the average for the device over the temperature range Tc to Th . Thus, η depends mainly on the ΔT and materials’ performance: where α is the Seebeck coefficient, σ is the electrical conductivity, κ is the total thermal conductivity. [1] A. Shakouri, Annu. Rev. Mater. Res. 41 (2011) 399–431 [2] D.M. Rowe, CRC Handbook of Thermoelectrics: Macro to Nano, CRC Press, 2006 [3] G.J. Snyder, E.S. Toberer, Nat. Mater. 7 (2008) 105–114 Thermoelectrics 1 1 , 1 c h c h h Carnotcycle Т Т ZT Т ZT Т Т − + − = + + Th Tc 2 zT T =
[4] V. Johnson, W. Jeitschko, J. Solid State Chem. 11 (1974) 161–166. [5] M. Palazzi, C. Carcaly, J. Flahaut, J. Solid State Chem. 35 (1980) 150–155. [6] M. Palazzi, S. Jaulmes, Acta Crystallogr. Sect. B Struct. Crystallogr. Cryst. Chem. 37 (1981) 1337–1339. [7] L.N. Kholodkovskaya, L.G. Akselrud, A.M. Kusainova, V.A. Dolgikh, B.A. Popovkin, Mater. Sci. Forum 133–136 (1993) 693–696. [8] A.M. Kusainova, P.S. Berdonosov, L.G. Akselrud, L.N. Kholodkovskaya, V.A. Dolgikh, B.A. Popovkin, J. Solid State Chem. 112 (1994) 189–191. [9] R. Pöttgen, D. Johrendt, Zeitschrift Fur Naturforsch. - Sect. B J. Chem. Sci. 63 (2008) 1135–1148. • Quaternary ZrCuSiAs and HfCuSiAs silicidoarsenides were firstly synthesized in 1974 by V. Johnson and W. Jeitschko [4]; • R3+T+S2-O2- oxysulfides (R – rare-earth elements, T – transition metals) were synthesized in 1980. They crystallize in the same ZrCuSiAs structural type and have been studied as promising oxide materials for solar cells with attractive optical properties and ionic conductivity [5,6]; • Oxychalcogenides Ln3+Cu+Ch2-O2- (Ln – Bi or lanthanides, Ch - chalcogenide) were synthesized at Moscow State University and Lviv State University in 1993. Only structural studies [7,8]; • 1990’s – R3+T2+Pn3-O2- oxypnictides (Pn – pnictide [nitrogen subgroup]) as potential high-Tc superconductors (but no superconductivity) [9];
[10] T. Ohtani, Y. Tachibana, Y. Fujii, J. Alloys Compd. 262–263 (1997) 175–179. [11] H. Hiramatsu, H. Yanagi, T. Kamiya, K. Ueda, Chem. Mater. 20 (2008) 326–334. [12] L.D. Zhao, D. Berardan, Y.L. Pei, C. Byl, L. Pinsard-Gaudart, N. Dragoe, Appl. Phys. Lett. 97 (2010) 092118. [13] Y. Liu, L.-D. Zhao, Y. Zhu, Y. Liu, F. Li, M. Yu, D.-B. Liu, W. Xu, Y.-H. Lin, C.-W. Nan, Adv. Energy Mater. 6 (2016) 1502423. • First study on electrical transport properties of BiCuSeO with Sr doping at Bi site and Cu vacancy formation in 1997 [10]; • In early 2000’s oxychalcogenides RCuChO were studied as widegap transparent p-type semiconductors, ‘‘natural multiple quantum wells’ concept; • Late 2000’s – superconductivity in RFePnO at low temperature (< 55 K); • It was firstly shown in 2008 that BiCuChO exhibits much lower bandgap of 0.5- 1.1 eV that that for RCuChO (2.5-3.2 eV) [11]; • Firstly reported zT value for Sr-doped BiCuSeO by the Nita Dragoe group in 2010 [12]; The beginning of active research on BiCuSeO as promising thermoelectric materials; • The highest zTmax value of ~1.5 achieved in dually doped BiCuSeO with Ca and Pb at Bi site [13].
14 Simple carrier counting: [14] A. Novitskii, T. Mori, Preprint (2020) DOI: 10.13140/RG.2.2.15661.10727. ( ) 2 1 2 1 2(1 ) 2 2 2 2 2(Bi CuSeO) (Bi O ) (Cu Se ) 2 x x x x x M M xh − + − • − − = + + ( ) ( ) 2 1 2 ' 1 2 2 2 2 1 2(BiCu SeO) (Bi O ) (Cu Se ) 2 2 Cu V h + − + • − − = + + + Eform (VCu ) ~ 0 eV
18 raw powders mixing, cold-pressing solid state reaction in quartz tube SPS BiCuSeO disc-shaped bulk samples in 40 – 70 hours ball milling & cold- pressing ball milling or hand grinding − Not industrially friendly; − Cumbersome; − Energy intensive; − Time consuming.
/ 22 March 2021 20 raw powders ball milling SPS [20] J. Wu, F. Li, T.-R. Wei, Z. Ge, F. Kang, J. He, J.-F. Li, J. Am. Ceram. Soc. 99 (2016) 507–514. Methods. Mechanochemical synthesis
/ 22 March 2021 21 raw powders ball milling SPS [20] J. Wu, F. Li, T.-R. Wei, Z. Ge, F. Kang, J. He, J.-F. Li, J. Am. Ceram. Soc. 99 (2016) 507–514. Methods. Mechanochemical synthesis
Main advantages: • One of the best p-type Pb-free polycrystalline thermoelectric with zTmax = 1.4 at 923 K and zTav = 1.1 between 623 - 923 K; • It is possible to synthesize BiCuSeO via scalable powder metallurgy methods; Main trends: • Double doping combining various approaches Still much work to do: • Find suitable n-type material, Bi2 O2 Se? • Contact and diffusion barrier layers? • Mechanical properties?
attention The study was carried out with financial support from the Russian Science Foundation (project no. 19-79-10282). @anovitzkij @energy_misis [email protected]
anovitzkij
maleehafatima
aronwalsh
psasa
tereka114
.png){kind=avatar}
academix
lcolladotor
tagtag
genomethica
sshimizu2006
arafkarsh
dotmariusz
rasmusluckow
phodgson
stephaniewalter
aki_iinuma
zenorocha
myddelton
mclloyd
shlominoach
tmm1
shpigford
philnash
![Overview BiCuSeO oxyselenides / 22 March 2021 5 [13] Y.](https://files.speakerdeck.com/presentations/9f2026a2dd96464c9761e4230dc88f85/slide_4.jpg){kind=link}
