Journal of Energy Storage 98 (2024) 112821

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Journal of Energy Storage

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Research Papers

Two-dimensional layered Ti3C2 MXene nanosheets decked with ZrO2

nanospheres for the high-performance solid-state hybrid supercapacitors
Pradeepa S.S. a , Sutharthani K. a , Suba Devi R. a,* , Yen-Pei Fu b,* , Sivakumar M. a,*
a
120, Energy Materials Lab, Department of Physics, Science Block, Alagappa University, Karaikudi 630003, Tamil Nadu, India
b
Department of Materials Science and Engineering, National Dong Hwa University, Shou-Feng, Hualien 974301, Taiwan

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

Keywords: Two-dimensional (2D) MXenes have developed as promising materials for high-performance supercapacitors
Two-dimensional material owing to their distinctive layered structure, facilitating both high redox surface sites and enhanced ion transport
Titanium carbide kinetics. In our present study, we successfully synthesized titanium carbide‑zirconium oxide nanocomposites
Energy density
(Ti3C2-ZrO2 NC) in a facile and budgetary manner, positioning them as viable materials for electrochemical
Zirconium oxide
supercapacitor applications. The 2D layered Ti3C2 nanosheets in Ti3C2-ZrO2 NC hetrojunction elevated the
Hybrid supercapacitor
charge-carrier separation efficiency by diminishing the insertion distance to reach the surface of the electrode.
Galvanostatic charge-discharge (GCD) profiles showcased the nonlinear behaviour of Ti3C2-ZrO2 NC electrode,
revealing their battery-like charge storage process that delivers exceptional performance with a high specific
capacity of 483.6C/g at 1 A/g of current density along with an impressive capacitive retention of 88.85 % even
after 5000 charge-discharge cycles. The assembled Ti3C2-ZrO2//AC solid-state hybrid supercapacitor (SHSC)
device exhibited notable energy and power densities of 75.60 Wh/kg and 1445 W/kg respectively. These findings
underscore the pivotal role of 2D layered MXene structure in enhancing the conductivity and reaction kinetics
that facilitate exceptional charge storage mechanisms and position them as promising materials for future energy
storage devices.

1. Introduction redox reactions occur on the surface of the working electrodes, while
faradic processes are used to generate charges and an energy storage
The expansion of the world population and growth of the world mechanism. Finally, the hybrid supercapacitors combine both the EDLC
economy are causing serious environmental pollution and energy scar- and pseudocapacitor, in which the charge is stored by surface adsorp-
cities. Energy-saving technologies are the most important to deal with tion/desorption reaction at one electrode and the reversible redox re-
the major issue of energy crisis [1]. To maintain a stable power supply, action happens at another electrode. In general, the structure and
energy harvesters for renewable energy are usually coupled with energy properties of electrode materials have a significant impact on the elec-
storage devices; In this situation, a long cycle life for an energy storage trochemical performance of supercapacitors [4]. One of the most
device is highly desirable. Because of energy storage systems, super- exciting electrode materials is a two-dimensional (2D) material. The
capacitors have received increasing attention as an energy storage and high surface-to-volume ratio of 2D materials facilitates the provision of
power delivery device due to their exceptional energy density levels, extensive active surface area for charge storage through EDLC or rapid
rapid charge-discharge rates, and excellent cycling stability compared to surface redox reaction (i.e., pseudocapacitance) [5].
regular electrochemical capacitors and batteries [2]. Based on their MXenes, one of the most attractive new families of 2D materials,
charge accumulation characteristics, supercapacitors can be categorized which shown great potential for a new generation of high-performance
into three different types. Initially, electric double-layer capacitors supercapacitor electrodes. These MXenes have recently received much
(EDLCs), store charges through physical adsorption and desorption attention due to their unique properties, including surface functional
rather than chemical redox processes which separate charges between groups, virtuous electrical conductivity, high specific surface area, and
the electrolyte and the electrode as a result of the Helmholtz double- hydrophilicity and thereby have wide range of applications viz., catal-
layer effect [3]. Then, pseudocapacitors, in which reversible and rapid ysis, electromagnetic interference protection, water treatment, energy

* Corresponding authors.
E-mail addresses: [email protected] (S.D. R.), [email protected] (Y.-P. Fu), [email protected] (S. M.).

https://doi.org/10.1016/j.est.2024.112821
Received 15 April 2024; Received in revised form 4 June 2024; Accepted 4 July 2024
Available online 24 July 2024
2352-152X/© 2024 Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
P. S.S. et al. Journal of Energy Storage 98 (2024) 112821

storage devices, etc. [6,7]. Mxenes are prepared by etching MAX phases applications, ranging from precise oxygen sensors to cutting-edge fuel
(Mn+1AXn, “A” refers to group III or IV A elements) with selective cells and efficient catalysts, underlining its pivotal role in advanced
removal of the “A” layer by acid etching, which is usually denoted technology and industry. The synergistic interplay between 2D materials
Mn+1XnTx (n = 1, 2, 3, or 4). In which, M is the initial transition metal, X and pure oxide components manifests as a potent mechanism, elevating
is carbon or/and nitrogen, and Tx are surface terminal groups such as = the capacitive performance of the resulting material [15]. This cooper-
O, -OH, –F, and –Cl species [8]. Notably, Ti3C2Tx nanosheets were the ative effect brings about a broader potential window, heightened elec-
first MXene materials formed by etching Al atoms from a Ti3AlC2 MAX trical conductivity, increased availability of active sites, and fortified
precursor. Strong van der Waals interactions between Ti3C2 nanosheets stability. These combined attributes represent a promising avenue for
make interlayer stacking possible, preventing ion access to active sites, enhancing the overall performance and functionality of the prepared
and reducing the accessibility of electrolyte ions [9]. Ti3C2Tx has good material in various electrochemical applications. The distinctive char-
stability and excellent physicochemical properties. Numerous reports acteristics of these materials hold immense significance in the realm of
have been found based on the Ti3C2Tx for supercapacitor applications. electrochemical materials due to their versatile structure. This structure
Recently, Zhao et al. [10] achieved the creation of a Ti3C2 composite facilitates effective contact between the electrode and electrolyte at the
incorporating carbon nanotube (CNT). This composite exhibited an interface, which is the key for electrochemical performance [16]. While
impressive specific capacitance of 350 F/cm3 at 2 mV/s in a 1 M MgSO4 the composite material, Ti3C2-ZrO2, indeed demonstrates superior
solution. Furthermore, Syamsai et al. [11] reported noteworthy findings electrochemical properties, including enhanced capacity, when
in their research, highlighting the process of Ti3C2-based electrodes compared to pure Ti3C2 and ZrO2. It is worthy in acknowledging that the
using HF and simple ball-milling. In their study, these electrodes composite fabrication process can be intricate and time-consuming. This
delivered an exceptional specific capacitance of 450 and 447 F/g at a complexity poses challenges that hinder the widespread adoption of 2D
scan rate of 1 mV/s while using 3 and 6 M KOH electrolyte solution MXene materials for large scale practical applications [17]. Efforts in
respectively. These findings underscore the significance of Ti3C2-based simplifying and scaling up the production processes for such composites,
material in the realm of energy storage and electrochemical applica- are crucial to realize their full potential in various electrochemical and
tions. Conversely, its potential in energy fields is curtailed by several energy storage applications.
limitations. The propensity for spontaneous layer stacking, inherent In the wide MXene family, Ti3C2 stands out as one of the most
drawbacks associated with single-component electrodes, and relatively lightweight members. For this significant property, this research
low theoretical efficiency collectively restrict its broader application in focussed on Ti3C2 MXene as the promising material. The Ti3C2-based
the energy sector [12]. A planned strategy comprises the inclusion of MXene powders were meticulously synthesized through the precise
several pillars in order to increase the electrochemically active surface process of etching aluminum from the Ti3AlC2 MAX phase, setting the
area and elevate the electrochemical potential of Ti3C2Tx. These pillars stage for furtherance in our research endeavours [18]. In this work, we
can encompass a range of materials, together with carbon-based sub- unveil the exceptional electrochemical performance of the solid state
stances, conductive polymers, and, metal oxides all of which serve to hybrid supercapacitor (SHSC) device featuring a ground-breaking
enrich the properties of the MXene layers. This synergistic integration combination of Ti3C2 and ZrO2. This marks the first instance where
holds the promise of unlocking enhanced electrochemical performance Ti3C2-based MXene composite demonstrate superior capabilities in the
and expanding the utility of Ti3C2Tx in various applications. realm of energy storage devices area.
On the other hand, Zirconia (ZrO2) stands out as a coveted material
across diverse industrial domains, owing to its multifaceted attributes 2. Experimental
[13]. These characteristics encompass high density, exceptional hard-
ness, electrical conductivity, remarkable wear resistance, biocompati- 2.1. Materials
bility, robust mechanical strength, and a cost-effective profile [14].
Consequently, Zirconia finds extensive utility in an expansive array of Titanium Aluminum Carbide (Ti3AlC2), Dimethyl sulfoxide (DMSO),

Scheme 1. Schematic illustration for the synthesis procedure of Ti3C2-ZrO2 NC.

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P. S.S. et al. Journal of Energy Storage 98 (2024) 112821

Hydrofluoric acid (HF), Zirconium nitrate (Zr(NO3)4), Urea (CH4N2O), 100 kHz - 0.1 Hz, the internal impedance and diffusion behaviour were
Ammonium fluoride (NH4F), Poly(vinyl alcohol) (PVA), and Potassium analyzed. The specific capacity was calculated from the CV and GCD as
hydroxide (KOH) were purchased from Sigma-Aldrich. All the chemicals ∫
I (V)dV
were used in this investigation without further purification. C1 = (1)
m1 × v

2.2. Preparation of multi-layered MXene (Ti3C2) I × Δt

C2 = (2)
m
10 ml of HF solution (48 wt%) and 1 g of MAX (Ti3AlC2) were mixed
and magnetically stirred at room temperature for 36 h. Multi-layered where, C1 and C2 were the specific capacities (C/g) obtained from CV
∫
MXene was formed via centrifuging after multiple washing with and GCD studies, m1 is the active mass of the electrode, I (V)dV rep-
deionized water and absolute alcohol and then dried in an oven at room resents the integral area (V) obtained from the CV curve, Δt is the gal-
temperature. vanostatic discharge time (s), and v is the scan rate (mV/s).

2.3. MXene exfoliation 2.7. Preparation of PVA-KOH gel electrolyte

0.8 g of multi-layered MXene was stirred in 15 ml of dimethyl sulf- 1 g of PVA was dissolved in 30 ml of DI water with constant stirring
oxide (DMSO) for 18 h in air. The sample was centrifuged to extract and heated at 90 ◦ C for 3 h and then 1 g of KOH pellets were incorpo-
DMSO-intercalated MXene after diluting it with deionized water for five rated into the solution. After 3 h, the clear solution turned into a
minutes at 3500 rpm. After that, ultrasonication was made for 6 h to yellowish gel, signifying the production of gel electrolyte. Then, the
disperse the resulting powder in deionized water. Exfoliated MXene resultant gel was applied to the anode and cathode, and it was allowed to
sheets were obtained by centrifuging MXene at 3500 rpm for one hour solidify partially in view of avoiding spilling.
and dried at room temperature in the oven.
Using the selective etching method, ‘A’ layers etched from the MAX
phase. 2.8. Materials characterization

3 The structure, crystallinity, and phase purity of the as-synthesized

Mn+1 AXn + 3HF→Mn+1 Xn + AF3 + H2 (a)
2 materials were studied by an X-ray diffractometer (XRD, Rigaku D/
Using the above equation (a), we arrive the following equation, Max-II; Japan) with CuKα radiation (=1.54 Å) at 30 kV and 50 mA at
a scanning rate of 3 ◦ C min− 1. A field emission scanning electron mi-
2Ti3 AlC2 + 6HF→2AlF3 + 2Ti3 C2 + 3H2 (b) croscope (JEOL JSM-7000F; Japan) and transmission electron micro-
scopy (Philips Tecnai G2F30) were used to visualize the morphology,
2.4. Synthesis of ZrO2 surface nature, and particle size of the prepared nanoparticles. To
ascertain the chemical composition of the composites, X-ray photo-
0.1 M Zr(NO3)4, 0.3 M CH4N2O, and 0.1 M NH4F were mixed and electron spectroscopy (XPS; VGS Thermo K-Alpha; USA) was used with
dispersed in 30 ml of DI water, all while stirring continuously at room Al K radiation as the excitation source. An electrochemical workstation
temperature. The dispersed solution was then placed in a Teflon-lined (CHI 7273D, USA) was used to perform all the electrochemical
stainless-steel autoclave and heated for 18 h at 180 ◦ C in a muffle measurements.
furnace. Subsequently, the product was washed with ethanol and DI
water, and dried for 3 h at 80 ◦ C in the oven. After that the powder was 3. Results and discussion
calcined at 600 ◦ C for 3 h to get ZrO2 nanoparticles.
3.1. XRD
2.5. Synthesis of Mxene-ZrO2 nanocomposites
The crystal structure and phase identification of the prepared ma-
Ti3C2 and ZrO2 (7:3) mixture was ultrasonicated for 1 h with 50 ml of terial were analyzed by X-ray diffraction from 2θ = 10◦ to 70◦ . The XRD
DI water. The resulting solution was centrifuged for 5 min at 3000 rpm pattern shows a crystalline nature of Ti3AlC2 (hexagonal structure) with
to produce Ti3C2-ZrO2 nanocomposites (Ti3C2-ZrO2 NC) and then dried a desired coordination along the (104) plane and well matched with the
overnight at room temperature. Finally, Ti3C2-ZrO2 NC was obtained JCPDS 52-0875. The prominent peaks appeared at 2θ = 9.05◦ , 18.93◦ ,
and shown in Scheme 1. 33.76◦ , 36.32◦ , 38.49◦ , 41.28◦ , 47.94◦ , 59.97◦ , and 73.71◦ corre-
sponding to the (002), (004), (100), (008), (104), (105), (107), (110),
2.6. Electrochemical characterization and (118) planes, respectively. The peak at 2θ = 8.84◦ , corresponds to
the (002) plane, has migrated towards lower angle after HF etching,
To achieve a thoroughly cleaned surface, 1 M of HCl, ethanol and DI whereas the peak with the highest intensity appeared at 38.49◦ vanished
water were used to a 1 cm × 2 cm piece of nickel foam, which was then completely. This reveals the successful etching of the Al layer from the
vacuum dried at 80 ◦ C for overnight. The active material for the working Ti3AlC2 to form Ti3C2 MXene [19]. The XRD pattern of Ti3C2 MXene is
electrodes was prepared in amounts of 9.6 mg, 1.2 mg of PVdF, and 1.2 well matched with the JCPDS 32-1383 (Cubic), which confirms the
mg of activated carbon. A slurry mixture was created by adding N- formation of the pure phase. Due to the HF etching process, the absence
Methyl-2-pyrrolidone (NMP) dropwise, and the mixture was then coated of plane (104) and the shifting of the Ti3AlC2 peak at 9.05◦ corresponds
on nickel foam having the area 1 × 1 cm2. The mixture was vacuum to the (002) plane is showing a successful HF etching process.
dried at 80 ◦ C for 12 h. Electrochemical characterization was performed Similarly, in case of ZrO2, the diffraction peaks at 2θ = 17.01◦ ,
using platinum wire as the counter electrode and Hg/HgO as reference 23.93◦ , 28◦ , 31.28◦ , 34.04◦ , 35.10◦ , 38.51◦ , 40.61◦ , 44.82◦ , 49.02◦ ,
electrode in three electrode configuration. At various scan rates between 50.06◦ , 53.88◦ , 55.19◦ , 61.63◦ , 62.94◦ , and 65.70◦ can be assigned to
10 and 200 mV/s, cyclic voltammetric measurements were conducted the (001), (110), (− 111), (111), (200), (002), (120), (− 112), (211),
within the working potential range 0–0.6 V. The galvanostatic charge (220), (022), (220), (310), (131), (113), and (222) planes of the
discharge (GCD) were performed at various current densities ranging monoclinic structure, which agreed with the standard JCPDS No: 37-
from 1 to 5 A/g, in the potential window 0 to 0.6 V. Additionally, using 1484 [20]. There are no diffraction peaks of any other crystal phases
Electrochemical Impedance Spectroscopy (EIS) in the frequency range of observed in the prepared samples, indicating that they are pure

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P. S.S. et al. Journal of Energy Storage 98 (2024) 112821

demonstrates the even distribution of Ti, C, Zr, and O components

without impurities.

3.3. HR-TEM and SAED analysis

The structural morphology, particle size, and d-spacing of the as-

prepared Ti3C2-ZrO2 NC were analyzed by HR-TEM analysis. The
typical layered structure of Ti3C2 with ZrO2 nanospheres was shown in
Fig. 3 (a&b) which promotes the intercalation/de-intercalation of ions
between the layers and excellent charge transfer kinetics that facilitates
the sufficient number of electrochemically active sites for the surface
redox reaction and delivers high specific capacitance [25]. Lattice
fringes with different spacing of 0.2, 0.18, and 0.21 nm correspond to
(111) of Ti3C2, (200), and (220) of ZrO2, respectively shown in Fig. 3 (c).
The polycrystalline pattern of Ti3C2-ZrO2 NC is shown by the well-
defined diffraction rings in the selected area electron diffraction
(SAED) pattern, as illustrated in Fig. 3 (d) [26]. The obtained planes of
(111) and (200) can be indexed to the observed rings, which is in good
agreement with the XRD results.

3.4. BET analysis

The surface characteristics of Ti3C2, ZrO2, and Ti3C2-ZrO2 NC were

thoroughly examined using the Brunauer-Emmett-Teller method to
determine their surface area and pore diameter. The type V hysteresis
loop isotherms of the H-3 type could be seen in all of the samples N2
adsorption/desorption isotherms. Notably, the Ti3C2-ZrO2 NC demon-
strated substantial enhancements in adsorption/desorption properties
compared to the other samples, indicating a significantly increased
specific surface area [27]. Specifically, the specific surface areas for
Ti3C2, ZrO2, and Ti3C2-ZrO2 NC were 47.86 m2/g, 20.68 m2/g, and
53.61 m2/g, respectively, as illustrated in Fig. 4 (a). Furthermore, the
pore volume of each sample was calculated by the Barrett-Joyner-
Halenda method. The results indicated pore sizes of 2.37 nm for Ti3C2,
Fig. 1. XRD pattern of Ti3C2, ZrO2 and Ti3C2-ZrO2 NC.
2.71 nm for ZrO2, and 5.64 nm for Ti3C2-ZrO2 NC, as depicted in Fig. 4
(b). These findings underscore the mesoporous nature of these materials,
monoclinic ZrO2 NP. Particularly, the XRD patterns of Ti3C2-ZrO2 NC
facilitating efficient ion penetration through the surface and thereby
show that the co-existence of both Ti3C2 and ZrO2 peaks without any
enhancing the specific capacity, which is of paramount importance for
additional impurities is evidenced in Fig. 1.
their potential supercapacitor applications [28].
From the Debye-Scherrer formula, the average crystallite size can be
evaluated by
3.5. XPS analysis
D = 0.9λ/βcosθ (3)
The surface chemical composition and oxidation states of Ti3C2,
Here, ‘λ’- X-ray wavelength, ‘β’ - Full width at half maximum
ZrO2, and Ti3C2-ZrO2 NC were estimated using XPS. While there is no Al
(FWHM) intensity, and ‘θ’ represents Bragg's angle [21]. The calculated
peak was found in the pure Ti3C2 MXene (Fig. 5 (a)), there are strong C 1
average crystallite sizes of Ti3C2, ZrO2, and Ti3C2-ZrO2 NC were 23, 21,
s, Ti 2p, O 1s, and F 1s peaks were observed which shows the HF acid
and 28 nm respectively.
treatment removes the Al layers, and introducing oxygen and fluorine
[29]. The high-resolution spectrumTi2p in Fig. 5 (b) shows three main
3.2. FE-SEM, EDS spectrum and mapping analysis peaks at 455.1, 458.8 and 464.3 eV correspond to Ti (I, II, and IV), TiO2,
and Ti–O bonds, respectively. The XPS spectrum of C 1s in Ti3C2, as
The SEM images of Ti3C2, ZrO2, and Ti3C2-ZrO2 NC were displayed in illustrated in Fig. 5 (c), shows the major elements of C–O (287.09 eV)
Fig. 2, clearly showing the morphology variation in selectively etched Al and C–C (284.7 eV), while the second is a C–Ti (281.1 eV) bond,
layers from Ti3AlC2 MAX phase using HF solution and Ti3C2 MXene respectively. The deconvolution core-level Zr3d XPS spectra shown in
nanosheets. Using DMSO, the Ti3C2 stacked layers were successfully Fig. 5 (d), reveals two peaks at 182 eV and 184.3 eV that are attributed
exfoliated to form Ti3C2 nanosheets, showed the particle size in the to Zr3d5/2 and Zr3d3/2, respectively [30]. The prominent peak was
range of 4–8 μm was shown in Fig. 2 (a&b) [22]. From Fig. 2(c, d) the observed at 530 eV, indicating the presence of O 1 s in the prepared
morphology of the ZrO2 nanostructure reveals a well-aggregated sphere- nanocomposite which arises due to the existence of ZrO2 as seen in Fig. 5
like morphology with a smooth surface, and the size of the particles was (e).
2–5 μm [23]. Additionally, the Ti3C2-ZrO2 NC SEM image showed that
the Ti3C2 nanosheets wrapped the ZrO2 sphere surface, with particle 3.6. Electrochemical three electrode performances
widths ranging from 3 to 6 μm (Fig. 2(e)). The chemical composition and
purity of Ti3C2-ZrO2 NC were confirmed by EDS analysis to be free of any To investigate the electrochemical properties of Ti3C2-ZrO2 nano-
further impurities, as shown in Fig. 2(f-h) [24]. composites (NC), a comprehensive electrochemical analysis was con-
EDS mapping analysis was used to determine the purity and ducted by utilizing a three-electrode setup. The experimental
elemental composition of the as-prepared NC. The EDS mapping of arrangement featured an Hg/HgO (reference electrode), platinum
Ti3C2-ZrO2 NC in supporting information shown in Fig. 2 (i-l) (counter electrode), and Ti3C2-ZrO2 NC (working electrode) immersed

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P. S.S. et al. Journal of Energy Storage 98 (2024) 112821

Fig. 2. (a-e) FE-SEM, (f-h) EDS image of Ti3C2, ZrO2, and Ti3C2-ZrO2 NC, EDS mapping of (Fig. 2(e)) Ti3C2-ZrO2 NC (i) Ti, (j) C, (k) Zr, and (l) O elements.

in a 3 M KOH electrolytic medium. For comparative purposes, electro- storage capabilities and augments the overall electrochemical behaviour
chemical studies were separately performed on Ti3C2 and ZrO2 nano- of the composite material.
particles (NPs). Fig. 6 shows the Cyclic voltammograms (CV) were In our analysis, Trasatti and Dunn's method quantifies the proportion
recorded at different scan rates spanning from 10 to 200 mV/s for Ti3C2, of electric double-layer capacitance (EDLC) and pseudocapacitive
ZrO2, and Ti3C2-ZrO2 NC electrodes, revealing the intercalation and de- behaviour within the overall redox activity. This method enables us to
intercalation of ions through the interlayers of the nanosheets which is evaluate the capacitive contribution of the electrode material and get
responsible for the different faradic curves exhibited by all the elec- insights into the charge accumulation process. Trasatti technique pro-
trodes, indicating their battery-like behaviour. Remarkably, strong vides a valuable framework for understanding the relationship between
redox humps continued even at a high scan rate of 200 mV/s, high- charge storage contribution and scan rate. It allows us to establish a
lighting the tremendous reversibility and robust rate capability of the connection between them, revealing the complex interaction between
material. EDLC and pseudocapacitive behaviour in the electrochemical system.
Furthermore, notable differences were observed across different 1
current density ranges. Due to the synergistic effect, the interaction Q*(V) = kv− 2 + Q*outer (4)
between Ti3C2 and ZrO2 NPs, the CV of Ti3C2-ZrO2 NC encompassed a
1
larger integral area compared to that of the individual NPs. This Q− 1 *(V) = kv2 + Q−outer
1*
(5)
observation signifies an obvious enhancement in electrochemical ac-
1 1
tivity, further confirming the benefits of the composite materials with Plotting Q− 1* (V) vs v2 and Q* (V) vs v− 2 yields the overall capaci-
unique stoichiometry composition and layered structure that facilitate tance and outer capacitance values required to understand how the
ion intercalation and de-intercalation processes [31]. The specific ca- charge is stored on the electrode structure.From extrapolating the Q* to
pacity of Ti3C2 (Fig. 6(a))was found to be 558.9, 520.2, 499.2, 458.5, V = 0 and V = ∞, the total capacitance (Q*total) and outer surface
and 393.6C/g and the specific capacity for ZrO2 was determined to be (Q*outer) of the electrode can be calculated [32].The total charge stored
277.7, 254.5, 238.8, 210.4, and 180.5C/g with respect to the scan rates at the prepared electrode material was calculated to be 641, 331.1, and
of 10, 25, 50, 100, and 200 mV/s (Fig. 6(b)). Remarkably, the Ti3C2- 1076.2C/g from the resulting plots as depicted in supporting informa-
ZrO2 NC demonstrated significantly elevated specific capacitance (Cs) tion Fig.S1(a, c, and e), while the charge stored at the outer surface was
values across the scan rates from 10 to 200 mV/s. The Cs values of Ti3C2- 387.8, 171.8, and 444.2C/g Ti3C2, ZrO2, and Ti3C2-ZrO2 NC, respec-
ZrO2 NC were measured at 832.5, 763.1, 673.3, 583.5, and 484.6C/g, tively (Fig.S1(b, d, and f)).(Inner capacity was 253.2, 159.2, and
underscoring their exceptional electrochemical activity shown in Fig. 6 631.9C/g Ti3C2, ZrO2, and Ti3C2-ZrO2 NC, respectively).
(c). This exceptional performance can be attributed to the synergistic The battery type behaviour of the electrodes was confirmed by the
interaction between the Ti3C2 and ZrO2 NPs, which enhances charge fitting results, indicating that it is a diffusion-controlled charge storage

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P. S.S. et al. Journal of Energy Storage 98 (2024) 112821

Fig. 3. (a-c) HR-TEM, and (d) SAED pattern of Ti3C2-ZrO2 NC.

Fig. 4. BET data for (a) Surface area, and (b) pore size distribution of Ti3C2, ZrO2, and Ti3C2-ZrO2 NC.

process. Fig.S2 9(a-f) displays log of peak current (i) and scan rate (ν1/2) (b = 0.61, b = 0.62), ZrO2 (b = 0.64, b = 0.74) and Ti3C2-ZrO2 NC (b =
of as-prepared Ti3C2, ZrO2, and Ti3C2-ZrO2 NC electrodes and are rep- 0.58, b = 0.53). Since, all electrodes display battery-like behaviour and
resented by the following formula, the obtained ‘b’ values are close to 0.5, it is evident that both surface-
confined and diffusion-controlled actions are occurring.
i (V) = icap + idiff = avb (6) From Dunn's method [33], Surface controlled reactions and Faradaic
reaction's relative contributions to the charge storage process can be
where, ‘b’ - plotting log(ip) against log(ν), and plot slope gives ‘b’ value.
calculated as.
log i (V) = log a + b log v (7)
C* I
C* I (%) = x 100% (8)
It is found that when b = 1, the charge storage mechanism is surface C* T
controlled, and when b = 0.5, it is diffusion controlled. The calculated b
value of the anodic and cathodic scans is presented respectively by Ti3C2

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P. S.S. et al. Journal of Energy Storage 98 (2024) 112821

Fig. 5. XPS for (a) Survey spectrum, and high-resolution spectrum of (b) Ti 2p, (c) C 1s, (d) Zr 3d, and (e) O 1 s of Ti3C2-ZrO2 NC.

Fig. 6. Cyclic voltammetry study of (a) Ti3C2, (b) ZrO2, and (c) Ti3C2-ZrO2 NC.

C* o Electrochemical impedance spectroscopy (EIS) serves as a valuable

C* o (%) = x 100% (9) tool for assessing the internal characteristics of electrode materials,
C* T
shedding light on their resistance, capacitive performance, and charge
The calculated percentage of surface-controlled contribution was
transfer kinetics [34]. When examining the Nyquist plot, the high-
found to be 60.49 %, 51.91 %, and 41.27 % and their corresponding
frequency region typically features a semi-circle, which provides in-
percentage of Faradaic reaction contribution was 39.5 %, 48.08 %, and
sights into Solution resistance (Rs) and Charge transfer resistance (Rct).
58.72 % for Ti3C2, ZrO2, and Ti3C2-ZrO2 NC as depicted in Fig. 7(a).
In Ti3C2, ZrO2, and Ti3C2-ZrO2 NC, the observed Rs values were as

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P. S.S. et al. Journal of Energy Storage 98 (2024) 112821

Fig. 7. (a) Capacitive-diffusion contribution, (b) EIS, GCD of (c) Ti3C2, (d) ZrO2, and (e) Ti3C2-ZrO2 NC, (f) cyclic stability of Ti3C2-ZrO2 NC.

through cycling performance tests conducted at the constant current

Table 1 density of 3 A/g. Remarkably, Ti3C2-ZrO2 NC exhibited excellent
Experimental and Fitted values of Ti3C2, ZrO2, and Ti3C2-ZrO2 NC impedance
capacitive retention, retaining 88.85 % of its initial capacitance even
spectra.
after 5000 cycles (Fig. 7(f)) [36]. This remarkable stability further
Material Experimental values Fitted values highlights the durability and long-term performance potential of Ti3C2-
Rs (Ω) Rct(Ω) Rs (Ω) Rct(Ω) ZrO2 NC in practical electrochemical applications.
Ti3C2 1.19 0.62 1.23 0.51
ZrO2 0.19 1.09 0.21 1.1
Ti3C2-ZrO2 NC 1.28 0.18 1.30 0.22 3.7. The performance of the solid-state hybrid supercapacitor device using
Ti3C2-ZrO2 NC

follows: 1.19 Ω for Ti3C2, 0.19 Ω for ZrO2, and 1.28 Ω for Ti3C2-ZrO2 NC. The solid-state hybrid supercapacitor device (SHSC) was precisely
Correspondingly, the Rct values were: 0.62 Ω for Ti3C2, 1.09 Ω for ZrO2, assembled, featuring Ti3C2-ZrO2 NC as the cathode, activated carbon
and 0.18 Ω for Ti3C2-ZrO2 NC (Fig. 7(b)). Notably, the Ti3C2-ZrO2 NC (AC) acting as the anode, Whatman filter paper serving as a separator,
displayed lower impedance and exhibited enhanced charge transport and a solid-state electrolyte comprising PVA-KOH gel. The solid-state
kinetics. This suggests a higher level of electrical conductivity and hybrid supercapacitor device was fabricated by the balancing the
improved ion diffusion within the composite material, leading to charges of the cathode and the anode based on the equation
increased electrochemical activity. These findings underscore the ad-
vantageous properties of the Ti3C2-ZrO2 nanocomposites, making them m+ C− ΔV−
= (10)
a promising candidate for various electrochemical applications. The m− C+ ΔV+
fitted equivalent circuit agrees well with the experimentally obtained
values and the values are shown in Table.1. where, (m+) mass of the cathode material, (m− ) mass of the anode
Galvanostatic charge-discharge (GCD) provided insights into the material and the resultant mass balance ratio was found to be 1.6:1.
charge storage characteristics of Ti3C2, ZrO2, and Ti3C2-ZrO2 NC within Operating within a potential window of 0–1.8 V, the cyclic voltammetry
a potential range of 0 to 0.6 V at various current densities ranging from 1 (CV) profile of the Ti3C2-ZrO2//AC SHSC exhibited a distinctive com-
to 5 A/g. The existence of asymmetric non-linear discharge curves in the bination of electric double-layer capacitance (EDLC) and faradaic
shapes indicated the faradic nature of the prepared electrode materials. behaviour [37]. Notably, as increased the scan rates from 10 to 100 mV/
Especially, owing to a synergistic effect resulting from the combination s, both oxidation and reduction peaks were observed, demonstrating the
of Ti3C2 and ZrO2 NPs, the discharge profiles of Ti3C2-ZrO2 NC device with robust reversibility and redox activity as depicted in Fig. 8
demonstrated superior electrochemical performance in comparison to (a).
individual Ti3C2 and ZrO2 NPs as depicted in Fig. 7(c-e). This observa- For a more comprehensive analysis of the SHSC device, electro-
tion shows up the beneficial impact of the composite materials unique chemical impedance spectroscopy (EIS) was employed to assess key
composition and structure on charge storage and discharge processes parameters such as Rs and Rct. From Fig. 8(b) the Nyquist plot revealed
[35]. Rs and Rct values of 1.37 Ω and 3.2 Ω, respectively, indicating speedy ion
Furthermore, the electrode stability was rigorously evaluated transfer kinetics and a low equivalent series resistance (ESR) [38].
Moreover, the enhanced slope at low frequencies featured the superior

8
P. S.S. et al. Journal of Energy Storage 98 (2024) 112821

Fig. 8. (a) CV, (b) EIS, (c) GCD, (d) Ragone plot, and (e) cyclic stability for Ti3C2-ZrO2//AC SHSC.

capacitive behaviour of the supercapacitor device. The obtained Nyquist

Table 2
plot and the fitted (insert) equivalent circuit agree quite well.
Comparison table for the electrochemical performance of Ti3C2-ZrO2//AC SHSC
Charge-discharge characteristics were scrutinized through galvano-
with other literature.
static charge-discharge (GCD) analysis within the voltage range of 0–1.7
Materials Specific Energy Power Ref.
V. GCD profiles exhibited characteristic non-linear curves with minimal
capacitance density density
voltage drop even at high current densities, signifying the battery-like Wh/kg W /kg
behaviour of the Ti3C2-ZrO2//AC SHSC with prolonged discharge ca-
MBN/Ws2–3// 140 F/g 19.4 997.7 [43]
pabilities [39]. The specific capacitances obtained from the discharge Ti3C2Tx at 1 A g− 1
profiles with respect to the current densities of 1, 2, 3, 4, and 5 A/g were NiMoO4/ 545.5C g− 1 33.36 400.08 [44]
measured to be 328.7, 295.3, 101.5, 92.5, and 30.8C/g, respectively Ti3C2Tx// Rgo at 0.5 A g− 1
shown in Fig. 8 (c). These results highlighted the supercapacitors Carbon xerogel- 180 F/g 27.1 140 [45]
1
ZrO2 at 0.125 A g−
excellent conductivity, exceptional rate capability, and remarkable
Carbon coated 125 F/g 25 1201 [46]
electrode stability. Impressively, even after 5000 consecutive charge- ZrO2
discharge cycles, the Ti3C2-ZrO2//AC SHSC device maintained a supe- Zirconia- V2CTx 1200 F/g at 0.5 15.39 4000 [47]
rior capacitive retention rate of 83.8 % (Fig. 8(e)). mVs− 1
From CV (Fig. S3), when compared to 7:3 ratio of Ti3C2-ZrO2 NC as Ti3C2/CNTs/ 823 at 1 A g− 1 49.5 350 [48]
MnCo2S4
the cathode, AC acting as the anode, the 6:4 ratio of Ti3C2-ZrO2 NC
NiCoFe-LDH/ 876.17 at 10 A 54.4 895.1 [49]
cathode gives a lower integral area. Nyquist plot revealed Rs and Rct Ti3C2//rGO g− 1
values of 2.65 and 8.15 Ω respectively. The specific capacities obtained N-Ti3C2/ 1243.1 at 5 mV/s 162.8 2700 [50]
from the discharge profiles with respect to the current densities of 1, 2, MnCo2S4//AC
Ti3C2-ZrO2//AC 188.43C g ¡1
75.63 1445 This
3, 4, and 5 A/g were measured to be 144, 108, 98, 76, and 25.8C/g,
at 1 A g¡1 work
respectively shown in Fig. S3(a-c) is lower than the (7:3 ratio of Ti3C2-
ZrO2 NC) Ti3C2-ZrO2//AC SHSC.
Crucially, the energy and power densities are fundamental de- commendable stability. Furthermore, it delivered a specific energy of
terminants of practical utility in supercapacitor devices. Ragone plot 94.46 Wh/kg at a power density of 2882 W/kg, showcasing its potential
effectively illustrated the relationship between energy density and for high-performance energy storage applications. Additionally,
power densities for the fabricated device. In contemporary research, a Elmouwahidi et al. [45] contributed to the field with a report on a
rich body of literature highlights the remarkable advancements ach- symmetric supercapacitor employing carbon xerogel-ZrO2 composites.
ieved through the creation of nanocomposites utilizing 2D Ti3C2 nano- This supercapacitor exhibited exceptional electrochemical performance,
sheets to enhance the performance of supercapacitors. Notably, Mansi boasting a high capacitance of 180 F/g at 0.123 A/g, robust retention of
et al. [40] recently presented a ground breaking study wherein a capacitance, and an impressive energy and power density are 27.1 Wh/
MnCo2/Ti3C2//AC supercapacitor device exhibited exceptional energy kg and 140 W/kg. Remarkably, the Ti3C2-ZrO2//AC SHSC demonstrated
storage properties with a specific capacitance of 126.58 F/g at 0.8 A/g, competitive energy densities ranging from 75.6 to 51.9 Wh/kg and
coupled with the high energy density of 40 Wh/kg and demonstrated a corresponding power densities from 1445 to 7225 W/kg at 1–5 A/g,
power density of 4828 W/kg. Similarly, Wang et al. [41] conducted affirming (Fig. 8 (d)) its competency as a high-performance energy
research on an asymmetric supercapacitor, featuring a monolayer storage applications [42]. The comparison of obtained energy and
Ti3C2/NiCo2O4//AC setup. This configuration achieved a maximum power densities of Ti3C2-ZrO2//AC SHSC with other reported literature
specific capacitance of 73.8 F/g at a current density of 1 A/g, along with and tabulated in Table 2.

9
P. S.S. et al. Journal of Energy Storage 98 (2024) 112821

Fig. 9. (a) Initial, (b) 30s, (c) 2 min, (d) 3 min, (e) 4 min and (f) 5 min of red LED illumination for Ti3C2-ZrO2//AC SHSC. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)

In order to support the practical use of the Ti3C2/ZrO2//AC solid review & editing, Writing – original draft, Visualization, Validation,
state hybrid supercapacitor, the red LED indication can be illuminated Supervision, Software, Resources, Project administration, Methodology,
by connecting the two devices in series and charging them for 30 s at 3 V. Investigation, Funding acquisition, Formal analysis, Data curation,
It suggests a high level of charge storage capacity as shown in Fig. 9(a-f) Conceptualization.
[51].

4. Conclusion Declaration of competing interest

In conclusion, the two-dimensional (2D) Ti3C2 was synthesized by The authors declare that they have no known competing financial
the exfoliation technique. The preparation of Ti3C2, ZrO2, and Ti3C2- interests or personal relationships that could have appeared to influence
ZrO2 NC electrodes, demonstrating their potential in energy storage the work reported in this paper.
applications. Furthermore, the Ti3C2-ZrO2//AC solid-state hybrid
supercapacitor (SHSC) device fabricated by using PVA-KOH as gel Data availability
polymer electrolyte, exhibited a notable energy density of 75.6 Wh/kg
and a power density of 1445 W/kg at 1 A/g. The Ti3C2-ZrO2//AC SHSC No data was used for the research described in the article.
delivers exceptional cycling stability of 83.8 % capacitive retention after
5000 cycles, highlighting the positive impact of cross-linked MXene Acknowledgement
structures in enhancing conductivity and reaction kinetics. Thus, all of
the findings in this study corroborate that the Ti3C2-ZrO2 NC will be a All the authors acknowledge the financial support by Ministry of
feasible alternative for the next generation of innovative technology. Human Resource Development RUSA- Phase 2.0 grant sanctioned vide
Lt.No.F-24-51/2014 U Policy (TNMulti Gen), Dept. of Education, Govt.
CRediT authorship contribution statement of India.

Pradeepa S.S.: Writing – original draft, Validation, Methodology, Appendix A. Supplementary data
Investigation, Formal analysis, Data curation. Sutharthani K.: Visuali-
zation, Validation, Methodology, Investigation, Formal analysis. Suba Supplementary data to this article can be found online at https://doi.
Devi R.: Writing – review & editing, Writing – original draft, Visuali- org/10.1016/j.est.2024.112821.
zation, Validation, Supervision, Software, Resources, Project adminis-
tration, Methodology, Investigation, Funding acquisition, Formal
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