PDF (20.3 MB)
Collect
Submit Manuscript
Research Article | Open Access | Online First

MnO2 doping induced structural tuning drives superior piezoelectric response in CaBi4Ti4O15-based ceramics

Qilai Wen1,2,3,Huan-Huan Guo1,2,3,Zong-Yang Shen1,2,3()Zhumei Wang1,2,3Tao Zeng1,2,4Wenqin Luo1,2,3Fusheng Song1,2,4
Jiangxi Key Laboratory of Advanced Ceramic Materials, Jingdezhen 333403, China
China National Light Industry Key Laboratory of Functional Ceramic Materials, Jingdezhen 333403, China
School of Materials Science and Engineering, Jingdezhen Ceramic University, Jingdezhen 333403, China
National Engineering Research Center for Domestic & Building Ceramics, Jingdezhen 333403, China

Qilai Wen and Huan-Huan Guo contributed equally to this work.

Show Author Information

Graphical Abstract

View original image Download original image

Abstract

Composition optimization and domain engineering modulation with diverse elements and structural tuning are favorable pathways that can be implemented to increase piezoelectric properties. Here, CaBi4Ti3.89(W1/2Co1/2)0.11O15+x wt%MnO2 (CBTWC–xMn, x = 0–0.25) ceramics with superior piezoelectric responses were prepared via a solid-state sintering method. The mechanism of the high piezoresponse was examined by integrating visual crystal structure analysis with piezoresponse force microscopy, revealing that the introduction of MnO2 led to greater distortion of the [TiO6] octahedron and a more oriented domain structure, both of which are critical factors contributing to the enhanced piezoelectric response. The optimized CBTWC–0.1Mn ceramics achieved an ultrahigh piezoelectric constant (d33 = 27.3 pC/N), which was 50% greater than that of the pure CBTWC ceramics. Furthermore, the CBTWC–0.1Mn ceramics exhibited better ferroelectric properties, a high Curie temperature (TC = 754.7 °C), low dielectric loss (tanδ = 6.7% at 500 °C), and excellent thermal stability, and their d33 (26.3 pC/N) maintained over 95% of its initial value after annealing at 500 °C. This work provides a feasible strategy for improving the properties of bismuth layer-structured piezoelectric ceramics, which has important prospects for the application of high-temperature piezoelectric devices.

Electronic Supplementary Material

Download File(s)
JAC1051_ESM.pdf (431.3 KB)

References

[1]

Li GH, Wang Q, Chen JN, et al. Spark plasma sintering of sodium bismuth niobate that exhibits superior piezoelectric performance. J Am Ceram Soc 2024, 107: 7364–7372.

[2]

Chen JN, Wang Q, Zhao X, et al. Significantly enhanced DC electrical resistivity and piezoelectric properties of Tb-modified CaBi2Nb2O9 ceramics for high-temperature piezoelectric applications. J Am Ceram Soc 2022, 105: 4815–4826.

[3]

Xie SX, Xu Q, Chen Q, et al. Realizing super-high piezoelectricity and excellent fatigue resistance in domain-engineered bismuth titanate ferroelectrics. Adv Funct Mater 2024, 34: 2312645.

[4]
Wang CL, Hou LM, Huan Y. Study on the structure and properties of (1−x)KNNS–xBFANZ lead-free piezoelectric ceramics. Adv Ceram 2023, 44 : 490–496. (in Chinese)
[5]

Saito Y, Takao H, Tani T, et al. Lead-free piezoceramics. Nature 2004, 432: 84–87.

[6]

Wu JG, Xiao DQ, Zhu JG. Potassium-sodium niobate lead-free piezoelectric materials: Past, present, and future of phase boundaries. Chem Rev 2015, 115: 2559–2595.

[7]

Subbarao EC. Crystal chemistry of mixed bismuth oxides with layer-type structure. J Am Ceram Soc 1962, 45: 166–169.

[8]

Newnham RE, Wolfe RW, Dorrian JF. Structural basis of ferroelectricity in the bismuth titanate family. Mater Res Bull 1971, 6: 1029–1039.

[9]

Luo XG, Yan ZN, Luo H, et al. Greatly improved piezoelectricity and thermal stability of (Na,Sm) co-doped CaBi2Nb2O9 ceramics. Adv Powder Mater 2023, 2: 100116.

[10]

Luo XG, Wang MS, Yuan X, et al. Piezoelectricity in excess of 30 pC N−1 with a high Curie temperature of 950 °C in strongly textured CaBi2Nb2O9 ceramics. J Mater Chem A 2025, 13: 2121–2130.

[11]

Li XD, Chen ZN, Sheng LS, et al. Large enhancement of piezoelectric properties and resistivity in Cu/Ta co-doped Bi4Ti3O12 high-temperature piezoceramics. J Am Ceram Soc 2019, 102: 7366–7375.

[12]

Zhao TL, Wang CM, Wang CL, et al. Enhanced piezoelectric properties and excellent thermal stabilities of cobalt-modified Aurivillius-type calcium bismuth titanate (CaBi4Ti4O15). Mater Sci Eng B 2015, 201: 51–56.

[13]

Shen ZY, Luo WQ, Tang YX, et al. Microstructure and electrical properties of Nb and Mn co-doped CaBi4Ti4O15 high temperature piezoceramics obtained by two-step sintering. Ceram Int 2016, 42: 7868–7872.

[14]

Shen ZY, Sun HJ, Tang YX, et al. Enhanced piezoelectric properties of Nb and Mn co-doped CaBi4Ti4O15 high temperature piezoceramics. Mater Res Bull 2015, 63: 129–133.

[15]

Shen ZY, Qin C, Luo WQ, et al. Ce and W co-doped CaBi2Nb2O9 with enhanced piezoelectric constant and electrical resistivity at high temperature. J Materiomics 2020, 6: 459–466.

[16]

Xi JW, Chen H, Tan Z, et al. Origin of high piezoelectricity in CBT-based aurivillius ferroelectrics: Glide of (Bi2O2)2+ blocks and suppressed internal bias field. Acta Mater 2022, 237: 118146.

[17]

Yan HX, Zhang Z, Zhu WM, et al. The effect of (Li,Ce) and (K,Ce) doping in Aurivillius phase material CaBi4Ti4O15. Mater Res Bull 2004, 39: 1237–1246.

[18]

Long CB, Chang Q, Wu Y, et al. New layer-structured ferroelectric polycrystalline materials, Na0.5Nd x Bi4.5− x Ti4O15: Crystal structures, electrical properties and conduction behaviors. J Mater Chem C 2015, 3: 8852–8864.

[19]

Hu ZM, Koval V, Zhang HF, et al. Enhanced piezoelectricity in Na and Ce co-doped CaBi4Ti4O15 ceramics for high-temperature applications. J Adv Ceram 2023, 12: 1331–1344.

[20]
Yan HX, Li CG, Zhou JG, et al. A-site (MCe) substitution effects on the structures and properties of CaBi4Ti4O15 ceramics. Jpn J Appl Phys 2000, 39 : 6339.
[21]

Liu Y, Huang PM, Zhang YH, et al. Improved electrical properties in Nb/Fe co-modified CaBi4Ti4O15 high-temperature piezoceramics. Mater Res Express 2019, 6: 126334.

[22]

Li LL, Yuan HB, Huang PM, et al. Enhanced piezoelectricity and excellent thermal stabilities in Nb–Mg co-doped CaBi4Ti4O15 Aurivillius high Curie temperature ceramics. Ceram Int 2020, 46: 2178–2184.

[23]

Liu Y, Zhang YH, Zhu LL, et al. Enhanced piezoelectric activity with good thermal stability and improved electrical resistivity in Ta–Mn co-doped CaBi4Ti4O15 high-temperature piezoceramics. Ceram Int 2020, 46: 22532–22538.

[24]

Wang F, Li X, Xu Q, et al. Simultaneous enhancement of electrical and mechanical properties in CaBi2Nb2O9-based ceramics. J Eur Ceram Soc 2022, 42: 4196–4211.

[25]

Chen ZR, Hao YS, Huang J, et al. Poling above the Curie temperature driven large enhancement in piezoelectric performance of Mn doped PZT-based piezoceramics. Nano Energy 2023, 113: 108546.

[26]

Jabeen N, Hussain A, Nawaz S, et al. Thermally stable piezoelectric performance of MnO2 inserted pseudo-tetragonal phase existent CaBi2Nb2O9-based ceramics. Mater Technol 2022, 37: 2702–2710.

[27]

Nibou L, Aftati A, El Farissi M, et al. Chemical fabrication SrBi4Ti4O15 thin films. J Eur Ceram Soc 1999, 19: 1383–1386.

[28]

Liu Y, Yu Y, Yin CY, et al. Achieving remarkable piezoelectric activity in Sb–Mn co-modified CaBi4Ti4O15 piezoelectric ceramics. Trans Nonferrous Met Soc China 2021, 31: 2442–2453.

[29]

Xi JW, Xing J, Chen H, et al. Crystal structure and electrical properties of Li/Mn co-doped NBT-based Aurivillius-type ceramics. J Alloys Compd 2021, 868: 159216.

[30]
Toby BH, Von Dreele RB. GSAS-II: The genesis of a modern open-source all purpose crystallography software package. J Appl Cryst 2013, 46 : 544–549.
[31]

Tellier J, Boullay P, Manier M, et al. A comparative study of the Aurivillius phase ferroelectrics CaBi4Ti4O15 and BaBi4Ti4O15. J Solid State Chem 2004, 177: 1829–1837.

[32]

Xie XC, Zhou ZY, Liang RH, et al. Significantly enhanced piezoelectric performance in Bi4Ti3O12-based high-temperature piezoceramics via oxygen vacancy defects tailoring. J Materiomics 2021, 7: 59–68.

[33]

Li GR, Zheng LY, Yin QR, et al. Microstructure and ferroelectric properties of MnO2-doped bismuth-layer (Ca,Sr)Bi4Ti4O15 ceramics. J Appl Phys 2005, 98: 064108.

[34]

Shannon RD. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr Sect A 1976, 32: 751–767.

[35]

Xu JG, Xie SX, Xu Q, et al. Significantly enhanced performance and conductivity mechanism in Nb/Mn co-doped CaBi4Ti4O15 ferroelectrics. J Materiomics 2024, 10: 652–669.

[36]

Xu Q, Xie SX, Wang F, et al. Bismuth titanate based piezoceramics: Structural evolutions and electrical behaviors at different sintering temperatures. J Alloys Compd 2021, 882: 160637.

[37]

Osada M, Tada M, Kakihana M, et al. Cation distribution and structural instability in Bi4− x La x Ti3O12. Jpn J Appl Phys 2001, 40: 5572.

[38]

Tanwar A, Sreenivas K, Gupta V. Effect of orthorhombic distortion on dielectric and piezoelectric properties of CaBi4Ti4O15 ceramics. J Appl Phys 2009, 105: 084105.

[39]

Zhu J, Chen XB, Zhang ZP, et al. Raman and X-ray photoelectron scattering study of lanthanum-doped strontium bismuth titanate. Acta Mater 2005, 53: 3155–3162.

[40]

He XH, Wang B, Fu XY, et al. Structural, electrical and piezoelectric properties of V-, Nb- and W-substituted CaBi4Ti4O15 ceramics. J Mater Sci Mater El 2014, 25: 3396–3402.

[41]

Ding YQ, Li P, He JT, et al. Simultaneously achieving high energy-storage efficiency and density in Bi-modified SrTiO3-based relaxor ferroelectrics by ion selective engineering. Compos Part B Eng 2022, 230: 109493.

[42]

Zhu RF, Fang BJ, Zhao XY, et al. Ferroelectric phase transition and electrical properties of high- TC PMN–PH–PT ceramics prepared by partial oxalate route. J Eur Ceram Soc 2018, 38: 1463–1472.

[43]

Zhang SJ, Kim N, Shrout TR, et al. High temperature properties of manganese modified CaBi4Ti4O15 ferroelectric ceramics. Solid State Commun 2006, 140: 154–158.

[44]

Hu ZM, Koval V, Yue YJ, et al. Structural evolution and coexistence of ferroelectricity and antiferromagnetism in Fe,Nb co-doped BaTiO3 ceramics. J Eur Ceram Soc 2023, 43: 2460–2468.

[45]

Jiang ZH, Yang HC, Cao L, et al. Enhanced breakdown strength and energy storage density of lead-free Bi0.5Na0.5TiO3- based ceramic by reducing the oxygen vacancy concentration. Chem Eng J 2021, 414: 128921.

[46]
Wu ZC, Shen ZY, Song FS, et al. Effect of A-site Ce doping on electrical properties of CaBi4Ti4O15 bismuth layered high-curie-temperature piezoelectric ceramics. J Ceram 2022, 43 : 296–301. (in Chinese)
[47]

Zhang LN, Zhao SC, Yu HF, et al. Microstructure and electrical properties of tungsten-doped bismuth titanate ceramics. Jpn J Appl Phys 2004, 43: 7613–7617.

[48]

Xue MP, Tang YC, Shan ZH, et al. Deciphering the leakage conduction mechanism of BiFeO3–BaTiO3 lead-free piezoelectric ceramics. J Adv Ceram 2023, 12: 1844–1856.

[49]

Shulman HS, Testorf M, Damjanovic D, et al. Microstructure, electrical conductivity, and piezoelectric properties of bismuth titanate. J Am Ceram Soc 1996, 79: 3124–3128.

[50]

Zhang FF, Shi W, Guan SY, et al. Enhanced electrical properties and thermal stability of W/Cr co-doped BIT-based high‐temperature piezoelectric ceramics. J Alloys Compd 2022, 907: 164492.

[51]

Zhu W, Shen ZY. Optimizing dielectric energy storage properties of BNT-based relaxor ferroelectric ceramics modified via Ba0.4Sr0.6TiO3. J Mater Sci 2024, 59: 2998–3008.

[52]

Chen XY, Ma ZQ, Li B, et al. Enhanced piezoelectric performance of Cr/Ta non-equivalent co-doped Bi4Ti3O12-based high-temperature piezoceramics. J Adv Ceram 2024, 13: 263–271.

[53]

Qi H, Xie AW, Zuo RZ. Local structure engineered lead-free ferroic dielectrics for superior energy-storage capacitors: A review. Energy Storage Mater 2022, 45: 541–567.

[54]

Yang ZT, Gao F, Du HL, et al. Grain size engineered lead-free ceramics with both large energy storage density and ultrahigh mechanical properties. Nano Energy 2019, 58: 768–777.

[55]

Qiao Y, Wang LL, Zhang DY, et al. Effects of heterovalent ions doping-induced oxygen octahedral distortion and defect chemical change on piezoelectric characteristics and thermal stability of PHT-PIN ceramics. Chem Eng J 2024, 485: 150145.

[56]

Xiao P, Guo YQ, Tian MJ, et al. Improved ferroelectric/piezoelectric properties and bright green/UC red emission in (Li,Ho)-doped CaBi4Ti4O15 multifunctional ceramics with excellent temperature stability and superior water-resistance performance. Dalton Trans 2015, 44: 17366–17380.

[57]

Sheng LS, Du X, Chao QY, et al. Enhanced electrical properties in Nd and Ce co-doped CaBi4Ti4O15 high temperature piezoceramics. Ceram Int 2018, 44: 18316–18321.

[58]

Xi JW, Xing J, Yuan J, et al. Preparation and characterization of Zn-modified CaBi4Ti4O15 piezoelectric ceramics with lower sintering temperature. J Mater Sci Mater Electron 2020, 31: 8805–8814.

[59]

Chen H, Xi JW, Xing J, et al. Deciphering the synergistic action of multiple factors inducing high piezoresponse in CaBi4Ti4O15-based piezoelectric ceramics. J Am Ceram Soc 2024, 107: 3277–3289.

Journal of Advanced Ceramics
Cite this article:
Wen Q, Guo H-H, Shen Z-Y, et al. MnO2 doping induced structural tuning drives superior piezoelectric response in CaBi4Ti4O15-based ceramics. Journal of Advanced Ceramics, 2025, https://doi.org/10.26599/JAC.2025.9221051
Metrics & Citations  
Article History
Copyright
Rights and Permissions
Return