Energy Storage Materials 45 (2022) 1040–1051

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Energy Storage Materials

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Ultra-stable flexible Zn-ion capacitor with pseudocapacitive 2D layered

niobium oxyphosphides
Swati J. Patil a, Nilesh R. Chodankar a, Seung-Kyu Hwang b,c, Ganji Seeta Rama Raju a,
Kugalur Shanmugam Ranjith a, Yun Suk Huh b,c,∗, Young-Kyu Han a,∗
a
Department of Energy and Materials Engineering, Dongguk University-Seoul, Seoul 100-715, Republic of Korea
b
NanoBio High-Tech Materials Research Center, Department of Biological Engineering, Inha University, Incheon 22212, Republic of Korea
c
Department of Biological Sciences and Bioengineering, Inha University, Incheon 22212, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Keywords: Multivalent aqueous Zn-ion capacitors (ZICs) are promising next-generation electrochemical energy storage sys-
Zn-ion capacitor tems (ESSs) owing to distinctive features including good safety characteristics, low costs, and better electrochem-
Additive electrolyte ical parameters than those of conventional supercapacitors. The key challenge of existing ZICs is their low energy
NaClO4
density and limited cycling ability due to carbon cathode materials and conventional electrolyte systems. This
ZnSO4
paper presents a dual strategy in which the electrode and electrolyte features are engineered to improve the
Specific capacitance
Energy density overall electrochemical performance of ZICs. First, the capacitance of the cathode material is improved by engi-
Electrochemical energy storage systems neering reduced graphene oxide (rGO)-incorporating, pseudocapacitive, layered niobium oxyphosphide (NbPO)
material; second, the electrochemical stability of the Zn metal anode is improved via an additive to the traditional
Zn-electrolyte. The aqueous ZIC with rGO–NbPO cathode and NaClO4 additive electrolyte exhibits the highest
capacitance (191.88 F g−1 ), maximal energy density (56.03 Wh kg−1 ), and excellent energy efficiency (approxi-
mately 50% to 55%). The prepared flexible solid-state rGO–NbPO ZIC has an ultra-long lifespan of over 50,000
cycles with approximately 76.81% capacitance retention (at 4 A g−1 ) and excellent mechanical tractability. The
results provide guidance for improving the design of safe aqueous ESSs with high-level efficiency and long-term
stability.

1. Introduction ied. However, these alkali metals are highly responsive, and the use of
flammable organic electrolytes for cells in research can cause severe en-
An ever‐increasing number of rechargeable energy storage devices vironmental and security issues [5,6]. In [7–9], multivalent ion storage
are being developed to meet the demands for environmentally friendly, mechanisms based on Zn2+ , Mg2+ , Al3+ , and Ca2+ have been presented;
cost-effective, highly portable and flexible energy storage systems for they can provide quick-charge transfer dynamics and good energy and
use in rechargeable battery-powered vehicles, uninterrupted informa- power characteristics. Due to their excellent characteristics, Zn-ion bat-
tion processing and transmission for Internet of Things (IoT) technolo- teries and capacitors (ZICs) are considered promising energy storage
gies, and conformable autonomous integrated devices [1]. Modern elec- devices; for example, Zn anodes exhibit a high theoretical capacity (vol-
tronic systems require low-cost, high-performance, safe energy storage umetric: 5849 mAh cm−3 ; gravimetric: 819 mAh g−1 ) [10,11] and a
systems (ESSs). Among the numerous ESSs available, rechargeable aque- low redox potential (−0.76 V relative to that of a standard hydrogen
ous ESSs are preferred in practical applications because they are inher- electrode). In addition, owing to the inherent characteristics of Zn-ions,
ently safe and inexpensive [2]. However, the low energy storing capacity ZICs provide high-level safety conditions during operation, can be eas-
and poor rate capability of current aqueous ESSs prevent their real-life ily manufactured, and are composed of an earth-abundant metal; these
application. For example, commercial aqueous lead- and nickel-based factors add to their promising candidacy for next-generation ESSs.
rechargeable batteries provide an approximate maximum of 45 Wh kg−1 In general, ZICs are composed of a battery-like Zn-metal anode and
energy density, which is significantly lower than that of current Li-ion a capacitive or pseudocapacitive cathode in an ion-conducting aque-
batteries (approximately 150 Wh kg−1 )[3,4]. ous electrolyte. ZICs have long lifetime Coulombic efficiencies but pose
Many monovalent metal ion capacitors using lithium ions, sodium other challenges such as the inadequate mass diffusion of divalent Zn2+
ions, and potassium ions and their unique hybrids have been stud- cations, which prevents robust electrostatic interactions with the host

∗
Corresponding author.
E-mail addresses: [email protected] (Y.S. Huh), [email protected] (Y.-K. Han).

https://doi.org/10.1016/j.ensm.2021.10.040
Received 17 May 2021; Received in revised form 27 October 2021; Accepted 31 October 2021
Available online 3 November 2021
2405-8297/© 2021 Elsevier B.V. All rights reserved.
S.J. Patil, N.R. Chodankar, S.-K. Hwang et al. Energy Storage Materials 45 (2022) 1040–1051

material, and unstable cathode and anode structures in aqueous envi- series (an important property of suitable Zn salts). These characteristics
ronments [12,13]. Various approaches have been used to resolve these provide 2D rGO–NbPO ZICs with extraordinary flexibility, reversibility,
issues; for example, the exterior structure has commonly been altered to and ultra-long stability (76.81% capacitance retention for more than
suppress H2 evolution reactions, and tailored nanostructures based on 50,000 cycles). The presented study thus provides a deeper understand-
framework designs have been prepared. ing of the relationship between Nb species and inherent Zn-ion aqueous-
To improve the energy storing capacity and stability of ZICs, a suit- electrolyte properties, which can be exploited in graphene-boosted 2D
able electrolyte must be chosen to mitigate dendrite formation and side layered NbPO nanomaterials for electrochemical energy applications.
reactions on the Zn-anode. In many previous research studies, ZICs
have been prepared with conventional ZnSO4 , ZnCl2 , and Zn(CH3 CO2 )2 ; 2. Results and discussion
however, the developed cells failed after a few hundred cycles[14–16].
Furthermore, a Zn(CF3 SO3 )2 -based electrolyte (rather than ZnSO4 and The design of the hybrid rGO-boosted 2D layered NbPO architecture
ZnCl2 ) has been used in ZICs to achieve longer cycling stability and to is shown in Schematic 1. Our concept involves the preparation of 2D lay-
inhibit side reactions; unfortunately, Zn(CF3 SO3 )2 is approximately 37 ered NbPO nanostructures via chemical synthesis; the resulting devices
times more expensive than conventional ZnSO4 electrolyte [17]. are interesting candidates for electrode materials. First, the niobium
Different additive electrolytes have been used to reduce Zn disso- phosphorus hydroxide compound materials were prepared with one-
lution and to prevent the formation of Zn dendrites. Adequate elec- step hydrothermal synthesis. The compound materials were annealed;
trolytes with divalent ions (Zn2+ ) with a higher polarization strength the resulting Nb1.91 P2.82 O12 was studied via physico-electrochemical
and charge density have greatly enhanced diffusion kinetics, owing to analysis. The growth of rGO-boosted Nb1.91 P2.82 O12 on the surface im-
the additive monovalent ions (Li+ , Na+ , K+ ); these are used to accom- proves the electronic conductivity and electrochemical properties of
modate/compensate for the dissolution of active materials. Moreover, the system since graphene has remarkable mechanical stiffness and ex-
the charge transmission efficiency, ion conductivity, and Coulombic ef- cellent electronic characteristics. Furthermore, graphene used in hy-
ficiency of the devices must be improved. Combining ZnSO4 with low- drothermal material synthesis can modify 2D nanostructures, which pre-
cost additive electrolytes is a more effective strategy for suppressing the vents Nb1.91 P2.82 O12 layers from staking through 𝜋-𝜋 interactions. Fur-
side reactions of Zn-anodes and thereby improve the cycling stability of ther details of the experimental synthesis are provided in the Supporting
ZICs. Combining ZICs with pseudo-solid-state aqueous electrolytes also Information.
avoids the use of flammable substances, prevents electrolyte spillage, Field-emission scanning electron microscopy (FE-SEM) was used to
and improves energy density. examine the microstructural characteristics of the prepared samples.
Niobium oxides are considered promising electrode materials for en- The FE-SEM micrographs of the NbPO and rGO–NbPO materials are
ergy storage and conversion applications due to their numerous advan- presented in Fig. 1(a) and (b), respectively. The soft, agglomerated 2D
tages: strong redox-active behavior (Nb5+ /Nb4+ and Nb4+ /Nb3+ ), mul- layers clearly confirm the existence of NbPO. The rGO–NbPO sample
tiple phases, various stoichiometries, and layered structures [18–21]. shows a 2D layered nanostructure wrapped by rGO nanosheets with
Despite several interesting engineering approaches and its outstand- no apparent stacking order, whereas the nanostructure of the NbPO
ing characteristics, the electrochemical performance of niobium oxide is unchanged. The fine orthorhombic surface nanostructure was fur-
(Nb2 O5 ) is restricted by its low surface area, poor electrical conduc- ther investigated using field-emission transmission electron microscopy
tivity (approximately 3 × 10−6 S cm−1 ), limited theoretical capacity (FE-TEM) (Fig. 1(c–g)). Evidently, parts of the NbPO system are inter-
(202 mAh g−1 )[22], and synthesis difficulties during the chemical pro- weaved and stacked, with diameters of 100–200 nm (Fig. 1(c)). In addi-
cess. In response, altering the electronic structure and synergistic effect tion, separated rGO–NbPO nanosheets with approximately 50–100 nm
of niobium oxides by introducing non-metal anions represents a new average diameters can be observed (Fig. 1(d)). In the high‐resolution
approach to enhancing its electrochemical characteristics. Indeed, in- TEM results, the rGO–NbPO nanosheets display a mainly amorphous
troducing non-metal anions such as P (phosphorus) in transition metal rGO pattern outside and localized polycrystalline NbPO phases inside
oxides has been shown to result in excellent stability, owing to the ro- (Fig. 1(e)). The clear TEM view of the interface of the rGO coating on
bust M–P–O metal bonds [23]. Niobium oxyphosphide has a vital effect the NbPO surface is presented in Fig. 1(f). Moreover, the magnified TEM
on electrochemical performance, and P modifies the electron configura- images of the rGO nanosheets are shown in Fig. 1(j). Whereas different
tion, yielding a stable structure. Therefore, because of their multivalent lattice planes co-exist in the prepared 2D nanomaterials, the 0.43 and
states and tunable multifunctionality, these materials can be used in the 0.30 nm interplanar spacings correspond to the (211) and (022) lat-
preparation of efficient 2D layered niobium oxyphosphide-hybrid mate- tice planes of the orthorhombic NbPO phase in the interweaved chan-
rials for electrochemical applications. nel (Fig. S1), respectively. At the same time, the successful formation
This paper presents a dual strategy for improving the energy stor- of layered rGO–NbPO nanosheets with slightly greater interplanar dis-
ing capacity and cycling stability of ZICs. A graphene-boosted 2D lay- tances (0.45 and 0.30 nm) has been influenced by the incorporation of
ered NbPO nanosheets array was designed as the cathode material us- rGO nanosheets (Fig. 1(g)). The interplanar distances of areas 1 and 2
ing a single-step hydrothermal method. This unique design represents were determined with DigitalMicrograph (Figs. 1(g) and S1). The se-
an interwoven and stacked network that promotes the fast diffusion of lected area electron diffraction (SAED) patterns in Fig. 1(h, i) confirm
zinc ions in the electrode material. The reduced graphene oxide (rGO) the polycrystalline natures and orthorhombic structures of the NbPO
nanosheets are evenly wrapped on the surface of NbPO and can be and rGO–NbPO nanosheets. Fig. 1(k) shows that the rGO nanosheets
used as a buffer layer to stabilize the NbPO structure and alleviate have no evident lattice fringes.
the volume change caused by the intercalation/deintercalation of Zn The crystal structures of the prepared materials were successfully
ions. The synergistic effect between the conductive rGO nanosheets and identified with X-ray powder diffraction analysis; the results are pre-
stacked NbPO network facilitates the transfer of electrons through the sented in Fig. 2 (a). The XRD patterns of the obtained samples were
highly conductive rGO channel; consequently, rGO–NbPO ZICs achieve fitted with X’Pert Highscore Plus software with the best matched JCPDS
excellent rate performance characteristics. Their electrochemical per- card number #01–083–0415. In addition, the XRD pattern of niobium
formance in concentrated additive aqueous electrolyte with Zn-ion salt oxyphosphide was analyzed via Rietveld refinement using FullProf soft-
centered was evaluated, and the influence of the anions on the solution ware. The results show that the synthesized niobium oxyphosphide has
structure and their suitability for aqueous ZICs were investigated. In ad- a Pbcn space group. The corresponding crystal structural pattern was vi-
dition, the minimal required Zn salt concentration for stable cycling at sualized with VESTA (Fig. 2(a’)). In Fig. 2(a’’), the major peaks at 20.45°,
1.6 V with an additive electrolyte (ZnSO4 /NaClO4 ) was determined to 28.92°, 41.82°, 46.62°, 61.33°, and 64.78° 2𝜃 correspond to the (211),
build an rGO–NbPO ZIC that exhibits great solubility and Hofmeister (022), (422), (233), (434), and (344) crystal faces of Nb1.91 P2.82 O12 with

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S.J. Patil, N.R. Chodankar, S.-K. Hwang et al. Energy Storage Materials 45 (2022) 1040–1051

Schematic 1. Preparation of hybrid architecture of rGO-boosted 2D layered niobium oxyphosphide.

an orthorhombic phase according to the JCPDS card #01–083–0415, re- terial, respectively. The spin‐orbit splitting energy of 2.68 eV is consis-
spectively[24]. The characteristic peaks of rGO at 20° to 30° and 42.75° tent with the core-levels of the Nb5+ state[28]. The shift of the peaks
confirm the evident growth of rGO–NbPO with a short-range order in with 0.10 and 0.33 eV belong with the higher intensity of the Nb 3d3/2
the stacked graphene layers. The graphene content in the NbPO pre- peak compared to that of Nb 3d5/2 confirms the successful formation
cursor solution is relatively low according to the Raman spectroscopy of rGO–NbPO. The chemical interaction between GO and NbPO can be
results. To investigate the chemical structural features and defect de- attributed to the formation of Nb-O-C bonds. The Nb 3d BE is positively
grees of the prepared materials, the Raman spectroscopy results are shifted when compared to the BE of Nb metal (207 eV), indicating that
displayed in Fig. 2(b). The strong peak at around 281 cm−1 can be Nb in NbPO has positive charge (𝛿 + ) and P in NbPO has negative charge
attributed to O−Nb deformation, whereas the weak band at 450 and (𝛿 − ). As a result, an electron density transfer from Nb to P takes place
740 cm−1 reveals the existence of P−O−P stretching due to bridging [29]. The narrow-scan P 2p region in Fig. 2(e) indicates that the doublet
oxygen species. All Raman peaks below 448.20 cm−1 can be attributed peaks at 132.88 and 134.23 eV correspond to the BEs of P 2p3/2 and P
to O−P−O and O−Nb−O bending vibrations [25]. Moreover, the strong 2p1/2 , respectively, caused by the surface oxidation of phosphide. The
peak at 980 cm−1 and the weak peak at 1115 cm−1 can be assigned to additional broad peak was observed at a higher BE of 135.77 eV, that
Nb-P and P-O stretching modes, which become active when the NbO6 oc- corresponds to phosphorus oxidation. The O 1 s narrow-scan spectra are
tahedra are distorted owing to non-bridging oxygen species with or- presented in Supporting Information Fig. S2. The core-level XPS spectra
thophosphate (PO4 3– ) and pyrophosphate (P2 O7 4− ) groups, respectively of C 1 s further reveal the chemical nature of the elements in the rGO–
[26]. The strong signal at around 822 cm−1 in rGO–NbPO corresponds NbPO material. As shown in Fig. 2(f), the peaks at 283.46 eV correspond
to niobyl groups. However, the peak strength of niobium oxyphosphate to niobium-carbide (Nb5+ −C)[30], and the peaks at 284.80 eV can be
decreases and slightly shifts to 970 cm−1 due to Nb=O stretching vibra- attributed to sp3 C = C in rGO and sp2 -hybridized C–C bonds in aromatic
tions. The rGO–NbPO sample has two dominant peaks centered at 1337 rings[31]. The small peak at approximately 287.2 eV corresponding to
and 1592 cm−1 , which correspond to the well-matched D and G bands C–O bonds confirms the reduction in GO [32]. Moreover, the EDX and
of graphene, respectively [27]. The presence of multilayer graphene in STEM images and elemental maps present the coherent distribution of
the rGO–NbPO material is confirmed by the 2D band at approximately Nb, P, and O in rGO–NbPO (Fig. 2(g, h)). The presence of Nb, O, and P
2870 cm−1 . Furthermore, the 1.19 ID/IG ratio indicates an increased ions in NbPO is also quantified using ICP, with 0.21, 0.31, and 1.28%
degree of disorder caused by NbPO in the rGO–NbPO material. recorded, respectively. Presence of Nb, O, P and C ions in rGO–NbPO
XPS analysis was conducted to determine the chemical composition is also measured using ICP-MS and is recorded as 0.31, 0.43, 0.55 and
and bonding environment of the NbPO and rGO–NbPO materials. Their 1.29%, respectively.
full XPS spectra exhibit the characteristic peaks of Nb 3d, P 2p, O 1 s,
and C 1 s, as shown in Fig. 2(c). According to Fig. 2(d), the binding 2.1. Electrochemical measurements for aqueous ZIC
energy (BE) peaks of Nb 3d are 210.14 and 207.46 eV, indicating the
co‐existence of 3d3 /2 and 3d5/2 components in the prepared NbPO ma- Owing to their ability to balance energy and power densities and
their long-life cycle expectancy, ZICs have been considered promising

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Fig. 1. (a, b) FE-SEM micrographs and (c, d) FE-TEM images of NbPO and rGO–NbPO materials. Insets present magnified images. (e, f) FE-TEM image of rGO coating
on NbPO surface. HR-TEM images of (g) rGO–NbPO nanosheets and corresponding highlighted regions 1 and 2. SEAD patterns of (h) NbPO and (i) rGO–NbPO. (j)
TEM image of rGO and (k) corresponding amorphous SAED pattern.

and safe energy storage devices in the field of electrochemistry. The changed after the first electrochemical activation cycle. The cyclic area
electrochemical characteristics of NbPO and rGO–NbPO hybrid nano- under the CV curve of the rGO–NbPO ZIC is much greater than that of
materials were evaluated in aqueous solutions containing 0.2 M ZnSO4 the NbPO ZIC without additive electrolyte. The characteristic CVs of the
(without additive (w/o)) and 0.2 M ZnSO4 with 5 M NaClO4 salt (with high scan rate suggest that the charge storage process is strongly sup-
additive (w/a)). The electrochemical coin-cell fabrication processes are pressed in the ZnSO4 electrolyte. The improved capacitance value is due
explained in supporting information. The electrolyte concentration was to the coactive role of the graphene nanosheets in the 2D NbPO material.
optimized by performing electrochemical experiments with different ad- The rGO–NbPO sample with additive electrolyte exhibits more than two
ditive salt concentrations (Fig. S4). For more than 5 M additive salt times higher specific capacitance values: 123.07 F g−1 at 40 mV s–1 scan
concentration, crystallization occurred in 0.2 M ZnSO4 electrolyte so- rate (Fig. S5(a)). This confirms that the use of 2D layered rGO–NbPO
lution. Therefore, an optimized additive electrolyte was used in the nanosheets as the electrode and additive electrolyte enables Zn2+ -ions
electrochemical studies. To demonstrate the beneficial effect of NaClO4 to be inserted into or extracted from the cathode material.
as an additive electrolyte on ZICs, systematic electrochemical analysis The ZICs with 2D NbPO and rGO–NbPO electrodes were also studied
was conducted. The representative cyclic voltammograms (CVs) of the via galvanostatic charge/discharge (GCD) measurements at 2.5 A g−1
NbPO and rGO–NbPO electrodes at 40 mV s−1 scan rate at 0.15–1.6 V current density (Fig. 3(b)). The results present significant electrochem-
are shown in Fig. 3(a). The CV with the predominant oxidative peak at ical differences between the samples with and without additive elec-
1.11 V and the reverse scan segment were examined. A well‐defined re- trolytes. The energy storing performance of the rGO–NbPO nanosheets
ductive peak was detected at 0.8 V; otherwise, the CV has not evidently is improved in contrast to that of the NbPO ZIC. The combination of

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S.J. Patil, N.R. Chodankar, S.-K. Hwang et al. Energy Storage Materials 45 (2022) 1040–1051

Fig. 2. Structural characterizations: (a) XRD data and observed refinement results of niobium oxyphosphide material, (a’) structural pattern (green, orange, and red
represent Nb, P, and O, respectively), and (a”) XRD patterns of niobium oxyphosphide and rGO–NbPO. (b) Raman spectra and (c) wide-scan XPS spectra of NbPO
and rGO–NbPO materials. Core-level narrow-scan XPS spectra of (d) Nb 3d, (e) P 2p, and (f) C 1 s. (g) EDX spectrum of rGO–NbPO. (h) STEM image and elemental
maps of Nb, P, O, and C in rGO–NbPO.

2D rGO–NbPO nanosheets and additive electrolyte results in a high- and rGO–NbPO (Rs and Rct : 37.84 and 15.50 Ω cm2 , respectively, 𝜏:
power ZIC prototype. In addition, the average charge/discharge time 11.81 ms) cathode materials. The lower solution resistance for the ad-
of the rGO–NbPO ZIC with additive electrolyte slightly increases with ditive electrolyte is credited to increase ionic conductivity, inhibit wa-
improved specific capacitance (117.32 F g−1 ) at 2.5 A g−1 (Fig. S5(b)). ter activity, and minimize the number of free water molecules. There-
Electrochemical impedance spectroscopy (EIS) measurements were per- fore, the rGO–NbPO electrode material with additive electrolyte was fur-
formed to differentiate the electrochemical phenomena caused by the ther investigated through additional electrochemical studies. The CVs of
intercalation of Zn2+ -ions. The resulting impedance results of the NbPO the rGO–NbPO ZIC with typical pseudocapacitive rectangular shapes in-
and rGO–NbPO ZICs are shown in Nyquist plots in Fig. 3(c); the corre- clude superimposed Zn humps and no evident distortion (Fig. 3(d)). The
sponding best fitted equivalent circuits are presented in Fig. S6. All EIS undeteriorated CVs at an increasing scan rate (from 1 to 100 mV s−1 )
curves are mainly composed of a solution resistance (Rs ), charge trans- demonstrate the outstanding reversibility and superior power charac-
fer resistance (Rct ), equivalent series resistance, and slope line (ionic teristics of the 2D rGO–NbPO material. Furthermore, the change in the
diffusion resistance) in the high, medium, and low frequency ranges. specific capacitance of the rGO–NbPO ZIC with additive electrolyte as
The insignificant differences between the two spectra of the samples a function of the scan rate was investigated and compared to those of
with and without additive electrolyte confirm that ion diffusion and the NbPO and rGO–NbPO ZICs without additive electrolyte. The NbPO
electrolyte dissemination in the cathode material have decreased. More- and rGO–NbPO ZICs without additive electrolyte achieve maximal spe-
over, a steeper slope is observed in the low frequency part with addi- cific capacitance (46.94 and 87.95 F g−1 , respectively) at a low scan
tive electrolyte, indicating quicker diffusion kinetics. The small resis- rate (1 mV s−1 ) and 31.48% and 37.39% capacitance retention, respec-
tance and fast charge transfer time constant (Rs and Rct : 4.80 and 3.80 Ω tively, up to a scan rate of 100 mV s−1 (Fig. S5(c)). The rGO–NbPO ZIC
cm2 , respectively, 𝜏: 4.63 ms) of the rGO–NbPO ZIC with additive elec- with additive electrolyte exhibits 161.53, 130.67, 120.87, and 108.11
trolyte demonstrate superior conductivity and short electron/ion trans- F g−1 specific capacitance values at 1, 10, 50, and 100 mV s−1 , respec-
port pathways. Furthermore, the longer charge transfer time constant tively, and 66.93% capacitance retention.
(19.08 ms) in 0.2 M ZnSO4 indicates slower Zn2+ intercalation pro- The charge storage mechanism in the prepared electrode material
cesses in the NbPO (Rs and Rct : 41.22 and 265.75 Ω cm2 , respectively) was thoroughly investigated. Moreover, the intercalation behavior and

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Fig. 3. Electrochemical analysis of NbPO and rGO–NbPO ZICs: comparative (a) CVs and (b) charge/discharge curves recorded with (w/a) and without (w/o) additive
electrolyte at a constant scan rate. (c) Comparative Nyquist plots of NbPO and rGO–NbPO ZICs. Inset shows enlarged Nyquist plot in the high-frequency range. (d)
CVs of rGO–NbPO ZIC with additive electrolyte at 1–100 mV s−1 scan rate. (e) Meshed area in CV shows capacitance-controlled contribution to total contribution at
30 mV s−1 scan rate. (f) Probable charging/discharging processes in rGO–NbPO ZIC.

kinetic mechanism of the charge storage process were verified based on long-term stability. During charging, the perceived cathodic peak at
the power law (𝑖 = 𝑎𝑣𝑏 ), which is a function of the current density (i) 1.19 V in the CV corresponds to the electrochemical extraction of zinc
and scan rate (Ʋ) [33]. The constant b-value was increased from 0 to ions into the rGO–NbPO nanosheets (relative to Zn/Zn2+ ). During dis-
1. The response current of the designed ZIC was measured at various charging, the anodic peak at around 1.56 V is mainly due to the insertion
scan rates at 1.25 V vs. Zn2+ /Zn. Fig. S7 presents the log (i) vs. log (Ʋ) of zinc ions from the internal rGO–NbPO nanosheets. At this stage, the
curve at lower 1–30 mV s−1 scan rate; the b-value of the rGO–NbPO ZIC niobium ions oxidize. During charging/discharging, zinc is deposited
with additive electrolyte obtained through the slope of the plotted curve and stripped from the surface. The SEM images of the samples with ad-
is 0.93. Accordingly, electrochemical kinetics occur in the ZIC, and the ditive electrolyte in Fig. 13(e) show that the formed, smooth surface
main reaction current is influenced by the rapid surface capacitance- protects the zinc anode and that the enhanced fast capacitive charge
controlled process and Zn-ion diffusion-controlled process. storage mechanism in the rGO–NbPO anode inhibits the growth of zinc
Fig. 3(f) shows that the charge storage characteristics of the rGO– dendrites.
NbPO ZIC is mainly due to surface Zn2+ adsorption by electrolyte ions Furthermore, GCD measurements of the rGO–NbPO ZIC with addi-
on the surface of the electrode material; this has been confirmed by the tive electrolyte were conducted at different current densities, as shown
calculated total specific capacity (Fig. S5(d)). Simultaneously, the dif- in Fig. 4(a). The symmetric shape of the charge/discharge curves in-
fusion in the bulk material owing to Zn2+ insertion by electrolyte ions dicates excellent reversibility. The superior rate capability with addi-
provides a minor capacitance contribution. Moreover, the charge stor- tive electrolyte is evident from the GCD results. The rGO–NbPO ZIC
age contributions at a fixed scan rate were determined by fitting the exhibits 191.88 F g−1 specific capacitance at 1 A g−1 with 39.10% ca-
CV data with the 𝑖(𝑉 ) = 𝑘1 𝑣 + 𝑘2 𝑣1∕2 power law[34], where 𝑘1 𝑣 repre- pacitance retention at a high current density of 30 A g−1 (Fig. 4(b)). By
sents the capacitance (surface/interface)-controlled current, and 𝑘2 𝑣1∕2 contrast, without additive electrolyte, the rGO–NbPO ZIC has 16.50%
represents the diffusive (or bulk)-controlled current. The CV of the rGO– capacitance retention at 10 A g−1 . The higher capacitance and better
NbPO ZIC at 30 mV s−1 scan rate in Fig. 3(e) indicates the separation of rate performance prove that optimized ZnSO4 material and electroac-
the capacitance-controlled contribution (the meshed region highlights tive salt additive should be used in the design of additive electrolytes;
the capacitive current response) from the total charge storing capacity. their combination effectively improves the electroactive interface con-
The capacitive contribution rate of the rGO–NbPO ZIC increases with ductivity of 2D rGO–NbPO electrodes.
the scan rate (1–30 mV s−1 ), as shown in Fig. S8(a); the 93.53% ratio The excellent energy and power densities of the rGO–NbPO ZIC are
indicates a dominant capacitance-controlled process with high poten- clearly presented in the Ragone plot in Fig. 4(c). The rGO–NbPO ZIC dis-
tial. plays outstanding specific energy (56.03 Wh kg−1 ) and specific power
The intercalation electrochemical charging/discharging processes characteristics (1000 W kg−1 ), which are higher than those calculated
that occurred in the rGO–NbPO cathode material with and without addi- for the NbPO and rGO–NbPO ZICs without additive electrolyte (specific
tive electrolyte are presented in Fig. 3(f). During charging/discharging, energies of 2.40 and 14.10 Wh kg−1 at 1000 W kg−1 specific power, re-
characteristics related to Zn2+ intercalation/deintercalation were ob- spectively). These results are compared with niobium-based and other
served, as presented in the ex-situ Zn 2p narrow scan spectra (Fig. electrode materials in Table S1; the rGO–NbPO ZIC has outstanding per-
S9(b)). Surface-adsorbed Na+ contributes fairly marginal to electro- formance characteristics and can be used in environmentally friendly en-
chemical performance. The electrochemical redox characteristics of 2D ergy storage applications in the near future. According to Fig. 4(c), the
rGO–NbPO in the additive electrolyte provide satisfactory capacity and rGO–NbPO ZIC achieves a higher and comparable specific energy den-

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S.J. Patil, N.R. Chodankar, S.-K. Hwang et al. Energy Storage Materials 45 (2022) 1040–1051

Fig. 4. (a) Charge/discharge profiles of rGO–NbPO ZIC with additive electrolyte at different current densities. Comparison of (b) specific capacitance and (c) Ragone
plots of NbPO and rGO–NbPO ZICs. (d) Ex-situ charge/discharge profile of rGO–NbPO ZIC with additive electrolyte in states 1–5 and corresponding narrow-scan
XPS spectra of (e) Nb 3d and (f) P 2p.

sity than conventional ZICs, LICs and state-of-the-art batteries[35–52]. 2p1/2 formation at the surface electrode. For Zn intercalation in state
This demonstrates the promising energy-saving features of the designed 3, the 139.73 eV peak is higher than the 134.80 eV peak because the
multivalent metal-ion capacitor with two distinct electrolytes. interplanar spacing distance increases at the surface. Thus, the metal–
To study the Zn-ion charge storage mechanism, the structural vari- phosphate ligands contribute to the charge storing process since a large
ations and reaction sites for intercalation in the 2D rGO–NbPO ac- amount of the electrode material generates an electric charge at the in-
tive electrode material during charging and discharging were an- terface surface.
alyzed (Fig. 4d). The highlighted states in the charge/discharge The Coulombic efficiency and cyclic reversibility of the rGO–NbPO
curves (1–5, representing pristine, charged/discharged, and fully ZIC with additive electrolyte can be directly assessed in the GCD profiles
charged/discharged states, respectively) were investigated with ex-situ at different current densities in Fig. 5(a). Although the charge/discharge
XPS, as shown in Figs. 4(e, f) and S9 . In state 1 (pristine), the decon- current density returns to the original values, the resulting charge and
voluted Nb peaks at 211.34 and 208.67 eV can be attributed to 3d3/2 discharge capacitances and Coulombic efficiency do not differ greatly
and 3d5/2 of Nb5+ (Fig. 4(e)), respectively. In the subsequent charging from their original values; this indicates that the rGO–NbPO ZIC has ex-
process at 0.85 V (state 2), the intensity of XPS peaks corresponding cellent reversibility and 100% Coulombic efficiency. The stability mea-
to Nb 3d5/2 (208.46 eV) decreases significantly, and the Nb 3d3/2 peak surements of the designed ZICs were performed for 10,000 cycles in
(211.34 eV) partially disappears. In the fully charged state (state 3), the aqueous electrolytes. Fig. 5(b) presents the capacitance retention plot
reappearance of Nb 3d3/2 (209.68 eV) and Nb 3d5/2 (207.95 eV) peaks and Coulombic efficiency during the charge/discharge cycles at a fixed
indicates the presence of lower-valence niobium ions in the Nb4+ oxida- current density (4 A g−1 ). Regarding the state after 10,000 CD cycles,
tion state; thus, Nb5+ is fully reduced to Nb4+ [28], which can improve Fig. 5(b) reveals that the capacitance retention rate of the rGO–NbPO
charge storing capacity. In the subsequent discharging process (state ZIC with additive electrolyte exceeds 100%; those of the NbPO (46.1%)
4), the XPS peaks shift to higher BEs, such as in the voltage profiles in and rGO–NbPO (59.07%) ZICs without additive electrolytes are signifi-
state 2, where most XPS peaks corresponding to Nb4+ are partially oxi- cantly lower. The slight decrease in the capacitance retention rate after
dized to Nb5+ . A low peak corresponding to Nb 3d3/2 (210.97 eV) and 2000 cycles may be due to the formation of byproducts, which is a com-
a high peak corresponding to Nb 3d5/2 (208.54 eV) appear. Therefore, mon phenomenon in aqueous ESSs[54]. However, the average specific
the Zn2+ intercalation process during discharging is dominated by the capacitance of the rGO–NbPO ZIC with additive electrolyte increased af-
oxidation of Nb4+ to Nb5+ . In the fully discharged state (state 5), the ter 5000 cycles; this significantly affects its distinctive structural char-
XPS peaks reappear at their original positions. These may be ascribed acteristics. The increase in capacitance reflects the transformation of
to the oxidation of Nb4+ to the original Nb5+ . Fig. S9(b) presents the the charge storing mechanism from capacitive- to battery-type. The b-
XPS spectra of Zn 2p during charging/discharging. The Zn 2p peak can- value of the ZIC before stability is 0.93, decreasing to 0.59 after the
not be detected in state 1. The Zn 2p peaks with 2p3/2 –2p1/2 spin–orbit cycling test. The capacitive contribution rate (93.53%) indicates a dom-
doublets appearing during charging/discharging in states 2–4, confirm- inant capacitance-controlled process with high potential before stabil-
ing effective deintercalation/intercalation of Zn2+ in the 2D rGO–NbPO ity, while 48.20% contribution from diffusion-controlled Faradaic reac-
material. The adsorption of Na+ ions on the active rGO–NbPO surface in tions was observed after the stability test. Thereafter, the irreversible
the first cycles is represented by the XPS peak at 1072.10 eV of Na 1 s in activities decrease and eventually disappear owing to the formation
Fig. S9(c). The P 2p signal (Fig. 4(f)) appears in states 1 and 5; the XPS of a protective solid–electrolyte interphase (SEI), which stabilizes the
peak at approximately 134.8 eV originates from phosphate species [53]. electrode surface [55]. In addition, the rGO–NbPO ZIC without addi-
Regarding states 2–4, the new peak at 139.73 eV can be assigned to P tive electrolyte retains the high Coulombic efficiency throughout the

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Fig. 5. (a) Rate capability and Coulombic efficiency of rGO–NbPO ZIC with additive electrolyte at low to high current densities (1.5–20 A g−1 ); current density
returns to preliminary current density during a cycle. (b) Evolution of capacitance retention and Coulombic efficiency of NbPO and rGO–NbPO ZICs with and without
additive electrolytes during 10,000 charge/discharge cycles. Post electrochemical characterizations of rGO–NbPO ZIC with additive electrolyte: (c) Raman spectra
and core-level XPS spectra of (d) Nb 3d, (e) P 2p, and (f) C 1 s for rGO–NbPO material after 10,000 charge/discharge cycles.

cyclic stability tests due to the intercalation of different ionic species. the electrolyte solution. Owing to some structural modifications that oc-
The representative CVs of the rGO–NbPO ZIC after 10,000 stability cy- cur during intercalation/deintercalation, the strong niobium polyphos-
cles recorded at different scan rates at 0.15–1.6 V are presented in phate peak shifts to 952 cm−1 given the change in the Nb−O bonds
Fig. S10(a). However, the rGO–NbPO ZIC displays an evident change and NbO6 sites[58]. The XRD and wide-scan XPS spectra of the rGO–
in its impedance (Fig. S10(b)) after the stability tests; hence, different NbPO ZIC after 10,000 charge/discharge cycles are presented in Sup-
Faradaic reactions are involved in the rGO–NbPO ZIC. porting Information (Fig. S12(a) and (b)). The deconvoluted Nb 3d dou-
The comparative CVs before and after the stability tests are shown blet core-level spectra with 2.45 eV spin–orbit splitting value are shown
in Fig. S11(a). The shapes of the CVs change owing to the addition of in Fig. 5(d). The weak intensity peak at 134.3 eV due to phosphate 2p3/2
well-defined pairs of redox peaks at 0.75 and 1.1 V, which are caused (P−O) generated by Zn2+ /NbPO decomposition has evidently decreased.
by Zn-ion deintercalation/intercalation during charging and discharg- The strong peak at 140.14 eV corresponds to the mixed phase of the
ing[56]. The calculated specific capacitances at scan rates of 1, 10, 50, phosphate group present in the electrode (Fig. 5(e)). Moreover, the C 1 s
and 100 mV s− 1 are 338.15, 201.60, 103.44, and 82.55 F g−1 , respec- core-level spectra with 284.56, 286.24, and 288.56 eV are ascribed to
tively, with 24.49% capacitance retention. The fast redox reaction de- C=C/C−C, C−O, and O−C=O groups, respectively (Fig. 5(f)). The strong
creases the rate capability of the 2D rGO–NbPO material after 10,000 doublet spin–orbit Zn 2p peak is shown in Fig. S12(c). The nanosheets
stability cycles. Based on the presented power law [34], the calculated promote Zn2+ diffusion and fast electron transport kinetics; in addition,
b-value (0.59) indicates that capacitance performance is controlled by the energy barrier for Zn2+ deintercalation is reduced owing to the mi-
diffusion dynamics rather than surface reactions (Fig. S11(b)). The con- crostructure transformation of the rGO–NbPO nanodisks [59,60]. Thus,
tributions from capacitance- and diffusion-controlled dynamics are con- the structural stability and progressive effects of Zn-ion-based additive
firmed by the separate CVs at 30 mV s−1 scan rate in Fig. S11(c). Thus, electrolytes significantly affect the cycling performance of rGO–NbPO
the hybrid rGO–NbPO nanostructure manages the complementary con- ZICs.
tributions from two types of reactions: the major charge contribution Fig. S13(a) presents the polarization curves of the Zn/Zn cell with
originates from diffusion-controlled Faradaic reactions (48.2% contri- and without additive electrolyte at a constant current density (3 mA
bution), capacitance-controlled fast ion adsorption, and surface redox cm−2 ). Regarding the voltage hysteresis of the sample without additive
reactions according to the bar diagram (Fig. S8(b)). electrolyte, the Zn plating/stripping process only takes several minutes;
The structural and morphological characteristics of the rGO–NbPO further polarization is accompanied by an increase in overpotential. In
nanostructure were systematically analyzed after the stability test. The addition, the additive electrolyte causes the voltage hysteresis to remain
inset in Fig. S11(b) shows that the porous nanosheets of the 2D rGO– at 0.20 throughout the entire Zn plating/stripping process. The XRD pat-
NbPO material shorten the diffusion pathways and, consequently, en- terns with peaks at 36.15°, 39.02°, 43.20°, 54.22°, 70.45°, and 77.03° 2𝜃
able fast electrolyte ion and electron transport; this leads to excellent corresponding to a Zn hexagonal crystal structure (JCPDS card # 00–
electrochemical stability for 10,000 cycles. This is confirmed by the 004–0831) are presented in Fig. S13(b). Moreover, Zn dendrites have
post-electrochemical Nyquist plot (Fig. S10(b)) with Rs and Rct values grown on the sample without additive electrolytes. Fig. S13(c) shows
of 3.85 and 1.15 Ω cm2 , respectively. The Raman and XPS results in the smooth surface morphology of the pristine Zn foil. Fig. S13(e) shows
Fig. 5(c–f) confirm the transformation of the structural phase of the 2D no evident dendrite formation owing to the strong blocking effect in the
rGO–NbPO material. As shown in Fig. 5(c), the new peak at approxi- additive-containing electrolyte, indicating the successful suppression of
mately 485 cm−1 corresponds to Zn−O bond stretching [57]. The two dendrite growth and the preservation of the smooth surface. By con-
strong peaks at 620.50 and 653.21 cm−1 correspond to SO4 2− groups in trast, the zinc electrode without additive electrolyte exhibits a mossy,

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Fig. 6. Electrochemical performance of FSS-rGO–NbPO ZIC: (a) cycling performance and (b) charge/discharge measurements at different scan rates. (c) Nyquist
plots before and after 25,000 and 50,000 stability cycles. Flexibility test: (d) CVs at different bending angles (scan rate of 100 mV s−1 ). (e) Rate capability recorded
at 0.25–8 A g−1 current density and back for five cycles. (f) Long-term cyclic stability measurements for 50,000 cycles. (g) Bar diagram comparing electrochemical
cycle lifespans of FSS-rGO–NbPO ZICs and those presented in previously published reports[35,36,48–51,63–68,37,69,38–42,46,47]. (h) Photographs of fabricated
flexible solid-state rGO–NbPO ZIC at different bending angles. (i) Two combined FSS-rGO–NbPO ZICs for lighting light-red and green LEDs.

nanoflake-like surface due to the accumulation of generated Zn den- The positive shift of the potential of the redox process can be at-
drites, which grow fast during the plating process (Fig. S13(d)). This is tributed to the ion activity change in additive electrolytes. Here, the
because the additives improve the dispersion and cathodic polarization activity of species containing Zn2+ increases significantly, which in turn
of the electrolyte, which leads to the deposition of finer zinc particles increases the redox potential according to the Nernst equation [62].
on the zinc electrode. In addition, there is no evolution of the hydro- This effect can cause Zn-ion-based ESSs to become unstable and exhibit
gen, which results in uniform Zn deposition (Fig. S18). The fine zinc weak energy and Coulombic efficiency. Hence, the additive electrolyte
particles formed during charging prolong the charge–discharge lifetime suppresses the growth of Zn dendrites on the anode surface, thereby
and increase the current efficiency of the ZIC. Consequently, a higher improving the long-term stability and energy efficiency of multivalent
cutoff potential is realized in the electrolyte given the increased onset capacitors. In this study, an ion-enriched strategy was used to optimize
potential of the oxygen evolution reaction [61]. aqueous electrolytes for moderate interfacial reactions on an anode sur-
face to form an SEI as an intermediary to reconcile zinc–electrolyte inter-

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S.J. Patil, N.R. Chodankar, S.-K. Hwang et al. Energy Storage Materials 45 (2022) 1040–1051

face. The formation mechanism of the SEI is explained in Fig. S13(f). The The stability and durability characteristics of the fabricated device
major aim of electrolyte modification is uniform zinc deposition via were examined at 4 A g−1 current density in 50,000 charge/discharge
the adjustment of the Zn2+ adsorption mechanism on the anode sur- cycles; 76.81% capacitance retention indicates that the FSS-rGO–NbPO
face for the formation of an SEI layer, as in Li-batteries. Fewer wa- ZIC possesses an excellent cycle lifespan (Fig. 6(f)). The Coulombic ef-
ter molecules in the additive electrolyte induce fast exchange between ficiency remains approximately 100%, and the energy efficiency is 50–
ClO4 − /water and a high Na+ concentration that ensures high ionic con- 55% during the entire charge/discharge test. The Nyquist plots (best
ductivity. This indicates the efficient reduction of ClO4 − , which results fitted equivalent circuit) of the FSS-rGO–NbPO ZIC before and after
in a Cl− -containing layer on the Zn surface; this ensures a potential gra- 25,000 and 50,000 charge/discharge cycles are shown in Fig. 6(c). Be-
dient across the surface layer, which allows Zn plating underneath [61]. fore the stability test, the FSS-rGO–NbPO ZIC exhibits 2.27 Ω cm2 Rs
Such findings demonstrate the synergistic effect between the high ClO4 − and 0.09 Ω cm2 Rct with an excellent electrode/electrolyte interface.
concentration and limited free water content in the additive electrolyte, The Nyquist plot shows shifts in the mid–high-frequency range with in-
which enables stable and reversible Zn deposition. The obtained ZnSO4 creasing semicircle diameter and Rct values after 25,000 (Rs : 2.42 Ω cm2
electrolyte with NaClO4 additive can effectively create a uniform zinc and Rct : 0.35 Ω cm2 ) and 50,000 (Rs : 3.1 Ω cm2 and Rct : 2.36 Ω cm2 )
plating layer since the reduction potential of Na+ is lower than that of charge/discharge cycles. The exceptional long-term cycling stability of
Zn2+ and the charged electrostatic layer formed on the initial zinc plate the FSS-rGO–NbPO ZIC is presented in a bar diagram in Fig. 6(g). The
can inhibit further zinc growth. An SEI is generated on the Zn-anode superior stability of the fabricated FSS-rGO–NbPO ZIC with nanosheet
during the first few charging cycles. The SEI functions as a passivation arrays remains constant, with increasing interspace between the sheets;
layer on the Zn-electrode surface, inhibiting further electrolyte decom- thus, the device can withstand the volumetric alterations in 2D rGO–
position and boosting long-term cycling stability. NbPO during charging/discharging. The use of the additive electrolyte
therefore enables the production of ZICs with improved energy density,
electrochemical stability, and high-level safety.
2.2. Flexible rGO–NbPO ZIC measurements
3. Conclusion
Metal ion capacitors have been designed for energy storage and
power electronic appliances. The latest energy storage devices have ex- A highly efficient graphene-boosted 2D layered niobium oxyphos-
ceptional characteristics and have been used in the field of adaptable phide nanomaterial was designed and used to prepare flexible solid-
electronics. To verify the flexibility and practical applicability of lay- state ZICs. In addition, the promising characteristics of Zn‐based elec-
ered 2D materials with additive electrolytes, a high-performance flexible trolyte were exploited to prepare 2D layered rGO–NbPO nanostructures
solid-state rGO–NbPO//Zn-foil (FSS-rGO–NbPO) ZIC was designed. The for advanced, flexible, ultra-long cycle lifespan ZICs for large‐scale en-
detailed device fabrication procedure is provided in the supporting in- ergy storage units. The use of aqueous additive Zn-electrolyte in an
formation. The rGO–NbPO and Zn-foil function as positive and negative rGO–NbPO ZIC results in a device with a specific capacitance of 191.88
electrodes with a polymeric gel electrolyte (ZnSO4 +NaClO4 //PVA), re- F g−1 , specific energy of 56.03 Wh kg−1 , and high specific power of
spectively; the result is a flexible ZIC for practical applications. Fig. 6(h) 1000 W kg−1 . The fabricated flexible polymer gel-based Zn-hybrid elec-
presents photographs of the assembled FSS-rGO–NbPO ZIC. The CVs of trolyte has 89.10% rate capability (at 8 and 0.25 A g−1 ) and excellent
the FSS-rGO–NbPO ZIC at different operating voltages are presented in reversibility. The capacity retention rate after 50,000 cycles (at 4 A g−1 )
Fig. S14. In addition, the CV and CD measurements of the fabricated is 76.81%. Thus, the presented Nb-based hybrid flexible ZICs with ultra-
flexible ZIC at different scan rates at 0–1.8 V are presented in Fig. 6(a) long cycle lifespans are promising candidates for future aqueous ZICs.
and (b). The semi-triangular shape and symmetric properties of the GCD
curves indicate the robust reversibility of the fabricated flexible device
Declaration of Competing Interest
at different current densities. In addition, the FSS-rGO–NbPO ZIC has
outstanding rate capability: 69.85 mF cm−2 real capacitance and 48.82
The authors declare that they have no known competing financial
F g−1 specific capacitance at a current density of 0.25 A g−1 , which cor-
interests or personal relationships that could have appeared to influence
responds to 24.67% capacitance retention at 8 A g−1 . The inferior rate
the work reported in this paper.
characteristics of the FSS-rGO–NbPO ZIC are shown in Fig. S15. The as-
sembled capacitive device stores 29.71 F g−1 specific capacitance at 1 A
g−1 current density with excellent specific energy (13.37 Wh kg−1 ) and CRediT authorship contribution statement
101.73 W kg−1 specific power.
The flexibility features of the FSS-rGO–NbPO ZIC at various bending Swati J. Patil: Conceptualization, Methodology, Investigation, For-
angles are presented in Fig. 6(i). The fabricated ZIC has a thickness of mal analysis, Writing – original draft, Writing – review & editing.
0.2 mm; it can be bent to different angles; the corresponding bending Nilesh R. Chodankar: Conceptualization, Methodology, Formal anal-
CVs are shown in Fig. 6(d). The capacitance plot indicates that the fab- ysis, Writing – original draft, Writing – review & editing. Seung-Kyu
ricated device exhibits strong electrochemical characteristics without a Hwang: Visualization. Ganji Seeta Rama Raju: Writing – review &
decrease in capacitance (Fig. S16(a)). In addition, the flexible perfor- editing. Kugalur Shanmugam Ranjith: Writing – review & editing.
mance was studied in over 1000 bending cycles at 60° bending angle; Yun Suk Huh: Supervision, Writing – review & editing, Project admin-
the results demonstrate the excellent flexibility (78.94%) of the fabri- istration, Funding acquisition. Young-Kyu Han: Supervision, Writing –
cated ZIC (Fig. S16(c)). The ability to (de)intercalate Zn-ions at low to review & editing, Project administration, Funding acquisition.
high current densities (and vice versa) with a return to the former low
current density is confirmed by the rate capability protocol results in Acknowledgments
Fig. 6(e). The non-flammable polymer gel (Zn-ions with additive elec-
trolyte) displays a high-rate capability with specific capacitance values This work was supported by the National Research Foundation
of 11.56, 29.71 and 48.82 F g–1 at 8, 1 and 0.25 A g−1 charge/discharge of Korea (NRF) grant funded by the Korean Government (MSIT)
current densities, respectively. The device can withstand current den- (2020R1A4A3079710). This Research has been performed a by the In-
sities of up to 1 A g−1 with 28.30 F g−1 capacitance. Even when the dustrial Strategic Technology Development Program-Strategic core ma-
current density slowly returns to 0.25 A g−1 , the specific capacitance terial Independent technology development project (20010193, Devel-
returns to its nearly original value (43.50 F g−1 ); hence, the fabricated opment of Electrode Fabrication Technology using Pitch for MCDI Sys-
FSS-rGO–NbPO ZIC has excellent reversibility without significant loss. tem Applied to Lithium Recovery from Low Grade Brine and Waste

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S.J. Patil, N.R. Chodankar, S.-K. Hwang et al. Energy Storage Materials 45 (2022) 1040–1051

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