www.acsanm.

org Article

Effects of Film Confinement on Dielectric and Electrical Properties of

Graphene Oxide and Reduced Graphene Oxide-Based Polymer
Nanocomposites: Implications for Energy Storage
Farzana Hasan Likhi, Maninderjeet Singh, Shubham Vasant Chavan, Thomas Cao, Mina Shanbedi,
and Alamgir Karim*
Cite This: ACS Appl. Nano Mater. 2023, 6, 11699−11714 Read Online
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
Downloaded via UNIVERSIDADE DO PORTO 01100 on July 15, 2025 at 10:15:13 (UTC).

ABSTRACT: 2D nanofillers such as graphene oxide (GO) and reduced GO (rGO)-based polymer nanocomposites have emerged
as crucial materials for various applications, from flexible solid-state capacitors to electromagnetic interference (EMI) shielding
devices. Specifically, the dielectric breakdown strength (EBD) and dielectric constant of polymer nanocomposite capacitors determine
their ability to store energy, whereas frequency-dependent loss is crucial for EMI shielding applications. The miniaturization of
energy storage and electronic devices demands a detailed understanding of the behavior of these polymer nanocomposites in the
thin-film regime (micron to sub-micron thicknesses). In this work, we demonstrate the effect of confinement on the dielectric,
electrical, and capacitive energy storage properties of the polyvinylidene fluoride (PVDF)−GO and PVDF−rGO films. We show that
the dielectric permittivity is significantly impacted by the nanofiller confinement in thin (≈1 μm) PVDF polymer films, which is
comparable to the lateral dimension of these 2D nanofillers. In thin PVDF−GO films, the nanofillers (and associated surface
dipoles) become oriented quasi-parallel to the film interfaces, affecting the relative projected area to the applied electric field. The
conductivity and loss tangent values increased as a function of frequency with reduced film thickness, which is beneficial to EMI
shielding application. The EBD of the confined GO-based films was found to be relatively independent of the filler fraction, whereas
rGO-based films increased with the filler fraction after an initial decrease. These results provide fundamental insights into rational
design principles for using ultrathin GO and rGO-based polymer nanocomposite films in next-generation flexible electronic and
energy storage devices.
KEYWORDS: confinement effect, polymer nanocomposites, graphene oxide, reduced graphene oxide, energy storage, dielectric breakdown,
capacitive energy density

■ INTRODUCTION
Electronic device miniaturization trends in recent decades for
many types of polymers; however, the dielectric constant is
inadequate to satisfy the demands of many device applications.
various reasons (low power, flexibility, and ergonomics) have Metal particles (Ag and Cu)10,11 and conductive fillers based
driven structural components into ever-decreasing dimensions.
Numerous applications in energy harvesting,1,2 pulsed electric
power systems,3 electromagnetic interference (EMI) shielding Received: April 14, 2023
devices,4 electronic skin,5 sensors,6 wearable devices,7 and Accepted: June 8, 2023
other electric devices8,9 make polymer-based nanocomposites Published: June 21, 2023
appealing. Due to the inherent high breakdown strength and
processing flexibility, polyvinylidene fluoride (PVDF) and its
copolymer modifications are attractive options among the

© 2023 American Chemical Society https://doi.org/10.1021/acsanm.3c01674

11699 ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

on carbon like carbon nanotubes,12−14 carbon black,15 and

graphene16,17 are typically used to create composite materials
with enhanced dielectric properties. Additionally, because of
the minimal filler content required to produce large dielectric
and electrical changes, the composites have outstanding
mechanical characteristics and flexibility of the polymer.
Two-dimensional (2D) conductive fillers like graphene
oxide (GO) and reduced GO (rGO) have piqued a great
deal of interest among conductive fillers because of their
exceptional electrical capabilities and distinctive structural
makeup. However, maintaining uniform 2D nanofiller
dispersion in a polymer matrix continues to be a challenging
task. Notably, if these fillers come into contact with one
another, the dielectric loss in these composites caused by
leakage current will grow.18 Polymer nanocomposites with
high dielectric permittivity values were developed using GO
and rGO as nanofillers during the past few years. GO has two
different structural types: the sp2 structure, derived from the
crystal structure of its carbon atoms as a honeycomb lattice,
and the sp3 structure, which is connected to carbon atoms with
oxygen functional groups made using Hummer’s technique to
create hexagonal ring networks.19 The dielectric permittivity of
GO is often described by the surface area and strong
polarization induced by a sufficient amount of surface
functional groups, like epoxy, carboxyl, and hydroxyl groups. Figure 1. (a) Schematic illustration of 2D nanofillers (GO/rGO)
The groups containing oxygen at the edge and surface of the embedded in 100 μm and 1 μm confined film. AFM images of (b)
GO structure ensure hydrophilicity, homogeneous dispersion, GO flake and (c) rGO flake via the tapping mode.
and modifiable surface area.20 On the other hand, one
appealing method to get graphene-like properties is the
reduction of GO. Removing the oxygen-containing compounds systems. Furthermore, PVDF and GO/rGO composites are
from the GO structure and subsequent restoration of the sp2 ideal for high-performance flexible electronic devices due to
structure following the reduction process are directly their high dielectric constant and resilience in this thin-film
responsible for these modifications.21 range.
Numerous studies have been conducted on applying GO In this study, we describe the relationship between dielectric
and rGO as nanofillers to prepare bulk polymer nano- properties and nanomaterial loading frequency in thin PVDF
composite films.18,22 By scaling the fundamental properties of films containing GO and rGO with thicknesses of 1 μm and
the nanocomposite up to the macroscopic level, certain 100 μm. In a regulated laboratory environment, GO was
microstructure-based theories have been put forward that reduced using a microwave. The relative responses of GO,
directly relate the AC frequency to the dielectric permittivity rGO, and pristine PVDF are compared in terms of their
and effective electrical conductivity of the nanocomposites.23,24 dielectric constants, loss tangent, and AC conductivity data
Only a few research studies have investigated the impact of using a dielectric spectrometer spanning the frequency range of
film confinement in the thin-film regime at the micron to 1 kHz to 1 MHz. We found that the confinement in polymer
submicron scales. We may anticipate film confinement effects thin films (1 μm) significantly influences the electrical
on platelet orientation in this range of film thickness, when it is conductivity and dielectric permittivity, with the permittivity
rising by as much as 50% in 2 wt % GO-based nanocomposites.
comparable to the lateral size of the GO and rGO nanosheets
The alignment of GO surface dipoles along the direction of the
(Figure 1), and accordingly, we expect that it will affect its
E-Field (perpendicular to the GO plane) may help explain this
relative projection area and thereby orientation of surface
phenomenon. The quality of these nanocomposite films and
dipoles to the applied electric (E) field.
the film morphology were evaluated using atomic force
It is widely known that Maxwell−Wagner−Sillars (MWS)
microscopy (AFM) and scanning electron microscopy
polarization has a significant impact on the dielectric response
(SEM). For a thorough understanding and equivalent
at low frequencies for composites that incorporate conductive
comparison of frequency-dependent dielectric spectroscopic
fillers in insulating polymers25,26 The percolation threshold,
measurements, the characterization investigations are per-
MWS polarization, aspect ratio, and the additional frequency-
formed on PVDF−GO and PVDF− (microwave annealed and
driven hopping of electrons are some examples of the
converted) rGO composites, with varied weight percentages of
microstructural aspects that directly contribute to the
GO and rGO nanofillers.
extraordinary properties of these nanocomposites. As the
polymer matrix has restricted conductivity, MWS polarization
results from the buildup of charges at the polymer−filler
interface.27 This enhances the polarization of the polymer by
■ MATERIALS AND METHODS
rGO Synthesis. In this work, we used the microwave reduction
technique to prepare rGO powder. Single-layer GO powder with a
concentrating the field in its local vicinity. However, we note lateral dimension of 0.5−5 μm and thickness of 0.8−1.2 nm (prepared
that the filler−polymer interface is generally oriented randomly via Hummer’s method) was purchased from ACS material and used as
in bulk films with respect to the applied E-field, so the MWS received. We used n-methyl-2-pyrrolidone (NMP) purchased from
has an average enhancing effect for isotropic filled polymer Sigma-Aldrich as the solvent for the microwave reduction process

11700 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

Figure 2. Schematic illustration of (a) polymer−nanofiller blend preparation. (b) Film casting technique of PVDF−2 wt % GO/rGO film of 1 μm
thickness. (c) Film casting technique of PVDF−2 wt % GO/rGO film of 100 μm thickness. (d) α and β phase structures of the PVDF polymer.

because it is a polar solvent with a high boiling temperature (202 °C) from Sigma-Aldrich, was used as a solvent for dissolving PVDF beads
(Figure S1). Therefore, applying microwave to the system could at a concentration of 400 mg/mL and stirred on a hot plate (70 °C)
ensure a substantial and quick temperature rise inside the vial without for 8 h to ensure complete dissolution (Figure 2a). GO and PVDF
the danger of pressure build-up inside the vessel. For the microwave were mixed separately in the same solvent (DMF). Afterward, the GO
reduction process, we treated the GO in NMP solution using the solution was gradually added in a controlled manner to the
microwave at 800 W for 2 min. As the GO turns into rGO, the continuously stirring PVDF solution. The PVDF−GO solution was
solubility keeps decreasing (Figure S1b). We could see a distinct color stirred for 24 h at 80 °C (Figure 2a). To minimize the chances of GO
change from brown to black due to the reduction of GO to rGO agglomeration in the polymer solution and ensure homogeneous
(Figure S1a). Subsequently, the solution was transferred to the
dispersion, bath sonication was used, followed by probe sonication
centrifuge and rinsed with deionized water several times until the
right before casting the films.
supernatant was completely free of NMP. Then, the resulting mixture
was dried in an oven at 100 °C for 24 h to ensure that no residual The rGO nanosheets prepared via a microwave reduction process
water remained in the system. Finally, the final dried product is stored were dissolved in DMF following the same route as GO. In this study,
in a vial at room temperature (Figure S1c) and further used for the we wanted to be consistent with the choice of the solvent for the
polymer solution blend. This simple and time-efficient process can be polymer and the filler to avoid the unprecedented complexity arising
scaled up to produce grams of rGO nanoparticles on a regular basis. from solvent immiscibility.28 GO has greater surface energy due to the
Solution and Film Casting. PVDF beads were purchased from presence of oxygen-bearing groups, as opposed to the rGO (increased
Sigma-Aldrich with an average molecular weight of 180,000 g/mol hydrophobicity due to the lack of surface dipole).29 Due to the
and used as purchased. N,N-Dimethylformamide (DMF), purchased shortage of surface functional groups containing oxygen, rGO has less

11701 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

Figure 3. (a) ATR−FTIR spectra of GO and rGO. (b) FTIR spectra of PVDF−no filler, PVDF−2 wt % GO, and PVDF−2 wt % rGO
nanocomposite films of 100 μm thickness. (c) XPS survey spectrum of GO and rGO. High-resolution C 1s spectrum of (d) GO and (e) rGO.

solubility than GO in DMF.29 As a result, for the same amount of the sheets of GO are produced by the creation and spread of fractures
sonication cycle, rGO tends to be less dispersive in DMF than GO. across defect zones, particularly in areas with sp3 bonds such as −C−
To tackle this dispersion issue without changing the solvent, we OH and O−C−O.33 The presence of structural defect (sp3 bonds) in
incorporated 1 min extra sonication time for rGO. The literature the atomic structure is the reason behind this phenomenon.32 From
showed that due to the lack of defect sites in rGO, compared to GO, the Raman spectra (Figure S11), we have observed that the ID/IG
it takes a longer time of sonication for rGO to break into smaller ratio is higher for GO, which indicates the presence of a higher
pieces.30 number of defective sp3 structures in GO. Besides, the sonic wave
As the rGO sheet stacking is led by π−π stacking, due to the short helps with the adsorption of the PVDF chain (�CF2) on rGO (with
period of sonication, the number of rGO stacking reduces rather than the limited carbonyl group on the rGO surface), which improves the
breaking into smaller pieces (Figure S9d).31 Due to the short period dispersion of rGO.34
of sonication, the newly introduced surface area contributes to better The doctor blading method was used as a film casting procedure
dispersion in polar solvents. The literature showed that it takes hours for preparing 100 μm films on a glass substrate (Figure 2b). 1 μm
of sonication to break rGO into smaller pieces,30 whereas GO takes films were cast on an aluminum (as the electrode)-coated Si wafer
20 min to break into pieces.32 According to the literature, smaller using the flow coating technique (Figure 2c). We chose flow coating

11702 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

for this study because it is a benign process that requires a minimal peaks, at 3853.58, 3185.79, 1734.38, 1617.48, 1375.17, and
amount of solution (helps conserve GO/rGO) for film casting and 1045.40 cm−1, in the GO spectra, were attributed to the O−H
reduces solvent wastage.35 stretch (alcohol), O−H stretch (−COOH), C�O stretch
Characterization. Infrared measurements were conducted on the
samples using a Thermo Scientific iD7 Nicolet iS5 attenuated total
(−CHO), C�C stretch (−COOH), O−H bending
reflectance−Fourier transform infrared (ATR−FTIR) spectrometer. (−COOH), and C−O stretch (carbonyl) respectively. The
The dielectric properties of the nanocomposite films were determined O−H stretch peak (−COOH) at 3185.79 cm−1 is flattened but
using the E4980AL Precisión LCR meter (20 Hz to 1 MHz) at not eliminated. This phenomenon signifies that the hydroxyl
ambient temperature. The Bruker dimension icon AXS atomic force group is not entirely eliminated. From the detailed study
microscope was used to acquire phase and height images in the conducted by Gao et al., we found that the hydroxyl groups
tapping mode. For optical microscopy of bulk polymer films, Olympus attached at the edge have higher binding energy, hence better
MX51 was used. A Thermo Fisher Scientific scanning electron stability than those located at the basal plane. Other than that,
microscope (SEM) was used for secondary and backscattered electron
detection mode imaging. The dielectric breakdown tests were they mentioned that the crucial dissociation point for hydroxyl
performed using the PK-CPE 1801 Polyk test system with a ramp groups at the edge of the nanosheets is 650 °C. They also
rate of 20 V/s on film with thicknesses ∼1 μm. For tensile testing, we observed that the reduction of carboxyl groups starts at around
used TA.XT_plus C Texture analyzer. ASTM D882 was used as the 100−150 °C. Temperatures greater than 1000 °C and
testing standard for the 100 μm films. For X-ray photoelectron extremely low pressure are required to completely eliminate
spectroscopy (XPS) measurement, photons were gathered on a the carbonyl group by thermal reduction.42 Using the same
Physical Electronics model 5700 XPS instrument. These were created peak identification sensitivity in OMNIC software (Figure
using a monochromatic Al k X-ray source running at 350 W at 1486.6
eV. 800 μm, 5, and 45° were chosen as the investigated area,
S10), we can observe that for rGO, the peak intensity of
collecting solid cone and take-off-angle, respectively. An energy oxygen functional groups became weak. (i.e., 3151.90 cm−1
resolution of greater than 0.51 eV was achieved by applying a pass O−H stretch peak). Although the evident peaks at 1735 cm−1
energy of 11.75 eV. Once a vacuum of at least 5 × 10−9 Torr was (carboxyl or carbonyl stretching vibration) and 1375 cm−1
achieved, all spectra were obtained. Multipak software package was (carboxylic acid O−H bending) disappeared, a peak at 1045
used for peak deconvolution and fitting of the collected XPS data. cm−1 (carbonyl) can be seen in the rGO spectra proving our
Raman spectroscopy (Renishaw inVia confocal Raman spectroscope) previous statement about carboxyl and carbonyl group
with the Renishaw Centrus 2KMP11 detector was used to analyze the
elimination. The temperature goes up to 185 °C inside the
quality of the GO and produced rGO at the wavelength 1100−2200
cm−1 that utilized excitation at 532 nm wavelength with the power of vial during microwave reduction. The literature shows that
100%. oxygen can be eliminated by 27% when heated to 180 °C and
another 10% when heated over 180 °C.43
■ RESULTS AND DISCUSSION
Figure 1a,b depicts the AFM image (morphology and size
The spectrum resulting from the rGO sample using
microwave heating shows peaks at 2923.80, 2113.26,
1633.71, 1404.01, 1303.22, 1050, and 802 cm−1 due to the
distribution) of GO and rGO 2D nanosheets. The thickness of C−H stretching (−CH3), C�C stretching, C�C stretching,
the nanosheet can be characterized using the height profile C−H bending, C−N stretching, C−O stretching, and C�C
(NanoScope Analysis 1.9 software) along the line drawn on bending, respectively. These new peaks in the product from the
GO and rGO sheets (Figure S9). According to Figure S9c, the
microwave synthesis process indicate the presence of residual
height profile (across the red line) shows that the GO sheet is
NMP.44,45 After cleaning the reduced solution using deionized
approximately 4 nm thick, indicating that the sheet is four-
water, we dried the clean centrifuged product at 100 °C for 24
layered. The oscillations on the peak of around 1 nm height
h under vacuum. Our main goal was to eliminate the absorbed
indicates the presence of a single layer on top. Figure S9d
shows that the rGO sheet is around 3 nm, which indicates the moisture and prevent any further structural change or
sheet is three layered. The literature also showed the presence reduction caused by the drying. The literature reports that
of layers in other nanofiller-based studies as well.36−38 above 200 °C, the water, hydroxyl, epoxide, and carboxyl
However, due to sonication, rGO has less number of layers groups get removed from the system.46 From the thermal
in one sheet compared to GO. The bright white areas in the reduction kinetics study conducted by Sengupta et al., we note
GO/rGO AFM images suggest sheet folding or layers.37 We that GO samples go through a sharp decrease in weight
can observe flake size variation for both GO and rGO. percentage at 177 °C due to the reduction of functional
However, the predominant size for the sheets is 2−5 μm. groups.47 As the boiling point of NMP is 202 °C, a small
Ultrahigh sonication promotes smaller pieces of nanosheets in amount of NMP stays in the system even after an extensive
the system which helps with homogeneous distribution cleaning procedure.
eventually. Figure 3a depicts the ATR−FTIR spectra of GO Figure 3b depicts the ATR−FTIR spectra of PVDF−no filler
and rGO nanofillers. It is difficult to find C−O stretch modes vs PVDF−2 wt % GO vs 2 wt % rGO films. PVDF contains
in the 2200−3000 cm−1 area of the GO spectrum because it repeating units of fluorinated hydrocarbons. Depending on the
overlaps with the wide C−OH region (2800−3600 cm−1), processing technique and crystallization condition, PVDF can
resulting from a wide range of functional groups (tertiary manage to be in four distinct phases, which are α, β, γ, and σ.
alcohols, enols, phenols, and −COOH).39 Karousis et al. The characteristic bands of the α phase in the PVDF−no
detected and ascribed bands 3616 and 3490 cm−1 to hydroxyl filler spectrum can be identified at 1070.87 (−C−C−C-
groups.40 Hontoria-Lucas et al.41 observed a wide band at bending), 874.13 (−CF2 stretching), and 765.31 cm−1, and the
3000−3700 cm−1 showing a shoulder and two maxima at β phase can be identified at 1166.25, 1231.41, 1429.08 (−CH2
around 3500 cm−1. These peaks were attributed to the in plane bending), and 836.26 (−CH 2 rocking, −CF2
hydroxyl groups of absorbed water and the ones attached to stretching) cm−1.48 Gregorio observed in one of their studies
the GO surface. Our study has seen similar GO spectra trends that by heating the film between 70 to 110 °C, a mixture of the
and characterized the peaks accordingly. The characteristics α and β phase can be attained.49 As we followed the solution
11703 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

Figure 4. Surface SEM image of 100 μm thick films of (a) PVDF−no filler (inset scale bar 10 μm), (b) PVDF−2 wt % GO, and (c) PVDF−2 wt %
rGO. Cross-sectional SEM image of 100 μm thick films of (d) PVDF−no filler, (e) PVDF−2 wt % GO, and (f) PVDF−2 wt % rGO. Surface SEM
image of 1 μm thick films of (g) PVDF−no filler (inset scale bar 10 μm), (h) PVDF−2 wt % GO, and (i) PVDF−2 wt % rGO. All the images
including insets have 10 μm scale bar.

casting method and our annealing temperature was 80 °C, we synthesized using Hummer’s method, where concentrated
produced a PVDF film consisting of a mixture of α−β phases. sulfuric acid and potassium permanganate solution were used
From the ATR−FTIR spectra of PVDF−2 wt % GO and to oxidize graphite. Eigler et al. discussed in one of their studies
PVDF−2 wt % rGO, we can see no significant change in the that GO made via the Hummers method exhibits one
spectra due to the low concentration of nanoparticles organosulfate group per 20 carbon atoms.54 These groups
introduced to the system. However, the GO and rGO additives can be found along the borders of the GO flakes as well as
weaken the 765.31 cm−1 peak (which is specific to the pure α- above and below the carbon skeleton. These sulfur-containing
phase). The decrease in the α phase could be specifically groups decompose at around 250 °C and are challenging to
because of the interaction among the carbonyl groups (>C� eliminate. As a result, we can also observe the S�O stretching
O) attached to the surface and edge of GO and the (>CF2) peak in rGO.
fluorine group located at the PVDF chain.34,50 Also, solvent Elemental analysis of GO and rGO was carried out with
polarity can enhance the chances of β-polymorph formation in XPS. Figure 3c shows the survey spectrum of XPS for both GO
the nanocomposite system. We used DMF as the film-casting and rGO. We can observe a drastic increment in the C/O ratio
solvent, facilitating the alignment of the dipoles in the PVDF in the rGO spectra due to the reduction of oxygen-bearing
chain.51 According to research by Yu et al., a considerable functional groups. Besides, the N 1s peak is sharper in the rGO
energy barrier between the adsorption energies of the α and β spectra, which could be attributed to the residual NMP in the
phases may exist between the TGTG (trans−gauche trans−
rGO during the reduction process mentioned in the previous
gauche) and TT (trans−trans) conformations, making it
FTIR section.
challenging for TGTG to spontaneously transition to TT
The high-resolution C 1s spectrum (Figure 3d) shows two
during crystallization (Figure 2d). If the mixture is sonicated,
sharp peaks, which indicates a high amount of oxidation in
the TGTG conformation can overcome the energy barrier by
GO.55 After peak fitting and background subtraction, peak
using the energy gained from sonication and transforming to
TT conformation (β polymorph).52 Also, we can notice the deconvolution and assignment of the C 1s peaks were carried
introduction of a new peak at 1671 cm−1 (−C�O stretch) in out (Table S1). C 1s of GO showed two distinct peaks at
GO, rGO-infused PVDF films, which confirms partial 286.78 eV (C−O) and 284.53 eV (C�C) and three smaller
adsorption of PVDF on the GO surface with the help of peaks at 287.92 eV (>C�O), 288.94 eV (−O−C�O), and
sonic waves produced by the sonication. The TGTG chain is 283.61 eV (C with S).56 After peak deconvolution, the C1s
partially extended into TT confirmation because of this peak of rGO shows (C�C) at 284.41 eV, (C−C) at 285.09
adsorption. The nucleating substance for the β PVDF phase eV, (C�O) at 287.93 eV, and a small satellite peak (due to
formation is the adsorption of TT confirmation on the GO delocalized π conjugate, which is a feature of aromatic C
surface. GO and rGO-based PVDF films yield a combination structure)55 at 290.51 eV. Despite the assignments’ inherent
of α and β phases, presumably because they do not possess ambiguity, the peak assignment is consistent with the
enough carbonyl groups to nucleate all the PVDF chain into literature.57,58 According to the XPS study discussed above,
TT confirmation.53 In both PVDF−GO and PVDF−rGO the bulk amounts of oxygen-bearing functional groups have
spectra, we observe a peak at 1333 cm−1 (S�O stretching been eliminated, which increased the number of sp2 structures
bond), indicating the presence of sulfur species in the GO on the rGO basal plane.58 Raman spectroscopy (Figure S11)
powder purchased from ACS materials. The GO powder was provides additional data showing a low ID/IG ratio (compared
11704 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

Figure 5. Frequency-dependent (1 kHz to 1 MHz) study of PVDF−no filler, PVDF−GO 2 wt %, and PVDF−rGO 2 wt % (a) dielectric constant,
k, (b) loss tangent, and (c) electrical conductivity of 1 μm films. (d) Dielectric constant, k, (e) loss tangent, (f) electrical conductivity of 100 μm
films, (g) percentage change in dielectric constant, k value in thick films with respect to frequency, and (h) percentage change in the electrical
conductivity value in thick films with respect to frequency.

to GO) in the rGO sample, which bolsters the aforementioned SEM micrography of 100 μm thick pure PVDF film surface
shows a comparatively smoother surface than the PVDF−2 wt
statement about sp2 structures on the rGO basal plane. % GO and PVDF−2 wt % rGO film surfaces (Figure 4a−c).
11705 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

The surface SEM images depict that both the 100 μm thick used to express the reaction of the material to an applied E-
pure PVDF films and the PVDF−GO/rGO nanocomposite field
films exhibit the spherulitic structural feature. However, the
*( ) = ( ) i ( ) (1)
dimension of the spherulites in the PVDF film shrank when
nanofillers were added. Besides, the shape of the spherulites where ε′ stands for the real part of permittivity, which displays
became irregular, and the pore size among each spherulite material polarizability due to delocalized electron distortion,
changed with the introduction of nanofillers. The spherulite dipole reorientation, or interfacial polarization. ε″ denotes
size is correlated with the crystallization dynamics of the imaginary part of permittivity, which determines how much
polymer.59 It depends on both the nucleation capacity of the energy is lost in the material when it is exposed to an external
nanofillers and the growth ratio of the spherulites. The most electrical field, while ω stands for the angular frequency (2πf).
efficient nucleating agent was GO nanosheets, which led to From the capacitance (Cp) values obtained using the LCR
more nucleation spots and more compact spherulites since meter, we can calculate the frequency-dependent dielectric
there was less room for unhindered development. The addition constant (k) values of the materials from this relation
of GO/rGO to the PVDF matrix acts as nucleation sites for
Cp·d
crystallization.60 Typically, the TT conformation (β-phase) in k=
PVDF segments is induced by contact between nanofillers and 0· A (2)
PVDF chains, and this structure subsequently spreads during
crystal development.61 where d stands for the thickness of the film, A is the area under
Both secondary and backscattered electron detection the electric (E) field, and ε0 is the absolute permittivity of free
methods were used for better differentiation between the space.
The ratio between the imaginary and real parts of the
matrix and filler (Figure S3). We can see the formation of
complex permittivity is the loss tangent, commonly referred to
spherulites for 1 μm thick pure PVDF films. This spherulite
as the dissipation factor D. The equation for the imaginary part
formation has been confirmed by AFM images also (Figure
of permittivity
S2). The introduction of nanofillers causes disruption of the
spherulite formation, and we can identify the GO and rGO in = ·tan (3)
the thin film oriented horizontally with the substrate. The frequency (ω)-dependent electrical conductivity was
The SEM fractography, as depicted in Figure 4d−f, provides calculated using the formula
a clear insight into the confinement effect as we could not see
the random sheet orientation of GO and rGO in the SEM = · 0· = · 0 · ·tan (4)
surface image of 100 μm thick films. The samples were
We have also measured the absolute permittivity of the
fractured at the liquid nitrogen temperature to produce all the
material, which is the measure of the amount of energy stored
cross-sections. Pure PVDF film cross section shows a flat,
in a material from an external E-field and can be expressed as
continuous, and smooth surface. The stress−strain curve
obtained via the tensile strength tensing setup at room = k· 0 (5)
temperature showed a distinct ductile behavior of the pure
PVDF films (Figure S8). This shows that the semi-crystalline The loss factor quantifies the amount of energy lost from a
polymer PVDF (glass transition −35 °C) has a ductile−brittle material due to an external E-field.
transition point somewhere in between room temperature and Loss factor = k ·tan (6)
liquid nitrogen temperature.62 PVDF nanocomposites con-
The frequency (ω)-dependent dielectric constant of PVDF−
taining 2 wt % GO and rGO show a rough fracture surface
no filler, PVDF−2 wt % GO, and PVDF−2 wt % rGO films are
which is substantial evidence of the filler and matrix adhering depicted for 1 μm (Figure 5a) and 100 μm (Figure 5d) thick
at the interface. An excellent ductile fracture with uneven films. Compared to pure PVDF films, the PVDF−2 wt % GO
surfaces and ripped edges was visible on the PVDF−GO and PVDF−2 wt % rGO nanocomposite films have a higher
surface. These findings depicted that GO addition to the permittivity. It is conjectured in the literature that the
polymer matrix significantly increased the ductility of the numerous “micro capacitors” formation is responsible for the
nanocomposites and prevented the expansion of the PVDF noteworthy increment of the dielectric constant of PVDF−GO
brittle fracture under liquid nitrogen temperature.63 From the and PVDF−rGO nanocomposite films. The addition of
stress−strain curve (room temperature), we can see that the nanofillers to the system creates more micro-capacitance
nanofiller (GO/rGO) addition improves the Young’s modulus structures and larger interfacial areas in the nanocomposite,
(stiffness) of the PVDF films (Figure S8). As GO has better which results in a higher k value than pure PVDF. Moreover,
dispersibility in PVDF, it promotes better interfacial stress due to the disparity in their dielectric constant and
transmission and hinders polymer chain mobility, which results conductivity, charges may accumulate at the interfaces of the
in higher ultimate tensile strength for PVDF−GO films. Also, GO/rGO and PVDF matrix. Consequently, the MWS effect
we can see randomly oriented nanosheets embedded in the (interfacial polarization) may significantly improve the low-
polymer matrix from the fractography, which further reinforces frequency dielectric constant values of PVDF−GO and
our hypothesis about the nanosheet orientation. PVDF−rGO nanocomposite films.65
Dielectric Properties. Dielectric spectroscopy is a useful Due to the discrepancy between the conductivity values of
method for investigating molecular dynamics and electrical the PVDF matrix and GO/rGO nanofillers, we observe a
polarizability in polymer nanocomposites.64 Material dipoles or higher dielectric constant in nanocomposite films. PVDF−2 wt
polarizable elements interact and oscillate at variable temper- % rGO shows the highest dielectric constant value, higher than
atures and frequencies (ω) whenever a material is subjected to PVDF−GO for the same amount of nanofiller loading. rGO
an E-field. The complex dielectric permittivity is commonly has higher conductivity than GO; therefore, the conductivity
11706 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

difference between the filler and matrix is higher in the PVDF− rGO−PVDF film shows high loss tangent values at higher
2 wt % rGO nanocomposite film. Xia et al. explained a similar frequencies.
phenomenon in their study by introducing the MWS effect From Figure 5c,f, we can see that the conductivity values are
using a parallel capacitor-resistor circuit model24 unaffected by the frequency change for pure PVDF films. For
PVDF−GO and PVDF−rGO films, we see a sharp increase in
MWS k· conductivity after 100 kHz. At this higher-frequency range, the
( )= 2 2
1+ (7) dipoles created inside the matrix cannot change direction
quickly; hence, current leakage (loss) and conductivity
where β = RC is a characteristic time of the equivalent increase. The reduction in the total resistance of PVDF−
nanocapacitor, Δσ = difference in conductivity of the matrix rGO nanocomposite films suggests a simple conduit for charge
and filler, ω = angular frequency, and k is a time coefficient. transfer in the polymer matrix, where the charge is stored. The
It is observed that the decrease in dielectric constant with equation below gives a clear insight into the influence of MWS
respect to increasing frequency is sharper in 1 μm thick films polarization on the AC conductivity value of polymer
than that in 100 μm films. The permittivity of nanocomposites nanocomposite films
decreases as frequency increases because, at low frequencies,
2
the E-field changes slowly, giving enough time for the MWS k
( )=
polarization to respond.66 At the high-frequency range, the 1+ 2 2
(9)
lack of the interfacial polarization’s impact on overall
polarization resulted in a reduction in the k (dielectric where β = RC is the characteristic time of the equivalent
constant) values of polymer nanocomposite films. Low k nanocapacitor, Δσ = difference in conductivity of the matrix
values occur at higher frequencies because the E-field oscillates and filler, and ω = angular frequency.
quickly, and the charge build-up phenomena at the nanofiller− As PVDF−rGO nanocomposite films have higher Δσ values
polymer interface cannot keep up with that faster pace.67 than PVDF−GO films, the contribution of MWS to the
Additionally, we observed a higher k for PVDF−GO and conductivity values is higher for PVDF−rGO films.24 More-
PVDF−rGO films in general, which could be because of the over, the total conductivity is proportional to the increased
number of effectual micro capacitors inside the polymer matrix. permittivity value brought on by a stronger MWS interfacial
Specifically, highly oriented fillers in 1 μm thick films result in polarization.10 The conductivity is almost constant up to 100
parallel micro capacitors, which cause high dielectric constant kHz, and then, it shows a sharp increase. This kind of behavior
in the low-frequency range. is characteristic of irregular solid material and seems to follow
Frequency-dependent loss tangent values of PVDF−no filler, the AC universal principle. It is considered to be a major input
PVDF−2 wt % GO, and PVDF−2 wt % rGO films are plotted of charge migration via the hopping process.70
for 1 μm (Figure 5b) and 100 μm (Figure 5e) thick films. For From Figure 5g, we can see that PVDF−2 wt % GO films
the 1 μm thickness film, we can see that the loss tangent values show around a 30−50% increase in dielectric constant (k)
show a decreasing trend before 10 kHz and then increase until value because of the confinement effect. For PVDF−2 wt %
1 MHz. Up to 50 kHz, rGO−PVDF films show less lossy rGO films, we can see that at a lower frequency (<100 kHz),
behavior than the PVDF−GO counterpart films, and the loss there is an increase in k values due to the thickness reduction;
keeps increasing till 1 MHz. On the other hand, in a 100 μm however, for higher frequencies, the k values decrease. We see
film, due to the lack of chain confinement effect, the loss values an interesting decrement in the dielectric constant for pure
are lower.68 Loss tangent for 100 μm decreases with frequency, PVDF films due to the chain confinement. As GO has surface
but the decay is not abrupt. This could be the case because, dipoles, when we apply E-field, they have the tendency to align
beyond a certain frequency range, changes in the externally parallel to the field, and as a result, we see a sharp jump in
applied E-field may cause variations in the hopping frequency dielectric constant due to confinement. On the other hand, the
of charge carriers.10 rGO has fewer surface dipoles compared to GO, which could
For a better understanding of the loss tangent phenomenon, be the reason behind this limited increase in dielectric constant
we can introduce Maxwell’s equation at higher frequencies. For pure PVDF films, this decrement in
dielectric constant is expected due to the restriction of the
ij yz dipole movement due to the confinement of the polymer
× H = Ji + j jj1 j j zzE
k { (8) chain. This particular property may be connected to spatial
limitations on the mobility of microscopic layers in a global
where Ji = excitation electric current density, E = applied E- chain.68 Fumagalli et al. also reported comparatively small
field, and H = magnetic field strength. This equation shows dielectric constant values in a constrained water layer. Near
that there is a contribution of the primary two terms to the loss surfaces, it is anticipated that dipole rotational freedom would
tangent values. The first term depicts the loss caused by decrease.71 Motevaselian et al. showed in a similar study that
electron colliding with other atoms and electrons. The second the reduction in dielectric constant could be because of the
advantageous in-plane dipole−dipole electrostatic coupling of
refers to the quantity of energy dissipated as motion and the dynamic interfacial region.72
heat because of the external E-field. The last term often Figure 5h shows approximately a 1000% increase in
predominates the first term in a dielectric material. The two conductivity for PVDF−rGO nanocomposites and around a
variables stay relatively in balance in semiconductor materi- 1500% increase for the PVDF−GO nanocomposite system
als.69 Therefore, in our case, we can see that the loss tangent is over pure PVDF films. For pure PVDF films, we see a
a synergistic outcome of the real and imaginary part of effective significant increase in conductivity (around 8000%) due to the
permittivity. Although the rGO shows high charge storing increase in leakage current with decreasing thickness. From eq
capability, due to the conductivity being higher for rGO, the 4, we can see that the conductivity is directly dependent on the
11707 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

Figure 6. Frequency-dependent (1 kHz to 1 MHz) (a) dielectric constant, k, (b) loss tangent, (c) conductivity of 1 μm PVDF−no filler and
PVDF−GO 1, 2, 3, 4, 5, 7, 10 wt % composite films. (d) Dielectric permittivity, (e) loss tangent, and (f) conductivity of 1 μm PVDF−no filler and
PVDF−lab-synthesized rGO 1, 2, 3, 4, 5, 7, 10 wt % composite films.

loss tangent values of the composite. As the PVDF film has mentioned above regarding the electrical conductivity and
higher loss due to the confinement of the polymer chain, as dielectric constant.
mentioned previously, we are seeing extremely high con- To understand the nanocomposite system better, we
ductivity values. Interestingly, due to the introduction of GO performed a concentration variation study on the thin 1 μm
and rGO nanosheets to the system, we are observing enhanced films. Figure 6 depicts the dielectric properties of 1−10 wt %
dielectric constant compared to the pure PVDF film, although PVDF−GO and PVDF−rGO nanocomposite films. We can
the pure PVDF film is becoming lossy as the thickness goes observe that pure PVDF (no fillers) shows less dependence on
down. Due to the introduction of GO and rGO to the system, the frequency. We see a decreasing trend for both PVDF−GO
not only do the permittivity values increase but also they have and PVDF−rGO films; however, for PVDF−rGO films, the
a significant increase in conductivity. We can see an inverse trend is evident. After 10 kHz, we see a sharp decrease in the
trend in the dielectric constant and conductivity change as we dielectric constant for PVDF−rGO films. However, for both
introduce fillers to the system. As the AC conductivity value PVDF−GO and PVDF−rGO composites, the frequency
depends on the loss tangent value of the materials, when the dependence gets stronger when the nanofiller content is
films become more lossy due to the decreased thickness, the higher than 4 wt %. For PVDF−GO nanocomposite films, the
conductivity increases. The SEM fractography, as depicted in decrease is gradual, whereas for PVDF−rGO, the decrease with
Figure 4d−f, provides additional evidence for the conclusions respect to frequency is sharp. In dielectric composite systems
11708 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

Figure 7. (a) Dielectric constant, k and loss tangent vs GO weight fraction (%) for 1 μm thick films, (b) dielectric constant, k and loss tangent vs
rGO weight fraction (%) for 1 μm thick films at 10 kHz frequency.

filled with conductive fillers, this phenomenon is frequently in the dielectric constant comes at the expense of a substantial
observed. It has been well established that composites rise in the dielectric loss.22 PVDF−GO composites show more
containing a high k nanofiller within a polymer matrix exhibit stable lossy behavior concerning frequency than the PVDF−
enhanced dielectric properties. The improved permittivity rGO composites. PVDF−rGO shows a decreasing trend till 10
value was attributed physically to the matrix’s enhancement of kHz and then plateaus or increases a small amount till 1 MHz.
the E-field, and the Maxwell−Garnett equation can be Higher concentration filler composites show strong frequency
employed to express the effective dielectric constant of that dependence supporting the MWS theory mentioned pre-
nanocomposite.73 viously.
Figure 6c,f shows the frequency-dependent conductivity for
( f + 2 p) + 2P( f p) PVDF−GO and PVDF−rGO 1−10 wt %. We can see a
eff = p
( f + 2 p) P( f p) (10) distinct difference between the trend of frequency-dependent
conductivity curves of GO and rGO. For all of them, electrical
where P represents the volume fraction of the nanofiller, and εf conductivity elevates with increasing AC frequency and filler
and εp stand for permittivity of the nanofiller and polymer concentration because of the availability of more charge
matrix, respectively, in the polymer nanocomposite system. carriers, reduced spacing between neighboring 2D sheets, and
Effective medium theory can be applied to explain the increased packing density. Such phenomena can be understood
correlation between the dielectric constant values of nano- by the polymer−nanofiller interfacial interaction
composites (with low nanofiller concentration) and their total static
constituents (matrix and filler). This equation depicts that the = +i (11)
dielectric behavior of a composite is dependent upon two where σtotal is the overall electrical conductivity of a system,
factors: σstatic is the DC conductivity part, and iωε represents the
1. Higher volume fraction of the filler (P) results in higher frequency-dependent (AC) part. The frequency-dependent
permittivity hence dielectric constant value. portion of electrical conductivity is not dominant when the
2. Discrepancy between the permittivity values of the frequency is small.76 The static (DC) component of the
matrix and filler (εf − εp) leads to higher effective interface electrical conductivity, which is strongly correlated
permittivity. with the filler concentration and the distance between nearby
nanofillers, predominates. The static portion of electrical
Additionally, eq 7 proves that the disparity between the conductivity barely increases at lower nanofiller concentrations
conductivity of the filler and matrix also leads to a high because of the wide separation between neighboring fillers. As
permittivity value. The high conductivity value of rGO explains frequency rises, frequency-facilitated electron hopping takes
the high dielectric constant for the rGO−PVDF films. precedence over static electrical conductivity in determining
Therefore, the notably high dielectric constant values of the total electrical conductivity.
PVDF−rGO composites compared to PVDF−GO nano- The polymer serves as an insulating layer in between the
composites can be understood from eqs 7 and 10. Previous nanofillers preventing direct contact. For PVDF−GO nano-
studies have demonstrated that some material (i.e., SiC) shows composites, we observe saturated AC frequency over the whole
lower dielectric constant than their composite polymer frequency range for 0−4 wt %; however, for 5−10 wt %
materials due to the induced polarization in the polymer− PVDF−GO, we see two phases of conductivity
nanofiller interface.74,75 Therefore, introducing a high amount
of filler material improves the dielectric constant of the • Almost unchanged conductivity till 100 kHz
nanocomposites by building numerous micro capacitors inside • Exponential increase in conductivity from 100 kHz to 1
the matrix. MHz
From Figure 6b,e, we can observe that the dielectric loss We can also observe similar behavior for PVDF−rGO,
values elevate with the increasing filler concentration. This is a although the two-phase nature starts showing up after 3 wt %.
typically noticed feature of conductive nanofiller-filled Multiple phases of conductivity in the nanocomposite system
dielectric polymer composites, where a considerable increase may be caused by lattice polarization around charges in a
11709 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

Figure 8. Dielectric strength and maximum energy density of the confinement-induced oriented GO and rGO nanosheet-based PVDF
nanocomposites. (a) Dielectric strength of PVDF−GO nanocomposites decreases on the addition of GO nanosheets and remains relatively
unchanged with the GO fraction. (b) Dielectric strength of PVDF−rGO nanocomposites decreases significantly on the addition of rGO nanosheets
and increases with the increasing rGO fraction. (c) Maximum energy density of confined PVDF−GO nanocomposites as a function of the GO
fraction. (d) Maximum energy density of confined PVDF−rGO nanocomposites as a function of the rGO fraction. The maximum energy density of
PVDF−rGO nanocomposites increases significantly on account of increasing permittivity and dielectric strength.

confined state. The one-dimensional electrical structure of the increases, a conductive network of nanofillers eventually forms
polymer chains in the disordered regions causes localization in in the PVDF matrix, supporting the percolation theory.78 This
these regions. Based on the filler structure, the transport is is a common feature of conductive nanosheet-filled dielectric
dominated by delocalization in the disordered areas induced by polymer composites, where a considerable increment in the
phonon, hopping, or even tunneling across conductive filler dielectric constant comes at the expense of a notable increment
islands.77 in the dielectric loss.22
Figure 7 summarizes the dielectric characteristics of PVDF− At 10 wt % GO, the highest k (dielectric constant) of 101.11
GO and PVDF−rGO composites, as evaluated at a reference was attained at the expense of a comparatively low dielectric
frequency of 10 kHz. For PVDF−GO nanocomposites, we loss of 0.16. However, for PVDF−rGO nanocomposite films,
observe a gradual increase in the dielectric constant value till 4 we observe that at 10 wt %, we get a k of 196.38 at the cost of a
wt %, and after that value, there is an abrupt increase in both high loss value of 0.58. Intense interfacial polarization resulting
loss tangent and dielectric constant. Likewise, in PVDF−rGO, from the conductive character of rGO sheets is responsible for
when rGO concentration is larger than 3 wt %, the loss and the rGO−PVDF composites’ moderately high dielectric losses
dielectric constant both exhibit sudden increases. These and high dielectric constants.79 Wu et al. explained in their
sudden slope changes can be ascribed to the conductive study that conducting filler composites cannot have both a low
network formation inside the matrix. As filler loading dielectric loss and high k, which is applicable to our PVDF−
increased, nanofillers interacted with one another, causing GO 1 μm films, where we have found that at the highest k
the interfacial rGO sheets to come into contact and value, the loss is not the highest. Li et al. observed a much
subsequently generate conductive networks. As filler loading lower k value at the same weight percentage for their 20 μm
11710 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

thick PVDF-BT@GO/rGO system.80 Also, 100 μm films reach increased dielectric strength might be due to the excessive
the percolation threshold at a much lower filler percent (i.e., at scattering from the breakdown via the electrical “treeing” effect
1 vol % of rGO in PVDF) and show an increasing trend for with the conductive nanosheets. Figure 8c,d shows the
both k and loss for increasing filler percentage.22 Surprisingly, maximum energy density (Umax) at 10 kHz calculated from
in our case, we see a different trend for the loss tangent values eq 12 that can be stored in the nanocomposite dielectrics. We
in 1 μm thick films due to the confinement effect. Apparently, observe that the Umax for both GO and rGO nanosheet-based
the horizontal alignment of the nanofillers enhanced the nanocomposites is lower than that of PVDF for low fractions
dielectric constant of the thin-film system. In bulk systems, the (∼1 wt %) of nanosheets on account of lower dielectric
2D nanofillers are oriented randomly. As a result, there is a strength and a low increase in permittivity. On further
greater probability of creating a conductive channel within the increasing the concentration of nanosheets, the energy density
matrix. On the other hand, due to the horizontal orientation, increases. The energy density for both nanocomposites
we have some control over the architecture inside the matrix increases significantly after ∼3 wt % filler fraction due to the
and hence a higher percolation level. For energy storage sharp increase in the nanocomposite permittivity. Further-
purposes, low loss and high dielectric constant are useful more, the increase in energy density is significantly higher for
properties, which are observed in PVDF−GO films at 4 and 10 the rGO nanocomposites due to the sharper increase in the
wt %. However, for EMI shielding purposes, high k and loss dielectric strength compared to that in GO nanocomposites.
tangent values are useful, which can be achieved by the Nonetheless, although the rGO-based nanocomposites show
PVDF−rGO system as we can see a sharp increasing trend of higher energy density, they also show a higher loss as
both k and loss values with increasing filler percentage. compared to the GO-based nanocomposites.
Given that we have studied and elucidated the effect of
confinement on the permittivity and loss tangent of GO and
rGO-based nanocomposites, we further look at the potential of
■ CONCLUSIONS
In this work, we demonstrate a significant influence of
confined nanocomposites for dielectric energy storage confinement on the loss tangent, dielectric permittivity, and
applications. One critical aspect of dielectric energy storage electrical conductivity of the GO and rGO-based PVDF
is dielectric strength (EBD)2, which determines the upper limit nanocomposite films within the measured frequency range.
of the E-field that the material can withstand. Furthermore, the One of the major mechanisms for determining the filler−
maximum energy density (Umax) that can be stored inside the matrix interaction in the confined thin film is the MWS
dielectric materials for a linear dielectric can be calculated as polarization. High dielectric constant values at low frequencies
1 2 are produced by parallel micro capacitors created by strongly
Umax = 0 rE BD orientated fillers in 1 μm thick films. Evidently, high k and low
2 (12)
loss values of the 1 μm thick film system were achieved by the
where ε0 is the permittivity of free space, εr is the relative nanofillers’ horizontal alignment compared to the bulk films
permittivity, and EBD is the dielectric strength (breakdown reported in the other literature (Table S2). Low loss and high
voltage/film thickness). The dielectric breakdown strengths dielectric constant are preferred for energy storage, and these
(EBD) are calculated using the two-parameter Weibull characteristics are achieved in PVDF−GO films at 4 and 10 wt
probability function (Figure S7), with the breakdown strength %. On the other hand, high k and loss tangent values are
at 63.2% probability of failure. The PVDF−GO or rGO advantageous for EMI shielding purposes and may be attained
nanocomposites are expected to show relatively linear by PVDF−rGO systems as we can observe a strong rising
behavior,81 and as such, the maximum energy density of trend of both k and loss values with increasing filler percentage.
these nanocomposites can be calculated using this equation. Developing a conductive network and hopping-dominated
Given that Umax is proportional to the square of dielectric electron transfer among the parallel-oriented 2D filler nano-
strength, the dielectric strength plays a significant role in fillers have a synergistic impact in increasing loss tangent and
determining the maximum energy density of the nano- conductivity values for thinner films. This research will provide
composite dielectric. Figure 8a shows the dielectric strength different insights into how 2D nanofiller-based polymer
of confinement-oriented PVDF−GO nanocomposites. Inter- nanocomposite films with adjustable thickness and concen-
estingly, the dielectric strength decreases upon adding the GO tration might potentially attain tunable dielectric characteristics
nanosheets and stays relatively constant upon increasing the for thin devices of the future.
weight fraction of GO. This might be due to the charge-
transfer pathways via GO nanosheets, and as such, the
nanosheets might not block breakdown trees efficiently,
■
*
ASSOCIATED CONTENT
sı Supporting Information
following the general observation that nanofillers in polymer The Supporting Information is available free of charge at
nanocomposites reduce dielectric strength. https://pubs.acs.org/doi/10.1021/acsanm.3c01674.
Interestingly, the dielectric strength of rGO nanosheets
based confinement-oriented nanocomposite films decreases Optical microscopy, AFM images, secondary and
significantly with the addition of nanosheets initially and then backscattered electron SEM images, dielectric spectros-
starts to increase as the fraction of the nanosheets increases, as copy data of 1 μm thick PVDF−commercial rGO (C
shown in Figure 8b. The initial decrease in the dielectric rGO) nanocomposite films, XPS data analysis details,
strength might be due to the increased charge transfer through comparison between this work and existing literature,
the nanocomposites. However, with the further addition of absolute permittivity, and loss factor data for GO/rGO-
nanosheets, the dielectric strength starts to increase. Interest- based PVDF nanocomposite films, Weibull plots for
ingly, this is in contrast with the case of the confined PVDF− breakdown strength measurements, mechanical testing
GO nanocomposites, where the dielectric strength does not data (stress−stain curve) for the 100 μm films, AFM
change significantly with increased nanosheet fraction. The height image analysis using the line profile, raw FTIR
11711 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

spectra for the fillers (GO and rGO) and nanocomposite (4) Kumar, P.; Kumar, A.; Cho, K. Y.; Das, T.; Sudarsan, V. An
films using OMNIC software, and Raman spectroscopy Asymmetric Electrically Conducting Self-Aligned Graphene/Polymer
of GO and rGO data (PDF) Composite Thin Film for Efficient Electromagnetic Interference
Shielding. AIP Adv. 2017, 7, 015103.

■ AUTHOR INFORMATION
Corresponding Author
(5) Mannsfeld, S. C. B.; Tee, B. C.-K.; Stoltenberg, R. M.; Chen, C.
V. H.-H.; Barman, S.; Muir, B. V. O.; Sokolov, A. N.; Reese, C.; Bao,
Z. Highly Sensitive Flexible Pressure Sensors with Microstructured
Rubber Dielectric Layers. Nat. Mater. 2010, 9, 859−864.
Alamgir Karim − Materials Science and Engineering,
(6) Liu, X.; Sun, H.; Liu, S.; Jiang, Y.; Yin, Z.; Yu, B.; Ning, N.; Tian,
University of Houston, Houston, Texas 77004, United States; M.; Zhang, L. Dielectric Elastomer Sensor with High Dielectric
Chemical and Biomolecular Engineering, University of Constant and Capacitive Strain Sensing Properties by Designing
Houston, Houston, Texas 77004, United States; Polar-Nonpolar Fluorosilicone Multiblock Copolymers and Introduc-
orcid.org/0000-0003-1302-9374; Email: akarim3@ ing Poly(Dopamine) Modified CNTs. Composites, Part B 2021, 223,
central.uh.edu 109103.
(7) Wu, H.; Huang, Y.; Xu, F.; Duan, Y.; Yin, Z. Energy Harvesters
Authors for Wearable and Stretchable Electronics: From Flexibility to
Farzana Hasan Likhi − Materials Science and Engineering, Stretchability. Adv. Mater. 2016, 28, 9881−9919.
University of Houston, Houston, Texas 77004, United States (8) Singh, M.; Dong, M.; Wu, W.; Nejat, R.; Tran, D.; Pradhan, N.;
Maninderjeet Singh − Chemical and Biomolecular Raghavan, D.; Douglas, J.; Wooley, K.; Karim, A. Enhanced Dielectric
Engineering, University of Houston, Houston, Texas 77004, Strength and Capacitive Energy Density of Cyclic Polystyrene Films.
United States; orcid.org/0000-0001-8891-8454 ACS Polym. Au 2022, 2, 324−332.
Shubham Vasant Chavan − Chemical and Biomolecular (9) Kim, J.-Y.; Kim, H.; Kim, T.; Yu, S.; Suk, J. W.; Jeong, T.; Song,
S.; Bae, M. J.; Han, I.; Jung, D.; Park, S. H. A Chlorinated Barium
Engineering, University of Houston, Houston, Texas 77004,
Titanate-Filled Polymer Composite with a High Dielectric Constant
United States and Its Application to Electroluminescent Devices. J. Mater. Chem. C
Thomas Cao − Chemical and Biomolecular Engineering, 2013, 1, 5078−5083.
University of Houston, Houston, Texas 77004, United (10) Tuichai, W.; Karaphun, A.; Ruttanapun, C. Improved Dielectric
States; orcid.org/0009-0004-0285-9991 Properties of PVDF Polymer Composites Filled with Ag Nanoma-
Mina Shanbedi − Materials Science and Engineering, terial Deposited Reduced Graphene Oxide (RGO) Hybrid Particles.
University of Houston, Houston, Texas 77004, United States Mater. Res. Bull. 2022, 145, 111552.
(11) da Silva, A. B.; Arjmand, M.; Sundararaj, U.; Bretas, R. E. S.
Complete contact information is available at:
Novel Composites of Copper Nanowire/PVDF with Superior
https://pubs.acs.org/10.1021/acsanm.3c01674 Dielectric Properties. Polymer 2014, 55, 226−234.
(12) Liu, S.; Tian, M.; Zhang, L.; Lu, Y.; Chan, T. W.; Ning, N.
Notes Tailoring Dielectric Properties of Polymer Composites by Controlling
The authors declare no competing financial interest. Alignment of Carbon Nanotubes. J. Mater. Sci. 2016, 51, 2616−2626.

■ ACKNOWLEDGMENTS
This work was sponsored in part by the US Army DEVCOM
(13) Zhang, W.; Zhou, Z.; Li, Q.; Chen, G.-X. Controlled Dielectric
Properties of Polymer Composites from Coating Multiwalled Carbon
Nanotubes with Octa-Acrylate Silsesquioxane through Diels−Alder
Cycloaddition and Atom Transfer Radical Polymerization. Ind. Eng.
Solder Center contract agreement W911QY-19-9-0011 and Chem. Res. 2014, 53, 6699−6707.
has been approved for public release. Any opinions and (14) Yao, S.; Yuan, J.; Mehedi, H.; Gheeraert, E.; Sylvestre, A.
conclusions expressed in this material are those of the Carbon Nanotube Forest Based Electrostatic Capacitor with Excellent
author(s) and do not necessarily reflect the views of the U.S. Dielectric Performances. Carbon 2017, 116, 648−654.
Government. The authors would like to express their gratitude (15) Huang, M.; Tunnicliffe, L. B.; Zhuang, J.; Ren, W.; Yan, H.;
to Dr. Devin L. Shaffer, Assistant Prof., Civil & Environmental Busfield, J. J. C. Strain-Dependent Dielectric Behavior of Carbon
Engineering, University of Houston, for his support with the Black Reinforced Natural Rubber. Macromolecules 2016, 49, 2339−
ATR−FTIR and Raman Spectroscopy measurements and Dr. 2347.
Makarenko Boris, Research Associate Prof., Chemistry Depart- (16) Sun, J.; Xue, Q.; Guo, Q.; Tao, Y.; Xing, W. Excellent Dielectric
ment, University of Houston, for helping with the XPS Properties of Polyvinylidene Fluoride Composites Based on Sandwich
measurements. Also, the authors want to thank Ugur Aslan for Structured MnO2/Graphene Nanosheets/MnO2. Composites, Part A
2014, 67, 252−258.
helping with substrate preparation and Wafa Tonny for (17) Tong, W.; Zhang, Y.; Yu, L.; Luan, X.; An, Q.; Zhang, Q.; Lv,
assisting with the ATR−FTIR measurement. F.; Chu, P. K.; Shen, B.; Zhang, Z. Novel Method for the Fabrication

■ REFERENCES
(1) Zhang, X.; Shen, Y.; Xu, B.; Zhang, Q.; Gu, L.; Jiang, J.; Ma, J.;
of Flexible Film with Oriented Arrays of Graphene in Poly(Vinylidene
Fluoride-Co-Hexafluoropropylene) with Low Dielectric Loss. J. Phys.
Chem. C 2014, 118, 10567−10573.
Lin, Y.; Nan, C. W. Giant Energy Density and Improved Discharge (18) Song, S.; Zheng, Z.; Bi, Y.; Lv, X.; Sun, S. Improving the
Efficiency of Solution-Processed Polymer Nanocomposites for Electroactive Phase, Thermal and Dielectric Properties of PVDF/
Dielectric Energy Storage. Adv. Mater. 2016, 28, 2055−2061. Graphene Oxide Composites by Using Methyl Methacrylate-Co-
(2) Singh, M.; Apata, I. E.; Samant, S.; Wu, W.; Tawade, B. V.; Glycidyl Methacrylate Copolymers as Compatibilizer. J. Mater. Sci.
Pradhan, N.; Raghavan, D.; Karim, A. Nanoscale Strategies to 2019, 54, 3832−3846.
Enhance the Energy Storage Capacity of Polymeric Dielectric (19) Schniepp, H. C.; Li, J.-L.; McAllister, M. J.; Sai, H.; Herrera-
Capacitors: Review of Recent Advances. Polym. Rev. 2022, 62, Alonso, M.; Adamson, D. H.; Prud’homme, R. K.; Car, R.; Saville, D.
211−260. A.; Aksay, I. A. Functionalized Single Graphene Sheets Derived from
(3) Barber, P.; Balasubramanian, S.; Anguchamy, Y.; Gong, S.; Splitting Graphite Oxide. J. Phys. Chem. B 2006, 110, 8535−8539.
Wibowo, A.; Gao, H.; Ploehn, H. J.; zur Loye, H.-C. Polymer (20) Ammar, A. M. Reduction of Graphene Oxide Using Microwave
Composite and Nanocomposite Dielectric Materials for Pulse Power And Its Effect on Polymer Nanocomposites Properties. Ph.D. Thesis,
Energy Storage. Materials 2009, 2, 1697−1733. University of Akron, 2018. https://etd.ohiolink.edu/apexprod/rws_

11712 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

olink/r/1501/10?clear=10&p10_accession_num= (39) Szabó, T.; Tombácz, E.; Illés, E.; Dékány, I. Enhanced Acidity
akron1533123263694685 (accessed April 3, 2023). and PH-Dependent Surface Charge Characterization of Successively
(21) Lui, C. H.; Liu, L.; Mak, K. F.; Flynn, G. W.; Heinz, T. F. Oxidized Graphite Oxides. Carbon 2006, 44, 537−545.
Ultraflat Graphene. Nature 2009, 462, 339−341. (40) Karousis, N.; Sandanayaka, A.; Hasobe, T.; Economopoulos, S.;
(22) Chen, Z.; Liu, Y.; Fang, L.; Jiang, P.; Huang, X. Role of Sarantopoulou, E.; Tagmatarchis, N. Graphene Oxide with Covalently
Reduced Graphene Oxide in Dielectric Enhancement of Ferroelectric Linked Porphyrin Antennae: Synthesis, Characterization and Photo-
Polymers Composites. Appl. Surf. Sci. 2019, 470, 348−359. physical Properties. J. Mater. Chem. 2011, 21, 109−117.
(23) Xia, X.; Wang, Y.; Zhong, Z.; Weng, G. J. A Frequency- (41) Hontoria-Lucas, C.; López-Peinado, A.J.; López-Gonzalez, J.d.
Dependent Theory of Electrical Conductivity and Dielectric D.; Rojas-Cervantes, M.L.; Martin-Aranda, R.M. Study of oxygen-
Permittivity for Graphene-Polymer Nanocomposites. Carbon 2017, containing groups in a series of graphite oxides: Physical and chemical
111, 221−230. characterization. Carbon 1995, 33 (11), 1585−1592.
(24) Xia, X.; Zhong, Z.; Weng, G. J. Maxwell−Wagner−Sillars (42) Gao, X.; Jang, J.; Nagase, S. Hydrazine and Thermal Reduction
Mechanism in the Frequency Dependence of Electrical Conductivity of Graphene Oxide: Reaction Mechanisms, Product Structures, and
and Dielectric Permittivity of Graphene-Polymer Nanocomposites. Reaction Design. J. Phys. Chem. C 2010, 114, 832−842.
Mech. Mater. 2017, 109, 42−50. (43) Park, S.; An, J.; Jung, I.; Piner, R. D.; An, S. J.; Li, X.;
(25) Meier, J. G.; Klüppel, M. Carbon Black Networking in Velamakanni, A.; Ruoff, R. S. Colloidal Suspensions of Highly
Elastomers Monitored by Dynamic Mechanical and Dielectric Reduced Graphene Oxide in a Wide Variety of Organic Solvents.
Spectroscopy. Macromol. Mater. Eng. 2008, 293, 12−38. Nano Lett. 2009, 9, 1593−1597.
(26) McLachlan, D. S.; Heaney, M. B. Complex Ac Conductivity of a (44) NIST’s Office of Data and Informatics. NIST Chemistry
Carbon Black Composite as a Function of Frequency, Composition, WebBook, 2023.
and Temperature. Phys. Rev. B: Condens. Matter Mater. Phys. 1999, 60, (45) López-López, M.; García-Ruiz, C. Infrared and Raman
12746−12751. Spectroscopy Techniques Applied to Identification of Explosives.
(27) Brüesch, P.; Stucki, F.; Baumann, Th.; Kluge-Weiss, P.; Brühl, TrAC, Trends Anal. Chem. 2014, 54, 36−44.
B.; Niemeyer, L.; Strümpler, R.; Ziegler, B.; Mielke, M. Electrical and (46) Jin, M.; Jeong, H.-K.; Yu, W. J.; Bae, D. J.; Kang, B. R.; Lee, Y.
Infrared Dielectrical Properties of Silica Aerogels and of Silica- H. Graphene Oxide Thin Film Field Effect Transistors without
Aerogel-Based Composites. Appl. Phys. A 1993, 57, 329−337. Reduction. J. Phys. D: Appl. Phys. 2009, 42, 135109.
(28) Yeh, S.-C.; Wu, C.-H.; Huang, Y.-C.; Lee, J.-Y.; Jeng, R.-J. In (47) Sengupta, I.; Chakraborty, S.; Talukdar, M.; Pal, S.;
Search of a Green Process: Polymeric Films with Ordered Arrays via a Chakraborty, S. Thermal Reduction of Graphene Oxide: How
Water Droplet Technique. Polymers 2019, 11, 1473. Temperature Influences Purity. J. Mater. Res. 2018, 33, 4113−4122.
(29) Konios, D.; Stylianakis, M. M.; Stratakis, E.; Kymakis, E. (48) Arshad, A. N.; Rozana, M. D.; Wahid, M. H. M.; Mahmood, M.
Dispersion Behaviour of Graphene Oxide and Reduced Graphene K. A.; Sarip, M. N.; Habibah, Z.; Rusop, M. Enhanced Dielectric and
Oxide. J. Colloid Interface Sci. 2014, 430, 108−112. Electrical Properties of Annealed PVDF Thin Film. AIP Conf. Proc.
(30) Gholampour, A.; Valizadeh Kiamahalleh, M.; Tran, D.; 2018, 1963, 020010.
(49) Gregorio, R., Jr. Determination of the α, β, and γ crystalline
Ozbakkaloglu, T.; Losic, D. Physiochemical and Mechanical Proper-
phases of poly(vinylidene fluoride) films prepared at different
ties of Graphene Oxide (GO)-Cement Mortar Composite. Conference:
conditions. J. Appl. Polym. Sci. 2006, 100, 3272−3279.
20th International Conference on Composite Structures (ICCS20), 2017.
(50) Ataur Rahman, M.; Lee, B.-C.; Phan, D.-T.; Chung, G.-S.
(31) Smith, A. T.; LaChance, A. M.; Zeng, S.; Liu, B.; Sun, L.
Fabrication and Characterization of Highly Efficient Flexible Energy
Synthesis, Properties, and Applications of Graphene Oxide/Reduced
Harvesters Using PVDF−Graphene Nanocomposites. Smart Mater.
Graphene Oxide and Their Nanocomposites. Nano Mater. Sci. 2019,
Struct. 2013, 22, 085017.
1, 31−47. (51) Zhou, Y.; Liu, W.; Tan, B.; Zhu, C.; Ni, Y.; Fang, L.; Lu, C.; Xu,
(32) Gonçalves, G.; Vila, M.; Bdikin, I.; de Andrés, A.; Emami, N.; Z. Crystallinity and β Phase Fraction of PVDF in Biaxially Stretched
Ferreira, R. A. S.; Carlos, L. D.; Grácio, J.; Marques, P. A. A. P. PVDF/PMMA Films. Polymers 2021, 13, 998.
Breakdown into Nanoscale of Graphene Oxide: Confined Hot Spot (52) Yu, S.; Zheng, W.; Yu, W.; Zhang, Y.; Jiang, Q.; Zhao, Z.
Atomic Reduction and Fragmentation. Sci. Rep. 2014, 4, 6735. Formation Mechanism of β-Phase in PVDF/CNT Composite
(33) Gacka, E.; Majchrzycki, Ł.; Marciniak, B.; Lewandowska- Prepared by the Sonication Method. Macromolecules 2009, 42,
Andralojc, A. Effect of Graphene Oxide Flakes Size and Number of 8870−8874.
Layers on Photocatalytic Hydrogen Production. Sci. Rep. 2021, 11, (53) Ansari, S.; Giannelis, E. P. Functionalized Graphene Sheet�
15969. Poly(Vinylidene Fluoride) Conductive Nanocomposites. J. Polym. Sci.,
(34) El Achaby, M.; Arrakhiz, F. Z.; Vaudreuil, S.; Essassi, E. M.; Part B: Polym. Phys. 2009, 47, 888−897.
Qaiss, A. Piezoelectric β-Polymorph Formation and Properties (54) Eigler, S.; Dotzer, C.; Hof, F.; Bauer, W.; Hirsch, A. Sulfur
Enhancement in Graphene Oxide − PVDF Nanocomposite Films. Species in Graphene Oxide. Chem.�Eur. J. 2013, 19, 9490−9496.
Appl. Surf. Sci. 2012, 258, 7668−7677. (55) Ganguly, A.; Sharma, S.; Papakonstantinou, P.; Hamilton, J.
(35) Stafford, C. M.; Roskov, K. E.; Epps, T. H.; Fasolka, M. J. Probing the Thermal Deoxygenation of Graphene Oxide Using High-
Generating Thickness Gradients of Thin Polymer Films via Flow Resolution In Situ X-Ray-Based Spectroscopies. J. Phys. Chem. C
Coating. Rev. Sci. Instrum. 2006, 77, 023908. 2011, 115, 17009−17019.
(36) Rahimi, S.; van Leeuwen, D.; Roshanzamir, F.; Pandit, S.; Shi, (56) NIST. NIST XPS Database, Selected Element Search Result.
L.; Sasanian, N.; Nielsen, J.; Esbjörner, E. K.; Mijakovic, I. https://srdata.nist.gov/xps/EngElmSrchQuery.aspx?EType=
Ginsenoside Rg3 Reduces the Toxicity of Graphene Oxide Used for PE&CSOpt=Retri_ex_dat&Elm=C (accessed May 23, 2023).
PH-Responsive Delivery of Doxorubicin to Liver and Breast Cancer (57) Zhang, J.; Xu, Y.; Liu, Z.; Yang, W.; Liu, J. A Highly Conductive
Cells. Pharmaceutics 2023, 15, 391. Porous Graphene Electrode Prepared via in Situ Reduction of
(37) Sun, X.; Luo, D.; Liu, J.; Evans, D. G. Monodisperse Graphene Oxide Using Cu Nanoparticles for the Fabrication of High
Chemically Modified Graphene Obtained by Density Gradient Performance Supercapacitors. RSC Adv. 2015, 5, 54275−54282.
Ultracentrifugal Rate Separation. ACS Nano 2010, 4, 3381−3389. (58) Shin, Y.-E.; Sa, Y. J.; Park, S.; Lee, J.; Shin, K.-H.; Joo, S. H.; Ko,
(38) Romero, M. P.; Marangoni, V. S.; de Faria, C. G.; Leite, I. S.; e H. An Ice-Templated, PH-Tunable Self-Assembly Route to Hierarchi-
Silva, C. d. C. C.; Maroneze, C. M.; Pereira-da-Silva, M. A.; Bagnato, cally Porous Graphene Nanoscroll Networks. Nanoscale 2014, 6,
V. S.; Inada, N. M. Graphene Oxide Mediated Broad-Spectrum 9734−9741.
Antibacterial Based on Bimodal Action of Photodynamic and (59) Lopes, A. C.; Caparros, C.; Ferdov, S.; Lanceros-Mendez, S.
Photothermal Effects. Front. Microbiol. 2020, 10, 2995. Influence of Zeolite Structure and Chemistry on the Electrical

11713 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714
ACS Applied Nano Materials www.acsanm.org Article

Response and Crystallization Phase of Poly(Vinylidene Fluoride). J. (77) Kalyane, S. AC Conductivity Study of Polyaniline/NiCuFe2O3
Mater. Sci. 2013, 48, 2199−2206. Composites. Int. J. Mech. Eng. Technol. 2014, 5, 10−12.
(60) Chakhchaoui, N.; Farhan, R.; Eddiai, A.; Meddad, M.; (78) Lv, L.; Huang, L.; Zhu, P.; Li, G.; Zhao, T.; Long, J.; Sun, R.;
Cherkaoui, O.; Mazroui, M.; Boughaleb, Y.; Van Langenhove, L. Wong, C. SiO2 Particle-Supported Ultrathin Graphene Hybrids/
Improvement of the Electroactive β-Phase Nucleation and Piezo- Polyvinylidene Fluoride Composites with Excellent Dielectric
electric Properties of PVDF-HFP Thin Films Influenced by TiO2 Performance and Energy Storage Density. J. Mater. Sci.: Mater.
Nanoparticles. Mater. Today: Proc. 2021, 39, 1148−1152. Electron. 2017, 28, 13521−13531.
(61) Jaleh, B.; Jabbari, A. Evaluation of Reduced Graphene Oxide/ (79) Wu, Y.; Wang, Z.; Shen, X.; Liu, X.; Han, N. M.; Zheng, Q.;
ZnO Effect on Properties of PVDF Nanocomposite Films. Appl. Surf. Mai, Y.-W.; Kim, J.-K. Graphene/Boron Nitride−Polyurethane
Sci. 2014, 320, 339−347. Microlaminates for Exceptional Dielectric Properties and High Energy
(62) Garcia-Gonzalez, D.; Garzon-Hernandez, S.; Rusinek, A.; Densities. ACS Appl. Mater. Interfaces 2018, 10, 26641−26652.
Bernier, R.; Arias, A. Low Temperature Mechanical Behaviour of (80) Li, Y.; Yang, W.; Ding, S.; Fu, X. Z.; Sun, R.; Liao, W.-H.;
PVDF: Cryogenic Pre-Treatment, Quasi-Static, Cyclic and Dynamic Wong, C. P. Tuning Dielectric Properties and Energy Density of
Experimental Testing and Modelling. Mech. Mater. 2020, 147, Poly(Vinylidene Fluoride) Nanocomposites by Quasi Core−Shell
103436. Structured BaTiO3@graphene Oxide Hybrids. J. Mater. Sci.: Mater.
(63) Yu, C.; Li, D.; Wu, W.; Luo, C.; Zhang, Y.; Pan, C. Mechanical Electron. 2018, 29, 1082−1092.
Property Enhancement of PVDF/Graphene Composite Based on a (81) Mokhtari, F.; Spinks, G. M.; Sayyar, S.; Cheng, Z.; Ruhparwar,
High-Quality Graphene. J. Mater. Sci. 2014, 49, 8311−8316. A.; Foroughi, J. Highly Stretchable Self-Powered Wearable Electrical
(64) Schönhals, A.; Kremer, F. Theory of Dielectric Relaxation. In Energy Generator and Sensors. Adv. Mater. Technol. 2021, 6,
Broadband Dielectric Spectroscopy; Kremer, F., Schönhals, A., Eds.; 2000841.
Springer: Berlin, Heidelberg, 2003; pp 1−33.
(65) Liu, L.; Zhang, Y.; Lv, F.; Tong, W.; Ding, L.; Chu, P. K.; Li, P.
Polyimide Composites Composed of Covalently Bonded BaTiO3@
GO Hybrids with High Dielectric Constant and Low Dielectric Loss.
RSC Adv. 2016, 6, 86817−86823.
(66) Ma, W.-S.; Wu, L.; Yang, F.; Wang, S.-F. Non-Covalently
Modified Reduced Graphene Oxide/Polyurethane Nanocomposites
with Good Mechanical and Thermal Properties. J. Mater. Sci. 2014,
49, 562−571.
(67) Luo, S.; Yu, S.; Sun, R.; Wong, C.-P. Nano Ag-Deposited
BaTiO3 Hybrid Particles as Fillers for Polymeric Dielectric
Composites: Toward High Dielectric Constant and Suppressed
Loss. ACS Appl. Mater. Interfaces 2014, 6, 176−182.
(68) Cho, Y.-K.; Watanabe, H.; Granick, S. Dielectric Response of
Polymer Films Confined between Mica Surfaces. J. Chem. Phys. 1999,
110, 9688−9696.
(69) The Relationship Between Loss, Conductivity and Dielectric
Constant|PDF; Scribd. https://www.scribd.com/doc/163712677/
The-Relationship-Between-Loss-Conductivity-and-Dielectric-
Constant (accessed Nov 14, 2022).
(70) Elashmawi, I. S.; Alatawi, N. S.; Elsayed, N. H. Preparation and
Characterization of Polymer Nanocomposites Based on PVDF/PVC
Doped with Graphene Nanoparticles. Results Phys. 2017, 7, 636−640.
(71) Fumagalli, L.; Esfandiar, A.; Fabregas, R.; Hu, S.; Ares, P.;
Janardanan, A.; Yang, Q.; Radha, B.; Taniguchi, T.; Watanabe, K.;
Gomila, G.; Novoselov, K. S.; Geim, A. K. Anomalously Low
Dielectric Constant of Confined Water. Science 2018, 360, 1339−
1342.
(72) Motevaselian, M. H.; Aluru, N. R. Universal Reduction in
Dielectric Response of Confined Fluids. ACS Nano 2020, 14, 12761−
12770.
(73) Mahani, A. A.; Motahari, S.; Nayyeri, V. Electromagnetic and
Microwave Absorption Characteristics of PMMA Composites Filled
with a Nanoporous Resorcinol Formaldehyde Based Carbon Aerogel.
RSC Adv. 2018, 8, 10855−10864.
(74) Feng, Y.; Gong, H.; Xie, Y.; Wei, X.; Yang, L.; Zhang, Z. Strong
induced polarity between Poly(vinylidene fluoride-co-chlorotrifluoro-
ethylene) and α-SiC and its influence on dielectric permittivity and
loss of their composites. J. Appl. Phys. 2015, 117, 094104.
(75) Feng, Y.; Miao, B.; Gong, H.; Xie, Y.; Wei, X.; Zhang, Z. High
Dielectric and Mechanical Properties Achieved in Cross-Linked
PVDF/α-SiC Nanocomposites with Elevated Compatibility and
Induced Polarization at the Interface. ACS Appl. Mater. Interfaces
2016, 8, 19054−19065.
(76) Ravindran, A. R.; Feng, C.; Huang, S.; Wang, Y.; Zhao, Z.;
Yang, J. Effects of Graphene Nanoplatelet Size and Surface Area on
the AC Electrical Conductivity and Dielectric Constant of Epoxy
Nanocomposites. Polymers 2018, 10, 477.

11714 https://doi.org/10.1021/acsanm.3c01674
ACS Appl. Nano Mater. 2023, 6, 11699−11714