JPH08204240A - Thermoelectric cooling material and production of thermoelectric conversion element - Google Patents
Thermoelectric cooling material and production of thermoelectric conversion elementInfo
- Publication number
- JPH08204240A JPH08204240A JP7013022A JP1302295A JPH08204240A JP H08204240 A JPH08204240 A JP H08204240A JP 7013022 A JP7013022 A JP 7013022A JP 1302295 A JP1302295 A JP 1302295A JP H08204240 A JPH08204240 A JP H08204240A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- thermoelectric
- composition
- conversion element
- cooling material
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000001816 cooling Methods 0.000 title claims description 21
- 238000006243 chemical reaction Methods 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000843 powder Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000000465 moulding Methods 0.000 claims description 11
- 101710134784 Agnoprotein Proteins 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000010791 quenching Methods 0.000 abstract description 5
- 230000000171 quenching effect Effects 0.000 abstract description 4
- 238000011978 dissolution method Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000005679 Peltier effect Effects 0.000 description 2
- 230000005678 Seebeck effect Effects 0.000 description 2
- 230000005680 Thomson effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910016339 Bi—Sb—Te Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000005184 irreversible process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 230000005676 thermoelectric effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は熱電変換による熱電冷却
等に応用される熱電冷却用材料及びその熱電変換素子の
製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoelectric cooling material applied to thermoelectric cooling by thermoelectric conversion and a method of manufacturing the thermoelectric conversion element.
【０００２】[0002]
【従来の技術】種類が異なる２物質を接合させ、２箇所
の接合部を有する回路を構成し、一方の接合部を高温に
加熱し、他方の接合部を低温に冷却すると、接合部の温
度差に基づく起電力が発生する。この現象をゼーベック
効果という。2. Description of the Related Art When two different substances are joined to form a circuit having two joints and one joint is heated to a high temperature and the other joint is cooled to a low temperature, the temperature of the joint is lowered. An electromotive force is generated based on the difference. This phenomenon is called the Seebeck effect.
【０００３】また、同様に接合させた２物質に直流電流
を流すと、一方の接合部で熱を吸収し、他方の接合部で
熱を発生する。この現象をペルチェ効果という。Similarly, when a direct current is passed through the two bonded materials, one of the bonded parts absorbs heat and the other bonded part generates heat. This phenomenon is called the Peltier effect.
【０００４】更に、均質な物質に温度勾配を設け、この
温度勾配がある方向に電流を流すと、この物質内で熱の
吸収又は発生がある。この現象をトムソン効果という。Furthermore, when a temperature gradient is provided in a homogeneous substance and an electric current is passed in the direction in which this temperature gradient is present, heat is absorbed or generated in this substance. This phenomenon is called the Thomson effect.
【０００５】これらのゼーベック効果、ペルチェ効果及
びトムソン効果は熱電効果といわれる可逆反応であり、
ジュール効果及び熱伝導等の非可逆現象と対比される。
これらの可逆過程及び非可逆過程を組み合わせて、電子
冷熱に利用されている。These Seebeck effect, Peltier effect and Thomson effect are reversible reactions called thermoelectric effects.
Contrast with irreversible phenomena such as Joule effect and heat conduction.
These reversible processes and irreversible processes are combined and used for electronic cold heat.
【０００６】ところで、従来の熱電冷却用材料として
は、多用されているＢｉ−Ｓｂ−Ｔｅ系の外に、Ｃｕ4
ＳｎＳ4合金がある。By the way, as a conventional thermoelectric cooling material, in addition to the Bi-Sb-Te system which is widely used, Cu 4
There is SnS 4 alloy.
【０００７】このような熱電冷却用材料又は熱電変換素
子において、素子の性能は下記数式１にて表される性能
指数で評価される。In such a thermoelectric cooling material or thermoelectric conversion element, the element performance is evaluated by the performance index expressed by the following mathematical formula 1.
【０００８】[0008]
【数１】 Ｚ＝α2σ／κ 但し、αは熱電能（ゼーベック係数） σは電気伝導度 κは熱伝導度 である。即ち、性能指数Ｚが大きい方が熱電材料として
の性能が優れている。## EQU1 ## Z = α 2 σ / κ where α is thermoelectric power (Seebeck coefficient) σ is electrical conductivity κ is thermal conductivity. That is, the larger the performance index Z, the better the performance as a thermoelectric material.
【０００９】[0009]
【発明が解決しようとする課題】しかしながら、この従
来のＣｕ4ＳｎＳ4の組成を有する熱電冷却用材料は、性
能指数Ｚが０．８×１０-3／Ｋ程度であり、熱電冷却材
料として十分なものではなかった。However, this conventional thermoelectric cooling material having a composition of Cu 4 SnS 4 has a figure of merit Z of about 0.8 × 10 −3 / K, which is a sufficient thermoelectric cooling material. It wasn't.
【００１０】また、この従来の熱電冷却材料は比抵抗ρ
が高く、抵抗値が高いため、使用しにくいという難点が
ある。例えば、熱電材料として多用されているＢｉ−Ｓ
ｂ−Ｔｅ系の材料は比抵抗ρが（１〜２）×１０-5Ω・
ｍであるのに対し、Ｃｕ4ＳｎＳ4はρが（１〜２）×１
０-3Ω・ｍと大きい。このため、Ｃｕ4ＳｎＳ4は熱電材
料として使用しにくいという難点がある。また、比抵抗
が大きいということは、熱電材料としての性能指数も低
いことになり、その性能が十分なものではなかった。Further, this conventional thermoelectric cooling material has a specific resistance ρ
Has a high value and a high resistance value, so that it is difficult to use. For example, Bi-S widely used as a thermoelectric material
The specific resistance ρ of the b-Te type material is (1-2) × 10 −5 Ω ·
In contrast to Cu, Cu 4 SnS 4 has a ρ of (1-2) × 1
It is as large as 0 -3 Ω · m. For this reason, Cu 4 SnS 4 is difficult to use as a thermoelectric material. Further, the fact that the specific resistance is large means that the figure of merit as a thermoelectric material is also low, and the performance was not sufficient.
【００１１】本発明はかかる問題点に鑑みてなされたも
のであって、比抵抗を低下させることにより性能指数Ｚ
を向上させることができる熱電冷却材料及び熱電変換素
子の製造方法を提供することを目的とする。The present invention has been made in view of the above problems, and the figure of merit Z is reduced by decreasing the specific resistance.
It is an object of the present invention to provide a thermoelectric cooling material and a method for manufacturing a thermoelectric conversion element that can improve the temperature.
【００１２】[0012]
【課題を解決するための手段】本発明に係る熱電冷却材
料は、Ｃｕ4（Ｓｎ1-xＡx）Ｓ4［但し、ＡはＣ、Ｓｉ、
Ｇｅからなる群より選ばれた１種又は２種以上、０≦ｘ
≦１］の組成を有する合金の結晶の粒界にＡｇが分散し
ていることを特徴とする。The thermoelectric cooling material according to the present invention is Cu 4 (Sn 1-x A x ) S 4 [where A is C, Si,
One or more selected from the group consisting of Ge, 0 ≦ x
It is characterized in that Ag is dispersed in the grain boundaries of the crystal of the alloy having the composition [1].
【００１３】本発明に係る熱電冷却材料は、Ｃｕ4（Ｓ
ｎ1-xＡx）Ｓ4［但し、ＡはＣ、Ｓｉ、Ｇｅからなる群
より選ばれた１種又は２種以上、０≦ｘ≦１］の組成を
有する合金粉末と、Ａｇ粉末とを混合した後、粉末固化
成形法により固化成形することを特徴とする。The thermoelectric cooling material according to the present invention is Cu 4 (S
n 1-x A x ) S 4 [where A is one or more selected from the group consisting of C, Si and Ge, 0 ≦ x ≦ 1], and an Ag powder and an alloy powder. Is mixed and then solidified and molded by a powder solidification molding method.
【００１４】本発明に係る熱電冷却材料は、Ｃｕ4（Ｓ
ｎ1-xＡx）Ｓ4［但し、ＡはＣ、Ｓｉ、Ｇｅからなる群
より選ばれた１種又は２種以上、０≦ｘ≦１］の組成を
有する合金粉末を、ＡｇＮｏ3溶液に浸漬し、乾燥させ
た後、粉末固化成形法により固化成形することを特徴と
する。The thermoelectric cooling material according to the present invention is Cu 4 (S
n 1-x A x ) S 4 [where A is one or more selected from the group consisting of C, Si and Ge, and 0 ≦ x ≦ 1] is used as an AgNo 3 solution. It is characterized in that it is immersed in, dried and then solidified by a powder solidification molding method.
【００１５】尚、ＡとしてＣ、Ｓｉ、Ｇｅから２種以上
を用いる場合は、その総量が０≦ｘ≦１を満たすものと
する。When two or more kinds of C, Si and Ge are used as A, the total amount thereof should satisfy 0 ≦ x ≦ 1.
【００１６】[0016]
【作用】本発明によれば、Ｃｕ4（Ｓｎ1-xＡx）Ｓ4の組
成を有する材料にＡｇを添加しているので、Ａｇが粒界
に分散することにより、電気伝導度が向上する。また、
この電気伝導度の向上の結果として、性能指数Ｚが向上
する。According to the present invention, Ag is added to the material having the composition of Cu 4 (Sn 1-x A x ) S 4 , so that Ag is dispersed in the grain boundaries, so that the electric conductivity is improved. To do. Also,
As a result of this improvement in electrical conductivity, the figure of merit Z is improved.
【００１７】このＡｇの添加方法には、請求項２に記載
のように、前記組成の粉末とＡｇ粉末とを混合した後、
粉末固化成形法により固化成形する方法と、請求項３に
記載のように、前記組成の粉末をＡｇＮＯ3溶液に浸漬
し、乾燥させた後、粉末固化成形する方法とがある。This Ag addition method is carried out by mixing the powder of the composition and the Ag powder as described in claim 2, and then adding
There are a method of solidifying and molding by a powder solidifying method, and a method of immersing the powder having the composition in an AgNO 3 solution, drying the powder, and then solidifying and molding the powder.
【００１８】これにより、容易にＣｕ4（Ｓｎ1-xＡx）
Ｓ4の組成を有する合金の粒界にＡｇが分散した熱電冷
却材料又は熱電変換素子を得ることができる。As a result, Cu 4 (Sn 1-x A x ) can be easily formed.
It is possible to obtain the thermoelectric cooling material or the thermoelectric conversion element in which Ag is dispersed in the grain boundaries of the alloy having the composition of S 4 .
【００１９】[0019]
【実施例】以下、本発明の実施例について、具体的に説
明する。先ず、本実施例の熱電冷却材料の製造方法につ
いて説明する。 原料粉末（Ｃｕ、Ｓｎ、Ｓと、Ｇｅ、Ｓｉ又はＣ）の
秤量工程 先ず、原料粉末のＣｕ、Ｓｎ、Ｓと、Ｇｅ、Ｓｉ又はＣ
を所定のＣｕ4（Ｓｎ1 -xＡx）Ｓ4［但し、ＡはＣ、Ｓ
ｉ、Ｇｅからなる群より選ばれた１種又は２種以上、０
≦ｘ≦１］の組成になるように秤量する。 溶解方法又は液体急冷法による固化工程 秤量した原料粉末を混合した後、溶解する。そして、先
ず、第１の溶解方法は、必要量の原料粉末を配合し、溶
解し、通常の冷却速度で冷却して固化する。EXAMPLES Examples of the present invention will be specifically described below. First, a method for manufacturing the thermoelectric cooling material of this example will be described. Weighing process of raw material powder (Cu, Sn, S and Ge, Si or C) First, Cu, Sn, S and Ge, Si or C of raw material powder
Is given Cu 4 (Sn 1 -x A x ) S 4 [where A is C, S
1 or 2 or more selected from the group consisting of i and Ge, 0
Weigh so that the composition is ≦ x ≦ 1]. Solidification process by dissolution method or liquid quenching method The measured raw material powders are mixed and then dissolved. Then, first, in the first melting method, necessary amounts of raw material powders are mixed, melted, and cooled at a normal cooling rate to be solidified.
【００２０】第２の液体急冷法は、単ロール法、双ロー
ル法又はＡｒガスを使用するガスアトマイズ法等で、１
０4〜１０6Ｋ／秒の速度で急冷し、液体急冷薄片又は急
冷粉末を作成する。 粉砕工程 上述の如く、溶解法又は液体急冷法により固化した原料
を平均粒径３００μｍ以下の粉体に粉砕する。 Ａｇ添加工程 この粉末にＡｇ微粉末を所定量添加し、混合して粉砕す
る。このＡｇの添加量は０〜２０原子％、例えば１０原
子％である。The second liquid quenching method is a single roll method, a twin roll method, a gas atomizing method using Ar gas, or the like.
Quench at a rate of 0 4 to 10 6 K / sec to produce liquid quenched flakes or quenched powders. Crushing Step As described above, the raw material solidified by the melting method or the liquid quenching method is crushed into powder having an average particle size of 300 μm or less. Ag addition step A predetermined amount of Ag fine powder is added to this powder, mixed and pulverized. The amount of Ag added is 0 to 20 atom%, for example, 10 atom%.
【００２１】又は、原料粉末をＡｇＮＯ3（硝酸銀）溶
液中に浸漬し、銀を原料粉末に吸着させることによりＡ
ｇを添加する。この場合のＡｇの添加量の一例は１原子
％である。但し、このＡｇＮＯ3溶液は、その濃度及び
量を、溶液中のＡｇ+イオンが全て化合物粉末に吸着す
るとしてその濃度が０乃至２０原子％になるように決め
る。Alternatively, by immersing the raw material powder in an AgNO 3 (silver nitrate) solution and adsorbing silver to the raw material powder, A
g is added. An example of the amount of Ag added in this case is 1 atom%. However, the concentration and amount of this AgNO 3 solution are determined so that the concentration becomes 0 to 20 atomic% assuming that all Ag + ions in the solution are adsorbed by the compound powder.
【００２２】ＡｇＮＯ3溶液中への浸漬後、粉末を乾燥
し、次いで粉砕する。 成形工程 得られたＡｇ添加粉末を、例えば、８０ｋｇｆ／ｍｍ2
の圧力を印加した状態で、６５０℃に１０分間加熱する
ことにより成形するホットプレス法により成形するか、
又は４０ｋｇｆ／ｍｍ2の圧力を印加して固めた圧粉を
得た後、６５０℃に１６時間加熱して焼結することによ
り成形する。After immersion in the AgNO 3 solution, the powder is dried and then ground. Molding step The obtained Ag-added powder is, for example, 80 kgf / mm 2
Molding is performed by heating at 650 ° C. for 10 minutes while applying the pressure of
Alternatively, after applying a pressure of 40 kgf / mm 2 to obtain a compacted powder, the powder is heated to 650 ° C. for 16 hours and sintered to form the powder.
【００２３】次に、溶製材を粉砕した後、６５０℃に１
０分間加熱するホットプレス法により固化成形すること
により、熱電冷却材料を製造し、その特性を評価した結
果について説明する。下記表１はその組成及びＡｇ添加
量と、比抵抗及び室温での性能指数とを示す。Next, after crushing the ingot, it was heated to 650 ° C. for 1 hour.
The thermoelectric cooling material is manufactured by solidification molding by the hot press method of heating for 0 minutes, and the results of evaluating the characteristics will be described. Table 1 below shows the composition, the amount of Ag added, the specific resistance and the figure of merit at room temperature.
【００２４】[0024]
【表１】 [Table 1]
【００２５】但し、原料粉末はＣｕ4ＳｎＳ4を溶解法に
より作成した。Ａｇの添加は、ＡｇＮＯ3溶解中に原料
粉末を浸漬することにより行った。ＡｇＮＯ3の量は原
料粉末１ｇ当たり、５０モル１ｍ3のＡｇＮＯ3水溶液１
０-6ｃｍ3とした。However, the raw material powder was prepared by melting Cu 4 SnS 4 . The addition of Ag was performed by immersing the raw material powder in AgNO 3 dissolution. The amount of AgNO 3 is 50 mol 1 m 3 of AgNO 3 aqueous solution per 1 g of raw material powder.
It was set to 0 -6 cm 3 .
【００２６】この表１から明らかなように、Ｃｕ4（Ｓ
ｎ1-xＡx）Ｓ4［但し、ＡはＣ、Ｓｉ、Ｇｅからなる群
より選ばれた１種又は２種以上、０≦ｘ≦１］の組成を
有する材料にＡｇを添加することにより、性能指数が従
来の０．８×１０-3／Ｋよりも高く、室温での比抵抗ρ
が０．７７×１０-5以下となり、熱電冷却材料として性
能が従来の熱電冷却材料よりも優れている。As is clear from Table 1, Cu 4 (S
n 1-x A x ) S 4 [where A is one or more selected from the group consisting of C, Si and Ge, 0 ≦ x ≦ 1] and Ag is added to the material. Therefore, the figure of merit is higher than the conventional value of 0.8 × 10 -3 / K, and the resistivity at room temperature ρ
Is 0.77 × 10 −5 or less, and the performance as a thermoelectric cooling material is superior to that of conventional thermoelectric cooling materials.
【００２７】[0027]
【発明の効果】以上説明したように、本発明はＣｕ
4（Ｓｎ1-xＡx）Ｓ4［但し、ＡはＣ、Ｓｉ、Ｇｅからな
る群より選ばれた１種又は２種以上、０≦ｘ≦１］の組
成にＡｇを添加した組成を有する熱電冷却材料であるの
で、比抵抗が低く、性能指数が高く、熱電冷却材料とし
て優れている。また、本発明の製造方法によれば、この
熱電変換素子を容易に製造することができる。As described above, according to the present invention, the Cu
4 (Sn 1-x A x ) S 4 [where A is one or more selected from the group consisting of C, Si and Ge, 0 ≦ x ≦ 1] and Ag is added to the composition. Since it is a thermoelectric cooling material, it has a low specific resistance, a high figure of merit, and is excellent as a thermoelectric cooling material. Further, according to the manufacturing method of the present invention, this thermoelectric conversion element can be easily manufactured.
Claims (3)
Ｃ、Ｓｉ、Ｇｅからなる群より選ばれた１種又は２種以
上、０≦ｘ≦１］の組成を有する合金の結晶の粒界にＡ
ｇが分散していることを特徴とする熱電冷却用材料。1. A composition of Cu 4 (Sn 1-x A x ) S 4 [wherein A is one or more selected from the group consisting of C, Si and Ge, 0 ≦ x ≦ 1] A at the grain boundaries of the crystals of the alloy
A material for thermoelectric cooling, wherein g is dispersed.
Ｃ、Ｓｉ、Ｇｅからなる群より選ばれた１種又は２種以
上、０≦ｘ≦１］の組成を有する合金粉末と、Ａｇ粉末
とを混合した後、粉末固化成形法により固化成形するこ
とを特徴とする熱電変換素子の製造方法。2. A composition of Cu 4 (Sn 1-x A x ) S 4 [wherein A is one or more selected from the group consisting of C, Si and Ge, 0 ≦ x ≦ 1] A method for producing a thermoelectric conversion element, which comprises mixing the alloy powder having the above and Ag powder, and then solidifying and molding by a powder solidification molding method.
Ｃ、Ｓｉ、Ｇｅからなる群より選ばれた１種又は２種以
上、０≦ｘ≦１］の組成を有する合金粉末を、ＡｇＮｏ
3溶液に浸漬し、乾燥させた後、粉末固化成形法により
固化成形することを特徴とする熱電変換素子の製造方
法。3. A composition of Cu 4 (Sn 1-x A x ) S 4 [wherein A is one or more selected from the group consisting of C, Si and Ge, 0 ≦ x ≦ 1]. The alloy powder having AgNo
(3) A method for producing a thermoelectric conversion element, which comprises soaking in a solution, drying, and then solidifying and molding by a powder solidifying and molding method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7013022A JPH08204240A (en) | 1995-01-30 | 1995-01-30 | Thermoelectric cooling material and production of thermoelectric conversion element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7013022A JPH08204240A (en) | 1995-01-30 | 1995-01-30 | Thermoelectric cooling material and production of thermoelectric conversion element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08204240A true JPH08204240A (en) | 1996-08-09 |
Family
ID=11821526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7013022A Pending JPH08204240A (en) | 1995-01-30 | 1995-01-30 | Thermoelectric cooling material and production of thermoelectric conversion element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08204240A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8097885B2 (en) | 2007-06-11 | 2012-01-17 | Canon Kabushiki Kaisha | Compound semiconductor film, light emitting film, and manufacturing method thereof |
-
1995
- 1995-01-30 JP JP7013022A patent/JPH08204240A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8097885B2 (en) | 2007-06-11 | 2012-01-17 | Canon Kabushiki Kaisha | Compound semiconductor film, light emitting film, and manufacturing method thereof |
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