Preparation and Electrical Properties of Co Doped Na0.5Bi4.5Ti4O15 Bismuth-Layered Lead-Free Piezoelectric Ceramics

doi:10.16553/j.cnki.issn1000-985x.2024.0258

Abstract

Abstract: High Curie temperature bismuth-layered lead-free piezoelectric ceramics based on Na_0.5Bi_4.5Ti_4-_x Co _x O₁₅ （x=0， 0.025， 0.050， 0.075） were prepared by conventional solid state reaction method. The crystal structure， fracture morphology， oxygen vacancy status， as well as the dielectric， piezoelectric and ferroelectric properties of the samples were characterized by XRD， SEM， EDS， XPS and related electrical parameter testing systems. The influence of different doping contents of Co on the ceramic properties was investigated. The results show that when the doping content of Co is 0.050， the sample exhibits a single and uniform phase composition， with a lamellar structure and high densification. The piezoelectric constant is 34.7 pC/N. The dielectric loss is only 0.30% and the Curie temperature is 672 ℃. The high temperature resistivity at 500 ℃ is 1.62×10⁷ Ω·cm. Meanwhile， the sample demonstrates excellent temperature stability， suggesting that the doped Na_0.5Bi_4.5Ti_3.95Co_0.05O₁₅ ceramic has potential market applications value in high-temperature and high- frequency fields.

Key words: Co doping; bismuth-layered lead-free piezoelectric ceramics; solid state reaction method; piezoelectric property; thermal stability; electrical property

CLC Number:

TQ174.1

ZHANG Feiyang, YAN Feng, LOU Yue, LI Bojiang, LI Jie. Preparation and Electrical Properties of Co Doped Na_0.5Bi_4.5Ti₄O₁₅ Bismuth-Layered Lead-Free Piezoelectric Ceramics[J]. Journal of Synthetic Crystals, 2025, 54(6): 1061-1067.

Figures/Tables 9

Fig.1 XRD patterns of NBT ceramics doped with different Co content

Fig.2 Fracture surfaces SEM images of NBT ceramics doped with different Co content （a）~（d） and EDS spectrum （e） of area A in Fig.（c）. （a） x=0；（b） x=0.025；（c） x=0.050；（d） x=0.075

Table 1 Physical properties such as dielectric and piezoelectric properties of NBT ceramics doped with different Co content at room temperature

Sample	ρ_d/（g·cm^-3）	ρ_rd/%	ε_r	tan δ/%	d₃₃/（pC·N^-1）	k_p/%
NBT	6.48	84.9	138	0.68	17.5	3.9
NBT-0.025	6.72	88.1	140	0.45	28.1	4.8
NBT-0.050	7.13	93.4	146	0.30	34.7	5.4
NBT-0.075	6.98	91.5	150	0.54	27.7	5.0

Fig.3 Dielectric permittivity of NBT ceramics doped with different Co content. （a） Relative dielectric constant；（b） dielectric loss

Fig.4 Variation of resistivity of NBT ceramics doped with different Co content with temperature

Fig.5 High resolution O 1s XPS of NBT （a） and NBT-0.050 （b） ceramics

Fig.6 Hysteresis loop of NBT and NBT-0.050 ceramics

Fig.7 Effect of annealing temperature on d33 of NBT-0.050 ceramics

Fig.8 Variation of d33 of NBT-0.050 ceramics with temperatures

References 34

1	冯端. 固体物理学大辞典［M］. 北京：高等教育出版社， 1995.
	FENG D. Dictionary of solid state physics［M］. Beijing： Higher Education Press， 1995 （in Chinese）.
2	宗立超，曾江涛，赵苏串，等. 含铋层状结构陶瓷CaBi₂Nb₂O₉的A位掺杂改性研究［J］. 无机材料学报， 2012， 27（7）： 726-730.
	ZONG L C， ZENG J T， ZHAO S C， et al. Study on A-site cation doping of CaBi₂Nb₂O₉ with bismuth layered structure［J］. Journal of Inorganic Materials， 2012， 27（7）： 726-730 （in Chinese）.
3	RÖDEL J， JO W， SEIFERT K T P， et al. Perspective on the development of lead-free piezoceramics［J］. Journal of the American Ceramic Society， 2009， 92（6）： 1153-1177.
4	TAKENAKA T， NAGATA H. Current status and prospects of lead-free piezoelectric ceramics［J］. Journal of the European Ceramic Society， 2005， 25（12）： 2693-2700.
5	YAN H， ZHANG H， UBIC R， et al. A lead-free high-curie-point ferroelectric ceramic， CaBi₂Nb₂O₉ ［J］. Advanced Materials， 2005， 17（10）： 1261-1265.
6	ABAH R， GAI Z G， ZHAN S Q， et al. The effect of B-site （W/Nb） co-substituting on the electrical properties of sodium bismuth titanate high temperature piezoceramics［J］. Journal of Alloys and Compounds， 2016， 664： 1-4.
7	MOURE A. Review and perspectives of aurivillius structures as a lead-free piezoelectric system［J］. Applied Sciences， 2018， 8（1）： 62.
8	FEI C L， ZHAO T L， WANG D F， et al. High frequency needle ultrasonic transducers based on lead-free co doped Na_0.5Bi_4.5Ti₄O₁₅ piezo-ceramics［J］. Micromachines， 2018， 9（6）： 291.
9	黄新友，童晓峰，徐国强，等. MBi₄Ti₄O₁₅基陶瓷的研究现状与发展趋势［J］. 电子元件与材料， 2013， 32（1）： 79-84.
	HUANG X Y， TONG X F， XU G Q， et al. Research and development of MBi₄Ti₄O₁₅-based ceramics［J］. Electronic Components and Materials， 2013， 32（1）： 79-84 （in Chinese）.
10	WANG C M， ZHAO L， WANG J F， et al. Enhanced piezoelectric properties of sodium bismuth titanate （Na_0.5Bi_4.5Ti₄O₁₅） ceramics with B-site cobalt modification［J］. Physica Status Solidi （RRL）-Rapid Research Letters， 2009， 3（1）： 7-9.
11	WANG X S， ISHIWARA H. Polarization enhancement and coercive field reduction in W- and Mo-doped Bi_3.35La_0.75Ti₃O₁₂ thin films［J］. Applied Physics Letters， 2003， 82（15）： 2479-2481.
12	NOGUCHI Y， MIYAYAMA M. Large remanent polarization of vanadium-doped Bi₄Ti₃O₁₂ ［J］. Applied Physics Letters， 2001， 78（13）： 1903-1905.
13	陈丹玲，黄志强，何新华. Ta掺杂Na_0.5Bi_4.5Ti₄O₁₅陶瓷的显微结构和电性能［J］. 材料工程， 2020， 48（9）： 93-99. DOI
	CHEN D L， HUANG Z Q， HE X H. Microstructure and electrical properties of Ta-doped Na_0.5Bi_4.5Ti₄O₁₅ ceramics［J］. Journal of Materials Engineering， 2020， 48（9）： 93-99 （in Chinese）.
14	江向平，傅小龙，陈　超，等. Co、Mn共掺杂铋层状Na_0.5Bi_4.5Ti₄O₁₅无铅压电陶瓷的显微结构及电性能［J］. 硅酸盐学报， 2014， 42（12）： 1513-1519.
	JIANG X P， FU X L， CHEN C， et al. Microstructure and electrical properties of bismuth layer-structured Na_0.5Bi_4.5Ti₄O₁₅ lead-free piezoelectric ceramics by Co， Mn co-modification［J］. Journal of the Chinese Ceramic Society， 2014， 42（12）： 1513-1519 （in Chinese）.
15	张飞洋，闫锋，郇正利，等. NaCe掺杂CaBi₂Nb₂O₉铋层状压电陶瓷的制备及性能研究［J］. 陶瓷学报， 2019， 40（5）： 650-654.
	ZHANG F Y， YAN F， HUAN Z L， et al. Preparation and electrical properties of NaCe doped CaBi₂Nb₂O₉bismuth-layered piezoelectric ceramic［J］. Journal of Ceramics， 2019， 40（5）： 650-654 （in Chinese）.
16	张飞洋，闫锋，郇正利，等. 烧结温度对Ca_0.9（NaCe）_0.05Bi₂Nb₂O₉无铅压电陶瓷性能的影响［J］. 人工晶体学报， 2018， 47（11）： 2330-2333.
	ZHANG F Y， YAN F， HUAN Z L， et al. Influence of sintering temperature on properties of Ca_0.9（NaCe）_0.05Bi₂Nb₂O₉ lead-free piezoelectric ceramic［J］. Journal of Synthetic Crystals， 2018， 47（11）： 2330-2333 （in Chinese）.
17	DU X F， CHEN I W. Ferroelectric thin films of bismuth-containing layered perovskites： part III， SrBi₂Nb₂O₉ and c-oriented Bi₄Ti₃O₁₂ template［J］. Journal of the American Ceramic Society， 1998， 81（12）： 3265-3269.
18	YAO Z H， LIU H X， LIU Y， et al. High-temperature relaxor cobalt-doped （1-x）BiScO_3- _x PbTiO₃ piezoelectric ceramics［J］. Applied Physics Letters， 2008， 92（14）： 142905.
19	周昌荣，刘心宇，江民红，等. BiCoO₃对BNT-BKT陶瓷压电性能与退极化温度的影响［J］. 中南大学学报（自然科学版）， 2010， 41（5）： 1796-1800.
	ZHOU C R， LIU X Y， JIANG M H， et al. Effect of BiCoO₃ on piezoelectric properties and depolarization temperature of BNT-BKT piezoelectric ceramics［J］. Journal of Central South University （Science and Technology）， 2010， 41（5）： 1796-1800 （in Chinese）.
20	JIANG X P， FU X L， CHEN C， et al. High performance Aurivillius type Na_0.5Bi_4.5Ti₄O₁₅ piezoelectric ceramics with neodymium and cerium modification［J］. Journal of Advanced Ceramics， 2015， 4（1）： 54-60.
21	DU H L， SHI X. Dielectric and piezoelectric properties of barium-modified aurivillius-type Na_0.5Bi_4.5Ti₄O₁₅ ［J］. Journal of Physics and Chemistry of Solids， 2011， 72（11）： 1279-1283.
22	WATCHARAPASORN A， SIRIPRAPA P， JIANSIRISOMBOON S. Grain growth behavior in bismuth titanate-based ceramics［J］. Journal of the European Ceramic Society， 2010， 30（1）： 87-93.
23	SHI W， WU Y T， TU H， et al. Enhanced piezoelectric response of Bi₄Ti₃O₁₂-based ceramics through engineered domain configuration and grain size［J］. Scripta Materialia， 2025， 258： 116493.
24	李博森，廖忠新，高大强. BNZ组分对KNN基无铅压电陶瓷结构和性能的影响［J］. 材料研究学报， 2024， 38（1）： 51-60.
	LI B S， LIAO Z X， GAO D Q. Effect of BNZ component on structure and property of KNN based lead-free piezoelectric ceramics［J］. Chinese Journal of Materials Research， 2024， 38（1）： 51-60 （in Chinese）.
25	刘迎春. BaTiO₃基陶瓷的高压电性及高效能量收集特性［D］. 哈尔滨：哈尔滨工业大学， 2019.
	LIU Y C. High piezoelectric properties and efficient energy harvesting for BaTiO₃ based ceramics［D］. Harbin： Harbin Institute of Technology， 2019 （in Chinese）.
26	PENG Z H， CHEN Q， LIU D， et al. Evolution of microstructure and dielectric properties of （LiCe）-doped Na_0.5Bi_2.5Nb₂O₉ Aurivillius type ceramics［J］. Current Applied Physics， 2013， 13（7）： 1183-1187.
27	盖志刚，王矜奉，苏文斌，等. LiCe掺杂对铋层材料K_0.5Bi_2.5Nb₂O₉的影响［J］. 压电与声光， 2008， 30（4）： 446-449.
	GAI Z G， WANG J F， SU W B， et al. The effect of（Li， Ce） doping in aurivillius phase material K_0.5Bi_2.5Nb₂O₉ ［J］. Piezoelectrics & Acoustooptics， 2008， 30（4）： 446-449 （in Chinese）.
28	KAWADA S， OGAWA H， KIMURA M， et al. High-power piezoelectric vibration characteristics of textured SrBi₂Nb₂O₉ ceramics［J］. Japanese Journal of Applied Physics， 2006， 45（9S）： 7455.
29	LI Z T， LIU H， THONG H C， et al. Enhanced temperature stability and defect mechanism of BNT-based lead-free piezoceramics investigated by a quenching process［J］. Advanced Electronic Materials， 2019， 5（3）： 1800756.
30	郑来奇，江向平，陈　超，等. 氧空位对0.94Na_0.5Bi_0.5Ti_0.99Cu_0.01O₃-0.06BaTiO₃无铅压电陶瓷的温度稳定性的影响［J］. 陶瓷学报， 2020， 41（4）： 551-556.
	ZHENG L Q， JIANG X P， CHEN C， et al. Effect of oxygen vacancy on thermal stability of 0.94Na_0.5Bi_0.5Ti_0.09Cu_0.01O₃-0.06BaTiO₃ lead-free piezoceramics［J］. Journal of Ceramics， 2020， 41（4）： 551-556 （in Chinese）.
31	胡　浩，江向平，陈　超，等. Ce³⁺掺杂Na_0.5Bi_8.5Ti₇O₂₇铋层状陶瓷的结构与电性能研究［J］. 无机材料学报， 2019， 34（9）： 997-1003.
	HU H， JIANG X P， CHEN C， et al. Influence of Ce³⁺ substitution on the structure and electrical characteristics of bismuth-layer Na_0.5Bi_8.5Ti₇O₂₇ ceramics［J］. Journal of Inorganic Materials， 2019， 34（9）： 997-1003 （in Chinese）.
32	TIAN X X， QU S B， PEI Z B， et al. Microstructure， dielectric， and piezoelectric properties of Ce-modified CaBi₂Nb₂O₉ ceramics［J］. Ferroelectrics， 2010， 404（1）： 127-133.
33	WANG C M， WANG J F， ZHENG L M， et al. Enhancement of the piezoelectric properties of sodium lanthanum bismuth titanate （Na_0.5La_0.5Bi₄Ti₄O₁₅） through modification with cobalt［J］. Materials Science and Engineering： B， 2010， 171（1/2/3）： 79-85.
34	JIANG Y L， JIANG X P， CHEN C， et al. Structural and electrical properties of La³⁺-doped Na_0.5Bi_4.5Ti₄O₁₅-Bi₄Ti₃O₁₂ inter-growth high temperature piezoceramics［J］. Ceramics International， 2017， 43（8）： 6446-6452.

[1]	LI Shuai, ZHANG Lei. Research Progress on Near-Infrared Group Ⅳ-Ⅵ Semiconductor Quantum Dot Optical Fibers [J]. Journal of Synthetic Crystals, 2025, 54(5): 757-771.
[2]	SUN Rujun, ZHANG Jinghui, LI Yifan, HAO Yue, ZHANG Jincheng. Review on Mg Doping of Ga₂O₃ [J]. Journal of Synthetic Crystals, 2025, 54(3): 361-370.
[3]	HUANG Qu, JIANG Hongxi, ZHOU Bo. Luminescent Properties of CaLa₂(WO₄)₄∶Eu³⁺,Sm³⁺ as Novel Red Phosphor for White LEDs [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2025, 54(1): 69-76.
[4]	JIANG Xiaokang, GAO Feng, ZHOU Hengwei. Synthesis and Luminescence Properties of Y₂MgTiO₆∶Eu³⁺ Red-Emitting Phosphor [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(7): 1170-1176.
[5]	HU Zhengkai, YANG Weibin, XIONG Feibing, GUO Yisheng, BAI Xin, LI Mingming. Preparation and Luminescence Properties of Sm³⁺ Doped Na₅Y_1-x(MoO₄)_4-y(WO₄)_y Phosphors with High Thermal Stability [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(6): 1016-1025.
[6]	CAI Xiaoyong, JIANG Hongxi. Preparation and Luminesent Property of CaWO₄∶Eu³⁺,Bi³⁺ Red Phosphors [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(5): 833-840.
[7]	MIAO Jian, SHAO Hui, CAO Ruilong. Effect of K_0.5Na_0.5NbO₃ Doping on the Energy Storage Performance of 0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃ Ceramics [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(5): 882-888.
[8]	LI Yuqiang, YANG Jian, WANG Shuai, ZHENG Jiyuan, ZHAO Yan, ZHOU Hengwei, LIU Yuxue. Upconversion Luminescence and Temperature Sensing Properties of High Thermal Stabilized CaGdAlO₄∶Er³⁺/Yb³⁺ Phosphors [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(4): 649-655.
[9]	SHENG Xingxing, LYU Jinbin, XIAO Feng. Luminescence Properties of Non-Rare Earth Activated Thermal Stability Blue-Violet Zn₃B₂O₆∶Bi³⁺ Phosphor [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(2): 322-328.
[10]	SONG Mingjun, YU Dianchen, WANG Jing, ZHOU Weiwei, ZHAO Wang. Preparation and Spectral Properties of La₂Mg_4/3Sb_2/3O₆∶Mn⁴⁺ Red Phosphor for Plant Growth Illumination [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(10): 1759-1768.
[11]	CHEN Peiran, JIAO Teng, CHEN Wei, DANG Xinming, DIAO Zhaoti, LI Zhengda, HAN Yu, YU Han, DONG Xin. Fabrication and Characteristics of p-Si/n-Ga₂O₃ Heterojunction [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(1): 73-81.
[12]	PENG Qianwen, JI Xiang. Effect of Annealing Temperature on Electrical Properties of BCZT Epitaxial Films and Its Conductivity Mechanism [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(1): 82-89.
[13]	BAI Xin, YANG Weibin, XIONG Feibing, LI Mingming, HU Zhengkai, GUO Yisheng, FU Xingyu. Luminescence Performance of Alkaline Metal Ion Co-Doped Sr₃Ga₂Ge₄O₁₄∶Dy³⁺ [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(1): 97-106.
[14]	CHEN Shaohua, MU Wenxiang, ZHANG Jin, DONG Xuyang, LI Yang, JIA Zhitai, TAO Xutang. Optical and Electrical Properties of Ni-Doped β-Ga₂O₃ Single Crystal [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2023, 52(8): 1373-1377.
[15]	MA Chunlin, WANG Ziheng, FAN Yuxiang, HU Ying, HU Yazhou. Preparation and Photoluminescence Properties of Sm³⁺-Doped 0.96Na_0.5Bi_0.5TiO₃-0.04CaTiO₃ Ceramics [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2023, 52(8): 1509-1515.

Preparation and Electrical Properties of Co Doped Na_0.5Bi_4.5Ti₄O₁₅ Bismuth-Layered Lead-Free Piezoelectric Ceramics

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 9

References 34

Related Articles 15

Recommended Articles

Metrics

Comments