JP2002353521A - Plastic or glass thermoelectric power generating module, and manufacturing method therefor - Google Patents
Plastic or glass thermoelectric power generating module, and manufacturing method thereforInfo
- Publication number
- JP2002353521A JP2002353521A JP2001157065A JP2001157065A JP2002353521A JP 2002353521 A JP2002353521 A JP 2002353521A JP 2001157065 A JP2001157065 A JP 2001157065A JP 2001157065 A JP2001157065 A JP 2001157065A JP 2002353521 A JP2002353521 A JP 2002353521A
- Authority
- JP
- Japan
- Prior art keywords
- thermoelectric semiconductor
- type thermoelectric
- semiconductor substrate
- type
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004033 plastic Substances 0.000 title claims abstract description 22
- 229920003023 plastic Polymers 0.000 title claims abstract description 22
- 239000011521 glass Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000004065 semiconductor Substances 0.000 claims abstract description 84
- 239000000758 substrate Substances 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 238000010248 power generation Methods 0.000 claims description 23
- 235000012489 doughnuts Nutrition 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000005060 rubber Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005992 thermoplastic resin Polymers 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 description 12
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 9
- 239000004020 conductor Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- QEBDLIWRLCPLCY-UHFFFAOYSA-N selanylidenebismuth Chemical compound [Bi]=[Se] QEBDLIWRLCPLCY-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- -1 specifically Polymers 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 230000005678 Seebeck effect Effects 0.000 description 3
- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910021332 silicide Inorganic materials 0.000 description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 3
- 230000005679 Peltier effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000036760 body temperature Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- OQRNKLRIQBVZHK-UHFFFAOYSA-N selanylideneantimony Chemical compound [Sb]=[Se] OQRNKLRIQBVZHK-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- DDJAGKOCVFYQOV-UHFFFAOYSA-N tellanylideneantimony Chemical compound [Te]=[Sb] DDJAGKOCVFYQOV-UHFFFAOYSA-N 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、冷却素子や熱電発
電器などとして幅広く使用できる熱電発電モジュール及
びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoelectric power module that can be widely used as a cooling element, a thermoelectric generator, and the like, and a method of manufacturing the same.
【０００２】[0002]
【従来の技術】ビスマス・テルル、鉛・テルル、シリコ
ン・ゲルマニウム、珪化鉄などの合金は、熱電半導体と
して公知であり、種々の分野で広く利用されている。こ
のような熱電半導体の特徴は、電気の良導体であり、熱
の不良導体である。その性能は次の式で表される、2. Description of the Related Art Alloys such as bismuth tellurium, lead tellurium, silicon germanium and iron silicide are known as thermoelectric semiconductors and are widely used in various fields. Such a thermoelectric semiconductor is a good conductor of electricity and a poor conductor of heat. Its performance is expressed by the following equation:
【式１】 Z = （α2・σ）/κ＝α2/（κ・ρ） （式中、αは、ゼーベック係数、σは、電気伝導率、κ
は、熱伝導率、ρは、電気抵抗率である。) 従って、電気抵抗率が低く、熱伝導性が悪く、ゼーベッ
ク係数が大きいものが良い熱電発電素子ということにな
る。通常、電気の良導体は熱の良導体でもあるので、両
性質の折衷が望まれる。現行のＺの値は大体３×１０-3
／Kであり、素子の利用温度によって、この値は変わっ
てくる。また熱電発電素子を構成する物質において最大
のＺの値が得られる温度は異なっており、物質によって
得意な使用温度領域がある。[Equation 1] Z = (α 2 · σ) / κ = α 2 / (κ · ρ) (where α is the Seebeck coefficient, σ is the electric conductivity, κ
Is the thermal conductivity, and ρ is the electrical resistivity. Therefore, a thermoelectric power generation element having a low electric resistivity, poor thermal conductivity and a large Seebeck coefficient is a good thermoelectric power generation element. Usually, a good conductor of electricity is also a good conductor of heat, so a compromise between the two properties is desired. The current value of Z is about 3 × 10 -3
/ K, and this value changes depending on the use temperature of the element. In addition, the temperature at which the maximum value of Z is obtained differs among the substances constituting the thermoelectric power generation element, and there is an excellent use temperature range depending on the substance.
【０００３】従来、熱電素子は、図１に示すように、ｐ
型とｎ型の半導体をギリシャ文字のΠ（パイ）のような
形態に接合してあり、このモジュールによって２つの機
能、ペルチエ効果とゼーベック効果とを持たせている。
ここで、ペルチエ効果は、２つの素子の回路へ直流電圧
を印加することによって、Πの素子Ａ側又はＢ側のどち
らか一方が冷やされたり、温められたりする効果であ
る。電圧の極性を逆にすれば、温と冷を逆に出来る。ゼ
ーベック効果は温度差により発電するという効果であ
る。たとえば素子Ａを温め、素子Ｂを冷やし、素子Ａと
Ｂの間で温度差をつくると、図１のＶで示したように起
電力が発生する。つまりひとつのモジュールで、冷却
（あるいは加熱）と発電の両特性を持たせることができ
ることが熱電半導体を使ったモジュールの特徴である。
しかしながら、従来、熱電半導体は合金で形成されてい
るため、その形状は珪化鉄を使ったモジュールが馬蹄形
であることを除くと、図１に示すようなΠ型が主たるも
のであり、利用しやすい形態に成型することが困難であ
った。Conventionally, as shown in FIG.
Type and n-type semiconductors are joined in the form of the Greek letter Π (pi), and this module provides two functions, the Peltier effect and the Seebeck effect.
Here, the Peltier effect is an effect in which one of the element A side and the element B side is cooled or heated by applying a DC voltage to a circuit of two elements. By reversing the polarity of the voltage, the temperature and the cold can be reversed. The Seebeck effect is an effect of generating power by a temperature difference. For example, when the element A is heated and the element B is cooled, and a temperature difference is created between the elements A and B, an electromotive force is generated as shown by V in FIG. That is, it is a feature of a module using a thermoelectric semiconductor that one module can have both characteristics of cooling (or heating) and power generation.
However, conventionally, since a thermoelectric semiconductor is formed of an alloy, its shape is mainly a Π shape as shown in FIG. 1 except that a module using iron silicide has a horseshoe shape, and it is easy to use. It was difficult to mold into a form.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、任意の形態
に簡易に成型できる熱電発電モジュールを提供すること
を目的とする。本発明は、又、このような優れた熱電発
電モジュールを効率よく製造できる製造法を提供するこ
とを目的とする。本発明は、又、上記熱電発電モジュー
ルを用いた熱電発電器を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoelectric power module which can be easily formed into an arbitrary form. Another object of the present invention is to provide a manufacturing method capable of efficiently manufacturing such an excellent thermoelectric power generation module. Another object of the present invention is to provide a thermoelectric generator using the thermoelectric power module.
【０００５】[0005]
【課題を解決するための手段】本発明は、熱電半導体の
微粉末を、導電性を付与したゴムや樹脂などのプラスチ
ックスといった有機物やガラスへ添加・分散させ、混練
すると、使う場所に応じた形状に熱電半導体基体を容易
に成型でき、上記課題を効率的に解決できるとの知見に
基づいてなされたのである。すなわち、本発明は、導電
性プラスチック又はガラス中にｎ型熱電半導体粒子を分
散させてなるｎ型熱電半導体基体と、導電性プラスチッ
ク又はガラス中にｐ型熱電半導体粒子を分散させてなる
ｐ型熱電半導体基体とを複合化させたことを特徴とする
熱電発電モジュールを提供する。本発明は、又、導電性
プラスチック又はガラス中にｎ型熱電半導体粒子を分散
させてなるｎ型熱電半導体基体と、導電性プラスチック
又はガラス中にｐ型熱電半導体粒子を分散させてなるｐ
型熱電半導体基体とを複合化させることを特徴とする上
記熱電発電モジュールの製造方法を提供する。本発明
は、又、上記熱電発電モジュールにおけるｎ型熱電半導
体基体とｐ型熱電半導体基体のそれぞれに電極が設けら
れ、該電極間に回路が形成されており、ｎ型熱電半導体
基体とｐ型熱電半導体基体間の温度差を電流として回路
から取り出すことを特徴とする熱電発電器を提供する。SUMMARY OF THE INVENTION According to the present invention, a fine powder of a thermoelectric semiconductor is added to and dispersed in an organic material such as plastics such as rubber or resin having conductivity, or glass, and kneaded. This is based on the finding that a thermoelectric semiconductor substrate can be easily formed into a shape, and the above problem can be solved efficiently. That is, the present invention provides an n-type thermoelectric semiconductor substrate in which n-type thermoelectric semiconductor particles are dispersed in conductive plastic or glass, and a p-type thermoelectric semiconductor in which p-type thermoelectric semiconductor particles are dispersed in conductive plastic or glass. Provided is a thermoelectric power generation module characterized by being combined with a semiconductor substrate. The present invention also provides an n-type thermoelectric semiconductor substrate in which n-type thermoelectric semiconductor particles are dispersed in conductive plastic or glass, and a p-type in which p-type thermoelectric semiconductor particles are dispersed in conductive plastic or glass.
And a method for manufacturing the above thermoelectric power generation module, wherein the thermoelectric power generation module is combined with a thermoelectric semiconductor substrate. According to the present invention, the n-type thermoelectric semiconductor substrate and the p-type thermoelectric semiconductor substrate in the thermoelectric power generation module are each provided with an electrode, and a circuit is formed between the electrodes. Provided is a thermoelectric generator characterized in that a temperature difference between semiconductor substrates is taken out of a circuit as a current.
【０００６】[0006]
【発明の実施の形態】本発明で用いる導電性プラスチッ
ク又はガラスとしては、電気伝導度が体積固有抵抗値で
１０の３乗からマイナス４乗のものを用いるのが好まし
く、より好ましくは１０の０乗以下である。このような
導電性ガラスとしては、銀やリチウムを含むモリブデン
系ガラスをあげることが出来る。また、導電性プラスチ
ックとしては、導電性粒子、例えば、グラファイト、カ
ーボンブラック、金属粉、導電性セラミック粉等を充填
した各種熱可塑性樹脂、熱硬化性樹脂、天然及び合成ゴ
ムなどがあげられる。これらの導電性プラスチックのう
ち、導電性エラストマーが好ましい。又、導電性粒子と
して特に好ましいのは、ハイペリオン・キャタリシス・
インターナショナル社のグラファイト・フィブリルＢＮ
あるいはＣＣ、ケッチェン・ブラック・インターナショ
ナル社のケッチェン・ブラックＥＣあるいはＥＣ６００
ＪＤである。これらは１種又は２種以上の混合物として
用いることができる。これらのうち、グラファイト・フ
ィブリル及び導電性カーボンブラックを組み合わせて用
いるのが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION As the conductive plastic or glass used in the present invention, it is preferable to use one having an electrical conductivity of 10 3 to −4 in terms of volume resistivity, more preferably 10 0. It is less than the power. As such a conductive glass, a molybdenum-based glass containing silver or lithium can be given. Examples of the conductive plastic include various thermoplastic resins, thermosetting resins, natural and synthetic rubbers filled with conductive particles such as graphite, carbon black, metal powder, and conductive ceramic powder. Among these conductive plastics, a conductive elastomer is preferable. Particularly preferred as the conductive particles are Hyperion Catalysis.
International's Graphite Fibril BN
Or CC, Ketjen Black EC or EC600 from Ketjen Black International
JD. These can be used alone or as a mixture of two or more. Among these, it is preferable to use a combination of graphite fibrils and conductive carbon black.
【０００７】プラスチックとしては、具体的には、ポリ
エチレン、ポリプロピレン、ナイロン、ポリエステル、
（メタ）アクリル樹脂、ＡＢＳ樹脂、ポリウレタン、エ
ポキシ樹脂、ＥＰＤＭ、ＮＢＲ、ＳＢＲ、ＰＩＢ、Ｃ
Ｒ、シリコーンゴム、ヒドリルゴムなどがあげられる。
これらのうちＥＰＤＭおよびシリコーンが好ましい。本
発明で用いるｎ型及びｐ型熱電半導体粒子としては、ビ
スマス・テルル（ＢｉＴｅ）、アンチモン・テルル（Ｓ
ｂＴｅ）、ビスマス・アンチモン・テルル（ＢｉＳｂＴ
ｅ）、ビスマス・セレン（ＢｉＳｅ）、アンチモン・セ
レン（ＳｂＳｅ）、ビスマス・セレン・テルル（ＢｉＳ
ｅＴｅ）、鉛・テルル、シリコン・ゲルマニウム、珪化
鉄などを用いることができる。又、これらにドーピング
材を添加することもできる。具体的には、ビスマス・ア
ンチモン・テルル（ＢｉＳｂＴｅ）をｐ型熱電半導体と
し、ビスマス・セレン・テルル（ＢｉＳｅＴｅ）をｎ型
熱電半導体とすることもでき、さらにビスマス・セレン
・テルル（ＢｉＳｅＴｅ）にｎ型のドーピング材として
ＣｕＢｒあるいはＳｂＩ3を加えることもできる。これ
らのうち、ｎ型としてビスマス・セレン・テルル、ｐ型
としてビスマス・アンチモン・テルルが好ましい。[0007] As the plastic, specifically, polyethylene, polypropylene, nylon, polyester,
(Meth) acrylic resin, ABS resin, polyurethane, epoxy resin, EPDM, NBR, SBR, PIB, C
R, silicone rubber, hydryl rubber and the like.
Of these, EPDM and silicone are preferred. The n-type and p-type thermoelectric semiconductor particles used in the present invention include bismuth tellurium (BiTe) and antimony tellurium (S
bTe), bismuth antimony tellurium (BiSbT)
e), bismuth selenium (BiSe), antimony selenium (SbSe), bismuth selenium tellurium (BiS)
eTe), lead / tellurium, silicon / germanium, iron silicide, or the like can be used. Further, a doping material can be added to these. Specifically, bismuth antimony tellurium (BiSbTe) can be a p-type thermoelectric semiconductor, bismuth selenium tellurium (BiSeTe) can be an n-type thermoelectric semiconductor, and bismuth selenium tellurium (BiSeTe) can have n CuBr or SbI 3 can also be added as a doping material for the mold. Among them, n-type is preferably bismuth selenium tellurium, and p-type is preferably bismuth antimony tellurium.
【０００８】本発明で用いるｎ型及びｐ型熱電半導体粒
子としては粉状物をものを用いるのが好ましく、平均粒
子径が５００μｍ以下のものが好ましく、例えば１０ミ
クロン以下の粒子や２００−３００ミクロンの粒子を用
いることができる。熱電半導体粒子の導電性プラスチッ
クやガラスへの添加量は、電気伝導度が１０の３乗以下
となる限り任意の量とすることができるが、一般的には
３０重量％以上にするのが良い。又所望の形状に成形で
きる限度で添加するのがよく、８０重量％以下であるの
が好ましい。本発明では、導電性プラスチック中への熱
電半導体粒子の分散を良好にするために、分散剤を併用
してもよい。As the n-type and p-type thermoelectric semiconductor particles used in the present invention, it is preferable to use powdery ones, and those having an average particle diameter of 500 μm or less, for example, particles of 10 μm or less and 200-300 μm or less. Can be used. The amount of the thermoelectric semiconductor particles added to the conductive plastic or glass can be any amount as long as the electric conductivity is not more than 10.sup.3, but is generally preferably 30% by weight or more. . Also, it is preferable to add it to the extent that it can be formed into a desired shape, and it is preferably 80% by weight or less. In the present invention, a dispersant may be used in combination to improve the dispersion of the thermoelectric semiconductor particles in the conductive plastic.
【０００９】熱電半導体粒子の導電性プラスチックへの
分散は、バンバリーミキサー、１軸や２軸押出機などの
各種混練機を用いることができる。又、ガラス中への分
散は、ガラス原料と熱電半導体粒子とを均一に混合し、
次いで溶融することにより行うことができる。ｎ型熱電
半導体基体とｐ型熱電半導体基体との複合化は、両者を
固定させる常法により行うことができる。例えば、両者
を幾何学的に接合させること、通常の固定手段を用いて
接合させること、ｎ型熱電半導体基体とｐ型熱電半導体
基体を中間層を介して接合させることなどにより行うこ
とができる。ここで、中間層としては、絶縁層や導電層
を用いることができる。尚、本発明では、ｎ型熱電半導
体基体とｐ型熱電半導体基体との複合化を、一端を導電
層を介して、他端を絶縁層を介して行うのがよい。For dispersing the thermoelectric semiconductor particles in the conductive plastic, various kneaders such as a Banbury mixer, a single screw or a twin screw extruder can be used. Also, the dispersion in the glass, glass material and thermoelectric semiconductor particles are uniformly mixed,
Then, it can be performed by melting. The composite of the n-type thermoelectric semiconductor substrate and the p-type thermoelectric semiconductor substrate can be performed by a conventional method of fixing both. For example, the bonding can be performed by geometrically bonding the two, bonding by using ordinary fixing means, and bonding the n-type thermoelectric semiconductor substrate and the p-type thermoelectric semiconductor substrate via an intermediate layer. Here, an insulating layer or a conductive layer can be used as the intermediate layer. In the present invention, it is preferable that the combination of the n-type thermoelectric semiconductor substrate and the p-type thermoelectric semiconductor substrate be performed at one end via a conductive layer and at the other end via an insulating layer.
【００１０】本発明で用いるｎ型熱電半導体基体とｐ型
熱電半導体基体は、組成物のベースがプラスチックスや
ガラスであるため、従来用いられていた金属に比べて加
工が容易であり、所望の形態及び大きさに簡易に成形す
ることができる。このうち、図２に示すドーナツ状に形
成するのが好ましい。ここで、熱電発電モジュール１
は、ｎ型熱電半導体基体２とｐ型熱電半導体基体３と
が、中央に空間（内部ともいう）４を有するドーナツ型
になるように、ｎ型熱電半導体基体２とｐ型熱電半導体
基体３のそれぞれの端部５と６とを上述した手段により
接合して複合化されている。一方、本発明では、上記熱
電発電モジュールにおけるｎ型熱電半導体基体とｐ型熱
電半導体基体のそれぞれに電極を設け、該電極間に回路
を形成し、ｎ型熱電半導体基体とｐ型熱電半導体基体間
の温度差を設けると、ｎ型熱電半導体基体とｐ型熱電半
導体基体間に電流が生じ、この電流を回路から取り出す
ことを特徴とする熱電発電器を構築することができる。The n-type thermoelectric semiconductor substrate and the p-type thermoelectric semiconductor substrate used in the present invention are easy to process as compared with conventionally used metals, since the base of the composition is plastics or glass. It can be easily formed into a shape and size. Of these, it is preferable to form the donut shown in FIG. Here, the thermoelectric generation module 1
Is such that the n-type thermoelectric semiconductor substrate 2 and the p-type thermoelectric semiconductor substrate 3 have a donut shape having a space (also referred to as an interior) 4 at the center. The ends 5 and 6 are joined by the above-described means to form a composite. On the other hand, in the present invention, an electrode is provided on each of the n-type thermoelectric semiconductor substrate and the p-type thermoelectric semiconductor substrate in the thermoelectric power generation module, and a circuit is formed between the electrodes. When the temperature difference is provided, a current is generated between the n-type thermoelectric semiconductor substrate and the p-type thermoelectric semiconductor substrate, and a thermoelectric generator characterized by extracting this current from the circuit can be constructed.
【００１１】この際、図２に示すドーナツ型の熱電発電
モジュール１を用いて熱電発電器をの構築するのが好ま
しい。このようにして構築した熱電発電器７の概略図を
図３に示す。図３中、数値１〜６は図２におけるのと同
じものを示し、ｎ型熱電半導体基体２とｐ型熱電半導体
基体３のそれぞれに電極８、９を設け、該電極間に回路
１０が形成されている。ここで、電極８、９は、ｎ型熱
電半導体基体２とｐ型熱電半導体基体３のそれぞれの全
体を覆うように形成してもよいが、少なくともその一部
に接触していればよい。電極の材質及び形状は特に限定
されず、通常発電機に用いるものを使用することができ
る。又、ｎ型熱電半導体基体２とｐ型熱電半導体基体３
のそれぞれの端部５と６を、一方を導電体で他方を絶縁
体で接着するのがよい。又、ドーナツ状の内部、例えば
片側に導電部材１１を設けても良い。このような構造の
熱電発電器７の内部４を加熱し、一方、熱電発電器７の
外面を室温又は冷却すると、熱電発電器７の外部と内部
との間に温度差が生じ、ゼーベック効果により電子の流
れ（図中ｅが電子を表す。）が生じ、回路を電流が流れ
て、電気を取り出すことができる。図中、負荷とは、例
えば、充電するための器具（携帯電話など）、電球やヒ
ーターなどである。At this time, it is preferable to construct a thermoelectric generator using the doughnut-shaped thermoelectric generation module 1 shown in FIG. FIG. 3 shows a schematic diagram of the thermoelectric generator 7 constructed in this manner. In FIG. 3, numerical values 1 to 6 indicate the same as those in FIG. Have been. Here, the electrodes 8 and 9 may be formed so as to cover the entirety of the n-type thermoelectric semiconductor substrate 2 and the entirety of the p-type thermoelectric semiconductor substrate 3, but only need to be in contact with at least a part thereof. The material and shape of the electrode are not particularly limited, and those usually used for a generator can be used. An n-type thermoelectric semiconductor substrate 2 and a p-type thermoelectric semiconductor substrate 3
The ends 5 and 6 are preferably bonded to each other with a conductor and the other with an insulator. Further, the conductive member 11 may be provided inside the donut shape, for example, on one side. When the inside 4 of the thermoelectric generator 7 having such a structure is heated, and the outer surface of the thermoelectric generator 7 is cooled to room temperature or cooled, a temperature difference occurs between the outside and the inside of the thermoelectric generator 7, and the Seebeck effect occurs. A flow of electrons (e represents an electron in the drawing) occurs, a current flows through the circuit, and electricity can be extracted. In the figure, the load is, for example, a charging device (such as a mobile phone), a light bulb, a heater, or the like.
【００１２】[0012]
【発明の効果】本発明によると、任意の形態に簡易に成
型できる熱電発電モジュールを提供することができる。
この熱電発電モジュールを用いると、クリーンで、静か
な局所エネルギ−を創出できる熱電発電器を製造するこ
とができる。特に、廃熱利用のように温度差をもった所
では、それを利用して、発電をすることも出来る。又、
熱電発電モジュールを冷却素子として使う要請があれ
ば、電流を流し、高温と低温部分をつくることができ
る。従って、本発明によれば、色々な形状や大きさの熱
電発電モジュールができ、複雑な場所、円筒形の所、さ
らには建材など、様々な場所において、冷やしたり、暖
めたりできる。具体的には、光ファイバーのコネクタ部
分に巻いて冷却することができる。さらには建材などで
は、冷暖房として、また外と内の温度差から、発電も可
能となる。僅かな温度差での発電を考えたとき、本発明
の熱電発電モジュールを利用して、体温と空気の温度差
で発電をすることによって、携帯電話などの充電用への
使用の可能性が出てくることから広範囲の分野で利用で
きる。次に実施例により本発明を説明する。According to the present invention, it is possible to provide a thermoelectric power module that can be easily formed into an arbitrary form.
Using this thermoelectric generator module, a thermoelectric generator that can create clean and quiet local energy can be manufactured. In particular, where there is a temperature difference, such as the use of waste heat, power can be generated by using the difference. or,
If there is a request to use a thermoelectric power generation module as a cooling element, a current can be applied to create a high and low temperature part. Therefore, according to the present invention, thermoelectric power generation modules having various shapes and sizes can be formed, and can be cooled or heated in various places such as a complicated place, a cylindrical place, and a building material. Specifically, it can be cooled by winding it around the connector portion of the optical fiber. Furthermore, in the case of building materials and the like, it is possible to generate electricity as a cooling and heating system or due to a temperature difference between outside and inside. When power generation with a slight temperature difference is considered, by using the thermoelectric power generation module of the present invention to generate power with a temperature difference between body temperature and air, there is a possibility of use for charging mobile phones and the like. Can be used in a wide range of fields. Next, the present invention will be described with reference to examples.
【００１３】[0013]
【実施例】実施例１ プラスチックスとして、ＥＰＤＭゴム（日本合成ゴム社
のＥＰ２１）を使用し、これにｎ型またはｐ型半導体で
あるビスマス・テルル（Bi2Te3）(平均粒子径３００μ
ｍ)をそれぞれ３５重量％となるように添加し（ｎ型半
導体にはドーピング材としてSbI3を添加した）、二本ロ
ールで混練し、混合物をプレス成形し、厚さ５ｍｍ、幅
２００ｍｍ、長さ２００ｍｍの板状の熱電半導体基体
を、直方体状（５０×５０×５ｍｍ）の形態に作り、図
１のように銀電極を上下に取り付け下部をホットプレー
トで加熱し、上部を氷水で冷却し、起電力をデジタルボ
ルトメーターで測定した。測定した結果を表１に示す。
尚、基体の電気抵抗は数オームｃｍのオーダーであっ
た。EXAMPLES Example 1 EPDM rubber (EP21 manufactured by Japan Synthetic Rubber Co., Ltd.) was used as plastics, and bismuth tellurium (Bi 2 Te 3 ), an n-type or p-type semiconductor, having an average particle diameter of 300 μm was used.
m) was added to each so as to be 35% by weight (SbI 3 was added as a doping material to the n-type semiconductor), kneaded with two rolls, and the mixture was press-formed to a thickness of 5 mm, a width of 200 mm and a length of A plate-shaped thermoelectric semiconductor substrate having a thickness of 200 mm is formed in the shape of a rectangular parallelepiped (50 × 50 × 5 mm), silver electrodes are mounted vertically as shown in FIG. 1, the lower part is heated with a hot plate, and the upper part is cooled with ice water. The electromotive force was measured with a digital voltmeter. Table 1 shows the measurement results.
The electric resistance of the substrate was on the order of several ohm cm.
【００１４】[0014]
【表１】 表１ 低温部（℃） 高温部（℃） 温度差 起電力（ｍＶ） ２０ ３１ １１ ０.０９９ ２２ ３５ １３ ０.１５４ ２５ ４１ １６ ０.３２５ ３０ ５５ ２５ ０.７３３ ４０ ７０ ３０ ０.９１１ [Table 1] Table 1 Low temperature part (° C) High temperature part (° C) Temperature difference Electromotive force (mV) 20 31 11 0.099 22 35 13 0.154 25 41 16 0.325 30 55 25 0.733 40 70 30 0.911
【００１５】実施例２ 実施例１で製造した板状ゴム形態のｎ型熱電半導体基体
及びｐ型熱電半導体基体を所定の大きさに切り、半円型
にした。ｎ型熱電半導体基体の内側１１及び端部５に銀
ペーストを塗布し（導電層を形成）、端部６にはαシア
ノアクリレート系接着剤（商品名アロンアルファー：絶
縁層を形成）を塗布してｎ型熱電半導体基体及びｐ型熱
電半導体基体を接合して、図３に示すドーナツ型熱電発
電モジュールを組み立てた。さらに、このドーナツ型熱
電発電モジュール７の外側の一部８と９にも銀ペースト
を塗布して電極８と９を形成し、これらの電極を導線で
つないで回路１０を形成した。このようにして製造した
ドーナツ型熱電発電モジュール７の内部４を体温（Ｔ
ｉ：３６.５℃）で暖め、ドーナツ型熱電発電モジュー
ル７の外部が室温（例えば、Ｔｒ：２０℃）であると、
導電層５と１１から電子がｎ型熱電半導体基体２に入
り、外側の電極８へ拡散し、導線を通って負荷を経由
し、電極９へ入る。その結果、温度差ΔＴ（１６.５）=
Ｔｉ−Ｔｒ（３６.５−２０）に応じた起電力が発生す
る。この場合、推定される発電は０.３２５ｍＶであ
り、０.１ｍＡ程度の電流が流れる。Example 2 The n-type thermoelectric semiconductor substrate and the p-type thermoelectric semiconductor substrate in the form of a rubber plate manufactured in Example 1 were cut into a predetermined size to form a semicircle. A silver paste is applied to the inner side 11 and the end 5 of the n-type thermoelectric semiconductor substrate (forming a conductive layer), and an α-cyanoacrylate-based adhesive (trade name: Aron Alpha: forming an insulating layer) is applied to the end 6. Then, the n-type thermoelectric semiconductor substrate and the p-type thermoelectric semiconductor substrate were joined to assemble the donut-type thermoelectric power generation module shown in FIG. Further, silver paste was applied also to parts 8 and 9 outside the donut-type thermoelectric power generation module 7 to form electrodes 8 and 9, and these electrodes were connected by a conductor to form a circuit 10. The inside 4 of the donut-type thermoelectric generation module 7 manufactured in this manner is heated to the body temperature (T
i: 36.5 ° C.), and when the outside of the donut type thermoelectric generation module 7 is at room temperature (for example, Tr: 20 ° C.),
Electrons from the conductive layers 5 and 11 enter the n-type thermoelectric semiconductor substrate 2, diffuse to the outer electrode 8, pass through a conductor, pass through a load, and enter the electrode 9. As a result, the temperature difference ΔT (16.5) =
An electromotive force corresponding to Ti-Tr (36.5-20) is generated. In this case, the estimated power generation is 0.325 mV, and a current of about 0.1 mA flows.
【図１】 従来のΠ（パイ）型形態の熱電発電モジュー
ルの概略図を示す。FIG. 1 shows a schematic view of a conventional Π-type thermoelectric power generation module.
【図２】 本発明の熱電発電モジュールをドーナツ型に
形成したものの概略図を示す。FIG. 2 shows a schematic view of a thermoelectric power generation module of the present invention formed in a donut shape.
【図３】 図２に示す本発明のドーナツ型熱電発電モジ
ュールを組み込んだ熱電発電器の概略図を示す。図中、
１は熱電発電モジュール、２はｎ型熱電半導体基体、３
はｐ型熱電半導体基体、５は熱電半導体基体の導電層を
介した接合部，６は熱電半導体基体の絶縁層を介した接
合部、７は熱電発電器、８、９は電極、１０は回路を表
す。3 shows a schematic view of a thermoelectric generator incorporating the donut-type thermoelectric power module of the present invention shown in FIG. In the figure,
1 is a thermoelectric power generation module, 2 is an n-type thermoelectric semiconductor substrate, 3
Is a p-type thermoelectric semiconductor substrate, 5 is a junction of the thermoelectric semiconductor substrate via a conductive layer, 6 is a junction of the thermoelectric semiconductor substrate via an insulating layer, 7 is a thermoelectric generator, 8, 9 are electrodes, and 10 is a circuit. Represents
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０２Ｎ 11/00 Ｈ０２Ｎ 11/00 Ａ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H02N 11/00 H02N 11/00 A
Claims (7)
熱電半導体粒子を分散させてなるｎ型熱電半導体基体
と、導電性プラスチック又はガラス中にｐ型熱電半導体
粒子を分散させてなるｐ型熱電半導体基体とを複合化さ
せたことを特徴とする熱電発電モジュール。1. An n-type thermoelectric semiconductor substrate comprising n-type thermoelectric semiconductor particles dispersed in conductive plastic or glass, and a p-type thermoelectric semiconductor comprising p-type thermoelectric semiconductor particles dispersed in conductive plastic or glass. A thermoelectric power generation module characterized by being combined with a base.
体とを接合させることにより複合化されている請求項１
記載の熱電発電モジュール。2. The composite of claim 1, wherein the n-type thermoelectric semiconductor substrate and the p-type thermoelectric semiconductor substrate are joined together.
A thermoelectric generation module as described.
体が中間層を介して接合されることにより複合化されて
いる請求項１記載の熱電発電モジュール。3. The thermoelectric power generation module according to claim 1, wherein the n-type thermoelectric semiconductor substrate and the p-type thermoelectric semiconductor substrate are combined by being joined via an intermediate layer.
樹脂、熱硬化性樹脂又はゴムである請求項１〜３のいず
れか１項記載の熱電発電モジュール。4. The thermoelectric power module according to claim 1, wherein the conductive plastic is a conductive thermoplastic resin, a thermosetting resin, or a rubber.
体が、中央に空間を有するドーナツ型に複合化されてい
る請求項１〜４のいずれか１項記載の熱電発電モジュー
ル。5. The thermoelectric power module according to claim 1, wherein the n-type thermoelectric semiconductor substrate and the p-type thermoelectric semiconductor substrate are combined in a donut shape having a space in the center.
熱電半導体粒子を分散させてなるｎ型熱電半導体基体
と、導電性プラスチック又はガラス中にｐ型熱電半導体
粒子を分散させてなるｐ型熱電半導体基体とを複合化さ
せることを特徴とする請求項１〜５のいずれか１項記載
の熱電発電モジュールの製造方法。6. An n-type thermoelectric semiconductor substrate in which n-type thermoelectric semiconductor particles are dispersed in conductive plastic or glass, and a p-type thermoelectric semiconductor in which p-type thermoelectric semiconductor particles are dispersed in conductive plastic or glass. The method for manufacturing a thermoelectric power module according to any one of claims 1 to 5, wherein the method comprises forming a composite with a substrate.
発電モジュールにおけるｎ型熱電半導体基体とｐ型熱電
半導体基体のそれぞれに電極が設けられ、該電極間に回
路が形成されており、ｎ型熱電半導体基体とｐ型熱電半
導体基体間の温度差を電流として回路から取り出すこと
を特徴とする熱電発電器。7. An n-type thermoelectric semiconductor substrate and a p-type thermoelectric semiconductor substrate in the thermoelectric power generation module according to any one of claims 1 to 5, wherein a circuit is formed between the electrodes. A thermoelectric generator for extracting a temperature difference between an n-type thermoelectric semiconductor substrate and a p-type thermoelectric semiconductor substrate from a circuit as a current.
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| JP2001157065A JP3919469B2 (en) | 2001-05-25 | 2001-05-25 | Thermoelectric generator module made of plastic or glass and manufacturing method thereof |
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Cited By (6)
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| WO2004061982A1 (en) * | 2002-12-27 | 2004-07-22 | Japan Science And Technology Agency | Cooling device for electronic component using thermo-electric conversion material |
| JP2005217353A (en) * | 2004-02-02 | 2005-08-11 | Yokohama Teikoki Kk | Thermoelectric semiconductor element, thermoelectric transformation module, and method of manufacturing the same |
| EP1875524A2 (en) * | 2005-04-28 | 2008-01-09 | Cool Shield, Inc. | Moldable peltier thermal transfer device and method of manufacturing same |
| WO2015022197A1 (en) * | 2013-08-12 | 2015-02-19 | Siemens Aktiengesellschaft | Thermoelectric element |
| KR20180121601A (en) * | 2016-03-09 | 2018-11-07 | 웨이크 포리스트 유니버시티 | Thermoelectric generator |
| GB2577572A (en) * | 2018-09-28 | 2020-04-01 | Sumitomo Chemical Co | Thermoelectric device |
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| JP2000258256A (en) * | 1999-03-10 | 2000-09-22 | Babcock Hitachi Kk | Thermocouple for measuring temperature of pipe wall and its manufacture |
| JP2002076452A (en) * | 2000-09-04 | 2002-03-15 | Japan Aviation Electronics Industry Ltd | Thermoelectric conversion material and method for producing the same |
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| JP2005217353A (en) * | 2004-02-02 | 2005-08-11 | Yokohama Teikoki Kk | Thermoelectric semiconductor element, thermoelectric transformation module, and method of manufacturing the same |
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| EP1875524A4 (en) * | 2005-04-28 | 2008-12-31 | Cool Shield Inc | Moldable peltier thermal transfer device and method of manufacturing same |
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| KR20180121601A (en) * | 2016-03-09 | 2018-11-07 | 웨이크 포리스트 유니버시티 | Thermoelectric generator |
| JP2019512879A (en) * | 2016-03-09 | 2019-05-16 | ウェイク フォレスト ユニバーシティ | Thermal voltage generator |
| KR102379266B1 (en) * | 2016-03-09 | 2022-03-29 | 웨이크 포리스트 유니버시티 | thermoelectric piezoelectric generator |
| GB2577572A (en) * | 2018-09-28 | 2020-04-01 | Sumitomo Chemical Co | Thermoelectric device |
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