Electrochimica Acta 356 (2020) 136837

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Morphological modulation of NiCo2 Se4 nanotubes through

hydrothermal selenization for asymmetric supercapacitor
Shan Li a,b, Yunjun Ruan a,b,∗, Quan Xie a,b
a
College of Big Data and Information Engineering, Guizhou University, Guiyang 550025, China
b
Institute of Advanced Optoelectronic Materials and Technology, Guizhou University, Guiyang 550025, China

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

Article history: Transition metal selenide electrodes have attracted much attention in supercapacitor applications, due
Received 31 March 2020 to their high electrical conductivity, superior electroactivity, and excellent structural stability. However,
Revised 27 May 2020
preparing the transition metal selenide with elaborate nanostructures remains a challenge. Herein, a
Accepted 25 July 2020
two-step hydrothermal method was utilized to design NiCo2 Se4 electrode with hollow nanotubes. By
Available online 29 July 2020
controlling the feeding of selenium in the selenization process, the formation mechanism of NiCo2 Se4
Keywords: nanotubes was investigated. In detail, the characterization methods, such as FESEM, TEM, XRD, EDS, and
Nanotubes Raman spectroscopy, were implemented to study the influence of selenium on the morphology, structure
Nickel cobalt selenide composition, and electrochemical performance of NiCo2 Se4 electrode. Moreover, an asymmetric superca-
Selenization mechanism pacitor was fabricated using the optimized NiCo2 Se4 as positive electrode and activated carbon (AC) as
Supercapacitor negative electrode, showing high energy density of 25.0 Wh kg−1 at a power density of 490 W kg−1 and
excellent cycle stability (93% of initial capacitance after 50 0 0 cycles). This study will shed light on the
facile design of transition metal selenide electrode with high electrochemical performance for superca-
pacitor applications.
© 2020 Published by Elsevier Ltd.

1. Introduction performance supercapacitors based on transition metal oxide elec-

trodes.
Due to the high power density, fast charge/discharge time, ex- Recently, transition metal selenides, such as NiSe [8], CoSe
cellent cycling stability, and reliable safety, Supercapacitor (SC) has [9], and Co3 Se4 [10], have drawn much interest as promising
great potential in portable electronics, power grid, hybrid electric electrode materials for supercapacitors [11], lithium-ion batter-
vehicle and so on. As is well known to us, the electrode material ies [12], sodium-ion battery [13], and water splitting [14], be-
plays a crucial part in the electrochemical performance of a super- cause of their high electrical conductivity, high electroactivity,
capacitor, which can be divided into electric double-layered capac- and good structural stability. For example, Chen et al. utilized
itive (EDLC) and pseudocapacitive materials based on the charge a two-step hydrothermal selenization to synthesize Nix Co(1- x ) Se
storage mechanism [1]. Compared with EDLC materials, such as (0≤x≤1) nanoparticles and the best electrode shows a specific
activated carbon (AC) and graphene, pseudocapacitive materials capacitance of 535 C g−1 at 1 A g−1 [15]. Xu et al. synthe-
could store much more charges owing to the fast faradic redox re- sized Ni0.34 Co0.66 Se2 nanorods arrays on carbon cloth (CC) via
actions occurred at the surface [2]. Most transition metal oxides, a simple chemical vapor deposition (CVD) selenization of (Ni,
like MnO2 [3,4], NiO [5,6], Co3 O4 [7], etc., have attracted much Co)(CO3 )0.5 OH precursors, which exhibits a high areal specific ca-
attention in recent years, due to their low cost, high theoretical pacitance (2.61 F cm−2 at 4 mA cm−2 ), good rate capability (75% at
specific capacitances, and environmentally friendly nature. How- 20 mA cm−2 ), and excellent long-term cycling stability (7.4% loss
ever, their poor electrical conductivity leads to the slow kinetic after 60 0 0 cycles) [16]. Wang et al. used 3D graphene on nickel
process of pseudocapacitance redox reactions, low specific capaci- foam as substrate to prepare NiCo2.1 Se3.3 nanosheets by a two-step
tance and energy density, and high internal resistance. These short- hydrothermal method, delivering an excellent specific capacitance
comings have greatly limited the large-scale applications of high- of 742.4 F g–1 at 1 mA cm–2 [17]. Xia et al. grew (Ni,Co)0.85 Se
nanotubes on CC through a two-step hydrothermal method and
the (Ni,Co)0.85 Se//porous graphene supercapacitor affords a areal
∗
Corresponding author at: College of Big Data and Information Engineering,
and stack capacitance of 529.3 mF cm−2 and 6330 mF cm−3 at
Guizhou University, Guiyang 550025, China.
E-mail address: yjruan@gzu.edu.cn (Y. Ruan).
1 mA cm−2 , respectively [18]. It can be seen that transition metal

https://doi.org/10.1016/j.electacta.2020.136837
0013-4686/© 2020 Published by Elsevier Ltd.
2 S. Li, Y. Ruan and Q. Xie / Electrochimica Acta 356 (2020) 136837

selenides, especially nickel cobalt selenide, are promising electrode

material for supercapacitor applications. However, the mechanism
of hydrothermal selenization is lack of study, leading to unpre-
dictable and uncontrollable chemical composition and morphology
of as-prepared nickel cobalt selenides.
Herein, the selenization process of NiCo2 Se4 hollow nanotubes
was detailly investigated to disclose the concentration of the se-
lenium reactant. The effect of morphology and chemical structure
of different nickel cobalt selenides (Ni-Co selenides) on their elec-
trochemical performance was systematically discussed, in order to
gain deep understanding of the electroactive nature of the Ni-Co
selenides. Moreover, an asymmetric supercapacitor was assembled
by using optimized Ni–Co–Se-2 and AC as positive and negative
electrode, respectively, which exhibits high energy density and ex-
cellent cycling stability.
Fig. 1. Morphology of the Ni-Co selenides prepared with different concentrations
of Se reactant.
2. Materials and experimental

2.1. Synthesis of the Ni-Co precursors 2.4. Electrochemical measurements

All reagents except AC (YEC-8A, Shenzhen Naxin Materials The working electrodes were prepared by mixing 80 wt% active
Co. Ltd.) were of analytical grade without further treatment and material, 10 wt% acetylene black (AB), and 10 wt% polytetrafluo-
purchased from Sinopharm Chemical Reagent Co. Ltd. 3 mmol roethylene (PTFE), and then the mixture was pressed on a nickel
NiCl2 •6H2 O, 6 mmol CoCl2 •6H2 O, and 10 mmol urea were dis- foam (with 12 MPa force) serving as a current collector. The geo-
solved in 60 mL de-ion (DI) water under stirring. The solution metric area of electrodes was about 1 cm2 with active material’s
was transferred into a 100 mL Teflon lined stainless steel autoclave mass loading of about 3–4 mg cm−2 . The electrodes were dried
maintained at 120 °C for 6 h. After naturally cooled to room tem- in a vacuum oven at 60 °C for 12 h. The electrochemical mea-
perature, the Ni–Co precursors were collected, washed with DI wa- surements were conducted by CHI760E electrochemical station in
ter and ethanol, and finally dried in vacuum at 60 °C for 12 h. a three-electrode cell with Pt foil as the counter electrode and
Hg/HgO electrode as the reference electrode in 6 M KOH aque-
ous electrolyte. The specific capacitance of the working electrode
2.2. Synthesis of the Ni-Co selenide
and asymmetric supercapacitor was calculated from galvanostatic
charge-discharge curves according to the equation: [19]
Before second hydrothermal reaction, a fresh 0.4 mol L−1 NaHSe
was prepared by dissolving 25 mmol NaBH4 and 12 mmol Se pow- 2i
Cs = ∫ V dt (1)
der in 30 mL Ar-saturated DI water. The reaction equation is de- V
|
V 2 Vif
scribed as follows: [18]
where Cs , i, V, and ∫ V dt denote the specific capacitance (F g−1 ),
4NaBH4 + 2Se + 7H2 O → 2NaHSe + Na2 B4 O7 + 14H2 ↑
discharging current density (A g−1 ), potential with initial and fi-
Then, 100 mg Ni-Co precursor was dispersed in 50 mL Ar- nal values of Vi and Vf (V), and the integral galvanostatic discharge
saturated DI water by stirring. Different volume of NaHSe solu- curve area (V s), respectively.
tion was gently adding into the above Ni-Co precursor solution. The asymmetric supercapacitor was measured by a two-
Finally, Ar-saturated DI water was used to adjust the volume of electrode cell in 6 M KOH, which utilized AC as negative electrode.
the mixed solution to 60 mL, which was transferred into 100 mL To take full advantage of potential windows of positive and nega-
Teflon-lined stainless steel autoclave and heated in an electric oven tive electrodes, the stored charge in both electrodes should be bal-
at 180 °C for 20 h. After the autoclave was cooled down to room anced by their mass using the following equations: [20]
temperature, the precipitate was collected, washed with DI water
and ethanol several times, and then dried in vacuum at 60 °C for Q+ = Q− (2)
12 h. The adding moles of Se were 0.5 mmol, 1 mmol, 2 mmol,
3 mmol, and 4 mmol, the product of which were termed as Ni–  
Co–Se-0.5, Ni–Co–Se-1, Ni–Co–Se-2, Ni–Co–Se-3, and Ni–Co–Se-4,
Q = m × Cs × V f − Vi (3)
respectively.
The energy density (E, Wh kg−1 ) and power density (P, W kg−1 )
of the device were calculated from the galvanostatic discharge
2.3. Materials characterization
curves as follows: [21]

The morphology of the as-prepared products was obtained by

1
the field-emission scanning electron microscopy (FESEM, SU8010, E= CsV 2 (4)
Hitachi) and transmission electron microscopy (TEM, JEM-2100, 2
JEOL). The crystalline structures were characterized by X-ray E
diffraction (XRD, Empyrean, PANalytical B. V.) equipped with Cu P= (5)
t
Kα radiation (λ = 0.15418 nm). The nitrogen adsorption-desorption
isotherms were obtained by Micromeritics ASAP 2460 at 77 K. X-
ray photoelectron spectroscopy (XPS, K-Alpha Plus, Thermo Fisher) 3. Results and discussion
and Raman spectroscopy (532 nm laser, LabRAM HR Evolution,
HORIBA Jobin Yvon S.A.S.) were also conducted to obtain the chem- The morphology of as-prepared products is illustrated in Fig. 1,
ical states and surface compositions of the products. where the Ni-Co selenides are synthesized by a typical two-step
 S. Li, Y. Ruan and Q. Xie / Electrochimica Acta 356 (2020) 136837 3

Fig. 2. FESEM and TEM images of (a) the Ni-Co precursor, (b) Ni-Co-Se-0.5, (c) Ni-Co-Se-1, (d) Ni-Co-Se-2, (e) Ni-Co-Se-3, and (f) Ni-Co-Se-4. (g) TEM images, (h) elemental
maps of Ni, Co, and Se, and (i) EDS of Ni-Co-Se-2.

hydrothermal method. Firstly, the Ni-Co precursor reveals urchin- and some Ni-Co hydroxide carbonate nanosheets were also formed
like nanosphere morphology constructed by numerous nanorods. during the second hydrothermal method, implying the Ni-Co pre-
When a small amount (0.5 mmol) of Se powder was used to re- cursor on the surface of nanorods would dissolve and recrystallize
act with Ni-Co precursor, the morphology of the product has no in the presence of a small amount of NaHSe (Fig. S2). Increasing
obvious change except that only a few nanoparticles adhered to the content of Se, Fig. 2c and Fig. S1c reveal that parts of round
the surface of the Ni-Co precursor nanorods, implying a very low nanorods in Ni-Co-Se-1 change to hollow nanotubes with diame-
degree of selenization of the Ni-Co precursor. With increasing the ter and wall thickness of about 100 nm and 18 nm, respectively.
content of Se powder, parts of the Ni-Co precursor nanorods trans- The formation mechanism of nanotubes can be attributed to the
form to the Ni-Co selenide nanotubes with small nanoparticles Kirkendall effect mentioned above. When the amount of Se pow-
on the surface. Continuously raising the amount of Se powder to der increases to 2 mmol, Fig. 2d and g and Fig. S1d clearly dis-
2 mmol, the Ni-Co precursor completely reacts with Se to form close that Ni-Co-Se-2 has completely transformed to hollow tubu-
Ni-Co selenide nanotubes though the Kirkendall effect. In detail, lar nanostructure with the same diameter and wall thickness as
during the second hydrothermal process, the outward transport of Ni-Co-Se-1. However, continuously raising the content of Se, Ni-Co-
Ni2+ and Co2+ ions and inward transport of Se2− occur at the in- Se-3 (Fig. 2e and Fig. S1e) has not only smaller tubular diameter
terface of solvent and solid rod-like precursors, generating vacancy (75–80 nm), but also some broken shorter nanotubes and irregu-
to balance the unequal diffusion rate of these ions. As the reac- lar nanoparticles together. Fig. 2f and Fig. S1f show that Ni-Co-Se-
tions progress, vacancies gather together gradually to form cavity 4 has the smallest tubular diameter (60–70 nm) and is composed
and finally evolve a tubular nanostructure. However, an excessive of numerous granular structures and broken nanotubes. It suggests
amount of Se powder (≥3 mmol) shrinks the diameter of nan- that the excessive concentration of Se causes the violent seleniza-
otubes and shatters parts of the Ni-Co precursor to smaller frag- tion reaction to tear the round rod-like precursor into many frag-
ments, perhaps due to the violent selenization reaction under high ments and aggregates. Moreover, with the increase feed of Se, the
concentration of Se reactant. diameter of nickel cobalt selenide nanotubes gradually decreases.
In order to verify the morphology change mentioned above, It is perhaps because that high concentration of Se2− in the hy-
FESEM and TEM were implemented to investigate the morphol- drothermal selenization would accelerate ions diffusion at the in-
ogy and nanostructure of the as-prepared products. Fig. 2a shows terface of Ni-Co precursor and solution, i.e. the Kirkendall effect,
the urchin-like Ni-Co precursor consisting of numerous smooth leading to the reduction of tubular diameters and formation of
nanorods, whose diameter is about 160 nm (Fig. S1a). The diam- more pores inner the nanotubes. But it is also worth noting that
eter of the nanorod gradually shrinks to form a needle-like shape. the Ni-Co precursor possesses needle-like nanostructure instead
To study the effect of the Se amount on the morphology, differ- of ideal cylinder, implying the measurement of tubular diameter
ent moles of Se powder were added in the hydrothermal reaction perhaps has some deviation. Fig. 2h shows the scanning SEM and
to obtain corresponding Ni-Co selenides. As displayed in Fig. 2b, corresponding elemental mapping images of Ni-Co-Se-2, confirm-
Ni-Co-Se-0.5 almost maintains the rod-like structure of the Ni-Co ing the uniform distribution of the Ni, Co, and Se elements in the
precursor, but the surface becomes relatively rough. It means that nanotubes cluster. Fig. 2i displays the EDS spectrum of Ni-Co-Se-2,
the amount of Se is so small that most of the Ni-Co precursor has suggesting the existence of Ni, Co, Se, Au, and Pd elements. Among
not transformed to Ni-Co selenide. Interestingly, Fig. S1b shows the them, Au and Pd are derived from the spraying pretreatment to
diameter of Ni-Co-Se-0.5 nanorods decreases to 140 nm or 100 nm increase the conductivity of the sample before testing. It is known
4 S. Li, Y. Ruan and Q. Xie / Electrochimica Acta 356 (2020) 136837

Fig. 3. (a) XRD patterns of as-prepared products. (b) Raman spectra, (c) Nitrogen adsorption-desorption isotherms, and (d) the corresponding BJH (desorption) pore size
distributions of the Ni-Co selenides.

that the content of Co in Ni-Co-Se-2 is about double that of Ni, in M-O, respectively [25]. For the Ni-Co selenides, the intensity of the
accordance with the adding ratio of Ni and Co in the Ni-Co precur- above carbonate and oxide peaks weakens and new Raman peaks
sor. appear at the same time. The peaks at 176 and 192 cm−1 are an-
Fig. 3a shows the crystalline structures of all as-prepared prod- tisymmetric, symmetrically stretching vibrations of M-Se bond, re-
ucts. The obvious diffraction peaks of the Ni-Co precursor can spectively [27].
completely match the Co(CO3 )0.35 Cl0.20 (OH)1.10 •0.74H2 O (JCPDS no. To evaluate the surface area and porosity of the as-prepared Ni-
38-0547) without other impurities. In consideration of the very Co selenides, the nitrogen adsorption-desorption isotherms were
similar ionic radius of Ni2+ and Co2+ and EDS of Ni-Co-Se-2, carried out at 77 K. According to the shape, the isotherms (Fig. 3c)
Ni atoms should exist in the Ni-Co precursor and replace parts of all Ni-Co selenides are Type-IV and show an H3 hysteresis
of Co atoms in the crystal structure. In other words, the Ni- loop at a high relative pressure, which means there are numer-
Co nanorods precursor shares the similar crystalline structure ous slit-shaped mesopores in the materials. The desorption pore
with Co(CO3 )0.35 Cl0.20 (OH)1.10 •0.74H2 O, which has been reported distribution of the Ni-Co selenides was calculated by BJH (Barrett-
in some literatures [22,23]. Subsequently, the effect of different Joyner-Halender) method, shown in Fig. 3d. The BET (Brunauer–
amounts of Se on the crystalline structures of the Ni-Co se- Emmett–Teller) surface area, average pore radius, and total pore
lenides has also been investigated. For Ni-Co-Se-0.5 and Ni-Co- volume were calculated by desorption isotherms and summarized
Se-1, the diffraction peaks meet Co(CO3 )0.35 Cl0.20 (OH)1.10 •0.74H2 O in Table 1. The BET surface area and cumulative volume of pores
and Co3 Se4 (JCPDS no. 98-009-9990) simultaneously. Because gradually increase with the feed of Se except Ni-Co-Se-0.5, while
the amount of Se is insufficient in the selenization reaction, the average pore radius decreases. Considered with TEM analysis,
the as-prepared products have both the crystalline structures. the tubular diameters of all nickel cobalt selenides decrease with
With the amount of Se increasing, the diffraction peaks of the feed of Se. And high concentration of selenium would tear
Co(CO3 )0.35 Cl0.20 (OH)1.10 •0.74H2 O gradually weaken and those of the Ni-Co precursor nanorods into plenty of nanoparticles or frag-
Co3 Se4 increase. When the adding amount of selenium exceeds ments. Therefore, these smaller nanotubes and nanoparticles give
2 mmol, the diffraction peaks at 17.0°, 33.8°, 45.9°, 51.4°, 61.6°, rise to the increase of BET surface area and total volume of pores.
and 63.0° of Ni-Co-Se-2, Ni-Co-Se-3, and Ni-Co-Se-4 can be well For Ni-Co-Se-0.5, FESEM image (Fig. S2a) shows that Ni-Co-Se-0.5
indexed to the (200), (111), (311), (200), (313̄), (711̄), and (422̄) has both nanorods and nanosheets, which greatly increase its BET
planes of Co3 Se4 , respectively, without any diffraction peaks of the surface area. But EDS (Fig. S2b) show the chemical composition
Ni-Co precursor. It is suggested that 2 mmol of Se can completely of these nanosheets is Ni-Co hydroxide carbonate, which has low
transforms the Ni-Co precursor to corresponding selenide. More- electrochemical activity.
over, according to the EDS results (Fig. 2i), the molecular formula Furthermore, the surface elemental composition and valence
of Ni-Co-Se-2 can be written as NiCo2 Se4 . states of Ni-Co-Se-2 were implemented by XPS. Fig. 4a shows the
Raman spectrum in Fig. 3b shows a wide band at about survey spectrum, implying the existence of Ni, Co, Se, C, and O. The
3508 cm−1 of the Ni-Co precursor, which can be attributed to C element comes from the pretreatment and O element may origi-
stretching vibrations of M-OH and OH− [24,25]. The peaks located nate from the unavoidable adsorption of oxygen from the environ-
at 537, 749, and 1088 (and 1046) cm−1 are A2 , Eg , and A1 g mode ment. Both high-resolution Ni 2p and Co 2p spectra can be decon-
of (CO3 )2− , respectively [26]. Other peaks at 160 and 450 cm−1 are voluted into two spin-orbit doublets and two shake-up satellites
caused by bending vibration of O-M-O and stretching vibration of (Sat.). In the Ni 2p spectrum (Fig. 4b), the peaks at 854.0 eV and
 S. Li, Y. Ruan and Q. Xie / Electrochimica Acta 356 (2020) 136837 5

Table 1
Physical properties of the Ni-Co selenides.

Species BET surface area (m2 g−1 ) Average pore radius (nm) Cumulative volume of pores (cm3 g−1 )

Ni-Co-Se-0.5 16.85 9.51 0.0856

Ni-Co-Se-1 8.25 8.41 0.0395
Ni-Co-Se-2 10.35 7.32 0.0457
Ni-Co-Se-3 11.40 6.29 0.0466
Ni-Co-Se-4 13.55 6.10 0.0487

Fig. 4. XPS spectra of Ni-Co-Se-2: (a) survey, (b) Ni 2p, (c) Co 2p, and (d) Se 3d.

871.1 eV are ascribed to Ni 2p1/2 and 2p3/2 of the Ni-Se bond, while Fig. 5c is GCD curves of the different Ni-Co selenides at a cur-
the peaks at 855.4 eV and 873.4 eV correspond to those of the NiO rent density of 1 A g−1 , where obvious charge and discharge plat-
formed by surface oxidation, respectively. The similar peaks also forms at about 0.25 V in all curves evidence the occurrence of
can be observed in Co 2p spectrum, as shown in Fig. 4c. The peaks electrochemical redox reactions, consistent with the CV curves.
centered at 779.0 eV and 794.0 eV are attributed to Co 2p1/2 and Notably, under the same current density, the discharge time of
2p3/2 of the Co-Se bond, while the peaks located at 779.8 eV and Ni-Co-Se-2 is the longest of all Ni-Co selenides, indicating that
795.3 eV imply the existence of Co-O bond, respectively [27,28]. In its specific capacitance is the best. When feeding selenium ex-
Se 3d spectrum (Fig. 4d), the two peaks at 54.7 eV and 55.6 eV ceeded 2 mmol, the Ni-Co selenides achieve less specific capaci-
correspond to Se 3d5/2 and 3d3/2, respectively. Besides, the bind- tance. Fig. 5d shows the GCD curves of Ni-Co-Se-2 at different cur-
ing energy of 60.3 eV is ascribed to SeOx [29,30]. rent densities, where the curves with a shape of distorted trian-
The electrochemical performance of the Ni-Co selenides was gle also indicate that the redox reactions occur on the Ni-Co-Se-
evaluated by cyclic voltammetry (CV), galvanostatic charge dis- 2 electrode during charge and discharge processes. Based on the
charge (GCD) and A.C. impedance in 6 M KOH aqueous electrolyte. galvanostatic discharge curves and Eq. (1), the specific capacitance
Fig. 5a shows CV curves of the different Ni-Co selenides at a scan values of the Ni-Co selenides at current densities of 1, 2, 3, 5, 7, 10,
rate of 1 mV s−1 . An obvious pair of redox peaks appears in all 15, 20 A g−1 are calculated in Table 2 and plotted in Fig. 5e. It can
CV curves of the electrodes, indicating that the electrochemical be- be clearly seen that the specific capacitance values of Ni-Co-Se-2
havior of all Ni-Co selenides is pseudocapacitive redox reactions. electrode are the highest at all current densities. Moreover, when
Among them, the current density peak value of Ni-Co-Se-2 is the the current density increases from 1 A g−1 to 20 A g−1 , the specific
highest, which demonstrates that more faradic redox reactions oc- capacitance of Ni-Co-Se-2 can still be maintained at 76%, implying
cur on the surface of the electrode. Fig. 5b is CV curves of Ni- its excellent rate performance.
Co-Se-2 at a potential window between 0 and 0.6 V and a scan In order to evaluate the electrochemical stability of Ni-Co-Se-
rate from 1 to 50 mV s−1 . All curves are almost symmetrical, illus- 2 electrode, cycling performance was conducted by 20 0 0 times
trating the high reversibility of this redox process. The shapes of charge and discharge cycles at a current density of 5 A g−1 . In
the CV curves disclose that this electrode has typical pseudocapac- Fig. 5f, the specific capacitance of Ni-Co-Se-2 slightly increases
itive characteristics, which is different from the traditional electric in the first dozens of cycles, because parts of the Ni-Co selenide
double-layer capacitance with a shape close to a rectangle. nanostructures were not completely wetted by the electrolyte in
6 S. Li, Y. Ruan and Q. Xie / Electrochimica Acta 356 (2020) 136837

Fig. 5. Electrochemical tests: (a) CV curves of the Ni-Co selenides at a scan rate of 1 mV s−1 , (b) CV curves of Ni-Co-Se-2 at different scan rates, (c) GCD curves of the Ni-Co
selenides at a current density of 1 A g−1 , (d) GCD curves of Ni-Co-Se-2 at different current densities, (e) current density versus specific capacitance, (f) cycling stability of
Ni-Co-Se-2 at a current density of 5 A g−1 .

Table 2
Specific capacitance of the Ni-Co selenides at different current densities (F g−1 ).

Current density (A g−1 ) 1 2 3 5 7 10 15 20

Ni-Co-Se-0.5 377 368 360 349 337 327 308 298

Ni-Co-Se-1 349 343 337 328 323 318 311 304
Ni-Co-Se-2 461 442 427 411 397 387 362 351
Ni-Co-Se-3 439 417 399 381 366 350 332 317
Ni-Co-Se-4 289 278 268 259 250 240 229 214

the initial cycles. With the charge-discharge process progressing, in Fig. 6c measured at a voltage of 1.6 V and different scan rates
the repeated redox reactions may collapse parts of the Ni-Co se- exhibit distorted rectangular shapes, indicating both pseudocapac-
lenide nanostructures, leading to the fade of specific capacitance. itance and electric double layered capacitance make contribution
After the cycling test, the specific capacitance value of Ni-Co-Se- to the charge storage in the electrochemical processes. The GCD
2 electrode can still maintain 86.5% of the initial value. And it is curves (Fig. 6d) of the ASC were complemented at different cur-
worth noting that the coulombic efficiency of the electrode has rent densities in a potential window of 0–1.6 V. The plateaus in
been maintained above 99.4% throughout the charge and discharge the charge-discharge processes are attributed to the redox reac-
processes, indicating that highly reversibility in electrochemical re- tion of Ni-Co-Se-2 electrode, consistent with CV curves. From the
actions. galvanostatic discharge curves and Eq. (1), the specific capacitance
To evaluate the Ni-Co-Se-2 electrode for the practical applica- (CASC ) of the ASC is calculated to be 70.2 F g−1 based on the total
tions, an asymmetric supercapacitor (ASC) was fabricated using Ni- mass of active materials on both electrodes at a current density of
Co-Se-2 and commercial AC (Fig. S3) as positive and negative elec- 0.5 A g−1 and still remains 32.9 F g−1 at a high current density of
trode, respectively, and 6 M KOH aqueous solution as electrolyte. 10 A g−1 (Fig. 6e). As comparison, AC//AC symmetric supercapac-
Fig. 6a displays comparative CV curves of individual Ni-Co-Se-2 itor was also fabricated, whose specific capacitance values at all
and AC electrodes at a scan rate of 10 mV s−1 in a three-electrode current densities are obvious lower than Ni-Co-Se-2//AC (Fig. S4).
configuration. Ni-Co-Se-2 electrode can be operated within a po- To better explore the electrochemical performance of the Ni-Co-
tential window of 0–0.6 V, while AC electrode possesses a poten- Se-2//AC device, electrochemical impedance spectroscopy (EIS) was
tial window of −1 to 0 V. Therefore, the device voltage can be ex- carried out and corresponding Nyquist plots are shown in Fig. 6f.
pressed as the sum of the potential range of Ni-Co-Se-2 and AC According to the enlarged Nyquist plots on the bottom inset of
electrode. To obtain an ASC with a voltage of 1.6 V, the mass of Fig. 6f, the bulk solution resistance (Rs = 2.78 ) of the device
the active materials on the positive and negative electrodes should was obtained from the intercept of the real axis. Meanwhile, the
be balanced by the Eqs. (1)–(3). Based on the specific capacitance charge-transfer resistance (Rct = 4.87 ) and interfacial diffusive
and potential window of positive and negative electrodes, the mass resistance (Warburg impedance, Zw = 0.045 ) of the device are
ratio of Ni-Co-Se-2 and AC is calculated to be 0.71. Fig. 6b shows simulated by the equivalent circuit in the top inset of Fig. 6f. The
the CV curves of the optimized ASC with different voltages mea- low resistance of the device results in high electrochemical perfor-
sured at a scan rate of 50 mV s−1 , illustrating that the stable volt- mance.
age can be extended up to 1.6 V. Further increasing the voltage In addition, the cycling stability, energy density, and power
to 1.7 V, an obvious polarized current peak can be observed ow- density of the Ni-Co-Se-2//AC ASC are significant requirements
ing to the decomposition of electrolyte. The CV curves of the ASC in practical applications. The cycling stability was measured by
 S. Li, Y. Ruan and Q. Xie / Electrochimica Acta 356 (2020) 136837 7

Fig. 6. Electrochemical performance of Ni-Co-Se-2//AC asymmetric supercapacitor: (a) individual Ni-Co-Se-2 and AC electrodes measured at a scan rate of 10 mV s−1 before
assembly, (b) CV curves at a scan rate of 50 mV s−1 with different voltages, (c) CV curves at different scan rates with a voltage of 1.6 V, (d) GCD curves at different current
densities, (e) the relationship between specific capacitance and current density, (f) Nyquist plots (the top inset is equivalent circuit, while the bottom inset is enlarged
Nyquist plots at high frequency region).

Fig. 7. (a) Cycling stability and (b) Ragone plots of Ni-Co-Se-2//AC supercapacitor.

continuous charge-discharge processes at constant current den- chemical structure of the as-prepared Ni-Co selenides was system-
sity of 5 A g−1 (Fig. 7a). After 50 0 0 successive cycles, the device atically studied. In a word, the lack of selenium could only trans-
shows approximately 93% retention of the initial capacitance. No- form parts of the Ni-Co precursor into the Ni-Co selenide, while
tably, the coulombic efficiency maintains above 97% in the whole excessive selenium would destroy the specific microstructure of
charge-discharge processes. Ragone plots, revealing the relation- the precursor. The optimized NiCo2 Se4 nanotubes shows high spe-
ship of power density (P) and energy density (E), are further used cific capacitance and excellent cycling stability, which was used
to evaluate the electrochemical performance of as-fabricated ASC as positive electrode and assembled with AC negative electrode to
(Fig. 7b). The Ni-Co-Se-2//AC ASC delivers a high energy density fabricate a high-performance asymmetric supercapacitor. These re-
of 25.0 Wh kg−1 at a power density of 490 W kg−1 and remains sults suggest that the as-prepared NiCo2 Se4 nanotubes is a promis-
11.7 Wh kg−1 at a high power density of 8.6 kW kg−1 . The per- ing electrode material as a candidate for high-performance energy
formance of Ni-Co-Se-2//AC device is superior to that of AC//AC, storage devices.
Ni0.85 Se//AC [31], Ni0.9 Co1.92 Se4 //AC [32], CoSe//AC [33], Ni0.85 Se-
2//AC [34], NiSe2 //AC [35] and Ni3 Se2 //AC [36]. Declaration of Competing Interest

4. Conclusions The authors declare no conflict of interest.

In summary, microstructure-controlled NiCo2 Se4 nanotubes CRediT authorship contribution statement

were synthesized by a facile two-step hydrothermal route. By con-
tinuously adjusting the feeding of selenium during the second hy- Shan Li: Methodology, Data curation, Writing - original draft.
drothermal selenization, the evolution process of morphology and Yunjun Ruan: Project administration, Data curation, Writing - re-
8 S. Li, Y. Ruan and Q. Xie / Electrochimica Acta 356 (2020) 136837

view & editing, Supervision. Quan Xie: Resources, Writing - review [16] P. Xu, W. Zeng, S. Luo, C. Ling, J. Xiao, A. Zhou, Y. Sun, K. Liao, 3D Ni-Co se-
& editing, Supervision. lenide nanorod array grown on carbon fiber paper: towards high-performance
flexible supercapacitor electrode with new energy storage mechanism, Elec-
trochim. Acta 241 (2017) 41–49.
Acknowledgement [17] Y. Wang, W. Zhang, X. Guo, K. Jin, Z. Chen, Y. Liu, L. Yin, L. Li, K. Yin,
L. Sun, Y. Zhao, Ni-Co selenide nanosheet/3D graphene/nickel foam binder-free
electrode for high-performance supercapacitor, ACS Appl. Mater. Interfaces 11
This work was financially supported by the National Natu- (2019) 7946–7953.
ral Science Foundation of China (Grant No. 61264004), High-level [18] C. Xia, Q. Jiang, C. Zhao, P.M. Beaujuge, H.N. Alshareef, Asymmetric supercapac-
Creative Talent Training Program in Guizhou Province of China itors with metal-like ternary selenides and porous graphene electrodes, Nano
Energy 24 (2016) 78–86.
(Grant No. [2015]4015), the Natural Science Special (Distinguished
[19] Y. Ruan, L. Lv, Z. Li, C. Wang, J. Jiang, Ni nanoparticles@Ni-Mo nitride nanorod
Professor) Research Foundation of Guizhou University (Grant No. arrays: a novel 3D-network hierarchical structure for high areal capacitance
[2019]12), Guizhou Science and Technology Plan Project (Grant No. hybrid supercapacitors, Nanoscale 9 (2017) 18032–18041.
[20] Y. Ruan, D. Zha, L. Lv, B. Zhang, J. Liu, X. Ji, C. Wang, J. Jiang, Al-doped β -NiS
[2018]5781), and Guizhou University Introduced Talent Research
mesoporous nanoflowers for hybrid-type electrodes toward enhanced electro-
Project (Grant No. [2018]58). chemical performance, Electrochim. Acta 236 (2017) 307–318.
[21] Y. Ruan, C. Wang, J. Jiang, Nanostructured Ni compounds as electrode materi-
Supplementary materials als towards high-performance electrochemical capacitors, J. Mater. Chem. A 4
(2016) 14509–14538.
[22] J. Yang, C. Yu, X. Fan, C. Zhao, J. Qiu, Ultrafast self-assembly of graphene ox-
Supplementary material associated with this article can be ide-induced monolithic NiCo-carbonate hydroxide nanowire architectures with
found, in the online version, at doi:10.1016/j.electacta.2020.136837. a superior volumetric capacitance for supercapacitors, Adv. Funct. Mater. 25
(2015) 2109–2116.
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