Journal of Power Sources 452 (2020) 227832

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Journal of Power Sources

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

Chemically sodiated ammonium vanadium oxide as a new generation

high-performance cathode
Ananta Sarkar, Sagar Mitra *
Electrochemical Energy Laboratory, Department of Energy Science and Engineering, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, Maharashtra, India

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

� Chemically sodiated ammonium vana­

date cathode (SNVO) for SIBs.
� Enhancement of thermal and electro­
chemical stability.
� Nominal potential enhancement from
2.1 to 2.8 V.
� Doped-SNVO cathode provides an
extremely high energy density of 770
Wh kg-1.
� High energy density (220 Wh kg-1) full-
cell prototype (Zr-SHNVO-3) // H-
Na2Ti3O7.

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

Keywords: Sodium-ion battery technologies must have low cost, safe, and high energy density cathode with prolonging cycle
Sodiated ammonium vanadium oxide life propositions for any commercial utilizations. Herein, we present for the first time an extremely high energy
Cathode density (770 W h kg 1) and excellent electrochemical performance of a sodiated and doped ammonium vana­
High energy density
dium oxide (Zr-SNVO) cathode. The cathode delivers a high discharge capacity of 255 mAh g 1 with 95% ca­
Full-cell
Sodium-ion battery
pacity retention after 100 cycles at a current rate of 200 mA g 1. Furthermore, the present report demonstrates
the full-cell performance with our cathode against a hydrogenated doped sodium titanium oxide (Zr-HNTO)
anode, capable of delivering a high energy density of 220 W h kg 1 (both active mass of cathode and anode are
considered). The present study shows a way to produce a high-performance rechargeable sodium-ion battery full-
cell using alternative cathode and anode with a comparable energy density of current lithium-ion technology.
The present study gives us a direction to make such cells for future renewable energy storage systems.

1. Introduction competitive cycling performance) compare to any other transition metal

In recent times, transition metal-based layered oxides became a state
of arts for higher energy density and safe cathode materials for sodium-
ion battery [1–5]. Among all, vanadium-based oxide materials have
been attracted attention due to its superior redox behavior (wide range
of oxidation state, higher specific capacity, better rate capability, and
oxides [6–10]. As vanadium oxides have a large interlayer spacing,
which accumulates more number of sodium-ions that facilitate the
diffusion process of larger size sodium-ion into/from the host matrix
[11,12]. Besides, the electronic behavior of most of the vanadium ox­
ides, changes from an insulator to semiconductor or metallic character,
during the intercalation process at normal temperature (273–333 K)

* Corresponding author.
E-mail address: sagar.mitra@iitb.ac.in (S. Mitra).

https://doi.org/10.1016/j.jpowsour.2020.227832
Received 12 September 2019; Received in revised form 13 December 2019; Accepted 31 January 2020
Available online 2 March 2020
0378-7753/© 2020 Elsevier B.V. All rights reserved.
A. Sarkar and S. Mitra Journal of Power Sources 452 (2020) 227832

may help to enhance the rate capability of the electrode [13,14].
Many vanadium-based materials like V2O5, NH4V4O10, Na3V2(PO4)3,
Na3V2(PO4)3Fx, VOPO4, etc. have been extensively studied in recent
years as battery cathode materials [9,15–18]. Among all, Na3V2(PO4)3,
Na3V2(PO4)3F, Na2V6O16.nH2O, and VOPO4 cathodes showed a high
rate and stable cycling performances against sodium metal, however, is
limited by lower specific capacity (nearly 120 mAh g 1) [16,19–21].
Whereas, the other vanadium cathode materials like V2O5, Na2VTi
(PO4)3 and NaxV2O5⋅nH2O have a higher specific capacity but an issue of
either lower nominal potential or/and poor cycling stability [22–24].
Recently, we investigated ammonium vanadium oxide (NH4V4O10)
based cathode material for a sodium-ion battery. It provided a discharge
capacity of 225 mAh g 1 at a higher current density of 200 mA g 1 [25].
We further enhanced the specific capacity and rate capability of the
electrode by zirconium metal doping to it [26]. This cathode provides
the highest specific capacity (375 mAh g 1 at 100 mA g 1 current
density) among all other reported cathode materials existing in
sodium-ion battery technology with an efficient average Coulombic ef­
ficiency of 99.5%. We improved the energy density of about 1.5 times of
the cathode material by metal doping. However, these cathode materials
having inherent lower potential operation characteristics leads to low
energy density and more importantly it is a sodium-free cathode causes
problem in battery manufacturing process.
Therefore, it is necessary to enhance our cathode potential and need
to incorporate sodium-ion into the cathode material during the chemical
synthesis process. Here, we introduce a chemically sodiated NH4V4O10
(SNVO) cathode materials for SIB first time in literature. The same hy­
drothermal procedure was followed to prepare SNVO materials; only
sodium-containing salt was added to this process. By this process, we are
not only incorporate the sodium source into the cathode materials and

Fig. 1. Structural and morphological characterizations of as prepared sodiated ammonium vanadium oxide (SNVO-n); (a) X-ray diffraction (XRD) pattern of different
SNVO-n cathode materials with corresponding JCPDS card no. 035–0075 showed beyond 4 mol sodiation, the monoclinic structure completely converted to different
phase, (b) characteristic XRD pattern of SNVO-3 analyzed by commercial FullProf Suite software, (c) Crystal structure of chemically pre-sodiated NVO (SNVO-3),
yellow Na, red O, blue NHþ 4 , brown V, (d) FEG-SEM image of SNVO-3, (e) FEG-TEM image of SNVO-3 materials showed nanobelts morphology with an average length
of 2–3 μm and width 300–600 nm, (f) HR-TEM image of SNVO-3 indicating the interlayer d spacing is 0.355, 0.203 nm corresponds (110) and ( 205) plane
respectively and inset image shows SEAD pattern revealed single-crystalline pattern of SNVO-3 cathode material, (g,h) In-situ high-temperature XRD of SNVO
electrode material at 5 � C min 1 heating rate under Ar atmosphere; (g) NH4V4O10 (NVO) and (h) SNVO material. (For interpretation of the references to colour in this
figure legend, the reader is referred to the Web version of this article.)

2
A. Sarkar and S. Mitra
also improved the overall potential and exhibited improved electro­
chemical performances.
2. Results and discussion
To construct a sodium-ion full-cell battery, either cathode or anode
should have a sodium source in its matrix. The electrochemical pre-
sodiation process is not an obvious choice to make it commercially
viable. The energy density is considered one of the significant charac­
teristic parameters for the practical application, and it should be as high
as possible. The overall energy density of a battery can be improved by
(1) enhancing the specific capacity of the active materials, and (2)
increasing the cell voltage because most of the consumer electronics
items and ICS are powered above 3 V. In this manuscript; we attempt to
enhance the overall energy density of the battery by improving the
nominal potential of the cell by sodiated our cathode (NH4V4O10) ma­
terial by a simple chemical process.
Herein, we adopted a single-step hydrothermal process to make
sodiated NH4V4O10 cathode material. The different concentration of
sodiated NH4V4O10 (SNVO-n) samples were synthesized by adding
different mole concentration of sodium salt in the precursor during the
hydrothermal process at 190 � C for 6 h (the synthesis procedure was
discussed in details in the experimental section in Supporting Informa­
tion). SNVO-n symbol means n-mole sodium-containing salt was added
to 1 mol of V2O5 precursor by an in-situ process (where n ¼ 1, 2, 3, 4, 5,
6). X-ray diffraction pattern (XRD) of SNVO-n at different mole con­
centration with corresponding JCPDS file no 031–0075 was shown in
Fig. 1a. Fig. 1a showed that with chemical sodiation, the major peaks at
around 9.3, 49.8, and 64.6� of two-theta value were shifted a little to the
higher two theta value, indicating the shrinkage of the interlayer
d spacing (Fig. 1a). When sodium-ion is intercalated during the chemical
pre-sodiation process, strong interaction builds between the sodium-ion
and vanadium layers, and that reduces the interlayer spacing. As Fig. 1a
also indicated that with increasing the sodiation concentration above 4
mol, new peaks were appeared at ca. 18 and 21� of two theta scale and at
6-mol sodiation concentration (SNVO-6), monoclinic NH4V4O10 (NVO)
phase was converted to a different phase (mixed phase of monoclinic
NH4V4O10 and NaxV2O5) [27]. Fig. 1a also described that (111) to (400)
plane intensity ratio was increased with sodiation (preferable sodium
diffusion). The lattice parameters of as prepared SNVO-3 sample were
evaluated by FullProf Suite software shown in Fig. 1b [28]. The evalu­
ated lattice parameters of SNVO-3 are a ¼ 11.698 Å, b ¼ 3.690 Å, c ¼
9.735 Å, α ¼ 90.0, β ¼ 101.121 and γ ¼ 90.0 with space group C12/m1
significantly changed from the standard JCPDS data i.e. a ¼ 11.71 Å, b ¼
3.76 Å, c ¼ 9.85 Å, α ¼ 90.0, β ¼ 101.0 and γ ¼ 90.0. Here, the lattice
parameters a, b, c values are reduced which signify the contraction of the
lattice due to the increase of attraction forces between the atoms. This
indicates that the individual Naþ intercalation into the matrix. Here, the
growth of the materials preferred in z-axis and sodium-ion are interacted
in b-direction as well as in the gallery space. Some of the NHþ 4 ions are
connected with O atoms by weak Van Der Wall bond, and others occupy
the gallery space (Fig. 1c) [12,26].
The morphology of as-prepared materials of different mole concen­
tration SNVO-n was analyzed by the field emission gun scanning elec­
tron microscopy (FEG-SEM) and field emission gun transmission
electron microscopy (FEG-TEM). Fig. S1 indicates nanorod types
morphology for all sodiated NH4V4O10 cases, except SNVO-6. Fig. S1
clearly shows that with increasing the sodiation concentration, the
particle size of the nanorods were increased. The average length of the
SNVO-1 particles (Figs. S1a and b) was observed around 500 nm to 1.2
μm and width was ~100 nm, whereas SNVO-2 particles length (Figs. S1c
and d) was ~ 2–3 μm and width was about 150–200 nm. With a further
increase in the sodiation concentration to 3 mol (SNVO-3), the particle-
sized was enlarged to 500 nm in width and 2.5–3.5 μm in length, shown
in Fig. 1d,e. Whereas, the particles size of SNVO-4 further increased to
above 3–4 μm, observed in Figs. S1g and h. But in the case of SNVO-5
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Journal of Power Sources 452 (2020) 227832
and SNVO-6, these 2D particles were becoming the 3D materials. The
average dimension of SNVO-5 material was observed as length 2.5–6
μm, width 500 nm and height ca. 200 nm (Figs. S1i and j). However,
SNVO-6 shape is converted to irregular shapes with 1–1.3 μm average
diameter (Fig. S1k and l). Fig. 1f and Figs. S2a–d showed the HR images
of SNVO-3 at different magnifications. Figs. S2b and c further indicates
that the preferred growth direction of the SNVO-3 particles were in
(001) plane. Here, the inter planer d spacing was estimated as ~0.353
nm corresponds to (110) plane, whereas 0.203 nm inter planer d spacing
represents the ( 205) plane (Fig. S2d). Fig. 1f (inset) showed a single
crystal selected area electron diffraction (SAED) pattern of SNVO-3
sample which also matched with the corresponding XRD data. To
know the composition of as-prepared SNVO-3 materials, SEM-EDS
pattern was shown in Fig. S2e. It shows the presence of Na, V, N, O,
and very minute amounts of F in the materials. ICP analysis was done to
find out the final product for each level sodiation process as shown in
Table S1. The final formula of SNVO-1, SNVO-2, SNVO-3, SNVO-4, and
SNVO-5 materials are Na0.28NH4V4O10, Na0.40NH4V4O10,
Na0.74NH4V4O10, Na0.96NH4V4O10, Na1.12NH4V4O10 respectively.
To know the thermal stability of different ammonium vanadium
oxides, in-situ high-temperature XRD patterns, and thermogravimetric
analysis (TGA) data were analyzed very carefully (Fig. 1g,h and Fig. S3).
Sodiated NH4V4O10 is thermally stable under the nitrogen atmosphere
till 700 � C where pure NH4V4O10 (NVO) and zirconium-doped
NH4V4O10 (Zr-NVO) materials are stable up to 350 � C in the same
environment. Initial decomposition of the materials is attributed to the
decomposition of absorbed solvent molecules like water, sodium hy­
droxide, and ammonium hydroxide for SNVO-3 (325 � C) and water and
ammonium hydroxide for Zr-NVO and NVO (bellow 100 � C) shown in
Fig. S3 [29–31]. After 350 � C, NVO and Zr-NVO cathode materials start
to decompose and form V2O5, NH3, and water (12.5% weight loss due to
evaporation of water and ammonia) [29,31]. However, SNVO-3 mate­
rials are stable up to 650 � C (only 5.7% weight degradation) (Fig. S3).
Similar phenomena also observed in (in-situ high-temperature) XRD
experiment of different NVO materials (Fig. 1g and h). After 350 � C,
(001) main characteristic peak of NVO was disappeared (as the material
decomposed and ammonia is coming out at this temperature), means
monoclinic NVO material was converted to a different phase. The
possible thermal decomposition reaction is 2NH4V4O10 → 2NH3 þ
4V2O5 þ H2. However, this monoclinic phase of SNVO-3 sample was
sustained up to 600 � C (after 650 � C V2O5 itself start to decompose).
During the chemical sodiation process, Naþ intercalated into the NVO
layers as well as in the gallery space whereas some of the NHþ 4 (ions) are
attached with the oxygen by weak van der Waals attraction (Fig. 1c) and
as a result, the thermal stability of the SNVO-3 materials was improved.
However, in NVO, NHþ 4 (ions) are occupying the gallery space which was
easily decomposed at 350 � C (Fig. 1g and h).
The X-ray photo absorption spectroscopy (XPS) was shown in Fig. 2
to analyze the effect of the sodiation process on the individual compo­
nent’s oxidation state of various SNVO-n. Fig. 2a–d showed the vana­
dium oxidation state of various SNVO-n, which revealed that vanadium
was in the mixed-phase of V4þ of V5þ. The vanadium oxidation state of
pristine (NVO) and zirconium-doped NH4V4O10 (ZrNVO) showed the
mixed phase of V5þ and V4þ in 3:1 ratio (shown in our previous studies)
[25,26]. Fig. 2a showed the vanadium oxidation state of the SNVO-1
sample, and the V5þ and V4þ 2p3/2 peaks are observed at 516.94 eV
and 515.50 eV, and the ratio of the peak is ~2.60:1 (estimated by the
area under the curve method). Whereas for SNVO-2 sample, the peaks
were noticed at 516.96, and 515.52 eV corresponds to V5þ and V4þ
oxidation state respectively, and the ratio was estimated ~1.66 : 1
(Fig. 2b). However, for SNVO-3, SNVO-4 electrodes, the 2p3/2 peaks of
V5þ and V4þ were noticed at 516.97 and 515.55 eV; 516.94 and 515.64
eV respectively, and the peak ratio of V5þ to V4þ was further decreased
to 1.51:1 and 1.32:1 respectively (Fig. 2c and d). It was also noticed that
with increasing sodiation concentration in the composition, V5þ to V4þ
ratio was decreased, and both V5þ and V4þ peaks position shifted to the
A. Sarkar and S. Mitra Journal of Power Sources 452 (2020) 227832

Fig. 2. X-ray photo absorption spectroscopy (XPS) analysis of as prepared different SNVO-n electrode; (a) vanadium V2p spectrum of SNVO-1, (b) vanadium
spectrum of SNVO-2, (c) vanadium spectrum of SNVO-3, (d) vanadium spectrum of SNVO-4; XPS spectrum of vanadium of all different SNVO-n suggested the
coexistence of V4þ and V5þ phase in the materials and ratio of V5þ to V4þ was decreased, (e–h) O1s spectrum of different SNVO-n; (e) SNVO-1, (f) SNVO-2, (g) SNVO-
3, (h) SNVO-4; O1s spectra also suggested that V5þ to V4þ state was decreased with sodiation concentration increased, (i) Na1s spectrums of different SNVO-n, (j)
nitrogen absorption peaks of different SNVO-n, (k) fluorine spectrums of different SNVO-n suggested the absence of F1s peak in SNVO-1, SNVO-2 and SNVO-3 but
intense spectrum was observed in SNVO-4 and (l) survey scan of SNVO-3 confirmed the presence of individual elements vanadium, sodium, oxygen, and nitrogen.

higher binding energy state. As more and more sodium was inserted into
NH4V4O10 matrix, more no of V5þ was converted to V4þ state, and as a
result, V5þ to V4þ oxidation state ratio was decreasing from 3 to 1.32
(NVO to SNVO-4) which again confirmed the sodium-ion insertion into
the matrix by the chemical process. A small V5þ satellite peak is also
noticed in V2p spectrum for all SNVO-n materials. For further confir­
mation, the high-resolution XPS of SNVO-n electrodes of oxygen (O1s)
spectra were recorded as shown in Fig. 2e–h. It was noticed that O1s
peaks divided into two prominent peaks after the sodiation (only single
O1s peak observed for NH4V4O10 with doped or without doped; Fig. S4)
process. The O1s peak at lower binding energy ~529.50 eV is due to the
bonding of oxygen with higher vanadium oxidation (V5þ) state, and O1s
peak at higher binding energy ~ 532.0 eV represents the oxygen
bonding to the vanadium having lower oxidation state (V4þ) of SNVO-n
(Fig. 2e–h) [32,33].
The O1s peak at lower binding energy was noticed at 529.49 eV,
529.44 eV, and 529.52 eV, whereas the higher energy O1s peaks
observed at 531.96 eV, 532.02 eV and 531.80 eV for SNVO-2, SNVO-3
and SNVO-4 electrode respectively (Fig. 2f–h). Another small peak was
also seen at around 530.6 eV is due to the V–O–V bond formation
(Fig. 2e–h). It was also interesting to notice that with increasing the
chemical sodiation process, the higher binding energy (oxygen bind
with Vþ4) O1s peak intensity (area under the curve) is rising signifi­
cantly compared with lower binding energy O1s peak (oxygen bind with
higher state Vþ5) [32,33]. Therefore, XPS analysis of both oxygen and
vanadium oxidation states again confirmed the sodium insertion by the
chemical process into ammonium vanadium oxide matrix, and the so­
dium intercalation is also increased with sodiation concentration up to a
limit. Further, sodium (Na1s) peak position at 1070.92 eV was shifted
towards lower binding energy and became wider with more sodiation
(Fig. 2i). Fig. 2j showed N1s oxidation peak was a slightly moved to­
wards the lower binding energy from its original position (at 400.80 eV)
after more sodium insertion into NVO. Generally, when sodium is
inserted into a layered oxide, both N1s and Na1s peak intensity increases
and it becomes broader, and the peak position shifted towards the lower
binding energy with more number of sodium-ion insertion [34]. A sharp
fluorine peak at 684.72 eV binding energy was observed for the SNVO-4
sample. However, no significant F1s peak was observed for SNVO-1,
SNVO-2, and SNVO-3 samples (Fig. 2k), and that indicates that there
is no presence of fluorine in SNVO-1, SNVO-2, and SNVO-3 electrode
and reconfirms again the chemical sodiation process. The survey scan of
SNVO-3 presented in Fig. 2l and the scan confirmed the all elements like
N, V, O, and Na are present in SNVO-n matrix but no fluorine. The
detailed XPS fitting parameters of all SNVO-n samples were evaluated to
know the phase of the materials accurately and tabulated in Table S2.
In previous reports, the NH4V4O10 nanobelts as a high capacity and
useful cathode material have been documented for both sodium and
lithium-ion battery [12,26]. But this cathode material provides a low
nominal potential of 1.95 V, which corresponds to 1.68 V full-cell
voltage. Not only that, this cathode material is a sodium-free elec­
trode. These two combined effects hinder this particular cathode from
the commercial applications, although it has a very high energy density
ca. 655 W h kg 1 [26]. Herein, we addressed these issues and conse­
quently enhanced the nominal potential as well as incorporated
sodium-ion into this cathode materials by a simple combined chemical
sodiation process.

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A. Sarkar and S. Mitra
Among all chemically sodiated ammonium vanadium oxide, SNVO-3
showed the best electrochemical performances (details electrochemical
performances of all SNVO-n were shown in supporting information).
Here, we have selected SNVO-3 composition as cathode materials for
further experiments. The cyclic voltammetry (CV) of the SNVO-3 cath­
ode materials against Naþ/Na was performed in a half-cell configuration
at a scanning rate of 0.1 mV s 1 over the potential window 1.4 V–4.3 V
vs. Na/Naþ (Fig. 3a). The CV curve exhibited multiple oxidation-
reduction peaks of vanadium as usual. The oxidation and reduction
peaks at 3.65 V and 3.52 V corresponding to V5þ/V4þ redox couple,
whereas at the lower potential oxidation and reduction peaks at 2.04 V
and 1.78 V represent to V4þ/V3þ redox couple. Some minor reduction
peaks were also noticed at 2.3 V, 2.5 V, 2.75 V, and 3.25 V whereas, the
corresponding oxidation peaks appeared at the potential of 2.55 V, 2.7
V, 2.9 V, and 3.4 V, respectively. These minor peaks appeared due to the
step by step phase transformation process during sodium insertion/
deinsertion of/from the host materials, as shown in our previous report
[25,26]. The active elements have mixed phase of V5þ/V4þ (also
confirmed by XPS), and in the first cycle, during the reduction process,
the only V4þ phase was transfer to V3þ phase by inserting 3–4 Naþ
stepwise at 2.04 V. During the oxidation process (V4þ to V5þ), phase
formation was happened stepwise due to 0.5, 1, 3 and 4 Naþ insertions
in the electrode. At 3.53 V all V5þ phases were converted to V4þ phase by
reduction, and the process continued. Here, no irreversible peak at 3.91
V was observed for SNVO-3 electrode which means these sodiated ma­
terials become more stable at higher potential (for better comparison CV
of NH4V4O10 was shown in Fig. S5). As we inserted more and more
sodium-ion (up to 5 sodium-ion insertions) into NVO matrix, it becomes
more stable, and ammonium-ion did not come out from the structure (as
it is bounded with O atoms by week van der Waals attraction) at higher
potential (3.91 V) during the charging process. It was also noticed that
the intensity of reduction peak at 3.52 V (V5þ → V4þ) was increased
whereas peak intensity at 1.78 V (V5þ → V4þ) was reduced. However, for
oxidation case, exact opposite phenomena were noticed; lower oxida­
tion peak (V3þ → V4þ) intensity increases and while higher oxidation
peak (V4þ → V5þ) intensity reduces. So, the intercalation process was
Fig. 3. Electrochemical performances of SNVO-3 and Zr-doped SNVO-3 electrode at 20 � 2 � C; (a) cyclic voltammetry (CV) of SNVO-3 at a scan rate of 0.1 mV s 1
over 1.4–4.3 V potential window, (b) cycling performance of SNVO-3 at 200 mA g 1 current density over 1.4–4.0 V potential window up to100 cycles, (c) charge-
discharge profile of SNVO-3, (d) cycling performance of Zr-SNVO-3 at 200 mA g 1 current rate with Coulombic efficiency over 1.5–3.9 V potential window, (e) 2nd
cycle charge-discharge profile of Zr-SNVO-3 at different current rate and (f) electrochemical performance comparison of different ammonium vanadium oxides; NVO,
Zr-NVO, SNVO-3 and Zr-SNVO-3 at 100 mA g 1 current density.
5
Journal of Power Sources 452 (2020) 227832
more favorable at higher reduction potential, and deintercalation pro­
cess fascinated at lower oxidation potential which helps to enhance the
overall nominal potential of the cathode material.
The charge-discharge curve of different SNVO cathode materials at
the current rate of 100 mA g 1 over 1.4 V–4.2 V potential window was
displayed in Fig. S6. From this Fig. S6a, it was noticed that only SNVO-1
delivered poor cycling stability. Fig. S6 showed an initial discharge ca­
pacity of ca. 190 mAh g 1, 225 mAh g 1, 200 mAh g 1, 125 mAh g 1, 95
mAh g 1 and 70 mAh g 1 for SNVO-1, SNVO-2, SNVO-3, SNVO-4,
SNVO-5, and SNVO-6 respectively. It was also noticed that after sodia­
tion, the nominal voltage of the cathode is increased to 2.43 V from 2.1
V. Among all SNVO-3 exhibited best electrochemical performances,
showing an initial discharge capacity of 200 mAh g 1 with stable cycling
performance at 100 mA g 1 current density. So, we choose SNVO-3 as
cathode materials for further study.
Fig. 3b and c shows the cycling performance of SNVO-3 cathode
against Naþ/Na at 100 mA g 1 current density over 1.4 V–4.0 V po­
tential window. SNVO-3 sample exhibited an initial discharge capacity
of 170 mAh g 1 with 93% capacity retention after 100 cycles with a high
average Coulombic efficiency of 99.8%. It showed a high rate electro­
chemical performances and displayed an initial discharge capacity of
~250 mAh g 1, 200 mAh g 1, 170 mAh g 1, 133 mAh g 1 and 112 mAh
g 1 at the current rate of 50 mA g 1, 100 mA g 1, 200 mA g 1, 500 mA
g 1 and 1000 mA g 1 current rate with ~84%, 96%, 98%, 96% and
100% capacity retention after 50 cycles respectively (Fig. S7). It was
interesting to notice that the nominal potential of the cell was enhanced
to 2.43 V. We further increased the electrochemical performances by
zirconium doping on vanadium side of SNVO-3
(Zr0.03Na0.78NH4V3.88O9.88) samples without incorporating any extra
process. Details characterization of zirconium-doped sodiated ammo­
nium vanadium oxide (Zr-SNVO-3) was shown in the Supporting In­
formation, Figs. S8 and 9). Fig. 3d reveled the charge-discharge cycling
performance of Zr-SNVO-3 at 200 mA g 1 current density over 1.5–3.9 V
potential window. This electrode was capable of delivering a high
discharge capacity of 275 mAh g 1 in its initial cycle and stable to 255
mAh g 1 after 2nd cycle. The electrode sustained its 95% initial capacity
A. Sarkar and S. Mitra Journal of Power Sources 452 (2020) 227832

after 100 cycles (Fig. 3d), and 88% capacity after 200 cycles (Fig. S10a)
with an average 97.98% Coulombic efficiency. The 2nd cycle charge-
discharge profile at the different current rates was shown in Fig. 3e
for all the samples as a comparison. The Zr-doped SNVO-3 electrode
exhibited a high discharge capacity of 275 mAh g 1, 255 mAh g 1, 182
mAh g 1, and 145 mAh g 1 at a current density of 100 mA g 1, 200 mA
g 1, 500 mA g 1, and 1000 mA g 1 respectively, (Fig. 3e and Fig. S10b).
The nominal potential of the cathode was further increased to 2.80 V
from 2.43 V by the chemical sodiation and doping processes. It was
interesting to notice that a prolong discharge plateau at 3.52 V was
observed in Zr-SNVO-3 electrode (similar behavior also found in the CV,
Fig. 3a), which help to enhance the nominal potential of the cathode
materials. However, other electrode did not show the prominent
discharge plateau at 3.52 V. The chemical sodiation process opens some
active sites (like (010), (110) and (111) planes become more active in
XRD pattern, Fig. S8) for sodium-ion insertion at higher discharge state
(reduction of V5þ to V4þ) and with zirconium doping the sodium
insertion channels becomes wider, helping to enhance the nominal po­
tential. The comparison of the electrochemical performance of
NH4V4O10 (NVO), Zr– NH4V4O10 (Zr-NVO), SNVO-3 and Zr-SNVO-3
(Zr0.03Na0.78NH4V3.88O9.88) were shown in Fig. 3f and Table S3 at
100 mA g 1 current density vs. Naþ/Na. The NVO electrode delivered a
specific discharge capacity of 210 mAh g 1 with the nominal potential of
2.1 V, corresponds to a high energy density of 441 W h kg 1. However,
with zirconium doping, the specific capacity was enhanced to 367 mAh
g 1, and the overall energy density increased to 702 W h kg 1 (nominal
potential 1.91 V). The discharge capacity is decreased to 190 from 205
mAh g 1 after chemical sodiation of NVO materials, but the nominal
voltage is increased to 2.37 V from 2.1 V. Therefore, we obtained almost
similar energy density (450 W h kg 1) from the current studied material.
However, after zirconium doping on SNVO-3, the specific capacity of the
materials further improved to 275 mAh g 1 with an average nominal
potential of 2.80 V. Therefore, we achieved an overall energy density of
770 W h kg 1 from the current cell in coin cell configuration. This is one
of the highest energy density obtained in any kind of cathode materials
used in lithium or sodium-ion battery (details comparison study shown
in Table S4 and Table S5).
Encouraged by the above outstanding electrochemical performance
of zirconium-doped sodiated NH4V4O10 cathode, we constructed a
sodium-ion full-cell based on this cathode material and zirconium-doped
hydrogenated sodium titanium oxide (Zr–HNa2Ti3O7) anode material
(half-cell electrochemical performance of anode as shown in Fig. S11)
[35]. In the full-cell, loading of an active cathode to anode mass ratio
was about 1:1. Fig. 4 shows the electrochemical performances of the
sodium-ion full-cell constructed with the above-mentioned cathode and
anode materials without further modification. The cyclic voltammetry
(CV) of the full-cell was carried out at a scan rate of 0.05 mV s 1 over
1.4–4.0 V to identify the intercalation-deintercalation potential range
(Fig. 4a).
The CV exhibited one prominent reduction peak ca. 2.80 V and three
oxidation peaks at 3.10, 3.23, and 3.38 V. Some minor reduction (at 1.78
and 2.05 V) and oxidation peaks (at 1.86 and 2.13 V) were also
observed. Fig. 4b displayed the charge-discharge profile of the full-cell
at a current density of 200 mA g 1 (cathode base) over 1.2–3.7 V po­
tential window. At this current rate, the full-cell provided a specific
discharge capacity of 176 mAh g 1 (cathode base) with a high nominal
voltage of 2.5 V. This full-cell is capable of delivering a high energy
density of 440 W h kg 1 (cathode base). However, if we combine both
active mass of anode and cathode materials, it still provided a high
energy density of 220 W h kg 1, which is comparable with the existing
commercial lithium-ion battery technology. The cycling performance of
the full-cell was shown in Fig. 4c. The full-cell showed initial discharge
capacity ca. 176 mAh g 1, and after 90 cycles and sustained its 83%
initial capacity with an average Coulombic efficiency of 99.58% with
excellent rate capability (Fig. 4d). The comparison study of the essential
electrochemical parameters such as specific capacity, voltage, energy
density and power density of recent sodium-ion full-cell prototype was
exhibited in Fig. 4e and f, and Table S6. Fig. 4e and f attributed that our
full-cell prototype delivered higher energy density and superior power
density compare with any other sodium-ion full-cell exit in the litera­
ture. We also demonstrate a practical application of this sodium-ion full-
cell in coin cell configuration (Fig. 4h). A single coin-cell constructed

Fig. 4. Electrochemical performance of the Zr-doped sodiated NH4V4O10 (Zr–SHNVO-3)//H–Na2Ti3O7 full-cell prototype with an active mass loading of cathode to
anode is 1:1 at 20 � 2 � C, (a) cyclic voltammetry at scan rate 0.05 mV s 1 over potential window 1.4–4.0 V, (b) charge-discharge at 200 mA g 1 current rate (with
respect to cathode) (c) cycling performance over 100 cycles at 200 mA g 1 current density, (d) Power cycling performance up to 200 cycles, (e–f) comparison of all
recent work on sodium-ion full-cell with our Zr-SNVO-3//H–Na2Ti3O7 full-cell, (e) Specific capacity vs. full-cell voltage profile of different of sodium-ion full-cell
developed in recent time (f) Ragone plot of different sodium-ion full-cell published in recent years with our prototype, and (g) a demonstration of prototype using a
light-emitting diode (LED) study lamp powered by a single coin-cell using our prototype full-cell.

6
A. Sarkar and S. Mitra
with this cathode and anode material, lighten a study table lamp made
with 36 LED bulbs in series.
3. Conclusions
In brief, ammonium vanadium oxide was chemically sodiated by a
single step hydrothermal technique without adding any extra process. In
SNVO materials, the ammonium-ions are bounded with oxygen by weak
van der Waals’s forces, and as a result, it showed better thermal and
electrochemical stability than NVO materials. This 1-D growth SNVO
nanobelts cathode materials exhibited better electrochemical perfor­
mance for SIB with the highest discharge capacity of ~200 mAh g 1 (at
the current rate of 100 mA g 1) and high stability with excellent rate
capability. Further, the specific capacity was enhanced by zirconium
doping into SNVO. Here, we achieved a high discharge capacity of ~225
mAh g 1 at 200 mA g 1 current density and the nominal potential
further improved to 2.80 V from 2.1 V. Hence, the overall energy density
of the cathode material was achieved to 770 W h kg 1 which is one the
best among all other cathode materials used in SIB or LIB system. Here, a
new class of sodium-ion full-cell was developed by constructing a cell
consists of Zr-SNVO-3//Zr–HNa2Ti3O7, which showed an excellent
reversible capacity of 176 mAh g 1 at 200 mA g 1 current rate with
stable cyclic performance up to 200 cycles with an average 99.58%
Coulombic efficiency. This high-performance sodium-ion full-cell
exhibited an excellent and high energy density of 220 W h Kg 1 (w.r.t
cathode and anode mass) with a high nominal potential of 2.5 V even at
a high rate of 200 mA g 1. The sodium-ion full-cell prototype showed
one of the best performing and promising performance in the sodium-
ion battery literature. This technology could be one of the best alter­
nates to the existing lithium-ion battery technology for renewable en­
ergy storage applications shortly.
Author contributions
The manuscript was written through the contributions of all authors.
All authors have approved the final version of the manuscript.
Funding sources
The authors are thankful for the financial support provided by MHRD
(Ministry of Human Resource Development) and NCPRE (Grant No. 31/
09/2015-16/PVSE-R&D) funded by the Ministry of New Renewable
Energy, Govt. of India.
Decalartion of competing interest
The authors declare that the research was conducted in the absence
of any commercial or financial relationships that could be construed as a
potential conflict of interest.
Acknowledgments
The authors are indebted to SAIF, IIT-B, for their assistance in FEG-
TEM, NCPRE for FEG-SEM facility, and DESE for XRD analysis and
IRCC, IITB for their assistance in XPS. We are very thankful to Arnab
Ghosh for helping us to propose the reaction mechanism. We are also
grateful to Dr. Sudeep Sarkar and all the ECEL members for their
continuous support and encouragement.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpowsour.2020.227832.
7
Journal of Power Sources 452 (2020) 227832
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