AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
PDF (1.9 MB)
Submit Manuscript AI Chat Paper
Show Outline
Show full outline
Hide outline
Show full outline
Hide outline
Research Article | Open Access

Tunable polarization-drived superior energy storage performance in PbZrO3 thin films

Tiandong Zhanga,bZhuangzhuang ShiaChao YinaChanghai ZhangaYue ZhangaYongquan ZhangaQingguo ChenaQingguo Chia( )
Key Laboratory of Engineering Dielectrics and Its Application, Ministry of Education, Harbin University of Science and Technology, Harbin 150080, China
Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Republic of Korea
Show Author Information

Graphical Abstract


Antiferroelectric PbZrO3 (AFE PZO) films have great potential to be used as the energy storage dielectrics due to the unique electric field (E)-induced phase transition character. However, the phase transition process always accompanies a polarization (P) hysteresis effect that induces the large energy loss (Wloss) and lowers the breakdown strength (EBDS), leading to the inferior energy storage density (Wrec) as well as low efficiency. In this work, the synergistic strategies by doping smaller ions of Li+–Al3+ to substitute Pb2+ and lowering the annealing temperature (T) from 700 to 550 ℃ are proposed to change the microstructures and tune the polarization characters of PZO films, except to dramatically improve the energy storage performances. The prepared Pb(1−x)(Li0.5Al0.5)xZrO3 (P(1−x)(L0.5A0.5)xZO) films exhibit ferroelectric (FE)-like rather than AFE character once the doping content of Li+–Al3+ ions reaches 6 mol%, accompanying a significant improvement of Wrec of 49.09 J/cm3, but the energy storage efficiency (η) is only 47.94% due to the long-correlation of FE domains. Accordingly, the low-temperature annealing is carried out to reduce the crystalline degree and the P loss. P0.94(L0.5A0.5)0.06ZO films annealed at 550 ℃ deliver a linear-like polarization behavior rather than FE-like behavior annealed at 700 ℃, and the lowered remanent polarization (Pr) as well as improved EBDS (4814 kV/cm) results in the superior Wrec of 58.7 J/cm3 and efficiency of 79.16%, simultaneously possessing excellent frequency and temperature stability and good electric fatigue tolerance.

Electronic Supplementary Material

Download File(s)
JAC0728_ESM.pdf (948.5 KB)


Yang XR, Li WL, Zhang YL, et al. High energy storage density achieved in Bi3+–Li+ co-doped SrTi0.99Mn0.01O3 thin film via ionic pair doping-engineering. J Eur Ceram Soc 2020, 40: 706–711.
Liu XJ, Zheng MS, Chen G, et al. High-temperature polyimide dielectric materials for energy storage: Theory, design, preparation and properties. Energy Environ Sci 2022, 15: 56–81.
Zhang YL, Li WL, Qiao YL, et al. 0.6ST–0.4NBT thin film with low level Mn doping as a lead-free ferroelectric capacitor with high energy storage performance. Appl Phys Lett 2018, 112: 093902.
Feng Y, Xue JP, Zhang TD, et al. Double-gradients design of polymer nanocomposites with high energy density. Energy Storage Mater 2022, 44: 73–81.
Feng Y, Tang WX, Zhang Y, et al. Machine learning and microstructure design of polymer nanocomposites for energy storage application. High Volt 2022, 7: 242–250.
Shao YL, El-Kady MF, Sun JY, et al. Design and mechanisms of asymmetric supercapacitors. Chem Rev 2018, 118: 9233–9280.
Wang G, Lu ZL, Li Y, et al. Electroceramics for high-energy density capacitors: Current status and future perspectives. Chem Rev 2021, 121: 6124–6172.
Winter M, Brodd RJ. What are batteries, fuel cells, and supercapacitors? Chem Rev 2004, 104: 4245–4270.
Sazali N, Wan Salleh WN, Jamaludin AS, et al. New perspectives on fuel cell technology: A brief review. Membranes 2020, 10: 99.
Ko DL, Hsin T, Lai YH, et al. High-stability transparent flexible energy storage based on PbZrO3/muscovite heterostructure. Nano Energy 2021, 87: 106149.
Sun ZX, Wang Z, Tian Y, et al. Progress, outlook, and challenges in lead-free energy-storage ferroelectrics. Adv Electron Mater 2020, 6: 1900698.
Thatikonda SK, Huang WH, Du XR, et al. Sm-doping induced large enhancement of antiferroelectric and energy storage performances of (111) oriented PbZrO3 thin films. Ceram Int 2019, 45: 23586–23591.
Li YZ, Wang ZJ, Bai Y, et al. High energy storage performance in Ca-doped PbZrO3 antiferroelectric films. J Eur Ceram Soc 2020, 40: 1285–1292.
Qiao LL, Song C, Sun YM, et al. Observation of negative capacitance in antiferroelectric PbZrO3 films. Nat Commun 2021, 12: 4215.
Hao XH, Zhai JW, Zhou J, et al. Structure and electrical properties of PbZrO3 antiferroelectric thin films doped with barium and strontium. J Alloys Compd 2011, 509: 271–275.
Hao XH, Zhai JW, Yao X. Improved energy storage performance and fatigue endurance of Sr-doped PbZrO3 antiferroelectric thin films. J Am Ceram Soc 2009, 92: 1133–1135.
Parui J, Krupanidhi SB. Enhancement of charge and energy storage in sol–gel derived pure and La-modified PbZrO3 thin films. Appl Phys Lett 2008, 92: 192901.
Ye M, Li T, Sun Q, et al. A giant negative electrocaloric effect in Eu-doped PbZrO3 thin films. J Mater Chem C 2016, 4: 3375–3378.
Zhang TD, Zhao Y, Li WL, et al. High energy storage density at low electric field of ABO3 antiferroelectric films with ionic pair doping. Energy Storage Mater 2019, 18: 238–245.
Zhang J, Zhang YY, Chen QQ, et al. Enhancement of energy-storage density in PZT/PZO-based multilayer ferroelectric thin films. Nanomaterials 2021, 11: 2141.
Guo X, Ge J, Ponchel F, et al. Effect of Sn substitution on the energy storage properties of high (001)-oriented PbZrO3 thin films. Thin Solid Films 2017, 632: 93–96.
Ye M, Sun Q, Chen XQ, et al. Effect of Nb doping on preferential orientation, phase transformation behavior and electrical properties of PbZrO3 thin films. J Alloys Compd 2012, 541: 99–103.
Carabatos-Nedelec C, El Harrad I, Handerek J, et al. Structural and spectroscopic studies of niobium doped PZT 95/5 ceramics. Ferroelectrics 1992, 125: 483–488.
Cordero F, Buixaderas E, Galassi C. Damage from coexistence of ferroelectric and antiferroelectric domains and clustering of O vacancies in PZT: An elastic and Raman study. Materials 2019, 12: 957.
Sa TL, Qin N, Yang GW, et al. W-doping induced antiferroelectric to ferroelectric phase transition in PbZrO3 thin films prepared by chemical solution deposition. Appl Phys Lett 2013, 102: 172906.
Dobal PS, Katiyar RS, Bharadwaja SSN, et al. Micro-Raman and dielectric phase transition studies in antiferroelectric PbZrO3 thin films. Appl Phys Lett 2001, 78: 1730–1732.
Shangguan DD, Duan YN, Wang BL, et al. Enhanced energy-storage performances of (1−x)PbZrO3xPbSnO3 antiferroelectric thin films under low electric fields. J Alloys Compd 2021, 870: 159440.
Lin ZJ, Chen Y, Liu Z, et al. Large energy storage density, low energy loss and highly stable (Pb0.97La0.02)(Zr0.66Sn0.23Ti0.11)O3 antiferroelectric thin-film capacitors. J Eur Ceram Soc 2018, 38: 3177–3181.
Gao R, Reyes-Lillo SE, Xu RJ, et al. Ferroelectricity in Pb1+δZrO3 thin films. Chem Mater 2017, 29: 6544–6551.
Hao XH, Zhai JW, Kong LB, et al. A comprehensive review on the progress of lead zirconate-based antiferroelectric materials. Prog Mater Sci 2014, 63: 1–57.
Fang Y, Bai Y, Li YZ, et al. Improved energy storage performance of PbZrO3 antiferroelectric thin films crystallized by microwave radiation. RSC Adv 2021, 11: 18387–18394.
Qi H, Zuo RZ. Linear-like lead-free relaxor antiferroelectric (Bi0.5Na0.5)TiO3–NaNbO3 with giant energy-storage density/efficiency and super stability against temperature and frequency. J Mater Chem A 2019, 7: 3971–3978.
Qi H, Zuo RZ, Xie AW, et al. Ultrahigh energy-storage density in NaNbO3-based lead-free relaxor antiferroelectric ceramics with nanoscale domains. Adv Funct Mater 2019, 29: 1903877.
Yang CH, Qian J, Han YJ, et al. Design of an all-inorganic flexible Na0.5Bi0.5TiO3-based film capacitor with giant and stable energy storage performance. J Mater Chem A 2019, 7: 22366–22376.
Ke SM, Fan HQ, Huang HT, et al. Lorentz-type relationship of the temperature dependent dielectric permittivity in ferroelectrics with diffuse phase transition. Appl Phys Lett 2008, 93: 112906.
Shvartsman VV, Zhai J, Kleemann W. The dielectric relaxation in solid solutions BaTi1−xZrxO3. Ferroelectrics 2009, 379: 77–85.
Peng BL, Zhang Q, Li X, et al. Large energy storage density and high thermal stability in a highly textured (111)-oriented Pb0.8Ba0.2ZrO3 relaxor thin film with the coexistence of antiferroelectric and ferroelectric phases. ACS Appl Mater Interfaces 2015, 7: 13512–13517.
Wei XY, Feng YJ, Yao X. Dielectric relaxation behavior in barium stannate titanate ferroelectric ceramics with diffused phase transition. Appl Phys Lett 2003, 83: 2031–2033.
Jeon SC, Kang SJL. Coherency strain enhanced dielectric–temperature property of rare-earth doped BaTiO3. Appl Phys Lett 2013, 102: 112915.
Shvartsman VV, Lupascu DC. Lead-free relaxor ferroelectrics. J Am Ceram Soc 2012, 95: 1–26.
Zhang Y, Li Y, Hao XH, et al. Flexible antiferroelectric thick film deposited on nickel foils for high energy-storage capacitor. J Am Ceram Soc 2019, 102: 6107–6114.
Yang CH, Lv PP, Qian J, et al. Fatigue-free and bending-endurable flexible Mn-doped Na0.5Bi0.5TiO3–BaTiO3–BiFeO3 film capacitor with an ultrahigh energy storage performance. Adv Energy Mater 2019, 9: 1803949.
Zou D, Liu SY, Zhang C, et al. Flexible and translucent PZT films enhanced by the compositionally graded heterostructure for human body monitoring. Nano Energy 2021, 85: 105984.
Li YZ, Lin JL, Bai Y, et al. Ultrahigh-energy storage properties of (PbCa)ZrO3 antiferroelectric thin films via constructing a pyrochlore nanocrystalline structure. ACS Nano 2020, 14: 6857–6865.
Rabuffetti FA, Brutchey RL. Tailoring the mechanism of the amorphous-to-crystalline phase transition of PbTiO3 via kinetically controlled hydrolysis. Chem Mater 2011, 23: 4063–4076.
Chen YN, Wang ZJ, Yang T, et al. Crystallization kinetics of amorphous lead zirconate titanate thin films in a microwave magnetic field. Acta Mater 2014, 71: 1–10.
Zhang TD, Li WL, Zhao Y, et al. High energy storage performance of opposite double-heterojunction ferroelectricity-insulators. Adv Funct Mater 2018, 28: 1706211.
Zhang TD, Yin C, Zhang CH, et al. Self-polarization and energy storage performance in antiferroelectric-insulator multilayer thin films. Compos Part B 2021, 221: 109027.
Zhang YL, Li WL, Wang ZY, et al. Ultrahigh energy storage and electrocaloric performance achieved in SrTiO3 amorphous thin films via polar cluster engineering. J Mater Chem A 2019, 7: 17797–17805.
Liang ZS, Liu M, Ma CR, et al. High-performance BaZr0.35Ti0.65O3 thin film capacitors with ultrahigh energy storage density and excellent thermal stability. J Mater Chem A 2018, 6: 12291–12297.
Zhang TD, Yang LY, Zhang CH, et al. Polymer dielectric films exhibiting superior high-temperature capacitive performance by utilizing an inorganic insulation interlayer. Mater Horiz 2022, 9: 1273–1282.
Chen P, Wu SH, Li P, et al. Great enhancement of energy storage density and power density in BNBT/xBFO multilayer thin film hetero-structures. Inorg Chem Front 2018, 5: 2300–2305.
Koo CY, Eum YJ, Hwang SO, et al. Development of high energy capacitors using La-doped PbZrO3 anti-ferroelectric thin films. Ferroelectrics 2014, 465: 89–95.
Hu ZQ, Ma BH, Liu SS, et al. Relaxor behavior and energy storage performance of ferroelectric PLZT thin films with different Zr/Ti ratios. Ceram Int 2014, 40: 557–562.
Tong S, Ma BH, Narayanan M, et al. Lead lanthanum zirconate titanate ceramic thin films for energy storage. ACS Appl Mater Interfaces 2013, 5: 1474–1480.
Li YZ, Wang ZJ, Bai Y, et al. Enhancement of energy storage density in antiferroelectric PbZrO3 films via the incorporation of gold nanoparticles. J Am Ceram Soc 2019, 102: 5253–5261.
Ahn CW, Amarsanaa G, Won SS, et al. Antiferroelectric thin-film capacitors with high energy-storage densities, low energy losses, and fast discharge times. ACS Appl Mater Interfaces 2015, 7: 26381–26386.
Yang BB, Guo MY, Li CH, et al. Flexible ultrahigh energy storage density in lead-free heterostructure thin-film capacitors. Appl Phys Lett 2019, 115: 243901.
Song DP, Yang J, Sun JX, et al. Controlling the crystallization of Nd-doped Bi4Ti3O12 thin-films for lead-free energy storage capacitors. J Appl Phys 2020, 127: 224102.
Pan H, Zeng Y, Shen Y, et al. BiFeO3–SrTiO3 thin film as a new lead-free relaxor-ferroelectric capacitor with ultrahigh energy storage performance. J Mater Chem A 2017, 5: 5920–5926.
Han YJ, Qian J, Yang CH. Time-stable giant energy density and high efficiency in lead free (Ce,Mn)-modified (Na0.8K0.2)0.5Bi0.5TiO3 ceramic film capacitor. Ceram Int 2019, 45: 22737–22743.
Liang ZS, Liu M, Shen LK, et al. All-inorganic flexible embedded thin-film capacitors for dielectric energy storage with high performance. ACS Appl Mater Interfaces 2019, 11: 5247–5255.
Pan H, Li F, Liu Y, et al. Ultrahigh-energy density lead-free dielectric films via polymorphic nanodomain design. Science 2019, 365: 578–582.
Hoffmann M, Fengler FPG, Max B, et al. Negative capacitance for electrostatic supercapacitors. Adv Energy Mater 2019, 9: 1901154.
Han CC, Zhang XH, Chen D, et al. Enhanced dielectric properties of sandwich-structured biaxially oriented polypropylene by grafting hyper-branched aromatic polyamide as surface layers. J Appl Polym Sci 2020, 137: 48990.
Liu FH, Li Q, Li ZY, et al. Poly(methyl methacrylate)/boron nitride nanocomposites with enhanced energy density as high temperature dielectrics. Compos Sci Technol 2017, 142: 139–144.
Chi QG, Zhou YH, Yin C, et al. A blended binary composite of poly(vinylidene fluoride) and poly(methyl methacrylate) exhibiting excellent energy storage performances. J Mater Chem C 2019, 7: 14148–14158.
Feng MJ, Zhang TD, Song CH, et al. Improved energy storage performance of all-organic composite dielectric via constructing sandwich structure. Polymers 2020, 12: 1972.
Zhang TD, Zhao XW, Zhang CH, et al. Polymer nanocomposites with excellent energy storage performances by utilizing the dielectric properties of inorganic fillers. Chem Eng J 2020, 408: 127314.
Feng Y, Zhou YH, Zhang TD, et al. Ultrahigh discharge efficiency and excellent energy density in oriented core–shell nanofiber-polyetherimide composites. Energy Storage Mater 2020, 25: 180–192.
Xue JP, Zhang TD, Zhang CH, et al. Excellent energy storage performance for P(VDF–TrFE–CFE) composites by filling core–shell structured inorganic fibers. J Mater Sci Mater Electron 2020, 31: 21128–21141.
Journal of Advanced Ceramics
Pages 930-942
Cite this article:
Zhang T, Shi Z, Yin C, et al. Tunable polarization-drived superior energy storage performance in PbZrO3 thin films. Journal of Advanced Ceramics, 2023, 12(5): 930-942.








Web of Science






Received: 05 December 2022
Revised: 15 January 2023
Accepted: 30 January 2023
Published: 04 May 2023
© The Author(s) 2023.

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made.

The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.

To view a copy of this licence, visit