Journal Pre-proof

Carbon-coated NiCo2S4 multi-shelled hollow microspheres with

porous structures for high rate lithium ion battery applications

Xintao Zuo, Yue Song, Mengmeng Zhen

PII: S0169-4332(19)32816-8
DOI: https://doi.org/10.1016/j.apsusc.2019.144000
Reference: APSUSC 144000

To appear in: Applied Surface Science

Received date: 14 May 2019

Revised date: 30 July 2019
Accepted date: 12 September 2019

Please cite this article as: X. Zuo, Y. Song and M. Zhen, Carbon-coated NiCo2S4 multi-
shelled hollow microspheres with porous structures for high rate lithium ion battery
applications, Applied Surface Science(2019), https://doi.org/10.1016/
j.apsusc.2019.144000

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© 2019 Published by Elsevier.

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Carbon-Coated NiCo2S4 Multi-Shelled Hollow Microspheres with Porous

Structures for High Rate Lithium Ion Battery Applications

Xintao Zuo+,a,b, Yue Song+,b, Mengmeng Zhena,*

a
Tianjin Key Laboratory of Clean Energy and Pollution Control, School of Energy
and Environmental Engineering, Hebei University of Technology, Tianjin 300401, P.R.
China
b
Institute for New Energy Materials & Low-Carbon Technologies, School of

of
Materials Science and Engineering, Tianjin University of Technology, Tianjin 300071,

ro
P.R. China
+
Authors contributed equally
-p
re
Keywords: template-free; multi-shelled hollow structures; carbon-coated layers;
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anodes; lithium-ion battery.

na
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Author information
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* Corresponding author:
E-mail: zhenmengmeng1989@163.com

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ABSTRACT:

Carbon-coated multi-shelled hollow nanomaterials with porous structures are

regarded as promising anode materials for high performances lithium storage.

However, a great challenge to the construction of carbon-coated multi-shelled hollow

structures is the need for a facile and template-free route. Herein, we develop a

sample solvothermal route followed with high-temperature pyrolysis method to

of
construct carbon-coated NiCo2S4 multi-shelled hollow microspheres with porous

structures. As an anode material for lithium-ion batteries, it exhibits a high specific

ro
capacity of 1946.7 mAh g−1 at a current density of 0.2 A g−1 and outstanding
-p
long-term cycling performances of 1242.8 and 656.4 mAh g−1 after 1000 cycles at
re

high current densities of 2 and 5 A g−1, respectively.

lP

1. Introduction
na

The fast consumption of fossil resources and serious environmental pollution has

prompted numerous research efforts to develop and utilize sustainable and renewable
ur

energy resources [1-3]. The high efficiency energy storage and conversion technology
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are one of the most important components in the development of sustainable energy

storage systems [4-6]. In this respect, lithium-ion batteries (LIBs) are indispensable in

applicable power storage sources for portable devices and electric vehicles [7-9]. For

the current battery systems utilizing anodes, conventional graphite materials cannot

meet the growing need for further development of high-performance LIBs, owing to

the low theoretical capacity of 372 mAh g-1, poor rate capability and cycling stability

[10]. Many efforts have been devoted to research novel and high-performance anode

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materials.

Among potential electrode materials, transition-metal sulfides (TMSs) have

attracted considerable attention due to their specific capacities about 2~3 times as

large as those based on graphite [11-13]. Compared with their oxide counterparts,

TMSs possess a lower band gap, higher electrical conductivity and better mechanical

stability, as well as more redox sites [14-16]. In particular, NiCo2S4 materials are

of
emerging as promising electrode materials for energy conversion and storage. The

high theoretical capacity (~1000 mAh g-1) of NiCo2S4 materials is attributed to

ro
complex chemical compositions and favorable synergistic effects from both Co and
-p
Ni species [11, 17]. For example, Yuan et al. [14] reported NiCo2S4 multi-shelled
re

hollow polyhedrons, the anode materials showed good cycle reversibility (745.5 mAh
lP

g−1 at 100 mA g−1 after 100 cycles). Unfortunately, although the actual specific
na

capacity of NiCo2S4 electrodes has reached ~1000 mAh g -1 at low current densities

( ＜ 1.0 A g-1) through the use of NiCo2S4 micro-/nanomaterials, the practical

ur

application of NiCo2S4 materials is still largely hindered by the low intrinsic

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electronic conductivity, large volume expansion and gradually reduced crystallinity

during discharge/charge process [18, 19].

To well address these issues, three strategies have been proposed. (1) Constructing

NiCo2S4-based electrode materials with porous nanostructures which can provide

enough free space to alleviate volume expansion and enhance structural stability [20,

21]; (2) Coating a physical buffer layer of carbon on the surface of NiCo2S4 could

improve electrical conductivity by altering the band structure and buffer the large

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mechanical strain during Li+ insertion/extraction processes [22]. For example, Yao et

al. [23] fabricated porous carbon-coated mesoporous SnO2/graphene/mesoporous

SnO2 nanosheets as novel anode materials for LIBs, which showed superior cycling

performances. (3) Designing hollow structures, especially multi-shelled hollow

micro-/nanostructures, which can exhibit high surface area and large

electrode/electrolyte contact area, as well as improve the weight fraction of active

of
species, thus enhancing the energy density of anode materials [24-26]. More

importantly, the multi-shelled hollow structures not only reduce diffusion and

ro
transport paths for Li+ and e-, but also provide more Li+ insertion sites, leading to high
-p
cycling performances and long cycle life [27]. For example, Wang et al. [18] used
re

carbonaceous microspheres as templates to prepare multi-shelled Co3O4 hollow

lP

microspheres with outstanding electrochemical performances. Xu et al. [28] prepared

na

multi-shelled Cu2O hollow spheres through a multilamellar-micelle templating

method. Yan et al.[22] fabricated carbon-doped Co3O4 hollow nanofibers as excellent

ur

anode materials for LIBs by combining electrospinning technique with hydrothermal

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method. Despite these significant achievements, the synthesis methods of

carbon-coated multi-shelled hollow structures are still limited because of the tedious

synthetic procedures and the employment of sacrificial templates [29]. Until now,

there is no simple and template-free strategy to achieve the above three structural

designs.

Herein, we report a facile and efficient route without any additional templates to

construct carbon-coated multi-shelled NiCo2S4 (NiCo2S4@C) hollow microspheres

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with porous structures. This unique configuration design provides a large surface area

for surface Faradaic reaction and buffer space for volume change during the cycling

process. The coated-carbon layers act as a highway to accelerate the transfer of

electrons. As expected, the multi-shelled NiCo2S4@C hollow microspheres as anode

materials for LIBs, not only deliver a high specific capacity of 1946.7 mAh g−1 at a

current density of 0.2 A g−1 and enhance rate performances, but also maintain high

specific capacities of 1242.8 and 656.4 mAh g−1 at high current densities of 2 and 5 A

of
g−1 after 1000 cycles, respectively.

2. Experimental
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-p
2.1 Materials synthesis
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Synthesis of hierarchical Ni-Co precursor solid spheres:

lP

All chemical reagents were purchased and used without any purification. Typically,
na

Ni(NO3)2·6H2O (0.1 mmol) and Co(NO3)2·6H2O (0.2 mmol) were dissolved in

acetone (10 ml) and N,N-Dimethylformamide (10 ml) mixtures under vigorous
ur

stirring, and then added slowly p-phthalic acid (0.2 mmol) to form a solution by
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stirring for 6 h. After that, the solution was transferred into a 25 ml Teflon-sealed

autoclave and maintained at 160 °C for 4 h. After cooling to room temperature, the

Ni-Co precursor was generated by centrifugation and washed repeatedly with ethanol,

and then dried at 40 °C for 12 h in a vacuum oven.

Synthesis of multi-shelled NiCo2O4/NiCo2S4/NiCo2S4@C hollow microspheres:

The as-prepared Ni-Co precursor was annealed at 500 °C for 10 min in a tube furnace

under air at a heating rate of 1 °C min-1 to get multi-shelled NiCo2O4 hollow

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microspheres. Accordingly, the NiCo2O4 hollow microspheres were calcined at

500 °C for 4 h under Ar/H2S flow (95%/5% in volume ratio) at a temperature

elevation rate of 2 °C min-1 to obtain multi-shelled NiCo2S4 hollow microspheres.

For the fabrication of NiCo2S4@C hollow microspheres, 30 mg above-mentioned

NiCo2O4 microspheres were dispersed in 10 mM Tris-buffer solution (100 ml, pH =

8.5) and ultrasonically dispersed for 0.5 h. Then 30 mg of dopamine hydrochloride

of
was slowly added under magnetic stirring and continuously kept mixing for 4 h. The

obtained NiCo2O4@C precursors were collected by centrifugation, washed three times

ro
with deionized water and ethanol, and then dried at 40 °C for 12 h in a vacuum oven.
-p
The obtained composite was transferred to a quartz tube furnace, calcined at 500 °C
re

for 4 h under H2S atmosphere at a heating rate of 2 °C min-1 to get multi-shelled

lP

NiCo2S4@C hollow microspheres.

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2.2 Material characterization

X-ray diffraction (XRD) patterns of the as-prepared precursors and final products
ur

were collected on a Rigaku SmartLab 9 KW diffractometer with Cu Kα radiation

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(λ=0.15406 nm). Data were recorded in a 2θ range from 5o to 80o with a step size of

0.01o, and the step interval is 2 seconds. Raman spectrum was measured and collected

using a Laser Micro-Raman Spectrometer (Renishaw inVia) with 532 nm laser

excitation under ambient conditions. The morphologies and structures of these

resultant samples were investigated by using ultrahigh-resolution scanning electron

microscopy with FEG (SEM, Verios 460L, FEI) at an acceleration voltage of 3 kV,

high-resolution transmission electron microscopy with FEG (HRTEM, Talos F200X,

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FEI) at an acceleration voltage of 100 kV. The data of nitrogen adsorption isotherms

and Brunauer–Emmett–Teller (BET) surface area of these samples were implemented

on a Quantachrome iQ-MP analyzer at 77 K. X-ray photoelectron spectroscopy (XPS,

Thermo Scientific ESCALAB 250Xi) was employed to characterize the chemical

state of the samples using Al-Kα line as the excitation source.

2.3 Electrochemical measurements

of
The slurry-coating method was used to prepare working electrodes, specifically, 70

wt % active materials (multi-shelled NiCo2O4/NiCo2S4/NiCo2S4@C hollow

ro
microspheres), 20 wt % Ketjen black and 10 wt % carboxy methyl cellulose binders
-p
(CMC) were mixed in deionized water under magnetic stirring to form a
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homogeneous slurry. Then, the slurry was pasted uniformly onto copper foil current
lP

collector and dried in vacuum oven at 120 °C for 12 h. The areal mass loading of the
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electrodes was controlled at 1-1.2 mg cm-2. Electrochemical performance was

measured using CR-2032 coin cells assembled in a high-purity argon filled glove box
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(H2O, O2 < 0.1 ppm, MBraun), lithium foil as the counter electrode and the reference
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electrode, and Celgard 2400 as the separator. 1.0 M LiPF6 dissolved in a 1:1:1 mixture

of ethylene carbonate (EC), ethylene methyl carbonate (EMC) and dimethyl carbonate

(DMC) was used as the electrolyte. Galvanostatic charge/discharge measurements

were performed on a cell test instrument (Land CT2001A) at various current rates in

the voltage range of 0.001-3.0 V (vs. Li/Li+). Cyclic voltammetry (CV) and

electrochemical impedance spectroscopy (EIS) testing were conducted on a CHI 760E

electrochemical workstation (scan rate of 0.5 mV s−1, potential window: 0.01−3.0 V;

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scanning frequency: 100 kHz to 100 mHz).

3. Results and discussion

The fundamental synthetic routes of as-prepared multi-shelled hollow microspheres

are schematically illustrated in Scheme 1. Firstly, the Ni-Co precursors were first

prepared via a solvothermal reaction of Co2+ and Ni2+ ions with terephthalic acid

(TPA) (I). Multi-shelled NiCo2O4 hollow microspheres were obtained by direct

of
pyrolysis of Ni-Co precursors under air atmosphere (II). The formation of this

multi-shelled hollow structure could be ascribed to the integrated effects of

ro
contraction and adhesion forces generated by the oxidative degradation of the organic
-p
species and the release of CO2 gas from the decomposition of organic species during
re

the annealing under air atmosphere [30]. Subsequently, the as-prepared NiCo2O4
lP

hollow microspheres were further calcined under Ar/H2S atmosphere to get

na

multi-shelled NiCo2S4 hollow microspheres (III). Finally, a layer of dopamine (PDA)

was coated onto the surface of the multi-shelled NiCo2O4 hollow microspheres and
ur

then thermal-treated at under H2S/Ar atmosphere to obtain the multi-shelled

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NiCo2S4@C hollow microspheres (IV).

The morphologies and microstructures of these as-prepared samples were

characterized by scanning electron microscopy (SEM) and transmission electron

microscopy (TEM). The low-magnification SEM (Fig. S2a) and TEM images (Fig.

S1) reveal that the Ni-Co precursors are composed of uniform solid spheres with an

average diameter of 1-2 μm. After calcination treatment, the overall microspheres

morphology of these Ni–Co precursors is well inherited by annealed samples (Fig.

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S2b). The phase composition of the samples was investigated by X-ray diffraction

(XRD, Fig. S3). The XRD patterns could be assigned to a cubic phase NiCo2O4

(JCPDS card no. 20-0781). The obtained NiCo2O4 microspheres with a rough surface

are presented in Fig. S2b. The hollow interior and nanoparticles can be observed

clearly from some cracked hollow spheres. The structure of multi-shelled NiCo2O4

hollow microspheres was further revealed by TEM images. As shown in Fig. 1a,

of
well-defined multi-shelled hollow microsphere structures can be clearly discerned.

After sulfurization treatment under H2S/Ar atmosphere, the NiCo2O4

ro
microspheres converted to NiCo2S4 hollow microspheres, as shown in the XRD
-p
patterns (Fig. S3). The microspheres morphology and multi-shelled hollow structures
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of these NiCo2O4 microspheres are retained by NiCo2S4 microspheres (Fig. S2c and
lP

Fig. 1b). Notably, the carbon-coated multi-shelled hollow microspheres are obtained
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through coating carbon and further carbonization and sulfurization of NiCo2O4

microspheres (Fig. S2d). From the XRD patterns (Fig. S3), the crystallographic phase
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of the obtained samples can be identified as NiCo2S4@C (JCPDS card no. 20-0782)
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with cubic structures. Under TEM observations (Fig. 1c and d), it can be seen that the

NiCo2S4@C microspheres possess a unique ball-in-ball-in-ball hollow architecture, in

which obvious gaps between the outer and inner shells can be clearly seen. The outer

carbon layer and inner nanopores can be clearly seen by magnified TEM images (Fig.

1c-e) of a single NiCo2S4@C microsphere. A High-resolution TEM (HRTEM) image

exhibits that the thickness of the carbon layer is approximately 7-11 nm (Fig. 1e). A

typical lattice spacing of 0.28 nm corresponds to the (311) crystal plane of the cubic

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phase NiCo2S4 (Fig. 1f) [31], which is consisted of XRD patterns. The elemental

mapping images further validated the presence of Ni, Co, S and C elements in the

NiCo2S4@C microspheres (Fig. S2(e-h)). The nanoparticle-constructed multi-shelled

hollow NiCo2S4@C microspheres are expected to possess a high surface area,

abundant lithium insertion sites, facilitated charge transport and enhanced cycling

performances for LIBs.

of
The specific surface area and porous structure of these multi-shelled hollow

microspheres were investigated by the Brunauer–Emmett–Teller (BET) measurements,

ro
which are shown in Fig. 2. The N2 adsorption/desorption isotherms of as-prepared
-p
samples are categorized as Type IV isotherm, further confirming hierarchical pores
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structure [32]. The coexistence of macro- and mesopores in microspheres allows it to

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be an ideal electrode material. The specific surface area and total pore volume of
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NiCo2S4@C microspheres (47 m2 g−1 and 0.18 cm3 g−1 ) are much larger than that of

NiCo2O4 (22 m2 g−1 and 0.07 cm3 g−1) and NiCo2S4 microspheres (43 m2 g−1 and 0.16
ur

cm3 g−1). Besides, Fig. 2b presents that the pore size of NiCo2S4@C microspheres
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mainly distributes in a wide range of 5–70 nm, which is similar to that of NiCo2O4

and NiCo2S4 microspheres. It is noteworthy that the high surface area and porous

structure can provide abundant electrochemical active sites for redox reactions,

enlarge electrode-electrolyte contact area and facilitate easier electrolyte ion

penetration into the surface of active materials [33-35].

The graphitization degree and surface chemical composition of NiCo2S4@C and

NiCo2S4 microspheres were characterized by Raman spectra (Fig. S4a) and X-ray

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photoelectron spectroscopy (XPS) analysis (Fig. S4b and Fig. 3). Compared with the

Raman spectra of NiCo2S4, that of NiCo2S4@C microspheres displays two distinct

peaks centered at 1358 cm−1, which are ascribed to the disordered carbon (D band)

and ordered graphitic carbon (G band), respectively [36]. A broad 2D band peak

appeared at (~2684 cm-1) suggests that carbon-coated mainly consists of

inhomogeneous multilayer graphene-like layer [37]. Such coated-carbon layers can

of
serve as a conductive matrix to accelerate electron transport. The XPS overall spectra

(Fig. S4b) further confirmed the presences of Ni, Co, S and C atoms in NiCo2S4@C

ro
microspheres. The O elements are due to exposure to the air. The high-resolution Ni
-p
2p or Co 2p XPS spectrum (Fig. 3a and b) can be fitted with two spin-orbit doublets,
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which can be assigned to Ni2+ and Ni3+ (or Co2+ and Co3+), and two shake-up satellites
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(denoted as Sat.) [32, 38, 39]. The S 2p spectrum (Fig. 3c) can be fitted with one
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shake-up satellite and two main peaks. The binding energies at 163.5, 162.1 eV can be

attributed to S 2p1/2 and S 2p3/2, respectively. The shake-up satellite in NiCo2S4@C

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microspheres presents a negative shift compared to NiCo2S4 microspheres, maybe due

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to the increased electron cloud density in NiCo2S4 after coating carbon layers [40],

further testifying the interaction between the carbon-coated and NiCo2S4. Moreover,

four major peaks at 284.8, 285.8, 286.9 and 288.9 eV correspond to C=C, C=N, C-S

and C=O bonds, respectively, in the high-resolution C 1s XPS spectrum (Fig. 3d).

Combined with the HRTEM images (Fig. 1e and f), the XPS overall spectra (Fig. S4b)

and the C elemental mapping image of NiCo2S4@C microspheres, the high-resolution

C 1s XPS spectrum further indicating the formation of coated-carbon layers on the

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surface of NiCo2S4 microspheres [19, 41, 42].

The lithiation/delithiation mechanism of as-prepared NiCo2S4@C electrodes was

investigated by testing cyclic voltammetry (CV) measurements in a half-cell. Fig. 4a

shows representative CV curves for the 1st, 5th, 10th, 20th cycles at a scan rate of 0.5

mV s−1 in the voltage window of 0.01–3.0 V vs. Li/Li+. In the first cathode scan, two

reduction peaks at 1.11 V and 1.49 V can be corresponded to Li+ insertion into

NiCo2S4 lattice to form LixNiCo2S4, and then Li+ and NiCo2S4 were converted to form

of
Ni, Co and amorphous Li2S matrix [43]. And a weak reduction peak at ~ 0.56 V is

ro
associated with the decomposition of organic electrolyte to form an irreversible solid
-p
electrolyte interface (SEI) [33]. During the first anodic scan, the oxidation peaks at
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2.13 and 2.42 V could be ascribed to the conversion of metallic Ni and Co to nickel
lP

sulfide and cobalt sulfide [44]. In the following cycles, the major reduction peaks shift
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to higher potentials of 1.20 and 1.67 V, might be because of irreversible phase change

of NiCo2S4 after the first cycle [14, 45, 46]. Therefore, on the basis of the above CVs
ur

analysis and previous reported, the lithium insertion/extraction reactions for the
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NiCo2S4@C electrode can be described as follows:

NiCo2S4 + xLi+ + xe‒ → LixNiCo2S4 (1)

LixNiCo2S4 + (8 – x)Li+ + (8 – x)e‒ → Ni + Co + 4Li2S (2)

Ni + Li2S → NiS + 2Li+ + 2e- (3)

Co + Li2S → CoS + 2Li+ + 2e- (4)

NiS + 2Li+ + 2e‒ → Ni + Li2S (5)

CoS + 2Li+ + 2e‒ → Co + Li2S (6)

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To better research the high-rate electrochemical behaviors of NiCo2S4@C electrode,

CV measurements were performed at different scanning rates from 0.1 to 10.0 mV s-1.

The redox peaks for the NiCo2S4@C electrodes could be clearly observed even at

high scanning rates (Fig. 4b), indicating good reversibility of NiCo2S4@C

microspheres. The voltage hysteresis became obvious, especially at high scanning

rates due to the dramatically increasing polarization. The linear relationship between

of
scanning rates and peak current densities (Fig. 4c) indicates obvious surface lithium

storage [47].

ro
Typical discharge-charge voltage profiles of NiCo2O4, NiCo2S4 and NiCo2S4@C
-p
electrodes at a current density of 0.2 A g−1 in the potential range from 0.01 to 3.0 V
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are shown in Fig. 4d. The NiCo2S4@C electrodes deliver higher discharge/ charge
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capacities (1946.7/1308.7 mAh g-1) at the 1st cycle than NiCo2O4 (1181.2/682.9 mAh
na

g-1) and NiCo2S4 electrodes (1504.8/1038.8 mAh g-1). The irreversible capacity loss of

the 1st cycle in these electrodes is attributed to the formation of SEI layers or
ur

incomplete restoration of metallic Ni and Co into the original sulfide or oxide [48].
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Interestingly, the specific capacities of NiCo2S4@C electrodes start to increase

gradually from the 4th cycle. Such phenomenon of increasing capacity upon cycling

has also been reported in other carbon-coated metal oxide/sulfide materials [19],

which maybe attribute to the gradual access of more electrolyte molecules through the

carbon layer into the active materials [49] or the reversible growth of

pseudocapacitive polymeric film [22, 34, 50, 51]. After 100 cycles, the specific

capacity of NiCo2S4@C electrodes keeps at 1840.2 mAh g-1, which is much higher

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than that of NiCo2O4 (727.3 mAh g-1) and NiCo2S4 (1062.6 mAh g-1) electrodes (Fig.

5a).

To further confirm the advantages of NiCo2S4@C electrodes for lithium storage,

we evaluated the rate capability at various current rates (from 0.1 to 5.0 A g-1). As

exhibited in Fig. 5b, the average specific capacities of NiCo2S4@C electrodes are

1677.8, 1300.9, 1138.9, 1039.5, 906.9 and 550.5 mAh g-1 at current rates of 0.1, 0.2,

0.5, 1.0, 2.0 and 5.0 A g-1, respectively. When the current rate drops to 0.5 A g-1, the

of
specific capacity of NiCo2S4@C electrodes recovers to 1140.7 mAh g-1. In contrast,

ro
the specific capacities of NiCo2O4 (883.7, 812.3, 649.4, 433.4, 196.9 and 64.3 mAh
-p
g-1) and NiCo2S4 electrodes (1274.4, 1000.8, 839.3, 718.5, 579.3 and 390.8 mAh g-1)
re

are relatively low at different current rates. These results mean that the NiCo2S4@C
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materials possess strong structure stability, which can resist the collapse effect coming
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from the impact of a large current.

Long-term cycling performances of electrodes at high current densities are a

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critical factor for practical applications of LIBs. The electrodes were first activated at
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a current density 0.1 A g−1 for 5 cycles, and then cycled at a high current density of

1.0 A g−1 for long-term tests. After activation, the NiCo2S4@C electrodes maintain a

higher specific capacity (1094.8 mAh g−1) with a lower capacity fading (~0%) each

cycle after 300 cycles than NiCo2S4 (655.2 mAh g−1/0.11%) and NiCo2O4 electrodes

(340.0 mAh g−1/0.20%), further testifying the superior cycling stability of

NiCo2S4@C electrodes (Fig. 5 c and d). Besides, the long-term cycling performances

of NiCo2S4@C electrodes at high current densities of 2.0 and 5.0 A g-1 were also

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evaluated (Fig. 6). After activation of 5 cycles at a current density of 0.1 A g-1, the

NiCo2S4@C electrodes deliver high initial discharge/charge capacities of

1174.4/1086.2 and 990.8/878.2 mAh g-1 at current densities of 2.0 A g-1 and 5.0 A g-1,

corresponding to high Coulombic efficiencies (CE) of 92.5% and 88.6%, respectively.

It is important to note that the decreased firstly and then increment in specific

capacities could be observed during cycling process. The capacity reduction of

of
electrodes can be attributed to some possible incomplete reaction of metallic Ni/Co

into the sulfides or the formation of an SEI layer [51, 52]. The increasing capacity

ro
after ~150 cycles maybe derives from the reversible formation of a polymeric gel-like
-p
film [53], the enhanced reaction kinetics (shown in the decreased resistance after
re

cycling, Fig. 7) and an activation process of electrodes. After 1000 cycles, the
lP

NiCo2S4@C electrodes kept strikingly high specific capacities of 1242.8 and 656.4
na

mAh g-1 at current densities of 2.0 and 5.0 A g-1, and its CE remained at ~100%. The

outstanding long-term cycling performances at high current densities are superior to

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those of reported similar electrodes, such as NiCo2S4 nanotube arrays@NDCF,

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NiCo2S4@C hollow nanospheres, as specifically tabulated in Table 1 [11, 14, 46,

54-59].

The reaction kinetics difference for NiCo2S4 and NiCo2S4@C electrodes before

and after cycling was studied by the electrochemical impedance spectra (EIS). As

presented in Fig. 7a, the Nyquist plots are composed of a short line in the low

frequency areas and a semicircle in the high-middle frequency areas. The low

frequency straight, high-middle middle frequency is represented to the Li+ diffusion in

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the bulk electrode (Rs) and charge-transfer resistance (Rct) from the

electrode-electrolyte interface, respectively [60, 61]. The semicircle diameter of the

NiCo2S4@C electrodes in the high frequency region is smaller than that of the

NiCo2S4 electrodes before or after cycling, verifying the improved electrical

conductivity by coating carbon layer in the outer shell of NiCo2S4 microspheres.

Compared to fresh NiCo2S4@C electrodes, the reduced charge-transfer resistance (Rct)

of
of electrodes after cycling suggests better contact between the electrolyte and

electrode materials, and decreases the internal resistance to improve the reaction

ro
kinetics of electrode materials [51, 62]. For NiCo2S4 and NiCo2S4@C electrodes,
-p
these sloping lines before or after cycling, are parallel nearly, which suggest that the
re

coated carbon layers do not influence the Li+ diffusion in the bulk electrode.
lP

The NiCo2S4@C electrode after long cycling tests at 1.0 A g−1 was investigated by
na

TEM images (Fig. 8) to examine the structural stability of the NiCo2S4@C

microspheres. It can be clearly observed that the overall microspheres morphology

ur

and the multi-shelled hollow structure (Fig. 8a-d) of NiCo2S4@C electrodes before
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and after cycling show marginal difference. As exhibited in the EDX mapping images

(Fig. 8e-h), the distribution of C, Ni, Co and S elements is rather uniform throughout

the entire NiCo2S4@C microspheres. Therefore, the coated-carbon layers and the

multi-shelled hollow structure are beneficial to maintain structural stability and

withstand the impact of a large current.

4. Conclusion

In summary, we have successfully constructed of unique carbon-coated

16
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multi-shelled NiCo2S4 hollow microspheres as high cycling performances anode

materials for LIBs. The Ni-Co precursors are simply annealed under air at high

temperature to obtain the unique multi-shelled hollow microspheres. The method is

simple, easy to use and template-free. Benefit from the synergistic effect of

coated-carbon layers and the multi-shelled hollow structures, the NiCo2S4@C

electrodes show excellent cycling performances. Specifically, the electrodes keep high

specific capacities of 1242.8 and 656.4 mAh g−1 at high current densities of 2 and 5 A

of
g−1 after 1000 cycles. We believe that this synthetic scheme could be applicable for

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the facile synthesis of carbon-coated multi-shelled architecture, which can be widely
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applied in sustainable energy storage and conversion systems.
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Acknowledgements
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This work was supported by fundings from the National Natural Science Foundation
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of China (51702236 and 21701125) and Key Project Natural Science Foundation of

Tianjin (18JCZDJC39800).
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References
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Figures and Tables
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Scheme 1 The fundamental synthetic routes of as-prepared multi-shelled hollow

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microspheres.

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Fig. 1 The TEM images of the as-prepared NiCo2O4 (a), NiCo2S4 (b) and NiCo2S4@C
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hollow microspheres (c-d). The HRTEM images of NiCo2S4@C hollow microspheres
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(e-f).
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Fig. 2 The pore size distributions (a-c) and nitrogen adsorption/desorption isotherms
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(d-f) of as-prepared samples.

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Fig. 3 The XPS Ni 2p (a), Co 2p (b) and S 2p (f) spectra of NiCo2S4 and NiCo2S4@C
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hollow microspheres. The XPS C 1s spectra (d) of NiCo2S4@C hollow microspheres.

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Fig. 4 CV profiles of the NiCo2S4@C electrodes at a scan rate of 0.5 mV s−1 (a) and

different scan rates from 0.1 to 10.0 mV s−1 (b). The linear relationship between the

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peak current densities and scanning rates in the cathodic process (c) and galvanstatic

discharge-charge curves of the NiCo2S4@C electrodes at a current density of 0.2 A g-1

(d).

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Fig. 5 Cycle performance at 0.2 A g−1 (a) and rate performances (b) of the NiCo2O4,
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NiCo2S4 and NiCo2S4@C electrodes. Galvanstatic discharge-charge curves (c) and

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long-term performances of NiCo2S4@C electrodes at a high current density of 1.0 A

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g−1 (d).

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Fig. 6 Long cycling performance of NiCo2S4@C electrodes at 2.0 A g−1 (a) and 5.0 A
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g−1 (b).
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Fig. 7 Nyquist plots for the EIS data (a) and the corresponding equivalent circuit

mode of the EIS of NiCo2S4 and NiCo2S4@C electrodes before (b) and after cycling

(c).

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Fig. 8 The TEM (a-d) and EDX mapping (e-h) images of cycled NiCo2S4@C

electrodes at 1.0 A g−1.

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Table 1 Compared cycling performances of reported similar electrode materials with
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different current rates.

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Electrode Synthesis Current Cycle Specific Refs.

materials methods density life capacity
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[A g−1] [cycles] [mAh g−1]

Multi-shelled Template-free 0.2 100 1946.7 This
NiCo2S4@C hollow work
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1.0 500 1075.7

microspheres 2.0 1000 1242.8
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5.0 1000 656.4

NiCo2S4 nanotube Surfactant-assisted 0.5 100 1182 11
arrays@NDCF hydrothermal
Bundle-like High-temperature 2.0 800 749 46
NiCo2O4@TiO2 pyrolysis
hybrid
NiCo2S4@C hollow Template-engaged 0.5 1178 200 54
nanospheres precipitation
Hollow NiCo2O4 cages Template-assisted 0.2 793 100 59
NiCo2S4 mesoporous Hydrothermal and
0.1 1163.7 100 57
nanoparticles solvothermal

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NiCo2S4 Cation adsorption 0.2 813 200

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nanocores@GS
2.0 535 100

NiCo2S4 multi-shelled Metal-organic- 0.1 745.5 100 14

hollow polyhedrons framework
-engaged
Hybrid pH–controlled 2.0 777 200 58
NiCo2O4-NiCo2S4 ammonia evaporation
Nanoflakes on Ni
foam
Double-Shelled Co-precipitation and 0.2 624 50 55

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CoMn2O4 Hollow annealing
Microcubes

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Graphical abstract

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Highlights
1. Carbon-coated multi-shelled NiCo2S4 hollow microspheres were constructed by a
facile and template-free route.
2. The unique structure is beneficial to accelerate e- transfer and Li+ diffusion, and
enhances structural robustness.
3. Excellent cycling performances and rate capability at high current densities for
lithium storage can be achieved.

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