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Protective coating suitable for CoSb3 base thermoelectric material and preparation method thereof

A technology of thermoelectric materials and protective coatings, applied in metal material coating processes, coatings, chemical instruments and methods, etc., can solve the problem of reducing the thermoelectric properties of thermoelectric materials, reducing the conversion efficiency of thermoelectric devices, and low density of protective coatings. problem, to achieve the effect of good interface bonding, reduced volatilization and good product performance

Active Publication Date: 2012-06-27
UNIV OF JINAN
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, T. Caillat of the Jet Propulsion Laboratory (Jet Propulsion Laboratory) in the United States has deposited a Mo coating on the CoSb3 based thermoelectric arm by magnetron sputtering at its high temperature end (Tests results of skutterudite based thermoelectric uncouples, Energ Convers Manage, 48, 2007), however, because the Mo coating has higher electrical conductivity and thermal conductivity than the skutterudite thermoelectric material, a large number of electrical shunts and heat shunts are generated on the Mo layer, reducing The conversion efficiency of thermoelectric devices is improved, and the thermal expansion coefficient of Mo (5.5~6.5×10-6 / K) is much lower than that of skutterudite-based thermoelectric materials (10~12×10-6 / K), it is easy to peel off under long-term high temperature conditions; Jeffrey et al. in the United States have tried to spray a layer of MgAl on the N-type CoSb3 material by plasma spraying 2O4 coating (spinel) and Mg2SiO4 coating (US7480984B1), however The interface bonded well within 1 week of working under 850K vacuum conditions, but the temperature of the coating formed by plasma spraying was too high, which exceeded the volatilization temperature of the CoSb3 material itself, thus reducing the thermoelectric material itself. Excellent thermoelectric performance, and the protective coating formed by plasma spraying is not dense, and the pores in the coating may become a "short circuit" channel for the volatilization of Sb atoms in the material

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  • Protective coating suitable for CoSb3 base thermoelectric material and preparation method thereof
  • Protective coating suitable for CoSb3 base thermoelectric material and preparation method thereof
  • Protective coating suitable for CoSb3 base thermoelectric material and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0031] YSZ layer, Y 2 o 3 The mass percentage is 8%, and the balance is ZrO 2 , the coating preparation method is:

[0032] CoSb 3 Polish the surface, sonicate in alcohol for 3 min, dry it and place it on the substrate, place the YSZ target and the W target in two crucibles, and then evacuate the main vacuum chamber to 10 -3 Pa; heat the substrate to 500°C, adjust the electron beam current to 2.0A, the substrate speed to 20r / min, evaporate the W target material, the deposition time is 10min, and the thickness is about 5um; then evaporate the YSZ target material at the same substrate temperature, and adjust the electron beam The flow rate is 3.0A, the deposition time is 40min, and the thickness is about 20um; after the completion, the substrate temperature is cooled to 100°C, and the vacuum chamber is opened to take out the sample to complete the CoSb 3 coating deposition process.

[0033] The bonding strength of the protective coating obtained in this example and the subs...

Embodiment 2

[0035] YSZ layer composition (mass percentage): 8.5%Y 2 o 3 , the balance being ZrO 2 , the coating preparation method is: with Sn 0.2 co 4 Sb 12 As the substrate, its surface was polished, ultrasonicated in alcohol for 5 min, dried and placed on the substrate, the YSZ and W targets were placed in two crucibles, and the vacuum was evacuated to 10 -3 Pa; heat the substrate to 520°C, adjust the electron beam current to 1.0A, the substrate speed to 10r / min, evaporate the W target material, the deposition time is 20 min, and the thickness is about 10um; then evaporate the YSZ target material at the same substrate temperature, adjust The electron beam current is 3.0A, the deposition time is 80 minutes, and the thickness is about 40um; after the completion, when the substrate is cooled to 100°C, open the vacuum chamber to take out the sample to complete the CoSb 3 Coating deposition process.

[0036] The bonding strength of the protective coating obtained in this example and t...

Embodiment 3

[0038] YSZ layer composition (mass percentage): 10%Y 2 o 3 , the balance being ZrO 2 . The coating preparation method is: with In 0.1 co 4 Sb 12 As the substrate, its surface was polished, ultrasonically cleaned in alcohol for 5 min, dried and placed on the substrate in the working room, YSZ and W targets were placed in two crucibles, and the vacuum was evacuated to 10 -3 Pa; then heat the substrate to 550°C, adjust the electron beam current to 2.0A, the substrate speed to 15r / min, evaporate the W target material, the deposition time is 40 min, and the thickness is about 20um; then evaporate the YSZ target material at the same substrate temperature, Adjust the electron beam current to 3.0A, the deposition time is 200min, and the thickness is about 100um; after the completion, keep the vacuum state, and when the temperature cools down to 100°C, open the vacuum chamber to take out the sample to complete the CoSb 3 Coating deposition process.

[0039] The bonding strength ...

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Abstract

The invention discloses a protective coating suitable for CoSb3 base thermoelectric material. The protective coating comprises an upper layer and a lower layer; the lower layer is made of metal W, and the upper layer is a mixture of Y2O3 and ZrO2; and the Y2O3 accounts for 7-10 wt% of the mixture. The protective coating of the invention can substantially reduce Sb volatilization of CoSb3 base thermoelectric material during high temperature working, and has high coating density and good interface combination. Experiments have proved that the coating has a bonding strength with the matrix greater than 5MPa; and after 30 day continuous experiment under 500 DEG C, the coating sample has unit area weight loss less than 2*10<-3> g / cm<2>, which is far smaller than 1.8*10<-2> / cm<2> of an uncoated sample. The invention employs an electron beam physical vapor deposition method to prepare the protective coating; the method is easily practical; and the obtained product has good performance and can effectively prevent Sb volatilization of CoSb3 during high temperature working.

Description

technical field [0001] The invention relates to a protective coating suitable for skutterudite-based thermoelectric materials and a preparation method thereof, belonging to the field of thermoelectric materials and devices. Background technique [0002] Thermoelectric materials are materials that use the Seebeck effect of semiconductor materials to directly convert thermal energy into electrical energy. Thermoelectric devices made of thermoelectric materials can not only effectively convert infrared light in solar energy into electrical energy, but also effectively realize waste heat recovery and utilization in industries such as steel, electrolytic aluminum, thermal power generation, and industrial waste heat. attention. The performance characteristics of thermoelectric materials are characterized by thermoelectric figure of merit (ZT), where ZT=S 2 T / ρκ, S is the Seebeck coefficient, ρ is the resistivity, κ is the thermal conductivity, and T is the absolute temperature. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B32B9/04B32B15/00C23C14/30C23C14/08C23C14/14
CPCY02T50/60
Inventor 赵德刚耿浩然滕新营
Owner UNIV OF JINAN