Aguirre, Myriam H.

Constantinescu, Gabriel

Costa, Florinda M.

Ferreira, Nuno M.

Frade, Jorge R.

Kovalevsky, Andrei V.

Lopes, Diogo

Patrício, Sónia G.

Weidenkaff, Anke

Xie, Wenjie

English

Repositório Institucional da Universidade de Aveiro

Thermoelectric oxides:challenges and selected approaches for materials designAndrei V. KovalevskyWenjie Xie, Myriam H. Aguirre, Nuno M. Ferreira, SóniaG. Patrício, Diogo Lopes, Gabriel Constantinescu, Florinda M. Costa, Jorge R. Frade, Anke Weidenkaff29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsGreetings from Aveiro, Portugal29.06.2020 - 1st Online Workshop on Sustainable Thermoelectrics29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsIntroduction - oxidesCarter, C.B. and Norton, M.G. (2013). Ceramic Materials: Science andEngineering, 546. Springer.He, J., Liu, Y., & Funahashi, R. (2011). Journal of Materials Research, 26(15), 1762-1772.AbundanceStabilityRich family, rich/unique propertiesYuan-Hua Lin, Jinle Lan, Cewen Nan, Oxide Thermoelectric Materials. From basic principles to applications, Wiley, 2019.TE oxides – challenges29.06.2020 - 1st Online Workshop on Sustainable Thermoelectrics29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsMain thermoelectric oxide familiesLayered cobaltites Ca3Co4O9, NaxCoO2 and Bi2Ca2Co2O9, ZT reaching 0.3-0.7 at 1000 K.Butt, S.; Xu,W.; He,W.Q.; Tan, Q.; Ren, G.K.; Lin, Y.; Nan, C.W. Enhancement of Thermoelectric Performance in Cd-Doped Ca3Co4O9 via Spin Entropy, Defect Chemistry and Phonon Scattering. J. Mater. Chem. A, 2014,2, 19479.Saini, S.; Yaddanapudi, H.S.; Tian, K.; Yin, Y.; Magginetti, D.; Tiwari, A. Terbium Ion Doping in Ca3Co4O9: A Step Towards High-Performance Thermoelectric Materials, Sci. Rep. 2017, 7, 1.JECS 39 (2019) 1237Perovskite-type(SrTiO3- and CaMnO3-based) materials, ZTreaching 0.3-0.5 at1200 K.A.V. Kovalevsky, A.A. Yaremchenko, S. Populoh, P. Thiel, D.P. Fagg, A. Weidenkaff, J.R. Frade, Phys. Chem. Chem. Phys. 16 (2014) 26946-26954.Bocher, L.; Aguirre, M.H.; Logvinovich, D.; Shkabko, A.; Robert, R.; Trottmann, M.; Weidenkaff, A. CaMn1-xNbxO3 (x < 0.08) Perovskite-Type Phases As Promising New High-Temperature n-Type Thermoelectric Materials. Inorg. Chem. 2008, 47, 8077–8085.J. Wang et al., Record high thermoelectric performance in bulk SrTiO3 via nano-scale modulation doping, Nano Energy 35 (2017) 387.ZnO-based materials,ZT reaching 0.1-0.6 at 1100-1300 K.M.  Ohtaki,  T.  Tsubota,  K.  Eguchi,  and  H.  Arai,J., High-temperature thermoelectric properties of (Zn1−xAlx)O, Appl.Phys. 79, 1816 (1996).M. Ohtaki, K.Araki, and K. Yamamoto, High thermoelectric performance of duallydoped ZnO ceramics, Journal of Electronic Materials, vol. 38, no. 7, pp. 1234 (2009).Jood, P.; Mehta, R.J.; Zhang, Y.; Peleckis, G.;Wang, X.; Siegel, R.W.; Borca-Tasciuc, T.;Dou, S.X.; Ramanath, G. Al-Doped Zinc Oxide Nanocomposites with EnhancedThermoelectric Properties. Nano Lett. 2011, 11, 4337–4342.In2O3-based materials, ZT reaching 0.2-0.4 at 1000 K.Guilmeau, E.; Bérardan, D.; Simon, Ch.; Maignan, A.; Raveau, B.; Ovono Ovono, D.;Delorme, F. Tuning the transport and thermoelectric properties of In2O3 bulk ceramicsthrough doping at in-site. J. Appl. Phys. 2009, 106, 053715.Yong Liu, Wei Xu, Da-Bo Liu, Meijuan Yu, Yuan-Hua Lin and Ce-Wen Nan, Enhanced thermoelectric properties of Ga-dopedIn2O3ceramicsviasynergistic band gapengineering and phonon suppression, Phys.Chem.Chem.Phys.,2015,17, 11229.Liu, Y.; Lin, Y.-H.; Xu, W.; Cheng, B.; Lan, J.; Chen, D.; Zhu, H.; Nan, C.-W. High-temperature transport property of In2-xCexO3 (0 ≤x ≤0.10) fine grained ceramics. J. Am. Ceram. Soc. 2012, 95, 2568–2572.Strontium titanate as a TE platform29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsLn3+3+Me5+3+3+A.V. Kovalevsky, M.H. Aguirre, S. Populoh, S.G. Patrício, N.M.Ferreira, S.M. Mikhalev, D.P. Fagg, A. Weidenkaff, J.R. Frade,Designing strontium titanate-based thermoelectrics: insight intodefect chemistry mechanisms, J. Mater. Chem. A, 2017, vol. 5, pp.3909-3922.29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsStrontium titanate as a TE platformHow the defect types can be controlled?Example: SrTi1-xTaxO3±δ and Sr1-x/2Ti1-xTaxO3±δ series ×•××+′′−++′′+++−+−→−++OlayerRPSrTiTiSrOOxSrOxVxxTaTixSrxTiOxSrOOTax3)2/)1(()2/()2/()1()2/1()1()2( 252ββββ )()2/()3()21()2()2/()2/1()1()21()2(2252gOVOTixiTxTaVxSrxTiOxSrOxOTaxOOTiTiTiSrSrδδδδδ ++−+−−+′+++′′+−→−+−+••××•×For both:  2)2/(22 OViTOTi OTixOTi δ++′→+ ••×(more oxygen-rich planar defects)(more A-site and oxygen vacancies)F. Lichtenberg et al. Prog. Solid State Chem. 29 (2001) 1-70.A.A. Yaremchenko, S. Populoh, S.G. Patrício, J. Macías, P. Thiel,D.P. Fagg, A. Weidenkaff, J.R. Frade, A.V. Kovalevsky, Boostingthermoelectric performance by controlled defect chemistryengineering in Ta-substituted strontium titanate, Chem. Mater.,2015, vol. 27, p. 4995.29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsSrTiO3 – effects of oxygen deficiency0.00 0.10 0.20 0.30x (Ta)2345κph, W×m−1×K-10.00.10.20.30.4ZT600 K3.0023.0773.0073.0412.9752.950 2.9271200 KSrTi1-xTaxO3±δSr1-x/2Ti1-xTaxO3±δ3±δ 2)2/(22 OViTOTi OTixOTi δ++′→+ ••×Highly reducing conditions are essential:1500ºC (10h) in 10%H2-N2A.A. Yaremchenko, S. Populoh, S.G. Patrício, J. Macías, P. Thiel,D.P. Fagg, A. Weidenkaff, J.R. Frade, A.V. Kovalevsky, Boostingthermoelectric performance by controlled defect chemistryengineering in Ta-substituted strontium titanate, Chem. Mater.,2015, vol. 27, p. 4995.A.V. Kovalevsky, A.A. Yaremchenko, S. Populoh, P. Thiel, D.P. Fagg, A.Weidenkaff, J.R. Frade, Towards a high thermoelectric performance in rare-earth substituted SrTiO3: Effects provided by strongly-reducing conditions,Phys. Chem. Chem. Phys., 2014, vol. 16, pp. 26946-26954.29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsSrTiO3 – effects of cation deficiency400 600 800 1000 1200T, K23456κph, W×m−1×K-1SrTi0.8Nb0.2O3±δSr0.97Ti0.8Nb0.2O3±δSr0.94Ti0.8Nb0.2O3±δSr0.90Ti0.8Nb0.2O3±δSr0.80Pr0.20TiO3±δSr0.70Pr0.30TiO3±δSr0.70Pr0.20TiO3±δSr0.55Pr0.30TiO3±δA.V. Kovalevsky, A. A. Yaremchenko, S. Populoh, A. Weidenkaff andJ. R. Frade, J. Phys.Chem. C 2014, vol. 118, pp. 4596-4606.Popuri, S.R.; Scott, A.J.M.; Downie, R.A.; Hall, M.A.; Suard, E.; Decourt, R.; Pollet, M.; Bos, J.-W.G. RSC Adv. 2014, 4, 33720-33723.Glass-like thermal conductivity?Formation of A–O–□ linkages could lead to softening A–O bonds and the emergence of a rattling mode and phonon-glass state.SryTi0.90Nb0.10O3±δA.V. Kovalevsky, M.H. Aguirre, S. Populoh, S.G. Patrício, N.M.Ferreira, S.M. Mikhalev, D.P. Fagg, A.Weidenkaff, J.R. Frade,Designing strontium titanate-based thermoelectrics: insight into defectchemistry mechanisms, J. Mater. Chem. A, 2017, vol. 5, pp. 3909.29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsSrTiO3 – effects of cation deficiencySr1.05Ti0.90Nb0.10O3±δSr1.00Ti0.90Nb0.10O3±δ“stoichiometric”Sr0.97Ti0.90Nb0.10O3±δSr0.95Ti0.90Nb0.10O3±δmore,moreSr0.93Ti0.90Nb0.10O3±δ29.06.2020 - 1st Online Workshop on Sustainable Thermoelectrics "••[Ti3+]/[Ti]totA.V. Kovalevsky, M.H. Aguirre, S. Populoh, S.G. Patrício, N.M. Ferreira, S.M. Mikhalev, D. P. Fagg, A. Weidenkaff and J. R. Frade,J. Mater. Chem. A, 2017, vol. 5, pp. 3909-3922.SryTi0.90Nb0.10O3±δmore oxygen andcation vacanciesintroducing A-site deficiency isfavorable for enhancing the mobilityof the charge carriesSrTiO3 – effects of cation deficiencyA.V. Kovalevsky, K.V. Zakharchuk, M.H. Aguirre, W. Xie, S.G. Patrício, N.M. Ferreira, D. Lopes, S.A. Sergiienko, G. Constantinescu, S.M. Mikhalev, A. Weidenkaff, J.R. Frade, Redox engineering of strontium titanate-based thermoelectrics, 2020, J. Mater. Chem. A, vol. 8, p. 7317.29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsSrTiO3 – redox-promoted composites20 µmOxRed (Mo)H220 µm+OX 	, ´´ ,    	,   	+RED	, ´´ ,  	++composite lattice29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsSrTiO3 – redox-promoted composites	, ´´ ,   	 + +Redox composition?Mo 3d240 237 234 231 228 225Binding Energy (eV)Intensity(a.u.)Mo 3dMo(0)Mo(IV)Mo(V)Mo(VI)Cation-stoichiometric matrixMo 3d240 237 234 231 228 225Binding Energy (eV)Intensity(a.u.)Mo(IV)Mo(V)Mo(VI)Mo(0)Mo 3dCation-deficient matrixA.V. Kovalevsky, K.V. Zakharchuk, M.H. Aguirre, W. Xie, S.G. Patrício, N.M. Ferreira, D. Lopes, S.A. Sergiienko, G. Constantinescu, S.M. Mikhalev, A. Weidenkaff, J.R. Frade, Redox engineering of strontium titanate-based thermoelectrics, 2020, J. Mater. Chem. A, vol. 8, p. 7317.29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsSrTiO3 – redox-promoted compositescicecoaveiro institute of materialsPower factor PF=σ×α2 Thermal conductivityPower factor Wm-1K-2Power factor Wm-1K-2Power factor Wm-1K-2A.V. Kovalevsky, K.V. Zakharchuk, M.H. Aguirre, W. Xie, S.G. Patrício, N.M. Ferreira, D. Lopes, S.A. Sergiienko, G. Constantinescu, S.M. Mikhalev, A. Weidenkaff, J.R. Frade, Redox engineering of strontium titanate-based thermoelectrics, 2020, J. Mater. Chem. A, vol. 8, p. 7317.Improvement of the power factor dueto enhancement of the Seebeck coefficient (carrier filtering effects?).Phonon scattering at redox-promotedinterfaces.29.06.2020 - 1st Online Workshop on Sustainable Thermoelectrics400 600 800 1000 1200T, K0.00.10.20.3Sr0.9La0.1TiO3Mo-cont. Sr0.9La0.1TiO3SrTiO3 – redox-promoted compositesA.V. Kovalevsky, K.V. Zakharchuk, M.H. Aguirre, W. Xie, S.G. Patrício, N.M. Ferreira, D. Lopes, S.A. Sergiienko, G. Constantinescu, S.M. Mikhalev, A. Weidenkaff, J.R. Frade, Redox engineering of strontium titanate-based thermoelectrics, 2020, J. Mater. Chem. A, vol. 8, p. 7317.CaO+MnO2RedCa1-xMnxO(rock-salt)OxCaMnO3+Ca4Mn3O10+CaMn2O4S. Prakash Singh, N. Kanas, T. Desissa, M.-A. Einarsrud, T. Norby, K. Wiik, Thermoelectric properties of non-stoichiometric CaMnO3-δ compositesformed by redox-activated exsolution, J. Europ. Ceram. Soc. 40 (2020) 1344.29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsCa3Co4O3 – redox-promoted compositesCa3Co4O9natural superlattice with promising TE propertiesA. C. Masset, C. Michel, A. Maignan, M. Hervieu, O. Toulemonde, F. Studer, B. Raveau and J. Hejtmanek, Phys. Rev. B, 2000, 62, 166; Y. Miyazaki, M. Onoda, T. Oku, M. Kikuchi, Y. Ishii, Y. Ono, Y. Morii and T. Kajitani, J. Phys.Soc. Jpn., 2002, 71, 491–497.100 µm 10 µmHigh grain anisotropy – low densificationG. Constantinescu, A.R. Sarabando, Sh. Rasekh, D. Lopes, S. Sergiienko, P. Amirkhizi, J.R. Frade, A.V.Kovalevsky, Redox-promoted tailoring of the high-temperature electrical performance in Ca3Co4O9materials by metallic cobalt addition, Materials, 2020, 13, p. 1060.29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsCa3Co4O3 – redox-promoted composites+OX349  	 ! ".  	+349 !"	$34 %&& 	composite ceramics900ºC (2h)CoCa349'!(" Ca3Co4O9 + Co3O429.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsCa3Co4O3 – redox-promoted composites500 600 700 800 900 1000T, K304050607080500 600 700 800 900 1000T, K110120130140150160170180500 600 700 800 900 1000T, K6090120150180210pristine (1st), 56% densepristine (2st), 80% dense3%Co (1st), 61% dense6%Co (1st), 59% densepristine (1st), 56% densepristine (2st), 80% dense3%Co (1st),61% dense6%Co (1st)59% denseG. Constantinescu, A.R. Sarabando, Sh. Rasekh, D. Lopes, S. Sergiienko, P. Amirkhizi, J.R. Frade, A.V.Kovalevsky, Redox-promoted tailoring of the high-temperature electrical performance in Ca3Co4O9materials by metallic cobalt addition, Materials, 2020, 13, p. 1060.29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsZnO – self-organization in compositesProblems limiting the applications:Efficiency ZT (thermal conductivity, …)Degradation of electrical conductivityat high temperaturesNanocomposite formed by an addition of external nanoparticles29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsZnO – self-organization in compositesZn(Al)O + ZrO2 nanoparticlesK.V. Zakharchuk, M. Widenmeyer, D.O. Alikin, W. Xie, S. Populoh, S.M. Mikhalev, A. Tselev, J.R. Frade,A. Weidenkaff, A.V. Kovalevsky, A self-forming nanocomposite concept for ZnO-based thermoelectrics,J. Mater. Chem. A, 2018, vol. 6, pp.13386-13396.29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsSelf-forming composite….Zn(Al)O+ZrO2Zn(Al,Zr)O+ZnAl2O4Al Zr0 400 800distance, nmAlZrK.V. Zakharchuk, M. Widenmeyer, D.O. Alikin, W. Xie, S.Populoh, S.M. Mikhalev, A. Tselev, J.R. Frade, A. Weidenkaff,A.V. Kovalevsky, A self-forming nanocomposite concept forZnO-based thermoelectrics, J. Mater. Chem. A, 2018, vol. 6,pp.13386-13396.ZnO – self-organization in compositesK.V. Zakharchuk, M. Widenmeyer, D.O. Alikin, W. Xie, S.Populoh, S.M. Mikhalev, A. Tselev, J.R. Frade, A. Weidenkaff,A.V. Kovalevsky, A self-forming nanocomposite concept forZnO-based thermoelectrics, J. Mater. Chem. A, 2018, vol. 6,pp.13386-13396.29.06.2020 - 1st Online Workshop on Sustainable Thermoelectrics, WmK-1, WmK-1600 750 900 1050 1200T, K0.000.050.100.150.20Thermal conductivityPower factorOverall performance - ZTPerformance improvement mainly dueto electrical properties…1173 K-9.3%+5.4%-4.7%+0.4%more stable electrical performanceZnO – self-organization in composites29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsZnO – self-organization in compositesZn(Al)O + CeO2 nanoparticlesMixing and high-temperature sintering400 600 800 1000 1200T, K04080120160200400 600 800 1000 1200T, K0100200300400pristine Zn0.993Al0.007O5% vol. CeO210% vol. CeO220% vol. CeO229.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsZnO – self-organization in compositesZn(Fe)O + CeO2 nanoparticlesMixing and high-temperature sintering400 600 800 1000 1200T, K020406080100400 600 800 1000 1200T, K0100200300400pristine Zn0.993Fe0.007O10% vol. CeO229.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsConclusionsUnique redox propertiesComplex behavior on substitution and self-organization29.06.2020 - 1st Online Workshop on Sustainable ThermoelectricsAcknowledgementsCICECO – Aveiro Institute of Materials (ref. UIDB/50011/2020 & UIDP/50011/2020)REMOTE project (POCI-01-0145-FEDER-031875)

Thermoelectric oxides: challenges and selected approaches for materials design

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Thermoelectric oxides: challenges and selected approaches for materials design

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