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Electrospun TiO 2–PVDF Nanocomposite

Membranes for High-Performance Liquid–Solid
Triboelectric Nanogenerators with Cascaded
Architecture

MD Fajla Rabbi, Duy Linh Vu, Kyoung Kwan Ahn

PII: S0925-8388(25)04092-7
DOI: [Link]
Reference: JALCOM182531

To appear in: Journal of Alloys and Compounds

Received date: 12 May 2025
Revised date: 4 July 2025
Accepted date: 23 July 2025
Please cite this article as: MD Fajla Rabbi, Duy Linh Vu and Kyoung Kwan
Ahn, Electrospun TiO2–PVDF Nanocomposite Membranes for High-
Performance Liquid–Solid Triboelectric Nanogenerators with Cascaded
Architecture, Journal of Alloys and Compounds, (2025)
doi:[Link]
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Electrospun TiO2–PVDF Nanocomposite Membranes for High-
Performance Liquid–Solid Triboelectric Nanogenerators with Cascaded
Architecture
MD Fajla Rabbia, Duy Linh Vub, Kyoung Kwan Ahna*
a
Fluid Power & Machine Intelligence (FPMI) Laboratory, School of Mechanical Engineering, University of Ulsan, 93,
Daehak-ro, Nam-gu, Ulsan 44610, South Korea
b
Faculty of Electrical and Electronic Engineering, Phenikaa University, Yen Nghia, Ha Dong, Hanoi 12116, Vietnam

∗ Corresponding author.

E-mail address: kkahn@[Link] (K.K. Ahn)

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Abstract

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This study presents a high-performance electrospun nanocomposite membrane composed of poly
(vinylidene fluoride) (PVDF) and different phases of titanium dioxide (TiO₂) for liquid–solid
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triboelectric nanogenerator (LS-TENG) applications. To address the low surface charge density and
dielectric constant of pristine PVDF, anatase and rutile TiO2 nanoparticles were incorporated into the
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polymer matrix through electrospinning, which promoted the formation of the electroactive β-phase
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essential for enhancing triboelectric performance. Among them, rutile TiO₂ at 5 wt% significantly
promoted the formation of the electroactive β-phase (up to 87.6%), resulting in an eightfold
enhancement in electrical output compared to the pure PVDF membrane. The optimized nanogenerator
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achieved an output voltage of 6.9 V, a current of 71.03 μA, and a peak power density of 0.55 W/m². A
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cascaded TENG architecture was further developed by stacking multiple nanocomposite membranes,
effectively amplifying output through sequential liquid–solid contact. The resulting device
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demonstrates excellent energy conversion efficiency, long-term stability, and strong sensitivity to fluid
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flow and pH changes, highlighting its potential for self-powered sensing and environmental monitoring.
This work provides a scalable strategy for designing electrospun functional composites for advanced
triboelectric energy harvesting applications.

Keywords: triboelectric nanogenerator, liquid-solid, electrospinning, nanocomposite,

hydrophobicity, sensors
1. Introduction
Traditional energy systems dominated by carbon-based fuels cannot meet future energy demands
as more people connect to the grid and the concept of smart cities with Internet of Things (IoT) sensors
become increasingly realistic[1-3]. The ever-increasing use of smart sensors and sensing systems,
coupled with advancements in artificial intelligence (AI) and the Internet of Things (IoT), will present
challenges in powering these devices[4-6]. The integration of various green energy harvesting
technologies with decentralized power systems is essential for sustainable development. To address this

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challenge, extensive research is being conducted in various energy harvesting systems, including
piezoelectric, triboelectric, thermoelectric, and electromagnetic nanogenerators[7-11]. These

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technologies offer potential solutions by converting mechanical, thermal, and electromagnetic energy
from the environment into usable electrical power, thus enabling the development of self-sustaining,
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low-power devices for applications ranging from wearable electronics to IoT systems [12-19]. Among
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these, triboelectric nanogenerators (TENGs) have gained considerable attention as a promising solution
for energy harvesting due to their structural simplicity, portability, cost-effectiveness, efficient energy
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conversion, and potential for miniaturization[20-22]. In 2012, Professor Zhong Lin Wang pioneered
the concept of the triboelectric nanogenerator (TENG), a micro-nano power source designed to convert
small-scale mechanical energy into electricity which is the synergistic effects of contact electrification,
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also known as triboelectrification, and electrostatic induction, offering a novel approach to energy
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harvesting at the micro and nanoscale.[11, 23-25]. The liquid-solid triboelectric nanogenerator (LS-
TENG) specifically utilizes the contact electrification between liquids and solids, demonstrating
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significant potential for energy harvesting applications involving fluid flow and interactions in diverse
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environmental conditions. In liquid-solid TENG, the contact electrification and the formation of the
electric double layer (EDL) is responsible for the charge displacement and power generation [26-31].
The limitations of existing materials used in liquid-solid TENGs owing to low polarization and surface
charge density result in low triboelectrification and reduced output power, significantly restricting their
energy conversion efficiency.

Poly (vinylidene fluoride) (PVDF) and its copolymers have been extensively studied for their wide-
ranging applications in triboelectric systems, including energy harvesting, self-power sensing and
electronics, due to their efficient energy conversion capabilities[32-35]. This is due to a strong
triboelectric effect, excellent thermal stability, and superior mechanical strength, along with the
advantage of diverse and cost-effective synthesis methods, making it an ideal candidate for a range of
triboelectric applications. PVDF characterized by its repeating unit of the CF2-CH2 monomers
configuration, exhibits polymorphism in generally α, β, and γ forms; among these, the polar crystalline
β phase exhibits remarkable triboelectric properties due to its all-trans planar zigzag configuration,
which enhances charge separation and increases overall energy conversion efficiency [36-38].
Therefore, increasing the concentration of the β phase is an effective approach to improving the
performance of PVDF as a more efficient nanogenerator. While the α phase is the most common and
easiest to obtain, acquiring the β phase is more difficult. However, most of the methods, such as heat
treatment, rapid cooling from melt, mechanical stretching, spin coating and humidity variation, have
drawbacks and are not suitable for mass production. Electrospinning, a simple and versatile technique

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characterized by strong electric field-induced polarization, can be an economical approach that reduces
or eliminates the need for supplementary postprocessing steps to produce high concentration β-phase

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PVDF membranes[39-44].

Significant advancements have been made in developing triboelectric materials through

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incorporating nanostructures such as Zinc Oxide (ZnO), Graphene Oxide, Barium Titanate (BaTiO 3),
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Manganese Dioxide (MnO2), Cobalt Ferrite (CoFe2O4), and Tin (IV) Oxide (SnO2), enhancing
triboelectric performance by improving charge transfer, energy conversion, and overall efficiency,
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thereby contributing to optimizing triboelectric energy harvesting technologies [45-48]. The addition
of ferromagnetic or dielectric materials significantly improves polyvinylidene fluoride (PVDF)
performance by enhancing the electroactive β-phase. Among nonpiezoelectric materials, titanium
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dioxide (TiO2) is notable due to its distinctive crystal structure, excellent chemical and thermal stability,
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non-toxicity, and affordability [49, 50].

Anatase and rutile TiO2 exhibit distinct structural and dielectric properties critical for liquid-solid
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triboelectric nanogenerator (LS-TENG) applications. Structurally, rutile adopts a dense tetragonal

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lattice with strong Ti–O bonds, ensuring mechanical stability under fluid shear stress, while anatase
features an open tetragonal arrangement that offers higher surface energy and reactivity[51]. However,
rutile’s high dielectric constant (ε ≈ 90–170) plays a crucial role in enhancing interfacial polarization
and local electric field strength within the PVDF matrix, promoting more effective β-phase nucleation
and overall charge induction efficiency[52]. Although anatase exhibits a more open tetragonal structure
with higher surface area and lower surface energy, which aid in dispersion and surface interactions, it
tends to be less mechanically robust and offers a lower dielectric constant (ε ≈ 30–75), limiting its
effectiveness in maximizing triboelectric output [49, 53]. Furthermore, the strong interfacial field
gradients generated by rutile nanoparticles better align PVDF dipoles during electrospinning,
facilitating the transition to the electroactive β-phase [51, 54]. Anatase's lower processing temperature
requirements and superior dispersibility make it advantageous for temperature-sensitive polymer
processing, allowing for better preservation of polymer properties during composite fabrication [55].
These complementary properties position both phases as valuable for LS-TENGs, with rutile excelling
in dielectric enhancement and anatase contributing through superior surface interactions and processing
advantages. However, regulating TiO2 concentration in nanocomposite membranes remains
challenging, particularly with high TiO2 loading. Excessive TiO2 loading often leads to nanoparticle
agglomeration within the polymer matrix, negatively impacting structural integrity and performance.
Proper dispersion techniques are thus critical. Electrospinning effectively addresses these challenges
by controlling nanomaterial dispersion through fibrous morphology formation, promoting uniform

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nanoparticle distribution and enhancing β-phase induction in PVDF fibers.
In this study, a highly polarized TiO2-PVDF nanocomposite membrane was fabricated using

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electrospinning as the triboelectric layer. The impact of anatase and rutile phase TiO2 within the PVDF
matrix is analyzed in relation to its triboelectric performance. Thin films with varying weight
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percentages of anatase and rutile TiO2 in the PVDF matrix were synthesized to find out optimal
combinations for better triboelectric performance. We found that the addition of 5% rutile TiO₂ to PVDF,
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combined with optimal electrospinning parameters, significantly enhances performance, with the β-
phase content reaching the highest level (87.6%) among all the tested combinations. Consequently, the
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electrical output of RT/PVDF-5 TENG is reached 0.55 mW/m2, which is 8 times greater than PVDF
TENG. Additionally, the optimized RT/PVDF-5 TENG demonstrates impressive performance,
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generating an output current of 71.03 μA and a voltage of 6.2 V. Furthermore, the TENG device
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demonstrates excellent durability and stability which is crucial for energy harvesting applications. We
also introduce a cascading configuration that strategically layers triboelectric interfaces, facilitating
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sequential charge transfer and amplifying the overall output. This cascading structure, when combined
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with TiO2 nanoparticle-enhanced PVDF films, achieves a significant boost in triboelectric output,
expanding the potential of TENGs for applications such as environmental monitoring and autonomous
low-power devices.
2. Experimental section

2.1 Materials and chemicals

Polyvinylidene fluoride (MW = 570 000), N, N-dimethylformamide (DMF, AR 99,5%) and acetone
were acquired from Samchun Chemical (Korea). Titanium (IV) oxide powder, rutile and anatase, were
obtained from Sigma-Aldrich, USA. Indium tin oxide (ITO) (Sigma-Aldrich, USA) with resistivity of
10 to 12 Ω/sq was used as the electrode.
 2.2. Fabrication of TiO2-PVDF nanocomposite membrane and TENG devices

Nanocomposite membranes with various concentrations of anatase and rutile phase TiO2 were
obtained through electrospinning (NS1, INNOVESTO Co., Ltd.) followed by drying in a convection
oven. The experimental procedure was carried out as follows: First, DMF and acetone were mixed in a
6:4 ratio and stirred with a magnetic stirrer for 15-20 minutes at 30°C. Second, various amounts of
anatase and rutile phase TiO2 were added to the solution and ultrasonicated for 30 minutes. Third, 1.6
g of PVDF powder was introduced into the solutions, and the mixture was stirred with a magnetic stirrer
for 20 hours to form the electrospinning precursor solutions. The precursor solutions were then placed
in an ultrasonic bath for another 30 minutes to remove any bubbles and achieve a homogeneous

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PVDF/TiO2 solution. Fourth, the resulting precursor solutions were loaded into a 10 mL syringe fitted.
The electrospinning parameters were as follows: high voltage source 15 kV, needle-to-collector

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distance 16 cm, and syringe pump speed 0.9 mL/h. Fifth, the synthesized nanofiber membranes were
dried in a convection oven at 90°C for 5 hours to eliminate residual solvents.
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Additionally, PVDF nanofiber films without TiO2 fillers were prepared using the same method.
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Details of the fabrication method are shown in Scheme. 1. The fabricated TENG device is based on a
droplet-based electricity generator (DEG) with slight modification. Electrospun nanofiber was deposed
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on an ITO substrate, serves as the bottom electrode. The top electrode is positioned at the end of the
triboelectric polymer surface.
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Table 1. Nomenclature of membranes.

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Scheme. 1. Schematic illustration of preparation of RT/PVDF and AT/PVDF nanocomposite

membranes.
 PVDF DMF/Acetone Anatase TiO2 Rutile TiO2
Sample Code
Concentration ratio Concentration Concentration
PVDF 15% 6:4 0 0
AT/PVDF-1 15% 6:4 1% 0
AT/PVDF-3 15% 6:4 3% 0
AT/PVDF-5 15% 6:4 5% 0
AT/PVDF-7 15% 6:4 7% 0
RT/PVDF-1 15% 6:4 0 1%
RT/PVDF-3 15% 6:4 0 3%
RT/PVDF-5 15% 6:4 0 5%

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RT/PVDF-7 15% 6:4 0 7%

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2.3 Characterization and Measurements

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The field emission scanning electron microscope (FE-SEM) analysis was conducted to examine the
microstructure and morphology of the electrospun nanofibers (JSM-7600, JEOL Co.). An atomic force
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microscope (AFM) (MFP-3D Stand Alone AFM) was used to analyze the roughness of the membrane
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surface. The chemical structure of the membrane was analyzed using Fourier transform infrared (FTIR)
spectroscopy (Nicolet iS5, Thermo Fisher Scientific). The crystalline phase compositions were
analyzed using X-ray diffraction (XRD; Ultima IV, Rigaku Corporation) with Cu Kα (λ = 0.154056
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nm) radiation and a 2θ scanning range of 10–30°. The hydrophobic properties of each membrane were
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assessed by measuring the water contact angle and sliding angle with a SmartDrop device (FemtoFAB).
For dielectric characterization, capacitors were prepared using PVDF, AT/PVDF and RT/PVDF
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nanocomposite membranes by depositing gold (Au) electrodes onto the film surfaces. The electrodes
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were applied using a shadow mask with a circular pattern of 200 μm diameter to ensure uniform
electrode geometry and precise measurement, as schematically shown in Fig. S4 (Supporting
Information). These capacitor structures enabled accurate evaluation of the dielectric properties of the
membranes. Frequency-dependent dielectric permittivity was measured using an Agilent 4294A
precision impedance analyzer, with measurements performed over a frequency range of 10 Hz to 100
kHz. This analysis allowed for the assessment of dielectric behavior under varying electrical stimuli
and provided insights into the influence of TiO2 nanoparticles on the dielectric performance of the
composite membranes. A Keithley digital electrometer (model DMM7510) was used to measure the
current and voltage data.
 For all electrical output characterization experiments, a peristaltic pump was employed to precisely
regulate the delivery of deionized water droplets. The pump was calibrated to release droplets with a
consistent volume of 50 μL and the droplets were dispensed from a height of 20 cm to ensure an optimal
balance between kinetic impact and surface wetting, while avoiding splashing. To facilitate efficient
runoff and minimize water accumulation on the membrane surface, the LS-TENG device was
positioned at a surface inclination angle of 60°. This standardized setup ensured repeatable and
consistent testing conditions across all samples, improving the reliability of triboelectric output
measurements.

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3. Results and discussions
3.1. Characterization of the membrane

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Fig. 1. Morphological analysis of AT/RT/PVDF nanofibers with varying concentrations of TiO2. (a)
SEM image of PVDF (b-d) SEM image of AT/PVDF-1,3,5 (e-g) SEM image of RT/PVDF-1,3,5 (g)
EDS mapping image of RT-PVDF nanocomposite membrane (i) SEM image of membrane cross-
section. Distribution of fiber diameters (J) PVDF (k)AT/PVDF-5 (l)RT/PVDF-5.
 FE-SEM measurements were performed to observe the detailed morphology of each membrane
(Fig. 1). The SEM images reveal that all electrospun membrane exhibit a uniform fibrous structure,
indicating the successful preparation of the films with minimal bead formation. The nanofibers are
randomly oriented, creating a network with varying fiber diameters as it was deposed on flat collectors.
The nanofibers exhibit smooth surfaces with no noticeable defects or beading, which indicates the
solution preparation and fabrication of nanofiber by electrospinning were done under optimal
conditions. As illustrated in Fig. 1 (a), the PVDF membrane consists of randomly arranged fibers with
uniform surfaces. The smooth surface minimizes the available surface area and lacks microstructural
features, such as pores or rough textures. In contrast, SEM images of the TiO2-PVDF membrane fibers

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showed noticeable nano protrusions emerging on the fiber surfaces, becoming more prominent as the
TiO2 content in the dispersion increased (Fig. 1 (b-g)).

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The uniform distribution of TiO2 within the polymer matrix significantly contributed to the stability
of the electrospun fibers, preventing bead formation. FE-SEM images (Fig. 1(a–g)) revealed well-
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defined, smooth nanofibers without visible defects or beads, confirming the successful electrospinning
of the TiO₂-loaded PVDF solution. Energy-dispersive X-ray spectroscopy (EDS) line mapping (Fig.
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S1) confirms the successful incorporation and homogeneous distribution of TiO2 nanoparticles in the
electrospun PVDF fibers, with increasing Ti and O content corresponding to higher TiO₂ loading levels.
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EDS mapping was also performed on the electrospun fiber membrane to visualize the elemental
distribution (Fig. 1(h)). The mapping images clearly demonstrate the uniform distribution of carbon
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(C), fluorine (F), titanium (Ti), and oxygen (O). Here, F and C are intrinsic to the PVDF polymer, while
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Ti and O signify the presence of TiO2 nanoparticles. The clear and uniform presence of Ti and O
throughout the fibers indicates effective and homogeneous dispersion of the TiO2 nanoparticles within
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the PVDF matrix. SEM analysis of the membrane cross-section (Fig. 1(i)) further confirms a consistent
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and homogeneous thickness of approximately 155 µm, demonstrating the uniformity and stability of
electrospinning conditions and material composition
After incorporating TiO2 nanoparticles into the PVDF, a noticeable increase in nanofiber diameter
was observed. The average fiber diameter increased from approximately 465 nm for pure PVDF
nanofibers to 535 nm for the AT/PVDF-5 and 604 nm for the RT/PVDF-5 composite fibers. This
increase in fiber diameter can primarily be attributed to the enhanced viscosity of the polymer solution
resulting from the addition of TiO2 nanoparticles. The TiO₂ nanoparticles interact strongly with PVDF
polymer chains, restricting their mobility and increasing intermolecular entanglement. These enhanced
entanglements significantly raise the viscosity and elasticity of the solution, leading to a more
pronounced resistance against elongational forces during electrospinning. Furthermore, the
nanoparticles induce changes in electrospinning jet dynamics, including increased charge density
variations and altered electric field distributions around the polymer jet. Such variations result in
reduced stretching and whipping instability of the electrospinning jet, ultimately producing thicker
nanofibers. Additionally, the presence of nanoparticles can induce rapid solvent evaporation from the
polymer jet surface, further hindering jet elongation and promoting the formation of fibers with larger
diameters. Histograms representing the distribution of fiber diameters for pure PVDF, AT/PVDF-5, and
RT/PVDF-5 fibers (Fig. 1(j–l)) exhibit Gaussian distributions, indicating a uniform and controlled
electrospinning process. The increase in fiber diameter correlates directly with higher viscosity due to
TiO2 nanoparticle addition, aligning with previous reports on polymer-nanoparticle composite
electrospinning. Furthermore, the surface morphology of the AT/PVDF-5 and RT/PVDF-5 nanofibers

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remained smooth and continuous, without visible nanoparticle agglomerations, underscoring good
nanoparticle dispersion within the fiber matrix. This uniform dispersion is crucial for effective

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application in sensors and energy harvesting devices. However, at higher TiO2 concentrations (up to 7
wt.%), nanoparticles began to aggregate locally at fiber surfaces and junctions, slightly increasing fiber
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diameter and indicating the onset of nanoparticle saturation and aggregation. Despite minor aggregation
at higher concentrations, the fibers maintained their overall cylindrical morphology and integrity,
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supporting their potential application in sensors and energy harvesting devices.
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Fig. 2 (a) AFM image of (a) PVDF (b) AT/PVDF-5 (c) RT/PVDF-5. Height map of (d) PVDF (e)
AT/PVDF-5 (f) RT/PVDF-5 (g) Root-mean-square value of different membranes (h) Water contact
angle of different membranes.
Membrane surface roughness is a critical factor that influences the membrane's surface structure, and
it strongly impacts the membrane's wettability. Fig. 2(a-f) demonstrates how the surface morphology
and roughness of electrospun PVDF membranes significantly improve with the addition of TiO 2
nanomaterials. The AFM images reveal distinct surface changes: pristine PVDF membranes exhibit
relatively moderate roughness, while the addition of TiO2 (AT/PVDF and RT/PVDF samples) results
in increased roughness and more nanostructured features. Quantitatively, the RMS roughness (Rq)
significantly increases with the introduction of TiO2 nanoparticles into the PVDF matrix. Specifically,
the pristine PVDF membrane has an RMS roughness of 62 nm, indicating a relatively smooth surface
at the nanoscale. However, upon adding TiO2, the RMS roughness increases notably to 94.5 nm for the

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Fig. 3 (a) XRD pattern of PVDF, AT/PVDF and RT/PVDF (b) FT-IR spectra of Pristine PVDF and
different mass fraction ratios of Anatase and Rutile TiO2. Beta phase fractions of different
membranes with varying TiO2 concentration (c) RT/PVDF (d) AT/PVDF
AT/PVDF membrane, demonstrating enhanced surface irregularities and texture. The RT/PVDF
membrane shows an even greater roughness, with an RMS value of 103.9 nm. These increases in Rq
values clearly indicate the creation of more surface features and a more complex topography at both
micro- and nanoscales. Correspondingly, water contact angle measurements Fig.2 (h) demonstrates a
direct correlation between increased roughness and improved hydrophobicity. The neat PVDF
membrane exhibits a contact angle of 132°, whereas AT/PVDF and RT/PVDF membranes show
significantly higher angles (142.3° and 144.6°, respectively). This enhancement in hydrophobicity can
be attributed to the increased surface area and the hierarchical nanostructures created by incorporating
TiO₂ nanoparticles, effectively reducing surface wettability and enhancing the membrane's anti-wetting

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performance.

The formation of the β-phase in PVDF was confirmed by FTIR and XRD analysis, indicating that

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both the incorporation of TiO₂ nanoparticles and the electrospinning process promote the desired phase
transition. Fig. 3(a) shows the XRD patterns of electrospun PVDF, anatase TiO2-PVDF (AT-PVDF),
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and rutile TiO2-PVDF (RT-PVDF) membranes. The pure PVDF membrane exhibits characteristic
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diffraction peaks around 18.3° (α-phase) and 20.3° (β-phase), indicating a mixture of crystalline
polymorphs. Upon introducing anatase TiO2 nanoparticles into PVDF (AT-PVDF), a distinct anatase
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peak (A(101)) at approximately 25.3° emerges, corresponding to the anatase crystal structure (JCPDS
99−0008) and confirming the successful incorporation of TiO2 nanoparticles. In membranes containing
rutile TiO2 (RT-PVDF), a pronounced diffraction peak at around 27.5° (R (210)) appears, confirming
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the presence of the rutile phase (JCPDS 99−0090). These results suggest that incorporating rutile TiO2
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nanoparticles into PVDF effectively promotes β-phase formation, more than anatase TiO2, and
significantly more than in the pure PVDF membrane. The high-voltage electric field applied during
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electrospinning plays a pivotal role in directing the molecular orientation and phase transformation of
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PVDF fibers, thereby significantly influencing their structural evolution. Under high-voltage conditions,
the electric field stretches the polymer solution jet and induces alignment of PVDF molecular chains
along the fiber axis, which energetically favors the formation of the electroactive β-phase. This process
facilitates enhanced dipole orientation and promotes a higher fraction of β-phase compared to
conventional methods lacking such field-driven alignment. This field-induced stretching and alignment
of PVDF chains is a critical factor in enhancing the β-phase content, which directly correlates with the
observed improvements in the functional properties of the membranes. This is further supported by
FTIR analysis.
 The crystalline phase composition of the polymer fibers was analyzed using Fourier Transform
Infrared Spectroscopy (FTIR), as presented in Fig. 3(b). This technique allows for the identification of
specific molecular vibrations, providing detailed information about the crystalline phases present
within the polymer structure. Such insights are essential for understanding the material’s structural
properties and their impact on the overall performance of the fibers. The nonpolar α phase corresponds
peaks at 613, 762, and 976 cm-1 whereas the absorption peaks at 840, 1275, and 1430 cm-1 correspond
to the polar β phase[56, 57]. Among them, C-C skeletal stretching, CH2 rocking, and CF2 stretching
are the main impacting factor for polar β phase formation at 840 cm-1[58]. The absorption peak
intensity at 762 cm⁻¹ is reduced after doping TiO₂ into the PVDF matrix, indicating that the introduction

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of TiO2 significantly enhances the polar β-phase content in the nanocomposite membranes while
reducing the nonpolar α-phase. The β phase percentage content in PVDF, AT/PVDF and RT/PVDF can

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be calculated using the Lambert−Beer law,

A𝛽
F(𝛽) =
(
Kα
Kβ
-p
) Aα + Aβ
*100% (1)
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Where Kβ and Kα is the ratio of the absorption coefficients for the β and α phases. Aα and Aβ are the
absorbances of the phases at 764 and 840 cm-1[59]. As shown in Fig. 3(c, d), a clear trend is observed
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wherein the incorporation of both rutile and anatase TiO₂ into PVDF results in a substantial increase in
β-phase content. For both TiO₂ phases, the β-phase percentage increases sharply as the TiO₂ loading
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rises from 0 to approximately 5 wt.%. Specifically, in the case of rutile TiO₂ (RT/PVDF), the β-phase
content increases from 77.5% to approximately 87.3%, while for anatase TiO₂ (AT/PVDF), it increases
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from 75.4% to 83.6%. Beyond this point, a slight decline in β-phase content is observed as the filler
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concentration increases to 7 wt.%. These behaviors are governed by several synergistic mechanisms
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where TiO₂ nanoparticles act as nucleating agents that facilitate the transformation of PVDF chains into
the all-trans (TTT) conformation associated with the electroactive β-phase. During electrospinning, the
high dielectric nature of TiO2 particularly the rutile phase amplifies the local electric field within the
polymer jet, enhancing dipole alignment and strong interfacial interactions, such as dipole–dipole
coupling between the negatively charged TiO2 surface and the polarized –CH₂ groups of PVDF, further
promote β-phase stabilization[60]. Additionally, rutile TiO2 contributes to enhanced dielectric
performance through Maxwell–Wagner–Sillars (MWS) interfacial polarization, which increases
effective dipole density via charge accumulation at nanoparticle–polymer boundaries[61]. While
excessive TiO2 loading beyond 5 wt.% may cause nanoparticle agglomeration, slightly reducing β-phase
content due to disrupted chain ordering, the continued rise in dielectric constant at 7 wt.% suggests that
interfacial polarization effects remain dominant, emphasizing the need for careful optimization of filler
concentration to balance structural ordering and dielectric enhancement.

3.2 Working mechanism

As illustrated in Scheme 2, an equivalent circuit model was developed to explain the charge transfer
mechanism of a water droplet under various dynamic positions at the solid-liquid interface. The
interface between the water droplet and triboactive PVDF composite membrane is represented by the
capacitor CW/P, while the PVDF-ITO interface is depicted by the capacitor CP/I. Similarly, the water
droplet-Al electrode interface is regarded as the capacitor CW/A , and the ITO-Al electrode interface
corresponds to the capacitor CI/A. The droplet itself is treated as a resistor RW, and the inherent

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resistance of the circuit is denoted as R. When water droplets impact the triboactive PVDF composite
membrane surface, the droplets become positively charged, while the PVDF membrane acquires a

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negative charge due to the contact electrification effect. During this process, the switch SW/P remains

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open. This is equivalent to charging the CW/P capacitor within the circuit. As the water droplets slide
across, the physical contact between the droplet and the PVDF composite membrane allows the
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neutralization of opposite charges at the interface, which prevents electrostatic induction and results in
no electrical signal being generated in the circuit. As the droplet continues to slide and contacts the
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aluminum (Al) electrode, the switch SW/A closes, completing the circuit. The positive charge stored in
the CW/P capacitor is rapidly discharged, while the other capacitors CW/A , CI/A , CP/I in the circuit begin
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to charge. This switching mechanism significantly reduces the charge transfer time, thereby enhancing
the output of solid-liquid electrification. During this process, as the droplet spreads on the Al surface,
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the contact areas between water droplets and PVDF composite membrane , as well as between water
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Scheme 2. Working principle of the droplet based TENG device

droplets and the Al electrode, change continuously, causing variations in the capacitance values of CW/P,
CP/I, and CW/A. Consequently, the capacitors in the circuit undergo rapid cycles of charging and
discharging. Ultimately, due to the presence of resistances RW and R, the charges within the circuit are
fully dissipated.

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3.3 Electrical characterizations

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Fig. 4. (a) The single peak current of LS-TENG. Comparison of voltage and current of PVDF,
AT/PVDF and RT/PVDF TENG (b-e) Comparison of optimal Current, voltage, Charge transfer and
frequency dependence dielectric constant of PVDF, AT/PVDF, RT/PVDF TENG
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In Fig. 4a, the step-by-step process of current signal generation in relation to the dynamic motion
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of droplets falling onto the LS-TENG surface is demonstrated. When a water droplet falls from an
elevated height and makes contact with the hydrophobic surface, it initially spreads across the surface
u

without establishing contact with the top electrode. During this stage, the induced charges are localized
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on the bottom electrode, as shown in Fig. 4a (iii). As the spreading droplet eventually touches the top
electrode, electrons flow from the bottom electrode to the top electrode to neutralize the potential
difference, resulting in a peak positive current signal, as depicted in Fig. 4a (vi). Upon reaching
maximum spreading, the droplet begins to retract and slide off the hydrophobic surface. As the contact
area reduces during contraction, an opposite set of charges is induced in the bottom electrode to balance
the positive charges on the surface, generating a corresponding negative current peak, illustrated in Fig.
4a (v). Since the charge induction during the retraction phase is more gradual, the relaxation time of
the signal is relatively longer. Once the droplet fully detaches and no longer contacts the top electrode,
the current signal diminishes and eventually disappears.
To investigate the effect of TiO2 doping with different crystalline phases, namely anatase and rutile,
on the triboelectric properties of PVDF, their electrical output is compared with a similar test set-up(Fig.
S1). As shown in Fig. 4 (b), the transferred charge increased significantly after incorporating TiO2
nanoparticles into the PVDF matrix, rising from 0.67 μC for pristine PVDF to 1.89 μC for AT/PVDF
and further to 2.36 μC for RT/PVDF. The output current increased from 15.75 μA for the PVDF TENG
to 53.69 μA for the AT/PVDF TENG and further to 71.60 μA for the RT/PVDF TENG, highlighting the
significant enhancement in performance with the addition of TiO2, particularly with the rutile phase
(Fig. 4c). Similarly, the obtained output voltage (Voc) is highest in the RT/PVDF TENG compared to
both the AT/PVDF and PVDF TENG. Adding TiO2 to PVDF enhances triboelectric performance by
increasing surface roughness for better charge transfer efficiency and raising the dielectric constant due
to TiO2's high intrinsic dielectric properties, enabling greater charge storage and improved electrical

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output. In the case of AT/PVDF and RT/PVDF nanofibers, RT/PVDF nanofibers exhibit slightly higher
output voltage and short-circuit current (Isc). This is due to the stronger dipole interaction between

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rutile and the PVDF matrix, as rutile's higher dielectric constant compared to anatase enhances the
alignment of PVDF polymer chains, promoting more effective β phase formation, with the highest β
-p
phase peak observed in RT/PVDF nanofibers, indicating a more oriented crystalline structure compared
to the AT/PVDF membrane. Previous studies have demonstrated that the β-phase of PVDF nanofibers
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enhances the triboelectric effect, leading to higher electrical performance in TENGs[62]. The β-phase
is primarily generated through the pulling force exerted on the nanofibers during the electrospinning
lP

process. Rutile TiO2, due to its higher conductivity, exerts a greater pulling force during electrospinning,
which facilitates the generation of more β phase[63]. As a result, the RT/PVDF nanofibers demonstrated
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superior electrical performance compared to other nanofibers.

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Given the operating principles of LS-TENGs, which rely on electrostatic induction and
triboelectrification at the liquid–solid interface, the dielectric properties of the solid membrane play a
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pivotal role in modulating charge generation and transfer efficiency. The frequency-dependent
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dielectric properties of each membrane were evaluated over the frequency range of 1 Hz to 100 kHz,
as illustrated in Fig. 4(f). The pristine PVDF membrane exhibited a dielectric constant of approximately
10.8 at 1 Hz, which gradually decreased with increasing frequency, which is consistent with previously
reported results [64]. Upon the incorporation of TiO₂ nanoparticles, a pronounced increase in dielectric
constant was observed, with values at 1 kHz measured as 14.1, 18.5, and 27.5 for PVDF, AT/PVDF,
and RT/PVDF membranes, respectively. This improvement is attributed to the enhanced interfacial
polarization induced by the heterogeneity between the TiO₂ nanoparticles and the PVDF matrix, as well
as the increased density and alignment of molecular dipoles. The rutile phase, due to its higher intrinsic
dielectric constant and stronger surface polarizability compared to anatase, amplifies local electric
fields during electrospinning and promotes the formation of the electroactive β-phase. As reported in
earlier studies [64], the charge accumulation (Q) in a tribo-membrane functioning as a capacitor can be
described by
−𝑡
𝑄 = 𝐶𝑉 [1 − 𝑒 𝑅𝐶 ]

Where C, V, t, and R are the capacitance, input voltage, charging time, and resistance, respectively.
Assume that V is constant, the maximum capacitance (Cmax) of the membrane can be calculated by
ε0 ε𝑟 𝐴
𝐶max =
𝑑
Where ε0 is the vacuum permittivity, ε𝑟 is the dielectric permittivity of the triboelectric membrane, A
is the contact area, and d is the thickness of the membrane. Since ε𝑟 is directly proportional to 𝐶max ,

of
which in turn is proportional to the stored charge Q, an increase in dielectric constant leads to higher
charge density and thus improved triboelectric output performance. This relationship is quantitatively

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supported by the superior electrical output of the RT/PVDF membrane, which demonstrates the highest
charge transfer (2.36 μC), current (71.6 μA), and voltage (6.9 V) among all samples. Therefore, the
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improved dielectric performance resulting from TiO2 doping, particularly with rutile phase plays a
pivotal role in enhancing the triboelectric energy harvesting efficiency of the device.
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a lP
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Fig. 5. (a-c) Comparison of optimal Current, voltage and output of RT/TENG with various rutile TiO2
concentrations. (d-e) Charge transfer (f) Frequency dependence dielectric constant comparison with
various rutile TiO2 concentrations.
 A series of RT/PVDF TENG devices with different rutile TiO2 weight ratios were fabricated to
identify the optimal content for maximizing output performance. The electrical output of each
RT/PVDF TENG was then evaluated under consistent operating conditions to determine the best-
performing composition. Fig.5 (a-c) illustrates the relationship between the rutile TiO2 doping mass
ratios and the Voc/Isc output. It is observed that the Voc and Isc of RT/PVDF TENG initially increase
with rising TiO2 content, reaching an optimum at 5 wt.% doping mass ratio before decreasing as the
TiO2 content continues to increase. This trend may be attributed to the agglomeration of TiO 2
nanoparticles at higher concentrations within the PVDF matrix. When the TiO2 nanoparticle
concentration exceeds a certain threshold, stuttering at the electrospinning needle tip becomes more

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likely due to the high nanoparticle content, which hinders the stretching of PVDF polymer chains,
leading to a reduction in β-phase formation. As shown in Fig. 5(a, b), the Voc and Isc of RT/PVDF

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TENG with the optimal rutile TiO2 proportion (5%) reach 6.9 V and 71.03 μA, respectively. The
transferred charges of RT/PVDF TENG were approximately 1.8, 2.1, 2.3, and 1.9 μC, corresponding
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to rutile TiO2 contents of 1, 3, 5, and 7 wt.%, respectively. This result suggests that moderate TiO2
loading enhances charge generation by increasing the dielectric constant, surface area, and β-phase
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content, improving dipole alignment and charge separation. However, at higher concentrations (7 wt.%),
excessive TiO2 likely leads to nanoparticle agglomeration, disrupting charge transfer pathways and
lP

reducing performance. Thus, 5 wt.% is the optimal concentration for maximizing electrical output.
Furthermore, to gain deeper insight into the influence of rutile TiO₂ concentration on dielectric
a

behavior, Fig. 5(f) presents the frequency-dependent dielectric constants of RT/PVDF membranes with
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varying nanoparticle loadings (1–7 wt.%). The measurements, conducted from 1 kHz to 100 kHz,
reveal a systematic increase in dielectric constant with increasing rutile TiO₂ content, a trend consistent
u

with typical dielectric responses observed in polymer–ceramic nanocomposites [65-68]. At 1 kHz, the
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dielectric constant rose from 19.3 for RT/PVDF-1 to 24.9 for RT/PVDF-3, 27.9 for RT/PVDF-5, and
reached a maximum of 31.1 for RT/PVDF-7. This progressive enhancement is primarily attributed to
improved interfacial polarization arising from the increased volume fraction of TiO₂, which serves as a
high-permittivity filler and introduces additional interfaces within the PVDF matrix. These interfaces
act as efficient dipole polarization centers that trap space charges and intensify local electric fields
under an applied alternating field, thereby elevating the effective dielectric permittivity. Moreover,
higher TiO₂ concentrations promote better dispersion and connectivity among filler domains,
facilitating Maxwell–Wagner–Sillars (MWS) interfacial polarization at the TiO₂–PVDF boundaries.
This enhancement in dielectric properties directly correlates with the increased triboelectric output
observed in RT/PVDF-based TENGs, reinforcing the critical role of optimized nanoparticle loading in
tuning the dielectric and energy-harvesting performance of composite membranes.
 of
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Fig. 6. (a-c) current and voltage change depending on different water flowrates (d) Output current of
RT/TENG using the aqueous solution at different pH (e) Charging curves for various capacitors (f)
lP

power output density of the RT/TENG at 5 ml.

For energy harvesting applications, the performance of RT/PVDF-5 TENG was thoroughly
a

evaluated, demonstrating its potential for a wide range of practical uses, as shown in Fig. 6. The
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performance of the RT/PVDF-5 TENG was thoroughly analyzed under varying flow rates. Fig. 6 (a, b)
shows the influence of water flow rate on current and voltage, measured between 1.0 ml/s and 5.0 ml/s.
u

As the flow rate increased, both the current and voltage outputs rose consistently, with the current
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increasing from 38.5 μA to 71.03 μA and the voltage from 2.9 V to 6.9 V. Moreover, the frequency of
the peaks also saw a noticeable rise, shifting from 1.5 Hz to 4.5 Hz, corresponding to the higher flow
rates. This indicates that greater water flow enhances the device's electrical performance by boosting
output and peak frequency. The increase in output with higher water flow rates can be partially
explained by the behavior of the electric double layer (EDL). At greater flow velocities, the formation
of the EDL is accelerated, and its thickness decreases, facilitating more efficient charge separation and
transfer. This results in improved power output and higher electrical peak frequencies. However, despite
these benefits, the material properties of the RT/PVDF-5 TENG limit its ability to handle rapid charging
and discharging efficiently, leading to potential instability in the triboelectric output at elevated flow
rates. Moreover, the current and voltage outputs show a strong linear relationship with the water flow
rate, exhibiting correlation coefficients of 0.988 and 0.979, respectively. This excellent linearity
highlights the potential of the RT-TENG as a reliable self-powered flow rate sensor.
The performance of the RT/PVDF TENG was evaluated under different pH conditions in water, as
illustrated in Fig. 6(d), to assess its environmental adaptability and stability across a broad pH range.
The electrical outputs are notably higher when neutral water, with a pH range of 5 to 6.5, is utilized.
This suggests that the pH level plays a crucial role in optimizing the performance of the TENG, as the
near-neutral pH likely enhances charge transfer efficiency between the water and the triboelectric
surface. The current output of the RT/PVDF-5 device significantly decreases from 71.03 μA to 37.45
μA when exposed to acidic water. The output performance consistently decreases with an increase in

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hydrogen ion concentration (corresponding to a decrease in pH). This indicates that the RT/PVDF-5
TENG device is highly sensitive to hydrogen ions, with minimal influence from the accompanying

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anions[69]. Thus, the potential of this device to effectively distinguish acid rain conditions is
demonstrated, showcasing its capability as a self-powered environmental pH sensor. Fig. 6(e) shows
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the charging performance of the RT/PVDF TENG for 2.2 µF and 4.7 µF capacitors, where the 2.2 µF
capacitor charges up to ~2.7 V in about 60 seconds, while the 4.7 µF capacitor reaches ~1.1 V in the
re
same duration, indicating more efficient energy storage at lower capacitance. To demonstrate its
potential for powering low-energy electronic devices, the power density was measured with various
lP

external load resistors. As the load resistance increased from 10 kΩ to 10 MΩ, a gradual reduction in
output current was observed, with higher resistances leading to a steady decline in current output. The
a

power density of the RT/PVDF-5 TENG, as shown in Fig. 6(f), exhibits an initial rise until a peak value
rn

is reached, followed by a decline as the load resistance continues to increase. The maximum power
density of the RT/PVDF-5 TENG was recorded at 0.55 W/m² with a load resistance of 500 kΩ.
u

A cascading system for integrating RT/PVDF TENGs is proposed to enhance output performance.
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In contrast to conventional LS-TENG configurations that rely on only parallel or series connection of
multiple independent units, the present design employs a vertically cascaded architecture in which a
single droplet traverses through multiple stacked membranes[70]. This enables sequential contact
electrification across multiple layers, allowing cumulative charge transfer with a single fluid source.
While stacked up architectures have been studied in solid–solid TENGs, such as multilayered contact-
separation devices, their adaptation to liquid–solid systems have remained limited[71, 72]. Prior LS-
TENG systems enhanced output by connecting devices electrically, not through utilizing fluid-based
cascading architectures where same droplet travels multiple membrane to generate power. Our
approach addresses this limitation by using a gravity-driven droplet path and surface tilt to guide water
through multiple triboelectric interfaces, resulting in enhanced voltage and current output. This strategy
simplifies device integration while increasing output density, making it suitable for compact, scalable
energy harvesting applications.

As shown in Fig. 7(a), the schematic illustrates a multilayered cascading structure, where multiple
TENG cells are systematically stacked to effectively amplify the overall electrical output through
synchronized energy harvesting. This design leverages the liquid-solid interface to maximize the output
by enabling repeated interactions of water droplets with multiple layers of triboelectric surfaces, thus
boosting the overall charge generation. The cascaded configuration promotes efficient transfer of
energy, taking advantage of the cumulative effect of multiple TENG layers to produce a higher voltage
output. In Fig. 7 (b), a photograph of the 3D-printed cascading structure is presented, featuring two

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PVDF-TiO2 membranes stacked in a tilted arrangement. This layout allows water droplets to
successively contact each triboelectric surface, each interaction contributing to increased charge

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transfer. Fig. 7(c) presents a schematic diagram of the electrical configuration for the cascading
RT/PVDF TENG system. Fig. 7 (d, e) provides a comparative voltage and current output graph,
-p
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a lP
u rn
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-p
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a lP
u rn
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Fig. 7. (a) Schematic of the proposed cascading structure (b) 3D-printed cascading structure featuring
two membranes (c) TENG cells in series configuration. Output Comparison: Single Cell vs. Two
Cells (Cascading) (d) Voltage (e) Current (f) (g) Output stability check over 500 seconds

contrasting a single TENG cell with the cascaded two-cell setup. The results demonstrate a significant
increase in voltage output for the cascaded configuration, indicating that the layered arrangement
indeed amplifies the generated power. Fig. 7(f) displays the practical demonstration of the cascading
RT/PVDF TENG system used to power an array of LEDs. Finally, Fig. 7 (g) depicts the stability of the
current output over 500 seconds, with a consistent current profile indicating the reliability and durability
of the cascading TENG system. This stability ensures that the device can operate effectively in real-
world applications, making it suitable for sustainable energy harvesting and environmental monitoring
applications.

Conclusion:

This study effectively demonstrates the fabrication and enhancement of a TiO2-doped PVDF-based
liquid-solid triboelectric nanogenerator (TENG) via electrospinning. The incorporation of rutile TiO2
nanoparticles plays a crucial role in boosting the electroactive β-phase in PVDF, leading to a marked
improvement in triboelectric performance. The optimized RT/PVDF-5 composite membrane exhibits

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substantial gains in output voltage, current, and power density, along with exceptional durability and
stability. Additionally, the membrane’s sensitivity to variations in water flow rate and pH levels

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underscores its potential for environmental monitoring applications. Moreover, this work introduces an
innovative cascaded TENG configuration, further enhancing the device’s power output by sequentially
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layering triboelectric cells. This cascading structure amplifies charge generation through repeated
interactions of liquid droplets with multiple active surfaces, offering a scalable solution for increasing
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energy output. The cascading design, combined with TiO2-enhanced PVDF, demonstrates consistent
lP

and stable performance over extended periods, making it highly suitable for practical applications in
energy harvesting. The findings from this study highlight a versatile approach for the development of
high-performance TENGs that can serve as self-powered sensors and energy harvesters in diverse
a

environments, including remote areas, water-based applications, and smart environmental monitoring
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systems.
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Graphical abstract

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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships that
could have appeared to influence the work reported in this paper.

☐ The authors declare the following financial interests/personal relationships which may be considered as
potential competing interests:

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Highlights

• A high-performance TiO2-PVDF-based liquid-solid triboelectric nanogenerator (TENG) is

developed.

• The optimized TENG demonstrates an output current of 71.03 μA and a voltage of 6.9 V.

• The power density reaches 0.55 W/m², which is a significant improvement over the pure PVDF

TENG.

• The TENG shows excellent durability and stability, making it suitable for energy harvesting and

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environmental sensing applications.

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• The cascading structure within the TENG system, significantly boosting the output by enabling

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sequential charge transfer through layered interfaces.
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