DOI: 10.1002/slct.

201702197 Full Papers

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2 z Electro, Physical & Theoretical Chemistry
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Nano Co3O4 as Anode Material for Li–Ion and Na-Ion
6 Batteries: An Insight into Surface Morphology
7
8 Subalakshmi Palani[b] and Sivashanmugam Arumugam*[a]
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10
11 Co3O4 is regarded as a competent anode material for lithium after 40 cycles as Li-ion battery anode and exhibited stable
12 and sodium ion batteries having high theoretical capacity of discharge behaviour up to 130 cycles with high rate capability.
13 890 mAh g-1 obtained through metal displacement reaction Nano Co3O4 in Na-ion configuration delivered discharge
14 with Li or Na. Nano Co3O4 consisting of 20–30 nm-sized capacity of 101 mAh g-1 at 0.1 C rate even after 30 cycles. At
15 particles was synthesized through a simple precipitation higher current rates Co3O4 electrodes exhibited severe capacity
16 method and characterized through X-ray diffraction, Fourier- fading due to the huge volume change occurred during
17 transform infrared spectroscopy, scanning electron microscopy, sodiation / desodiation. Ex-situ SEM and elemental analyses
18 Transmission electron microscopy and X-ray photoelectron evidenced that disintegration of electrode structure resulting
19 spectroscopy. Electrochemical evaluation of the nano Co3O4 as from volume change and continuous decomposition of electro-
20 anode material for Li-ion and Na-ion batteries was performed lyte were responsible for the poor electrochemical performance
21 through cyclic voltammetry, electrochemical impedance spec- of Co3O4 with Na + ions while in Li-ion configuration nano
22 troscopy and charge-discharge cycling studies. Nano Co3O4 Co3O4 outshined in cycling performance.
23 delivered high discharge capacity of 423 mAh g-1 at 0.1 C even
24
25
lithiation / delithiation or sodiation / desodiation results in
26 1. Introduction
pulverization of electrode microstructure and affects extensive
27
Today, humans are more dependent on electronics for their day charge-discharge cycling performance of the cells with severe
28
to day activities, giving rise to the need for a compact energy capacity decay. Generally, transition metal oxides are poor
29
system like Li-ion batteries (LIBs) to power these electronic electronic conductors leading to low rate capability.[2,4] Many
30
devices.[1] As lithium resources are getting depleted the search researchers intended to improve the electrochemical perform-
31
for an alternative is inevitable. Sodium ion batteries (NIBs) have ance of conversion anodes for LIBs and NIBs by increasing the
32
gained attention for large scale energy storage applications conductivity of TMOs and providing space for accommodating
33
such as smart grids due to their low cost and natural volume expansion during sodiation / desodiation through
34
abundance.[2–4] The chemistry of Li and Na are distinctively different methods. Carbon coating was found to be one of the
35
similar and the working principle of NIBs resemble with LIBs. effective ways to improve the performance of TMOs by
36
There are three types of anode reactions occur in NIBs namely increasing the conductivity of active material and also accom-
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insertion, alloying and conversion as in LIBs. However, more modating large volume expansion.[9–15] Nano structured active
38
positive ionization potential and larger ionic radius of Na + (Na + materials with high surface to volume ratio enhanced the
39
: 1.02 Å vs Li + : 0.76 Å) limit the choice of electrode materials for conductivity of TMOs.[16–20] Reducing the particle size was also
40
Na-ion batteries.[1,5–7] Amid all anode materials, transition metal an efficient methodology to improve the electrochemical
41
oxides (TMOs) are highly endorsed, due to their attractive performance by shortening the diffusion path length and to
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theoretical specific capacities varying from 600 to 1100 mAh g- create larger contact area between the electrode-electrolyte
43 1 [8]
. TMOs undergo conversion type reactions involving multi interface.[21,22] Co3O4 is considered as a suitable anode material
44
electron transfer and yield high specific capacity making them for LIBs and NIBs with high theoretical capacity of about 890
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suitable for high energy applications. However, large volume mAh g-1 via multi electron transfer reaction.[23–27] However, the
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expansion accompanied with the conversion reaction during large volume expansion associated with the cycling reaction
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limits its commercial viability. Many researchers attempted to
48
overcome the hindrance of volume expansion by modified
49 [a] Prof. Dr. Sivashanmugam Arumugam
methods. Shale like Co3O4 had been synthesized from Co-
50 Electrochemical Power Sources Division, CSIR-Central Electrochemical
Research Institute, Karaikudi – 630 006, Tamil Nadu, India based metal organic frameworks and studied as anode material
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E-mail: sivashanmugam@ymail.com for LIB and NIB. The modified synthetic procedure tuned the
52 sivashanmugam@cecri.res.in morphology of the active material for better electrochemical
53 [b] Dr. Subalakshmi Palani
performance.[28] Quasi single crystalline Co3O4 nano belts
54 Electrochemical Power Sources Division, CSIR-Central Electrochemical
Research Institute, Karaikudi – 630 006, Tamil Nadu, India obtained through topotactic thermal decomposition route
55
Supporting information for this article is available on the WWW under delivered synergetic electrochemical performance of 1400 mAh
56
https://doi.org/10.1002/slct.201702197 g-1 which is higher than the theoretical specific capacity of bulk
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Co3O4.[29] Longoni reported different morphological Co3O4
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grains delivering 500 mAh g-1 even after 50 cycles attributing to
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the distinctive morphology, decreasing the irreversible capacity
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in the first cycle and improves cyclability.[30] Co3O4 with nitrogen
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doped carbon derived from metal organic framework for NIBs
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delivered high capacity of 506 mAh g-1 at 100 mA g-1 current
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density. The admirable electrochemical performance was as-
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signed to the incorporation of heteroatom into carbon which
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provided more active sites and enhanced the chemical
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wetability.[31] Rahman reported electrochemical sodiation and
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desodiation of Co3O4 anchored carbon nano tubes delivering
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stable capacity of 403 mAh g-1 at 50 mA g-1 current density
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beyond 100 cycles. The improved performance was due to the
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efficient sodium uptake and release obtained through excellent
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conductivity of CNT.[32]
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In this present study, Co3O4 nano particles were synthe-
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sized by a simple precipitation method without adding any
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surfactant or size directing agent to modify the morphology.
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This simple method could be easily scaled up for commercial
19
applications. Physical and electrochemical characterizations
20
have been carried out to understand the performance of Co3O4
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as an anode material for Li-ion and Na-ion batteries. Ex-situ
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morphological and elemental analyses of cycled electrodes
23
were also performed to establish the influence of ionic size of
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Li + / Na + ions and morphological changes occur during
25
lithiation / sodiation reactions. Elemental analysis gave clear
26
evidence about the SEI layer formation and influence of foreign
27
atoms over the reversibility of electrode reaction on the
28 Figure 1. XRD spectra of nano crystalline Co3O4 prepared from different
electrode-electrolyte interface. The present investigations ex- precursor concentrations.
29
plained in detail about the volume expansion and contraction
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during the electrochemical reaction of Co3O4 in LIBs / NIBs and
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correlated the understanding towards the stability and rate
32
capability. interstitials and mechanically induced strains developed during
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nucleation.[20] Co3O4 formation mechanism is given as below:[33]
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2. Results and Discussion Co2þ þ 6H2 O ! ½CoðH2 OÞ6 2þ ð1Þ
36

37 2.1 XRD studies NH3 þ H2 O ! NH4þ þ OH ð2Þ
38
X-ray diffraction patterns of Co3O4 derived from different 
39 ½CoðH2 OÞ6 2þ þ 2OH ! CoðOHÞ2 þ 6H2 O ð3Þ
precursor concentrations were assignable to spinel with cubic
40
face centered structure and matching with standard diffraction 6Co ðOHÞ þ O2 ! 2Co3 O4 þ 6H2 O ð4Þ
41 2
data of ICSD No. 01–074-2120 and the indexed peaks are in
42
good agreement with standard pattern (Figure 1). Absence of
43
any other peaks in the spectrum confirmed that the synthe-
44 2.2 FTIR studies
sized Co3O4 was phase pure and free from impurities. The hkl
45
values corresponding to the standard 2q values were (111), Fourier-transform infrared (FT-IR) spectra of Co3O4 synthesized
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(220), (311), (400), (511) and (440). The ‘a’ value for the Co3O4 from 0.5 M and 1 M precursors were obtained (Figure 2). The
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samples obtained from 0.5 and 1.0 M concentrations were spectrum peaks around 3400 and 1631 cm-1 were due to
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8.0678 Å and 8.0767 Å respectively which were matching with stretching and bending vibration of hydroxyl group adsorbed
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the standard value of 8.0840 Å and the corresponding cell on the surface of Co3O4. Both spectra exhibited two distinct
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volumes (525.1282 Å3, 526.8680 Å3) were also matching to the peaks at ~ 567 and 665 cm-1 representing the stretching
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standard cell volume of about 528.298 Å3 with a slight variation. vibration of metal oxides for tetrahedrally coordinated Co2 +
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The variation in lattice constant value was caused due to and octahedrally linked Co3 + metal ions.[34,35]
53
variation in crystallite size contributed by several factors like
54
surface energy, lack of outermost bonding on the surface
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atoms and intra-crystalline pressure. In the present investiga-
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tion the observed variation in ‘a’ values was due to the self-
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deformed globular granules. The average grain size was around
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20 nm in the long range. The TEM images of Co3O4 prepared
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from 0.5 M (Figures 3b-d) concentration also depicted agglom-
3
erated pattern with infused morphology. Interstitial pores could
4
be seen in the lumpy clusters. The shape of the particles did
5
not follow specific geometry. While the Co3O4 grains obtained
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from 1 M concentration (Figures 3e-g) were of nearly spherical
7
and the nano particles were of ~ 20 nm size, appeared
8
distinctly with clear grain boundary. Presence of concentric
9
circles in SAED pattern confirmed the polycrystalline nature of
10
Co3O4 in both the cases. Considering the uniform morphology
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and nano dimension the Co3O4 particles obtained from 1 M
12
precursor concentration would be a choice of material and
13
would exhibit superior electrochemical performance. Hence, for
14
all electrochemical studies electrodes were prepared using
15
nano sized Co3O4 particles obtained from 1 M precursor
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Figure 2. FT-IR spectra of nano Co3O4 prepared from different precursor concentration.
17
concentrations.
18
19 2.4 XPS studies
20
XPS spectra were obtained for Co3O4 particles synthesized from
21
0.5 and 1 M precursor concentrations (Figure 4). In the Co2p
22 2.3 Surface morphology studies
spectrum (Figure 4b) two distinct peaks were observed at 785
23
Surface morphology (FESEM and TEM) and the overall textures and 800 eV corresponding to Co 2p3/2 and Co 2p1/2 respectively
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of Co3O4 particles synthesized from 0.5 and 1 M precursor with a spin orbit splitting of 15 eV responsible for Co3O4
25
concentrations were significantly different (Figure 3). Particles phase.[36,37] The actual value of Co 2p1/2 and Co 2p3/2 was shifted
26
derived from 0.5 M concentration (Figure 3a) were cohesive in to higher binding energy of approximately 4 eV which was due
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nature and the texture appeared as fused grain boundaries. to chemical shift of main spin orbit components. Co-cations
28
Though the morphology resembled to a nano sized granular interacted chemically with surface adsorbed hydroxyl group as
29
pattern, the fused grains were present as large lumps. observed from FT-IR studies and was responsible for the
30
However, in case of Co3O4 particles formed from 1 M positive chemical shift.[38] The decomposed Co-2p peaks
31
precursor (Figure 3e) exhibited rather uniform surface morphol- showed the co-existence of Co3 + and Co2 + states. The relatively
32
ogy with clear grain boundaries. The particles appeared as higher peak intensity of Co2 + than Co3 + peaks confirmed the
33
uniformly dispersed pattern throughout with very little presence of more Co2 + ions than Co3 +.[39] Figure 4 (c and f)
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56 Figure 3. FESEM and TEM images of Co3O4 prepared from 0.5 M (a  d) and 1.0 M (e  h) precursor concentrations.
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54 Figure 4. XPS analysis of Co3O4 prepared from 0.5 M (a  c) and 1.0 M precursor (d  f) concentrations.
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showed the O 1s spectrum of Co3O4 synthesized from 0.5 and Cyclic voltammogram of Co3O4 electrodes assembled with
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1 M precursors. The peak around 531 eV was responsible for O2- Na foil were recorded in the potential range of 0.01 to 2.8 V at
2
species from Co3O4. The peak around 535 eV was associated the scan rate of 0.1 mVs-1 (Figure 5b). In the first cycle sodiation
3
with various physisorbed and chemisorbed OH- group ad- occurred and a broad peak centered at 0.4 V with a shoulder
4
sorbed on the surface.[40] peak at 0.7 V was due to reduction of Co3O4 to metallic Co,
5
electrochemical formation of Na2O and solid electrolyte inter-
6
phase (SEI) layer. In the anodic region, peaks observed around
7 2.5 Cyclic voltammetry studies
0.8 and 1.3 V were corresponding to oxidation of Co to Co3O4
8
Cyclic voltammogram were recorded for Co3O4 electrodes as Li- and decomposition of Na2O.[30] The electrochemical reaction of
9
ion battery anode in the potential range of 0.01 to 3.0 V at 0.1 Co3O4 with Na can be written as:
10
mVs-1 scan rate (Figure 5a). In the cathodic region a small broad
11 Co3 O4 þ 2Naþ þ 2e- ! Na2 O þ 3CoO ð5Þ
12
13 3CoO þ 6Naþ þ 6e- ! 3Na2 O þ 3Co ð6Þ
14
15 From the second cycle onwards no peaks were observed
16 around 0.4 V in the cathodic region confirmed that the
17 formation of SEI layer was only during the first cycle. The peak
18 intensity and the integral area of all cycles except first cycle
19 were very close to each other confirming that the reaction was
20 electrochemically reversible. In both Li and Na-ion cell config-
21 urations Co3O4 electrodes exhibited broad reduction peak with
22 a shoulder indicating that Co3O4 was reduced to CoO and
23 further reduced to Co. When compared to Li-ion cell, it was
24 difficult to get the strong redox peaks in Na-ion batteries due
25 to the large size, heavy mass and poor ionic mobility of Na +
26 ions.[41–43]
27
28
29 2.6 Charge-discharge studies
30
Figure 6 (a, b and c) showed the charge-discharge studies of
31
Co3O4 electrode as Li-ion battery anode. At 0.1 C rate Co3O4
32
delivered discharge and charge capacity of 918 and 450 mAh
33
g1 respectively in the first cycle with 50% coulombic efficiency.
34
In the second cycle, it exhibited discharge capacity of 366 mAh
35
g-1. Irreversible capacity of 552 mAh g-1 was due to the
36
electrolyte decomposition and stable SEI layer formation. After
37
2nd cycle, the discharge capacity increased continuously till 648
38
mAh g-1. The increase in capacity was due to pulverisation of
39
particles owing to the electrochemical milling and reversible
40
growth of gel typed pseudo capacitive polymeric film which
41
reduced diffusion path length of Co3O4 electrode and enhanced
42
the conductivity through higher Li + ion diffusion.[44,45] Further,
43 Figure 5. Cyclic voltammogram of Co3O4 as anode material for (a) Li-ion and
(b) Na-ion cell. the reduced particle size of active material in nanometres
44
efficiently supported the volume change and also reduced the
45
structural strain caused during cycling thereby exhibited
46
superior cycling performance.[46] The loss in capacity after initial
47
peak observed in the potential range 1.1 V was attributed to increase was attributed to the unstable nature of the polymeric
48
the electrolyte decomposition and SEI layer formation which film during repetitive cycles.
49
were not observed in the subsequent cycles. A sharp reduction After 15 cycles, a decrease in the discharge capacity was
50
peak found at 0.7 V was due to the electrochemical lithiation observed due to volume expansion and contraction associated
51
process and the same was shifted to 1.04 V in the following with electrochemical lithiation / delithiation process. Beyond 30
52
cycles. In the anodic region, a well-defined anodic peak cycles capacity fading was minimized and the electrode
53
observed at 2.2 V was corresponding to delithiation process. delivered nearly stable discharge capacity of 423 and 382 mAh
54
The steady anodic peaks exhibited the highly reversible nature g-1 at 30th and 40th cycle respectively. Nano Co3O4 electrode
55
of delithiation process.[26] exhibited discharge capacity of 321 mAh g-1 in the 60th cycle.
56
Capacity fading observed during initial cycles was due to the
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47 Figure 6. Charge-discharge studies of Co3O4 as anode material for Li-ion (a, b and c) and Na-ion (d, e and f) cell.
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49
50
associated volume expansion. The coulombic efficiency of around 210 mAh g-1 with 98% coulombic efficiency and at 0.5 C
51
Co3O4 was maintained above 90% and this characteristic rate it exhibited discharge capacity of 110 mAh g-1 indicating
52
indicated that the material was able to exhibit higher high reversibility and stable SEI layer formation which was not
53
reversibility as a result of better electrode kinetics. Rate affected by higher current drain. When the current drain was
54
capability of Co3O4 electrode was also evaluated at different changed back to 0.1 C rate, the cell resumed stable reversible
55
current drains viz., 0.2 and 0.5 C as represented in Figure 6c. At capacity of ~ 270 mAh g-1 even after high current rate which
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0.2 C rate the material delivered stable reversible capacity of was greater than commercial Co3O4 (244 mAh g1).[47] Co based
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one dimensional metal-organic compound obtained from
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hydrothermal reaction exhibited discharge capacity of 270 mAh
2
g1 at 100 mA g1 current density.[48] These observations proved
3
the stability and high rate capability of nano Co3O4 electrode.
4
Figure 6 (d, e and f) showed charge-discharge studies of
5
nano Co3O4 as Na-ion battery anode. In the first cycle Co3O4
6
nano spheres delivered discharge and charge capacity of 500
7
and 168 mAh g-1 at 0.1 C rate respectively. During 1st cycle, the
8
irreversible capacity of 332 mAh g-1 observed was due to
9
electrolyte decomposition and SEI layer formation. In the
10
second and third cycle, the discharge capacity was maintained
11
and the coulombic efficiency increased from 33 to 71%
12
showing improved reversible conversion reaction. After five
13
cycles a sudden fall in discharge capacity was observed. In the
14
6th cycle, discharge capacity decreased from 500 to 429 mAh g-1
15
and subsequently continuous capacity degradation was ob-
16
served and decreased to 243 mAh g-1 in the 10th cycle. These
17
results were comparable with the different morphologies of
18
Co3O4 (bowl like hollow structure and hierarchical Co3O4
19
spheres) intertwined with CNTs.[24,42] After 10 cycles, high order
20
of capacity fading (7 mAh g-1cycle-1) was observed. At the end
21
of 30 cycles Co3O4 delivered about 101 mAh g-1 which was 5
22
times lesser than the initial discharge capacity. However, the
23
coulombic efficiency remained around 92%.
24
Figure 6f showed the discharge capacity of nano Co3O4 at
25
different current rate viz., 0.2 and 0.5 C. At 0.1 C rate nano
26
Co3O4 delivered 101 mAh g-1 up to 30 cycles. When the current
27
rate was increased to 0.2 C, capacity fading also increased due
28
to the increased internal resistance resulting from activation
29
polarization and capacity decreased to 76 mAh g-1 at the end of
30
41st cycle. At the end of 60th cycle it delivered only 43 mAh g-1
31
and the capacity fading was controlled. At 0.5 C rate Co3O4
32
delivered discharge capacity of 27 mAh g-1 which was very low
33
and realized a capacity fading of ~ 1 mAh g-1 cycle-1. The poor
34 Figure 7. Impedance spectra of Co3O4 (a) Li-ion cell (b) Na-ion cell.
current capability at high current rate was attributed to
35
significant volume expansion occurred during the initial cycles
36
and was moderate after 10 cycles. When the cell was cycled
37
again at 0.1 C rate after higher current rate cycling, it delivered straight line was responsible for the diffusion process.[30] The
38
the same capacity of 30 mAh g-1 which showed failure of charge transfer resistance (Rct) of the as assembled cell (1550
39
contact thereby affecting the integrity of electrode surface. W) was higher than that of the one after cycling (230 W). Nano
40
During conversion reaction the volume expansion affected the Co3O4 efficiently reduced the diffusion path length and higher
41
surface morphology of the electrode to a greater extent and Li + diffusion occurred across the interface and enhanced the
42
the loss of contact between the active material leads to severe conductivity between electrode electrolyte interfaces.[49–51] This
43
capacity fading in the initial cycles. The cell delivered a stable improved electrode kinetics facilitated charge transfer and
44
capacity of ~ 30 mAh g-1 after 120 cycles indicated that the improve the reversibility and rate capability of the cell as
45
modification or disintegration of electrode surface affected the evidenced from superior performance realised from charge
46
performance of the cell. discharge studies, integrity of the electrodes and connectivity
47
of particles as observed from ex-situ morphological studies
48
(Figure 8) of cycled electrodes.[52]
49 2.7 Electrochemical impedance spectroscopy analysis
Electrochemical impedance spectra of Co3O4 were recorded
50
Electrochemical impedance spectroscopy (EIS) of Co3O4 as Li- before and after cycling as anode material for Na-ion battery
51
ion battery anode was recorded (Figure 7a) to extensively (Figure 7b). Before cycling, Co3O4 cell exhibited Rct value of 110
52
understand the capacitive behaviour and the kinetics of the W. After high rate cycling the Rct value of the same cell was 350
53
cell. In the Nyquist plot, a depressed semi-circle was observed W. After 120 cycles the cell exhibited very high charge transfer
54
from medium to high frequency range followed by a straight resistance due to the increased internal resistance. The cause
55
line.[28] The semi-circle was attributed to charge transfer for the raise in internal resistance upon cycling was attributed
56
resistance (Rct) of the electrode electrolyte interface and the to the formation of cracks in the active electrode surface area
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35 Figure 8. Ex-situ FESEM images of Co3O4 electrode at different magnification in Li-ion and Na-ion cell after 100 cycles.
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as evidenced from ex-situ morphology analysis (Figure 8). The accommodated the volume changes during cycling resulted in
39
cracks led to disintegration and isolation of certain area of improved electrochemical performance of the active material.
40
active material from the rest. Loss of contact between the From the FESEM images (Figures 8c and 8d) of the surface
41
active materials increased the internal resistance of the morphology of Co3O4 electrode as NIB anode obtained after
42
electrode. 120 cycles, it was apparent that the electrode morphology was
43
entirely different from that of the electrodes served as Li-ion
44
battery anode. Large well developed cracks with clear boun-
45 2.8 Ex-situ surface morphology studies
dary extending to the full thickness of coating isolated the
46
FESEM images of the surface morphology of Co3O4 electrode as active mass as large lumps and affected the integrity of the
47
LIB anode after 130 cycles were studied (Figures 8a and 8b). A electrode. This was due to the associated volume expansion
48
closely packed arrangement of spherical nano particles showed leading to pulverization of electrode structure. Further, contin-
49
sustained connectivity between particles throughout cycling. uous decomposition of the electrolyte led to increase in
50
The connectivity of particles and integrity of the electrode thickness of the SEI layer and reduced the Na + ion diffusion
51
remained unaltered. The surface was covered with the SEI layer reaction. In some regions of the electrode, especially over the
52
and the volume expansion during lithiation and delithiation edges of the cracks flower like morphological recrystallized
53
was also absorbed in LIB. The reduced Li + ion diffusion path NaCl was observed which also boosted up the cracks formation.
54
length with conductive carbon network and nano sized particle The loss of contact between the active materials reflects on
55
of Co3O4 enhanced the conductivity of active material and also capacity fading over the 120 cycles as indicated from charge-
56
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2.9 Elemental analysis reaction of Co3O4. In the case of LIB volume change during
1
lithiation / delithiation was well manipulated by nano struc-
2
Elemental analysis of cycled Co3O4 electrodes served as LIB and tured architecture of Co3O4 particles and accommodated the
3
NIB anodes were recorded (Tables 1 and 2). EDAX images are volume change during cycling and delivered better electro-
4
chemical performance. In contrast, the larger size of Na + ion
5
increased the volume change during sodiation / desodiation
6 Table 1. Elemental Analysis of Co3O4 after Cycling as Li-ion Cell Anode. and caused cracks and loss of contact between Co3O4 particles
7
Element Weight (%) Atomic (%) thereby led to severe capacity fading.
8
9 C 24.61 36.53
O 21.49 23.94
10 Supporting Information Summary
F 35.85 33.64
11 P 1.68 0.97 Synthesis of Co3O4, method of preparation of electrodes for
12 Co 15.18 4.59
Cu 1.19 0.33
electrochemical studies and EDAX analysis of Co3O4 electrodes
13
Total 100.00 100.00 after cycling are presented.
14
15
16 Acknowledgements
Table 2. Elemental Analysis of Co3O4 after Cycling as Na-ion Cell Anode.
17
Element Weight (%) Atomic (%)
The authors thank CSIR-CECRI and TAPSUN project (NWP-56) for
18
financial assistance.
19 C 16.19 23.99
20 O 50.04 55.88
21 Na 18.83 14.63 Conflict of Interest
Cl 5.18 2.61
22
Co 5.86 1.78 The authors declare no conflict of interest.
23 Cu 3.96 1.11
24 Total 100.00 100.00
25 Keywords: anode material · cobalt oxide · lithium ion battery ·
26 nano size · sodium ion battery
27
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