to permeate and impregnate from the outside of the laminate to the inside can be formed. Therefore, an electric double layer capacitor excellent in productivity can be obtained.
又，由於包含滿足0.7≦Λ≦1.15之必要條件之複合材料之絕緣性接著層具有所需之接著性，故而可獲得具有積層構造且生產性優異之電雙層電容器。 Moreover, since the insulating adhesive layer containing the composite material satisfying the requirements of 0.7≦Λ≦1.15 has the desired adhesiveness, an electric double layer capacitor having a laminated structure and excellent productivity can be obtained.
又，由於不必要求分隔層具有接著性等功能，故而可進行追求作為分隔層之功能之設計，從而可實現特性之提高。 Further, since it is not necessary to require the partition layer to have functions such as adhesion, it is possible to carry out the design which is a function of the partition layer, and it is possible to improve the characteristics.
於上述實施例中，作為蓄電裝置係以電雙層電容器為例進行說明，但本發明亦可應用於鋰離子二次電池、鋰離子電容器等。 In the above embodiment, the electric double layer capacitor is described as an example of the electric storage device. However, the present invention is also applicable to a lithium ion secondary battery, a lithium ion capacitor, or the like.
於任一蓄電裝置中，均於如下方面具有共同之構造：正極層與負極層係介隔陶瓷層及絕緣性接著層予以積層，且 正極層與負極層介隔絕緣性接著層予以積層，並且與電解液一併收容於外包材內。 In any of the power storage devices, the first structure has a common structure: 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 separated by a barrier layer, and the layers are laminated and housed in the outer covering together with the electrolytic solution.
再者，例如作為鋰離子二次電池或鋰離子電容器，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 are exemplified.
於鋰離子二次電池中，使用如下電極作為正極層：使用例如鋁箔作為正極集電體層，並於該鋁箔上設置包含鋰複合氧化物之合劑層作為正極活性物質層。 In the lithium ion secondary battery, the following electrode is used as the positive electrode layer: for example, an aluminum foil is used as the positive electrode current collector layer, and a mixture layer containing a lithium composite oxide is provided as the positive electrode active material layer on the aluminum foil.
又，使用如下電極作為負極層：使用例如銅箔作為負極集電體層，並於該銅箔上設置包含石墨之合劑層作為負極活性物質層。 Further, an electrode is used as the negative electrode layer: for example, a copper foil is used as the negative electrode current collector layer, and a mixture layer containing graphite is provided as the negative electrode active material layer on the copper foil.
繼而，將正極層與負極層介隔陶瓷層及絕緣性接著層積層而形成積層體，並且例如將使1 mol/l之LiPF6溶解於碳酸伸乙酯與碳酸二乙酯之混合溶劑中而成者用作電解液(非水電解液)，藉此可獲得鋰離子二次電池。 Then, the positive electrode layer and the negative electrode layer are interposed between the ceramic layer and the insulating layer to form a laminate, and for example, 1 mol/l of LiPF 6 is dissolved in a mixed solvent of ethyl carbonate and diethyl carbonate. The resultant is used as an electrolyte (nonaqueous electrolyte), whereby a lithium ion secondary battery can be obtained.
於鋰離子電容器中，使用如下電極作為正極層：使用例如鋁箔作為正極集電體層，並於該鋁箔上設置包含活性碳之合劑層作為正極活性物質層。 In the lithium ion capacitor, an electrode is used as a positive electrode layer: for example, an aluminum foil is used as a positive electrode current collector layer, and a mixture layer containing activated carbon is provided on the aluminum foil as a positive electrode active material layer.
又，使用如下電極作為負極層：使用例如銅箔作為負極集電體層，並於該銅箔上設置包含石墨之合劑層作為負極活性物質層；進而於該負極層中預摻雜鋰離子。 Further, an electrode is used as the negative electrode layer: for example, a copper foil is used as the negative electrode current collector layer, and a mixture layer containing graphite is provided as a negative electrode active material layer on the copper foil; and lithium ions are pre-doped in the negative electrode layer.
繼而，將正極層與負極層介隔陶瓷層及絕緣性接著層積層而形成積層體，並且例如將使1 mol/l之LiPF6溶解於碳 酸伸乙酯與碳酸二乙酯之混合溶劑中而成者用作電解液(非水電解液)，藉此可獲得鋰離子電容器。 Then, the positive electrode layer and the negative electrode layer are interposed between the ceramic layer and the insulating layer to form a laminate, and for example, 1 mol/l of LiPF 6 is dissolved in a mixed solvent of ethyl 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之各實施例，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等)、電解液之種類、外包材之構成或構造材料等，於發明之範圍內可施加各種應用、變形。 In addition, the present invention is not limited to the above-described respective embodiments, and the 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, and separator layer). Various types of applications and deformations can be applied 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 structure 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‧‧‧正極集合片材 20‧‧‧ positive collection sheet
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‧‧‧負極集合片材 40‧‧‧Negative collection sheet
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‧‧‧正極負極集合片材 51‧‧‧positive anode collection sheet
52‧‧‧集合片材積層體 52‧‧‧Collected sheet laminate
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‧‧‧基座部 70b‧‧‧Base section
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)之構成之前視剖面圖。 Fig. 1 is a front cross-sectional view 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之平面剖面圖。 Fig. 2 is a plan 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之一步驟中，在基材膜上形成有正極集電體層之狀態之圖，(a)為平面圖，(b)為前視剖面圖。 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 plan view. 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)為平面圖，(b)為前視剖面圖。 Fig. 4 is a view showing a state in which a positive electrode active material layer is formed on the positive electrode 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。 Fig. 5 is a view showing a state in which a separator layer is formed on the positive electrode collector layer shown in Fig. 4;
圖6(a)係表示藉由於圖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材之圖，圖6(b)係表示同樣地形成之負極集合片材之圖。 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. Figure.
圖7係表示使正極集合片材與負極集合片材相互對向而 配置之狀態之圖。 Figure 7 is a view showing that the positive electrode assembly sheet and the negative electrode assembly sheet are opposed to each other. A diagram of the status of the configuration.
圖8係表示藉由將正極集合片材與負極集合片材接合而形成之正負極集合片材之圖。 Fig. 8 is a view showing a positive and negative electrode assembly sheet formed by joining a positive electrode assembly sheet and a negative electrode assembly sheet.
圖9係表示使一對正負極集合片材相互對向而配置之狀態之圖。 Fig. 9 is a view showing a state in which a pair of positive and negative electrode assembly sheets are arranged to face each other.
圖10係表示接合一對正負極集合片材而形成之集合片材積層體之圖。 Fig. 10 is a view showing a laminated sheet laminate formed by joining a pair of positive and negative electrode assembly sheets.
圖11係表示使圖10之集合片材積層體與正負極集合片材相對向而配置之狀態之圖。 Fig. 11 is a view showing a state in which the collective sheet laminate of Fig. 10 is placed facing the positive and negative electrode sheets.
圖12係表示接合圖10之集合片材積層體與正負極集合片材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 aggregate sheet laminate of Fig. 10 and the positive and negative electrode assembly sheets.
圖13係模式性地表示本發明之實施例中製作之積層集合體之構成之前視剖面圖。 Fig. 13 is a front cross-sectional view schematically showing the constitution of a laminated assembly produced in an embodiment of the present invention.
圖14係說明分割圖13之積層集合體之步驟之前視剖面圖。 Fig. 14 is a front cross-sectional view showing the steps of dividing the laminated body 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之前視剖面圖。 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 in 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‧‧‧基座部 70b‧‧‧Base section
A‧‧‧電雙層電容器 A‧‧‧Electrical double layer capacitor
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