Energy Storage Materials 48 (2022) 325–334

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Energy Storage Materials

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Nitrogen and sulfur co-doped graphene nanoribbons with well-ordered

stepped edges for high-performance potassium-ion battery anodes
Juhyung Choi a,‡, Aihua Jin b,‡, Hyun Dong Jung c,‡, Dongjin Ko a, Ji Hyun Um b,
Yoon Jeong Choi b, So Hee Kim d, Seoin Back c,∗, Seung-Ho Yu b,∗, Yuanzhe Piao a,e,∗
a
Department of Transdisciplinary Studies, Graduate School of Convergence Science and Technology, Seoul National University, 145 Gwanggyo-ro, Yeongtong-gu,
Suwonsi, Gyeonggi-do 16229, Republic of Korea
b
Department of Chemical and Biological Engineering, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul 02841, Republic of Korea
c
Department of Chemical and Biomolecular Engineering, Institute of Emergent Materials, Sogang University, Seoul 04107, Republic of Korea
d
Advanced Analysis Center, Korea Institute of Science and Technology, Seoul 02792, Republic of Korea
e
Advanced Institutes of Convergence Technology, 145 Gwanggyo-ro, Yeongtong-gu, Suwon-si, Gyeonggi-do 16229, Republic of Korea

a b s t r a c t

Graphitic carbon materials, particularly few-layered graphene, exhibit great potentials as potassium-ion battery (PIBs) anodes. However, bulk graphene-based ma-
terials have the disordered structure owing to randomly stacked graphene layers, which causes the high migration barrier during K+ intercalation/deintercalation
reactions and thus the surface-dominated capacitive response. Here, we present a novel nanoarchitecture of nitrogen and sulfur co-doped graphene nanoribbons with
well-ordered stepped edges (NS–sGNR) via the electrochemical unzipping of multiwalled carbon nanotubes (MWCNTs) and the subsequent N/S co-doping process
for high-performance PIB anodes. As an anode material for PIBs, the prepared sample exhibits high initial capacity (329.1 mAh g−1 at 50 mA g−1 ), superior rate
capability (211.7 mAh g−1 at high current density, 2000 mA g−1 ), outstanding reversibility of K-staging, and stable long-term cyclability. Theoretical calculations
were conducted to demonstrate that sGNRs with NS co-doping (NS–sGNR) exhibit much improved K+ intercalation properties, such as the K+ adsorption energy,
charge transfer, and migration barriers, compared with the parallel-edged GNRs. Particularly, the migration barrier (the rate-determining step) can be substantially
reduced at the stepped edges during K+ intercalation.

1. Introduction
Owing to their high energy density and cycle stability, as well as
low self-discharge rate, lithium-ion batteries (LIBs) are the most uti-
lized electrical energy storage (EES) devices [1–4]. However, LIBs are
still susceptible to issues relating to the lithium source, and this could
limit the development of the EES field [5]. Therefore, the development
of attractive battery systems that are based on earth-abundant materials
is attracting enormous attention [6–11]. Potassium-ion batteries (PIBs)
are among the most promising alternatives to LIBs owing to the high
abundance, inexpensiveness, and low redox potential (−2.93 V vs. stan-
dard hydrogen electrode) of potassium [12–20].
Carbon-based materials are considered attractive anode materials
for PIBs because of their inexpensiveness and high physical/chemical
stabilities. Among these materials, ordered mesoporous carbon and N-
doped porous carbon nanosheets with enlarged interlayer spacing exhib-
ited increased specific capacity and enhanced reaction kinetics [21–23].
These materials improved the electrochemical activities of PIBs. How-
ever, non-graphitic carbon anodes still display surface-driven capaci-
tive behaviors; they exhibit sloping curves rather than flat plateaus be-
low 0.5 V in their voltage profiles. Notably, these predominant surface-
driven capacitive behaviors reduced the energy density when the full-
battery device was assembled [24,25]. Furthermore, the short-range or-
der of the carbon structure negatively influences the electrical conduc-
tivity in the electrochemical process [26]. Thus, graphite is ideal because
it exhibits a distinct plateau, which is associated with the staging process
that produces K-graphite intercalation compounds (K-GICs), at a low po-
tential [12]. In addition to graphite, few-layered graphene can increase
the storage capacity and rate capability of PIBs via the efficient forma-
tion of GICs [27]. Further, it has been demonstrated that the doping of
graphitic networks with heteroatoms (e.g., N, S, O, and B) could suffi-
ciently mitigate the K+ adsorption energy and enhance the electrochem-
ical properties of PIBs [27,28]. However, the number of electroactive
sites could be substantially reduced by graphene stacking owing to the
𝜋–𝜋 interaction between the interlayers [29,30]. Additionally, the disor-
dered graphene structure suffers from poor rate capability, which is due
to the high migration barrier that is the rate-determining step, during
the intercalation/deintercalation process [31], and this could limit the
K-staging capacity and induce surface-dominated capacitive charge stor-
age. Therefore, a rational design is required for graphene-based materi-
als to facilitate the reaction kinetics and consolidate the superior struc-
tural advantages of high-performance anode materials. Furthermore, in-

∗
Corresponding authors.
E-mail addresses: sback@sogang.ac.kr (S. Back), seunghoyu@korea.ac.kr (S.-H. Yu), parkat9@snu.ac.kr (Y. Piao).
‡
These authors equally contributed to this work.

https://doi.org/10.1016/j.ensm.2022.03.041
Received 28 December 2021; Received in revised form 10 March 2022; Accepted 24 March 2022
Available online 26 March 2022
2405-8297/© 2022 Published by Elsevier B.V.
J. Choi, A. Jin, H.D. Jung et al.
depth theoretical studies are required to avail valuable insights into the
intrinsic energy kinetics of K+ intercalation in the desired structure.
Herein, we report N/S co-doped graphene nanoribbons with numer-
ous stepped edges (NS–sGNR), which were produced via the precise
electrochemical unzipping of MWCNTs, followed by an in situ N/S co-
doping process. The systemic investigation of NS–sGNR indicated that it
comprised few-layered GNR sheets (≤ 6 layers) containing highly meso-
porous and long-range ordered stepped edges. The open MWCNT stems
are expected to accelerate ion and electron transport, and the unique
structure of NS–sGNR could enhance the reaction kinetics. NS–sGNRs
maintained a high reversible capacity (> 280 mAh g−1 over 150 cycles
at a current density of 50 mA g−1 ) when they were applied as anodes
in PIBs. Moreover, they exhibited remarkable rate performance (211.7
mAh g−1 at a high current density of 2000 mA g−1 ). Operando X-ray
diffraction (XRD) and ex situ transmission electron microscopy (TEM)
were performed to demonstrate the highly reversible staging behaviors
of GICs in NS–sGNR during potassiation and depotassiation. These ex-
cellent properties might correlate with the enhanced kinetics due to the
presence of the stepped edges and additional N/S co-doping. Detailedly,
density functional theory (DFT) calculations confirmed the significantly
decreased migration barrier of K+ intercalation at the stepped edges
compared with that at the parallel ones.
2. Results and discussion
2.1. Structural characterization
Fig. 1a shows the schematic of the experimental procedure for pro-
ducing the quasi-one-dimensional NS–sGNR from commercial MWCNTs.
Briefly, the sGNRs were synthesized through the electrochemical unzip-
ping of the MWCNTs that were recently developed by our group [32].
When a galvanostatic current of 0.2 A g−1 was applied to the electro-
chemical cell for 2.5 h, the bisulfate anions (HSO4 − ) were intercalated
into the MWCNT, thereby initiating the lengthwise unzipping of its con-
centric walls [33]. The constant anodic charging current further induced
the oxidation of the unzipped MWCNTs into exfoliated sGNRs. Finally,
NS–sGNRs were subsequently produced via the co-pyrolysis of thiourea
and the sGNR mixture in an Ar atmosphere at 800 °C. Following its ther-
mal decomposition at a high temperature, thiourea can afford highly
reactive N and S species, such as NH3 , H2 S, and CS2 , to execute the N/S
co-doping process [34].
Scanning electron microscopy (SEM) and transmission electron mi-
croscopy (TEM) analyses were performed to characterize the morphol-
ogy of the as-obtained products. It was observed that the MWCNTs were
directly unzipped into the quasi-one-dimensional sGNRs without appar-
ently shortening of the pristine tubes (Figs. 1b and c). Moreover, the
TEM image of sGNR revealed the lengthwise view of the GNRs com-
pared with those of the MWCNTs (Figs. 1f and e). This result confirms
that the electrochemically unzipped MWCNTs could produce the edge-
created and opened GNR structures, which were attached to the MWCNT
core, and there was no significant morphological change after the an-
nealing process (Figs. 1d and g). Additionally, the histograms of the
widths (Figs. 1h–j) revealed that the widths of the graphene layers in
sGNR and NS–sGNR are largely identical. Their widths were measured
employing the TEM images (Fig. S1 in Supporting Information), and the
average widths of MWCNT, sGNR, and NS–sGNR were 149.5, 216.2,
and 226.7 nm, respectively, indicating that lengthwise nanoribbon lay-
ers were produced in sGNR and NS–sGNR.
A closer observation of the surface of NS–sGNR (Fig. 2a) revealed
the opened nanostructure through which the outer GNR layers were
seamlessly connected to the MWCNT stems. The detailed morphology
of NS–sGNR (the inset of Fig. 2a) indicated that the “stepped” edges
comprised thin nanoribbon sheets. It appeared that the stepped GNR
sheets originated from different radial diameters of the rolled-up car-
bon sheets. The high-resolution TEM (HR-TEM) image of NS–sGNR re-
vealed the edge-rich step layer that exhibited the few-layered GNR lay-
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Energy Storage Materials 48 (2022) 325–334
ers (≤ 6 layers) (Fig. 2b). The distance between the edges of each step
increased as the step approached the outer regions (ca. 1–5 nm). No-
tably, this morphological characteristic is unique, particularly when it
is compared with those of the carbon layers in pristine MWCNTs (Fig.
S2a). Furthermore, the HR-TEM image also revealed that the interlayer
spacing of NS–sGNR (0.346 nm) was larger than that of pristine MWCNT
(0.334 nm) (refer to Fig. S2b for the TEM image of pristine MWCNT).
Before the co-doping process, sGNR exhibited much larger interlayer
spacing (0.361 nm) owing to the presence of the oxygen functional
groups, which exhibited significant amorphous characters (Figs. S2c and
d). This result indicated that the interlayer spacing was reduced by re-
moving the oxygen functional groups, thus rendering the carbon layers
more ordered during NS co-doping. The energy-dispersive X-ray spec-
troscopy (EDX) mapping of NS–sGNR confirmed the uniform dispersions
of N and S in the carbon-based material (Fig. 2c). The N and S contents
of the material, 0.80 and 1.15 wt%, respectively, were determined via
elemental analysis (EA) (Table S1). X-ray photoelectron spectroscopy
(XPS) was performed to elucidate the chemical and oxidation states,
as well as the chemical compositions of the as-prepared samples at the
surface. Fig. 2d shows the high-resolution C 1 s spectrum of NS–sGNR,
which revealed the existences of C–C/C = C (284.6 eV), C–O/C–S/C–N
(285.6 eV), C = O (287.4 eV), O–C = O (289.1 eV), and 𝜋–𝜋 ∗ (290.5 eV)
[35]. The high-resolution S 2p spectrum indicated that the fitted S 2p3/2
and S 2p1/2 peaks were located at 164.0 and 165.2 eV, respectively.
Another peak that was observed at 168.2 eV was ascribed to the SOx
peak (Fig. 2e) [35,36]. Contrarily, the S 2p spectrum of sGNR only re-
vealed the SOx peak (Fig. S3b), which originated from the intercalated
sulfuric acid. Furthermore, the high-resolution N 1 s spectrum of NS–
sGNR could be deconvoluted into four peaks, namely the pyridinic N
(398.4 eV), pyrrolic N (399.8 eV), graphitic N (401.6 eV), and oxidized
N (403.8 eV) (Fig. 2f) [35,37]. Dissimilar to the graphitic N, which was
surrounded by carbon atoms, the pyridinic and pyrrolic N species were
located at the edges of the carbon frameworks; thus, they would accept
more charges from the adjunct K atom to improve the reversible capac-
ities of PIBs [37,38]. Furthermore, the atomic fractions of the four N
species were 37.3% (pyridinic N), 28.4% (pyrrolic N), 26.2% (graphitic
N), and 8.1% (oxidized N), and the ratio of the edge at N-6 and N-5
to those at N-G ((N-6 + N-5)/N-G) was 2.3, indicating that the nitro-
gen moiety dominated the exposed edge of the GNRs. Additionally, the
calculated XPS survey spectra revealed that the oxygen/carbon (O/C)
ratios of MWCNT, sGNR, and NS–sGNR were 0.04, 0.18, and 0.06, re-
spectively (Fig. S3a), indicating that the thermal annealing process of
co-doping N/S effectively decreases the number of oxygen species; this
result correlates well with the TEM results and was further confirmed
by the thermogravimetric analysis (TGA) results (Fig. S4).
The structural evolution of the as-prepared products was further in-
vestigated via Raman spectroscopy, X-ray diffraction (XRD), and the
Brunauer–Emmett–Teller (BET) analyses. A sharp (002) peak was ob-
served in the XRD patterns of pristine MWCNTs, indicating their highly
graphitic layered structure (Fig. 2g). Conversely, the XRD patterns of
sGNR revealed a broad (002) peak, which corresponds to the disor-
dered characteristics of carbon. Moreover, a (001) peak, which origi-
nated from the evolution of the C–O bonds at the basal planes, was ob-
served [32]. Dissimilar to the oxidized sGNR, NS–sGNR exhibited a rela-
tively strong (002) peak and restored the (004) peak, indicating that the
long-range ordered (≥ 4 layers) graphitic structure was recovered after
the annealing process [39]. The Raman spectra of MWCNT, sGNR, and
NS–sGNR revealed that the intensity ratios of their D (ca. 1338 cm−1 ) to
G (ca. 1567 cm−1 ) bands (ID /IG ) were 0.05, 0.48, and 0.32, respectively
(Fig. 2h). Notably, the higher ID /IG values of sGNR and NS–sGNR com-
pared with that of pristine MWCNT correspond to the new edges that
were formed from the unzipped MWCNT [33]. However, the dominant
D‘ (ca. 1609 cm−1 ) band of sGNR corresponds to the graphene oxide
(GO) phase, and this agrees well with the XRD results. All the samples
exhibited intense 2D (ca. 2690 cm−1 ) bands, which were closely related
to the non-oxidized graphitic phase in the MWCNT core [33]. Concur-
J. Choi, A. Jin, H.D. Jung et al. Energy Storage Materials 48 (2022) 325–334

Fig. 1. Synthesis of NS–sGNR. (a) Schematic of the preparation of NS–sGNR. SEM and TEM images of (b, e) MWCNT, (c, f) sGNR, and (d, g) NS–sGNR. The histograms
of the width of the as-prepared samples of (h) MWCNT, (i) sGNR, and (j) NS–sGNR, as determined from the TEM images.

rently, the longitudinal opening in MWCNTs can induce additional pores
in its structure [32]. The nitrogen adsorption–desorption isotherms were
measured to determine the surface area and pore size distribution of
all the samples (Fig. 2i). Further, the specific surface areas (SSAs) of
MWCNT, sGNR, and NS–sGNR were 15.65, 29.79, and 33.18 m2 g−1 ,
respectively (the SSA and total pore volumes of all the samples are pre-
sented in Table S2). The pore size distributions, which were determined
from the isotherms, indicated that sGNR and NS–sGNR exhibited meso-
pores and macropores that mainly originated from the opened cap, as
well as the formation of edges, in their structures (Fig. S5). Moreover,

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J. Choi, A. Jin, H.D. Jung et al. Energy Storage Materials 48 (2022) 325–334

Fig. 2. Characterization of NS–sGNR. (a) TEM and (b) corresponding HR-TEM images of the selected area (brown box). (c) EDX mappings of the C, S, and N elements
in NS–sGNR (inset of Fig. 2a is the corresponding high-magnification TEM image). (d–f) High-resolution C 1 s, S 2p, and N 1 s XPS spectra of NS–sGNR. (g) XRD
patterns, (h) Raman spectra, and (i) N2 adsorption/desorption isotherms of MWCNT, sGNR, and NS-sGNR (inset of Fig. 2i is the pore size distribution below 6 nm,
as derived via the Barrett–Joyner–Halenda (BJH) method.

the increasing value of the pore volumes of NS–sGNR, which was cen- To further elucidate the mechanisms of the potassiation and depotas-
tered at 2.6 nm, was partly due to the long-range ordered GNR layers siation processes in NS–sGNR, operando XRD was performed at a cur-
(inset of Fig. 2i) [30]. rent density of 200 mA g−1 as shown in Fig. 3c (see Fig. S6 for en-
larged XRD patterns at the selected regions). In the potassiation region
(from the initial state to 0.32 V), the (002) peak of NS–sGNR at 26.2°
2.2. Electrochemical performance
gradually vanished mainly because of the initiation of K+ intercalation
into carbon. In Stage 3, a weak peak, which was attributed to KC36 ,
The electrochemical properties of NS–sGNR and sGNR were evalu-
appeared at 29.4°, and its strength increased until the end of Stage 3.
ated for PIB anodes in the voltage range of 0.01–3.0 V (vs. K+ /K). Cyclic
Following further potassiation (in Stage 2), the KC36 peak shifted con-
voltammetry (CV) was performed at a scan rate of 0.1 mV s−1 . Fig. 3a
tinuously toward 30.6° to form KC24 . The diffraction peaks of KC8 at
shows that three well-defined peaks were observed around 0.65, 0.32,
16.5° and 33.5° evolved during the initial parts of Stage 1, and their
and 0.10 V in the first cathodic process. The peak at 0.65 V was at-
dominance increased until the end of the potassiation. A precise re-
tributed to the decomposition of electrolyte and formation of the SEI
versible reaction proceeded during the depotassiation process, and it
layer [40]. This peak disappears in the subsequent cycles, showing that
confirmed that the (002) peak of NS–sGNR was recovered after the first
stable SEI layer is formed during the initial cycle. sGNR (Fig. 3b) also
cycle [12,38,41,42]. This high reversibility of producing K-GICs during
has similar irreversible peak at 0.78 V during the initial cathodic pro-
cycling is very essential for achieving stable and high-energy-density
cess. The redox couple of 1.42/1.91 V could only be observed in sGNR,
PIBs.
which is probably attributed to the oxygen-related functional groups.
The K+ intercalation/deintercalation properties were evaluated via
This peak gradually disappears during cycling, suggesting that the re-
the galvanostatic charging/discharging of the cells at a constant current
action occurred at this potential is also irreversible. The sharp peak at
(50 mA g−1 ) (Fig. 3d; Fig. S7 shows the corresponding voltage profiles).
about 0.1 V is found in NS–sGNR during the initial cathodic process,
NS–sGNR delivered an initial depotassiation capacity of 329.1 mAh g−1 ,
which is attributed to intercalation of K ions into NS–sGNR to form K–
whereas sGNR delivered 274.5 mAh g−1 . Additionally, NS–sGNR main-
GIC. This peak is maintained during the subsequent cycles, and they are
tained a high capacity (> 287.0 mAh g−1 ) for 150 cycles, whereas sGNR
well overlapped, showing high reversibility of NS–sGNR.

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J. Choi, A. Jin, H.D. Jung et al.
Fig. 3. Electrochemical performance of NS–sGNR. Cyclic voltammograms of (a) NS–sGNR and (b) sGNR at a scan rate of 0.1 mV s−1 . (c) Operando XRD patterns of
NS–sGNR at a current density of 200 mA g−1 . (d) Cycle performance of sGNR and NS–sGNR at a current density of 50 mA g−1 .
reached 183.5 mAh g−1 . The corresponding cycle retentions of NS–sGNR
and sGNR during 150 cycles were 87.0% and 66.8%, respectively. The
voltage profiles (Fig. S7) indicated that the slope region to 0.50 V during
the initial discharge process originated from the irreversible decompo-
sition and formation of the electrolyte and the SEI film, respectively, as
mentioned in CV curves, and a similar slope was also observed in the
voltage profiles of sGNR. NS–sGNR exhibited a lower voltage plateau
with much smaller voltage hysteresis compared with sGNR, particu-
larly in the K-GIC formation-related regions [43,44]. The widened low-
voltage plateau was mainly attributed to the long-range ordered carbon
structure and doping effects.
The rate capabilities of NS–sGNR and sGNR were also tested by in-
ducing a stepwise change in the current density stepwise from 50 to
2000 mA g−1 . Fig. 4a shows that the reversible charge capacities of NS–
sGNR were 274.6, 264.2, 257.5, 248.3, 237.4, and 211.7 mAh g−1 at
50, 100, 200, 500, 1000, and 2000 mA g−1 , respectively, indicating the
excellent rate capabilities of NS–sGNR even at very high current den-
sities (1000 and 2000 mA g−1 ). However, the reversible charge capac-
ities of sGNR dropped rapidly to 51.8 and 26.0 mAh g−1 at those cur-
rent densities. Moreover, both samples recovered their initial capacities
when the current density returned to 50 mA g−1 . To further highlight
the excellent rate capability of NS–sGNR, the second voltage profiles of
sGNR and NS–sGNR at each current density were plotted in Fig. 4b and
Fig. 4c, respectively. The corresponding voltage profiles at various cur-
rent densities clearly show that the shapes of the profiles of NS–sGNR
were generally maintained even at high current densities, wheareas the
plateau in the K-GIC-related region was almost invisible in sGNR. The
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Energy Storage Materials 48 (2022) 325–334
long cycle performance at a high current density of 500 mA g−1 is shown
in Fig. 4d. NS–sGNR and sGNR became stable after several initial cy-
cles (Coulombic efficiency ≥ 95%). sGNR exhibited initial Coulombic
of 38.96%, but NS-sGNR exhibited much improved initial Coulombic
efficiency (55.06%). During the initial several cycles, Coulombic effi-
ciencies were stabilized in both electrodes and reached above 95%. At
250th cycle, Coulombic efficiencies were 99.87 and 99.73% in NS-sGNR
and sGNR, respectively (see Figs. S8 and S9). The reversible capacity
of NS–sGNR was 224.0 mAh g−1 after 500 cycles, exhibiting cycle re-
tention of 84.8%. Even at 500th cycle, NS–sGNR exhibited very high
Coulombic efficiency (100%). These electrochemical properties of NS-
sGNR electrode are highly competitive with those of recently reported
carbonaceous PIB anodes (Table S3).
In order to clarify the effect of doping on the electrochemical prop-
erties, a sample was prepared by annealing sGNR in an Ar atmosphere
without thiourea (this sample was hereafter referred to as sGNR@Ar)
for comparison. The TEM image of sGNR@Ar products clearly shows
the one-dimensional GNR structures with no structural deformation. In
addition, the corresponding HR-TEM image confirms that the lattice
spacing is 3.38 Å, supporting the removal of oxygen groups (Figs. S10a
and b). Fig. S10c presents the XRD patterns of sGNR and sGNR@Ar.
Compared with sGNR, sGNR@Ar has a relatively strong (002) peak,
but no (001) peak, which comes from GO phase, indicating the restora-
tion of the graphitic structure in sGNR@Ar. Moreover, the surface area
and pore size distribution of sGNR@Ar obtained from the BET and BJH
analysis are presented in Fig. S10d and Table S2. sGNR@Ar exhibits
the largest total pore volume (0.2573 cm3 g−1 ) and specific surface area
J. Choi, A. Jin, H.D. Jung et al.
Fig. 4. Rate properties of NS-sGNR. (a) Rate properties of sGNR and NS–sGNR at various current densities. Voltage profiles of (b) sGNR and (c) NS–sGNR at various
current densities. (d) Cycle performance of NS–sGNR and sGNR at a current density of 500 mA g−1 .
(99.63 m2 g−1 ), followed by those of MWCNT, sGNR, and NS–sGNR. This
result suggests the removal of oxygen functional groups and highly in-
compact stacking of GNR layers in sGNR@Ar. The capacity of sGNR@Ar
was much lower compared with that of NS–sGNR (Fig. S11), indicating
the contribution of NS doping to the electrochemical properties. The
TEM images of NS–sGNR after 50 cycles (Fig. S12a) show that its mor-
phology was largely maintained after the cycling test. Electrochemical
impedance spectroscopy (EIS) was conducted before the cycling test
and after the 1st cycle (Fig. S13). The semicircles of NS–sGNR before
and after the 1st cycle were much smaller than those of sGNR, demon-
strating that the charge transfer in NS–sGNR had increased significantly
[22,45,46] (see Fig. S14 for GITT curves of NS–sGNR and sGNR). In
both electrodes, the impedance increases after the 1st cycle compared
to that before cycle, which might be related to the formation of pas-
sivation layer [47,48]. Furthermore, we evaluate the electrochemical
properties of commercial graphite and compare with those of NS–GNR
(See Fig. S15a for SEM image of graphite and Fig. S15b. for XRD pat-
tern of graphite). Fig. S16a-c present cycle performance of graphite at
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Energy Storage Materials 48 (2022) 325–334
a current density of 15 and 500 mA g–1 and rate properties of graphite,
respectively. In all these conditions, the electrochemical properties of
graphite are lower compared to those of NS–sGNR, which supports the
superior properties of stepped edges beyond the parallel edges.
The excellent electrochemical performance of NS–sGNR was proba-
bly due to the enlarged interlayer distances, the “stepped” edges for ad-
ditional active sites, and the excellent structural stability for long-term
cycling. Moreover, nitrogen and sulfur co-doping might have improved
the electrical conductivity and availed additional active sites for K+ in-
tercalation. The origins of the improved electrochemical performance
of NS–sGNRs were further studied via DFT calculations in the following
section.
2.3. DFT calculations
DFT calculations were conducted to compare the thermodynamics
and kinetics of GNRs exhibiting parallel edges (pGNR), sGNR, and NS–
sGNR and to elucidate the effects of the stepped edges and NS co-doping
J. Choi, A. Jin, H.D. Jung et al. Energy Storage Materials 48 (2022) 325–334

Fig. 5. Theoretical calculations of NS–sGNR. (a) Schematic illustration of the intercalation of K+ . The migration pathways are shown in the inset Figs. Therein, the
transparent and solid green atoms correspond to the intermediate and final positions of K+ in the barrier calculations, respectively. (b) The largest migration barriers
among the three processes. (c) Adsorption energies of K+ at the IS and TS of the rate-limiting step, the internal migration, for the undoped parallel and stepped edges.
(d) Average local interlayer distances (dint ) between the carbon atoms in the top and the bottom layers that are adjacent to the migrating K+ . (e) Adsorption energies
of an additional K+ at the parallel and stepped edge sites with and without NS co-doping. (f) Charge density difference (Δ𝜌) of the additional adsorption of K+ at
the (left) sGNR and (right) NS-sGNR (N-doped site), where the yellow and blue areas represent the electron accumulation and depletion with an isosurface level of
0.005 e/Å3 , respectively. Δ𝜌 was calculated as 𝜌𝐾∗ − 𝜌∗ − 𝜌𝐾 , where 𝜌𝐾∗ , 𝜌∗ and 𝜌𝐾 represent the charge densities of the system with and without additional K and
isolated K, respectively.

on the battery performance. The adsorption energy of K+ was calculated, or (2) corresponded to the rate-limiting steps in all the cases, indicating
as follows: that the intercalation kinetics near the edges must be facile to maximize
( ) ( ) the kinetic performance of the PIB. The calculated MAX (ΔEa1 , ΔEa2 ,
ΔEK ∗ = E K ∗ − E ∗ − E(K ) (1) and ΔEa3 ) of the stepped edges were generally lower compared with
those of the parallel edges, indicating improved kinetics for the stepped
where E(K∗ ), E(∗ ), and E(K) are the electronic energies of the K+ -
edges (Fig. S19a). Furthermore, the maximum barriers of the N/S co-
adsorbed systems, K+ -removed systems, and body-centered cubic (BCC)
doped stepped edges were 0.51 eV (the N-doped site) and 0.42 eV (the
bulk K per atom, respectively (negative binding energies indicated en-
S-doped site), which were much lower than that of the undoped coun-
hanced adsorption; the Supplementary Methods section contains addi-
terpart (0.99 eV) (Fig. S19b). This could be correlated with the experi-
tional information on the computational modeling of each process).
mentally observed higher kinetics of NS–sGNR compared with those of
It could be assumed that K+ intercalation comprises three successive
sGNR (Fig. 4a). Moreover, the maximum barriers of the N/S co-doped
migration processes: (1) the approach of K+ to the exposed edge sites,
stepped edges were lower than those of their singly N-doped (0.95 eV)
(2) the internal migration from the edge sites to the bulk regions, and
or S-doped (0.80 eV) counterparts, indicating the synergistic effect of
(3) the migration in the bulk regions (Fig. 5a). Among these three, the
NS co-doping. These results confirmed that the generation of abundant
largest migration barriers of the parallel and stepped edges with and
stepped edge sites and N/S co-doping are effective strategies for enhanc-
without NS co-doping were plotted and compared since the migration
ing the kinetic properties of PIBs. The additional DFT calculations of the
step with the largest barrier represented the rate-limiting step of the en-
undoped and NS−doped models were performed to provide an insight
tire K+ intercalation process (Fig. 5b). It was observed that Process (1)

331
J. Choi, A. Jin, H.D. Jung et al.
into the effect of C − O bond on the K+ migration at the basal plains.
Fig. S20a highlights the position of adsorbed O on the top layer (dashed
red circle) based on the bulk region system (i. e. Process 3), which is
located near the migration pathway of K+ ion. As shown in Fig. S20b,
the calculated migration energies with a C − O bond indicate 0.524 and
0.344 eV of undoped and NS−doped, respectively, while those without a
C − O bond reveal the lower migration energies of 0.479 and 0.292 eV.
Accordingly, the effect of the C − O bond on the migration barrier is
negligible, as manifested by the low energy differences (about 0.05 eV)
between with C − O bond and without C − O bond of undoped (0.045 eV)
and NS-doped (0.052 eV), respectively.
To elucidate the source of such improvements, the atomic structures
and ∆EK∗ were analyzed at the initial states (IS) and the transition states
(TS) of the rate-limiting step, where the energy difference determines
the migration barrier. It was observed that the ∆EK∗ of IS in the un-
doped parallel edge (−1.39 eV) was much stronger than that of the un-
doped stepped edge (−0.79 eV), while the differences in the ∆EK∗ of
TSs in the parallel and stepped edges were much smaller (−0.13 and
0.20 eV, respectively), thus increasing the migration barrier of the par-
allel edge (Fig. 5c). This can be attributed to the significantly different
local atomic structures of the IS of the parallel and stepped edges, while
their TS atomic structures were nearly equivalent. To further investigate
the effect of N/S co-doping on the migration barriers, the average local
interlayer distances (dint ) between the carbon atoms in the top and bot-
tom layers adjacent to the migrating K+ were compared (Fig. 5d). It was
observed that ∆dint (dint,TS − dint,IS ) increased very evidently with the co-
doping of NS at the stepped edge, indicating that a very flexible stepped
edge would reduce the migration barriers near the edge sites (Fig. 5d
and Table S4). Notably, regarding the layered carbon materials, such as
pGNR/sGNR/NS–sGNR in this work, the increased interlayer distances
generally reduced the migration barriers [22]. DFT calculations of paral-
lel and stepped edge, including pGNR, NS−pGNR, sGNR, and NS−sGNR,
in the bi-layer graphene system models were conducted to confirm that
the interlayer distance increases according to NS co-doping in Fig. S21.
As summarized in Table S5, for the N/S co-doped systems, the interlayer
distances (Å) of pGNR and sGNR is 3.396 and 3.40 Å, respectively, when
they were doped with N and S, suggesting the reduced migration barri-
ers during K+ intercalation reaction.
After the full intercalation of K+ between the pGNR/sGNR/NS–sGNR
bilayers, additional K+ could be adsorbed at the edge sites to increase the
total capacity (Fig. S22) [49]. The stepped edges generally bound the ad-
ditional K+ more strongly than the parallel edges, and the effect of N/S
co-doping on the adsorption strength of the additional K+ was signifi-
cant (Fig. 5e) probably owing to the charge transfer from the adsorbed
K+ to nearby adsorption sites. The calculated Bader charges [50] indi-
cated that the adsorbed K+ at the parallel and stepped edges lost 0.81–
0.83 e− and 0.86–0.89 e− , respectively, thus ensuring enhanced binding
of the additional K+ at the latter (Fig. S23), as visualized in the charge
density difference plot (Fig. 5f and Fig. S24). Consequently, DFT calcu-
lations confirmed that the stepped edges and N/S co-doping effectively
enhanced the kinetics and total capacity of PIBs. Particularly, the atomic
configurations at the beginning of K+ intercalation were crucial in de-
termining the aforementioned properties.
3. Conclusions
NS–sGNR was fabricated via the electrochemical unzipping of MWC-
NTs, followed by an in situ co-doping process. The prepared NS–sGNR
exhibited the following excellent electrochemical properties: (1) a high
capacity of 329.1 mAh g−1 at a current density of 50 mA g−1 , (2) supe-
rior cycle retention of 87.0% during 150 charging/discharging cycles,
(3) remarkable rate performance (211.7 mAh g−1 ) at a very high cur-
rent density of 2000 mA g−1 , and (4) outstanding reversibility of the
K-GICs formation process during the cycling, as confirmed via operando
XRD. The in-depth theoretical simulations adequately demonstrate the
fast intercalation kinetics of the two major counterparts, namely (1)
332
Energy Storage Materials 48 (2022) 325–334
the stepped vs. parallel edges and (2) the NS co-doped stepped edges
vs. the N or S singly doped stepped edges. Compared with the parallel
edges, the migration barrier of K+ intercalation (the rate-determining
step) could be lowered at the stepped edges, which could also play a
crucial role in providing the additional K+ adsorption site. The study
also demonstrated the extensive decrease in the migration barrier of the
N/S co-doped stepped edges compared with that of the N or S singly
doped sGNRs, and the enhanced interlayer spacing between the bilayer
NS–sGNR enhanced the intercalation dynamics. Our findings avail new
insights into the rational design of carbon-based electrodes for high-
performance PIBs, which can be extended to other energy storage sys-
tems.
4. Experimental section
4.1. Chemicals and materials
MWCNTs with an outer diameter and length of 110–170 nm and 5–
9 𝜇m, respectively (Sigma-Aldrich,); thiourea (CH4 N2 S, Sigma-Aldrich,
>99%); and concentrated sulfuric acid (H2 SO4 , Samchun Chemicals,
>96%) were employed without, as received.
4.2. Preparation of sGNR
MWCNTs were electrochemically unzipped performed employing
the two-electrode configuration in 18 M H2 SO4 [32]. First, to prepare
the working electrode, 50 mg of MWCNTs was poured into a glass fiber
membrane via vacuum-assisted filtration. Thereafter, the MWCNT mem-
brane was placed in a homemade jig and connected to a current collector
(a platinum wire that was attached to a platinum disk). The prepared
MWCNT film and a platinum ring were employed as the working and
counter electrodes, respectively. A galvanostatic charging process was
performed on a ZIVE Lab electrochemical workstation. A constant cur-
rent of 10 mA (0.2 A g–1 ) was applied to the assembled cell for 2.5 h.
Afterward, the collected product was washed several times with deion-
ized water and dried overnight at 60 °C.
4.3. Preparation of NS–sGNR
The as-obtained sGNR (0.1 g) was mixed well with 1 g of thiourea
and vacuum dried for 3 h at 60 °C. Next, the solid mixture was an-
nealed for 2 h at 800 °C and a heating rate of 5 °C min−1 in an Ar
atmosphere. For comparison, sGNR was also annealed for 2 h at 600 °C
without thiourea, and the obtained sample was denoted as sGNR@Ar.
4.4. Material characterization
The morphologies and structures of the materials were observed via
SEM (Hitachi Regulus 8230 and Hitachi S-4800) and TEM (JEOL JEM-
ARM200F), as well as EDX. The XRD measurements were conducted
on a Bruker D8 Advance diffractometer exhibiting Cu K𝛼 radiation
(𝜆 = 1.5406 Å). The Raman spectra were obtained at an excitation wave-
length of 532 nm (LabRAM HV Evolution). XPS analysis was performed
via AXIS-His-spectroscopy employing Al K𝛼 as the X-ray source. The ni-
trogen adsorption/desorption isotherms were obtained with a Belsorp-
mini II instrument. EA was performed on a Thermo Fisher Scientific
Flash 2000. TGA was performed on a thermal analyzer (TGA/DSC1) in
a nitrogen atmosphere at a heating rate of 5 °C min−1 .
4.5. Electrochemical characterization
All the electrode slurries were prepared by adding the active ma-
terials (70 wt%), super P (15 wt%), and poly(acrylic acid) (15 wt%)
to N-methyl-2-pyrrolidinone. Thereafter, the slurries were coated on
Cu foil and vacuum dried overnight. KPF6 (0.8 M) in ethylene carbon-
ate/diethyl carbonate (volume ratio = 1:1) and a Whatman GF/C glass
J. Choi, A. Jin, H.D. Jung et al.
fiber were employed as the electrolyte and separator, respectively. All
the 2032-coin cells were assembled in an Ar-filled glove box and cycled
by a WBCS3000 cycler (WanATech, Korea) in the range of 0.01–3.0 V
(vs. K+ /K) at 25 °C. Further, the operando XRD data were obtained from
the beamline 3D at Pohang Light Source II (PLS II), Korea. EIS was per-
formed with a ZIVE MP1 (WonATech, Korea) in the frequency range of
100 kHz–10 mHz.
4.6. Theoretical calculation
The DFT calculations were conducted employing the Vienna ab ini-
tio simulation package (VASP version 5.4.4) [51,52]. The generalized
gradient approximation employing the Perdew–Burke–Ernzerhof func-
tional (GGA-PBE) [53] was employed to describe the exchange correla-
tions of the electron interactions. The D2 correction by Grimme [54] was
applied to include the van der Waals interactions to the systems com-
prising GNR and the K atoms. The ionic cores were described by the
projector augmented-wave (PAW) pseudopotentials [55] with an energy
cutoff of 400 eV. The energy and force convergence criteria were set to
10−4 eV and 0.05 eV/Å, respectively. (6 × 6 × 6) and (12 × 12 × 1)
Monkhorst-Pack k-meshes [56] were sampled for the BCC bulk K (MPID:
mp-58) and bulk graphene, respectively, while (1 × 1 × 1) was em-
ployed for all the other calculations because of the large number of
computational cells. The climbing image-nudged elastic band (CI-NEB)
method [57] with 3–9 intermediate images was employed to calculate
the energy barriers of the migration processes of K+ . The computational
details are available in the Supplementary Methods.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
CRediT authorship contribution statement
Juhyung Choi: Conceptualization, Data curation, Formal analysis,
Writing – original draft. Aihua Jin: Conceptualization, Data curation,
Formal analysis, Writing – original draft. Hyun Dong Jung: Conceptual-
ization, Data curation, Formal analysis, Writing – original draft. Dongjin
Ko: Data curation, Formal analysis. Ji Hyun Um: Data curation, For-
mal analysis. Yoon Jeong Choi: Data curation, Formal analysis. So Hee
Kim: Data curation, Formal analysis. Seoin Back: Conceptualization,
Funding acquisition, Supervision, Writing – review & editing. Seung-Ho
Yu: Conceptualization, Funding acquisition, Supervision, Writing – re-
view & editing. Yuanzhe Piao: Conceptualization, Funding acquisition,
Supervision, Writing – review & editing.
Acknowledgments
J. Choi, A. Jin, and H. D. Jung contributed equally to this work.
Y. P. acknowledges the support of the Basic Science Research Program
through the National Research Foundation of Korea (NRF) funded by
the Ministry of Education (NRF-2021R1A2C1008380) and the Nano Ma-
terial Technology Development Program (NRF-2015M3A7B6027970)
of MSIP/NRF. S.-H. Y. acknowledges the support of the National Re-
search Foundation of Korea (NRF) through a grant funded by the Ko-
rean government (MSIT) (NRF-2020R1C1C1012308). S. B. acknowl-
edges the support from the National Research Foundation of Korea
(NRF) through a grant that was funded by the Ministry of Science
and ICT (2015M3D3A1A01064929) and the generous supercomputing
time from KISTI (KSC-2021-CRE-0060). A. J. acknowledges the support
of theNational Research Foundation of Korea (NRF) through a grant
funded by the Korean government (MSIT) (NRF-2020R1A2C1012342).
J. H. U. acknowledges the support provided by Basic Science Research
Program through the National Research Foundation of Korea (NRF)
funded by the Ministry of Education (NRF-2021R1I1A1A01044891).
333
Energy Storage Materials 48 (2022) 325–334
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.ensm.2022.03.041.
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