JP2016538715A - 経年劣化性能が改善されたウルトラキャパシタ - Google Patents
経年劣化性能が改善されたウルトラキャパシタ Download PDFInfo
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- JP2016538715A JP2016538715A JP2016525046A JP2016525046A JP2016538715A JP 2016538715 A JP2016538715 A JP 2016538715A JP 2016525046 A JP2016525046 A JP 2016525046A JP 2016525046 A JP2016525046 A JP 2016525046A JP 2016538715 A JP2016538715 A JP 2016538715A
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
これらのファラデー的電荷移動プロセスは、EDLCの正電極及び不電極それぞれにおける酸化及び還元反応として表れる。このような不可逆的なファラデー的電荷移動プロセスは、電極の電位の好ましくないシフトを引き起こし得る。これは図1に概略的に示されており、
3つの異なる例に関する、連続的な充電(C)及び放電(D)サイクルを通しての電位の応答を示す。最も左側の枠では、ファラデー的反応は発生していない。正電極におけるファラデー的酸化(FO)反応に対応する中央の枠では、正電極の電位は酸化電位(OP)においてシフトし、これは、正電極の正味の負電位シフト並びに電解質の電位窓の還元限界への負電極の正味の負電位シフト(一方向矢印で示す)をもたらす。同様に、右側の枠では、負電極におけるファラデー的還元(FR)が還元電位(RP)において示されており、これは、電解質の電位窓の酸化限界への正電極のシフトを含む、正味の正電位シフトを引き起こす。これらの酸化又は還元メカニズムは、関連するデバイスの性能に悪影響を及ぼす場合がある。
第2の活性炭材料のみを各電極に組み込むことにより、比較例のEDLCを製作した。第2の活性炭の粒子をPTFE(DuPont601A)及びカーボンブラック(Cabot BP2000)と、85:10:5の比(重量)で、中程度の強度のLabMasterミキサを室温で用いて混合した。フィブリル化を支援するために、およそ5重量%のIPAを混合物に添加した。2軸スクリュー式オーガを用いてフィブリル化プロセスを実施して細粒を得て、これをフィッツミルで破砕して微細な粉体を得た。
第1の活性炭材料のみを使用して正電極を形成し、第2の活性炭材料のみを使用して負電極を形成した以外は、実施例1の手順を用いて、比較例のセルを製作した。
実施例2の調整されたセルの構成に関連する、静電容量の大きな劣化に対処するために、第1及び第2の活性炭材料の混合物を各電極に使用して、EDLCを製作した。この実施例では、75%の第1の活性炭と25%の第2の活性炭との混合物を用いて、正電極を製作した。負電極は、25%の第1の活性炭と75%の第2の活性炭との混合物を用いて製作した。
混合型電極を用いて更なるEDLCを製作した。本実施例の製造を簡略化するために、正及び負電極それぞれを、第1及び第2の活性炭材料の50:50混合物を用いて製作した。
実施例1に記載のプロセスを用いて第1の活性炭材料を各電極に組み込むことにより、更なる比較例のEDLCを製作した。2.7Vのストレス試験後、このセルの初期静電容量は491Fであり、ESRは3.4mΩであった。図4に示すように、80%正規化静電容量までの時間は450時間であった。
実施例2の調整されたセル構成を、1.2MのTEA‐TFB(テトラエチルアンモニウムテトラフルオロボレート)系電解質の代わりにアセトニトリル中のTEMA‐TFB(テトラエチルメチルアンモニウムテトラフルオロボレート)電解質の1.2M溶液を用いて繰り返した。
TEA‐TFB電解質を内包する定格2000Fの2.7Vデバイスである、市販のEDLC(Maxwell‐BCAP2000 P270 K04)を、3.0V及び65℃でのストレス試験に供した。初期静電容量は2118Fであり、ESRは0.5mΩであった。80%正規化静電容量までの時間は300時間であった。
実施例2の構成を繰り返し、セルを状態調節した後、3.0Vの定電圧ストレス試験に供した。初期静電容量は2911Fであり、ESRは0.66mΩであった。80%正規化静電容量までの時間は185時間であった。
実施例6の構成を繰り返し、セルを状態調節した後、3.0Vの定電圧ストレス試験に供した。初期静電容量は2867Fであり、ESRは0.46mΩであった。80%正規化静電容量までの時間は285時間であった。この実施例は実施例8と比較できる。80%正規化静電容量までの時間を比較すると、調整されたセル構成において、TEMA‐TFB電解質が、TEA‐TFBよりも高い長期安定性をもたらすことは明らかである。
12 筐体
14 第1の炭素マット
16 第2の炭素マット
18 多孔質セパレータ、多孔質セパレータ層
20 電解質
22 集電体
24 集電体
26 電気リード線
28 電気リード線
Claims (5)
- エネルギ貯蔵デバイスにおいて、
それぞれ第1の活性炭材料及び第2の活性炭材料を含む正電極及び負電極、
を備えたエネルギ貯蔵デバイスであって、
前記第1の活性炭材料と前記第2の活性炭材料の細孔サイズ分布は異なっており、前記第1の活性炭材料及び前記第2の活性炭材料はそれぞれ、>2nmのサイズのいずれの細孔の合計で<0.15cm3/gの細孔容積を有する、エネルギ貯蔵デバイス。 - 前記第1の活性炭材料は:
合計で>0.3cm3/gの細孔容積をもたらす≦1nmのサイズの細孔;及び
合計で≧0.05cm3/gの細孔容積をもたらす>1nmから≦2nmまでのサイズの細孔
を含み、
前記第2の活性炭材料は:
合計で≦0.3cm3/gの細孔容積をもたらす≦1nmのサイズの細孔;及び
合計で≧0.05cm3/gの細孔容積をもたらす>1nmから≦2nmまでのサイズの細孔
を含む、請求項1に記載のエネルギ貯蔵デバイス。 - 前記正電極中の活性炭含有量は、50〜75重量%の前記第1の活性炭材料及び25〜50重量%の前記第2の活性炭材料であり、
前記負電極中の活性炭含有量は、25〜50重量%の前記第1の活性炭材料及び50〜75重量%の前記第2の活性炭材料である、請求項1又は2に記載のエネルギ貯蔵デバイス。 - 前記第1の活性炭材料は、合計で>0.3〜0.5cm3/gの細孔容積をもたらす≦1nmのサイズの細孔を含み、
前記第2の活性炭材料は、合計で0.2〜0.3cm3/gの細孔容積をもたらす≦1nmのサイズの細孔を含む、請求項1〜3のいずれか1項に記載のエネルギ貯蔵デバイス。 - エネルギ貯蔵デバイスを作製する方法であって、
第1の活性炭材料及び第2の活性炭材料を有する炭素系正電極を形成するステップ;
第1の活性炭材料及び第2の活性炭材料を有する炭素系負電極を形成するステップ;並びに
前記炭素系正電極及び前記炭素系負電極をエネルギ貯蔵デバイスに組み込むステップ
を有してなり、
前記第1の活性炭材料と前記第2の活性炭材料の細孔サイズ分布は異なっており、前記第1の活性炭材料及び前記第2の活性炭材料はそれぞれ、>2nmのサイズのいずれの細孔の合計で<0.15cm3/gの細孔容積を有する、エネルギ貯蔵デバイスを作製する方法。
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US9607776B2 (en) | 2017-03-28 |
TW201530583A (zh) | 2015-08-01 |
US10211001B2 (en) | 2019-02-19 |
EP3061108A1 (en) | 2016-08-31 |
WO2015061268A1 (en) | 2015-04-30 |
CN105849838A (zh) | 2016-08-10 |
KR20160077137A (ko) | 2016-07-01 |
US20170092440A1 (en) | 2017-03-30 |
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US20150116905A1 (en) | 2015-04-30 |
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