Issue

Vol. 17 (2025)

Defect Engineering with Rational Dopants Modulation for High-Temperature Energy Harvesting in Lead-Free Piezoceramics

https://doi.org/10.1007/s40820-024-01556-5
Kaibiao Xi
Key Laboratory of Advanced Functional Materials, Ministry of Education, College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, People’s Republic of China
Jianzhe Guo
Key Laboratory of Advanced Functional Materials, Ministry of Education, College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, People’s Republic of China
Mupeng Zheng
Key Laboratory of Advanced Functional Materials, Ministry of Education, College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, People’s Republic of China
Mankang Zhu
Key Laboratory of Advanced Functional Materials, Ministry of Education, College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, People’s Republic of China
Yudong Hou
Key Laboratory of Advanced Functional Materials, Ministry of Education, College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, People’s Republic of China

Corresponding Author: Yudong Hou

ydhou@bjut.edu.cn

Nano-Micro Letters, Vol. 17 (2025), Article Number: 55

Abstract

High temperature piezoelectric energy harvester (HT-PEH) is an important solution to replace chemical battery to achieve independent power supply of HT wireless sensors. However, simultaneously excellent performances, including high figure of merit (FOM), insulation resistivity (ρ) and depolarization temperature (Td) are indispensable but hard to achieve in lead-free piezoceramics, especially operating at 250 °C has not been reported before. Herein, well-balanced performances are achieved in BiFeO3–BaTiO3 ceramics via innovative defect engineering with respect to delicate manganese doping. Due to the synergistic effect of enhancing electrostrictive coefficient by polarization configuration optimization, regulating iron ion oxidation state by high valence manganese ion and stabilizing domain orientation by defect dipole, comprehensive excellent electrical performances (Td = 340 °C, ρ250 °C > 107 Ω cm and FOM250 °C = 4905 × 10–15 m2 N−1) are realized at the solid solubility limit of manganese ions. The HT-PEHs assembled using the rationally designed piezoceramic can allow for fast charging of commercial electrolytic capacitor at 250 °C with high energy conversion efficiency (η = 11.43%). These characteristics demonstrate that defect engineering tailored BF-BT can satisfy high-end HT-PEHs requirements, paving a new way in developing self-powered wireless sensors working in HT environments.


Highlights:
1 The solution limit of manganese ion in BiFeO3–BaTiO3 (BF–BT) was determined by combining multiple advanced characterization methods.
2 The defect engineering associated with fine doping can realize the co-modulation of polarization configuration, iron oxidation state and domain orientation.
3 The BF–BT–0.2Mn piezoelectric energy harvester shows excellent power generation capacity at 250 °C, which is an important breakthrough for lead-free piezoelectric devices.

Keywords

Lead-free piezoceramic Defect engineering Dopants modulation High-temperature Piezoelectric energy harvester
Xi, Kaibiao, Jianzhe Guo, Mupeng Zheng, Mankang Zhu, and Yudong Hou. 2024. “Defect Engineering With Rational Dopants Modulation for High-Temperature Energy Harvesting in Lead-Free Piezoceramics”. Nano-Micro Letters 17 (November):55. https://doi.org/10.1007/s40820-024-01556-5.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. N. Sezer, M. Koç, A comprehensive review on the state-of-the-art of piezoelectric energy harvesting. Nano Energy 80, 105567 (2021). https://doi.org/10.1016/j.nanoen.2020.105567
  2. J.Y. Park, T.A. Duong, S.S. Lee, C.W. Ahn, B.W. Kim et al., Effect of Li2CO3 doping on phase transition and piezoelectric properties of 0.96K0.5Na0.5NbO3–0.04SrTiO3 ceramics. J. Korean Inst. Electr. Electron. Mater. Eng. 36(5), 513–519 (2023). https://doi.org/10.4313/JKEM.2023.36.5.12
  3. Q. Xu, Z. Wang, J. Zhong, M. Yan, S. Zhao et al., Construction of flexible piezoceramic array with ultrahigh piezoelectricity via a hierarchical design strategy. Adv. Funct. Mater. 33(41), 2304402 (2023). https://doi.org/10.1002/adfm.202304402
  4. Z. Yu, J. Yang, J. Cao, L. Bian, Z. Li et al., A PMNN-PZT piezoceramic based magneto-mechano-electric coupled energy harvester. Adv. Funct. Mater. 32(25), 2111140 (2022). https://doi.org/10.1002/adfm.202111140
  5. S. An, X. Gao, M. Zheng, M. Zhang, P. Liu et al., Boosting power output performance of Ba0.85Ca0.15Snx Zr0.1-xTi0.9O3 piezoelectric nanogenerators via internal resistance regulation strategy. Nano Energy 123(123), 109420 (2024). https://doi.org/10.1016/j.nanoen.2024.109420
  6. X. Yu, S. Jiang, K. Xi, W. Xu, M. Zheng et al., Realizing excellent electromechanical coupling performance in BiScO3-Bi(Zn2/3Nb1/3)O3-PbTiO3 ternary high-temperature perovskite ceramics. J. Eur. Ceram. Soc. 44(8), 5001–5007 (2024). https://doi.org/10.1016/j.jeurceramsoc.2024.02.054
  7. H.Y. Zhao, Y.D. Hou, X.L. Yu, J. Fu, M.P. Zheng et al., A wide temperature insensitive piezoceramics for high-temperature energy harvesting. J. Am. Ceram. Soc. 102(9), 5316–5327 (2019). https://doi.org/10.1111/jace.16409
  8. H.Y. Zhao, Y.D. Hou, X.L. Yu, X.D. Liu, M.P. Zheng et al., Building high transduction coefficient BiScO3-PbTiO3 piezoceramic and its power generation characteristics. J. Electroceram. 43(1–4), 123–130 (2019). https://doi.org/10.1007/s10832-019-00180-9
  9. Y. Dong, Z. Zhou, R. Liang, X. Dong, Excellent piezoelectric constant and thermal stability in BiScO3–PbTiO3 piezoelectric ceramics via domain engineering. J. Materiomics 8(2), 319–326 (2022). https://doi.org/10.1016/j.jmat.2021.09.004
  10. Y.-C. Tang, Y. Yin, A.-Z. Song, H.-Z. Li, B.-P. Zhang, High-performance BiFeO3-BaTiO3 lead-free piezoceramics insensitive to off-stoichiometry and processing temperature. J. Materiomics 9(2), 353–361 (2023). https://doi.org/10.1016/j.jmat.2022.09.016
  11. D. Tai, B. Li, H. Xue, T. Zheng, J. Wu, BiFeO3-BaTiO3 ferroelectrics: Decrypting the mechanism of rare earth doping-induced electrical property discrepancy via scaling behavior and multi-level structure. Acta Mater. 262, 119411 (2024). https://doi.org/10.1016/j.actamat.2023.119411
  12. J. Lin, F. Lv, Z. Hong, B. Liu, Y. Wu et al., Ultrahigh piezoelectric response obtained by artificially generating a large internal bias field in BiFeO3–BaTiO3 lead-free ceramics. Adv. Funct. Mater. 1, 2313879 (2024). https://doi.org/10.1002/adfm.202313879
  13. Z. Yang, B. Wang, T. Brown, S.J. Milne, A. Feteira et al., Re-entrant relaxor ferroelectric behaviour in Nb-doped BiFeO3–BaTiO3 ceramics. J. Mater. Chem. C 11(6), 2186–2195 (2023). https://doi.org/10.1039/d2tc04702k
  14. F. Chen, B.Q. Zhao, K. Huang, X.F. Ma, H.Y. Li et al., Dual-defect engineering strategy enables high-durability rechargeable magnesium-metal batteries. Nano-Micro Lett. 16(1), 184 (2024). https://doi.org/10.1007/s40820-024-01410-8
  15. J. Guo, B. Tong, J. Jian, J. Chen, T. Zhou et al., Enhanced transduction coefficient in piezoelectric PZT ceramics by mixing powders calcined at different temperatures. J. Eur. Ceram. Soc. 40(8), 3348–3353 (2020). https://doi.org/10.1016/j.jeurceramsoc.2020.02.064
  16. F. Luo, Z. Li, J. Chen, Y. Yan, D. Zhang et al., High piezoelectric properties in 0.7BiFeO3–0.3BaTiO3 ceramics with MnO and MnO2 addition. J. Eur. Ceram. Soc. 42(3), 954–964 (2022). https://doi.org/10.1016/j.jeurceramsoc.2021.10.052
  17. B. Li, C. Li, T. Zheng, J. Wu, Property regulation principle in Mn-doped BF–BT ceramics: competitive control of domain switching by defect dipoles and domain configuration. Adv. Electron. Mater. 8(11), 2200609 (2022). https://doi.org/10.1002/aelm.202200609
  18. K. Xi, Y. Hou, X. Yu, M. Zheng, M. Zhu, Diffuse multiphase coexistence renders temperature-insensitive lead-free energy-harvesting piezoceramics. J. Mater. Chem. A 11(7), 3556–3564 (2023). https://doi.org/10.1039/d2ta08962a
  19. X. Yu, Y. Hou, M. Zheng, M. Zhu, Multiscale heterogeneity strategy in piezoceramics for enhanced energy harvesting performances. ACS Appl. Mater. Interfaces 13(15), 17800–17808 (2021). https://doi.org/10.1021/acsami.1c01409
  20. K. Xi, Y. Hou, M. Zheng, M. Zhu, Elastic polarization configuration coupled with activity rattling space boosts energy harvesting performance of lead-free piezoceramic. Adv. Funct. Mater. 1, 2401487 (2024). https://doi.org/10.1002/adfm.202401487
  21. Z. Jiang, R. Zhang, F. Li, L. Jin, N. Zhang et al., Electrostriction coefficient of ferroelectric materials from ab initio computation. AIP. Adv. 6(6), 065122 (2016). https://doi.org/10.1063/1.4954886
  22. L. Jin, J. Pang, Y. Pu, N. Xu, Y. Tian et al., Thermally stable electrostrains and composition-dependent electrostrictive coefficient Q33 in lead-free ferroelectric ceramics. Ceram. Int. 45(17), 22854–22861 (2019). https://doi.org/10.1016/j.ceramint.2019.07.328
  23. L. Zhang, R. Jing, Y. Huang, Q. Hu, D.O. Alikin et al., Ultrahigh electrostrictive effect in potassium sodium niobate-based lead-free ceramics. J. Eur. Ceram. Soc. 42(3), 944–953 (2022). https://doi.org/10.1016/j.jeurceramsoc.2021.11.037
  24. L. Yang, C. Chen, X. Jiang, X. Huang, X. Nie et al., Enhanced ferroelectric and piezoelectric properties of BiFeO3–BaTiO3 lead-free ceramics by simultaneous optimization of Bi compensation and sintering conditions. Ceram. Int. 48(9), 12866–12874 (2022). https://doi.org/10.1016/j.ceramint.2022.01.158
  25. Z. Li, H.C. Thong, Y.F. Zhang, Z. Xu, Z. Zhou et al., Defect engineering in lead zirconate titanate ferroelectric ceramic for enhanced electromechanical transducer efficiency. Adv. Funct. Mater. 31(1), 2005012 (2020). https://doi.org/10.1002/adfm.202005012
  26. Y. Sudo, M. Hagiwara, S. Fujihara, Grain size effect on electrical properties of Mn-modified 0.67BiFeO3–0.33BaTiO3 lead-free piezoelectric ceramics. Ceram. Int. 42(7), 8206–8211 (2016). https://doi.org/10.1016/j.ceramint.2016.02.030
  27. C. Li, T. Zheng, J. Wu, Competitive mechanism of temperature-dependent electrical properties in BiFeO3-BaTiO3 ferroelectrics controlled by domain evolution. Acta Mater. 206, 116601 (2021). https://doi.org/10.1016/j.actamat.2020.116601
  28. D.J. Kim, M.H. Lee, T.K. Song, Comparison of multi-valent manganese oxides (Mn4+, Mn3+, and Mn2+) doping in BiFeO3-BaTiO3 piezoelectric ceramics. J. Eur. Ceram. Soc. 39(15), 4697–4704 (2019). https://doi.org/10.1016/j.jeurceramsoc.2019.07.013
  29. H. Luo, S. Tang, H. Liu, Z. Sun, B. Gao et al., Revealing structure behavior behind the piezoelectric performance of prototype lead-free Bi0.5Na0.5TiO3-BaTiO3 under in-situ electric field. J. Materiomics 8(6), 1104–1112 (2022). https://doi.org/10.1016/j.jmat.2022.07.004
  30. H.-S. Ma, M.-K. Lee, B.-H. Kim, K.-H. Park, J.-J. Park et al., Role of oxygen vacancy defects in piezoelectric thermal stability characteristics of Mn-doped (K, Na, Li)NbO3 piezoceramics. Ceram. Int. 47(19), 27803–27815 (2021). https://doi.org/10.1016/j.ceramint.2021.06.207
  31. T. Wu, W. Zhang, F. Liu, Z. Dou, S. Han et al., Enhanced piezoelectric properties in BF-BT based lead-free ferroelectric ceramics for high-temperature devices. Ceram. Int. 49(2), 1820–1825 (2023). https://doi.org/10.1016/j.ceramint.2022.09.145
  32. S.O. Leontsev, R.E. Eitel, Dielectric and piezoelectric properties in Mn-modified (1–x)BiFeO3–xBaTiO3 ceramics. J. Am. Ceram. Soc. 92(12), 2957–2961 (2009). https://doi.org/10.1111/j.1551-2916.2009.03313.x
  33. L. Zhang, R. Jing, H. Du, Y. Huang, Q. Hu et al., Ultrahigh electrostrictive effect in lead-free ferroelectric ceramics via texture engineering. ACS Appl. Mater. Interfaces 15(43), 50265–50274 (2023). https://doi.org/10.1021/acsami.3c11432
  34. F. Zeng, J. Zhang, C. Zhou, L. Jiang, H. Guo et al., Enhanced electric field-induced strain properties in lead-free BF-BT-based piezoceramics by local structure inhomogeneity. ACS Sustain. Chem. Eng. 10(3), 1277–1286 (2022). https://doi.org/10.1021/acssuschemeng.1c07359
  35. B. Yang, Q. Zhang, H. Huang, H. Pan, W. Zhu et al., Engineering relaxors by entropy for high energy storage performance. Nat. Energy 8, 956–964 (2023). https://doi.org/10.1038/s41560-023-01300-0
  36. L. Chen, H. Yu, J. Wu, S. Deng, H. Liu et al., Large energy capacitive high-entropy lead-free ferroelectrics. Nano-Micro Lett. 15(1), 65–79 (2023). https://doi.org/10.1007/s40820-023-01036-2
  37. L. Zhao, Y. Hou, C. Wang, M. Zhu, H. Yan, The enhancement of relaxation of 0.5PZN-0.5PZT annealed in different atmospheres. Mater. Res. Bull. 44(8), 1652–1655 (2009). https://doi.org/10.1016/j.materresbull.2009.04.018
  38. X. Lv, X. Wang, Y. Ma, X.-X. Zhang, J. Wu, Temperature stability of perovskite-structured lead-free piezoceramics: evaluation methods, improvement strategies, and future perspectives. Mater. Sci. Eng. R. Rep. 159, 100793 (2024). https://doi.org/10.1016/j.mser.2024.100793
  39. D.Y. Hyeon, G.-J. Lee, S.-H. Lee, J.-J. Park, S. Kim et al., High-temperature workable flexible piezoelectric energy harvester comprising thermally stable (K,Na)NbO3-based ceramic and polyimide composites. Compos. Part. B-Eng. 234, 109671 (2022). https://doi.org/10.1016/j.compositesb.2022.109671
  40. Z. Zhu, L. Luo, F. Wang, P. Du, X. Zhou et al., Improved depolarization temperature via the ordered alignment of defect dipoles in (Na0.5Bi0.5)TiO3-BaTiO3 ceramics. J. Eur. Ceram. Soc. 40(3), 689–698 (2020). https://doi.org/10.1016/j.jeurceramsoc.2019.10.041
  41. Y. Yang, J. Zhao, Y. Li, H. Zhang, G. Wang et al., Defect engineering in barium titanate ferroelectric ceramic showing simultaneous enhancement of piezoelectric coefficient and mechanical quality factor. J. Eur. Ceram. Soc. 44(2), 891–897 (2024). https://doi.org/10.1016/j.jeurceramsoc.2023.09.034
  42. B. Li, T. Zheng, J. Wu, Structural disorder and oxygen octahedron evolution via defect engineering for properties enhancement in BF–BT ceramics. J. Am. Ceram. Soc. 107, 4789–4800 (2024). https://doi.org/10.1111/jace.19766
  43. X. Yan, M. Zheng, X. Gao, L. Li, J. Rödel et al., Ultrahigh energy harvesting performance in lead-free piezocomposites with intragranular structure. Acta Mater. 222, 117450 (2022). https://doi.org/10.1016/j.actamat.2021.117450
  44. W. Xu, Y. Hou, K. Xi, X. Yu, M. Zheng et al., Grain refinement and polarization enhancement synergistically triggered NBT-based piezoceramics enabling sustainable high power generation. J. Alloys Compd. 968, 172253 (2023). https://doi.org/10.1016/j.jallcom.2023.172253
  45. K. Xi, Y. Hou, X. Yu, M. Zheng, M. Zhu, Optimizing output power density in lead-free energy-harvesting piezoceramics with an entropy-increasing polymorphic phase transition structure. ACS Appl. Mater. Interfaces 15, 51330–52338 (2023). https://doi.org/10.1021/acsami.3c10426
  46. J. Guo, Y. Hou, K. Xi, X. Yu, M. Zheng et al., High-temperature stable power generation capacity of BF-BT-based piezoceramics with rationally modulated MPB structure. J. Alloys Compd. 990, 174438 (2024). https://doi.org/10.1016/j.jallcom.2024.174438
  47. X.D. Yan, M.P. Zheng, Y.D. Hou, M.K. Zhu, H. Yan, High energy conversion efficiency in Mn-modified Ba0.9Ca0.1Ti0.93Zr0.07O3 lead-free energy harvester. J. Am. Ceram. Soc. 101(6), 2330–2338 (2018). https://doi.org/10.1111/jace.15396
  48. A.E. Kubba, K. Jiang, Efficiency enhancement of a cantilever-based vibration energy harvester. Sensors (Basel) 14(1), 188–211 (2013). https://doi.org/10.3390/s140100188
  49. Y.C. Shu, I.C. Lien, Efficiency of energy conversion for a piezoelectric power harvesting system. J. Micromech. Microeng. 16(11), 2429–2438 (2006). https://doi.org/10.1088/0960-1317/16/11/026
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY FILE
Statistic
Read Counter : 659 Download : 492