JP2013168373A - Separator, electrochemical element, and method for producing separator - Google Patents

Separator, electrochemical element, and method for producing separator Download PDF

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JP2013168373A
JP2013168373A JP2013058624A JP2013058624A JP2013168373A JP 2013168373 A JP2013168373 A JP 2013168373A JP 2013058624 A JP2013058624 A JP 2013058624A JP 2013058624 A JP2013058624 A JP 2013058624A JP 2013168373 A JP2013168373 A JP 2013168373A
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separator
binder
layer
porous
slurry
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JP2013168373A5 (en
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Atsushi Nishino
西野　　敦
Mutsuhiro Ito
睦弘 伊藤
Akihiro Serizawa
明洋 芹澤
Mitsuteru Ogawa
光輝 小川
Tatsuya Asano
達也 浅野
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Fuji Silysia Chemical Ltd
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Fuji Silysia Chemical Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/52—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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H01M50/437—Glass
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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

Abstract

PROBLEM TO BE SOLVED: To provide a separator whose warpage can be suppressed, a method for producing a separator, and an electrochemical element provided with the separator.SOLUTION: The separator includes a porous layer and a coating layer which contains at least one selected from a group consisting of porous silica, activated carbon, and zeolite and is formed on one surface or both surfaces of the porous layer.

Description

本発明は、セパレータ、電気化学素子、及びセパレータの製造方法に関する。   The present invention relates to a separator, an electrochemical element, and a method for manufacturing the separator.

従来、第１世代のセパレータとして、オレフィン系樹脂、ＰＤＦ系樹脂、ＰＡＮ系樹脂、ＰＭＭＡ系樹脂、及びウレタン系樹脂のいずれかから成るセバレータが知られている。このセパレータは、携帯電話、デジタルカメラのような小型携帯機器用の二次電池や電気二重層キャパシタ（以下、ＥＤＬＣと略す）に用いられる。なお、二次電池の外観は、小型角形であった。   Conventionally, as a first generation separator, a segregator made of any one of an olefin resin, a PDF resin, a PAN resin, a PMMA resin, and a urethane resin is known. This separator is used for a secondary battery or an electric double layer capacitor (hereinafter abbreviated as EDLC) for small portable devices such as mobile phones and digital cameras. The appearance of the secondary battery was a small square.

また、加工性、及び価格の観点から、オレフィン系樹脂（特に、超高分子量のポリプロピレン（ＰＰ）やポリエチレン（ＰＥ））と微粒子状のアルミナやシリカとを混練し、一軸または二軸延伸法を用いて生産されたセパレータが実用化されてきた（特許文献１、２）。   Also, from the viewpoint of processability and cost, an olefin resin (particularly, ultrahigh molecular weight polypropylene (PP) or polyethylene (PE)) and fine particulate alumina or silica are kneaded, and a uniaxial or biaxial stretching method is performed. Separators produced using these have been put into practical use (Patent Documents 1 and 2).

図７Ａ、図７Ｂ、及び図７Ｃは、代表的な第１世代のセパレータの構造を示す。図７Ａは、ＰＰの単層１０１から成るセパレータを示す。図７Ｂは、ＰＥの単層１０３から成るセパレータを示す。図７Ｃは、ＰＰの層１０５、ＰＥの層１０７、及びＰＰの層１０９を積層したセパレータ１１１を示す。   7A, 7B, and 7C show the structure of a representative first generation separator. FIG. 7A shows a separator composed of a single layer 101 of PP. FIG. 7B shows a separator consisting of a single layer 103 of PE. FIG. 7C shows a separator 111 in which a PP layer 105, a PE layer 107, and a PP layer 109 are stacked.

第２世代のセパレータは、パソコン（ＰＣ）、電動工具、ロボット電源等を用途とする２次電池に使用される。なお、この二次電池は、１８６５０型や２６６５０型の中型捲同型、又は角形である。第２世代のセパレータを用いた二次電池は、第１世代を用いた二次電池よりも、高容量、高出力が要求される。また、高容量化にともない、充電時間の短縮化が要請される。さらに、二次電池の大型化により、一層の安全性が要請される。   Second generation separators are used in secondary batteries for applications such as personal computers (PCs), power tools, robot power supplies and the like. In addition, this secondary battery is a 18650 type, a 26650 type middle size homogenous type, or a square shape. A secondary battery using the second generation separator is required to have a higher capacity and higher output than a secondary battery using the first generation. In addition, as the capacity increases, it is required to shorten the charging time. Furthermore, further safety is required by increasing the size of the secondary battery.

上記の安全性を確保するために、セパレータにセラミック層を形成する方法が提案されている。例えば、図８Ａに示す構造は、セパレータ１１７、陽極１１９、陽極集電体１２１、陰極１２３、及び陰極集電体１２５から成り、セパレータ１１７において、セパレータの本体１１３の表面にアルミナの絶縁層（ＨＲＬ（ＨｅａｔＲｅｓｉｓｔａｎｃｅＬａｙｅｒ）層）１１５がコーティングにより形成されている。このＨＲＬ層１１５は、耐熱性絶縁機能と金属のデンドライト防止機能とを奏する（特許文献３、４）。この構造は、Ｐａｎａｓｏｎｉｃ（株）で開発され、実用化されたものである。   In order to ensure the safety, a method of forming a ceramic layer on the separator has been proposed. For example, the structure shown in FIG. 8A includes a separator 117, an anode 119, an anode current collector 121, a cathode 123, and a cathode current collector 125. In the separator 117, an alumina insulating layer (HRL) is formed on the surface of the separator body 113. (Heat Resistance Layer) layer 115 is formed by coating. The HRL layer 115 has a heat resistant insulating function and a metal dendrite preventing function (Patent Documents 3 and 4). This structure was developed and put to practical use by Panasonic Corporation.

また、図８Ｂに示す構造は、セパレータ１２７、陽極１２９、陽極集電体１３１、陰極１３３、及び陰極集電体１３５から成り、セパレータ１２７においては、セパレータの本体１３７の陽極側に、アルミナ等の無機微粒子（比表面積＝４〜６ｍ２／ｇ）をコーティングした層１３９を備えるとともに、陰極側に、板状の微粒子（７〜１０ｍ２／ｇ）をコーティングした層１４１を備える（特許文献５、６）。この構造は、日立マクセル（株）で開発製品化された構造である。 8B includes a separator 127, an anode 129, an anode current collector 131, a cathode 133, and a cathode current collector 135. In the separator 127, the anode side of the separator main body 137 is made of alumina or the like. A layer 139 coated with inorganic fine particles (specific surface area = 4 to 6 m 2 / g) is provided, and a layer 141 coated with plate-like fine particles (7 to 10 m 2 / g) is provided on the cathode side (Patent Document 5, 6). This structure is a structure developed by Hitachi Maxell, Ltd.

特許第４４５０４４２号公報Japanese Patent No. 4450442 特開１９９９−３１７２１２号公報JP 1999-317212 A 特許第４６５４７００号公報Japanese Patent No. 4654700 特開２００９−３２６６８号公報JP 2009-32668 A 特開２０１１−０６５８４９号公報JP 2011-065849 A 特開２０１１−０６５８５０号公報JP 2011-0665850 A

しかしながら、図７Ａに示すセパレータ１１７では、片面にＨＲＬ１１５をコーティングし、乾燥させるときに、セパレータ１１７が反ってしまうという問題が生じる。また、図８Ｂに示すセパレータ１２７でも、層１３９と層１４１とで組成が異なるため、セパレータ１２７が反ってしまうという問題が生じる。   However, the separator 117 shown in FIG. 7A has a problem that when the HRL 115 is coated on one side and dried, the separator 117 is warped. Further, the separator 127 shown in FIG. 8B also has a problem that the separator 127 is warped because the compositions of the layer 139 and the layer 141 are different.

本発明は、反りを抑制できるセパレータ、そのセパレータを備えた電気化学素子、及びセパレータの製造方法を提供することをその一側面とする。   One aspect of the present invention is to provide a separator capable of suppressing warpage, an electrochemical element including the separator, and a method for manufacturing the separator.

本発明のセパレータは、多孔質層と、多孔質シリカ、活性炭、及びゼオライトから成る群がら選ばれた１種以上を含み、前記多孔質層の片面又は両面に形成された被覆層と、を備えることを特徴とする。本発明のセパレータは、反りが生じにくい。   The separator of the present invention comprises a porous layer and a coating layer formed on one or both sides of the porous layer, including one or more selected from the group consisting of porous silica, activated carbon, and zeolite. It is characterized by. The separator of the present invention is less likely to warp.

本発明のセパレータの製造方法は、（Ａ）多孔質シリカ、活性炭、及びゼオライトから成る群がら選ばれた１種以上、（Ｂ）バインダー、（Ｃ）スラリー安定剤、及び（Ｄ）コーティング助剤を含むスラリーを、多孔質層の片面又は両面に塗布して被覆層を形成することを特徴とする。本発明のセパレータの製造方法によれば、反りが生じにくいセパレータを容易に製造することができる。   The separator manufacturing method of the present invention comprises (A) one or more selected from the group consisting of porous silica, activated carbon, and zeolite, (B) a binder, (C) a slurry stabilizer, and (D) a coating aid. The coating slurry is formed by applying the slurry to be contained on one or both sides of the porous layer. According to the separator manufacturing method of the present invention, it is possible to easily manufacture a separator that is unlikely to warp.

複合セパレータの構造を表す側断面図である。It is a sectional side view showing the structure of a composite separator. 複合セパレータの構造を表す側断面図である。It is a sectional side view showing the structure of a composite separator. セパレータの製造方法を表す説明図である。It is explanatory drawing showing the manufacturing method of a separator. コイン型ＥＤＬＣの構成を表す説明図である。It is explanatory drawing showing the structure of coin type | mold EDLC. 捲同型ＥＤＬＣの構成を表す説明図である。It is explanatory drawing showing the structure of the same type EDLC. リチウムイオン電池の構成を表す説明図である。It is explanatory drawing showing the structure of a lithium ion battery. 図７Ａ、図７Ｂ、及び図７Ｃは、第１世代のセパレータの構成を表す側断面図である。7A, 7B, and 7C are cross-sectional side views showing the configuration of the first generation separator. 図８Ａ、及び図８Ｂは、第２世代のセパレータの構成を表す側断面図である。8A and 8B are side sectional views showing the configuration of the second generation separator.

本発明の実施形態を説明する。本発明における多孔質層としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリアクリロニトリル樹脂、フッ化ビニリデン樹脂、アクリル樹脂、及びウレタン樹脂のうちのいずれかから成るものが挙げられる。特許文献１、２に記載されているオレフィンセパレータを多孔質層としてもよい。また、市販の微多孔質セパレータを多孔質層としてもよい。   An embodiment of the present invention will be described. Examples of the porous layer in the present invention include those composed of any one of polyethylene resin, polypropylene resin, polyacrylonitrile resin, vinylidene fluoride resin, acrylic resin, and urethane resin. The olefin separator described in Patent Documents 1 and 2 may be a porous layer. A commercially available microporous separator may be used as the porous layer.

また、他の多孔質層として、ポリオレフィン系樹脂（例えば超高分子量のポリオレフィン系樹脂）にアルミナ（Ａｌ２Ｏ３）やシリカ（ＳｉＯ２）を添加し、一軸または二軸延伸法で得られるものが挙げられる。 Further, as another porous layer, one obtained by adding uniaxial or biaxial stretching method by adding alumina (Al 2 O 3 ) or silica (SiO 2 ) to polyolefin resin (for example, ultra-high molecular weight polyolefin resin). Is mentioned.

多孔質層の膜厚は、１０〜１１０μｍの範囲が好適である。特に、ＥＤＬＣに用いるセパレータの場合は、耐熱性を高めるため、４０〜１１０μｍの膜厚が好ましい。また、ポリオレフィン系樹脂から成る多孔質層の場合は、膜厚が８〜２０μｍであり、多孔度が高いことが好ましい。こうすることにより、抵抗を小さくすることができる。   The thickness of the porous layer is preferably in the range of 10 to 110 μm. In particular, in the case of a separator used for EDLC, a film thickness of 40 to 110 μm is preferable in order to improve heat resistance. Moreover, in the case of the porous layer which consists of polyolefin resin, a film thickness is 8-20 micrometers and it is preferable that a porosity is high. By doing so, the resistance can be reduced.

本発明における被覆層は、多孔質シリカ、活性炭、及びゼオライトから成る群がら選ばれた１種以上を含む。多孔質シリカとしては、電気化学素子の実用温度範囲において結晶型がアモルファスであり、多孔質であるものが好ましい。   The coating layer in the present invention contains one or more selected from the group consisting of porous silica, activated carbon, and zeolite. As the porous silica, those having an amorphous crystal form and a porous structure in the practical temperature range of the electrochemical element are preferable.

被覆層は、セパレータを電気化学素子に適用した場合、多量の電解液を含浸できる。そのため、注液時間を短縮化し、濃度分極を減少させることができる。また、瞬時に急速充放電を行っても、デンドライトの成長を抑制できる。また、被覆層を備えることにより、セパレータの機械的強度が向上する。   The coating layer can be impregnated with a large amount of electrolyte when the separator is applied to an electrochemical element. Therefore, the time for injecting can be shortened and the concentration polarization can be reduced. Further, even if rapid charge / discharge is performed instantaneously, dendrite growth can be suppressed. Moreover, the mechanical strength of a separator improves by providing a coating layer.

また、被覆層を備えることにより、寸法収縮率が改善される（寸法安定性が向上する）。その結果、内部ショートを防止し、セパレータの機械的強度を改善することができる。
また、被覆層を備えることにより、浸液性が向上する。その結果、電解液が早く含浸し、コンベアースピードを向上することができる。 Moreover, by providing a coating layer, a dimensional shrinkage rate is improved (dimensional stability is improved). As a result, an internal short circuit can be prevented and the mechanical strength of the separator can be improved.
Moreover, immersion property improves by providing a coating layer. As a result, the electrolytic solution can be impregnated quickly, and the conveyor speed can be improved.

また、被覆層を備えることにより、デンドライトが改善される。その結果、安全性、信頼性、歩留まりが向上する。
また、被覆層を備えることにより、保液性が向上する。その結果、効率的な放電が可能になる。 Moreover, a dendrite is improved by providing a coating layer. As a result, safety, reliability, and yield are improved.
Moreover, liquid retention improves by providing a coating layer. As a result, efficient discharge becomes possible.

また、被覆層を備えることにより、耐熱性が向上する。その結果、急速充電特性が向上する。
被覆層の膜厚は、０．５〜５０μｍ（好ましくは３〜１５μｍ）の範囲が好ましい。０．５μｍ以上であることにより、被覆層を均一に形成しやすくなる。また、５０μｍ以下であることにより、被覆層に亀裂が生じにくくなる。セパレータを捲同型の電気化学素子に適用する場合は、膜厚が１５μｍ以下であることが好ましい。 Moreover, heat resistance improves by providing a coating layer. As a result, quick charge characteristics are improved.
The film thickness of the coating layer is preferably in the range of 0.5 to 50 μm (preferably 3 to 15 μm). By being 0.5 μm or more, it becomes easy to form a coating layer uniformly. Moreover, it becomes difficult to produce a crack in a coating layer because it is 50 micrometers or less. When the separator is applied to a homogeneous electrochemical device, the film thickness is preferably 15 μm or less.

被覆層は、多孔質層の片面に形成されていてもよいし、両面に形成されていてもよい。両面に形成すると、セパレータの反りを一層軽減することができる。
多孔質シリカの物性は、例えば、以下の範囲が好ましい。 The coating layer may be formed on one side of the porous layer, or may be formed on both sides. When formed on both sides, the warpage of the separator can be further reduced.
The physical properties of porous silica are preferably in the following range, for example.

平均粒子径：０．１〜８μｍ
比表面積：２５０〜８００ｍ２／ｇ
吸油量：５０〜３５０ｍｌ／１００ｇ
物性が上記の範囲内であることにより、本セパレータを適用した電気化学素子において、大電流の充放電や非接触瞬時充電が可能となる。また、平均粒子径が０．１μｍ以上であることにより、被覆層の形成に用いるスラリーにおけるスラリー安定剤の量が少なくて済む。また、平均粒子径が８μｍ以下であることにより、被覆層を均一化しやすくなる。 Average particle size: 0.1-8 μm
Specific surface area: 250-800 m 2 / g
Oil absorption: 50-350ml / 100g
When the physical properties are within the above range, the electrochemical device to which the separator is applied can charge and discharge a large current and contactless instantaneous charging. Further, when the average particle size is 0.1 μm or more, the amount of the slurry stabilizer in the slurry used for forming the coating layer can be reduced. Moreover, it becomes easy to make a coating layer uniform because an average particle diameter is 8 micrometers or less.

また、比表面積が２５０ｍ２／ｇ以上であることにより、本セパレータを電気化学素子に適用した場合、電解液含液量を多くすることができる。また、シリカの比表面積が８００ｍ２／ｇ以下であることにより、シリカの凝集粒子の機械的強度を高めることができる。その結果、充放電時におけるシリカ粒子の破壊を抑制できる。 Moreover, when this separator is applied to an electrochemical element because the specific surface area is 250 m 2 / g or more, the electrolyte solution content can be increased. In addition, when the specific surface area of silica is 800 m 2 / g or less, the mechanical strength of the aggregated particles of silica can be increased. As a result, it is possible to suppress the destruction of the silica particles during charging and discharging.

また、吸油量が５０ｍｌ／１００ｇ以上であることにより、本セパレータを電気化学素子に適用した場合、電解液含液量を多くすることができる。また、吸油量が３５０ｍｌ／１００ｇ以下であることにより、被覆層の機械的強度が向上する。   Moreover, when the amount of oil absorption is 50 ml / 100 g or more, when this separator is applied to an electrochemical element, the electrolyte solution content can be increased. Further, when the oil absorption is 350 ml / 100 g or less, the mechanical strength of the coating layer is improved.

なお、平均粒子径の測定、比表面積の測定、及び吸油量の測定は、それぞれ、以下のとおりである。
平均粒子径の測定：レーザ回折式粒度分布測定装置により測定
比表面積の測定：容量法（より詳しくは、ＪＩＳ Ｋ１１５０“シリカゲル試験方法”に準拠する方法）により測定
吸油量の測定：ＪＩＳ Ｋ５１０１−１３−１“顔料試験方法−第１３部吸油量”に準拠する方法により測定
本発明における導電層は、例えば、被覆層を構成する粒子の表面に形成することができる。例えば、被覆層を構成する粒子を、オキシチオフェン（ＥＤＯＴ）、ポリエチレンジオキシチオフエン（ＰＥＤＯＴ）、酸化インジウムスズ（ＩＴＯ）、ポリピロール、及びポリアニリンから選ばれた１種以上を含む塗料に含浸し、風乾、及び加熱乾燥（例えば１５０℃程度の温度での乾燥）を順次行うことで粒子の表面に導電層を形成できる。そして、導電層を備える粒子を用いて、被覆層を形成することができる。また、被覆層を形成した後、その上に導電層を積層してもよい。 In addition, the measurement of an average particle diameter, the measurement of a specific surface area, and the measurement of oil absorption amount are as follows, respectively.
Measurement of average particle diameter: measured by laser diffraction type particle size distribution measuring apparatus Measurement of specific surface area: measured by volume method (more specifically, a method based on JIS K1150 “silica gel test method”) Measurement of oil absorption: JIS K5101-13 Measurement by a method based on -1 “Pigment Test Method—Part 13 Oil Absorption” The conductive layer in the present invention can be formed on the surface of the particles constituting the coating layer, for example. For example, the particles constituting the coating layer are impregnated with a paint containing at least one selected from oxythiophene (EDOT), polyethylene dioxythiophene (PEDOT), indium tin oxide (ITO), polypyrrole, and polyaniline, A conductive layer can be formed on the surface of the particles by sequentially performing air drying and heat drying (for example, drying at a temperature of about 150 ° C.). And a coating layer can be formed using particle | grains provided with a conductive layer. Moreover, after forming a coating layer, you may laminate | stack a conductive layer on it.

導電層を形成する材料としては、例えば、ＥＤＯＴ、ＰＥＤＯＴ、ＩＴＯ、ポリピロール、及びポリアニリンから選ばれた１種以上が挙げられる。導電層は、被覆層の抵抗を、例えば、１０−１〜１０−２程度低くすることで、セパレータの静電気トラブルを軽減できる。なお、静電気トラブルとしては、静電気によってセパレータが延伸したり、断裂するトラブルが挙げられる。 Examples of the material for forming the conductive layer include one or more selected from EDOT, PEDOT, ITO, polypyrrole, and polyaniline. The conductive layer can reduce the static electricity trouble of the separator by reducing the resistance of the coating layer, for example, by about 10 −1 to 10 −2 . In addition, as a static electricity trouble, the trouble which a separator extends | stretches or tears by static electricity is mentioned.

本発明の電気化学素子としては、例えば、一次電池、二次電池、電気二重層キャパシタ（ＥＤＬＣ）、擬似電気二重層キャパシタ等が挙げられる。
本発明のセパレータは、例えば、（Ａ）多孔質シリカ、活性炭、及びゼオライトから成る群がら選ばれた１種以上、（Ｂ）バインダー、（Ｃ）スラリー安定剤、及び（Ｄ）コーティング助剤を含むスラリーを、多孔質層の片面又は両面に塗布して被覆層を形成することで製造できる。 Examples of the electrochemical element of the present invention include a primary battery, a secondary battery, an electric double layer capacitor (EDLC), and a pseudo electric double layer capacitor.
The separator of the present invention includes, for example, (A) one or more selected from the group consisting of porous silica, activated carbon, and zeolite, (B) a binder, (C) a slurry stabilizer, and (D) a coating aid. It can be manufactured by applying the slurry to one or both sides of the porous layer to form a coating layer.

バインダーとしては、例えば、オレフィン系バインダー、スチレンーブタジエンゴム系バインダー（ＳＢＲ系バインダー）、変性スチレンーブタジエンゴム系バインダー（変性ＳＢＲ系バインダー）、アタリレート系バインダー、セルロース系バインダー、弗素系バインダー（例えば、ＰＴＦＥ、ＰＶＤＦ等）、水系バインダー等が挙げられる。   Examples of the binder include an olefin binder, a styrene-butadiene rubber binder (SBR binder), a modified styrene-butadiene rubber binder (modified SBR binder), an acrylate binder, a cellulose binder, and a fluorine binder (for example, , PTFE, PVDF, etc.), aqueous binders and the like.

特に、水系バインダー又はオレフィン系バインダーである第１のバインダーと、スチレンーブタジエンゴム系バインダー、変性スチレンーブタジエンゴム系バインダー（例えばアクリルドープ型）、アタリレート系バインダー、セルロース系バインダー、ビニールピロリドン、及び弗素系バインダーから成る群がら選ばれた１種以上である第２のバインダーとの混合バインダーが好ましい。この混合バインダーを用いることにより、多孔質層に対するスラリーの濡れ性が向上し、また、多孔質層と被覆層との接着強度が向上する。   In particular, a first binder that is a water-based binder or an olefin-based binder, a styrene-butadiene rubber-based binder, a modified styrene-butadiene rubber-based binder (for example, an acrylic dope type), an acrylate binder, a cellulose binder, vinyl pyrrolidone, and A mixed binder with at least one second binder selected from the group consisting of fluorine binders is preferred. By using this mixed binder, the wettability of the slurry with respect to the porous layer is improved, and the adhesive strength between the porous layer and the coating layer is improved.

混合バインダーを用いる場合、第１のバインダーの配合量は、（Ａ）成分１００重量部に対し、０．５〜２．０重量部の範囲が好ましく、第２のバインダーの配合量は、２〜５重量部の範囲が好ましい。これらの範囲内であることにより、上述した混合バインダーの効果が一層顕著になる。   When the mixed binder is used, the blending amount of the first binder is preferably in the range of 0.5 to 2.0 parts by weight with respect to 100 parts by weight of the component (A), and the blending amount of the second binder is 2 to 2 parts. A range of 5 parts by weight is preferred. By being in these ranges, the effect of the mixed binder mentioned above becomes further remarkable.

また、アタリレート系バインダーを用いる場合、その配合量は、（Ａ）成分１００重量部に対し、２〜５重量部の範囲が好ましい。２重量部以上であることにより、被覆層の曲げ強度が向上する。また、５重量部以下であることにより、被覆層の注液含浸性が向上する。   Moreover, when using an atelate-type binder, the compounding quantity has the preferable range of 2-5 weight part with respect to 100 weight part of (A) component. By being 2 parts by weight or more, the bending strength of the coating layer is improved. Moreover, the liquid injection impregnation property of a coating layer improves by being 5 weight part or less.

スラリー安定剤としては、例えば、水溶性ポリマー、界面活性剤等が挙げられる。水溶性ポリマーとしては、ブロック型で、スルホン化率が５〜３０％のものが好ましい。すなわち、スルホン酸系水溶性ポリマーが好ましい。界面活性剤としては、弗素系のノニオン界面活性剤が好ましい。スラリーにスラリー安定剤を配合することにより、スラリーの調製が容易になり、スラリー寿命が延びる。   Examples of the slurry stabilizer include a water-soluble polymer and a surfactant. The water-soluble polymer is preferably a block type having a sulfonation rate of 5 to 30%. That is, a sulfonic acid-based water-soluble polymer is preferable. As the surfactant, a fluorine-based nonionic surfactant is preferable. By adding a slurry stabilizer to the slurry, the preparation of the slurry is facilitated and the life of the slurry is extended.

コーティング助剤としては、例えば、Ｎａ中和ＣＭＣ、又はアンモニア中和ＣＭＣ等が挙げられる。コーティング助剤を含むことにより、スラリーの安定性、被覆層の均一性が向上する。また、セパレータを電池やＥＤＬＣに適用した場合、それらの寿命が向上する。   Examples of the coating aid include Na-neutralized CMC and ammonia-neutralized CMC. By including a coating aid, the stability of the slurry and the uniformity of the coating layer are improved. Moreover, when a separator is applied to a battery or EDLC, those lifetimes improve.

本発明のセパレータは、例えば、図１に示す複合セパレータ１に適用することができる。複合セパレータ１は、セパレータ３と、陽極５と、陰極７とから構成される。セパレータ３は、多孔質層９と、その両側の被覆層１１、１３を備える。この複合セパレータ１は、種々の電気化学素子（例えば、一次電池、二次電池、ＥＤＬＣ等）に適用できる。   The separator of the present invention can be applied to, for example, the composite separator 1 shown in FIG. The composite separator 1 includes a separator 3, an anode 5, and a cathode 7. The separator 3 includes a porous layer 9 and coating layers 11 and 13 on both sides thereof. The composite separator 1 can be applied to various electrochemical elements (for example, a primary battery, a secondary battery, an EDLC, etc.).

また、本発明のセパレータは、例えば、図２に示す複合セパレータ２１に適用することができる。複合セパレータ２１は、セパレータ２３と、陽極２５と、陰極２７とから構成される。セパレータ２３は、多孔質層２９と、その両側の被覆層３１、３３と、さらにその外側の導電層３５、３７を備える。この複合セパレータ２１は、種々の電気化学素子（例えば、一次電池、二次電池、ＥＤＬＣ等）に適用できる。
実施例１
１．スラリーの調製
（１）スラリーＳ１
スラリーＳ１の製造方法を、図３に基づいて説明する。まず、多孔質シリカ（ＳｉＯ２）を乾式混合し（Ｐ１）、次に、水とＣＭＣ（コーティング助剤）とを加えて湿式混合し（Ｐ２）、混練する（Ｐ３）。その後、オレフィン系バインダー（図３ではＢｉｎｄｅｒ１と表記）、変性ＳＢＲ系バインダー（図３ではＢｉｎｄｅｒ２と表記）、及びスラリー安定剤を添加し、スラリーを得る（Ｐ４）。 Moreover, the separator of this invention is applicable to the composite separator 21 shown in FIG. 2, for example. The composite separator 21 includes a separator 23, an anode 25, and a cathode 27. The separator 23 includes a porous layer 29, coating layers 31 and 33 on both sides thereof, and conductive layers 35 and 37 on the outside thereof. The composite separator 21 can be applied to various electrochemical elements (for example, a primary battery, a secondary battery, an EDLC, etc.).
Example 1
1. Preparation of slurry (1) Slurry S1
The manufacturing method of slurry S1 is demonstrated based on FIG. First, porous silica (SiO 2 ) is dry-mixed (P1), then water and CMC (coating aid) are added, wet-mixed (P2), and kneaded (P3). Thereafter, an olefin-based binder (indicated as Binder 1 in FIG. 3), a modified SBR-based binder (indicated as Binder 2 in FIG. 3), and a slurry stabilizer are added to obtain a slurry (P4).

ここで、上記の配合成分は、具体的には、それぞれ以下のものである。
ＣＭＣ：ダイセルファインケム（株）製 ＤＮ−８００Ｈ
オレフィン系バインダー：三井化学（株）製 ケミパールＳ１００
変性ＳＢＲ系バインダー：ＪＳＲ株式会社製 ＳＢラテックス
スラリー安定剤：水溶性ポリマー（ＪＳＲ株式会社製の界面活性剤）
また、使用した多孔質シリカの物性は、それぞれ以下のものである。 Here, the above-described blending components are specifically as follows.
CMC: DN-800H manufactured by Daicel FineChem Co., Ltd.
Olefin-based binder: Chemipearl S100 manufactured by Mitsui Chemicals, Inc.
Modified SBR binder: SB latex manufactured by JSR Corporation Slurry stabilizer: Water-soluble polymer (surfactant manufactured by JSR Corporation)
The physical properties of the used porous silica are as follows.

平均粒子径：２．７μｍ
比表面積：３００ｍ２／ｇ
吸油量：３３０ｍｌ／１００ｇ
また、スラリーＳ１における各成分の配合量（単位は重量部）を表１に示す。
［表１］
Average particle diameter: 2.7 μm
Specific surface area: 300 m 2 / g
Oil absorption: 330ml / 100g
In addition, Table 1 shows the amount of each component (unit: parts by weight) in the slurry S1.
[Table 1]

（２）スラリーＳ２
まず、スラリーＳ１の調製で用いたものと同一の多孔質シリカの粒子表面に前もってＥＤＯＴから成る導電層を形成し、その後は、スラリーＳ１の場合と同様の工程により、スラリーＳ２を調製した。 (2) Slurry S2
First, a conductive layer made of EDOT was formed in advance on the same porous silica particle surface as used in the preparation of the slurry S1, and thereafter, a slurry S2 was prepared by the same process as that of the slurry S1.

多孔質シリカの表面にＥＤＯＴから成る導電層を形成する方法は以下のとおりである。すなわち、多孔質シリカをＥＤＯＴ導電性塗料に含浸させ、風乾により表面乾燥後、さらに１５０℃で乾燥することで、多孔質シリカの表面にＥＤＯＴから成る導電層を形成する。この導電層により、多孔質シリカは、静電気除去機能を有する。   A method of forming a conductive layer made of EDOT on the surface of porous silica is as follows. That is, EDOT conductive paint is impregnated with porous silica, surface-dried by air drying, and further dried at 150 ° C. to form a conductive layer made of EDOT on the surface of the porous silica. Due to this conductive layer, the porous silica has a static electricity removing function.

多孔質シリカの表面に存在するＥＤＯＴの量は、多孔質シリカ１００重量部に対し、３重量部である。
（３）スラリーＳ３
基本的にはスラリーＳ１の場合と同様の方法であるが、多孔質シリカの代わりに比表面積７００ｍ２／ｇである同量の椰子殻活性炭を用いてスラリーＳ３を調製した。
（４）スラリーＳ４
基本的にはスラリーＳ１の場合と同様の方法であるが、多孔質シリカの代わりに同量の合成ゼオライトを用いてスラリーＳ３を調製した。
２．セパレータの製造
市販のＰＰ樹脂から、延伸法を用いて、厚さ１５μｍのフィルムと、厚さ２５μｍのフィルムとを製造した。このフィルムは微多孔性である。このフィルムを多孔質層として、その両側に、ブレードコーティング法でスラリーを塗布（Ｐ５）、乾燥して厚さ３μｍの被覆層を形成し（Ｐ６）、セパレータを製造した（Ｐ７）（図３参照）。 The amount of EDOT present on the surface of the porous silica is 3 parts by weight with respect to 100 parts by weight of the porous silica.
(3) Slurry S3
Basically, the method was the same as in the case of the slurry S1, but slurry S3 was prepared using the same amount of coconut shell activated carbon having a specific surface area of 700 m 2 / g instead of porous silica.
(4) Slurry S4
The method is basically the same as in the case of the slurry S1, but the slurry S3 was prepared using the same amount of synthetic zeolite instead of the porous silica.
2. Manufacture of Separator A film having a thickness of 15 μm and a film having a thickness of 25 μm were manufactured from a commercially available PP resin using a stretching method. This film is microporous. Using this film as a porous layer, slurry was applied to both sides thereof by a blade coating method (P5) and dried to form a coating layer having a thickness of 3 μm (P6), thereby producing a separator (P7) (see FIG. 3). ).

上記の製造方法において、多孔質層の膜厚（１５μｍ又は２５μｍ）、及び塗布するスラリーの種類（Ｓ１〜Ｓ４）を変えて、表２に示すＥ１〜Ｅ６までの６種類のセパレータを製造した。Ｅ１、Ｅ２についてはスラリーＳ１を使用し、Ｅ３、Ｅ４についてはスラリーＳ２を使用し、Ｅ５についてはスラリーＳ３を使用し、Ｅ６についてはスラリーＳ４を使用した。   In the production method described above, six types of separators E1 to E6 shown in Table 2 were produced by changing the thickness of the porous layer (15 μm or 25 μm) and the type of slurry to be applied (S1 to S4). Slurry S1 was used for E1 and E2, slurry S2 was used for E3 and E4, slurry S3 was used for E5, and slurry S4 was used for E6.

また、スラリーを塗布しない厚さ１５μｍのフィルムをセパレータＲ１とし、スラリーを塗布しない厚さ２５μｍのフィルムをセパレータＲ２とした。
［表２］
Further, a film having a thickness of 15 μm without applying slurry was designated as separator R1, and a film having a thickness of 25 μm without applying slurry was designated as separator R2.
[Table 2]

３．セパレータの評価
（１）ガーレー値
ＪＩＳ Ｐ８１１７に準拠して、各セパレータのガーレー値（通気度）を測定した。その結果を上記表２に示す。セパレータＥ１〜Ｅ６の通気度は、被覆層を形成しても殆ど低下していないことが確認できた。
（２）熱風温度での収縮率
各セパレータに熱風を１時間吹きかける処理を行い、処理前に状態に対する収縮率（％）を測定した。測定は、熱風の温度が１２０℃の場合と、１５０℃の場合とのそれぞれについて行った。測定結果を上記表２に示す。セパレータＥ１〜Ｅ６は、セパレータＲ１、Ｒ２に比べて、収縮率が小さかった。このことから、セパレータＥ１〜Ｅ６は、反りにくいことが確認できた。
（３）ＥＭＩＢＦ４の２μｍ含浸時間
粘度の高いイオン液体（ＥＭＩＢＦ４）を各セパレータの上に２μｍ滴下し、そのイオン液体がセパレータ表面に拡散するまでの時間（ｓｅｃ）を測定した。その結果を上記表２に示す。セパレータＥ１〜Ｅ６の場合は、短時間でイオン液体が拡散した。このことから、セパレータＥ１〜Ｅ６は、液体（例えば電解液）に対する含浸性が高いことが確認できた。
（４）−６５℃静電気防止特性
露点−６５℃のドライルーム内において、帯電試験を実施し、静電気防止特性を評価した。その評価基準は以下のとおりである。 3. Evaluation of Separator (1) Gurley Value Based on JIS P8117, the Gurley value (air permeability) of each separator was measured. The results are shown in Table 2 above. It was confirmed that the air permeability of the separators E1 to E6 hardly decreased even when the coating layer was formed.
(2) Shrinkage rate at hot air temperature A process of blowing hot air to each separator for 1 hour was performed, and the shrinkage rate (%) with respect to the state was measured before the treatment. The measurement was performed for each of the cases where the temperature of the hot air was 120 ° C and 150 ° C. The measurement results are shown in Table 2 above. The separators E1 to E6 had a smaller shrinkage rate than the separators R1 and R2. From this, it was confirmed that the separators E1 to E6 are difficult to warp.
(3) 2 μm impregnation time of EMIBF4 2 μm of a highly viscous ionic liquid (EMIBF4) was dropped on each separator, and the time (sec) until the ionic liquid diffused on the separator surface was measured. The results are shown in Table 2 above. In the case of separators E1 to E6, the ionic liquid diffused in a short time. From this, it has confirmed that the separators E1-E6 had high impregnation property with respect to a liquid (for example, electrolyte solution).
(4) Antistatic property at −65 ° C. In a dry room with a dew point of −65 ° C., a charging test was performed to evaluate the antistatic property. The evaluation criteria are as follows.

◎：帯電なし
○：わずかに帯電
×：帯電有り
評価結果を上記表２に示す。セパレータＥ１〜Ｅ６は、静電気を生じにくいことが確認できた。この特性は、セパレータを量産機械に適用した場合に有用である。すなわち、セパレータ、及びそれを備えた電気化学素子の製造工程において、静電気の発生を防止することができる。
実施例２
１．ＥＤＬＣの構成
（１）コイン型ＥＤＬＣ３９の構成
コイン型ＥＤＬＣ３９の構成を図４に基づいて説明する。コイン型ＥＤＬＣ３９は、直径４．８ｍｍ、厚さ１．４ｍｍのコイン形状を有する。コイン型ＥＤＬＣ３９は、セパレータ４１と、陽極４３と、陰極４５とから成る積層構造を有する。さらに、セパレータ４１は、多孔質層４７と、その両側の被覆層４９、５１を備える。多孔質層４７は、耐熱性仕様の微多孔性ＰＰフィルムから成る。 A: Not charged O: Slightly charged X: Charged Evaluation results are shown in Table 2 above. It was confirmed that the separators E1 to E6 hardly generate static electricity. This characteristic is useful when the separator is applied to a mass production machine. That is, it is possible to prevent the generation of static electricity in the manufacturing process of the separator and the electrochemical device including the separator.
Example 2
1. Configuration of EDLC (1) Configuration of Coin-type EDLC 39 The configuration of the coin-type EDLC 39 will be described with reference to FIG. The coin-type EDLC 39 has a coin shape with a diameter of 4.8 mm and a thickness of 1.4 mm. The coin-type EDLC 39 has a laminated structure including a separator 41, an anode 43, and a cathode 45. Further, the separator 41 includes a porous layer 47 and coating layers 49 and 51 on both sides thereof. The porous layer 47 is made of a heat-resistant microporous PP film.

被覆層４９、５１は、多孔質層４７の表面にスラリーＳ１を塗布、乾燥することによって形成した。また、陽極４３及び陰極４５は、活性炭、アセチレンブラック、バインダー、及びＰＴＦＥ粉末から成る組成物を５００μｍ厚にシート成型し、所定の形状に打ち抜く方法で作成した。電解液には、ＥＭＩＢＦ４の１００％原液を用いた。   The coating layers 49 and 51 were formed by applying and drying the slurry S1 on the surface of the porous layer 47. The anode 43 and the cathode 45 were prepared by a method in which a composition comprising activated carbon, acetylene black, a binder, and PTFE powder was formed into a sheet having a thickness of 500 μm and punched into a predetermined shape. As the electrolytic solution, a 100% stock solution of EMIBF4 was used.

多孔質層４７の膜厚、及び被覆層４９、５１の膜厚を変えて、表３に示すＥ１１〜Ｅ１４のコイン型ＥＤＬＣ３９を製造した。Ｅ１１〜Ｅ１４のコイン型ＥＤＬＣ３９は、４１４型面実装キャパシタである。   The coin-type EDLC 39 of E11 to E14 shown in Table 3 was manufactured by changing the film thickness of the porous layer 47 and the film thicknesses of the coating layers 49 and 51. The coin type EDLC 39 of E11 to E14 is a 414 type surface mount capacitor.

また、被覆層４９、５１を形成せずに、その他の点はＥ１１〜Ｅ１４のコイン型ＥＤＬＣ３９と同様にして、Ｒ１１、Ｒ１２のコイン型ＥＤＬＣを製造した。
［表３］
Further, without forming the coating layers 49 and 51, the coin-type EDLCs R11 and R12 were manufactured in the same manner as the coin-type EDLC 39 of E11 to E14.
[Table 3]

（２）捲同型ＥＤＬＣ５３の構成
捲同型ＥＤＬＣ５３の構成を図５に示す。捲同型ＥＤＬＣ５３は、直径１８ｍｍ、長さ４０ｍｍの円筒形状を有するキャパシタである。捲同型ＥＤＬＣ５３は、２つのセパレータ５５と、陽極５７と、陰極５９とを積層したシートを捲き回した構造を有する。さらに、それぞれのセパレータ５５は、多孔質層６１と、その両側の被覆層６３、６５を備える。多孔質層６１は、耐熱性仕様の微多孔性ＰＰフィルムから成る。 (2) Configuration of the homogeneous EDLC 53 The configuration of the homogeneous EDLC 53 is shown in FIG. The isomorphous EDLC 53 is a capacitor having a cylindrical shape with a diameter of 18 mm and a length of 40 mm. The homogeneous EDLC 53 has a structure in which a sheet in which two separators 55, an anode 57, and a cathode 59 are laminated is wound. Further, each separator 55 includes a porous layer 61 and coating layers 63 and 65 on both sides thereof. The porous layer 61 is made of a heat-resistant microporous PP film.

被覆層６３、６５は、多孔質層６１の表面にスラリーＳ１を塗布、乾燥することで形成した。また、陽極５７及び陰極５９は、活性炭、アセチレンブラック、バインダー、及びＰＴＦＥ粉末から成る組成物を５００μｍ厚にシート成型し、所定の形状に打ち抜く方法で作成した。電解液には、ＥＭＩＢＦ４の１００％原液を用いた。   The coating layers 63 and 65 were formed by applying and drying the slurry S1 on the surface of the porous layer 61. The anode 57 and the cathode 59 were prepared by a method in which a composition comprising activated carbon, acetylene black, a binder, and PTFE powder was formed into a sheet having a thickness of 500 μm and punched into a predetermined shape. As the electrolytic solution, a 100% stock solution of EMIBF4 was used.

多孔質層６１の膜厚、及び被覆層６３、６５の膜厚を変えて、表４に示すＥ１５〜Ｅ１８の捲同型ＥＤＬＣ５３を製造した。Ｅ１５〜Ｅ１８の捲同型ＥＤＬＣ５３は、１８４０型である。   By changing the film thickness of the porous layer 61 and the film thicknesses of the coating layers 63 and 65, E15 to E18 homozygous EDLCs 53 shown in Table 4 were produced. The homomorphic EDLC 53 of E15 to E18 is the 1840 type.

また、被覆層６３、６５を形成せずに、その他の点はＥ１５〜Ｅ１８の捲同型ＥＤＬＣ５３と同様にして、Ｒ１３、Ｒ１４の捲同型ＥＤＬＣを製造した。
［表４］
Also, the coating layers 63 and 65 were not formed, and the other points were manufactured in the same manner as the E15 to E18 homomorphic EDLC 53, and the R13 and R14 homomorphic EDLCs were produced.
[Table 4]

２．ＥＤＬＣの評価
各ＥＤＬＣについて、イオン液体含浸性、ＥＳＲ、及び漏液性を評価した。
ここで、イオン液体含浸性の評価方法は、セパレータにＥＭＩＢＦ４電解液５μＬを滴下し、染み込むまでの時間を測定する方法である。染み込むまでの時間が最も短いものから、◎、○、△、×と評価した。 2. Evaluation of EDLC Each EDLC was evaluated for ionic liquid impregnation, ESR, and liquid leakage.
Here, the evaluation method of the ionic liquid impregnation property is a method in which 5 μL of EMIBF4 electrolyte solution is dropped into the separator and the time until the soaking is measured is measured. The samples with the shortest time until soaking were evaluated as ◎, ○, Δ, and ×.

ＥＳＲ（等価直列抵抗）は、電池試料のインピーダンス周波数特性により評価した。
漏液性の評価方法は、コイン型ＥＤＬＣの場合は、１００個のコイン型ＥＤＬＣを２６０℃の温度環境下に１０ｓｅｃさらし、電解液が漏洩したものの個数を求める方法である。また、捲同型ＥＤＬＣの場合は、１００個の捲同型ＥＤＬＣを８０℃の温度環境下に２００時間保持し、電解液の漏れが生じるか、本体に膨れが生じたものの個数を求める方法である。 ESR (equivalent series resistance) was evaluated by the impedance frequency characteristic of the battery sample.
In the case of coin-type EDLC, the liquid leakage evaluation method is a method in which 100 coin-type EDLCs are exposed to a temperature environment of 260 ° C. for 10 seconds, and the number of leaked electrolytes is obtained. In the case of the homozygous EDLC, 100 homozygous EDLCs are held in a temperature environment of 80 ° C. for 200 hours, and the number of electrolytes leaking or swelling of the main body is obtained.

評価結果を上記表３、及び上記表４に示す。Ｅ１１〜Ｅ１８のＥＤＬＣは、イオン液体含浸性、ＥＳＲ、及び漏液性において優れていることが確認できた。
実施例３
１．リチウムイオン電池６７の構成
リチウムイオン電池６７の構成を図６に示す。リチウムイオン電池６７は、直径１８ｍｍ、長さ６５ｍｍの円筒形状を有する電池である。 The evaluation results are shown in Table 3 and Table 4. It was confirmed that the EDLCs of E11 to E18 were excellent in ionic liquid impregnation property, ESR, and liquid leakage property.
Example 3
1. Configuration of Lithium Ion Battery 67 The configuration of the lithium ion battery 67 is shown in FIG. The lithium ion battery 67 is a battery having a cylindrical shape with a diameter of 18 mm and a length of 65 mm.

リチウムイオン電池６７は、２つのセパレータ６９と、陽極７１と、陰極７３とを積層したシートを捲き回した構造を有する。さらに、それぞれのセパレータ６９は、多孔質層７５と、その両側の被覆層７７、７９と、さらにその外側の導電層８１、８３を備える。多孔質層７５は、耐熱性仕様の微多孔性ＰＰフィルムから成る。   The lithium ion battery 67 has a structure in which a sheet in which two separators 69, an anode 71, and a cathode 73 are stacked is rolled. Further, each separator 69 includes a porous layer 75, coating layers 77 and 79 on both sides thereof, and conductive layers 81 and 83 on the outside thereof. The porous layer 75 is made of a microporous PP film having heat resistance specifications.

被覆層７７、７９は、多孔質層７５の表面にスラリーＳ１を塗布、乾燥することで形成した。また、導電層８１、８３は、ＥＤＯＴを含む塗布液を塗布、乾燥することで形成した。また、陽極７１は、Ａｌ集電体上に公知の方法で形成されたＬｉＣｏＯｘである。また、陰極７３は、Ｃｕ箔集電体に人造黒鉛から成る陰極スラリーを塗布、乾燥して形成したものである。電解液には、濃度１．２ｍｏｌ／ＬのＬｉＰＦ６（溶媒はＥＭＣ）を用いた。 The coating layers 77 and 79 were formed by applying and drying the slurry S1 on the surface of the porous layer 75. The conductive layers 81 and 83 were formed by applying and drying a coating solution containing EDOT. The anode 71 is LiCoOx formed on the Al current collector by a known method. The cathode 73 is formed by applying and drying a cathode slurry made of artificial graphite on a Cu foil current collector. LiPF 6 (solvent is EMC) having a concentration of 1.2 mol / L was used as the electrolytic solution.

多孔質層７５の膜厚、及び被覆層７７、７９の膜厚を変えて、表５に示すＥ２１〜Ｅ２４のリチウムイオン電池６７を製造した。このリチウムイオン電池６７は、１８６５０）型円筒型リチウムイオン電池である。
［表５］
E21 to E24 lithium ion batteries 67 shown in Table 5 were manufactured by changing the thickness of the porous layer 75 and the thicknesses of the coating layers 77 and 79. This lithium ion battery 67 is a 18650) type cylindrical lithium ion battery.
[Table 5]

また、被覆層７７、７９を形成せずに、その他の点はＥ２１〜Ｅ２４のリチウムイオン電池６７と同様にして、Ｒ２１、Ｒ２２のリチウムイオン電池を製造した。
２．リチウムイオン電池の評価
各リチウムイオン電池について、電解液含浸性、膨れ一短絡個数を評価した。 In addition, R21 and R22 lithium ion batteries were manufactured in the same manner as the E21 to E24 lithium ion batteries 67 without forming the covering layers 77 and 79.
2. Evaluation of Lithium Ion Battery For each lithium ion battery, the electrolyte impregnation property and the number of blisters and short circuits were evaluated.

ここで、電解液含浸性の評価方法は、セパレータにＥＭＩＢＦ４電解液５μＬを滴下し、染み込むまでの時間を測定する方法である。染み込むまでの時間が最も短いものから、◎、○、△、×と評価した。   Here, the electrolytic solution impregnation evaluation method is a method in which 5 μL of EMIBF4 electrolytic solution is dropped into the separator and the time until the soaking is measured is measured. The samples with the shortest time until soaking were evaluated as ◎, ○, Δ, and ×.

膨れ一短絡個数の評価方法は、１００個のリチウムイオン電池を６０℃の温度環境下で２００時間保持し、電池本体が膨れたもの、又は再充電できなくなったものの個数を求める方法である。   The evaluation method of the number of blisters and short circuits is a method in which 100 lithium ion batteries are held in a temperature environment of 60 ° C. for 200 hours, and the number of battery bodies that swell or cannot be recharged is obtained.

評価結果を上記表４に示す。Ｅ１１〜Ｅ１８のＥＤＬＣは、電解液含浸性において優れ、膨れや短絡が生じにくいことが確認できた。
電解液含浸性が優れることにより、リチウムイオン電池の製造において、濃厚電解液の注入が容易になる。また、電解液を電極近傍に豊富に含浸することができるので、リチウムイオン電池が低抵抗化し、また、デンドライト形成を防止することができる。 The evaluation results are shown in Table 4 above. It was confirmed that the EDLCs of E11 to E18 were excellent in electrolytic solution impregnation property and were less likely to swell or short-circuit.
The excellent electrolytic solution impregnation property facilitates the injection of the concentrated electrolytic solution in the manufacture of lithium ion batteries. In addition, since the electrolyte solution can be impregnated in the vicinity of the electrode, the resistance of the lithium ion battery can be reduced and dendrite formation can be prevented.

１、２１…複合セパレータ、３、２３、４１、５５、６９…セパレータ、５、２５、４３
、５７、７１…陽極、７、２７、４５、５９、７３…陰極、９、２９、４７、６１、７５
…多孔質層、１１、１３、３１、３３、４９、５１、６３、６５、７７、７９…被覆層、
３５、３７、８１、８３…導電層、３９…コイン型ＥＤＬＣ、５３…捲同型ＥＤＬＣ、６
７…リチウムイオン電池 1, 21 ... Composite separator, 3, 23, 41, 55, 69 ... Separator, 5, 25, 43
57, 71 ... anode, 7, 27, 45, 59, 73 ... cathode, 9, 29, 47, 61, 75
... porous layer, 11, 13, 31, 33, 49, 51, 63, 65, 77, 79 ... coating layer,
35, 37, 81, 83 ... conductive layer, 39 ... coin-type EDLC, 53 ... homogeneous EDLC, 6
7 ... Lithium ion battery

Claims (12)

多孔質層と、
多孔質シリカ、活性炭、及びゼオライトから成る群がら選ばれた１種以上を含み、前記多
孔質層の片面又は両面に形成された被覆層と、を備えることを特徴とするセパレータ。 A porous layer;
A separator comprising one or more selected from the group consisting of porous silica, activated carbon, and zeolite, and a coating layer formed on one or both sides of the porous layer. 前記多孔質層が、ポリエチレン樹脂、ポリプロピレン樹脂、ポリアクリロニトリル樹脂、
フッ化ビニリデン樹脂、アクリル樹脂、及びウレタン樹脂のうちのいずれかから成ること
を特徴とする請求項１記載のセパレータ。 The porous layer is made of polyethylene resin, polypropylene resin, polyacrylonitrile resin,
The separator according to claim 1, wherein the separator is made of any one of vinylidene fluoride resin, acrylic resin, and urethane resin. 前記多孔質層の膜厚が１０〜１１０μｍの範囲内にあることを特徴とする請求項１又は２
記載のセパレータ。 The thickness of the porous layer is in the range of 10 to 110 µm.
The separator described. 前記被覆層が多孔質シリカを含み、
その多孔質シリカの物性が以下のとおりであることを特徴とする請求項１〜３のいずれか
１項記載のセパレータ。
平均粒子径：０．１〜８μｍ
比表面積：２５０〜８００ｍ２／ｇ
吸油量：５０〜３５０ｍｌ／１００ｇ The coating layer includes porous silica;
The separator according to any one of claims 1 to 3, wherein physical properties of the porous silica are as follows.
Average particle size: 0.1-8 μm
Specific surface area: 250-800 m 2 / g
Oil absorption: 50-350ml / 100g 前記被覆層の膜厚が０．５〜５０μｍの範囲内にあることを特徴とする請求項１〜４のい
ずれか１項記載のセパレータ。 The thickness of the said coating layer exists in the range of 0.5-50 micrometers, The separator of any one of Claims 1-4 characterized by the above-mentioned. 前記被覆層を構成する粒子の表面に、ＥＤＯＴ、ＰＥＤＯＴ、ＩＴＯ、ポリピロール、及
びポリアニリンから選ばれた１種以上を含む導電層を備えることを特徴とする請求項１〜
５のいずれか１項記載のセパレータ。 The surface of the particles constituting the coating layer is provided with a conductive layer containing one or more selected from EDOT, PEDOT, ITO, polypyrrole, and polyaniline.
The separator according to any one of 5. 請求項１〜６のいずれか１項記載のセパレータを備えた電気化学素子。 The electrochemical element provided with the separator of any one of Claims 1-6. 一次電池、二次電池、電気二重層キャパシタ、及び擬似電気二重層キャパシタのうちのい
ずれかであることを特徴とする請求項７記載の電気化学素子。 The electrochemical device according to claim 7, wherein the electrochemical device is any one of a primary battery, a secondary battery, an electric double layer capacitor, and a pseudo electric double layer capacitor. （Ａ）多孔質シリカ、活性炭、及びゼオライトから成る群がら選ばれた１種以上、（Ｂ）
バインダー、（Ｃ）スラリー安定剤、及び（Ｄ）コーティング助剤を含むスラリーを、多
孔質層の片面又は両面に塗布して被覆層を形成することを特徴とするセパレータの製造方
法。 (A) one or more selected from the group consisting of porous silica, activated carbon, and zeolite, (B)
A method for producing a separator, wherein a coating layer is formed by applying a slurry containing a binder, (C) a slurry stabilizer, and (D) a coating aid to one or both sides of a porous layer. 前記バインダーが、水系バインダー又はオレフィン系バインダーである第１のバインダー
と、スチレンーブタジエンゴム系バインダー、変性スチレンーブタジエンゴム系バインダ
ー、アタリレート系バインダー、セルロース系バインダー、ビニールピロリドン、及び弗
素系バインダーから成る群がら選ばれた１種以上である第２のバインダーとの混合バイン
ダーであることを特徴とする請求項９記載のセパレータの製造方法。 The binder is a first binder which is an aqueous binder or an olefin binder, a styrene-butadiene rubber binder, a modified styrene-butadiene rubber binder, an acrylate binder, a cellulose binder, vinyl pyrrolidone, and a fluorine binder. 10. The method for producing a separator according to claim 9, wherein the separator is a mixed binder with at least one second binder selected from the group consisting of: 前記コーティング助剤が、Ｎａ中和ＣＭＣ、又はアンモニア中和ＣＭＣを含むことを特徴
とする請求項９又は１０記載のセパレータの製造方法。 The method for producing a separator according to claim 9 or 10, wherein the coating aid contains Na-neutralized CMC or ammonia-neutralized CMC. 前記スラリー安定剤が、界面活性剤、又はスルフォン酸系水溶性ポリマーを含むことを特
徴とする請求項９〜１１のいずれか１項記載のセパレータの製造方法。 The method for producing a separator according to any one of claims 9 to 11, wherein the slurry stabilizer contains a surfactant or a sulfonic acid-based water-soluble polymer.
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