JP6581983B2 - 透明な自動光充電式電気化学的デバイス - Google Patents
透明な自動光充電式電気化学的デバイス Download PDFInfo
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- JP6581983B2 JP6581983B2 JP2016534701A JP2016534701A JP6581983B2 JP 6581983 B2 JP6581983 B2 JP 6581983B2 JP 2016534701 A JP2016534701 A JP 2016534701A JP 2016534701 A JP2016534701 A JP 2016534701A JP 6581983 B2 JP6581983 B2 JP 6581983B2
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- alkali metal
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/46—Accumulators structurally combined with charging apparatus
- H01M10/465—Accumulators structurally combined with charging apparatus with solar battery as charging system
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
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Description
− 正極フィルムがその上に被着された透明な導電性キャリアを含んでなる正極であって、前記正極フィルムが正極活物質としてn型半導体を含んでなり、前記n型半導体がバンドギャップEgを有しかつアルカリ金属M1のイオンをインターカレート及びデインターカレート可能な、該正極と;
− 前記アルカリ金属M1、前記アルカリ金属M1の合金、及び前記アルカリ金属M1の金属間化合物から選択される成分を含んでなる負極と、及び
− 前記アルカリ金属M1の塩と有機溶媒とを含んでなる非水性液体電解質とを、
含んでなることを特徴とし、
− 前記正極及び負極が、それぞれ電極電位E1及びE2を有し、ここで、E1>E2であり、E1及びE2が、M1+/M10カップルの電極電位に対して計算される、該デバイスである。
− 式MM’PO4[式中、M=Li又はNa、かつM’=Fe、Co、Mn、Ni、又はそれらの混合物]に関係するカンラン石;
− 式MxM”PO4F、MxM”PO4.OH、及びMxM”PO4.O[式中、Mは上記と同じ定義を有し、M”=Fe、Co、Mn、Ni、V、又はTiであり、かつxは、0から2までの範囲である]に関係するフッ素化、ヒドロキシル化、及び酸素化された誘導体;
− 式M3M’PO4CO3[式中、M及びM’は上記と同じ定義を有する]に関係するカルボノホスフェート;及び最後に
− 式MxM’P2O7[式中、M、M’、及びxは、上記と同じ定義を有する]に関係するピロリン酸塩。
i)前記再充電されたデバイスを得る目的で、前記デバイスを、好ましくは前記正極を含んでなる前記デバイスの側面において、少なくとも30分間、及び好ましくは少なくとも1時間にわたり光波源に暴露すること、
を含んでなることを特徴とする。
i’)前記デバイスを、好ましくは前記デバイスの前記正極を含んでなる側面において、少なくとも10時間、及び好ましくは少なくとも12時間にわたり光波源に暴露すること;
ii’)工程i’)のデバイスを用いて電気機器に電力を供給すること;及び
iii’)前記再充電されたデバイスを取得する目的で、工程ii’)の装置を少なくとも6時間、及び好ましくは少なくとも12時間にわたり暗中で緩和させること、
を含んでなることを特徴とする。
1.1 「n型半導体」としての使用のためのアナターゼTiO 2 の調製
チタンイソプロポキシド(Ti(OiPr)4)30mlを水300mlに添加し、次いで、得られた溶液を完全な加水分解まで約4時間激しく攪拌した。得られた白色沈殿を次に真空又は遠心濾過し、水で数回、次いでエタノールで洗浄し、室温で乾燥させた。
前記乾燥沈殿を、0.1mol/リットルのNH4F水溶液の存在下に60℃で7日間置いた。
直径約4から6nmまでの範囲の、かつ約235〜300m2/g(B.E.T.法)の比表面積のTiO2ナノ粒子が得られた。
正極は、上記工程1.1において調製されたような12gのアナターゼTiO2、7.2gのヒドロキシエチルセルロース、及び65gのテルピネオールを含んでなる印刷可能なペーストを、透明な導電性FTOキャリア上に、スクリーン印刷によって被着することにより得られた。ペーストは一般に、30から50mPasまでの粘度範囲のヒドロキシエチルセルロース22重量%、及び5から15mPasまでの粘度範囲のヒドロキシエチルセルロース38重量%を、65gのテルピネオール及び前記ペースト中のTiO2のいかなる初期量についても含んでなる。
本発明によるデバイスは:
− 正極としての、工程1.2において上記で調製されたような電極と;
− 負極及び基準電極としての、リチウムシートと;及び
− 液体電解質としての、有機エチレンカーボネート/ジメチルカーボネート(1/1、重量で)溶媒中の1mol/LのLiPF6リチウム塩の溶液と、
を含んでなる、透明なソーダガラス製の光電気化学的セルを、アルゴンを充填されたグローブボックス中に配置することによって得られた。
添付の図2は、上記で得られたような本発明の電気化学的デバイスの電流密度(mA/cm2)を、Li+/Liカップルに対する電位(ボルト、V)の関数として示す。白丸を用いた曲線は、照明なしの(暗中での)放電中の本発明の電気化学的デバイスの挙動を例示し、一方黒丸を用いた曲線は、正極(TiO2)が強度約3000mW/cm2の光波源に暴露された場合の放電中の本発明の電気化学的デバイスの挙動を例示する。2つの曲線は、0.5mV/sの速度で1.5Vの電圧(対Li+/Li)が得られるまでスキャンすることにより記録された。種々の実験において電圧又は電流を適用すること(即ち、閉回路)は、デバイスが電気化学的に放電されることを可能にする。しかしながら、デバイスの放電は、デバイスが電気器具に電力を供給するための「電池」として使用される場合、自然に、即ち電圧又は電流の適用なしに起こることが思い出されよう(即ち、開回路)。
添付の図5(点A、B、D、F、及びGにより特徴づけられる曲線)は、本発明の電気化学的デバイスが以下の工程に供された場合の、前記デバイスの単位面積当たりの電気容量の関数としての、Li+/Liカップル(ボルト、V)に対する電位を示している。:
− セル開回路電位から1.5V(対Li+/Li)まで、電流密度100μA/cm2を適用することにより達成される、暗中での第1の放電(閉回路)(図5、曲線A−B);
− 強度約3W/cm2の光波源への1時間にわたる暴露(開回路)(図5、曲線B−D);
− セル開回路電位から1.5V(対Li+/Li)まで、電流密度100μA/cm2を適用することにより達成される、暗中での第2の放電(閉回路)(図5、曲線D−F);及び
− 強度約3000mW/cm2の光波源への1時間にわたる暴露(開回路)(図5、曲線F−G)
− セル開回路電位から1.5V(対Li+/Li)まで、電流密度100μA/cm2を適用することにより達成される、暗中での第1の放電(閉回路)(図5、曲線A−B);
− 暗中で1時間の緩和(開回路)(図5、曲線B−C);及び
− セル開回路電位から1.5V(対Li+/Li)まで、電流密度100μA/cm2を適用することにより達成される、暗中での第2の放電(閉回路)(図5、曲線C−E)、
− セル開回路電位から1.5V(対Li+/Li)まで、電流密度100μA/cm2を適用することにより達成される、暗中での第1の放電(閉回路)(図6、曲線A−B);及び
− 強度約3000mW/cm2の光波源への1時間にわたる暴露(開回路)(図6、曲線B−C)、
既に充電された本発明によるデバイスは、以下の工程:
− 強度約3000mW/cm2の光波源への12時間にわたる暴露(開回路);
− セル開回路電位から1.5V(対Li+/Li)まで、電流密度100μA/cm2を適用することにより達成される、暗中での放電(閉回路);及び
− 1時間、6時間、又は12時間続く、暗中での緩和時間(開回路)、
に供された。
Claims (13)
- 透明な光充電式電気化学的デバイスであって、前記デバイスが:
− 正極フィルムがその上に被着された透明な導電性キャリアを含んでなる正極であって、前記正極フィルムが正極活物質としてn型半導体を含んでなり、前記n型半導体がバンドギャップEgを有しかつアルカリ金属M1のイオンをインターカレート及びデインターカレート可能な、該正極と;
− 前記アルカリ金属M1、前記アルカリ金属M1の合金、及び前記アルカリ金属M1の金属間化合物から選択される成分を含んでなる負極と、及び
− 前記アルカリ金属M1の塩と有機溶媒とを含んでなる非水性液体電解質とを、
含んでなることを特徴とし、
− 前記正極及び負極が、それぞれ電極電位E1及びE2を有し、ここで、E1>E2であり、E1及びE2が、M1+/M10カップルの電極電位に対して計算され、
前記n型半導体が、TiO 2 、Fe 2 O 3 、Fe 3 O 4 、MnO 2 、CoO、Co 3 O 4 、SnO 2 、RuO 2 、Bi 2 O 3 、VO 2 、V 2 O 5 、Cr 2 O 3 、Nb 2 O 5 、及びZnOから選択される、
該デバイス。 - 前記アルカリ金属M1が、リチウム、ナトリウム、及びカリウムから選択されることを特徴とする、請求項1に記載のデバイス。
- 前記n型半導体がTiO2であることを特徴とする、請求項1又は請求項2に記載のデバイス。
- 前記n型半導体が、最大で4.0eVのバンドギャップEgを有することを特徴とする、請求項1から3のいずれか1項に記載のデバイス。
- 前記n型半導体が、直径2から50nmまでの範囲の粒子を含んでなることを特徴とする、請求項1から4のいずれか1項に記載のデバイス。
- 前記n型半導体が、20m 2 /gから500m 2 /gまでの範囲の、B.E.T法により測定される比表面積を有することを特徴とする、請求項1から5のいずれか1項に記載のデバイス。
- 前記正極フィルムが、少なくともメソ細孔を含んでなる多孔質構造を有することを特徴とする、請求項1から6のいずれか1項に記載のデバイス。
- 前記正極フィルムがさらに、少なくとも1種の色素及び/又は少なくとも1種の光のリフレクタを含んでなることを特徴とする、請求項1から7のいずれか1項に記載のデバイス。
- 前記透明な導電性キャリアが、FTO型、ITO型、又はZITO型の透明な導電性ガラスであることを特徴とする、請求項1から8のいずれか1項に記載のデバイス。
- 前記正極フィルムが、0.1から25μmまでの範囲の厚さを有することを特徴とする、請求項1から9のいずれか1項に記載のデバイス。
- 請求項1から10のいずれか1項において定義された透明な光充電式電気化学的デバイスを光充電するための方法であって、以下の工程:
i)再充電されたデバイスを得る目的で、前記デバイスを少なくとも30分間にわたり光波源に暴露すること、
を含んでなることを特徴とする、該方法。 - 請求項1から10のいずれか1項において定義された透明な光充電式電気化学的デバイスを暗中で再充電するための方法であって、以下の工程:
i’)前記デバイスを少なくとも10時間にわたり光波源に暴露すること;
ii’)工程i’)のデバイスを用いて電気機器に電力を供給すること;及び
iii’)前記再充電されたデバイスを取得する目的で、工程ii’)の装置を少なくとも6時間にわたり暗中で緩和させること、
を含んでなることを特徴とする、該方法。 - 請求項1から10のいずれか1項において定義された透明な光充電式電気化学的デバイスにおける、正極活物質としてのn型半導体の使用。
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PCT/FR2014/053056 WO2015079170A1 (fr) | 2013-11-28 | 2014-11-27 | Dispositif électrochimique autophotorechargeable transparent |
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US10333181B2 (en) | 2019-06-25 |
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