Journal of Energy Storage 99 (2024) 113321

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Journal of Energy Storage

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Research papers

Microwave-assisted synthesis of perovskite hydroxide-derived Co3O4/

SnO2/reduced graphene oxide nanocomposites for advanced hybrid
supercapacitor devices
Sumanta Sahoo a , Ahamed Milton a , Ankur Sood a , Rajesh Kumar b , Soonmo Choi a , Chandan
Kumar Maity c, * , Sung Soo Han a, *
a
School of Chemical Engineering, Yeungnam University, 280 Daehak-ro, Gyeongsan 38541, South Korea
b
Department of Mechanical Engineering, Indian Institute of Technology, Kanpur 208016, Uttar Pradesh, India
c
Department of Chemistry, Gachon University, 1342 Seongnam-daero, Sujeong-gu, Seongnam-si, Gyeonggi-do 13120, South Korea

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

Keywords: The current article reports a facile, ultrafast, and cost-effective, solid-state microwave (MW) synthetic route for
Supercapacitor the conversion of perovskite hydroxide (CoSn(OH)6) to crystalline metal oxides (Co3O4 and SnO2) with the help
Reduced graphene oxide of reduced graphene oxide (rGO) nanosheets. In a domestic MW oven, the Co3O4/SnO2/rGO (CSO-rGO) nano-
Co3O4
composite was synthesized within a quick reaction time of only 30 s. The study deeply focused on analyzing the
SnO2
Microwave irradiation
surface morphology, metal oxide attachment on the surfaces of rGO nanosheets, the specific surface area, and the
electrochemical performance of supercapacitor devices from the CSO-rGO nanocomposite. As a positive electrode
for supercapacitors, the synthesized hybrid electrode displayed a good capacity (146.4C/g) and enhanced cycling
stability (103.2 % after 15,000 cycles). Moreover, the corresponding aqueous hybrid supercapacitor device with
MW-synthesized rGO as a negative electrode displayed a maximum energy density of 27 Wh/kg and promising
cycling stability of 102.4 % after 10,000 cycles. As a whole, compared to the common time-consuming synthetic
approaches, the MW-assisted synthetic approach is highly beneficial in terms of short reaction time, cost-
effectiveness, and straightforwardness. The MW synthesis methodology employed in this study can be utilized
for analogous composite electrodes that incorporate other layered conductive architectures in addition to metal
oxides.

1. Introduction explored as SC electrodes because of their high theoretical capacity,

enhanced conductive nature, and improved redox activity. Such MOs
Energy has become an essential component of the modern world. The displayed improved electrochemical performance as pseudocapacitive
crisis of such a crucial component has become a global issue today. To material. However, the cycling stability of MOs is a critical issue. To
overcome this, modern science and technology have been significantly overcome this, MOs have been extensively combined with carbon-based
focused on exploring alternating energy resources. Despite having materials like carbon nanotubes, reduced graphene oxide (rGO), acti-
diverse sustainable energy resources, these have not been explored in vated carbon, etc. Such carbonaceous materials not only enhanced the
full fledge. Several electrochemical energy devices like batteries, cycle life of the MO-based electrodes but also acted as suitable templates
supercapacitors (SC), etc. have been explored in this aspect [1–3]. SC is for the growth of MO nanoparticles (NPs). The rGO has been widely
one such electrochemical energy storage device that expressively ad- explored for fabricating advanced SC electrodes because of its high
vances the modern automobile industry [4–6]. Because of its fast surface area, enhanced conductivity, high porosity, and rich electro-
charge/discharge process, enhanced power density, and promising cycle chemical characteristics [7–9]. Furthermore, this astonishing carbon
life, such devices have grown rapidly encouragement among energy material can construct 3D network structures along with the MO NPs.
researchers worldwide in recent times. The combination of graphene materials and two or more transition
Over the years, various metal oxides (MOs) have been extensively MOs to synthesize ternary nanocomposites has been considered a

* Corresponding authors.
E-mail addresses: ckmkorea@gachon.ac.kr (C.K. Maity), sshan@yu.ac.kr (S.S. Han).

https://doi.org/10.1016/j.est.2024.113321
Received 3 June 2024; Received in revised form 25 July 2024; Accepted 9 August 2024
Available online 17 August 2024
2352-152X/© 2024 Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
S. Sahoo et al. Journal of Energy Storage 99 (2024) 113321

fruitful strategy for developing high-performance SC electrodes. In this the X-ray source (λ = 1.5406 Å). The Raman spectra (XploRA plus
aspect, Obodo et al. reported the hydrothermal synthesis of graphene HORIBA) of rGO and CSO-rGO were carried out with the laser excitation
oxide/Co3O4/NiO composite that exhibited the specific capacitance of 532 nm. The surface analysis of CSO-rGO was carried out using X-ray
(Csp) of 1612 F/g at 1 A/g current density (CD) [10]. However, the photoelectron spectroscopy (XPS, Thermo Scientific, Al kα). The
electrode exhibited a cycling stability of 88.6 % after 10,000 cycles. In morphology of rGO, CSOH, and CSO-rGO was examined by scanning
another work, a thermal reduction process was adopted to synthesize electron microscopy (SEM, Hitachi, S- 4800), which was operated at an
ternary SnO2/Co3O4/N-doped graphene oxide composite, that demon- accelerating voltage of 10 kV. Moreover, the structural evaluation and
strated a maximum Csp of 375 F/g and cycling stability of 93 % after the elemental mapping of CSO-rGO were performed through high-
10,000 cycles [11]. Moreover, in a recent work, a fusion method was resolution transmission electron microscopy (HRTEM, FEI Tecani G2
adopted to synthesize the quaternary rGO/MnO2/NiO/CuO composite F20), which was operated under an acceleration voltage of 200 kV. The
which displayed a maximum Csp of 816.51 F/g [12]. The corresponding HRTEM sample was prepared by drop-casting the aqueous dispersion of
symmetric device further exhibited a cycling stability of 86.46 % over the active electrode material onto a carbon-coated copper grid (300
5000 cycles. In another work, Nagarani et al. reported the synthesis of mesh). On the other hand, the Brunauer–Emmett–Teller (BET) surface
ZnO/CuO/rGO composite via a co-precipitation method that displayed a area measurement and the pore size distribution were carried out using
maximum Csp of 260.7 F/g and cycling stability of 98.7 % after 10,000 the N2 adsorption-desorption method (Micromeritics, 3Flex Surface
cycles [13]. Furthermore, the ternary rGO/ZnO/SnO2 composite dis- Characterization Analyzer). Before the BET analysis, the sample was
played a maximum Csp of 581.8 F/g and a cycling stability of 98 % after degassed at 150 ◦ C for 12 h.
1000 cycles [14]. For constructing such hybrid SC electrodes, diverse
synthetic approaches like hydrothermal/solvothermal, co-precipitation, 2.3. Electrochemical characterization & device fabrication
sol-gel, electrospinning, microwave (MW), etc. have been explored over
the years. Among these, hydrothermal processes are the most common, The electrochemical measurements were performed in the Autolab
requiring a high-temperature process over a long reaction time. In workstation. The electrochemical analyses were done through cyclic
contrast, the solid-state MW process generally requires a very short re- voltammetry (CV), galvanostatic charge-discharge (GCD), and electro-
action time and has the advantage of cost-effectiveness [15–17]. chemical impedance spectroscopy (EIS) using a 3 M KOH electrolyte in a
Among the MOs, Co3O4 (theoretical capacity – 890 mAh/g) and SnO2 three-electrode setup. The mass loading of the active electrode was 1
(theoretical capacity – 1494 mAh/g) have been significantly utilized to mg/cm2. For the construction of the working electrode, a slurry of CSO-
fabricate SC electrodes because of their high theoretical capacity, cost- rGO, carbon black, and PVDF (wt. ratio of 80:10:10) was prepared with
effective synthetic approaches, enhanced electrochemical activity, and the NMP solvent. The slurry was further coated on Nickel foam (NF) and
eco-friendly nature [18,19]. On the other hand, CoSn(OH)6 (CSOH) is a dried in the Vacuum oven at 70 ◦ C for 24 h. The Ag/AgCl and Pt were
common perovskite hydroxide, which is generally utilized for the syn- used as the reference and counter electrodes in the 3-electrode set-up.
thesis of amorphous CoSnO3 perovskite oxide [20–23]. However, the The negative electrode was prepared by making a slurry of rGO, car-
current article attempts to synthesize crystalline oxides from CSOH bon black, and PVDF (wt. ratio of 80:10:10) in NMP solvent and then
within a short time duration. It is evident that the Sn-based mixed metal coating on NF. To construct the aqueous hybrid supercapacitor (AHSC)
hydroxides generally require time-consuming, high-temperature calci- device, the positive and negative electrodes (1 × 1 cm2) were assembled
nation processes for their conversion to corresponding MOs. Herein, a in the split cell along with the electrolyte (3 M KOH). A piece of filter
novel synthetic approach is proposed for converting such mixed metal paper was used as the separator, which was placed in between the
hydroxides to MOs within a few seconds. positive and negative electrodes.
The prime object of this work is to fabricate the SC device with high
cycling stability by utilizing graphite oxide (GO) as an MW susceptor. As 2.4. Synthesis of graphite oxide (GO)
compared to the common time-consuming synthetic approaches, the
current adopted synthetic protocol is innovative and highly advanta- GO was synthesized from graphite by following one of the previous
geous in terms of short reaction time, cost-effectiveness, and straight- reports [24,25]. In brief, 5 g of graphite was stirred with conc. H2SO4
forwardness. In a commercial MW oven, within a quick reaction time of and conc. HNO3 (volumetric ratio 3:1). After that, 55 g of KClO3 was
only 30 s, the GO was exfoliated and reduced to form rGO. Moreover, the added slowly to the soln. in ice-cold conditions. The stirring was
perovskite hydroxide was dehydrated to form MO NPs on the surface of continued for a week. After diluting the soln. with DI water, it was
rGO. The fabricated hybrid Co3O4/SnO2/rGO (CSO-rGO) electrode repeatedly washed with dil. HCl, H2O2, and DI water. The centrifugation
demonstrated high specific capacity (Cs), moderate rate capability, and and drying of the solution produced the GO.
enhanced cycling stability. Furthermore, the corresponding hybrid de-
vice exhibited good energy density and promising cycling stability. To 2.5. Synthesis of CoSn(OH)6 (CSOH)
the best of the authors’ knowledge, the current work is the first report on
the ultrafast conversion of perovskite hydroxides to corresponding MOs The perovskite hydroxide CSOH was synthesized following a previ-
in the MW route. ously reported hydrothermal process [26]. In a typical process, initially,
1.46 g of Co(NO3)2.6H2O was dissolved in 20 ml of DI water through
2. Experimental stirring to prepare soln. A. In another beaker, 1.33 g of Na2SnO3.3H2O
was dissolved in 20 ml of DI water through continuous stirring to pre-
2.1. Materials pare solution B. In the next step, solution A was mixed with solution B
through drop-wise addition. After some time, 1 ml of ammonia solution
The MO precursors, i.e. Co(NO3)2.6H2O and Na2SnO3.3H2O were (diluted) was added to the solution and the stirring was continued for 1
purchased from Alfa Aesar. For the synthesis of GO, the required h. After that, the solution was hydrothermally treated at 180 ◦ C for 24 h
chemicals like conc. H2SO4, conc. HNO3, KClO3, HCl, H2O2, and ethanol to obtain CSOH.
were supplied by Duksan Pure Chemicals Co. Ltd.
2.6. Synthesis of Co3O4/SnO2/rGO (CSO-rGO) nanocomposites
2.2. Instrumentation & characterization techniques
The final CSO-rGO nanocomposite was synthesized through a fast
The crystallinity of CSO-rGO and CSOH was inspected by X-ray MW irradiation technique in a commercial MW oven. Prior to the MW
diffraction (XRD, PANalytical, X’Pert-PRO MPD) using the Cu kα line as treatment, 50 mg of CSOH was mixed with 100 mg of GO in a 40 ml

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S. Sahoo et al. Journal of Energy Storage 99 (2024) 113321

ethanol solution through stirring for 6 h. After that, the solution was time. In contrast, the adopted MW approach requires only a few seconds
dried in an open tray. In the next step, the dried powder was MW treated at room temperature for successive conversion of CSOH to the corre-
at the power of 800 W for 30 s to obtain the light-weight CSO-rGO sponding MOs, indicating significant advantages in terms of cost-
nanocomposite. For the fabrication of the negative electrode, rGO was effectiveness and low processing time.
synthesized from GO following the same reaction condition without the To confirm the formation of perovskite hydroxide and the related
addition of CSOH. MOs, the XRD analyses of CSOH and CSO-rGO nanocomposites were
conducted. As shown in Fig. 2(a), the characteristic peaks of CSOH can
3. Results and discussion be indexed to the cubic crystal structure of perovskite-type CoSn(OH)6
(space group Pn-3m) according to the JCPDS card no. 13–0356 [28]. The
The synthetic approach of the CSO-rGO nanocomposite is schemat- absence of any peaks for the impurities like SnO2 or Co(OH)2 indicates
ically shown in Fig. 1. In this process, at first, the perovskite hydroxide high purity and good crystallinity of CSOH. On the other hand, the sharp
CSOH was hydrothermally prepared for its utilization as the MO pre- peak at the 2θ value of 26.9◦ in the XRD pattern of CSO-rGO nano-
cursor. The chemical reaction between the Co2+, Sn4+, and OH− led to composite corresponds to the (002) plane of rGO. Moreover, the char-
the formation of CSOH under hydrothermal conditions (Eq. (1)). acteristic peaks at the diffraction angles of 18, 30.7, 43.4, 55.1, and
60.6◦ indicate the (111), (220), (400), (422), and (511) planes of Co3O4,
Co2+ + Sn4+ + 6OH− →CoSn(OH)6 (1)
respectively (JCPDS card no. 42-1467) [11]. The other characteristic
In the next step, a fast, cost-effective, solid-state MW approach was peaks at the 2θ values of 34.2, 44.2, 52, 58.1, and 66.2◦ can be assigned
adopted to convert the perovskite hydroxide to crystalline MOs (Co3O4 to the (101), (210), (211), (002), and (301) planes of SnO2, respectively
and SnO2) by utilizing GO as the MW susceptor. During such short in- (JCPDS card no. 41-1445). Additionally, the peaks at 38.2◦ can be
tervals of MW treatment, several processes have occurred as follows – (i) assigned to the (200) plane of SnO2 or (222) plane of Co3O4. Similarly,
exfoliation of GO, (i) reduction of GO to produce rGO nanosheets, (iii) the characteristic peak at 65◦ can be designated as the (112) plane of
conversion of CSOH to produce crystalline MOs i.e. Co3O4 and SnO2, and SnO2 or (440) plane of Co3O4. The slight shifting of the peaks from their
(iv) deposition of MO NPs on the surface and edges of rGO nanosheets. ideal position indicates the interactions of MOs with rGO. On the other
Initially, the oxygen functionalities present on GO absorbed the MW hand, the low-intense peaks at the 2θ values of 23 and 63◦ can be
irradiation and exfoliated the graphene nanosheets with the release of assigned to the presence of a small quantity of unreacted CSOH as the
some carbon-containing gases like CO or CO2 [27]. Because of the impurities. Overall, the XRD analysis confirms the formation of MOs
release of such gases, the GO was reduced to form rGO. On the other along with rGO through the successive conversion of CSOH.
hand, at the same time, a large amount of heating was generated The Raman spectroscopic analysis further confirms the presence of
through the dipole rotation induced by the MW field. At this high graphene and the structural changes in the CSO-rGO nanocomposite.
temperature, the perovskite hydroxide CSOH was dehydrated due to its Fig. 2(b) represents the Raman spectra of rGO and CSO-rGO nano-
inadequate thermal stability and converted into MOs i.e. SnO2 and composite. For rGO nanosheets, the prominent peaks at ~1351 and
Co3O4. The synthetic approach is a novel pathway to convert mixed ~1581 cm− 1 correspond to the D and G bands, respectively. Herein, the
metal hydroxide to corresponding MOs within a short time interval. As D band is associated with the defect formation on the graphene struc-
summarized in Table S1, the high-temperature calcination/annealing/ ture. On the other hand, the G band designates the in-plane stretching of
sintering processes are generally reported for synthesizing MOs from Sn- the sp2-hybridized carbon. Additionally, the peak at ~2705 cm− 1 rep-
based mixed hydroxides, which required a minimum of 2 h of reaction resents the 2D band, which indicates the construction of multi-layered

Fig. 1. Schematics of the synthesis process of CSO-rGO nanocomposite.

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S. Sahoo et al. Journal of Energy Storage 99 (2024) 113321

Fig. 2. (a) XRD patterns of CSO-rGO nanocomposite and CoSn(OH)6 (CSOH), (b) Raman spectra of CSO-rGO and rGO; high-resolution XPS spectrum of CSO-rGO: (c)
Co 2p, (d) Sn 3d, (e) O 1s, and (f) C1s.

graphene nanosheets. In the case of CSO-rGO nanocomposite, the intensity of the 2D band for CSO-rGO nanocomposite was reduced as
presence of the D, G, and 2D bands confirms the presence of graphene. compared to rGO, which was caused by the change in graphene layers.
The distinctive D and G bands are observed at ~1347.5 and ~ 1588.5 The intensity ratio of 2D and G bands (I2D/IG) gives a clear idea of the
cm− 1, respectively. Herein, compared to rGO, the blue shift in the G layers of graphene nanosheets. Herein, the calculated I2D/IG value is
band for CSO-rGO nanocomposite can be ascribed to the electronic found to be higher for CSO-rGO nanocomposite as compared to rGO
interaction between the MOs and graphene nanosheets [29]. Addition- nanosheets, which indicates the decrease of graphene layers upon the
ally, the appearance of a few Raman scattering peaks within the range of formation of MOs on graphene nanosheets through MW irradiation [30].
400–700 cm− 1 indicates different vibrational modes of the MOs. Additionally, the broadening of the 2D band also indicates the reduction
Moreover, the intensity ratio of D and G band (ID/IG) for CSO-rGO of graphene layers in CSO-rGO nanocomposite. On the other hand, the
nanocomposite (0.98) is found to be higher than rGO (0.77), which in- four bands at the range of 295–600 cm− 1 in the Raman spectrum of
dicates the creation of significant defects on the graphene nanosheets CSOH correspond to the breathing vibrational modes of M − OH and
through the coating of MO NPs. It is interesting to note that, the peak bending modes of M − OH − M bonds, respectively, which is in good

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agreement with previous reports [28,31] (Fig. S1). As a whole, Raman nanocomposite at low and high magnifications. As evident from the
spectra clearly designate the structural changes (including the defect SEM images of the CSO-rGO nanocomposite, the MO NPs are not only
formation) on graphene nanosheets upon the coating of MO NPs. coated on the rGO surfaces but also coated on the edges (Fig. 3(a–d)).
The XPS study was used to examine the surface configuration and However, the particles are found to be in agglomerated form, which may
chemical states of all the elements in the synthesized CSO-rGO nano- be caused by the generation of high temperatures during MW irradiation
composite. Fig. S2 displays the XPS complete scan spectrum survey of within a short time interval. It has already been well-established that the
the CSO-rGO nanocomposite, indicating the existence of various com- rGO nanosheets contain oxygen functionalities on the surfaces and
ponents including C 1s, Co 2p, Sn 3d, and O 1s, along with auger electron edges. Among such functional groups, mostly the epoxide and carbonyl
peaks representing the chemical states [32,33]. As depicted in Fig. 2(c), functional groups are situated on the basal plane, whereas the hydroxyl
the prominent peaks with high resolution correspond to the Co 2p3/2 and and carboxyl groups are located on the edges of the graphene nanosheets
Co 2p1/2 spin-orbit peaks, whose binding energy are located at 780.8 eV [39]. During the MW process, such functional groups played a signifi-
and 797.0 eV, respectively, confirming the formation of Co3O4 NPs. cant role in growing the MO NPs by acting as nucleation active sites.
Additionally, there are satellite peaks at 786.0 eV and 802.5 eV related It has also been evident that the current MW approach is found to be
to the Co3O4 phase. The deconvoluted XPS spectrum of Sn 3d, as beneficial in synthesizing wrinkled graphene nanosheets, which usually
depicted in Fig. 2(d), displays two distinct peaks at the binding energies have a high aspect ratio. The formation of such wrinkles on the graphene
of 486.9 and 495.4 eV. These peaks correspond to the Sn 3d5/2 and Sn surface is evident from HRTEM images (Fig. 4(a, b)). Notably, the con-
3d3/2 spin-orbit peaks of SnO2, confirming the synthesis of SnO2 in the struction of wrinkles is advantageous for charge storage by restricting
composite [34,35]. On the other hand, the O1s spectrum in Fig. 2(e) the re-stacking of graphene nanosheets, enhancing the surface area, as
displays two characteristic peaks at 530.8 eV and 531.6 eV, providing well as making the nanosheets more flexible [40]. Moreover, such gra-
evidence for the existence of oxygen atoms in the Co3O4/SnO2 oxide as phene composite is expected to showcase long-term cycling performance
the presence of oxygen functionalities on rGO nanosheets [36]. by restricting the plausible structural damage during continuous inter-
Furthermore, the deconvolution of the C 1s spectrum in Fig. 2(f) displays calation/deintercalation of electrolyte ions. Furthermore, the rGO
two distinguished peaks at around the binding energies of 284.6 and nanosheets are found to be highly transparent. On the other hand, the
285.5 eV. These peaks are often linked with the formation of C=C/C-C HRTEM images of the CSO-rGO nanocomposite demonstrate the proper
and C– –O bonds, respectively [37,38]. The existence of the C 1s spec- distribution of MO NPs on the wrinkled graphene surfaces (Fig. 4(c–e)).
trum designates the presence of rGO in the composite. Therefore, the The NPs are found to be in the range of 5–10 nm. The expanded view of
XPS spectra confirm the existence of dissimilar MOs along with rGO. the HRTEM image further demonstrates the presence of characteristic
The morphological analyses of CSO-rGO nanocomposite further planes of the MOs on the rGO sheets (Fig. S4). The corresponding SAED
demonstrate the impact of rGO nanosheets on the growth of MO NPs. pattern further confirms the good crystallinity of the composite, which is
The thin nanosheets of graphene with open edges are clearly visible in in good agreement with the XRD analysis (Fig. 4(f)). Moreover, it also
the SEM images of rGO nanosheets (Fig. S3(a, b)). Such a porous designates characteristic planes of the corresponding MOs. Furthermore,
network of rGO nanosheets acts as a superior supporting template for the the elemental mapping measurement of the composite confirms the
deposition of MO NPs. Moreover, the perovskite CSOH NPs are spherical homogeneous distribution of C, Co, Sn, and O elements (Fig. 4(g)).
in size (Fig. S3(c, d)). Fig. 3(a–d) displays the SEM images of CSO-rGO Porosity plays a significant role in the electrochemical performance

Fig. 3. (a–d) SEM images of CSO-rGO nanocomposite at low and high magnifications.

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Fig. 4. (a, b) HRTEM images of rGO nanosheets at low and high magnifications; (c–e) HRTEM images of CSO-rGO nanocomposite at low and high magnifications, (f)
corresponding SAED pattern, and (g) elemental mapping of CSO-rGO displaying the presence of C, Co, Sn, and O.

of SC electrodes. In this aspect, BET surface area analysis of CSO-rGO

− C = O + H + + e− ↔ − C − O − H (2)
was performed to understand the pore size distribution and surface
characteristics. Fig. S5(a–c) represents the characteristic N2 adsorption- The appearance of the redox peaks can be ascribed to the following
desorption, pore size distribution, and cumulative pore volume curves. electrochemical reactions of MOs [47,48]:
The BET surface area was calculated to be 50.35 m2/g. The adsorption-
desorption isotherm can be specified into the category of type IV with an Co3 O4 + H2 O + OH− ↔ 3CoOOH + e− (3)
H4 hysteresis loop, indicating the mesoporous structure of the nano-
CoOOH + OH− ↔ CoO2 + H2 O + e− (4)
composite with the presence of narrow slit-like pores [41]. The average
size and cumulative pore volume were found to be 15.1 nm and 0.18
SnO2 + H2 O + e− ↔ SnOOH + OH− (5)
cm3/g, respectively. Therefore, the pore size distribution further con-
firms the presence of mesopores of CSO-rGO. It is evident that the SnOOH + e− ↔ SnO + OH− (6)
mesoporous structure of the electrode is highly efficient for the smooth
penetration of electrolyte ions during the electrochemical test [42]. It is also evident that the anodic and cathodic peaks of the composite
To analyze the application potential of CSO-rGO nanocomposite in are shifted towards more anodic and cathodic positions with increasing
SCs, the electrochemical tests were performed in an aqueous KOH SRs, indicating the reversible redox activity of the composite. In general,
electrolyte. The equations used for the electrochemical evaluation of the previously reported MO-based composite electrodes demonstrate
CSO-rGO nanocomposite are summarized in Section S1. Fig. 5(a) rep- well-maintained redox peaks within the SRs of 100 mV/s. Over such
resents the cyclic voltammetry (CV) profiles of CSO-rGO nanocomposite high SRs, the reported electrodes experience severe distortion in the
at different scan rates (SRs) ranging from 5 to 200 mV/s. The CV profiles shape of the CV curves. On the contrary, even at a high SR of 200 mV/s,
deviate from the rectangular shapes and are also asymmetric in nature, the CSO-rGO nanocomposite electrode still displayed a distinguished
representing the battery-type characteristics of the composite [43,44]. redox pair, indicating good rate performance and fast redox kinetics
Herein, along with the MOs, rGO nanosheets also significantly contrib- [49]. The galvanostatic charge/discharge (GCD) profiles at different
uted towards the Faradaic charge storage because of the presence of current densities (CDs) further exhibit battery-type characteristics
oxygen-containing functional groups. The following reaction is respon- (Fig. 5(b)). At a low CD of 1 A/g, the composite revealed a maximum Cs
sible for the generation of pseudocapacitance in rGO [45,46]: of 146.4C/g (40.6 mAh/g). Notably, even at a high CD of 20 A/g, it still

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Fig. 5. Electrochemical performance of CSO-rGO nanocomposite in 3 M KOH electrolyte: (a) CV profiles at different SRs, (b) GCD curves at various CDs, (c) Cs values
at various CDs, (d) fitted Nyquist plot (Inset shows the equivalent circuit for fitting), (e) cycling stability curve up to 15,000 cycles (inset demonstrates the evaluation
of the cycling stability of CSO-rGO nanocomposite with other reported electrode materials).

demonstrated a Cs of 86C/g. Therefore, the composite retained ~60 % of comparative CV and GCD profiles (Fig. S6). At the scan rate of 1 A/g,
its initial capacity upon a 20-fold increment of the CD (Fig. 5(c)). rGO displayed a Cs of 58C/g. Therefore, CSO-rGO achieved ~2.5 times
Moreover, CSO-rGO also displayed superior current response and higher higher Cs than rGO.
discharge time than MW-synthesized rGO, as observed from the Fig. 5(d) represents the fitted Nyquist plot and the corresponding

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equivalent circuit of the CSO-rGO nanocomposite electrode. The elec- diffusion to the surface of the electrode. The steeper slope line indicates
trode exhibited a low equivalent series resistance (ESR) of 0.5 Ω. Such a the fast ion diffusion of the composite electrode [50]. The high porosity
low value of ESR is associated with the enhanced conductivity of the of the composite is responsible for such low RCT and fast diffusion rate.
composite due to the presence of rGO nanosheets. Such high conduc- Cycling stability is one of the supreme parameters in evaluating the
tivity is advantageous for smooth electron and charge transfer during performance of supercapacitor electrodes. Herein, the stability test of
the electrochemical test. Furthermore, the plot also displayed a the CSO-rGO nanocomposite electrode was performed by continuing the
depressed semicircle, indicating low charge transfer resistance (RCT) charge/discharge cycles 15,000 times at the CD of 10 A/g (Fig. 5(e)). It
(2.51 Ω). On the other hand, the straight line at the low-frequency re- is interesting to note that, the Cs have been improved gradually over
gion signifies the Warburg impedance, which is associated with the ion such a long-term cycle life. The increment in capacity during initial

Fig. 6. Electrochemical performance of the CSO-rGO//rGO AHSC in 3 M KOH electrolyte: (a) schematics of the fabricated device, (b) CV curves of positive and
negative electrodes at the SR of 20 mV/s, (c) CV curves at different SRs, (d) GCD profiles at various CDs, (e) comparison of Csp at various CDs, and (f) the Ragone plot.

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cycles is associated with the activation of the electrode material due to

the gradual penetration of the electrolyte ions into the pores of the
electrode material. After 15,000 cycles, the initial Cs of 101C/g (at 10 A/
g CD) was enhanced to 104.2 C/g, indicating a ~103.2 % capacity
retention. Moreover, the coulombic efficiency has also not significantly
deteriorated and remained almost constant during the cycling, indi-
cating the excellent cycle-life of the composite. Notably, the composite
electrode exhibited higher cycling stability than a series of Sn-based
electrodes like SnO2/Co3O4/N-doped graphene oxide (95.4 % after
10,000 cycles) [11], SnO2/CoFe2O4/Fe3O4 (96 % after 5000 cycles)
[51], Co3O4/SnO/SnO2 (91.5 % after 2000 cycles) [52], Sn/SnO2/car-
bon (100 % after 5000 cycles) [53], SnO2/WO3/graphene (85.75 % after
1000 cycles) [54], and CoSnO3/ZnSnO3/rGO (85 % after 1100 cycles)
[55]. The boosted cycling stability of the CSO-rGO composite can be
attributed to its porous network structure. On the other hand, the steady
increment in charge storage over cycling can be ascribed to the gradual
activation of the composite electrode and the electrochemical recon-
struction [56,57].
To explore the possibility of practical application, an AHSC was Fig. 7. Cycling stability of CSO-rGO//rGO AHSC over 10,000 cycles (inset
fabricated using CSO-rGO nanocomposite as the positive and rGO demonstrates the comparison of the cycling stability of CSO-rGO//rGO AHSC
nanosheets (MW-synthesized) as the negative electrode. A schematic of with other reported rGO-based SC devices. Comparison data sources are pro-
the AHSC along with the electrolyte ions (electrolyte - 3 M KOH) is vided in Table S2).
shown in Fig. 6(a). The voltage of the device was chosen to be 1.5 V,
based on the potential limits of positive and negative electrodes. The CV 2. Apart from serving as a suitable template for the growth of MO NPs,
profiles of both electrodes at the SR of 20 mV/s are shown in Fig. 6(b) to rGO also enhanced the electrochemical performance through pseu-
justify the selection of the optimal voltage limit. It is important to note docapacitive contribution. Furthermore, the formation of wrinkled
that, the CV profile of rGO nanosheets displays a pseudocapacitive na- graphene is found to be beneficial for improving the cycling stability
ture, because of the presence of oxygen functionalities, as described of the composite and the corresponding SC device.
earlier. The CV curves at different SRs for the device indicate the 3. The 3D network structure of the composite is advantageous for fast
pseudocapacitive characteristics (Fig. 6(c)). Similar to that of the CSO- redox kinetics through the easy transport of electrons and ions.
rGO nanocomposite, the corresponding device also displayed the pres- 4. The mesoporous nature of the composite accelerated the charge
ence of distinguished redox pairs at a high SR of 200 mV/s. A similar transport during the electrochemical test.
trend has also been observed for the GCD profiles at various CDs (Fig. 6
(d)). The device exhibited a maximum Csp of 87 F/g at the CD of 1 A/g. Overall, the promising electrochemical performance of an “all-MW
Furthermore, at a high CD of 10 A/g, it still achieved a Csp of 32.6 F/g, synthesized AHSC device” demonstrates the significant impact of MW-
indicating moderate rate capability (Fig. 6(e)). assisted synthetic approaches in SC technology.
For energy storage devices, energy density (ED) and power density
(PD) are crucial parameters, which determine their efficiency towards 4. Conclusion
commercialization. The ED and PD of the fabricated AHSC are compared
with other reported asymmetric devices and the corresponding Ragone A ternary Co3O4/SnO2/rGO (CSO-rGO) nanocomposite was succes-
plot is shown in Fig. 6(f). The MW-synthesized CSO-rGO//rGO AASC sively synthesized by microwave irradiation through the conversion of
device displayed a maximum ED of 27 Wh/Kg at the corresponding PD hydrothermally synthesized CoSn(OH)6 with the help of GO nanosheets
of 751.7 W/kg. Moreover, at a high PD of 7484.7 W/kg, the device still as the MW susceptor. The synthesized mesoporous nanocomposite dis-
maintained a moderate ED of 10 Wh/kg. Notably, the device exhibited played promising electrochemical performance in terms of good specific
superior ED than several reported asymmetric devices like ZnO/gra- capacity, enhanced cycle life, and low ESR as the positive electrode for
phene//AC (13.4 Wh/kg) [58], RuO2/TiO2//AC (12.5 Wh/kg) [59], SCs. Furthermore, the corresponding “all-MW synthesized aqueous SC
NiCo2O4/NiO//Fe2O3 (19 Wh/kg) [60], Co Mn LDH//AC (4.4 Wh/kg) device” demonstrated excellent cycling stability over a long-term cycle
[61], Ni–Co Oxide//AC (12 Wh/kg) [62], rGO/Co3O4//AC (20 Wh/kg) life of 10,000 cycles, indicating a good commercial perspective of the
[63], Zn/Co oxide/GO//AC (18.7 Wh/kg) [64], Ni-Co-S//AC (22.6 Wh/ adopted synthetic protocol. In particular, this ultrafast synthetic
kg) [65], NiCoP/rGO//AC (21 Wh/kg) [66], Fe2O3/rGO//Co3O4/rGO approach can be extended for quick conversion of other Sn-based mixed
(21.6 Wh/kg) [67]. metal hydroxides to the corresponding oxide for SC applications.
The cycling stability test of the device was performed by continuing Therefore, the adopted efficient methodology demonstrates a significant
the GCD cycle 10,000 times at the CD of 5 A/g. The device exhibited impact on the fabrication of advanced electrode materials for next-
higher capacitance retention of 102.4 % over such a long cycle run, generation SCs.
indicating a promising impact of the device in energy storage technology
(Fig. 7). Moreover, the coulombic efficiency also remained constant or CRediT authorship contribution statement
slightly enhanced after cycling signifies long cycle life of the device. It is
noteworthy to mention that, the device displayed superior cycling sta- Sumanta Sahoo: Writing – review & editing, Writing – original
bility than a series of rGO-based devices, as shown in the inset of Fig. 7. draft, Methodology, Formal analysis, Conceptualization. Ahamed Mil-
The corresponding comparison table is also included in the Supporting ton: Validation, Methodology, Formal analysis. Ankur Sood: Writing –
information section (Table S2). review & editing, Writing – original draft, Validation, Formal analysis.
The superior electrochemical performance of CSO-rGO nano- Rajesh Kumar: Writing – review & editing, Writing – original draft,
composite can be accredited to the following factors – Validation. Soonmo Choi: Formal analysis, Investigation. Chandan
Kumar Maity: Writing – review & editing, Writing – original draft, Data
1. The enhanced theoretical capacitance and pseudocapacitive nature curation. Sung Soo Han: Writing – review & editing, Supervision,
of the MOs improved the Cs of the composite. Funding acquisition.

9
S. Sahoo et al. Journal of Energy Storage 99 (2024) 113321

Declaration of competing interest hybrid high energy density supercapacitors, Diamond Relat. Mater. 136 (2023)
110076.
[15] R. Kumar, S. Sahoo, W.K. Tan, G. Kawamura, A. Matsuda, K.K. Kar, Microwave-
The authors declare that they have no known competing financial assisted thin reduced graphene oxide-cobalt oxide nanoparticles as hybrids for
interests or personal relationships that could have appeared to influence electrode materials in supercapacitor, Journal of Energy Storage 40 (2021)
the work reported in this paper. 102724.
[16] M. Yang, K.G. Lee, S.J. Lee, S.B. Lee, Y.-K. Han, B.G. Choi, Three-dimensional
expanded graphene–metal oxide film via solid-state microwave irradiation for
Data availability aqueous asymmetric supercapacitors, ACS Appl. Mater. Interfaces 7 (40) (2015)
22364–22371.
[17] R. Kumar, S. Sahoo, E. Joanni, R.K. Singh, K.K. Kar, Microwave as a tool for
Data will be made available on request. synthesis of carbon-based electrodes for energy storage, ACS Appl. Mater.
Interfaces 14 (18) (2021) 20306–20325.
Acknowledgment [18] Y. Ma, P. Liu, Q. Xie, C. Zhang, L. Wang, D.-L. Peng, Intrinsic performance
regulation in hierarchically porous Co3O4 microrods towards high-rate lithium ion
battery anode, Materials Today Energy 16 (2020) 100383.
The authors are thankful to the National Research Foundation of [19] P. Deng, J. Yang, S. Li, T.-E. Fan, H.-H. Wu, Y. Mou, H. Huang, Q. Zhang, D.-
Korea (NRF) (Grant No. 2021R1I1A3059994, and Grant No. L. Peng, B. Qu, High initial reversible capacity and long life of ternary SnO2-Co-
carbon nanocomposite anodes for lithium-ion batteries, Nano-Micro Letters 11
2020R1A6A1A03044512), and Korea Basic Science Institute (National (2019) 1–13.
Research Facilities and Equipment Center) grant by Ministry of Educa- [20] J. Huang, Y. Ma, Q. Xie, H. Zheng, J. Yang, L. Wang, D.L. Peng, 3D graphene
tion (2019R1A6C1010046, and 2022R1I1A1A01071419) for their sup- encapsulated hollow CoSnO3 nanoboxes as a high initial coulombic efficiency and
lithium storage capacity anode, Small 14 (10) (2018) 1703513.
port. R. Kumar acknowledges the financial support under the
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