Materials Chemistry and Physics 316 (2024) 129049

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Influence of ZnO/MWCNTs based hybrid electrodes for boosting the

performance of photovoltaic and supercapacitor devices
Nandhakumar Eswaramoorthy a, *, Sathish Rajendran b, B. Arjun Kumar c,
Senthilkumar Nallusamy a, Marimuthu Rengasamy d, Yogapriya Selvaraj e,
Sambasivam Sangaraju c, Thiyagarajan Krishnan f, G. Kumaresan g, Kamatchi Rajaram d, **
a
Centre for Computational Modeling, Chennai Institute of Technology, Chennai, 600069, Tamil Nadu, India
b
Department of Chemistry, School of Advanced and Sciences, Vellore Institute of Technology, Vellore, 632 014, Tamil Nadu, India
c
National Water and Energy Center, United Arab Emirates University, Al Ain, 15551, United Arab Emirates
d
School of Mechanical Engineering, Vellore Institute of Technology, Vellore, 632 014, Tamil Nadu, India
e
Department of Chemistry, Vinayaka Mission’s Kirupananda Variyar Arts & Science College, Vinayaka Mission’s Research Foundation Deemed to be University, Salem-
636308, Tamil Nadu, India
f
School of Electrical Engineering, Vellore Institute of Technology, Vellore, 632 014, India
g
Department of Mechanical Engineering. Bannari Amman Institute of Technology, Erode, 638401, Tamil Nadu, India

H I G H L I G H T S

• 1, 3 and 5 wt.% MWCNTs mixed ZnO are prepared by sonication approach.

• Optical and charge transfer behavior of MWCNTs mixed ZnO is better than pure ZnO.
• The efficiency of DSSC is 4.37% when ZnO/3 wt.% MWCNTs used.
• ZnO/3 wt.% MWCNTs electrode exhibits 115.72 F g− 1 specific capacitance value.

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, multi-wall carbon nanotubes (MWCNTs with 1, 3 and 5 wt.%) are mixed with zinc oxide (ZnO) to
Nanocomposites prepare nanocomposites for energy conversion and storage applications. Further, UV–Vis spectra of synthesized
Light harvesting pure ZnO and ZnO/MWCNTs nanocomposite material shows enhanced light absorption in the visible region.
Photovoltaic
Hexagonal wurtzite crystal structure of the nanocomposites is confirmed by X-ray diffraction (XRD) spectra. Field
Supercapacitor
Charge transfer
emission scanning electron microscopy (FE-SEM) and High resolution-transmission electron microscopy (HR-
TEM) images explores the formation of nanocomposite with flake like ZnO and tube structured MWCNTs at
nanoscale region. Dye sensitized solar cells (DSSC) are constructed with pure and nanocomposite material as
photoanode and the effect of addition of MWCNTs on the performance of solar cells are studied. Further, the
cyclic voltammetry (CV), galvanic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS)
are employed to examine the electrochemical characteristics of the prepared electrode in a 1 M Na2SO4 elec­
trolyte. In three electrode configuration, the CV and GDC curves exhibits good reversibility and attains a specific
capacitance value of 115.7 F g− 1 with the addition of MWCNTs onto the ZnO. Also, the asymmetric super­
capacitor device exhibits the improved storage performance. The EIS spectra shows lowest Rs and Rct resistance,
indicating the prepared electrode is favorable for DSSC and supercapacitor application.

* Corresponding author.
** Corresponding author.
E-mail addresses: [email protected] (N. Eswaramoorthy), [email protected] (K. Rajaram).

https://doi.org/10.1016/j.matchemphys.2024.129049
Received 7 November 2023; Received in revised form 24 January 2024; Accepted 11 February 2024
Available online 13 February 2024
0254-0584/© 2024 Elsevier B.V. All rights reserved.
N. Eswaramoorthy et al. Materials Chemistry and Physics 316 (2024) 129049

1. Introduction nanocomposites improves the PCE of ~6.14% under 1 sun illumination.

The presence of rGO material decreases the interfacial resistance and
Low carbon sustainable energy technology is the major focus of improves electron transport properties of photoanode [26].
world due to energy crisis and increased pollution from fossil fuel. Supercapacitor is the one which could store the electrical energy
Recently, researchers are working on smart materials with hybrid ar­ with excellent charge/discharge rates, high energy density and good life
chitecture to harvest energy and storage in very compact device [1]. cycle performance [27,28]. The electrodes such as metal-organic
Particularly, research on solar cells integrated with supercapacitor ar­ frameworks, covalent organic frameworks, oxy-hydroxide, rare earth
chitecture called photocapacitor grows exponentially in the short span hydroxide, chlorocuprates and metal oxides are used in the construction
of time. Dye sensitizer solar cells (DSSC)-family of third generation solar of supercapacitor [ [29–33]]. As compared with all other materials,
cell technology is a promising candidate for the generation of green metal oxides are widely used due to low cost, mass production for energy
energy due to environmental friendliness and ease of construction. storage applications. The widely used metal oxides are titanium oxide
Hence, the research on DSSC with high light harvesting photoanode (TiO2), cobalt oxide (Co3O4), manganese oxide (MnO2) and nickel oxide
materials is on the rise [2,3]. (NiO) electrodes. In recent years, hexagonal structured ZnO nano­
In the last decade, n-type semiconductors materials (metal oxides- material is fascinated greater attention in supercapacitor application
titanium di-oxide (TiO2), niobium oxide (Nb2O5), iron oxide (Fe2O3), due to better non-toxic properties, intrinsic richness, and reasonable cost
cerium oxide (CeO2) and tin oxide (SnO2). Sulfides-zinc sulfide (ZnS), tin [34,35]. ZnO-based materials will provide higher electron-conductivity
sulfide (SnS2)) and 2D materials (MXene, black phosphorus)) used as and outstanding mechanical support. Besides, ZnO material has better
photoanodes in dye sensitizer photovoltaics. The photoanode plays a electrochemical performances and superior stability. However, the
major role in electron extraction from dye into conductive surface [ charge transfer kinetics between the electrodes are poor. Therefore, to
[4–9]]. Mostly, brookite (orthorhombic), anatase and rutile (tetragonal) reduce this issue, the carbonous materials such as graphene, graphite
in crystal structures of titanium di-oxide (TiO2) photoanode is majorly and black carbon materials are added with ZnO material [36,37].
utilized in DSSCs [10]. However, TiO2 photoanode material has less Moreover, CNTs material provide good mechanical strength, high sta­
light absorbance behaviour and requires a high temperature of ~500 ◦ C bility, superior ionic and electric conductivities. Carbon nanotube ma­
for photoanode deposition. At this deposition temperature, the terials loaded metal oxide nanocomposite received more attention
conductive substrates like FTO and ITO surface suffers from poor con­ because of their improved power densities and superior specific capac­
ductivity, low UV stability and surface defects [ [11,12]]. Alternatively, itances [38]. Recently, Yousefipour et al. investigated MWCNT/NiMoO4
ZnO material is used due to high excitons binding energy, high mobility, composite via ball milling method and achieved 727.2 F g− 1 in specific
wide band gap (E.g. ~3.28 eV) and high light absorbance behaviour capacitance and 86.8% in cyclic stability after 2000 cycle [39]. The
[13]. Different structures of ZnO such as (i) one dimensional (1D) (ii) addition of MWCNTs with ZnO nanostructure enhances charge transport
two dimensional (2D) and (iii) three dimensional (3D) materials are capabilities. Recently, Gayathri et al. investigated the different elec­
introduced in photoanodes. trodes such as CuCo2S4, CuCo2S4/MWCNT and GQD/CuCo2S4/MWCNT
Recently, Hezam et al. achieved the maximum PCE of 0.71% and nanocomposites material for dual energy applications. The maximum
1.29% by introducing nanosheet/nanowire structured ZnO photoanode. effective specific capacity of GQD/CuCo2S4/MWCNT is 402 C g− 1 and
The ZnO morphologies are tuned by varying concentration of sodium the PCE of DSSC is 4.15% respectively [40]. Gayathri et al. investigated
hydroxide material by 0.1–1.5 M. These modifications are enhanced the the NiS@SnS@Ni3Sn2S2 mixed phase nanostructure prepared by mi­
light absorbance and transportation properties of DSSCs [14]. In addi­ crowave method. In addition, MWCNT added NiS@SnS@Ni3Sn2S2
tion, Nandi et al. compared the different ZnO nanostructures like electrode has achieved PCE of 6.0%, specific capacitance of 766 F g− 1,
nanoflower, nanorods and nanoparticles and showed a PCE of 4.42%, cyclic stability of 94%. When 10 mA cm− 2 is applied on catalyst, it
1.87% and 3.71% respectively. Also, the ZnO nanoflower structure produces hydrogen evaluation reaction of 290 mV and oxygen evalua­
attained more light absorbance as compared with other ZnO nano­ tion reaction of 274 mV under 1.0 M KOH solution [41]. Moreover,
structures [15]. From the reported literature, it is observed that the Kumar et al. hydrothermally prepared three different type bismuth
photoanode morphologies majorly influences the DSSC performance ferrite (BiFeO3), mullite (Bi2Fe4O9) and sillenite (Bi25FeO40) material
and electron charge transfer. Although ZnO surface has the hydroxyl comparatively studied for DSSC and supercapacitor applications.
compounds, it rapidly degrades the sensitizer molecules and reduces the Particularly, sillenite material electrode achieved with a high power
performance of DSSC [16,17]. To overcome this issue, recent re­ density of 3240 W kg− 1, PCE of 0.33% and Voc of 4 mA cm− 2 respectively
searchers are focused on the ZnO surface modification with plasmonic [42].
nanoparticles, metal organic frame work, polymer and carbonaceous From the reported literature, a very limited research work is reported
materials. on ZnO/MWCNTs nanocomposite electrode for dual energy conversion
In general, one-dimensional carbon nanotubes (CNTs) materials en­ and storage applications. In this study, an ultrasonication assisted
hances the interfacial electrical conductivity and electron transfer be­ technique is adopted for the preparation of ZnO/MWCNTs nano­
tween the photoanode/absorber interfaces. Hence, CNTs is used in the composite. Here, the different weight percentage (1, 3 and 5 wt.%) of
fabrication of DSSC [18]. The CNTs material has high electrical con­ MWCNTs are mixed with flake like-ZnO material. The prepared nano­
ductivity, better mechanical and good in chemical stability properties. It composite is then used for the development of electrode by spin coating
is categorized into two types (i) single wall carbon nanotubes (SWCNTs) technique. The fabricated electrode is used for dye sensitizer solar cell
and (ii) multiwall carbon nanotubes (MWCNTs) [19]. Commonly, and supercapacitor applications. These nanocomposite electrodes will
SWCNTs structure has less electron transport property in comparison be more suitable for integrated energy conversion and storage devices in
with MWCNTs. Also, MWCNTs enhance the light harvesting ability, high future.
electron transfer between interfaces and reduces the surface defects in
photoanode [20,21]. So, photoanode/cathode with modified MWCNTs 2. Experimental
is majorly focused in the recent years. Also, MWCNTs based nano­
composites enhances the physical and electrical properties of DSSC. The 2.1. Chemicals
design and construction of photoanode with TiO2-MWCNT,
MWCNT/Cr2O3, RuS2/MWCNT/RGO and MWCNT/PANI nano­ Zinc acetate (Zn(CH3COO)2⋅2H2O, 99.99%), sodium hydroxide pel­
composites materials are previously investigated in DSSCs applications [ lets (NaOH, 99.9%), ethanol (C2H5OH, 99.99%), N-methyl- 2-pyrroli­
[22–25]]. Recently, Subalakshmi et al. (2023) investigated the Eosin Y done, multiwall carbon nanotubes (MWCNTs, 98%), carbon cloth,
and Coumarin co-sensitizer dyes incorporated with the rGO-TiO2 polyvinylidene fluoride (PVDF) were purchased from Sigma-Aldrich. All

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N. Eswaramoorthy et al. Materials Chemistry and Physics 316 (2024) 129049

chemicals and solvents were used as received without any further Here, open circuit voltage (Voc), short circuit current density (Jsc),
purification. Maximum voltage Vmax and maximum current density (Jmax), FF is the
fill factor and Pin is input photons.
2.2. Sonochemical synthesis of ZnO nanoparticles
2.6. Characterization
The pure ZnO were prepared by ultrasonic technique by utilizing 0.1
M zinc acetate as a starting precursor. Further, the precursor is dispersed The composite absorbance analysis using ultraviolet–visible spec­
in 100 ml MilliQ water (pH 6.7) using ultrasonic bath (Bandelin troscopy (UV–Vis, JASCO (V-670 PC)). The crystallographic parameters
Sonorex, (35 kHz)) at room temperature condition. In addition, 3 M of the fabricated electrode substances were evaluated by X-ray diffrac­
NaOH solution was slowly added during sonication until the PH of the tion (XRD) using nickel-filtered Cu-Kα radiation exhibiting a λ of 1.5418
solution reaches 11. The process continues till the solution reaches white Å. Moreover, the functional groups (400–4000 cm− 1 range) of the
colour formation. Further, the obtained solution was then washed and composite material were measured by Fourier transform-infrared spec­
centrifuged (5000 rpm at 5 min) for several times. The collected pure troscopy (FT-IR, JASCO-6800). The surface morphology and elemental
ZnO nanoparticles was dried at ~100 ± 5 ◦ C in hot air oven until the composition of the product were characterized by Field emission elec­
moisture were removed. Finally, the prepared pure ZnO powder was tron microscopy coupled with energy-dispersive (FE-SEM-EDX, Quanta
stored in glass bottle for further characterization. 200-FEG) and Transmission electron microscopy (TEM, FEI-Tecnai G2
20 Twin) operated by 200 kV. The chemical states of the prepared
2.3. Preparation of ZnO/MWCNTs nanocomposite composite were examined by X-ray photoelectron spectroscopy (XPS,
PHI 5000) instrument.
The ZnO and MWCNTs material composition ratio is used as 5:0 wt.
%, 10:1 wt.%, 10:3 wt.%, and 10:5 wt.% for this present work. Initially, 3. Results and discussion
50 ml of DD water is poured in the 100 ml glass beaker. Simultaneously,
white colored 5 wt.% of ZnO powder was added slowly and sonicated for 3.1. UV–visible absorbance spectra
about 20 min at 30 Hz. Further, 1 wt.% MWCNTs was added in the above
solution during the sonication. The obtained solution was centrifuged at The UV–Visible spectra is used to measure the light absorption
3500 rpm for 10 min. Then, the collected ZnO/MWCNTs nanocomposite capability of synthesized pure ZnO, 1, 3 and 5 wt.% of MWCNTs mixed
was dried at ~60 ± 5 ◦ C in hot air oven to remove the moisture present with ZnO material. In general, pure ZnO and MWCNTs sample has less
in the material. Finally, it is cooled down to room temperature and visible absorption region (Fig. 1a (a, b)); however, when MWCNTs are
stored in the glass bottle, named as ZnO/1 wt.%MWCNTs. Similar pro­ incorporated with ZnO nanostructure, the band gap narrows and visible
cedure is adopted for the preparation of 3 wt% and 5 wt% of MWCNTs absorption is observed. Fig. 1a (c-e) demonstrates an increase in ab­
mixed with ZnO to obtain ZnO/3 wt.% MWCNTs and ZnO/5 wt.% sorption due to the formation of effective nanocomposites after loading
MWCNTs. different percentages of MWCNTs on ZnO. When compared to pristine
ZnO and MWCNTs, the light absorbing property of nanocomposite is
2.4. Fabrication of supercapacitor electrode improved. The bandgap of pristine ZnO, MWCNTs and ZnO/MWCNTs
nanocomposites are determined using the Tauc plot, as shown in Fig. 1
The fabricated supercapacitor electrode materials pure ZnO, ZnO/1 (b). ZnO has high energy bandgap (3.06 eV). When the MWCNTs is
wt.%MWCNTs, ZnO/3 wt.%MWCNTs and ZnO/5 wt.%MWCNTs were loaded on the surface of ZnO, the bandgap is reduced due to the for­
first ground with PVDF and acetylene black in the agate mortar at a mass mation of effective heterojunction and rapid π conjugation [43]. The
ratio of 8:1:1, and an appropriate amount of NMP was added as the bandgap of different percentage loaded nanocomposites such as ZnO/1
solvent. After stirring into a paste, evenly apply the paste on the carbon wt.%MWCNTs, ZnO/3 wt.%MWCNTs and ZnO/5 wt.%MWCNTs are
cloth that has been cleaned by 1 cm2 and dry it in a vacuum drying oven calculated as 3.12, 3.17 and 3.20 eV, respectively.
at 75 ± 5 ◦ C for 8 h to obtain the pure ZnO, ZnO/1 wt.%MWCNTs, ZnO/
3 wt.%MWCNTs and ZnO/5 wt.%MWCNTs supercapacitor electrodes. 3.2. XRD analysis

2.5. Fabrication of DSSCs XRD spectrum analysis is used to investigate the structural modifi­
cation as well as crystallinity of the nanocomposites. Here, different
The fabrication of DSSC was given as follows: The photoanode was materials like MWCNTs, ZnO and ZnO/1 wt.%MWCNTs, ZnO/3 wt.%
prepared using synthesized nanomaterial (ZnO/1 wt.%MWCNTs, 95%) MWCNTs and ZnO/5 wt.%MWCNTs nanocomposites have been exam­
with the addition of binding agent (PVDF 5%) and it was continuously ined. The sharp peaks of pure ZnO at 32◦ , 34.5◦ , 36.4◦ ,47.7◦ , 56.86◦ ,
agitated using n-methyl pyrrolidine for 6 h. The prepared slurry was 63.19◦ , 66.4◦ , 68.2◦ , 69.4◦ , 72.6◦ and 77.0◦ denote its crystalline nature
coated on cleaned fluorine doped tin oxide (FTO) substrate via Dr.Blade with hexagonal wurtzite ZnO phase having corresponding h k l planes
coating method and followed by drying at 80 ◦ C for 12 h. The prepared (100), (002), (101), (102), (110), (103), (200), (112), (201) (004) and
photoanodes were dipped in 5 mM of N719 organic dye for 24 h. The (202). The absence of additional peaks proven that the purity of the
counter electrode were prepared using 10 mM of chloroplatinic acid was formed ZnO nanoparticle with well matched with JCPDS No: 89–1397
spin coated on FTO plate annealed in 500 ◦ C for 30 min. Then, both (Fig. 1c (a)) [44]. The XRD pattern of a single sharp peak at 26◦ and a
photoanode and counter electrode was sandwiched with iodide- mere hump at 43.5◦ for elemental carbon with amorphous character
triiodide gel electrolyte. The prepared Devices were subjected to the denotes the equivalent reflection of the planes (200) and (100) for the
characterization under 1 sun simulation (A.M. 1.5) light. The photon presence of elemental carbon (Fig. 1c (b)). Even with a range of loading,
conversion efficiency of the DSSC has been calculated using the the peaks of ZnO are kept in the composite’s XRD spectra at their
following formula. respective 2 theta values, which indicates a stronger crystalline char­
acter. The peaks corresponding to the MWCNTs are not visible in the
Voc X Jsc X FF
η= (1) composite spectra due to their less concentration. The peak intensities of
Pin
all the nanocomposites are identical, indicating the synthesized com­
Vmax X Jmax posite’s predominance in crystalline nature which is shown in Fig. 1b
FF = (2) (c-e) [45]. The main benefit of this material is that the XRD reflections of
Voc X JSc
bare ZnO are preserved during the nanocomposite formation process, it

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Fig. 1. (a) UV–Vis (b) Tauc plot and (c) XRD analysis of pure ZnO, pure MWCNTs, ZnO/1 wt.%MWCNTs, ZnO/3 wt.%MWCNTs and ZnO/5 wt.%MWCNTs nano­
composite, (d) 2theta (24–38 range) values of nanocomposite.

nevertheless performs well as a nanocomposite with hexagonal wurtzite region, the distinctive ZnO peak has been seen at 467 cm− 1. Fig. 2 de­
character shown in the enhanced spectra in Fig. 1 (d). scribes the intermolecular hydrogen bonding arises between the –COOH
of ZnO and hydroxyl functional groups of MWCNTs [48]. The devel­
3.3. FT-IR analysis opment of sharp peaks for the corresponding ZnO at higher loading
percent of MWCNTs justify the bond formation between the ZnO surface
FT-IR spectrum analysis is used to explain the functionalities around groups and functional groups of MWNCNTs and dominating Zn–O bond,
bare ZnO and interaction between ZnO and MWCNTs with various which has not been undergone any modifications.
loading. The –OH functional group with credible intramolecular
hydrogen bonding is shown by a strong peak in the FT-IR spectra of bare
ZnO over the range of 3400 cm− 1 (Fig. 2). The range between 1800 and 3.4. PL analysis
2200 cm− 1 was indicated the weak alkyne C ≡C and allene C=C=C)
stretching vibration [46]. The peak position at 2981 cm− 1 indicted the Fig. 3 displays the emission and electrochemical changes of the
asymmetric and symmetric vibrations of organic moieties (C–H). Zn synthesized pure ZnO, excited under 410 nm and the strong emission
acetate is one of the precursors used to make ZnO and contributes to the
acid C=O and O–C–O with respective asymmetric and symmetric
stretching at 1412 and 1290 and 886 cm− 1 [47]. In the fingerprint

Fig. 2. FT-IR analysis of (a) pure ZnO, (b) pure MWCNTs (c) ZnO/1 wt.% Fig. 3. PL analysis of (a) pure ZnO, (b) ZnO/1 wt.%MWCNTs (c) ZnO/3 wt.%
MWCNTs (d) ZnO/3 wt.%MWCNTs (e) ZnO/5 wt.%MWCNTs nanocomposites. MWCNTs (d) ZnO/5 wt.%MWCNTs nanocomposite.

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peak is observed at 620 nm. It indicates pure ZnO which has less pho­ 3.5. Morphological studies
toelectric conversion and electrochemical activity because of higher
electron hole pair recombination. To overcome this drawbacks, The morphology of the pure ZnO, MWCNTs, and different 1, 3, and 5
MWCNTs is introduced in different wt.% into the pure ZnO. Due to wt.% of MWCNTs added ZnO composites are studied using FE-SEM
effective formation of nanocomposite, the intensity is reduced gradually analysis. Fig. 4 (a, b) shows flake like-ZnO structure, measured over
with the increase of MWCNTs. This reduction indicates the lower elec­ the range of 30–50 nm. The fiber nature of MWCNTs tangled up together
tron hole pair recombination and increased photovoltaic performance and forms a mesh as depicted in Fig. 4 (c, d). The radius of each strand of
[49]. MWCNTs is measured and exhibits the range of 20–30 nm. The FE-SEM
images (Fig. 4 (e-j)) of ZnO/1 wt.%MWCNTs, ZnO/3 wt.%MWCNTs and
ZnO/5 wt.%MWCNTs composites are analyzed and observed the com­
bined structures of spherical nanoparticles mess up with single-stranded

Fig. 4. FE-SEM analysis of (a, b) pure ZnO, (c, d) pure MWCNTs, (e, f) ZnO/1 wt.% MWCNTs (g, h) ZnO/3 wt.%MWCNTs (i, j) ZnO/5 wt.%MWCNTs nanocomposite.

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wires. A substantial number of wires has been observed in the case of 5 composition and existence of various elements in the ZnO/MWCNTs
wt.% loaded composite. Moreover, EDX analysis confirms the presence composite. In Fig. 6 (a), the survey spectrum clearly shows the presence
of pure ZnO, MWCNT and composites without impurities, which is of C, O and Zn elements in nanocomposite. The presence of different
illustrated in Figure S1 (a-e). The percentage of material compositions orbits of ZnO including Zn 2p3/2, Zn 2p1/2, Zn 3p, Zn3s, Zn 3d, ZnLMM,
are tabulated as inset of EDX analysis. In addition, the presence of car­ ZnL2MM and ZnL3MM that confirms the existence of ZnO nanoparticles
bon, oxygen and zinc elemental distribution are illustrated in elemental in ZnO/3 wt.% MWCNTs nanocomposite. The deconvoluted Zn2p
mapping analysis (Figs. S2–S4) respectively. spectra exhibits two binding energy transition peaks at 1021 and 1045
Fig. 5 consists of transmission electron microscopy (TEM), lattice eV with respective spin orbits is Zn 2p3/2 and Zn 2p1/2. The difference in
fringes and selected area electron diffraction (SAED) pattern of ZnO/3 binding energy between these two lines is 24 eV which is in good
wt.% nanocomposite samples. The curled circular structured MWCNTs agreement with the ZnO reference value, shown in Fig. 6 (b). The
aggregate and formed with bundle like structure is observed. Also, these deconvoluted spectra of O 1s exhibits two Gaussian fits at 530 and 531
material surface coupled with flake like tiny size ZnO nanostructure is eV, with the peak at 530 eV attributed to physically adsorbed oxygen in
observed in Fig. 5 (a). In addition, several places are observed at dark the surface of the nanocomposite. Another peak at 531 eV denotes ox­
colored formation due to the aggregation of ZnO nanomaterial. Fig. 5 (b, ygen vaccines of nanocomposite, represented in Fig. 6 (c). The carbon
c) illustrates the stacked thin carbon walls that are confirmed with deconvoluted spectra depicts three different peaks at 283, 284 and 288
MWCNTs material. This material cross-section is zoomed with 10 nm eV (Fig. 6 (d)) which indicates C–C/C–H, adventitious hydrocarbon and
range for observed at lattice fringes pattern. Also, it clearly indicates structural carbonate species containing C=O [52].
inter planar distance of ZnO (d = 0.26 nm) and MWCNTs (d = 0.34 nm)
material corresponding to the (101) and (002) planes and these results 3.7. DSSC photovoltaic performance analysis
are closely matches with previously reported d spacing values of Kim
et al. [50] and Wang et al. [51] respectively. Moreover, Fig. 5 (d) dis­ 3.7.1. J-V characteristics and EIS analysis of fabricated DSSCs
plays SAED pattern of ZnO/3 wt.%MWCNTs nanocomposite, indexing to Fig. 7 (a) represents J-V characteristics of pure ZnO, ZnO/1 wt.%
(002) (100), (002), (101), (102), (110) and (103) h k l values that are MWCNTs, ZnO/3 wt.%MWCNTs and ZnO/5 wt.%MWCNTs composite
well matched with XRD results ((Fig. 1 (c)). In addition, the bright ring photoanodes. The short circuit current density (Jsc), open circuit voltage
formation with clear dotted SAED pattern confirms the MWCNTs surface (Voc), fill factor (FF) and power conversion efficiency (PCE) are calcu­
immersed in polycrystalline in ZnO material. lated by equations (1) and (2). The observed results are listed in Table 1.
As observed, 1, 3 and 5 wt.% MWCNTs added ZnO photoanode exhibits
3.6. XPS analysis Jsc (~7.10, ~10.20 and ~8.90 mA/cm2) and Voc (~0.71, ~0.71 and
~0.71V) electrical characterizes better than pure ZnO photoanode (Jsc
X-ray photoelectron spectroscopy is used to measure the chemical ~8.80 mA/cm2, and Voc ~0.70V). Moreover, FTO/ZnO/3 wt.%

Fig. 5. (a) TEM image (b, c) Lattice fringes and (d) SAED pattern of ZnO/3 wt.% MWCNTs nanocomposite.

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Fig. 6. XPS analysis of ZnO/3%wt.%MWCNTs nanocomposite (a) full survey (b) C1s (c) O1s (d) Zn 2p.

Fig. 7. (a) J-V Characteristics and (b) EIS spectra of 1, 3, and 5 wt.%MWCNTs incorporated ZnO nanocomposites in DSSCs (c) possible working mechanism of ZnO/
MWCNTs nanocomposites.

MWCNTs/N719 dye/Pt constructed DSSC has achieved the maximum ZnO. This composites network provides electron transfer to the external
performance as compared with other DSSC devices. The overall circuit of DSSC. The 3 wt.% MWCNT added ZnO photoanode Jsc (10.10
MWCNTs modified photoanode exhibit FF of 0.62 and pure ZnO (FF of mA/cm2) values is higher than FTO/ZnO/1 wt% MWCNT/N719 dye/Pt
0.50) are observed. Commonly, MWCNTs added ZnO photoanode and FTO/ZnO/5 wt.% MWCNTs/N719 dye/Pt) whose values are ~7.10
enhance the light harvesting and power conversion efficiency (PCE of and 8.90 mA/cm2 respectively. Particularly, pure ZnO photoanode (Jsc
3.18%, 4.57% and 3.99%) under AM 1.5 solar lighting condition. The of ~8.80 mA/cm2) is obtained as lower than 1% of MWCNTs added ZnO
presence of MWCNTs materials act as (i) electron transfer bridges be­ due to mismatch bandgap alignment of fabricated DSSC. Therefore, the
tween the FTO and ZnO grain boundaries (ii) visible light absorbance obtained results show that the MWCNTs modified DSSC device perfor­
enhancement for formation of Zinc-oxygen-carbon (Zn–O–C) bonds in mance and light absorption is slightly reduced due to the addition of

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Table 1 photoanodes to improve the DSSC performance.

J-V values for fabricated ZnO/MWCNTs nanocomposite based DSSCs.
Device Jsc Voc FF PCE Rs RCT-1 RCT-2
structure (mA/ (V) (%) (Ω) (Ω) (Ω) 3.8. Electrochemical study analysis
cm2)

ZnO (std. 8.80 0.70 0.50 3.13 12.9 41.22 43.96

The electrochemical performance of pure flake like-ZnO and ZnO
device) modified with 1, 3 and 5 wt.% MWCNTs are investigated in three-
ZnO/1 wt.% 7.10 0.71 0.62 3.18 16.3 51.13 45.93 electrode configuration which consists of active material as working
MWCNTs electrode, platinum wire act as counter electrode and Ag/AgCl act as
ZnO/3 wt.% 10.20 0.71 0.62 4.57 10.9 27.49 42.38
reference electrode under 1 M Na2SO4 as electrolyte condition. Fig. 8 (a-
MWCNTs
ZnO/5 wt.% 8.90 0.71 0.62 3.99 16.41 39.38 43.62 d) shows the CV curves of pure ZnO and ZnO/MWCNTs nanocomposites
MWCNTs which is recorded at different scan rates ranging from 5 to 150 mV/s
with the potential window of 0–0.5 V. The observed CV curves shows
quasi reversible shaped curves which confirms the electrode material
higher wt.% of MWCNTs and agglomeration of MWCNTs in ZnO. This has pseudo-capacitive behavior along with double-layer capacitance.
effect reduces the light transmittance and induced the rapid charge These peaks are driven by faradaic reactions stemming from the elec­
recombination [53,54]. The PCE of fabricated ZnO/MWCNTs composite trode’s charge transfer kinetics of ZnO. Meanwhile, MWCNTs primarily
photoanode is compared with the literature results, as shown in Table 2. serves as a hub for the electrostatic/non-Faradaic mode of charge stor­
The electrochemical impedance spectroscopy (EIS) analysis is used age mechanism and enhances electronic conductivity by facilitating
for the measurement of the electrochemical transfer and transportation access to its larger surface area for electrolyte ions [60]. From Fig. 8 (e),
properties of fabricated DSSC devices. Fig. 7 (b) illustrates the EIS it is evident that the ZnO modified with 3 wt.% MWCNTs exhibits a
spectrum of DSSC displayed in three semicircles in the 10Hz-70 Hz significantly higher peak current and higher integral area as compared
frequency ranges. The first (1st) semicircles corresponds to the charge with ZnO and ZnO/1 wt.%MWCNTs and ZnO/5 wt%MWCNTs at a scan
transfer resistance at the counter electrode/electrolyte (Rct1), second rate of 20 mV/s. From these results, the ZnO modified using 3 wt.%
(2nd) semicircles indicate the photoanode/electrolyte (Rct2) and third MWCNTs shows excellent redox reaction kinetics and superior electro­
(3rd) semicircle represents the Warburg diffusion process (Rw) of the chemical performance as compared with pure ZnO and 1 wt.% and 5 wt.
redox I/I3 coupled in electrolyte. The pure ZnO and MWCNTs mixed % MWCNTs mixed ZnO. Therefore, the specific capacitance value (Csp)
ZnO photoanode Rct1 and Rct2 variations are displayed in Table 1. The of ZnO/3 wt.% MWCNTs shows highest specific capacitance of 115.7 F
charge recombination rate indicates the Rct2 semicircles. The pure ZnO g− 1 than other electrodes, which is indicated in Table 3. The Csp of the
photoanode Rct2 values are smaller than that of MWCNTs mixed ZnO synthesized electrodes is determined from CV curves using the following
devices. Particularly, 3 wt.% MWCNTs added ZnO photoanode delivers equation (3).
the charge transfer values of 27.49 Ω (Rct-1), 42.38 Ω (Rct-2) and series ∫
resistance of 10.9 (Rs) the lower resistance values compared to pure ZnO IdV
CSP = (3)
and other nanocomposites predominantly shows that charge recombi­ νm ∗ ΔV
nation is significantly reduced due to the suitable amount of MWCNTs.
Also, it improves the electron transport and conductivity of the ZnO Where, m-weight of sample (g); I-current (A); v-scan rate (mV s− 1) and
material [59]. ΔV- potential windows (V). The specific capacitance values of fabricated
The open atmospheric fabricated DSSCs (FTO/ZnO/MWCNT com­ ZnO/MWCNTs composite electrode is compared with the existing
posite/N717 dye/Pt) device working mechanism under sun irradiation literature results, as depicted in Table 4. Fig. 9 (a-d) shows the galva­
is displayed in Fig. 7 (c). The conductive oxide (FTO) substrate deposited nostatic charge–discharge (GCD) for all the composites at the current
ZnO/MWCNT composite photoanode structures absorbs the electrons density at 1 to 7 Ag− 1. The GCD shows non-linear shaped curve which
(e− ) from photo-excited N719 dye. The e− are transferred to the con­ clearly indicates that the electrode exhibits pseudocapacitance in addi­
duction band (CB) in MWCNTs. Further, the absorbed e− from the tion to double-layer capacitance nature. This observation is consistent
conduction band (MWCNTs) is transferred to the conduction band of with the results obtained in the CV study. As compared to other elec­
ZnO, which is e− quickly transfer to the FTO surface. This reaction is trodes, ZnO/3 wt.% MWCNTs electrode has higher charging and dis­
occurred without any recombination process. In contrast, pure ZnO charging time at 1 A g− 1 of current density which is shown in Fig. 9 (e).
photoanode DSSC device have a wide-band structure but the light ab­ The results reveal that the ZnO/3 wt.%MWCNTs exhibits a longer dis­
sorption and rapid electron transfer is reduced which will affect the charging time and higher electrochemical performance. This is due to its
device performance. To overcome this issue MWCNT is added into ZnO ability to facilitate the penetration of electrolyte ions into the surface
and inner layers of the electrode material, consequently enhancing the
insertion/extraction processes. Hence, as evident from the results,
achieving this exceptional performance as an energy storage device
Table 2
Photoanode efficiency of ZnO/MWCNTs compared with previous reported necessitated not only the EDLC exhibited by MWCNTs but also a sig­
works. nificant contribution of pseudocapacitance from both ZnO and
MWCNTs. The Nyquist (N-q) plots of the developed electrode material
Photoanode Synthesis Jsc Voc FF PCE Ref.
Method (mA/ (V) (%) with frequencies ranging from 100 kHz to 10 MHz are shown in Fig. 10.
cm2) The Electrochemical impedance spectroscopy (EIS) curve consist two
ZnO/NW/ Sol-gel spin 2.19 0.49 0.66 0.72 [55]
distinct regions: (i) In the high-frequency region, a semicircle is
TiO2-GO coating observed, which corresponds to the charge transfer resistance (Rct) of
(10%) method the electrode associated with the electronic and ionic impedances
SnO2/ZnO Dual anodic 13.45 0.64 0.42 3.64 [56] arising from charge diffusion at the electrode/electrolyte interface. (ii)
dissolution
In the low-frequency region, a vertical line is appeared due to the
ZnO/CuO Chemical co- 6.17 0.67 0.62 2.56 [57]
precipitation Warburg impedance, which is associated with the diffusive resistance
ZnO-NR/ Solution route 8.06 0.64 0.62 3.76 [58] between the electrode pores and the electrolyte ions [61]. Table 5 rep­
NH2/GO resents the solution resistance (Rs) and Rct values for pure ZnO and ZnO
ZnO/3 wt.% Sonication 10.20 0.71 0.62 4.57 Present modified with 1, 3, and 5 wt%MWCNTs, respectively. From the results,
MWCNTs method work
the pure ZnO exhibits elevated Rs and Rct values, suggesting reduced ion

8
N. Eswaramoorthy et al. Materials Chemistry and Physics 316 (2024) 129049

Fig. 8. (a–d) Cyclic voltametric curves of pure ZnO, ZnO/1 wt.%MWCNTs ZnO/3 wt.%MWCNTs and ZnO/5 wt.%MWCNTs nanocomposite at different scan rates
ranging from 5 to 150 mVs− 1 and (e) Electrochemical performance of pure ZnO, 1, 3 and 5 wt.% MWCNTs mixed ZnO nanocomposite electrodes investigated in three
electrodes configuration in 1 M Na2SO4 electrolyte.

Table 3 Table 4
Specific capacitance values of ZnO/MWCNTs nanocomposite electrodes. Comparative studies on different electrode materials for supercapacitor-specific
Materials Specific Capacitance Values at various scan rates (mVs− 1)
capacitive behavior.
Electrode Material Electrolyte Scan Specific Ref.
5 10 20 40 60 80 100 150
rate capacitance
ZnO 73.6 70.3 68.3 58.6 51.3 44.9 41.1 34.8 (mV) (mVs− 1)
1% 79.9 66.0 58.6 54.0 46.8 41.4 37.7 31.8
PANI/SnO2 1 M H2SO4 5 305.3 [62]
3% 115.7 85.8 74.3 70.6 65.4 59.8 55.7 48.4
AC/ZnO composite 1M 5 123 [63]
5% 87.4 79.3 68.9 58.6 51.4 46.0 41.9 35.4
Na2SO4
G-ZnO composite 1 M KCl 100 11 [64]
film
diffusion and charge transfer. The ZnO/3 wt.%MWCNTs nanocomposite CNT-ZnO 1 M KCl 50 323.9 [65]
exhibits a lower resistance as compared to other electrode materials, nanocomposites
which is primarily attributed to enhance charge transport within the ZnO/RGO 1M 10 95 [66]
electrodes. composite Na2SO4
ZnO/3 wt.% 1M 5 115.7 Present
The as prepared ZnO/3 wt.%MWCNTs nanocomposite was carry
MWCNTs Na2SO4 work
forward to the fabrication and analysis of supercapacitor. The following
procedure was followed for the fabrication of asymmetrical device: the C- Carbon; AC- Activated carbon; G- Graphene; CNT-Carbon nanotube; RGO-
nanocomposite coated Ni foam and activated carbon were considered as Reduced graphene oxide.
cathode and anode respectively. 1 M Na2SO4 electrolyte was used with
separator of cellulose paper (Whatman filter paper) and the electrodes were sandwiched and sealed for further analysis. The cyclic

9
N. Eswaramoorthy et al. Materials Chemistry and Physics 316 (2024) 129049

Fig. 9. (a–d) Charge-discharge profile at different current densities of pure ZnO, ZnO/1 wt.% MWCNTs, ZnO/3 wt.% MWCNTs and ZnO/5 wt.% MWCNTs nano­
composite electrodes (e) Cyclic voltametric curves of pure ZnO, 1, 3 and 5 wt.% MWCNTs incorporated ZnO nanocomposites at a scan rate of 20 mVs− 1.

Table 5
ElS parameters of ZnO/MWCNTs nanocomposite electrodes.
Electrodes RS (Ω) RCT (Ω)

ZnO 0.92 0.63

ZnO/1% MWCNTs 0.94 0.51
ZnO/3% MWCNTs 0.67 0.39
ZnO/5% MWCNTs 1.11 0.49

voltammetry (CV) curves were performed with potential window of

0–1.5 V and are shown in Fig. 11 (a). The CV was performed with
different scan rates 10 mV/s to 80 mV/s. The oxidation and reduction
peaks were appeared evidently and current of the device was increasing
with respect to the scan rate. The galvanostatic charge-discharge were
shown in Fig. 11 (b). It delivers the rapid charge and discharge with
various current density of 1, 2, 3, 4 A/g. The specific capacitance of the
device was also found to be 84, 75,63, 48 F g− 1 respectively (Fig. 11c).
During the charging process, when a voltage is applied, positive ions
move to the negatively charged electrode, while negative ions move to
the positively charged electrode, adsorbing on their surfaces. This re­
Fig. 10. EIS spectra of (a) pure ZnO, (b) ZnO/1 wt.%MWCNTs, (c) ZnO/3 wt.%
sults in the electrostatic separation of charges, storing energy. When
MWCNTs (d) ZnO/5 wt.%MWCNTs nanocomposite incorporated DSSCs.
connected to an external circuit for discharging, the released ions move

10
N. Eswaramoorthy et al. Materials Chemistry and Physics 316 (2024) 129049

Fig. 11. Asymmetric supercapacitor device (a) Cyclic voltametric curves at different scan rates (b) Charge-discharge profile of at different current densities (c)
specific capacitance value for different current densities and (d) EIS spectra for ZnO/3 wt.%MWCNTs nanocomposite.

back into the electrolyte, generating an electric current that can power Thiyagarajan Krishnan: Validation. G. Kumaresan: Formal analysis.
connected devices. Supercapacitors are prized for their high power Kamatchi Rajaram: Supervision.
density and rapid charge/discharge cycles. The electrochemical spec­
troscopy was performed and depicted in Fig. 11 (d) which reveals that
the charge transfer resistance of the fabricated device. It was observed Declaration of competing interest
that the Rct was 1.32 Ω and series resistance (Rs) was 1.58 Ω respec­
tively. It clearly delivers that the prepared ZnO/3 wt.%MWCNTs The authors declare that they have no known competing financial
nanocomposite is suitable for the supercapacitor devices. interests or personal relationships that could have appeared to influence
the work reported in this paper.
4. Conclusion
Data availability
In summary, ultrasonic techniques is followed to prepare 2D/1D
structured ZnO/MWCNTs nanocomposite electrode for dye sensitizer Data will be made available on request.
solar cell and supercapacitor applications. In general, the performance
of DSSCs is affected the presence of hydroxyl groups on the surface of Acknowledgement
ZnO. To overcome this, different wt.% of MWCNTs are mixed with ZnO
to improve light absorbance and tuning the band gap. Here, 0.3 wt.% Nandhakumar Eswaramoorthy gratefully acknowledges the Center
MWCNTs mixed with ZnO device has achieved a maximum PCE under for Computational Modeling, Chennai Institute of Technology, India for
solar light condition. In DSSCs, the ZnO/MWCNTs nanocomposite providing support under the following funding number: CIT/CCM/
photoanodes improves the charge separation and significantly reduces 2024/RP-013.
the recombination losses. In supercapacitor, these electrodes show good S. Sambasivam acknowledges the UAEU-AUA joint research program
reversibility on oxidation and reduction process in the presence of 1 M under grant no. 12R179 and the National Water and Energy Center,
Na2SO4 electrolyte. The fastest redox kinetics of Zn ion, charge carriers United Arab Emirates University, UAE.
mobility of electrolytic ions, surface morphological of the composites Kamatchi Rajaram thanks to Vellore Institute of Technology, Vellore,
improve the electrochemical properties with lowest Rs and Rct resis­ India for providing financial support under Seed Grant: SG20220026.
tance. 3 wt.% MWCNTs mixed ZnO demonstrated the improved energy
storing performance in supercapacitor device. The fabricated 2D/1D Appendix A. Supplementary data
architectural nanocomposite is favorable for future integrated energy
conversion and storage device applications. Supplementary data to this article can be found online at https://doi.
org/10.1016/j.matchemphys.2024.129049.
CRediT authorship contribution statement
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