JP5529653B2 - ナノ構造のバルク熱電材料 - Google Patents
ナノ構造のバルク熱電材料 Download PDFInfo
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- JP5529653B2 JP5529653B2 JP2010153262A JP2010153262A JP5529653B2 JP 5529653 B2 JP5529653 B2 JP 5529653B2 JP 2010153262 A JP2010153262 A JP 2010153262A JP 2010153262 A JP2010153262 A JP 2010153262A JP 5529653 B2 JP5529653 B2 JP 5529653B2
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/857—Thermoelectric active materials comprising compositions changing continuously or discontinuously inside the material
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
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Description
本発明に係わる材料及びデバイスを製造するために、いろいろな方法を用いることができる。例えば1)多孔質マトリクス、例えばメソ多孔質シリカセラミックマトリクス又は多孔質モノリスを電気化学的方法によって充填する、2)セラミック/半導体ナノ複合粒子(例えば、セラミックマトリクス中を通っている半導体ナノワイヤを有する粒子)を含む粉末をホットプレスする、及び3)セラミック粒子と半導体ナノ粒子の混合物を含む粉末をホットプレスする、などである。「粉末」という用語は、一つ以上のタイプの粒子を含む粒状物質を指す。多孔質モノリスはセラミック粉末をホットプレスして形成できる。これらのアプローチやその他のアプローチについては以下でさらに詳しく説明する。
メソ多孔質シリカモノリスをテンプレートとして用いて、電着によってナノワイヤ及びナノメッシュモノリスを製造する方法は次の二つのステップを含む。1)シリカテンプレートの作成、及び2)テンプレートのメソ多孔質チャンネル内部での金属又は半導体の電気化学的成長。メソ多孔質シリカはいろいろな方法で製造できる。マトリクス物質はまたどんな多孔質物質であってもよく、ポア(孔)構造はナノスケールの特徴を含むものでもよい。
電着は、界面活性剤アプローチによって作られた構造に限らず、どんな多孔質構造でも用いることができる。
多孔質シリカテンプレートが界面活性剤をポロゲンとして用いて調製された。用いられた界面活性剤は、PLURONIC界面活性剤P123(EO20PO70EO20), F127 (EO100PO70EO100), Brij-58(C16H33EO20),及びセチルトリメチル臭化アンモニウム(CTAB)などである、ここでEOとPOはそれぞれ、エチレン及びプロピレンオキシドを表す。テンプレートは界面活性剤テンプレート化プロセスによって調製された。F127, P123, Brij-58, 及びCTABによってテンプレート化されたポア(孔)の平均ポア直径はそれぞれ、約12、9、6、及び2nmであった。
PLURONIC界面活性剤P123をテンプレートとしてゾル−ゲル法によって、キセロゲルメソ多孔質シリカが作製された。調製された状態の六角形メソ構造シリカのポア(孔)直径は約9nmであった。Bi2Te3の前駆体溶液は、60℃の150mL 6M HNO3に0.00225 mol Teと0.015 mol Bi(NO3)35H2Oを溶かして調製された。
電着の条件及び前駆体組成を変えることによって、化学的組成とドーピングに対するコントロールを改善できる。例えば、CdSe, CdTe, CdS, PbSe, PbTe, 及びPbSなどの半導体をメソ多孔質チャンネル内部にデポジットできる。このような組成コントロールは、さらにデバイスの輸送性質の調整を可能にする。
粒子は内部ナノ構造を有するものであってもよい。粒子は、半導体を浸潤させたナノ多孔質絶縁物質を粉砕して形成できる。粒子はセラミック又はその他の電気的に絶縁性の物質内部にナノ構造の包含物を有する。
熱電複合材料を形成するプロセスの一例は次のようなものである。第一のステップで、半導体とセラミックのナノ粒子が高エネルギーボールミル粉砕又はその他の機械的又は化学的方法によって形成される。第二のステップで、ナノ粒子が適当な比で混合され、機械プレスで予備プレスされ、不活性気体中で高温等方プレス(HIP)によって2000℃までの温度で60,000psiを超える圧力に圧縮される。この方法の一つの利点は、比較的複雑な形をHIPプロセス又は他の固化プロセスで作製することができ、サンプルに非等方性が生じないことである。さらに、金属電極などの追加される層をHIPプロセスで熱電材料の表面に直接融合できる。温度、圧力、及び加圧気体の組成をすべてHIPステップでコントロールできるこのプロセスで得られる生成物の密度は理論値に近い。
第一の成分は、半導体又は金属などの導電性物質が可能である。第一の成分は無機物質であっても、導電性ポリマーや有機半導体などの有機物質であってもよい。
本発明に係わる熱電複合材料はさらに、他の物質及び/又は構造、例えば空気(ボイド内に)、半導体又は電気絶縁体のナノ層がデポジットされる電気絶縁性コア、及び機械的強度を高めるための結合剤又はファイバー、を含むことができる。
本発明に係わる熱電材料及びデバイスのその他の応用は当業者には明らかであろう。応用は、自動車などの車両、飛行機、及び宇宙船における電力発生を含む。熱的な勾配を、エンジンの運転、燃料の燃焼、太陽エネルギー、又はその他のエネルギー源によって生成できる。
Claims (13)
- 粒状形態を有する第一の粉末成分、この第一の粉末成分は導電性である、及び
粒状形態を有する第二の粉末成分、この第二の粉末成分は前記第一の粉末成分よりも実質的に小さな導電度を有する、
を含む熱電バルク材料であって、
前記第一の粉末成分と第二の粉末成分は熱電バルク材料中で粒状形態を保持し、
前記第二の粉末成分はその内部に連続な半導体ネットワークを含み、
前記熱電バルク材料は前記第一の粉末成分から形成された導電性のナノ構造ネットワーク及び第二の粉末成分から形成された連続なセラミックマトリクスを含む、熱電バルク材料。 - 最小の物理的寸法が1mmを超える厚膜である、請求項1に記載の熱電バルク材料。
- 第一の粉末成分の導電度が第二の粉末成分の導電度より100倍以上大きい、請求項1に記載の熱電バルク材料。
- 導電性ナノ構造ネットワークは三次元連続ネットワークである、請求項1に記載の熱電バルク材料。
- 第一の粉末成分が半導体であり、第二の粉末成分が電気絶縁体である、請求項1に記載の熱電バルク材料。
- 第一の粉末成分がセレン又はテルルを含む半導体化合物であり、かつ
第二の粉末成分が電気絶縁性の無機酸化物である、請求項1に記載の熱電バルク材料。 - 第一の粉末成分が、テルル含有半導体、及びシリコン−ゲルマニウム合金から成る群から選ばれ、
第二の粉末成分が、アルミナ、コバルト酸ランタン、コバルト酸ナトリウム、シリカ、酸化錫、酸化亜鉛、酸化ジルコニウム、酸化イットリウム、フラーレン、カーボンナノチューブ、窒素、及び空気から成る群から選ばれる物質を含む、請求項1に記載の熱電バルク材料。 - 第一の粉末成分がテルル化ビスマスを含み、第二の粉末成分がシリカを含む、請求項1に記載の熱電バルク材料。
- 第一の粉末成分の熱電係数が量子サイズ効果によって増強される、請求項1に記載の熱電バルク材料。
- 半導体ナノ粒子及び電気絶縁性物質の粒子を含む、請求項1に記載の熱電バルク材料。
- 熱電バルク材料を形成する方法であって、
導電性である第一の粉末成分と電気絶縁性である第二の粉末成分を含む粒状形態の粉末混合物を用意するステップ、
前記粉末混合物をプレスして、粒状形態を保持しかつ前記第二の粉末成分はその内部に連続な半導体ネットワークを含む熱電バルク材料を形成するステップ、
を含み、
前記熱電バルク材料は前記第一の粉末成分から形成された導電性のナノ構造ネットワーク及び第二の粉末成分から形成された連続なセラミックマトリクスを含む、方法。 - 前記第一の粉末成分が半導体である、請求項11に記載の方法。
- さらに前記粉末混合物を加熱するステップを含む、請求項11に記載の方法。
Applications Claiming Priority (4)
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US63391804P | 2004-12-07 | 2004-12-07 | |
US60/633,918 | 2004-12-07 | ||
US11/120,731 US7309830B2 (en) | 2005-05-03 | 2005-05-03 | Nanostructured bulk thermoelectric material |
US11/120,731 | 2005-05-03 |
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JP2007545449A Division JP5139073B2 (ja) | 2004-12-07 | 2005-10-18 | ナノ構造のバルク熱電材料 |
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JP2010278449A JP2010278449A (ja) | 2010-12-09 |
JP5529653B2 true JP5529653B2 (ja) | 2014-06-25 |
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JP2007545449A Expired - Fee Related JP5139073B2 (ja) | 2004-12-07 | 2005-10-18 | ナノ構造のバルク熱電材料 |
JP2010153262A Expired - Fee Related JP5529653B2 (ja) | 2004-12-07 | 2010-07-05 | ナノ構造のバルク熱電材料 |
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US (1) | US7309830B2 (ja) |
EP (1) | EP1820224B1 (ja) |
JP (2) | JP5139073B2 (ja) |
CN (2) | CN100550450C (ja) |
WO (1) | WO2006062582A2 (ja) |
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JP2008523614A (ja) | 2008-07-03 |
WO2006062582A3 (en) | 2007-03-01 |
JP5139073B2 (ja) | 2013-02-06 |
CN101656293B (zh) | 2012-01-11 |
EP1820224A4 (en) | 2012-10-31 |
US7309830B2 (en) | 2007-12-18 |
CN101156255A (zh) | 2008-04-02 |
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