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Enhanced Electrochemical Performance of Ti3C2T x MXene film based super-

capacitors in H2SO4/KI Redox Additive Electrolyte

Jianjian Fu, Lei Li, Damin Lee, Je Moon Yun, Bong Ki Ryu, Kwang Ho Kim

PII: S0169-4332(19)33066-1
DOI: https://doi.org/10.1016/j.apsusc.2019.144250
Reference: APSUSC 144250

To appear in: Applied Surface Science

Received Date: 18 August 2019

Revised Date: 28 September 2019
Accepted Date: 30 September 2019

Please cite this article as: J. Fu, L. Li, D. Lee, J. Moon Yun, B. Ki Ryu, K. Ho Kim, Enhanced Electrochemical
Performance of Ti3C2T x MXene film based supercapacitors in H2SO4/KI Redox Additive Electrolyte, Applied
Surface Science (2019), doi: https://doi.org/10.1016/j.apsusc.2019.144250

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 Enhanced Electrochemical Performance of Ti3C2Tx MXene film based

supercapacitors in H2SO4/KI Redox Additive Electrolyte

Jianjian Fua,†, Lei Lib,c†, Damin Leea, Je Moon Yunb, Bong Ki Ryu a,*, Kwang Ho Kima,b,*

a
School of Materials Science and Engineering, Pusan National University, 2, Busandaehak-ro,

63beon-gil, Geumjeong-gu, Busan 46241, Republic of Korea

b
Global Frontier R&D Center for Hybrid Interface Materials, Pusan National University, 2,

Busandaehak-ro, 63beon-gil, Geumjeong-gu, Busan 46241, Republic of Korea

c
School of Physics and Electrical Engineering, Anyang Normal University, Anyang 455000,

P.R.China

†
These authors contributed equally to this work.

*
Corresponding author:

E-mail: bkryu@pusan.ac.kr (Bong Ki Ryu)

kwhokim@pusan.ac.kr (Kwang Ho Kim)

1
Abstract

The introduction of redox additives into the electrolyte is considered to be an effective and facile

approach to increase the specific capacitance of supercapacitors (SCs), as these additives facilitate

redox reactions at the electrode/electrolyte interfaces. Herein, a freestanding titanium carbide

Ti3C2Tx (MXene) film was prepared through lithium fluoride/hydrochloric acid (LiF/HCl) etching

method and subsequent vacuum filtration process. Subsequently, the electrochemical behavior of

freestanding Ti3C2Tx film based symmetric SCs was improved via the addition of potassium iodide

(KI), as a redox additive. The optimized Ti3C2Tx//H2SO4/KI//Ti3C2Tx redox additive electrolyte

SCs (RAESs) assembled using Ti3C2Tx film as both positive and negative electrodes and H2SO4/KI

as electrolyte show a volumetric capacitance of 601 F cm–3 and a volumetric energy density of

83.5 Wh L–1 at a power density of 1800 W L–1. These results suggest the importance of KI redox

additive electrolyte in developing Ti3C2Tx based SCs.

Keywords: MXene Ti3C2Tx film; KI redox additive electrolyte; High volumetric capacitance

supercapacitor.

2
1. Introduction

With the rapid growth of the economy, the need for sustainable energy storage and conversion

devices has become urgent [1-4]. Supercapacitors (SCs), which possess high charge/discharge rate,

superior power density, and long cycling life, have attracted considerable attentions [5-7]. To date,

various materials such as carbonaceous materials, transition metal compounds, conductive

polymers et al. have been utilized as electrode materials for SCs [8-10]. Recently, two dimensional

(2D) transition metal carbide/nitride termed as MXenes have shown substantial potentials as

promising electrodes for SCs because of their metallic conductivity and hydrophilic surfaces [11-

14]. To date, the frequently studied MXene material is Ti3C2Tx and the freestanding Ti3C2Tx films

can be used as electrode directly [15-17]. So far, the electrochemical performance of the Ti3C2Tx

has been studied in various electrolyte such as alkaline solution [18], sulfuric acid [19], neutral

aqueous solution [20], organic [21], and ionic liquid electrolytes [22]. Interestingly, the

electrochemical performance of the Ti3C2Tx films in sulfuric acid (H2SO4) show superior

electrochemical performance due to the intercalation of the small size of the hydronium between

the Ti3C2Tx layers [23]. However, there are a lot of space to improve the electrochemical

performance in sulfuric acid. More importantly, developing a facile and rapid way to improve the

electrochemical performance is very necessary.

Recently, redox additive electrolyte supercapacitor (RAES), which involve redox additives in the

electrolyte, have attracted considerable attentions due to improved capacitance and energy density

compared with original SCs without the additives [24-26]. The main benefit of the RAES is the

facile and safe operation process, which can be straightforwardly realized by introducing redox

additives into pristine H2SO4 or KOH electrolyte at ambient temperature without any

3
difficulty. Until now, various redox additive have been applied such as potassium ferricyanide

(K3Fe(CN)6) [27-29], potassium iodide (KI) [30], potassium bromide (KBr) [31], p-

phenylenediamine (PPD) [32, 33], catechol [34], resorcinol [35], hydroquinone (HQ) [36, 37],

and p-nitroaniline (PNA) [38]. Liu et al. reported a nanoporous carbon electrode using a

hybrid PPD/KOH electrolyte, which exhibited high specific capacitance of 557 F g−1 at 0.1 A g−1

due to the presence of the PPD redox additive [33]. Xie et al. investigated the faradaic

pseudocapacitance effect of the HQ additive on the electrochemical performance of PANI

electrodes [37]. They found that those electrodes exhibit excellent specific capacitance of 584 F

g–1, which was larger than that of the original value of 403 F g–1 without adding HQ. Among these

additives, KI has been referred as an excellent redox additive, which causes reversible redox

reactions at the electrolyte/electrode interface due to its various chemical states and increased ionic

conductivity [39]. More importantly, they have tiny iodide species with small size such as I− (0.39

nm), I3− (0.63 nm), I5− (1.2 nm), and IO3− (0.57 nm), which are easily accessible to the surface of

the electrode [40, 41]. Gala et al. examined the effect of the KI additive on the Na2SO4 electrolyte

for the SrRuO3-RGO electrode [42]. The electrode exhibited an excellent specific capacitance

value of 907 F g−1 due to the faradaic effect of the reversible redox reactions of the iodine ions.

Herein, with the aim of improving the electrochemical performance of Ti3C2Tx film, we introduce

KI as a redox additive into H2SO4 electrolyte. The effects of the electrolyte on the electrochemical

performance are discussed in two-electrode system. Benefit from the presence of the redox

reaction from the iodide species at the electrode/electrolyte interface, the

Ti3C2Tx//H2SO4/KI//Ti3C2Tx RAESs exhibit maximum volumetric specific capacitance with 601 F

cm–3. Moreover, the RAES delivers a volumetric energy density of 83.5 Wh L–1 at a power density

4
of 1800 W L–1. In addition, the material characteristics of Ti3C2Tx dry film after cycling test were

characterized through X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy

(SEM) analyses. All these results suggest that the introduction of KI into the H2SO4 electrolyte is

an effective way to enhance the electrochemical performance of Ti3C2Tx film based SCs.

2. Experimental details

2.1. Synthesis of Ti3AlC2 MAX phase monolith

Ti3AlC2 MAX phase powder was prepared similar with our previously described method [43].

Generally, Ti, Al, and graphite powder were mixed together in molar ratio of 3: 1.1: 2 for 6 h using

ball mill method. In particular, excess Al was used to offset the loss of Al in the high temperature

sintering process. Subsequently, Ti3AlC2 MAX phase monolith was obtained via a spark plasma

sintering process at temperature of 1100 °C for 20 min under a pressure of 20 MPa, according to

the reaction: 3Ti + 1.1Al + 2C → Ti3AlC2. Finally, the Ti3AlC2 powder was prepare through

crushing the Ti3AlC2 monolith using a pulverizer machine (QE-100, Yili Tools Co., China). The

final powder was obtained through a sieve with a particle size of 72 µm.

2.2. Preparation of delaminated Ti3C2Tx nanosheets

Delaminated Ti3C2Tx nanosheets was prepared by etching Ti3AlC2 powder in LiF/HCl solution

according to the reported method [44]. Typically, the as obtained Ti3AlC2 powder was immersed

and vigorously stirred in LiF (0.5 g) and HCl (10 mL, 9 M) mixture solution at 50 °C for 24 h. The

resulting precipitate was rinsed with HCl (9 M) and distilled (DI) water for 3 times until the pH

was approximately 6. Afterward, the precipitate was redispersed in DI water and mechanically

sonicated for 6 h in ice bath under argon gas atmosphere. Finally, the dark green supernatant of

Ti3C2Tx suspension was collected after centrifugation at 4000 rpm for 60 min.

5
2.3. Preparation of freestanding Ti3C2Tx film

Freestanding Ti3C2Tx film was obtained through vacuum filtration process through a mixed

cellulose filter paper (Celgard, pore size 0.45 μm). Generally, 21 mL of 1 mg mL–1 Ti3C2Tx

suspension was vacuum filtered through filter paper and then vacuum dried at room temperature

overnight. Finally, the Ti3C2Tx film with a thickness of 4.6 μm and diameter of 4 cm was obtained

after being separated with the filter paper.

2.4. Materials characterization

X-ray diffraction (XRD) patterns were obtained using a D8 Advance X ray diffractometer (Bruker,

Germany) with a copper Kα source (λ = 0.15418 nm). The morphologies were examined using

field emission scanning electron microscopy (FESEM, Hitachi S4800, Japan). Transmission

electron microscopy (TEM), high resolution TEM (HRTEM), selected area electron diffraction

(SAED) pattern, and high angle annular dark field scanning TEM (HAADF-STEM) images were

collected on Titan G2 60-300 instrument with an energy dispersive X ray spectrometer (EDX)

attachment. The depth profile was determined by atomic forced microscopy (AFM, Nanoscope

IIIa Multimode instrument, California). The particle size distribution was collected using a particle

size analyzer (zetasizer nano series, Malvern). The electrical conductivity of the film was obtained

through a four point probe device (CMT-SR1000N). XPS data were acquired using an Escalab 250

X ray photoelectron spectrometer (Thermo Fisher).

6
2.5. Electrochemical performance

An IviumnStat electrochemical workstation (Ivium, Netherlands) was used to analyze the

electrochemical performance through cyclic voltammetry (CV), galvanostatic charge/discharge

(GCD), and electrochemical impedance spectral (EIS) data. The EIS analysis was performed in

the frequency range of 100 kHz to 0.01 Hz at an open circuit potential with an alternating current

perturbation of 5 mV.

The RAES device was fabricated using Ti3C2Tx film as both positive and negative electrodes. The

electrolyte was 3M H2SO4 with various concentrations of KI (0, 0.1, 0.3, and 0.5 M). A Celgard

3501 polymer membrane was used as the separator. The gravimetric (Cdevice-g, F g–1) and volumetric

(Cdevice-v, F cm–3) specific capacitance of the device were estimated from the GCD curves using

equations (1) and (2).

I ×Δt
Cdevice-g = (1)
M × ΔV

Cdevice-v=ρ × Cdevice-g (2)

where, I (mA) is the applied current, Δt (s) is the discharge time, M (mg) is the total active mass

of positive and negative electrodes, ΔV (V) is the voltage window of the device, and ρ (g cm–3) is

the density of the Ti3C2Tx film which could be determined according to equation (3):

ρ=m/(S × d)=m/(π ×R2 × d) (3)

where m (g) is the mass of the Ti3C2Tx film, S (cm2) is the area of the Ti3C2Tx film, R (cm) is the

radius of the Ti3C2Tx film, and d (cm) is the thickness of the Ti3C2Tx film. In this study, the mass

7
of the Ti3C2Tx film was approximately 21 mg. The diameter and thickness were approximately 40

mm and 4.6 µm, respectively. Thus, the calculated density of the Ti3C2Tx film was 3.63 g cm–3.

The gravimetric energy density (Eg, W h kg−1) and power density (Pg, W kg−1) of the

Ti3C2Tx//H2SO4/KI//Ti3C2Tx RAES devices were estimated from the GCD curves by equations (4)

and (5):

1
Eg = 2 × Cdevice-g × ΔV2 (4)

Pg= Eg/Δt (5)

where Δt (s) is the discharge time. The volumetric energy density (Ev, Wh L–1) and the power

density (Pv, W L–1) of the Ti3C2Tx//H2SO4/KI//Ti3C2Tx RAES devices were calculated from

equations (6) and (7):

Ev = ρ × Eg (6)

Pv = ρ × Pg (7)

8
3. Results and discussion

3.1. Material characterization

Figure 1 shows the schematic illustration of the preparation process of Ti3C2Tx film. The Ti3C2Tx

film was selected as the working electrode and electrochemically characterized in H2SO4/KI redox

additive electrolyte. The delaminated Ti3C2Tx nanosheets are obtained in a mixture solution of

LiF/HCl which could generate diluted HF. In this process, the Al was etched away by the HF and

the Li+ ions simultaneously intercalate into the interlayer space of the Ti3C2Tx nanosheets, resulting

a swelled structure [44]. Then, the expanded Ti3C2Tx nanosheets were mechanically sonicated to

obtain the delaminated Ti3C2Tx nanosheets. Because of the 2D characteristic of Ti3C2Tx nanosheets,

a uniform freestanding Ti3C2Tx film can be easily obtained due to the stack of the delaminated

Ti3C2Tx nanosheets. At last, the Ti3C2Tx film was used as a binder free electrode. The

electrochemical performance of the Ti3C2Tx film based symmetric SCs was studied in H2SO4/KI

redox additive electrolyte.

As precursor, the structures and morphologies of Ti3AlC2 MAX phase were characterized by SEM

measurements. In Figure S1, the Ti3AlC2 MAX phase powder was observed with a lateral average

size of 3 to 4 µm. As shown in Figure 2a, the Tyndall effect was observed in Ti3C2Tx suspension,

indicating the stable suspension nature of the Ti3C2Tx solution. Figure 2b, c show the photographs

of the Ti3C2Tx film (diameter: 40 mm) with high mechanical flexibility. Furthermore, the Ti3C2Tx

sheets with electron transparent on anodized aluminum oxide (AAO) substrate were observed as

shown in Figure 2d. The particle size distribution of the MXene nanosheet range from 200 to 1000

nm show an obvious Gaussian distribution, as shown in the inset of the Figure 2d. In Figure 2e,

f, the AFM images of Ti3C2Tx nanosheets reveal the thickness of nanosheets is about 1~2 nm. The

9
top view and cross-section view of Ti3C2Tx film were also observed. Figure 2g exhibits the

wrinkled surface of the Ti3C2Tx film with a crumpled and rough surface. Figure 2h,i show the

cross section SEM images of the Ti3C2Tx film under different magnifications with a thickness of

4.6 µm, revealing the stacked parallel layer-by-layer arrange of the nanosheets with some void

gaps, which enable high specific surface area, extra electroactive sites, and more accessible of the

electrolyte. Additionally, the conductivity of the Ti3C2Tx film was measured to be about 4895 S

cm−1 according to typical four-probe test.

TEM was used to furtherly check the morphologies of the delaminated Ti3C2Tx nanosheet. It can

be clearly seen that the nanosheets of Ti3C2Tx are very thin and the electron can readily transmitted,

suggesting the ultrathin 2D characterization of the Ti3C2Tx nanosheets (Figure 3a,b). The SAED

pattern (Figure 3c) shows hexagonally organized diffraction dots, demonstrating the hexagonal

structure of the Ti3C2Tx nanosheet, which can be assigned to the (100) planes of Ti3C2Tx (space

group: P63/mmc, a = b = 3.073 Å, and c = 18.557 Å) [45]. Figure S2 and Figure 3d present EDX

spectrum and elements mapping images of the MXene nanosheets, indicating the even distribution

of Ti, C, O, and F elements.

XRD patterns of the Ti3AlC2 MAX phase and Ti3C2Tx film are presented in Figure 4a. All

observed diffraction peaks of the Ti3AlC2 MAX phase are consistent with the standard JCPDS

Card No. 29-0095. The major peaks located at 9.5°, 19.1°, 34.0°, 36.7°, 39.0°, 41.7°, 48.5°, 56.3°,

60.2°, 65.4°, 70.4°, and 74.0° were indexed to the (0 0 2), (0 0 4), (1 0 1), (1 0 3), (1 0 4), (1 0 5),

(1 0 7), (1 0 9), (1 1 0), (1 0 11), (1 1 8), and (1 0 13) planes of the hexagonal Ti3AlC2 MAX phase

10
[46]. For the Ti3C2Tx film, the Al layers in MAX phases were selectively removed, so that the (002)

peak was shifted from 9.52° (interlayer space: 9.28 Å) to 7.04° (interlayer space: 12.54 Å).

According to the Brag’s equation, a lower diffraction angel (2θ) indicated a larger interlayer space

[47]. XPS was used to analyze the chemical state of the elements. The full survey spectrum in

Figure 4b confirms the presence of Ti, C, O, and F elements. It is noteworthy that the detection

of O and F elements demonstrate the presence of =O, –OH, and –F functional groups that confer

the hydrophilicity of Ti3C2Tx. As shown in Figure 4c, the Ti 2p spectrum can be deconvoluted into

five pairs of doublets, corresponding to Ti−C (455.4, 461.1 eV), Ti (II) (455.8, 461.5 eV), Ti (III)

(456.6, 462.3 eV), Ti (IV) (457.7, 463.4 eV), and Ti−F (458.9, 464.6 eV) [48]. The C 1s spectrum

(Figure 4d) shows the peaks centered at 284.8, 285.7, and 287.2 eV, which are ascribed to C–Ti,

C–C, and –CO bonds, respectively [49]. The F 1s spectrum (Figure 4e) is related to the Ti-F

chemical bond corresponding to the peaks centered at 685.3 eV [48, 49]. The O 1s spectrum

(Figure 4f) shows four peaks deconvoluted into 531.2, 531.8, 532.5, and 533.4 eV indexed to the

TiO2, Ox, –OH, and Ti–H2O groups [48].

3.2. Pseudocapacitive effect of KI redox additive in two symmetric electrode system

The introduction of redox additive into the electrolyte has been considered a useful method for

improving the performance of the SCs via the redox reactions at or near the interface between the

electrode and the electrolyte [40, 50-52]. In this study, two symmetric electrode system was used

to figure out the electrochemical characteristics. The reason to choose two-electrode system is

because the KI are relatively stable in positive potential (~0.4V) [53]. Moreover, compared with

the measurement in three-electrode system which only study the electrochemical behavior of the

single electrode, the investigation in two electrode systems is more crucial for the practically

11
applications of the SCs [54]. The H2SO4 aqueous solution was selected as the electrolyte in this

study due to its high ionic conductivity (0.26 S cm–1) [55] and small diameter of the H+ ion

(hydrated ion: 0.564 nm) [11, 41]. To further improve the electrochemical performance of

Ti3C2Tx//Ti3C2Tx SCs, KI with different concentrations (0, 0.1, 0.3, and 0.5 M) was added in the 3

M H2SO4 electrolyte, and the RAES devices were assembled as shown in Figure 5a. Figure

5b and Figure S3 present comparative CV curves for the 3M H2SO4 based electrolyte with

different concentrations of KI. The symmetric Ti3C2Tx//Ti3C2Tx SC device in pure H2SO4

electrolyte has a potential window of 0~1 V, which exhibits a stable capacitance behavior without

significant distortion. As expected, after the introduction of the KI additive electrolyte, the CV

curves of the devices show a humped shape in the range of 0.4~1.0 V, demonstrating the

pseudocapacitive effect of the reversible KI redox reactions at the electrolyte/electrode interface

[51, 56]. Besides, the effect of KI concentrations from 0 to 0.5 M was systematically discussed.

Impressively, the 3M H2SO4+0.3M KI device exhibited the most dynamic faradaic reaction with

the largest current response and integrated area. When the concentration of KI increased to 0.5 M,

the current response decreased and the excessive KI deteriorated the electrochemical performance.

Excessive KI may aggregate and crystallize in the aqueous H2SO4 solution during charging and

discharging process which could inhibit the adsorption/desorption of the redox additive ions,

thereby hindering the faradaic reactions at the electrode/electrolyte interface [57, 58]. Furthermore,

the comparative GCD curves of devices at 1 A g–1 in H2SO4 and H2SO4/KI electrolyte are shown

in Figure 5c. It can be observed that the GCD curve show near-liner shape in H2SO4 electrolyte,

indicating the intercalation pseudocapacitance mechanism during the charge/dischrage process.

Besides, the GCD curve in H2SO4/KI electrolyte show a quasi-line with a slight distortion,

corresponding to the redox reaction of the KI. In particular, the GCD curves of the SC in 3M

12
H2SO4+0.3M KI electrolyte exhibits the largest deviation from the triangular shape because of the

enhanced pseudocapacitance effect of KI additive. Moreover, Figure S4 show the GCD curves at

different current densities. All the curves are almost symmetric, suggesting the high reversibility.

In addition, for the SC in 3M H2SO4+0.3M KI electrolyte, its volumetric and gravimetric

capacitances at different current densities are shown in Figure 5d and Figure S5a. These results

exhibited enhanced specific capacitance of 166 F g–1 (volumetric capacitance of 601 F cm–3) at 1

A g–1, compared to that of 61 F g–1 (volumetric capacitance of 220 F cm–3) of the symmetric SC

device without KI additive. Figure 5e shows the cycling performance of the device in 3M

H2SO4+0.3M KI electrolyte. Their capacitance almost keep 100%, suggesting the extraordinary

cycling stability of the devices. To evaluate the electrical conductivity of the RAESs, EIS was

performed in the frequency range from 0.01 Hz to 100 kHz (Figure S6). Typically, electrolyte

resistance (Rs) is corresponding to the intersection of the plot with the X-axis at the high-frequency

range. On the other hand, the charge-transfer resistance (Rct) can be derived from the diameters of

semicircle [59]. After the addition of the KI, the charge transfer resistance was decrease, indicating

the improvement of the ionic conductivity [50]. It can be seen that, when the concentration of KI

up to 0.3 M, Rs and Rct were reduced obviously. Therefore, it can be concluded that the electrolyte

conductivity was improved. However, at the concentration of KI is 0.5 M, excess iodine species

may hamper the reversible redox reaction, thus resulting in the increase of Rs and Rct incidentally.

Similar results can be observed on other studies [58, 59]. In general, the RAESs has

smaller Rs and Rct in 3M H2SO4 + 0.3 M KI electrolyte, which is good for the ion diffusion and

charge transfer. The energy and power density are important parameters to evaluate the practical

application of the electrode. The Ti3C2Tx//H2SO4+KI//Ti3C2Tx RAESs with a voltage of 1 V

deliver an optimized energy density of 23.19 Wh kg–1 (83.5 Wh L–1) at a power density of 500 W

13
kg–1 (1800 W L–1) (Figure 5f and Figure S5b). In Figure 5f, the RAES with 3M H2SO4+0.3M KI

presents the highest electrochemical performance, such as MX-rHGO3//MX-rHGO3[16], M/G-

5%//M/G-5%[14], MP-MX1.5//MP-MX1.5[15], ak-Ti3C2Tx film//ak-Ti3C2Tx film [60], and

Ti3C2Tx/PANI//Ti3C2Tx/PANI [61]. In a word, the above electrochemical results indicated that the

KI additive can be an excellent candidate for enhancing the electrochemical performance of the

Ti3C2Tx film.

Figure 6a shown the charge storage mechanism of Ti3C2Tx film based electrode in H2SO4/KI

electrolyte. It has been demonstrated that, in the pure H2SO4 electrolyte, the Ti3C2Tx film show

intercalation pseudocapacitance, stem from the changes of the Ti oxidation states along with the

intercalation/deintercalation H+ ions into the Ti3C2Tx layers [15, 16]. After the introduction of the

KI into the H2SO4, extra redox reactions (3I–/I3–, 2I–/I2, 2I3–/3I2, and I2/2IO3) will be took place in

the electrode/electrolyte interface according to the following Eq. (8)–(11) [12]:

3I– ↔I3– +2e– (8)

2I–↔I2 + 2e– (9)

2I3–↔3I2 + 2e– (10)

I2+6H2O↔2IO3–+12H++10e– (11)

It can be concluded that the improved electrochemical performance of the

Ti3C2Tx//H2SO4/KI//Ti3C2Tx RAESs can be attribute to the synergic effect as bellow: (i) 2D free-

standing paper like Ti3C2Tx electrode without additional additive and binder, preventing extra dead

volume, which could significantly endow the favorable charge storage at electrode/electrolyte

interface and enhance the charge transfer efficiency. (ii) H2SO4 with high ionic conductivity (0.26

14
S cm–1) [55] and small ionic size (hydrated ion: 0.564 nm) [11, 41], are the ideal electrolyte to

boost the capacitive ability of the Ti3C2Tx film. (iii) KI redox additive species with smaller sizer

(I− hydrated ion: 0.662 nm, I3−: 0.63 nm, IO3– hydrated ion: 0.748 nm) facilitate more accessible

on the deep adsorption sites between Ti3C2Tx layers, thus generate extra faradic redox reactions

and providing more electrochemical capacitance [40, 41]. Combining these contributions, the

Ti3C2Tx//H2SO4/KI//Ti3C2Tx RAESs achieve improved electrochemical performance.

In order to get more information about the behavior of the Ti3C2Tx film in H2SO4 and H2SO4/KI

electrolyte, XPS and SEM analyze for the Ti3C2Tx dry film after 5000 cycles of repeat

charge/discharge process were carried out. The peaks of the I3d and K2s were emerged suggesting

that the KI additive plays a key role in the electrochemical performance. In Figure 6c, the two

peaks centered at 620.2 eV in I 3d5/2 and 630.9 eV in I 3d3/2. After the cycling test, the full survey

XPS spectra of the two electrodes showed the presence of S peaks, corresponding to the SO 42−

species, due to the adsorption of the H2SO4 electrolyte during the charge/discharge process, as

shown in Figure 6d. The almost unchanged Ti 2p peaks of the Ti3C2Tx film after the cycling test

show high chemical stability of the Ti3C2Tx in the presence of the KI additives (Figure 6e). In

order to check the effect of electrolytes on the morphologies of the Ti3C2Tx surface, SEM images

are also shown in Figure 7b. From the plane and cross-section views of these Ti3C2Tx films, no

significant deformation or deterioration was observed after the charge/discharge process,

indicating the high stability of Ti3C2Tx film in those electrolytes. Furthermore, Figure S7, 8 show

EDX mapping images and electron spectrum after the cycling test. For the sample after the cycling

test in H2SO4 electrolyte, O, Ti, C, and S can be detected. While the sample tested in H2SO4/KI

15
electrolyte show the presence of O, Ti, C, S, I, and K elements. These results are well agree well

with the XPS results.

4. Conclusions

In summary, freestanding Ti3C2Tx film was prepared through vacuum filtration process. The

electrochemical performance of the Ti3C2Tx//Ti3C2Tx RAESs was systematically studied in

H2SO4/KI electrolyte. Owing to the combinational effect of the pseudocapacitance performance

of the MXene and reversible redox reaction of KI additive, the Ti3C2Tx//H2SO4/KI//Ti3C2Tx

RAESs exhibits an optimized volumetric specific capacitance of 601 F cm–3 (gravimetric specific

capacitance of 166 F g–1) at current density of 1 A g−1. Moreover, the device delivered a volumetric

energy density of 83.5 Wh L–1 at a volumetric power density of 1800 W L–1. This excellent

electrochemical performance of the RAES device suggests the importance of KI additive with

enhanced redox reactions for high performance Ti3C2Tx based energy storage devices.

Acknowledgements

We gratefully acknowledge the support of this work by the Global Frontier Program through the

Global Frontier Hybrid Interface Materials (GFHIM) of the National Research Foundation of

Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (2013M3A6B1078874).

The authors are very grateful to the members of the National Core Research Centre (NCRC) for

their excellent experimental assistance.

Conflicts of interest

16
There are no conflicts of interest to declare.

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Figure 1 Schematic illustration of synthesis process of the Ti3C2Tx film.

21
Figure 2 Characterization of Ti3C2Tx nanosheets and Ti3C2Tx film. (a) Photograph of the Tyndall

effect of Ti3C2Tx suspension. (b and c) Photographs of the Ti3C2Tx film with a diameter of 40 mm

and its flexible feature. (d) SEM image of the Ti3C2Tx nanosheets on AAO substrate (inset is the

particle size distribution of the Ti3C2Tx nanosheets). (e) AFM image of the Ti3C2Tx nanosheets on

a mica substrate and (f) height profile of a Ti3C2Tx nanosheet. (g) Top view SEM images of the

Ti3C2Tx film. (h, i) Cross-section SEM images of the Ti3C2Tx film under different magnifications.

22
Figure 3 (a, b) TEM and HRTEM images of the Ti3C2Tx nanosheets. (c) SAED pattern image. (d)

Elemental mapping images of Ti, C, O, and F elements.

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Figure 4 (a) XRD patterns of Ti3AlC2 MAX phase and Ti3C2Tx film. XPS results of the Ti3C2Tx

film: (b) full survey spectrum; (c) Ti 2p; (d) C 1s; (e) F 1s; and (f) O 1s.

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Figure 5 The electrochemical performance of the Ti3C2Tx//Ti3C2Tx RAES devices at various KI

concentrations (0, 0.1, 0.3, 0.5 M). (a) Schematic of the RAES device configuration. (b)

Comparative CV curves at a scan rate of 5 mV s–1. (c) Comparative GCD curves at a current

density of 1 A g–1. (d) Volumetric capacitance at different current densities. (e) Cycling stability in

0.3M KI additive 3M H2SO4 at a current density of 5 A g–1 through 5000 charge-discharge cycles.

(f) Volumetric Ragone plot of the RAES devices and comparison with previous reported works.

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Figure 6 (a) Schematic illustration of electrochemical mechanism of the Ti3C2Tx in KI additive

H2SO4 electrolyte. (b) Full survey XPS of the Ti3C2Tx dry films. High-resolution XPS spectrum

of (c) I 3d, (d) S 2p, (e) Ti 2p of the Ti3C2Tx dry film.

26
Figure 7 (a) Top view and cross-section view SEM images of the Ti3C2Tx dry film in (a) H2SO4

electrolyte and (b) KI additive H2SO4 electrolyte.

27
Highlights

 Freestanding Ti3C2Tx MXene film was prepared through vacuum filtered process.
 The electrochemical behavior of the Ti3C2Tx film based supercapacitor was enhanced by
KI redox-additive.
 The Ti3C2Tx based supercapacitor with KI redox additive electrolyte show volumetric
capacitance of 601 F cm–3.
 The optimized volumetric energy density is 83.5 Wh L–1 at power density of 1800 WL–1.

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Declaration of Interest Statement

There are no conflicts of interest to declare.

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