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OPEN Supercapacitors and triboelectric

nanogenerators based
on electrodes of greener iron
nanoparticles/carbon nanotubes
composites
Glaydson Simoes dos Reis 1,7*, Helinando Pequeno de Oliveira 2,7,
Iuri Custodio Montes Candido 2, Andre Luiz Freire 2, Palanivel Molaiyan 3,
Guilherme Luiz Dotto 4, Alejandro Grimm 1 & Jyri‑Pekka Mikkola 5,6

The development of supporting materials based on carbon nanotubes (CNTs) impregnated with iron
nanoparticles via a sustainable and green synthesis employing plant extract of Punica granatum L.
leaves was carried out for the iron nanoparticle modification and the following impregnation into the
carbon nanotubes composites (CNT-Fe) that were also coated with polypyrrole (CNT-Fe + PPy) for use
as electrode for supercapacitor and triboelectric nanogenerators. The electrochemical characterization
of the materials by cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD) assays
revealed that the CNT-Fe + PPy gave rise to better performance due to the association of double-layer
capacitance behavior of carbon derivative in association with the pseudocapacitance contribution
of PPy resulting in an areal capacitance value 202 mF/ ­cm2 for the overall composite. In terms of the
application of electrodes in triboelectric nanogenerators, the best performance for the composite
of CNT-Fe + PPy was 60 V for output voltage and power density of 6 μW/cm2. The integrated system
showed that the supercapacitors can be charged directly by the nanogenerator from 0 to 42 mV in
300 s. The successful green synthesis of iron nanoparticles on CNT and further PPy coating provides a
feasible method for the design and synthesis of high-performance SCs and TENGs electrode materials.
This work provides a systematic approach that moves the research front forward by generating data
that underpins further research in self-powered electronic devices.

Keywords Green synthesis, Iron nanoparticles, Flexible electrodes, Energy harvesting and storage

The fast depletion of fossil fuels and environmental pollution are driving forces that motivate the research on
renewable and green energy sources. Electrochemical devices for energy storage such as supercapacitors (SCs)
and batteries, and the harvesting of energy such as triboelectric nanogenerators (TENGs) have been widely
employed in portable and wearable electronic devices. The storage and release of energy in SCs are governed by
the electrochemical interactions between electrolytes (ions) and ­electrodes1–3 being considered powerful devices
with fast charging/discharging, large power density, and long cyclability, which render them very suitable for
integration with energy-harvesting devices such as TENGs, which have been extensively explored as promising
templates to harvest energy from mechanical m ­ ovement4. An alternative that has been recently explored for
TENGs is the association with magnetic nanoparticles. The incorporation of magnetic domains in friction layers

1
Department of Forest Biomaterials and Technology, Biomass Technology Centre, Swedish University of
Agricultural Sciences, 901 83 Umeå, Sweden. 2Institute of Materials Science, Federal University of Sao
Francisco Valley, Petrolina 56304‑205, Brazil. 3Research Unit of Sustainable Chemistry, University of Oulu,
P.O. Box 3000, 90014 Oulu, Finland. 4Research Group On Adsorptive and Catalytic Process Engineering
(ENGEPAC), Federal University of Santa Maria, Av. Roraima, 1000‑7, Santa Maria, RS 97105–900, Brazil. 5Technical
Chemistry, Department of Chemistry, Umeå University, 90187 Umeå, Sweden. 6Industrial Chemistry and
Reaction Engineering, Johan Gadolin Process Chemistry Centre, Åbo Akademi University, 20500 Åbo‑Turku,
Finland. 7These authors contributed equally: Glaydson Simoes dos Reis and Helinando Pequeno de Oliveira. *email:
glaydson.simoes.dos.reis@slu.se

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is an additional source for repulsive forces in substitution to conventional mechanic restoring forces and in the
induction of electric potential in copper-based e­ lectrodes5. Several applications have been explored for these
materials such as the use in tilt sensing systems, noncontact mode TENG by the action of an external magnetic
­field6, or for magnetic field d­ etection7.
The energy harvesting from TENGs is based on the contact/separation of tribopairs that takes place from
the processes of contact electrification and electrostatic induction that are established at the interface between
dielectric and conductive electrode material layers, acting as current collectors to give suitable current transfer
to an external load resistance. TENG converts mechanical energy into electrical energy and makes possible the
conversion of the body’s movement into electricity. Besides, both TENGs and SCs can be integrated to create
a self-charging, uninterrupted power supply system. Compensating energy consumption and extending the
working duration of electronic devices’ materials have proven to be essential in the integration of TENGs and
supercapacitors, providing a viable solution for developing efficient, lightweight, and flexible energy harvesting
and storage devices. Both SCs and TENGs possess the advantages of lightweight, wide-ranging materials selection
and simple fabrication process, being considered as a promising energy source for wearable electronics such as
smart ­bracelets8, smart textiles and c­ lothing9,10, and flexible d
­ isplays11. The high performance of the SCs strongly
relies on the electrode properties making necessary the research for efficient active electrode materials for high-
capacity ­SCs12,13. Overall, SC electrodes are commonly composed of carbon-based m ­ aterials14,15, transition metal
composite ­materials16, and polymer-based ­materials17.
Some of these compounds such as metals and their respective oxides present both high conductivity and
capacitance, however, they face poor electrochemical reversibility, and poor energy harvesting behavior due to
their unsuitable elastic properties, which hinders their efficient application in stable and high-performance S­ Cs18
and ­TENGs19. On the other hand, carbon materials including carbon cloth, graphene, and carbon nanotubes
are widely employed as suitable electrodes for SC and TENG applications due to their excellent conductivity,
chemical stability, and resistance to ­corrosion14,20.
For instance, carbon nanotubes (CNTs) exhibit important advantages for application in electrodes for SCs
and TENGs, such as high specific surface area, high density, outstanding conductivity and chemical stability, and
unique hollow and layered structure, which facilitate ion transport; in addition, CNTs have good mechanical flex-
ibility being considered good carriers for metal o ­ xides21 which makes it very suitable for TENGs a­ pplication4,22.
However, carbon-based SCs and TENGs may face issues related to limited conductivity. A strategy to circumvent
this drawback is the combination of carbon nanotubes with metal nanoparticles/conducting polymers if con-
sidering the excellent performance of pure carbon electrodes with the boosting in the electrochemical stability/
performance provided by the ­fillers23,24.
Over the years, the fabrication of nanomaterials for a wide range of applications including energy harvest
and storage has exponentially ­increased25–27. Several methods are employed for the synthesis of nanomateri-
als including chemical vapor deposition, plasma-assisted physical vapor deposition, aerosol processes, spray
pyrolysis, and ­others28. However, these methods have been gradually substituted by green synthesis methods due
to the serious disadvantages related to the large energy and chemical consumption, use of complex equipment
and synthesis ­conditions29,30, and toxic r­ eagents31,32. A sustainable and greener synthesis has been based on the
combination of biomasses in conjunction with metal nanoparticles to be impregnated on the CNT ­structure32,33.
This technique brings important environmental and economic gains due to the use of non-toxic, low-cost, and
naturally abundant resources for metal-nanoparticles (NP) s­ ynthesis34, which explores the chemical reduction
of the metal employing bio-based extracts from plants, fungi, bacteria sources, etc.35. The formation of stable
metal-NPs in a support material, e.g., carbon nanotubes, can be produced by the immersion of the support mate-
rial into the desired metal solution and the reducing agent e­ xtract36. The literature reports different bio-based
materials that have been employed as reduction agents in the metal-NPs syntheses including banana p ­ eel37, yellow
trumpetbush ­leaves38, etc. Meanwhile, common support materials are reported to be ­activated39 such as ­silica40,
carbon ­nanotubes41, and g­ raphene42–44. The incorporation of metal nanoparticles (e.g., iron nanoparticles) on
CNT structure is an interesting approach for high-performance electrodes for SCs due to the combined/synergic
effects of each material such as CNT assists in maintaining mechanical integrity and high electrical conductiv-
ity of the overall electrodes due to their superior mechanical properties, good electrochemical stability, and
excellent ­conductivity21,45,46. The iron oxide nanoparticles dispersed on the CNT structure can greatly shorten
the diffusion and migration paths of electrolyte ions during the rapid charge–discharge process, which assures
better electrochemical p ­ roperties21,46,47.
This work describes the synthesis of an advanced flexible electrode material for application in SCs and TENGs
through a sustainable and greener approach using eggshell membrane as flexible support material and a plant-
based reductant (Punica granatum L. Leaves) to form and deposit iron NPs on the carbon nanotube structure. The
iron-NPs-CNTs were successfully applied as electrodes for SCs and TENGs. With this aim, mechanical support
was provided by the eggshell membranes that were coated with iron-NPs-NT material to serve as sustainable
and flexible electrodes. Further, the coated eggshell membranes with iron-NPs-NTs material were subjected to
a chemical polymerization of polypyrrole (PPy), which creates a layer over the flexible electrode that preserves
the electrochemical properties of additives (EDLC and PC) and the mechanical characteristics of the eggshell
membrane. The flexible electrodes were fully characterized in detail to evaluate the effect of both iron-NPs-NTs
and PPy on their physicochemical and electrochemical properties for both applications.

Materials and methods

Green synthesis route
The commercial CNTs were impregnated with iron nanoparticles based on the method described by Wang et al.32
and its schematics are shown in Fig. 1. Extracts of pomegranate were employed as a green strategy to coat the

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Figure 1.  Synthesis process of the carbon electrode materials.

CNTs with iron nanoparticles. Firstly, 60 g of pomegranate leaves (fallen leaves, waste biomass) were mixed with
1 L of deionized water at 80 °C and agitated for 1 h. Then, the solution was cooled, and filtrated to obtain a solid
material from the vegetal extract. The preparation of the metallic solution containing iron nanoparticles was
done by, first, diluting 1.5 wt% (mass volume) of iron salt (­ FeSO4·7H2O). After that, the solution containing 2 g
of CNTs, and the salt were added and mixed with the plant extract. A ratio of 2:1 in volume (40 mL of extract
and 20 mL of salt solution) was used. The solution containing all compounds was agitated (160 rpm) using a
stirrer at 25 °C and for 24 h. As a final step, the solid materials were separated through filtrations and dried at
105 °C for 24 h for further use.

Removal and treatment of eggshell membranes (ESM)

The eggshells were obtained from the local market in the city of Juazeiro-BA, Brazil, and the cleaning and mem-
brane extraction procedure was carried out according to the procedure described by Alcaraz-Espinoza et al.48
According to the reported procedure, the eggshells were disposed of in 1 M HCl solution for 30 min. Subse-
quently, the eggshell membranes (ESM) were separated from the shell and washed several times with ultrapure,
deionized water (Milli-Q water). Then, the samples were cut into 8 mm diameter discs for further use.

Electrode preparation
Three samples, viz. Fe + CNT, PPy, and CNT-Fe + PPy were prepared to evaluate the influence of components in
the overall response of the modified eggshell membranes applied as electrodes of the electrochemical devices. The
preparation steps are described as follows: The synthesis of sample PPy provided the free growth of polypyrrole
on the unmodified eggshell membrane that was conducted according to the procedure reported in Ref.49: two
solutions (S1 and S2) were prepared. The solution S1 was prepared with 25 mL of HCl (1 M) in which pyrrole
(35 μL) was added to a beaker and stirred for 5 min. Subsequently, the membrane was added and the solution
was stirred for 30 min in an orbital shaker at room temperature. For the preparation of the solution S2, 81.1 mg of
­FeCl3 was added to 25 mL of HCl (1 M) and kept under intense stirring. As a following step, the solution S2 was
slowly dropped into S1 and stirred for 24 h on the orbital shaker, at room temperature. After that, the membrane
was removed washed with ultrapure water, and dried at room temperature. After drying, a medium weight for
the PPy sample transferred to ESM of 4.7 mg was obtained—thickness of 74 µm. Disks of 8 mm in diameter were
applied as electrodes for supercapacitors while samples of 2 cm × 3 cm were applied in the harvesting of energy
as electrodes of TENGs. Photos of the resulting electrodes are shown in Fig. S1.
A mother solution containing 10 mg/mL of Fe + CNT aqueous solution was used to transfer under sonication
the modified carbon nanotubes to the ESM. After two cycles of sonication of membranes into Fe + CNT solution
of 45 min, the medium of mass for adhered nanostructures is 2.5 mg—thickness of 79.5 µm. The sample CNT-
Fe +/PPy is prepared by the combination of two steps in which an initial deposition of Fe + CNT (as previously
described) is followed by an additional step of polymerization of PPy (as described for sample PPy). Under the
combination of these steps, the final weight of the impregnated material was in the order of 6.7 mg—thickness
of 78 µm.

Results and discussion

Morphological and structural characterization
The morphology of PPy (Fig. 2a,b), CNT-Fe (Fig. 2c,d), and CNT-Fe + PPy (Fig. 2e,f) deposited on ESM were
evaluated from SEM images. As can be observed, the overall morphology of the ESM supports is composed of
a distribution of tubular structures with different diameters and 3D micrometer sizes; the overlapping of CNTs
seems to create random voids and spaces (yielding porous structures). The CNT-Fe + PPy structure showed a
much different morphology with the disappearance of 3D tubular structures and bigger voids, but the resulting

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Figure 2.  Morphology of modified ESM templates at different magnifications (a, b) for PPy, (c, d) CNT-Fe, and
(e, f) for CNT-Fe + PPy.

morphology with agglomerates was a coherent surface feature, indicating a highly stable PPy loading and good
compatibility. It can be stated that the CNT-Fe + PPy electrode surface demonstrated a 3D-fine porous stacking
formation, with a network of conducting PPy structure. CNT-Fe + PPy can be characterized as a layered growth of
nanofoam features over the CNT-Fe structure. It is expected for the CNT-Fe + PPy system to a better conductivity
and electrochemical performances when tested as flexible SCs. Furthermore, EDS images are shown in Fig. S2,
which confirms the presence of nitrogen and iron elements, with the presence of the N justified by the coating
with PPy, confirming the adequate modification with PPy.
The pore structure characteristics without and under doping with the PPy on ESM + CNT-Fe were also evalu-
ated. The results show that after PPy doping the sample-specific surface area decreased from 68 ­m2 ­g−1 (CNT-Fe)
­ 2 ­g−1 (CNT-Fe + PPy). Both samples exhibited a more pronounced presence of mesopores (see Table 1).
to 14 m
These results agree with the data reported in the ­literature50,51. The SSA decrease is due to the deposition of PPy
over the CNT-Fe surface covering the pores and filling the voids of the CNT-Fe agglomerates.
The FTIR analysis (Fig. 3a) of the PPy and CNT-Fe + PPy electrodes gives valuable information about the
surface chemical characteristics regarding the presence of surface groups induced by the polymerization of
polypyrrole on ESM and CNT-Fe structure. For the CNT-Fe + PPy sample, the presence of absorption bands at
1651, 1536, 1390, 1188, 1040, and 775 ­cm−1 was observed, which is by the PPy data reported in l­iterature52. In
comparison with the PPy spectrum, it is possible to confirm the presence of peaks at 1651, 775, and 3440 ­cm−1,
respectively, are attributed to the C–N, and N–H stretching vibration in the PPy ­ring53. The above data suggest
that the PPy was successfully incorporated into the CNT-Fe sample, which could implicate improved electro-
chemical/energy performances when used as electrodes for SCs and TENGs, ­respectively50,54.
The microcrystalline and amorphous structure of the CNT-Fe and CNT-Fe + PPy samples were evaluated by
using wide-angle X-ray diffraction (Fig. 3b). The XRD patterns of CNT-Fe shows one broad peak assigned to

SSA AMicro AMeso Pore volume

(m2 ­g−1) (cm2 ­g−1)
CNT-Fe 68 22 46 0.46
CNT-Fe + PPy 12 3.4 8.6 0.092

Table 1.  CNT-Fe and CNT-Fe + PPy surface area properties.

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Figure 3.  (a) FTIR spectra of the PPy, CNT-Fe, and CNT-Fe + PPy electrodes, and (b) XRD patterns of the PPy,
CNT-Fe, and CNT-Fe + PPy electrodes.

the (002) lattices of hexagonal graphite have appeared at 2θ = 25.8°; a low-intensity peak appeared at 43.2°, cor-
responding to diffractions of the graphitic planes (100). A small diffraction line at 2θ of 50.9° may correspond
to ­Fe3O4 (JCPDS No 19-0629) is identified in CNT-Fe55. The PPy sample exhibited a broad diffraction peak
(amorphous nature) of PPy between 10° and 26° characteristic of an amorphous structure of ­polypyrrole56,57. The
XRD patterns CNT-Fe + PPy exhibited a similar amorphous nature of PPy between 10° and 26° characteristic due
to the influence of polypyrrole. These patterns are similar to the literature’s results regarding carbon nanotubes
doped with P ­ Py56,57. These data indicate that green synthesis did not affect the crystallinity of carbon nanotubes,
preserving their structure while the incorporation of PPy changed to a completely amorphous structure.

Electrochemical performance of CNT‑Fe and CNT‑Fe + PPy based supercapacitor

The pure PPy, CNT-Fe, and CNT-Fe + PPy samples were integrated into symmetric supercapacitors utilizing
a KOH electrolyte (1 M) impregnated into a Celgard membrane separator to assess the electrochemical per-
formance at scan rates ranging from 10 to 200 mV ­s−1 (see Fig. 4a–c). The curves displayed distinct behaviors,
thus evidencing the role of the PPy on the electrochemical performance of the SCs. For both CNT-Fe and CNT-
Fe + PPy systems, a quasi-rectangular behavior was more evident in CNT-Fe (in special at a low scan rate) while
the curve for the PPy-based SC appeared as a more cone-shaped, even at a low scan rate. With the increase of
the scan rate values, the curve format acquired a more prolate behavior, with a cone-shaped response at a high
limit (200 ­mVs−1) for both CNT-Fe and CNT-Fe + PPy, SCs. Pure PPy exhibited a completely distorted form of
the CVs with very low areas compared to the CNT-Fe and CNT-Fe + PPy SCs, respectively because of the absence
of EDLC contribution from a carbonaceous derivative. It is worth mentioning that the area enclosed by the CV
curves is related to the specific capacitance of the studied S­ Cs50. A bigger CV curve area indicates better electro-
chemical performance and, therefore, more efficient SCs. In this sense, CNT-Fe + PPy displayed higher areas of
the CV curves under the selected scan rates, suggesting that the incorporation of PPy on previously deposited
CNT + Fe introduced the SCs changes possibly due to the pseudocapacitive behavior of the PPy that led to an
increase in the areal or gravimetric capacitance. The largest CV area was found to be of the CNT-Fe + PPy SCs,
which indicates its best capacitive performance. The comparison of samples at the same scan rate (100 ­mVs−1)
is provided in Fig. S3.
The electrochemical performance of the symmetric SCs was further evaluated by galvanostatic charge–dis-
charge (GCD) curves, at different current densities (see Fig. 5a–c, respectively). The results show that pure PPy
gave rise to very unstable GCD curves with a much shorter time compared to CNT-Fe and PPy + CNT-Fe SCs (see
Fig. 5a–c, respectively). The discharge time of the symmetric SCs supercapacitor assembled by CNT-Fe + PPy was
nearly 150 s and 90 s at 600 µA and 1 mA, respectively, which was much longer than that of CNT-Fe, indicating
its excellent energy storage characteristics due to the PPy l­oading58. Such results agree with the observed CV
profiles: The better electrochemical performance of CNT-Fe + PPy is suggested to be caused by prolonged time
in the GCD curves. This improvement behavior of the PPy was already reported by Dos Reis et al.51 that coated
a biomass-derived activated carbon with PPy. Further, the evident deviation from the ideal straight line in the
GCD curves is due to Faradaic (pseudocapacitive) mechanisms.
The areal capacitances for the three  SCs systems (PPy, CNT-Fe, d CNT-Fe + PPy) were calculated from the
idt
area below the discharge curve (­ CA = AV ) where A is the area of electrodes and ∆V is the voltage window. The
areal capacitance for PPy SCs was extremely low—less than 1 mF ­cm−2—and CNT-Fe delivered an areal capaci-
tance of around 7 mF ­cm−2. However, when CNT-Fe was coated with PPy, the SCs delivered a very high areal
capacitance of 202 mF ­cm−2 and it remained stable for all the current densities (see Fig. 6). This indicates that
the PPy coating on the CNTs surface was vital to improve the electrochemical performance of the CNT-Fe + PPy
electrode. The areal capacitance of various electrode materials for SCs is depicted in Table 2. The areal capaci-
tance of CNT-Fe + PPy is among the highest values, which demonstrates its feasibility as an efficient electrode
for supercapacitor applications.

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Figure 4.  CV curves at different scan rates for SCs composed with PPy, CNT-Fe, and CNT-Fe + PPy samples.

The Nyquist plot’s semi-circle identification is a crucial parameter since it facilitates the understanding of the
key limitation of the interface resistance, which enables a proper SC ­optimization65. Minimizing resistance and
maximizing capacitance is extremely important to fabricate high-performance electrodes for SC ­applications65.
The capacitive features of the SCs’ samples are further evaluated taking into consideration the relative variation
in the linear line slope at a low frequency, while the intersection with the x-axis gives the estimated value for the
internal resistance. Nyquist plots (shown in Fig. 7) were evaluated to provide additional information about the
outstanding performance observed for CNT-Fe+ PPy samples. The curves reveal the relevance and the impact
of the PPy on the electrochemical properties of our CNT-Fe electrode. Nyquist plot of CNT-Fe (curve in red in
Fig. 7a) reaches resistance in the order of 600 Ω at a low frequency while the corresponding system prepared with
the coating of PPy reduces this value to 100 Ω. On the other hand, an extremely high resistance is obtained for
electrodes of PPy, justifying the low performance for PPy-based supercapacitors, in clear evidence that a previous
deposition of a conductive layer is critical to improve the pseudocapacitance of polypyrrole (more homogenous
deposition with minimal formation of aggregates of grains, as shown in SEM images for CNT-Fe + PPy).
To quantitatively evaluate the EIS of the three electrode materials, the overall spectrum was fitted by an
equivalent circuit (inset of Fig. 7a), the Randles circuit, which shows the straight line in the low frequency by the
incorporation of a Warburg component in the circuit, and the depressed semicircle by a constant phase element
(CPE), while resistors Rs reproduces the bulk resistance. The low values for Rs (0.606 Ω, CNT-Fe, and 0.846 Ω,
CNT-Fe + PPy) compared to much higher PPy value (46.23 Ω) confirm that both SCs electrodes preserve low
bulk resistance with added small resistance attributed to the addition of Fe nanoparticles. However, these results
confirm that both CNT-Fe and CNT-Fe + PPy electrodes have favorable kinetics for ion diffusion. The lower Rs
could be caused by the synergistic effect of CNT and iron nanoparticles, which can effectively shorten the electron
transportation pathway and improve electrical conductivity and charge transportation kinetic of the ­electrodes66.
The capacitive behavior of the CNT-Fe, CNT-Fe + PPy, and PPy materials in SCs systems was further evaluated
through their frequency ­analysis67,68 (see Fig. 7c,d, respectively). Figure 7c, (for the real part of the capacitance—
C′) shows the variation of the available stored energy with the frequency. As can be observed, the capacitance of
the three-based SCs is available at long frequency intervals (from lower to higher). The CNT-Fe + PPy presented

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Figure 5.  Galvanostatic charge–discharge (GCD) curves at various current densities for SCs composed with
PPy, CNT-Fe, and CNT-Fe + PPy samples.

Figure 6.  Areal capacitance values for the three SCs systems.

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Electrode material Areal capacitance Electrolyte Current density Reference

Raw Pleurotus eryngii 4.6 F ­cm−2 6 M KOH 10 mA ­cm−2 59

−2 −1 −1 60
Bamboo shells 1.53 F ­cm 1 mol ­L ­H2SO4 1 A ­g
−2 −2 61
Bacterial cellulose 2106 mF ­cm 6 M KOH 10 mA ­cm
Soybean root 3.5 F ­cm−2 EMIM ­BF4 or 6 M KOH 1 A ­g−1 62

−2 −1 63
Wheat bran 2.8 F ­cm 1 M ­Na2SO4 0.5 A ­g
−2 −2 64
Coffee grounds 3.9 F ­cm 6 M KOH 1.2 mA ­cm
PPy 1 mF ­cm−2 KOH 1 mA ­g−1 This work
CNT-Fe 7 mF ­cm−2 KOH 1 mA ­g−1 This work
CNT-Fe + PPy 202 mF ­cm−2 KOH 1 mA ­g−1 This work

Table 2.  The areal capacitances of different electrode materials for supercapacitors.

Figure 7.  (a) Nyquist diagram of CNT-Fe and CNT-Fe + PPy SCs (0.01 Hz–1 MHz), (b) Nyquist diagram PPy
(0.01 Hz–1 MHz), (c) real part of areal capacitance versus frequency, and (d) imaginary part of capacitance
versus frequency.

the highest capacitance among all but only at the narrow frequency interval near ­10–1 Hz, while CNT-Fe exhib-
ited the highest capacitance at the interval of 0.3 to 100 Hz. In addition, the typical behavior for the real part of
capacitance was observed for both experimental systems with an increase from almost zero at higher frequencies
to a maximum value at lower frequencies—characterizing a typical transition from resistive to capacitive behavior
confirmed from the peak in the imaginary part of the capacitance.

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Electrical performance of CNT‑Fe and CNT‑Fe + PPy based triboelectric nanogenerator

Modified eggshell membranes were also applied as electrodes of triboelectric nanogenerators, that explore the
combination of contact electrification (tribopositive and tribonegative layers) and electrostatic induction pro-
cesses that separate positive and negative charges under contact resulting in an electric field under release/
compressing forces. The charge circulation along with the electrode is mutually dependent on the conductivity
of the electrode and the rugosity of the resulting friction layers that are kept in contact with the tribonegative
component. The assembled device schematically shown in Fig. 8 is composed of a moving 3D printed layer of
polylactic acid (PLA) of 4 cm × 4 cm and a layer of Ecoflex™ of 2 cm × 3 cm that is disposed on the electrode
of ESM modified with PPy, Fe + CNT, and CNT-Fe + PPy, respectively. Device operating parameters are 7 Hz
frequency, 4.5 N load, and 3 cm separation distance.
As shown, the proposed mechanism is composed of a cyclic sequence of steps in which the tribopairs are con-
tacted and separated. In the first step, in which the layers are contacted one against the other, charges accumulate
on the opposite sides of electrodes and create a resulting electric field under the release of the pressing force. This
release contributes to the circulation of electrical charges in the direction of the load resistance. At the condition
of the complete release of this force, the current in the load resistance tends to zero and returns in the opposite
direction under pressing, providing the behavior of an alternating current generator with a cycle defined at the
end of the complete compression step of layers. Based on these constitutive aspects, the triboelectric nanogenera-
tors produced at different conditions for surface modification were tested at different frequencies of operation.
Results in Fig. 9a indicate that the response of open circuit voltage increases with the frequency of operation
in response to the energy transfer ratio from tribopairs to the electrode. In addition, higher performance was
observed for samples modified with CNT-Fe + PPy in comparison with PPy and Fe + CNT electrodes. In cor-
respondence, the same behavior was observed in the short-circuit current (see Fig. 9b). The measurement of the
medium of peaks is plotted in Figs. S4a and S4b indicate that higher voltage is observed for devices prepared
with PPy + CNT-Fe with a slight increase in the values for samples modified with Fe + CNT in comparison with
samples modified with PPy. The best performance observed for CNT-Fe + PPy agrees with the best conductiv-
ity observed for the electrodes incorporating CNT-Fe + PPy and the fibrilar structure of the resulting material.
Based on these considerations, the best device was defined as the TENG prepared with the electrode of CNT-
Fe + PPy and operated at 7 Hz. It is worth mentioning that there are two distinct regions regarding the electrical
output performance of TENGs as a function of the excitation frequency. At low-frequency regions (typically for
f < 7 Hz) the typical behavior is of electrical output increase with increasing excitation f­ requency69, in a process
attributed to the activation of additional triboelectric charges that are not completely neutralized during the
contact-separation process at higher frequencies. On the other hand, for all frequencies, the performance (for
both open circuit voltage and short circuit current) follows the order CNT-Fe + PPy > CNT-Fe > PPy which agrees
with the order in electrochemical performance of supercapacitors, characterizing those electrical properties as
the most relevant parameter to define the performance of TENG since lower internal resistance facilitates the
charge transference (for short circuit current) and offers available sites for charge accumulation improving the
open circuit voltage response by the adequate accumulation of charges at interfaces.

Figure 8.  Scheme for device assembly and proposed working mechanism for the charge accumulation and
transference to load resistance under cyclic contact-separation process.

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Figure 9.  (a) Open circuit voltage at frequencies of 3 Hz, 5 Hz, and 7 Hz for samples coated with PPy, CNT-Fe,
and CNT-Fe + PPy, (b) short circuit current at frequencies of 3 Hz, 5 Hz. and 7 Hz for samples coated with PPy,
CNT-Fe, and CNT-Fe + PPy.

(a) 2.2 (b) 7

60
2.0
6
50 1.8

Power density (µW/cm2)

5
40 1.6

Current (µ A)
Voltage (V)

4
1.4
30
1.2 3
20 1.0 2

10 0.8
1
0.6
0 0
0.4
106 107 108 106 107 108
Load resistance (Ω) Load resistance (Ω)

Figure 10.  (a) Dependence of the output current and voltage as a function of the load resistance and (b) power
density of the device as a function of the load resistance (curves acquired at 7 Hz for sample CNT-Fe + PPy).

For this configuration, the output performance of the device was evaluated for different load resistances.
Curves in Fig. 10a for current and voltage indicate the typical crossover due to the inverse variation of func-
tions: while the current decreased with the increasing value of the load resistance the voltage increased reaching
a maximum value in the order of 60 V while a maximum current is observed at 2 µA. The power density of the
device as a function of the load resistance is shown in Fig. 10b, a clear direct relationship is observed between
both loading resistance and power density with a well-defined maximum power output density at 6 μW/cm2
(see Fig. 10b and Table 3).

Electrode materials VOC (V) ISC (µA) P (µW ­cm−2) Ref.

70
Pani@WCT​ 350 45 1130
71
CNT 7 0.18 –
72
PPy 60 8.8 8.3
73
C-coffee ground 150 2.1 6.38
74
Organogel 40 1.2 4
75
Carbon fiber 42.9 0.51 0.6
76
Degradable microbial cellulose 1010 – 870
CNT-Fe + PPy 60 2 6 This work

Table 3.  The performances of different electrode materials for TENGs from the literature and this work.

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(a) 150 (b)

100
Recfier
bridge

o
50

Voltage (V)
do

0 S-TENG o

-50 o

-100

-150
0 2000 4000 6000
(c) Number of cycles (d)
8
1 µF 45 Supercapacitor
4.7 µF
40
10 µF
6 35

Voltage (mV)
30
Voltage (V)

4 25

20

15
2
10

5
0 0
0 20 40 60 80 100 0 30 60 90 120 150 180 210 240 270 300 330
Time (s) Time (s)

Figure 11.  (a) Retention in the value of the generated voltage at successive 6000 cycles operation of the device,
(b) circuit with a rectifier bridge applied in the charge of capacitors, (c) curves of charge of the capacitor of
1, 4.7, and 10 µF, and (d) sample CNT-Fe + PPy-based supercapacitor, disposed of in the output of the TENG
(curves acquired at 7 Hz for sample CNT-Fe + PPy).

Another important factor to be considered for the prolonged use of the device is the retention of the electri-
cal properties under repeated operation. As shown in Fig. 11a, negligible variation in the output voltage was
observed indicating that prolonged operation minimally affects the performance of the device after 6000 cycles
of operation. For the application of TENG as a charging element of conventional capacitors and supercapaci-
tors, the circuit shown in Fig. 11b was implemented to provide a pulsed DC signal to charge the capacitors and
supercapacitors in an integrated combination of TENG/SC.
For comparison in the performance of charging processes, the response of conventional capacitors (1, 4.7, and
10 µF) disposed of in the output of the TENG via a rectifier bridge and the supercapacitor based on the sample
CNT-Fe + PPy were evaluated. Under the operation at 7 Hz, curves in Fig. 11c indicate that higher voltages are
accumulated for capacitors with lower capacitance—due to the dependence of voltage V with the capacitance C
(V = q/C). As observed, the greater the capacitance, the longer the time for reaching higher voltage on terminals.
As expected, the corresponding curve for the supercapacitor integrated with the TENG is shown in Fig. 11d,
in which a variation in the accumulated voltage of 42 mV is observed after 300 s of operation of the TENG,
confirming the potential of integration between TENG and SC with the same substrate (CNT + PPy on ESM).

Conclusions
The synthesis of advanced flexible SCs and TENGs’ electrode materials through a sustainable and greener
approach using eggshell membrane as flexible support material and a plant-based reductant (Punica Granatum)
as a reducing agent to form and deposit iron NPs on carbon nanotube structure acting as a support for electrode
fabrication was successfully conducted. The eggshell membranes were coated with iron-NPs-NT material to
serve as sustainable and flexible electrodes. Further, the coated eggshell membranes with iron-NPs-NTs mate-
rial were subjected to a chemical polymerization with polypyrrole (PPy), which creates a layer over the flexible
electrode that preserves the electrochemical properties of additives (EDLC and PC). The flexible electrodes were
fully characterized in detail to evaluate the role of PPy on the physicochemical and electrochemical properties
of SCs and TENGs. The physicochemical characterization data suggested a very high influence of the PPy on
the CNT-Fe structure. The electrochemical data revealed that the incorporation of PPy owned better electro-
chemical performance due to the combination of quasi-electric double-layer capacitance behavior added to the
pseudocapacitance contribution. The areal capacitance values were 7 and 202 mF/cm2 at 1 mA/g for CNT-Fe and
CNT-Fe + PPy samples, respectively. When tested as electrodes in TENGs, they indicated performances of 60 V
for output voltage and power density of 6 μW/cm2 for the CNT-Fe + PPy sample. The integrated system showed

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that the supercapacitors can be successfully charged directly by the nanogenerator from 0 to 42 mV in 300 s. The
successful green synthesis of iron nanoparticles on CNT and further PPy coating provides a feasible method for
the design and synthesis of high-performance SCs and TENGs electrode materials as integrated components.

Data availability
The data that support the findings of this study are available from the corresponding author upon reasonable
request.

Received: 20 January 2024; Accepted: 2 May 2024

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Acknowledgements
The authors wish to thank Bio4Energy, a strategic research environment appointed by the Swedish government,
as well as the Swedish University of Agricultural Sciences for supporting this work. Financial support from Inter-
reg Aurora (Grant No. 20361711), the Swedish Research Council Formas (Grant No. 2021–00877), and Kempes
Foundation (Grant No. JCSMK23-0145) is gratefully acknowledged. This work is also a part of the activities of
the Johan Gadolin Process Chemistry Centre at Åbo Akademi University in Finland. The authors thank CNPq,
FINEP, and CAPES from Brazil for partially supporting this research.

Author contributions
G.S.R., H.P.O.: conceptualization, methodology, data curation, investigation, formal analysis, writing and edit-
ing original draft preparation; I.C.M.C., A.L.F.: methodology, formal analysis, investigation; P.M., G.L.D, A.G.,
J.P.M.: data curation, review. All authors have read and approved the manuscript.

Funding
Open access funding provided by Swedish University of Agricultural Sciences.

Competing interests
The authors declare no competing interests.

Additional information
Supplementary Information The online version contains supplementary material available at https://​doi.​org/​
10.​1038/​s41598-​024-​61173-5.
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