Materials Letters 273 (2020) 127950

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Titanium based layered O3-NaTi7/10Ni3/20Mg3/20O2 anode material

for sodium ion batteries
K. Kannan, M. Kouthaman, P. Arjunan, R. Subadevi ⇑, M. Sivakumar ⇑
#120, Energy Materials Lab, Department of Physics, Alagappa University, Karaikudi 630 003, Tamil Nadu, India

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

Article history: Here, we prepared O3-NaTi7/10Ni3/20Mg3/20O2 anode material via conventional solid-state reaction for
Received 10 April 2020 sodium-ion batteries. The prepared anode material revealed the rhombohedral structure with the space
Received in revised form 2 May 2020 group of R-3m. The existence of Na-O bond was identified using Fourier-Transform Infrared spectra. The
Accepted 7 May 2020
hexagonal shaped morphology of the material was observed. The layered O3-NaTi7/10Ni3/20Mg3/20O2
Available online 7 May 2020
anode material delivered a reversible capacity of 113.08 mAh g 1 in the voltage range of 0.2–2.5 V at
0.1 C rate.
Keywords:
Ó 2020 Elsevier B.V. All rights reserved.
Composite materials
Structural
XPS
Microstructure

1. Introduction O3-Na0.73Li0.36Ti0.73O2 [6], O3-Na0.66Mg0.34Ti0.66O2 [7]. Here, we

Last few decades, usage of lithium ion batteries (LIBs) in energy
storage devices has been tremendously increased and fascinated.
However, owing to the inadequate availability of lithium reserves
and concerning about the cost of LIBs, an alternative energy storage
device are highly desirable. Nowadays, sodium-ion batteries (SIBs)
have engrossed the researchers’ attention due to its attracting
properties like environmental friendliness and available in low
prices [1]. In order to satisfy the need for large scale energy storage
applications, a suitable electrode material with good reversible
capacity and long term stability is required. In the sodium-ion bat-
teries, diverse anode materials viz., metal oxides or sulfides such as
TiO2, FeS2, Co3O4, Fe3O4 and MoS2, non-metallic materials such as
hard carbon and phosphorus have been reported. Although, in
sodium-ion batteries, few of these materials exhibit large specific
capacities but achieving the practical usage of cycling life still
remains to be difficult.
According to the positioning of Na-ion in octahedral and pris-
matic sites, the layered sodium transition metal oxides have been
categorized as O3 and P2 type [2]. Recently, P2-type intercalated
layered oxides such as P2-Na2/3Ni1/6Mg1/6Ti2/3O2 [3], P2-Na2/3
Co1/3Ti2/3O2 [4], P2-Na0.67Ni0.33Ti0.67O2 [2], P2-Na2/3Ni1/3Ti2/3O2
[5] has been investigated in plenty. But, limited number of articles
has been reported on O3-type intercalated materials such as
⇑ Corresponding authors.
E-mail addresses: susimsk@yahoo.co.in (R. Subadevi), susiva73@yahoo.co.in
(M. Sivakumar).
report exploration of O3-NaTi7/10Ni3/20Mg3/20O2 anode material
prepared via conventional solid-state reaction. All the as-prepared
anode material was characterized and reported.
2. Experimental
The layered O3-NaTi7/10Ni3/20Mg3/20O2 anode material was pre-
pared by a conventional solid state reaction. Stoichiometric
amount of Na2CO3 (98% Alfa Aesar), TiO2 anatase (99.6% Alfa
Aesar), NiO (99% Alfa Aesar), MgO (99.99% Sigma Aldrich) powder
was mixed by mortar and pestle, then the mixture was calcined at
900 °C for 12 h under Ar atmosphere. Finally, layered O3-
NaTi7/10Ni3/20Mg3/20O2 powder was successfully obtained.
The prepared precursor was analyzed by Simultaneous Thermo
Analysis (STA-Q600) to determine the calcination temperature. The
crystal structure of the synthesized material was characterized by
(X’pertpro-PANalytical model) with CuKa radiation (k = 1.5406 Å)
in the range 2h = 10–80°. The functional group vibration was stud-
ied by Thermo Nicolet 380 FTIR spectrometer. The morphological
studies of the prepared material was investigated by Field emission
scanning electron microscopy (FESEM Quanta FEG 250) and Chem-
ical valence states of the elements were examined by X-ray photo-
electron spectroscopy (PHI 5000 versa probe III).
The electrochemical measurements of the prepared materials
were studied using CR-2032 type coin-cell assembled in Argon
(Ar) filled glove box. The working electrodes were composed of
the active material, Super-P carbon, and poly(vinylidenefluoride)
(PVdF) with mass ratio of 75:15:10 using N-methyl Pyrrolidene

https://doi.org/10.1016/j.matlet.2020.127950
0167-577X/Ó 2020 Elsevier B.V. All rights reserved.
2 K. Kannan et al. / Materials Letters 273 (2020) 127950

(NMP) as solvent to obtain uniform slurry. Then obtained slurry
was coated on Aluminum foil and dried in vacuum oven for 12 h.
The coin cells were assembled in Ar-filled glove box, using sodium
metal, glass fiber, and 1 M NaClO4 in propylene carbonate (PC) as
the counter electrode, separator, and electrolyte respectively. The
Cyclic voltammetry (CV) and charge and discharge measurements
were carried out using a biologic (BCS-815, France) battery tester
between 0.2 and 2.5 V vs. Na/Na+ cell couple at room temperature.
3. Results and discussion
Thermogravimetric (TG) analysis performed on the precursor
(Na2CO3, (anatase) TiO2, NiO and MgO) of layered O3-
NaTi7/10Ni3/20Mg3/20O2 is denoted in Fig. 1(a), with two regions,
i.e. 33–101 and 178–881 °C whose weight losses (~4 and 25%)
are attributed to the removal of surface water and decomposition
of carbonate precursor of the prepared material. Further, there is
no weight loss observed after 873 °C, which reveals that the forma-
tion of O3-NaTi7/10Ni3/20Mg3/20O2 material takes place around
900 °C [8].
The X-ray diffraction pattern of the prepared material was
shown in Fig. 1(b) and indexed to rhombohedral structure with
R-3m space group (ICDD-PDF-2 #01-070-6690, No. 166) [9]. The
diffraction peaks are located at 2h = 16.23, 33.18, 33.68, 36.18,
40.97, 52.86, 57.65 and 61.47° corresponding to the (h k l) values
of (0 0 3), (0 0 6), (1 0 1), (0 1 2), (1 0 4), (1 0 7), (0 1 8) and
(1 1 0) planes obviously indicate the formation of O3-
NaTi7/10Ni3/20Mg3/20O2 prepared material. The lattice parameters
of the prepared sample have been calculated as of a = b = 3.018
and c = 16.193 Å, and the cell volume was found to be 126.75 Å3,
which is in line with previous report [1]. Fig. 3 shows the FTIR
spectrum of the as-prepared material. In general, the metal oxide

Fig. 1. (a) TG of precursor (b) X-ray diffraction pattern, (c) FT-IR spectrum of O3-NaTi7/10Ni3/2Mg3/2O2 material.

Fig. 2. XPS spectra of prepared layered O3-NaTi7/10Ni3/2Mg3/2O2 anode material (a) wide range, (b) Na 1s, (c) Ti2p, (d) Ni 2p, (e) Mg 2s and (f) O 1s.
 K. Kannan et al. / Materials Letters 273 (2020) 127950
Fig. 3. (a, b) SEM images (c) typical charge/discharge profiles at 0.1C rate (d) Cyclic voltammetry of O3-NaTi7/10Ni3/2Mg3/2O2 anode material at a scan rate 0.1 mV s
represents the peaks below 1000 cm 1 as a result of inter-atomic
vibrations. The peaks appeared at 475, 867 and 1446 cm 1 is cor-
responding to the Ti–O–Ti, Ti–O stretching vibrations, and Na–O
bond respectively [10]. The peak appeared at 3454 cm 1 is due
to the O–H stretching vibration of the prepared material [11].
The XPS spectra (Fig. 2(a, b–f)) show survey and high-resolution
spectra of Na1s, Ti2p, Ni2p, Mg2s and O1s respectively of the pre-
pared material. The binding energy values of Na1s at 1070.35,
1071.52 and 1072.01 eV correspond to the presence of Na+ leap
with oxygen. The peak of the Ni can be separated into Ni2p3/2
(857.55 eV) and satellite (863.14 eV), proposing the existence of
Ni elements with Ni2+. In the Ti2p XPS spectrum, two peaks at
460.12 and 464.32 eV are perceived, which are consistent with
the characteristic values of Ti2p3/2 and Ti2p1/2for Ti4+. The peak
located at 461.26 eV can be attributed to the Ti3+ [3]. The binding
energy value retained at 89.43 eV assigned to Mg2s. The peak
appeared at 531.32 eV can be attributed to the O1s [12].
The surface morphology of layered O3-NaTi7/10Ni3/20Mg3/20O2
(Fig. 3(a, b)) collected at 5 and 10 K explored the hexagonal shape
with an average particle size 5 mm. The micro-sized structure leads
to easy pathway for diffusion of ions in charge/discharge process
[13]. Fig. 3(c) exposed the cyclic voltammetry curve of O3-
NaTi7/10Ni3/20Mg3/20O2 anode material at a scan rate of 0.1 mVs 1.
The reduction peak at 0.47 V and the oxidation peak at 0.45 V are
attributed to the redox reaction of Ti3+/Ti4+ and also the reduction
peak appeared at 0.06 V due to the electrolyte participation [9].
3
1
.
The electrochemical performance of O3-NaTi7/10Ni3/20Mg3/20O2
anode material has been examined using charge-discharge analysis
in the voltage range 0.2–2.5 V at 0.1C rate under room temperature
(Fig. 3(d)). Wang et al. [3] reported P2-type anode material, in
which the reversible capacity attained at 92 mAh g 1 and Li et al.
[9] examined the O3-type layered bipolar material delivers the ini-
tial reversible capacity is 109.6 mAh g 1. In the present work, a
reversible capacity of 113.08 mAh g 1 has been achieved due to
the increased sodium content and also the limited Ni and Mg sub-
stitution in Titanium sites considerably improved the reversibility
of the Na+ intercalation and de-intercalation process [14,15]. The
reversible capacities of the prepared material at 1, 5, 10, 20 and
30th cycles were found to be 113, 101, 92, 81 and 63 mAh g 1
respectively confirming good electrochemical performance of the
material. Moreover, the capacity retention of the prepared material
is 55.81%, which reveals better cyclability.
4. Conclusion
In summary, layered O3-NaTi7/10Ni3/20Mg3/20O2 anode material
was prepared by conventional solid state reaction. The prepared
O3-NaTi6/10Ni3/10Mg1/10O2 material retained the good reversible
capacity at 113.08 mAh g 1. Further, the capacity retention of the
material reveals better cyclability. From these results, we believe
that the O3-NaTi7/10Ni3/20Mg3/20O2 is a suitable candidate as an
anode material for sodium ion batteries.
4 K. Kannan et al. / Materials Letters 273 (2020) 127950
CRediT authorship contribution statement
K. Kannan: Methodology, Validation, Software, Formal analysis,
Investigation, Writing - original draft, Visualization, Data curation.
M. Kouthaman: Methodology, Validation, Software, Formal analy-
sis, Investigation, Writing - original draft, Visualization, Data cura-
tion. P. Arjunan: Validation, Formal analysis, Software,
Visualization, Data curation. R. Subadevi: Conceptualization,
Methodology, Resources, Investigation, Writing - review & editing,
Supervision, Project administration. M. Sivakumar: Conceptualiza-
tion, Methodology, Validation, Formal analysis, Investigation,
Resources, Writing - review & editing, Visualization, Supervision,
Project administration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
All the authors from Alagappa University acknowledge the
financial support by DST-SERB, New Delhi under the Physical
sciences, grant sanctioned vide EMR/2016/006302, PURSE and FIST
programme, sponsored by Department of Science and Technology
(DST), New Delhi, Govt. of India and Ministry of Human Resource
Development RUSA-Phase 2.0 grant sanctioned vide Lt.No. F-24-
51/2014 U Policy (TNMulti Gen), Dept. of Education, Govt. of India.
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