JP2003272437A - Hydrophilic gel for gel-form electrolytic solution, separator containing hydrophilic gel, and its manufacturing method - Google Patents
Hydrophilic gel for gel-form electrolytic solution, separator containing hydrophilic gel, and its manufacturing methodInfo
- Publication number
- JP2003272437A JP2003272437A JP2002073600A JP2002073600A JP2003272437A JP 2003272437 A JP2003272437 A JP 2003272437A JP 2002073600 A JP2002073600 A JP 2002073600A JP 2002073600 A JP2002073600 A JP 2002073600A JP 2003272437 A JP2003272437 A JP 2003272437A
- Authority
- JP
- Japan
- Prior art keywords
- gel
- hydrophilic
- hydrophilic gel
- monomer
- electrolytic solution
- 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.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000008151 electrolyte solution Substances 0.000 title abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 21
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000011245 gel electrolyte Substances 0.000 claims description 28
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 22
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 230000014759 maintenance of location Effects 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 claims description 6
- 229920006037 cross link polymer Polymers 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000011244 liquid electrolyte Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 230000000717 retained effect Effects 0.000 abstract description 7
- 238000001704 evaporation Methods 0.000 abstract description 6
- 230000008020 evaporation Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 40
- 239000007864 aqueous solution Substances 0.000 description 22
- -1 alkali metal salts Chemical class 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 16
- 239000003990 capacitor Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 229960005070 ascorbic acid Drugs 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000002211 L-ascorbic acid Substances 0.000 description 4
- 235000000069 L-ascorbic acid Nutrition 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000001741 Ammonium adipate Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940048053 acrylate Drugs 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000019293 ammonium adipate Nutrition 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- DZGUJOWBVDZNNF-UHFFFAOYSA-N azanium;2-methylprop-2-enoate Chemical compound [NH4+].CC(=C)C([O-])=O DZGUJOWBVDZNNF-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- RLQOUIUVEQXDPW-UHFFFAOYSA-M lithium;2-methylprop-2-enoate Chemical compound [Li+].CC(=C)C([O-])=O RLQOUIUVEQXDPW-UHFFFAOYSA-M 0.000 description 1
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 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
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電池、電解コンデ
ンサーにおいてゲル状電解液構成材料として使用可能な
親水性ゲル、電池、電解コンデンサーにおいてセパレー
ターとして使用可能な、親水性ゲルを含浸・保持する親
水性ゲル含有セパレーターに関する。本発明の親水性ゲ
ル含有セパレーターは、特にニッケル水素電池用セパレ
ーターとして好適である。TECHNICAL FIELD The present invention relates to a hydrophilic gel which can be used as a gel electrolyte component in batteries and electrolytic capacitors, and a hydrophilic gel which can be used as a separator in batteries and electrolytic capacitors and which is impregnated with and holds hydrophilic gel. Gel-containing separator. The hydrophilic gel-containing separator of the present invention is particularly suitable as a nickel hydrogen battery separator.
【０００２】[0002]
【従来の技術】電池、電解コンデンサーはその構造にお
いて、電極間にイオンを透過させるサイズの孔を有する
多孔質膜であるセパレーターと電解液とからなる層が設
けられている。2. Description of the Related Art In a structure of a battery or an electrolytic capacitor, a layer composed of a separator, which is a porous membrane having pores permeable to ions, and an electrolytic solution is provided between electrodes.
【０００３】従来から一般的に製造されているアルカリ
電池、ニッケル水素電池等においては、ＫＯＨ水溶液が
電解液として使用されており、かかる電解液は強いアル
カリ性を示し、漏液すると電池を使用している機器を腐
食、損傷することになる。このため、電池、コンデンサ
ーにおいては漏液防止が重要な技術である。漏液防止の
ために、従来からケース内にゴムシール材等のシール材
料を使用して封入するなどの特別の配慮がなされている
が、なお完全ではなく、改善が求められている。In conventional alkaline batteries, nickel-hydrogen batteries, etc., which have been generally manufactured, KOH aqueous solution is used as an electrolytic solution, and such electrolytic solution shows strong alkalinity, and when the battery leaks, the battery is used. Corrosion and damage to existing equipment. For this reason, leakage prevention is an important technology in batteries and capacitors. In order to prevent liquid leakage, special consideration has conventionally been given such as enclosing a case with a sealing material such as a rubber sealing material, but it is still not perfect, and improvement is required.
【０００４】また使用中に、電解コンデンサーには、定
格より高い電圧が印加される場合があり、かかる場合に
はコンデンサーの温度が上昇して、電解液を構成する水
の蒸気圧が高くなり、また電気化学反応によって水素ガ
スも発生してコンデンサーの内圧が上昇する。その結
果、コンデンサーの内圧がケースやシールの耐圧限界を
超えると、水が気化して水素ガスと共に電解液が噴出す
るという問題があった。電池の場合にも充電中、使用中
の温度上昇により、同様な問題が発生する。Further, during use, a voltage higher than the rating may be applied to the electrolytic capacitor, and in such a case, the temperature of the capacitor rises and the vapor pressure of water constituting the electrolytic solution increases, Also, hydrogen gas is generated by the electrochemical reaction, and the internal pressure of the condenser rises. As a result, when the internal pressure of the condenser exceeds the withstand pressure limit of the case or the seal, water is vaporized and the electrolytic solution is ejected together with the hydrogen gas. In the case of batteries as well, similar problems occur due to temperature rise during charging and during use.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、高い
電解液保持率を有していて従来の電解液とセパレーター
とを使用した場合と同等の性能を有し、かつ電解液を構
成する水の蒸発が抑制され、漏液の起こらないゲル状電
解液を構成可能な親水性ゲル、かかる親水性ゲルを含有
するセパレーター並びにその製造方法を提供することに
ある。SUMMARY OF THE INVENTION An object of the present invention is to have a high electrolytic solution retention rate and to have the same performance as in the case of using a conventional electrolytic solution and a separator, and to configure the electrolytic solution. It is an object of the present invention to provide a hydrophilic gel capable of forming a gel electrolyte solution in which water evaporation is suppressed and leakage does not occur, a separator containing the hydrophilic gel, and a method for producing the separator.
【０００６】[0006]
【課題を解決するための手段】本発明のゲル状電解液用
親水性ゲルは、親水性アクリル系モノビニルモノマーと
芳香族ポリビニルモノマーとを共重合して得られ、水系
電解液の保持率が６倍（重量比）以上、より好ましくは
８倍以上のゲル状電解液を形成可能であることを特徴と
する。The hydrophilic gel for a gel electrolyte of the present invention is obtained by copolymerizing a hydrophilic acrylic monovinyl monomer and an aromatic polyvinyl monomer, and has an aqueous electrolyte retention of 6%. It is characterized in that it is possible to form a gel electrolyte at least twice (weight ratio), more preferably at least eight times.
【０００７】かかる親水性ゲルは、高い電解液保持率を
有していて従来の電解液とセパレーターとを使用した場
合と同等の性能を有し、かつ電解液を構成する水の蒸発
が抑制され、漏液の起こらないゲル状電解液を構成可能
である。親水性ゲルの電解液保持率は高いほど好まし
い。本発明の親水性ゲルは、電解液を２０倍程度まで保
持可能であり、安定的な電解液保持率は１５倍である。Such a hydrophilic gel has a high electrolytic solution retention rate and has a performance equivalent to that obtained when a conventional electrolytic solution and a separator are used, and evaporation of water constituting the electrolytic solution is suppressed. It is possible to configure a gel electrolyte that does not leak. The higher the electrolytic solution retention rate of the hydrophilic gel, the more preferable. The hydrophilic gel of the present invention can retain an electrolytic solution up to about 20 times, and the stable electrolytic solution retention rate is 15 times.
【０００８】上述の親水性ゲルにおいては、前記親水性
アクリル系モノビニルモノマーは、（メタ）アクリル
酸、（メタ）アクリル酸塩から選択される少なくとも１
種であることが好ましい。In the above hydrophilic gel, the hydrophilic acrylic monovinyl monomer is at least one selected from (meth) acrylic acid and (meth) acrylic acid salt.
It is preferably a seed.
【０００９】かかる親水性モノマーの使用により、電解
質としてＫＯＨを使用するニッケル水素電池用のゲル状
電解液に好適な親水性ゲルが得られる。By using such a hydrophilic monomer, a hydrophilic gel suitable for a gel electrolyte for a nickel hydrogen battery using KOH as an electrolyte can be obtained.
【００１０】また前記芳香族ポリビニルモノマーは、ジ
ビニルベンゼン、ジビニルトルエンの少なくとも１種で
あることが好ましい。The aromatic polyvinyl monomer is preferably at least one of divinylbenzene and divinyltoluene.
【００１１】これらのポリビニルモノマーは親水性アク
リル系モノビニルモノマーとの共重合性に優れ、得られ
た親水性ゲルは、電解液としてＫＯＨ水溶液等の強アル
カリ液を使用した場合でも、高い電解液保持率を有する
ゲル状電解液を実現可能であり、しかも、耐熱性に優れ
たゲル状電解液を形成可能である。These polyvinyl monomers have excellent copolymerizability with hydrophilic acrylic monovinyl monomers, and the obtained hydrophilic gel has a high electrolyte retention even when a strong alkaline liquid such as KOH aqueous solution is used as the electrolyte. It is possible to realize a gel electrolyte having a high rate, and it is possible to form a gel electrolyte having excellent heat resistance.
【００１２】本発明の親水性ゲル含有セパレーターは、
親水性アクリル系モノビニルモノマーと芳香族ポリビニ
ルモノマーとを共重合して得られる親水性ゲルを付着保
持する多孔性基材からなることを特徴とする。The hydrophilic gel-containing separator of the present invention comprises
It is characterized by comprising a porous substrate on which a hydrophilic gel obtained by copolymerizing a hydrophilic acrylic monovinyl monomer and an aromatic polyvinyl monomer is attached and held.
【００１３】かかる構成を有するセパレーターを従来の
セパレーターに代えて使用すると、電解液は、親水性ゲ
ルに含浸保持され、その結果水の蒸発が抑制され、従来
よりはるかに漏液を起こしにくい電池、コンデンサーが
形成される。親水性ゲルは、親水性アクリル系モノビニ
ルモノマーと芳香族ポリビニルモノマーとを含有してお
り、そのために水性電解液を架橋重合体に対して重量比
にて６倍以上、好ましくは８倍以上含有可能であって電
解液保持率が高く、従ってイオン伝導性が高く、該親水
性ゲル含有セパレーターを使用することにより、従来の
電解液とセパレーターとを使用した場合と同等の性能を
有する電池、コンデンサーを形成可能である。When the separator having such a structure is used in place of the conventional separator, the electrolytic solution is impregnated and held in the hydrophilic gel, and as a result, the evaporation of water is suppressed, and the battery is much less likely to leak than the conventional battery. A condenser is formed. The hydrophilic gel contains a hydrophilic acrylic monovinyl monomer and an aromatic polyvinyl monomer. Therefore, the weight ratio of the aqueous electrolytic solution to the crosslinked polymer can be 6 times or more, preferably 8 times or more. The electrolyte retention rate is high, and therefore the ionic conductivity is high, and by using the hydrophilic gel-containing separator, a battery having the same performance as when using a conventional electrolyte and a separator, a capacitor can be obtained. Can be formed.
【００１４】上記セパレーターにおいては、前記親水性
アクリル系モノビニルモノマーが、（メタ）アクリル
酸、（メタ）アクリル酸塩から選択される少なくとも１
種であることが好ましい。In the above separator, the hydrophilic acrylic monovinyl monomer is at least one selected from (meth) acrylic acid and (meth) acrylic acid salt.
It is preferably a seed.
【００１５】かかる親水性モノマーの使用により、特に
電解液保持率が高い親水性ゲル含有セパレーターが得ら
れる。By using such a hydrophilic monomer, a hydrophilic gel-containing separator having a particularly high electrolyte retention rate can be obtained.
【００１６】前記芳香族ポリビニルモノマーが、ジビニ
ルベンゼン、ジビニルトルエンの少なくとも１種である
ことが好ましい。The aromatic polyvinyl monomer is preferably at least one kind of divinylbenzene and divinyltoluene.
【００１７】多孔質基材に対する親水性ゲルの付着量
は、特に限定されるものではないが、乾燥状態にて１〜
５０ｇ／ｍ2 であることが好ましい。The amount of the hydrophilic gel attached to the porous substrate is not particularly limited, but is 1 to 1 in the dry state.
It is preferably 50 g / m 2 .
【００１８】付着量が少なすぎると電解液保持効果が十
分に発揮されず、漏液する可能性が高くなり、多すぎる
と乾燥工程後に多孔質基材から剥落する重合体の粒子が
多くなる。If the adhered amount is too small, the electrolyte retaining effect is not sufficiently exerted, and the possibility of liquid leakage increases, and if the adhered amount is too large, a large number of polymer particles are exfoliated from the porous substrate after the drying step.
【００１９】本発明の親水性ゲル含有セパレーターの製
造方法は、架橋重合体形成モノマー組成物を重合させて
重合体とする重合工程、前記架橋重合体を溶媒と混合し
て親水性ゲル分散液とする分散工程、前記親水性ゲル分
散液を多孔性基材に塗布、含浸させる塗布工程、及び前
記親水性ゲル分散液を塗布、含浸された前記多孔性基材
を乾燥して親水性ゲル含有セパレーターとする乾燥工程
とからなり、前記架橋重合体形成モノマー組成物は、親
水性アクリル系モノビニルモノマーと芳香族ポリビニル
モノマーとを含有することを特徴とする。The method for producing a hydrophilic gel-containing separator of the present invention comprises a step of polymerizing a monomer composition for forming a crosslinked polymer to obtain a polymer, and mixing the crosslinked polymer with a solvent to prepare a hydrophilic gel dispersion liquid. Dispersing step, coating step of applying and impregnating the hydrophilic gel dispersion liquid to the porous substrate, and applying the hydrophilic gel dispersion liquid, drying the impregnated porous substrate to obtain a hydrophilic gel-containing separator And a cross-linking polymer-forming monomer composition, wherein the cross-linked polymer-forming monomer composition contains a hydrophilic acrylic monovinyl monomer and an aromatic polyvinyl monomer.
【００２０】上記の親水性ゲル含有セパレーターの製造
方法においては、前記親水性アクリル系モノビニルモノ
マーが、（メタ）アクリル酸、（メタ）アクリル酸塩か
ら選択される少なくとも１種であり、前記芳香族ポリビ
ニルモノマーが、ジビニルベンゼン、ジビニルトルエン
の少なくとも１種であることが好ましい。In the above method for producing a hydrophilic gel-containing separator, the hydrophilic acrylic monovinyl monomer is at least one selected from (meth) acrylic acid and (meth) acrylic acid salt, and the aromatic The polyvinyl monomer is preferably at least one kind of divinylbenzene and divinyltoluene.
【００２１】[0021]
【発明の実施の形態】本発明に使用する原料について説
明する。親水性アクリル系モノビニルモノマーである
（メタ）アクリル酸塩としては、アクリル酸カリウム、
アクリル酸ナトリウム、アクリル酸リチウム、メタクリ
ル酸カリウム、メタクリル酸ナトリウム、メタクリル酸
リチウム等の（メタ）アクリル酸アルカリ金属塩、アク
リル酸アンモニウム、メタクリル酸アンモニウム等の
（メタ）アクリル酸アンモニウムが例示される。これら
の化合物は、用途に応じて適宜選択使用される。例え
ば、（メタ）アクリル酸アルカリ金属塩は、ニッケル水
素電池用として好ましく、（メタ）アクリル酸アンモニ
ウムはアルミ電解コンデンサー用として好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Raw materials used in the present invention will be described. As the (meth) acrylic acid salt, which is a hydrophilic acrylic monovinyl monomer, potassium acrylate,
Examples thereof include alkali metal salts of (meth) acrylic acid such as sodium acrylate, lithium acrylate, potassium methacrylate, sodium methacrylate and lithium methacrylate, and ammonium (meth) acrylate such as ammonium acrylate and ammonium methacrylate. These compounds are appropriately selected and used according to the application. For example, alkali metal (meth) acrylate is preferable for nickel-hydrogen batteries, and ammonium (meth) acrylate is preferable for aluminum electrolytic capacitors.
【００２２】（メタ）アクリル酸と（メタ）アクリル酸
塩とを併用する場合、（メタ）アクリル酸塩の比率
（（メタ）アクリル酸の中和度）は、２０〜１００％で
あることが好ましい。When (meth) acrylic acid and (meth) acrylic acid salt are used in combination, the ratio of the (meth) acrylic acid salt (the degree of neutralization of (meth) acrylic acid) is 20 to 100%. preferable.
【００２３】中和度が低すぎると電解液保持効果が低下
し、ゲル状電解質としたときのイオン伝導度が十分でな
い場合が生じる。If the degree of neutralization is too low, the electrolyte retaining effect will be reduced, and the ionic conductivity of the gel electrolyte may be insufficient.
【００２４】本発明の親水ゲルにおいては、芳香族ポリ
ビニルモノマーに加えて、本発明の目的を損なわない範
囲で親水性アクリル系ポリビニルモノマーであるポリオ
キシアルキレンポリオールポリ（メタ）アクリレート、
例えばポリオキシエチレングリコールジアクリレート、
ポリオキシエチレングリコールジメタクリレート、ポリ
オキシエチレン−プロピレンジアクリレート、ポリオキ
シエチレン−プロピレンジメタクリレート、ポリオキシ
プロピレンジメタクリレート、ポリオキシプロピレンジ
アクリレート等を併用してもよい。In the hydrophilic gel of the present invention, in addition to the aromatic polyvinyl monomer, polyoxyalkylene polyol poly (meth) acrylate, which is a hydrophilic acrylic polyvinyl monomer, is added within the range not impairing the object of the present invention.
For example polyoxyethylene glycol diacrylate,
You may use together polyoxyethylene glycol dimethacrylate, polyoxyethylene-propylene diacrylate, polyoxyethylene-propylene dimethacrylate, polyoxypropylene dimethacrylate, polyoxypropylene diacrylate, and the like.
【００２５】ポリオキシアルキレンポリオールポリ（メ
タ）アクリレートを構成するポリオキシアルキレン基
は、オキシアルキレンの繰り返し単位数（重合度）が２
〜２０であることが好ましく、４〜１６であることがよ
り好ましい。ポリオキシアルキレン基は、ポリオキシエ
チレン基又はポリオキシエチレン・プロピレン基である
ことがより親水性が高く、好ましい。The polyoxyalkylene group constituting the polyoxyalkylene polyol poly (meth) acrylate has a number of oxyalkylene repeating units (degree of polymerization) of 2
It is preferable that it is -20, and it is more preferable that it is 4-16. The polyoxyalkylene group is preferably a polyoxyethylene group or a polyoxyethylene / propylene group because it has higher hydrophilicity.
【００２６】親水性アクリル系モノビニルモノマーと芳
香族ポリビニルモノマーの混合比率は、モノビニルモノ
マー：ポリビニルモノマーのモル比にて３０：１〜１０
００：１であることが好ましい。この比が３０：１より
もポリビニルモノマーが多すぎると架橋密度が高くなっ
て電解液の保持率が低下し、親水性ゲル含有セパレータ
ーのイオン伝導度が低下する。またモノビニルモノマ
ー：ポリビニルモノマーの比が１０００：１よりもポリ
ビニルモノマーが多すぎると形成されるゲル状電解質が
流動性を帯びるようになり、好ましくない。The mixing ratio of the hydrophilic acrylic monovinyl monomer and the aromatic polyvinyl monomer is 30: 1 to 10 in terms of the molar ratio of monovinyl monomer: polyvinyl monomer.
It is preferably 00: 1. When the ratio is more than 30: 1 and the amount of the polyvinyl monomer is too large, the crosslink density becomes high, the retention rate of the electrolytic solution decreases, and the ionic conductivity of the hydrophilic gel-containing separator decreases. If the ratio of monovinyl monomer: polyvinyl monomer is more than 1000: 1, the gel electrolyte formed becomes fluid, which is not preferable.
【００２７】電解液成分として使用する電解質は、電
池、コンデンサーの電解質として公知であり、水溶性の
安定な電解質が用途に応じて適宜選択して使用される。
具体的には、ＫＯＨ，ＮａＯＨ，ＬｉＯＨ等のアルカリ
金属水酸化物、アジピン酸アンモニウム、アクリル酸ア
ンモニウム等のカルボン酸アンモニウム塩が例示され
る。The electrolyte used as an electrolyte solution component is known as an electrolyte for batteries and capacitors, and a water-soluble and stable electrolyte is appropriately selected and used according to the application.
Specific examples thereof include alkali metal hydroxides such as KOH, NaOH and LiOH, and ammonium carboxylates such as ammonium adipate and ammonium acrylate.
【００２８】親水性ゲル含有セパレーターの構成材料で
ある多孔性基材は、従来、電池やコンデンサーのセパレ
ーターとして使用されていた材料が限定なく使用可能で
あり、ポリエチレン、ポリプロピレン、ポリ四フッ化エ
チレン等の樹脂の多孔質膜、不織布、クラフト紙やマニ
ラ紙などの紙類が例示される。樹脂製多孔質膜は、架橋
構造を有するものであってもよい。As the porous base material which is a constituent material of the hydrophilic gel-containing separator, materials conventionally used as separators for batteries and capacitors can be used without limitation, such as polyethylene, polypropylene and polytetrafluoroethylene. Examples of the resin include a porous film, a non-woven fabric, and papers such as kraft paper and Manila paper. The resin porous membrane may have a crosslinked structure.
【００２９】本発明の親水性ゲル含有セパレーターの製
造においては、多孔性基材に塗布、含浸する親水性ゲル
分散液の溶媒は親水性溶媒であることが好ましいから、
上記のセパレーター材料のなかでも表面が親水性の材料
を使用することが好ましい。クラフト紙やマニラ紙など
の紙類は、親水性が高い素材であり、そのまま使用可能
である。ポリエチレンやポリプロピレンを素材として使
用したセパレーターの場合には、コロナ放電処理、プラ
ズマ処理などを行うことにより、親水性にして多孔性基
材として使用することができる。またこれら多孔性基材
の中でも、ゲル保持性能が優れていることから、不織布
もしくはクラフト紙やマニラ紙などの紙類の使用が特に
好ましい。In the production of the hydrophilic gel-containing separator of the present invention, the solvent of the hydrophilic gel dispersion liquid applied to and impregnated on the porous substrate is preferably a hydrophilic solvent.
Among the above separator materials, it is preferable to use a material having a hydrophilic surface. Papers such as kraft paper and Manila paper are highly hydrophilic materials and can be used as they are. In the case of a separator using polyethylene or polypropylene as a material, it can be made hydrophilic by using corona discharge treatment, plasma treatment or the like and used as a porous substrate. Among these porous substrates, the use of non-woven fabric or paper such as kraft paper and Manila paper is particularly preferable because of its excellent gel retention performance.
【００３０】本発明において使用する多孔性基材は、電
解液が親水性ゲルによって保持されるために従来のセパ
レーターよりも孔径が大きいものであってもよく、孔の
中にゲルが入り込んでいてもよい。The porous substrate used in the present invention may have a pore size larger than that of the conventional separator because the electrolytic solution is retained by the hydrophilic gel, and the gel enters the pores. Good.
【００３１】本発明の親水性ゲル含有セパレーターの製
造方法は上述のように、親水性重合性モノマーを重合さ
せて重合体とする重合工程、前記重合体を溶媒と混合し
て親水性ゲル分散液とする分散工程、前記親水性ゲル分
散液を多孔性基材に塗布、含浸させる塗布工程、及び前
記親水性ゲル分散液を塗布、含浸された前記多孔性基材
を乾燥して親水性ゲル含有セパレーターとする乾燥工程
とを有する。As described above, the method for producing the hydrophilic gel-containing separator of the present invention comprises the step of polymerizing a hydrophilic polymerizable monomer to give a polymer, and mixing the polymer with a solvent to obtain a hydrophilic gel dispersion. Dispersing step, coating step of applying and impregnating the hydrophilic gel dispersion liquid to the porous substrate, and applying the hydrophilic gel dispersion liquid, and drying the impregnated porous substrate to contain the hydrophilic gel A separator and a drying step.
【００３２】親水性重合性モノマーを重合させて重合体
とする重合工程は、溶液重合、バルク重合のいずれであ
ってもよい。溶液重合を行う場合、使用する溶剤は、モ
ノマーを溶解するものであれば、特に限定なく使用可能
である。The polymerization step of polymerizing the hydrophilic polymerizable monomer to form a polymer may be either solution polymerization or bulk polymerization. When carrying out the solution polymerization, the solvent to be used can be used without particular limitation as long as it dissolves the monomer.
【００３３】親水性モノマーとして（メタ）アクリル酸
とその（メタ）アクリル酸塩の双方を使用する場合にお
いては、（メタ）アクリル酸を例えば水酸化アルカリ金
属化合物やアンモニアの水溶液に溶解して重合させるこ
とにより、（メタ）アクリル酸とその金属塩の双方を含
有する親水性重合体が得られる。When both (meth) acrylic acid and its (meth) acrylic acid salt are used as the hydrophilic monomer, the (meth) acrylic acid is dissolved in an aqueous solution of an alkali metal hydroxide compound or ammonia for polymerization. By doing so, a hydrophilic polymer containing both (meth) acrylic acid and its metal salt can be obtained.
【００３４】水に代えて、もしくは水と共にアルコール
類、ジオキサン等のエーテル化合物、メチルセロソルブ
等のセロソルブ類等の親水性有機溶剤を使用することも
好適な態様であり、乾燥工程における乾燥時間を短縮す
る効果が得られる。It is also a preferred embodiment to use a hydrophilic organic solvent such as an alcohol, an ether compound such as dioxane, or a cellosolve such as methyl cellosolve instead of or together with water, and shorten the drying time in the drying step. The effect is obtained.
【００３５】重合方法としては、重合開始剤を使用する
方法、紫外線、電子線等の活性エネルギー線を使用する
方法等の公知の重合方法が使用可能である。水系溶媒を
使用し、重合開始剤を使用して重合体を製造する場合に
は、水が沸騰しない温度で重合する必要があり、レドッ
クス系重合開始剤を使用することが好ましく、とりわけ
重金属イオンを含有しないレドックス系重合開始剤の使
用が好適である。As the polymerization method, known polymerization methods such as a method using a polymerization initiator and a method using active energy rays such as ultraviolet rays and electron rays can be used. Using a water-based solvent, when producing a polymer using a polymerization initiator, it is necessary to polymerize at a temperature at which water does not boil, it is preferable to use a redox-based polymerization initiator, especially heavy metal ions It is preferable to use a redox-based polymerization initiator that does not contain it.
【００３６】かかる水系レドックス系開始剤としては、
過酸化水素、過硫酸カリウム、過硫酸ナトリウム、過硫
酸リチウム、過硫酸アンモニウム等の過硫酸塩とＬ−ア
スコルビン酸等の還元剤の組合せが好適なものとして例
示される。これらの開始剤は、公知の添加量にて使用す
る。Examples of such water-based redox initiators include
A preferable combination of persulfates such as hydrogen peroxide, potassium persulfate, sodium persulfate, lithium persulfate and ammonium persulfate and a reducing agent such as L-ascorbic acid is exemplified. These initiators are used in known addition amounts.
【００３７】重合工程にて得られた親水性ゲルである重
合体は、親水性ゲル分散液として多孔性基材に塗布、含
浸する。重合体を親水性ゲル分散液とする方法として
は、重合体を粉砕して適宜の溶媒に分散する方法、重合
体を溶媒にて膨潤させた後に粉砕して分散液とする方法
のいずれによってもよい。溶液重合して全体として含溶
媒親水性ゲルとなったものにさらに溶媒を添加し、分散
機にて分散して微粒子状態に分散する方法、バルク重合
により得られた重合体もしくは含溶媒親水性ゲルを乾燥
して得られた重合体を微粉状に粉砕し、これを溶媒に分
散する方法機により分散可能であり、好ましい。The polymer, which is the hydrophilic gel obtained in the polymerization step, is applied and impregnated on the porous substrate as a hydrophilic gel dispersion liquid. As a method for making the polymer a hydrophilic gel dispersion liquid, any of a method of pulverizing the polymer and dispersing it in an appropriate solvent, and a method of swelling the polymer with a solvent and then pulverizing the dispersion liquid to form a dispersion liquid may be used. Good. A method in which a solvent is further added to a solution-polymerized hydrophilic gel as a whole and dispersed by a disperser into a fine particle state, a polymer obtained by bulk polymerization or a solvent-containing hydrophilic gel. It is possible and preferable to be able to disperse the obtained polymer by pulverizing the obtained polymer into a fine powder and dispersing it in a solvent.
【００３８】含溶媒親水性ゲルとなったものにさらに溶
媒を添加し、分散機にて分散する方法に使用する分散機
としては、適当なせん断力を有する撹拌機を使用するこ
とができ、ディゾルバー、ディスパー、ホモジナイザー
等の撹拌機を使用することができる。As a disperser used in the method of further adding a solvent to the solvent-containing hydrophilic gel and dispersing it with a disperser, a stirrer having an appropriate shearing force can be used. A stirrer such as a disperser, a disperser, or a homogenizer can be used.
【００３９】含溶媒親水性ゲルに添加する溶媒として
は、重合工程において使用する溶媒と同じものが使用可
能であり、水であることがより好ましい。As the solvent added to the solvent-containing hydrophilic gel, the same solvent as used in the polymerization step can be used, and water is more preferable.
【００４０】セパレーター材料である多孔性基材に親水
性ゲル分散液を塗布、含浸する方法としては、公知の塗
装方法は限定なく使用可能である。具体的には、含浸法
（ディッピング法）、ロールコーターやドクターブレー
ド等を使用したコーティング法、スプレー塗装法等が例
示される。As a method for coating and impregnating the hydrophilic gel dispersion liquid on the porous base material which is the separator material, known coating methods can be used without limitation. Specific examples include an impregnation method (dipping method), a coating method using a roll coater or a doctor blade, and a spray coating method.
【００４１】本発明により得られた親水性ゲル含有セパ
レーターは、従来のセパレーターと同様に用途に応じた
サイズに裁断し、電極部材と積層して電池やコンデンサ
ーに使用可能である。本発明の親水性ゲル含有セパレー
ターを使用して電解液を電極間に充填すると、該電解液
は親水性ゲルに吸収、保持される。その結果、温度上昇
しても水の蒸気圧の上昇が従来より小さく、ケースが破
損しても電解液が漏洩することが防止される。The hydrophilic gel-containing separator obtained by the present invention can be cut into a size according to the application like conventional separators and laminated with an electrode member to be used in batteries and capacitors. When the electrolytic solution is filled between the electrodes using the hydrophilic gel-containing separator of the present invention, the electrolytic solution is absorbed and retained by the hydrophilic gel. As a result, even if the temperature rises, the rise in vapor pressure of water is smaller than in the conventional case, and the electrolyte is prevented from leaking even if the case is damaged.
【００４２】[0042]
【実施例】以下、本発明の構成と効果を具体的に示す実
施例等について説明する。
＜親水性ゲル、ゲル状電解液の製造例＞
（実施例１）水酸化カリウム（ナカライ製）４９．４ｇ
（０．７５ｍｏｌ）を６０ｇのイオン交換水に溶解して
水酸化カリウム水溶液を調製した。この水酸化カリウム
水溶液とアクリル酸（ナカライ製）７２ｇ（１．０ｍｏ
ｌ）を混合して中和することにより部分中和アクリル酸
水溶液（中和度７５％）を得た。上記の部分中和アクリ
ル酸水溶液１６０ｇとジビニルベンゼン（ナカライ製）
２．６ｇを水／１−ペンタノール（水／１−ペンタノー
ル＝１．１／１（重量比））混合溶媒４３．６ｇ中にて
混合し、得られた混合溶液に、ラジカル重合開始剤とし
て過酸化水素水（濃度３０％）２．３４ｇ，Ｌ−アスコ
ルビン酸０．１８２ｇを添加、混合して親水性ゲル形成
組成物Ａを得た。得られた親水性ゲル形成組成物Ａを撹
拌しながら５０℃にて１時間加熱することにより共重合
体である親水性ゲル（ｇ１）を得た。得られた親水性ゲ
ル（ｇ１）を１ｃｍ角程度に切断した後、１５０℃で２
４時間加熱乾燥させることにより、重合体粗粉末を得
た。続いて、該重合体粗粉末を遠心粉砕機を用いて微粉
砕化することにより、部分中和アクリル酸の親水性ゲル
微粉末（ｐ１）を作製した。得られた親水性ゲル微粉末
（ｐ１）に対して７Ｍ−ＫＯＨ水溶液を、（親水性ゲ
ル）：（７Ｍ−ＫＯＨ水溶液）＝１：１０（重量比）と
なるように混合し、減圧下に空気泡を脱泡してゲル状電
解質（Ｇ１）を作製した。上記ゲル状電解質（Ｇ１）
は、室温におけるイオン伝導度は３．２×１０-2Ｓ／ｃ
ｍであり、イオン伝導性に優れたものであった。またゲ
ル状電解質（Ｇ１）は形状安定性がよく、自己保持性を
示した。さらに、１５０℃の耐熱性評価を行ったとこ
ろ、１０００時間後においても元のゲル形状を保持して
おり、優れた耐熱性を有していた。EXAMPLES Examples and the like specifically showing the constitution and effects of the present invention will be described below. <Production Example of Hydrophilic Gel and Gel Electrolyte> (Example 1) 49.4 g of potassium hydroxide (manufactured by Nakarai)
(0.75 mol) was dissolved in 60 g of ion-exchanged water to prepare an aqueous potassium hydroxide solution. This potassium hydroxide aqueous solution and acrylic acid (made by Nakarai) 72g (1.0mo
l) was mixed and neutralized to obtain a partially neutralized acrylic acid aqueous solution (neutralization degree: 75%). 160 g of the above partially neutralized acrylic acid aqueous solution and divinylbenzene (made by Nakarai)
2.6 g of water / 1-pentanol (water / 1-pentanol = 1.1 / 1 (weight ratio)) mixed solvent 43.6 g was mixed, and the radical polymerization initiator was added to the obtained mixed solution. As a solution, 2.34 g of hydrogen peroxide solution (concentration 30%) and 0.182 g of L-ascorbic acid were added and mixed to obtain a hydrophilic gel-forming composition A. The hydrophilic gel-forming composition A thus obtained was heated at 50 ° C. for 1 hour with stirring to obtain a hydrophilic gel (g1) as a copolymer. The hydrophilic gel (g1) thus obtained is cut into 1 cm square pieces, and then 2 ° C. at 150 ° C.
A polymer coarse powder was obtained by heating and drying for 4 hours. Subsequently, the polymer coarse powder was finely pulverized using a centrifugal pulverizer to prepare a hydrophilic gel fine powder (p1) of partially neutralized acrylic acid. The obtained hydrophilic gel fine powder (p1) was mixed with 7M-KOH aqueous solution so that (hydrophilic gel) :( 7M-KOH aqueous solution) = 1: 10 (weight ratio), and the mixture was mixed under reduced pressure. Air bubbles were removed to prepare a gel electrolyte (G1). The gel electrolyte (G1)
Has an ionic conductivity of 3.2 × 10 -2 S / c at room temperature.
m, and was excellent in ionic conductivity. Further, the gel electrolyte (G1) had good shape stability and exhibited self-holding property. Furthermore, when the heat resistance was evaluated at 150 ° C., the original gel shape was retained even after 1000 hours, and it had excellent heat resistance.
【００４３】（実施例２）水酸化カリウム（ナカライ
製）３３．０ｇ（０．５０ｍｏｌ）を６０ｇのイオン交
換水に溶解して水酸化カリウム水溶液を調製した。この
水酸化カリウム水溶液とアクリル酸（ナカライ製）７２
ｇ（１．０ｍｏｌ）を混合して中和することにより部分
中和アクリル酸水溶液（中和度５０％）を得た。上記の
部分中和アクリル酸水溶液１５０．２ｇとジビニルベン
ゼン（ナカライ製）０．２６ｇを水／１−ペンタノール
混合溶媒（水／１−ペンタノール＝３．１／１（重量
比））３７．７ｇ中にて混合し、得られた混合溶液にラ
ジカル重合開始剤として過硫酸カリウム１．０２ｇ，Ｌ
−アスコルビン酸０．０１３ｇを添加して混合して親水
性ゲル形成組成物Ｂを得た。得られた親水性ゲル形成組
成物Ｂを撹拌しながら５０℃にて１時間加熱することに
より共重合体である親水性ゲル（ｇ２）を得た。得られ
た親水性ゲル（ｇ２）を１ｃｍ角程度に切断した後、１
５０℃で２４時間加熱乾燥させることにより、重合体粗
粉末を得た。続いて、該重合体粗粉末を遠心粉砕機を用
いて微粉砕化することにより、部分中和アクリル酸の親
水性ゲル微粉末（ｐ２）を作製した。得られた親水性ゲ
ル微粉末（ｐ２）に対して７Ｍ−ＫＯＨ水溶液を、（親
水性ゲル）：（７Ｍ−ＫＯＨ水溶液）＝１：１０（重量
比）となるように混合し、減圧下に空気泡を脱泡してゲ
ル状電解質（Ｇ２）を作製した。上記ゲル状電解質（Ｇ
２）は、室温におけるイオン伝導度は３．１×１０-2Ｓ
／ｃｍであり、イオン伝導性に優れたものであった。ま
たゲル状電解質（Ｇ２）は形状安定性がよく、自己保持
性を示した。さらに、１５０℃の耐熱性評価を行ったと
ころ、１０００時間後においても元のゲル形状を保持し
ており、優れた耐熱性を有していた。Example 2 A potassium hydroxide aqueous solution was prepared by dissolving 33.0 g (0.50 mol) of potassium hydroxide (manufactured by Nakarai Co., Ltd.) in 60 g of ion-exchanged water. This potassium hydroxide aqueous solution and acrylic acid (made by Nakarai) 72
g (1.0 mol) was mixed and neutralized to obtain a partially neutralized acrylic acid aqueous solution (neutralization degree: 50%). 150.2 g of the partially neutralized acrylic acid aqueous solution and 0.26 g of divinylbenzene (manufactured by Nakarai) were mixed with water / 1-pentanol mixed solvent (water / 1-pentanol = 3.1 / 1 (weight ratio)). 7 g, and the obtained mixed solution was added with potassium persulfate as a radical polymerization initiator 1.02 g, L
-0.013 g of ascorbic acid was added and mixed to obtain a hydrophilic gel-forming composition B. The hydrophilic gel-forming composition B thus obtained was heated at 50 ° C. for 1 hour with stirring to obtain a hydrophilic gel (g2) as a copolymer. After cutting the obtained hydrophilic gel (g2) into 1 cm square pieces, 1
A polymer coarse powder was obtained by heating and drying at 50 ° C. for 24 hours. Then, the polymer coarse powder was finely pulverized using a centrifugal pulverizer to prepare a hydrophilic gel fine powder (p2) of partially neutralized acrylic acid. The obtained hydrophilic gel fine powder (p2) was mixed with 7M-KOH aqueous solution so that (hydrophilic gel) :( 7M-KOH aqueous solution) = 1: 10 (weight ratio), and the mixture was decompressed. Air bubbles were removed to prepare a gel electrolyte (G2). The gel electrolyte (G
2) has an ionic conductivity of 3.1 × 10 -2 S at room temperature.
/ Cm, which was excellent in ionic conductivity. Further, the gel electrolyte (G2) had good shape stability and exhibited self-holding property. Furthermore, when the heat resistance was evaluated at 150 ° C., the original gel shape was retained even after 1000 hours, and it had excellent heat resistance.
【００４４】（実施例３）アンモニア水（アンモニア濃
度２８％、ナカライ製）４５．５ｇ（０．７５ｍｏｌ）
とアクリル酸（ナカライ製）７２ｇ（１．０ｍｏｌ）を
混合して中和することにより部分中和アクリル酸水溶液
（中和度７５％）を得た。上記の部分中和アクリル酸水
溶液１１７．５ｇとジビニルベンゼン（ナカライ製）
０．２６ｇを水／エタノール混合溶媒（水／エタノール
＝１／１（重量比））５２．３ｇ中にて混合し、得られ
た混合溶液に開始剤として過酸化水素水（濃度３０％）
１．９３ｇ，Ｌ−アスコルビン酸０．１５ｇを添加して
混合して親水性ゲル形成組成物Ｃを得た。得られた親水
性ゲル形成組成物Ｃを撹拌しながら５０℃にて１時間加
熱することにより共重合体である親水性ゲル（ｇ３）を
得た。得られた親水性ゲル（ｇ３）を１ｃｍ角程度に切
断した後、１５０℃で２４時間加熱乾燥させることによ
り、重合体粗粉末を得た。続いて、該重合体粗粉末を遠
心粉砕機を用いて微粉砕化することにより、部分中和ア
クリル酸の親水性ゲル微粉末（ｐ３）を作製した。得ら
れた親水性ゲル微粉末（ｐ３）に対して電解液としてア
ジピン酸アンモニウムの１ｍｏｌ／ｌ水溶液を、（親水
性ゲル）：（電解液）＝１：１０（重量比）となるよう
に混合し、減圧下に空気泡を脱泡してゲル状電解質（Ｇ
３）を作製した。上記ゲル状電解質（Ｇ３）は、室温に
おけるイオン伝導度は３．１×１０-3Ｓ／ｃｍであり、
イオン伝導性に優れたものであった。またゲル状電解質
（Ｇ３）は形状安定性がよく、自己保持性を示した。さ
らに、１５０℃の耐熱性評価を行ったところ、１０００
時間後においても元のゲル形状を保持しており、優れた
耐熱性を有していた。(Example 3) Ammonia water (ammonia concentration 28%, made by Nakarai) 45.5 g (0.75 mol)
And 72 g (1.0 mol) of acrylic acid (made by Nakarai) were mixed and neutralized to obtain a partially neutralized acrylic acid aqueous solution (neutralization degree: 75%). 117.5 g of the above partially neutralized acrylic acid aqueous solution and divinylbenzene (made by Nakarai)
0.26 g was mixed in 52.3 g of water / ethanol mixed solvent (water / ethanol = 1/1 (weight ratio)), and the resulting mixed solution was hydrogen peroxide water (concentration 30%) as an initiator.
Hydrophilic gel-forming composition C was obtained by adding and mixing 1.93 g and 0.15 g of L-ascorbic acid. The hydrophilic gel-forming composition C thus obtained was heated at 50 ° C. for 1 hour with stirring to obtain a hydrophilic gel (g3) as a copolymer. The obtained hydrophilic gel (g3) was cut into 1 cm square pieces, and then dried by heating at 150 ° C. for 24 hours to obtain a polymer coarse powder. Then, the polymer coarse powder was finely pulverized using a centrifugal pulverizer to prepare a hydrophilic gel fine powder (p3) of partially neutralized acrylic acid. A 1 mol / l aqueous solution of ammonium adipate was mixed as an electrolytic solution with the obtained hydrophilic gel fine powder (p3) so that (hydrophilic gel) :( electrolytic solution) = 1: 10 (weight ratio). Then, the air bubbles are removed under reduced pressure to remove the gel electrolyte (G
3) was produced. The gel electrolyte (G3) has an ionic conductivity at room temperature of 3.1 × 10 −3 S / cm,
It had excellent ionic conductivity. Further, the gel electrolyte (G3) had good shape stability and exhibited self-holding property. Furthermore, when the heat resistance at 150 ° C. was evaluated, it was 1000
The original gel shape was retained even after a lapse of time, and it had excellent heat resistance.
【００４５】（実施例４）アンモニア水（ナカライ製、
アンモニア濃度２８％）１５．２ｇ（０．２５ｍｏｌ）
とアクリル酸（ナカライ製）７２ｇ（１．０ｍｏｌ）を
混合して中和することにより部分中和アクリル酸水溶液
（中和度５０％）を得た。上記の部分中和アクリル酸水
溶液８７．１ｇとジビニルベンゼン（ナカライ製）１．
３ｇを水／エタノール混合溶媒（水／エタノール＝１．
９／１（重量比））６６．６ｇ中にて混合し、得られた
混合溶液に開始剤として過酸化水素水（濃度３０％）
１．７６ｇ，Ｌ−アスコルビン酸０．１３７ｇを添加し
て混合して親水性ゲル形成組成物Ｄを得た。得られた親
水性ゲル形成組成物Ｄを撹拌しながら５０℃にて１時間
加熱することにより共重合体である親水性ゲル（ｇ４）
を得た。得られた親水性ゲル（ｇ４）を１ｃｍ角程度に
切断した後、１５０℃で２４時間加熱乾燥させることに
より、重合体粗粉末を得た。続いて、該重合体粗粉末を
遠心粉砕機を用いて微粉砕化することにより、部分中和
アクリル酸の親水性ゲル微粉末（ｐ４）を作製した。得
られた親水性ゲル微粉末（ｐ４）に対して電解液として
アジピン酸アンモニウムの１ｍｏｌ／ｌ水溶液を、（親
水性ゲル）：（電解液）＝１：１０（重量比）となるよ
うに混合し、減圧下に空気泡を脱泡してゲル状電解質
（Ｇ４）を作製した。上記ゲル状電解質（Ｇ４）は、室
温におけるイオン伝導度は３．４×１０-3Ｓ／ｃｍであ
り、イオン伝導性に優れたものであった。またゲル状電
解質（Ｇ４）は形状安定性がよく、自己保持性を示し
た。さらに、１５０℃の耐熱性評価を行ったところ、１
０００時間後においても元のゲル形状を保持しており、
優れた耐熱性を有していた。(Example 4) Ammonia water (made by Nakarai,
Ammonia concentration 28%) 15.2 g (0.25 mol)
And 72 g (1.0 mol) of acrylic acid (made by Nakarai) were mixed and neutralized to obtain a partially neutralized acrylic acid aqueous solution (neutralization degree: 50%). 87.1 g of the above partially neutralized acrylic acid aqueous solution and divinylbenzene (manufactured by Nakarai) 1.
3 g of water / ethanol mixed solvent (water / ethanol = 1.
9/1 (weight ratio)) 66.6 g, and the resulting mixed solution is hydrogen peroxide water (concentration 30%) as an initiator.
Hydrophilic gel-forming composition D was obtained by adding 1.76 g and 0.137 g of L-ascorbic acid and mixing. The resulting hydrophilic gel-forming composition D was heated at 50 ° C. for 1 hour with stirring to obtain a hydrophilic gel (g4) which is a copolymer.
Got The obtained hydrophilic gel (g4) was cut into 1 cm square pieces, and then dried by heating at 150 ° C. for 24 hours to obtain a polymer coarse powder. Then, the polymer coarse powder was finely pulverized by using a centrifugal pulverizer to prepare a hydrophilic gel fine powder (p4) of partially neutralized acrylic acid. A 1 mol / l aqueous solution of ammonium adipate was mixed as an electrolytic solution with the obtained hydrophilic gel fine powder (p4) so that (hydrophilic gel) :( electrolytic solution) = 1: 10 (weight ratio). Then, air bubbles were removed under reduced pressure to prepare a gel electrolyte (G4). The gel electrolyte (G4) had an ionic conductivity at room temperature of 3.4 × 10 −3 S / cm, and was excellent in ionic conductivity. Further, the gel electrolyte (G4) had good shape stability and exhibited self-holding property. Furthermore, when the heat resistance at 150 ° C. was evaluated, it was 1
The original gel shape is retained even after 000 hours,
It had excellent heat resistance.
【００４６】＜親水性ゲル含有セパレーターの製造例＞
実施例１にて得られた親水性ゲル微粉末（ｐ１）１０ｇ
に水１００ｇを加え、十分に撹拌し、親水性ゲル分散液
（ｄ１）を調製した。この親水性ゲル分散液（ｄ１）
を、多孔性基材として従来からセパレーターとして使用
されている不織布セパレーターＷＰＳＤ４０Ｃ１００
（日本高度紙工業社製）に目付量３０ｇ／ｍ2 となるよ
うに塗布したのち、乾燥させることにより、親水性ゲル
含有セパレーター（Ｓ１）を得た。<Production Example of Hydrophilic Gel-Containing Separator>
10 g of hydrophilic gel fine powder (p1) obtained in Example 1
100 g of water was added to and the mixture was sufficiently stirred to prepare a hydrophilic gel dispersion liquid (d1). This hydrophilic gel dispersion (d1)
Is a non-woven fabric separator WPSD40C100 which has been conventionally used as a separator as a porous substrate.
A hydrophilic gel-containing separator (S1) was obtained by applying a coating weight of 30 g / m 2 (manufactured by Nippon Kogaku Kogyo Co., Ltd.) and drying.
【００４７】得られた親水性ゲル含有セパレーター（Ｓ
１）に対して７Ｍ−ＫＯＨ水溶液を、（ゲル付着量）：
（７Ｍ−ＫＯＨ水溶液）＝１：１０（重量比）となるよ
うに含浸させ、ゲル状電解液保持セパレーターを作製し
た。このゲル状電解液保持セパレーターについて、開放
状態で８０℃にて保持したところ、不織布セパレーター
ＷＰＳＤ４０Ｃ１００に電解液を含浸させたものと比較
すると、２４時間後の重量減少率、即ち電解液の蒸発減
量率は、約３０％小さかった。本発明の親水性ゲル含有
セパレーターは電解液含有率が高く、しかも水の蒸発が
抑制され、従来よりはるかに漏液を起こしにくい電池、
コンデンサーが形成可能であることが分かる。The resulting hydrophilic gel-containing separator (S
7M-KOH aqueous solution to 1), (gel adhesion amount):
(7M-KOH aqueous solution) = 1:10 (weight ratio) was impregnated to prepare a gel electrolyte retaining separator. When this gel electrolyte holding separator was held at 80 ° C. in an open state, as compared with a non-woven fabric separator WPSD40C100 impregnated with the electrolyte, the weight reduction rate after 24 hours, that is, the evaporation loss rate of the electrolyte Was about 30% smaller. The hydrophilic gel-containing separator of the present invention has a high electrolytic solution content, and further, evaporation of water is suppressed, and a battery that is much less likely to leak than before,
It can be seen that a capacitor can be formed.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｇ 9/035 Ｈ０１Ｍ 10/30 Ａ Ｈ０１Ｍ 2/16 Ｈ０１Ｇ 9/02 ３１１ 10/30 9/24 Ａ Ｆターム(参考） 4J100 AB15Q AB16Q AJ03P AK03P AK08P CA04 DA36 EA03 JA43 5G301 CA16 CA17 CA30 CD01 5H021 AA06 BB12 BB13 CC02 EE03 EE06 EE15 EE33 5H028 AA05 BB03 BB04 BB05 BB06 EE06 FF06 FF09 FF10 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 7 Identification code FI theme code (reference) H01G 9/035 H01M 10/30 A H01M 2/16 H01G 9/02 311 10/30 9/24 A F term (Reference) 4J100 AB15Q AB16Q AJ03P AK03P AK08P CA04 DA36 EA03 JA43 5G301 CA16 CA17 CA30 CD01 5H021 AA06 BB12 BB13 CC02 EE03 EE06 EE15 EE33 5H028 AA05 BB03 BB04 BB05 BB06 EE06 FF06FF06FF06FF
Claims (8)
芳香族ポリビニルモノマーとを共重合して得られ、水系
電解液の保持率が６倍（重量比）以上のゲル状電解液を
形成可能であるゲル状電解液用親水性ゲル。1. A gel obtained by copolymerizing a hydrophilic acrylic monovinyl monomer and an aromatic polyvinyl monomer, capable of forming a gel electrolyte having a retention rate of the aqueous electrolyte of 6 times (weight ratio) or more. Gel for liquid electrolyte.
ーが、（メタ）アクリル酸、（メタ）アクリル酸塩から
選択される少なくとも１種である請求項１に記載のゲル
状電解液用親水性ゲル。2. The hydrophilic gel for a gel electrolyte according to claim 1, wherein the hydrophilic acrylic monovinyl monomer is at least one selected from (meth) acrylic acid and (meth) acrylic acid salt.
ニルベンゼン、ジビニルトルエンの少なくとも１種であ
る請求項１又は２に記載のゲル状電解液用親水性ゲル。3. The hydrophilic gel for a gel electrolyte according to claim 1, wherein the aromatic polyvinyl monomer is at least one of divinylbenzene and divinyltoluene.
芳香族ポリビニルモノマーとを共重合して得られる親水
性ゲルを付着保持する多孔性基材からなる親水性ゲル含
有セパレーター。4. A hydrophilic gel-containing separator comprising a porous substrate that adheres and holds a hydrophilic gel obtained by copolymerizing a hydrophilic acrylic monovinyl monomer and an aromatic polyvinyl monomer.
ーが、（メタ）アクリル酸、（メタ）アクリル酸塩から
選択される少なくとも１種である請求項４に記載の親水
性ゲル含有セパレーター。5. The hydrophilic gel-containing separator according to claim 4, wherein the hydrophilic acrylic monovinyl monomer is at least one selected from (meth) acrylic acid and (meth) acrylic acid salt.
ニルベンゼン、ジビニルトルエンの少なくとも１種であ
る請求項４又は５に記載の親水性ゲル含有セパレータ
ー。6. The hydrophilic gel-containing separator according to claim 4 or 5, wherein the aromatic polyvinyl monomer is at least one kind of divinylbenzene and divinyltoluene.
せて重合体とする重合工程、前記架橋重合体を溶媒と混
合して親水性ゲル分散液とする分散工程、前記親水性ゲ
ル分散液を多孔性基材に塗布、含浸させる塗布工程、及
び前記親水性ゲル分散液を塗布、含浸された前記多孔性
基材を乾燥して親水性ゲル含有セパレーターとする乾燥
工程とからなり、 前記架橋重合体形成モノマー組成物は、親水性アクリル
系モノビニルモノマーと芳香族ポリビニルモノマーとを
含有することを特徴とする親水性ゲル含有セパレーター
の製造方法。7. A polymerization step of polymerizing a crosslinked polymer-forming monomer composition to form a polymer, a dispersion step of mixing the crosslinked polymer with a solvent to form a hydrophilic gel dispersion, and the hydrophilic gel dispersion. A coating step of coating and impregnating the porous base material, and a drying step of coating the hydrophilic gel dispersion liquid and drying the impregnated porous base material to obtain a hydrophilic gel-containing separator. The method for producing a hydrophilic gel-containing separator, wherein the coalescence-forming monomer composition contains a hydrophilic acrylic monovinyl monomer and an aromatic polyvinyl monomer.
ーが、（メタ）アクリル酸、（メタ）アクリル酸塩から
選択される少なくとも１種であり、前記芳香族ポリビニ
ルモノマーが、ジビニルベンゼン、ジビニルトルエンの
少なくとも１種である請求項７に記載の親水性ゲル含有
セパレーターの製造方法。8. The hydrophilic acrylic monovinyl monomer is at least one selected from (meth) acrylic acid and (meth) acrylic acid salt, and the aromatic polyvinyl monomer is at least divinylbenzene and divinyltoluene. The method for producing a hydrophilic gel-containing separator according to claim 7, which is one kind.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002073600A JP2003272437A (en) | 2002-03-18 | 2002-03-18 | Hydrophilic gel for gel-form electrolytic solution, separator containing hydrophilic gel, and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002073600A JP2003272437A (en) | 2002-03-18 | 2002-03-18 | Hydrophilic gel for gel-form electrolytic solution, separator containing hydrophilic gel, and its manufacturing method |
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| Publication Number | Publication Date |
|---|---|
| JP2003272437A true JP2003272437A (en) | 2003-09-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2002073600A Withdrawn JP2003272437A (en) | 2002-03-18 | 2002-03-18 | Hydrophilic gel for gel-form electrolytic solution, separator containing hydrophilic gel, and its manufacturing method |
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| JP (1) | JP2003272437A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007078688A1 (en) * | 2005-12-21 | 2007-07-12 | General Electric Company | Method and apparatus for reducing water loss |
| JP2009081210A (en) * | 2007-09-25 | 2009-04-16 | Rubycon Corp | Electrolyte for driving electrolytic capacitor, and electrolytic capacitor |
| CN114457379A (en) * | 2022-01-24 | 2022-05-10 | 天津市大陆制氢设备有限公司 | Gel filling film for alkaline electrolytic cell and preparation method thereof |
-
2002
- 2002-03-18 JP JP2002073600A patent/JP2003272437A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007078688A1 (en) * | 2005-12-21 | 2007-07-12 | General Electric Company | Method and apparatus for reducing water loss |
| JP2009081210A (en) * | 2007-09-25 | 2009-04-16 | Rubycon Corp | Electrolyte for driving electrolytic capacitor, and electrolytic capacitor |
| CN114457379A (en) * | 2022-01-24 | 2022-05-10 | 天津市大陆制氢设备有限公司 | Gel filling film for alkaline electrolytic cell and preparation method thereof |
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