Journal of Power Sources 359 (2017) 277e284

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Journal of Power Sources

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

Na2MnSiO4 as an attractive high capacity cathode material for

sodium-ion battery
Markas Law, Vishwanathan Ramar, Palani Balaya*
Department of Mechanical Engineering, National University of Singapore, 117575, Singapore

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Na2MnSiO4 is prepared via a modi-

fied two-step route.

It delivered the highest discharge
capacity for a polyanion-based
compound.

Na2MnSiO4 registered impressive so-
dium storage performance of
210 mAh g1 at 0.1 C.

Electrolyte additive VC forms a meta-
stable passivation film on electrode
surface.

The amount of VC added greatly in-
fluences electrochemical perfor-
mance of Na2MnSiO4.

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

Article history: Here we report a polyanion-based cathode material for sodium-ion batteries, Na2MnSiO4, registering
Received 25 March 2017 impressive sodium storage performances with discharge capacity of 210 mAh g1 at an average voltage of
Received in revised form 3 V at 0.1 C, along with excellent long-term cycling stability (500 cycles at 1 C). Insertion/extraction of
12 May 2017
~1.5 mol of sodium ion per formula unit of the silicate-based compound is reported and the utilisation of
Accepted 19 May 2017
Available online 29 May 2017
Mn2þ ! Mn4þ redox couple is also demonstrated by ex-situ XPS. Besides, this study involves a systematic
investigation of influence of the electrolyte additive (with different content) on the sodium storage
performance of Na2MnSiO4. The electrolyte additive forms an optimum protective passivation film on the
Keywords:
Sodium manganese silicate
electrode surface, successfully reducing manganese dissolution.
Sodium-ion battery © 2017 Elsevier B.V. All rights reserved.
Cathode material
Energy storage
Polyanion compound

1. Introduction has soared to unprecedented heights. Large-scale energy storage

Rechargeable lithium battery technologies have been the fore-
runner in stationary and mobile energy storage, and have now
evolved to empower green electric vehicles. Ever since its com-
mercialisation in 1990, demand for the lithium battery technology
* Corresponding author.
E-mail address: mpepb@nus.edu.sg (P. Balaya).
systems utilised in the micro-grids and the hybrid vehicles require
huge amounts of lithium [1], which resulted in the anxiety con-
cerning the shortage of lithium reserves. This issue has become the
driving force to recognise sodium battery as a promising replace-
ment because of the abundance and wide distribution of sodium
resources for power-grid applications where space/volume is not a
big concern [2,3]. However, energy density of this technology is
limited because of its low capacity and slow kinetics, owing to the

http://dx.doi.org/10.1016/j.jpowsour.2017.05.069
0378-7753/© 2017 Elsevier B.V. All rights reserved.
278 M. Law et al. / Journal of Power Sources 359 (2017) 277e284
relatively heavier and larger ionic radius of the sodium ion [4]. Due
to this fact, compounds which have lower molecular weight or
those which could exchange more than 1 mol of sodium per for-
mula unit are crucial to achieve high energy density. Besides, ma-
terials with an open framework are essential for facile sodium ion
intercalation reaction.
In view of the above, significant interests have been devoted to
sodium-based oxide compounds (NaxMO2, where M ¼ transition
metal) because of their relatively lower molecular weight, as well as
open structure. Driven by high discharge capacity and high oper-
ating potential, early contributions have been made mostly by
Delmas et al. in the beginning of 1980s [5e7]. Very recently how-
ever, Liu et al. [8] reported a new O3-type Na0.78Li0.18Ni0.25Mn0.58O2
which is obtained by electrochemical Na-Li ionic exchange process
of Li1.167Ni0.25Mn0.583O2. This oxide material shows the highest
discharge capacity of 240 mAh g1 in the voltage range 1.5e4.5 V.
Prior to that, Yabuuchi et al. [9] demonstrated the highest obtained
reversible capacity of 220 mAh g1 with their new P2-type Na2/
3Mg0.28Mn0.72O2 cycled over a voltage window 1.5e4.4 V. Another
compound is the P2-type Na2/3Fe1/2Mn1/2O2 proposed by Yabuuchi
et al. [10], which delivers 190 mAh g1 of reversible capacity in the
voltage range 1.5e4.2 V, utilising electrochemically active Fe3þ/
Fe4þ redox couple. Yet another O3-type NaNi0.5Mn0.5O2 is reported
in 2012 by Komaba et al. [11] demonstrating high discharge ca-
pacity of 185 mAh g1 in the voltage range 2.2e4.5 V. The revers-
ibility is further improved by adding fluoroethylene carbonate into
electrolyte solution. More recently, the same group [12] discovered
a new lithium-excess P2-type Na5/6Li1/4Mn3/4O2 which delivers
high reversible capacity of 190 mAh g1 when cycled at a voltage
window 1.5e4.4 V. However, it is a known fact that oxide-based
compounds suffer numerous safety issues, resulting from the
weak M-O bond which makes them unstable at too high potentials
and requires special attention using battery management system to
assure safely [1,13].
In the case of polyanion, only a handful of compounds exceeded
reversible storage capacity of 110 mAh g1 because of its relatively
higher molecular weight and sluggish kinetics [14e16], and plau-
sible failure to utilise more than 1 mol of Naþ per formula unit
[17e19]. Nonetheless, Park et al. [20] revealed a fluorophosphate-
based Na1.5VPO4.8F0.7 cathode capable of delivering a discharge
capacity of 134 mAh g1 in the voltage window 2.0e4.5 V, involving
1.2 electron exchange per formula unit (V3.8þ ! V5þ). Saravanan
et al. [21] prepared carbon coated Na3V2(PO4)3 cathode material
which was able to provide 116 mAh g1 discharge capacity over the
voltage window 2.3e3.9 V involving 1.88 mol of Naþ. Although
Li2MnSiO4 compounds are well-explored for lithium-ion battery, its
sodium analogue has seen very little development. In 2011, Duncan
et al. [22] successfully synthesised Pn-Na2MnSiO4 by a sol-gel
method. Pn-Li2MnSiO4 was obtained via ion exchange of the syn-
thesised Pn-Na2MnSiO4 and electrochemical performance was
investigated in a lithium-ion cell. However, no electrochemical
study was performed to investigate sodium storage. Chen et al. [23]
synthesised Na2MnSiO4 by the sol-gel method and achieved
reversible capacity of 125 mAh g1 at 0.1 C in ionic liquid electro-
lyte. Only one electron transfer was possible in this work, and
115 mAh g1 was obtained at moderate 1 C rate.
To address various limitations of such previous reports, we
present here a polyanion-based Na2MnSiO4 framework as a po-
tential cathode material with excellent storage capability involving
manganese redox couple successfully delivering ~1.5 electrons per
formula unit. This compound registered the highest-ever discharge
capacity so far for a polyanion-based cathode material.
2. Experimental section
2.1. Material synthesis
Nanostructured pure Na2MnSiO4 is synthesised via a two-step
method. All precursors are mixed in stoichiometric ratio unless
stated otherwise. In glass bottle A, tetraethyl orthosilicate (TEOS)
(C8H20O4Si; Alfa Aesar; purity 98%) is added to a well-mixed solvent
of ethanol (Merck Millipore) and Milli-Q water (2:1 vol ratio), and
stirred at room temperature for 1 h. In a separate glass bottle B,
1 mmol of citric acid (C6H8O7; Alfa Aesar; 99þ%) is added to ethanol
and Milli-Q water mixture (2:3 vol ratio) and stirred until citric acid
is fully dissolved. The addition of citric acid provides an acidic
medium for phase formation [22]. This is then followed by addition
of manganese (II) acetate tetrahydrate (Mn(CH3COO)2$4H2O; Strem
Chemicals; 99þ%) and further stirred for 1 h. These solutions in
bottle A and bottle B are then combined and stirred further at room
temperature for 24 h to ensure homogeneous mixture of the
chemicals.
The ethanol-water solvent is evaporated using a rotary evapo-
rator (Heidolph Hei-VAP Precision ML/G3). The obtained white
precipitate is ground to powder and calcined in a tubular furnace
(Carbolite Limited, UK) at 700  C for 6 h under argon atmosphere.
The resultant black powder is mixed with sodium carbonate (20%
excess) (Na2CO3; Alfa Aesar; 98%) using a high-energy ball mill,
HEBM (Fritsch Planetary Micro Mill PULVERISETTE 7 premium line)
at 500 rpm for 30 min. A 20 ml zirconium oxide grinding bowl with
stainless steel casing and five 10 mm zirconium oxide balls are used
for the HEBM process. This is followed by addition of 1 mmol of
citric acid as a carbonising agent and ball milled at 500 rpm for
10 min. The sample is calcined in the tubular furnace at 750  C for
8 h under argon. The obtained Na2MnSiO4 sample is further ball
milled at 500 rpm for 4 h with Super P carbon black (Alfa Aesar,
>99%) in the weight ratio 4:1 [17,24]. This sample is finally annealed
in the tubular furnace at 750  C for 6 h under argon to release any
accumulated lattice strain during the course of ball milling [25].
2.2. Material characterisation
Powder X-ray diffraction (PXRD) is carried out with a D8
ADVANCE ECO X-ray powder diffractometer (Bruker, Germany)
over 2q angle of 10 e100 using Cu-Ka radiation operated at 40 kV
and 25 mA. Rietveld refinement is performed using TOPAS version
4.2 software on the acquired high resolution PXRD data. Physical
characteristics of synthesised sample are examined using a field-
emission scanning electron microscope (FESEM, JEOL JSM-7000F;
Japan) operated at 15 kV and 20 mA. Energy-dispersive X-ray
spectroscopy (EDS) and elemental mapping are performed to
obtain elemental composition of the samples. Prior to FESEM and
EDS, the sample is sputtered with a thin platinum layer using auto
fine coater (JFC-1600; JEOL, Japan) to increase surface conductivity.
Transmission electron microscopy (TEM, JEM-2010F; JEOL, Japan)
operated at 20 kV is used to observe thickness of the carbon coating
around the Na2MnSiO4 particles. For the TEM analysis, the sample is
dispersed in ethanol by sonication and a drop of this suspension is
loaded on the Cu grid and dried. Thermogravimetric analysis (TGA)
is carried out using Discovery TGA Analyser (TA Instruments, USA)
to estimate the total carbon content in the sample. For the TGA
study, 12e15 mg of sample is heated at 5  C min1 in air from room
temperature to 800  C. Composition of the elements present in the
sample as well as Mn dissolution analysis are assessed using Op-
tima 5300 DV (PerkinElmer, USA) inductively coupled plasma
 M. Law et al. / Journal of Power Sources 359 (2017) 277e284
optical emission spectrometry (ICP-OES) system. For elemental
analysis, the sample is digested with HNO3/HCl and top up to 10 mL
with deionised water so as to form a precipitate. Prior to Mn
dissolution measurements, the electrodes are aged for 30 days in
the coin cell (cells are assembled with and without 5 vol% VC) and
the electrodes are carefully retrieved by dismantling the coin cells
in the glove box. The retrieved electrodes are immersed in the
respective electrolytes at room temperature and the electrolyte
samples are taken for examination over a time interval of 5-days for
a total of 30 days. The Brunauer-Emmett-Teller (BET) specific sur-
face area is determined using a Nova 2200e surface area analyser
(Quantachrome, USA). Sample degassing is made at 110  C for 16 h
under vacuum prior to the experiment. The BET surface area is
determined from nitrogen adsorption isotherm at P/P0 of 0.05e0.3.
The total pore volume is evaluated from adsorption region at P/P0 of
~0.99. X-ray photoelectron spectroscopy (XPS) analysis is carried
out with an AXIS Ultra DLD (Kratos Analytical Ltd, UK) at 15 kV and
5 mA utilising a mono Al-Ka radiation. During XPS measurement,
working pressure of 1  109 Torr and base pressure 1  109 Torr
are applied. XPSPEAK software version 4.1 is used to fit XPS spectra
with a Shirley-type background. The accuracy of binding energies
(BE) is within ±0.1 eV.
2.3. Electrochemical characterisation
Electrochemical measurement on the reported system Na2Mn-
SiO4 is carried out using 2016-type coin cells. Na2MnSiO4 electrode
is prepared by mixing the as-prepared sample and polyvinylidene
fluoride (PVdF; Kynar 2801) binder in the weight ratio 9:1 with N-
methyl-2-pyrrolidone (NMP; Merck) as the solvent. No extra ad-
ditive carbon is used to the prepare slurry. The viscous slurry is
coated on a 0.015 mm-thick etched aluminium current collector
(Shenzhen Vanlead, China) using a doctor blade and dried at 110  C
for 6 h in a vacuum oven (Memmert, Germany). The dried electrode
is then cold-pressed using a roller-pressing machine (Hohsen
Corporation, Japan) before being cut into circular discs. The elec-
trodes are dried in a vacuum antechamber at 110  C for 6 h before
the cell assembly. The geometrical area of the studied electrode is
2.01 cm2 for the 2016-type cell and 0.95 cm2 for the Swagelok-type
cell. In both the cells, the electrode has a typical active material
loading of 1.4e1.6 mg cm2. The coin cells are assembled in an
argon-filled glove box (MBraun, Germany) with metallic sodium as
the counter electrode and glass microfiber filters (Whatman; Grade
GF/C) as the separator. In a three-electrode setup (MTI Corporation,
USA), metallic sodium acts as both counter and reference elec-
trodes, with Na2MnSiO4 as working electrode. The electrolyte used
is 1 M NaPF6 in ethylene carbonate (EC; Sigma-Aldrich)-propylene
carbonate (PC; Sigma-Aldrich) (1:1 vol ratio) with varying amount
of vinylene carbonate (VC; Sigma-Aldrich) as additive. Sodium
storage performance is analysed using a battery testing system (BT-
2000 Arbin Instruments, USA) operated in galvanostatic mode be-
tween 2.0 and 4.3 V at room temperature. Constant voltage (CV)
mode is initiated at the end of the charge cycle at 4.3 V for 2 h.
Electrochemical impedance spectroscopy (EIS) is performed over
the frequency range 10 mHze1 MHz on a three-electrode cell using
a VMP3 multi-channel potentiostat (BioLogic Science Instruments,
France) equipped with an analysis software EC-Lab version 10.19.
3. Results and discussion
3.1. Structural and morphological analysis
Fig. 1a presents PXRD pattern of the as-synthesised Na2MnSiO4,
which clearly shows single-phase formation of Na2MnSiO4 without
any observable impurity phases. A zoomed-in PXRD pattern over
279
narrow 2q range is illustrated in Fig. S1, confirming that there are no
unidentified weak peaks in the pattern, as reported by Duncan et al.
[22] The Rietveld refinement with good reliability factor values
indicates that the synthesised Na2MnSiO4 crystallises in the
monoclinic phase with Pn space group. The obtained lattice pa-
rameters [a ¼ 7.01944 (45) Å, b ¼ 5.61377 (35) Å, c ¼ 5.33185 (33) Å,
b ¼ 89.8085 (17) ] and atomic positions (Table S1) show close
agreement to the values obtained by GGA ab initio DFT calculations
(ICDD Card No. 00-055-0638) that are used as the initial structural
data for the Rietveld refinement [22]. In addition, the degree of
crystallinity calculated from Rietveld refinement is 97.8%, suggest-
ing that the synthesised sample has high crystallinity.
The crystal structure (viewed along b-axis) generated from the
refinement is displayed in the inset of Fig. 1a (for crystal structure
viewed along a- and c-axes, refer Fig. S2). The FESEM image in
Fig. 1b of the Na2MnSiO4 reveals small particles with a pseudo-
spherical morphology and their size falls in the nano-range
60e90 nm. The total carbon content determined by TGA is 24 wt
% (Fig. S3a). The BET analysis reveals a specific surface area of
71.1 m2 g1 for the Na2MnSiO4 sample featuring a well-defined
Type-IV isotherm, which can be classified as mesoporous mate-
rials (Fig. S5). The molar ratio (normalised to the manganese con-
tent) for the synthesised sample has a stoichiometric ratio of 2:1:1
for Na:Mn:Si, corresponding to the molecular formula of Na2Mn-
SiO4 (Table S2). From the TEM image in Fig. S6, it is clear that a
uniform layer of amorphous carbon coating with thickness around
2e3 nm is present on the Na2MnSiO4 nanoparticles. This layer of
surface carbon coating is essential to ensure good electronic con-
ductivity for efficient electron charge transfer between the parti-
cles. In addition, diffused rings in the SAED pattern confirm the
amorphous nature of the carbon coating (inset to Fig. S6). Lattice
fringes are clearly visible from the TEM image, confirming the high
degree of crystallinity obtained from Rietveld refinement of PXRD
data.
3.2. Sodium storage performance
The charge-discharge profiles obtained at a current rate of 0.1 C
for the Na2MnSiO4 half-cell (using NaPF6 electrolyte in EC:PC vol-
ume ratio 1:1, with 5 vol% vinylene carbonate (VC) additive) with
the constant current-constant voltage (CCCV) mode of charging at
4.3 V is presented in Fig. 2a. The 5 vol% VC used here is an optimised
content upon a systematic variation, which will be discussed later.
It can be seen that the initial sodium extraction follows a sloppy
profile ascending to the upper cut-off voltage of 4.3 V at which a
constant voltage mode is applied for 2 h. It should be noted that the
operated voltage during constant voltage mode is well within the
stability window of the electrolyte [26], which means that the extra
capacity obtained is purely from the active material and is not
related to any electrolyte degradations. The discharge process be-
gins at 4.3 V and decreases steeply until a shallow plateau at ~3.4 V
before descending to the lower cut-off voltage of 2.0 V, giving rise
to discharge capacity of 155 mAh g1. Surprisingly, as cycling pro-
gresses, a charge plateau begins to appear at ~3.9 V resulting in an
increase in charge capacity. As a result, discharge capacity increases
to 210 mAh g1 in the 10th cycle corresponding to ~1.5 mol of Naþ
storage per formula unit of Na2MnSiO4 (1 mol contributes to
discharge capacity of 139 mAh g1). In order to confirm that the
change in the shape of the voltage profiles as seen in Fig. 2a is not
due to any structural changes, ex-situ XRD measurements are per-
formed at the end of different discharge cycles.
Fig. 3 demonstrates ex-situ PXRD patterns of Na2MnSiO4 elec-
trode at the end of selected discharge cycles. All the major peaks of
Na2MnSiO4 are seen, suggesting that the sample retains its struc-
ture during cycling. This confirms the fact that the change in the
280 M. Law et al. / Journal of Power Sources 359 (2017) 277e284
Fig. 1. (a) PXRD pattern, with inset showing refined crystal structure viewed along b-axis, Naþ yellow sphere, Mn2þ magenta sphere, Si4þ green sphere, O2 red sphere; and (b)
FESEM image of the synthesised Na2MnSiO4. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 2. Charge-discharge profiles cycled at 0.1 C using NaPF6 electrolyte in EC:PC v/v 1:1 (a) with 5 vol% VC and (b) without 5 vol% VC.
Fig. 3. Ex-situ PXRD of the Na2MnSiO4 electrode recorded at the end of different
discharge cycles.
voltage profile is not due to any structural changes. It is also worth
noting that Na2MnSiO4 does not result in amorphisation during
cycling, unlike its lithium analogue, Li2MnSiO4 [27e29].
As a control experiment, a Na2MnSiO4 half-cell is fabricated
using NaPF6 electrolyte in EC:PC (volume ratio 1:1) without 5 vol%
VC, and its charge-discharge profile at 0.1 C is illustrated in Fig. 2b. It
is clearly seen that this control experiment does not exhibit the
similar trend as described earlier with 5 vol% VC even after 20
cycles. The obtained discharge capacity in this control experiment
is similar to a recent report on Na2MnSiO4 using ionic liquid elec-
trolyte [23]. Thus, inclusion of 5 vol% VC plays a vital role in sta-
bilising the electrode-electrolyte interface during cycling and the
effect of varying the VC content on the electrochemical perfor-
mance will be discussed in the following section.
Interestingly, high and stable discharge capacity is obtained for
the Na2MnSiO4 sample with 5 vol% VC electrolyte additive at
various current rates, as shown in Fig. 4a. Even at 5 C rate, a
discharge capacity close to 100 mAh g1 could still be achieved,
which promises this material to be a high power density cathode.
Notably, the electrode is able to regain 100% of its initial capacity
when cycling is reverted to 0.1 C after its performance at 5 C. Be-
sides the good rate performance, this material exhibits 89.5% ca-
pacity retention even after 500 cycles at 1 C (note that the capacity
retention is calculated from the 12th cycle onwards) as shown in
Fig. 4b. A similar increasing trend is observed in the initial
discharge capacity at 1 C, which will be further elaborated in the
following section. More importantly, a high average coulombic ef-
ficiency of 99.5% is achieved throughout the cycling. The impressive
rate performance and durable cyclability of Na2MnSiO4 implies
high structural integrity and robustness of the host framework,
which is manifested by the ex-situ PXRD shown in Fig. 3.
3.3. The effect of electrolyte additive
EIS is employed to understand the influence of electrolyte ad-
ditive on the sodium storage performance and formation mecha-
nism of the solid-electrolyte interface. Impedance spectra is
recorded on Na2MnSiO4 working electrode (WE) with different VC
content (namely 0, 3, 5, 7 and 10 vol% VC) at the end of different
discharge cycles. The measurements are performed using a three-
 M. Law et al. / Journal of Power Sources 359 (2017) 277e284 281

Fig. 4. (a) Rate performance and (b) long-term cycling performance at 1 C of the Na2MnSiO4 sample with 5 vol% VC.

Fig. 5. Nyquist plots at end of different discharge cycles of Na2MnSiO4 WE with various amount of VC content; (a) 0 vol%, (b) 3 vol%, (c) 5 vol%, (d) 7 vol% and (e) 10 vol% VC.

electrode setup where only the impedance response of WE is
measured. All measurements are performed at a fully discharged
state, when the open-circuit potential of the WE vs. reference
electrode (RE) reaches equilibrium.
The Nyquist plots of the Na2MnSiO4 sample with various VC
content at the end of different discharge cycles are shown in Fig. 5.
The Nyquist plots constitute mainly two depressed semicircles at
the high- and medium-frequency regions. The high-frequency
semicircle is attributed to resistance of the passivation film, while
the semicircle at the medium-frequency region refers to charge
transfer resistances across the surface film and electrode interfaces
for electrons and Naþ [30,31]. The size or diameter of the depressed
semicircle gives the magnitude of resistance of each process. As it is
more interesting to analyse how the diameter of the semicircle
282 M. Law et al. / Journal of Power Sources 359 (2017) 277e284
evolves during cycling with different amount of VC, the fitting to
the EIS Nyquist plots is purposefully avoided to prevent any
complicated analysis, which is also suggested by Burns et al. and
Aurbach et al. [32,33].
When no VC is used in the electrolyte, the size of the semicircle
remains unchanged at different charge-discharge cycles, as can be
seen in Fig. 5a. When the amount of VC is increased to 3 and 7 vol%,
a small but steady decrease in the size of the semicircle is observed
(Fig. 5b and d, respectively). Interestingly, when 5 vol% VC is added,
the diameter of the semicircle of the EIS plots decrease significantly
during cycling (Fig. 5c). When 10 vol% VC is added, a detrimental
outcome is noted in the resistances associated with the storage
processes (Fig. 5e), where the size of the depressed semicircle in-
creases drastically after each cycle.
Analogous to the impedance response, it is interesting to note
that increasing additive VC content up to 5 vol% resulted in an
improved discharge capacity at 0.1C (Fig. S7). However, as the VC
concentration is increased above 5 vol%, a decrease in discharge
capacity is noticed. In other words, although inclusion of VC up to a
certain limit (5 vol%) improves discharge capacity and decreases
cell impedance as cycling progresses (Fig. 5), excess additive
beyond 5 vol% leads to detrimental effect in cell impedance and
subsequently on sodium storage performance. Thus, the addition of
optimum amount of VC into 1 M NaPF6 in EC:PC electrolyte forms a
meta-stable passivation film on Na2MnSiO4 WE, resulting in
obvious decrease in the cell impedance as a function of cycle life.
The influence of VC on the surface film resistance of the WE is
consistent with the earlier report by Aurbach et al. [33]. Besides, the
influence of electrolyte additives on storage performance is very
well documented for lithium-ion battery [34e37]. This observation
confirms that VC plays a crucial role in controlling the meta-stable
passivation film on the surface of the working electrode. We believe
that this passivation film dissolves during the course of cycling
which reflects the decrease in passivation film and charge transfer
resistances (as demonstrated by a decrease in the diameter of the
semicircle in the EIS plots), and the degree of dissolution depends
largely on the amount of VC. On the other hand, no such observa-
tion is made from the EIS measurement of the sodium counter
electrode (CE) (as seen in Fig. S8) for the 5 vol% VC, which clearly
reveals that the impedance changes arise only from the passivation
film occurring on the surface of the Na2MnSiO4 WE.
3.4. Manganese dissolution
Transition metal dissolution can be suppressed by creating op-
timum protective surface film on the electrode surface using elec-
trolyte additives [38,39]. This technique is proven to be one of the
most effective methods to improve the electrode-electrolyte
interface stability [40]. To understand the nature of the surface
passivation film, Mn dissolution test is carried out on an aged
electrode using ICP-OES analysis.
Fig. 6 represents the amount of Mn dissolution in the respective
electrolytes (with 0 vol% and 5 vol% VC) of the Na2MnSiO4 elec-
trodes over an interval of 5 days for a total of 30 days. It can be seen
that the Mn dissolution in the Na2MnSiO4 electrodes are signifi-
cantly suppressed with 5 vol% VC in electrolyte as compared to
electrolyte without VC. Less Mn dissolution of this electrode in
electrolyte over time for 5 vol% of VC additive results in good rate
performance (Fig. 4a) and stable long-term cycling (Fig. 4b). Be-
sides, the battery is expected to have greater shelf life.
Based on the analyses of impedance measurement on electrodes
upon cycling and Mn dissolution on aged electrodes, we present
schematic drawings of formation of the passivation film as a
function of VC content as shown in Fig. 7. It is believed that the
difference in the thickness of passivation film on the electrode
Fig. 6. Amount of manganese dissolution estimated by immersing the Na2MnSiO4
electrodes in respective electrolytes (with 0 vol% vs. 5 vol% VC) at room temperature
for 30 days.
surface explains the variation in cell impedance, as well as the
degree of Mn dissolution and electrochemical performance. When
less than 5 vol% VC is used (Fig. 7a and b), the passivation film
formed does not sufficiently wrap the entire electrode surface
leading to high Mn dissolution. Conversely, when the concentration
of VC is increased beyond the optimum amount of 5 vol%, the
passivation film becomes much thicker, thus explaining the in-
crease in the passivation film and the associated charge transfer
resistances during storage processes with cycle life as evidenced
from the increase in size of semicircles of Nyquist plots of the
electrode (see Fig. 5e).
Please note that presently, the actual reason for the observed
increase in both the charge and discharge capacities when 5 vol%
VC is added is still unclear (as seen in Figs. 2a and 4). However, we
are claiming that the reason leading to this increase in capacity
might be due to a significantly suppressed manganese dissolution,
which is caused by an optimised passivation layer formed on the
electrode surface. Nonetheless, more in-depth analysis has to be
conducted to fully understand the role of this passivation layer.
Another possible explanation for the observed increase in storage
capacity in the first 10 cycles is that the liquid electrolyte might
penetrate slowly into the bulk of the mesoporous electrode mate-
rial investigated here as cycling progresses, thus promoting more
electrochemically active sites with cycling [41,42].
3.5. Redox reaction of Mn2þ during cycling
The observed high discharge capacity of over 200 mAh g1 is
mostly associated with the transition of Mn redox species to higher
oxidation state (Mn4þ). The reversible compositional changes of
Na2MnSiO4 ! Na2xMnSiO4 (0  x  2) is expected during charge-
discharge cycles, where Mn is oxidised from þ2 to þ4 during
charge, and reduced from þ4 to þ2 during discharge. In order to
confirm such a redox reaction, ex-situ XPS spectra are recorded on a
fresh, 20, 40, 50, 60, 80 and 100% state-of-charge (SoC) electrodes,
and a fully discharged electrode. It should be noted that the fittings
yield a c2 value of less than 0.3, which indicates a good fit. From
Fig. 8a, Mn in the fresh electrode has binding energy (BE) of
640.2 eV, corresponding to the BE of Mn2þ 2p3/2 [43e47]. There is
no Mn3þ or Mn4þ species detected at this stage. At a 20% SoC,
deconvolution of the spectra results in two peaks located at 640.2
and 641.2 eV, which belong to Mn2þ 2p3/2 and Mn3þ 2p3/2,
 M. Law et al. / Journal of Power Sources 359 (2017) 277e284 283

Fig. 7. Schematic illustrations of formation of the passivation film with (a) 0 vol%, (b) 3 vol%, (c) 5 vol%, (d) 7 vol% and (e) 10 vol% VC.

Fig. 8. Ex-situ XPS spectra of Mn2þ/Mn3þ/Mn4þ redox couples obtained on electrode at (a) fresh, 20%, 40% and 50% SoC and (b) 60%, 80% and 100% SoC and 100% DoD.
284 M. Law et al. / Journal of Power Sources 359 (2017) 277e284
respectively [43,46,47]. Upon continuation of charge, the Mn3þ
peak is seen to increase in intensity at the expense of the Mn2þ
peaks until a 60% SoC (Fig. 8b). The Mn2þ peaks disappear
completely as charge progresses, and an onset of Mn4þ peaks are
detected at 642.2 eV corresponding to Mn4þ 2p3/2 [43,47,48]. The
intensity of this peak increases until a 100% SoC, where the co-
existence of both Mn3þ and Mn4þ peaks are observed. Upon a
100% DoD, all Mn3þ and Mn4þ species are fully reduced to Mn2þ.
We recognise the fact that the XPS experiment is surface-
sensitive and the results represent information only on surface
processes during battery operation. Careful fitting of the XPS data
reveals that Mn ions on the surface are oxidised from Mn2þ to Mn4þ
at the end of the charge process and reduced to Mn2þ at the end of
the discharge process. As a result, charge-discharge processes
involve multiple moles of Naþ, which is confirmed by utilisation of
~1.5 mol of Naþ during galvanostatic cycling. This explains the
impressive discharge capacity of 210 mAh g1 achieved for the
Na2MnSiO4 compound in this study.
4. Conclusions
In summary, a silicate-based, Na2MnSiO4 compound is proposed
as an excellent cathode material for sodium-ion battery registering
impressive discharge capacity of 210 mAh g1, highest amongst
those reported so far for polyanion framework. Rate performance
shows that this material is able to deliver a reversible discharge
capacity close to 100 mAh g1 at 5 C. In addition, it exhibits
excellent long-term cycling performance at 1 C, achieving capacity
retention close to 90% after 500 cycles. Electrochemical perfor-
mance of this compound is found to be extremely dependent on
additive VC content; the better performance being obtained at 5 vol
% VC. It is seen that adding an optimum amount of VC in the
electrolyte forms a meta-stable passivation film on Na2MnSiO4,
which decreases the cell impedance as a function of cycle number.
Through chemical analysis of the electrolyte, it is found that the
surface film provides a passivation on the electrode surface,
resulting in significantly suppressed Mn dissolution over time. Ex-
situ XPS analysis reveals that Mn2þ/Mn3þ/Mn4þ is the active redox
species during charge and discharge cycles, involving utilisation of
~1.5 mol of Naþ per formula unit of Na2MnSiO4 cathode material.
The superior electrochemical performance obtained in this study is
due to the interdependent effect of both the structural stability of
the Na2MnSiO4 electrode, as well as the optimised electrolyte and
additive mixture.
Acknowledgements
Markas thanks NUS, Singapore for research scholarship. PB
thanks NUS for funding sodium battery research (WBS No. R-261-
510-001-646). The authors thank MoE, Singapore (WBS: R-265-
000-510-112) and EMA, Singapore (WBS No. R-265-000-568-279)
for funding support.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jpowsour.2017.05.069.
References
[1] S.-W. Kim, D.-H. Seo, X. Ma, G. Ceder, K. Kang, Adv. Energy Mater. 2 (2012)
710e721.
[2] S.Y. Hong, Y. Kim, Y. Park, A. Choi, N.-S. Choi, K.T. Lee, Energy Environ. Sci. 6
(2013) 2067.
[3] B.L. Ellis, L.F. Nazar, Curr. Opin. Solid State Mater. Sci. 16 (2012) 168e177.
[4] M.D. Slater, D. Kim, E. Lee, C.S. Johnson, Adv. Funct. Mater. 23 (2013) 947e958.
[5] C. Delmas, J.-J. Braconnier, C. Fouassier, P. Hagenmuller, Solid State Ion. 3e4
(1981) 165e169.
[6] J. Molenda, Claude Delmas, P. Hagenmuller, Solid State Ion. 9e10 (1983)
431e435.
[7] A. Mendiboure, C. Delmas, P. Hagenmuller, J. Solid State Chem. 57 (1985)
323e331.
[8] H. Liu, J. Xu, C. Ma, Y.S. Meng, Chem. Commun. 51 (2015) 4693.
[9] N. Yabuuchi, R. Hara, K. Kubota, J. Paulsen, S. Kumakura, S. Komaba, J. Mater.
Chem. A 2 (2014) 16851.
[10] N. Yabuuchi, M. Kajiyama, J. Iwatate, H. Nishikawa, S. Hitomi, R. Okuyama,
R. Usui, Y. Yamada, S. Komaba, Nat. Mater. 11 (2012) 512.
[11] S. Komaba, N. Yabuuchi, T. Nakayama, A. Ogata, T. Ishikawa, I. Nakai, Inorg.
Chem. 51 (2012) 6211e6220.
[12] N. Yabuuchi, R. Hara, M. Kajiyama, K. Kubota, T. Ishigaki, A. Hoshikawa,
S. Komaba, Adv. Energy Mater. 4 (2014) 1301453.
[13] D. Kundu, E. Talaie, V. Duffort, L.F. Nazar, Angew. Chem. Int. Ed. 54 (2015),
3431e3344.
[14] J.M. Clark, P. Barpanda, A. Yamada, M.S. Islam, J. Mater. Chem. A 2 (2014)
11807.
[15] P. Barpanda, G. Liu, C.D. Ling, M. Tamaru, M. Avdeev, S.-C. Chung, Y. Yamada,
A. Yamada, Chem. Mater. 25 (2013) 3480.
[16] P. Barpanda, G. Oyama, S.-i. Nishimura, S.-C. Chung, A. Yamada, Nat. Commun.
5 (2015) 4358.
[17] M. Law, V. Ramar, P. Balaya, RSC Adv. 5 (2015) 50155.
[18] H. Zou, S. Li, X. Wu, M.J. McDonald, Y. Yang, ECS Electrochem. Lett. 4 (2015)
A53.
[19] Y. Zhong, Z. Wu, Y. Tang, W. Xiang, X. Guo, B. Zhong, Mater. Lett. 145 (2015)
269.
[20] Y.-U. Park, D.-H. Seo, H.-S. Kwon, B. Kim, J. Kim, H. Kim, I. Kim, H.-I. Yoo,
K. Kang, J. Am. Chem. Soc. 135 (2013) 13870.
[21] K. Saravanan, C.W. Mason, A. Rudola, K.H. Wong, P. Balaya, Adv. Energy Mater.
3 (2013) 444.
[22] H. Duncan, A. Kondamreddy, P.H.J. Mercier, Y.L. Page, Y. Abu-Lebdeh,
M. Couillard, P.S. Whitfield, I.J. Davidson, Chem. Mater. 23 (2011) 5446e5456.
[23] C.-Y. Chen, K. Matsumoto, T. Nohira, R. Hagiwara, Electrochem. Commun. 45
(2014) 63e66.
[24] V. Ramar, P. Balaya, Phys. Chem. Chem. Phys. 15 (2013) 17240.
[25] N. Yabuuchi, M. Sugano, Y. Yamakawa, I. Nakai, K. Sakamoto, H. Muramatsu,
S. Komaba, J. Mater. Chem. 21 (2011) 10035.
[26] A. Ponrouch, E. Marchante, M. Courty, J.-M. Tarascon, M.R. Palacin, Energy
Environ. Sci. 5 (2012) 8572e8583.
[27] V. Ramar, P. Balaya, J. Power Sources 306 (2016) 552e558.
[28] M. Moriya, M. Miyahara, M. Hokazono, H. Sasaki, A. Nemoto, S. Katayama,
Y. Akimoto, S.-i. Hirano, J. Electrochem. Soc. 161 (2014) A97eA101.
[29] R. Dominko, J. Power Sources 184 (2008) 462e468.
[30] A. Rudola, D. Aurbach, P. Balaya, Electrochem. Commun. 46 (2014) 56e59.
[31] D. Aurbach, J. Power Sources 89 (2000) 206e218.
[32] J.C. Burns, R. Petibon, K.J. Nelson, N.N. Sinha, A. Kassam, B.M. Way, J.R. Dahn,
J. Electrochem. Soc. 160 (2013) A1668eA1674.
[33] D. Aurbach, K. Gamolsky, B. Markovsky, Y. Gofer, M. Schmidt, U. Heider,
Electrochimica Acta 47 (2002) 1423e1439.
[34] J. Li, W. Yao, Y.S. Meng, Y. Yang, J. Phys. Chem. C 112 (2008) 12550e12556.
[35] K.S. Kang, S. Choi, J.-H. Song, S.-G. Woo, Y.N. Jo, J. Choi, T. Yim, J.-S. Yu, Y.-
J. Kim, J. Power Sources 253 (2014) 48e54.
[36] E.-G. Shim, T.-H. Nam, J.-G. Kim, H.-S. Kim, S.-I. Moon, J. Power Sources 172
(2007) 901e907.
[37] T.-H. Nam, E.-G. Shim, J.-G. Kim, H.-S. Kim, S.-I. Moon, J. Electrochem. Soc. 154
(2007) A957eA963.
[38] C.M. Julien, A. Mauger, K. Zaghib, H. Groult, Inorganics 2 (2014) 132e154.
[39] J. Wang, Q. Zhang, X. Li, Z. Wang, K. Zhang, H. Guo, G. Yan, B. Huang, Z. He,
Electrochem. Commun. 36 (2013) 6e9.
[40] K. Xu, Chem. Rev. 104 (2004) 4303e4418.
[41] R. Dominko, M. Bele, M. Gaberscek, M. Remskar, D. Hanzel, J.M. Goupil,
S. Pejovnik, J. Jamnik, J. Power Sources 153 (2006) 274e280.
[42] C. Sun, S. Rajasekhara, J.B. Goodenough, F. Zhou, J. Am. Chem. Soc. 133 (2011)
2132e2135.
[43] M.C. Biesinger, B.P. Payne, A.P. Grosvenor, L.W.M. Lau, A.R. Gerson,
R.S.C. Smart, Appl. Surf. Sci. 257 (2011) 2717e2730.
[44] D. Choi, J. Xiao, Y.J. Choi, J.S. Hardy, M. Vijayakumar, M.S. Bhuvaneswari, J. Liu,
W. Xu, W. Wang, Z. Yang, G.L. Graff, J.-G. Zhang, Energy Environ. Sci. 4 (2011)
4560e4566.
[45] V. Ramar, P. Balaya, Phys. Chem. Chem. Phys. 15 (2013) 17240e17249.
[46] Y. Liu, Q. Wang, Y. Gao, J. Pan, M. Su, B. Hai, G. Zhu, S. Liu, J. Alloys Compd. 646
(2015) 112e118.
[47] M. Kuezma, S. Devaraj, P. Balaya, J. Mater. Chem. 22 (2012) 21279.
[48] L. Yunjian, L. Xinhai, G. Huajun, W. Zhixing, H. Qiyang, P. Wenjie, Y. Yong,
J. Power Sources 189 (2009) 721e725.