Journal of Electroanalytical Chemistry 799 (2017) 134–141

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Journal of Electroanalytical Chemistry

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Electrochemical impedance studies of Na/MnO2 primary cells MARK

⁎
Brij Kishore, Munichandraiah Nookala
Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bengaluru 560012, India

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

Keywords: Primary Na/MnO2 cells are expected to gain importance for replacement of primary Li/MnO2 cells in future akin
Na/MnO2 primary cells to the Na-ion cells as alternative for Li-ion cells. Amorphous MnO2 is prepared by a drop-wise addition of KMnO4
Depth-of-discharge solution to MnSO4 solution, and coin cells of Na/MnO2 are fabricated in a non-aqueous electrolyte of Na salt. The
Surface film electrochemical impedance spectroscopy (EIS) data provides a high resistance of Na metal due to the surface
Delayed response
passive film. On subjecting the cell for discharge, the surface film causes a delay response of the cell voltage and
Electrochemical impedance spectroscopy
the closed circuit voltage reaches the normal discharge level following dielectric breakdown of the film. The EIS
data measured at different stages of cell discharge are subjected to non-linear least square fitting with the aid of
an appropriate equivalent circuit. The impedance parameters are examined to throw light on state-of-charge of
Na/MnO2 primary cells.

1. Introduction Zn/HgO primary cells by differential AC resistance method. Measure-

There has been increasing interest on Na-based non-aqueous re-
chargeable batteries in research and development laboratories for a
viable substitution for Li-based batteries [1,2]. This is because of in-
creasing demand for Li-ion batteries in spite of the fact that the global
resources of Li are limited and they are distributed unevenly [3,4].
Primary batteries based on Li are also widely used for several appli-
cations [5]. Similar to the substitution of Li in Li-ion batteries resulting
in Na-ion batteries, Na-based primary batteries are expected to be vi-
able substitutes for Li-based primary batteries. Recently, we have re-
ported studies on Na/MnO2 primary cells and compared the results with
Li/MnO2 primary cells, which were fabricated and evaluated under
similar experimental conditions [6]. The performance of Na/MnO2 cells
is comparable to that of Li/MnO2 cells, except that the discharge pla-
teau voltage of the former is less by about 0.4 V.
Electrochemical impedance spectroscopy (EIS) is a useful technique
to evaluate various properties of electrochemical systems [7–10]. The
technique involves application of a small alternating current (AC) signal
over a wide frequency range on the electrochemical cell and measuring
current response. The analysis of EIS data allows separation of resistive
and capacitive components of the electrochemical cell and, therefore,
several electrochemical parameters can be evaluated. Several battery
systems were studied by EIS as a non-destructive technique to evaluate
state-of-charge (SOC) and kinetic parameters of electrochemical reac-
tions [11–15]. There are only a few reports available in the literature on
impedance studies of primary cells. Winter et al. [16], studied SOC of
ments of current-voltage characteristics, and AC impedance at different
currents and frequencies were reported. Slopes of current-voltage
curves above a certain cell current were nearly constant. These slopes
had linear relation to the charge expended and were used as a basis for
state-of-charge indication. Impedance parameters and SOC estimation
studies of Zn/MnO2 and Mg/MnO2 primary cells were reported by
Gopikanth and Sathyanarayana [17]. The problem of non-destructive
determination of SOC of these cells was examined from the view point
of impedance parameters and open-circuit voltage at equilibrium. The
equivalent series/parallel resistance and capacitance, modulus of im-
pedance and phase shift of commercial Zn/MnO2 and prototype Mg/
MnO2 cells were measured at different SOC values. For an un-dis-
charged Mg/MnO2 cell, the Nyquist plot was a straight line with slope
greater than unity, which was ascribed due to protective surface film
present on the Mg anode. However, the Nyquist plot exhibited a
semicircle, after the cell was subjected to partial discharge, due to
breakdown of surface film on Mg. The area under the semicircle de-
creased with a decrease in SOC indicating a decrease in polarization
resistance with a progressive discharge of the cells. In the case of Zn/
MnO2 primary cells, there was a progressive change from charge-
transfer control of impedance at SOC ≈ 1 to diffusion control at
SOC ≈ 0. It was concluded that determination of SOC was not possible
for Mg/MnO2 and Zn/MnO2 cells by measuring equivalent series/par-
allel resistance and capacitance, modulus of impedance or phase shift
due to large fluctuations caused by film break down and reformation
processes. In another study of aged Mg/MnO2 primary cells, impedance

⁎
Corresponding author.
E-mail address: muni@ipc.iisc.ernet.in (M. Nookala).

http://dx.doi.org/10.1016/j.jelechem.2017.05.038
Received 27 December 2016; Received in revised form 16 May 2017; Accepted 22 May 2017
Available online 23 May 2017
1572-6657/ © 2017 Elsevier B.V. All rights reserved.
B. Kishore, M. Nookala
parameters were examined at several SOC values and also ageing time
dependence of partially discharged cells [18]. It was shown that the
frequency (fmax) corresponding to the maximum value of the imaginary
component of the high frequency semicircle exhibited a nearly linear
increase from about 2 Hz (virgin cell) to about 40 Hz (fully discharged
cell). It was thus concluded that fmax was a suitable parameter for the
estimation of SOC or residual capacity of aged Mg/MnO2 cells. For a
partially discharged Mg/MnO2 cell, resistance parameters increased
linearly with ageing time.
In the present work, Na/MnO2 non-aqueous primary cells are as-
sembled and studied by EIS at several stages of discharge. The EIS data
are analyzed using an appropriate equivalent circuit. The variation of
impedance parameters with depth-of-discharge (DOD) is studied to
identify the cell's state-of-charge.
2. Experimental
The performance of Na/MnO2 primary cell strongly depends on the
crystallographic nature of MnO2, which in turn depends on the syn-
thetic route [19,20]. The performance of cells assembled using poorly
crystalline MnO2 was superior to that of cells made with crystalline
MnO2 [6]. In the present study, amorphous MnO2 was synthesized by a
different route. It was synthesized by redox reaction between KMnO4
(SRL) and MnSO4·H2O (HIMEDIA). In brief, 0.727 g of KMnO4 was
dissolved in 50 ml of double distilled (DD) water and added drop wise
to 50 ml aqueous solution containing 1.166 g of MnSO4·H2O under
constant stirring. After the complete addition, the contents were stirred
for additional 6 h. The product was collected by filtration, washed co-
piously with DD water, then with ethanol and dried at 70 °C for about
12 h. The quantity of sample prepared in each batch was about 1.0 g.
The MnO2 samples were characterized by powder X-ray diffraction
(XRD) using a Philips X'Pert Pro diffractometer at 45 kV and 30 mA
with Cu Kα (λ = 1.5418 Å) as the radiation source and the data were
collected at 2θ range from 10 to 90° at a rate of 2° per min. The mor-
phology was examined using a FEI Co scanning electron microscope
(SEM) model Sirion. Nitrogen adsorption-desorption isotherms were
recorded at −196 °C using Micromeritics surface area analyzer model
ASAP2020. The specific surface area was calculated by the Brunauer-
Emmett-Teller (BET) method from the adsorption branch. The pore size
distribution was calculated by Barrett-Joyner-Halenda (BJH) method
from desorption branch of the isotherm. The oxidation states of Mn on
the surface of the sample was examined by high resolution X-ray pho-
toelectron spectroscopy (XPS: Kratos Axis Ultra DLD system) with dual
Al source of 1486.6 eV, 300 μm × 700 μm aperture size and the C 1s
signal as the reference in ultrahigh vacuum. The stoichiometry was
checked via Inductively Coupled Plasma-Optical Emission Spectrometry
(ICP-OES) with a Perkin Elmer Optima 2100DV Analytical Instruments.
Thermogravimetric analysis (TGA) was carried out under argon flow at
a heating rate of 10 °C min−1 from room temperature to 900 °C using
TG 209 F1 Iris, NETZSCH instrument.
For fabrication of electrodes, the active material (70 wt%), acet-
ylene black (20 wt%, Alfa Aesar) and polytetrafluoroethylene suspen-
sion (10 wt%, Aldrich) were mixed in a mortar and ground well. The
dough, thus, formed was rolled into a sheet on a glass plate. Stainless
steel (SS) mesh of 0.3 mm thickness and mesh size 80 was used as the
current collector. The pre-treatment of SS mesh was carried out by first
etching it in 5 N HCl (SDFCL), followed by etching in 5 N HNO3
(SDFCL). It was then washed thoroughly with DD water, rinsed with
acetone (SDFCL) and air dried. The rolled sheet of electrode material
was transferred onto a mesh of 16 mm diameter such that the loading
level of the active material was 10–12 mg cm−2. The electrodes were
then dried at 100 °C under reduced pressure for 12 h. Coin cells CR2032
(Hohsen Corporation, Japan) were assembled where Na (SDFCL) metal
foil (about 30 mg cm−2) was used as the anode and MnO2 as the
cathode. Whatman filter paper grade GF/C was used as the separator
and 1 M NaPF6 (Aldrich) dissolved in a mixed solvent of ethylene
135
Journal of Electroanalytical Chemistry 799 (2017) 134–141
carbonate (Aldrich) and propylene carbonate (Aldrich) (1:1 by volume)
was used as the electrolyte. Coin cells were assembled in argon filled
MBraun glove box model Unilab. Galvanostatic discharge experiments
were carried out using Biologic SA multichannel potentiostat/galva-
nostat model VMP3. Electrochemical impedance spectroscopy mea-
surements were carried out using a CH Instrument model CHI608C. For
the purpose of recording EIS at intermittent stages of cell discharge, the
cell was galvanostatically discharged at 100 μA for the required dura-
tion, disconnected from the potentiostat/galvanostat and allowed at
rest for 30 min before recording EIS. The cell was again discharged for
the required duration and EIS was measured following the above steps.
All experiments were carried out at 22 ± 1 °C.
3. Results and discussions
There are various synthetic routes known for the preparation of
MnO2, which include oxidation of Mn2+ ions by a suitable oxidizing
agent, reduction of Mn7+ by a reducing agent and electrochemical
deposition [19,20]. In the present study, the synthesis of MnO2 was
carried out by adding drop-wise a neutral aqueous solution of KMnO4 to
an aqueous solution of MnSO4. The redox reaction between Mn7+ and
Mn2+ results in the formation of MnO2.
2KMnO4 + 3MnSO4 + 2H2 O → 5MnO2 + K2 SO4 + 2H2 SO4 (1)
The reaction was carried out at room temperature. The product was
washed and dried at 70 °C.
There are several reports on synthesis of MnO2 from the redox re-
action between Mn2+ and Mn7+ ions [21,22]. DeGuzman et al., pre-
pared MnO2 of different crystal phases by varying pH and temperature
from the redox reaction between KMnO4 and MnSO4 [21]. Chen et al.,
prepared α-MnO2 from KMnO4 and H2SO4 at 70–95 °C by the redox
reaction between Mn7+ and Mn2+, the latter being formed by reduc-
tion of KMnO4 in strong acidic conditions [22]. Crystalline MnO2 na-
noparticles were prepared by mixing aqueous solutions of KMnO4 and
MnSO4 at ambient conditions and aging for different durations at 25
and 85 °C. It is understood from the above reports that the redox re-
action between KMnO4 and MnSO4 produces different crystalline
phases by varying the reaction conditions. Unlike the formation of
crystalline phases of MnO2 in these reports, an amorphous MnO2 is
obtained in the present study from the reaction between aqueous so-
lutions of KMnO4 and MnSO4, as detailed below. The formation of
amorphous MnO2 is attributed to a slow drop-wise addition of KMnO4
solution to MnSO4 solution.
The MnO2 sample was subjected to chemical analysis by ICP and
TGA. There was a loss of 11.29 wt% up to 250 °C when the sample was
subjected to TGA. The results of chemical analysis after applying cor-
rection of 11.29 wt% water was Mn 60.32, K 1.47, and O 33.90 wt%.
Thus the composition of the sample becomes MnK0.033O2.17. Taking
account of water present in the as prepared sample, the manganese
dioxide formula thus becomes MnK0.033O2.17.0.6H2O. The hydrated
oxide is referred to as MnO2 hereafter.
It is known that MnO2 forms in different polymorphs depending on
the way MnO6 octahedra are inter-linked [23]. Powder XRD pattern
(not given) of MnO2 sample prepared in the present study indicated that
it was poorly crystalline. Minor broad peaks were observed at 2θ values
of 36.6°, 41.1°, 54.7° and 65.9° corresponding to the α-phase. For α-
MnO2, the octahedra are linked at the corners to form a (2 × 2) and a
(1 × 1) channels. This structure allows the Na+ ion diffusion. The XPS
spectrum for Mn 2p3/2 signal of the sample is shown in Fig. 1. On de-
convolution of the spectrum [24], oxidation states of +2, +3 and +4
are identified for Mn, but the major oxidation state is +4. The mor-
phology of MnO2 sample as seen in scanning electron micrograph
(Fig. 2a) appears globules, which consist of short fibers as reflected in
transmission electron micrograph (Fig. 2b). Nitrogen adsorption/deso-
rption isotherms and BJH curves of S70 sample are shown in Fig. 3.
There is a wide hysteresis loop in the isotherm (Fig. 3), which is an
B. Kishore, M. Nookala Journal of Electroanalytical Chemistry 799 (2017) 134–141

220

Quantity of N2 adsorbed / cm3 g-1

3 -1 -1
200

dV/dD / cm g nm
0.4

0.3
180
4+ 0.2
Mn
Intensity / a.u.

160 0.1

140 0.0
0 1 2 3 4 5 6 7 8 9 10
120 Pore diameter / nm

100
Mn3+
80

Mn2+
60
40
638 640 642 644 646 648
20
Binding energy / eV 0.0 0.2 0.4 0.6 0.8 1.0
o
Fig. 1. X-ray photoelectron spectra of MnO2 sample in Mn 3P3/2 region.
Relative pressure (p/p )
Fig. 3. Nitrogen adsorption/desorption isotherm of MnO2 sample and in the inset is BJH
indication of porous nature of the sample. The BET specific surface area pore distribution curve.
for the sample is 184 m2 g−1. The BJH curve (Fig. 3 inset), shows a very
narrow pore size distribution at pore diameter of 3.5 nm. 3.5 3.5
A Na/MnO2 coin cell was subjected to galvanostatic discharge at
0.50 mA (0.25 mA cm−2) and the voltage profile is presented in Fig. 4. 3.0
The open circuit voltage of the cell before discharge is 3.32 V. On in- 3.0

Cell voltage / V
Cell voltage / V
itiation of galvanostatic discharge, there is a sudden decrease in cell 2.5

voltage followed by a rise to about 3.05 V. Thereafter, the cell voltage

decreases gradually down to the cut-off voltage of 1.0 V. The time re- 2.5 2.0

quired to complete the discharge is 7 h (i.e. C/7 rate) and the discharge 1.5
capacity obtained is 3.5 mAh. This value is close to the theoretical value
2.0
(308 mAh g−1), which is calculated on the basis of MnO2. The dis- 1.0
charge voltage profile is similar to that of Li/MnO2 cells, which are 0 1 2 3 4 5 6 7
assembled under similar conditions to that of Na/MnO2 cells [6]. The 1.5 Time / h
discharge capacity of both Li/MnO2 and Na/MnO2 cells are also the
same. However, the voltage of Na/MnO2 cell is less than that of Li/
MnO2 cell by about 0.4 V, which arises due to the difference in po- 1.0
tentials of Li/Li+ and Na/Na+ electrodes.
Nyquist and Bode plots of a fresh Na/MnO2 cell are shown in Fig. 5. 0 1 2 3 4 5 6 7
The Nyquist plot (Fig. 5a) consists of a high frequency intercept on the Time / h
real axis, a semicircular region in the frequency range from 100 kHz to
1 Hz and a linear region, which is parallel to the real axis. The Bode Fig. 4. Discharge curve of Na/MnO2 cell during continuous discharge and the curve with
intermittent discharges in the inset.
plots (Fig. 5b) suggest a resistive region at low frequency (phase angle
(θ): −2° and impedance (| Z |): 3.8 kΩ) as well as at high frequency
regions (θ: −10° and | Z|: 100 Ω), and a capacitive behavior with θ: the flow of current. Among these components, the anode and cathode
−60° at mid frequency region. The cell consists of Na metal foil as the are expected to contribute significantly to the total cell impedance. In
anode and MnO2 powder pressed on SS mesh as the cathode in the non- order to understand which of the two electrodes decide the cell im-
aqueous electrolyte. The cell impedance is expected due to the con- pedance, Na/Na and MnO2/MnO2 symmetrical cells were assembled
tribution of all cell components, which constitute the electric circuit for and their impedance spectra were recorded at the open circuit voltage,

Fig. 2. (a) Scanning electron micrograph and (b) trans-

mission electron micropgraph of MnO2 sample.

136
B. Kishore, M. Nookala Journal of Electroanalytical Chemistry 799 (2017) 134–141

4000 9000
a a
3500
7500
3000
6000
2500
-Z'' / Ω

-Z" / Ω
2000 4500
31 Hz
1500 81 Hz 14 Hz
3000
253 Hz
1000 4.5 Hz
0.01 Hz
1 kHz 1.4 Hz 0.08 Hz
500 1500

0
0 500 1000 1500 2000 2500 3000 3500 4000 0
Z' / Ω 0 1500 3000 4500 6000 7500 9000
Z' / Ω
1000
150
b b
60 125
-Phase / Degree

800
45 100

-Z'' / Ω
30 75

600
15
-Z'' / Ω 50

0 25
400
0
3.6 0 25 50 75 100 125 150
Z' / Ω
log (|Z| / Ω)

3.2
200
2.8
2.4
0
2.0
0 200 400 600 800 1000
1.6 Z' / Ω
-2 -1 0 1 2 3 4 5
log (freq / Hz) Fig. 6. Nyquist plots of (a) Na/Na and (b) MnO2/MnO2 symmetrical cells.

Fig. 5. (a) Nyquist and (b) Bode EIS plots of as assembled Na/MnO2 cell. The measured
spectrum is shown by data points and the fit spectrum by smooth curve. Frequencies 3.20
corresponding to some data points are indicated in (a). The NLLS fit was carried out V1
between 100 KHz and 1 mHz. 3.15

which was close to 0.0 V in each case (Fig. 6). It is seen that the re-
Cell voltage / V

3.10
sistance measured from low frequency region for Na/Na symmetrical
cell is about 9 kΩ, whereas it is about 50 Ω for MnO2/MnO2 symme- 3.05 delay time
trical cell. Thus, the impedance of Na/Na cell is greater than that of
MnO2/MnO2 cell by about 180 times. MnO2 electrodes are fabricated V3
3.00
using high surface area MnO2 particles pressed on SS mesh current
collecting substrate. As a result, MnO2 electrodes have low impedance.
2.95
As Na and MnO2 electrodes in a Na/MnO2 cell are present in series
combination, the impedance characteristics of the cell (Fig. 5) are at-
2.90
tributed essentially to the contribution of Na anode of high impedance.
This is due the fact that Na metal is covered with a passivating layer in V2
2.85
contact with the electrolyte. The passive film acts as a barrier for the 0 5 10 15 20 25 30 35 40 45 50
flow of charge across the Na anode. The presence of passive film is
confirmed by analysis of discharge voltage profile, which is discussed Time / s
below in detail. Fig. 7. Voltage transient (delay action) of Na/MnO2 coin cell on initiation of galvano-
The voltage profile of Na/MnO2 coin cell at the beginning of gal- static discharge at 100 μA.
vanostatic discharge at 100 μA is shown in Fig. 7. The cell voltage drops
from the open circuit voltage of 3.17 V to 2.87 V instantaneously at the Na/MnO2 cell is 13 s (Fig. 7). This delay time is caused by the surface
commencement of galvanostatic discharge, followed by an increase protective film present on the metal, which initially acts as a barrier for
approaching about 3.0 V and then the voltage follows a normal course the passage of current through the cell. Thus, there is a decrease in the
of cell discharge. Thus, there is a time lag between the initiation of cell voltage due to the film resistance. In the non-aqueous Li primary
discharge and commencement of actual discharge. This time lag is cells consisting of soluble SOCl2 or SO2Cl2, which serves as both the
known as the ‘delay action’ or ‘delay time’ in the literature of Li metal- solvent and the cathode active material, the Li metal undergoes oxi-
as well as Mg metal-based battery systems [25–31]. The delay time of dation resulting in the formation of film of LiCl on its surface. The LiCl

137
B. Kishore, M. Nookala
film formed at the initial stages of contact of Li with the solution acts as
a barrier to protect the underlying Li metal and also as the inter-elec-
trode separator. When the cell is subjected to discharge, the LiCl film
undergoes a break-down or rupture, thus, allowing the Li surface to
make contact with the electrolyte and undergo oxidation. A delay ac-
tion is observed at this stage [25,26]. In a similar way, aqueous based
Mg/MnO2 cells also exhibit delay action when the oxide film present on
Mg breaks down on initiation of cell discharge [29–31]. The delay time
behavior observed for Na/MnO2 cell in the present study (Fig. 7) is
similar to Li/SOCl2 or Li/SO2Cl2 cells [26,27]. Thus, it is inferred that
the Na foil used as the anode in Na/MnO2 cell is covered with a pas-
sivating layer, which acts as a barrier for the electrochemical oxidation
of Na in the non-aqueous electrolyte. Thus, the high impedance ob-
served in Fig. 5 for Na/MnO2 cell and also in Fig. 6a for Na/Na sym-
metrical cell is associated with the resistance of passivating film. On
initiation of galvanostatic discharge, the surface film undergoes di-
electric breakdown or rupture at weak spots resulting in exposure of
film-free regions of Na surface. It is expected that now a fraction of Na
metal surface is covered with film and the rest (film-free region) of the
surface can allow the electrochemical oxidation of Na.
The reaction expected at the film-free region of the Na anode during
discharge of Na/MnO2 cell is given in Eq. (2).
Na → Na+ + e− (2)
The electrical equivalent circuit appropriate for the Na electrode
with film covered and film free regions is shown in Fig. 8a. The film
covered region is characterized by a parallel combination of the film
resistance (Rf) and its capacitance (Cf). The surface of Na exposed to the
electrolyte is characterized by charge-transfer resistance (Rct) of reac-
tion (2), diffusion controlled Warburg resistance (W) and double-layer
capacitance (Cdl). The Nyquist plot of impedance is expected to consist
of two semicircles and a linear spike as shown in Fig. 8b. The high
frequency impedance of the Nyquist plot provides the value of ohmic
resistance (RΩ) of the cell. The value of Rf can be calculated from the
diameter of high frequency semicircle and film capacitance Cf from the
following relationship.
Cf = 1⁄ (2πf ∗Rf ) (3)
where f* is the AC frequency corresponding to the maximum in the
imaginary component (−Z”) on the high frequency semicircle. Simi-
larly, Rct can be calculated from the diameter of the high frequency
semicircle and Cdl from the following equation.
Cdl = 1⁄ (2πf #R ct) (4)
138
Journal of Electroanalytical Chemistry 799 (2017) 134–141
where f# is the AC frequency corresponding to the maximum of the
imaginary component (−Z”) on the low frequency semicircle.
However, the Nyquist plot of Na/MnO2 cell shown in Fig. 5a ap-
pears as a single semicircle. The semicircle is depressed and distorted,
which is likely due to porous nature of the surface film. The EIS spec-
trum of fresh Na/MnO2 cells (Fig. 5) was subjected to non-linear least
squares (NLLS) fitting procedure using the equivalent circuit (Fig. 8). As
the low frequency data do not exhibit Warburg, the Warburg element is
excluded for the purpose of data fit. The capacitances are replaced by
constant phase elements (CPE). A CPE is defined as
ZCPE = 1 ((jω) nY) (5)
where ω = 2πf, f being the frequency and n is a constant. For n = 0, the
CPE represents a resistance with R = Y−1; for n = 1, a capacitance
with C = Y; for n = 0.5, a Warburg and for n = −1, inductance with
L = Y−1 [32]. The necessity of using CPE in the place of capacitance
arises because of its microscopic distribution over finite size electrodes,
which possess a large number of surface defects such as kinks, jags, and
edges, local charge inhomogeneities, two-or-three-phase regions, ad-
sorbed species, and variations in composition and stoichiometry [32].
The impedance parameters obtained from the NLLS fit procedure are
listed in Table 1. The theoretical spectrum generated from the fit pro-
cedure is shown as smooth curves in both Nyquist and Bode plots and
the experimental data points are presented as open circles. It is seen
that the theoretical spectrum passes through the data points and the χ2
of NLLS fit is 1 × 10−4. These observations suggest the impedance
parameters obtained are reliable. The total resistance (Rs + Rf + Rct) is
4210 Ω. This value is close to the high frequency intercept of Bode plot
(Fig. 5b). The phase angle is about −60° suggesting capacitance nature
of the system in the frequency range around 500 Hz.
A Na/MnO2 cell was discharged at C/7 rate to depth of discharge
(DOD) of 0.04, allowed at rest for about 15 min and impedance spec-
trum was recorded (Fig. 9). DOD is the ratio of charge removed from
the cell by discharge to the total capacity of the cell. It is seen from both
Nyquist and Bode plots that the cell resistance has decreased to 500 Ω
from 4210 Ω measured before the discharge (Fig. 5). At the com-
mencement of discharge, the surface film is ruptured exhibiting voltage
dip and delay action (Fig. 7) resulting in a decreased coverage of the
surface film. A large fraction of the Na surface is free from the surface
film and therefore the film resistance is expected to decrease. The EIS
spectrum was subjected to NLLS fit procedure, and the fit parameters
are listed in Table 1. As expected, there is a decrease of Rf to 112 Ω from
1620 Ω measured before the cell is subjected to a short discharge.
Fig. 8. (a) Equivalent circuit and (b) Nyquist representation of
EIS.
B. Kishore, M. Nookala Journal of Electroanalytical Chemistry 799 (2017) 134–141

Table 1
Impedance parameters of a Na/MnO2 cell at different depth of discharge values. Yf and nf correspond to constant phase element of surface film on Na; Ydl and ndl correspond to constant
phase element of double-layer, χ2 is goodness of NLLS fitting and other symbols are defined in the text.

DOD RΩ (Ω) Rf (Ω) Yf (F snf − 1) nf Rct (Ω) Ydl (F sndl − 1) ndl f⁎ (Hz) χ2

0.000 60.0 1620.0 8.96 × 10− 5 0.34 2530.00 2.75 × 10− 6 0.890 37.56 0.00014
0.036 52.6 112.6 6.85 × 10− 5 0.434 343.80 5.85 × 10− 6 0.859 214.80 0.00011
0.071 59.5 87.3 3.90 × 10− 5 0.494 192.70 7.41 × 10− 6 0.849 371.10 0.00011
0.214 56.8 88.8 2.36 × 10− 5 0.534 127.10 1.04 × 10− 5 0.819 664.10 0.00002
0.357 60.8 83.4 9.63 × 10− 6 0.519 78.79 1.31 × 10− 5 0.899 966.80 0.00002
0.500 63.8 86.3 6.58 × 10− 6 0.695 65.69 1.44 × 10− 5 0.811 966.90 0.00005
0.643 69.7 75.9 2.70 × 10− 6 0.748 61.56 1.16 × 10− 5 0.783 1172.00 0.00009
0.786 67.3 87.5 3.23 × 10− 6 0.776 48.53 1.07 × 10− 5 0.769 1465.00 0.00013
0.929 71.7 88.8 2.58 × 10− 6 0.789 46.24 1.28 × 10− 5 0.742 1465.00 0.00016
1.000 71.1 88.3 2.32 × 10− 6 0.781 52.45 1.41 × 10− 5 0.761 1172.00 0.00015

600
a 300
a
500 250

400 200
-Z'' / Ω

-Z'' / Ω
300 150
1 kHz 312 Hz
200
3.7 kHz 100 0.01 Hz
69 Hz 0.01 Hz
21 kHz 8 kHz 1.4 kHz 0.03 Hz
81 kHz
100 81 kHz 175 Hz 0.3 Hz
50

0
0 100 200 300 400 500 600 0
Z' / Ω 0 50 100 150 200 250 300
Z' / Ω
35
b
-Phase / Degree

30
25 15 b
-Phase / Degree

20 12
15
9
10
5 6
0 3
0

2.8
2.5
2.6 2.4
log (Z / Ω)

log (Z / Ω)

2.4 2.3
2.2 2.2
2.0 2.1
1.8 2.0
-2 -1 0 1 2 3 4 5 1.9
log (freq / Hz) -2.1 -1.1 0.1 1.1 2.1 3.1 4.1 5.1
log (freq / Hz)
Fig. 9. (a) Nyquist and (b) Bode plots of Na/MnO2 cell at DOD = 0.04. The measured
spectrum is shown by data points and the fit spectrum by smooth curve. Frequencies Fig. 10. (a) Nyquist and (b) Bode plots of Na/MnO2 cell at DOD = 0.8. The measured
corresponding to some data points are indicated in (a). spectrum is shown by data points and the fit spectrum by smooth curve. Frequencies
corresponding to some data points are indicated in (a).

Assuming Rf is a measure of coverage (Θ) of surface film, Θ can be

defined as density (io) of reaction (2) is calculated using Eq. (7)

Θ = Rf(DOD) Rf(initial) (6) i o = −RT (FAR ct) (7)

The surface coverage on Na electrode at DOD = 0.04 becomes 0.07. where R is gas constant, T is absolute temperature, F is Faraday con-
This indicates that a large fraction of area of Na electrode has become stant and A is electrode area. As Θ is very low as discussed above, A is
free from its surface film after initiation of galvanostatic discharge. approximated to the geometrical area of Na electrode. From the Rct
Similar to the decrease in Rf, there is a decrease in Rct from 2530 Ω value of 344 Ω, the value of io calculated at 25 °C for Na electrode, thus,
before discharge to 344 Ω at DOD = 0.04. A substantial decrease in Rct becomes 38 μA cm−2 at DOD = 0.04 (it is assumed that the area of Na
indicates that the reaction (2) in the non-aqueous electrolyte is more electrode does not undergo variation by cell discharge).
facile after the dielectric rupture of surface film. The exchange current The Na/MnO2 cell was subjected to discharge at C/7 rate and EIS

139
B. Kishore, M. Nookala Journal of Electroanalytical Chemistry 799 (2017) 134–141

100
a 1600 200 b

Film resistance (Rf) / Ω

Solution resistance (Rs) / Ω
80 1400 160

Film resistance (Rf) / Ω

1200 120

60 1000 80

800
40
40
600
0
0.0 0.2 0.4 0.6 0.8 1.0
400 Depth of discharge
20
200

0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
a Depth of discharge Depth of discharge

1600
c d
Charge transfer resistance (Rct) / Ω

Charge transfer resistance (Rct) / Ω

2500 500
1400

400 1200
2000
300 1000
1500

f* / Hz
200 800

1000 100 600

0 400
500 0.0 0.2 0.4 0.6 0.8 1.0
Depth of discharge
200
0
0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Depth of discharge Depth of discharge
Fig. 11. Dependence of (a) RΩ, (b) Rf, (c) Rct, and (d) f⁎ of Na/MnO2 cell on depth of discharge. The Y-axes between DOD = 0.04 and 1.0 are expanded and shown in insets of (b) and (c).

data were measured at several stages of discharge. The voltage versus τ = Rf Cf = 1 2πf ∗ (8)
time of discharge curve (Fig. 4 inset) shows that the cell voltage in- ⁎
an increase in f indicates a decrease in τ of surface film present on Na.
creases by about 0.20 V at open-circuit conditions from the closed
discharge circuit condition after terminating the discharge at the re- 4. Conclusions
quired DOD. The EIS measurements were made at the equilibrated
open-circuit cell voltage. The two overlapped semicircles as observed Primary Na/MnO2 cells are fabricated employing amorphous MnO2
above at DOD ≈ 0.04, were seen well separated at higher DODs. Ny- and electrochemical impedance measurements are carried out at dif-
quist and Bode plots recorded at DOD ≈ 0.80, for instance, are pre- ferent stages of cell discharge. The cell impedance is dominated by Na
sented in Fig. 10. The presence of two semicircles and the low fre- metal anode due to the surface film present on its surface initially for an
quency linear Warburg region are clearly seen in the Nyquist plot undischarged cell. On initiation of cell discharge, the surface passive
(Fig. 10a). The Bode plots also reflect a pair of time constants. The film undergoes dielectric breakdown resulting in a significant decrease
impedance parameters obtained from fitting of the data at all DODs are in cell impedance. The impedance parameters are examined in view of
presented in Table 1. The values of f⁎ corresponding to the high fre- identifying a suitable parameter that exhibits a strong dependence on
quency semicircle are also listed in Table 1. The variations of RΩ, Rf, Rct depth of discharge of the cell. The frequency maximum f⁎ increases
and f⁎ with DOD are presented in Fig. 11. It is seen that there is an from about 100 Hz for the undischarged cell to about 1400 Hz for a
increase in ohmic resistance (RΩ) from 60 Ω to about 70 Ω when the completely discharged cell. Thus, f⁎ is a suitable impedance parameter
Na/MnO2 cell is discharged completely. This marginal linear increase which strongly depends on the depth of discharge of Na/MnO2 primary
(Fig. 11a) is likely due to variation in electrolyte composition and also cell.
die to progressive percolation of the electrolyte into the pores of
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