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Role of Electrolytes on the Electrochemical Characteristics of

Fe3 O4 /MXene/RGO Composites for Supercapacitor Applications

Thirumurugan Arun , Ankita Mohanty , Andreas Rosenkranz ,

Bo Wang , Jinhong Yu , Mauricio J. Morel , R. Udayabhaskar ,
Samuel A. Hevia , Ali Akbari-Fakhrabadi , R.V. Mangalaraja ,
Ananthakumar Ramadoss

PII: S0013-4686(20)31866-1
DOI: https://doi.org/10.1016/j.electacta.2020.137473
Reference: EA 137473

To appear in: Electrochimica Acta

Received date: 17 August 2020

Revised date: 6 November 2020
Accepted date: 11 November 2020

Please cite this article as: Thirumurugan Arun , Ankita Mohanty , Andreas Rosenkranz , Bo Wang ,
Jinhong Yu , Mauricio J. Morel , R. Udayabhaskar , Samuel A. Hevia , Ali Akbari-Fakhrabadi ,
R.V. Mangalaraja , Ananthakumar Ramadoss , Role of Electrolytes on the Electrochemical Char-
acteristics of Fe3 O4 /MXene/RGO Composites for Supercapacitor Applications, Electrochimica Acta
(2020), doi: https://doi.org/10.1016/j.electacta.2020.137473

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Highlights:

 Hybrid composite Fe3O4/MXene/RGO (FMR) is fabricated by a simple chemical

process.

 FMR, FMX and F worked in the potential window -1.0 to 0 V.

 The order of supercapacitor performance is 5 M LiCl > 1 M Na2SO4 > 1 M KOH.

 FMR electrode exhibits 82.1 % of cyclic stability even after 5000 cycles.

1
 Role of Electrolytes on the Electrochemical Characteristics of
Fe3O4/MXene/RGO Composites for Supercapacitor Applications

Thirumurugan Arun1*, Ankita Mohanty2, Andreas Rosenkranz3, Bo Wang4, Jinhong Yu4, Mauricio J. Morel1,
R. Udayabhaskar1, Samuel A. Hevia5, Ali Akbari-Fakhrabadi6, R.V. Mangalaraja7, 8, Ananthakumar
Ramadoss2*

1
Instituto de Investigación Científica y Tecnológica (IDICTEC), Universidad de Atacama, Copayapu 485,
Copiapo, Chile.
2
Laboratory for Advanced Research in Polymeric Materials, Central Institute of Plastics Engineering and
Technology, Bhubaneswar, 751024, India.
3
Department of Chemical Engineering, Biotechnology and Materials, FCFM, Universidad de Chile, Santiago,
Chile.
4
Key Laboratory of Marine New Materials and Related Technology, Zhejiang Key Laboratory of Marine
Materials and Protection Technology, Ningbo Institute of Material Technology & Engineering, Chinese
Academy of Sciences, Ningbo 315201, People’s Republic of China
5
Instituto de Física y Centro de Investigación en Nanotecnología y Materiales Avanzados (CIEN-UC),
Pontificia Universidad Católica de Chile, Santiago 7820436, Chile.
6
Advanced Materials Laboratory, Department of Mechanical Engineering, University of Chile, Santiago,
Chile.
7
Advanced Ceramics and Nanotechnology Laboratory, Department of Materials Engineering, Faculty of
Engineering, University of Concepción, Concepción, 4070409, Chile.
8
Technological Development Unit (UDT), University of Concepcion, Coronel Industrial Park, Coronel, Chile

2
……………..

*Corresponding authors E-mail Addresses: [email protected] and

[email protected]

3
Abstract

This study aims at developing hybrid composite materials consisting of iron oxide

(Fe3O4) /MXene /reduced graphene oxide (RGO) without any impurities using optimized

experimental parameters to be utilized in next-generation supercapacitor applications and

the searching of suitable electrolyte for the developed hybrid electrode materials. We have

generated Fe3O4-decorated MXene nanosheets on RGO by a simple chemical oxidation

method. The initial grain size of Fe3O4 of about 43 nm is further reduced to 30 nm when

prepared with MXene nanosheets. The as-prepared samples are used as a negative electrode

material and their capacitive performance is analyzed in potassium hydroxide (KOH),

sodium sulphate (Na2SO4) and lithium chloride (LiCl) electrolytes. Fe3O4/MXene/RGO

nanocomposites showed the best performance. Regarding the electrolytes, the following

order has been obtained 5 M LiCl > 1 M Na2SO4 > 1 M KOH, which matches well with the

bare ion size order. Moreover, Fe3O4/MXene/RGO electrode exhibits an 82.1% of cyclic

stability up to 5000 charge/discharge cycles at a current density of 5 A g-1 demonstrating

the best performance.

Keywords: MXene nanosheets; Magnetic nanoparticles; Electrolytes; Capacitance;

Supercapacitor

4
Introduction

Two-dimensional (2D) materials have various applications in the area of materials

science such as energy storage, dielectrics, optical modulation, optoelectronics,

electrocatalysis and sensors [1–7]. Among 2D materials, MXene nano-sheets can be

considered as a novel class of 2D materials with an outstanding performance in several

fields such as metal ion batteries, supercapacitors, water splitting, photocatalysis,

lubrication and electronics [8–14]. MXene nano-sheets are typically synthesized based

upon MAX-phases, which are three-dimensional layered ternary metal nitrides, carbides

and any combination of them [15]. An increasing number of members of the MXene family

with different early transition metal and variable stoichiometry has been recently observed

and a greater number of members can be expected in the near future [16]. MXene nano-

sheets have been used for electrochemical supercapacitor applications due to their enhanced

volumetric capacitance, which helped to improve the electronic conductivity, active

intercalation sites, and surface area [17,18]. Among the MXene family, the most studied

and prominent member is Ti3C2Tx, for which TX stands for potentially existing surface

terminations including -O2, -(OH)2 and -F2 functional groups. Ti3C2Tx nano-sheets have

been utilized for electrochemical energy storage applications [19–22]. Owing to the

existence of these surface terminations, Ti3C2Tx nano-sheets have proven to demonstrate an

enhanced electronic conductivity. In this context, high purity Ti3C2Tx nano-sheets showed a

conductivity of around 6500 S cm-1, and even Ti3C2Tx prepared by HF etching presented a

conductivity of about 1000 S cm-1 [22–24]. The theoretical capacity of the MXene nano-

sheets is predicted to be 615 C g-1 [25]. It has been reported that the capacitance of MXene

nano-sheets could be enhanced by proper cation interaction and suitable surface

modifications [26]. Few composites using MXene nano-sheets have been developed to
5
improve the electronic and surface characteristics of MXene with Ag, MnO2, Fe2O3,

Mn3O4, Bi2MoO6, carbon nanotubes (CNTs) and reduced graphene oxide (RGO) [27–33].

Concerning metal oxides, Fe3O4 magnetic nanoparticles (MNPs) seem to be interesting to

be used as a negative electrode material for supercapacitor applications due to its high

theoretical capacitance, which has not been experimentally achieved so far [34]. Magnetite

stems from the ferrite family with an inverse spinel structure [35] and can be easily

prepared by chemical processes using low-cost chlorides. The formation of composites with

Fe3O4 and carbon materials is promising due to their good chemical stability, better

electrical conductivity, high electron mobility, larger surface area and tunable magnetic

properties [36–38]. Regarding carbon-based materials, RGO is of special interest due to its

superior electrochemical properties required for excellent electrode materials for

electrochemical applications [39–41]. Various metal oxides along with RGO have been

used to develop hybrid electrode materials. An improvement of the capacitive performance

of the electrode materials with the addition of RGO has been verified [42–51].

The doping and surface modification of graphene based carbon materials are

evaluated for the energy storage and conversion processes [52,53]. The process of making

RGO also important as the final product properties, depending on the synthesis process

[54]. Graphene, graphene derivative, 2D analogous materials and their composites are also

attempted and found some improvement in the electrochemical applications [55,56].

Excellent capacitance retention has been showed by developing the graphene oxide sheets

with simultaneous reduction and covalent grafting of polythiophene on graphene oxide

sheets [57]. The addition of inorganic materials such as NiO, MnO2, ZnO, Mn3O4, Fe2O3,

Fe3O4 and MoS2 along with graphene based carbon materials showed the improved

physicochemical characteristics [58–61].

6
 Apart from the electrode material, the electrolyte is important regarding the

resulting electrochemical performance. Only a limited number of studies have tried to

address the effect of the electrolyte and the electrolyte’s concentration on the

electrochemical characteristics of the materials [62–65]. However, the electrochemical

response of each electrode material would depend on the respective electrolyte and their

compatibility. Therefore, it is important to evaluate the performance of the electrode

materials in different electrolytes.

This study aims at developing hybrid composite materials consisting of

Fe3O4/MXene/RGO to be used in next-generation supercapacitor applications. We have

generated Fe3O4-decorated MXene nano-sheets on RGO by a relatively simple chemical

oxidation method. The structural, morphological, and magnetic characteristics of the

Fe3O4/MXene/RGO composites have been assessed. The electrochemical characteristics of

these novel composite electrode materials have been studied using three different

electrolytes including KOH, Na2SO4 and LiCl to understand the role of the electrolyte on

the electrochemical performance of the Fe3O4/MXene/RGO hybrid nanocomposites.

Experimental

Fe3O4 MNPs were synthesized by chemical oxidation using NaOH and KNO3 as

additives [66]. RGO was prepared by a microwave-assisted synthesis process using L-

ascorbic acid [67]. Regarding the synthesis of MXene nano-sheets, the initial Ti3AlC2-

powder was purchased from FORSMAN SCIENTIFIC Co. Ltd., Beijing (China). In order

to create multi-layer Ti3C2Tx-nano-sheets, 10 g of Ti3AlC2-powder were immersed in 100

ml of a 40% hydrofluoric acid solution. The mixture was stirred for three minutes and, then

kept at room temperature for two hours. The as-prepared suspension was then washed using

deionized water several times until reaching a pH above 6 and, subsequently, centrifuged to
7
separate the powder. Afterward, the washed powder was filtered under vacuum conditions

and dried at room temperature for 24 hours. Optimized amounts of ferrous chloride were

dissolved in 100 ml of double distilled water and heated to 60 ºC. Then, 200 mg of MXene

nano-sheets dispersed in water were added to the solution to decorate the ferrous ions on

the layered structure of MXene nano-sheets. In another experimental batch, ferrous ions

were mixed with a MXene (200 mg) / RGO (100 mg) dispersion. Afterward, appropriate

amounts of NaOH and aqueous KNO3 were added to the solution. The chemical reaction

was going on for 2 hours at 90 ºC before cooling the reactor down to room temperature.

The formed MNPs were washed several times with double distilled water thus removing

the unreacted initial species. During washing, a magnetic bar was used to allow a fast

separation of magnetic materials from unreacted species (excess of non-magnetic MXene

and RGO). The synthesis process of the Fe3O4/MXene/RGO hybrid nanocomposites is

schematically shown in Fig. 1. Bare Fe3O4, Fe3O4/MXene and Fe3O4/MXene/RGO samples

are abbreviated as F, FMX and FMR.

Fig. 1. Schematic illustration of the processing steps to develop Fe3O4 /MXene/RGO hybrid

nanocomposites.

8
Characterization

X-ray diffraction (XRD) patterns were recorded using a Bruker D8 X-ray

diffractometer equipped with a Cu-Kα radiation source for phase analysis. Fourier

Transform Infra-Red spectroscopy (FTIR) was performed using a Perkin Elmer FTIR

spectrophotometer. A vibrating sample magnetometer (VSM) (Model 7404, Lakeshore,

USA) was utilized to record the magnetic hysteresis loop at room temperature. The

morphology of the bare and composite materials was examined by field emission scanning

electron microscopy (FESEM) (FEI Quanta 250 FEG) and transmission electron

microscopy (TEM) (Tecnai F20 FEG TEM with 200 kV accelerating voltage).

The overall supercapacitor performance is mainly based on the interaction between the

electrode and electrolyte, which is a crucial function apart from the operating voltage. The

electrolyte plays a significant role in the electrochemical parameters including cycling

stability, operating temperature, power density, equivalent series resistance and self-

discharge rate of the supercapacitors. Therefore, it is highly important to investigate the

electrochemical performance of the as-prepared materials in different electrolytes. Herein

we have studied the electrochemical performance of as-prepared materials in different

electrolyte ion size including 5 M LiCl, 1 M Na2SO4 and 1 M KOH. All electrochemical

experiments were done using a PARSTAT MC-1000 electrochemical workstation with a

VERSA STUDIO software. The electrochemical characterizations included cyclic

voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance

spectroscopy (EIS). All experiments were done for three electrode systems, for which the

synthesized composites, Hg/HgO or Ag/AgCl and platinum electrodes were used as

working electrode, reference electrode and counter electrode respectively. In the case of

9
electrolyte of 1 M KOH, Hg/HgO was used as a reference electrode, whereas Ag/AgCl was

utilized for this purpose for 1 M Na2SO4 and 5 M LiCl electrolytes.

The electrodes were prepared based upon a binder approach. The active material, PVDF

(as a binder) and carbon black (as conductive agent) were used in mass ratios of 75:15:10

and grounded finely using a mortar pastel to form a smooth slurry. The slurry was coated

over an area of 1cm2 of pre-cleaned stainless steel (SS) substrates of a total area of 2 cm × 1

cm. In order to circumvent the insulating effect of the binder, a conducting agent was used

during the preparation of the slurry. In order to mix the slurry, N-methyl pyrrolidone

(NMP) was used as a solvent and the coated electrodes were kept at 80 °C overnight. After

drying, the mass of the electrodes was measured. The active mass of the electrode was

obtained by subtracting the final mass of the coated SS substrate from the original mass of

SS substrate.

Based upon the CV and GCD analysis, the specific capacitance of the as-prepared

electrodes was calculated using the following equations:

∫
From CV, Cs = (1)

From GCD, Cs = (2)

where, ∫ is the area under the CV curve (A V), m is the active mass of the electrode

(gm), ΔV is the working potential window (V), ν is the scan rate (mV s-1), Δt is the

discharge time (s) and I is the discharge current (A).

The CV and GCD analyses were accomplished in the potential window between -

1.0 and 0 V. For CV, the electrodes were tested with various scan rates ranging from 5 to

10
125 mV s-1. Similarly, GCD profiles were obtained for various current densities ranging

from 0.2 to 1 A g-1.

Results and Discussion

The single phase of Fe3O4 in bare, MXene and MXene/RGO composites is

confirmed from the XRD pattern with reference to the JCPDS card no 82-1533 as shown in
Figure 2. The average grain size of the bare Fe3O4 MNPs was estimated to be 43 nm based
upon the Scherrer’s equation [68]. When introducing MXenes in the composite, the average
grain size reduced to 30 nm. The reduction of the average grain size of Fe3O4 in FMX
might be due to the distribution of nucleation seeds over the MXene surface. It is important
to note that no secondary or impurity phases were detected for FMX. However, it is
pertinent to mention that no characteristic diffraction peaks of MXene nano-sheets were
observed, which can be connected to the low fraction of MXene in the composites or the
disappearance of characteristics reflections due to the alignment effect. Moreover, the
average grain size increased to 46 nm for FMR composites. The XRD peaks from (111),
(220), (311), (222), (400), (422), (511), (440), (620), (533), (622) and (444) reflections
belong to Fe3O4. A small and broad peak located at 26 ° observed for FMR composites
belongs to (002) reflections from RGO (enlarged view in
Fig. 2c). The XRD pattern of pure RGO is shown in Figure S1.

11
 Fig. 2. XRD patterns for (a) F, (b) FMX and (c) FMR.

The bare Fe3O4 showed the maximum saturation magnetization of 89 emu g-1. As

can be seen in Figure S2, the maximum saturation magnetization reduced with the addition

of MXene and RGO. For the FMX sample, a reduced magnetization of 70 emu g-1 was

detected, while a further reduction to 62 emu g-1 was confirmed for the FMR composites.

The reduction in the saturation magnetization can be traced back to the addition of

nonmagnetic nano-materials such as MXenes and RGO to the nanocomposites. Based upon

the absolute value of the saturation magnetization, the MXene’s fraction in the FMX

nanocomposites can be estimated to be about 21%. The nonmagnetic fraction in the FMR is

estimated at 30%. Using the estimated MXene’s fraction in FMX, the contribution of RGO

in FMR is derived to be 9%. Based on TGA measurements (Figure S3), the fraction of

RGO is estimated to be 5% in FMR. From the variations observed for the saturation

12
magnetization of the nanocomposites, it is understood that the net saturation magnetization

can be tuned by adjusting the nonmagnetic fractions of MXene and RGO, which seems to

be a promising approach for different applications. The coercivity of the bare Fe3O4, FMX

and FMR was detected to be 134, 125 and 177 Oe, respectively.

Figure 3 shows the micrographs for (a) FMX and (d) FMR acquired by FESEM.

Magnified views of the FMX nanocomposite are shown in Fig.3 b and c. Octahedral

shaped Fe3O4 was observed for bare Fe3O4 on the layered MXene nano-sheets. The layered

structure of pristine MXenes can be observed in the FESEM micrograph shown in Figure

S4. Due to the surface modification with Fe3O4, MXene nano-sheets transformed into a

few-layered MXene. It is important to mention that the MXene nano-sheets are covered

with octahedral shaped Fe3O4 having a particle size ranging from 80 to 120 nm. For the

FMR nanocomposites, an average size of RGO of about few microns were observed. Fe3O4

MNPs decorated MXene layers were detected on the RGO sheets. Moreover, single

particles or clusters of Fe3O4 MNPs have also been observed on RGO as shown Fig.3e. The

octahedral morphology of the Fe3O4 MNPs was slightly changed, thus showing different

morphologies for the FMR samples, which was further studied by TEM.

13
Fig. 3. FE-SEM micrographs of (a) the FMX nanocomposites with close-ups (b and c) and

(d) the FMR nanocomposites with their close-ups (e and f).

Figure S5 summarizes the obtained TEM-micrographs for (a) the bare Fe3O4, (b)

the FMX and (c) the FMR nanocomposites. The individual layer structure of MXene with a

size of few microns can be seen in Figure S5 a. Smaller sized MXene layer have been also

observed on the larger sized MXene nano-sheets. The octahedral shaped Fe3O4

nanoparticles entirely cover the MXene nano-sheets as observed from Figure S5 (b). For

14
the FMR nanocomposite, Fe3O4-covered MXenes and individuals or groups of Fe3O4

MNPs can be found on the RGO sheets, which is also evidenced by FESEM.

Figure S6 shows the FTIR spectra obtained for (a) F, (b) FMX and (c) FMR. The

metal oxide bond was observed around 600 cm-1 for all samples. The peak at 430 cm-1

belongs to the vibrations of Fe-O from the octahedral site. The Fe-O stretching vibrations

from the tetrahedral sites were observed around 580 cm-1. The splitting of the stretching

vibrations from the tetrahedral site was observed at 570 and 640 cm-1 as shown in Error!

Reference source not found. (II). The absence of this symmetry in the metal oxide bonds

was observed for the FMX and FMR samples, which might be due to the improvement of

the cation’s distribution within the inverse spinel structure. Pronounced O-H stretching

vibrations are observed for all samples at around 3400 cm-1 and the H-OH bending

vibration is observed at around 1600 cm-1. The stretching vibration from C-F was observed

at around 1200 cm-1, which is due to the synthesis process of MXene. This contribution was

not observed for the FMR samples. The small peak at 1380 cm-1 for the FMR sample

belongs to vibrations from C-H groups, which confirms the interaction of RGO in the

composites.

The surface area of the samples was measured using BET surface area

measurements. The recorded isotherms are shown for each sample in Figure S7. All

samples showed a type-II adsorption/desorption isotherm. The pristine Fe3O4 MNPs and

FMX exhibited a surface area of 13 and 15 m2 g-1, respectively. An enhanced surface area

of 57 m2 g-1 was found for the FMR samples, which can be correlated to the RGO present in

this sample. The pores size of the Fe3O4, FMX and FMR samples were estimated to be 5.4,

5.6 and 7 nm, respectively.

15
 The electrochemical activity of the electrodes was analyzed through CV, GCD and

EIS experiments. The study was focused on the effect of different electrolytes on the

electrochemical properties of the as-prepared electrodes. Herein, three electrolytes were

used including 1 M KOH, 1 M Na2SO4 and 5 M LiCl. In the case of 5 M LiCl, Hg/HgO

was used as a reference electrode. The CV analysis was done for different scan rates

ranging from 5 to 125 mV s-1 in the potential window between -1 and 0 V. All electrodes

(F, FMX, FMR) showed either a pseudocapacitive and EDLC (electric double layer

capacitor) mixed behavior or only a pseudocapacitive nature as observed from the

corresponding non-rectangular CV curves. The maximum specific capacitance was

obtained for the FMR electrode with a value of about 42.8 F g-1 for a scan rate of 5 mV s-1,

whereas the F and FMX samples delivered for the same scan rate 12.9 and 36.2 F g-1,

respectively. The added MXene and RGO improved the electrochemical performance of F.

The rate capability of the FMR electrode was 58% even after a scan rate of 125 mV s-1,

whereas, for Fe3O4 and FMX, a specific capacitance was retained up to 46.1 and 40.3% of

its value at 5 mV s-1 after 125 mV s-1. The CV comparison graph for all electrodes obtained

for a scan rate of 50 mV s-1 is given in Figure 4 a. From the GCD profiles of the as-

prepared electrodes, the maximum specific capacitance for FMR electrode was 45.8 F g-1

for a current density of 0.2 A g-1. In the case of F and FMX electrodes, the maximum

specific capacitance values were 11 F g-1 and 35.6 F g-1 at current density 0.2 A g-1,

respectively. The GCD comparison graph for all electrodes at a current density of 0.2 A g-1

is given in Figure 4 b. The specific capacitance vs current density plot over current density

ranging from 0.2 to 1 A g-1 is shown in Figure 4 c. EIS analysis was used to observe the

electrical conductivity of the electrodes and realized via a Nyquist diagram. The EIS was

observed in the frequency range between 0.1 Hz and 100 kHz produced by an applied
16
sinusoidal current of constant amplitude. The Nyquist plots for all electrodes are given in

Figure 4 d. The electrochemical performance of all three electrodes implied that, the FMR

composite showed enhanced performance compared to FMX and F electrodes. The

improved performance of FMX electrode compared to F, can be attributed to the addition

of MXene element to the composite, which may contribute high intercalation sites, better

surface area and electrical conductivity to the electrode material. Moreover, the addition of

RGO provides mechanical and structural stability, improved electrical conductivity to the

active material. Hence the electrochemical performance trend is in the order of FMR >

FMX > F.

17
Fig. 4. (a) CV, (b) GCD, (c) specific capacitance vs current density and (d) EIS plot for F,

FMX and FMR electrodes for an electrolyte of 5 M LiCl.

The X-intercept of the Nyquist plot in the high frequency region refers to the

equivalent series resistance (ESR) related to the contact resistance, solution resistance (Rs)

and resistance of the current collector, whereas the X-intercept at the low frequency region

is denoted as the addition of Rs and charge transfer resistance (Rct) formed due to the

contribution of diffusion controlled redox reaction between electrolyte ion and the electrode

structure [69]. The steep tangent (~45°) in the low frequency region is attributed to the

Warburg impedance [69]. In the case of 5 M LiCl, the FMR electrode showed an enhanced

conductivity compared to the other electrodes. The Rs and Rct values for the FMR electrode

were 2.74 and 4.42 Ω, respectively. For F and FMX electrodes, the Rs values were 2.55 and

1.99, Ω respectively. Regarding the charger transfer resistance, the F sample exhibited the

highest charge-transfer resistance of 49.85 Ω, while the FMX electrode obtained a value of

16.25 Ω.

For experiments using an electrolyte of 1 M Na2SO4, the electrodes showed a

similar pseudocapacitive and EDLC mixed behavior for the FMR electrode, whereas for F

and FMX electrodes exhibited a purely pseudocapacitive behavior. The maximum specific

capacitance obtained was 34.1 F g-1 at scan rate of 5 mV s-1 for the FMR electrode. For the

F and FMX electrodes, the maximum specific capacitance at scan rate 5 mV s-1 was 11 and

23.9 F g-1, respectively. Similar trends for the electrodes were observed in the case of 1 M

Na2SO4 electrolyte.

18
Fig. 5. (a) CV, (b) GCD, (c) specific capacitance vs current density and (d) EIS plot for F,

FMX and FMR electrodes for an electrolyte of 1 M Na2SO4.

The CV comparison graph for all electrodes at a scan rate of 50 mV s-1 is presented

in Figure 5 a. The electrochemical performance was in the order of F < FMX < FMR. The

GCD analysis revealed the same trend. The discharge time was maximal for the FMR

electrode and minimal for the F electrode, while keeping the current density constant. The

GCD comparison graph for all electrodes at a current density of 0.2 A g-1 is given in Figure

5 b. The specific capacitance vs current density graph over current density ranging from 0.2

to 1 A g-1 is shown in Figure 5 c for an electrolyte of 1 M Na2SO4. The maximum specific

capacitance was 32 F g-1 at a current density of 0.2 A g-1 for FMR sample in 1 M Na2SO4

electrolyte. The rate capability was only 30.1% after a current density of 1 A g-1. The

maximum specific capacitance for the F and FMX electrodes was 8 and 21.4 F g-1,

19
respectively. Hence, these results revealed that the electrochemical performance of all

electrodes was poor in 1 M Na2SO4 electrolyte compared to 5 M LiCl electrolyte. EIS

analysis results matched well with the electrochemical activity obtained from CV and GCD

profiles for all electrodes. The Nyquist plots for all electrodes are given in Figure 5 d. The

resistance was reduced for the 5 M LiCl electrolyte compared to the values observed for 1

M Na2SO4 electrolyte, which implies that the electrical conductivity was improved. The Rs

values for the F, FMX and FMR electrodes were 3.71, 3.11 and 4.89 Ω, respectively.

Similarly, the Rct values for the F, FMX and FMR electrodes were 71.8, 37.79 and 5.31 Ω,

respectively.

Fig. 6. (a) CV, (b) GCD, (c) specific capacitance vs current density and (d) EIS plot for F,

FMX and FMR electrodes for an electrolyte of 1 M KOH.

20
 Moreover, the electrodes were also tested in the presence of 1 M KOH electrolyte.

All electrodes were stable in this electrolyte and gave the same pseudocapacitive and

EDLC mixed nature or pseudocapacitive behavior. However, a downgraded

electrochemical activity was observed for this electrolyte. The CV comparison graph for all

electrodes at a scan rate of 50 mV s-1 is shown in Figure 6a. The maximum specific

capacitance was 31.4 F g-1 at a scan rate of 5 mV s-1 for the FMR electrode. The F and

FMX electrode showed the highest specific capacitance value of 9.6 and 13.1 F g-1 at a scan

rate of 5 mV s-1, respectively. The rate capability for the FMR electrode was only 9% of its

value at 5 mV s-1 after 125 mV s-1. Similarly, the GCD profiles of all electrodes showed

similar trends with the worst performance among all electrolytes. The GCD comparison

graph for all electrodes at a current density of 0.2 A/g is given in Figure 6b. The specific

capacitance vs current density graph over current density ranging from 0.2 to 1 A g-1 is

depicted in Figure 6c. The maximal specific capacitance delivered by F, FMX and FMR

electrode was 7.2 F g-1, 7 F g-1 and 24.2 F g-1 at current density 0.2 A g-1, respectively. EIS

analysis revealed that the Rs and Rct values for FMR electrode were 3.18 and 40.88 Ω,

respectively. The Rs value for F electrode was 2.12 Ω, while the Rct value was nearly 351.23

Ω. For FMX electrode, the Rs value was 3.39 Ω. All Nyquist plots for all electrodes are

shown in Figure 6d.

Additionally, the role of the electrolytes regarding the electrochemical activity of all

electrodes (F, FMX and FMR) was studied. Figure S8a shows the comparison of the CV

plots for the F electrode at a scan rate of 50 mV s-1. It is clearly visible that the area under

the CV curve for 5 M LiCl electrolyte is the highest and for the 1 M KOH the smallest.

Hence, the electrochemical performance under the 5 M LiCl electrolyte is best compared to

1 M KOH and 1 M Na2SO4. The same trend regarding the electrochemical performance
21
was observed for GCD analysis as shown in Figure S8b and c. Again, the electrical

conductivity of the F electrode was derived using Figure S8d. Based upon that, it can be

concluded that the resistance is least in the case of 5 M LiCl electrolyte and highest for 1 M

KOH. A comparison of the electrochemical behavior of the FMX electrodes for all

electrolytes is depicted in Figure S9a-d. Similar to the F electrode, FMX electrodes also

delivered the same electrochemical activity. The order of the electrochemical activity can

be given as 5 M LiCl > 1 M Na2SO4 > 1 M KOH. For FMR electrodes (Figure 7a-d), the

specific capacitance values with respect to the current density (Figure 7c), area under the

CV curve (Figure 7a) and the electrical conductivity (Figure 7d) was maximum for 5 M

LiCl and least for 1 M KOH as observed in case of both F and FMX electrodes.

Fig. 7. Comparison of (a) CV, (b) GCD, (c) specific capacitance vs current density and (d)

EIS plot for the FMR electrodes in all electrolytes.

22
 The interaction between the electrode and the electrolyte plays a major role in the

electrochemical performance of supercapacitor electrode. Electrolytes may influence many

parameters of the electrochemical parameters such as specific capacitance, energy density,

power density, cyclic stability and equivalent series resistance, among others. The ionic

radius, ionic conductivity, ion type, ionic concentration of the electrolytes are factors on

which the supercapacitor performance depends. The unsolvated bare ion size can affect the

ion intercalation/deintercalation among the electrode material. In this study, we have used

three different types of electrolytes. In these electrolytes, Li+, Na+ and K+ are the

electrolyte’s ions, which actively take part in the pseudocapacitive ion

intercalation/deintercalation process. The bare ion size for Li+, Na+ and K+ are in the order

of Li+ (0.6 Å) < Na+ (0.95 Å) < K+ (1.33 Å) [70–72]. The low bare ion size can enhance the

rate of ion intercalation/deintercalation. As a consequence, the electrochemical

performance of the F, FMX and FMR electrodes in the three electrolytes are in the order of

5 M LiCl > 1 M Na2SO4 > 1 M KOH, which matches well with the bare ion size order. The

electrode materials were found to be dependent on the pseudocapacitive faradaic ion

intercalation and deintercalation process. In this regard, the matching between the

electrode’s pore size with electrolyte ion size is a crucial factor for a faster ion

transportation and, thus, a better specific capacitance. Additionally, the pore size of three

electrodes is in the order of F (5.4 nm) < FMX (5.6 nm) < FMR (7.0 nm) as obtained by the

BET analysis. The larger pore size of the electrode material simplifies easy access of

electrolyte ions to the electroactive surface and reduced diffusion path lengths for ions and

electrons. Hence, the electrochemical performance of the three electrodes are in the order of

F < FMX < FMR. Moreover, Li+ exhibits the smallest bare ion size among Li+, Na+ and K+,

which implies that the small ion’s size coupled with the greatest electrode’s pore size is the
23
best match for an optimal electrochemical performance. This assumption is proved by the

fact that the best performance is obtained for FMR electrode in the 5M LiCl electrolyte.

Fig. 8. Cyclic test of FMR at 5 A g-1 showing (a) voltage vs elapsed time plot, (b)

capacitance retention vs cycle number profile and (c) Nyquist plot before and after cyclic

test in 5 M LiCl electrolyte (inset depicts the equivalence circuit model).

In accordance with the results obtained from electrochemical characterization, the

best electrode (FMR electrode) was further characterized by cyclic stability tests for 5000

charge-discharge cycles at a current density of 5 A g-1 (Figure 8a). The initial specific

capacitance was retained up to 82.1% even after 5000 continuous charge-discharge cycles,

which proved the good cyclic stability of the FMR electrode in 5 M LiCl electrolyte

(Figure 8b). The electrical conductivity was measured prior to and after the cyclic stability

test. The Nyquist plot (Figure 8c) revealed that the Rs and Rct values prior to the stability

test were 2.73 and 3.92 Ω, respectively, whereas these values changed to 2.23 and 6.49 Ω,

respectively, after the cyclic tests. This result proves that the resistance related to electron

transfer reaction (Rct) increased, whereas the resistance associated with surface layer (Rs)

decreased after continuous charge-discharge cycles. This observation may be attributed to

the fact that some electrode’s material dissolves in the electrolyte with increasing cycle

number, which may have caused a decrease in electrical conductivity. The equivalent

24
circuit model (inset of Figure 8c) is drawn in accordance with the result of the Nyquist plot

prior to and after the cyclic test. This model consists of four different parameters, which

include Rs, Rct, constant phase element (CPE) and Warburg impedance (W). The semicircle

in the initial part of the Nyquist plot is depicted by a simple Randles circuit, which means

that Rs is in series with a parallel circuit between Rct and CPE. The Warburg impedance

factor is in series with the simple Randles circuit due to the presence of a tangent line in the

Nyquist plot.

Fig. 9. Plot between real Z vs. inverse square root of frequency for FMR electrode before

and after stability test in 5M LiCl electrolyte.

Moreover, the diffusion coefficient value of the FMR electrode before and after

cycle test in 5M LiCl electrolyte (diffusion coefficient value for all the three electrodes in

all three electrolytes is given in Figure. S10 and Table. S1) was calculated using the

following relations (3 & 4) [73,74].

(3)
√

25
 (4)

Where, is the Warburg coefficient (Ω Hz1/2) value calculated from the slope of the

plot between real Z vs. inverse square root of frequency, R is the universal gas constant (J

mol-1K-1), T is the temperature during the experiment (K), n is the number of electrons

transferred, A is the active area of the electrode (cm2), Di is the diffusion of the electrolyte

ion (cm2 s-1), Ci is the concentration of the electrolyte (mol cm-3) & F is the faraday

constant (C mol-1).

Equation (4) is used to get the value of warburg coefficient which can be seen in the

Figure 8 (a-c). The real impedance of the FMR electrode showed linear behaviour with

respect to inverse square root of the frequency. Furthermore, using Equation (3) the

diffusion coefficient values were calculated for all the electrodes in three different

electrolytes. The calculated diffusion coefficient values before and after stability test was

9.49271×10-11 cm2 s-1 and 4.13654×10-11 cm2 s-1 respectively (Figure 9). The increased

value of diffusion coefficient after stability test refers to the enhancement in the ion

interaction through the electrode-electrolyte interfaces.

Conclusions

Magnetic nanocomposites consisting of Fe3O4/MXene and Fe3O4/MXene/RGO

were generated by chemical oxidation without any impurities. The saturation magnetization

of bare Fe3O4 was about 89 emu g-1 and decreased to 70 and 62 emu g-1 due to the addition

of Mxene and Mxene/RGO, respectively. A detailed analysis of the resulting morphologies

showed the sheet-like morphology of MXene decorated with Fe3O4. The Fe3O4-decorated

MXenes and bare Fe3O4 MNPs were decorated on RGO sheets to generate

RGO/MXene/Fe3O4 nanocomposites. All electrochemical experiments concluded that

26
various parameters such as ion size, ionic conductivity, ionic mobility, electrolyte viscosity

need to be taken into account to find an electrolyte with a high supercapacitive

performance. All these factors may greatly affect the supercapacitor potential window,

specific capacitance, energy density, power density, equivalent series resistance, among

others. The correlation between the electrolyte’s ion size and the electrode’s pore size was

shown to play a crucial role in determining the electrochemical efficiency of the

electrochemical system. In this context, the 5 M LiCl electrolyte exhibited the best

performance among all electrolytes, whereas the FMR electrode demonstrated the highest

electrochemical activity among the electrodes. This may be explained by the fact that the

lowest bare ion size of Li+ ion coupled with the highest pore size of the FMR sample

allowed for the fastest ion transportation kinetics and, thus, good ion

intercalation/deintercalation. The addition of MXene and RGO into the bare Fe3O4

enhanced the output current range of the final FMR electrode due to an increased specific

surface area, increased electrical conductivity and enlarged pore size. Based upon the

electrochemical experiments conducted, FMR nanocomposites can be considered as an

excellent candidate for supercapacitor negative electrode material in 5 M LiCl, where the

invention of negative electrode material has come to saturation.

Credit Author Statement

Thirumurugan Arun- Conceptualization, Methodology, Investigation and Writing -

Original Draft

Ankita Mohanty- Investigation and Writing - Original Draft

Andreas Rosenkranz- Writing - Original Draft

Bo Wang-Resource
27
Jinhong Yu-Resource

Mauricio J. Morel-Resource

R. Udayabhaskar- Investigation and Resource

Samuel A. Hevia- Investigation and Resource

Ali Akbari-Fakhrabadi-Resource

R.V. Mangalaraja-Resource

Ananthakumar Ramadoss- Investigation, Resource and Writing - Original Draft

Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

Acknowledgement

Arun Thirumurugan gratefully acknowledges the University of ATACAMA for the

financial support. The authors also express their gratitude to Dr. R. Justin Joseyphus

(Department of Physics, National Institute of Technology, Tamil Nadu, India) for the VSM

measurements. A. Rosenkranz gratefully acknowledges the financial support given by

ANID-CHILE within the project Fondecyt 11180121 as well as the VID of the University

of Chile in the framework of “U-Inicia UI013/2018”. A. Rosenkranz and B. Wang

acknowledge the financial support of Chinese Academy of Sciences President’s

International Fellowship Initiative (2020VEC0006). S. A. Hevia acknowledges the

financial support of Fondequip EQM150101.

28
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Graphical Abstract:

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