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Energy & Environmental Science Accepted Manuscript

ARTICLE

Electroactive Edge Site-Enriched Nickel-Cobalt Sulfide into

Graphene Frameworks for High-performance Asymmetric
Received 00th January 20xx,
Accepted 00th January 20xx
Supercapacitors
a a a a a a a
DOI: 10.1039/x0xx00000x Juan Yang, Chang Yu, Xiaoming Fan, Suxia Liang, Shaofeng Li, Huawei Huang, Zheng Ling, Ce
a a
Hao, and Jieshan Qiu *
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www.rsc.org/

Tailor-made edge site-enriched inorganics coupled graphene hybrids hold a promising platform material for
high-performance supercapacitors. Herein, we report a simple strategy for fabricating edge site-enriched
nickel-cobalt sulfide (Ni-Co-S) nanoparticles decorated on graphene frameworks to form integrated hybrid
architectures (Ni-Co-S/G) via an in-situ chemically converted method. The Kirkendall effect-involved anion
2-
exchange reaction, e.g. the etching-like effort of the S ions, plays a crucial role for the formation of edge
site-enriched nanostructure. Density functional theory (DFT) calculations reveal that the Ni-Co-S edge sites
-
have a high electrochemical activity and strong affinity for OH in the electrolyte, which are responsible for
the enhanced electrochemical performance. Benefiting from the integrated structures of Ni-Co-S
nanoparticles and conductive graphene substrate, the resultant Ni-Co-S/G hybrid electrodes exhibit a high
-1 -1
specific capacitance of 1492 F g at the current density of 1 A g , superior rate capability of 96% when the
-1
current density is increased to 50 A g , and excellent electrochemical stabilities. An asymmetric
supercapacitor fabricated using the edge site-enriched Ni-Co-S/G hybrids as the positive electrode and
−1
porous carbon nanosheets (PCNS) as negative electrode shows a high energy density of 43.3 Wh kg at a
−1 −1
power density of 0.8 kW kg , and an energy density of 28.4 Wh kg can be retained even at a high power
−1
density of 22.1 kW kg .

Broader context performance supercapacitors. The present strategy that is in-situ

configuration of the integrated hybrids with ultra-rich edge sites
The integrated architectures configured via graphene and
may be extended to construct many other composite electrodes for
inorganics are one of ideal electrode materials for the surface-
high-performance supercapacitors or other energy-related devices.
dependent electrochemical supercapacitors. Nevertheless, most
inorganic species/graphene hybrids available now level off
inorganic electroactive species accompanied with the low degrees
1. Introduction
of exposed edge sites on graphene, which may result in the low
specific capacitance and decreased redox reaction kinetics. In this Supercapacitors with high power density, fast charge/discharge rate,
study, the integrated hybrid architectures (Ni-Co-S/G) composed of and excellent reliability have drawn intensive attention in the fields
1, 2
edge site-enriched nickel-cobalt sulfide (Ni-Co-S) nanoparticles and of energy-storage and -conversion. In particular,
graphene as advanced materials for supercapacitors are configured, pseudocapacitors employing the fast reversible multi-electron
delivering a superb rate capability. An asymmetric supercapacitor surface Faradaic redox reactions over electrode materials can
based on the Ni-Co-S/G hybrids and porous carbon nanosheets deliver a very high specific capacitance, holding great promise for
(PCNS) achieves high energy density and power density, indicative constructing high energy-storage nanodevices. Along this line, a
of their potential as a promising candidate material for high- series of pseudocapacitive electrode materials such as transition
metal oxides/hydroxides (RuO2, Co3O4, Ni(OH)2, etc.) and
conducting polymers (polyaniline, polypyrrole, poly(3,4-
2, 3, 4
ethylenedioxythiophene), etc.), have been developed and
employed to achieve the high-performance pseudocapacitors.
Nevertheless, these electrode materials available now still suffer
from low rate capability and/or poor electrochemical stability
because of their high dependence on surface Faradaic redox

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-1 -1
reactions and unfavorable reaction kinetics in general under fast increased from 1 A g to 50 A g . An asymmetric supercapacitor
View Article Online
4, 5
charge/discharge rates, inhibiting the large-scale practical with the Ni-Co-S/G hybrids as the positiveDOI: 10.1039/C5EE03633J
electrode and porous
application of supercapacitors to a great degree. It is not carbon nanosheets (PCNS) as negative electrode (Ni-Co-S/G // PCNS)
−1
uncommonly believed that decorating nano-structured is constructed, achieving a high energy density of 28.4 Wh kg at an

Energy & Environmental Science Accepted Manuscript

−1
pseudocapacitive electroactive species on the carbonaceous ultrahigh power density of 22.1 kW kg , and excellent
supports is considered as one of promising and effective strategies electrochemical stabilities.
to solve the problem aforementioned, in which high utilization of
electroactive species and favorable reaction kinetics are well
guaranteed. 2. Experimental
Graphene, a two-dimensional (2D) “aromatic” monolayer carbon 2.1 Material preparation
material, featuring a high surface area and electric conductivity, can Fabrication of the Ni-Co precursor/G: All the chemicals were
be coupled with inorganic materials such as metal oxide/hydroxide, directly used after purchase without further purification. For a
endowing nanohybrids with unique structural characteristics and typical run, a certain amount of NiCl2·6H2O, CoCl2·6H2O and urea
synergistically electrochemical properties derived from both (molar ratio of 1:1:6) were dissolved into the 10 mL of GO colloidal
6, 7
counterparts. Benefiting from this, numerous functional -1
solution (2 mg mL in water) under vigorous stirring and ultra-
alternate-component nanohybrids comprising inorganics and
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sonication for 30 min, the solution was then transferred into a

graphene sheet have been successfully constructed for achieving o
Teflon-lined stainless steel autoclave and kept at 150 C for 24 h.
7, 8
highly pseudocapacitive performances. Moreover, it has also The as-synthesized samples were collected and washed for several
been demonstrated that the integrated electroactive species-on- times with water and ethanol, respectively, and then dried at 80 C
o

sheet hybrid architectures can bring the required conductivity to for 12 h.

individual electroactive species and shorten the transport length for Fabrication of the integrated Ni-Co-S/G hybrids: In a typical
electrolyte ions in their nano-scaled dimension, and further deliver chemical transformation procedure, the as-synthesized Ni-Co
a superior rate capability, which could also inhibit the aggregation precursor/G in the first step were dispersed into 40 mL of water to
9
of both graphene sheets and loaded species. Nevertheless, most form a composite dispersion, and then desired amount of
inorganic species/graphene hybrids available now level off thioacetamide (TAA) was added to composite solution above under
inorganic electroactive species accompanied with the low degrees vigorous stirring for 10 min, the ratio between Ni-Co precursor/G
of exposed edge sites on graphene, which may result in the low and TAA (sulfur source) was maintained at 1:2. After that, the
specific capacitance and decreased redox reaction kinetics. In this composite solution was transferred into a Teflon-lined stainless
regard, it still remains a major challenge to develop a facile and o
steel autoclave and kept at 180 C for 12 h. A series of the Ni-Co-
general strategy for the tailored fabrication of the integrated edge S/G hybrids were fabricated using Ni-Co precursor/G with different
site-enriched inorganic species/graphene hybrid architectures for weight ratios (1:3, 1:6, 1:9 and 1:12) of GO to metal salts (cobalt or
high-performance pseudocapacitors. nickel salts) in the first step of the synthesis, yielding samples
Recently, electrochemically active transition metal sulfides (TMS), labeled as Ni-Co-S/G-1, Ni-Co-S/G-2, Ni-Co-S/G, and Ni-Co-S/G-3,
especially bimetallic nickel cobalt sulfides, have emerged as novel respectively. For comparison, the Ni-Co-S species were also
pseudocapacitive electrode materials due to good electrical prepared under the same conditions in the absence of GO and the
conductivity of about 2 orders higher than that of the oxide Ni-Co-S/G hybrids were also directly fabricated from metal salts,
10, 11, 12
counterparts. Compared with the monometallic sulfides TAA, and GO via one-step hydrothermal method, yielding hybrids
(nickel sulfide or cobalt sulfide), the electrochemical contributions named B-Ni-Co-S/G.
from both nickel and cobalt ions in the bimetallic sulfides can 2.2 Material Characterization
provide relatively rich redox reactions, resulting in higher specific The as-obtained samples were examined by field-emission scanning
11, 13, 14
capacitance. It is noteworthy that such sulfide species can electron microscopy (FE-SEM, FEI NOVA NanoSEM 450),
also be readily reconstructed from their corresponding metal 2
transmission electron microscopy (TEM, Tecnai G 20), and high-
oxide/hydroxide precursors based on anion exchange reactions and resolution transmission electron microscopy (HR-TEM, JEOL 2100F),
Kirkendall effects, finally leading to multiform and tunable ion-conductive plasma (ICP), X-ray diffraction (XRD) (Cu Kα,
morphologies, such as nanoparticles, nanowires/nanotubes and λ=1.5406 Å), Fourier transform infrared spectroscopy (FT-IR),
11, 14, 15 16
nanosheets. Inspired by the previous work, herein, we Raman spectrum, and X-ray photoelectron spectroscopy (XPS).
report a simple strategy for fabricating edge site-enriched nickel- Thermogravimetric analysis (TGA) was carried out using a STA 449
cobalt sulfide (Ni-Co-S) nanoparticles anchored on graphene o
F3 instrument in a temperature range of 30-650 C with the heating
frameworks to form integrated hybrid architectures (Ni-Co-S/G) via o -1
rate of 10 C min in air.
an in-situ chemical transformation from their pre-fabricated 2.3 Density Function Theory (DFT) Calculations
hydroxide precursor. The Kirkendall effect-involved anion exchange The spin-polarized DFT calculations were performed using projector
2-
reaction, e.g. the etching-like effort of the S ions, is responsible for augmented wave (PAW) potentials and the Perdew-Burke-
the formation of such edge site-enriched Ni-Co-S nanoparticles on Ernzarhof (PBE) functional implemented in the Vienna ab initio
graphene. Superb edge site-enriched characteristics and strongly simulation package (VASP), for details, please refer to supporting
coupled effects with graphene result in the fast redox reaction information.
kinetics. The resultant Ni-Co-S/G hybrid electrodes exhibit a 2.4 Electrochemical Characterization
superior rate capability of 96% when the current density is

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The electrochemical properties of the samples were evaluated by a nanoparticles. The morphology and structure of View theArticle
as-made
Online
CHI 760D electrochemical workstation in a three-electrode cell in 6 materials are completely different from that DOI: 10.1039/C5EE03633J
produced at high
M KOH aqueous electrolyte, in which platinum foil and Hg/HgO temperature gas-solid reaction and/or one-pot refluxing process,
electrodes were used as the counter and reference electrodes, where the morphology has no significant change before and after

Energy & Environmental Science Accepted Manuscript

17 2-
respectively. The working electrode was fabricated by mixing the sulfurized process. In the present system, the abundant S ions
sample powder, carbon black, and poly (tetrafluoroethylene) with derived from TAA act as the dual roles: sulfur source and etching-
o
ethanol in a mass ratio of 80:15:5. The mixture was dried at 100 C like agents, and are responsible for the formation of edge site-
18, 19
overnight under vacuum, and then was pressed onto nickel foams enriched nanoparticles. It is also noted that the nano-
to make electrodes. The tap density of the Ni-Co-S/G hybrids was conversion in structure and components will contribute to the
estimated by directly measuring the mass and physical dimensions following enhanced electrochemical performance. Compared with
-3
occupied, which is about 0.4 g cm . The mass loading of the previous reported work, such as the controllable morphology of the
−2
samples on nickel foam was 3.0 ~ 3.5 mg cm , and the contribution Ni-Co-S species or free-standing structure directly grown on metal
11, 20, 21
of the nickel foam substrate towards the capacitance is negligible substrate, the graphene within hybrids functions as a
under the conditions adopted in the present work. The specific substrate and has a capability of anchoring and immobilizing these
capacitance of single electrode was calculated by the following edge site-enriched nanoparticles to inhibit self-aggregation, yielding
formula: integrated hybrid architectures, and thus delivering the high
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Cs = (I ∆t) / (m ∆V) utilization of electroactive species and favorable reaction kinetics.

-1
where Cs is specific capacitance of electrodes (F g ), I is the Accordingly, the Ni-Co-S/graphene hybrids were also directly
discharge current (A), ∆t is the discharge time (s), ∆V is the voltage fabricated from metal salts, TAA, and graphene oxide (GO) via one-
range after ohmic drop (V), and m is the mass of the active material step hydrothermal method (Strategy II), in which Ni-Co-S species
(g). tend to form bulky sphere, yielding hybrids labeled as B-Ni-Co-S/G.
The asymmetric supercapacitors were fabricated with the Ni-Co-S/G
hybrid as the positive electrode and porous carbon nanosheets
(PCNS) as the negative electrode. The tap density of PCNS is about
-3
0.05 g cm , and the corresponding PCNS-based negative electrode
was prepared by mixing the electroactive material, carbon black,
and poly(tetrafl uoroethylene) with ethanol in a mass ratio of
80:10:10. The mass ratio of the PCNS to Ni-Co-S/G hybrids is around
2.5 according to the specific capacitance calculated from the CV
-
curves and the total tap density of two electrodes is about 1.5 g cm
3
. The energy density (E) and power density (P) of asymmetric
supercapacitors for the two electrodes were calculated based on
the total mass of the active materials using the following formulas: Figure 1. Schematic illustrations of the in-situ formation for the integrated
C = (I ∆t) / (M ∆V) edge site-enriched Ni-Co-S/G hybrid architectures (Strategy I), which is
E = 0.5 C ∆V
2
fabricated by the Kirkendall effects-involved anion exchange reaction of the
P = E / ∆t NiCo-precursor on graphene with abundant S2- ions derived from TAA. The
where C is specific capacitance of asymmetric supercapacitor B-Ni-Co-S/G hybrids were directly fabricated via one-step hydrothermal
-1
devices (F g ) and M is the total mass of active materials on both method (Strategy II).
electrodes (g).
The crystal phases of the samples are characterized by X-ray
diffraction (XRD) technique, of which the detailed information is
3. Results and discussion shown in Figure 2a. It is observed that all the diffraction peaks of
3.1 Fabrication of the integrated edge site-enriched Ni-Co-S/G the integrated edge site-enriched Ni-Co-S/G hybrids are indexed to
hybrids (111), (220), (311), (400), (511), and (440) plane reflections of the
The strategy for the fabrication of the integrated edge site-enriched cubic phase (Ni, Co)3S4 from the partial substitution of Co ions by Ni
Ni-Co-S/G hybrids is illustrated in Figure 1 (Strategy I). The Ni-Co ions in the Co3S4 (JCPDS Card no. 47-1738), which is completely
hydroxide precursor with nanowire-shaped structure is first grown different from that of Ni-Co hydroxide precursor (Figure S2, NiCo-
on the graphene through a facile hydrothermal process, which has carbonate hydroxides, JCPDS Card no. 48-0083). Further, the
16
been reported in our previous work. Then the Ni-Co hydroxide corresponding molar ratio of Ni, Co and S is about 1:1:2.69 in the
precursor is in-situ transformed into edge site-enriched Ni-Co-S edge site-enriched Ni-Co-S/G hybrids based on EDS analysis. For the
nanoparticles in the presence of thioacetamide (TAA). Thereinto, detailed information, please refer to Figure S1 and Table S1. It is
2-
the abundant S ions, produced by the thermal decomposition of also noted that the as-made sample is made of Co, Ni, S, C, and O
- 2-
TAA in solution, quickly exchange with anions (OH and CO3 ) of Ni- species (Figure S1, elemental mapping). The O species are mainly
Co hydroxide precursor meanwhile accompanied by the Kirkendall attributed to some oxygen-containing functional groups on
effects to form Ni-Co-S species. The lattice mismatch caused by graphene surface, which is consistent with the following C1s XPS
transformation of crystal structure can give rise to the quick strain spectrum result. Meanwhile, the atom ratio of Ni and Co in the Ni-
release and further lead to formation of edge site-enriched Co-S/G hybrids was also determined by ICP (Table S2). It was also

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found that the Ni-Co-S species in the hybrids exist in the form of the anion-exchange reaction method, the Ni-Co-S/G Viewhybrids at
Article Online
Ni1.5Co1.5S4, which is in agreement with the above EDS and XRD different reaction stages were collected andDOI: the 10.1039/C5EE03633J
corresponding FE-
results. This implies that the successful transformation of Ni-Co SEM and transmission electron microcopy (TEM) images are shows
hydroxides to Ni-Co sulfides, basing on an anion exchange reaction in Figure S3. When the Ni-Co precursor reacts with TAA for 3 h

Energy & Environmental Science Accepted Manuscript

2- - 2-
between S from TAA solution and OH and CO3 in the Ni-Co (Figure S3b), the nanowire-shaped Ni-Co precursor (Figure S3a) is
precursor under hydrothermal environment. These combined gradually changed into the certain amounts of hollow nanotube-
results also further confirm that the impurities derived from shaped structure species. And the edge site-enriched nanoparicles
reactants (e.g. Ni-Co hydroxides and TAA) were completely appear on graphene surface. This may be attributed to the
transformed and removed after careful washing with water and Kirkendall effect, which plays a critical role for formation hollow
13, 19
ethanol, respectively. For B-Ni-Co-S/G hybrids, the crystal structure shell-shaped Ni-Co-S species. Meanwhile, the lattice mismatch
is consistent with that of the as-obtained integrated edge site- caused by transformation of crystal structure can give rise to the
enriched Ni-Co-S/G hybrids, e.g. the adopted strategy has no quick strain release and lead to formation of edge site-enriched
18, 19
influence on crystal structure of the Ni-Co-S within hybrid matrix nanoparticles. Such a transformation can be further confirmed
and cubic phase transition metal sulfide is a thermodynamically by the corresponding as-made products for 6 h (Figure S3c), in
stable phase in the finally obtained hybrids. No diffraction peaks which hollow intermediate products gradually disappear and edge
can be observed in the pattern of graphene because of its low site-enriched nanoparticles become more and more obvious. These
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amount and relatively low diffraction intensity. Nevertheless, the results suggest that Kirkendall effect-involved anion exchange
2-
presence of graphene can be confirmed by the Raman spectrum. reaction, e.g. such an etching-like effort of the S ions, is
Two characteristic peaks of the D and G bands of the integrated responsible for the formation of edge site-enriched nanostructures.
edge site-enriched Ni-Co-S/G hybrids are observed at about 1350 It should be also noted that the pristine Ni-Co-S species tend to
-1
and 1580 cm (Figure 2b), respectively. Compared with the GO, the form aggregations made of nanoparicles with a large size of 50-100
ID/IG ratios of the graphene nanosheets obtained by reduction of nm (Figure S5) in the absence of graphene, which is unfavorable for
the GO and Ni-Co-S/G hybrids increase slightly from 0.95 to 1.07 retaining the largely accessible contact area with electrolyte to fully
and 1.15, respectively, indicating that more structural defects are fulfill the redox reaction kinetics of the electroactive species. For
present on the edge site-enriched Ni-Co-S/G hybrids, which is the B-Ni-Co-S/G hybrids that were directly fabricated from metal
obviously related to the intimate anchoring of Ni-Co-S species on salts, TAA, and graphene oxide (GO) via one-step hydrothermal
22
the graphene surface. method, the typical FE-SEM images are shown in Figure 3d-f. The
particle size of the Ni-Co-S species with irregular bulky sphere
shapes ranges from 200-500 nm, and it was difficult to identify
integrated hybrid structures with strong interaction between Ni-Co-
S species and graphene (Figure 3d, e). The high-resolution FE-SEM
images show that some smaller Ni-Co-S particles with a size of 20-
50 nm are also present and anchored on graphene surfaces (Figure
3f), which may be attributed to in-situ growth of metal ions
absorbed on the GO surfaces. These results indicate that the
structure and morphology of Ni-Co-S species are a dependent-
Figure 2. Structure characterization of the samples: (a) typical XRD patterns process behavior, nevertheless, this is not the case for the
of the integrated edge site-enriched Ni-Co-S/G and B-Ni-Co-S/G hybrids; (b) component and crystal structure.
Raman spectra of GO, graphene, and integrated edge site-enriched Ni-Co-
S/G hybrids.

The typical FE-SEM image of the Ni-Co precursor/G is shown in

Figure S3a, in which Ni-Co precursor species exhibit a nanowire-
shaped structure and uniformly anchor on graphene surface.
Surprisingly, in sharp contrast with the Ni-Co precursor/G, the
nanowire-shaped structures disappear and the Ni-Co-S
nanoparticles anchored on the graphene to form the integrated
electroactive specie-on-sheet architectures can be clearly observed
when the TAA is present under hydrothermal environment for 12 h
(Figure 3a and b). Further high-resolution FE-SEM images reveal
that the Ni-Co-S nanoparticles with the size of 15-20 nm and ultra-
Figure 3. Typical FE-SEM images of samples: (a, b, c) integrated edge site-
rich edge sites derived from small-sized effects (red arrows) are
enriched Ni-Co-S/G hybrids; (d, e, f) B-Ni-Co-S/G hybrids directly obtained
uniformly deposited on both sides of graphene sheets (Figure 3c), in
from metal salts, TAA, and GO under hydrothermal environment.
which graphene sheets with fully exposed high surface area make it
possible for ultrahigh loading of Ni-Co-S species (about 91.7%, The morphology and structure of the pristine Ni-Co-S species in
based on TGA analysis, Figure S4) in the hybrids. To have an insight absence of graphene, integrated edge site-enriched Ni-Co-S/G, and
into the structure transformation mechanism of Ni-Co-S species by B-Ni-Co-S/G hybrids were further examined by TEM and high-

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resolution TEM (HR-TEM). As shown in Figure 4a and 4b, the In order to obtain detailed information aboutView the surface
Article Online
pristine Ni-Co-S species with a particle size of 50-100 nm disorderly electronic states of as-fabricated integratedDOI: edge10.1039/C5EE03633J
site-enriched Ni-
stack together to form an aggregated structure in large visual fields. Co-S/G hybrids, X-ray photoelectron spectroscopy (XPS)
For the Ni-Co-S/G hybrids, the low-magnification TEM image shows measurements were performed and results are presented in Figure

Energy & Environmental Science Accepted Manuscript

a relatively uniform distribution of the Ni-Co-S species and ultrahigh 5. The Ni 2p3/2 and Ni 2p1/2 emission spectra (Figure 5a) were fitted
2+ 3+
loading on the graphene surface (Figure S6a). An enlarged view with two spin-orbit doublet characteristics of Ni and Ni . In
reveals that the Ni-Co-S nanoparticle species with size of 15-20 nm details, the Ni 2p3/2 spectrum shows a peak at 853.5 eV that
2+
and ultra-rich edge sites were well decorated and anchored on corresponds to the Ni ions located in the octahedral sites and a
3+
graphene (Figure 4c), which is obviously different from the B-Ni-Co- peak at 854.8 eV that corresponds to Ni ions located in the
12, 23
S/G hybrids with irregular bulky sphere shapes (Figure S6b, c). This tetrahedral sites. This is also the case for Co 2p XPS spectrum.
2-
implies that the etching-like effort of the S ions plays the critical The strong peaks at 778.9 eV for Co 2p3/2 and 795.5 eV for Co 2p1/2
role for the formation of edge site-enriched nanostructures, which are demonstrated in Figure 5b, indicative of the existence of both
3+ 2+ 23, 24
is also in agreement with the FE-SEM results as discussed above. Co and Co . These results show that the chemical
2+
Further HR-TEM images of the Ni-Co-S/G hybrids reveal that the Ni- composition of the as-fabricated Ni-Co-S/G hybrids contain Ni ,
3+ 2+ 3+
Co-S nanoparticles feature the rich edge sites (Figure 4d, red Ni , Co , and Co , which will play a role for the high
25, 26
arrows). The visible lattice fringes with spacing of about 0.28 nm, electrochemical performance of electrode materials. Figure 5c
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attributing to the (311) planes of the cubic (Ni, Co)3S4 phase, and shows the high-resolution S 2p spectrum, in which the two major
Fast-Fourier Transform (FFT) image from yellow square region peaks about 163.2 and 162.0 eV correspond to metal-sulfur bonds
2- 12
demonstrate the {311} plane preferential orientation for the Ni-Co- and the S in low coordination on the surface, respectively. For
S edges. Furthermore, the nanoparticles with thickness of about 5 the C1s XPS spectrum of Ni-Co-S/G hybrids, the spectrum can be
nm in the Ni-Co-S/G hybrids were also observed (Figure 4e, the red fitted and divided into four peaks: the aromatic-linked carbon (C=C,
region), indicative of a plate-like structure for small-sized 284.6 eV); the C in oxygen single-bonded carbon bonds (C-O, 285.1
nanoparticles. And the lattice spacing of 0.33 nm corresponding to eV); the carbonyl carbon (C=O, 286.1 eV), and the carboxylate
27, 28
the (220) planes is observed (Figure 4e, the red region). In the case carbon (O-C=O, 288.9 eV) (Figure 5d). This implies that some
of B-Ni-Co-S, it is apparent that the edge sites just extends to the oxygen-containing functional groups are still present on the
first few layers since the FFT pattern in the interior differs from that graphene surface under the hydrothermal conditions, which is
in the edges (Figure S6d), indicative of the relatively poor exposure consistent with the EDS results. Moreover, these oxygen-containing
for edge sites on bulky sphere surface. In addition, scanning TEM functional groups are beneficial for intimate anchoring Ni-Co-S
(STEM) image of the Ni-Co-S/G hybrids and corresponding species on graphene and enhancing structural stability of hybrid
elemental mapping from the square region marked in Figure 4f electrodes.
further reveal a uniform distribution of the Ni-Co-S species and
ultrahigh loading on graphene surfaces, and intimate interaction
between them.

Figure 5. High-resolution XPS spectra of (a) Ni 2p, (b) Co 2p, (c) S 2p, and (d)
C 1s for the integrated edge site-enriched Ni-Co-S/G hybrids.
Figure 4. TEM and HR-TEM images of samples: (a, b) TEM images of the
pristine Ni-Co-S in absence of graphene; (c) TEM and (d, e) HR-TEM images
of the integrated edge site-enriched Ni-Co-S/G hybrids, the inset is FFT 3.2 Electrochemical performance of the integrated edge site-
(Fast-Fourier Transform) images obtained from the yellow square region; (f) enriched Ni-Co-S/G hybrids
STEM image of the integrated edge site-enriched Ni-Co-S/G hybrids and The electrochemical performance of the as-fabricated samples
corresponding elemental mapping of C, Ni, Co, and S from the square region was evaluated in a three-electrode cell in 6 M KOH aqueous
marked in (f). It is noted that the bright part in C elemental mapping is electrolyte. It should be noted that the bare Ni foam substrate
attributed to carbon film from copper grid. shows a smaller current in comparison to the edge site-enriched Ni-

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Co-S/G hybrid electrodes, indicative of the negligible contribution of amount of edge active sites derived from small-sized effects
View Article of
Online
the Ni foam substrate towards the capacitance under the nanoparticles. In addition, optimal balance of DOI: 10.1039/C5EE03633J
active species within
conditions adopted in the present work (Figure S7). The CV curves hybrid matrix, short transport distance of electron and electrolyte
of the pristine Ni-Co-S, integrated edge site-enriched Ni-Co-S/G ions in integrated nano-scaled dimension, together with strong

Energy & Environmental Science Accepted Manuscript

-
hybrids, and B-Ni-Co-S/G hybrids at a constant scan rate of 10 mV s interaction between graphene and nanoparticles will synergistically
1
are shown in Figure 6a. It can be seen that all of the CV curves contribute to the enhanced reaction kinetics to some degree. To
have similar shapes, and exhibit a pair of intense redox peaks at our best knowledge, such a superior rate performance has been
about 0.35 and 0.15 V, implying that the specific capacitance is rarely observed for pseudocapacitor-type electrode materials, even
11, 13, 26, 27, 29, 30
primarily attributed to the fast and reversible electrochemical redox the carbon materials. Such an integrated
2+ 3+ 4+ 2+ 3+
reaction processes of Co /Co /Co and Ni /Ni redox couples characteristic leads to fast redox reaction kinetics, which is
11, 13
based on the following reactions: confirmed by electrochemical impedance spectroscopy as shown in
- -
CoS + OH ⇄ CoSOH + e Figure S12. The cycling stability of the Ni-Co-S/G hybrids was further
- -
CoSOH + OH ⇄ CoSO + H2O + e investigated by the capacitance retention at current density of 6 A
- - −1
NiS + OH ⇄ NiSOH + e g (Figure 6d). Remarkably, the specific capacitance can retain ca.
It is also noted that the as-made integrated edge site-enriched Ni- 90% of the initial value after 8000 cycles, which is better than that
13, 30, 31
Co-S/G hybrids also show an increased CV curve area and redox reported in the literatures, demonstrating the excellent long-
Published on 14 January 2016. Downloaded by RMIT Uni on 15/01/2016 02:41:24.

peak intensity compared to other electrodes, implying a term electrochemical stability.

significantly improved specific capacitance and fast redox reaction
kinetics processes. The galvanostatic charge/discharge curves of the
edge site-enriched Ni-Co-S/G hybrids are carried out at different
-1
current densities (1-50 A g ). As shown in Figure 6b, the potential-
time curves at all current densities are almost symmetric, indicative
of a high Coulombic efficiency due to the highly reversible redox
reactions of the Ni-Co-S/G hybrid electrode on the charge/discharge
process. The variation of IR drop at different discharge-current
densities (Figure S8, S9) confirms that the integrated edge site-
enriched Ni-Co-S/G hybrids have a small internal resistance, further
demonstrating that the integrated hybrid structures made of the
edge site-enriched Ni-Co-S nanoparticles intimately anchored on
graphene can effectively reduce the charge-transfer resistance, and
improve the transport and collection of electrons.
The specific capacitances of the as-obtained pristine Ni-Co-S,
integrated edge site-enriched Ni-Co-S/G hybrids, and B-Ni-Co-S/G
-1
hybrids at a low current density of 1 A g were calculated to be
-1
1257, 1492, and 1354 F g , respectively (Figure 6c). And the Figure 6. Electrochemical performance of the samples for supercapacitors:
corresponding volumetric capacitance of the as-made Ni-Co-S/G (a) CV curves of the Ni-Co-S, integrated edge site-enriched Ni-Co-S/G hybrids,
-3
hybrid electrodes was also estimated to be about 597 F cm based and B-Ni-Co-S/G hybrids at a scan rate of 10 mV s−1; (b) galvanostatic
-3
on the tap density (0.4 g cm ). It is striking that the capacitance of charge/discharge curves of the integrated edge site-enriched Ni-Co-S/G
-1
Ni-Co-S/G can achieve as high as 1433 F g at a current density of hybrids at different current densities from 1-50 A g−1; (c) the specific
-1
50 A g with a capacitive retention rate of 96%, although the Ni-Co- capacitances of the pristine Ni-Co-S, integrated edge site-enriched Ni-Co-S/G
2 -1
S/G has the low specific surface area of about 25 m g (Figure S10). hybrids, and B-Ni-Co-S/G hybrids at different current densities; (d) cycling
This further suggests that rich edge sites play a pivotal role for the performance of the integrated edge site-enriched Ni-Co-S/G hybrids at a
enhanced capacitance and redox reaction kinetics, which will current density of 6 A g−1.
contribute to delivering the superior rate capability. However, for B-
Ni-Co-S/G hybrids, the specific capacitance rapidly decreases to 101 3.3 DFT calculation
-1 -1
F g when current density increased to 30 A g with a very low To further reveal and understand the edge site effects on the
capacitive retention rate of 7%, which is far lower than that of the redox reaction activity of Ni-Co-S nanoparticles, the DFT
pristine Ni-Co-S species (ca. 79%) and Ni-Co-S/G hybrids (ca. 96%). calculations were performed. Combining with the aforementioned
Moreover, a series of the Ni-Co-S/G hybrid electrodes were also results from HR-TEM and FFT images, the model of spinel Ni-Co-S
fabricated using G/Ni-Co precursors with different weight ratios of species was constructed, in which the Co atoms in Co3S4 were
GO to metal salts (cobalt and nickel salts) (1:3, 1:6, 1:9 and 1:12) in partially replaced by Ni atoms, e.g. Ni1.5Co1.5S4 (Figure S13). And the
the first step of the synthesis, yielding samples labeled as Ni-Co- corresponding Ni-Co-S (311) and (220) surfaces that include three
S/G-1, Ni-Co-S/G-2, Ni-Co-S/G, and Ni-Co-S/G-3, respectively. As and four atomic layers, respectively, were modeled as the p (1×1)
shown in Figure S11, the as-made Ni-Co-S/G hybrids sample also periodic slab. It is found that the optimized (311) surface show the
-2
show the highest specific capacitance at all current densities in higher surface energy (1.278 J m ) than that of (220) surface (0.457
-2
comparison to other samples. In this case, the superb performance J m ) due to the different surface reconstructions and
of Ni-Co-S/G hybrids is mainly attributed to exposure of the large configurations (Figure 7 and Table S3). This implies that the Ni-Co-S

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with the (311) surface also possesses rich active sites (a-m) in k 1.79 3.17 View Article Online
comparison to that with the (220) surface (a-h). That is to say, the l 1.81 2.77 DOI: 10.1039/C5EE03633J
Ni-Co-S edge sites are electroactive site-enriched, being responsible m 1.81 2.78
for the high electrochemical activity.

Energy & Environmental Science Accepted Manuscript

average 1.82 2.88
−
The adsorption properties of OH in electrolyte on the Ni-Co-S
surfaces were also calculated to further evaluate the effects of the 3.4 Electrochemical performance of the Ni-Co-S/G hybrid //
edge sites on redox reaction kinetics. It is found that the O atom of porous carbon nanosheet asymmetric supercapacitor
-
OH are strongly coupled with metal atoms of the (311) surface, and Asymmetric supercapacitors featuring both high energy and power
-
the corresponding distance (dM-O) and adsorption energies (EOH ) of densities are highly sought after for practical application of
-
OH adsorbed on these metal atoms are listed in Table 1. It was supercapacitors. Herein, we have constructed an asymmetric
-
found that the average distance of about 1.82 Å between the OH supercapacitor by employing the integrated edge site-enriched Ni-
and the metal atoms of (311) surface is demonstrated, being Co-S/G hybrids as positive electrode and 2D porous carbon
shorter than that of (220) surfaces (1.91 Å), further revealing that nanosheets (PCNS) as negative electrode (Figure 8a). The PCNS was
-
the Ni-Co-S edge sites have a stronger capability of adsorbing OH . prepared by a layered-nanospace-confinement strategy using
- -
Correspondingly, the calculated average EOH of OH on (311) surface montmorillonite (MMT) as nanotemplate and gelatin as carbon
atoms is 2.88 eV, being larger than that on (220) surfaces (1.77 eV), 32
Published on 14 January 2016. Downloaded by RMIT Uni on 15/01/2016 02:41:24.

source based on our previous work. The representative SEM

indicating that the Ni-Co-S edge sites feature high adsorption ability images (Figure 8b) reveal that PCNS with a high specific surface area
-
and stability for OH in the electrolyte. These combined theoretical 2 -1
of about 3000 m g and tap density of 0.05 g cm is composed of
-3

and experimental results further suggest that the edge site- wrinkled carbon nanosheets and tends to a relatively loose and
enriched Ni-Co-S particles play a pivotal role for enhancing redox open structure. The mass ratio of the two electrode materials was
reaction kinetics and superior electrochemical performance. balanced before making the asymmetric supercapacitor devices,
and the voltage window of the asymmetric supercapacitors was
determined to be 1.6 V, according to their individual
electrochemical behaviors (Figure S14). As shown in Figure 8c, the
−1
CV curves at scan rates from 5 to 100 mV s demonstrate that the
as-fabricated asymmetric supercapacitor shows an excellent
capacitive behavior at 0-1.6 V. The typical galvanostatic
-1
charge/discharge curves at different current densities (1-30 A g )
show that the potential-time curves at all current densities are
almost symmetric, indicative of a high Coulombic efficiency (Figure
8d). The specific capacitance calculated from typical galvanostatic
charge/discharge curves at different current densities show a
−1
specific capacitance of around 122 F g was obtained at a current
−1 −1
density of 1 A g (Figure 8e), which was still 105 F g with the 86%
−1
of capacitance retention rate at 10 A g , which is higher that of
fabricated the Ni-Co-S/G//activated carbon asymmetric
Figure 7. Optimized structural models of the Ni-Co-S with different surfaces:
supercapacitor (74%). The specific capacitance of the asymmetric
(a) top view and (c) side view of (311) surface, in which thirteen metal atoms −1 −1
supercapacitor remains at 95 F g even at 30 A g , and 78% of the
(a-m) are exposed; (b) top view and (d) side view of (220) surface, in which
specific capacitance was retained, which further evidences the high
eight metal atoms (a-h) are exposed.
capacitance and excellent rate performance of the Ni-Co-S/G//PCNS
asymmetric supercapacitor. These results are comparable to data
Table 1 The distance (dM-O) of OH- and metal atoms on the (311) and (200) 11, 20, 33-35
reported in the literatures. Figure 8f shows a Ragone plot,
plane surfaces, and OH- adsorption energies (EOH-) on metal atoms of the
which demonstrates the relationship between the energy and
(311) and (200) plane surfaces.
power density of the asymmetric supercapacitors. It can be seen
Ni-Co-S (311) plane surface Ni-Co-S (220) plane surface −1
that an energy density of 43.2 Wh kg (6.48 mWh cm ) at an
-3

metal atom dM-O / Å EOH- / eV metal atom dM-O / Å EOH- / eV average power density of 0.8 kW kg
−1
can be achieved, and
a 1.82 2.94 a 1.88 1.73 -3
corresponding to the volumetric energy density of 6.48 mWh cm
b 1.82 2.91 b 1.93 1.71 based on the total tap density of two electrodes. Moreover, an
1.82 2.92 1.87 1.80 −1
c c energy density of 28.4 Wh kg can be kept for a power density of
−1
d 1.82 2.94 d 1.93 1.79 22.1 kW kg . These results are much better than Ni-Co-S/G // AC
−1 −1
e 1.79 3.10 e 1.86 1.82 symmetric supercapacitor (19.9 Wh kg at 6.8 kW kg ), and some
f 1.78 3.10 f 1.93 1.82 reported values in the literatures, such as Co3O4 // carbon (15 Wh
−1 −1 33 −1 −1 36
g 1.83 2.89 g 1.88 1.81 kg at 8 kW kg ), CoMoO4 // AC (19.9 Wh kg at 6.8 kW kg ),
−1 −1 20
h 1.82 2.88 h 1.97 1.64 NiCo2S4 // G/CS (22.9 Wh kg at 10.2 kW kg ), Ni(OH)2 // AC (12.6
−1 −1 34 −1
i 1.83 2.85 average 1.91 1.77 Wh kg at 1.67 kW kg ), GSP-LDH // SGC (20.4 Wh kg at 9.3 kW
−1 37 −1 −1 38
j 1.87 2.23 kg ), MnO2/G // MoO3/G (42.6 Wh kg at 0.28 kW kg ). In a

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ARTICLE Journal Name

word, our present work provides a new yet efficient strategy for In summary, a simple strategy has been demonstrated for
View Article Online
fabricating high-rate and high-energy density asymmetric DOI: 10.1039/C5EE03633J
fabricating integrated hybrid architectures composed of edge site-
supercapacitors by combining the Ni-Co-S/G hybrids with PCNS enriched Ni-Co-S nanoparticles and graphene via an in-situ chemical
electrode materials. The cycling performance of the Ni-Co- transformation from their pre-fabricated hydroxide species. The

Energy & Environmental Science Accepted Manuscript

S/G//PCNS asymmetric supercapacitors was evaluated at a high DFT calculations reveal that the Ni-Co-S edge sites have a high
−1 -
current density of 10 A g , of which the results are shown in Figure electrochemical activity and strong affinity for OH in the electrolyte
8g. It can be clearly seen that the Ni-Co-S/G//PCNS asymmetric that is responsible for the enhanced electrochemical performance.
supercapacitor displays excellent cycling stability with about 85% of Combining highly rich electroactive edge sites, short transport
the initial specific capacitance even after 10000 cycles. distance of electron and electrolyte ions in integrated nano-scaled
dimension, together with intimate interaction between Ni-Co-S
nanoparticles and conductive graphene substrate, the as-obtained
Ni-Co-S/G hybrid electrodes exhibit a high specific capacitance and
superior rate capability. Two-electrode asymmetric supercapacitor
made of the Ni-Co-S/G hybrids and PCNS shows a high energy
density and power density, indicative of their potential as a
promising candidate material for high-performance supercapacitors.
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Acknowledgements
J. Y. and C. Y. contributed equally to this work. This work was partly
supported by the Natural Science Foundation of China (Nos.
21361162004, 21522601) and the Education Department of the
Liaoning Province of China (No. T2013001).

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DOI: 10.1039/C5EE03633J

Electroactive Edge Site-Enriched Nickel-Cobalt Sulfide into Graphene

Energy & Environmental Science Accepted Manuscript

Frameworks for High-performance Asymmetric Supercapacitors

Juan Yang, Chang Yu, Xiaoming Fan, Suxia Liang, Shaofeng Li, Huawei Huang,
Zheng Ling, Ce Hao, and Jieshan Qiu*

TOC
Published on 14 January 2016. Downloaded by RMIT Uni on 15/01/2016 02:41:24.

The integrated hybrid architectures composed of edge site-enriched nickel-cobalt

sulfide (Ni-Co-S) nanoparticles and graphene as advanced materials for asymmetric
supercapacitors are configured, delivering a superb rate capability.