Journal of Energy Storage 100 (2024) 113754

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Journal of Energy Storage

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Research Papers

Folic acid-assisted in situ solvothermal synthesis of Ni-MOF/MXene

composite for high-performance supercapacitors
Deepali S. Shivade a , Akash N. Kurade a , Rutuja K. Bhosale a , Somnath S. Kundale a ,
Anjali R. Shelake a , Amruta D. Patil a , Pradyumna P. Waifalkar b, Rajanish K. Kamat c,d,
Aviraj M. Teli e,* , Tukaram D. Dongale a,*
a
Computational Electronics and Nanoscience Research Laboratory, School of Nanoscience and Biotechnology, Shivaji University, Kolhapur 416004, India
b
Department of Basic Science and Humanities, Bharati Vidyapeeth (Deemed to be University) College of Engineering, Pune 411043, India
c
Department of Electronics, Shivaji University, Kolhapur 416004, India
d
Dr. Homi Bhabha State University, 15, Madam Cama Road, Mumbai 400032, India
e
Division of Electronics and Electrical Engineering, Dongguk University-Seoul, Seoul 04620, Republic of Korea

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

Keywords: The synthesis of Ni-based metal-organic framework (MOF) and Ti3C2Tx MXene nanosheets is achieved via a
Supercapacitor straightforward solvothermal method, resulting in the formation of Ni-MOF/MXene composite material. This
Metal-organic framework study introduces an innovative strategy that employs the biomolecule folic acid for the solvothermal synthesis of
MXene
Ni-MOF/MXene nanosheets, intending to achieve high-performance supercapacitors. This approach effectively
Solvothermal
Asymmetric supercapacitor
prevents the oxidation and restacking of MXene nanosheets and ensures the uniform dispersion of Ni-MOF on the
surface of MXene nanosheets. The Ni-MOF/MXene composite exhibits an outstanding specific capacitance of
716.19 F/g at 1 A/g current density. Furthermore, an asymmetric supercapacitor device was assembled using
activated carbon and Ni-MOF/MXene composite as negative and positive electrodes, respectively. The asym­
metric device exhibited an impressive energy density of 23.28 Wh/kg at a power density of 2.841 KW/kg, along
with good cyclic stability. These results establish an excellent potential of the Ni-MOF/MXene composite ma­
terial as a candidate for next-generation energy devices.

1. Introduction electrical double-layer capacitors (EDLCs) and pseudocapacitors based

on their charge-storage mechanisms. Carbon-based materials in super­
The recent explosive growth of the electronic sector and the regular capacitor electrodes store energy through the formation of an electric
usage of electronic equipment in daily life have sparked the creation of double layer at the electrode-electrolyte interface, utilizing kinetic po­
clean and sustainable energy storage and conversion technologies. En­ tentials (EDLCs). On the other hand, conducting polymers and de­
ergy storage and conversion is an evolutionary aspect of the emerging rivatives of metal oxides store electrochemical energy through
world. As a result, some electrochemical devices have been employed for reduction-oxidation processes in the presence of potential in
energy conversion and storage applications, including fuel cells, solar pseudocapacitors.
cells, lithium-ion secondary batteries, zinc-ion secondary batteries, and Choosing the appropriate electrode materials for a supercapacitor
supercapacitors. Supercapacitors are gaining prominence as promising device can enhance its performance. Various materials such as metal
energy storage devices due to their high power density, extended cycle oxides, metal hydroxides, metal chalcogenides, and conducting poly­
life, and quick charge-discharge capabilities. These attributes position mers were utilized in the past as electrode materials for supercapacitor
them as potential candidates for enhancing energy storage systems [1]. devices. The appeal of MXene materials to material scientists stems from
The supercapacitor bridges the gap between batteries and capacitors, their diverse structural configurations, extensive surface chemistry, and
offering higher energy density than capacitors and greater power den­ intriguing physicochemical characteristics. MXene belongs to the cate­
sity than batteries. Typically, supercapacitors are categorized into gory of two-dimensional (2D) materials, encompassing transitional-

* Corresponding authors.
E-mail addresses: avteli.teli@gmail.com (A.M. Teli), tdd.snst@unishivaji.ac.in (T.D. Dongale).

https://doi.org/10.1016/j.est.2024.113754
Received 2 February 2024; Received in revised form 27 July 2024; Accepted 8 September 2024
Available online 11 September 2024
2352-152X/© 2024 Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
D.S. Shivade et al. Journal of Energy Storage 100 (2024) 113754

metal carbides, nitrides, and carbonitrides. With a 2D morphology, combination of MXene and Ni-MOF widens the potential window in
MXene exhibits a substantial surface area, good electrical conductivity, which the supercapacitor can operate, expanding the range of applica­
excellent redox activity, and adjustable physicochemical properties tions in energy storage.
achievable by modifying the interlayer spacing. MXenes found appli­
cations in electrocatalysts, batteries, and supercapacitors [2,3]. 2. Experimental section
Recently, an extensive amount of research work has been conducted
on Metal-organic frameworks (MOFs) due to their excellent porous 2.1. Chemicals
structure, high surface area, and well-organized frameworks with
interconnected metallic nodes and organic ligands [4–7]. Ni-MOF is All the chemicals used to prepare the Ni-MOF/MXene composite
mostly suitable for supercapacitor applications. Typically, Ni-MOF can were an analytical grade and used without further purification. Ti3AlC2
be synthesized with different organic linkers such as 4,4′-biphenyldi­ powder (≥90 % purity) and folic acid were purchased from Sigma
carboxylic acid (BPDC) [8], benzenedicarboxylic acid (BDC) [9], p- Aldrich. Hydrofluoric acid (≥90 %) was purchased from Thomas Baker.
phthalic acid [10], Trimeric acid [11], etc. The MOF introduced by Ni(NO3).6H2O (≥99 %), N, N-dimethylformamide (DMF), and N-
Yaghi and colleagues in 1995, is a category of porous materials char­ methyl-2-pyrrolidone (NMP) and ethanol (≥99.7 %) were all obtained
acterized by strong coordination connections between metal ions and from SRL.
organic ligands [12]. The MOFs exhibit unique properties, making them
suitable for diverse applications such as sensing [13], biomedicine [14], 2.2. Synthesis procedure
memory storage devices [15], and energy storage devices [16]. Notably,
their high surface area, controllable structure, and abundant pseudo­ 2.2.1. Synthesis of Ni-MOF
capacitive redox center positions make them potential electrode mate­ The Ni-MOF was synthesized according to the previous report [29].
rials for supercapacitors (SCs) [17]. Despite being generally weak 30 mL DMF was ultra-sonicated for 30 min with 3 mM Ni (NO3).6H2O
electrical conductors, the direct use of MOFs as supercapacitor electrode and 0.5 mM Folic acid and thereafter, continuously stirred for 20 min.
materials remains relatively uncommon [18]. To address the challenge The mixture solution was transferred into a 50 mL Teflon-lined stainless
of low conductivity in MOFs, a potential solution involves creating still autoclave and placed in a furnace at 150 ◦ C for 12 h. Subsequently,
composites with advanced 2D materials such as graphene, layered allow the autoclave to cool naturally to room temperature. The obtained
double hydroxides (LDHs) [19], MXene [20], and 2D chalcogenides brownish-colored resultant residue was washed by centrifugation with
[21]. The MOF/MXene composite is considered a good material for ethanol and DMF several times and dried in a vacuum oven at 80 ◦ C for
photocatalytic, electrocatalytic, and energy storage and conversion de­ 12 h, and obtained product was called Ni-MOF.
vices [22].
A variety of synthetic approaches can be used to synthesize Ni-MOF/ 2.2.2. Synthesis of MXene
MXene composite and its derivatives. Some techniques are MXene- At the outset, 1 g of Ti3AlC2 powder was immersed in a 50 mL so­
derived MOF hybrids (MXene/Ni-MOF), in situ synthesis of MOF/ lution of 40 % hydrofluoric acid (HF) at 50 ◦ C and stirred for 24 h to
MXene hybrids, a simple mixing approach that uses both MOFs and facilitate the removal of the Al layers [30,31]. Afterward, the solid
MXene nanosheets to generate hybrid MOFs/MXene, and MOF or MXene residue was washed with deionized water and then centrifuged at 8000
self-sacrificial templates to form MOF/MXene derivatives [14,23,24]. rpm several times until the pH of the supernatant was above 6, and then
Among these techniques, we have used in situ synthesis of MOF/MXene the wet sediments were subjected to vacuum freeze-drying at 80 ◦ C for
hybrids by simple solvothermal method. The most significant aspects of 12 h to obtain the dry Ti3C2Tx powder.
the in-situ synthesis technique are the ease of synthesizing hetero/
nanostructures, the preservation of structural properties in individual 2.2.3. Synthesis of Ni-MOF/MXene composite
components, and the enhancement of the stability of MOFs. For the synthesis of Ni-MOF/MXene composite, 0.05 g of Ti3C2Tx in
This research focuses on the synthesis of electrodes based on Ni-MOF 30 mL of DMF was ultra-sonicated for 30 min. After that, 3 mM of Ni
and MXene without the use of binders, employing a solvothermal (NO3).6H2O and 0.5 mM Folic acid were added with 20 min of contin­
method. Taking a step further, a composite electrode, Ni-MOF/MXene is uous stirring. A similar solvothermal synthesis procedure and parame­
developed by incorporating the biomolecule folic acid as an organic ters were utilized to synthesize of Ni-MOF/MXene composite. The
bridge. Folic acid, abundant in common foods like carrots and spinach, typical synthesis process of Ni-MOF/MXene composite is shown in
serves to effectively prevent the oxidation and restacking of MXene Fig. 1.
nanosheets during the preparation process. The intercalation of MOFs
between MXene nanosheets eliminates the restacking of sheets. The 2.3. Material characterizations
strong interaction between the organic ligands of Ni-MOF and surface
functional groups of MXene plays a key role in reducing surface func­ The structural analysis was studied by X-ray diffraction (XRD)
tional exposure of MXene, mitigating the oxidation of MXene, and technique using Bruker D8 instrument (Germany). Fourier-transform
increasing its layer spacing, overall facilitating the rapid ion transport infrared (FTIR) spectroscopy was utilized to detect functional groups
[25,26]. MXene derived from layered transition metal carbides or ni­ present in materials using ALPHA Bruker (Germany). The morphological
trides, demonstrates exceptional electrical conductivity, facilitating and elemental compositions of the synthesized samples were investi­
efficient electron transport within the electrode material. This property gated using a field emission scanning electron microscope (FESEM, SU-
is crucial for enabling rapid charge and discharge processes, making it 70, HITACHI Ltd. Japan). The surface oxidation states of the material
highly suitable for energy storage applications [27]. Additionally, Ni- were confirmed using an X-ray photoelectron spectroscopy technique
MOF exhibits a porous structure with a high surface area. The metal (XPS, K-alpha, Thermo Scientific, UK). The electrochemical measure­
centers in Ni-MOF display redox activity, allowing for supplementary ments were carried out using three and two-electrode-based electro­
charge storage through faradaic reactions [28]. This characteristic chemical workstations (VSP and battery cycler-BCS 815, BioLogic,
provides numerous active sites for the adsorption and desorption of France).
electrolyte ions, thereby enhancing overall energy storage capacity. The Electrochemical properties were investigated in detail with cyclic
synergy of MXene and Ni-MOF in a composite electrode maximizes the voltammetry (CV), Galvanostatic charge-discharge (GCD), and electro­
advantages of both materials. MXene contributes high electrical con­ chemical impedance spectroscopy (EIS) techniques in three and two-
ductivity, while Ni-MOF adds a porous structure, resulting in a com­ electrode configurations. For the three-electrode system, a synthesized
posite electrode with improved overall performance. Furthermore, the electrode, platinum helical coil, and Ag/AgCl were used as working,

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D.S. Shivade et al. Journal of Energy Storage 100 (2024) 113754

Fig. 1. Schematic of solvothermal synthesis of Ni-MOF/MXene composite.

counter, and reference electrodes, respectively. These measurements NMP. The prepared slurry was coated on a pre-weighted current col­
were undertaken in 1 M KOH as an aqueous electrolyte. The working lector (Ni foam) of area 1 × 1 cm2. The electrodes were vacuum dried at
electrode was fabricated by making a slurry of active material (80 wt%), 150 ◦ C for 12 h and further active masses were calculated (1–1.5 mg).
carbon black (10 wt%), and polyvinyl difluoride (PVDF) (10 wt%) in Before electrochemical measurements, the working electrodes were

Fig. 2. (a) XRD pattern of synthesized Ni-MOF, MXene, and Ni-MOF/MXene composite. (b) FTIR spectra of synthesized Ni-MOF, MXene, and Ni-MOF/MXene
composite. (c) XPS survey spectra of Ni-MOF/MXene composite.

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D.S. Shivade et al. Journal of Energy Storage 100 (2024) 113754

activated by the CV technique (50 cycles) at 100 mV/s.

The electrochemical performances such as specific capacitance (Csp),
energy density (E), and power density (P) of fabricated electrodes (Ni-
MOF, MXene, and Ni-MOF/MXene composite) were evaluated from GCD
curves using the following equations [32].
I × dt
Cs = (1)
m × dV

1
E= CV 2 (2)
2 × 3.6

E
P= (3)
dT × 3600

where I is current (A), dT is the discharging time (s), m is the mass of the
active material (g) and dV is a potential window (V).

3. Results and discussion

Fig. 2(a) shows the XRD patterns of Ni-MOF, MXene, and Ni-MOF/
MXene composite measured at an angle of 2θ between 5◦ to 90◦ . From
the XRD pattern, it is observed that diffraction peaks located at 12.98◦ Fig. 3. XPS core level spectra of the Ni-MOF/MXene composite showing (a) Ni
(010), 36.32◦ (111), 44.34◦ (111), 51.65◦ (200) and 59.42◦ (110) are in 2p, (b) Ti 2p, (c) O 1s, and (d) C 1s.
good agreement with the Ni and NiO lattice planes (JCPDS card number
65-2865), confirms the formation of Ni-MOF [25,33–35]. The XRD Ti 2p was deconvoluted into four peaks at a binding energy of 454.9 eV,
pattern of MXene shows diffraction peaks at 9.30◦ , 17.97◦ , 27.47◦ and 456.8 eV, 458.9 eV, and 462.5 eV for Ti–C, Ti2+, Ti3+, and TiO2,
60.71◦ with hkl planes of (002), (006), (008), and (110), respectively, respectively. The presence of Ti peaks at respective binding energies is
confirming the formation of MXene phase after etching of MAX in HF the characteristic of Ti–C structure due to MXene in composite samples
[36–38]. Through comparison, it can be found that Ni-MOF/MXene [51,52]. Additionally, Fig. 3(c) presents the O 1s core level spectrum,
composite shows diffraction peaks at 6.79◦ , 20.2◦ , 27.06◦ , 34.9◦ , and which was deconvoluted into four sub-peaks. These peaks correspond to
60.9◦ with hkl planes of (002), (006), (008), (011), and (110), corre­ surface oxidation, including Ti-O2-X (529.9 eV), Ni–O (529.6 eV),
sponding to MXene and peaks at 12◦ , 42.3◦ , 52.9◦ 2θ values corre­ adsorbed water Ni-O-Ti (530.8 eV), and C-Ti-Ox (531.6 eV). The results
sponding to (010), (111), (200) lattice planes of Ni-MOF. In the Ni-MOF/ from Ti 2p and O 1s suggest that Ti3C2Tx is partially oxidized to TiO2 due
MXene composite, the peak at 9.3◦ in MXene undergoes a shift to 6.7◦ to the presence of more defects and a larger exposed surface of the
(002) at a lower angle. This shift suggests the presence of MXene nanosheets. However, no discernible peaks related to TiO2 are evident in
nanosheets in the composite [20,39–41]. the XRD pattern of the Ni-MOF/MXene sample. Furthermore, the high-
FTIR analysis was conducted to further clarify the presence of resolution spectra of C 1s were analyzed and depicted in Fig. 3(d). The C
functional groups within the synthesized materials. Fig. 2(b) demon­ 1s peak is fitted with three peaks at binding energies of 280.4 eV, 283.5
strates the stretching vibrations of Ti–O, C–F, C–H, -OH, and -COOH eV, and 285.9 eV, corresponding to Ti–C, C–C, and C–O, respectively
groups in the Ni-MOF, MXene, and Ni-MOF/MXene composite. From [10,53]. These findings confirm the formation of the Ni-MOF/MXene
Fig. 2(b), the characteristic peaks of Ti3C2Tx are observed at 553, 1199, composite phase.
1454, 2858, 2932, and 3449 cm− 1. The presence of a peak at 553 cm− 1 is The specific surface area and pore size distribution of the as-prepared
probably due to the deformation vibration of the Ti–C bond [42]. The Ni-MOF were analyzed using the Brunauer-Emmet-Teller (BET) tech­
stretching vibration of the C–F bond is attributed to the peak at 1199 nique. Fig. S1(a) shows the N2 adsorption-desorption isotherm used to
cm− 1, which is compatible with previous research [43]. Additionally, evaluate the specific surface area, while the pore diameter was esti­
the peaks at 2858 and 2923 cm− 1 are attributed to symmetric and mated based on the Barrett-Joyner-Halenda (BJH) plot, as shown in
asymmetric stretching vibrations of C–H bonds [11]. The well-defined Fig. S2(b). Fig. S1(a) exhibits a typical type IV isotherm with a type-H3
peak at 1454 and 3400 cm− 1 is associated with the stretching vibration hysteresis loop, indicating a mesoporous structure. Our synthesized Ni-
of the strongly bonded –OH group from water molecules [44]. Folic acid MOF sample demonstrates a large specific surface area of 131.77 m2/g,
depicts characteristic peaks at 1606 and 1632 cm− 1, corresponding to while the peak point of the BJH plot indicates that the majority of pores
the -COOH group and the benzene ring of Folic acid respectively. The have a diameter of about 4.44 nm. Additionally, we measured the
absorption around 479 cm− 1 can be attributed due to Ni–O bending conductivity of MXene, which was found to be 1.49 mS/cm. From these
vibration in Ni-MOF [45,46]. These results confirm the formation of Ni- observations, we can confirm that the Ni-MOF has good surface area and
MOF, MXene, and Ni-MOF/MXene composite [47,48]. porosity, while the MXene exhibits good electrical conductivity [41,54].
The surface electronic valence states and elemental composition of The porous nanostructure of Ni-MOF enhances electrolytic access and
the optimized Ni-MOF/MXene sample were analyzed using XPS anal­ exposure of active sites to the electrolyte. On the other hand, MXene’s
ysis. In Fig. 2(c), survey scan spectra reveal the major elements, high electrical conductivity provides effective electron transport path­
including Ti, Ni, C, and O, consistent with elemental mapping that ways from active materials to the current collector [55,56]. Given these
confirms the formation of the Ni-MOF/MXene composite phase. Further facts, the synergistic effect of Ni-MOF and MXene helps the composite
details are presented in Fig. 3(a), which displays a high-resolution material demonstrate excellent supercapacitor properties.
spectrum of Ni 2p for the composite materials belonging to Ni-MOF. The surface morphology and elemental composition of Ni-MOF,
This spectrum was deconvoluted into four peaks, with two peaks hav­ MXene, and the Ni-MOF/MXene composite were characterized
ing binding energies at 854.8 eV and 872.4 eV corresponding to Ni 2p3/2 through FE-SEM with EDS, as illustrated in Figs. 4 and 5. The FESEM
and Ni 2p1/2, respectively, along with two satellite peaks at 860.2 eV and images of Ni-MOF, MXene, and the Ni-MOF/MXene composite are pre­
878.8 eV. These binding energy peaks are consistent with existing re­ sented in Fig. 4. Ni-MOF exhibits a nanogranular morphology with an
ported values [49,50]. As shown in Fig. 3(b), the core level spectrum of average diameter of approximately ~100 nm, as depicted in Fig. 4(a1-

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D.S. Shivade et al. Journal of Energy Storage 100 (2024) 113754

Fig. 4. FESEM images of (a1-a2) Ni-MOF, (b1-b2) MXene, and (c1-c2) Ni-MOF/MXene composite, respectively.

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D.S. Shivade et al. Journal of Energy Storage 100 (2024) 113754

Fig. 5. Energy-dispersive X-ray analysis (EDS) of (a) Ni-MOF, (b) MXene, and (c) Ni-MOF/MXene composite, respectively. The inset represents observed elements
and respective Wt%. (d-g) Elemental mapping images of Ni-MOF/MXene composite.

a2). The FESEM image of MXene, presented in Fig. 4(b1-b2), illustrates Furthermore, an elemental mapping indicates the even distribution of
the exfoliation of the MAX phase (Ti3AlC2) and the successful formation Ti, Ni, O, and C elements across the surface of the Ni-MOF/MXene
of MXene with stacked nanosheets. A tiny amount of TiO2 particles are composite, as depicted in Fig. 5(d-g). Similarly, the elemental map­
formed on MXene surfaces due to the surface functional groups (-OH, ping of the Ni-MOF and MXene samples showcases a uniform distribu­
–O) and subsequent alkalization-calcination treatment which promotes tion of elements in a sample (Fig. S2). This observation highlights a
the Ti oxidation process [57]. Additionally, the FESEM image of the Ni- homogeneous coverage of Ni-MOF nanogranules on MXene nanosheets.
MOF/MXene composite is presented in Fig. 4(c1-c2). The FESEM images On the one hand, an absence of an F-element might result in a significant
shown in Fig. 4(c1-c2) indicate that nanograins of Ni-MOF were formed improvement in conductivity [59,60].
between and on the sides of the stacked MXene nanosheets. This for­ The electrochemical performance of Ni-MOF, MXene, and the Ni-
mation of nanograins within the stacked nanosheets mitigates the MOF/MXene composite electrodes was assessed in a three-electrode
agglomeration of MXene sheets, facilitating the complete utilization of system using a 1 M KOH aqueous electrolyte. To comprehensively
the formed nanosheets in an intercalation-type charge storage mecha­ evaluate the electrochemical capabilities of the fabricated electrodes for
nism. Furthermore, the generation of nanograins between and on the supercapacitor applications, systematic tests including cyclic voltam­
sides of nanosheets enhances the electrode/electrolyte interface, metry (CV), galvanostatic charge-discharge (GCD), and electrochemical
thereby contributing to an improved charge storage activity [58]. impedance spectroscopy (EIS) were conducted. CV measurements of the
The EDS elemental analysis and mapping provide insights into the electrodes were carried out in the respective electrolyte to comprehend
quantitative presence (expressed in weight percentage) and spatial dis­ the redox (reduction-oxidation) behavior, and charge storage mecha­
tribution of elements within a given sample. Fig. 5(a-c) illustrates the nism, and to define the operating potential in electrochemistry. In Fig. 6
EDS elemental analysis, depicting the elemental weight percentages of (a), the CV curves of Ni-MOF, MXene, and Ni-MOF/MXene electrodes
Ni-MOF, MXene, and Ni-MOF/MXene composite, respectively. are depicted, measured at a scan rate of 5 mV/s within a potential range

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D.S. Shivade et al. Journal of Energy Storage 100 (2024) 113754

Fig. 6. (a) CV curves of the Ni-MOF, MXene, and Ni-MOF/MXene composite electrode at a scan rate of 5 mV/s. (b) CV curves of Ni-MOF/MXene composite at a scan
rate of 5 to 100 mV/s. (c) The plot of peak current vs. scan rate of the Ni-MOF/MXene composite electrode. (d) GCD curves Ni-MOF, MXene, and Ni-MOF/MXene
composite electrodes at a current density of 1 A/g.

of 0 to 0.5 V Vs. Ag/AgCl. Notably, the area under the CV curve of the Ni- battery-type capacitive behavior, aligning well with the CV results.
MOF/MXene composite electrode surpasses that of individual MXene Notably, Fig. S4(c-d), exhibits the discharging curve of Ni-MOF/MXene
and Ni-MOF electrodes. This enhancement is attributed to the syner­ extends longer than those of MXene and Ni-MOF electrodes.
gistic effects of both Ni-MOF and MXene electrodes. The MOF contrib­ Specific capacitance, energy density, and power density for all
utes to structural stability and benefits from its porous nature for ion electrodes were calculated using Eqs. (1) to (3) from the GCD curves.
storage, while MXene enhances the electrical conductivity of the com­ From the electrochemical performance, it is evident that the Ni-MOF/
posite electrodes. Fig. S3(a-c) indicates the absence of distinct redox MXene composite electrode demonstrates a specific capacitance of
peaks for MXene when compared to Ni-MOF and Ni-MOF/MXene elec­ 716.19 F/g, surpassing that of MXene (212.50 F/g) and Ni-MOF (316 F/
trodes. The reduction and oxidation peaks observed in the CV curve for g) at an applied current density of 1 A/g. The heightened specific
the Ni-MOF electrode are due to the reversible redox reactions involving capacitance of the composite electrode can be attributed to the syner­
nickel ions (Ni2+/Ni3+) within the MOF structure. As the potential is gistic effects of the porous Ni-MOF structure and the conductivity of the
swept during CV, the nickel ions undergo oxidation and reduction, MXene phase. This combination results in an overall enhancement in
resulting in these characteristic peaks [61]. Notably, two peaks are electrode performance. MXene plays a pivotal role in facilitating effi­
readily observed for the reduction and oxidation processes of the Ni- cient charge transport within the electrode, contributing to superior
MOF electrode. The reduction peaks are identified at 0.32 V and 0.35 electrochemical performance. Additionally, MOFs typically possess
V, while the oxidation peak is observed at 0.45 V. In the case of the Ni- porous structures with large surface areas, and MXene, derived from
MOF/MXene composite electrode, a slight shift in a reduction potential layered transition metal carbides or nitrides, also offers a high electro­
from 0.35 V to 0.37 V compared to the Ni-MOF electrode is attributed to chemically active surface area. These features provide more active sites
the presence of the MXene phase [62]. for charge storage, contributing to an increased capacitance.
To gain deeper insights into an electrochemistry occurring at the Furthermore, the galvanostatic charge-discharge (GCD) curves of Ni-
electrode-electrolyte interfaces, CV measurements were conducted at MOF/MXene composite electrodes were meticulously recorded across
various scan rates (5 mV/s to 100 mV/s), as shown in Fig. 6(b) and various current densities, as shown in Fig. 7(a). The calculated specific
Fig. S4(a-b). These measurements confirm the consistent shape of the CV capacitance of the Ni-MOF/MXene composite demonstrated values such
curve even at high scan rates, and the absence of additional peaks in­ as 716.19, 606.47, 562.58, and 560.78 at 1, 2, 3, and 4 A/g respectively,
dicates the absence of side reactions [63]. Furthermore, Fig. 6(c) illus­ revealing the electrode’s extraordinary performance. This exceptional
trates the linearity of peak current versus scan rate, confirming the supercapacitive behavior can be attributed to the nanosheet-like
excellent reversibility of the Ni-MOF/MXene electrode even under high morphology, providing an abundance of electroactive sites for Faradic
scan rates (5–100 mV/s). To assess the electrochemical performance of redox reactions, coupled with the improved electrical conductivity
the prepared electrodes for supercapacitor applications, galvanostatic resulting from exfoliated MXene. The specific capacitances, derived
charge-discharge (GCD) curves were measured at a specific current. As from diverse current densities are illustrated in Fig. 7(b) for Ni-MOF,
depicted in Fig. 6(d), the GCD curves of Ni-MOF, MXene, and Ni-MOF/ MXene, and Ni-MOF/MXene composite electrodes. Notably, the Ni-
MXene electrodes were investigated at a current density of 1 A/g within MOF/MXene composite electrode showcases an impressive rate capa­
a potential range of 0 to 0.4 V vs. Ag/AgCl. The GCD curves exhibit bility, recording percentages of 84.61 %, 78.47 %, and 78.33 % at

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D.S. Shivade et al. Journal of Energy Storage 100 (2024) 113754

Fig. 7. (a) GCD curves of Ni-MOF/MXene composite electrode at current densities of 1 to 4 A/g. (b) The plot of specific capacitance at different current densities
along with error bars, (c) Nyquist plot of the Ni- MOF, MXene, and Ni-MOF/MXene composite electrode (frequency range: 100 kHz to 0.1 Hz). The fitted circuit is
shown in the inset. (d) Variation of log (i) Vs. log (scan rate) for calculation of the ‘b’ value (power low) of the Ni-MOF/MXene composite electrode.

corresponding current densities ranging from 2 to 4 A/g. This exemplary lower resistance compared to Ni-MOF and MXene. This lower Rct is
rate capability is underpinned by a robust interfacial structure and significant, as it serves as a limiting factor for specific power. The
porous nanostructures, enhancing both the electrical conductivity and reduced Rct values for the Ni-MOF/MXene electrode in supercapacitors
reactivity of the composite electrode. indicate a higher specific power, underscoring its enhanced charge
Electrochemical impedance spectroscopy (EIS) is a powerful tech­ transfer kinetics and superior performance.
nique employed to gain comprehensive insights into the interfacial and To obtain a thorough understanding of an electrochemical reaction
charge transfer kinetic properties of prepared electrode materials. As process, a systematic analysis of charge storage mechanisms in the
illustrated in Fig. 7(c), the Nyquist plot of Ni-MOF, MXene, and Ni-MOF/ prepared Ni-MOF, MXene, and Ni-MOF/MXene electrodes was con­
MXene electrodes were meticulously obtained over a frequency range of ducted. This involved an examination of CV curves at low scan rates
100 kHz to 0.1 Hz in a 1 M aqueous KOH electrolyte at open circuit ranging from 1 to 5 mV/s. The capacitive and redox behaviors of these
potential. For more clarity, the magnified Nyquist plot of the Ni-MOF, electrodes were discerned by applying the power-law relationship as
MXene, and Ni-MOF/MXene composite electrodes is depicted in detailed below [67,68].
Fig. S5. The Nyquist plot reveals distinctive features in different fre­
quency regions. The high-frequency region encompasses the series i = aϑb (4)
resistance (Rs), influenced by the collective impact of electrode resis­
where ‘a’ and ‘b’ are adjustable parameters. This expression captures the
tance, bulk electrolyte resistance, and contact resistance between the
change in current (‘i’) concerning the scan rate (ϑ). The ‘b’ value is
electrode and current collector at higher frequencies. The mid-frequency
indicative of either a diffusion-controlled process (b ≤ 0.5) or capacitive
region is associated with charge transfer resistance (Rct), while the
behavior (b = 1) and is determined by plotting log (current) Vs. log (scan
lower frequency region reflects the diffusion and mass transfer processes
rate). In the case of the Ni-MOF/MXene composite electrode, the b
[64–66]. The values of Rs and Rct were extracted by fitting the data with
values of ~0.6 and 0.7 were observed for the anodic and cathodic peaks,
an equivalent circuit model, and the results for Ni-MOF, MXene, and Ni-
respectively (Fig. 7(d)). This finding implies a synergistic interplay of
MOF/MXene composite are summarized in Table 1. Notably, the Rs
capacitive and diffusion-controlled processes, signifying a substantial
values of Ni-MOF and MXene are found to be lower than that of Ni-MOF/
capacity for charge storage in Ni-MOF/MXene composite electrodes via
MXene composite, possibly due to their porosity and conductivity,
an electron-involved redox reaction.
respectively. In terms of Rct values, Ni-MOF/MXene composite exhibits

Table 1
The equivalent circuit values of Ni-MOF, MXene, Ni-MOF/MXene electrodes, and Ni-MOF/MXene//AC device.
Device Rs Rct Q1 α1 C Q2 α2 R3
(Ω) (Ω) (F/s) (F/s) (F/s) (Ω)

Ni-MOF 0.5621 1.318 0.2778 0.5482 2.517 × 10− 12 – – 49.17

MXene 0.8481 1.082 1.72 × 10− 3 0.6607 – 8.58 × 10− 3
0.7667 –
Ni-MOF/MXene 0.8655 1.204 0.05316 0.4515 1.25 × 10− 3 – – 57.67
Ni-MOF/MXene//AC 0.1854 3.816 5.16 × 10− 3 0.6436 1.396 × 10− 3 – – 1929
After stability 0.192 7.739 1.679 × 10− 3 0.793 0.1029 × 10− 3 – – 387.1

8
D.S. Shivade et al. Journal of Energy Storage 100 (2024) 113754

By Applying the Dunn method, quantitative contributions of capac­ composite served as the positive electrode, while activated carbon
itive and diffusive-controlled processes were computed based on the ‘b’ (AC) functioned as the negative electrode. The CV of activated carbon
value, utilizing the following Eq. (5). was recorded at a scan rate of 100 mV/s in 1 M KOH electrolyte which
indicates the negative active region (Fig. S6). The electrochemical
i(V) = K1 ϑ + K2 ϑ1/2 (5) characteristics of the ASC device were systematically evaluated using
cyclic voltammetry (CV) galvanostatic charge-discharge (GCD), and
where i(V) represents the current response at a specific voltage, ϑ is the
electrochemical impedance spectroscopy (EIS) tests within the frame­
scan rate, K1 ϑ denotes the capacitive contribution (slope), and K2 ϑ1/2
work of a conventional three-electrode system. A schematic represen­
represents the diffusion contribution (y-axis intercept of a straight line).
tation of the ASC device is depicted in Fig. 8(b). The mass ratio between
Fig. 8(a) and Fig. S3(d-e) illustrate the percentages of capacitive and
the positive and negative electrodes was determined in accordance with
redox contributions Vs. scan rate showed that, at 1 mV/s, the diffusive-
the charge balance theory, calculated by a specified Eq. (6).
controlled contributions were approximately 72.9 %, 84.8 %, and 97.84
% for Ni-MOF, MXene, and Ni-MOF/MXene electrodes, respectively. The m+ C− × dV
= + (6)
significantly higher diffusive-controlled contribution observed in the Ni- m− C × dV
MOF/MXene composite electrode, as compared to other samples, sub­
stantiates the notion that redox behavior plays a crucial role in the su­ where m is the mass of an electrode (g), C is a specific capacitance (F/g),
perior performance of the electrode [69,70]. Moreover, an analysis of and dV is a potential window range for the charge-discharge process (V).
the contributions of capacitive and diffusive processes concerning the The optimized ratio mass of positive–negative electrodes is 1:3.
scan rate revealed an augmentation in capacitive contribution with Electrochemical studies were conducted to optimize the voltage
higher scan rates. This observation corresponds to the recognized phe­ window of the ASC device. The curves were analyzed at a constant scan
nomenon wherein Faradaic processes, entailing ion diffusion to and rate of 60 mV/s across various potential ranges to optimize the voltage
from the electrode surface, impose limitations at elevated scan rates. As window, as depicted in Fig. 8(c). It was observed that the stable opti­
a result, the capacitive contribution becomes more prominent [52]. The mized voltage extended up to 1.5 V, beyond which polarization was
Ni-MOF/MXene composite electrode demonstrates a combination of observed [71]. The CV curves of the ASC device were further investi­
capacitive and diffusion-controlled charge storage mechanisms. This gated at different scan rates, as indicated in Fig. 8(d), revealing excellent
indicates that the composite electrode primarily stores charge through a capacitive behavior with distinct redox peaks. This suggests that the
Faradic process, leading to a swift charge transport process in compar­ overall energy storage performance of Ni-MOF/MXene//AC originates
ison to Ni-MOF and MXene individually. from the combined double layer. Moreover, the shape of the CV curves
To assess the practical viability of the Ni-MOF/MXene composite of the ASC device was maintained even at high scan rates, indicating
electrode, we fabricated an asymmetric supercapacitor (ASC) device high-rate capabilities. In Fig. 9(a), the GCD profile of the asymmetric
with dimensions of 3 × 3 cm2. In this setup, the Ni-MOF/MXene supercapacitor (ASC) device is presented, conducted at current densities
of 4, 4.5, 5, and 5.5 A/g, resulting in corresponding specific capacitances

Fig. 8. Capacitive and diffusion-controlled contribution of (a) Ni-MOF/MXene composite electrode as a function of scan rates (1–5 mV/s). (b) Schematic illustration
of the fabrication of Ni-MOF/MXene//AC ASCs device. (c) CV curve recorded at different potential windows ranges from 1.0 to 1.5 V at a scan rate of 60 mV/s. (d) CV
curve of Ni-MOF/MXene//AC ASC device at different scan rates (20–100 mV/s).

9
D.S. Shivade et al. Journal of Energy Storage 100 (2024) 113754

P
o
rw
d
e
(ytisn
k/W
)g

P ower densi ty ( W /k g)
Fig. 9. (a) GCD curves of Ni-MOF/MXene//AC ASC device at various current densities. (b) Nyquist plot of the Ni-MOF/MXene//AC ASCs device (frequency range:
100 kHz to 0.1 Hz). The fitted circuit is shown in the inset. (c) The cyclic stability with capacitance retention of Ni-MOF/MXene composite electrode at a current
density of 5 A/g for 2000 cycles. (d) Regone plot of energy density and power density of the Ni-MOF/MXene//AC ASC device.

of 78.64, 63.09, 54.40, 52.36 F/g, respectively. The Nyquist plot asso­
ciated with the constructed asymmetric supercapacitor (ASC) device
recorded before and after the cyclic stability test to study the electrical
conductivity of the electrode material, was examined within a frequency
range of 105 Hz to 0.1 Hz at open circuit potential, as illustrated in Fig. 9
(b) and Fig. S3(f). The accompanying equivalent circuit, as indicated in
the inset of a figure, is used to investigate a value for Rs and Rct. The
recorded Rs and Rct values of an ASC device, approximately 0.18 Ω, and
3.18 Ω, respectively, signify that a device has been well-fabricated.
The constructed asymmetric supercapacitor (ASC) device underwent
additional cycling performance studies within a voltage range of 0–1.5 V
at a current density of 5 A/g over 2000 GCD cycles. As shown in Fig. 9
(c), the ASC device exhibited a ~20 % loss in initial capacitance after
750 continuous GCD cycles, highlighting its commendable electro­
chemical stability. Notably, the initial rise in the stability curve could be
attributed to the penetration of the electrolyte solution into the interior
of the electrode material, facilitating the involvement of more active
sites in the surface redox reaction for enhanced energy storage [72]. The
decline in the stability performance of the ASC device is linked to
modifications in the nanostructures of MXene/Ni-foam electrodes,
potentially influencing the surface intercalation of electrolytic ions and
storage, thus resulting in a gradual increase in the capacity. The energy Fig. 10. (a-f) Photographs of the LED light by two Ni-MOF/MXene//AC ASC
density and power density relationship of the ASC device is illustrated in devices, connected in series combination.
the Ragone plot, as in Fig. 9(d). The asymmetric device demonstrates a
peak energy density of 23.28 Wh/kg at a power density of 2.841 KW/kg the promise of Ni-MOF/MXene composite as an electrode, combining
and shows an energy density of 16.59 Wh/kg at a maximum power both conductivity and porosity, making it a noteworthy candidate for
density of 4.182 KW/kg. The obtained results of the ASC device are applications in energy storage applications [78,79]. The performance of
comparable to those reported for previously studied asymmetric de­ the present Ni-MOF/MXene composite is compared with previously re­
vices, as indicated in the Ragone plot [8,25,51,72–77]. The practical ported MOF-based supercapacitors (Table S1). The fabricated Ni-MOF/
applicability of the constructed ASC device is validated by integrating it MXene composite demonstrates a capacitance of 716.19 F/g in a 1 M
with a red LED, which is assembled through the series connection of two KOH electrolyte. In contrast, previously reported materials required 2 M
fabricated supercapacitors, as illustrated in Fig. 10(a-f). The device was to 6 M KOH electrolytes to achieve only slightly higher capacitance. This
charged using a 2 V constant voltage supplier over a duration of 120 s. comparison highlights the significance of our fabricated materials for
Subsequently, the luminosity of a red LED was examined at various in­ supercapacitor applications, showcasing their superior performance at
tervals within a timeframe of up to 60 s. The present results underscore lower electrolyte concentrations.

10
D.S. Shivade et al. Journal of Energy Storage 100 (2024) 113754

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