Science Bulletin xxx (2018) xxx–xxx

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Science Bulletin
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Article

One-pot synthesis of nickel-cobalt hydroxyfluorides nanowires with

ultrahigh energy density for an asymmetric supercapacitor
Jian-Fang Zhang a, Yan Wang a,b,⇑, Xia Shu a, Cui-Ping Yu a, Ming-Feng Xiao a, Jie-Wu Cui a,
Yong-Qiang Qin a, Hong-Mei Zheng a, Yong Zhang a, Dong Chen c, Pulickel M. Ajayan b, Yu-Cheng Wu a,d,⇑
a
School of Materials Science and Engineering, Hefei University of Technology, Hefei 230009, China
b
Department of Material Science and Nanoengineering, Rice University, Houston, TX 77005, USA
c
School of Instrument Science and Opto-electronics Engineering, Hefei University of Technology, Hefei 230009, China
d
Key Laboratory of Advanced Functional Materials and Devices of Anhui Province, Hefei 230009, China

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

Article history: A novel and unique nickel-cobalt hydroxyfluorides (NiCo-HF) nanowires material is fabricated by one-pot
Received 14 November 2017 solvothermal synthesis method for asymmetric supercapacitor. The synthesis mechanism and factors
Received in revised form 3 January 2018 that influence the formation of the NiCo-HF nanowires have been further discussed. The as-prepared
Accepted 23 January 2018
NiCo-HF electrode exhibits a high specific capacitance of 3,372.6 F g
1, and the capacitance retention
Available online xxxx
of 94.3% can be achieved at a high current density of 20 A g
1 after 10,000 cycles. The outstanding elec-
trochemical performance of the electrode can be attributed to the synergistic effect of the nanowires
Keywords:
morphology and complicated redox process of active material. Furthermore, an asymmetric supercapac-
Nickel-cobalt hydroxyfluorides
Solvothermal synthesis
itor assembled with NiCo-HF nanowires as positive electrode and activated carbon as the negative elec-
Asymmetric supercapacitor trode shows an ultrahigh energy density of 83.6 Wh kg
1 at a power density of 379.4 W kg
1 and an
Energy density excellent cycling stability with 86.3% capacitance retention after 10,000 cycles, indicating that this novel
material has great promise for potential application in energy storage device.
Ó 2018 Science China Press. Published by Elsevier B.V. and Science China Press. All rights reserved.

1. Introduction
With the rapidly increasing of global warming and environmen-
tal pollution, it is extremely urgent to look for renewable energy
sources to replace the traditional fossil energy [1,2]. Supercapaci-
tors, as a novel efficient energy storage devices, have attracted con-
siderable research interest due to their fast charge-discharge
ability, high power density and long cycling life [3,4]. However,
construction of high-performance supercapacitor with high energy
density, as well as high power density is still a challenging work.
Therefore, the continuous exploration of high energy density mate-
rials has been a major target for the development of supercapaci-
tors [5–7]. It is known that the energy density can be enhanced
by increasing the specific capacitance of the electrode or the oper-
ation potential window [8]. Recently, asymmetric supercapacitors,
which combine a capacitor-type electrode and battery-type Faradic
electrode, have become very promising energy storage devices due
⇑ Corresponding authors at: School of Materials Science and Engineering, Hefei
University of Technology, Hefei 230009, China.
E-mail addresses: stone@hfut.edu.cn (Y. Wang), ycwu@hfut.edu.cn (Y.-C. Wu).
to the increased operation potential window and thus the energy
density [9,10].
Generally, transition metal hydroxides or oxides have been
widely applied in gas sensor, solar cell, Li-ion batteries, as well as
supercapacitor owing to their fast redox reaction between the mul-
tiple oxidation states [11–16]. Among various transition metal
hydroxides or oxides, Co(OH)2 and Ni(OH)2 have received wide
attention in asymmetric supercapacitors due to their layered struc-
tures and characteristic redox reaction [17,18]. However, owing to
the poor electrical conductivity, the low rate capability and cycling
life limit their practical application. Recently, instead of single
transition metal hydroxides or oxides, the mixed hydroxides or
oxides materials have been employed to make materials more
stable and durable for long-term use. In particular, Ni-Co double
hydroxide nanostructure materials have been most investigated
because of their high electrical conductivity and high specific
capacitance. For example, Yan et al. [19] demonstrated Ni-Co dou-
ble hydroxide microspheres offered an excellent supercapacitor
performance with the specific capacitance of 2,275.5 F g
1 at cur-
rent density of 1 A g
1. Chen et al. [20] reported the Ni-Co layered
double hydroxide hybrid film displayed an enhanced specific
capacitance of 2,682 F g
1 at current density of 3 A g
1. The

https://doi.org/10.1016/j.scib.2018.01.024
2095-9273/Ó 2018 Science China Press. Published by Elsevier B.V. and Science China Press. All rights reserved.

Please cite this article in press as: Zhang J-F et al. One-pot synthesis of nickel-cobalt hydroxyfluorides nanowires with ultrahigh energy density for an
asymmetric supercapacitor. Sci Bull (2018), https://doi.org/10.1016/j.scib.2018.01.024
2 J.-F. Zhang et al. / Science Bulletin xxx (2018) xxx–xxx
asymmetric supercapacitor based on the Ni-Co layered double
hydroxide hybrid film achieved an ultrahigh energy density of
188 Wh kg
1 at an average power density of 1,499 W kg
1. Cheng
et al. [21] synthesized layered Co-Ni double hydroxide/graphene
composites at first and then assembled them into films by
integrating with carbon nanotubes. The hybrid Co-Ni double
hydroxide/graphene/carbon nanotube (CNT) self-standing elec-
trode exhibited the maximum specific capacitance of 2,360 F g
1
at current density of 0.5 A g
1 and still kept value of 2,030 F g
1
at current density of 20 A g
1.
Except for the mixing the single transition metal hydroxides or
oxides with other transition metal cations, the supercapacitor per-
formance also can be improved by introduction of anions into tran-
sition metal hydroxides or oxides materials. Up to now, some
nanostructured transition metal sulphides [22,23], phosphates
[24], fluorides [25], and carbonate-hydroxides [26] have been
developed for applying in supercapacitor. Among them, metal car-
bonate hydroxides with divalent metal ions have been attracted
extensive research attention in application for supercapacitor,
which the hydrophilic CO2
3 ion can sufficiently increase the wetta-
bility of electrode surface [27,28]. For instance, Zhao et al. [29] syn-
thesized single-layered binary Ni-Co hydroxyl carbonate through
hydrothermal method, which exhibited a maximum specific capac-
itance of 2,266 F g
1 at 0.5 A g
1, and the relevant asymmetric
supercapacitor showed high energy density of 50 Wh kg
1 at 78
W kg
1. Recent research on Ni-Co hydroxyfluorides (NiCo-HF) is
limited, however, their application on the lithium-ion batteries
enlighten us to explore their potential application in supercapaci-
tors [30,31]. Inspired by the excellent performance of Ni-Co fluo-
rides and carbonate hydroxides, NiCo-HF should become an
outstanding electrode materials for supercapacitors because they
offer much more redox reactions than the single components,
which is similar way as layered double hydroxides compared with
the single component hydroxides [32].
Besides, the supercapacitor performance can be further
improved by controlled the nanostructure of the electrode to raise
the specific surface area, which contribute to fast redox reactions
and ion/electron transport at the electrode/electrolyte interface.
Active materials with nanowire structures can provide high speci-
fic surface area and accelerate the ion diffusion and electron trans-
port, which lead to the high specific capacitance. Herein, we report
a simple, one-pot solvothermal method to synthesize NiCo-HF
nanowires used as the electrode for supercapacitor. The novel
NiCo-HF nanowires exhibit a high specific capacitance of 3,372.6
F g
1 at a current density of 1 A g
1 and maintain the specific
capacitance of 2,505.7 F g
1 at a current density of 20 A g
1. More-
over, about 94.3% of the initial specific capacitance is maintained at
20 A g
1 after 10,000 cycles. In addition, the as-assembled NiCo-
HF//activated carbon (AC) asymmetric supercapacitor shows high
energy density (86.3 Wh kg
1 at 379.4 W kg
1) with high power
density (7,490 W kg
1 at 65.4 Wh kg
1) and cycling retention of
86.3% after 10,000 charge-discharge cycles.
2. Materials and methods
2.1. Synthesis of NiCo-HF nanowires
All materials and reagents were of analytical grade and were
used without further purification. In the typical synthesis process,
2 mmol Ni(CH3COO)24H2O, 2 mmol Co(CH3COO)24H2O, 4 mmol
NH4F and 10 mmol urea were dissolved in 40 mL isopropyl
alcohol-water mixture solution (volume ratio is 1:1). After ultra-
sonic for 30 min, the resulting solution was sealed in a 50 mL
Teflon-lined autoclave and heated to 140 °C for 10 h, then cooled
to room temperature naturally. The NiCo-HF nanowires were
Please cite this article in press as: Zhang J-F et al. One-pot synthesis of nickel-cobalt hydroxyfluorides nanowires with ultrahigh energy density for an
asymmetric supercapacitor. Sci Bull (2018), https://doi.org/10.1016/j.scib.2018.01.024
collected by filtration and washed with absolute ethanol and
deionized water several times, and then dried at 60 °C overnight.
The Ni-HF and Co-HF were obtained by adding Ni(CH3COO)24H2O
(4 mmol) and Co(CH3COO)24H2O (4 mmol) respectively in the
starting materials, while keeping the other experimental conditions
unchanged. Moreover, in order to gain the growth mechanism of
NiCo-HF nanowires, the reaction temperatures at different stages
(120, 140, 160 and 180 °C) were carefully carried out, at the same
time the other experimental conditions were kept unchanged.
2.2. Characterization
The morphologies of Ni-HF, Co-HF and NiCo-HF samples were
characterized using an SU8020 field-emission scanning electron
microscopy (FESEM, Hitachi, Japan), respectively. The chemical
composition and distribution of as-prepared samples were
recorded by energy dispersive X-ray spectroscopy (EDS). The struc-
tures and crystalline phases were investigated by X-ray powder
diffraction (XRD, Rigaku, Japan). High resolution transmission
electron microscopy (HRTEM) images were observed using a
JEM-2100F (JEOL, Japan) operating at 200 kV. X-ray photoelectron
spectroscopy (XPS) spectra were recorded on ESCALAB250 (Thermo,
USA) using a monochromatic Al Ka X-ray beam. The specific surface
area and pore size distribution of samples were examined by the
Brunauer-Emmett-Teller (BET) method and the Barrett-Joyner-
Halenda (BJH) model (SA3100 Surface Area Analyzer).
2.3. Fabrication of NiCo-HF//AC asymmetric supercapacitors
The working electrodes were prepared by mixing the as-
prepared samples, acetylene black and polyvinylidone fluoride
(PVDF) at a weight ratio of 8:1:1 in 1-methyl-2-pyrrolidinone sol-
vent to form the slurry and coating on the nickel foam uniformly.
Prior to prepare the electrode, Ni foam was pretreated with 5%
HCl solution to remove the surface oxide layer and ultrasonically
washed with acetone, ethanol and deionized water, respectively.
The mass loading density of the electrode material on the nickel
foam was about 5 mg cm
2. The asymmetric supercapacitor was
assembled by combining the NiCo-HF nanowires positive electrode
and the commercial AC negative electrode face-to-face with poly
(vinyl alcohol) (PVA)-KOH gel electrolyte and dried at 60 °C until
the gel electrolyte was solidified with the evaporation of water.
The PVA-KOH gel electrolyte was prepared as follows: 3 g of PVA
powder was dissolved in 30 mL deionized water under vigorous
stirring at 90 °C until PVA dissolved completely, and then 3.4 g
KOH powder was slowly added into the viscous solution with suf-
ficient stirring until the solution became clear. The mass ratio of
the positive electrode and negative electrode was calculated
according to the following Eq. (1) [33]:
mþ C s
 DV

¼ ð1Þ
m
C sþ  DV þ
where m, Cs and DV are the mass, the specific capacitance and the
potential window for positive (+) and negative (
) electrodes,
respectively. The optimal mass ratio of NiCo-HF to AC can be calcu-
lated to be m+/m
= 0.74.
2.4. Electrochemical measurements
The electrochemical measurements of the as-fabricated elec-
trodes were carried out in three-electrode cell with 2 mol L
1
KOH aqueous solution as the electrolyte at room temperature.
The as-fabricated electrode was used as the working electrode,
while the Ag/AgCl electrode and Pt wire electrode were used as
the reference and counter electrode, respectively. All the electro-
chemical performances were tested on a CHI760E electrochemical
 J.-F. Zhang et al. / Science Bulletin xxx (2018) xxx–xxx
workstation by combining using of cyclic voltammetry (CV), gal-
vanostatic charge-discharge (GCD), and electrochemical impe-
dance spectroscopy (EIS). The specific capacitance of the
electrode and asymmetric supercapacitor were calculated from
the GCD curves based on the following Eqs. (2) and (3), and the
energy density and power density of the NiCo-HF//AC asymmetric
supercapacitor were calculated from the following Eqs. (4) and (5):
it
Cs ¼ ; ð2Þ
DV  m
it
Cd ¼ ; ð3Þ
DV  M
0:5C d  ðDVÞ2
E¼ ; ð4Þ
3:6
E  3600
P¼ ; ð5Þ
t
where Cs is the specific capacitance of the single NiCo-HF electrode
(F g
1) and Cd is the specific capacitance of NiCo-HF//AC asymmetric
supercapacitor, E is the energy density (Wh kg
1), P is the power
density (W kg
1), m is the mass of active material on
the single NiCo-HF electrode (g), and M is the total mass of the
active materials on both the positive electrode and negative elec-
trode (M = m+ + m
), DV is the potential window in the discharge
process (V), and t is the discharge time (s).
3. Results and discussion
The morphologies of the samples were characterized by FESEM.
As shown in Fig. 1a, the Ni-HF sample is mainly uniform
microspheres composed of nanoflakes. The thickness of the Ni-HF
nanoflakes is about 20 nm. It is interesting that when change the
Fig. 1. (Color online) FESEM images of Ni-HF (a), Co-HF (b) and NiCo-HF (c). (d) Corresponding XRD patterns of the samples.
Please cite this article in press as: Zhang J-F et al. One-pot synthesis of nickel-cobalt hydroxyfluorides nanowires with ultrahigh energy density for an
asymmetric supercapacitor. Sci Bull (2018), https://doi.org/10.1016/j.scib.2018.01.024
3
Ni(CH3COO)24H2O to Co(CH3COO)24H2O solution, the Co-HF sam-
ple presents nanowires structure under others synthesis condition
unchanged, as shown in Fig. 1b. When add Co(CH3COO)24H2O into
Ni(CH3COO)24H2O solution with the molar ratio of 1:1, the NiCo-
HF sample exhibits nanoflakes structure composed of nanowires
(Fig. 1c), which expose more porous and provide larger specific
surface area. Fig. 1d shows the XRD patterns of the Ni-HF, Co-HF
and NiCo-HF samples. For the Ni-HF sample, the peaks at 2h =
35°, 40.4°, 53.9° and 62.3° are corresponding to the diffraction of
Ni4(OH)F7 (JCPDS No. 28-0697). For Co-HF sample, all diffraction
peaks are well consistent with Co(OH)F (JCPDS No. 50-0827). Both
the diffraction peaks of Ni4(OH)F7 and Co(OH)F can be clearly seen
in NiCo-HF sample, demonstrating that the NiCo-HF is composed
with this two species. EDS spectra of the as-prepared samples
(Fig. S1 online) reveal they are composed of O, F, Ni or/and Co
elements.
The TEM image further illustrate the morphology of NiCo-HF
presents nanowires structure with diameter of 80–120 nm
(Fig. 2a). The visible lattice fringes with an interplanar spacing of
0.23 nm corresponds to the (2 1 1) plane of Co(OH)F (Fig. 2b). The
selected-area electron diffraction (SAED) pattern (inset of Fig. 2b)
shows well-defined ordered dots, suggesting its monocrystalline
structure. The elements distributions of the NiCo-HF are character-
ized by EDS mapping. As shown in Fig. 2c, a uniform distribution of
the elements of Ni, Co, O and F indicates the formation of a single
phase of NiCo-HF with the elements well dispersed.
XPS was carried out to investigate the chemical composition
and oxidation state of the as-prepared NiCo-HF. As shown in
Fig. S2 (online), the survey spectrum shows the existence of Ni,
Co, O and F in the NiCo-HF. A Gaussian fitting of the Co 2p spec-
trum in Fig. S2b (online) shows two major peaks with binding
energies of 783.8 and 799.5 eV, corresponding to the Co2+, and
other two peaks at 782.1 and 798.2 eV assigned to Co3+, respec-
tively. And two satellites sub-peaks are also fitted in the Co 2p
4 J.-F. Zhang et al. / Science Bulletin xxx (2018) xxx–xxx
Fig. 2. (Color online) TEM and corresponding EDS mapping of NiCo-HF. (a) TEM
image, (b) HRTEM image, and (c) EDS mapping, inset (b) shows the SAED pattern of
NiCo-HF.
spectrum. Similarly, as shown in Fig. S2c (online), the Gaussian fit-
ting of the Ni 2p spectrum also shows two spin-orbit doublets that
are characteristic of Ni2+ and Ni3+ and two shake-up satellites.
Fig. S2d (online) shows the F 1s spectrum with a peak at 685 eV,
which can be ascribed to the metal-fluorine bond. The XPS results
indicate that two couples of Co3+/Co2+ and Ni3+/Ni2+ are coexistent
in the synthesized NiCo-HF nanostructure.
The N2 adsorption/desorption isotherms patterns and the corre-
sponding pore size distribution of the Ni-HF, Co-HF and NiCo-HF
prepared at 140 °C are shown in Fig. S3 (online). All the isotherms
are identified as type IV, which demonstrate the existence of meso-
porous in the obtained samples. The BET specific surface areas of
Ni-HF, Co-HF and NiCo-HF are determined to be 29.16, 60.75 and
79.85 m2 g
1, respectively. Obviously, NiCo-HF possesses much
higher specific surface areas than Ni-HF and Co-HF, which is attrib-
uted to the unique structure of nanoflakes composed of nanowires,
as illustrated by FESEM. The BJH pore size distribution curves
(Fig. S3b, d and f online) reveal average pore size of Ni-HF, Co-HF
and NiCo-HF are successively 3.8, 4.2 and 6.3 nm. It is worth men-
tioning that the NiCo-HF prepared at 140 °C also shows higher
specific surface areas than other NiCo-HF prepared at different
temperature, as illustrated in Fig. S4 (online) (24.32, 52.67 and
48.43 m2 g
1 for NiCo-HF prepared at 120, 160 and 180 °C, respec-
tively). The high specific surface area and loose mesoporous struc-
ture of the NiCo-HF not only accelerate transfer rate of ion/electron
from electrolyte to the surface of electrode but also provide highly
electroactive sites during electrochemical reaction.
To further understand the formation mechanism of NiCo-HF
samples, experiments with different hydrothermal temperatures
were taken out and the corresponding FESEM images are shown
in Fig. 3. When the temperature keeps at 120 °C, homogeneous
NiCo-HF microspheres composed of nanoflakes are synthesized
and a few of nanowires are grown on the surface of microspheres.
By keeping the temperature at 140 °C, the morphology of NiCo-HF
becomes quite different from the previous one. The microspheres
have been disappeared and a mass of nanowires are obtained to
form porous interconnected nanoflakes morphology. When pro-
long the temperature at 160 °C, the morphology of NiCo-HF is
changed into slender nanowires, and no obvious nanosheets are
generated. By further increasing the temperature to 180 °C, the
diameter of nanowires become larger and the size of length
decreases.
Please cite this article in press as: Zhang J-F et al. One-pot synthesis of nickel-cobalt hydroxyfluorides nanowires with ultrahigh energy density for an
asymmetric supercapacitor. Sci Bull (2018), https://doi.org/10.1016/j.scib.2018.01.024
Fig. 3. FESEM of NiCo-HF prepared at different temperature. (a, b) 120 °C, (c, d) 140
°C, (e, f) 160 °C, and (g, h) 180 °C.
Based on the above FESEM results, a possible growth process of
NiCo-HF can be depicted in the schematic diagram in Scheme 1.
First, a homogeneous solution with the reactive species is trans-
ferred to Teflon-lined autoclave. Then, more of Ni2+ species are
inclined to participate in the reaction to form microspheres while
few of Co2+ species form nanowires at low temperature of 120 °C.
It should mentioned that Ni2+ species alone can grow microspheres
composed of nanoflakes and Co2+ species alone can form nano-
wires, as illustrated by FESEM images above. With the temperature
increasing, more and more Co2+ species take part in the reaction so
that it is more likely to form nanowires. The corresponding EDS
spectra (Fig. S5 online) of the NiCo-HF prepared by different tem-
perature reveal the atomic ratio of Co/Ni increases successively
with the increasing of the temperature, which further illustrate
the growth process of NiCo-HF samples. The formation process of
NiCo-HF can be described according to the following equations
[31]. During the solvothermal synthesis process, Ni(CH3COO)2
and Co(CH3COO)2 can release Ni2+, Co2+ and [CH3COO]
, and
NH4F can release [NH4]+ and F- when dissolved in water. Urea
can be degraded into CO2, OH
and [NH4]+ when react with water.
In main reaction, Ni2+ and Co2+ react with F
and OH
to produce
NiCo-HF. In the side reaction, very few of [NH4]+ and F
will hydro-
lyze to NH3H2O and HF, which can induce the oriented growth of
NiCo-HF to form nanowire structures.
Main reaction:
þ 2½CH3 COO

2þ
NiðCH3 COOÞ2 ! Ni
CoðCH3 COOÞ2 ! Co2þ þ 2½CH3 COO

 J.-F. Zhang et al. / Science Bulletin xxx (2018) xxx–xxx 5

Scheme 1. (Color online) Schematic diagram of the formation process of NiCo-HF.

NH4 F ! ½NH4 þ þ F
pares the CV curves of Ni-HF, Co-HF and NiCo-HF electrodes pre-
pared by 140 °C and pure Ni foam at a scan rate of 50 mV s
1,
COðNH2 Þ2 þ H2 O ! CO2 þ 2OH
þ 2½NH4 þ respectively. The enclosed area of CV curves represents the specific
capacitance of the electrodes, and the NiCo-HF electrode shows
Ni ðCo2þ Þ þ F
þ OH
! NiðCoÞðOHÞF
2þ much larger enclosed areas than that of the Ni-HF and Co-HF elec-
trodes at the same scan rate, indicating greatly enhanced specific
Side reaction: capacitance. The pure Ni foam exhibits an almost negligible cur-
rent compared to the prepared electrodes, indicating that the Ni
½NH4 þ þ H2 O ! NH3  H2 O þ Hþ
foam current collector does not increase the capacitance. More-
over, typical anodic and cathodic peaks can be seen from the
F
þ H2 O ! HF þ OH

curves of the Ni-HF, Co-HF and NiCo-HF electrodes, which illus-
The electrochemical performances of the as-prepared samples trate a continuously reversible redox reaction during the charge-
were investigated by CV, GCD and EIS tests in a three electrode cell discharge process. Fig. 4b shows the CV curves of NiCo-HF elec-
using 2 mol L
1 KOH aqueous solution as electrolyte. Fig. 4a com- trode at different scan rates ranging from 2 to 100 mV s
1 and

Fig. 4. The electrochemical performances of the as-prepared samples. (a) CV curves of Ni-HF, Co-HF and NiCo-HF electrodes at scan rate of 50 mV s
1. (b) CV curves of NiCo-
HF electrode at different scan rates range from 2 to 100 mV s
1. (c) Plots of logi versus logm from 2 to 100 mV s
1. (d) GCD curves of Ni-HF, Co-HF and NiCo-HF electrodes at 5
A g
1. (e) GCD curves of NiCo-HF electrode at different current densities range from 1 to 20 A g
1. Specific capacitance (f), Nyquist plots (g), Bode plots (h), and cycling
performance and Coulombic efficiencies (f) of Ni-HF, Co-HF and NiCo-HF electrodes.

Please cite this article in press as: Zhang J-F et al. One-pot synthesis of nickel-cobalt hydroxyfluorides nanowires with ultrahigh energy density for an
asymmetric supercapacitor. Sci Bull (2018), https://doi.org/10.1016/j.scib.2018.01.024
6 J.-F. Zhang et al. / Science Bulletin xxx (2018) xxx–xxx
the CV curves of Ni-HF, Co-HF electrodes are also given in Fig. S6a,
b (online). Obviously, the redox currents of the electrodes increase
with the increasing scan rate from 2 to 100 mV s
1. It is worth not-
ing that the redox peak positions shift to more positive and nega-
tive potentials at a fast scan rate, which can be attribute to the
polarization effect of the electrode. However, the oxidation and
reduction peaks are still shape even at a high scan rate of 100
mV s
1, illustrating the reversible redox reaction with fast ions dif-
fusion rate and high rate capability and conductivity of the elec-
trodes [33]. Fig. 4c exhibits the plots of logi versus logm from 2 to
100 mV s
1 for both anodic and cathodic peak, which provide an
effective judgement about whether the kinetics are controlled by
semi-infinite linear diffusion or surface-controlled [34]. The rela-
tionship between the peak current (i) and the scan rate (m) can
be denoted by the equation: logi = blogm + a, where a and b are
adjustable values. The b-value of 0.5 indicates that the current is
controlled by semi-infinite linear diffusion and b-value of 1 indi-
cates that the current is surface-controlled [34]. For the Ni-HF,
Co-HF and NiCo-HF electrodes, the b-values for both the anodic
and cathodic peaks are about 0.61, 0.58 and 0.4, respectively,
which are close to 0.5, indicating that the kinetics are semi-
infinite linear diffusion with battery characteristic. Additionally,
the CV curves of NiCo-HF electrodes prepared at different temper-
atures of 120, 160 and 180 °C are shown in Fig. S7a–c (online). The
CV curves of all the NiCo-HF electrodes display a pair of redox
peaks with unchanged shapes when the scan rates increase. The
NiCo-HF electrode prepared at 140 °C shows the highest current
compared with other three electrodes (Fig. S7d online), indicating
that it possesses the largest specific capacitance.
GCD tests of the Ni-HF, Co-HF and NiCo-HF electrodes prepared
at 140 °C were carried at a current density of 5 A g
1, as shown in
Fig. 4d. As expected, the NiCo-HF electrode shows the longest
charge-discharge time, indicating the largest specific capacitance,
which is consistent with the CV results. The enhancement of
current of NiCo-HF electrode can be attributed to the unique nano-
wires structure and complicated redox reaction between Ni2+/Ni3+
and Co2+/Co3+. Moreover, it is clearly seen that the GCD curves of
all electrodes show obvious platforms with symmetrical and
Fig. 5. The electrochemical performances of the NiCo-HF//AC asymmetric supercapacitors. (a) CV curves of AC and NiCo-HF electrode at the scan rate of 50 mV s
1. CV curves
at different potential windows (b) and various scan rates (c). (d) GCD curves at different current density. (e) Specific capacitance; (f) long-term cycling stability.
Please cite this article in press as: Zhang J-F et al. One-pot synthesis of nickel-cobalt hydroxyfluorides nanowires with ultrahigh energy density for an
asymmetric supercapacitor. Sci Bull (2018), https://doi.org/10.1016/j.scib.2018.01.024
unchanged in shape at various current densities ranging from 1
to 20 A g
1 (Fig. 4e and S6c, d (online)), revealing reversible prop-
erties of the redox reactions. The specific capacitances of the elec-
trodes were calculated from GCD curves, as shown in Fig. 4f. The
specific capacitances of Ni-HF, Co-HF and NiCo-HF electrode are
2,030.3, 2,603.4, 3,372.6 F g
1 at a low current density of 1 A g
1
and 1,408.8, 1,921.8, 2,505.7 F g
1 at a high current density of 20
A g
1, respectively. As expected, NiCo-HF electrode possesses the
highest specific capacitance and the best rate capability. The excel-
lent electrochemical performance of NiCo-HF electrode can be
ascribed to following reasons. First, the NiCo-HF possesses a
unique large size of interconnected nanoflakes composed of nano-
wires to form porous nanostructures, which provides large specific
surface area with more active sites and accelerates ions diffusion
and electrons transport during the charge/discharge process. Sec-
ond, the existent couples of Ni2+/Ni3+ and Co2+/Co3+ species provide
relatively complicated redox process, which can greatly improve
the electrochemical activity of the electrode. Third, the formation
of the fluoride derivative can supply higher redox potential due
to the higher ionicity of the metal-fluorine bonds. Benefiting from
the synergistic effect from all of these factors, the NiCo-HF elec-
trode exhibits better electrochemical performance than Ni-HF
and Co-HF electrodes.
To further evaluate electrochemical behaviours of the elec-
trodes, EIS measurements were investigated to understand the
electrical conduction and ion transfer. Typical Nyquist plots of
Ni-HF, Co-HF and NiCo-HF electrodes are shown in Fig. 4g, which
consisting of semicircles in the high frequency range and a straight
line with an angle at almost 45° with the real axis in the low fre-
quency range. It is accepted that the diameter of the semicircle
refers to the charge transfer resistance (Rct), which corresponding
to the faradic redox reactions, and the intercept on real axis stands
for series resistance (Rs) of the electrochemical system, which is
composed by the internal resistance of active materials, ionic resis-
tance, and the interface resistance between electrode and elec-
trolyte interface [35,36]. In order to obtain accurate information
of the electrodes, an equivalent circuit was used to fit the Nyquist
plots, as shown in inset of Fig. 4g. The values of Rct for Ni-HF, Co-HF
 J.-F. Zhang et al. / Science Bulletin xxx (2018) xxx–xxx 7

and NiCo-HF electrodes are 6.8, 5.2, 2.7 X, respectively. Appar-
ently, the NiCo-HF electrode possesses the lowest charge transfer
resistance that will enhance electron transfer and ions diffusion,
and thus improve electrochemical performance. Besides, Fig. 4h
shows the typical Bode phase plots of the Ni-HF, Co-HF and
NiCo-HF electrodes. They are quite different from the ideal capac-
itive behaviour of capacitor-type electrode which exhibits almost
vertical line on the Nyquist plot and the phase angle of about

90° on the Bode plot [37]. The phase angles of the Bode plots
for the Ni-HF, Co-HF and NiCo-HF electrodes are far below the
value of
90°, further demonstrating the battery characteristic
behaviour of the electrodes.
The long-term cycling stability of the electrodes was also exam-
ined by GCD tests at a current density of 20 A g
1 for 10,000 cycles,
as shown in Fig. 4i. After 10,000 cycles, the Ni-HF, Co-HF and
NiCo-HF electrodes show excellent electrochemical stability with
88.3%, 92.4% and 94.3% retention of initial specific capacitance,
respecitively. The CV tests at a scan rate of 20 mV s
1 also exam-
ined for the long-term cycling performance of NiCo-HF electrode.
As shown in Fig. S8 (online), after 10,000 cycles CV scan, the speci-
fic capacitance can be maintained at 92.3% with almost unchange-
able shape of CV curves. This outstanding cycling stability of our
NiCo-HF electrode can be attributed to its unique nanostructure
with high specific surface area and low charge transfer resistance,
which can increase the surface adsorption of ions on the electrode
and accelerate electron/ion diffusion in the electrolyte. In addition,
during the long-term cycling process, the coulombic efficiency of
the Ni-HF, Co-HF and NiCo-HF electrodes are relatively high at
approximately 97%.
In order to explore the NiCo-HF electrode for potential applica-
tion, an asymmetric supercapacitor device was constructed by
using the NiCo-HF as the positive electrode, AC as the negative

Table 1
Comparison of the performance of NiCo-HF//AC asymmetric supercapacitor with other reports in the literatures.

Materials Electrolyte Specific capacitance Cycling stability Ref.

NiCo-HF//AC PVA-KOH 267.8 F g
1 at 0.5 A g
1 86.3% after 10,000 cycles This work
Porous NiCo2O4//RGO 6 mol L
1 KOH 101.7 F g
1 at 1 A g
1 93.5% after 10,000 cycles [34]
NiCo2S4 mesoporous nanosheets//AC 3 mol L
1 KOH 71.6 F g
1 at 1.25 A g
1 85.6% after 4,000 cycles [35]
ZnCo2O4 NFs//ZnCo2O4 NW PVA-KOH 220.6 F g
1 at 2 A g
1 67.5% after 8,000 cycles [36]
Co3O4 nanowires//CA PVA-KOH 54.4 F g
1 at 1 A g
1 85% after 1,000 cycles [37]
NiCo2O4 MN//AC 2 mol L
1 KOH 127.5 F g
1 at 1 A g
1 89% after 4,000 cycles [38]
Ni@Ni1.5Co1.5S2//AC 2 mol L
1 KOH 109 F g
1 at 1 A g
1 100% after 2,000 cycles [39]
CoS@eRG//AC 2 mol L
1 KOH 80 F g
1 at 1 A g
1 70% after 10,000 cycles [40]
NiCo2S4@Co(OH)2//AC 2 mol L
1 KOH 100.94 F g
1 at 0.5 A g
1 70.01% after 5,000 cycles [41]
NiCo2S4//AC 1 mol L
1 KOH 100.06 F g
1 at 1 A g
1 84.2% after 2,000 cycles [42]

Fig. 6. (Color online) Characteristic of NiCo-HF//AC asymmetric supercapacitors. (a) Nyquist plots recorded before and after 10,000 cycles. (b) Ragone plot of the NiCo-HF//AC
asymmetric supercapacitor compared with the data reported elsewhere. (c) Optical photograph of three color-changing light emitting diodes (LEDs) lit by two charged
supercapacitors connected in series.

Please cite this article in press as: Zhang J-F et al. One-pot synthesis of nickel-cobalt hydroxyfluorides nanowires with ultrahigh energy density for an
asymmetric supercapacitor. Sci Bull (2018), https://doi.org/10.1016/j.scib.2018.01.024
8 J.-F. Zhang et al. / Science Bulletin xxx (2018) xxx–xxx
electrode. The electrochemical performance of asymmetric super-
capacitor device was assessed by CV tests. As shown in Fig. 5a, a
good matching of NiCo-HF and AC electrodes for assembling asym-
metric supercapacitor device was demonstrated through the CV
curves of these two electrodes in a three-electrode cell. Based on
this, the NiCo-HF//AC asymmetric supercapacitor can work at
potential window of 1.5 V. Fig. 5b displays CV curves of
NiCo-HF//AC asymmetric supercapacitor at different potential win-
dows range from 0.9 to 1.5 V at a scan rate of 50 mV s
1, indicating
the stable potential window of NiCo-HF//AC asymmetric superca-
pacitor can be extended to 1.5 V. Fig. 5c shows the CV curves of
NiCo-HF//AC asymmetric supercapacitor at various scan rates with
a potential window of 0 to 1.5 V. These CV curves exhibit both
pseudocapacitance and electrical double layer capacitance charac-
teristics between NiCo-HF and AC. The shapes of these CV curves
within a potential window of 1.5 V remained the same, suggesting
the good capacitive behaviour of the asymmetric supercapacitor.
The GCD curves of NiCo-HF//AC asymmetric supercapacitor at
different current densities are shown in Fig. 5d and the corre-
sponding calculated specific capacitances are shown in Fig. 5e.
The specific capacitance of the asymmetric supercapacitor is calcu-
lated based on the total mass of the active materials of the two
electrodes. The calculated specific capacitance of NiCo-HF//AC
asymmetric supercapacitor is 267.8 F g
1 at a current density of
0.5 A g
1, which is superior to those of previously reported asym-
metric supercapacitor devices (Table 1) [38–46]. The long-term
cycling stability of the NiCo-HF//AC asymmetric supercapacitor is
further investigated by GCD tests at the current density of 10 A
g
1 for 10,000 cycles. As shown in Fig. 5f, the specific capacitance
of asymmetric supercapacitor keeps 86.3% retention of the initial
capacitance after 10,000 cycles. The shape of GCD curves for the
last 10 cycles maintains more or less the same as the first 10 cycles
(Fig. S9 online). This result reflects that the NiCo-HF//AC asymmet-
ric supercapacitor has excellent cycling stability and good electro-
chemical reproducibility.
Fig. 6a shows the Nyquist plots of the NiCo-HF//AC asymmetric
supercapacitor before and after 10,000 cycles at a frequency range
from 100 kHz to 0.01 Hz. The Rct value was slightly increased after
10,000 cycles compared with the value of before cycling, suggest-
ing the enhanced charge transfer resistance of the electrode inter-
face in the charge-discharge process. Ragone plot of the NiCo-HF//
AC asymmetric supercapacitor displaying the energy density and
power density is shown in Fig. 6b. The asymmetric supercapacitor
in this work can work steadily at potential window of 1.5 V, and
can deliver an ultrahigh density of 86.3 Wh kg
1 at a power density
of 379.1 W kg
1 based on the total mass of the active materials.
Even at a high power density of 7,490 W kg
1, the energy density
can still be maintained at 65.4 Wh kg
1, which is superior to those
of previous reported devices in the literatures [47–53] (Table S1
online). Furthermore, two identical asymmetric supercapacitors
were connected in series and charged to 3 V. After that, they can
easily light up three color-changing LEDs (Fig. 6c) and can last
for up to 5 min (Fig. S10 online). The above results demonstrate
the NiCo-HF//AC asymmetric supercapacitor has great potential
for practical application.
4. Conclusion
In summary, novel and unique Ni-Co hydroxyfluorides
(NiCo-HF) nanowires were synthesized through a simple
solvothermal method. The NiCo-HF nanowires show high specific
surface area and loose mesoporous structure. Benefiting from this
nanostructure, the NiCo-HF electrode exhibits excellent
electrochemical performance. A high specific capacitance of
3,372.6 F g
1 can be achieved at a current density of 1 A g
1 with
Please cite this article in press as: Zhang J-F et al. One-pot synthesis of nickel-cobalt hydroxyfluorides nanowires with ultrahigh energy density for an
asymmetric supercapacitor. Sci Bull (2018), https://doi.org/10.1016/j.scib.2018.01.024
94.3% retention of the initial capacitance after 10,000 charge-
discharge cycles. The asymmetric supercapacitor based on
NiCo-HF//AC shows the specific capacitance of 267.8 F g
1 with
an ultrahigh energy density of 86.3 Wh kg
1 at a power density
of 379.4 W kg
1, indicating superior energy storage characteristics.
Moreover, two identical asymmetric supercapacitors connected in
series can light up three colored LEDs for 5 min, demonstrating
their practical application as energy storage device.
Conflict of interest
The authors declare that they have no conflict of interest.
Acknowledgments
This work was supported by the National Natural Science Foun-
dation of China (51772072, 51402081, and 51502071), Natural
Science Foundation of Anhui Province (1708085ME100,
1508085ME97, and 1608085QE105), and the Fundamental
Research Funds for the Central Universities (JZ2017HGTB0203,
JZ2016HGTB0719, and 201610359018). Dr. Yan Wang also would
like to thank the financial support from the China Scholarship
Council during his visit to Prof. Pulickel M Ajayan’s group at Rice
University.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.scib.2018.01.024.
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