JPH03250719A - Electric double layer capacitor - Google Patents
Electric double layer capacitorInfo
- Publication number
- JPH03250719A JPH03250719A JP2048488A JP4848890A JPH03250719A JP H03250719 A JPH03250719 A JP H03250719A JP 2048488 A JP2048488 A JP 2048488A JP 4848890 A JP4848890 A JP 4848890A JP H03250719 A JPH03250719 A JP H03250719A
- Authority
- JP
- Japan
- Prior art keywords
- conductive film
- porous conductive
- electric double
- double layer
- layer capacitor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 17
- 239000010416 ion conductor Substances 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims description 10
- 239000010408 film Substances 0.000 abstract description 31
- 239000010409 thin film Substances 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 4
- 238000011049 filling Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- -1 polyethylene Polymers 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229920000098 polyolefin Polymers 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000004020 conductor Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- IZQYYQFIBDSTPG-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluorobutane-1-sulfonic acid Chemical compound CC(F)(F)C(F)(F)C(F)(F)S(O)(=O)=O IZQYYQFIBDSTPG-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- OWNSEPXOQWKTKG-UHFFFAOYSA-M lithium;methanesulfonate Chemical compound [Li+].CS([O-])(=O)=O OWNSEPXOQWKTKG-UHFFFAOYSA-M 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Description
【発明の詳細な説明】 ３産業上の利用分野〕 本発明は電気二重コンデンサに係る。[Detailed description of the invention] 3 industrial application fields] The present invention relates to an electric double capacitor.
口従来の技術〕
電極材料として電気化学的に不活性で比表面積の大きい
活性炭を用い、電解質として比較的分解電圧の高い有機
電解質を用いる電気二重層コンデンサが提案されている
。この電気二重層コンデンサは、電気化学系の電極と電
解質との界面に生ずる電気二重層の容量が他の誘電体を
用いるキャパシタの容量とか半導体の表面および空間電
荷層の容量より著しく大きいので、大容量であり、かつ
リーク電流が少ないという特長を有する。[Background Art] Electric double layer capacitors have been proposed that use activated carbon, which is electrochemically inert and has a large specific surface area, as an electrode material and an organic electrolyte with a relatively high decomposition voltage as an electrolyte. This electric double layer capacitor has a large capacitance because the capacitance of the electric double layer that occurs at the interface between the electrochemical electrode and the electrolyte is significantly larger than the capacitance of capacitors using other dielectric materials or the capacitance of the semiconductor surface and space charge layer. It has the features of high capacity and low leakage current.
口発明が解決しようとする課題〕
非水素の電解質溶液を用いる電気二重層コンデンサは耐
電圧性が向上し、定格電圧を高くとれるが、等価直列抵
抗（ＥＳＲ）が大きくなるという問題点を有する。市販
品は電極間に圧力を加えたり、電極製造時にアセチレン
ブラックを添加したり、活性炭素繊維を用いたりする工
夫がなされている。[Problems to be Solved by the Invention] Electric double layer capacitors using a non-hydrogen electrolyte solution have improved voltage resistance and can have a high rated voltage, but have the problem of increased equivalent series resistance (ESR). Commercially available products have been devised by applying pressure between the electrodes, adding acetylene black during electrode manufacturing, and using activated carbon fiber.
しかし、依然としてＥＳＲは大きく、例えば、交流用と
して使うにはＥＳＲが大きいため、誘電損失が大きくな
り平滑作用をしない。However, the ESR is still large, and for example, the ESR is large for use in AC applications, resulting in large dielectric loss and no smoothing effect.
そこで本発明は大面積化の容易な薄膜電極構造を実現し
、ＥＳＲの小さい電気二重層コンデンサを提供すること
を目的とする。Therefore, an object of the present invention is to realize a thin film electrode structure that can easily be made into a large area, and to provide an electric double layer capacitor with low ESR.
従来技術は電極を無数の活性炭粒子、または活性炭素繊
維の集合体から構成し、数Ωから数万Ωの幅広い内部抵
抗を持つ数多くの小さいコンデンサが並列に分布してい
るとみることができる。この抵抗の分布の幅を狭く、か
つ小さくすることを目標として研究を進めた結果、本発
明に到達した。In the prior art, electrodes are composed of countless activated carbon particles or aggregates of activated carbon fibers, and can be seen as a large number of small capacitors distributed in parallel with internal resistances ranging from several ohms to tens of thousands of ohms. As a result of research aimed at narrowing and reducing the width of this resistance distribution, the present invention was achieved.
即ち本発明は、上記目的を達成するために、対向電極間
に電解質を有して成り、該対向電極が多孔性導電膜から
なり、該多孔性導電膜中の空孔中にイオン導電体が充填
されていることを特徴とする電気二重コンデンサを提供
する。That is, in order to achieve the above object, the present invention includes an electrolyte between opposing electrodes, the opposing electrode is made of a porous conductive film, and an ionic conductor is present in the pores of the porous conductive film. To provide an electric double capacitor characterized by being filled.
この多孔性導電膜は立体的に発達した網目構造の間に貫
通するチャンネルをもつゆえに比表面積が大きく、かつ
空孔に充填されたイオン導電体が入り込んでいるのでイ
オンの移動に関する抵抗成分を小さくできる。しかも、
波型れの心配はなく、全体としては固体として取扱うこ
とができる。This porous conductive film has a large specific surface area because it has channels that penetrate between the three-dimensionally developed network structure, and the ionic conductor filled in the pores reduces the resistance component related to the movement of ions. can. Moreover,
There is no need to worry about corrugation, and the entire product can be handled as a solid.
このような多孔性導電膜としては、一般に、膜厚が１〜
１０００ｍ、空孔率が３０〜９０％、比導電率が１Ｏ−
５Ｓ ｃｒｎ−’以上の薄膜が好適である。Generally, such a porous conductive film has a film thickness of 1 to
1000m, porosity 30-90%, specific conductivity 1O-
A thin film of 5S crn-' or more is suitable.
膜厚は一般に１〜１０００−＝、より好ましくは５〜５
００卿である。厚さが１−未満では、機械的強度および
取扱い性の観点から実用に供することが難しい。一方、
１００ＯＪ−を超える場合には、実効抵抗が大きくなり
、分極性電極としての体積効率も不利となる。The film thickness is generally 1 to 1000-=, more preferably 5 to 5
This is Lord 00. If the thickness is less than 1 mm, it is difficult to put it into practical use from the viewpoints of mechanical strength and handleability. on the other hand,
If it exceeds 100 OJ-, the effective resistance becomes large and the volumetric efficiency as a polarizable electrode becomes disadvantageous.
膜の空孔率は、３０〜９０％、好ましくは４０〜９０％
である。空孔率が３０％未満では、比導電率は向上する
が、電極材料として用いる場合の電解質溶液との界面が
少なくなり、電気二重層コンデンサとしての応用が実用
性の面から制約される。一方空孔率が９０％を超えると
、膜の機械的強度が不十分となる。The porosity of the membrane is 30-90%, preferably 40-90%
It is. When the porosity is less than 30%, the specific conductivity improves, but when used as an electrode material, the interface with the electrolyte solution decreases, and the application as an electric double layer capacitor is restricted from a practical standpoint. On the other hand, if the porosity exceeds 90%, the mechanical strength of the membrane will be insufficient.
さらに、本発明においては、特に限定されないが、粒子
透過法により測定される平均貫通孔径は、０、００１〜
０．７卿、好ましくは、０．０１〜０．１廁であるのが
よい。平均貫通孔径かり００１−未満では電極活性物質
や電解質溶液の空孔内への充填が幾何的制約のために困
難となり、０．７−を超えると毛管凝縮作用による溶液
の空孔内への充填および漏出防止が困難となる。Furthermore, in the present invention, although not particularly limited, the average through-hole diameter measured by a particle permeation method is 0,001 to
0.7 Liang, preferably 0.01~0.1 Liang. If the average through-pore diameter is less than 0.01 mm, it will be difficult to fill the pores with an electrode active material or electrolyte solution due to geometric constraints, and if it exceeds 0.7 mm, the solution will not fill the pores due to capillary condensation. and leakage prevention becomes difficult.
本発明の導電性多孔膜の比導電率は一般に１Ｏ−５Ｓｃ
＋ｎ−’以上、好ましくは１０’Ｓｃｍ’以上である。The specific conductivity of the conductive porous membrane of the present invention is generally 1O-5Sc
+n-' or more, preferably 10'Scm' or more.
比導電率が１０−５３ｃｍ−’未満では実効抵抗が大き
くなり、実用的でない。例えば、ここで、膜厚１−のと
き、実効抵抗は、１ｍ ／１０−” Ｓ ｃｍ ’即ち
１０Ωｃｆｆｌとなる。If the specific conductivity is less than 10-53 cm-', the effective resistance becomes large and is not practical. For example, here, when the film thickness is 1-, the effective resistance is 1 m/10-''S cm', or 10Ωcffl.
このような多孔性導電膜は、固体高分子多孔性薄膜中に
電子導電性材料を含有させて作製することができる。電
子導電性材料としては、各種の金属材料や半導体材料、
酸化物系および硫化物系の電子導電性材料、およびカー
ボンもしくはグラファイト材料がある。これらは、粒子
状、繊維状、フィブリル状、ウィスカー状等のいかなる
形状にあってもよく、微細なフィブリルもしくはウィス
カー状にあるのが好ましい。電子導電性材料として特に
好ましいものは、アセチレンブラック、ケッチエンブラ
ック（Ａｋｚｏ Ｃｈｅｍｉｅ社商標）、カーボンウィ
スカー、グラファイトウィスカー、グラファイトフィブ
リル等がある。例えば、米国Ｈｙｐｅｒｉｏｎ社の開発
したＧｒａｐｈｉｔｅ Ｆｉｂｒｉｌｓ （商標）は、
中空円柱状構造の直径３．５〜７０ｎｍ、アスペクト比
１００以上のフィブリルであり（特開昭６２−５００９
４３号公報）、好適である。Such a porous conductive film can be produced by incorporating an electronically conductive material into a solid polymer porous thin film. Examples of electronically conductive materials include various metal materials, semiconductor materials,
There are oxide-based and sulfide-based electronically conductive materials, and carbon or graphite materials. These may be in any shape such as particles, fibers, fibrils, whiskers, etc., and are preferably in the form of fine fibrils or whiskers. Particularly preferred electronically conductive materials include acetylene black, Ketchien black (trademark of Akzo Chemie), carbon whiskers, graphite whiskers, graphite fibrils, and the like. For example, Graphite Fibrils (trademark) developed by Hyperion, Inc. in the United States,
It is a fibril with a hollow cylindrical structure having a diameter of 3.5 to 70 nm and an aspect ratio of 100 or more (Japanese Patent Application Laid-Open No. 62-5009
No. 43) is suitable.
固体高分子材料としてはポリオレフィン、ポリカーボネ
ート、ポリエステノベポリアミドなどが用いることがで
きる。１つの好ましい材料はオレフィンの単独重合体ま
たは共重合体からなる結晶性の線状ポリオレフィンであ
り、重量平均分子量が５Ｘ１０’以上、好ましくは１×
１０６〜１×１０７の超高分子量ポリオレフィンを用い
る。ポリオレフィンとしては、ポリエチレン、ポリプロ
ピレン、エチレン−プロピレン共重合体、ポリブテン−
１、ポリ４−メチルペンテン−１などを挙げることがで
き、これらのうちではポリエチレンおよびポリプロピレ
ンが好ましい。ポリオレフィンの重量平均分子量は、得
られる膜の機械的強度に影響する。As the solid polymer material, polyolefin, polycarbonate, polyester polyamide, etc. can be used. One preferred material is a crystalline linear polyolefin consisting of an olefin homopolymer or copolymer, and has a weight average molecular weight of 5X10' or more, preferably 1X
An ultra-high molecular weight polyolefin of 10 6 to 1×10 7 is used. Polyolefins include polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-
1, poly-4-methylpentene-1, etc. Among these, polyethylene and polypropylene are preferred. The weight average molecular weight of the polyolefin influences the mechanical strength of the resulting membrane.
超高分子量ポリオレフィンは、超延伸による極薄で高強
度の膜の調製を可能にする。重量平均分子量が５Ｘ１０
５未満のポリオレフィンを同時に用いることができるが
、重量平均分子量が５Ｘ１０５以上のポリオレフィンを
含まない系では、超延伸により高強度の膜を得ることが
できない。Ultra-high molecular weight polyolefins allow the preparation of ultra-thin, high-strength membranes by ultra-stretching. Weight average molecular weight is 5X10
Although polyolefins having a weight average molecular weight of less than 5×10 5 can be used at the same time, a high-strength film cannot be obtained by ultra-stretching in a system that does not contain a polyolefin having a weight average molecular weight of 5×10 5 or more.
本発明の多孔性導電膜は、上記の電子導電性材料をポリ
オレフィンに配合し、製膜することにより得ることがで
きる。電子導電性材料の配合量は、１〜２００重量％、
特に５〜５０重量％であるのが好ましい。この配合量が
１重量％未満では十分な導電性が得られにくく、２００
重量％を超えると実用的に十分な強度の膜を得ることが
困難となる。The porous conductive film of the present invention can be obtained by blending the above electronically conductive material with polyolefin and forming a film. The blending amount of the electronically conductive material is 1 to 200% by weight,
In particular, it is preferably 5 to 50% by weight. If this amount is less than 1% by weight, it will be difficult to obtain sufficient conductivity;
If it exceeds % by weight, it becomes difficult to obtain a film with sufficient strength for practical use.
製膜は、例えば、次のようにして行うことができる。超
高分子量ポリオレフィンを含むポリオレフィンを流動パ
ラフィンのような溶媒中に１〜５０重量％を加熱溶解し
て均一な溶液とし、これに電子導電性材料を均一に配合
せしめる。この溶液からシートを形成し、急冷してゲル
状シートとする。Film formation can be performed, for example, as follows. 1 to 50% by weight of polyolefin including ultra-high molecular weight polyolefin is heated and dissolved in a solvent such as liquid paraffin to form a uniform solution, and an electronically conductive material is uniformly blended into this solution. A sheet is formed from this solution and rapidly cooled to form a gel-like sheet.
このゲル状シート中に含まれる溶媒を必要に応じて塩化
メチレンのような揮発性溶剤で抽出処理して、溶媒量を
１０〜９０重量％とする。このゲル状シートをポリオレ
フィンの融点以下の温度で加熱し、面倍率で１０倍以上
に延伸する。この延伸膜中に含まれる溶媒を再び塩化メ
チレンのような揮発性溶剤で抽出除去し、次いで乾燥す
る。If necessary, the solvent contained in this gel sheet is extracted with a volatile solvent such as methylene chloride to adjust the amount of the solvent to 10 to 90% by weight. This gel-like sheet is heated at a temperature below the melting point of the polyolefin and stretched to an areal magnification of 10 times or more. The solvent contained in this stretched film is extracted and removed again with a volatile solvent such as methylene chloride, and then dried.
さらに、ポリエステル、ポリメタアクリレート、ポリア
セターノへポリ塩化ビニリデンなどはポリオレフィンに
比して耐熱性に優れ、かつ同時二軸延伸または逐次延伸
が可能であり、延伸により薄膜化、高強度化を達成する
ことができる。Furthermore, polyester, polymethacrylate, polyacetano, polyvinylidene chloride, etc. have better heat resistance than polyolefins, and can be stretched simultaneously or sequentially, making it possible to achieve thinner films and higher strength by stretching. I can do it.
イオン導電体としてアルカリ金属塩、または第四級アン
モニウム塩を溶質として用い、溶媒としてプロピレンカ
ーボネート、Ｔ−ブチロラクトン、ニチレンカーボネー
ト、メチルフラン、ジメトキシニタン、ジオキソラン、
テトラヒドロフラン、アセトニトリノベジメチルホルム
アミド、ジメチルサルホキシト、メチルテトラヒドロフ
ラン、スルホラン、メチルチオフェン、メチルチアシー
ツベニトキシメトキシエタンの１種またはそれ以上を用
いる。さらに、イオン導電体としてはアルカリ金属塩ま
たは第四級アンモニウム塩と、ポリエーテノヘポリエス
テル、ポリイミン等の極性高分子との複合体、あるいは
これらの高分子をセグメントとして含有する網目状、又
は架橋状高分子との複合体を用いる二とができる。ポリ
エーテル、例えばポリエチレンゲルコールまたはポリプ
ロピレングリコールあるいはそれらの共重合体は分子量
および重合度の異なる液状および粉末状の試薬が市販さ
れており、簡便に用いることができる。すなわち、ポリ
エチレングリコール、ポリエチレングリコール・モノエ
ーテル、ポリエチレングリコール・ジエーテル、ポリプ
ロピレングリコール、ポリプロピレングリコール・モノ
エーテノベポリプロピレングリコール・ジエーテル等の
ポリエーテル類、またはこれらのポリエーテル類の共重
合体であるポリ （オキシエチレン・オキシプロピレン
）グリコーノベポリ （オキシエチレン・オキシプロピ
レン）グリコール・モノエーテル、マｆ：−ハボリ （
オキシエチレン・オキシプロピレン）グリコール・ジエ
ーテノベこれらのポリオキシアルキレン類と、エチレン
ジアミンとの縮合物、りん酸エステルや飽和脂肪酸また
は芳香族エステル等を用いることができる。さらにポリ
エチレングリコールとジアルキルシロキサンの共重合体
く例えば、成瀬ら、Ｐｏｌｙｍｅｒ Ｐｒｅｐｒｉｎｔ
ｓ、 Ｊａｐａｎνｏｆ、 ３４． Ｎｏ、 ７．２０
２１〜２０２４ （１９８５）、および特開昭６０−２
１７２６３号公報）、ポリエチレングリコールと無水マ
レイン酸の共重合体（例えばＣ，Ｃ，Ｌｅｅ ら、Ｐｏ
ｌｙｍｅｒ、 １９８２、Ｖｏｌ、２３ Ｍａｙ ６８
１〜６８９）、およびポ’Ｊニー１−Ｌ’ンクｌＪコー
ルのモノメチルエーテルとメタクリル酸との共重合体（
例えば、Ｎ、 Ｋｏｂａｙａｓｈｉ ら、Ｊ、 Ｐｈ
ｙｓｉｃａｌＣｈｅｍｉｓｔｒｙ、 Ｖｏｌ、８９．
Ｎｏ、６．９８７〜９９０１９８５） ）はそれぞれア
ルカリ金属イオンとの複合体を形成し、室温でのイオン
伝導度が１０−５〜１０−’ Ｓ −ｃｍ−’であるこ
とが知られており、有用な多孔性導電膜（電極材料）を
構成する材料として好適である。上記のポリエーテル１
ま分子量１５０以上の低分子量のものであってもよく、
また上記溶媒の１種またはそれ以上を加えてもよい。Using an alkali metal salt or a quaternary ammonium salt as an ion conductor as a solute, propylene carbonate, T-butyrolactone, nitylene carbonate, methylfuran, dimethoxynitane, dioxolane, as a solvent.
One or more of tetrahydrofuran, acetonitrinobedimethylformamide, dimethylsulfoxide, methyltetrahydrofuran, sulfolane, methylthiophene, methylthiabenthoxymethoxyethane is used. Furthermore, as an ionic conductor, a complex of an alkali metal salt or a quaternary ammonium salt and a polar polymer such as polyether, polyester, or polyimine, or a network or crosslinked structure containing these polymers as segments can be used. The second method is to use a complex with a polymer. Polyethers such as polyethylene gelcol, polypropylene glycol, or copolymers thereof are commercially available as liquid and powder reagents with different molecular weights and degrees of polymerization, and can be easily used. That is, polyethers such as polyethylene glycol, polyethylene glycol monoether, polyethylene glycol diether, polypropylene glycol, polypropylene glycol monoether, polypropylene glycol diether, or poly(oxy) which is a copolymer of these polyethers. Ethylene/oxypropylene) glycol monoether (oxyethylene/oxypropylene) glycol monoether,
Oxyethylene, oxypropylene) glycol, dietenove, condensates of these polyoxyalkylenes and ethylenediamine, phosphoric acid esters, saturated fatty acids, aromatic esters, etc. can be used. Furthermore, copolymers of polyethylene glycol and dialkyl siloxane, for example, Naruse et al., Polymer Preprint
s, Japan of, 34. No, 7.20
21-2024 (1985), and JP-A-60-2
17263), copolymers of polyethylene glycol and maleic anhydride (e.g. C, C, Lee et al., Po
lymer, 1982, Vol, 23 May 68
1-689), and a copolymer of monomethyl ether and methacrylic acid (
For example, N. Kobayashi et al., J. Ph.
physicalchemistry, Vol, 89.
No. 6.987-9901985)) are known to form complexes with alkali metal ions, and have ionic conductivities of 10-5 to 10-'S-cm-' at room temperature. It is suitable as a material constituting a useful porous conductive film (electrode material). Above polyether 1
It may also have a low molecular weight of 150 or more,
Also, one or more of the above solvents may be added.
これらの溶媒と共に用いる溶質あるいは高分子化合物と
複合体を形成するものとしては、アルカリ金属、第四級
アンモニウム塩またはプロトン酸を用いることができる
。陰イオンとしてはハロゲンイオン、過塩素酸イオン、
チオシアン酸イオン、トリフッ化メタンスルホン酸イオ
ン、ホウフッ化イオン等がある。テトラメチルアンモニ
ウム（ＴＭＡ）やテトラエチルアンモニウム（ＴＥＡ）
の過塩、素酸塩またはホウフッ化塩、フッ化リチウム（
ＬｉＦ） 、ヨウ化ナトリウム（Ｎａｌ） 、ヨウ化リ
チウム（Ｌ ｉ ｒ ）、過塩素酸リチウム（ＬｉＣｌ
口、）、チオシアン酸ナトリウＡ（ＮａＳＣＮ） 、）
リッツ化メタンスルホン酸リチウム（ＬｉＣＦ３ＳＯ３
）、ホウフッ化リチウム（ＬＩＢＦ４）、ヘキサフッ化
りん酸リチウム（ＬＩＰＦ６） 、りん酸（８３ＰＯ３
） 、硫酸（Ｈ２ＳＯ４） 、）リッツ化メタンスルホ
ン酸、テトラフッ化エチレンスルホン酸［：Ｃ２Ｆ４（
Ｓ［］３Ｈ）２ ］、ヘキサフッ化ブタンスルホン酸［
：Ｃ１Ｆ６ （ＳＯ３Ｈ） ４ ］及びこれらの酸の第
四級アンモニウム塩などを具体例として挙げることがで
きる。An alkali metal, a quaternary ammonium salt, or a protonic acid can be used as a substance that forms a complex with the solute or polymer compound used together with these solvents. Anions include halogen ions, perchlorate ions,
Examples include thiocyanate ion, trifluoromethanesulfonate ion, and borofluoride ion. Tetramethylammonium (TMA) and tetraethylammonium (TEA)
persalt, mate or borofluoride salt, lithium fluoride (
LiF), sodium iodide (Nal), lithium iodide (L i r ), lithium perchlorate (LiCl
mouth,), sodium thiocyanate A (NaSCN),)
Lithium methanesulfonate (LiCF3SO3)
), lithium borofluoride (LIBF4), lithium hexafluorophosphate (LIPF6), phosphoric acid (83PO3
), sulfuric acid (H2SO4),) litzated methanesulfonic acid, tetrafluorinated ethylene sulfonic acid [:C2F4(
S[ ]3H)2 ], hexafluorobutanesulfonic acid [
:C1F6 (SO3H) 4 ] and quaternary ammonium salts of these acids.
多孔性導電膜中にイオン導電体を充填する方法としては
以下の方法等を用いることができる。As a method for filling the ionic conductor into the porous conductive film, the following method etc. can be used.
■ 溶液状のイオン導電体、溶媒に溶解させたイオン導
電体、または溶媒中にゾル状またはゲル状に微分散させ
たイオン導電体を多孔性導電膜に含浸させるか、塗布ま
たはスプレーした後溶剤を除去する。■ A porous conductive film is impregnated with an ionic conductor in the form of a solution, an ionic conductor dissolved in a solvent, or an ionic conductor finely dispersed in a solvent in the form of a sol or gel, or after being applied or sprayed with a solvent. remove.
■ 多孔性導電膜の製造工程でイオン導電体の溶液また
は、そのゾルまたはゲル状の分散溶液を混合した後製膜
する。(2) In the manufacturing process of a porous conductive film, a solution of an ionic conductor or its sol or gel-like dispersion solution is mixed and then a film is formed.
■ イオン導電体の単量体や可溶性プレカーサーを多孔
性導電膜に含浸させるか、塗布またはスプレーした後、
空孔内で反応させる。■ After impregnating, coating, or spraying a porous conductive film with an ionic conductor monomer or soluble precursor,
React within the pores.
電極間に介在させるセパレータおよび電解質は特に限定
されない。液体電解質はもちろん、固体電解質を用いる
場合にも多孔性導電膜中に固定化されたイオン導電体が
多孔性導電膜自体と固体電解質との間をよく連続させる
のでその間の密着性に優れている。The separator and electrolyte interposed between the electrodes are not particularly limited. When using a solid electrolyte as well as a liquid electrolyte, the ionic conductor immobilized in the porous conductive membrane provides good continuity between the porous conductive membrane itself and the solid electrolyte, resulting in excellent adhesion between them. .
多孔性導電膜は多孔性でありながら導電性を有し、かつ
その空孔中にイオン導電体が固定化されている。多孔性
であるゆえにイオンの移動が容易になり、等個直列抵抗
が低くなる。また、イオン導電体が空孔中で多孔性導電
膜と接する界面が非常に大きく静電容量を大きくしてい
る。A porous conductive film is porous but has conductivity, and has an ionic conductor immobilized in its pores. The porous nature facilitates the movement of ions and lowers the equal series resistance. Furthermore, the interface between the ionic conductor and the porous conductive film in the pores is very large, increasing the capacitance.
実施例１
重量平均分子量４Ｘ１０’のポリエチレン１３．０重量
％と重量平均分子量２Ｘ１０６のポリエチレン２．０重
量％とケッチエンブラックＥＣ６００ＪＯ粉末５．０重
量％を含むホワイトオイル混合物１００重量部に酸化防
止剤を０．５重量部を加えて混合した。Example 1 An antioxidant is added to 100 parts by weight of a white oil mixture containing 13.0% by weight of polyethylene with a weight average molecular weight of 4X10', 2.0% by weight of polyethylene with a weight average molecular weight of 2X106, and 5.0% by weight of Ketchen Black EC600JO powder. 0.5 part by weight was added and mixed.
この混合物をオートクレーブに充填し、２００℃まで加
熱して約２時間撹拌した。この混合物を加熱した金型に
充填し、５０℃以下に急冷してシート状とした。得られ
た原反シートを１２５℃の温度で同時二軸延伸し、さら
に塩化メチレンで洗浄した後乾燥して多孔性導電膜を得
た。This mixture was filled into an autoclave, heated to 200° C., and stirred for about 2 hours. This mixture was filled into a heated mold and rapidly cooled to below 50°C to form a sheet. The obtained raw sheet was simultaneously biaxially stretched at a temperature of 125°C, further washed with methylene chloride, and then dried to obtain a porous conductive film.
この多孔性導電膜は膜厚０．３２卸、容積率は４５％、
比導電率が５×１０ ’ Ｓｃｍ−’であった。This porous conductive film has a film thickness of 0.32 mm, a volume ratio of 45%,
The specific conductivity was 5×10′ Scm−′.
１１〉９例１．で得られた一対の多孔性導電膜を膜厚１
０−１空孔率７８％、平均貫通孔径０．０２−のポリエ
チレン微多孔膜を介して対向させ、電解質としてＴＥＡ
Ｐ（テトラエチルアンモニウムの過塩素酸塩）を１モル
％含有するプロピレンカーボネートを用いて厚さ７６０
崗の電気二重層コンデンサを得た。11〉9 cases 1. The pair of porous conductive films obtained in
TEA was used as an electrolyte, facing each other through a polyethylene microporous membrane with a porosity of 78% and an average through-pore diameter of 0.02-1.
A thickness of 760 mm using propylene carbonate containing 1 mol% of P (perchlorate of tetraethylammonium)
Obtained a high-quality electric double layer capacitor.
静電容量は１０正角当り０．３２フアラツドであり、５
ｃＩ１１当りのＥＳＲは１．２Ωてあった。The capacitance is 0.32 farads per 10 square angles, and 5
The ESR per cI11 was 1.2Ω.
〔発明の効果；
本発明によれば、電極と電解質とを一体化した薄膜電極
を用いる電気二重層コンデンサが提供され、大面積化、
大容量化、低抵抗化に効果がある。[Effects of the Invention: According to the present invention, an electric double layer capacitor using a thin film electrode in which an electrode and an electrolyte are integrated is provided, which has a large area and
Effective for increasing capacity and lowering resistance.
Claims (1)
孔性導電膜からなり、該多孔性導電膜中の空孔中にイオ
ン導電体が充填されていることを特徴とする電気二重コ
ンデンサ。1. An electric double capacitor comprising an electrolyte between opposing electrodes, the opposing electrodes comprising a porous conductive film, and pores in the porous conductive film filled with an ionic conductor. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2048488A JPH03250719A (en) | 1990-02-28 | 1990-02-28 | Electric double layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2048488A JPH03250719A (en) | 1990-02-28 | 1990-02-28 | Electric double layer capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03250719A true JPH03250719A (en) | 1991-11-08 |
Family
ID=12804775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2048488A Pending JPH03250719A (en) | 1990-02-28 | 1990-02-28 | Electric double layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03250719A (en) |
-
1990
- 1990-02-28 JP JP2048488A patent/JPH03250719A/en active Pending
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