Electrochemistry Received: November 26, 2016

Accepted: January 20, 2017

Published: April 5, 2017

The Electrochemical Society of Japan http://dx.doi.org/10.5796/electrochemistry.85.179

Article Electrochemistry, 85(4), 179–185 (2017)

Effect of Concentrated Electrolyte on Aqueous Sodium-ion Battery

with Sodium Manganese Hexacyanoferrate Cathode
Kosuke NAKAMOTO,a Ryo SAKAMOTO,a Masato ITO,b
Ayuko KITAJOU,b and Shigeto OKADAb,*
a
Interdisciplinary Graduate School of Engineering Sciences, Kyushu University,
6-1 Kasuga-koen, Kasuga, Fukuoka 816-8580, Japan
b
Institute for Materials Chemistry and Engineering, Kyushu University,
6-1 Kasuga-koen, Kasuga, Fukuoka 816-8580, Japan
* Corresponding author: s-okada@cm.kyushu-u.ac.jp

ABSTRACT
From the viewpoint of the cost and safety, aqueous sodium-ion batteries are attractive candidate for large-scale
energy storage. Although the operating voltage range of the aqueous battery is theoretically limited to 1.23 V by the
electrochemical decomposition of water, the voltage restriction is a little bit eased in real aqueous battery system by
the charge/discharge overvoltage. Effect of the concentrated electrolyte on the operation voltage was studied in
aqueous Na-ion battery with Na2MnFe(CN)6 hexacyanoferrates cathode and NaTi2(PO4)3 NASICON-type anode, in
order to increase the discharge voltage. According to the cyclic voltammetry, the electrochemical window of diluted
1 mol kg−1 NaClO4 aqueous electrolyte is only 1.9 V, whereas the corresponding electrochemical window of
concentrated 17 mol kg−1 NaClO4 aqueous electrolyte is widen to 2.8 V. This wide electrochemical window of the
concentrated aqueous electrolyte allows the Na2MnFe(CN)6//NaTi2(PO4)3 aqueous sodium-ion system to work
reversibly. By contrast, the framework of Na2MnFe(CN)6 cathode was destroyed by the hydroxide anion generated
in diluted 1 mol kg−1 electrolyte.
© The Electrochemical Society of Japan, All rights reserved.

Keywords : Aqueous Sodium-ion Battery, Concentrated Electrolyte, Sodium Manganese Hexacyanoferrate, Water
Decomposition

1. Introduction decomposition of water. Most recently, however, several groups

There is growing interest in large-scale, highly cost-effective
energy storage systems that utilize intermittent renewable energy
sources such as solar and wind power efficiently. To date, lithium-ion
batteries (LIBs) as well as sodium sulfur batteries have been
commercialized as large-scale energy storage systems around the
world. LIBs are advantageous for their high voltage and high energy
density, but they have serious drawbacks in safety, cost, and
conductivity due to their reliance on non-aqueous electrolyte. In
addition, the yearly production of lithium for battery grade is limited
by the surface area of salt lake, because high quality lithium is mainly
provided by sun-drying of salt lakes. Current concern to Li shortage
by the strong demand of LIBs for electric vehicles brings the price
increase of lithium. Minor-metal-free sodium sulfur batteries are
attractive for large-scale energy storage due to their low initial cost,
whereas the problem is the high running cost necessitated by their
300°C operating temperature. Therefore, sodium-ion batteries (SIBs)
operating at room temperature by the similar intercalation mechan-
ism to that of LIBs are highly desired because of the abundance of
sodium resources. Nevertheless, SIBs neither meet sufficient safety
requirement nor have a significant cost-down effect as long as they
use non-aqueous electrolytes. For example, non-aqueous electrolytes
often induce exothermic decomposition by the release oxygen gas
from metal oxide cathode in SIBs.1,2 Besides, conventional non-
aqueous electrolytes are generally costly and have poor ionic
conductivity. To overcome these disadvantages, aqueous sodium-ion
batteries with aqueous electrolyte that are safe, cost effective, and
offer high ionic conductivity have been proposed as attractive
alternatives for large-scale energy storage.
The last but not least problem associated with aqueous electro-
lytes is the low operating voltage to avoid the electrochemical
have reported that certain kinds of aqueous electrolytes without free
water molecule have wider electrochemical window and reasoned
that the water molecules hydrated to lithium ion do not engage in
electrochemical decomposition. For example, 21 m lithium bis(tri-
fluoro methanesulfonyl)imide (LiTFSI) aq.,3 21 m LiTFSI + 7 m
lithium trifluoromethane sulfonate (LiOTf ) aq.,4 saturated LiNO3
aq.,5 and 0.25 M Li-PO4 buffer with saturated disodium propane-
1,3-disulfonate (PDSS) aq.,6 where m represents a molality unit
(molality [m] = mole of solute/weight of solvent [mol kg¹1]) and
M represents a molarity unit (molarity [M] = mole of solute/volume
of solution [mol L¹1]), respectively. In such highly concentrated
aqueous Li electrolytes, not only the water activity but also the
solubility of the electrode is reduced by water solvation and thick
solid electrolyte interface (SEI).
These positive results in aqueous LIBs encouraged us to study
the concentration effect of aqueous electrolytes containing sodium
ions on the practical electrochemical window of water. As highly
concentrated electrolytes of aqueous Na electrolytes, 2 M Na2SO4
aq.,7 5 M NaNO3 aq.,8 and 10 M NaClO4 aq.9,10 have been already
reported. Among them, 2 M Na2SO4 aq. molarity is insufficient.
Besides, the deterioration of the NASICON-type NaTi2(PO4)3 (NTP)
anode for aqueous SIBs by the corrosive side reaction in NaNO3
electrolyte has been reported.11 Accordingly, we focused on NaClO4
as a highly soluble conventional sodium salt, because its concen-
tration can be increased to 10 M, which corresponds to 17 m.12 Since
our first report about NTP,7 it has been used as actually unique anode
for aqueous SIB in many literatures.13–20 NTP has the 2.1 V (vs.
Na/Na+) flat voltage plateau derived from the Ti4+/Ti3+ redox. It is
slightly under H2 evolution potential at pH = 7, nevertheless it is
available as anode for aqueous SIB.

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 Electrochemistry, 85(4), 179–185 (2017)
On the other hand, many Prussian blue analogues (PBAs) have
been reported as cathode for SIB. They can contain varying amounts
of sodium ions in the open sites of the cyano-bridged jungle gym-
type metal organic framework (MOF) and the sodiated molecular
formula is written as NaxM[MB(CN)6]y·zH2O (0 ¯ x ¯ 2, 0 ¯ y ¯ 1,
0 ¯ z). In particular, many hexacyanoferrates (HCFs, MB = Fe) with
a variation of M (M = Ni,21,22 Cu,23 Co,24 Fe,25 and Mn10) have
been reported as cathode for aqueous SIB. According to the previous
reports for M = Ni and Cu, the redox center in aqueous electrolyte
was only the [Fe2+(CN)6]4¹/[Fe3+(CN)6]3¹, and neither Ni nor Cu
was active and their capacities were only about 60 mAh g¹1.
On the other hand, for M = Co and Fe, Co2+/Co3+ and Fe2+/Fe3+
as well as [Fe2+(CN)6]4¹/[Fe3+(CN)6]3¹ are active even in aqueous
electrolyte. Recently, it was reported that NMHCF (M = Mn)
in aqueous electrolyte also has two active redox couples,
[Fe2+(CN)6]4¹/[Fe3+(CN)6]3¹ and Mn2+/Mn3+, in half-cell config-
uration with active carbon as counter electrode and Ag-AgCl as
reference electrode.
In this study, in order to confirm the high-concentration effect
in NaClO4 aq. electrolyte, we have selected sodium manganese
hexacyanoferrate (NMHCF) as a cathode and NTP as an anode,
respectively. In addition, we investigated the operation and
deterioration mechanism of NMHCF//NTP aqueous SIB by tracing
pH, electrode elution, precipitation in electrolytes.
2. Experimental
2.1 Preparation of cathode
As a cathode active material, NMHCF was synthesized by the co-
precipitating method described previously.26,27 Briefly, Na4Fe(CN)6·
10H2O (99%, Sigma-Aldrich) and excess NaCl (99.5%, Nacalai
Tesque) were dissolved in a solution of distilled water and ethanol.
An aqueous solution of MnCl2·4H2O (99.0%, Wako Pure Chemical
Industries Ltd.) was dropped into the solution and stirred vigorously
for 2 h. The suspension was filtered and washed by a water/ethanol
solution three times, and a light green precipitate product was
obtained. The precipitate product was dried at 100°C in vacuum
overnight, after which a final light blue NMHCF powder was
obtained. The lattice structure of the product was characterized with
an X-ray powder diffractometer (XRD, 50 kV and 300 mA, Cu-KA,
RINT2100HLR/PC, Rigaku Corp.). The morphology of the product
was confirmed by scanning electron microscopy (SEM, JSM-6340F,
JEOL Ltd.). The chemical composition of the NaxMn[Fe(CN)6]y·
zH2O was ascertained using inductively coupled plasma-atomic
emission spectroscopy (ICP-AES, Optima 8300, PerkinElmer Co.,
Ltd.), atomic adsorption spectrophotometry (AAS, Z-5310, Hitachi
High-Tech Science Corp.), and thermogravimetric analysis (TGA,
Thermo Plus TG8110, Rigaku Corp.). To improve electronic
conductivity, NMHCF powder and acetylene black (AB, Denka
Co., Ltd.) were mixed in a mortar, and the resulting NMHCF/AB
mixture had a weight ratio of 70/25.
2.2 Preparation of anode
As an anode active material, NTP was prepared by a solid-state
method previously reported.16 A stoichiometric mixture of Na2CO3
(99.7%, Kishida Chemical Co., Ltd.), TiO2 (99%, Sigma-Aldrich),
and NH4H2PO4 (99%, Wako Pure Chemical Industries Ltd.) was
potted into an alumina container along with 3 mmT zirconia balls.
The precursor was subsequently prepared by wet ball-milling in
acetone at 400 rpm for 1 h. After the acetone was evaporated to
obtain a dry mass, the precursor was ground and decomposed at
350°C for 3 h in air to eliminate the ammonia. The resulting powder
was ground, pressed into cylindrical pellets, and calcined at 800°C
for 12 h in air. In a previously reported procedure,7 AB was added to
NTP powder, the mixture was vigorously ball-milled in an alumina
container along with 3 mmT zirconia balls, and the carbon-coated
180
powder was subsequently annealed at 800°C for 1 h in an Ar + H2
atmosphere furnace. The resulting NTP/AB had a weight ratio of
70/25.
2.3 Electrochemical evaluation
Cathode and anode pellets were fabricated by mixing NMHCF/
AB or NTP/AB with a polytetrafluoroethylene (Polyflon PTFE F-
104, Daikin Industries Ltd.) binder in a weight ratio of 95/5 and
subsequently punched into discs. The cathode and anode active
materials were approximately 20 and 30 mg cm¹2 weight loading,
respectively. The cathode and anode pellets were approximately
200 µm thick. These disc pellets were sandwiched by sheets of
titanium mesh (Thank Metal Co., Ltd.). The aqueous electrolytes
used here were NaClO4 aqueous solution with various concentration
of 1, 7, 14, and 17 m. Ag-AgCl/saturated KCl (RE-6, BAS Inc.)
and NTP disc were used as the reference and counter electrodes,
respectively. The cathode/anode weight balance for this ion-type
cell is 2:3, and the cathode/anode capacity balance is approximately
2:3. A three-electrode electrochemical cell (half cell) and a two-
electrode cell (full cell) using aqueous electrolytes were used to
measure the cyclic voltammetry (CV) and the galvanostatic charge/
discharge cycle test. The CV was performed with a Versastat 3
(AMETEK Inc.). Galvanostatic charge/discharge tests were carried
out with a cycler (Nagano & Co., Ltd.) at various constant current
densities.
2.4 Investigation of the properties of electrochemical cell
during charge/discharge process
To confirm the lattice behavior of NMHCF and the valence
changes of Mn and Fe in NMHCF during the charge/discharge
cycle, ex-situ XRD and ex-situ X-ray photoelectron spectroscopy
(XPS, JPS-9010MC/IV, JEOL Ltd.) were carried out. The measure-
ment points on the first charge/discharge cycle were the initial state,
charged states up to 0.9 V, 1.2 V, and 1.3 V, which were followed
by discharged states down to 0.7 V and 0.2 V vs. Ag/AgCl,
respectively. At these points, the electrochemical cells were
dismantled, and the cathode pellets were removed from the titanium
mesh, washed with water in a glove box filled with Ar, and vacuum-
dried at room temperature for 1 h before the measurements. At the
same points, to confirm the pH and mass of metal ions eluted into
the electrolyte, ICP-AES and pH measurements were performed.
Here, the ratios of cathode pellet and electrolyte in the electrochem-
ical cell were approximately 2 mg and 1 mL, respectively.
3. Results and Discussion
3.1 Cathode properties
As shown in Fig. 1(a), there were not any other peaks except
cubic NMHCF (ICSD # 75-4637) with a Pm-3m in the diffraction
profile of the obtained light blue powder. The morphology of the
obtained NMHCF sample is shown in Fig. 1(b). Instead of the
200 to 500 nm-sized nanocrystal cubes previously reported,24,25,28
approximately 200 nm-sized round particles were observed, which
were morphologically similar to particles reported by J. Song.26 On
the basis of elemental analysis by ICP-AES for Mn and Fe, AAS for
Na, and TGA for water content, the NMHCF molecular formula
was determined as Na1.24Mn[Fe(CN)6]0.81·1.28H2O. Although the
crystal water content in the sample depends on the temperature and
humidity,21 the theoretical capacity of this hydrate can be roughly
estimated as 120 mAh g¹1 on the basis of 1.24 Na+ extraction/
insertion.
3.2 Cyclic voltammetry
Figures 2(a) and (b) show the CV profiles of the titanium mesh
current collector in 1 m and 17 m NaClO4 aqueous electrolytes,
respectively. On the other hand, Figs. 2(c) and (d) show the CV
 Electrochemistry, 85(4), 179–185 (2017)

Figure 1. (a) XRD patterns and (b) SEM image of as-prepared NMHCF powder.

Figure 2. (a) CV profiles of titanium mesh in 1 m NaClO4 aq., (b) CV profiles of titanium mesh in 17 m NaClO4 aq., (c) CV profiles of
NMHCF and NTP in 1 m NaClO4 aq., and (d) CV profiles of NMHCF and NTP in 17 m NaClO4 aq., respectively.

profiles of NMHCF and NTP in 1 m and 17 m NaClO4 aqueous
electrolytes, respectively. The following potential values are
measured against the Ag-AgCl reference electrode. The gray
colored ranges in Figs. 2(a) and (b) indicate the theoretical
electrochemical window of water at each pH value of the aqueous
electrolytes. As shown in Fig. 2(a), oxidation/reduction (ox./red.)
peaks were observed at 1.29/¹0.62 V in 1 m NaClO4 aq. electrolyte.
By comparison with the theoretical water ox./red. potential
(0.618 V/¹0.612 at pH = 7), the oxygen overpotential (defined
as GO2,1m) on the titanium mesh was approximately 0.67 V in 1 m
NaClO4 aq. electrolytes shown in Fig. 2(a). However, there was
no hydrogen overpotential (GH2,1m µ 0.0 V) on the titanium mesh.
Hereby, a practical stability window of 1 m NaClO4 aq. electrolyte
was estimated to be approximately 1.9 V. On the other hand, as
shown in Fig. 2(b), ox./red. peaks were observed at 1.54/¹1.24 V
in 17 m NaClO4 aq. Electrolyte. By comparison with the theoretical
water ox./red. potential (0.677/¹0.553 V at pH = 6), GO2,17m and
GH2,17m on the titanium mesh current collector were approximately
0.86 and 0.69 V in concentrated 17 m NaClO4 aq. electrolyte,
respectively. Thus, a practical stability window of 17 m NaClO4 aq.
electrolyte was approximately enlarged to 2.8 V. The gray colored
ranges in Figs. 2(c) and (d) show the practical stability window of
each aqueous electrolyte estimated by Figs. 2(a) and (b).
As shown in Fig. 2(c), on the NMHCF cathode side in 1 m
NaClO4 aq. electrolyte, two pairs of ox./red. peaks were observed:
the first at 0.58/0.39 V derived from Fe3+/Fe2+, the second larger
peak at 1.17–1.23/1.00 V derived from Mn3+/Mn2+, and the third
lone oxidative peak from 1.36 V derived from O2 evolution. On
the NTP anode side in 1 m NaClO4 aq. electrolyte, as shown in
Fig. 2(c), one pair of ox./red. peaks was observed at ¹0.67/
¹0.93 V derived from Ti4+/Ti3+ redox reactions, and a lone
reduction peak was observed at ¹1.09 V derived from H2 evolution.
As in the O2 evolution on the cathode side, the NTP redox reaction
may contain H2 evolution partially because the Ti4+/Ti3+ reduction
peak neighbors the H2 evolution peak. In contrast to the case with
1 m NaClO4 aq. electrolyte in Fig. 2(c), redox peaks in 17 m NaClO4
aq. electrolyte were observed at higher potential, as shown in
Fig. 2(d). Similar tendency was also reported in an aqueous lithium-
ion battery with highly concentrated electrolyte,3 and it is explained
that redox potentials are shifted higher as guest cation activity
increases. The same explanation holds true for the present aqueous
sodium-ion system, because sodium-ion activity in concentrated
17 m NaClO4 aq. electrolyte is higher than in diluted 1 m electrolyte,
according to a previous report.29 On the NMHCF cathode side, two
pairs of ox./red. peaks were observed the first peak at 0.64/0.51 V
derived from Fe3+/Fe2+, the second peak at 1.20–1.37/1.03 V

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 Electrochemistry, 85(4), 179–185 (2017)

Figure 3. (a) First and second charge/discharge curves of NMHCF//NTP full cell and NTP//Zn half cell in 1 m NaClO4 aq., (b) First and
second charge/discharge curves of NMHCF//NTP full cell and NTP//Zn half cell in 17 m NaClO4 aq., (c) XRD profiles of NMHCF on the
first cycle in 1 m NaClO4 aq., and (d) XRD profiles of NMHCF on the first cycle in 17 m NaClO4 aq., respectively.

derived from Mn3+/Mn2+, and a very small third lone peak at
1.49 V derived from the O2 evolution. On the NTP anode side, a pair
of ox./red. peaks was observed at ¹0.55/¹0.84 V. The H2 evolution
peak in Fig. 2(b) was well separated from the NTP reduction peak in
Fig. 2(d), suggesting that the NTP anode in 17 m NaClO4 aq. could
work reversibly without any H2 evolution.
3.3 Cathode properties during charge/discharge process
Figure 3(a) show the charge/discharge profiles of the NMHCF//
NTP full cell and NTP anode half cell in 1 m NaClO4 aq. at a rate
of 2.0 mA cm¹2. On the other hand, Fig. 3(b) show them in 17 m
NaClO4 aq. The gray colored ranges in Figs. 3(a) and (b) show
the practical stability window of each electrolyte estimated from
Figs. 2(a) and (b). In association with the results of CV in Fig. 2(c),
on the NMHCF cathode side in 1 m NaClO4 aq. as shown in
Fig. 3(a), three voltage plateaus derived from Fe2+/Fe3+, Mn2+/
Mn3+ redox and O2 evolution were observed on the first charge,
followed by two very small plateaus derived from Fe3+/Fe2+ and
Mn3+/Mn2+ reduction were observed on discharge. The plateaus in
the second cycle were smaller than those in the first. This result
suggests that the dissolution of the NMHCF cathode into 1 m
NaClO4 aq. is more serious than NTP anode. Because the cyclability
of the NTP//Zn half cell in 1 m electrolyte were not so bad as shown
in Fig. 3(a). (The clear traces of the NMHCF cathode dissolution
into 1 m NaClO4 aq. are illustrated in Table 1). On the other hand,
on the NMHCF cathode side in 17 m NaClO4 aq. as shown in
Fig. 3(b), two plateaus derived from Fe2+/Fe3+ redox and Mn2+/
Mn3+ redox were observed on the first and second charge,
and the first charge/discharge capacities were 124/116 mAh g¹1,
respectively. These profiles and capacities were consistent with the
previous reports26,27 in non-aqueous electrolyte and the theoretical
capacity (120 mAh g¹1) of NMHCF hydrate, respectively.
The reversible capacity on the NTP anode side was higher in
17 m NaClO4 aq. than in 1 m NaClO4 aq. This positive effect can
be explained by the smaller amount of dissolved oxygen in
concentrated aqueous electrolyte than that in diluted aqueous
electrolyte17,30 and larger hydrogen overpotential (GH2,17m = 0.69 V)
in 17 m than that in 1 m NaClO4 aq. as estimated in Fig. 2(b).
Figures 3(c) and (d) compare the XRD patterns of NMHCF cathode
pellets worked in 1 m and 17 m NaClO4 aq. at each state of charge
point on the first charge/discharge cycle in Figs. 3(a) and (b),
respectively. According to the XRD patterns of NMHCF in 1 m
NaClO4 aq. as shown in Fig. 3(c), characteristic peaks were
observed in the range from initial to the charged state up to 0.9 V,
but the peaks disappeared on the followed charge and discharge.
In addition, at the 0.2 V fully discharged state, slight characteristic
peaks were observed again. The jungle-gym structure of NMHCF in
1 m NaClO4 aq. was broken on charge over 0.9 V, but the crystal

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 Electrochemistry, 85(4), 179–185 (2017)
Table 1. Behavior of the dissolved amounts of the transition metal ions and pH values in the diluted and concentrated aqueous electrolytes
of NMHCF/NaClO4 aq./NTP full cell on the first charge/discharge cycle.
State of charge 1 m NaClO4 aq. (pH = 7)
on the first cycle pH Fe/mol% Mn/mol% Coloration
Initial state 4 4.0 7.3 Yellow
Charged up to 0.9 V 6 6.8 8.0 Yellow
Charged up to 1.3 V 2 27 0.0 Yellow green
Discharged down to 0.7 V 2 26 0.0 Yellow green
Discharged down to 0.2 V 2 15 0.7 Yellow green
structure was partially recovered on discharge less than 0.7 V. On the
other hand, in the case of 17 m NaClO4 aq., the sharp characteristic
XRD peaks of the NMHCF cathode were kept at each point on the
first cycle as shown in Fig. 3(d) and the lattice behavior in 17 m
NaClO4 aq. on cycle was in good agreement with the previous
report26 of the NMHCF cathode in non-aqueous electrolyte except
the generation of new rhombohedral phase after 1 cycle. The
aqueous circumstance may disturb the generation of rhombohedral
anhydride.
3.4 Electrolyte properties during charge/discharge process
To estimate the charge/discharge reaction of NMHCF/NaClO4
aq./NTP full cell on the first cycle, dissolved amounts of the
transition metals (Fe, Mn and Ti) and pH value were monitored
during first cycle. However, Ti ion was never detected in either 1 m
or 17 m NaClO4 aq. in any state, which means that there are no
possibilities of dissolving from titanium mesh current collector or
the NaTi2(PO4)3 anode. As shown in Table 1, in the initial state, the
pH value of the 1 m NaClO4 aq. electrolyte was shifted to 4 and
both Fe and Mn ions were detected in 1 m NaClO4 aq. electrolyte. It
is assumed that soluble Na1.24Mn2+[Fe2+(CN)6]0.81·1.28H2O at the
Everitt’s salt (ES) state31 partially eluted into the 1 m diluted NaClO4
aq., so part of the NMHCF structure was broken, then yellow
[Fe2+(CN)6]4¹ ferrocyanide ion, Mn2+ and H3O+ hydronium ion
eluted into the 1 m NaClO4 aq. The acidic pH value at the initial
state can be explained by the elution of H3O+.27,31,32 At the charged
state up to 0.9 V in 1 m NaClO4 aq., detected metal ions amount in
the electrolyte and the coloration did not change much compared to
the initial state, but pH value shifted from 4 to 6. H+ concentration
is not increased, because the voltage of NMHCF cathode is much
lower than the potential of O2 evolution as shown in Fig. 3(a).
Meanwhile, the voltage plateau of the NTP anode is out of the
electrochemical window, so the alkaline shift of the pH (from 4 to 6)
at 0.9 V must be caused by OH¹ increasing along H2 evolution on
the NTP anode. But, charged state up to 1.3 V in 1 m NaClO4 aq.,
the pH value goes back to acidity (from 6 to 2). It is reasonable
behavior, because at this voltage range, the cathode voltage located
on the third voltage plateau jumped over the electrochemical
window and it brings H+ increasing along O2 evolution. Conversely,
there is no OH¹ increasing along H2 evolution in 17 m NaClO4 aq.,
because the NTP anode voltage is kept in electrochemical window
during cycling. So, the pH value in 17 m NaClO4 aq. becomes lower
than in 1 m NaClO4 aq. For the charged states up to 1.3 V in 1 m
NaClO4 aq., Fe ion increased, but Mn was not detected. The color
of 1 m NaClO4 aq. was changed from yellow to yellow-green and
green precipitation appeared at the bottom of the beaker-type cell.
It is assumed that OH¹, which was generated continuously on the
anode, decomposed the partially Na+ de-inserted Na0.43Mn2+-
[Fe3+(CN)6]0.81 cathode structure,33 and as a result green-yellow
[Fe3+(CN)6]3¹ ferricyanide ion was segregated and green Mn2+O
was precipitated at the bottom of the beaker-type cell, according to
the following equation;
17 m NaClO4 aq. (pH = 6)
Precipitation pH Fe/mol% Mn/mol% Coloration Precipitation
No 5 0.0 0.0 Transparent No
No 5 0.0 0.0 Transparent No
Green 0.5 0.0 0.0 Transparent No
Green 0.8 0.0 0.0 Transparent No
Green 0.8 0.0 0.0 Transparent No
Na0:43 Mn½FeðCNÞ6 0:81 þ 2NaOH
! 0:81Na3 ½FeðCNÞ6  þ MnO# þ H2 O
On the other hand, according to Nernst equation, H2 evolution
potential shifts to 0.30 V (= 0.058¦pH = 0.058 © (6–0.8)) when
pH = 0.8 in 17 m NaClO4 aq., so H2 gas should be easily generated
on NTP anode. However, due to the larger overpotential (GH,17m µ
0.69 V) than the Nernst shift, there was no OH¹ generation leading to
decomposition of NMHCF, and coloring of the electrolyte was not
observed.
3.5 Confirmation of cathode operation in 17 m NaClO4 aq.
Figure 4 shows XPS spectra of (b) Fe and (c) Mn, while (d) shows
the strongest (100) XRD peak of NMHCF at each state of charge
point: (i) initial state, (ii) charged state up to 0.9 V, (iii) charged state
up to 1.3 V, (iv) discharged state down to 0.7 V, and (v) discharged
state down to 0.2 V on (a) the first charge/discharge profile of
NMHCF cathode in 17 m NaClO4 aq. As shown in Fig. 4(b), the
binding energies (BE) of Fe3/2p and Fe1/2p increased on charge on the
lower voltage plateau from (i) to (ii) and decreased on discharge from
(iv) to (v). It strongly suggests the [Fe2+(CN)6]4¹/[Fe3+(CN)6]3¹
redox plays a role in the lower voltage region. On the other hand, the
BE of Mn3/2p and Mn1/2p shifted slightly higher from (ii) to (iii) and
lower from (iii) to (iv). It means the higher voltage plateau corre-
sponds to Mn2+/Mn3+ redox instead of [Fe2+(CN)6]4/[Fe3+(CN)6]3¹
redox as shown in Fig. 4(c). Assuming that all valence state of Fe
and Mn are 2+ in the initial composition of Na1.24Mn[Fe(CN)6]0.81·
1.28H2O, in fully desodiated state (Mn[Fe(CN)6]0.81·1.28H2O), the
valence state of Fe becomes 3+, meanwhile the valence state of
Mn becomes 2.43+. The smaller XPS peak shift of Mn (Fig. 4(c))
than that of Fe (Fig. 4(b)) can be explained by the smaller Mn
valence change between 2+ and 2.43+ on cycle.
Moreover, the complicated lattice behavior as shown in Fig. 4(d)
is caused by the Jahn-Teller instability of Mn3+ in MnN6 octahedra
and it is consistent with the previously reported NMHCF structural
changes among monoclinic ((i), (v)), cubic ((ii), (iv)), and tetragonal
(iii) during cycling in non-aqueous electrolyte.26
3.6 Cycle performances of NMHCF half cell
Figure 5(a) shows the cycle performance of NMHCF half cell
dependence on NaClO4 concentration in aqueous electrolyte. The
tendency of a higher NaClO4 concentration aqueous electrolyte
to derive better cyclability of NMHCF cathode is evident from
Fig. 5(a) and the best cycle performance was obtained in the
NMHCF half cell with the most highly concentrated (17 m)
electrolyte as shown in Fig. 5(b). In brief, highly concentrated
electrolyte brings stable cyclability by extending the practical
stability window. As shown in Fig. 5(b), the fraction of capacity
retention at the 100th cycle against the first cycle at rates of 0.5, 2.0,
and 5.0 mA cm¹2 were 43, 74, and 92%, respectively. As previous
studies3,30,34 about aqueous batteries have revealed, the cycle
performance of the concentrated electrolyte at a higher rate is better
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Figure 4. (a) Typical charge/discharge profile of the NMHCF cathode in 17 m NaClO4 aqueous electrolyte. The 5 sampling points for
ex-situ XPS and XRD measurements on the first cycle are as follows; (i) initial state, (ii) charged up to +0.9 V, (iii) charged up to +1.3 V,
(iv) discharged down to +0.7 V, and (v) discharged down to +0.2 V vs. Ag/AgCl. XPS spectra of (b) Fe and (c) Mn, while (d) shows detailed
XRD patterns of the NMHCF at selected potentials.

Figure 5. (a) Cyclability dependence on the NaClO4 concentration of aqueous NMHCF half cell at a rate of 2.0 mA/cm2 and (b) Cyclability
dependence on the current density of NMHCF half cell with 17 m NaClO4 aqueous electrolytes.

than a lower rate condition. This is probably because the large
charge/discharge overpotential at the high rate condition suppresses
the side reaction of the water decomposition. Conversely, it seems to
be difficult to suppress the water decomposition completely only by
the concentrated electrolyte.
3.7 Full cell performances
The charge/discharge profile and cyclability of the NMHCF//
17 m NaClO4 aq.//NTP aqueous sodium-ion battery are shown in
Fig. 6(a) and its inset, respectively. Owing to the 2.8 V practical
stability window of 17 m NaClO4 aq., the aqueous sodium-ion
battery exhibits 1.3, 1.5, and 1.8 V plateaus, and 117 mAh g¹1 first
discharge capacity at a rate of 2.0 mA cm¹2. As shown in the inset,
capacity retention at the 50th cycle against the first cycle was 81%.
As shown in Fig. 6(b), the aqueous sodium-ion battery exhibits 117,
98, 69, and 56 mAh g¹1 discharge capacities at current densities of
2.0, 5.0, 10, and 20 mA cm¹2, respectively. In spite of the thicker
200 µm electrode pellet, which is two to four times thicker than
electrodes of commercial lithium-ion batteries (i.e., 50 to 100 µm),
this relatively good rate capability is attributed to larger ionic
conductivity and lower viscosity of the aqueous electrolyte than the
conventional organic electrolyte. Besides, the 3D open structure of
NMHCF and NTP can be regarded as suitable framework for large
Na ion insertion.
4. Conclusions
We investigated the practical stability windows of 1 m and 17 m
NaClO4 aq., and revealed that the potential ranges of each
electrochemical window were 1.9 and 2.8 V, respectively. By virtue
of the extended stable potential window of 17 m NaClO4 aq., the
aqueous sodium-ion battery of Na1.24Mn[Fe(CN)6]0.81·1.28H2O//
NaTi2(PO4)3 was able to exhibit 1.3, 1.5, and 1.8 V discharge
plateaus and 117 mAh g¹1 of discharge capacity at the first cycle,
good rate capability, and good cyclability without serious degrada-
tion despite the incomplete crystallinity of the NMFCF cathode
with some defects. Conversely, the narrow stability window of 1 m
NaClO4 aq., led to severe deterioration after the first cycle. The
deterioration of the aqueous battery with 1 m electrolyte was mainly
attributed to H2 generation by the reductive water decomposition on
NTP anode and to the elution of the cathode by the alkalization of
the aqueous electrolyte. Higher concentrations of electrolyte under
higher rate condition supported more stable operation in this
aqueous sodium-ion system. Therefore, we were able to confirm that
Na1.24Mn[Fe(CN)6]0.81·1.28H2O//NaTi2(PO4)3 with highly concen-
trated electrolyte is one of the promising candidates for large-scale
energy storage.

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Figure 6. (a) First and second charge/discharge curves at a rate of 2.0 mA cm¹2 and (b) the rate capability of NMHCF/17 m NaClO4 aq./
NTP full cell.
Acknowledgments
This work was financially supported by the Elements Strategy
Initiative for Catalysts and Batteries Project and the Cooperative
Research Program of “Network Joint Research Center for Materials
and Devices”, MEXT, Japan.
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