Enhanced thermoelectric performance of spark plasma sintered p-type Ca3-xYxCo4O9+δ systems

doi:10.1016/j.jmst.2020.02.034

Abstract

Abstract:

Highly textured dense Ca_3-_xY_xCo₄O₉₊_δ (0 ≤ x ≤ 0.3) samples were fabricated by combining sol-gel process with spark plasma sintering (SPS). Y³⁺ substitution for Ca²⁺ simultaneously increased the Seebeck coefficient and reduced the thermal conductivity. The latter was attributed to the increase in lattice anharmonicity, structural distortion, and grain boundary area, which enhanced the phonon scattering. Ca_2.7Y_0.3Co₄O₉₊_δ showed the largest dimensionless figure-of-merit (ZT = 0.194) at 1073 K because it had the largest Seebeck coefficient and the lowest thermal conductivity. This ZT value was 55 % larger than that of undoped Ca₃Co₄O₉ (0.125 at 1073 K). Therefore, Y³⁺ substitution, sol-gel powder synthesis, and SPS are highly effective for enhancing the thermoelectric properties of Ca₃Co₄O₉.

Key words: Electrical conductivity, Ca₃Co₄O₉, Thermoelectric properties, Seebeck coefficient, Thermal conductivity, Spark plasma sintering

J.S. Cha, D.H. Kim, H.Y. Hong, K. Park. Enhanced thermoelectric performance of spark plasma sintered p-type Ca_3-_xY_xCo₄O₉₊_δ systems[J]. J. Mater. Sci. Technol., 2020, 55: 212-222.

Figures/Tables 16

Fig. 1. DTA/TGA curves of mixed Ca3-xYxCo4O9+δ (0 ≤ x ≤ 0.3) powders with x = (a) 0, (b) 0.1, (c) 0.2, and (d) 0.3.

Fig. 2. (a) XPS survey spectra of calcined Ca3-xYxCo4O9+δ (0 ≤ x ≤ 0.3) powders. High-resolution XPS spectra of (b) Ca 2p and (c) Y 3d in calcined Ca3-xYxCo4O9+δ (0 ≤ x ≤ 0.3) powders.

Fig. 3. High-resolution XPS spectra of Co 2p in calcined Ca3-xYxCo4O9+δ powders with x = (a) 0, (b) 0.1, and (c) 0.3. Note that “▼” in (c) indicates satellite peak. High-resolution XPS spectra of O 1s in calcined Ca3-xYxCo4O9+δ powders with x = (d) 0, (e) 0.1, and (f) 0.3.

Table 1 The relative concentration of Co3+ and Co4+ ions and the binding energies of Co and O ions in calcined Ca3-xYxCo4O9+δ (0 ≤ x ≤ 0.3) powders.

		Ca₃Co₄O₉	Ca_2.9Y_0.1Co₄O₉₊_δ	Ca_2.7Y_0.3Co₄O₉₊_δ
Relative concentrations of Co ions (%)	Co³⁺	28.1	45.6	69.0
Relative concentrations of Co ions (%)	Co⁴⁺	71.9	54.4	31.0
Binding energies of Co ions (eV)	Co³⁺ in Co 2p_1/2	794.1	795.2	794.8
	Co⁴⁺ in Co 2p_1/2	795.1	796.5	796.6
	Co³⁺ in Co 2p_3/2	779.1	780.2	779.9
	Co⁴⁺ in Co 2p_3/2	780.1	781.5	781.6
Binding energies of O ions (eV)	O 1s in CoO₂	528.6	528.9	529.0
	O 1s in CaO	531.2	531.3	531.4
	O 1s in absorbed H₂O	533.3	533.0	533.2

Fig. 4. (a) UV-visible diffuse reflectance spectra and (b) band gap of sintered Ca3-xYxCo4O9+δ (0 ≤ x ≤ 0.3).

Fig. 5. (a) XRD patterns and (b) Lotgering factors of sintered Ca3-xYxCo4O9+δ (0 ≤ x ≤ 0.3).

Fig. 6. Refined XRD profiles of sintered Ca3-xYxCo4O9+δ with x = (a) 0, (b) 0.2, and (c) 0.3. (d) Unit cell volume of sintered Ca3-xYxCo4O9+δ (0 ≤ x ≤ 0.3), obtained from the refined XRD data, as a function of Y3+ content.

Fig. 7. Crystal structure of the Ca2.7Y0.3Co4O9+δ fabricated using sol-gel processed powders, showing the CoO2 and Ca2CoO3 layers stacking alternatively along the c-axis direction of the unit cell.

Table 2 Crystallographic details and fitting parameters of Ca3-xYxCo4O9+δ (0 ≤ x ≤ 0.3) obtained from the XRD Rietveld refinement.

	Ca₃Co₄O₉	Ca_2.9Y_0.1Co₄O₉₊_δ	Ca_2.8Y_0.2Co₄O_9+δ	Ca_2.7Y_0.3Co₄O₉₊_δ
Crystal structure	Monoclinic	Monoclinic	Monoclinic	Monoclinic
Space group	C2/m	C2/m	C2/m	C2/m
Lattice parameters
a (?)	4.8332	4.8325	4.8200	4.8133
b₁ (?)	4.5505	4.5567	4.5350	4.5268
b₂ (?)	2.8189	2.8189	2.8189	2.7797
c (?)	10.8402	10.8147	10.7923	10.7894
β (°)	98.0	98.1	98.0	98.1
Reliability factors
R_wp (%)	8.39	7.14	8.26	8.01
R_exp (%)	2.47	2.56	2.53	2.63
GOF	3.39	2.79	3.26	3.04

Fig. 8. FE-SEM images of the thermally etched Ca3-xYxCo4O9+δ (0 ≤ x ≤ 0.3) with x = (a) 0, (b) 0.1, (c) 0.2, and (d) 0.3.

Fig. 9. (a, c) Bright-field images and (b, d) HRTEM lattice images taken from two different areas of sintered Ca2.7Y0.3Co4O9+δ.

Fig. 10. (a) Bright-field image, (b) [$\overline 2$10] SAED pattern, and (c) EDS spectrum of sintered Ca2.7Y0.3Co4O9+δ.

Fig. 11. (a) Electrical conductivity, (b) ln(σT) vs 1000/T, (c) Seebeck coefficient, and (d) power factor of Ca3-xYxCo4O9+δ (0 ≤ x ≤ 0.3).

Fig. 12. (a) Total thermal conductivity κtotal, (b) electronic thermal conductivity κel, and (c) phonon thermal conductivity κph of Ca3-xYxCo4O9+δ (0 ≤ x ≤ 0.3).

Table 3 The ratio of κph to κtotal for Ca3-xYxCo4O9+δ (0 ≤ x ≤ 0.3).

	Temperature (K)
	773	873	973	1073
Ca₃Co₄O₉	93.3	91.7	90.1	88.4
Ca_2.9Y_0.1Co₄O₉₊_δ	94.9	93.5	92.1	90.4
Ca_2.8Y_0.2Co₄O₉₊_δ	95.2	93.9	92.5	90.9
Ca_2.7Y_0.3Co₄O₉₊_δ	95.5	94.2	92.8	91.3

Fig. 13. Dimensionless figure-of-merit (ZT) of (a) Ca3-xYxCo4O9+δ (0 ≤ x ≤ 0.3) fabricated using sol-gel processed powders and of (b) Ca2.7Y0.3Co4O9+δ fabricated using sol-gel processed powders and commercial powders.

References 55

[1]	C. Chang, G. Tan, J. He, M.G. Kanatzidis, L.D. Zhao, Chem. Mater. 30 (2018) 7355-7367. DOI URL
[2]	L.D. Zhao, S.H. Lo, Y. Zhang, H. Sun, G. Tan, C. Uher, C. Wolverton, V.P. Dravid, M.G. Kanatzidis, Nature 508 (2014) 373-377. DOI URL
[3]	J.F. Li, W.S. Liu, L.D. Zhao, M. Zhou, NPG Asia Mater. 2 (2010) 152-158. DOI URL
[4]	C.M. Kim, J.W. Seo, S.-M. Choi, W.?S. Seo, S. Lee, Y.S. Lim, K. Park, Electron. Mater. Lett. 11 (2015) 276-281. DOI URL
[5]	J.W. Seo, J.S. Cha, S.O. Won, K. Park, J. Am. Ceram. Soc. 100 (2017) 3608-3617. DOI URL
[6]	A. Bhaskar, Y.C. Huang, C.J. Liu, Solid State Commun. 168 (2013) 24-27. DOI URL
[7]	N. Prasoetsopha, S. Pinitsoontorn, T. Kamwanna, V. Amornkitbamrung, K. Kurosaki, Y. Ohishi, H. Muta, S. Yamanaka, J. Alloys. Compd. 588 (2014) 199-205. DOI URL
[8]	G. Constantinescu, Sh. Rasekh, M.A. Torres, J.C. Diez, M.A. Madre, A. Sotelo, J. Alloys. Compd. 577 (2013) 511-515. DOI URL
[9]	S. Porokhin, L. Shvanskaya, V. Khovaylo, A. Vasiliev, J. Alloys. Compd. 695 (2017) 2844-2849. DOI URL
[10]	H.Q. Liu, Y. Song, S.N. Zhang, X.B. Zhao, F.P. Wang, J. Phys. Chem. Solids 70 (2009) 600-603. DOI URL
[11]	H.Q. Liu, X.B. Zhao, T.J. Zhu, Y. Song, F.P. Wang, Curr. Appl. Phys. 9 (2009) 409-413. DOI URL
[12]	A. Le Bail, H. Duroy, J.L. Fourquet, Mater. Res. Bull. 23 (1988) 447-452. DOI URL
[13]	M. James, M.L. Carter, J.N. Watson, J. Solid State Chem. 174 (2003) 329-333. DOI URL
[14]	H. Wattanasarn, U. Seetawan, C. Nakhowong, S. Boonmeethongyoo, T. Seetawan, J. Mater. Sci. Appl. Energy 1 (2012) 14-18.
[15]	S. Pinitsoontorn, N. Lerssongkram, A. Harnwunggmoung, K. Kurosaki, S. Yamanaka, J. Alloys. Compd. 503 (2010) 431-435. DOI URL
[16]	N. Prasoetsopha, S. Pinitsoontorn, V. Amornkitbamrung, Electron. Mater. Lett. 8 (2012) 305-308. DOI URL
[17]	C.S. Lim, C.K. Chua, Z. Sofer, O. Jankovsk′y, M. Pumera, Chem. Mater. 26 (2014) 4130-4136. DOI URL
[18]	Z. Shi, F. Gao, J. Zhu, J. Xu, Y. Zhang, T. Gao, M. Qin, J. Materiom. 5 (2019) 711-720.
[19]	Z. Shi, F. Gao, J. Xu, J. Zhu, Y. Zhang, T. Gao, M. Qin, M. Reece, H. Yan, J. Eur. Ceram. Soc. 39 (2019) 3088-3093. DOI URL
[20]	S. Butt, W. Xu, W.Q. He, Q. Tan, G.K. Ren, Y. Lin, C.W. Nan, J. Mater. Chem. A Mater. Energy Sustain. 2 (2014) 19479-19487. DOI URL
[21]	Y. Yin, S. Saini, D. Magginetti, K. Tian, A. Tiwari, Ceram. Int. 43 (2017) 9505-9511. DOI URL
[22]	S. Feng, W. Yang, J. Sol Gel Sci. Technol. 58 (2011) 330-333. DOI URL
[23]	K. Agilandeswari, A.R. Kumar, J. Magn. Magn. Mater. 364 (2014) 117-124. DOI URL
[24]	S. Salari, F.E. Ghodsi, J. Lumin. 182 (2017) 289-299. DOI URL
[25]	Y.S. Vidya, K.S. Anantharaju, H. Nagabhushana, S.C. Sharma, H.P. Nagaswarupa, S.C. Prashantha, C. Shivakumara, Danithkumar, Spectrochim. Acta A 135 (2015) 241-251.
[26]	G. Fu, G. Yan, L. Sun, H. Zhang, H. Guo, J. Wang, S. Wang, RSC Adv. 5 (2015) 26383-26387. DOI URL
[27]	D. Grebille, S. Lambert, F. Bourée, V. Petrícek, J. Appl. Cryst. 37 (2004) 823-831. DOI URL
[28]	H.Y. Choi, M.H. Lee, S.M. Choi, W.S. Seo, H.L. Lee, J. Ceram. Process. Res. 13 (2012) s206-s210.
[29]	R.D. Shannon, Acta Cryst. A 32 (1976) 751-767. DOI URL
[30]	N.Y. Wu, T.C. Holgate, N.V. Nong, N. Pryds, S. Linderoth, J. Eur. Ceram. Soc. 34 (2014) 925-931. DOI URL
[31]	S.W. Nam, Y.S. Lim, S.M. Choi, W.S. Seo, K. Park, J. Nanosci. Nanotechnol. 11 (2011) 1734-1737. DOI URL PMID
[32]	T. Huang, M.N. Rahaman, T.I. Mah, T.A. Parthasarathay, J. Mater. Res. 15 (2000) 718-726. DOI URL
[33]	I.P. Shapiro, R.I. Todd, J.M. Titchmarsh, S.G. Roberts, J. Eur. Ceram. Soc. 29 (2009) 1613-1624. DOI URL
[34]	A. Rittidech, P. Wisuwan, T. Pinkhunthod, Am. J. Appl. Sci. 15 (2018) 409-415. DOI URL
[35]	F.P. Zhang, X. Zhang, Q.M. Lu, J.X. Zhang, Y.Q. Liu, G.Z. Zhang, Solid State Sci. 13 (2011) 1443-1447. DOI URL
[36]	A. Bhaskar, Y.C. Huang, C.J. Liu, Ceram. Int. 40 (2014) 5937-5943. DOI URL
[37]	L. Xu, F. Li, Y. Wang, J. Alloys. Compd. 501 (2010) 115-119. DOI URL
[38]	P.H. Isasi, M.E. Lopes, M.R. Nunes, M.E.M. Jorge, J. Phys. Chem. Solids 70 (2009) 405-411. DOI URL
[39]	J.W. Seo, J.S. Cha, K. Park, Electron. Mater. Lett. 12 (2016) 113-120. DOI URL
[40]	S. Li, R. Funahashi, I. Matsubara, K. Ueno, S. Sodeoka, H. Yamada, Chem. Mater. 12 (2000) 2424-2427. DOI URL
[41]	J. Nan, J. Wu, Y. Deng, C.W. Nan, Solid State Commun. 124 (2002) 243-246. DOI URL
[42]	Y. Wang, Y. Sui, J. Cheng, X. Wang, J. Miao, Z. Liu, Z. Qian, W. Su, J. Alloys. Compd. 448 (2008) 1-5. DOI URL
[43]	J. Zhang, D. Wu, D. He, D. Feng, M. Yin, X. Qin, J. He, Adv. Mater. 29 (2017) 1703148. DOI URL
[44]	H. Wang, Z.M. Gibbs, Y. Takagiwa, G.J. Snyder, Energy Environ. Sci. 7 (2014) 804-811. DOI URL
[45]	J. Pei, G. Chen, N. Zhou, D.Q. Lu, F. Xiao, Physica B 406 (2011) 571-574. DOI URL
[46]	F. Zhang, Q. Lu, T. Li, X. Zhang, J. Zhang, X. Song, J. Rare Earths 31 (2013) 778-783. DOI URL
[47]	C. Boyle, P. Carvillo, Y. Chen, E.J. Barbero, D. Mcintyre, X. Song, J. Eur. Ceram. Soc. 36 (2016) 601-607.
[48]	W. Yang, H. Qian, J. Gan, W. Wei, Z. Wang, G. Tang, J. Electr. Mater. 45 (2016) 4171-4176. DOI URL
[49]	Y. Wang, Y. Sui, W. Su, J. Appl. Phys. 104 (2008) 093703.
[50]	Y. Wang, Y. Sui, F. Li, L. Xu, X. Wang, W. Sui, X. Liu, Nano Energy 1 (2012) 456-465. DOI URL
[51]	F.P. Zhang, X. Zhang, Q.M. Lu, J.X. Zhang, Y.Q. Liu, G.Z. Zhang, Solid State Ion. 201 (2011) 1-5. DOI URL
[52]	X. Shi, H. Kong, C.-P. Li, C. Uher, J. Yang, J.R. Salvador, H. Wang, L. Chen, W. Zhang, Appl. Phys. Lett. 92 (2008) 182101. DOI URL
[53]	M.E. Wieser, Pure Appl. Chem. Chem. 78 (2006) 2051-2066.
[54]	G. Saucke, S. Populoh, April, 1-5 2013, pp. 83-92.
[55]	J. Nan, J. Wu, Y. Deng, C.W. Nan, J. Eur. Ceram. Soc. 23 (2003) 859-863. DOI URL

Enhanced thermoelectric performance of spark plasma sintered p-type Ca_3-_xY_xCo₄O₉₊_δ systems

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