Advanced Energy Materials - 2020 - Yang - in Situ Formation of Co9S8 Quantum Dots in MOF Derived Ternary Metal Layered

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In Situ Formation of Co9S8 Quantum Dots in MOF-Derived

Ternary Metal Layered Double Hydroxide Nanoarrays
for High-Performance Hybrid Supercapacitors
Qingjun Yang, Qishun Wang, Yan Long, Fan Wang, Lanlan Wu, Jing Pan, Jie Han,
Yong Lei, Weidong Shi,* and Shuyan Song*
1. Introduction
Layered double hydroxides (LDHs) are promising cathode materials
for supercapacitors because of the enhanced flow efficiency of ions in the In recent years, layered double hydrox-
ides (LDHs) have been extensively used
interlayers. However, the limited active sites and monotonous metal species
as electrocatalysts or energy-storage elec-
further hinder the improvement of the capacity performance. Herein, cobalt trodes due to their rapid ion transport
sulfide quantum dots (Co9S8-QDs) are effectively created and embedded channels originating from their unique
within the interlayer of metal-organic-frameworks-derived ternary metal LDH lamellar structures and high electrical
nanosheets based on in situ selective vulcanization of Co on carbon fibers. conductivity based on their capability of
The hybrid CF@NiCoZn-LDH/Co9S8-QD retains the lamellar structure of the tuning the band gap energy and density of
states.[1–4] In particular, LDHs as cathode
ternary metal LDH very well, inheriting low transfer impedance of interlayer
materials of supercapacitors have shown
ions. Significantly, the selectively generated Co9S8-QDs expose more abundant satisfactory capacity performance over
active sites, effectively improving the electrochemical properties, such as 140 mAh g−1 (1000 F g−1) at a current
capacitive performance, electronic conductivity, and cycling stability. Due density of 1 A g−1.[5–7] However, the finite
to the synergistic relationship, the hybrid material delivers an ultrahigh number of active sites is still a critical
obstacle that limits further improvement
electrochemical capacity of 350.6 mAh g−1 (2504 F g−1) at 1 A g−1. Furthermore,
of the capacity performance.[8–10] There-
hybrid supercapacitors fabricated with CF@NiCoZn-LDH/Co9S8-QD and fore, numerous effective strategies based
carbon nanosheets modified by single-walled carbon nanotubes display an on LDHs, including the reconstruction of
outstanding energy density of 56.4 Wh kg−1 at a power density of 875 W kg−1, transition metal compounds,[11] adjusting
with an excellent capacity retention of 95.3% after 8000 charge–discharge the proportion of metal ions,[12] and carbon
cycles. Therefore, constructing hybrid electrode materials by in situ-created doping,[13] have been developed to explore
higher redox activity with abundant active
QDs in multimetallic LDHs is promising.
sites. Notably, modified LDHs, such as
NiCo-LDH/MMoSx heteronanostructures,[14]
Dr. Q. Yang, Prof. W. Shi
CNT@NiCo-LDH,[15] cactus-like NiCoP/NiCo-OH,[16] H-3DRG@
School of Chemistry and Chemical Engineering NiCo2S4 nanowires,[17] and core–shell structural (Ni, Co) Se2/
Jiangsu University NiCo-LDH,[18] have displayed novel structural features and consid-
Zhenjiang 212013, P. R. China erable exposed active sites. Nevertheless, the derived chemical spe-
E-mail: swd1978@ujs.edu.cn cies on the outer surfaces of LDHs impair the interlayer structure
Q. Wang, Dr. Y. Long, Dr. F. Wang, Dr. L. Wu, Dr. J. Pan, Prof. S. Song of LDHs to some extent and lead to pore blockage issues, which
State Key Laboratory of Rare Earth Resource Utilization
Institute of Applied Chemistry can decrease the structural stability of materials and increase the
Chinese Academy of Sciences mass transport resistance. Therefore, it is a major challenge to
Changchun 130022, P. R. China introduce functional chemical species within the interlamellar
E-mail: songsy@ciac.ac.cn spaces of LDHs in situ.
Prof. J. Han The ideal strategy is to selectively form a part of one metal
School of Chemistry and Chemical Engineering
Yangzhou University
element of the LDHs into highly active energy storage groups
Yangzhou, Jiangsu 225002, P. R. China and maintain the original LDH-layered structure at the same
Prof. Y. Lei time, which will construct a new class of hybrid electrode mate-
Institute of Physics & IMN MacroNano (ZIK) rials embedding highly active units in the interlamellar space of
Ilmenau University of Technology LDHs. To this end, Ho et al. successfully derived cobalt sulfide
Ilmenau 98693, Germany nanocrystals in the interlayer of a NiCo-LDH based on ZIF-67.
The ORCID identification number(s) for the author(s) of this article The hybrid electrode material displays an excellent electro-
can be found under https://doi.org/10.1002/aenm.201903193.
chemical performance of 231 mAh g−1 (1653 F g−1) at a cur-
DOI: 10.1002/aenm.201903193 rent density of 4 A g−1 because the cobalt sulfide species are
Adv. Energy Mater. 2020, 10, 1903193 1903193 (1 of 12) © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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incorporated into the spatially confined interlayer to effectively hydroxides and the smaller solubility product of the relevant
strengthen the structural stability and redox activity of electrode cobalt-based sulfide. The CF@NiCoZn-LDH/Co9S8-QD elec-
materials.[19,20] trode including 0D Co9S8-QD with abundant active sites, 1D
Apparently, in situ formation of cobalt sulfide within LDHs carbon fibers with good structural stability, 2D hybrid nanosheets
is a practical and effective method to derive more stable and with rapid ion/electron transmission, and 3D carbon fibers cloth
excellent electrode materials because of the unique advantages with enhanced mechanical flexibility, which have the electro-
of cobalt sulfide, such as weak CoS bonds, low solubility chemical advantages of both LDHs and QDs, displays an out-
product, easy conversion reaction, large theoretical capacity, standing electrochemical capacity of 350.6 mAh g−1 (2504 F g−1)
and high intrinsic conductivity.[21,22] However, large volume at 1 A g−1 and a high capacity retention rate of 62% as the
change and sluggish ion diffusion are still the major constraints current density increases from 1 to 20 A g−1. Moreover, a hybrid
to expanding the high electrochemical performance.[23,24] supercapacitor assembled with CF@NiCoZn-LDH/Co9S8-QD
Decreasing the size of cobalt sulfide to the nanoscale, especially nanoarrays and carbon nanosheets modified with single-walled
to the quantum dot (QD) scale, is the most effective approach carbon nanotubes (CNS-SCN) achieves a considerable energy
to maintain the integrity of the electrodes and shorten the ion density of 56.4 Wh kg−1 at a high power density of 875 W kg−1.
diffusion distance.[25] To the best of our knowledge, in situ- Therefore, the hybrid CF@NiCoZn-LDH/Co9S8-QD electrodes
formed LDH-cobalt sulfide QD electrode materials have not possess great application prospects for promoting the develop-
been reported for energy storage despite the strong demand. ment of energy storage and conversion.
Herein, we demonstrate a new strategy for designing and
synthesizing NiCoZn-LDH nanosheets embedded with Co9S8-
QDs on carbon fibers (CF@NiCoZn-LDH/Co9S8-QD). First, 2. Results and Discussion
using 2D Zn-MOF (metal-organic frameworks) nanosheets as
a sacrificial agent, purposeful synthetic CF@Ni2Co1Zn-LDH 2.1. Morphology and Structure
nanosheet arrays with the optimum proportion of Ni/Co and
a dense lamellar structure were prepared in deionized (DI) Figure 1a describes the fabrication strategy of the CF@
water at 120 °C for 24 h. Then, Co9S8-QDs were anchored in NiCoZn-LDH/Co9S8-QD electrode in detail, and the specific
situ within NiCoZn-LDHs based on an approach of selective methods are elaborated in the Experimental Section. Because
vulcanization of Co, which mainly occurs due to the superior the adsorption energy of the Co9S8 located between the LDH
physical and chemical properties of Co compared to those of layers is higher than that of the surface anchors, the intercala-
Ni and Zn, such as a lower binding energy in corresponding tion structure displays better thermodynamic stability,[19] which
Figure 1. a) Schematic illustration of the fabrication of hybrid CF@NiCoZn-LDH/Co9S8-QD nanosheet arrays. b) Optimized atomic configurations
and the possible mechanism of selective vulcanization.
demonstrates that the Co9S8-QDs are most likely embedded types of electrode materials or catalysts because of their easy-to-
in situ within the interlayer of the NiCoZn-LDHs. To further control framework.[27,28] However, the Zn-MOF has not received
highlight the characteristics of this hybrid electrode material, much attention due to the difficulties in controlling its nano-
the optimized atomic configurations of the Ni2Co1Zn-LDH and structure. In our study, by adjusting the proportion of Ni/Co
NiCoZn-LDH/Co9S8-QD are calculated based on the X-ray dif- metal ions (a total concentration of 3 × 10−3 m) in DI water, sev-
fraction (XRD) patterns, which effectively reflect the structures eral hierarchical Ni-Co-Zn ternary metal LDH nanosheets with
of the two kinds of crystals (Figure 1b). Theoretically, it is well unique lamellar structures were successfully constructed on
known that Co (2p 3/2) in Co(OH)2 has a lower binding energy carbon fibers (CF@NixCo3−xZn-LDH). As shown in the SEM
(781.0 eV) than Ni (2p 3/2, Ni(OH)2, 856.6 eV) and Zn (2p 3/2, images (Figure S1, Supporting Information and Figure 2d),
Zn(OH)2, 1022.7 eV), indicating that Co is more easily removed the morphologies of these nanoarrays are similar regardless of
from Co(OH)2 to create cobalt-based compounds. Moreover, the Ni/Co ratios. To determine the optimum Ni/Co ion ratio,
cobalt sulfide has a smaller solubility product (Ksp) (3.0 × 10−26) a series of cyclic voltammetry (CV) profiles was measured at
than nickel sulfide (1.4 × 10−24) and zinc sulfide (1.2 × 10−23) 5 mV s−1 (Figure S2, Supporting Information), and we found
under the same reaction conditions, which proves that the Co that the CF@Ni2Co1Zn-LDH has the optimal capacity perfor-
of LDHs is more easily transformed to cobalt sulfide. There- mance. As shown in Figure 2e, the reconstructed nanosheet
fore, in situ formation of cobalt sulfide crystals from purposeful has a thinner thickness (≈100 nm) than that of the Zn-MOF
synthetic LDHs is practicable in theory. and presents a curly shape. Apparently, Zn-MOF can effectively
2D Zn-MOF nanosheet arrays on carbon fibers (Figure 2a, induce Ni2+/Co2+ ion hydrolysis without any other sacrificial
CF@Zn-MOF) were first synthesized according to previous agent in DI water to form the corresponding layered hydrox-
reports.[26] Figure 2b reveals that the as-obtained Zn-MOF ides by reducing the concentration of H+. The relevant energy
displays a uniform pattern of triangular nanosheets with an dispersive X-ray spectroscopy (EDS) analysis (Figure S3, Sup-
average thickness of 130 nm. Specifically, the Zn-MOF presents porting Information) proves the existence of Zn, Ni, Co, and O,
a smooth surface according to the magnified field-emission demonstrating that a process of ion etching/exchange is effec-
scanning electron microscopy (FESEM) image (Figure 2c). 2D tively implemented.
MOFs, especially MOFs based on Co, have been widely used as To further promote CF@Ni2Co1Zn-LDH to expose more
precursors or versatile sacrificial templates to derive different active sites and obtain a better electrochemical performance,
Figure 2. SEM images of a–c) CF@Zn-MOF sacrificial agent. d–f) CF@Ni2Co1Zn-LDH nanosheet arrays. g–i) CF@NiCoZn-LDH/Co9S8-QD hybrid
nanosheet arrays.
Figure 3. a–d) The magnified TEM images of NiCoZn-LDH/Co9S8-QD nanosheets at different vulcanization time. e) HRTEM image of NiCoZn-LDH/
Co9S8-QD. f) The TEM images of NiCoZn-LDH/Co9S8-QD nanosheet at vulcanization time of 2.5 h and the inset is the size distribution of QDs.
g) Elemental mapping of NiCoZn-LDH/Co9S8-QD for Ni, Co, Zn, O, S.
a novel method of selective sulfurization of Co has been used structural stability. Significantly, the surface of the vulcanized
to generate embedded Co9S8-QDs within NiCoZn-LDH. In nanosheets changed from smooth (Figure 2f) to rough with
Figure S4 in the Supporting Information, a series of CV curves embedded Co9S8-QDs (Figure 2i). Moreover, the coexistence
is measured under different vulcanization conditions and we of Ni, Co, Zn, O, and S also reflects that the hybrid nanosheet
find that the optimum condition for the preparation of NiCoZn- arrays are successfully constructed (Figure S5, Supporting
LDH/Co9S8-QD is 2.5 h in a mixed solution with 30 mg thio- Information).
acetamide (TAA) and 20 mL ethanol at 120 °C. Too long The transmission electron microscopy (TEM) images of 2D
vulcanization time or insufficient TAA content cannot achieve Zn-MOF and Ni2Co1Zn-LDH are displayed in Figure S6 in
the best electrochemical capacity performance. At the same time, the Supporting Information and reveal a smooth interface for
according to the inductively coupled plasma-optical emission the two nanosheet electrode materials. As shown in the mag-
spectrometry elemental analysis of NiCoZn-LDH/Co9S8-QD nified TEM images (Figure 3a–d), as the vulcanization time
in different vulcanization conditions (Table S1, Supporting increased from 0 to 2.5 h, the Co9S8-QDs gradually increased
Information), when the weight percentage of S is 5.21 wt%, and embedded within the NiCoZn-LDH nanosheet in situ.
the optimal loading of Co9S8-QDs can be accurately located. The Co9S8-QDs show distinct aggregation at a prolonged vul-
Moreover, the molar ratio of Ni/Co in NiCoZn-LDH/Co9S8-QD canization time of 3.5 h (Figure S7, Supporting Information),
is 1.85:1, which is approximately consistent with the feeding which is the main reason for the electrochemical capacity
ratio of Ni/Co in the preparation. After vulcanization, the decrease. The morphology and structure of the NiCoZn-LDH/
curled nanosheets with an average thickness of ≈80 nm have Co9S8-QD hybrid nanosheets were further analyzed by high-
a sharp morphology, and the nanoarray structures are still well resolution TEM (HRTEM), as described in Figure 3e. The
maintained (Figure 2g,h), which demonstrates that the hybrid interplanar distances of 2.6 and 2.3 Å match well with the (012)
nanosheet arrays of CF@NiCoZn-LDH/Co9S8-QD have good and (110) planes of the Ni2Co1Zn-LDH phase, respectively.
Figure 4. a) XRD patterns of NixCo3−xZn-LDH and NiCoZn-LDH/Co9S8-QD. b) Co 2p, c) O 1s, d) Ni 2p, e) Zn 2p, and f) S 2p orbital XPS spectra for the
sample of Ni2Co1Zn-LDH and NiCoZn-LDH/Co9S8-QD nanosheet arrays.
The interplanar distance of 2.8 Å corresponds to the (222) plane exhibits two spin–orbit doublets of Co 2p3/2 and Co 2p1/2
of the Co9S8 phase. Significantly, the distinct lattice deforma- that correspond to a low energy peak of 778.9 eV and a high
tions (indicated by the orange arrows in Figure 3e) fully reflect energy peak of 797.6 eV, respectively. After vulcanization, the
the changes in the electronic structure, which further demon- two peaks are shifted to lower binding energies of 781.0 eV
strates the generation of Co9S8-QDs. According to Figure 3f, (Co 2p3/2) and 796.8 eV (Co 2p1/2) (the spin-energy separa-
many dispersed Co9S8-QDs are evenly embedded within the tion changes from 15.3 to 15.8 eV), which implies the electron
NiCoZn-LDH to construct the hybrid NiCoZn-LDH/Co9S8-QD transfer from the S molecules to Co atoms and the density of
nanosheets. In the HRTEM image, the embedded Co9S8-QDs the electron clouds from S increases, proving the Co2+/Co3+
have an average diameter of 6 nm, and we selected 100 points are maintained and reflecting the distinct chemical interac-
from Figure 3f to further verify the particle size in the inset. tion between S and Co.[31–33] Moreover, the XPS spectrum of O
Moreover, the corresponding EDS element mappings of the 1s has an obvious shift of 0.8 eV, demonstrating that the elec-
NiCoZn-LDH/Co9S8-QD are shown in Figure 3g, indicating a tronic structure of Ni2Co1Zn-LDH has changed (Figure 4c).[34]
homogenous distribution of the Ni, Co, Zn, S, and O in the However, the binding energy values of Ni 2p and Zn 2p did
hybrid nanosheet electrode. not exhibit obvious shifts, and the appearance of S 2p further
The XRD analysis of Ni1Co1Zn-LDH, Ni1Co2Zn-LDH, supported the formation of Co9S8-QDs based on the selective
Ni2Co1Zn-LDH, and NiCoZn-LDH/Co9S8-QD is shown in vulcanization of Co (Figure 4d–f).
Figure 4a. The crystallinity of these LDHs is quite similar, and
a series of diffraction peaks reflects their phases and can be
indexed to the (003), (006), (012), (013), (015), (018), (110), and 2.2. Electrochemical Performance
(115) planes, which is consistent with previous reports.[29,30]
After selective vulcanization, two new obvious diffraction To evaluate the capacity performance of the electrode materials,
peaks indexed to the (222) and (400) planes appear in the pat- a series of CV and galvanostatic charge/discharge (GCD) curves
tern, which correspond to the characteristics of the cubic Co9S8 were obtained based on a standard three-electrode system. In
phase (JCPDS no. 75–2023) and prove that the hybrid NiCoZn- Figure 5a, the closed curve area of CF@NiCoZn-LDH/Co9S8-QD
LDH/Co9S8-QD electrode material is successfully designed. To is larger than that of LDHs (CF@NiZn-LDH, CF@CoZn-
further confirm the valence state, elemental composition, and LDH, and CF@Ni2Co1Zn-LDH) and the corresponding oxide
variation in the electronic structure after the formation of the CF@NiCoZn-O, indicating that the hybrid CF@NiCoZn-LDH/
Co9S8-QDs, X-ray photoelectron spectroscopy (XPS) analyses of Co9S8-QD electrode has a higher capacity performance. In addi-
Ni2Co1Zn-LDH and NiCoZn-LDH/Co9S8-QD were analyzed in tion, the SEM and EDS images are displayed in Figure S8 in the
detail. As revealed in Figure 4b, the Co 2p of Ni2Co1Zn-LDH Supporting Information and show the structural characteristics
Figure 5. a) CV curves of the CF@NiCoZn-LDH/Co9S8-QD, CF@Ni2Co1Zn-LDH, CF@NiZn-LDH, CF@CoZn-LDH, and CF@NiCoZn-O electrodes
at a scan rate of 20 mV s−1. b) GCD curves of NixCo3−xZn-LDH and CF@NiCoZn-LDH/Co9S8-QD at current density of 5 A g−1. c) CV curves of CF@
NiCoZn-LDH/Co9S8-QD at various scan rates. d) GCD curves of CF@NiCoZn-LDH/Co9S8-QD at various current densities. e) The specific capacity and
capacity retention rate of CF@NiCoZn-LDH/Co9S8-QD at current densities of 1–20 A g−1. f) Nyquist plots of the CF@Ni2Co1Zn-LDH, CF@NiZn-LDH,
CF@CoZn-LDH, and CF@NiCoZn-LDH/Co9S8-QD electrodes, respectively.
of CF@NiZn-LDH, CF@CoZn-LDH, and CF@NiCoZn-O. The electronic/ionic transport and an electrochemical diffusion-con-
corresponding electrochemical performance test (CV and GCD) trolled process because of the reversible faradaic reactions of
curves of these electrode materials are depicted in Figures S9 NiCoZn-LDH and Co9S8-QDs. Although the scan rate reaches
and S10 in the Supporting Information. 100 mV s−1, the shapes of the CV curves based on different
Obviously, via the comparative analysis of the GCD curves, scan rates are quite similar, exhibiting excellent rate perfor-
the electrochemical capacity performance of the finally synthe- mance and efficient process of charge transfer kinetics. The
sized CF@NiCoZn-LDH/Co9S8-QD is obviously superior to possible faradaic reactions can be reasonably elaborated by the
that of CF@Ni2Co1Zn-LDH, CF@Ni1Co1Zn-LDH, and CF@ following[7,20,35–37]
Ni1Co2Zn-LDH that matches with the CV curves. The main
reason is due to the design of the unique layered structure Ni ( OH)2 + OH− ↔ NiOOH + H2 O+ e − (1)

and the synergistic effect between NiCoZn-LDH with a rapid
ion transport path and Co9S8-QDs with rich redox active sites.
Figure 5c depicts the typical CV curves of CF@NiCoZn-LDH/ Zn ( OH)2 + OH− ↔ ZnOOH + H2 O+ e − (2)

Co9S8-QD with distinct symmetric anodic and cathodic peaks
at diverse scan rates from 2 to 100 mV s−1, indicating fast Co ( OH)2 + OH− ↔ CoOOH + H2 O+ e − (3)
CoOOH + OH− ↔ CoO2 + H2 O+ e − (4) where v represents the scan rate and h1, h2, a, and b represent
the computational constants. The faradic reaction process can be
analyzed as a battery type, and the i of peaks varies avb, reflecting
Co 9S8 + OH− ↔ Co 9S8 OH + e − (5) a capacity process. According to the calculation (Figure 6b), the
index b values of 0.61 and 0.72 (0.5 < n < 1.0) correspond to
CF@Ni2Co1Zn-LDH and CF@NiCoZn-LDH/Co9S8-QD, respec-
Co 9S8 OH + OH− ↔ Co 9S8 O+ H2 O+ e − (6)
tively, which indicates that the hybrid CF@NiCoZn-LDH/
Co9S8-QD electrode materials have a more obvious and control-
The gravimetric capacity of the electrodes is shown in lable semiinfinite diffusion reaction than CF@Ni2Co1Zn-LDH.
Figure 5d at different current densities (1–20 A g−1). The spe- From the inset of Figure 6b, the percent capacitive contribution
cific capacity Qs (mAh g−1) is calculated based on the GCD of CF@NiCoZn-LDH/Co9S8-QD (21%) is evidently higher than
curves by the following equation that of CF@Ni2Co1Zn-LDH (14%) at a scan rate of 5 mV s−1,
further proving the capacity contribution advantage of the
Q s = i∆t /3.6 ∆m + (7) hybrid electrode materials. At 5 mV s−1, the capacity contribu-

tion analysis for these two materials is displayed in Figure 6c,d,
where i, Δt, and Δm+ stand for the discharge current (A), the respectively. Significantly, the percent capacitive contribution of
discharge time (s), and the mass loading of NiCoZn-LDH/ the CF@NiCoZn-LDH/Co9S8-QD increases from 16% to 81%
Co9S8-QD on carbon fibers, respectively. Specifically, the Qs of at variable scan rates from 2 to 100 mV s−1 (Figure 6e). There-
CF@NiCoZn-LDH/Co9S8-QD is 350.6 mAh g−1 (2504 F g−1) at fore, the excellent capacitive contribution suggests that surface
1 A g−1 and 218.5 mAh g−1(1560 F g−1) at 20 A g−1. Obviously, redox reaction processes are dominant during charge storage
the as-obtained hybrid CF@NiCoZn-LDH/Co9S8-QD electrodes at a high scan rate, which depends mainly on the formation of
display the highest capacity with a distinguished capacity reten- Co9S8-QDs with enhanced electrochemical performance.
tion of 62% as the current density increases from 1 to 20 A g−1 Furthermore, the Raman and XPS of CF@NiCoZn-LDH/
(Figure 5e), further highlighting the synergistic advantage of Co9S8-QD at different current densities of 1, 2, 5, 10 A g−1 after
the layered NiCoZn-LDH and the in situ-generated Co9S8-QDs. 200 cycles are described in detail. According to the Raman spectra
To further estimate the electrochemical behavior of the in Figure 6f, the characteristic peaks of Co9S8-QD and NiCoZn-
hybrid electrode materials, we compared CF@NiCoZn-LDH/ LDH can be clearly observed to slightly shift with the increase
Co9S8-QD with CF@Ni2Co1Zn-LDH, CF@CoZn-LDH, and of current densities, which may be due to the lattice tensile
CF@NiZn-LDH by Nyquist plots in the frequency range of strain and vibrations caused by oxygen vacancies or defects on
0.01–100 kHz (Figure 5f). Evidently, the CF@NiCoZn-LDH/ the surface of the active materials at a higher current state.[40–42]
Co9S8-QD displays a lower charge-transfer impedance and bulk Significantly, the corresponding XPS of Co and Ni are exhibited
resistance without obvious semicircles than LDHs of bimetallic in Figure 6g,h, respectively. As the current densities increase
and ternary metals. Therefore, the hybrid CF@NiCoZn-LDH/ from 1 to 10 A g−1, a polarization reaction is inevitable because of
Co9S8-QD has better capacitance characteristics with fast elec- that the extensive electrolyte ions will be adsorbed on the inter-
tron/ion transport than pure LDHs during electrochemical face between electrode and electrolyte, which may destroy the
energy storage processes. equilibrium potential and change the surface electronic structure
Compared with most other reported electrodes of superca- of the active materials, further leading to the decrease of binding
pacitors, the as-prepared CF@NiCoZn-LDH/Co9S8-QD elec- energy and reflecting the change of valence state.[31–33,43] There-
trode delivers a better electrochemical capacity performance, fore, the analysis of Raman and XPS may reflect the possible
which is mainly caused by the cooperative effect of the internal mechanism that the electrochemical capacity of electrode mate-
layered NiCoZn-LDHs and Co9S8-QDs with abundant active rials decreases with the increase of current densities.
sites (Figure 6a). First, ternary metal LDHs based on Ni, Co, As schematically illustrated in Figure 7a, the energy storage
and Zn with optimal proportions can accelerate the ion flow principle of hybrid supercapacitors (HSCs) is briefly described,
efficiency and decrease the resistance of ion transportation at and an HSC device was prepared using the CF@NiCoZn-LDH/
interlayers. Second, Co9S8-QDs based on the selective vulcani- Co9S8-QD as the positive electrode and carbon nanosheets
zation of Co in situ can stably interpenetrate the interlayer of modified by CNS-SCN as the negative electrode in a 3 m KOH
Ni2Co1Zn-LDH, which can effectively enhance the structural electrolyte. A stable and compatible voltage window for CF@
stability of CF@NiCoZn-LDH/Co9S8-QD and expose more NiCoZn-LDH/Co9S8-QD (0–0.5 V) and CNS-SCN (−1 to 0 V) at
active sites for the redox reaction. 50 mV s−1 is displayed in Figure 7b, which demonstrates the
To further explore the energy storage mechanism of the as- feasibility of assembling HSCs. Furthermore, the structure
obtained hybrid CF@NiCoZn-LDH/Co9S8-QD cathode, the characteristics and capacity performance of CNS-SCN are also
capacitive contribution (h1v) and the diffusion-controlled contri- described in Figure S11 in the Supporting Information, and the
bution (h2v1/2) are discussed in detail. Based on the CV curves negative electrode material delivered an excellent specific capac-
taken at different scan rates, the current density (i) obeys the itance of 236 F g−1 at 1 A g−1. To determine the voltage window
following exponential relations[38,39] of the HSCs, the GCD curves based on different voltage values
are shown in Figure 7c. Obviously, as the voltage window
i = av b (8) broadened to 0–1.8 V, a polarization reaction can be observed in
the GCD curves, which reflect that the stable voltage window of
i = h1 v + h2 v 1/2 (9) the HSCs device was 0–1.75 V.
Figure 6. a) Schematic illustration displaying the merits of hybrid CF@NiCoZn-LDH/Co9S8-QD electrode for energy storage. b) The anodic peak current
against the scan rate of the CF@Ni2Co1Zn-LDH and CF@NiCoZn-LDH/Co9S8-QD electrodes and the inset is the comparison of capacity contribution
between them at 5 mV s−1. c,d) Capacitive and diffusion-controlled contributions of CF@Ni2Co1Zn-LDH and CF@NiCoZn-LDH/Co9S8-QD electrodes
for charge storage at scan rates of 5 mV s−1. e) The capacitive contribution from surface and diffusion-controlled contribution for CF@NiCoZn-LDH/
Co9S8-QD electrode at different scan rates. f) Raman spectra, g) Co 2p XPS and Ni 2p XPS of CF@NiCoZn-LDH/Co9S8-QD at different current densities
of 1, 2, 5, 10 A g−1 after 200 charge–discharge cycles.
Figure 7d shows the CV curves of this HSCs device at var- 116.4, 109.0, and 106.4 F g−1 at 1, 2, 5, 8, and 10 A g−1, respec-
ious scan rates (2–100 mV s−1) for the voltage window of 1.75 V. tively. Moreover, with a 10-fold increase in current density, a
Although the scan rate increased to 100 mV s−1, there was high capacity retention rate of 80.2% was still well maintained,
no significant change in the shape of the CV curves, which also demonstrating the excellent electrochemical properties of
indicated the excellent rate capability of the assembled HSCs the HSCs device.
device. Additionally, the specific capacitance Cs (F g−1) of the The cyclic performance testing of the as-prepared HSC
HSCs was calculated based on the corresponding GCD curves device on the basis of the GCD curve at 3 A g−1 is shown in
by the following equation in Figure 7e Figure 8a. The hybrid capacitor shows an outstanding capaci-
tance retention of 95.3% after 8000 charge–discharge cycles.
Cs = I∆t /∆V (10) Based on the GCD curves of the first 10 cycles, the HSCs

device can maintain good reversibility. Simultaneously, the
where I, Δt, and ΔV stand for the discharge current density SEM images (the right inset of Figure 8a) show that the nanoar-
(A g−1), the discharge time (s), and the voltage window (V), rays of the CF@NiCoZn-LDH/Co9S8-QD are not destroyed by
respectively. In detail, the Cs of the HSC was 132.6, 128.2, long-term cycling. More importantly, according to the TEM
Figure 7. a) The principle of HSCs and schematic illustration of the HSC configuration adopted by the CF@NiCoZn-LDH/Co9S8-QD cathode and
CNS-SCN anode. b) CV curves of the CF@NiCoZn-LDH/Co9S8-QD and CNS-SCN electrodes with a scan rate of 50 mV s−1. c) GCD curves of the HSC
device collected in different scan voltage windows. d) CV curves of the HSC device at different scan rates. e) GCD curves of the HSC device at different
current densities and the inset reflects the capacity retention.
images and XRD patterns of NiCoZn-LDH/Co9S8-QD and 789.8 W kg−1),[48] NiMn-LDH/PPy/BC//AC (29.8 Wh kg−1 at
CNS-SCN after the long cycles (Figure S12, Supporting Infor- 299 W kg−1),[49] MnOOH/NiAl-LDH//AC (26.89 Wh kg−1 at
mation), the morphology has not changed and the character- 800 W kg−1),[50] rGO@NiMn-LDH@NF//AC (22.5 Wh kg−1
istic peaks also are clearly observed, reflecting that the cathode at 700 W kg−1),[51] and CoNi-LDH//AC (20.38 Wh kg−1 at
and anode materials all keep the excellent structural stability. 800 W kg−1).[52] To verify the practical application, two as-pre-
A Ragone plot based on the function of the energy density and pared HSCs devices connected in series can light many 5 mm
power density is displayed in Figure 8b. The CF@NiCoZn- light-emitting diodes (LEDs) after a short charge, showing great
LDH/Co9S8-QD//CNS-SCN full cell delivers a maximum energy potential for practical application of hybrid CF@NiCoZn-LDH/
density of 56.4 Wh kg−1 at a power density of 875.0 W kg−1 Co9S8-QD//CNS-SCN devices.
and still reaches 42 Wh kg−1 at a high-power density of
8200.0 W kg−1. In addition, the energy storage performance
of our devices is obviously better than that of other reported 3. Conclusions
homologous supercapacitors, such as Zn1Co2-LDH@rGO/NF//
AC (53.2 Wh kg−1 at 405 W kg−1),[44] NiV-S//AC (51 Wh kg−1 at In summary, we successfully constructed hybrid NiCoZn-
1600 W kg−1),[45] CSNTs@Ni-Co LDH NSs//AC (50 Wh kg−1 at LDH/Co9S8-QD nanosheet arrays on carbon fibers. Using 2D
893 W kg−1),[46] NiCo-LDH/PANI/BC//N-CBC/CC (47.3 Wh kg−1 MOFs as a sacrificial agent, the easily prepared Ni2Co1Zn-LDH
at 828.9 W kg−1),[47] NiCo-LDH/Co9S8//CNTs (39 Wh kg−1 at nanosheets with dense layered structures are the key factor for
2400 W kg−1),[19] NiAl-LDH/MnO2-6//AC (30.4 Wh kg−1 at the in situ formation of QDs. Compared with metal sulfide
Figure 8. a) Cycling performance of the HSCs device at a current density of 3 A g−1; the inset shows the corresponding charge–discharge curves of the
first ten cycles and the SEM images of the cathode material after 8000 cycles. b) Ragone plots of the HSCs device as compared with some reported
devices. c) The photograph of LEDs lit up by the two HSCs devices connected in series.
nanocrystals, the selective vulcanization of Co-induced Co9S8- were purchased from China Pharmaceutical Group Chemical Reagents
QDs within LDHs can result in better electrochemical capacity Co., Ltd. SCNs were purchased from XFNANO Company Limited,
China. Carbon fiber cloth (CF, 1 × 2 cm2) was cleaned up with acetone
performance due to the small particle size, easily exposed active
(CH3COCH3), ethanol (C2H6O), and DI water for 20 min, respectively.
sites, and structural stability resulting from the in situ trans- Preparation of CF@Zn-MOF: First, Zn(NO3)2·6H2O
formation. Moreover, the hybrid electrode materials not only (40 mL × 50 × 10−3 m) was added into 2MI (40 mL × 0.4 m). Then, a
inherit the merits of LDHs but also have the energy storage piece of CF (2 × 1 cm2) was put into the as-prepared mixed solution.
advantages of metal sulfide QDs. When employed as super- After 1 h, the CF was washed with DI water and dried at 60 °C for 24 h.
capacitors, the CF@NiCoZn-LDH/Co9S8-QD displays signifi- Preparation of CF@NiCoZn-LDH: CF@NiCoZn-LDH was synthesized
cantly enhanced electrochemical performance and excellent via a coprecipitation and ion etching process. First, NiCl2·6H2O and
CoCl2·6H2O (a total concentration of 3 × 10−3 m) were dissolved in
stability. Therefore, in situ creation of QDs within purpose- 50 mL autoclave with 30 mL DI water, forming a mixed solution. Then,
fully constructed LDHs is a very effective strategy to prepare a piece of as-obtained CF@Zn-MOF was immersed into the mixed
electrode materials or catalysts that can be further exploited to solution at 120 °C for 24 h. Finally, the sample was cleaned with DI water
create more extensive functional materials for energy storage, and dried at 60 °C.
catalysis, or environmental applications. Preparation of CF@NiCoZn-LDH/Co9S8-QD: Firstly, 0.3 mmol TAA
was dissolved in 20 mL ethanol solution and stirred gently for 30 min.
Then, the solution was transferred into a 50 mL Teflon-lined autoclave
4. Experimental Section and a piece of as-prepared CF@Ni2Co1Zn-LDH was immersed into
the solution. The obtained CF@NiCoZn-LDH/Co9S8-QD was taken out
Chemicals: N,N-Dimethylformamide (DMF), Zn(NO3)2·6H2O, after 2.5 h at 120 °C and washed with DI water. Moreover, the optimal
CoCl2·6H2O, TAA, NiCl2·6H2O, polyvinylidene (PVDF), polyvinyl alcohol reaction conditions were determined by adjusting the reaction time or
(PVA), 2-methylimidazole (2MI), and N-methyl-2-pyrrolidne (NMP) the concentration of TAA.
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Advanced Energy Materials - 2020 - Yang - in Situ Formation of Co9S8 Quantum Dots in MOF Derived Ternary Metal Layered

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In Situ Formation of Co9S8 Quantum Dots in MOF-Derived

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