Journal of Alloys and Compounds 834 (2020) 155111

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

In-situ electrolytic synthesis and superior lithium storage capability of

NieNiO/C nanocomposite by sacrificial nickel anode in molten
carbonates
Yang Qiu a, Hui Huang a, **, Wenlong Song b, Yongping Gan a, Kun Wang a, Jun Zhang a,
Yang Xia a, Chu Liang a, Xinping He a, Wenkui Zhang a, *
a
College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou, 310014, China
b
Zhejiang Tianneng Energy Technology Co., Ltd, Huzhou, 313100, China

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

Article history: Herein, we demonstrate a facile electrolytic strategy to synthesize a kind of NieNiO/C nanocomposite via
Received 4 February 2020 electroreduction of molten LieNaeK carbonates synchronously combined with sacrificial nickel anode.
Received in revised form Benefiting from its unique in situ synthesis mechanism, the NieNiO/C nanocomposite exhibits well-
30 March 2020
interconnected architecture with fine NieNiO nanoparticles embedded into electrolytic carbon matrix.
Accepted 8 April 2020
Available online 12 April 2020
The as-fabricated electrode shows ultra-long cycle stability (achieving a high capacity of 455 mA h g
1 at
1 A g
1 after 1500 cycles, average coulombic efficiency 99.88%) and impressively improved rate capa-
bility, comparing with the reported NieNiO/C nanocomposites. Such a superior lithium storage prop-
Keywords:
Lithium-ion batteries
erties originates from the in situ formed nanoarchitecture of NieNiO/C. This research offers a distinctive
Nickel oxides pathway for constructing novel composite materials for advanced lithium storage.
Nanocomposites © 2020 Elsevier B.V. All rights reserved.
Molten salts electrolysis
Carbonates

1. Introduction mitigate these problems [12e15]. The most common way is to

As the markets for portable electronic devices and intellectual
industry grow, the status of lithium-ion batteries (LIBs) is rising,
which is also the requirement of sustainable development [1e4]. To
meet the demands of high energy density and power density in
emerging applications, new materials with good ratability, high
specific capacity and low cost are urgently developed. Transition
metal oxides (TMO) appeal more competitive candidates due to
higher specific capacity than commercial graphite anodes. For
example, as a typical conversion reaction material, nickel oxide
(NiO) has grabbed increasing attention by reason of its high theo-
retical capacity of 718 mAh g
1 [5e8]. Whereas, NiO anode suffers
from serious capacity fade under the combined effects of poor
electrical conductivity and huge volume expansion during lith-
iation and de-lithiation processes, which hinder the long-term
durability [9e11]. So far, various methods have been developed to
* Corresponding author.
** Corresponding author.
E-mail addresses: hhui@zjut.edu.cn (H. Huang), msechem@zjut.edu.cn
(W. Zhang).
convert NiO into nanostructure while coating with carbonaceous
hybrid materials to enhance the conductivity and accommodate the
volume expansion phenomenon. Although these hybrids have
demonstrated certain success in improving electrochemical per-
formance, the rate capability and long-term durability is still not
satisfactory because carbonaceous materials lack of high conduc-
tivity and fast electron transport. It has been reported that
embedding of metal particles (Ni, Fe, Co) [16e18] into carbonaceous
hybrid materials is confirmed to be a feasible strategy to enhance
conductivity and facilitate electron transport. Deng et al. [19] re-
ported a bio-inspired synthesis of NiO nanowires and Ni nano-
particles on eggshell membrane substrate. Under the action of
partially reduction of NiO, metallic Ni nanoparticles are in-situ
incorporated in the nanowires, which could promote the revers-
ible storage of lithium and the SEI formation during charge and
discharge. Jiang et al. [20] fabricated a unique hybrid material of
hollow NieNiO nanoparticles embedded in porous carbon nano-
sheets though in situ oxidation strategy, exhibiting an ultra-long
cycle life for sodium-ion batteries. Hu et al. [21] synthesized Ni/C
by carbothermal reduction and Ni/C precursors further oxidized
into NieNiO/C with a high initial Coulombic efficiency (CE) of

https://doi.org/10.1016/j.jallcom.2020.155111
0925-8388/© 2020 Elsevier B.V. All rights reserved.
2 Y. Qiu et al. / Journal of Alloys and Compounds 834 (2020) 155111

70.92%. Cheng et al. [22] reported a templated electroless plating

method to fabricate Ni/PS precursors, coordinated the temperature
to control the decomposition of PS template and the oxidation of Ni
to NiO. The as-formed nanoporous NieNiO/C composites display
impressive rate capacities. These important results reveal an
effective improvement of the initial CE and rate performance as the
introduction of Ni metal into NiO/C. However, the above synthesis
methods are complicated including several steps, such as synthesis
of Ni/C or NiO/C, carbon coating, oxidation or reduction processes
to form NieNiO/C composites. Hence, it is of significance to pursue
a facile strategy for the efficient synthesis of NieNiO/C composites.
Molten salt electrolysis has been successfully applied in
extracting metals such as aluminium, and magnesium, etc.
Recently, various nanocarbons such as nanofibers [23], nanotubes
[24] and hollow carbon spheres [25] derived from molten salt
electrolysis exhibit outstanding Li storage capability. Alkali molten
carbonates are commonly used as the electrolyte as reasons of low
cost, high electronic conductivity, fast reaction kinetics, wide
electrochemical window. Jiao et al. [26] reported that carbon pre-
pared in molten LiCleLi2CO3 salt delivers a reversible capacity of
318 mA h g
1 over 100 cycles at 50 mA g
1. Wang et al. [27] syn-
thesized electrolytic-carbon in LieNaeK carbonate molten salts at Fig. 1. Schematic illustration of molten salt electrolytic synthesis of NieNiO/C
the temperatures of 450  C with the electrolysis voltage of 4.5 V. nanocomposite.
When performed as the LIB anode, the electrolytic-carbon shows a
high reversible capacity of 254 mA h g
1 at 0.5 A g
1. To date, there
is no report about molten salts as the electrolyte to synthesize Ni2þ þ O2
/ NiO (5)
carbonaceous hybrids. In this work, we report a unique one-step
synthesis of NieNiO/C nanocomposites by sacrificial anode via After electrolysis, Ni cathode was uplifted out of the molten salt
electroreduction of molten LieNaeK carbonates. The in-situ and naturally cooled to a safe temperature. The resultant product
formed NieNiO nanoparticles were tightly embedded into carbon on the cathode was collected and sonicated with hydrochloric acid
materials originated from the electroreduction of molten LieNaeK to remove carbonate impurities. Finally, the filtrate was washed
carbonates. Benefiting from the well-interconnected structure with with deionized water and vacuum freezing dried for 12 h to obtain
fine NieNiO nanoparticles embedded into the in-situ electrolytic the NieNiO/C nanocomposite.
carbon matrix, the NieNiO/C nanocomposites exhibit high specific
capacity, long-term cycling stability (455 mAh g
1 over 1500 cycles 2.2. Materials characterization
at 1 A g
1, average coulombic efficiency 99.86%) and impressive rate
capability (227, 342, 431, 523, 640 and 757 mA h g
1 at 5, 2, 1, 0.5, SEM images of NieNiO/C nanocomposite were determined with
0.2, and 0.1 A g
1) for LIBs. by Hitachi S-4800 field-emission scanning electron microscopy.
High resolution transmission electron microscopy images were
2. Experimental taken on TF20, Jeol 2100F TEM equipped with an energy dispersive
X-ray spectroscopy. X-ray diffraction (XRD) analysis was performed
2.1. In-situ fabrication of NieNiO/C nanocomposite on an X’PertPro diffractometer with applying Cu Ka radiation. TGA
was carried out on a Q5000IR thermal analyzer. The Raman spec-
Anhydrous carbonate salts (Li2CO3, Na2CO3 and K2CO3) mixture trum was measured at an excitation wavelength of 532 nm by an
were used as the electrolyte for electrolytic preparation. About 45 g Invia Reflex Renishaw spectrometer. MicroActive for ASAP 2460
LieNaeK mixture (1:1:1 wt%) was dried at 250  C for 15 h to Version 2.01 was used for the surveying and mapping of BET and
remove moisture and added into an alumina crucible (inner pore diameter distribution.
diameter: 34 mm, height: 137 mm). Then, the alumina crucible was
transferred into a sealed quartz crucible (inner diameter: 42 mm, 2.3. Electrochemical measurement
height: 150 mm), which was set in the vertical tube furnace. The
anode and cathode are two identical pieces of nickel sheets with an Electrochemical properties of the NieNiO/C nanocomposite
apparent area of 4.5 cm2. A possible in-situ synthesis mechanism of were characterized by using CR2032 coin-type cell. The slurry was
NieNiO/C nanocomposite via molten salt electrolysis is presented obtained by mixing 80 wt% NieNiO/C, 10 wt% Super-P and 10 wt%
in Fig. 1, and described as the following: polyvinylidene fluoride (PVDF) binder in N-methyl-2-pyrrolidene
Anode (Positive electrode): (NMP). The slurry was coated onto the Cu foil and dried in vac-
uum at 80  C overnight to fabricate the working electrode with the
2O2

4e
/ O2 (1) mass loading of about 1.5 mg cm
2. The working electrode was
assembled with a counter electrode of Li foil by choosing Celgard
Ni
2e
/ Ni2þ (2) 2300 membrane as the separator, 1 M LiPF6 dissolved in dimethyl
carbonate (DMC) and ethylene carbonate (EC) (1:1 in volume) as
Cathode (Negative electrode): the electrolyte. Galvanostatically discharge/charge measurements
were performed in the voltage window of 0.01e3.0 V (vs. Li/Liþ) at


CO2

3 þ 4e / C þ3O
2

(3) various current densities on a Neware battery-testing system. Cy-
clic voltammograms (CVs) were performed on a CHI650B electro-
Ni2þ þ 2e
/ Ni (4) chemical workstation at a scan rate of 0.1 mV s
1. Electrochemical
 Y. Qiu et al. / Journal of Alloys and Compounds 834 (2020) 155111
impedance spectroscopy (EIS) measurements were tested on a
Zennium electrochemical workstation (ZAHNER, Germany).
3. Result and discussion
Fig. 2a presents the time dependence of electrolytic tempera-
ture in the reactor. The crucible was raised from the RT to 700  C at
5  C min
1, and then maintained at this temperature for 30 min to
ensure carbonates dissolved in the molten state. The electrolytic
experiment was conducted at 500  C by applying a constant voltage
of 6 V. After electrolysis for 2 h, the electrode is taken out and the
molten salt was naturally cooled down. XRD, TG, Raman are
measured to characterize the structure of the as-collected cathodic
product (Fig. 2bed). The characteristic diffraction peaks of Ni and
NiO phases are detected from the XRD patterns of Fig. 2b. A broad
and weak peak between 20 and 30 indicates the amorphous
nature of electrolytic carbon [20,28]. The Rietveld refinement of the
XRD pattern tells that the weight ratio of NiO and Ni phase is close
to 3:2. In addition, the carbon content in NieNiO/C was determined
to be about 60 wt% by thermogravimetric analysis (TGA) from
Fig. 2C. So, it can be inferred that the weight ratio of Ni:NiO:C is
4:6:15. Although Ni will be oxidized to NiO, there is no evident
weight increase after 500  C due to the low Ni content. Fig. 2d is the
Raman spectrum of NieNiO/C to measure the degree of graphiti-
zation, where two characteristic peaks centered at about 1366 and
1581 cm
1 are corresponding to the D band and G band of carbon,
respectively. The intensity ratio of ID/IG is 0.88, revealing a low
graphitization degree. This further indicates that there are abun-
dance of topological defects and disorders in the electrolytic
NieNiO/C, which is much beneficial for lithium storage than crys-
talline graphite [29,30]. And not only that, the high-content carbon
in NieNiO/C is crucial to enhance the cycling stability of NieNiO
electrode.
Fig. 3a shows the SEM image of NiO particles, which are
collected from the bottom salts (Some Ni2þ will directly combine
with O2
in the molten salts to form NiO precipitation at the bottom
of the crucible, Fig. S1 is the XRD pattern). It is clear that the
Fig. 2. (a) Time dependence of electrolytic temperature of the NieNiO/C synthesis process, (b) Rietveld refinement of the XRD pattern, (c) TGA, (d) Raman spectrum of NieNiO/C.
3
agglomeration is very serious between NiO particles. By compari-
son, the in-situ electrolytic formed NieNiO/C particles show more
uniform distribution (Fig. 3b, Fig. S2). The NieNiO and carbon
particles are in-situ grew together, forming rich interstitial chan-
nels. The porosity of NieNiO/C was further verified employing the
nitrogen adsorption-desorption measurement. A distinct hysteresis
loop (0.43 < P/P0 < 0.98) is observed in the nitrogen adsorption/
desorption isotherm (Fig. 3c), which is a typical type-IV behavior of
mesoporous adsorbents [31,32]. The specific surface area of
NieNiO/C is calculated to be 521.7 m2 g
1 basing on the Brunauer-
Emmett-Teller model, suggesting the existence of numerous mes-
opores in NieNiO/C. From Fig. 3d, these mesopores are centered at
3e4 nm.
Furthermore, the NieNiO/C nanocomposite are examined by
TEM and HRTEM. As suggested in Fig. 4a, NieNiO particles are
randomly distributed in the bulk carbon. The SEAD in the inset of
Fig. 4a also affirms the presence of Ni, NiO and C. As marked with
red circles, there are some internal grey NieNiO dots with a “broad
beans” kind of structure. Such a unique structure can effectively
mitigate the huge volume change of NiO during Li ions insertion/
extraction. The HRTEM image in Fig. 4b clearly indicates that these
NieNiO particles are adhered with each other tightly, where the
inter-planar spacing of 0.20 nm and 0.24 nm assign to Ni (111) and
NiO (111) planes, respectively [20,21,33]. In Fig. 4b, we have marked
the TEM image of one NieNiO particle. There is some locally or-
dered carbon around it and the average lattice fringe value is
calculated as 0.33 nm. In addition, the rest part with the poor
crystallinity is amorphous carbon, revealing good mechanical
contact between NieNiO particles and carbon. The corresponding
elemental mappings reveal that Ni, O and C are homogeneously
distributed in the nanocomposite (Fig. 4c).
Benefiting from in situ one-pot hybridization, the unique inte-
grated architecture of NieNiO/C includes the advantages of inter-
connection of metallic Ni and NiO phases, high BET specific surface
area, high-content and amorphous nature of carbon, and so may be
expected as a potential lithium storage material. Fig. 5a displays the
cyclic voltammograms (CVs) of NieNiO/C for initial three cycles.
4 Y. Qiu et al. / Journal of Alloys and Compounds 834 (2020) 155111

Fig. 3. SEM images of (a) NiO and (b) NieNiO/C, (c) Nitrogen adsorption/desorption isotherm curves, and (d) corresponding pore diameter distribution of NieNiO/C.

Fig. 4. (a) TEM, (b) HRTEM images of NieNiO/C, (c) HAADF-STEM image of NieNiO/C and the corresponding EDS elemental mappings.

There is an obvious reduction peak appears at 0.57 V in the first
discharge progress, which is mainly attributed to the conversion of
NiO into Ni (NiOþ2Liþþ2e
/Ni þ Li2O) and the formation of the
solid electrolyte interface (SEI) layer [11,21]. The anodic peaks
located at 1.11 V and 2.30 V are due to the oxidation of Ni
(Ni þ Li2O/NiOþ2Liþþ2e
) and the decomposition of SEI
[21,34,35]. Starting with the 2nd cycle onward, the peaks and
curves are almost overlapped, revealing stable lithiation/delithia-
tion reactions between NiO and Ni particles. Fig. 5b displays the
selected charge-discharge profiles of NieNiO/C for the 1st, 2nd,
100th and 300th cycle at 0.1 A g
1. NieNiO/C delivers a discharge
capacity of 1471.17 mAh g
1 and a charge capacity of 914.11 mAh
g
1 in the 1st cycle. Note that the specific capacities are calculated
in terms of total mass of the NieNiO/C (Ni is not excluded). The
initial Coulombic efficiency (CE) is calculated to be 62.13%. Such a
large irreversible capacity (557.06 mAh g
1) is mainly relevant to
the formation of SEI on the large surface, and the amorphous
structure of electrolytic carbon [36]. The cycling performance of
NieNiO/C at 0.1 A g
1 is depicted in Fig. 5c. The specific capacity of
Ni/NiO/C gradually decays in the previous 100 cycles, and then
becomes stable with the CE close to 100%. After 300 cycles, the
specific capacity remains above 637 mAh g
1. More importantly,
even cycled at a higher current density of 1 A g
1 for 1500 cycles,
the NieNiO/C electrode also exhibits superior cycling stability. As
revealed in Fig. 5d, a reversible capacity of 455 mA h g
1 is main-
tained after 1500 cycles at 1 A g
1. The specific capacity and cycling
capability of the in-situ electrolytic synthesized sample are supe-
rior to most NieNiO/C composites, such as the reported hollow
NieNiO nanoparticles embedded in porous carbon nanosheet [20],
NiOeNi nanowire on carbonized eggshell membrane [19], and
other NieNiO/C composites prepared by ex-situ methods
[18,21,22]. This is mainly due to the in situ formed nanoarchitecture
of NieNiO/C with merits of in-situ growth, interconnected porous
structure and metallic Ni phase. As expected in Fig. 5e, the as-
fabricated NieNiO/C also displays impressive rate performance of
227, 342, 431, 523, 640 and 757 mA h g
1 over every 10 cycles at 5,
2, 1, 0.5, 0.2, and 0.1A g
1, respectively. After such a variable rate
cycling, the capacity still remains 626 mA h g
1 as the current
 Y. Qiu et al. / Journal of Alloys and Compounds 834 (2020) 155111 5

Fig. 5. (a) CV curves of NieNiO/C at 0.1 mV s
1, (b) Charge-discharge profiles at the 1st, 2nd, 100th and 300th cycle at 0.1 A g
1, Cycling performance (c) at 0.1 A g
1 and (d) at
1 A g
1. (e) Rate performance.

density comes back to 0.2 A g
1, indicating outstanding electro-
chemical reversibility.
EIS measurements of NieNiO/C are conducted before and after
the 50th cycle. As depicted in Fig. 6, the impedance curve of
NieNiO/C consists of a semicircle in the high frequency region and
a straight line in the low frequency region. An equivalent circuit
(inset in Fig. 6) is constructed to distinguish the resistance. The
intercept of semicircle on the horizontal axis is ascribed to the
electrolyte impedance Re, the diameter of the semicircle indicates
interfacial charge transfer resistance Rct, and the slope of straight
line reveals the resistance of Li-ion diffusion (Zw) [37]. After 50
cycles, Rct decreases from 127 U of pristine electrode to 75 U due to
full infiltration of the electrolyte and activation of the electrode. The
low Rct value enables fast charge transfer, ensuring good rate
capability [38]. Furthermore, the diffusion coefficient can be
determined by the following equation:
D ¼ R2T2/(A2n4F4C2s2) (6)
Where R is the universal gas constant, T is absolute temperature, A
is the surface area, n is number of electron, F is Faraday’s constant, C
is the electrolyte concentration, and s is the slope of Zreal vs.
(2pf)
1/2. Using this equation, the diffusion coefficients before and
after cycling are estimated as 1.44  10
17 cm2 s
1 and
2.40  10
17 cm2 s
1, respectively, indicating a faster Liþ diffusion.
The impressive electrochemical properties of NieNiO/C has
captured our great interests to investigate lithium storage mecha-
nism of composites. Part of the capacity is due to the conversion
mechanism of NiO. For purpose of quantitatively identifying the
carbon capacitive contribution during lithium ions insertion/
extraction process, the CV profiles of NieNiO/C were recorded at a
sweep rate from 0.2 to 3.2 mV s
1 (Fig. 7a). In general, the current
(i) response is a function of the sweep rate (v) which defer to the
6 Y. Qiu et al. / Journal of Alloys and Compounds 834 (2020) 155111
Fig. 6. Nyquist plots of NieNiO/C before and after 50 cycles.
power-law as follow [39e41].
i ¼ avb
Where a is a constant, b value is determined by the slope of the
log(i) vs. log(v) curve (Fig. 7b). As we know, the b value of 0.5 and 1
corresponds to Faradaic diffusion-controlled reaction and surface
capacitive effect, respectively. The relation between current density
Fig. 7. (a) CV curves of NieNiO/C at various scan rates, (b) Plots of log (scan rate) vs. log (peak current), (c) Surface capacitive contribution of NieNiO/C at 3.2 mV s
1, (d) Normalized
capacitive contribution ratio at different scan rates.
(i) and potential (V) is composed of the surface capacitive effect
(k1v) and the diffusion-controlled process (k2v1/2):
i ¼ k1v þ k2v1/2 (8)
Which can be further converted as:
i/v1/2 ¼ k1v1/2þk2 (9)
By plotting the line i/v1/2 vs. v1/2 at different potential, one can
get the values of k1 and k2, which are the slope and the intercept of
the line, respectively.
As presented in Fig. 7b, the log i has a linear relationship with
log v. At the reduction potential of 0.88 V and oxidation potential of
2.24 V, the slope of the fitting straight line is calculated as 0.64 and
0.76, respectively. It indicates that the lithium storage in the
NieNiO/C composite arises from both the surface capacitive effect
and diffusion-controlled process. The surface capacity mainly
contributed by electrolytic carbon reaches 50.8%, as illustrated in
Fig. 7c. As the sweep rate increases, so does capacitive contribution
increases as well. (Fig. 7d). The capacitive contribution ratio ex-
plains high lithium storage capacity well.
The SEM image of NieNiO/C after 300 cycles at 0.1 A g
1 is also
presented in Fig. 8. The NieNiO/C nanocomposites still retains in-
tegrated interconnected structure well after the repeated lithium
insertion/extraction. We believe that the exceptional lithium stor-
age properties of NieNiO/C are attributed to unique structural
characteristics, the presence of metal nickel nanoparticles, and the
(7) lithium storage capacity of electrolytic carbon. The integrated
structure can effectively adapt to large volume change of NiO, and
nickel particles are resultful for improving the conductivity of the
electrode materials and promote redox reactions in the electrode
reaction.
 Y. Qiu et al. / Journal of Alloys and Compounds 834 (2020) 155111
Fig. 8. SEM image of NieNiO/C after 300 cycles at 0.1 A g
1.
4. Conclusion
In summary, we developed a facile in-situ electrochemical
synthesis of NieNiO/C nanocomposites by sacrificial nickel anode
in molten carbonates. Benefiting from the synergistic effects of
electrolytic carbon and metallic nickel, as an anode in LIBs, the as-
prepared NieNiO/C electrode shows impressive electrochemical
lithium storage capacity including high specific capacity, stable
cycling and rate performance. All in all, this method can be used to
synthesize and design high-performance metal oxide/carbon
anode materials.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
CRediT authorship contribution statement
Yang Qiu: Investigation, Writing - original draft. Hui Huang:
Conceptualization, Writing - review & editing. Wenlong Song:
Investigation. Yongping Gan: Methodology. Kun Wang: Investi-
gation. Jun Zhang: Data curation. Yang Xia: Visualization. Chu
Liang: Formal analysis. Xinping He: Resources. Wenkui Zhang:
Supervision, Writing - review & editing.
Acknowledgements
The authors thank financial support from the Natural Science
Foundation of Zhejiang Province (Grant no. LY18B030008).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jallcom.2020.155111.
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