Materials Research Bulletin 73 (2016) 369–376

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Materials Research Bulletin

journal homepage: www.elsevier.com/locate/matresbu

Anodic electrochemical performances of MgCo2O4 synthesized by

oxalate decomposition method and electrospinning technique for
Li-ion battery application
Devendrasinh Darbara,b,c, M.V. Reddyc,d,* , S. Sundarrajanb , R. Pattabiramana ,
S. Ramakrishnab , B.V.R. Chowdaric
a
School of Mechanical and Building Science, Vellore Institute of Technology (VIT), Vellore 632014, Tamil Nadu, India
b
Department of Mechanical Engineering, National University of Singapore, 117576, Singapore
c
Department of Physics, National University of Singapore, 117542, Singapore
d
Department of Materials Science and Engineering, National University of Singapore, 117546, Singapore

A R T I C L E I N F O A B S T R A C T

Article history: Magnesium cobalt oxide, MgCo2O4 was synthesized by oxalate decomposition method and electrospinning
Received 14 July 2015 technique. The electrochemical performances, structures, phase formation and morphology of MgCo2O4
Received in revised form 8 September 2015 synthesized by both the methods are compared. Scanning electron microscope (SEM) studies show spherical
Accepted 20 September 2015
and fiber type morphology, respectively for the oxalate decomposition and electrospinning method.
Available online 25 September 2015
The electrospun nanofibers of MgCo2O4 calcined at 650
C, showed a very good reversible capacity of
795 mAh g1 after 50 cycles when compared to bulk material capacity of 227 mAh g1 at current rate of
Keywords:
60 mA g1. MgCo2O4 nanofiber showed a reversible capacity of 411 mAh g1 (at cycle) at current density
MgCo2O4
Oxalate decomposition
of 240 mA g1. Improved performance was due to improved conductivity of MgO, which may act as buffer
Electrospinning layer leading to improved cycling stability. The cyclic voltammetry studies at scan rate of 0.058 mV/s show
Anode main cathodic at around 1.0 V and anodic peaks at 2.1 V vs. Li.
Electrochemical properties ã 2015 Elsevier Ltd. All rights reserved.
Nanostructures

1. Introduction between 600–900 mAh g1 [4,5]. It was recently reported in a

Lithium ion batteries (LIBs) are widely used in storage
applications, portable electronics, hybrid electric vehicles, and
solar cell application, due to its light weight, high energy density,
less space requirement and low temperature capability [1,2].
Graphite is being used as the anode material commercially, which
has a theoretical capacity of 372 mAh g1 [3]. Metal oxides have
been studied as next-generation anode materials. In recent years,
researchers have focused their attention on studying alternatives
to metal oxides, which show good capacity, rate capability and
longevity. The anode material can function via four different
mechanisms Intercalation–de-intercalation mechanism, Elements
or metal can form alloys with Li metal, Conversion reaction and
conversion and alloying reaction with Li [4]. Spinel Co3O4 in the
form of particles, nanosheets, nanowires, nanofibers and thin films
were investigated and they showed reversible capacities in
* Corresponding author at: Department of Physics, National University of
Singapore, 117542, Singapore. Tel.: +65 65162607; fax: +65 67776126.
E-mail addresses: phymvvr@nus.edu.sg, msemvvr@nus.edu.sg,
reddymvvr@gmail.com (M.V. Reddy).
few oxide systems, wherein one Co atom is replaced partially by
other ternary metal ions such as MCo2O4 (M = Zn, Mn, Cu, Fe, Ni,
Mg) [6–12]. A reversible capacity of 850–1000 mAh g1 for
ZnCo2O4 [6], 900 mAh g1 for MnCo2O4 [13], 745 mAh g1 for
CuCo2O4 [11] 827 mAh g1 for FeCo2O4 [10], and 850–900 mAh g1
for NiCo2O4 [12,14].
The morphologies such as nanofibers, nanowires, nanopar-
ticles, nanotubes, nanosheets, nanorods and submicron/micron
sized particles of the anode material plays an important role in
electrochemical performances [4,15]. In general, nanostructured
materials showed high energy densities and better cycling stability
for lithium ion batteries (LIBs). The nanostructures electrodes will
also increase the active site of Li+ ion insertion or extraction.
Moreover, anodes made of transition metal oxide in LIBs shows
high reversible capacity, longevity or retention rate and stability.
Therefore, the nanostructures of transition metal oxides as anodes
in LIBs are being studied as a promising material [4].
MCo2O4 (M = Mg, Ni, Zn) was prepared by oxalate decomposi-
tion method [16]. Li-storage properties of MgCo2O4 prepared using
oxalate decomposition method using cobalt hydroxide and
magnesium acetate at 350
C and it showed a reversible capacity
of 102 mAh g1 after 50 cycles [6]. Whereas hydrothermal

http://dx.doi.org/10.1016/j.materresbull.2015.09.025
0025-5408/ ã 2015 Elsevier Ltd. All rights reserved.
370 D. Darbar et al. / Materials Research Bulletin 73 (2016) 369–376

synthesized MgCo2O4 followed by calcination at 400
C shows

reversible capacity below 200 mAh g1 after 50 cycles[17]. Very
recently MgCo2O4 was prepared by molten salt method for
supercapacitor application [18].
In this study, in order to understand the effect of matrix element
and morphology, MgCo2O4 was synthesized by oxalate decompo-
sition method and electrospinning technique. Although other
spinel oxides such as Co3O4 [19] and MnCo2O4 (but used for
glucose sensor) [20] were reported using electrospinning techni-
ques. Other reports on metal oxide materials prepared using
electrospinning technique are: NiCo2O4 [21], ZnCo2O4 [22],
NiFe2O4 [23], Fe3O4/C [24], Fe2O3 [25–27] Li4Ti5O12 [28], TiO2
[29], bare and Ta-doped Nb2O5 [30,31] and other materials [32]
were synthesized using electrospinning technique. Up to our
knowledge, we report for the first time preparation of MgCo2O4
nanofibers and studied its electrochemical properties.
Fig. 1. XRD pattern of the MgCo2O4 after thermal treatment (a) 350
C, (b) 550
C
and (c) 750
C prepared using oxlate decomposition (O.D.).
2. Experimental
blade technique [33]. The coated copper foil was dried in an air
2.1. Materials synthesis oven at 80
C for 12 h to evaporate NMP. The coated copper foil was
then pressed between a twin-roller to make coated surface
MgCo2O4 was synthesized by oxalate decomposition method by uniform. The foil was then cut into circular discs of 16 mm
mixing 2 moles of cobalt acetate (10.486 g) and one mole of diameter which formed the electrodes. Before fabrication of cell
magnesium acetate (4.514 g). The above compounds were dis- the cutted electrods were weighed and kept for drying in vacuum
solved in nitric acid which resulted in the formation of their air oven for 8 h. Then it was transferred to argon filled glove box
respective nitrates. The pH value of the solution was adjusted in the (MBraun, Germany). The coin cell of size 2016 (20 mm diameter
range, 6.5–7.0 by adding the ammonia solution. Then 2 wt. (or and 1.6 mm thick) was fabricated in the glove box using Li metal
mole)% of oxalic acid was poured into the nitrate solution to get the foil (Hohsen Corp., Japan) as counter electrode, 1 M LiPF6 in
pink coloured precipitate. The precipitate was filtered and washed ethylene carbonate (EC) and dimethyl carbonate (DMC) (1:1 by
with de-ionized water and dried at 100
C for 12 h [15]. The fine volume, Merck Selectipur LP40) was used as the electrolyte and
powder was heated at 350
C, 550
C and 750
C for 3 h in air and Celguard 2502 was used as separator. The cell was kept for rest for
cooled at room temperature. at least 12 h to stabilize the open circuit voltage. Then the
For electrospinning, 0.6346 g of magnesium acetate and fabricated batteries were subjected at room temperature to cyclic
1.4743 g of cobalt acetate were added slowly into Poly(vinyl- voltammetry (CV) and galvanostatic cycling (GC) testing using
pyrrolidone) (PVP)-N,N-dimethylformamide (DMF) solution (MacPile II, Biologic, France) and, Bitrode battery tester (model
(18.0 wt%, 20.0 mL). The electrospinning solution which is dark SCN, Bitrode, USA) respectively [34]. The cycling tests were carried
purple in colour was obtained under vigorous magnetic stirring for out in the voltage range of 0.005–3.0 V vs. Li, at current densities of
12 h at room temperature until it was completely dissolved. As PVP 60 mA g1 and 240 mAg 1and CV was carried at the potential
chains are highly flexible and non-toxic which makes easier for window of 0.005–3.0 V at a scan rate of 58 mV s1 [35].
electrospinning and also when the temperature is above the glass
transition temperature (Tg) of PVP, which facilitate the decompo- 3. Results and discussion
sition of oxalate compound. The obtained solution was used for
electrospinning. The electrospinning set up required a high voltage 3.1. Structure and morphology
power supply, a collector and electromechanical pump. The
solution was loaded into a 10 mL syringe. A positive voltage of Fig. 1 shows the XRD pattern along with the miller indices of
12 kV was applied between the needle tip and grounded MgCo2O4 synthesized by oxalate decomposition (O. D.) method at
aluminium collector of distance of 14 cm. The flow rate of the three different temperatures (350
C, 550
C, and 750
C).
solution was kept at 1 mL h1. Then, the prepared solution was
loaded into a syringe for electrospinning. The obtained composite
nanofibers were calcined in air atmosphere at 400
C, 650
C and
750
C for 3 h at a heating rate of 0.5
C min1 to decompose the
polymer into MgCo2O4 nanofibers.
To understand the crystallinity of the samples, X-ray diffraction
(XRD) patterns of the samples were recorded in 2u range of 20–80

using Cu Ka as X-ray source (l = 1.54 Å), Philips X’PERT MPD unit,
PANalytical). The morphology of the samples was analyzed using
Scanning Electron Microscopy (SEM; JEOL JSM-6390) and trans-
mission electron microscopy (JEOL JEM-2010F field emission
electron microscope). The XRD patterns were analysed using
TOPAS (v2.1) software. Micrometrics (Tristar USA) instrument was
used to measure Brunauer–Emmett–Teller (BET) surface area.
The working electrodes were made using a mixture of active
material, Super P carbon and binder (Kynar 2801) in the weight
ratios of 70%:15%:15%. The slurry was prepared in the above ratio
using N-methyl-2-pyrrolidone (NMP) as a solvent and it was Fig. 2. XRD pattern of MgCo2O4 electrospunned nanofibers after calcinated at
coated onto an etched copper foil (thickness10 mm) by doctor temperature (a) 400
C, (b) 650
C and (c) 750
C.
 D. Darbar et al. / Materials Research Bulletin 73 (2016) 369–376 371

Electrospun (E.S.) MgCo2O4 nanofibers calcined at 400
C, 650
C
and 750
C are shown in Fig. 2. All the diffraction peaks of Fig. 1a
and b can be well indexed to the standard cubic MgCo2O4 structure
with Fd-3m (227) space group JCPDS 81-0667. No other additional
phase or impurities can be observed at temperatures of 350
C and
550
C, whereas at 750
C two peaks at 2u = 42.81
and 62.04
,
which corresponds to (hkl) lines (2 0 0) and (2 2 0) reflections
respectively are observed in Fig. 1c which are due to MgO phase
(JCPDS data file no. 71-2179). The diffraction peaks at 2u = 31.31
,
36.79
, 38.67
, 44.79
, 55.61
, 59.29
, 65.21
, 77.19
and 78.29
are
corresponds to (2 2 0), (3 11), (2 2 2), (4 0 0), (4 2 2), (5 11), (4 4 0),
(5 3 3) hkl lines of spinel oxides. The refined lattice parameter

Fig. 3. SEM images of (a,b) as-spun PVP/Mg (cobalt acetate composite nanofibers. (c,d,e) nanofibers after calcination at temperature 650
C for 3 h. in air and (f,g,h) O.D.-
MgCo2O4 after heat treatment at 350
C, 550
C and 750
C.
372 D. Darbar et al. / Materials Research Bulletin 73 (2016) 369–376
Fig. 4. SAED pattern of electrospun MgCo2O4 before and after cycle (a,c) and HRTEM of electrospun MgCo2O4 before and after cycle (b,d).
values for O.D.—350
C are a = 8.119(3) Å; O.D.—550
C are a = 8.103
(4) Å and O.D.—750
C show 85 wt.% MgCo2O4 (a = 8.022 (3) Å) and
15 wt.% MgO (a = 4.224 Å), we note due to line broadening a slight
difference in lattice parameter values are noted. MgCo2O4 nano-
fibers after calcination at 400
C show a major phase of 60 wt.%
MgO and 40 wt.% MgCo2O4 phases Fig. 2a. Further calcination to
650
C, showed mixture of MgO and MgCo2O4 phases are shown in
Fig. 2b. Rietveld refinement studies show 20 wt.% MgO (a = 4.224 Å)
and 80 wt.% MgCo2O4 (a = 8.084 Å). We note our observed lattice
parameter value of ES-MgCo2O4 was lower than the OD prepara-
tion method and the values are close to literature report [18]. The
diffraction peaks agreed with reported value of JCPDS File no 81-
0667 JCPDS File no 71.2179 (MgO). The XRD pattern for the
nanofibers calcined at temperature 750
C are shown in Fig. 2c. As
the preparation temperature was increased, the intensity of MgO is
also increasing. Hence, the electrochemical performance and
morphology studies were carried out only for MgCo2O4 nanofibers
calcined at temperature of 650
C.
The morphology of as-spun PVP/Mg acetate/cobalt acetate
composite nanofibres and MgCo2O4 nanofibers obtained at 650
C
are shown in Fig. 3. From Fig. 3a and b, it can be seen that the as-
spun nanofibers have a web like type morphology with a smooth
surface and a uniform diameter of 150–220 nm. Fig. 3c, d and e
shows that the morphology of nanofibrous form is maintained for
the calcined fibers, the reduction in nanofiber diameter was
observed which is due to removal of PVP, and decomposition of
magnesium and cobalt acetate precursors into oxide form. The
nanofibers are uneven and fiber morphology is maintained. The
average diameter of the fibers is 120–160 nm. Similar shrinkage or
difference in the diameter was noted in literature [36]. The SEM
micrographs of synthesized materials by oxalate decomposition
method at temperatures of 350
C, 550
C and 750
C are shown in
Fig. 3f, g, and h respectively. The pure phase of MgCo2O4 is formed
at 350
C with the large lump formation, which is formed from the
aggregation of sub-micron particles. In the case of heat treated
MgCo2O4 sample at 550
C, more number of smaller lump
formation and aggregation of few particles were noticed. Whereas
at higher temperature (at 750
C), there is no lump formation
occurs, but rather nanoparticles agglomeration occur. The mea-
sured BET surface area of MgCo2O4 prepared by oxalate combus-
tion method prepared at 350, 550 and 750
C are 22.47, 4.8 and
4.4 m2 g1 respectively. Whereas electrospuuned MgCo2O4—650
C
show a surface area of 19.2 m2 g1 which is higher than 550 and
750
C prepared oxalate decomposition method. Similar decrease
of surface area with sintering temperature was noted with other
nanostructures [30,37]. Further morphology and microstructure of
electrospun MgCo2O4 nanofibers was investigated by high-
resolution transmission electron microscopy (HRTEM) and select-
ed area electron diffraction (SAED) analysis. The TEM images of
electrospun MgCo2O4 nanofibers were taken before and after
cycling at the charged state are shown in Fig. 4. The SAED pattern of
MgCo2O4 nanofibers before cycling is shown in Fig. 4a, which
shows the intense reflection spots of cubic structure MgCo2O4,
which agreed well with XRD pattern with the reported value in
JCPDS File no 81-0667 and relevant (hkl) value is marked. The
lattice fringes of E.S. MgCo2O4. Here, the lattice fringes with a
spacing of 2.42 Å and 2.85 Å is assigned to interplanar spacing
between the planes of E.S. MgCo2O4 can be clearly observed in the
 D. Darbar et al. / Materials Research Bulletin 73 (2016) 369–376
Fig. 5. The galvanostatic charge–discharge curves of oxalate decomposition (O.D.)
synthesized MgCo2O4 calcined at 350
C, 550
C, 750
C and electrospun (E.S.)
MgCo2O4 nanofibers calcine at 650
C electrode at current density of 60 mA g1 (a)
1st cycle and (b) 2nd cycle. Voltage range, 0.005–3.0 V vs. Li.
HRTEM image, which were indexed to (3 11) and (2 2 0) hkl lines.
Similarly, the SAED patterns of cycled MgCo2O4 electrodes (Fig. 4c)
in the charged state shows reformation of MgCo2O4 phase even
after 50 cycles, disorder in the diffraction rings which is due to
amorphous/nano crystalline in nature. Also the HRTEM image of
MgCo2O4 after 50 cycles shows the lattice fringes of spacing of
2.89 Å and 2.48 Å, which corresponds to (hkl) lines of MgCo2O4
(2 2 0) and (3 11) respectively.
3.2. Electrochemical properties
Fig. 5a shows the first cycle of charge and discharge curves of
MgCo2O4 synthesized by Oxalate decomposition (O.D.) method for
temperatures of 350
C, 550
C and 750
C and electrospun (E.S.)
MgCo2O4 nanofibers calcinated at 650
C of current density of
60 mA g1 in the range of 0.005–3.0 V and battery tests were
conducted at room temperature. As shown in Fig. 5a, discharge
cycling profiles of MgCo2O4 show the voltage drop drastically
followed by small plateau at 1.1 V (O.D.—350
C), 1.2 V (O.D.—
550
C), 1.15 V (O.D.—750
C) and 1.15 V (E.S.—650
C) which can be
assigned to co-existence of Li-intercalated phase, LixMgCo2O4.
Observed capacity in this plateau potential region corresponds to
140 mAh g1, 102 mAh g1, 70 mAh g1 and 75 mAh g1 respective-
ly. Further, reaction with Li results in larger plateau potential at
0.85 V (O.D.—350
C), 0.86 V (O.D.—550
C), 1.0 V (O.D.—750
C) and
0.95 V (E.S-nanofibers 650
C), due to conversion reaction,
structure destruction and solid electrolyte interphase (SEI), which
result into higher number of Li consumed per mole of MgCo2O4 and
obtainable capacity in this plateau region corresponds to 897 mAh
373
g1, 1078 mAh g1, 590 mAh g1 and 650 mAh g1 respectively.
After the plateau region, the voltage capacity curves takes a sloping
profile up to the end of discharge reaction and consumes additional
moles of Li is due to solid electrolyte interphase (SEI) [38]. Thus the
total first discharge capacity, MgCo2O4 synthesized by O.D. method
at a temperatures of 350
C, 550
C, and 750
C are 1829 mAh g1,
1960 mAh g1 and 1272 mAh g1 respectively whereas electrospun
MgCo2O4 nanofibers calcined at 650
C shows the specific capacity
of 1576 mAh g1. The one which is in pure phase MgCo2O4 shows
high value for initial discharge capacity in the order of O.D.—
550
C > O.D.—350
C > E.S.—650
C > O.D.—750
C.
The first charge profiles of MgCo2O4 (O.D.—350
C), (O.D.—
550
C), (O.D—750
C), (E.S—nanofibres at 650
C) (Fig. 5a) show
continuous increase of voltage up to 1.84 V, 1.86 V, 1.93 V and 1.95 V
vs. Li, respectively. Significant polarization happens beyond the
plateau region. The first charge capacity value were 981 mAh g1
(O.D.—350
C), 1287 mAh g1 (O.D.—550
C), 537 mAh g1 (O.D.—
750
C) and 924 mAh g1 (E.S.—nanofibers at 650
C). The differ-
ence between the discharge and charge capacities value shows the
irreversible capacity loss (ICL) in the first cycle, which corresponds
to 46% (O.D.—350
C), 34% (O.D.—550
C), 57% (O.D.—750
C) and
40% (E.S.—nanofibers at 650
C). The electrospun MgCo2O4 nano-
fibers calcinated at 650
C also show a ICL value is less
comparatively to O.D.—MgCo2O4 at 750
C. This difference in ICL
values was arises due to the differences in preparation method,
surface area values and pore volumes for example: E.S.-MgCo2O4
showed a 0.049 cm3 g1 and O.D.-MgCo2O4 showed 0.016 cm3 g1
and also differences in the morphology of samples. As can been
seen from Fig. 5b, the second discharge cycle is differ from the first
discharge cycle, which is due to the fact that main structural
modification occurs only at 1st cycle. It can be concluded that the
electrochemical performances of ES-MgCo2O4 at 650
C shows
good performance because of nanocrystalline, high porosity and its
fibrous morphology.
The capacity vs. cycle number graph is shown in Fig. 6a of
MgCo2O4 synthesized by O.D. method at a temperatures (350
C,
550
C and 750
C) and E.S.—650
C nanofibers at a current
densities 60 mA g1. It is observed that for O.D. MgCo2O4—
350
C, there is fading and it is relatively stable after 20 cycles,
but at very low specific capacity of around 227 mAh g1, whereas O.
D.-MgCo2O4—550
C shows fading continuously and has a specific
capacity of around 225 mAh g1. The MgCo2O4 nanofibers also
show fading for few cycles and then it started showing increased
specific capacity and the specific capacity becomes relatively stable
after 25 cycles. The gradual increase in reversible capacities during
cycling may result from the formation of a polymeric surface layer
on the active material and other reasons like more active
participation during electrochemical cycling. The polymer layer
builds-up on the surface and within the pores of the porous active
material, and thus increases the Li-storage, similar trend was noted
in other anode materials [4,39–42]. Fig. 6b shows the graph of
capacity vs. cycle number of at O.D. 750
C and MgCo2O4
electrospun nanofibers (ES-650
C) at higher current density of
240 mA g1 for 50 cycles. As both materials show comparative
trends in the capacity values. Both materials show fading for first
few cycles and after that the capacity increases. Here MgO acts as a
buffer layer to prevent agglomeration of metal nanoparticles and
improved conductivity [42]. But the capacity of MgCo2O4 nano-
fibers was observed to be higher 411 mAh g1 when compared to O.
D.-MgCo2O4 which has about 288 mAh g1. Due to nanofibrous
structure, the porosity for feasibility of Li+ ions diffusion and
electron transfer, unique continuous fiber morphology is main-
tained even after calcination at higher temperature. The SEM
images of nanofibers show with numerous pores which result into
highly porous structures which show good cyclability and good
rate capability.
374 D. Darbar et al. / Materials Research Bulletin 73 (2016) 369–376

Fig. 6. (a) The cycle number vs. capacity graph of of oxalate decomposition (O.D.)
synthesized MgCo2O4 350
C, 550
C and electrospun (E.S.) MgCo2O4 nanofiber
heated at 650
C at current density of 60 mA g1 and (b) The cycle number vs.
capacity graph of spinel Cobaltite MgCo2O4 heated 750
C and MgCo2O4 nanofibers
heated at 650
C at current density of 240 mA g1.

Further electrochemical measurement of the composite

MgCo2O4 prepared by O.D. and E.S. method was explored by cyclic
voltammetry (CV) with lithium as a reference and counter electrode.
Fig. 7a–c shows the CV curves of O.D.—MgCo2O4 prepared at 350
C,
550
C, 750
C and ES MgCo2O4 nanofibers prepared at 650
C is
shown in Fig. 7d. As shown in Fig. 7a during first cathodic scan, a two
broad cathodic peak at 0.48 V, and 2.1 V, which can determine the
reduction of MgCo2O4 to MgO and Co accompanied by reduction of
solvent in the organic electrolyte to form SEI layer, a minor peak at
2.1 V is due intercalation reaction LixMgCo2O4. During anodic scan
two broad peaks are located at 1.5 V and 2.2 V, which can be
attributed to the oxidation of Mg and Co metal nanoparticles to the
respective metal oxide. As the SEI layer is formed in the first cathodic
scan in the second cycle, the two cathodic peaks gradually move to
0.7 V and 1.06 respectively and two anodic scan moves to 1.49 and
2.12 respectively, which is different from the reduction peak in the
first discharge cycle, which is due different stages of reduction
process, due to its low temperature preparation and high surface area
[4]. After further cycling, cathodic peaks overlap on each other which
show good reversibility. In Fig. 7b during the cathodic scan, O.D.
MgCo2O4 heated at 550
C a broad cathodic peak at 0.78 V that
determined the reduction of MgCo2O4 to MgO and Co. Similarly, Fig. 7. The cyclic voltammetry curves of oxalate decomposition method- MgCo2O4
Fig. 7c shows the discharge cycles of O.D. MgCo2O4 heated at 750
C (a) 350
C, (b) 550
C (c) 750
C and (d) MgCo2O4 nanofibers heated at 650
C
electrode at a scan rate of 58 mV s1.
and three broad cathodic peaks at 0.77 V, 1.09, 1.46 and main anodic
peaks at 2.05 V, a minor additional peaks in the CV are due to the
impurities formation in the material. Fig. 7d shows the cathodic scan due to reversible oxidation of Co and MgO to respective metal oxides.
of MgCo2O4 nanofibers, a broad cathodic peak at 0.9 V due to Form the second cycle onwards the CV curves are almost the same
reduction of MgCo2O4 to MgO and Co. One broad anodic peak located when compared to the CV curves of MgCo2O4 by oxalate method,
at 2.1 V is due to oxidation of Co nanoparticles to the respective showing the good electrochemical reversibility. The main peak
oxides. However in the subsequent cycles the cathodic peak shifts to cathodic and anodic peak potentials other spinel oxides
1.0 V due to formation cycle, whereas anodic peaks located at 2.25 V [4,6,9,10,43,44] and broad peaks (Fig. 7a) in the CV is due to
 D. Darbar et al. / Materials Research Bulletin 73 (2016) 369–376
differences in the crystallinity of MgCo2O4 material. From the
observed galvanostatic cycling, cyclic voltammetry and ex-situ TEM
the following reaction can be interpreted.
MgCo2O4 + x Li + xe ! Li0.5 MgCo2O4 ! Li0.5MgCo2O4 + 5.5 Li+
+ 0.5 e ! MgO + 2Co + 3Li2O (discharge cycle) (1)
MgO + 2Co + 3Li2O ! MgCo2O4 or MgOCo3O4 (charge cycle) (2)
4. Conclusion
In summary, MgCo2O4 nanofibers were synthesized by electro-
spinning technique followed by calcination at 650
C. The MgCo2O4
nanofibers as anode material in lithium batteries application is
being discussed. The results are compared with the MgCo2O4
synthesized by oxalate decomposition method at three different
temperatures of 350
C, 550
C and 750
C. The MgCo2O4 nanofibers
show good stability, good cyclic performances at low and higher
rate. The superior lithium storage properties for MgCo2O4 nano-
fibers are due to nanocrystalline fiber type morphology and
improved surface area. In addition, MgO formation, acts like a
buffer layer to prevent the agglomeration of metal nanoparticles
and improved conductivity.
Acknowledgements
Mr. Devendrasinh thank to centre for nanofibers and nano-
technology and Advanced Batteries Lab at National University of
Singapore for providing facilities and VIT for partial support. Dr.
Reddy to National Research Foundation, Prime Minister’s Office,
Singapore under its Competitive Research Programme (CRP Award
No. NRF-CRP 10-2012-6) for research support.
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