JP2015534935A - 有機ゲル用組成物およびその熱分解生成物、その製造方法、熱分解生成物によって形成された電極、ならびに電極を含有するスーパーキャパシタ - Google Patents
有機ゲル用組成物およびその熱分解生成物、その製造方法、熱分解生成物によって形成された電極、ならびに電極を含有するスーパーキャパシタ Download PDFInfo
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- JP2015534935A JP2015534935A JP2015537384A JP2015537384A JP2015534935A JP 2015534935 A JP2015534935 A JP 2015534935A JP 2015537384 A JP2015537384 A JP 2015537384A JP 2015537384 A JP2015537384 A JP 2015537384A JP 2015534935 A JP2015534935 A JP 2015534935A
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Abstract
Description
C=ε.S/t(式中、εは媒体の誘電率、Sは二重層によって占有された表面積、およびtは二重層の厚さを示す)である。
E=1/2.C.V2(式中、Vはスーパーキャパシタの電位)である。
− 0.5%から5%の間の質量分率に従う、前記少なくとも1種のカチオン性高分子電解質P、ならびに/または
− 50未満、好ましくは10から25の間のR/P質量比に従う、前記少なくとも1種のカチオン性高分子電解質Pおよび前記1種または複数種のポリヒドロキシベンゼンR、ならびに/または
− 0.2から2の間、好ましくは0.3から1.3の間のR/W質量比に従う、前記1種または複数種のポリヒドロキシベンゼンRおよび前記水性溶媒W
を含むことができる。
− 0.1から1.2の間の密度、および/または
− 400m2/gより大きい比表面積、および/または
− 0.2から0.8cm3/gの間の細孔容積
を有する。
a)水溶液を得るために、前記1種または複数種のポリヒドロキシベンゼンRおよび1種または複数種のホルムアルデヒドFを、前記少なくとも1種のカチオン性高分子電解質Pおよび触媒の存在下で水性溶媒Wに溶解させるステップ、
b) 前記非架橋ゲル化組成物を形成する沈降プレポリマーを得るために、a)で得られた溶液が沈降するまで半重合させるステップ、
c) b)で得られた沈降プレポリマーを、2mm未満、好ましくは1.5mm未満の厚さで塗布または成型するステップ、
d) 多孔質キセロゲルを形成する乾燥した架橋ゲル化組成物を得るために、c)で塗布または成型したゲルを、好ましくは加湿オーブン中で、架橋および乾燥させるステップ、ならびに
e) 好ましくはモノリスの、多孔質炭素の形態である前記熱分解組成物を得るために、d)で得られた乾燥ゲルを熱分解するステップ
を含む。
− 0.5%から5%の間の質量分率に従う、前記少なくとも1種のカチオン性高分子電解質P、ならびに/または
− 50未満、好ましくは10から25の間のR/P質量比に従う、前記少なくとも1種のカチオン性高分子電解質Pおよび前記1種または複数種のポリヒドロキシベンゼンR、ならびに/または
− 0.2から2の間、好ましくは0.3から1.3の間のR/W質量比に従う、前記1種または複数種のポリヒドロキシベンゼンRおよび前記水性溶媒W
が使用される。
a1) 前記1種または複数種のポリヒドロキシベンゼンRを、好ましくは水からなる、前記水性溶媒W中に溶解させることによって、
a2) a1)で得られた溶液に、前記1種または複数種のホルムアルデヒドF、前記酸性または塩基性触媒Cおよび前記少なくとも1種のカチオン性高分子電解質Pを添加することによって、次いで
a3) 得られた混合物を撹拌し、そのpHを調整することによって
行われる。
以下の例は、本発明による4つのゲル化組成物G1〜G4、および組成物G1〜G4の熱分解によってそれぞれ得られる本発明による4つの熱分解組成物C1〜C4の調製を、3つの「対照」ゲル化組成物、G0、G0’およびG0”、ならびにG0’およびG0”それぞれの「対照」熱分解生成物、C0’およびC0”と比較して説明する。
− Acros Organics製レゾルシノール(R)、純度98%、
− Acros Organics製ホルムアルデヒド(F)、純度37%、
− 炭酸ナトリウムからなる触媒(C)、および
− ゲルG1〜G5用に、ポリ(ジアリルジメチルアンモニウムクロリド)(P)、純度35%(水W中溶液)
− R/F:レゾルシノールとホルムアルデヒドのモル比、
− R/W:レゾルシノールと水の質量比、
− Pは、高分子電解質の質量分率を示し、
− R/P:レゾルシノールと高分子電解質の質量比、および
− R/C:レゾルシノールと触媒の質量比。
電極の静電容量を、以下の装置および電気化学的試験を使用して電気化学的に特性評価した。
Claims (16)
- 水性ポリマーゲルを形成する非架橋ゲル化炭素系組成物(G2)であって、1種または複数種のポリヒドロキシベンゼンRおよび1種または複数種のホルムアルデヒドFから少なくとも部分的に誘導される樹脂をベースとし、少なくとも1種の水溶性カチオン性高分子電解質Pを含み、ずり減粘性物理ゲルを形成することを特徴とする、非架橋ゲル化炭素系組成物(G2)。
- 前記ずり減粘性ゲルを形成する沈降プレポリマーを含み、前記プレポリマーは、1種または複数種のポリヒドロキシベンゼンR、1種または複数種のホルムアルデヒドF、前記少なくとも1種のカチオン性高分子電解質Pおよび触媒Cの水性溶媒W中の水溶液の半重合および沈降反応の生成物であることを特徴とする、請求項1に記載の非架橋ゲル化組成物(G2)。
- 前記反応の生成物が、0.5%から5%の間の質量分率に従う前記少なくとも1種のカチオン性高分子電解質Pを含むことを特徴とする、請求項2に記載の非架橋ゲル化組成物(G2)。
- 前記反応の生成物が、50未満、好ましくは10から25の間のR/P質量比に従う、前記少なくとも1種のカチオン性高分子電解質Pおよび前記1種または複数種のポリヒドロキシベンゼンRを含むことを特徴とする、請求項2または3に記載の非架橋ゲル化組成物(G2)。
- 前記反応の生成物が、0.2から2の間、好ましくは0.3から1.3の間のR/W質量比に従う、前記1種または複数種のポリヒドロキシベンゼンRおよび前記水性溶媒Wを含むことを特徴とする、請求項2〜4のいずれか一項に記載の非架橋ゲル化組成物(G2)。
- 前記少なくとも1種の水溶性カチオン性高分子電解質Pが、第四級アンモニウム塩、ポリ(ビニルピリジニウムクロリド)、ポリ(エチレンイミン)、ポリ(ビニルピリジン)、ポリ(アリルアミンヒドロクロリド)、ポリ(トリメチルアンモニウムエチルメタクリレートクロリド)、ポリ(アクリルアミド−co−ジメチルアンモニウムクロリド)およびそれらの混合物からなる群から選択される有機ポリマーであることを特徴とする、請求項1〜5のいずれか一項に記載の非架橋ゲル化組成物(G2)。
- 前記少なくとも1種の水溶性カチオン性高分子電解質が、ポリ(ジアリルジメチルアンモニウムハライド)から選択される、第四級アンモニウムから得られる単位を含む塩であり、好ましくはポリ(ジアリルジメチルアンモニウムクロリド)またはポリ(ジアリルジメチルアンモニウムブロミド)であることを特徴とする、請求項6に記載の非架橋ゲル化組成物(G2)。
- Brookfield粘度計を使用して25℃で測定される粘度が、50回転/分のせん断速度で、100mPa.sより大きく、好ましくは150mPa.sから10000mPa.sの間であることを特徴とする、請求項1〜7のいずれか一項に記載の非架橋ゲル化組成物(G2)。
- 2mm未満、好ましくは1.5mm未満の塗り厚で塗布することができることを特徴とする、請求項1〜8のいずれか一項に記載の非架橋ゲル化組成物(G2)。
- 炭素モノリスからなる熱分解炭素系組成物であって、請求項1〜9のいずれかの一項に記載の非架橋ゲル化組成物を塗布、架橋、乾燥、次いで熱分解した生成物であり、前記炭素モノリスが、主としてミクロポーラスであり、1mm未満、好ましくは0.5mm以下の厚さを有するスーパーキャパシタ電極を形成することができることを特徴とする、熱分解炭素系組成物。
- − 0.1から1.2の間の密度、および/または
− 400m2/gより大きい比表面積、および/または
− 0.2から0.8cm3/gの間の細孔容積
を有することを特徴とする、請求項10に記載の熱分解組成物。 - 請求項1〜9のいずれか一項に記載の非架橋ゲル化組成物(G2)を調製するための方法であって、
a)水溶液を得るために、前記1種または複数種のポリヒドロキシベンゼンRおよび1種または複数種のホルムアルデヒドFを、前記少なくとも1種のカチオン性高分子電解質Pおよび触媒Cの存在下で水性溶媒W中に溶解させるステップ、
b) 前記非架橋ゲル化組成物(G2)を形成する沈降プレポリマーを得るために、a)で得られた溶液が沈降するまで半重合させるステップ、次いで
c) b)で得られた沈降プレポリマーを、2mm未満、好ましくは1.5mm未満の厚さで塗布または成型するステップ
を含むことを特徴とする方法。 - 請求項12に記載の非架橋ゲル化組成物(G2)を調製するための方法であって、ステップa)において、
− 0.5%から5%の間の質量分率に従う、前記少なくとも1種のカチオン性高分子電解質P、ならびに/または
− 50未満、好ましくは10から25の間のR/P質量比に従う、前記少なくとも1種のカチオン性高分子電解質Pおよび前記1種または複数種のポリヒドロキシベンゼンR、ならびに/または
− 0.2から2の間、好ましくは0.3から1.3の間のR/W質量比に従う、前記1種または複数種のポリヒドロキシベンゼンRおよび前記水性溶媒W
が使用され、
ステップa)が、
a1) 前記1種または複数種のポリヒドロキシベンゼンRを、好ましくは水からなる、前記水性溶媒Wに溶解させることによって、
a2) a1)で得られた溶液に、前記1種または複数種のホルムアルデヒドF、前記酸性または塩基性触媒Cおよび前記少なくとも1種のカチオン性高分子電解質Pを添加することによって、次いで
a3) 得られた混合物を撹拌し、そのpHを調整することによって
行われ、
かつ、ステップb)が、反応器内で、たとえば50から70℃の間の油浴に浸漬された反応器内で行われる
ことを特徴とする方法。 - 請求項10または11に記載の熱分解炭素系組成物を調製するための方法であって、
a)水溶液を得るために、前記1種または複数種のポリヒドロキシベンゼンRおよび1種または複数種のホルムアルデヒドFを、前記少なくとも1種のカチオン性高分子電解質Pおよび触媒Cの存在下で水性溶媒W中に溶解させるステップ、
b) 前記非架橋ゲル化組成物(G2)を形成する沈降プレポリマーを得るために、a)で得られた溶液が沈降するまで半重合させるステップ、
c) b)で得られた沈降プレポリマーを、2mm未満、好ましくは1.5mm未満の厚さで塗布または成型するステップ、
d) 多孔質キセロゲルを形成する乾燥した架橋ゲル化組成物を得るために、c)で塗布または成型したゲルを、好ましくは加湿オーブン中で、架橋および乾燥させるステップ、ならびに
e) モノリス多孔質炭素の形態である前記熱分解組成物を得るために、d)で得られた乾燥ゲルを熱分解するステップ
を含むことを特徴とする方法。 - スーパーキャパシタセルに装備するために、水性のイオン性電解質に浸漬されながら使用可能であり、金属製集電体を被覆する多孔質炭素電極であって、請求項10または11に記載の熱分解炭素系組成物からなり、1mm未満、好ましくは0.5mm未満の厚さを有することを特徴とする、多孔質炭素電極。
- 少なくとも2つの多孔質電極、これらの電極を互いに隔てる電気絶縁膜、およびこれらの電極が浸漬されるイオン性電解質を各々含むセルを含むスーパーキャパシタであって、各セルが、これらの電極でそれぞれ被覆された少なくとも2つの集電体を含み、これらの電極の少なくとも1つが、請求項15に定義した通りであることを特徴とする、スーパーキャパシタ。
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Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1259892 | 2012-10-17 | ||
FR1259892A FR2996849B1 (fr) | 2012-10-17 | 2012-10-17 | Composition pour gel organique ou son pyrolysat, son procede de preparation, electrode constituee du pyrolysat et supercondensateur l'incorporant. |
PCT/IB2013/059206 WO2014060904A1 (fr) | 2012-10-17 | 2013-10-08 | Composition pour gel organique et son pyrolysat, son procede de preparation, electrode constituee du pyrolysat et supercondensateur l'incorporant. |
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JP2015534935A true JP2015534935A (ja) | 2015-12-07 |
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EP (1) | EP2909138A1 (ja) |
JP (1) | JP6371771B2 (ja) |
KR (1) | KR20150083089A (ja) |
CN (1) | CN104736476B (ja) |
BR (1) | BR112015008422A2 (ja) |
CA (1) | CA2888484A1 (ja) |
FR (1) | FR2996849B1 (ja) |
MX (1) | MX2015004832A (ja) |
RU (1) | RU2648326C2 (ja) |
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ZA (1) | ZA201502681B (ja) |
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JP2017519053A (ja) * | 2014-04-07 | 2017-07-13 | ハッチンソンHutchinson | スーパーキャパシタ電極用のゲル化かつ架橋した未乾燥の水性高分子組成物、エアロゲル及び多孔質炭素、並びにその製造方法 |
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FR2996850B1 (fr) * | 2012-10-17 | 2016-01-08 | Hutchinson | Composition thermiquement isolante pour gel monolithique organique ou son pyrolysat, son utilisation et son procede de preparation. |
FR2996849B1 (fr) | 2012-10-17 | 2015-10-16 | Hutchinson | Composition pour gel organique ou son pyrolysat, son procede de preparation, electrode constituee du pyrolysat et supercondensateur l'incorporant. |
KR102168978B1 (ko) | 2014-02-12 | 2020-10-22 | 허친슨 | 유기 에어로겔을 포함하는 진공 단열 패널 |
FR3022248B1 (fr) * | 2014-06-11 | 2018-02-16 | Hutchinson | Composition polymerique aqueuse gelifiee, composition carbonee pyrolysee qui en est issue pour electrode de supercondensateur et leurs procedes de preparation. |
EP3045901A1 (en) | 2015-01-19 | 2016-07-20 | Hutchinson S.A. | Use of high specific surface area carbon materials as counter electrode for electrochemical measurements |
CN105977046A (zh) * | 2016-07-28 | 2016-09-28 | 北京化工大学 | 一体化超级电容器及其制备方法 |
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2013
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- 2013-10-08 BR BR112015008422A patent/BR112015008422A2/pt not_active Application Discontinuation
- 2013-10-08 CA CA2888484A patent/CA2888484A1/fr not_active Abandoned
- 2013-10-08 JP JP2015537384A patent/JP6371771B2/ja not_active Expired - Fee Related
- 2013-10-08 CN CN201380053706.8A patent/CN104736476B/zh not_active Expired - Fee Related
- 2013-10-08 MX MX2015004832A patent/MX2015004832A/es unknown
- 2013-10-08 WO PCT/IB2013/059206 patent/WO2014060904A1/fr active Application Filing
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- 2013-10-08 RU RU2015118267A patent/RU2648326C2/ru not_active IP Right Cessation
- 2013-10-08 EP EP13799107.1A patent/EP2909138A1/fr not_active Withdrawn
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2015
- 2015-04-21 ZA ZA2015/02681A patent/ZA201502681B/en unknown
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2019
- 2019-08-30 US US16/557,649 patent/US20190382614A1/en not_active Abandoned
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Cited By (1)
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JP2017519053A (ja) * | 2014-04-07 | 2017-07-13 | ハッチンソンHutchinson | スーパーキャパシタ電極用のゲル化かつ架橋した未乾燥の水性高分子組成物、エアロゲル及び多孔質炭素、並びにその製造方法 |
Also Published As
Publication number | Publication date |
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US20150299508A1 (en) | 2015-10-22 |
FR2996849B1 (fr) | 2015-10-16 |
CN104736476B (zh) | 2017-03-29 |
RU2015118267A (ru) | 2016-12-10 |
RU2648326C2 (ru) | 2018-03-23 |
WO2014060904A1 (fr) | 2014-04-24 |
KR20150083089A (ko) | 2015-07-16 |
JP6371771B2 (ja) | 2018-08-08 |
MX2015004832A (es) | 2016-01-08 |
CN104736476A (zh) | 2015-06-24 |
US10526505B2 (en) | 2020-01-07 |
EP2909138A1 (fr) | 2015-08-26 |
ZA201502681B (en) | 2016-01-27 |
US20190382614A1 (en) | 2019-12-19 |
CA2888484A1 (fr) | 2014-04-24 |
FR2996849A1 (fr) | 2014-04-18 |
BR112015008422A2 (pt) | 2017-07-04 |
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