JPS6237555B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoelectromotive element using a substance with a high absolute Seebeck coefficient, such as a copper ion conductive solid electrolyte or copper halide.

Conventionally, metals have attracted attention as substances that exhibit thermoelectromotive force, and have been used as thermometers. Recently, semiconductors have attracted attention as thermoelectric materials, and among them, oxides and chalcogenides such as sulfides, selenides, and tellurides, which are thought to have high conversion efficiency, are being studied. However, these methods have not been put to practical use because their conversion efficiency is extremely low compared to other power generation methods.

Furthermore, silver ion conductive solid electrolytes such as RbAg ₄ I ₅ , Ag ₃ SI, and Ag ₆ I ₄ WO ₄ have been recently developed and reported to have thermoelectromotive force approximately 10 times that of copper constantan.

One of the reasons why solid electrolytes and semiconductors of this type are not put to practical use even though they have a larger thermoelectromotive force than metals is that they undergo large changes over time.

The present invention relates to a thermoelectromotive force element using a copper ion-conducting solid electrolyte or copper halide, which prevents compositional changes due to infiltration of reactive gases and liquids such as moisture, has good precision, and exhibits stable characteristics over time. The purpose is to provide fewer elements. The present invention also prevents breakage when the heat capacity of the element itself is reduced by elongating the shape of the element,
Another object of the present invention is to provide a thermoelectromotive force element with good responsiveness.

The present invention will be explained below with reference to Examples. 1st
The figure shows the basic structure of the thermoelectromotive force element according to the present invention, in which 1 indicates phenol resin, epoxy resin,
It is a cylindrical body with open ends made of a heat-resistant and electrically insulating material such as polyimide resin, and is non-air permeable and liquid-impermeable. 2 is cylinder body 1
It is a molded body of powder of a semiconductor material made of copper ion conductive solid electrolyte or copper halide filled inside.

As a copper ion conductive solid electrolyte, the general formula
Cuprous halide represented by CuX [where X is Cl, Br, I], such as CuBr and the general formula RX (CH ₂ ) ₆ N ₄
or (RX) ₂ (CH ₂ ) ₆ N ₂ [However, R is H, CH ₃ ,
Alkyl group such as C ₂ H ₅ , X is the same as X in CuX]
It is expressed as Alkyl halides of pseudoadmantane compounds, such as CH ₃ Br(CH ₂ ) ₆ N ₄ or,
(CH ₃ Br) ₂ (CH ₂ ) ₆ N ₂ was mixed with CuBr at 87.5 mol% and the former mixture was heated at 160°C.
and, in the case of the latter mixture, to 230°C, respectively.
There is one made by heating for about 40 hours and then rapidly cooling, and the semiconductor used is one obtained by heating cuprous halide in air at a temperature of 300°C for 2 hours.

3 and 4 are copper electrodes made of copper caps attached to seal the opening of the cylindrical body. For these electrodes, the caps may be brought into direct contact with the powder bed compact 2, but as shown in the figure, copper powder is applied or copper is vapor-deposited on the ends of the compact 2 as shown at 3' and 4'. It is desirable to have the cap in contact with that surface for thermal and electrical contact. 5 and 6 are lead terminals for potential measurement.

In the above configuration, as the raw material powder for the compact
Using CuBr, the inner diameter of cylinder 1 is 3 mm and the wall thickness is 1 mm.
When we made several types of elements with different lengths and measured the maximum thermoelectromotive force when one side of the element was immersed in hot melt at a temperature of 150℃, we obtained the results shown in Figure 2. . From the figure, it can be seen that the thermoelectromotive force increases as the length of the cylinder increases up to 12 mm, but there is no change beyond that. This is thought to be because the electrode on the low temperature side causes a temperature rise due to heat conduction. Therefore, in all the comparisons below, the length of the cylinder was set to 12 mm.

FIG. 3 shows the change in thermoelectromotive force over time under the same conditions as above when the inner diameter of the cylindrical body 1 is changed in the above structure. In the figure, d represents the inner diameter of the cylindrical body 1. It can be seen that the smaller the inner diameter, the higher the response.

Next, FIG. 4 shows the change in thermoelectromotive force over time when the vicinity of the electrode on the high temperature side is exposed to an atmosphere with a temperature of 100° C. and a relative humidity of 100%. In the figure, A and a are when CuCl is used as the raw material powder for compact 2, and B and b are
In the case of CuBr, C and c are (CH ₃ Br) ₂ (CH ₂ ) ₆ N ₂ and
In the case of a solid electrolyte obtained from a mixture with CuBr,
A, B, and C have a cylindrical body 1 with an inner diameter of 3 mm,
a, b, and c represent the case in which the cylinder 1 was not used and the powder was formed into a cylinder with a diameter of 10 mm. Those that do not use the cylindrical body 1 as a package have a considerably high initial power and deteriorate over time.
It is recognized that the value using cylinder 1 maintains a constant value.

Figure 5 shows the change in thermoelectromotive force over time when the vicinity of the electrode on the high temperature side is exposed to an atmosphere with a temperature of 200°C and a relative humidity of 30%. Other conditions are the same as in the case of FIG. This result also shows that the characteristics change when the cylinder 1 is not included.

As described above, according to the present invention, it is possible to obtain a thermoelectromotive force element with good responsiveness and precision, and with little change over time.

[Brief explanation of the drawing]

Figure 1 is a longitudinal cross-sectional view of a thermoelectromotive force element in an embodiment of the present invention, Figure 2 is a diagram showing the relationship between the length of the element and thermoelectromotive force, and Figure 3 is the relationship between the diameter of the element and responsiveness. Figures 4 and 5 compare the changes in thermoelectromotive force over time with the presence or absence of an element package. Figure 4 shows the comparison under high humidity, and Figure 5 shows the comparison under high temperature. A comparison is shown below. 1... Cylindrical body, 2... Powder compact, 3, 4...
electrode.

Claims (1)

[Claims] 1 A heat-resistant, electrically insulating, non-ventilated cylinder with both ends open, a molded body of copper ion conductive solid electrolyte or copper halide powder filled inside the cylinder, and a cylinder with the openings open. A thermoelectromotive force element characterized by comprising a pair of copper electrodes hermetically sealed.