Large Electrocaloric Responsivity and Energy Storage Response in the Lead-Free Ba(GexTi1−x)O3 Ceramics
Abstract
:1. Introduction
2. Experimental Section
3. Structural Studies
3.1. X-ray Studies
3.2. Raman Spectroscopy
3.3. Microstructure Analysis
4. Dielectric Measurements
5. Ferroelectricity and Electrocaloric Effect
5.1. Ferroelectric Properties
5.2. Indirect Electrocaloric Effect
5.3. Direct Electrocaloric Measurement
6. Energy Storage Investigations
7. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
- Moya, X.; Kar-Narayan, S.; Mathur, N.D. Caloric materials near ferroic phase transitions. Nat. Mater. 2014, 13, 439–450. [Google Scholar] [CrossRef] [PubMed]
- Kaddoussi, H.; Gagou, Y.; Lahmar, A.; Allouche, B.; Dellis, J.L.; Courty, M.; Khemakhem, H.; El Marssi, M. Ferroelectric phase changes and electrocaloric effects in Ba(Zr0.1Ti0.9)1−xSnxO3 ceramics solid solution. J. Mater. Sci. 2016, 51, 3454–3462. [Google Scholar] [CrossRef]
- Ben Moumen, S.; Gagou, Y.; Chettab, M.; Mezzane, D.; Amjoud, M.; Fourcade, S.; Hajji, L.; Kutnjak, Z.; El Marssi, M.; El Amraoui, Y.; et al. Synthesis of La0.5Ca0.5−x□xMnO3 nanocrystalline manganites by sucrose assisted auto combustion route and study of their structural, magnetic and magnetocaloric properties. J. Mater. Sci. Mater. Electron. 2019, 30, 20459–20470. [Google Scholar] [CrossRef] [Green Version]
- Bai, Y.; Han, X.; Qiao, L. Optimized electrocaloric refrigeration capacity in lead-free (1−x)BaZr0.2Ti0.8O3-xBa0.7Ca0.3TiO3 ceramics. Appl. Phys. Lett. 2013, 102, 252904. [Google Scholar] [CrossRef]
- Chukka, R.; Vandrangi, S.; Shannigrahi, S.; Chen, L. An electrocaloric device demonstrator for solid-state cooling. Eur. Lett. 2013, 103, 47011. [Google Scholar] [CrossRef]
- Novak, N.; Kutnjak, Z.; Pirc, R. High-resolution electrocaloric and heat capacity measurements in barium titanate. Eur. Lett. 2013, 103, 47001. [Google Scholar] [CrossRef]
- Bai, Y.; Zheng, G.; Shi, S. Direct measurement of giant electrocaloric effect in BaTiO3 multilayer thick film structure beyond theoretical prediction. Appl. Phys. Lett. 2010, 96, 192902. [Google Scholar] [CrossRef] [Green Version]
- Aprea, C.; Greco, A.; Maiorino, A.; Masselli, C. Electrocaloric refrigeration: An innovative, emerging, eco-friendly refrigeration technique. J. Physics Conf. Ser. 2017, 796, 12019. [Google Scholar] [CrossRef]
- Kutnjak, Z.; Rožič, B.; Pirc, R. Electrocaloric Effect: Theory, Measurements, and Applications. In Wiley Encyclopedia of Electrical and Electronics Engineering; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2015; pp. 1–19. [Google Scholar] [CrossRef] [Green Version]
- Correia, T.; Zhang, Q. (Eds.) Electrocaloric Materials: New Generation of Coolers, 1st ed.; Springer: Berlin/Heidelberg, Germany, 2014. [Google Scholar] [CrossRef]
- Suchaneck, G.; Gerlach, G. Lead-free Relaxor Ferroelectrics for Electrocaloric Cooling. Mater. Today: Proc. 2016, 3, 622–631. [Google Scholar] [CrossRef]
- Lu, S.-G.; Zhang, Q.M.; Kutnjak, Z. The electrocaloric effect (ECE) in ferroelectric polymer films. In Thin Film Growth; Elsevier: Amsterdam, The Netherlands, 2011; pp. 364–383. [Google Scholar] [CrossRef] [Green Version]
- Mischenko, A.S.; Zhang, Q.; Scott, J.F.; Whatmore, R.W.; Mathur, N.D. Giant Electrocaloric Effect in Thin-Film PbZr0.95Ti0.05O3. Science 2006, 311, 1270–1271. [Google Scholar] [CrossRef] [Green Version]
- Cao, H.-X.; Li, Z.-Y. Electrocaloric effect in BaTiO3 thin films. J. Appl. Phys. 2009, 106, 94104. [Google Scholar] [CrossRef]
- Valant, M. Electrocaloric materials for future solid-state refrigeration technologies. Prog. Mater. Sci. 2012, 57, 980–1009. [Google Scholar] [CrossRef]
- Lidsky, T.I.; Schneider, J.S. Lead neurotoxicity in children: Basic mechanisms and clinical correlates. Brain 2003, 126, 5–19. [Google Scholar] [CrossRef] [PubMed]
- Meng, Y.; Tang, C.; Yu, J.; Meng, S.; Zhang, W. Exposure to lead increases the risk of meningioma and brain cancer: A meta-analysis. J. Trace Elem. Med. Biol. 2020, 60, 126474. [Google Scholar] [CrossRef]
- Li, W.-B.; Zhou, D.; Xu, R.; Wang, D.-W.; Su, J.-Z.; Pang, L.-X.; Liu, W.-F.; Chen, G.-H. BaTiO3-Based Multilayers with Outstanding Energy Storage Performance for High Temperature Capacitor Applications. ACS Appl. Energy Mater. 2019, 2, 5499–5506. [Google Scholar] [CrossRef]
- Mahmoud, A.; Moen, S.; Gerges, M.K. Enhanced Tunability Properties of Pure (Ba,Sr)TiO3 Lead free Ferroelectric by Polar Nano-region Contributions. Res. Sq. 2021. preprint. [Google Scholar] [CrossRef]
- Asbani, B.; Gagou, Y.; Trček, M.; Dellis, J.-L.; Amjoud, M.; Lahmar, A.; Mezzane, D.; Kutnjak, Z.; El Marssi, M. Dielectric permittivity enhancement and large electrocaloric effect in the lead free (Ba0.8Ca0.2)1-xLa2x/3TiO3 ferroelectric ceramics. J. Alloys Compd. 2018, 730, 501–508. [Google Scholar] [CrossRef]
- Horchidan, N.; Curecheriu, L.; Ciomaga, C.E.; Lupu, N.; Mitoseriu, L. Preparation and Functional Properties of BaTiO3–BaGeO3 Ceramics. IEEE Trans. Ultrason. Ferroelectr. Freq. Control 2021, 68, 279–287. [Google Scholar] [CrossRef] [PubMed]
- Garbarz-Glos, B.; Lisińska-Czekaj, A.; Czekaj, D.; Bąk, W. Effect of Semiconductor Element Substitution on the Electric Properties of Barium Titanate Ceramics. Arch. Met. Mater. 2016, 61, 887–890. [Google Scholar] [CrossRef]
- Köferstein, R.; Ebbinghaus, S.G. BaGeO3 as sintering additive for BaTiO3–MgFe2O4 composite ceramics. RSC Adv. 2015, 5, 71491–71499. [Google Scholar] [CrossRef] [Green Version]
- Chu, M.S.-H.; Bultitude, J.; Hood, C.; Nimmo, K.L.; Rand, M. Temperature Stable Dielectric. EU Patent No. EP 0,731,066,A1, 1996. [Google Scholar]
- Köferstein, R.; Jäger, L.; Zenkner, M.; Müller, T.; Abicht, H.-P. Shrinkage mechanism and phase evolution of fine-grain BaTiO3 powder compacts containing 10 mol% BaGeO3 prepared via a precursor route. Mater. Chem. Phys. 2008, 112, 531–535. [Google Scholar] [CrossRef] [Green Version]
- Guha, J.P.; Kolar, D. Phase equilibria in the system BaTiO3-BaGeO3. J. Mater. Sci. 1972, 7, 1192–1196. [Google Scholar] [CrossRef]
- Plessner, K.W.; West, R. Replacement of Ti in BaTiO3 Ceramic by Si and Ge. Proc. Phys. Soc. Sect. B 1955, 68, 1150–1152. [Google Scholar] [CrossRef]
- Pulvari, C.F. Effect of Impurities on Electrical Solid-state Properties of Barium Titanate. J. Am. Ceram. Soc. 1959, 42, 355–363. [Google Scholar] [CrossRef]
- Baxter, P.; Hellicar, N.J.; Lewis, B. Effect of Additives of Limited Solid Solubility on Ferroelectric Properties of Barium Titanate Ceramics. J. Am. Ceram. Soc. 1959, 42, 465–470. [Google Scholar] [CrossRef]
- Bai, Y.; Zheng, G.-P.; Shi, S.-Q. Abnormal electrocaloric effect of Na0.5Bi0.5TiO3–BaTiO3 lead-free ferroelectric ceramics above room temperature. Mater. Res. Bull. 2011, 46, 1866–1869. [Google Scholar] [CrossRef]
- Liu, H.; Yang, X. Theoretical prediction of electrocaloric effect based on non-linear behaviors of dielectric permittivity under temperature and electric fields. AIP Adv. 2015, 5, 117134. [Google Scholar] [CrossRef] [Green Version]
- Sanlialp, M.; Luo, Z.; Shvartsman, V.V.; Wei, X.; Liu, Y.; Dkhil, B.; Lupascu, D.C. Direct measurement of electrocaloric effect in lead-free Ba(SnxTi1−x)O3 ceramics. Appl. Phys. Lett. 2017, 111, 173903. [Google Scholar] [CrossRef] [Green Version]
- Singh, G.; Bhaumik, I.; Ganesamoorthy, S.; Bhatt, R.; Karnal, A.K.; Tiwari, V.S.; Gupta, P.K. Electro-caloric effect in 0.45BaZr0.2Ti0.8O3-0.55Ba0.7Ca0.3TiO3 single crystal. Appl. Phys. Lett. 2013, 102, 82902. [Google Scholar] [CrossRef]
- Asbani, B.; Dellis, J.-L.; Lahmar, A.; Courty, M.; Amjoud, M.; Gagou, Y.; Djellab, K.; Mezzane, D.; Kutnjak, Z.; El Marssi, M. Lead-free Ba0.8Ca0.2(ZrxTi1−x)O3 ceramics with large electrocaloric effect. Appl. Phys. Lett. 2015, 106, 42902. [Google Scholar] [CrossRef]
- Kaddoussi, H.; Lahmar, A.; Gagou, Y.; Dellis, J.-L.; Khemakhem, H.; El Marssi, M. Electro-caloric effect in lead-free ferroelectric Ba1−Ca (Zr0.1Ti0.9)0.925 Sn0.075O3 ceramics. Ceram. Int. 2015, 41, 15103–15110. [Google Scholar] [CrossRef]
- Wang, J.; Yang, T.; Chen, S.; Li, G.; Zhang, Q.; Yao, X. Nonadiabatic direct measurement electrocaloric effect in lead-free Ba,Ca(Zr,Ti)O3 ceramics. J. Alloy. Compd. 2013, 550, 561–563. [Google Scholar] [CrossRef]
- Liu, X.Q.; Chen, T.T.; Wu, Y.J.; Chen, X.M. Enhanced Electrocaloric Effects in Spark Plasma-Sintered Ba0.65Sr0.35TiO3-Based Ceramics at Room Temperature. J. Am. Ceram. Soc. 2013, 96, 1021–1023. [Google Scholar] [CrossRef]
- Rietveld, H.M. A profile refinement method for nuclear and magnetic structures. J. Appl. Crystallogr. 1969, 2, 65–71. [Google Scholar] [CrossRef]
- Shannon, R.D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr. Sect. A 1976, 32, 751–767. [Google Scholar] [CrossRef]
- Parsons, J.; Rimai, L. Raman spectrum of BaTiO3. Solid State Commun. 1967, 5, 423–427. [Google Scholar] [CrossRef]
- Pinczuk, A.; Taylor, W.; Burstein, E.; Lefkowitz, I. The Raman spectrum of BaTiO3. Solid State Commun. 1967, 5, 429–433. [Google Scholar] [CrossRef]
- Venkateswaran, U.D.; Naik, V.M.; Naik, R.R. High-pressure Raman studies of polycrystalline BaTiO3. Phys. Rev. B 1998, 58, 14256–14260. [Google Scholar] [CrossRef]
- DiDomenico, M.; Wemple, S.H.; Porto, S.P.S.; Bauman, R.P. Raman Spectrum of Single-Domain BaTiO3. Phys. Rev. 1968, 174, 522–530. [Google Scholar] [CrossRef]
- Wei, A.N.; Liu, T.-H.; Wang, C.-H.; Diao, C.-L.; Luo, N.-N.; Liu, Y.; Qi, Z.-M.; Shao, T.; Wang, Y.-Y.; Jiao, H.; et al. Assignment for Vibrational Spectra of BaTiO3 Ferroelectric Ceramic Based on the First-Principles Calculation. Acta Physico-Chim. Sin. 2015, 31, 1059–1068. [Google Scholar] [CrossRef]
- Pokorný, J.; Pasha, U.M.; Ben, L.; Thakur, O.P.; Sinclair, D.C.; Reaney, I.M. Use of Raman spectroscopy to determine the site occupancy of dopants in BaTiO3. J. Appl. Phys. 2011, 109, 114110. [Google Scholar] [CrossRef]
- Zhao, N.; Fan, H.; Li, C.; Huang, F.; Cao, J.; Li, Z. Enhanced energy storage density and efficiency in Sm3+-doped ((Bi0.5Na0.5)0.7(Sr0.7Bi0.2)0.3))TiO3 ceramics. J. Mater. Sci. Mater. Electron. 2021, 32, 24930–24938. [Google Scholar] [CrossRef]
- Mezzourh, H.; Belkhadir, S.; Mezzane, D.; Amjoud, M.; Choukri, E.; Lahmar, A.; Gagou, Y.; Kutnjak, Z.; El Marssi, M. Enhancing the dielectric, electrocaloric and energy storage properties of lead-free Ba0.85Ca0.15Zr0.1Ti0.9O3 ceramics prepared via sol-gel process. Phys. B Condens. Matter. 2021, 603, 412760. [Google Scholar] [CrossRef]
- Hanani, Z.; Mezzane, D.; Amjoud, M.; Razumnaya, A.G.; Fourcade, S.; Gagou, Y.; Hoummada, K.; El Marssi, M.; Gouné, M. Phase transitions, energy storage performances and electrocaloric effect of the lead-free Ba0.85Ca0.15Zr0.10Ti0.90O3 ceramic relaxor. J. Mater. Sci. Mater. Electron. 2019, 30, 6430–6438. [Google Scholar] [CrossRef] [Green Version]
- Veerapandiyan, V.; Benes, F.; Gindel, T.; DeLuca, M. Strategies to Improve the Energy Storage Properties of Perovskite Lead-Free Relaxor Ferroelectrics: A Review. Materials 2020, 13, 5742. [Google Scholar] [CrossRef]
Atoms | Atomic Positions | Compositions | ||||
---|---|---|---|---|---|---|
0.02 | 0.03 | 0.05 | 0.06 | 0.09 | ||
Ba | x | 0 | 0 | 0 | 0 | 0 |
y | 0 | 0 | 0 | 0 | 0 | |
z | −0.0422 (4) | 0.1827 (5) | −0.0293 (8) | 0.3342 (4) | 0.1724 (2) | |
Occ. | 1 | 1 | 1 | 1 | 1 | |
Biso | 1.664 | 0.795 | 0.586 | 1.074 | 1.581 | |
Ti | x | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
y | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |
z | 0.4798 (5) | 0.6677 (3) | 0.4874 (5) | 0.8681 (3) | 0.7117 (2) | |
Occ. | 0.98 | 0.97 | 0.95 | 0.94 | 0.91 | |
Biso | 2.1 | 1.272 | 1.218 | 1.433 | 1.874 | |
Ge | x | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
y | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |
z | 0.4798 (5) | 0.6677 (3) | 0.4874 (5) | 0.8681 (3) | 0.7117 (2) | |
Occ. | 0.02 | 0.03 | 0.05 | 0.06 | 0.09 | |
Biso | 2.1 | 1.272 | 1.218 | 1.433 | 1.874 | |
O1 | x | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
y | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |
z | −0.0481 (3) | 0.1413 (8) | −0.0068 (2) | 0.2753 (7) | 0.0853 (1) | |
Occ. | 1 | 1 | 0.9421 | 1 | 1 | |
Biso | 3.331 | 2.675 | 1 | 2.018 | 3.798 | |
O2 | x | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
y | 0 | 0 | 0 | 0 | 0 | |
z | 0.5064 (2) | 0.7333 (5) | 0.5447 (6) | 0.7720 (2) | 0.7306 (7) | |
Occ. | 1 | 1 | 0.98 | 1 | 1 | |
Biso | 1.974 | 0.222 | 2.982 | 0.438 | 3.034 | |
Symmetry Group | P4mm | P4mm | P4mm | P4mm | P4mm | |
Unit cell parameters | a(Å) | 3.9955 (9) | 3.9949 (3) | 3.9945 (6) | 3.9941 (7) | 3.9905 (5) |
c(Å) | 4.0364 (6) | 4.0350 (5) | 4.0358 (3) | 4.0324 (5) | 4.0309 (5) | |
Unit cell Volume V (Å3) | 64.4371 (7) | 64.3954 (8) | 64.3953 (5) | 64.3282 (1) | 64.1884 (2) | |
Nb Refined param. | 45 | 33 | 37 | 38 | 34 | |
Grain size (µm) | 3.63 | 5.45 | 10.90 | 8.32 | 18.77 | |
Theoretical Density (g/cm3) | 6.067 | 6.052 | 6.045 | 6.041 | 6.049 | |
Calculated Density (g/cm3) | 5.801 | 5.785 | 5.645 | 5.035 | 5.648 | |
Relative Density (%) | 96 | 95 | 93 | 83 | 93 | |
χ2 | 2.85 | 2.1 | 2.14 | 2.5 | 3.72 | |
Rwp | 5.57 | 3.84 | 3.07 | 3.18 | 4.62 | |
RP | 4.23 | 2.71 | 2.21 | 2.14 | 3.19 | |
RBragg | 4.64 | 6.54 | 5.26 | 3.37 | 3.5 | |
Ti-O1 (c-axis) | 1.8278 (7) | 1.7198 (8) | 1.9947 (7) | 2.0302 (3) | 1.8998 (6) | |
Ti-O2 (c-axis) | 2.2086 (6) | 2.3151 (0) | 2.0410 (2) | 2.0023 (4) | 2.1311 (3) | |
Goldschmidt factor | 0.9929 | 0.9932 | 0.9940 | 0.9944 | 0.9956 | |
Curie C (×105 K) | 3.78 | 3.42 | 3.87 | 3.40 | 3.44 | |
T0 (K) ± 1.00 K | 372.11 | 353.79 | 359.13 | 348.63 | 354.40 | |
TC (K) ± 0.12 K | 400.83 | 399.40 | 400.10 | 399.73 | 399.53 |
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Asbani, B.; Gagou, Y.; Ben Moumen, S.; Dellis, J.-L.; Lahmar, A.; Amjoud, M.; Mezzane, D.; El Marssi, M.; Rozic, B.; Kutnjak, Z. Large Electrocaloric Responsivity and Energy Storage Response in the Lead-Free Ba(GexTi1−x)O3 Ceramics. Materials 2022, 15, 5227. https://doi.org/10.3390/ma15155227
Asbani B, Gagou Y, Ben Moumen S, Dellis J-L, Lahmar A, Amjoud M, Mezzane D, El Marssi M, Rozic B, Kutnjak Z. Large Electrocaloric Responsivity and Energy Storage Response in the Lead-Free Ba(GexTi1−x)O3 Ceramics. Materials. 2022; 15(15):5227. https://doi.org/10.3390/ma15155227
Chicago/Turabian StyleAsbani, Bouchra, Yaovi Gagou, Said Ben Moumen, Jean-Luc Dellis, Abdelilah Lahmar, M’Barek Amjoud, Daoud Mezzane, Mimoun El Marssi, Brigita Rozic, and Zdravko Kutnjak. 2022. "Large Electrocaloric Responsivity and Energy Storage Response in the Lead-Free Ba(GexTi1−x)O3 Ceramics" Materials 15, no. 15: 5227. https://doi.org/10.3390/ma15155227