JPH01227418A - Electric double layer capacitor - Google Patents
Electric double layer capacitorInfo
- Publication number
- JPH01227418A JPH01227418A JP63052691A JP5269188A JPH01227418A JP H01227418 A JPH01227418 A JP H01227418A JP 63052691 A JP63052691 A JP 63052691A JP 5269188 A JP5269188 A JP 5269188A JP H01227418 A JPH01227418 A JP H01227418A
- Authority
- JP
- Japan
- Prior art keywords
- electric double
- double layer
- conductive
- layer capacitor
- added
- 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 43
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 16
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 15
- 229910052787 antimony Inorganic materials 0.000 claims description 11
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- -1 pyridine Chemical compound 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229940021013 electrolyte solution Drugs 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000011134 resol-type phenolic resin Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
【発明の詳細な説明】
を産業上の利用分野〕
本発明は、電気二重層コンデンサに係り、詳しくは分極
性電極と集電電極の間に設けられる導電性膜を改善した
ものに関する。DETAILED DESCRIPTION OF THE INVENTION FIELD OF INDUSTRIAL APPLICATION The present invention relates to an electric double layer capacitor, and more particularly to an improved conductive film provided between a polarizable electrode and a current collecting electrode.
Ｌ従来の技術１
電気二重層コンデンサは、従来のコンデンサに比較して
単位体積当たり数千倍にも及ぶ静電容量を持っているた
め、コンデンサと電池の両方の機能を有することかでき
、例えば後者よりの応用例としてバックアップ用電源に
用いられている。LConventional technology 1 Electric double layer capacitors have a capacitance per unit volume several thousand times that of conventional capacitors, so they can function as both a capacitor and a battery. As an example of the latter application, it is used as a backup power source.
電気二重層コンデンサは、例えば第４図に示すように、
非電子伝導性かつイオン透過性の多孔質セパレータａを
介して活性炭等からなる層に電解液を含浸させた１対の
分極性電極ｂ 、 ｂ’を設け、これらのそれぞれの分
極性電極に電子伝導性かつイオン不透過性の導電性集電
電極ｃ、ｃ”を設けて基本セルを構成し、この基本セル
を絶縁体ｄ、ｄ”により封止した構造を有するものであ
る。An electric double layer capacitor, for example, as shown in Fig. 4,
A pair of polarizable electrodes b and b' are provided with a layer made of activated carbon or the like impregnated with an electrolyte via a non-electron conductive and ion permeable porous separator a, and electrons are transferred to each of these polarizable electrodes. It has a structure in which conductive and ion-impermeable current collecting electrodes c and c'' are provided to constitute a basic cell, and this basic cell is sealed with insulators d and d''.
このような電気二重層コンデンサのセル抵抗は、充電時
間の速さや放電電流の取り出せる大きさに関係し、抵抗
値の小さいほど良い。The cell resistance of such an electric double layer capacitor is related to the speed of charging time and the amount of discharge current that can be extracted, and the smaller the resistance value, the better.
この抵抗値を小さくするためには、集電電極と分極性電
極の電気的接続を良（しなければならないが、一方、集
電電極が電解液に溶出すると分境性電極と電解液で決定
される電気化学的に安定な電位領域を有効に利用できな
いことになる。In order to reduce this resistance value, the electrical connection between the current collecting electrode and the polarizable electrode must be made good. Therefore, the electrochemically stable potential region cannot be effectively utilized.
このような観点から、−船釣な金属材料のアルミニウム
やステンレスチールは高耐電圧用の電気二重層コンデン
サの集電電極としては好ましいとは言えない。From this point of view, aluminum and stainless steel, which are common metal materials, cannot be said to be preferable as current collecting electrodes of electric double layer capacitors for high withstand voltages.
そこで、特開昭６０−１８２１２３号公報に記載されて
いるように、金属集電体基材に酸化錫の如き導電性金属
酸化物を被覆した集電体と、活性炭よりなる分極性電極
を接続し、分極性電極に電解液を含浸させた電気二重層
コンデンサが提案されている。Therefore, as described in JP-A-60-182123, a current collector in which a metal current collector base material is coated with a conductive metal oxide such as tin oxide and a polarizable electrode made of activated carbon are connected. However, an electric double layer capacitor in which polarizable electrodes are impregnated with an electrolyte has been proposed.
しかしながら、導電性金属酸化物として使用されている
酸化１（ＳｎＯ２）は電気伝導度が良くなく、高温環境
下において抵抗値が増大することがあり、また、分極性
電極との接触抵抗も低いとは言えないため、電気二重層
コンデンサの内部抵抗も小さくないという問題点を有す
る。However, oxide 1 (SnO2), which is used as a conductive metal oxide, has poor electrical conductivity and its resistance value may increase in high-temperature environments, and its contact resistance with polarizable electrodes is also low. Therefore, there is a problem that the internal resistance of the electric double layer capacitor is not small.
本発明の目的は、集電電極と分極性電極の間に設けられ
る導電性膜を電気伝導度が高く、接触抵抗が小さく、し
かも化学的に安定であるようにし、内部抵抗の小さい安
定性のある電気二重層コンデンサを提供することにある
。The purpose of the present invention is to make the conductive film provided between the current collecting electrode and the polarizable electrode high in electrical conductivity, low in contact resistance, and chemically stable. The purpose is to provide an electric double layer capacitor.
本発明は、上記課題を解決するために、非電子伝導性か
つイオン透過性の多孔質セパレータと、咳多孔質セパレ
ータの少なくとも一方の側に設けられる分極性電極とか
らなる構成体の両側に導電性集電電極を有する電気二重
層コンデンサにおいて、上記構成体の少なくとも陽極側
の集電電極と分極性電極の間に導電性金属酸化物にドナ
ー不純物を添加した導電性膜を有する電気二重層コンデ
ンサを提供するものである。In order to solve the above problems, the present invention provides electrical conductivity on both sides of a structure consisting of a non-electronically conductive and ion permeable porous separator and a polarizable electrode provided on at least one side of the porous separator. An electric double layer capacitor having a polarizable current collecting electrode, the electric double layer capacitor having a conductive film made of a conductive metal oxide doped with a donor impurity between the current collecting electrode and the polarizable electrode on at least the anode side of the above structure. It provides:
この際、ドナー不純物がフッ素及びアンチモンの少なく
とも一方であり、導電性金属酸化物に酸化錫（ＳｎＯ２
）を用いる場合に、フッ素の含有量は１〜８０ ａｔｍ
％が好ましく、アンチモンの含有量は０．１〜５ａｔｍ
％が好ましい。At this time, the donor impurity is at least one of fluorine and antimony, and the conductive metal oxide contains tin oxide (SnO2).
), the fluorine content is 1 to 80 atm
% is preferable, and the antimony content is 0.1 to 5 atm.
% is preferred.
次に本発明の詳細な説明する。Next, the present invention will be explained in detail.
本発明における電気二重層コンデンサにおいては、集電
電極の内、少なくとも陽極側の集電電極と分極性電極の
間に導電性金属酸化物にフッ素及びアンチモンの少なく
とも一方を含有させた導電膜を有する。The electric double layer capacitor of the present invention has a conductive film containing at least one of fluorine and antimony in a conductive metal oxide between at least the anode-side current collector electrode and the polarizable electrode. .
この導電性金属酸化物としては、酸化ルテニウム（ＲＬ
１０２）、酸化第二錫（ＳｎＯ２）、酸化インジウム（
Ｉｎ０２）あるいば酸化第二錫（ＳｎＯ２）と酸化イン
ジウム（Ｉｎ０２）の混合物でＩＴＯと呼ばれるもの、
さらにこれらを適宜混合したものが挙げられる。As this conductive metal oxide, ruthenium oxide (RL
102), tin oxide (SnO2), indium oxide (
In02) A mixture of tin oxide (SnO2) and indium oxide (In02) called ITO,
Further examples include appropriate mixtures of these.
この導電性金属酸化物にフッ素及びアンチモンの少なく
とも１方が含有されるが、この方法としては、例えば酸
化第二錫の場合、塩化錫（ＳｎＣ７！４ ）とフン化ア
ンモニウム等の錫化合物とフッ素化合物の酸性液を加熱
したアルミニウム、ステンレススチール等の金属材料に
噴霧することにより膜を形成することが挙げられる。This conductive metal oxide contains at least one of fluorine and antimony. For example, in the case of stannic oxide, tin compounds such as tin chloride (SnC7!4) and ammonium fluoride and fluorine An example of this is to form a film by spraying an acidic liquid of a compound onto a heated metal material such as aluminum or stainless steel.
このフッ素及びアンチモンの少なくとも一方を含有させ
る量は、フッ素の場合が、Ｆ／Ｓｎ ＋ Ｆ＝１〜８３
ａｔｍ％、アンチモンの場合が、Ｓｂ／Ｓｎ ＋ ５
ｂ＝０．１〜５ａｔｍ％が好ましい。The amount of at least one of fluorine and antimony is F/Sn + F=1 to 83 in the case of fluorine.
atm%, in the case of antimony, Sb/Sn + 5
b=0.1-5 atm% is preferable.
このようにして得られる膜は導電膜となるが、この導電
膜は集電電極、分極性電極のいずれか一方又は両方に形
成できる。この導電膜を形成する場合でも、しない場合
でも、集電電極としては、電解液に安定な金属箔、導電
性ゴム、不浸透処理した可撓性グラファイト等が使用で
きる。The film obtained in this manner becomes a conductive film, and this conductive film can be formed on either or both of the current collecting electrode and the polarizable electrode. Regardless of whether this conductive film is formed or not, metal foil, conductive rubber, or imperviously treated flexible graphite, which is stable in the electrolytic solution, can be used as the current collecting electrode.
本発明の電気二重層コンデンサの分極性電極としては、
活性炭、電解液等が含有されるが、活性炭としては、レ
ゾール型フェノール樹脂、レゾール／ノボラック型フェ
ノール樹脂、変性フエノール樹脂、レーヨン、ポリアク
リルニトリル、ピッチ系樹脂といった合成高分子材料か
らなる球状、無定形、繊維状等のものや、ヤシガラ、オ
ガクズ、石炭といった天然高分子材料等から作られる活
性炭も使用される。As the polarizable electrode of the electric double layer capacitor of the present invention,
Activated carbon, electrolyte, etc. are contained. Activated carbon includes spherical and non-spherical materials made of synthetic polymer materials such as resol type phenolic resin, resol/novolac type phenolic resin, modified phenolic resin, rayon, polyacrylonitrile, and pitch-based resin. Activated carbon made from fixed or fibrous materials, or natural polymer materials such as coconut shell, sawdust, and coal are also used.
また、電解液には、プロピレンカーボネート、γ−ブチ
ロラクトン等のエステル類、アセトニトリル等のニトリ
ル類、クロロホルム等のハロゲン化物類、アセトン等の
ケトン類、ジメチルホルムアミド等のアミド類、ピリジ
ン等のアミン類、テトラヒドロフラン等のエーテル類、
ブタノール等のアルコール類、ニトロメタン等のニトロ
化合物類、ジメチルスルホキシド等の硫黄化合物等の溶
媒にＣ１１０ａ”５ＢＦ４− 、 ＰＦ６− 、 Ａｓ
Ｆ；、Ａｔ ｃ停ｃｐ、、ｓｏ、。In addition, the electrolyte includes esters such as propylene carbonate and γ-butyrolactone, nitriles such as acetonitrile, halides such as chloroform, ketones such as acetone, amides such as dimethylformamide, amines such as pyridine, etc. Ethers such as tetrahydrofuran,
C110a"5BF4-, PF6-, As in solvents such as alcohols such as butanol, nitro compounds such as nitromethane, and sulfur compounds such as dimethyl sulfoxide.
F;,At cstopcp,,so,.
等のリチウム塩その他の金属塩、アルキルアンモニウム
塩、アルキルホスホニウム塩、あるいはこれらの混合物
等を熔解したものが挙げられるが、これに限定されるも
のではなく、酸、アルカリや塩類の水溶液の電解質液も
使用できる。Examples include, but are not limited to, those obtained by melting lithium salts, other metal salts, alkylammonium salts, alkylphosphonium salts, or mixtures thereof, and electrolyte solutions of aqueous solutions of acids, alkalis, and salts. can also be used.
また、分極性電極には、カーボンブラックや黒鉛等の導
電性物質、アクリル系、ビニル系、セルローズ系、ポリ
アミド系、ポリエステル、ポリテトラフルオロエチレン
（ＰＴＦＥ）系等のバインダー樹脂も併用できる。In addition, conductive substances such as carbon black and graphite, and binder resins such as acrylic, vinyl, cellulose, polyamide, polyester, and polytetrafluoroethylene (PTFE) may also be used in the polarizable electrode.
また、本発明に用いられる多孔質セパレータは、その材
質としてはセロハン、ポリプロピレンやポリエチレン等
の高分子材料や天然繊維が挙げられる。Further, the porous separator used in the present invention may be made of polymeric materials such as cellophane, polypropylene, and polyethylene, and natural fibers.
本発明の電気二重層コンデンサを製造するには、例えば
上記バインダー樹脂を電解液に加熱溶解し、そのままあ
るいは冷却してゲル伏（力を加えない限り流動、変形し
ない固形状態）にしてから活性炭、導電性物質を加える
か、樹脂、電解質液、活性炭、導電性物質を同時に加え
て例えば三本ロール等で混練する方法により分極性電極
を作成し、これを上記多孔質セパレータ、集電電極とと
もに従来の方法にしたがって所定の構造に組み立てる。In order to manufacture the electric double layer capacitor of the present invention, for example, the binder resin is heated and dissolved in an electrolytic solution, left as it is or cooled to form a gel (a solid state that does not flow or deform unless force is applied), and then activated carbon, A polarizable electrode is created by adding a conductive substance or by simultaneously adding a resin, an electrolyte solution, activated carbon, and a conductive substance and kneading it using, for example, a triple roll, and then adding it to the conventional method along with the porous separator and current collecting electrode. Assemble it into a predetermined structure according to the method.
また、ポリプロピレン等のプラスチックやゴム製ガスケ
７トに活性炭等の分極性電極材料を充填し、これを電解
質液に浸漬し、減圧含浸する。Further, a gasket 7 made of plastic or rubber such as polypropylene is filled with a polarizable electrode material such as activated carbon, and this is immersed in an electrolyte solution to impregnate it under reduced pressure.
これを２つ作り、多孔質セパレータの両側に重ねて配し
、以下上記と同様に集電電極とともに所定の構造に組み
立てる。このようにして基本セルができあがるが、これ
を封止容器に導電性接着剤で固定して収め、リード線を
接続できるようにすると電気二重層コンデンサができあ
がる。Two of these are made, placed one on top of the other on both sides of the porous separator, and then assembled into a predetermined structure together with the current collecting electrode in the same manner as above. In this way, a basic cell is completed, and when it is fixed in a sealed container with conductive adhesive and connected to lead wires, an electric double layer capacitor is completed.
本発明における電気二重層コンデンサには、多孔質セパ
レータの両側に分極性電極を有し、それぞれの分極性電
極に集電電極を有する構造のもののみならず、多孔質セ
パレータの片側に分極性電極を有し、この分極性電極と
多孔質セパレータのそれぞれに集電電極を設けたものも
含まれる。The electric double layer capacitor of the present invention includes not only a structure having polarizable electrodes on both sides of a porous separator and a current collecting electrode on each polarizable electrode, but also a structure in which a polarizable electrode is provided on one side of the porous separator. It also includes one in which the polarizable electrode and the porous separator are each provided with a current collecting electrode.
例えば酸化錫（ＳｎＯ２）は、ルチル型構造のｎ型半導
体であり、酸素不足型の非量論組成□（ＳｎＯｚ−ｘ）
をとる、この固有の酸素の欠陥は酸５（０）空孔あるい
は結晶格子間の錫（Ｓｎ）と考えられ、これがイオン化
して伝導電子を生じる。酸化錫（ＳｎＯ２）の比抵抗は
およそ１０−３Ω１であるが、フッ素（Ｆ）による一部
酸素の置換、あるいはアンチモン（Ｓｂ）による一部組
（Ｓｎ）の置換などドナーとなる不純物の添加により比
抵抗を減少しく≦ｌσ４Ωａｌ）、電解液等に対する化
学的耐性を向上させることができる。For example, tin oxide (SnO2) is an n-type semiconductor with a rutile structure, and has an oxygen-deficient non-stoichiometric composition (SnOz-x).
This inherent oxygen defect is thought to be an acid 5(0) vacancy or a tin (Sn) interstitial in the crystal lattice, which is ionized to generate conduction electrons. The specific resistance of tin oxide (SnO2) is approximately 10-3Ω1, but it can be reduced by adding impurities that serve as donors, such as replacing some oxygen with fluorine (F) or replacing some groups (Sn) with antimony (Sb). It is possible to reduce the specific resistance (≦lσ4Ωal) and improve chemical resistance to electrolytes and the like.
次に本発明の実施例を第１図ないし第３図に基づいて説
明する。Next, an embodiment of the present invention will be described based on FIGS. 1 to 3.
実施例１
水１５００ｇに塩化錫（５ｎＣ（１４）１９８．０ｇを
溶解した後、さらにフン化アンモニウム（ＮＨ４Ｆ）
１３６．３ｇヲ添加した。これに塩＠２ＱＯｍｆｆｉを
加えて、酸化錫（ＳｎＯ２）の母液とした。これは、Ｆ
／Ｓｎ ＋ Ｆ・８３ ａｔｍ％になる。Example 1 After dissolving 198.0 g of tin chloride (5nC(14)) in 1500 g of water, ammonium fluoride (NH4F) was further dissolved.
136.3g was added. Salt @2QOmffi was added to this to obtain a mother liquor of tin oxide (SnO2). This is F
/Sn+F・83 atm%.
次にステンレス板を３５０℃以上に加熱し、上記の酸化
錫（ＳｎＯ２）の母液を噴霧して酸化錫（ＳｎＯ２）に
フッ素を添加した導電性膜を形成する。この導電性膜を
形成したステンレス板から第１図に示す外装ケース１．
２（φ２０鶴、厚み１．８日）を打ち抜き、その電解液
に接する内面に導電性膜３．４を有する部材を作製する
。Next, the stainless steel plate is heated to 350° C. or higher, and the above-mentioned mother liquor of tin oxide (SnO2) is sprayed to form a conductive film in which fluorine is added to tin oxide (SnO2). The exterior case 1 shown in FIG.
2 (φ20 crane, thickness 1.8 days) is punched out to produce a member having a conductive film 3.4 on the inner surface in contact with the electrolyte.
次にカーボンブラック、活性炭及びバインダー樹脂から
なる混合物を三本ロールで混練して０．５■厚さのシー
ト状に成形し、これから直径１３ｎの分極性電極５．５
”を打ち抜き成形する。これらを多孔性セパレータ（ポ
リプロピレン製Ｈす０．０５ｍ）６の両側に重ねたもの
を外装ケース１の中央に載置し、この外装ケースと分極
性電極の間の空間に電解液（０，５モル過塩素酸テトラ
エチルアンモニウムのプロピレンカーボネート溶液）を
注入し、それぞれの分極性電極に電解液を含浸させる。Next, a mixture consisting of carbon black, activated carbon, and binder resin was kneaded with three rolls and formed into a sheet with a thickness of 0.5 cm. From this, a polarizable electrode with a diameter of 13 nm was
These are stacked on both sides of a porous separator (polypropylene H 0.05 m) 6 and placed in the center of the outer case 1, and in the space between the outer case and the polarizable electrode. An electrolytic solution (a 0.5 mol tetraethylammonium perchlorate solution in propylene carbonate) is injected to impregnate each polarizable electrode with the electrolytic solution.
そして、外装ケース１の内側周側にポリプロピレン製パ
ンキン７を内装し、このパツキンで上記多孔性セパレー
タの周端部を外装ケース１の底部に挟んでから、外装ケ
ース２を分極性電極５゛に重ね、その周端部と外装ケー
ス１の上端周端部とでこのパツキン７を挟んでカシメ、
封口する。Then, a polypropylene punch 7 is installed on the inner circumferential side of the exterior case 1, and the peripheral end of the porous separator is sandwiched between the bottom of the exterior case 1 and the exterior case 2 is attached to the polarizable electrode 5. Stack the gaskets 7 between the circumferential edges and the upper circumferential edge of the outer case 1, and swage them together.
Seal it.
このようにして得られた電気二重層コンデンサについて
市販のＬＣＲメータ（Ｙｌ（Ｐ ４２７４Ａ）を用い、
１、Ｋ Ｈｚ、１０ｍＡ、室温における等価直列抵抗（
初期内部抵抗）及び７０℃で印加電圧を２．８ｖとし、
充放電を１０００サイクル繰り返した後の等価直列抵抗
の初期のものに対する増加率を求め、その結果を表に示
す。Using a commercially available LCR meter (Yl (P 4274A)) for the electric double layer capacitor obtained in this way,
1. Equivalent series resistance at K Hz, 10 mA, room temperature (
initial internal resistance) and the applied voltage was 2.8 V at 70°C,
After 1000 cycles of charging and discharging, the rate of increase in equivalent series resistance with respect to the initial value was determined, and the results are shown in the table.
実施例２
実施例１において、フン化アンモニウム（ＮＨ，Ｆ）を
１８．７ｇにした以外は同様にして電気二重層コンデン
サを作製し、実施例１と同様に測定した結果を表に示す
。なお、Ｆ／Ｓｎ ＋ Ｆ＝４０ ａ ｔｍ％である。Example 2 An electric double layer capacitor was produced in the same manner as in Example 1 except that ammonium fluoride (NH,F) was changed to 18.7 g, and the results of measurements in the same manner as in Example 1 are shown in the table. Note that F/Sn + F=40 atm%.
実施例３
実施例１において、フン化アンモニウム（ＮＨ，Ｆ）を
０．３ ｇにした以外は同様にして電気二重層コンデン
サを作製し、実施例１と同様に測定した結果を表に示す
。なお、Ｆ／Ｓｎ＋Ｆ・ｌａｔｍ％である。Example 3 An electric double layer capacitor was produced in the same manner as in Example 1, except that ammonium fluoride (NH,F) was changed to 0.3 g, and the results were measured in the same manner as in Example 1, and the results are shown in the table. Note that F/Sn+F·latm%.
実施例４
水１５００ｇに塩化錫（５ｎＣＪａ ）１９８．０ｇを
熔解した後、さらに塩化アンチモン（ｓｂｃ ｅ３）９
．２ｇを添加した。これに塩！２００ｍｊ！を加えて、
酸化錫（ＳｎＯ２）の母液とした。これは、Ｓｂ／Ｓｎ
＋ Ｓｂ＝ ５ ａ ｔｎ＋％になる。Example 4 After dissolving 198.0 g of tin chloride (5nCJa) in 1500 g of water, antimony chloride (sbc e3) 9
．． 2g was added. Salt for this! 200mj! In addition,
This was used as a mother liquor of tin oxide (SnO2). This is Sb/Sn
+Sb=5a tn+%.
以下この母液を用い、第２図のように分極性電極５．５
′に接触する部分に導電膜３”、４”を形成した集電電
極１°、２′を使用した以外は実施例１と同様にして電
気二重層コンデンサを作製し、実施例１と同様に測定し
た結果表に示す。Below, using this mother liquor, as shown in Figure 2, polarizable electrode 5.5
An electric double layer capacitor was manufactured in the same manner as in Example 1, except that current collecting electrodes 1° and 2' were used with conductive films 3'' and 4'' formed on the portions in contact with . The measured results are shown in the table.
実施例５
実施例４において、塩化アンチモン（ＳｂＣＩ！３）３
．６Ｃにした以外は同様にして電気二重層コンデンサを
作製し、実施例１と同様に測定した結果を表に示す。な
お、Ｓｂ／Ｓｎ ＋Ｓｂ＝ ２ ａｔｍ％になる。Example 5 In Example 4, antimony chloride (SbCI!3) 3
．． An electric double layer capacitor was produced in the same manner except that 6C was used, and the results were measured in the same manner as in Example 1, and the results are shown in the table. Note that Sb/Sn +Sb=2 atm%.
実施例６
実施例４において、塩化アンチモン（ＳｂＣｚ３ ）０
．２ｇにした以外は同様にして電気二重層コンデンサを
作製し、実施例１と同様に測定した結果を表に示す。な
お、Ｓｂ／Ｓｎ ＋ Ｓｂ＝ ０．１ａ ｔ＋ｎ％にな
る。Example 6 In Example 4, antimony chloride (SbCz3) 0
．． An electric double layer capacitor was produced in the same manner as in Example 1 except that the weight was changed to 2 g. The results are shown in the table. Note that Sb/Sn+Sb=0.1a t+n%.
実施例７
水１５００ｇに塩化錫（Ｓｎ（、Ｉ！ａ ）１９８．０
ｇを溶解した後、さらにフッ化アンモニウム（ＮＨ４Ｆ
） １８．７ｇト［化アンチモン（ＳｂＣ１３）９．２
ｇを添加した。これに塩酸２００ｍ ｌを加えて、酸化
錫（ＳｎＯ）の母液とした。Example 7 Tin chloride (Sn(, I!a) 198.0 in 1500 g of water
After dissolving ammonium fluoride (NH4F
) 18.7g antimony chloride (SbC13) 9.2
g was added. 200 ml of hydrochloric acid was added to this to obtain a mother liquor of tin oxide (SnO).
これは、Ｓｂ ＋Ｆ／Ｓｎ＋Ｓｂ＋Ｆ＝ ４１．８ ａ
ｔｍ％になる。This is Sb + F/Sn + Sb + F = 41.8 a
It becomes tm%.
以下この母液を用いた以外は実施例１と同様にして第３
図に示すように外装ケース２１を作製し、外装ケース１
゛には白金板を用いて以下実施例１と同様にして電気二
重層コンデンサを作製し、実施例１と同様に測定した結
果を表に示す。Thereafter, the third step was carried out in the same manner as in Example 1 except that this mother liquor was used.
As shown in the figure, the outer case 21 is manufactured, and the outer case 1
An electric double layer capacitor was manufactured using a platinum plate in the same manner as in Example 1, and the results of measurements in the same manner as in Example 1 are shown in the table.
比較例
実施例１において、フン化アンモニウムを使用しなかっ
た以外は同様にして作製した酸化錫（ＳｎＯ２）母液を
用いた以外は同様にして電気二重層コンデンサを作製し
、実施例１と同様に測定した結果を表に示す。Comparative Example An electric double layer capacitor was produced in the same manner as in Example 1 except that a tin oxide (SnO2) mother liquor produced in the same manner as in Example 1 was used except that ammonium fluoride was not used. The measured results are shown in the table.
以上の結果より、実施例のものはいずれも内部抵抗が小
さく、その増加率を極めて低いのに対し、比較例のもの
は内部抵抗、その増加率のいずれも高く、特に後者は著
しく高い、これは、実施例のものが電気伝導性が良く、
分極性電極との接触抵抗が小さいとともに、化学的に安
定であることを示すものであり、信頼性の高い電気二重
コンデンサを提供することができる。From the above results, all of the examples have low internal resistance and an extremely low rate of increase, while the comparative examples have both high internal resistance and high rate of increase, especially the latter, which is extremely high. The one in the example has good electrical conductivity,
This shows that the contact resistance with the polarizable electrode is low and that it is chemically stable, so that a highly reliable electric double capacitor can be provided.
本発明によれば、集電電極と分極性電極の間に導電性酸
化膜にドナー不純物、例えばフッ素及びアンチモンの少
なくとも一方を添加させた導電性膜を設けたので、その
電気伝導性が良く、接触抵抗が小さくなることにより電
気二重コンデンサの内部抵抗を小さくできる。また、こ
の導電性膜は化学的に安定であるので電気二重コンデン
サの内部抵抗の増加率も小さ（、したがって動作の安定
なコンデンサ、すなわち信頼性の高いコンデンサを提供
することができる。According to the present invention, since a conductive film in which a donor impurity such as at least one of fluorine and antimony is added to a conductive oxide film is provided between the current collecting electrode and the polarizable electrode, the conductive film has good electrical conductivity. By reducing the contact resistance, the internal resistance of the electric double capacitor can be reduced. Furthermore, since this conductive film is chemically stable, the rate of increase in internal resistance of the electric double capacitor is small (therefore, a capacitor with stable operation, that is, a highly reliable capacitor can be provided).
第１図は本発明の一実施例の電気二重層コンデンサの断
面図、第２図は他の実施例の電気二重層コンデンサの断
面図、第３図はさらに他の実施例の電気二重層コンデン
サの断面図、第４図は従来の一般的な電気二重層コンデ
ンサの断面図である。
図中、１．２．１’、 ２°は外装ケース、３．４は導
電性膜、５．５゛は分極性電極、６は多孔性セパレータ
、７はパツキンである。
昭和６３年０３月０８日
第１図 、
第２図
第３図FIG. 1 is a sectional view of an electric double layer capacitor according to one embodiment of the present invention, FIG. 2 is a sectional view of an electric double layer capacitor according to another embodiment, and FIG. 3 is a sectional view of an electric double layer capacitor according to another embodiment. FIG. 4 is a cross-sectional view of a conventional general electric double layer capacitor. In the figure, 1.2.1' and 2° are an exterior case, 3.4 is a conductive film, 5.5' is a polarizable electrode, 6 is a porous separator, and 7 is a packing. March 8, 1988 Figure 1, Figure 2 Figure 3
Claims (4)
タと、該多孔質セパレータの少なくとも一方の側に設け
られる分極性電極とからなる構成体の両側に導電性集電
電極を有する電気二重層コンデンサにおいて、上記構成
体の少なくとも陽極側の集電電極と分極性電極の間に導
電性金属酸化物にドナー不純物を添加した導電性膜を有
することを特徴とする電気二重層コンデンサ。(1) An electric double layer having conductive current collecting electrodes on both sides of a structure consisting of a non-electronically conductive and ion permeable porous separator and a polarizable electrode provided on at least one side of the porous separator. An electric double layer capacitor characterized in that the capacitor has a conductive film made of a conductive metal oxide doped with a donor impurity between a current collecting electrode and a polarizable electrode on at least the anode side of the above-mentioned structure.
も一方であることを特徴とする特許請求の範囲第１項記
載の電気二重層コンデンサ。(2) The electric double layer capacitor according to claim 1, wherein the donor impurity is at least one of fluorine and antimony.
て、この酸化錫（ＳｎＯ＿２）に対してフッ素（Ｆ）を
錫（Ｓｎ）とフッ素（Ｆ）の合計（Ｓｎ＋Ｆ）に対して
１〜８３ａｔｍ％含有させたことを特徴とする特許請求
の範囲第２項記載の電気二重層コンデンサ。(3) The conductive metal oxide is tin oxide (SnO_2), and fluorine (F) is added to the tin oxide (SnO_2) to the sum of tin (Sn) and fluorine (F) (Sn+F). The electric double layer capacitor according to claim 2, wherein the electric double layer capacitor contains up to 83 atm%.
て、この酸化錫（ＳｎＯ＿２）に対してアンチモン（Ｓ
ｂ）を錫（Ｓｎ）とアンチモン（Ｓｂ）の合計に対して
０．１〜５ａｔｍ％含有させたことを特徴とする特許請
求の範囲第２項記載の電気二重層コンデンサ。(4) The conductive metal oxide is tin oxide (SnO_2), and antimony (SnO_2) is
The electric double layer capacitor according to claim 2, characterized in that b) is contained in an amount of 0.1 to 5 atm% based on the total of tin (Sn) and antimony (Sb).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63052691A JPH01227418A (en) | 1988-03-08 | 1988-03-08 | Electric double layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63052691A JPH01227418A (en) | 1988-03-08 | 1988-03-08 | Electric double layer capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01227418A true JPH01227418A (en) | 1989-09-11 |
Family
ID=12921915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63052691A Pending JPH01227418A (en) | 1988-03-08 | 1988-03-08 | Electric double layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01227418A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0443825A2 (en) * | 1990-02-20 | 1991-08-28 | Isuzu Motors Limited | Electric double layer capacitor |
| JPH0496835U (en) * | 1991-01-30 | 1992-08-21 | ||
| WO2005015587A1 (en) * | 2003-08-06 | 2005-02-17 | Enerland Co., Ltd. | Supercapacitor with reduced internal resistance |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5558363A (en) * | 1978-10-20 | 1980-05-01 | Roy Gerald Gordon | Improved tin oxide coat |
| JPS60182123A (en) * | 1984-02-28 | 1985-09-17 | 松下電器産業株式会社 | Electric couble layer capacitor |
-
1988
- 1988-03-08 JP JP63052691A patent/JPH01227418A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5558363A (en) * | 1978-10-20 | 1980-05-01 | Roy Gerald Gordon | Improved tin oxide coat |
| JPS60182123A (en) * | 1984-02-28 | 1985-09-17 | 松下電器産業株式会社 | Electric couble layer capacitor |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0443825A2 (en) * | 1990-02-20 | 1991-08-28 | Isuzu Motors Limited | Electric double layer capacitor |
| JPH0496835U (en) * | 1991-01-30 | 1992-08-21 | ||
| WO2005015587A1 (en) * | 2003-08-06 | 2005-02-17 | Enerland Co., Ltd. | Supercapacitor with reduced internal resistance |
| US7558050B2 (en) | 2003-08-06 | 2009-07-07 | Enerland Co., Ltd. | Supercapacitor with reduced internal resistance |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cottineau et al. | Nanostructured transition metal oxides for aqueous hybrid electrochemical supercapacitors | |
| US4226924A (en) | Thin metal-halogen cells | |
| US8599534B2 (en) | Active electrolyte electrochemical capacitor | |
| Cheng et al. | Proton-conducting polyoxometalates as redox electrolytes synergistically boosting the performance of self-healing solid-state supercapacitors with polyaniline | |
| Yamagata et al. | Alginate gel containing an ionic liquid and its application to non-aqueous electric double layer capacitors | |
| US3098770A (en) | Anhydrous electric battery | |
| Novák et al. | Composite polymer positive electrodes in solid‐state lithium secondary batteries | |
| CN109036858A (en) | A kind of all solid state plane interdigitation lithium-ion capacitor of flexibility and preparation method thereof | |
| KR102568421B1 (en) | Membrane electrode assembly and zinc-bromide supercapattery comprising the same | |
| JPH01227418A (en) | Electric double layer capacitor | |
| JPH04162510A (en) | Electric double layer capacitor | |
| JP3085250B2 (en) | Electric double layer capacitor | |
| JPH021104A (en) | Electric double layer capacitor | |
| JP2507125B2 (en) | Electric double layer capacitor and manufacturing method thereof | |
| JPH09205041A (en) | Electric double layered capacitor | |
| CN110299250A (en) | Electrolyte and electrochemical device for electrochemical device | |
| Yamagata et al. | Charge-Discharge Behavior of Electric Double-Layer Capacitor with Alginate/Ionic Liquid Gel Electrolyte | |
| RU2592863C1 (en) | Supercapacitor with inorganic solid electrolyte and carbon electrodes | |
| JPH08306365A (en) | Organic electrolyte-battery | |
| JP3418431B2 (en) | Electric double layer capacitor and method of manufacturing the same | |
| JPS63316422A (en) | Electric double layer capacitor | |
| JPS62239513A (en) | Electric double-layer capacitor | |
| JPH0265114A (en) | Electric double-layer capacitor | |
| JPS63102104A (en) | Ion conducting organic film | |
| JP2006024785A (en) | Electric double layer capacitor and nonaqueous electrolytic solution therefor |