Energy Storage Materials 25 (2020) 563–571

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Energy Storage Materials

journal homepage: www.elsevier.com/locate/ensm

Excellent oxidation resistive MXene aqueous ink for

micro-supercapacitor application
Chien-Wei Wu a, Binesh Unnikrishnan b, I-Wen Peter Chen c, Scott G. Harroun d,
Huan-Tsung Chang a, e, *, Chih-Ching Huang b, f, g, **
a
Department of Chemistry, National Taiwan University, Taipei, 10617, Taiwan
b
Department of Bioscience and Biotechnology, National Taiwan Ocean University, Keelung, 20224, Taiwan
c
Department of Applied Science, National Taitung University, Taitung City, 95092, Taiwan
d
Department of Chemistry, Universit
e de Montr
eal, Montr
eal, Qu
ebec, H3C 3J7, Canada
e
Department of Chemistry, Chung Yuan Christian University, Taoyuan City, 32023, Taiwan
f
Center of Excellence for the Oceans, National Taiwan Ocean University, Keelung, 20224, Taiwan
g
School of Pharmacy, College of Pharmacy, Kaohsiung Medical University, Kaohsiung, 80708, Taiwan

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

Keywords: Uniform and stable interdigitated electrodes are essential for planar micro-supercapacitor applications. Two-
MXene dimensional (2D) materials, such as transition-metal MXenes have become attractive nanomaterials for micro-
Sodium ascorbate supercapacitor applications due to their layered structure and high electrical conductivity. However, the low sta-
In-situ synthesis
bility of MXenes in aqueous media limits their long-term storage and application. Here, we demonstrate in-situ
Inkjet printing
Micro-supercapacitor
synthesis and capping of Ti3C2Tx MXenes with sodium ascorbate (SA) to obtain SA-MXene dispersion with high
resistance against oxidation even after 80 days of storage at ambient temperature and exposed to air. The in-situ
synthesis process increases the interlayer spacing of SA-MXene sheets, and increases their energy storage efficiency,
without compromising their electrical conductivity. A printable SA-MXene ink was prepared with Triton X-100 and
propylene glycol as modifiers to print interdigitated micro-supercapacitor electrodes with an inkjet printer. Our
solid-state micro-supercapacitor made without current collector exhibits areal and volumetric capacitance of
108.1 mF cm
2 and 720.7 F cm
3, respectively. This work highlights the potential application of ligand-capped
stable MXenes as a water-based ink in printing devices for the fabrication of micro-electronics and supercapacitors.

1. Introduction
Interdigitated micro-electrode has become an essential component of
micro-batteries and micro-supercapacitors (MSCs) to power miniaturized
electronic devices, such as micro-robot, remote-controlled and automatic
control devices, and a variety of portable sensors [1,2]. In addition, many
biosensors, especially electrochemical sensors, for diagnosing serious
diseases employ interdigital micro-electrodes printed on a suitable plat-
form [3,4]. Inkjet printing of interdigital electrodes is very simple,
cost-effective and can control the thickness of the film in nanometer to
micrometer range by controlling the number of repeated printing passes.
Planar and flexible MSCs require interdigitated electrodes with uniform
film, flexibility, and working stability.
Two-dimensional (2D) materials, such as graphene, chalcogenides,
MXenes, black phosphorus, transition metal oxides, and layered double
hydroxides, have emerged as promising materials for planar super-
capacitor applications [5–11]. However, inkjet printing of
nanomaterial-based ink has many barriers, size of the nanoparticles,
dispersion stability, stable droplet formation, viscosity, surface tension
and so on. Hersam et al. reported the essential characteristics of 2D
nanomaterial-based ink for inkjet printing [11]. In addition, the oxida-
tion stability of the active material and cyclic stability are important
factors for the successful application of MSC.
MXenes, consisting of transition metal carbides and nitrides, have
become a large family of 2D materials, with a base composition of
Mnþ1XnTx, where M is an early transition metal (e.g., Sc, Ti, V, Ta, Cr, Zr,
Nb, Mo, Hf), X is either carbon or nitrogen (n ¼ 1–3), and T denotes the
terminal group (–F, –OH, –O, etc.) that originates from the etchant

* Corresponding author. Department of Chemistry, National Taiwan University, 1, Section 4, Roosevelt Road, Taipei, 10617, Taiwan.
** Corresponding author. Department of Bioscience and Biotechnology, National Taiwan Ocean University, 2, Beining Road, Keelung, 20224, Taiwan.
E-mail addresses: changht@ntu.edu.tw (H.-T. Chang), huanging@ntou.edu.tw (C.-C. Huang).

https://doi.org/10.1016/j.ensm.2019.09.026
Received 27 May 2019; Received in revised form 12 September 2019; Accepted 18 September 2019
Available online 23 September 2019
2405-8297/© 2019 Elsevier B.V. All rights reserved.
C.-W. Wu et al.
[12–14]. Commonly, MXenes can be produced through a selective
chemical etching of “A” from layered ceramics called MAX phases
[12–14]. MAX phases are well organized and the atomically thin
A-element layers, typically Al or Si, separate the sheets of Mnþ1Xn. For
example, Ti3C2 MXenes are prepared by etching bulky Ti3AlC2 with hy-
drofluoric acid (HF), which is formed in situ from the reaction of hy-
drochloric acid (HCl) with lithium fluoride (LiF), or with
bifluoride-based etchants [e.g., ammonium hydrogen difluoride
(NH4HF2), potassium hydrogen difluoride (KHF2)] to remove the
aluminum layer from the crystal [15–18]. MXenes possessing distinct
properties such as metal-like electrical and thermal conductivity, and
high structural stiffness [18,19], have attracted attention for many ap-
plications, including electrochemical energy storage [20–23], energy
conversion [24], biosensing [25], photothermal therapy [26], water
purification [27], photocatalysis [28–30], CO2 capture [31], and
field-effect transistors [32].
Regardless of which type of MXene are employed for various appli-
cations, they typically undergo fast degradation in humid air and water
[33–36]. The oxidation rate of MXenes depends on their flake size,
morphology, composition, etching method, and storage conditions
[33–37]. Persson et al. reported that Nb2C MXenes prepared by
HF-mediated etching of Nb2AlC have Nb adatoms, which attract addi-
tional oxygen from the atmosphere to form a cluster [37]. These clusters
locally destabilize the structure of MXene, and eventually cause struc-
tural degradation across the entire MXene sheet. Recently, Zhang et al.
found that Ti3C2Tx MXene suspensions in open vials were completely
degraded after 15 days, and formed cloudy-white colloidal suspensions
containing primarily the anatase phase of TiO2 [33]. In contrast, MXenes
stored in hermetic Ar-filled bottles at low temperatures (5  C) only
degraded by 1.2% after 25 days, suggesting that dissolved oxygen is the
major oxidant. The study also suggested that the degradation starts at the
edges of the MXene nanosheet, and its degradation kinetics follows a
single exponential decay behavior. More recently, a study revealed that
water also plays a key role in the oxidation reactions leading to the
degradation of Ti3C2Tx MXene [33]. The oxidation of MXene in the
solid-state also was observed [35]. The Ti3C2Tx buckypaper shows a
significant drop in its conductivity (>90%) when stored in a relative
humidity of 80% for 26 days. On the basis of their conductivities, Ti3C2Tx
MXene stored in polymeric matrices [poly(vinyl alcohol) (PVA)] under
atmospheric conditions exhibits slower oxidation than that in liquid
media. However, regardless of the amount of PVA, they display very
similar trends in the decreased conductivity, revealing that the polymer
could not act as an effective barrier to prevent oxidation [35]. The pre-
vious studies implied that the oxidation of MXenes in the presence of
atmospheric humidity causes the material to collapse [31–34]. Also,
Scheme 1. Schematic representation of (A) the synthesis of stable SA-MXene nanocomposite and, (B) solid-state micro-supercapacitor fabricated through inkjet
printing of the SA-MXene nanocomposites.
564
Energy Storage Materials 25 (2020) 563–571
Beidaghi group has reported that V2CTx MXene undergoes oxidation at
high temperatures (>300  C) in CO2 and air atmosphere due to the
presence of water molecules in the layered structure [39]. A recent report
by Chae et al. shows that the main reason for MXene oxidation is due to
the temperature and exposure to water [40]. This is disadvantageous
since applications of MXene-based nanomaterials, such as solid-state
supercapacitors for wearable and portable electronics, require mate-
rials with high capacitance, electrical conductivity, and flexibility, and
perhaps most imperatively, long-term stability. Recently, Zhao et al. re-
ported that anti-oxidants such as sodium ascorbate could decrease the
oxidation rate of MXene, stabilize morphology and structure by pro-
tecting them from the attack of water at the nanosheet edge [41].
In this study, we demonstrate that the stability of Ti3C2Tx MXenes,
produced by an in situ etching method, is enhanced by incorporating
ascorbate ion as capping and anti-oxidizing agent at ambient temperature
and print interdigitated electrodes for MSC application. (Scheme 1A).
Sodium ascorbate-capped MXene (SA-MXene) shows high dispersity and
structural stability over 80 days in water solution and can be used as a
stable ink when printed on paper to form planer interdigital electrode
patterns using a simple office inkjet printer (Scheme 1B). Use of the
printed electrodes for construction of a solid-state MSC exhibits superior
mechanic flexibility, cycling stability, and specific capacitance.
2. Experimental
2.1. Materials
Titanium aluminum carbide (Ti3AlC2, MAX) was purchased from
Hello Nano Technology Co. Ltd. (Changchun, China). Ammonium citrate
(>97%) was purchased from Showa Chemical Co. Ltd. (Tokyo, Japan).
Lithium fluoride (LiF, >99.99%), poly(vinyl alcohol) (Mw:
85,000–124,000) (>99%), propylene glycol, hydrochloride solution
(37%), sulfuric acid solution (95–98%), Triton X-100, disodium
hydrogen phosphate (98%), sodium phosphate(96%), sodium oxalate
(>99.99%), oxalic acid (98%) ammonium (>99.98%), lithium hydroxide
(>98%), potassium hydroxide (>85%), sodium hydroxide (>98%), citric
acid (99%) and sodium citrate (>99%) were purchased from Sigma-
Aldrich (St. Louis, MO, USA). Ultrapure water (18.2 MΩ cm
1) from a
Milli-Q ultrapure system was used in this study. Photo paper (Canon, PP-
208) was purchased from a local market in Taiwan.
2.2. Synthesis of m-MXene
Multilayer Ti3C2Tx (m-MXene) colloidal suspension was prepared by
wet etching of relevant MAX phases [42]. Typically, 5 g of LiF was added
C.-W. Wu et al.
to 50 mL of HCl (9 M) solution in a plastic vial. After 0.5 h of stirring, 5 g
of Ti3AlC2 MAX was slowly added over the course of 0.5 h. Then, the vial
was transferred to the oil bath and allowed to react for 24 h at 40  C
under constant stirring. The as-formed m-MXene was separated by
centrifugation at a relative centrifugal force (RCF) of 3000 g for 10 min,
and the supernatant was decanted. The obtained residue was then
repeatedly subjected to centrifugation/washing cycles with deionized
(DI) water until the pH reached ~6 [42]. The concentration of the pu-
rified m-MXene in the solution (in terms of mg mL
1) was determined by
vacuum drying method.
2.3. Preparation of SA-MXene hybrid colloids
To delaminate m-MXene to SA-MXene hybrid colloid suspension,
20 mL of m-MXene dispersion (100 mg of m-MXene in 20 mL DI water)
was added to 80 mL of sodium ascorbate (SA) solution (12.5 mM, pH 7)
and stirred for 1 h at ambient temperature under Ar flow. The as-obtained
SA-MXene dispersion (100 mL) was continuously sonicated (100 W) for
1 h under Ar flow for delamination. To prepare SA-MXene printing ink,
the sonication time was extended to 4 h, which reduced the size to
~200 nm. During sonication, the temperature was maintained at 4  C,
while the frequency was set to 37 kHz and the power of amplitude was
60%. Then, the dispersion was centrifuged at RCF of 3000 g for 10 min to
separate the delaminated flakes from the unexfoliated and larger parti-
cles, and a dark green supernatant was collected. The supernatant was
denoted as SA-MXene colloidal suspension. To calculate the product
yield, the free ligands form the supernatant was removed by centrifu-
gation at RCF of 20,000 g for 20 min, and the product weight was
determined by the freeze-drying method. In addition to SA-MXene, we
prepared pristine Ti3C2Tx in the absence of any ligand-capped (p-
MXene), sodium citrate-capped Ti3C2Tx (SC-MXene), sodium oxalate-
capped Ti3C2Tx (SO-MXene), and sodium phosphate-capped Ti3C2Tx
(SP-MXene), with same experimental conditions. The sodium ascorbate,
sodium citrate, sodium oxalate, and sodium phosphate solutions at pH
7.0 were prepared by mixing separately with their corresponding acids.
The as-prepared ligand-capped MXenes were stored in open normal glass
bottles at ambient temperature to test their stability against oxidation.
2.4. Characterization of the MXene
Transmission electron microscopy (TEM) and scanning electron mi-
croscopy (SEM) images of the samples were recorded using a Philips/FEI
Tecnai 20 G2 S-Twin transmission electron microscope (Hillsboro, Ore-
gon, USA) and a Hitachi S-4800 Field Emission Scanning Electron Mi-
croscope (Hitachi High-Technologies, Tokyo, Japan), respectively.
Energy Dispersive X-ray Spectrometer QUANTAX Annular XFlash®
QUAD FQ5060 (Schaumburg, IL, USA) coupled to FE-SEM was used to
determine the composition of elements in the material. The UV–visible
spectra of the tested materials were recorded by Evolution 220 UV–Vi-
sible Spectrophotometers (Thermo Fisher Scientific Inc., Waltham, MA,
USA). X-ray photoelectron spectroscopy (XPS) of the materials was per-
formed using an ES-CALAB 250 spectrometer (VG Scientific, East Grin-
stead, UK) with Al Kα X-ray radiation as the X-ray source for excitation.
Binding energies were corrected using the C1s peak at 284.6 eV as the
standard. The X-ray diffraction (XRD) experiments were recorded using a
PANalytical X’ Pert PRO diffractometer (PANalytical B.V., Almelo,
Netherlands) and Cu–Kα radiation (λ ¼ 0.15418 nm); the samples
(~0.2 mg) were deposited onto Si substrates. The electrochemical char-
acterizations and the electrochemical impedance spectroscopy (EIS) of
the materials were performed with a potentiostat/galvanostat Autolab
PGSTAT204 (Metrohm, The Netherlands). The electrochemical imped-
ance spectroscopy was performed at open circuit potential with a small
sinusoidal amplitude of 5 mV, and frequencies of 0.01 Hz–10 kHz. The
conductivity of the tested materials was measured using a four-point
probe system using the DC voltage sweep method. A probe diameter of
80 μm and a distance of 1.6 mm between two adjacent probes were used.
565
Energy Storage Materials 25 (2020) 563–571
Measurements were performed using a KeithLink probe station (Keithley
Instruments, Inc., Cleveland, OH, USA) in order to provide current from

5 to 5 mA. An Agilent Cary 640 FT-IR spectrometer (Santa Clara, CA,
USA) was used to record FT-IR spectra of the materials. The Raman
characterization was performed using a Raman spectrometer
(Alpha300 R; WITec GmbH, Ulm, Germany) with a 532 nm excitation
laser source; the power of the laser was set at 100 mW, and the Raman
shift of Si (520.7 cm
1) was used for calibration before the test.
2.5. Preparation of solid-state micro-supercapacitor
Office printer Canon Pixma MG-2940 with standard cartridge PG-745
was used to print the interdigital electrodes. The SA-MXene ink was
prepared by adding 1 mL of propylene glycol to 9 mL of SA-MXene
dispersion, followed by the addition of 10 μL Triton X-100. Dynamic
viscosity of SA-MXene ink was determined at ambient temperature using
a Brookfield DV1 viscometer (Brookfield Engineering Lab- Inc, USA) with
a CPA
40Z cone spindle (30 rpm). Surface tension was measured by
using a Kyowa DY-500 tensiometer (Kyowa Kaimen Kagaku Co., Saitama,
Japan). Interdigitated electrode printing was carried out by replacing the
ink of a cartridge with SA-MXene ink. For inkjet printing of interdigital
electrode, photo paper of the A4 size was used in the high-quality photo
printing mode. The printer head has a droplet size of 2 pL and 1280
nozzles. The Pattern of SA-MXene interdigital electrode was applied
about 20 mg material in 30 passes to an area of 2.0  3.0 cm2 (including
the interspace of the arrays). The actual total electrode area (At) with the
active material printed on the photo paper was 5.8 cm2, and the film
thickness was about 1.5 μm (obtained from the cross-section image of
SEM). The printed ink was then vacuum-dried to obtain a uniform thin
film. Then, H2SO4/PVA gel was applied to the SA-MXene electrode
pattern. To prepare H2SO4/PVA gel electrolyte, 10 g of PVA was added to
20 mL of DI water in a beaker and the mixture was heated at 60  C under
continuous stirring for 2 h until a clear solution of PVA was obtained. The
obtained PVA solution was cooled to ambient temperature and 10 g of
H2SO4 was added drop by drop with continuous stirring for 1 h to obtain
a homogeneous H2SO4/PVA gel. The electrochemical measurements
(cyclic voltammetry and charge-discharge experiments) were conducted
using a potentiostat/galvanostat Autolab PGSTAT204 (Metrohm Auto-
lab, Utrecht, The Netherlands). The cyclic voltammograms were recor-
ded in the voltage range of 0–1.0 V. The same potential difference was
used for galvanostatic charge-discharge experiments with a constant
current. The areal capacitance (Careal) and volumetric capacitance (Cvol)
were calculated according to the following equations [43,44]:
Careal (F cm
2) ¼ (i  Δt) / (At  ΔV) (1)

3
Cvol (F cm ) ¼ (i  Δt) / (Vt  ΔV) (2)
where i is current, Δt is the discharge time, ΔV is the potential window, At
and Vt is total area and volume of the electrode, respectively.
The volumetric energy density (E, W h cm
3) and power density (P, W

3
cm ) values were calculated using the following equations:
E ¼ 0.5  Cvol  (ΔV)2 / 3600 (3)
P ¼ E  3600 / Δt (4)
where Cvol is the volumetric capacitance, ΔV is the volume, Δt is the
discharge time.
3. Results and discussion
3.1. Long-term stability of ligand-capped Ti3C2Tx MXene
To increase the dispersibility and stability of Ti3C2Tx MXene colloidal
suspensions we experimented with four different ligands during MXene
synthesis: sodium ascorbate (SA), sodium oxalate (SO), sodium citrate
(SC), and sodium phosphate (SP). Ti3C2Tx multilayer MXene (m-MXene)
C.-W. Wu et al.
were synthesized by selective etching of Al of Ti3AlC2 using LiF-HCl so-
lution [15,42]. To obtain monolayer or few-layer Ti3C2Tx MXene nano-
sheets, the purified m-MXene suspension was separately mixed with the
four ligand solutions followed by delamination by sonication for 1 h. The
complete synthesis details can be found in the experiment section. The
ligand-capped MXene colloidal suspensions were stored in open glass
bottles at room temperature (ca. 25 C) to study their oxidative stability.
The product yields of purified pristine MXene (p-MXene), SA-MXene,
SC-MXene, SO-MXene, and SP-MXene were determined to be 90.4%,
96.5%, 91.2%, 88.5%, and 86.2%, respectively. Photographs and relative
concentration of the freshly prepared pristine MXene (p-MXene-fresh)
and the MXenes capped with ligands after 80 days of storage
(L-MXenes-80, where L denotes the ligands: SA, SO, SC or SP) are pre-
sented in Fig. 1A and B, respectively. The p-MXene-fresh dispersion
(Fig. 1A(a)) has a dark green color, which changes to milky white after 80
days of storage (Fig. 1A(b)) due to the oxidation to TiO2 [33]. Among the
four L-MXenes, SA-MXene (Fig. 1A(c)) retains its dark green color as that
of p-MXene-fresh. SO-MXene, SC-MXene, and SP-MXene show differing
degrees of oxidation after 80 days (Fig. 1A(d
f)).
The absorption spectra of freshly prepared p-MXene and L-MXene are
presented in Fig. S1 in the Supporting Information. The broad absorbance
band from 700 to 900 nm is due to the plasmon resonance in the Ti3C2Tx
MXene [45]. In comparison with the absorption spectra of p-MXene, the
significantly increased absorbance in the 300–700 nm range for
SA-MXene indicates strong interactions of SA ligands with the Ti atoms
on the surface and/or edges of the MXene [46]. Surface titanium atoms
are chelated by the enediol group of SA to form a ligand-to-metal charge
transfer (LMCT) complex that induces a red-shift and increases the
absorbance [46]. Their stability was quantitatively assessed from the
Fig. 1. (A) Photographs, (B) relative concentration (C/C0), and (C) TEM images of (a) p-MXene-fresh, (b) p-MXene-80, (c) SA-MXene-80, (d) SC-MXene-80, (e) SO-
MXene-80, and (f) SP-MXene-80 suspension with the concentration 0.2 mg mL
1 in terms of Ti3C2Tx MXene. C0 and C in (B) represent the concentration of fresh and
stored MXenes, respectively.
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Energy Storage Materials 25 (2020) 563–571
relative concentration of the MXenes capped with various ligands after
80 days in the dispersion. The relative concentration of MXenes was
calculated from their absorbance at 800 nm based on Beer’s Law
(Fig. 1B), which shows SA-MXene has the highest stability against
oxidation. The time-course relative absorbance changes of the p-MXene
and L-MXenes at 800 nm displayed in Fig. S2 (Supporting Information)
show that except for SA-MXene, all of the others significantly undergo
oxidation and their absorbance values continuously decrease over
exposure time in the air. Similar to previous reports [33,34,41], the
p-MXene in aqueous suspension completely disintegrates within three
weeks (curve a in Fig. S2). The time constant (τ) of p-MXene through the
exponential decay fit was determined to be 6.7 days (R2 ¼ 0.97), which is
also consistent with the previous study [33]. The time constant for the
p-MXene in aqueous suspension was determined through the exponential
τ
decay fit, A ¼ A–t/
initial, where Ainitial and A represent the absorbance of
fresh and stored MXene nanosheets, respectively, and t is the storage time
in days [33].
The TEM image of p-MXene-fresh exhibits sheet-like structures,
confirming the formation of 2D structured MXenes (Fig. 1C(a)). The
structure of MXenes is severely damaged after 80 days of storage and
exposure to air (Fig. 1C(b)). In contrast, the 2D structure of SA-MXene
exhibits no significant differences from p-MXene-fresh even after 80
days of storage (Fig. 1C(c)). SC-MXene-80, SO-MXene-80, and SP-MXene-
80 show different extents of damage to the 2D structures (Fig. 1C(d
f)).
Raman spectroscopic analysis shows that the aqueous p-MXene-fresh
suspension exhibits bands of the A1g (205.2 and 710.2 cm
1) and Eg
(278.2, 392.0, and 583.0 cm
1) vibrational modes, thereby revealing
that it has the chemical formula of Ti3C2O2, Ti3C2(OH)2 or Ti3C2F2
(Fig. 2A) [47]. After 80 days of storage and exposure to air, p-MXene
C.-W. Wu et al.
Fig. 2. Raman spectra of (A) p-MXene-fresh, (B) p-MXene-80, (C) SA-MXene-80,
(D) SC-MXene-80, (E) SO-MXene-80, and (F) SP-MXene-80 with a 532 nm
excitation laser source.
exhibits only a band at 156 cm
1 attributed to the Eg vibrational mode of
the anatase structure, indicating it converts to anatase TiO2 through
oxidation (Fig. 2B) [48]. The oxidation reactions led by oxygen and water
could be represented by the following equations (5)
(8) [33,38].
Ti3C2O2(s) þ 3O2(g) → 3TiO2(s) þ C(s) þ CO2(g) (5)
Ti3C2O2(s) þ 4H2O → 3TiO2(s) þ 2C(s) þ 4H2(g) (6)
2Ti3C2(OH)2(s) þ 9O2(g) → 6TiO2(s) þ 4CO2(g) þ 2H2O (7)
2Ti3C2(OH)2(s) þ 11H2O → 6TiO2(s) þ CO(g) þ CO2(g) þ 2CH4(g) þ 9H2(g)(8)
The Raman spectrum of the SA-MXene-80 sample is almost the same
as that of the p-MXene-fresh, further supporting that the former has ul-
trahigh resistance to oxidation (Fig. 2C). Anatase TiO2 formation was
observed for SC-MXene, SO-MXene, and SP-MXene after 80 days as is
evident from their Raman spectra (Fig. 2D¡F). All of the above results
suggest that the surface ligand has a significant role in stabilizing the
MXenes. High stability of the SA-MXene could be due to the high affinity
of enediol compounds towards titanium [49,50]. Since degradation starts
at the edges [33], the protection of the edges and the Ti layer of the
crystal by the ascorbate ions effectively prevents their oxidation, thus
increasing stability. The enediol moiety of ascorbate coordinates with Ti
atoms on surface and/or edge of the MXene to form charge-transfer
complexes [49]. Also, the interaction of the SA on the surface of the
MXene prevents accumulation of adatoms of Ti from the etching process
and increases the stability [37].
In addition to protection of MXene by the ligand through suppression
of the degradation reaction, the mild reducing strength of ascorbate
probably also contributes to its protection for MXene (Fig. S3, Supporting
Information). We found that some reducing agents, such as glucose,
glutathione, and oxalic acid, also retard the oxidation rate of MXene
(Fig. S3, Supporting Information). However, their protective abilities are
not comparable to sodium ascorbate. On the other hand, relatively
stronger reducing agents, such as sodium borohydride and hydrazine,
cause significant aggregation of MXene after 5 days, probably because
they induced the loss of some surface functional groups (e.g., hydroxyl,
567
Energy Storage Materials 25 (2020) 563–571
fluoride) of the MXene [51]. Thus, SA acts not only as an effective
capping ligand on the MXene surface but also as an antioxidant to slow
down or even to prevent oxidation of the MXene.
3.2. Structure of SA-capped Ti3C2Tx MXene
Fig. 3A shows the high resolution transmission electron microscope
(HR-TEM) images (left) and diffraction pattern (right) of p-MXene-80
and SA-MXene-80. p-MXene-80 exhibits diffused rings, indicating
degradation of the crystalline structure during storage. The lattice
spacing of 0.35 nm and diffused bright rings in the diffraction pattern of
the p-MXene-80 are attributed to the (101) plane of anatase TiO2
(Fig. 3A(a)) [52]. Compared to the p-MXene-80, SA-MXene-80 exhibits
clear lattice fringes in the HR-TEM image. The lattice spacing of 0.26 nm
matches the (100) plane of the MXene. Similarly, the diffraction pattern
of SA-MXene-80 has very clear bright spots in a hexagonal fashion,
indicating its highly crystalline structure even after 80 days of storage
and exposure to air (Fig. 3A(b)). Fig. S4 (Supporting Information) shows
the XPS spectra of p-MXene-fresh, p-MXene-80, and SA-MXene-80. The
Ti2p3/2 spectrum of p-MXene-fresh has a deconvoluted peak at 455.3,
455.9 and 456.6 eV corresponding to Ti–C bonding, Ti(II) and Ti(III)
suboxide and/or hydroxide, respectively (Fig. S4A) [53]. The Ti(IV) and
Ti–Fx peak appear at 458.6 and 459.0 eV, respectively [41]. The per-
centages of Ti–C bonding, Ti(II)/Ti(III) suboxide and/or hydroxide,
Ti(IV) and Ti–Fx in Ti2p3/2 spectrum of p-MXene-fresh are ca. 41%, 51%,
5% and 3%, respectively, indicating the high purity of Ti3C2Tx structure
[41]. The amount of TiO2 in the MXene sample is related to the degree of
its oxidation. For the p-MXene-80, we observed an increase in the anatase
TiO2 (Ti(IV), 458.6 eV) peak up to ca. 75% (Fig. S4B). In contrast, the
ratio of Ti(IV) in the SA-MXene-80 is only ca. 9% (Fig. S4C). Therefore,
the XPS results strongly support the notion that capping of ascorbate li-
gands on the MXene’s surface minimizes oxidation and/or hydrolysis of
the MXene.
Fourier-transform infrared spectroscopy (FT-IR) of the purified SA-
MXene exhibits main bands of ascorbate corresponding to its vibra-
tional modes of C¼O stretching (1750 cm
1), C-H bending (1450 cm
1),
C¼C-OH (1305 cm
1, enol hydroxyl group), C-O-C stretching
(1120 cm
1), and C-O bending (1030 cm
1) (Fig. 3B(b)) [54], which
confirms the presence of SA on the surface of SA-MXene. The absorption
bands at 1665 cm
1 observed in the FT-IR spectrum of p-MXene were
assigned to the absorbed in-phase bending mode of the surface hydroxyl
group. However, the broadening and shifting of the absorption band at
1663 cm
1 in the FT-IR spectrum of SA-MXene indicates
hydrogen-bonding and/or strong coordination of ascorbate with MXene
[55]. The zeta potential of SA-MXene (
42.3  4.1 mV; n ¼ 5) is higher
than that of p-MXene (
30.6  3.4 mV; n ¼ 5). The XRD patterns of the
Ti3AlC2 MAX phase at different synthetic stages of the SA-MXene are
presented in Fig. 3C. The Ti3AlC2 MAX phase exhibits a sharp peak at a
2-theta (2θ) value of 9.7 corresponding to the (002) plane. After etching
the MAX with LiF-HCl solution, the peak shifted to 9.0 , indicating the
formation of multilayer Ti3C2Tx (m-MXene) [56]. After sonication of
m-MXene dispersion without adding any intercalating agent, a small peak
shifted from 9.0 to 6.9 for the as obtained pristine MXene (p-MXene),
revealing the poor delamination. However, the sonication of m-MXene in
sodium ascorbate (SA) solution resulted in a peak shifted from 9.0 to
5.8 , indicating the formation of delaminated SA-MXene sheets. Our re-
sults suggest delamination of m-MXene could be ascribed to the enhanced
exfoliation by sonication and the in situ protection by ascorbate ions
through their coordination with the surface and/or edge Ti atoms
[57–59]. The interlayer spacing of SA-MXene (15.4 Å) calculated by the
Bragg equation is larger than that of p-MXene (12.8 Å). Based on the
above results, we conclude that the ascorbate ions interact with the
surface and edges of the partially exfoliated MXene sheets during the
ultrasonication process and facilitate the delamination process, leading
to improved stability of the SA-MXene sheets.
We further studied the stability of MXene prepared by using different
C.-W. Wu et al.
Fig. 3. (A) HR-TEM (left) and diffraction pattern (right) of (a) p-MXene-80 and (b) SA-MXene-80. (B) FT-IR spectra of (a) p-MXene and (d) SA-MXene. (C) XRD
patterns of (a) MAX, (b) m-MXene, (c) p-MXene, and (d) SA-MXene.
salts of ascorbic acid at pH 4, 7 and 10 during the delamination of m-
MXene (Fig. S5, Supporting Information). The Ti3C2Tx MXenes
(1 mg mL
1) prepared in the presence of potassium ascorbate, sodium
ascorbate or lithium ascorbate solutions were all very stable at pH 4–10,
revealing that counterions do not affect the stability. A time-course
observation of the stability of MXene dispersed in SA (pH 7) with
various concentrations for a period of 20 days suggests that 10 mM so-
dium ascorbate is optimal (Fig. S6, Supporting Information). Lower
concentrations of SA (<10 mM) could not saturate the surface of MXene
with ascorbate. On the other hand, a higher concentration of sodium
ascorbate (i.e., 50 mM) causes precipitation of MXene due to decrease in
their surface zeta potential according to Deryagin-Landau-Vewey-
Overbeek (DLVO) theory [60].
3.3. Stability of inkjet printing of SA-MXene-based electrode
To investigate the utility of the stable SA-MXene for a practical
application, a solid-state micro-supercapacitor (MSC) with an interdigital
electrode pattern was fabricated through inkjet printing of SA-MXene on
photo paper. We optimized the lateral size of and dispersion medium for
SA-MXene [61]. To avoid clogging the nozzle, SA-MXene with a lateral
size of ~200 nm, which is less than 1/50th of the diameter of the nozzle,
was prepared by increasing the delamination sonication time to 4 h [33].
Fig. S7 shows the hydrodynamic diameter measured by dynamic light
scattering (DLS) of SA-MXene after sonication for the different duration
and TEM image of SA-MXene after 4-h sonication, which confirms the
flake size below 200 nm. The hierarchical arrangement of cellulose fibers
of photo paper has a porous structure and rough surface lead it possesses
good adhesion towards the ink. However, many inks are not jetable,
especially nanoparticle-based ink, due to poor droplet formation. For the
stable formation of ink droplet during printing with a given nozzle
diameter (α), the ink must have certain viscosity (η), surface tension (γ)
568
Energy Storage Materials 25 (2020) 563–571
aw well as density (ρ). The inverse of the Ohnesorge number, known as
the Z number, is commonly used to predict if the ink will form stable
pffiffiffiffiffiffiffiffiffiffiffiffi
drops: Z ¼ αγ ρ=η, where, α is the nozzle diameter, γ is the surface
tension, ρ is the density, and η is the viscosity. For a nozzle diameter of
21.5 μm, Z is ~39.6 for water. For inkjet printing, the ink of Z number
from 1 to 20 is considered to be in the printable range [62,63]. To lower Z
value, the surface tension must be reduced, meanwhile the viscosity must
be increased by adding additives. Here, Triton X-100 was used to
decrease the surface tension from ~73 to ~46 mN m
1, and propylene
glycol was used as co-solvent to increase the viscosity from 1 to 1.7 mPa s
[62,63]. The addition of Triton X-100 and propylene glycol also sup-
presses the weak Marangoni flow, which also reduce the coffee-ring ef-
fect [64]. Triton X-100, a non-ionic surfactant, was chosen as a surface
tension modifier to avoid disrupting the dispersion of SA-MXene. The
density (ρ) of the SA-MXene ink was determined to be ~1100 kg m
3.
The Z value of our SA-MXene ink was calculated to be 19.4, which
enabled a smooth printing of SA-MXene film on a photo paper. Fig. S8A
(Supporting Information) shows a typical example of an emblem printed
with SA-MXene ink at a concentration of 5 mg mL
1 (~0.5 wt%), with
sharp edges and uniform distribution. The amount of material deposition
can be perfectly controlled as in the case of pure printing ink through the
color depth (bit depth) of the picture and the number of printing passes.
Fig. S8B shows the lateral view SEM-EDS mapping of a cross-section of
printed SA-MXene on a paper surface. The image clearly reveals that the
MXene layers (1.5 μm in thickness) are homogeneously deposited on the
surface of the photo paper. The high-magnification cross-sectional SEM
image of SA-MXene shows highly ordered layers (Fig. S8C), revealing
that the printing approach is successful in the preparation of homoge-
neous SA-MXene films.
We fabricated an MSC using SA-MXene as the active material, and
poly(vinyl alcohol)/H2SO4 as electrolyte coated on the electrode surface
C.-W. Wu et al. Energy Storage Materials 25 (2020) 563–571

(Fig. 4A). The conductivity of the SA-MXene printed electrode on paper
increases significantly to 119 S cm
1 with the number of printing passes
without an external current collector (Fig. 4B). In addition, the conduc-
tivities of the SA-MXene printed electrode are very similar to that of the
p-MXene ones, suggesting that the capping of ascorbate ions on the
MXene does not affect its conductivity. We further compared the con-
ductivity of printed p-MXene and SA-MXene in solid and in colloidal
suspensions with various periods of storage time (Fig. 4C). As expected,
the conductivity of the printed electrode made from stored p-MXene
declined markedly relative to that of SA-MXene (Fig. 4C(a)). The con-
ductivity of printed electrode made from 20-day stored p-MXene sus-
pension drops by > 106 fold compared to that of fresh one (curve (i) in
Fig. 4C(a)). Although the electrode fabricated with the fresh p-MXene
shows much improvement toward resisting oxidation when stored in air,
its conductivity still drops by 68% after 20 days (cure (i) in Fig. 4C(b)).
The surfactant (Triton X-100) and poly(propylene glycol) matrices
mainly contribute to p-MXene resisting oxidation when stored in the air
[35]. In sharp contrast, we observed that the conductivity of
SA-MXene-fabricated electrode only drops by 22% (curve (ii) in
Fig. 4C(b)). These results indicate SA-MXenes exhibit superior stability
for the production of electronic devices.
3.4. Performance of SA-MXene-based MSC
The cyclic voltammograms (CV) of the MSC fabricated with p-MXene
and SA-MXene at a scan rate of 100 (mV s
1) in Fig. S9A (Supporting
Information) demonstrate SA-MXene exhibits two-fold higher current
density than that of p-MXene, implying that the increase in interlayer
spacing caused by ascorbate ions enhances the capacitance properties.
The shape of the voltammograms at different scan rates displayed in
Fig. S9B suggests that SA-MXene exhibits pseudocapacitance properties
in the acidic electrolyte [65]. The charge-discharge curves of the
p-MXene (solid black line) and SA-MXene (solid red line) MSC in the
voltage range of 0–1 V at a constant current of 1 A g
1 reveal an areal
capacitance of 48.4 and 108.1 mF cm
2 at a current density of 1 A g
1,
respectively, with a negligible IR drop (Fig. 4D). The interdigitated
electrode has a thickness of 1.5 μm and a total area of 5.8 cm2. The
volumetric capacitance of p-MXene and SA-MXene MSC were calculated
to be 322.4 and 720.7 F cm
3 at a current density of 1 A g
1. Fig. 4D also
shows that p-MXene MSC (dotted black line) exhibits a significant
IR-drop after 25 days, but this phenomenon in SA-MXene MSC is negli-
gible (dotted red line). Relative to the printed SA-MXene electrode that
still has somewhat a drop in conductivity after storage for 20 days (curve
(ii) in Fig. 4C(b)), the solid-state electrolyte minimizes the contact of
oxygen with the SA-MXene MSC, which avoids oxidation of the electrode
material and thus improves its long-term stability.
Both p-MXene- and SA-MXene-modified electrodes show very good
electrical conductivity at high frequency. In addition, they also exhibit
superior charge transfer characteristics as evident from the absence of a
semicircle in their Nyquist plots (Fig. 4E). However, SA-MXene MSC
exhibits much higher cyclic stability than that of p-MXene ones. The
specific capacitance of SA-MXene and p-MXene micro-supercapacitor
retains 94.7% and 72.4% of the initial specific capacitance, respec-
tively, after 4000 charge/discharge cycles at a current density of 1 A g
1
(Fig. 4F). Compared to previous reports of the MXene-based micro-
supercapacitor materials (60–676 F cm
3) [44,66–68], our SA-MXene
MSC possess superior volumetric capacitance as a result of its larger
interlayer spacing that improves the surface area ion exchange-featured
charge storage. The exceptional stability of the capacitors can be attrib-
uted to the highly protective efficacy of ascorbate and use of a gel elec-
trolyte. Photographs of two SA-MXene MSCs in series to power a digital
timer and light up a red LED are presented in Fig. 4G and Fig. S10,
respectively. The volumetric capacitance of the SA-MXene MSC at
charge/discharge current densities of 1, 2, 4, 8, 16, 20, and 25 A g
1
(Fig. S11A, Supporting Information) are 720.7, 667.6, 625.9, 589.9,
546.2, 303.4, and 284.5 F cm
3, respectively, indicating appreciable rate
capability. The volumetric energy and power densities of the SA-MXene
MSCs were calculated from the current charge/discharge curves and
converted to a Ragone plot to compare with that of previously reported
MXene-based supercapacitors (Fig. S11B) [44,67,68]. Volumetric energy
and power densities are important parameters to evaluate the perfor-
mance of micro-supercapacitors. SA-MXene MSC has a volumetric energy

Fig. 4. (A) Photograph of an interdigital electrode pattern printed with SA-MXene ink to prepare MSC on photo paper. (B) Conductivity against increasing numbers of
printing layers of (i) p-MXene and (ii) SA-MXene electrodes printed on photo papers. (C) (a) Conductivity of printed electrode fabricated from (i) p-MXene and (ii) SA-
MXene that had been stored at ambient temperature for different periods of time. (b) Relative conductivity of (i) p-MXene- and (ii) SA-MXene-printed electrode stored
for different periods of time at ambient temperature. (D) Galvanostatic charge/discharge curves of MSC freshly prepared with p-MXene (~3.3 mg cm
2; solid black
line), and SA-MXene (~3.3 mg cm
2; solid red line) at a current density of 1 A g
1. Black and red dashed lines are the corresponding supercapacitors after storage for
25 days in air. (E) Nyquist plot of p-MXene and SA-MXene electrodes in a solution containing only supporting electrolyte (1 M H2SO4). The inset figure shows the
expanded view at lower impedance. (F) Cyclic stability test results of the p-MXene and SA-MXene supercapacitors at a constant current of 1 A g
1. (G) Photograph of
the fabricated planar in a series solid-state supercapacitor that drives a timer. (For interpretation of the references to color in this figure legend, the reader is referred to
the Web version of this article.)

569
C.-W. Wu et al.
density of 100.2 mWh cm
3 at a power density of 1.9 W cm
3. Moreover,
the energy density of the SA-MXene MSC decreases gradually with an
increase in power density. Compared to the previously reported
MXene-based supercapacitors [44,67,68], SA-MXene MSC possesses
higher or comparable energy density at high power density values due to
its large surface area, interlayer spacing of SA-MXene sheets, low
oxidation, and high conductivity.
4. Conclusions
In summary, we have prepared a stable inject printable SA-MXene ink
with appropriate viscosity and surface tension modifiers. The ascorbate
ions enhance the dispersibility and oxidative stability, and increase the
interlayer distance of the MXene layers. We propose that the ascorbate
interacts with the undercoordinated Ti atoms on the surface and edges of
the MXene through hydrogen bonding and coordinate bonding. The
strong bonding of ascorbate and Ti atoms prevents oxidation from
starting at the edges of the MXene. The interdigitated electrodes were
printed with the SA-MXene ink on photo paper, without a current col-
lector to fabricate MSC. The increase in the interlayer spacing of SA-
MXene could be due to the intercalation of the ascorbate ions, which
results in the enhanced diffusion of electrolyte ions, thereby increasing
the charge/discharge capability and specific capacitance properties. The
MSC fabricated by SA-MXene exhibits improved cyclic stability and
specific capacitance compared to that of p-MXene. We will systematically
study the enediol-based molecules used for improving the oxidation
stabilities of various MXenes and also various energy storage applications
of such composites in the future.
Notes
The authors declare no competing financial interests.
Acknowledgment
This study was supported by the Ministry of Science and Technology,
Taiwan under the contracts 107-2113-M-002-015-MY3, 107-2113-M-
019-004-MY3, and 108-2638-M-002-001-MY2. The assistance of Ms. Ya-
Yun Yang and Ms. Ching-Yen Lin from the Instrument Center of National
Taiwan University (NTU) for TEM and SEM measurement is appreciated.
The Autolab instrument was supported by Prof. Cheng-Ju Yu from the
Department of Applied Physics and Chemistry of National Taipei Uni-
versity. We thank Wei-Ming Huang from National Taitung University for
assistance in Raman measurement.
Appendix A. Supplementary data
Supplementary data (Fig. S1¡S11) associated with this article can be
found in the online version at doi https://doi.org/10.1016/j.ensm.20
19.09.026.
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