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Synergistic effect of polydopamine–

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Cite this: Nanoscale Adv., 2019, 1, 2444

polyethylenimine copolymer coating on graphene
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oxide for EVA nanocomposites and high-

performance triboelectric nanogenerators†
Sunanda Roy, * Le Van Hai and Jaehwan Kim *

While the demand for lightweight high-strength nanocomposites is immense, their progress has been
severely limited due to inferior filler dispersion and filler–matrix interface adhesion. This article reports
a novel modification of graphene oxide (GO) encapsulated by the copolymer of polydopamine (PD) and
polyethylenimine (PEI) via a Michael addition reaction, aiming to create robust ethylene vinyl acetate
copolymer (EVA) nanocomposites even at very low amounts of filler loading by overcoming the above
hindrances. It has been found that the addition of only 1.2 wt% modified GO (i.e., PD–PEI–rGO)
increased the tensile strength, Young's modulus and storage modulus of EVA composites by 80%, 50%
and 24%, respectively. These increments surpass many recent claims on relevant composites. Excellent
molecular level dispersion was also observed from the fracture surface SEM images. Being amine-rich
with high electron-donating capability and mechanically robust, the nanocomposite served as an
outstanding tribopositive material, thereby generating 7.49 V and 4.06 mA output voltage and current,
respectively, when employed in a triboelectric nanogenerator (TENG). The high electrical outputs led the
Received 6th March 2019
Accepted 6th May 2019
device to light up 43 blue LEDs instantaneously upon hand pressing, demonstrating that the
nanocomposite is indeed a promising candidate for harvesting green energy. Moreover, the
DOI: 10.1039/c9na00142e
nanogenerator displayed outstanding cyclic performance stability (even after 8000 cycles) and
rsc.li/nanoscale-advances environmental durability.

are still exploring the hidden potentials of this material in order

Introduction to expand the scope of its application, because the improved
Among a variety of polymer nanocomposites, polymer–carbon properties achieved by graphene are still far lower than the
nanomaterial composites, especially carbon nanotubes (CNTs) theoretical predictions. Critical challenges that severely limit
and graphene-based ones, are of the highest priority of current the continuous advancement of graphene for structural appli-
research interests as they deliver high electrical, thermal, cations is its poor compatibility, non-uniform dispersion and
mechanical and barrier properties to the composites at signif- weak interface adhesion with the polymer matrices due to the
icantly low amounts.1–4 While graphene is an atomically thick, lack of adequate surface functionalities.1,8–10 Moreover, the
2-D sheet material composed of sp2 carbon atoms arranged in strong interlayer van der Waals forces cause the graphene
a honeycomb structure, CNTs are zero-dimensional cylindri- nanosheets to form irreversible agglomerates (or restack),
cally rolled sheets of graphene.5,6 Since 2004, the successful making it extremely difficult to handle. Thus, the prevention of
production and isolation of graphene7 have taken the nano- restacking should, therefore, be attained prior to incorporation
technology sector by storm, with exponential growth in its in any system. Moreover, the level of enhancements has been
applications. Graphene is regarded as the “magic bullet” for the found to depend signicantly on the degree of dispersion,
composite world, owing to its remarkably high mechanical, alignment and ller–matrix interface adhesion. Hence, to
electrical, thermal conductivity and gas and chemical barrier overcome the above drawbacks and enhance the chemical
properties. Despite its huge merits and the large amount of affinity towards polymer matrices and to successfully harness
published literature on graphene nanocomposites, scientists maximum reinforcement, the surface modication of graphene
has become imperative.
Therefore, this article aims herein to design a novel surface
Mechanical Engineering, Inha University, South Korea, 100, Inha-Ro, Nam-Ku, modication process for graphene oxide (GO) in order to
Incheon 22212, South Korea. E-mail: corporate00@gmail.com; jaehwan@inha.ac.kr develop mechanically stronger polymer nanocomposites even at
† Electronic supplementary information (ESI) available. See DOI: signicantly low amounts of loading. GO was selected, as it is
10.1039/c9na00142e

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the most widely preferred derivative of graphene material, The working mechanism of this device is based on the contact
containing various oxygenated functional groups (e.g., hydroxyl, electrication effect, where energy conversion occurs via surface
epoxide, carbonyl and carboxylic acid groups)1,8–10 that can be charge transfer resulting from periodic contact between two
used as an anchorage for further surface treatments depending dissimilar tribopolar materials, a triboelectric positive and
on the needs. Here, ethylene vinyl acetate copolymer (EVA) was a triboelectric negative material.15–17 Interestingly, the
chosen as the matrix, since it has widespread applications in nanocomposite-based TENG showed great performance to the
numerous areas including paints, adhesives, coatings, textiles, triboelectric response, with an output voltage and current 4 and
cables, automotive plastic fuel tanks, etc.11–14 The GO was 4.2 times higher, respectively, than that of the pristine EVA
modied with polyethylenimine (PEI) through the assistance of device. Moreover, the EVA nanocomposite TENG showed highly
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polydopamine (PD) coating via the Michael addition reaction, stable performance against severe constant cyclic load and
as demonstrated in Fig. 1. The surface chemistry and structural when exposed to ambient conditions for several weeks. Finally,
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properties of the modied GO (PD–PEI–rGO) were studied the novelty of this research lies in the concept of the modi-
comprehensively. The performance of the composites was cation of GO, whereby the large reinforcement, excellent
evaluated in terms of tensile strength and dynamic mechanical molecular-level dispersion and high triboelectric performance
properties. Super reinforcement was achieved by the addition of of the composite can be achieved concurrently at low ller
only 1.2 wt% PD–PEI–rGO, and the values were found to be loading.
much higher than most previously reported EVA
nanocomposites.
Besides the structural importance, we explored a new Results and discussion
potential application of this composite material as a sustainable Fig. 1 illustrates the plausible chemical reactions, which
energy harvesting device, called a triboelectric nanogenerator occurred during the synthesis of PD–PEI-modied GO. As can
(TENG). Recently, energy harvesting and conversion devices be seen, dopamine can be auto-oxidized to polydopamine (PD)
using lightweight materials have become an emerging trend in via several dehydrogenation steps, forming o-quinone units that
current science and technology, as they play an important role can instantly cyclize to indole moieties and/or form C–C bonds.
in building and driving self-powered nanodevices. To the best of The Michael reaction takes place at the o-quinone moieties
our knowledge, this is the rst article that introduced EVA/GO either at the carbonyl carbon atom or at the b-position of the
nanocomposites as a potential futuristic material for tribo- inherent Michael system in an alkaline medium.18 This leads to
electric energy harvesting application. Though graphene–poly- the self-polymerization of dopamine and the simultaneous
mer nanocomposites are a new attempt in TENG, Harnchana copolymerization with PEI. At the same time, the oxygenated
et al. recently reported the achievement of very high electrical groups on GO can form strong covalent and hydrogen bonds
output using a GO/PDMS porous-type nanocomposite.14 TENG with the PD–PEI layer, making it very suitable in dispersing
is a new type of clean and sustainable energy harvesting device various solvents and polymer matrices when added.
capable of harvesting energy from various mechanical vibra- FTIR analysis was performed rst to verify the chemical
tions (ocean waves, tides, raindrops and human motion).14–17 changes in GO as a result of the modication process. Fig. 2a

Fig. 1 Schematic illustrations of the preparation of PD–PEI–rGO.

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Fig. 2 (a) FTIR, (b) XPS survey spectra and (c) Raman spectra of GO and PD–PEI–rGO; (d) TGA profiles of PEI, GO and PD–PEI–rGO.

shows the FTIR spectrum of pristine GO and PD–PEI–rGO. As and PEI onto the GO surface. While the pristine GO sample had
can be seen in the FTIR spectrum for pristine GO, owing to C and O contents of 69.8 and 30.2%, respectively, the PEI–rGO
various oxygenated functional groups, several important char- sample showed 80.5% C, 14% O and 5.5% N contents. However,
acteristic peaks appeared. A broad peak for –OH stretching was for curiosity when we checked the XPS spectra for the PD–rGO
observed in the range of 3200–3640 cm
1. Other characteristic sample, only 3.7% N content was found (less than for the PD–
peaks for the C]O and C]C bonds, C–OH stretching vibra- PEI–rGO sample, results are not shown).
tions, epoxy (1224 cm
1) and C–O vibrations from alkoxy groups Next, Raman spectra were measured to understand the
were seen at 1725, 1624, 1351, 1224 and 1039 cm
1, respec- crystal structure, disorder and defects in the above GO speci-
tively.1,10 Aer modication with the mixture of PD–PEI, some mens. As can be seen from Fig. 2c, both materials have D and G
noticeable spectral changes appeared in the measurement. The peaks at 1350 and 1581 cm
1, corresponding to the rst-order
new absorption peaks at 2930 and 2831 cm
1 corresponded to scattering of the E2g phonon of sp2 C atoms and structural
the nonsymmetric and symmetric stretching vibrations of defects induced by the surface functional groups, respectively. It
methylene, respectively, while the new peaks at 1649 and is well-known that the height of the D band implies the size of
1569 cm
1 represent the stretching vibrations of NHC]O, the inplane sp2 domains.1,3,8 Therefore, the increase of the D
1453 cm
1 for the aromatic C]C bond, and 1220 cm
1 for the peak intensity indicates the formation of more defects in sp2
C–N bands.2,19 It is important to note here that the amine domains in the structure. As can be seen in Fig. 2c, the ID/IG
groups in PEI (owing to highly branched structure) will also ratio of PD–PEI–rGO is higher (1.12) than that of pristine GO
react with the carboxyl and epoxy groups of GO at the same (0.84), indicating that surface modication had led to an
time, resulting in the appearance of amide and C–N bonds in increase in the number of disorders or defects in the graphene
the respective spectrum. The peak at 3320 cm
1 can be ascribed sheets.
to the N–H group of PEI. To further ascertain the attachment of In order to understand the effect of modication on the
PEI onto GO and to learn about the surface chemical compo- thermal behavior of the GO, TGA analysis of pristine GO and
sitions, XPS analysis was carried out. Fig. 2b shows the survey PD–PEI–rGO was conducted, and the corresponding results
scan spectra of pristine GO and PD–PEI–rGO. As can be seen, were compared in Fig. 2d. It is apparent that pristine GO has
the survey spectra of GO is composed of two peaks, C 1s poor thermal stability and decomposes at below 200  C,
(binding energy ¼ 285 eV) and O 1s (binding energy ¼ 531 eV), presumably due to the loss of oxygen-containing functional
while PEI–rGO displayed an emerging new N 1s peak at groups that attach to the graphene sheets (epoxide, hydroxyl,
a binding energy of 401 eV along with the C 1s and O 1s peaks.20 and carboxyl groups).1 Following that, the decomposition,
This result clearly endorsed the successful attachment of PDA which brought about 20–22% more mass loss, was due to the

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thermal decomposition of the carbon skeleton. On the other Young's modulus (E) was obtained aer the addition of PD–PEI–
hand, the modied GO showed much higher thermal stability, rGO into EVA, and the values increased with increasing PD–PEI–
with only 5% weight loss at 240  C and 28% total loss at 800  C. rGO content. It was interesting to see that the addition of the
The losses at above 240  C can be attributed to the degradation same amount of modied GO (0.4 wt%) led to an increase in the
of the polydopamine and PEI molecules. The TGA results also T.S of the nanocomposite by 4.4-fold that of the pristine GO/EVA
revealed that there is 15–16 wt% of PD–PEI in the modied nanocomposite.
graphene oxide (PD–PEI–rGO). The higher thermal stability While the T.S and E for pure EVA were 6.02 and 0.62 MPA
clearly indicates that there are strong interactions between the aer the addition of only 1.2 wt% PEI–rGO, the values increased
GO and PD–PEI moieties, also endorsing the above FTIR spec- to 10.83 and 0.93 MPa, respectively, corresponding to an
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trum that showed the formation of amide bonds between GO increase of 80% and 50%, respectively, compared to that of the
and PD–PEI due to the modication. The presence of such large neat EVA. The above results clearly indicate that PD–PEI func-
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amounts of PD–PEI in GO also suggests that this can be a good tionalization had effectively improved the affinity of GO for the
ller for polymer nanocomposites. polymer matrix. Such a large increment in the overall
Fig. 3 shows typical FESEM surface morphologies of pristine mechanical properties of the EVA nanocomposites can be
GO and PD–PEI–rGO surfaces. It is apparent that before modi- attributed to the effects of: (i) strong interfacial adhesion
cation, the surface of the pristine GO sheets had clean and between the matrix and the modied graphene nanosheets
smooth surfaces and that the graphene sheets were nicely (owing to strong hydrogen bonding between the carbonyl of
interlinked through very thin and delicate three-dimensional EVA and the amine of the PEI), (ii) effective load transfer from
networks, resulting in a porous, loose sponge-like structure. the polymer matrix to the graphene nanosheets, and (iii)
However, aer modication (for PD–PEI–rGO) lots of wrinkles homogeneous dispersion of the graphene nanosheets
and corrugation appeared on the surfaces. Also, some level of throughout the polymer matrix. The higher mechanical
stacking in the graphene sheets were observed. The formation strength can also be explained by the greater mechanical
of rough and wrinkled structure clearly evidenced the covalent interlocking between the EVA polymer chains and modied
attachment of PD–PEI molecules onto the GO surfaces. The graphene oxide nanosheets, which possess higher surface
formation of stacking in the graphene sheets can be assumed to roughness. Interestingly, these values were found to be much
be due to the effects of p–p stacking interactions between the higher than that of many earlier reports on EVA nano-
PDA–graphene sheets and interlayer hydrogen bonds between composites (see Fig. 4b).11,21,22
the PD–PEI layers that are covalently graed onto the graphene Fig. 4c shows the storage modulus versus temperature curves
surfaces. of various nanocomposites. It can be seen that the storage
To explore the potential of PD–PEI–rGO as a ller material in modulus of neat EVA within the set temperature range (
70 to
the area of polymer composites, they were blended with 40  C) is considerably lower than that of the nanocomposites.
ethylene vinyl acetate copolymer (EVA) matrix to create the Aer the incorporation of GO, regardless of the type (unmodi-
nanocomposites. The composites were fabricated by solution ed or modied), the storage modulus of the nanocomposites
casting followed by a melt-blending process. The tensile and increased signicantly. While the storage modulus of neat EVA
DMA test results of the composites will be discussed next, as was found to be 1981 MPa, nanocomposites containing 0.4 wt%
they indicate the capability of the material for structural pristine GO displayed a storage modulus value of 2160 MPa,
performance. Low amounts of PD–PEI–rGO (i.e., 0.4, 0.8 and which was 9% higher than that of the neat EVA. Interestingly,
1.2 wt%) were added into the EVA matrix to fabricate various when the same amount of modied graphene oxide was added
nanocomposites. Fig. 4a shows the stress–strain results of (i.e., 0.4 wt% of PD–PEI–rGO into EVA), the storage modulus
various EVA nanocomposites as a function of ller content. It reached to up to 2320 MPa (17% higher), nearly double that of
was observed that the addition of pristine GO into the EVA the pristine GO-containing nanocomposite. The gradual addi-
matrix (0.4 wt%) led to an increase in the tensile strength (T.S) tion of PD–PEI–rGO (i.e., 0.8 and 1.2 wt%) further increased the
of the composite by only 8.63% due to the inherent reinforcing storage modulus to 2377 and 2457 MPa, which was 20% and
ability of GO. However, dramatic enhancement in the T.S and 24% higher than the storage modulus of the neat EVA, respec-
tively. Such large increments in the mechanical strengths of the
EVA nanocomposites with the use of such a small amount of
graphene oxide (1.2 wt%) clearly suggest the great potential of
our functionalization process and that of modied GO. The
tan d maximum value, which corresponds to the Tg of the
polymer, was also noted to increase with the addition of PD–
PEI–rGO (see Table 1). The maximum increment was found to
be 6.2  C in the case of the EVA/1.2 wt% PD–PEI–rGO nano-
composite (from
30.3  C for neat EVA to
24.1  C). The
increase in Tg for the nanocomposites clearly indicates that the
free motion of EVA chains in the matrix was inhibited by the GO
Fig. 3 FESEM images of (a) pristine GO and (b) PD–PEI–rGO. Images nanosheets due to strong ller/matrix interfacial interactions.
were taken under 5000 magnification at 1 mm scale bar. However, this was more profound in the case of EVA/PD–PEI–

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Fig. 4 (a and b) Stress–strain curves and (c) storage modulus of various EVA nanocomposites.

rGO nanocomposites due to greater amounts of hydrogen the surface roughness appeared to increase with the increase in
bonding between the amine of PD–PEI–rGO and the carbonyl of PD–PEI–rGO loadings. Compared to the pristine GO/EVA
EVA as a result of the homogeneous dispersion of GO nano- nanocomposite, the higher surface roughness for PD–PEI–
sheets within the PVA matrix (see the inset of Fig. 4c). rGO-based nanocomposites signies the higher energy
Based on the above mechanical test data, it is necessary to absorption during the tensile fracturing of the specimens due to
examine the dispersion behavior of the PD–PEI–rGO nano- the tighter embedment of the PD–PEI–rGO nanosheets into the
sheets in the matrix; therefore, the cross-sectional surface EVA matrix owing to strong ller–matrix interface adhesion.
morphology of the composites was investigated and presented Moreover, the roughness appeared all over the surfaces of the
in Fig. 5. The cross-sectional fracture surface of the neat EVA is PD–PEI–rGO/EVA nanocomposites, indicating that PD–PEI–rGO
shown in Fig. 5(i). It is apparent that neat EVA had a clean were homogeneously dispersed into the matrix. Based on the
surface with typical fracture patterns on the surfaces. In above results, it can be concluded that PD–PEI–rGO is indeed
contrast, the surfaces of the nanocomposites showed noticeable a potential ller in the development of strong EVA polymer
roughness. Fig. 5(ii–iv) shows the surface morphologies for nanocomposites.
EVA/0.4 wt% GO, EVA/0.8 wt% PD–PEI–rGO EVA/0.4 wt% PD– To understand the multifunctional role of the EVA nano-
PEI–rGO and EVA/1.2 wt% PD–PEI–rGO nanocomposites, composite, especially for energy harvesting application, tribo-
respectively. It has been observed that the surfaces of modied electric measurements were recorded. The construction of
PD–PEI–rGO-based nanocomposites possess much higher TENG is shown in Fig. 6a. Details of the fabrication process are
roughness than the pristine GO/EVA nanocomposite. Moreover, discussed in the experimental section. Fig. 6d illustrates the

Table 1 Tensile and dynamic mechanical results of EVA nanocomposites

Increment Increment Storage modulus Increment

Sample Tensile strength (MPa) (%) Young's modulus (E, MPa) (%) (MPa) (%) tan delta/Tg ( C)

EVA 6.02 (1.1) — 0.62 (16.8) — 1981 —
30.3

EVA/0.4 wt% GO 6.54 (1.3) 8.63 0.67 (17.1) 8.0 2160 9.0
29.7
EVA/0.4 wt% PD–PEI–rGO 8.31 (1.4) 38.0 0.81 (17.6) 30.6 2320 17.1
28.4
EVA/0.8 wt% PD–PEI–rGO 9.60 (1.3) 59.4 0.87 (18.7) 40.3 2377 20.0
27.3
EVA/1.2 wt% PD–PEI–rGO 10.83 (1.4) 80 0.93 (18.3) 50.0 2457 24.0
24.1

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Fig. 5 FESEM images of the tensile fractured surface of (i) raw EVA, (ii) EVA/0.4 wt% GO (iii) EVA/0.8 wt% GO and (iv) EVA/1.2 wt% GO
nanocomposites.

power generation mechanisms via TENG. Initially, there was no Fig. 6c and d compare the open-circuit voltage (Voc) and the
charge generation with no electric potential difference between short-circuit current (Isc) between the pristine GO/EVA nano-
the two electrodes of TENGs. When the external compressive composite and the PD–PEI–rGO/EVA nanocomposite-based
force was applied to the device, the two insulating polymeric TENGs, respectively. While the peak output voltage and
materials came in contact, and as a result, surface charge current for pristine GO/EVA nanocomposites were about 1.89 V
transfer took place at the interfaces due to the triboelectric and 0.97 mA, respectively, the PD–PEI–rGO/EVA composite
effect. According to the triboelectric series, a PVDF lm has TENG showed electrical outputs of about 7.49 V and 4.06 mA.
strong negative triboelectric polarity. Due to the amine-rich These values were 4 and 4.2 times higher than those of the
surface, the EVA nanocomposite surface was believed to output voltage (1.89 V) and current (0.97 mA) of pristine EVA,
possess tribopositive polarity. Hence, negative and positive respectively. The higher electrical output for the PD–PEI–rGO/
charges were generated on the PVDF and EVA nanocomposites EVA nanocomposite TENG can be attributed to the higher
surfaces, respectively. As both the materials (PVDF and EVA surface polarity and electron-donating ability owing to the
nanocomposite) are insulating in nature, the generated charges presence of the amine (from PEI) and OH groups (from DA)
at each surface would, therefore, remain there (or not be quickly when rubbed with a uoropolymer. Moreover, the embedded
neutralized), leading to no electric potential difference between GO nanoplatelets in the composite can act as charge trapping
the two electrodes. As soon as the compression force is released, sites, thereby promoting the relative dielectric property of the
a strong potential difference between the top and bottom elec- lm, leading to an increase in the triboelectric output perfor-
trodes was created due to the electrostatic induction effect or mance of the composite.14 To verify the feasibility of the above
strong dipolar difference. As a consequence, the electrons nanogenerator for practical uses, we connected 43 blue LEDs
began to ow from the negative to the positive potential directly (in parallel) to the output of the nanogenerator without
through the external circuit, resulting in the experimentally any circuit. Fig. 6e shows the digital photograph of 43 lightened
observed positive electric output signal (or say half of the blue LEDs taken aer the nanogenerator was activated. The
triboelectric charge cycle) on the screen. The electron transfer LEDs were lightened by hand pressing the TENG (see Fig. 6f) in
occurs until an electrostatic equilibrium is established. Upon order to see its ability for various modern portable and wireless
further pressing the TENG, the electrostatic equilibrium was electronics. A video of the lighting of LEDs was also presented in
disrupted, and the backow of electrons took place from the Video S1 (ESI†) for a better idea.
bottom electrode to the top electrode until a new equilibrium Next, the cyclic performance stability and time-dependent
was reached. This resulted in the generation of the opposite durability of the above TENG was tested, as it determines the
current, thereby causing reversed electrical signals to be quality and shelf-life of the device. From Fig. 7(a), it is apparent
observed. This is considered as the second half of the tribo- that the device can produce absolutely stable voltage even aer
electric charge cycle. a continuous 8000-cyclic load. The device was also capable of

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Fig. 6 (a) Schematic diagram of the EVA nanocomposite TENG. The right-hand side image shows the real device. (b) Schematic illustration of the
operating principle of the TENG device. Output (c) voltage and (d) current of said device. (e) Illumination of 43 blue LEDs. (f) The changes in
output voltage versus time for monitoring motions by hand pressing.

reproducing the same voltage signals when tested aer 21 days it could be concluded that the EVA nanocomposite is indeed
under similar mechanical force. These results clearly indicated a new multifunctional nanocomposite material with great
that the PD–PEI–rGO/EVA nanocomposite is literally very strong structural potential as well as able to harvest clean energy by
and robust. Thus, no loss or deterioration in the signal was means of the triboelectric nanogenerator. We believe that this
observed when subjected to severe continuous compression composite can readily be used for many potential applications
load. The higher Young's modulus (also indicates the rigidity) of including street tiles, night club dance oors, oor mats and
the nanocomposite was believed to be the key factor for the other sensing purposes where electricity can be harvested from
above performance stability. On the basis of the above ndings, mechanical energy, i.e., dancing or jumping.

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Fig. 7 (a) Cyclic durability performance of the EVA nanocomposite TENG tested for 8000 cycles at a frequency of 20 Hz. (b) Stability test of the
same device tested after immediate fabrication and 3 weeks. The device was stored under ambient conditions for 3 weeks.

achievements, it can be concluded that our functionalization

Conclusions
strategy was indeed a versatile platform for GO modication
We reported a novel and effective approach for GO modication and can hopefully attract great attention from various sectors to
to produce mechanically strong EVA nanocomposites with develop other lightweight and strong composites for wider
multifunctional capability. The surface modication was applications.
carried out by a unique mussel-inspired polydopamine-assisted
Michael addition reaction. This approach showed greater
promise in terms of molecular level dispersion and the interface
Experimental
adhesion of graphene nanosheets within the EVA matrix owing Materials
to strong hydrogen bonding interactions. As a result, the ach- Flaky graphite powders (300 mesh) were purchased from Hua-
ieved polymer nanocomposites showed radical improvements dong Graphite Factory (Pingdu, China). Dopamine, Trizma base
in the tensile strength (80%) and storage modulus (24%) even at and polyethylenimine (PEI, branched) with an average molec-
only 1.2 wt% of graphene content, clearly demonstrated the ular weight of 25 000 were purchased from Sigma Aldrich,
robustness of the functionalization process. Besides the high South Korea. Ethylene vinyl acetate copolymer (EVA, Levapren
reinforcing capability, the addition of modied GO (PD–PEI– 450, Lanxess) was obtained from India. Polyvinylidene uoride
rGO) turned the nanocomposite into an excellent triboelectric (PVDF) lm was purchased from Starlab Scientic Co., Ltd,
material owing to the amine-rich surfaces. As a result, the Korea.
composite triboelectric nanogenerator showed outstanding
electrical responses with an output voltage of 7.49 V and current
Preparation of PEI functionalized GO (PDA–PEI–rGO)
4.06 mA, thereby lighting up the 43 blue LEDs instantaneously.
Such a high output voltage also implied that our device would Firstly, GO was synthesized by a modied Hummers method
be very effective for large-scale industrial applications. This also from graphite akes following our earlier report.1 The as-
suggests that the performance of the device can be amplied synthesized GO was then thoroughly dispersed in 10 mM Tris
further by increasing the graphene content as well as the degree (pH 8.5) buffer solution using a probe sonicator at 20 Hz
of amine functionalization. Considering the above fascinating frequency for 30 min. Next, an equal amount of dopamine (DA)
and PEI (1 : 1) was added into the GO solution, and the mixture

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Nanoscale Advances Paper

was magnetically stirred for 6 h at 50  C. Aer that, the mixture by X-ray photoelectron spectroscopy (XPS) on a K-Alpha Thermo
was ltered by vacuum ltration and washed with large Scientic spectrometer with monochromatic Al Ka X-ray radia-
amounts of water and methanol repeatedly in order to remove tion. All XPS spectra were corrected according to the C 1s line at
any unattached DA and PEI. Then, the product was freeze-dried 284.8 eV. The Raman spectra of GO and PD–PEI–rGO were
overnight and labelled as PD–PEI–rGO. The ‘r’ represents the measured by an Alpha 300R WiTec confocal Raman microscope.
partial reduction of graphene oxide. The thermal stability of all specimens was tested using a TA
Instruments TGA 2950 from 30 to 800  C at a heating rate of
Preparation of PD–PEI–rGO/EVA nanocomposites 10  C min
1 under nitrogen gas medium. The tensile tests of
the EVA nanocomposites were performed at room temperature
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

Various PDA–PEI–rGO/EVA nanocomposites were prepared by

solution casting followed by the melt blending process. Briey, with a crosshead speed of 50 mm min
1. The storage modulus
of the composites was measured by a dynamic mechanical
Open Access Article. Published on 21 May 2019. Downloaded on 11/10/2024 8:03:08 AM.

PD–PEI–rGO of 100, 200 and 300 mg were dispersed separately

in 25 ml of toluene by ultrasonication at room temperature for analysis instrument (DMA Q800 TA) in the tension mode at
1 h. Concurrently, EVA (25 g in 100 ml) was dissolved in toluene a heating rate of 5  C min
1. The surface morphology of the
separately. Next, the above PD–PEI–rGO dispersions were added tensile-fractured samples was observed by eld emission scan-
separately into the EVA solution and mixed thoroughly with ning electron microscopy (FESEM, JEOL 6400F) aer coating
constant stirring at 100  C for 8 h and then cast on a glass Petri with platinum. Triboelectric performance of the TENGs was
dish. Aer complete drying in air followed by vacuum, the above measured as follows: the device was xed onto a metal zig, and
three different nanocomposite lms (containing 0.4, 0.8 and a 20 Hz square wave input was applied to the device from
1.2% PD–PEI–rGO) were cut into small pieces and melt blended a shaker (the Modal Shop K2004E01), which was controlled by
in a Haake mixture (MiniLab) at 145  C to obtain the desired a function generator (Keysight 33220A). The bottom electrode
composites. Dicumyl peroxide (DCP, 1 wt%) was used as was pressed up by a shaker with 14 N force, while the top
a curing agent during the blending process. The extruded strips electrode was xed onto a lab bench. The input force was
were then made into sheets (1–1.2 mm) by compression measured by a force transducer (Brüel & Kjær 8230-001). The
molding in a hot press at a temperature of 150  C with a holding output voltage and current data were collected using a pulse
pressure of 10 MPa for 5 min. For comparative study, a GO/ analyzer (Brüel & Kjær 3560-B-030) and PC.
EVA nanocomposite was also fabricated under identical
conditions. Conflicts of interest
Fabrication of the EVA nanocomposite-based TENG We have no conict of interest.
All TENGs used in this study were vertical contact types. There
were two active materials, i.e., EVA nanocomposite and PVDF Acknowledgements
lms, used to fabricate the device. The process of fabrication is
as follows: a 1.7 cm  1.7 cm  1 mm piece of PD–PEI–rGO/ This work was partially supported by the National Research
EVA nanocomposite lm was prepared. Then, the lm was Foundation of Korea (NRF-2015R1A3A2066301).
attached to the center of a strip of copper tape, which acted as
the top electrode. The Cu tape was further attached to a PET
lm in order to protect the electrode from damage and as a hard References
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