JP5784643B2 - カーボンナノチューブ浸出繊維を含有する電気装置とその製造方法 - Google Patents
カーボンナノチューブ浸出繊維を含有する電気装置とその製造方法 Download PDFInfo
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- JP5784643B2 JP5784643B2 JP2012556205A JP2012556205A JP5784643B2 JP 5784643 B2 JP5784643 B2 JP 5784643B2 JP 2012556205 A JP2012556205 A JP 2012556205A JP 2012556205 A JP2012556205 A JP 2012556205A JP 5784643 B2 JP5784643 B2 JP 5784643B2
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/43—Electric condenser making
- Y10T29/435—Solid dielectric type
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Description
本願は、2010年3月2日出願の米国仮特許出願第61/309,827号に基づき、合衆国法典第35巻(35 U.S.C.)第119条に従って優先権を主張するものであり、参照により全内容が本明細書に組み込まれる。
適用なし。
また、キラリティに加えてカーボンナノチューブの直径も、その電気伝導性と熱伝導性に関する性質とに影響を与える。カーボンナノチューブの合成において、カーボンナノチューブの直径は、一定サイズの触媒ナノ粒子を用いることにより制御可能である。カーボンナノチューブの直径は、通常、その形成に触媒作用を及ぼす触媒ナノ粒子の直径程度である。このため、カーボンナノチューブの性質は、例えば、カーボンナノチューブの合成に用いられる触媒ナノ粒子のサイズを調整することで、ある一面でさらに制御される。限定しない例として、直径約1nmの触媒ナノ粒子を用いることにより、繊維材料に単層カーボンナノチューブが浸出する。より大きな触媒ナノ粒子は、主に、多層カーボンナノチューブを生成するために用いられるが、これは、その複数のナノチューブ層のために、あるいは、単層及び多層カーボンナノチューブの混合のために、より大きな直径を有する。多層カーボンナノチューブは、通常、電流を不均一に再分配する個々のナノチューブ層の間に発生し、電流を不均一に再分配する層間反応のために、単層カーボンナノチューブよりも複雑な導電率プロファイル(conductivity profile)を有する。一方、単層カーボンナノチューブの異なる部分を通る電流は変化しない。
しかしながら、所定サイズのスーパーキャパシタにおいて、連続繊維201の隣接巻線間隔は、所望の静電容量を提供するために、必要に応じて変動可能である点に注目されたい。
スーパーキャパシタの作動原理は、第2電極層の周囲における電解質の過剰により著しく変化しない。これらの実施形態において、電解質貯蔵タンク(electrolyte reservoir)用の容器(container)は、スーパーキャパシタ300の外側絶縁体ケーシング307であると考えることができる。例えば、電解質貯蔵タンクは、プラスチックのバケツ、又は、容器と同等のものに含まれる。しかしながら、必要に応じて、他の方法でその周囲から電気的に絶縁可能であるとき、これらの実施形態において、電解質貯蔵タンク用の容器が絶縁体であるという必要性はない。
図2A,図2B及び図3によって例示されるスーパーキャパシタは、底面が長方形の角柱基板で示されたが、当然のことながら、本開示の精神及び範囲内でなお機能しつつ、上述の基板形状の全てを利用することができる。
当該技術分野で既知の標準的なカーボンナノチューブ合成反応器は横断面が円形である。これには、例えば、歴史的理由(研究所では円筒状の反応器がよく用いられる)及び利便性(流体力学は円筒状の反応器にモデル化すると容易になり、また、加熱器システムは円管チューブ(石英など)に容易に対応する)、並びに製造の容易性などの多くの理由がある。本開示は、従来の円筒形状を変えて、矩形横断面を有するカーボンナノチューブ合成反応器を提供する。変更の理由は以下の通りである。
比較的低温のパージゾーンを提供するチャンバーは、矩形合成反応器の両端から延びる。出願人は、仮に高温ガスが外部環境(すなわち、反応器の外部)と接触(mix)すると、繊維材料の劣化(degradation)が増加することを究明した。低温パージゾーンは、内部システムと外部環境間の緩衝となる。当該技術分野で既知のカーボンナノチューブ合成反応器の構成では、通常、基材を慎重に(かつ緩やかに)冷却することが求められる。本願の矩形カーボンナノチューブ成長反応器の出口における低温パージゾーンは、連続的なインライン処理に必要とされるような短時間の冷却を実現する。
ある実施形態において、金属製ホットウォール型(hot-walled)反応器(例えば、ステンレス鋼)が用いられる。この種類の反応器の使用は、金属、特にステンレス鋼が炭素の付着(すなわち、すす及び副生成物の形成)を受けやすいために、常識に反するようにも考えられる。したがって、大部分のカーボンナノチューブ合成反応器は、炭素の付着が殆どないため、また、石英は洗浄しやすく試料の観察を容易にするため、石英製である。しかしながら、出願人は、ステンレス鋼上におけるすす及び炭素付着物が増加することにより、より着実、より効率的、より高速、かつ、より安定的なカーボンナノチューブ成長がもたらされること、を見つけた。理論に拘束されるものではないが、大気圧運転(atmospheric operation)と連動して、反応器内で起こるCVDプロセスでは拡散が制限されることが示されている。すなわち、カーボンナノチューブ形成触媒に「過度に供給される(overfed)」、つまり、過量の炭素が、(反応器が不完全真空下で運転している場合よりも)その相対的に高い分圧により反応器システム内で得られる。結果として、開放システム(特に清浄な(clean)もの)では、過量の炭素がカーボンナノチューブ形成触媒の粒子に付着して、カーボンナノチューブの合成能力を低下させる。ある実施形態において、反応器に「汚れが付いて(dirty)」いる、すなわち、金属反応器壁にすすが付着している状態の場合に、矩形反応器を意図的に運転する。炭素が反応器壁上の単分子層に付着すると、炭素は、それ自体を覆って付着しやすくなる。得られる炭素の中には、この機構により「回収される(withdrawn)」ものがあるので、ラジカルの形で残っている炭素原料が、カーボンナノチューブ形成触媒を被毒させない速度でこの触媒と反応する。既存のシステムでは「清浄に(cleanly)」運転するが、連続処理のために開放状態であれば、減速した成長速度で、はるかに低い収率でしかカーボンナノチューブを生産できない。
本明細書に開示されたカーボンナノチューブ合成反応器において、触媒還元及びカーボンナノチューブ成長のいずれもが反応器内で起こる。還元工程が個別の工程として実施されると、連続プロセスに用いるものとして十分タイムリーに行えなくなるため、このことは重要である。当該技術分野において既知の標準的なプロセスにおいて、還元工程の実施には、通常1〜12時間かかる。本開示によれば、両工程は1つの反応器内で生じるが、これは、少なくとも1つには、炭素含有原料ガスを導入するのが、円筒状反応器を用いる当該技術分野では標準的となっている反応器の端部ではなく、中心部であることに起因する。還元プロセスは、繊維が加熱ゾーンに入ったときに行われる。この時点に至るまでに、ガスには、触媒を(水素ラジカルの相互作用を介して)還元する前に反応器壁と反応して冷える時間があるということである。還元が起こるのは、この移行領域である。システム内で最も高温の等温ゾーンでカーボンナノチューブの成長は起こり、反応器の中心近傍におけるガス入口の近位で最速の成長速度が生じる。
明の例示にすぎないことを容易に認識するであろう。当然のことながら、本発明の精神か
ら逸脱することなく、様々な変形例を考え出すことが可能である。
出願当初の特許請求の範囲は以下のようであった。
[請求項1]
第1電極層と、
第2電極層と、
を含んで構成され、
前記第1電極層及び前記第2電極層は、カーボンナノチューブが浸出した複数の連続繊維を含んで構成されることを特徴とする電気装置。
[請求項2]
基板と、
前記第1電極層と前記第2電極層との間に配置され、電解質のイオンに対して透過性である隔離材料の層と、
前記第1電極層及び前記第2電極層と接触する電解質と、
を更に含んで構成される請求項1に記載の電気装置。
[請求項3]
前記第1電極層の前記複数の連続繊維は、前記基板の周囲に等角的に巻回され、
前記第2電極層の前記複数の連続繊維は、前記隔離材料の層の周囲に等角的に巻回される請求項2に記載の電気装置。
[請求項4]
前記基板及び前記隔離材料層の周囲の隣接巻線における前記複数の連続繊維の重なり合いは略ない請求項3に記載の電気装置。
[請求項5]
少なくとも1つの隔離材料の付加層と、
カーボンナノチューブが浸出した複数の連続繊維を含んで構成される少なくとも1つの付加電極層と、
を更に含んで構成され、
各電極層は隔離材料の層によって互いに分離され、かつ、前記電解質は各電極層と接触している請求項3に記載の電気装置。
[請求項6]
外側絶縁体ケーシングを更に含んで構成される請求項5に記載の電気装置。
[請求項7]
前記基板、前記第1電極層、前記第2電極層及び前記隔離材料の層は、前記電解質の貯蔵タンク内に存在する請求項2に記載の電気装置。
[請求項8]
前記第1電極層の前記複数の連続繊維に接続される第1電極端子と、
前記第2電極層の前記複数の連続繊維に接続される第2電極端子と、
を更に含んで構成される請求項2に記載の電気装置。
[請求項9]
前記第1電極端子と前記第2電極端子は前記基板上に配置される請求項8に記載の電気装置。
[請求項10]
前記複数の連続繊維は、繊維トウ、繊維テープ、繊維リボン及びそれらの組合せからなる群より選択される繊維形態を含んで構成される請求項1に記載の電気装置。
[請求項11]
前記複数の連続繊維は、前記第1電極層及び前記第2電極層において互いに略平行である請求項1に記載の電気装置。
[請求項12]
前記連続繊維は、カーボンナノチューブが浸出する前に電気伝導性である請求項1に記載の電気装置。
[請求項13]
前記連続繊維は、連続金属繊維を含んで構成される請求項12に記載の電気装置。
[請求項14]
前記連続繊維は、連続炭素繊維を含んで構成される請求項12に記載の電気装置。
[請求項15]
前記連続繊維は、カーボンナノチューブが浸出する前に非電気伝導性である請求項1に記載の電気装置。
[請求項16]
前記第1電極層及び前記第2電極層と結合される導電率強化材を更に含んで構成され、
前記導電率強化材は、金属箔、金属リボン、金属粉、金属ナノ粒子及びそれらの組合せからなる群より選択される金属形態を含んで構成される請求項15に記載の電気装置。
[請求項17]
外側絶縁体ケーシングを更に含んで構成される請求項1に記載の電気装置。
[請求項18]
前記外側絶縁体ケーシングは、収縮ラップ材料を含んで構成される請求項17に記載の電気装置。
[請求項19]
スーパーキャパシタを含んで構成される請求項1に記載の電気装置。
[請求項20]
前記スーパーキャパシタは、連続繊維のグラム当りで、少なくとも約1Farad/gramの静電容量を有する請求項19に記載の電気装置。
[請求項21]
前記スーパーキャパシタは、連続繊維のグラム当りで、少なくとも約2Farad/gramの静電容量を有する請求項20に記載の電気装置。
[請求項22]
前記浸出したカーボンナノチューブは、前記連続繊維の表面に対して略垂直である請求項1に記載の電気装置。
[請求項23]
電解質は、非有機電解質を含んで構成される請求項1に記載の電気装置。
[請求項24]
電解質は、有機電解質を含んで構成される請求項1に記載の電気装置。
[請求項25]
カーボンナノチューブが浸出した複数の連続繊維を提供すること、
前記複数の連続繊維の第1部分から第1電極層を形成すること、及び、
前記複数の連続繊維の第2部分から第2電極層を形成すること、
を含んで構成されることを特徴とする方法。
[請求項26]
前記第1電極層と前記第2電極層との間に隔離材料の層を付加すること、
前記第1電極層と前記第2電極層を電解質にさらすこと、
を更に含んで構成され、
前記隔離材料は、電解質のイオンに対して透過性である請求項25に記載の方法。
[請求項27]
第1電極層の形成は、基板の周囲に等角的に前記複数の連続繊維の前記第1部分を巻回することを含んで構成され、
第2電極層の形成は、前記第1電極層上に等角的に前記複数の連続繊維の前記第2部分を巻回することを含んで構成される請求項26に記載の方法。
[請求項28]
基板の周囲に等角的に前記複数の連続繊維の前記第1部分を巻回すること、第1電極層上に等角的に前記複数の連続繊維の前記第2部分を巻回すること、及び、前記第1電極層と前記第2電極層との間に隔離材料の層を付加することは、全て同時に行われる請求項27に記載の方法。
[請求項29]
前記第1電極層及び前記第2電極層の隣接巻線における前記複数の連続繊維の重なり合いは略ない請求項27に記載の方法。
[請求項30]
前記第1電極層は、前記隔離材料の層の付加前に前記電解質にさらされる請求項26に記載の方法。
[請求項31]
前記第1電極層及び前記第2電極層は、前記電解質に対して同時にさらされる請求項26に記載の方法。
[請求項32]
前記第1電極層及び前記第2電極層は、前記電解質の貯蔵タンク内に同時に浸漬されることを特徴とする請求項31に記載の方法。
[請求項33]
前記第2電極層上に少なくとも1つの隔離材料の付加層を付加することと、
前記第2電極層上に少なくとも1つの付加電極層を巻回することと、
を更に含んで構成され、
前記少なくとも一つの付加電極層は、カーボンナノチューブが浸出した複数の連続繊維を含んで構成され、
各電極層は隔離材料の層によって互いに分離され、かつ、
前記電解質は各電極層と接触している請求項26に記載の方法。
[請求項34]
外側絶縁体ケーシングを付加することを更に含んで構成される請求項33に記載の方法。
[請求項35]
前記複数の連続繊維は、繊維トウ、繊維テープ、繊維リボン及びそれらの組合せからなる群より選択される繊維形態を含んで構成される請求項25に記載の方法。
[請求項36]
前記複数の連続繊維は、前記第1電極層及び前記第2電極層において互いに略平行である請求項25に記載の方法。
[請求項37]
外側絶縁体ケーシングを付加することを更に含んで構成される請求項25に記載の方法。
[請求項38]
前記連続繊維はカーボンナノチューブが浸出する前に電気伝導性であり、前記連続繊維は連続金属繊維、連続炭素繊維及びそれらの組合せからなる群より選択される請求項25に記載の方法。
[請求項39]
カーボンナノチューブが浸出した複数の連続繊維を提供することと、
基板の周囲に等角的に前記複数の連続繊維の一部を巻回することによって第1電極層を形成することと、
前記第1電極層上に等角的に前記複数の連続繊維の分離部分を巻回することによって前記第1電極層上に少なくとも2つの付加電極層を形成することと、
を含んで構成されることを特徴とする方法。
[請求項40]
各電極層の間に隔離材料の層を付加することと、
前記第1電極層及び前記少なくとも2つの付加電極層を電解質にさらすことと、
を更に含んで構成され、
前記隔離材料は、前記電解質のイオンに対して透過性である請求項39に記載の方法。
[請求項41]
前記第1電極層は、隔離材料の層を付加する前に前記電解質にさらされる請求項40に記載の方法。
[請求項42]
前記第1電極層及び前記少なくとも2つの付加電極層は、前記電解質に同時にさらされる請求項40に記載の方法。
[請求項43]
前記連続繊維はカーボンナノチューブが浸出する前に電気伝導性であり、前記連続繊維は連続金属繊維、連続炭素繊維及びそれらの組合せからなる群より選択される請求項39に記載の方法。
[請求項44]
前記複数の連続繊維は、繊維トウ、繊維テープ、繊維リボン及びそれらの組合せからなる群より選択される繊維形態を含んで構成される請求項39に記載の方法。
Claims (13)
- 第1電極層と、
第2電極層と、
基板と、
前記第1電極層と前記第2電極層との間に配置され、電解質のイオンに対して透過性である隔離材料の層と、
前記第1電極層及び前記第2電極層と接触する電解質と、
を有し、
前記第1電極層及び前記第2電極層は、カーボンナノチューブが浸出した複数の連続繊維を含み、
前記第1電極層の前記複数の連続繊維は、前記基板の周囲に巻回され、
前記第2電極層の前記複数の連続繊維は、前記隔離材料の層の周囲に巻回される、電気装置。 - 少なくとも1つの隔離材料の付加層と、
カーボンナノチューブが浸出した複数の連続繊維を含んで構成される少なくとも1つの付加電極層と、
を更に含んで構成され、
各電極層は隔離材料の層によって互いに分離され、かつ、前記電解質は各電極層と接触している請求項1に記載の電気装置。 - 前記複数の連続繊維は、前記第1電極層及び前記第2電極層において互いに略平行である請求項1に記載の電気装置。
- 前記連続繊維は、カーボンナノチューブが浸出する前に電気伝導性である請求項1に記載の電気装置。
- 前記連続繊維は、カーボンナノチューブが浸出する前に非電気伝導性である請求項1に記載の電気装置。
- 前記第1電極層及び前記第2電極層と結合される導電率強化材を更に含んで構成され、
前記導電率強化材は、金属箔、金属リボン、金属粉、金属ナノ粒子及びそれらの組合せからなる群より選択される金属形態を含んで構成される請求項5に記載の電気装置。 - カーボンナノチューブが浸出した複数の連続繊維を提供すること、
前記複数の連続繊維の第1部分から第1電極層を形成すること、
前記複数の連続繊維の第2部分から第2電極層を形成すること、
前記第1電極層と前記第2電極層との間に隔離材料の層を付加すること、及び、
前記第1電極層と前記第2電極層を電解質にさらすこと、
を含み、
前記隔離材料は、電解質のイオンに対して透過性であり、
前記第1電極層の形成は、基板の周囲に前記複数の連続繊維の前記第1部分を巻回することを含み、
前記第2電極層の形成は、前記隔離材料の周囲に前記複数の連続繊維の前記第2部分を巻回することを含む、方法。 - 基板の周囲に等角的に前記複数の連続繊維の前記第1部分を巻回すること、第1電極層上に等角的に前記複数の連続繊維の前記第2部分を巻回すること、及び、前記第1電極層と前記第2電極層との間に隔離材料の層を付加することは、全て同時に行われる請求項7に記載の方法。
- 前記第1電極層及び前記第2電極層の隣接巻線における前記複数の連続繊維の重なり合いは略ない請求項7に記載の方法。
- 前記第2電極層上に少なくとも1つの隔離材料の付加層を付加することと、
前記第2電極層上に少なくとも1つの付加電極層を巻回することと、
を更に含んで構成され、
前記少なくとも一つの付加電極層は、カーボンナノチューブが浸出した複数の連続繊維を含んで構成され、
各電極層は隔離材料の層によって互いに分離され、かつ、
前記電解質は各電極層と接触している請求項7に記載の方法。 - 前記複数の連続繊維は、前記第1電極層及び前記第2電極層において互いに略平行である請求項7に記載の方法。
- カーボンナノチューブが浸出した複数の連続繊維を提供することと、
基板の周囲に等角的に前記複数の連続繊維の一部を巻回することによって第1電極層を形成することと、
前記第1電極層上に等角的に前記複数の連続繊維の分離部分を巻回することによって前記第1電極層上に少なくとも2つの付加電極層を形成することと、
を含んで構成されることを特徴とする方法。 - 各電極層の間に隔離材料の層を付加することと、
前記第1電極層及び前記少なくとも2つの付加電極層を電解質にさらすことと、
を更に含んで構成され、
前記隔離材料は、前記電解質のイオンに対して透過性である請求項12に記載の方法。
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KR101818640B1 (ko) | 2018-01-15 |
BR112012021634A2 (pt) | 2019-09-24 |
CA2789664A1 (en) | 2011-09-09 |
CN102918612A (zh) | 2013-02-06 |
EP2543052B1 (en) | 2019-11-27 |
US8787001B2 (en) | 2014-07-22 |
EP2543052A4 (en) | 2018-03-28 |
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