通过双相BCZT掺杂策略实现纸基压电纳米发电机的高功率密度

doi:10.15541/jim20250064

摘要/Abstract

摘要： 高性能柔性压电纳米发电机(Piezoelectric Nanogenerators, PENG)的发展对于自供能传感和微电子器件的应用具有重要意义。本研究采用氢键替换策略,制备了基于纤维素/PVDF共混薄膜的多层PENG,并引入多相BCZT(0.1BaZr_0.2Ti_0.8O₃-0.9Ba_0.7Ca_0.3TiO₃)陶瓷填料以优化其性能。SEM和TEM表征结果表明,复杂的氢键网络有效促进了陶瓷填料在复合薄膜亚层中的均匀分散。为探究填料分布对PENG性能的影响,本研究制备并对比了单层与双层复合薄膜结构。结果表明,双层PENG的电学输出性能显著优于单层结构,其中D-L₃H₇构型的开路电压(Open Circuit Voltage, V_OC)达23 V,短路电流(Short Circuit Current, I_SC)达8 μA。这一性能提升归因于增大的层间界面,有效抑制了电荷注入与迁移,从而提高了电荷密度。此外,具有尖锐顶角的六方/四方相陶瓷纳米颗粒进一步诱导了局部电场增强效应,优化了器件的压电转换性能。

关键词: 压电纳米发电机, 纤维素, BCZT, 氢键工程策略

Abstract: The development of high performance, flexible piezoelectric nanogenerators (PENGs) is critical for advancing self-powered sensing and microelectronic applications. In this study, a hydrogen-bond replacement strategy was employed to fabricate a multi-layer PENG based on a cellulose/PVDF blend film matrix, incorporating multi-phase BCZT (0.1BaZr_0.2Ti_0.8O₃-0.9Ba_0.7Ca_0.3TiO₃) ceramic fillers. Structural characterization via SEM and TEM revealed that an intricate hydrogen-bond network facilitated the uniform dispersion of ceramic fillers within the composite film’s sublayers. In order to study the effect of filler distribution on piezoelectric performance, we produced and evaluated single and double layer composite films with varying BCZT configurations. The results demonstrated that double layer PENGs exhibited significantly enhanced electrical output compared to their single layer counterparts, with the D-L₃H₇ configuration achieving an Open Circuit Voltage (V_OC) of 23 V and Short Circuit Current (I_SC) of 8 μA. This enhancement is attributed to increased inter-layer interfaces, which effectively suppressed charge injection and migration, leading to improved charge density. Additionally, the presence of sharp tipped hexagonal tetragonal phase nanoparticles induced an electric field enhancement effect, further optimizing performance.

Key words: PENGs, cellulose, BCZT, hydrogen bond engineering strategy

中图分类号:

TM619

王斯婷, 孙梓雄, 刘鑫莹, 韩沛桥, 汪秀丽, 张素风. 通过双相BCZT掺杂策略实现纸基压电纳米发电机的高功率密度[J]. 无机材料学报, DOI: 10.15541/jim20250064.

WANG Siting, SUN Zixiong, LIU Xinying, HAN Peiqiao, WANG Xiuli, ZHANG Sufeng. Achieving High Power Density in Paper-based Piezoelectric Nanogenerators through Dual-Phase BCZT Doping Strategy[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250064.

参考文献

[1] HAN J, WANG M, ZHAO T,et al. Triboelectric nanogenerator based on graphene forest electrodes. Journal of Inorganic Materials, 2019, 34(8):839.
[2] ZHOU X, Li C, WU D,et al. Recent advances of cellular stimulation with triboelectric nanogenerators. Exploration, 2023, 3(4): 20220090.
[3] ANNAMALAI P K, NANJUNDAN A K, DUBAL D P,et al. An overview of cellulose‐based nanogenerators. Advanced Materials Technologies, 2021, 6(3): 2001164.
[4] ZHANG Y, GAO X, WU Y,et al. Self-powered technology based on nanogenerators for biomedical applications. Exploration, 2021, 1(1): 90.
[5] GUO Y, CHEN Z, WANG H,et al. Progress of inorganic filler based composite films for triboelectric nanogenerators. Journal of Inorganic Materials, 2021, 36(9): 919.
[6] WABG B, WEI X, ZHOU H,et al. Viscoelastic blood coagulation testing system enabled by a non-contact triboelectric angle sensor. Exploration, 2023, 4(1): 20230073
[7] CHEN Y, GAO Z, ZHANG F, et al. Recent progress in self-powered multifunctional e-skin for advanced applications. Exploration, 2022, 2(1): 20210112.
[8] RAM F, GUDADHE A, VIJAYAKANTH T,et al. Nanocellulose reinforced flexible composite nanogenerators with enhanced vibrational energy harvesting and sensing properties. ACS Applied Polymer Materials, 2020, 2(7): 2550.
[9] WANG X, ZHU Y, PENG Z,et al. Phase structure and piezoelectric property of (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1-xSn_x)O₃ lead-free piezoceramics. Journal of Inorganic Materials, 2022, 37(5):513.
[10] NAN B, ZANG J, LU W L,et al. Recent progress on additive manufacturing of piezoelectric ceramics. Journal of Inorganic Materials, 2022, 37(6):585.
[11] VULLERS R J M, VAN SCHAIJK R, DOMS I,et al. Micropower energy harvesting. Solid-State Electronics, 2009, 53(7): 684.
[12] MARZENCKI M, AMMAR Y, BASROUR S.Integrated power harvesting system including a MEMS generator and a power management circuit.Sensors and Actuators A: Physical, 2008, 145: 363.
[13] YUAN X, GAO X, YANG J,et al. The large piezoelectricity and high power density of a 3D-printed multilayer copolymer in a rugby ball-structured mechanical energy harvester. Energy & Environmental Science, 2020, 13(1): 152.
[14] HUANG A, ZHU Y, PENG S,et al. Improved energy harvesting ability of single-layer binary fiber nanocomposite membrane for multifunctional wearable hybrid piezoelectric and triboelectric nanogenerator and self-powered sensors. ACS Nano, 2023, 18(1): 691.
[15] RANA M M, KHAN A A, HUANG G,et al. Porosity modulated high-performance piezoelectric nanogenerator based on organic/inorganic nanomaterials for self-powered structural health monitoring. ACS Applied Materials & Interfaces, 2020, 12(42): 47503.
[16] BAGHALI M, JAYATHILAKA W, RANAKRISHNA S.The role of electrospun nanomaterials in the future of energy and environment.Materials, 2021, 14(3): 558.
[17] LU L, DING W, LIU J,et al. Flexible PVDF based piezoelectric nanogenerators. Nano Energy, 2020, 78: 105251.
[18] LUO X, WANG Z, YAN M,et al. One-pot three-step synthesis of PDMAEMA-b-PMMA-b-PNIPAM triblock block copolymer for preparing pH and thermal dual-responsive PVDF blend membranes. Polymer Engineering and Science, 2023, 63(10): 3343.
[19] YANG X, WANG R,et al. A robust-switchable poly(vinyl alcohol) gel with adjustable multiple hydrogen bonding interactions. European Polymer Journal, 2023, 195: 112192.
[20] SONG Y, SHI Z, HU G H,et al. Recent advances in cellulose-based piezoelectric and triboelectric nanogenerators for energy harvesting: a review. Journal of Materials Chemistry A, 2021, 9(4): 1910.
[21] CAUDA V, STASS S, BEJTKA K,et al. Nanoconfinement: an effective way to enhance PVDF piezoelectric properties. ACS Applied Materials & Interfaces, 2013, 5(13): 6430.
[22] DALLAEV R, PISARENKO T, SOBOLA D,et al. Brief review of PVDF properties and applications potential. Polymers, 2022, 14(22): 4793.
[23] WEI S, WANG X, ZHAO X,et al. Detection of pesticide residues on flexible and transparent fluorinated polyimide film based on surface-enhanced Raman spectroscopy technology. Analytica, Chimica Acta, 2023, 1283: 341958.
[24] HU R, ZHAO J, ZHU G,et al. Fabrication of flexible free-standing reduced graphene oxide/polyaniline nanocomposite film for all-solid-state flexible supercapacitor. Electrochimica Acta, 2018, 261: 151.
[25] LI C, XU S, YU J,et al. 3D hybrid MoS₂/AgNPs/inverted pyramid PMMA resonant cavity system for the excellent flexible surface enhanced Raman scattering sensor. Sensors and Actuators B-Chemical, 2018, 274: 152.
[26] MAGDY G, HASSANIN A H, KANDAS I,et al. PVDF nanostructures characterizations and techniques for enhanced piezoelectric response: a review. Materials Chemistry and Physics, 2024, 325: 129760.
[27] HE Z, RAULT F, LEWANDOWSKI M,et al. Electrospun PVDF nanofibers for piezoelectric applications: a review of the influence of electrospinning parameters on the β phase and crystallinity enhancement. Polymers, 2021, 13(2): 174.
[28] LI Y, HU Q, ZHANG R,et al. Piezoelectric nanogenerator based on electrospinning PVDF/cellulose acetate composite membranes for energy harvesting. Materials, 2022, 15(19): 7026.
[29] VENKATESAN M, CHEN W C, CHO C J,et al. Enhanced piezoelectric and photocatalytic performance of flexible energy harvester based on CsZn_0.75Pb_0.25I₃/CNC-PVDF composite nanofibers. Chemical Engineering Journal, 2022, 433: 133620.
[30] CHENG Y, FENG Y, PAN Z,et al. Multilayer nanocomposites with ultralow loadingsof nanofillers exhibiting superb capacitive energy storage performance. Energy & Environmental Science, 2023, 16(12): 5881.
[31] HU P, YAN L, ZHAO C,et al. Double-layer structured PVDF nanocomposite film designed for flexible nanogenerator exhibiting enhanced piezoelectric output and mechanical property. Composites Science and Technology, 2018, 168: 327.
[32] SUN Z, XIN H, DIWU L,et al. Boosting the energy storage performance of BCZT-based capacitors by constructing a Schottky contact. Materials Horizons, 2025, 12(7): 2328.
[33] SUN Z, BAI Y, JING H,et al. A polarization double-enhancement strategy to achieve super low energy consumption with ultra-high energy storage capacity in BCZT-based relaxor ferroelectrics. Materials Horizons, 2024, 11(14): 3330.
[34] SUN Z, ZHAO S, WANG T,et al. Achieving high overall energy storage performance of KNN-based transparent ceramics by ingenious multiscale designing. Journal of Materials Chemistry A, 2025, 12(27): 16735.
[35] SUN Z, WANG Z, TIAN Y,et al. Progress, outlook, and challenges in lead-free energy-storage ferroelectrics. Advanced Electronic Materials, 2020, 6(1): 1900698.
[36] SUN Z, BAI Y, LIU J,et al. Interface engineering in ferroelectrics: from films to bulks. Journal of Alloys and Compounds, 2022, 909: 164735.
[37] JI X, WANG C, HARUMOTO T,et al. Structure and electrical properties of BCZT ceramics derived from microwave-assisted Sol-Gel-hydrothermal synthesized powders. Scientific Reports, 2020, 10: 20352.
[38] CHUKHCHIN D G, MALKOV A V, TYSHUNOVA I V,et al. Diffractometric method for determining the degree of crystallinity of materials. Crystallography Reports, 2016, 61(3): 371.
[39] DANG S T, XUE L L, HE L F,et al. Dielectric and energy storage properties of Ba_0.85Ca_0.15Zr_0.1Ti_0.9O₃ ceramics with different aging temperature during the Sol-Gel process. Journal of Materials Science: Materials in Electronics, 2022, 33(35): 26100.
[40] KOU Q, YANG B, SUN Y,et al. Tetragonal (Ba, Ca)(Zr, Ti)O₃ textured ceramics with enhanced piezoelectric response and superior temperature stability. Journal of Materiomics, 2022, 8(2): 366.
[41] CHAKKCHAOUI N, FARHAN R, BOUTALDAT M,et al. Piezoelectric β-polymorph formation of new textiles by surface modification with coating process based on interfacialinteraction on the conformational variation of poly (vinylidene fluoride)(PVDF) chains. The European Physical Journal Applied Physics, 2020, 91(3): 31301.
[42] SUN Z, LIU J, WEI H,et al. Ultrahigh energy storage capacity in multilayer-structured cellulose-based dielectric capacitors caused by interfacial polarization-coupled Schottky barrier height. Journal of Materials Chemistry A, 2023, 11(37): 20089.
[43] SUN Z, WEI H, ZHAO S,et al. Utilizing the synergistic effect between the Schottky barrier and field redistribution to achieve high-density, low-consumption, cellulose-based flexible dielectric films for next-generation green energy storage capacitors. Journal of Materials Chemistry A, 2024, 12(1): 128.
[44] SUN Z, WANG S, ZHAO S,et al. Achieving low energy consuming bio-based piezoelectric nanogenerators via modulating the inner layer thickness for a highly sensitive pedometer. Journal of Materials Chemistry C, 2024, 12(3): 859.
[45] OTTA S, KAND L, DAS R K,et al. Piezoelectric, structural, vibration and optical properties of lead free based 0.5Ba(Ti_0.8Zr_0.2)O₃-0.5(Ba_0.7Ca_0.3)TiO₃ ceramic sample. Materials Today Communications, 2023, 35: 106191.
[46] JI W, FANG B, LUX,et al. Tailoring structure and performance of BCZT ceramics prepared via hydrothermal method. Physica B: Condensed Matter, 2019, 567: 65.
[47] TUAN D A, TUNG V T, VAN CHUONG T.Synthesis and Investigation of the Physical Properties of Lead-Free BCZT Ceramics//Perovskite and Piezoelectric Materials.IntechOpen, 2019.
[48] BARASKAR B G, KOLEKAR Y D, THOMBARE B R,et al. Enhanced piezoelectric, ferroelectric, and electrostrictive properties of lead‐free (1‐x)BCZT‐xBCST electroceramics with energy harvesting capability. Small, 2023, 19(37): 2300549.
[49] MISSAOUI S, BOUHAMED A, NOURI H,et al. Sustainable and flexible piezoelectric nanogenerator with hybrid nanocomposites based on high-performance synthesized BCZT powder. ACS Applied Electronic Materials, 2024, 6(8): 5608.
[50] LI Y, TAN J, LIANG K,et al. Enhanced piezoelectric performance of multi-layered flexible polyvinylidene fluoride-BaTiO₃-rGO films for monitoring human body motions. Journal of Materials Science: Materials in Electronics, 2022, 33(7): 4291.
[51] RAVINDRAN P, VIDYA R, KJEKSHUS A,et al. Theoretical investigation of magnetoelectric behavior in BiFeO₃. Physical Review B-Condensed Matter and Materials Physics, 2006, 74(22): 224412.
[52] YANG P, ZHAO L, SHI S,et al. The influence of interface on the dielectric and tunable properties of BCZT/BZT ceramic. Journal of Materials Science: Materials in Electronics, 2024, 35(8): 610.
[53] JI D, ZHANG M, SUN H,et al. Enhanced mechanical and dielectric properties of lignocellulosic composite papers with biomimetic multilayered structure and multiple hydrogen-bonding interactions. International Journal of Biological Macromolecules, 2024, 281: 136247.
[54] HANANI Z, MEZZANE D, AMIOUD M,et al. Structural, dielectric, and ferroelectric properties of lead-free BCZT ceramics elaborated by low-temperature hydrothermal processing. Journal of Materials Science: Materials in Electronics, 2020, 31(13): 10096.
[55] JAFFARI G H, SHAWANA H, MUMTAZ F,et al. Electrical response of PVDF/BaTiO₃ nanocomposite flexible free-standing films. Bulletin of Materials Science, 2023, 46(4): 227.
[56] SU C, HUANG X, ZHANG L,et al. Robust superhydrophobic wearable piezoelectric nanogenerators for self-powered body motion sensors. Nano Energy, 2023, 107: 108095.
[57] ZHANG Y, RUAN K, GU J.Flexible sandwich‐structured electromagnetic interference shielding nanocomposite films with excellent thermal conductivities.Small, 2021, 17(42): 2101951.