Calcium-manganese-oxygen thermoelectric material and preparation method thereof

A technology of calcium-manganese-oxygen thermoelectric and thermoelectric materials, which is applied in the direction of lead-out wire materials of thermoelectric devices, manufacture/processing of thermoelectric devices, etc., can solve the problem of high Seebeck coefficient and thermal conductivity, low thermoelectric conversion efficiency and difficult Industrial quantitative production and other issues, to achieve the effect of improving Seebeck coefficient, optimizing thermoelectric conversion efficiency, and reducing thermal conductivity

Pending Publication Date: 2022-06-24
PREGIS NEW MATERIALS (SHENZHEN) PTE LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The only variable independent of carrier concentration is κ L , κ L =Cvl / 3, C is the phonon heat capacity per unit area, v is the average phonon velocity, l is the phonon mean free path, the existing thermoelectric material Seebeck coefficient and thermal conductivity are relatively high, resulting in thermoelectric conversion efficiency Not high, and most thermoelectric materials in the prior art use SrTi 0.7 Nb 0.3O3 It is made of other materials, the material cost is high, and it is difficult to achieve industrial quantitative production by using plasma sintering (SPS). Secondly, the content of Nb element in the earth's crust is 20 parts per million, which is rare

Method used

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  • Calcium-manganese-oxygen thermoelectric material and preparation method thereof
  • Calcium-manganese-oxygen thermoelectric material and preparation method thereof
  • Calcium-manganese-oxygen thermoelectric material and preparation method thereof

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Experimental program
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Effect test

Embodiment 1

[0026] Embodiment 1, a kind of calcium manganese oxygen thermoelectric material, with cubic phase CaMnO 3 As the matrix phase, lamellar CaO is used as the intercalation phase, and the intercalation phase is dispersed and arranged in the matrix phase to form a tetragonal perovskite intergrowth structure CaO (CaMnO 3 ) m , where m=1, 2, 3... 15 -10^ 19 / cm^ 3 , so as to improve the Seebeck coefficient of the thermoelectric material, so as to further optimize the thermoelectric conversion efficiency of the thermoelectric material.

[0027] Further, the tetragonal perovskite intergrowth structure CaO (CaMnO 3 ) m Where m=2-10, m is a natural number. In the preferred structure, a sharper CaMnO can be formed 3 -CaO layered structure. Cubic CaMnO 3 The chimeric relationship with the intercalation phase CaO generates a Ruddlesden-Popper structure, which can increase the complexity of the structure, increase phonon diffraction, and reduce thermal conductivity. Specifically, i...

Embodiment 2

[0031] Embodiment 2, a preparation method of calcium manganese oxygen thermoelectric material, comprising the following steps:

[0032] S1, take CaO and MnO 2 Homogeneous mix, CaO and MnO 2 The ratio of the amount of substances is m+1:m, m=1, 2, 3...∞, and then high-temperature sintering is performed, the sintering temperature is 1200-1600 ° C, and the high-temperature sintering time is 4-18h;

[0033] S2. Ball milling the mixture sintered at high temperature to form powder, wherein the mass ratio of the ball to the mixture is 10-30:1, and the ball milling time is 0.5-4h, so that the particle size of the powder particles reaches 30-1000nm; further , the mass ratio of the ball to the mixture is preferably 15-25:1; further, the particle size of the powder particles formed is preferably 50-800 nm; further, the ball milling time is preferably 0.5-4h. In the present invention, the ball milling step is the basis for reducing the hot pressing process conditions. Therefore, when bal...

Embodiment 2-1

[0036] Example 2-1, take 22.533g of lamellar CaO and 17.4667g of MnO 2 Mix uniformly, then carry out high temperature sintering, the sintering temperature is 1200 ° C, and sintering for 4 hours; the high temperature sintered mixture is ball-milled to form powder, wherein the mass ratio of the ball to the mixture is 10:1. Until the particle size of the powder particles is 30-1000nm, the ball milling time is 0.5h; the powder is collected, and the powder is hot-pressed with a hot-pressing die under argon gas at a pressure of 40MPa, a temperature of 600°C, and a heating rate of 8°C / min. , the holding time is 15min, and the tetragonal perovskite intergrowth structure Ca is obtained. 2 MnO 4 Thermoelectric materials, quality inspection of thermoelectric materials, XRD calculation of materials before ball milling and finished samples (that is, samples after ball milling), quality inspection results are shown in figure 2 , Image 6 , Figure 7 , it can be seen from the test resul...

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Abstract

The invention discloses a calcium-manganese-oxygen thermoelectric material and a preparation method thereof, and the thermoelectric material is characterized in that cubic-phase CaMnO3 is used as a matrix phase, lamellar CaO is used as an embedded phase, the embedded phase is dispersed in the matrix phase and is directionally arranged, and a tetragonal perovskite symbiotic structure CaO (CaMnO3) m is formed; the preparation method comprises the following steps: uniformly mixing CaO and MnO2, and then carrying out high-temperature sintering; the mixture subjected to high-temperature sintering is subjected to ball milling, powder is formed, the ball milling mass ratio is (10-30): 1, the ball milling time is 0.5-4 h, and the diameter of the powder reaches 30-1000 nm; collecting powder, and carrying out hot pressing treatment on the powder under inert gas; calcium oxide and manganese oxide are used as raw materials, ball milling and hot pressing are performed to form the tetragonal perovskite symbiotic structure CaO (CaMnO3) m, so that the Seebeck coefficient of the thermoelectric material is improved, the ball milling mass ratio and the ball milling time are controlled, the heat conductivity is reduced, the thermoelectric conversion efficiency of the thermoelectric material is optimized, the cost is reduced, and industrial production is facilitated.

Description

technical field [0001] The invention relates to the technical field of thermoelectric materials, in particular to a calcium-manganese-oxygen thermoelectric material and a preparation method thereof. Background technique [0002] In recent years, with the increasingly serious crisis of fossil energy, the increasing awareness of environmental protection, and the increasing demand for sustainable new energy. The use of thermoelectric materials to generate cogeneration has attracted more and more attention from scientists and enterprises. Cogeneration uses the Seebeck effect in thermoelectric generators (TEGs, thermoelectric generators). When two different semiconductors, p-type and n-type, form a loop, and provide A temperature potential difference can generate a direct current. [0003] The thermoelectric conversion efficiency of the material is judged by its zT value, zT=S 2 σT / κ, where zT is dimensionless figure-of-merit, S is the Seebeck coefficient (μV K -1 ), σ is the ...

Claims

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Application Information

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IPC IPC(8): C04B35/01C04B35/622C04B35/645H01L35/22H01L35/34
CPCC04B35/016C04B35/622C04B35/645C04B2235/3208C04B2235/6562C04B2235/6567C04B2235/96C04B2235/77H10N10/855H10N10/01
Inventor 施翊璇汤弢
Owner PREGIS NEW MATERIALS (SHENZHEN) PTE LTD
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