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org Letter

Crystal-Water-Free Potassium Vanadium Bronze (K0.5V2O5) as a

Cathode Material for Ca-Ion Batteries
Meladia E. Purbarani, Jooeun Hyoung, and Seung-Tae Hong*
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ABSTRACT: The research to discover a suitable cathode material

for calcium-ion batteries (CIBs) remains challenging, despite their
Downloaded via UNIV OF SASKATCHEWAN on August 11, 2021 at 20:12:29 (UTC).

potential advantages of high energy density and cost-effectiveness.

Herein, we report K0.5V2O5 as a cathode material for CIBs. During
the initial charging of the electrode, potassium ions were replaced
with 0.12 Ca. The calcium-exchanged electrode exhibited a
reversible discharge capacity of ∼100 mAh g−1 at 0.1 C rate at
room temperature with an average voltage of ∼3.0 V (vs Ca/Ca2+).
The reversible capacity is higher than any reported cathode
materials without crystal water, demonstrating the feasibility of further development of high-capacity crystal-water-free CIB cathode
materials.
KEYWORDS: calcium-ion batteries, intercalation, potassium vanadium bronze, calcium vanadium bronze, cathode material

Mg0.25V2O5·H2O,15 VOPO4·2H2O,16 Ca0.13MoO3·(H2O)0.41,17

O ver the past three decades, the applications of lithium-
ion batteries (LIBs) have been expanded from portable
electronic devices such as smartphones and laptops, to electric
vehicles (EVs), as well as megawatt-scale stationary energy
storage systems.1 These applications, particularly in EV
applications, require significantly higher energy densities than
the present state-of-the-art LIB technologies can provide
because of the theoretical limitations of the LIB chemistry. To
overcome these limitations, battery researchers have been
investigating next-generation battery systems that can replace
LIBs.2
Recently, multivalent-ion batteries, utilizing magnesium,
calcium, zinc, or aluminum ions as the carrier ion instead of
lithium, have been considered as one of the post-LIB
technologies.3 In principle, multivalent ions can double or
triple the capacity of the host material because of their ability
to transfer two or three electrons per guest ion, provided that
the transferred electrons can be accommodated by the
transition metal of the host. Alternatively, we could achieve
the same capacity by filling only half or one-third of the
available crystallographic sites of the host. In this regard,
calcium-ion batteries (CIBs) have garnered increasing interest.
Their low reduction potential (−2.87 V vs standard hydrogen
electrode (SHE)) renders them capable of delivering a higher
voltage full-cell than those of magnesium-, zinc-, or aluminum-
based batteries.2,4−6 The low effective charge density of
calcium, due to its large ion, can lead to swift diffusion in the
host material.7,8 Moreover, calcium is the fifth most abundant
element in the Earth’s crust; it is cost-effective. Despite these
advantages, only a few cathode materials have been reported to
be effective for CIBs including CaCo2O4,9 CaxMoO3,10
NaFePO4F,11 TiS2,12 α-MoO3,13 Prussian-blue analogues,14
FePO4,18 NaV2(PO4)3,18,19 and α-V2O5.20
Vanadium oxides have been investigated as cathode
materials for LIBs because of their diverse crystal structures,
rich electrochemical intercalation chemistry, and high specific
capacities which are derived from wide oxidation states of
vanadium.21 However, binary vanadium oxides usually suffer
from structural instability during cycling, leading to capacity
fading.22 This structural instability can be alleviated by
introducing additional cations or water molecules into the
interlayer to form vanadium bronze.
Potassium vanadium bronze materials, such as KV3O8,
K0.5V2O5, K0.25V2O5, and K2V8O21, have been studied as
cathode materials for lithium- and zinc-ion batteries.21,23,24
The first two materials have a layered structure, while the latter
two have a one-dimensional tunnel structure. The additional
cations reside in the interlayer or in the tunnel, respectively. In
this study, we focused on K0.5V2O5 because it has a large
interlayer space between the double-sheet V2O5 layers, which
would be beneficial for the facile diffusion of cations with a
large ionic radius.25 This material has been previously studied
for lithium- and potassium-ion batteries23,26 but not for
multivalent-ion batteries. Herein, we report the electro-
chemical intercalation chemistry and insertion mechanism in
Received: April 22, 2021
Accepted: July 12, 2021

© XXXX American Chemical Society https://doi.org/10.1021/acsaem.1c01158

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ACS Applied Energy Materials www.acsaem.org Letter

Figure 1. (a) Crystal structure, (b) powder X-ray diffraction (XRD) Rietveld refinement, (c) scanning electron microscopy (SEM) image, (d)
transmission electron microscopy (TEM) image, (e) TEM elemental mapping, and (f) high-resolution (HR)-TEM image of K0.5V2O5 (KVO).

Figure 2. (a) X-ray diffraction (XRD) patterns of K0.5V2O5 (KVO) and (Ca0.12K0.01)V2O5 (CVO) electrodes. Electrochemical characterizations and
performance of the CVO electrode: (b) cyclic voltammetry (CV) profiles between −0.9 and 1.4 V (vs carbon) at a scanning rate of 0.05 mV s−1;
(c) galvanostatic discharge−charge voltage profiles; (d) cycling performance at a 0.5 C rate; and (e) rate capability at 0.1 C, 0.3 C, 0.5 C, and 1 C.

dried nonaqueous electrolytes as a potential high-performance
cathode material for CIBs.
K0.5V2O5 (denoted hereinafter as KVO) was synthesized via
a microwave-assisted method. The crystal structure of KVO is
shown in Figure 1a. It has a layered structure, wherein
potassium ions lie in the interlayer sandwiched between V2O5
double-sheet layers. The synthesized material was confirmed
by the powder X-ray Rietveld refinement (Figure 1b and Table
S1). All the diffraction peaks were identified as monoclinic
K0.486V2O5 (ICSD 81045) with the space group of C2/m
without any observable impurities.27,28 The refined lattice
parameters are a = 11.60 Å, b = 3.657 Å, c = 9.45 Å, and β =
92.46°. Note that KVO is not a line compound and can be an
end member of the solid solution with a formula KxV2O5 (0 <
x ≤ 0.5), where the available crystallographic sites limit the
maximum occupancy of potassium as 0.5 (see Table S1). Field
emission scanning electron microscopy (FE-SEM) and trans-
mission electron microscopy (TEM) were used to observe the
morphology and size of the KVO particles (Figure 1c,d),
revealing a belt-like morphology with a length of ∼500 nm and
B https://doi.org/10.1021/acsaem.1c01158
a width of ∼60 nm. TEM-energy dispersive X-ray (TEM-EDX)
elemental mapping clearly showed a uniform distribution of K,
V, and O elements (Figure 1e). A layer distance of ∼9.4 Å,
which is the distance between adjacent V2O5 double sheets,
was observed in the TEM image (Figure 1f), which
corresponds to the (001) peak in Figure 1b. The chemical
composition was confirmed by inductively coupled-plasma
elemental analysis (Table S2). Thermogravimetric analysis
showed no significant weight loss up to 400 °C, indicating the
excellent thermal stability of the material and proving that it
contains no crystal water (Figure S1).
The electrochemical performance of KVO was examined
using a homemade cell comprising KVO as the working
electrode and activated carbon (AC) pellet as the counter and
reference electrodes (Figure S2). The electrolyte was 0.5 M
Ca(ClO4)2 in propylene carbonate. The water content of the
electrolyte was below 3.5 ppm. The loading of the electrode
was approximately 1.0 mg per electrode with an area of 1.54
cm2.
ACS Appl. Energy Mater. XXXX, XXX, XXX−XXX
ACS Applied Energy Materials
The KVO electrode was initially charged to 1.2 V (vs AC) to
extract potassium from the structure. The initial charge
capacity was 45.3 mAh g−1, which corresponded to a 0.34
electron charge per formula unit (Figure S3), implying some
potassium ions should have remained in the structure.
Considering that interlayer cations could play the role as a
pillar significantly stabilizing the layered structure,24 extraction
of all interlayer cations might need a higher cutoff voltage
beyond the stable electrochemical window region of the used
electrolyte. Nonetheless, the ICP elemental analysis indicated
that potassium almost disappeared while calcium appeared
unexpectedly (Table S3). These results suggest that the
potassium extraction reaction occurred simultaneously with an
exchange reaction between the potassium which remained in
the structure and the calcium from the electrolyte during the
first charge process. Thus, the initially charged electrode can be
regarded as a calcium-exchanged electrode, and its chemical
formula could be expressed as (Ca0.12K0.01)V2O5 (denoted
hereinafter as CVO). In this sense, the chemically synthesized
KVO material can be considered as a precursor for the
electrochemically prepared CVO electrode. Chemical synthesis
of CVO and use of it as the initial electrode would be
preferred. Unfortunately, a chemical method to obtain CVO is
not known yet, which will be our future work. It is noteworthy
that when KVO is charged in the Ca-containing electrolyte, the
exchanged Ca ions play the role of a pillar instead of K ions.
The X-ray diffraction (XRD) pattern of the CVO electrode
was markedly changed from that of the pristine KVO electrode
(Figure 2a). The lowest-angle (001) peak at 9.3° shifted to
∼4°, and the corresponding higher-order (00l) peaks (l = 2, 3,
4, and so on) appeared distinctly, which indicated that the c-
axis parameter was doubled as the pristine one (from ∼9.5 to
∼21.5 Å), yielding a 2-fold superstructure. The superstructure
could not be solved using only the powder XRD pattern.
However, using the Le Bail fit refinement, we confirmed that
the charged electrode was single-phase (Figure S4).
The CVO electrode was washed thoroughly, and a new cell
was reassembled to prevent the reinsertion of the extracted
potassium into the material. Figure 2b shows the cyclic
voltammetry (CV) profiles of the first three scans for the CVO
electrode at 0.05 mV s−1 between −0.9 and 1.4 V (vs AC).
Overall, the CV profiles indicated an excellent reversibility of
the calcium intercalation during the cycle, despite the slight
changes, particularly the weak peaks on the shoulder of the
main broad peaks, as the cycle proceeded. As for the main
redox pair of the third CV profile, for instance, the cathodic
and anodic peaks were at −0.25 and 0.3 V, respectively. The
reduction peak is considerably broader than the oxidation
peak, revealing that the calcium intercalation reaction is slow,
whereas the deintercalation reaction is fast. Although the
minor change of the CV profiles with cycling was not clearly
understood for now, the three CV profiles indicated that
calcium intercalation into CVO was highly stable and
reversible.
The CVO electrode was tested with galvanostatic dis-
charge−charge cycling from −0.9 to 1.4 V (vs AC). A three
electrode system was applied to estimate the potential of AC,
using an Ag/Ag+ electrode as the reference electrode (Figure
S5). The AC electrode potential was estimated around 3.123 V
vs Ca/Ca2+ (Figure S6). Figure 2c exhibits potential profiles at
a 0.1 C rate at 25 °C. According to the capacity for one-
electron transfer of KVO, 1 C is described as 133.13 mA g−1,
where “n C rate” is explained as the rate of charges/discharges
C https://doi.org/10.1021/acsaem.1c01158
www.acsaem.org Letter
performed in 1/n h. The first discharge capacity was 92 mAh
g−1, which increased to ∼100 mAh g−1 in the second and third
cycles with an average discharge voltage of ∼3.0 V (vs Ca/
Ca2+), suggesting a minor activation cycle of the material. This
is most probably due to the extraction process of the remaining
potassium ions from the CVO material. The ICP elemental
analysis of the CVO at the first discharged state suggested that
potassium was indeed extracted completely, and its chemical
formula could be described as Ca0.45V2O5 (Table S4). It should
be noted that, considering the initial 0.12 Ca content of CVO,
a net of 0.33 Ca (= 0.45−0.12 Ca) per formula unit was
inserted into the host structure on the first discharge, which
corresponded to the calculated capacity of 87.8 mAh g−1,
reasonably matching the observed capacity of 92 mAh g−1. To
date, only materials with crystal water have shown a capacity
greater than 100 mAh g−1, such as Mg0.25V2O5·H2O (∼110
mAh g −1 ), 15 VOPO 4 ·2H 2 O (∼100 mAh g −1 ), 16 and
Ca0.13MoO3·(H2O)0.41 (∼190 mAh g−1),17 and the crystal
water appeared to play a critical role in the facile diffusion of
divalent ions by effectively shielding of the charge. The specific
capacity of ∼100 mAh g−1 for CVO is higher than that
reported for crystal-water-free CIB cathode materials.
The cyclability test at 0.5 C rate is presented in Figure 2d.
The initial capacity was 65 mAh g−1, and the capacity at 100
cycle was 60 mAh g−1 with a 92% capacity retention. The
cyclability test at a lower rate (0.1 C) is presented in Figure
S7a, together with voltage profiles for some selected cycles
shown in Figure S7b. The initial capacity was 92 mAh g−1, and
the capacity retention was poor, approximately 60% after 50
cycles. The rate performances are shown in Figure 2e, and the
voltage profiles of the first cycles at various C rates are also
presented in Figure S7c. The reversible capacities are 100, 87,
70, and 50 mAh g−1 at 0.1, 0.3, 0.5, and 1 C rates, respectively.
When the current returned to a low C rate (0.1 C), the
capacity was retained at 80 mAh g−1.
The broad shape of both the cathodic and anodic CV peaks
suggests that some portion of the capacity could partly be
attributed to the surface-capacitive reaction. To distinguish
between the capacitive and intercalation reactions, we
performed CV measurements at different scan rates from
0.05 to 5.0 mV s−1 (Figure S8).29,30 For the reduction reaction,
the capacitive contribution was 33% at 0.05 mV s−1, which
increased at higher rate to 69% at 1 mV s−1. These results
indicate that the diffusion-controlled intercalation reaction was
dominant at a lower rate, while the surface-limited capacitive
reaction was superior at a higher rate.
Calcium intercalation into the structure should involve a
structural change that can be monitored by XRD pattern
changes during a cycle, combined with the elemental analyses.
The main (00l) peaks of the CVO electrode were shifted to
lower angles with significant intensity reduction on discharge,
suggesting expanded d-spacing. The peaks returned to the
original positions upon charging (Figure 3a). The elemental
mappings from TEM-EDX showed that calcium concentration
clearly increased during discharge and decreased back upon
charging (Figure 3b−d). The combined analyses of XRD and
elemental mappings provided unambiguous evidence that
calcium ions were actually intercalated into the bulk structure
with an excellent reversibility. The reversible calcium
insertion/extraction into/from the material was further
confirmed by the X-ray photoelectron spectroscopy (XPS)
technique cycle. The Ca 2p peaks appeared on discharge and
decreased upon charge (Figure 4a). The V4+ 2p peaks
ACS Appl. Energy Mater. XXXX, XXX, XXX−XXX
ACS Applied Energy Materials
Figure 3. (a) X-ray diffraction (XRD) patterns of the (Ca0.12K0.01)-
V2O5 (CVO) samples discharged to −9 V and charged to 1.4 V vs
AC. Transmission electron microscopy-energy dispersive X-ray
(TEM-EDX) images of (b) CVO, (c) CVO discharged to −0.9 V,
and (d) CVO recharged to 1.4 V.
Figure 4. X-ray photoelectron spectroscopy (XPS) results of (a) Ca
2p and (b) V 2p for the (Ca0.12K0.01)V2O5 (CVO) electrode samples
during the discharge−charge.
increased during discharge and decreased upon charge (Figure
4b).
In summary, we demonstrated potassium vanadium bronze
as a potential cathode material for dried nonaqueous CIBs.
Ion-exchange occurred between potassium and calcium during
the first charging process, yielding a calcium vanadium bronze
electrode, which exhibited a reversible Ca-ion intercalation
capacity of ∼100 mAh g−1 at 0.1 C rate with the average
voltage ∼3.0 V vs Ca/Ca2+. Further, it displayed a high
structural stability during cycling with a capacity retention of
60% at the 50th cycle. The observed capacity was higher than
that of any reported crystal-water-free CIB cathode materials
without any crystal water. To profoundly understand the
intercalation mechanism, the 2-fold superstructure of the phase
after the first charging should be determined as a future study.
The observed capacity is still far below the theoretical
doubled capacity expected, owing to the divalency of calcium,
and even below that of the state-of-the-art LIB cathode
materials. Nonetheless, considering that CIBs are still in their
infancy development stage, this study can significantly facilitate
the discovery new crystal-water-free CIB cathode materials.
D https://doi.org/10.1021/acsaem.1c01158
■
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ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaem.1c01158.
Experimental procedures; TG, EDX, and ICP results;
scheme of test cell; TEM and SEM images; powder
XRD Le Bail fit profiles; ferrocene calibration test;
cycling performance and voltage profiles; and calculated
results of intercalation/adsorption ratio from CV (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Seung-Tae Hong − Department of Energy Science and
Engineering, DGIST (Daegu Gyeongbuk Institute of Science
and Technology), Daegu 42988, Republic of Korea; Energy
Science and Engineering Research Center, DGIST, Daegu
42988, Republic of Korea; orcid.org/0000-0002-5768-
121X; Email: st.hong@dgist.ac.kr; Fax: +82 53 785 6409
Authors
Meladia E. Purbarani − Department of Energy Science and
Engineering, DGIST (Daegu Gyeongbuk Institute of Science
and Technology), Daegu 42988, Republic of Korea
Jooeun Hyoung − Department of Energy Science and
Engineering, DGIST (Daegu Gyeongbuk Institute of Science
and Technology), Daegu 42988, Republic of Korea
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaem.1c01158
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the Samsung Research Funding &
Incubation Center of Samsung Electronics under Project
SRFC-MA1601-04. This work also was supported by the
Creative Materials Discovery Program through the National
Research Foundation of Korea funded by the Ministry of
Science, ICT and Future Planning (Grant
2015M3D1A1069707).
■
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