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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
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
Electrospun (E.S.) MgCo2O4 nanofibers calcined at 400 C, 650 C which corresponds to (hkl) lines (2 0 0) and (2 2 0) reflections
and 750 C are shown in Fig. 2. All the diffraction peaks of Fig. 1a respectively are observed in Fig. 1c which are due to MgO phase
and b can be well indexed to the standard cubic MgCo2O4 structure (JCPDS data file no. 71-2179). The diffraction peaks at 2u = 31.31,
with Fd-3m (227) space group JCPDS 81-0667. No other additional 36.79 , 38.67, 44.79 , 55.61, 59.29 , 65.21, 77.19 and 78.29 are
phase or impurities can be observed at temperatures of 350 C and corresponds to (2 2 0), (3 11), (2 2 2), (4 0 0), (4 2 2), (5 11), (4 4 0),
550 C, whereas at 750 C two peaks at 2u = 42.81 and 62.04 , (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 difference in the diameter was noted in literature [36]. The SEM
(4) Å and O.D.—750 C show 85 wt.% MgCo2O4 (a = 8.022 (3) Å) and micrographs of synthesized materials by oxalate decomposition
15 wt.% MgO (a = 4.224 Å), we note due to line broadening a slight method at temperatures of 350 C, 550 C and 750 C are shown in
difference in lattice parameter values are noted. MgCo2O4 nano- Fig. 3f, g, and h respectively. The pure phase of MgCo2O4 is formed
fibers after calcination at 400 C show a major phase of 60 wt.% at 350 C with the large lump formation, which is formed from the
MgO and 40 wt.% MgCo2O4 phases Fig. 2a. Further calcination to aggregation of sub-micron particles. In the case of heat treated
650 C, showed mixture of MgO and MgCo2O4 phases are shown in MgCo2O4 sample at 550 C, more number of smaller lump
Fig. 2b. Rietveld refinement studies show 20 wt.% MgO (a = 4.224 Å) formation and aggregation of few particles were noticed. Whereas
and 80 wt.% MgCo2O4 (a = 8.084 Å). We note our observed lattice at higher temperature (at 750 C), there is no lump formation
parameter value of ES-MgCo2O4 was lower than the OD prepara- occurs, but rather nanoparticles agglomeration occur. The mea-
tion method and the values are close to literature report [18]. The sured BET surface area of MgCo2O4 prepared by oxalate combus-
diffraction peaks agreed with reported value of JCPDS File no 81- tion method prepared at 350, 550 and 750 C are 22.47, 4.8 and
0667 JCPDS File no 71.2179 (MgO). The XRD pattern for the 4.4 m2 g1 respectively. Whereas electrospuuned MgCo2O4—650 C
nanofibers calcined at temperature 750 C are shown in Fig. 2c. As show a surface area of 19.2 m2 g1 which is higher than 550 and
the preparation temperature was increased, the intensity of MgO is 750 C prepared oxalate decomposition method. Similar decrease
also increasing. Hence, the electrochemical performance and of surface area with sintering temperature was noted with other
morphology studies were carried out only for MgCo2O4 nanofibers nanostructures [30,37]. Further morphology and microstructure of
calcined at temperature of 650 C. electrospun MgCo2O4 nanofibers was investigated by high-
The morphology of as-spun PVP/Mg acetate/cobalt acetate resolution transmission electron microscopy (HRTEM) and select-
composite nanofibres and MgCo2O4 nanofibers obtained at 650 C ed area electron diffraction (SAED) analysis. The TEM images of
are shown in Fig. 3. From Fig. 3a and b, it can be seen that the as- electrospun MgCo2O4 nanofibers were taken before and after
spun nanofibers have a web like type morphology with a smooth cycling at the charged state are shown in Fig. 4. The SAED pattern of
surface and a uniform diameter of 150–220 nm. Fig. 3c, d and e MgCo2O4 nanofibers before cycling is shown in Fig. 4a, which
shows that the morphology of nanofibrous form is maintained for shows the intense reflection spots of cubic structure MgCo2O4,
the calcined fibers, the reduction in nanofiber diameter was which agreed well with XRD pattern with the reported value in
observed which is due to removal of PVP, and decomposition of JCPDS File no 81-0667 and relevant (hkl) value is marked. The
magnesium and cobalt acetate precursors into oxide form. The lattice fringes of E.S. MgCo2O4. Here, the lattice fringes with a
nanofibers are uneven and fiber morphology is maintained. The spacing of 2.42 Å and 2.85 Å is assigned to interplanar spacing
average diameter of the fibers is 120–160 nm. Similar shrinkage or between the planes of E.S. MgCo2O4 can be clearly observed in the
D. Darbar et al. / Materials Research Bulletin 73 (2016) 369–376 373
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
Fig. 5. The galvanostatic charge–discharge curves of oxalate decomposition (O.D.)
good performance because of nanocrystalline, high porosity and its
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)
fibrous morphology.
1st cycle and (b) 2nd cycle. Voltage range, 0.005–3.0 V vs. Li. 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
HRTEM image, which were indexed to (3 11) and (2 2 0) hkl lines. densities 60 mA g1. It is observed that for O.D. MgCo2O4—
Similarly, the SAED patterns of cycled MgCo2O4 electrodes (Fig. 4c) 350 C, there is fading and it is relatively stable after 20 cycles,
in the charged state shows reformation of MgCo2O4 phase even but at very low specific capacity of around 227 mAh g1, whereas O.
after 50 cycles, disorder in the diffraction rings which is due to D.-MgCo2O4—550 C shows fading continuously and has a specific
amorphous/nano crystalline in nature. Also the HRTEM image of capacity of around 225 mAh g1. The MgCo2O4 nanofibers also
MgCo2O4 after 50 cycles shows the lattice fringes of spacing of show fading for few cycles and then it started showing increased
2.89 Å and 2.48 Å, which corresponds to (hkl) lines of MgCo2O4 specific capacity and the specific capacity becomes relatively stable
(2 2 0) and (3 11) respectively. after 25 cycles. The gradual increase in reversible capacities during
cycling may result from the formation of a polymeric surface layer
3.2. Electrochemical properties on the active material and other reasons like more active
participation during electrochemical cycling. The polymer layer
Fig. 5a shows the first cycle of charge and discharge curves of builds-up on the surface and within the pores of the porous active
MgCo2O4 synthesized by Oxalate decomposition (O.D.) method for material, and thus increases the Li-storage, similar trend was noted
temperatures of 350 C, 550 C and 750 C and electrospun (E.S.) in other anode materials [4,39–42]. Fig. 6b shows the graph of
MgCo2O4 nanofibers calcinated at 650 C of current density of capacity vs. cycle number of at O.D. 750 C and MgCo2O4
60 mA g1 in the range of 0.005–3.0 V and battery tests were electrospun nanofibers (ES-650 C) at higher current density of
conducted at room temperature. As shown in Fig. 5a, discharge 240 mA g1 for 50 cycles. As both materials show comparative
cycling profiles of MgCo2O4 show the voltage drop drastically trends in the capacity values. Both materials show fading for first
followed by small plateau at 1.1 V (O.D.—350 C), 1.2 V (O.D.— few cycles and after that the capacity increases. Here MgO acts as a
550 C), 1.15 V (O.D.—750 C) and 1.15 V (E.S.—650 C) which can be buffer layer to prevent agglomeration of metal nanoparticles and
assigned to co-existence of Li-intercalated phase, LixMgCo2O4. improved conductivity [42]. But the capacity of MgCo2O4 nano-
Observed capacity in this plateau potential region corresponds to fibers was observed to be higher 411 mAh g1 when compared to O.
140 mAh g1, 102 mAh g1, 70 mAh g1 and 75 mAh g1 respective- D.-MgCo2O4 which has about 288 mAh g1. Due to nanofibrous
ly. Further, reaction with Li results in larger plateau potential at structure, the porosity for feasibility of Li+ ions diffusion and
0.85 V (O.D.—350 C), 0.86 V (O.D.—550 C), 1.0 V (O.D.—750 C) and electron transfer, unique continuous fiber morphology is main-
0.95 V (E.S-nanofibers 650 C), due to conversion reaction, tained even after calcination at higher temperature. The SEM
structure destruction and solid electrolyte interphase (SEI), which images of nanofibers show with numerous pores which result into
result into higher number of Li consumed per mole of MgCo2O4 and highly porous structures which show good cyclability and good
obtainable capacity in this plateau region corresponds to 897 mAh 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.
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