ISSN 1023-1935, Russian Journal of Electrochemistry, 2020, Vol. 56, No. 12, pp. 1069–1083. © Pleiades Publishing, Ltd.

, 2020.

Chalcone as Anode Material for Aqueous Rechargeable

Lithium-Ion Batteries
Chaithra Munivenkatappaa, Vijeth Rajshekar Shettya, and Suresh Gurukar Shivappaa, *
aDepartment of Chemistry and Research Centre, NMKRV College for Women,
Jayanagar, Bangalore-560 011, Karnataka, India
*e-mail: sureshssmrv@yahoo.co.in
Received September 11, 2019; revised February 14, 2020; accepted March 6, 2020

Abstract—Utilization of environmental friendly, potentially sustainable, low cost, high capacity organic elec-
trode materials seem to be very promising for next generation rechargeable Lithium ion batteries. In fact,
numerous organic materials with electrochemically active carbonyl groups have been effectively stated as
electrode materials. Herein, we report an ideal organic species derived from aromatic ketone, namely chal-
cone (CLN). Synthesis of chalcone has been developed via Claisen–Schmidt condensation of benzaldehyde
and acetophenone in the presence of alumina sulfuric acid as environmentally benign, biodegradable and
reusable catalyst under solvent-free conditions followed by lithiation using ball-milling method. CLN and
lithiated chalcone (LiCLN) was synthesized and characterized using 1H-NMR, XRD and IR spectroscopy
techniques. Electrochemical techniques like cyclic voltammetry, galvanostatic cycling with potential limita-
tion and potentio electrochemical impedance were carried out to study the electrochemical properties and
performance in saturated aqueous Li2SO4 electrolyte. As an anode material, LiCLN showed exceptional per-
formance such as; good reversible capacity, excellent cyclability and high rate capability when tested in half-
cell configuration. The cell LiCLN | aqueous saturated Li2SO4 | LiFePO4 delivered a discharge capacity of
111.23 mA h g–1 at C/8 rate and maintains 91% capacity retention even after 1000 repeated cycles.

Keywords: alumina sulphuric acid, chalcone, cyclic voltammetry, lithium-ion batteries, lithium iron phos-
phate

DOI: 10.1134/S1023193520120162

INTRODUCTION materials. The structural integrity of the composites

Robust community of researchers focused on
developing innovative, cost-effective, compatible
energy storage materials to advance the stability,
power quality, and consistency in its action of energy
storage devices. Rechargeable lithium-ion battery
(RLIBs) systems have developed into the alternative
energy sources for electrical and electronic devices.
They are recognized as best choice which renders the
superior performance, flexibility, high atom economy,
good energy density and low impact on the eco system
[1–5].
A recent breakthrough shows that the use of an
aqueous medium as an electrolyte in RLIBs has con-
cerned wide attentions due to its high reliability, ionic
conductivity and comparatively large energy density
than that of Pb-acid or Ni–Cd cells [6–8], but in con-
cern with non-aqueous system, it shows bit low energy
density. To overcome these aspects, several develop-
ments have been initiated.
Most of the RLIBs are limited to transition-metal-
based inorganic composites which serve as electrode
depends on oxidation states of the metal. It involves
complex synthesis techniques and it has high cost
effective criterion. Moreover, the disposal of inorganic
waste leads to several intrinsic difficulties. Hence inor-
ganic complexes are not benign to the environment
[9, 10]. Utilization of environmental friendly, poten-
tially sustainable, low cost-high capacity organic elec-
trode material seems to be very promising electrode
materials for next generation RLIBs. Organic mole-
cules are considered as better alternative to the present
conventional inorganic moieties owing to its rapid
structural diversity and versatility, tunable properties
and eco-friendly [11].
Based on above factors, researchers have consid-
ered few organic molecules of in turn to develop elec-
trode materials such as, Dichloroisocyanuric acid, a
triazine derivative was the first organic compound
reported as cathode material for energy storage devices
[12], recently small organic molecules like quinines
[13], tetrahydro-hexaquinone [14], Poly(acetylene)s
[15], phthalocyanines [16], and heterocyclic polymers
compounds like polypyrrole, polythiophene and their

1069
1070 CHAITHRA MUNIVENKATAPPA et al.
derivative are used in lithium ion batteries as energy
harvesting units [17, 18]. In fact, numerous organic
materials with electrochemically active carbonyl
groups have been effectively tested as electrode mate-
rials for RLIBs due to their electroactivity, naturally
abundance, light weight and flexibility. Nonylbenzo-
hexaquinone was the first carbonyl compound
reported as electrode material with acceptable cycling
behavior [19, 20].
By consideration of above factors, here in, we
report a carbonyl moiety called chalcone or 1,3-diphe-
nyl-2-propene-1-one which has good structural flexi-
bility to undergo keto-enol conformation. To stabilize
the conjugated carbonyl moiety, undergoes one elec-
tron reduction to form an enolate anion which is ben-
eficiary for electrochemical redox reaction during its
electrochemical performance [21]. Chalcones belongs
to flavonoids with C6–C3–C6 skeleton in which the C6
subunits are aromatic rings and the C3 unit is α, β-
unsaturated carbonyl group. Among the reported syn-
thesis of Chalcones, Claisen–Schmidt-Condensation
C–S-C) reaction is of vast significance due to its char-
acteristic nature such as less reaction time and tem-
perature, no formation of side reactions [22]. Cur-
rently, heterogeneous catalysts in solvent-free condi-
tions are trending in current organic chemistry due to
their unique roles like reduced pollution, reusability
and low cost [23]. Many heterogeneous catalysts have
been used to synthesis Chalcone, for example, Bambo
char sulfonic acid [22], acid-clays [23], amino grafted
zeolites [24], Amberlyst-15 and Amberlite-200C [25].
Alumina sulfuric acid (ASA) is a novel heterogeneous
catalyst with high activity which can be employed in
various organic transformations [26].
In this perceptive, we used ASA as a heterogeneous
catalyst to accelerate the novel synthesis of chalcone
under neat microwave irradiation and used as an elec-
trode material for an aqueous RLIBs. The reduction of
Li-ions process is carried out by the carbonyl group in
chalcone compound and also aromaticity smoothes
the progress of electrons movements in the electro-
chemical reaction. The synthesis of chalcones has
been synthesized via Claisen–Schmidt condensation
of benzaldehyde and acetophenone in the presence of
alumina sulfuric acid as environmentally benign, bio-
degradable and reusable catalyst under solvent-free
condition followed by lithiation by Ball-milling
Al O
Cl OH
O OH + S Al(HSO4)3 +
Al O
Neutral alumina Chlorosulphonic acid
Scheme 1. Synthesis of Alumina sulfuric acid.
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
method. The electrochemical activity of chalcone and
its lithiated form were studied by cyclic voltammetry,
galvanostatic cycling with potential limitation and,
Potentio electrochemical impedance techniques
under aqueous Li2SO4 electrolyte. The cycling behav-
ior of lithiated chalcone shows the noticeable dis-
charge capacity of about 111.23 mA h g–1 by pairing
with lithium iron phosphate (LiFePO4) as a cathode
[27].The results assist the exploitation of chalcone in
energy storage sources in upcoming day.
EXPERIMENTAL
Materials and Methods
All Chemicals used in the present work were
acquired from commercial traders and pertained with-
out any further purification. Benzaldehyde (merck),
Acetophenone (merck), Sodium tungstate (SD Fine),
Neutral alumina (merck), Lithium hydroxide
(merck), polytetrafluoroethylene powder (12 micron),
N-methyl-2-pyrrolidone (sigma aldrich) and lithium
sulphate (Molychem) were obtained. Synthesis of
chalcone was carried out by novel method using het-
erogeneous catalyst called Alumina sulphuric acid
under microwave assisted synthetic route. The elec-
trochemical investigations were carried out in an
aqueous saturated lithium sulphate electrolyte. A stoi-
chiometric ratio of LiCLN/LiFePO4, carbon black,
and polytetrafluroacetylene were mixed with few
drops of N-methyl-2-pyrrolidone, the slurry was
coated on current collector and dried for overnight
under controlled temperature. For the CV, CVA,
GCPL and EIS measurements, a standard three-elec-
trode system was implemented.
Synthesis of Alumina Sulfuric Acid
Synthesis of alumina sulfuric acid was carried out
according to the Hamid R. Shaterian et al. [28] with
slight modification. Addition of known quantity of
chlorosulfonic acid into neutral alumina under
reduced pressure and the liberated HCl gas were
removed using CaCl2 drying tube connected to water
trap. Then the reaction mixture was stirred for 2 h at
RT and the obtained solid was washed repeatedly with
water followed by ethanol and dried at 120°C for 4 h
(Scheme 1).
Neat
H Cl
Alumina sulphuric acid
Vol. 56 No. 12 2020
 CHALCONE AS ANODE MATERIAL FOR AQUEOUS RECHARGEABLE LITHIUM-ION… 1071

Synthesis of Chalcone Using Heterogeneous
Catalyst ASA by Microwave Method
Synthesis of chalcone using heterogeneous catalyst
ASA by microwave method: A known stoichiometric
ratio of acetophenone and benzaldehyde were irradi-
ated using microwave reaction in the presence of ASA
as a catalyst for 8 min and the reaction mass was mon-
itored using TLC. The reaction mass was extracted
using ethyl acetate in a separating funnel. Then the
organic layer was washed with water, brine solution,
dried over anhydrous sodium sulphate and distilled
off. The crude was purified by silica gel (60–120 mesh)
column chromatography by using hexane: ethyl ace-
tate (10:90) as mobile phase to get the product. The
desired product was formed and confirmed by IR,
XRD and 1H-NMR (Scheme 2)

O O O
H ASA
+
MW, 8 min

Scheme 2. Synthesis of chalcone using ASA by microwave method.

Synthesis of Lithiated Chalcone equivalent of lithium hydroxide for about 20 min

by Ball-Milling Method [29, 30]. After ball-milling, LiCLN is obtained as a
The preparation of lithiated chalcone is straightfor- crystalline yellowish solid. 1H-NMR data [31] indi-
ward: chalcone is ball-milled with a stoichiometric cate the successful synthesis of LiCLN (Scheme 3).

Li
O
O

LiOH
Ball milling
for 20 min

Scheme 3. Synthesis of lithiated chalcone by ball-milling method.

RESULTS AND DISCUSSION Fourier Transform-Infrared Spectroscopy (FTIR)

Physical Characterization
Proton nuclear magnetic resonance (1H-NMR)
studies: The powder form of chalcone and lithiated
chalcone in deuterated chloroform were analyzed
using Bruker 400 MHz processor and Agilent-NMR
spectrometer at room temperature. In the Fig. 1a, the
1H-NMR of CLN shows two types of protons: an eth-
ylenic proton and the aromatic protons. The ethylenic
protons adjacent to the carbonyl group shows doublets
with a chemical shift values of 8.14 and 8.12 ppm. The
proton next to the carbonyl group exhibits higher
downfield which indicate the effect of polarization of
the C=C next to the C=O group [32].The chemical
shift value of 7.14–7.94 ppm is aassigned to the two
aromatic rings in CLN. In Fig. 1b, the NMR spectra
LiCLN exhibited a similar spectral signal which con-
firms that the lithiation was not formed at any aro-
matic ring that is, no displacement of protons hap-
pened. Hence lithiation of chalcone may occur at the
carbonyl group as a result of coordination of Li+ with
aldehyde carbonyl group [33].
was used to analyze the absorption of infrared radia-
tion by the sample of interest i.e., CLN and LiCLN
versus wavelength. Hence FTIR measurement was
performed to characterize the molecular components
in Chalcone as shown in Fig. 2. The IR spectrum of
Chalcone shows absorption bands in the range of
~3020–3050, ~2800, ~1690, ~1450 and ~750 cm–1.
The strong IR bands at ~1650 and ~1680 cm–1 are
assigned to the carbonyl stretching vibrations for the
enone group and keto group in the range of ~1690 in
chalcone [33, 34]. The CH2 stretching vibration and
aromatic bending peaks were observed at 2800 and
750 cm–1 respectively. The aromatic asymmetric and
symmetric C–H stretching absorption peaks are also
observed in the vicinity of ~3020 and ~3050 cm–1 with
low intensity. The spectra obtained for chalcone
match with the literature reported by Durairaj and co-
workers [34]. The IR spectrum of LiCLN confirms
that the lithiation has occurred at tautomerised car-
bonyl group with reduced absorbance band in the
vicinity of ~1690, and the C=O and C=C absorption
bands shift towards a lower wave number [35].

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 56 No. 12 2020

1072 CHAITHRA MUNIVENKATAPPA et al.

Fig. 1. 1H-NMR Spectra of (a) chalcone, (b) lithiated chalcone.

The Quantitative determination of crystallite size
of the powdered CLN and LiCLN structures were
illustrated by using X-ray powder diffraction method.
XRD patterns were recorded in the 2θ angle range of
10°–80° which as shown in Fig. 3. The peak at differ-
ent crystal angles and planes of chalcone between 10°
and 20° are relatively comparable to the reported
4'-Hydroxychalcone [36]. The diffraction peaks are
observed at the 2 theta value for the lithiated chalcone
which were relatively analogous to the synthesized

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 56 No. 12 2020

 CHALCONE AS ANODE MATERIAL FOR AQUEOUS RECHARGEABLE LITHIUM-ION… 1073

26 (а)
24
22
O
20 2 2'
3 1 1' 3'
18
16 4 6 6' 4'
14
T, %

5 5'

12
10
8
6
4
2
0
4000 3500 6000 2500 2000 1500 1000 400
cm–1
67 (b)
65
60
55
Li
50 O
45
T, %

40
35
30
25
20
15
14
4000 3500 6000 2500 2000 1500 1000 400
cm–1

Fig. 2. IR Spectra of (a) chalcone, (b) lithiated chalcone.

chalcone. The CLN exhibits Hexagonal crystal struc-

ture [36]. The crystallite size of CLN and LiCLN were
predicted by Debye Scherer’s method which is equiv- LiCLN
alent to 19.13 nm at 2h = 20.50; 23.03 nm at 2h =
Intensity, a.u

34.94; and 31.21 nm at 2h = 40.43 for LiCLN whereas

10.87 nm at 2h = 20.47; 30.11 nm at 2h = 35.57; and
11.12 nm at 2h = 40.18 for CLN respectively. Apart
from these distinct peaks, LiCLN shows Anorthic CLN
Crystal structure with new sharp diffracted peaks with
high intensity in counts per seconds which is due to the
presence of lithium ions sources [37].
Figures 4a–4d shows typical SEM photographs of 10 20 30 40 50 60 70 80
CLN and LiCLN as obtained after synthesis. The par- 2θ, deg
ticle size of CLN and LiCLN moieties were recorded
in the vicinity of 10–20 μm. CLN shows irregular
tube-like structure with smooth surface where as Fig. 3. XRD Spectra of (a) chalcone, (b) lithiated chal-
LiCLN is illustrated as clumpy profile in which it is cone.

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 56 No. 12 2020

1074 CHAITHRA MUNIVENKATAPPA et al.

(a) (b)

20 m 10 m
(c) (d)

20 m 10 m

Fig. 4. SEM images of (a) chalcone at 20 μm, (b) chalcone at 10 μm, (c) lithiated chalcone at 20 μm and (d) lithiated chalcone
at 10 μm.

difficult to recognize any structural organization
implying that the lithium particles are stacked together
on chalcone surface to form a loose aggregation by the
ion-exchange reaction [38].
Electrochemical studies of lithiated chalcone were
carried out using cyclic voltammetry, galvanostatic
charge/discharge technique and electrochemical
impedance spectroscopic techniques. CV is used to
study the electrochemical redox properties, mecha-
nism of redox reaction and to confirm anodic or
cathodic behavior. CV studies of α, β-unsaturated car-
bonyl system of lithiated chalcone was carried out at
the scan rate of 0.5 mV s–1 in an aqueous saturated lith-
ium sulphate electrolyte.
Before analyzing the CV in detail, we have tested
the active electrode material in different electrolytes,
pH and temperature respectively. Electrolyte is one of
the most influential components for energy storage
systems where it offers ionic conductivity and revers-
ible redox process for the storage of charge during
electrochemical reaction in the cell [39].
Table 1. Formal potentials of the LiCLN system at various
electrolyte solutions
Electrolyte solution, Formal potentials of the
Sl. no.
mol dm–3 redox reaction (Ef in V)
1 Sat. LiSO4 –0.505
2 Sat. LiCl –0.57
3 Sat. LiNO3 –0.59
4 Sat. LiOH –0.565
To study the influence the electrolytes on LiCLN
in detail, the CV was carried out using different aque-
ous electrolytes i.e., saturated LiCl, LiOH, LiNO3
and Li2SO4 at scan rate of 0.5 mV s–1 as shown in
Fig. 5a. Almost all the electrodes in different electro-
lytes show a pair of redox peaks with little dissimilarity
in the peak potentials as well as peak current. With
Saturated Li2SO4 solution, a pair of clear and well
defined sharp peaks was observed at the scan rate of
0.5 mV s−1 with open circuit voltage of –0.90 V indi-
cating redox process. It exhibits an oxidative peak at
‒0.49 V and a reductive peak potential of –0.64 V
owing to the ultrafast kinetics reaction. In Saturated
LiNO3, LiOH and LiCl electrolytes, the peaks appear
at more negative potentials with poor current response
signifying unfavorable redox kinetics of lithium ions
[[40]]. Among all the four electrolytes, Sat Li2SO4 is
found to establish a good reversibility, sharp peak cur-
rent and higher conductivity [41]. Hence, we used Sat.
Li2SO4 for rest of the electrochemical studies to attain
a good electrochemical performance.
The Formal potentials of the redox reactions (Ef)
during electrochemical process of LiCLN were evalu-
ated using the formula Ef = (Ea + Ec)/2 where, Ea is the
anodic peak potential, and Ec is the cathodic peak
potential. The results are shown in Table 1. We observe
a difference in the formal potentials which may be
attributed to the different degree of hydration of lith-
ium cations [42].
To study the effect of pH and temperature on lithi-
ated chalcone in aqueous Sat. Li2SO4 electrolyte, the
CV was performed at different PH values and at differ-

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 56 No. 12 2020

 CHALCONE AS ANODE MATERIAL FOR AQUEOUS RECHARGEABLE LITHIUM-ION… 1075

(а) (b) (c)

0 0 0
Current, mA

Current, mA

Current, mA
–0.03 Sat. LiCl
–0.03 –0.03
Sat. LiOH At acidic pH
Sat. LiNO3 At neutral pH At 10°C
Sat. Li2SO4 At RT
At basic pH
–0.06 At 50°C
–0.06 –0.06

–0.09
–0.8 –0.4 0 –0.8 –0.4 0 –0.8 –0.4 0
Potential, V vs. SCE Potential, V vs. SCE Potential, V vs. SCE

(d) (e)
0.05
0.04 ip.a ~ v1/2
Current, mA

0
0

ip, mA
Oxidation peak current
Oxidation linear fit data

1.0 mV/s Reduction peak current

–0.05 –0.04 Reduction linear fit data

0.1 mV/s
–0.08 ip.a ~ v1/2
–0.10
–1.0 –0.5 0 0.3 0.6 0.9
Potential, V vs. SCE v, (V s–1)1/2

Fig. 5. CyclicVoltammogram (a) at different electrolytes, (b) at different pH, (c) at different temperature, (d) Cyclic Voltammo-
gram advanced of lithiated chalcone curves at different scan rates of 0.1–1.0 (mV s–1 e) Randles–Sevcik plot for lithiated chalcone
at oxidation and reduction peak currents.

ent temperatures which as shown in Figs. 5b, 5c. In ated chalcone activity. Hence the rest of the experi-
general, aqueous electrolytes can be classified into ments were conducted in this solution medium. It is
three categories such as, acid, alkaline, and neutral important to study the electrochemical properties of
media. Figure 5b shows the pH of the electrolyte the LiCLN material at different temperatures in order
which was synchronized by using various concentra- to build up the energy storage lithium ion devices that
tions of 1 M H2SO4 and 1 M LiOH. In acidic electro- can be used in a broad temperature range. For the rea-
lyte, the CV of LiCLN exhibits a pair of weak and nar- son, we have carried out CV measurements at the tem-
row redox peaks with the redox potential of –0.28 and peratures range of 10–50°C. CV profiles of the LiCLN
–0.43 V. This peak mainly influenced by the high evo- electrode material at various temperatures are shown
lution of oxygen which renders the high interaction in Fig. 5c. We have observed the electrode material is
between oxygen during evolution and redox reactions. stable at RT where it exhibits redox peaks with inclined
The broad anodic peak is a characteristic feature for peak currents compared to high temperature which
the redox reaction where degradation of its amorphous supports the redox reaction of the active electrode
nature takes place due to the formation of solid elec- material [44].
trolyte interphase (SEI) [43]. The CV of LiCLN at The CV profile of LiCLN in Sat.Li2SO4 exhibits a
basic Li2SO4 medium exhibits only anodic peak pair of clear sharp curves at the scan rate of 0.5 mV s–1
potential at –0.43 V and no reduction peak was with open circuit voltage of –0.90 V. It exhibits an oxi-
obtained, this may be accompanied by the evolution of dative peak at –0.49 V in the cathodic direction and at
hydrogen in which the migration of lithium ions is an anodic direction, a reductive peak potential of –
barred. The clear picture of peak potential of LiCLN 0.64 V was observed owing to the ultrafast kinetics
was obtained in neutral Li2SO4 electrolyte medium. reaction [45]. The peaks remain almost unchanged in
The anodic peak potential was recorded at –0.45 V the subsequent cycles which indicate a redox reaction
and the cathodic peak potential at –0.60 V indicates of enolate groups in LiCLN with excellent reversibility
that the neutral electrolytic medium favored for lithi- during electrochemical cycling [46, 47]. The presence

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 56 No. 12 2020

1076 CHAITHRA MUNIVENKATAPPA et al.
of extended conjugation with complete delocalization
of pi electrons in LiCLN system stabilizes the system
by mesomeric effects and, which in turn prevents the
formation of unstable biradical in complete lithiated
CLN compound [48].
In continuation with the above aspects, we have
subjected the same cell to cyclic voltammetric studies
at different applied potential from 0.1–1.0 mV s–1 as
shown in Fig. 5d. This study renders the information
about the reversibility and cell performance at differ-
ent applied potentials. At a scan rate of 0.1 mV s–1, the
CV illustrates a pair of reversible sharp peaks and sym-
metric current-potential features attributable to the
redox reactions [49, 50]. There is no much difference
in the redox peaks found by changing the scan rates
due to the reversibility of carbonyl-enolate conversion
effect [51]. With the increase of the scan rate from
0.1–1.0 mV s–1, the shape of the CV remains relatively
similar without much distortion, which reveals fast
electrolyte ion transport during electrochemical reac-
tion and the current increases and the double layer
capacitance drastically decreases due to the degree of
polarization [52, 53].
The effect of scan rates on peak current and peak
potential can be enumerated using Randles–Sevcik
equation [54]. The relationship between scan rate and
peak current is given by the Randles–Sevcik formula
( )
12
ip = 0.4463nFAC nF v D ,
RT
where ip is the peak current of redox process, n is the
number of electrons per reaction species, A is the area
of electrode in contact with electrolytic solution, D is
the diffusion coefficient, C is the electrolyte concen-
tration, F is faraday constant, R is Rydberg constant, T
is the temperature and is the scan rate. In the present
work, the Randles–Sevcik relation has been measured
for LiCLN in the presence of aqueous Sat.Li2SO4
electrolyte. An apparent change in both the oxidation
and reduction peaks with scan rate range from 0.1–
1.0 mV s–1 is manifested from Randles–Sevcik plots.
This plot predicts that the peak current which is
ramped proportionally to the square root of scan rates
as shown in Fig. 4e, respectively. From Fig. 5e, we
observe a linear relation between the peaks current and
scan rate indicating the LiCLN obeys the Randles–
Sevcik equation [55].The electrochemical perfor-
mance of lithiated chalcone in an aqueous saturated
Li2SO4 electrolyte was investigated in half-cell as well
as in full-cell configuration.
To categorize the effects of higher current density,
capacity and the cyclability on LiCLN, the
charge/discharge profile was evaluated and compared
at the scan rate 0.2 mV s–1 for 100 cycles in half cell
configuration as shown in Fig. 6a. During electro-
chemical reaction, the GCPL curve exhibits a compa-
rable sloping nature without well-defined plateaus due
to the crystalline structural transformation of active
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
material from crystallinity to the amorphous phase
[56]. The first reversible discharge capacity of LiCLN
was observed at 368.87 mA h g–1 which is unexpectedly
superior to the theoretical capacity (123.95 mA h g–1) of
one electron redox process accompanied with trans-
formation involving lithium enolate. Incline of
charge/discharge capacity and voltage mainly corre-
sponds to the amorphous nature of LiCLN which
facilitates one electron transfer redox reaction [57].
The reversibility was obtained at second discharge
capacity of 305.10 mA h g–1 and optimized at 100th
cycle with discharge capacity of 279.70 mA h g–1. The
initial capacity loss was attributed to the fast dissolu-
tion of the LiCLN into the electrolyte over cycles
which hinder the electrochemical activity [58].
LiFePO4 is one of the most promising cathode
material, since Fe is an ample element whereas the
phosphate anion is potent anion to formulate the safe
LIBs with good theoretical capacity and rate capability
[59]. Conversely, their applications to ARLIBs are also
limited due to the surface instability issues [59] of
LiFePO4 in aqueous electrolyte, which causes the
capacity fading and poor rate capability. Hence, in the
present work, LiFePO4 is coated with Carbon to solve
its stability issues [59]. Oxygen evolution during the
charge/discharge process was controlled by maintain-
ing the pH values of the electrolytes [59]. The
charge/discharge profile of LiFePO4 was evaluated at
the scan rate 0.2 mV s–1 for 100 cycles in half cell con-
figuration as shown in Fig. 6b. The discharge capacity
of LiFePO4 was observed at 141 mA h g–1 which is
closely matches with the earlier reports and it naturally
exhibits negligible capacity loss after 100 cycles, indi-
cating excellent cycling stability, hence it is used as
cathode material in our studies [59].
To determine the rate capability at different rates
from 1 C to C/8 for lithiated chalcone | saturated Li2SO4
electrolyte | LiFePO4 was recorded and shown in
Fig. 6c. The GCPL curves exhibits a good rate capa-
bility with reversible charge–discharge capacities at
various C rates as shown in Table 2. The capacity fad-
ing is mainly endorsed to the active material dissolu-
tion into the electrolyte, phase transformation of elec-
trode material, decomposition of electrolyte etc. [60].
This type of reversible capacity demonstrates good
rate capacity and reversibility.
The galvanostatic charge/discharge process for
LiCLN | saturated Li2SO4 electrolyte| LiFePO4 cell at
C/8 rate for 1000 cycle was carried out in a two cell
electrode system where LiFePO4 was used as a cathode
material and LiCLN as an anode material. Figure 6d
exhibits its 1st, 10th, 100th, 500th and 1000th
charge/discharge curves. The potential window was
optimized between –0.7 to 1.2 V. The initial charge
capacity is about 101 mA h g–1 and discharge capacity
is about 110 mA h g–1 with 93% columbic efficiency
were observed, which is higher than the analogous
Vol. 56 No. 12 2020
 CHALCONE AS ANODE MATERIAL FOR AQUEOUS RECHARGEABLE LITHIUM-ION… 1077

(а) (b) (c)

1.0
0.7
0.7
Potential, V

Potential, V

Potential, V
0.5
0
0 C C/2 C/3 C/4 C/5 C/8
0
–0.7 –0.5
100th cycle 2st cycle 1st cycle 100th cycle, 2st cycle, 1st cycle
–0.7
0 110 220 330 0 50 100 150 200 0 40 80 120
Capacity, mA h g–1 Capacity, mA h g–1 Capacity, mA h g–1

Discharge capacity, mA h g–1

1.4 (d) (e) (f)
300 300

Coulombic efficiency
1.5
0.7
Potential, V

Potential, V

Coulombic efficiency
1.0 150 C/8
150
0
C/4 C/5
0.5 1C C/2 C/3
100.42 mA h g–1
0 0
–0.7 Discharge capacity
1000th, 500th, 100th, 1th cycle
0
0 70 140 210 0 50 100 150 0 5 10 15 20 25 30
Capacity, mA h g–1 Capacity, mA h g–1 Cycle number

Fig. 6. Galvanostaticcharge potential limit studies in saturated Li2SO4 solution (a) Half cell potential of chalcone at the scan rate
of 0.2 mV s–1 for 100 cycles (b) Half cell potential of LiFePO4 at the scan rate of 0.2 mV s–1 for 100 cycles (c) Lithiated chal-
cone | sat. Li2SO4| LiFePO4 cell at first cycle at various C rates (d) Galvanostatic charge/ discharge curve of the lithiated chal-
cone| sat. Li2SO4 | LiFePO4 cell up to 1000 cycles in a negative potential window values (e) Galvanostatic charge/ discharge curve
of the lithiated chalcone| sat. Li2SO4 | LiFePO4 cell up to 100 cycles in a positive potential window values (f) Columbic efficiency
of various C rates.

active materials reported earlier [61]. The acceptable discharge capacity is mainly because of dissolution of
cycling capacity with high columbic efficiency of the LiCLN and optimized over 1000 cycles [64]. Over-
LiCLN | saturated Li2SO4 electrolyte | LiFePO4 is all, the full cell exhibits a quite stable capacity upon
attributed to the one electron transfer redox reaction cycling.
via electrochemical oxidation and reduction of car- To study the stability of the LiCLN | saturated Li2SO4
bonyl group as a result of ultrafast kinetics of surface electrolyte| LiFePO4 cell, the galvanostatic charge/dis-
reaction in LiCLN with lithium ion in aqueous Li2SO4 charge process was tested in a potential window of posi-
[62, 63]. At 100th cycles, the reversible discharge tive values of 0.0 to 1.2 Vas shown in Fig. 6e. The initial
capacity is 75.18 mA h g–1 with capacity retention of discharge capacity is about 100.42 mA h g–1 which is
91%. After 500th cycle, there is a gradual decrease in almost close to the LiCLN | saturated Li2SO4 electrolyte
the capacity about 50.25 mA h g–1. The decline in the | LiFePO4 cell tested in the negative potentials her than

Table 2. Rate capability at different rates from 1C to C/8 for lithiated chalcone | saturated Li2SO4 electrolyte| LiFePO4
Electrode material LiCLN | saturated Li2SO4 electrolyte| LiFePO4 cell

Rate performance at C rates C/8 C/5 C/4 C/3 C/2 1C

Charge capacity, mA h g–1 101.23 82.1 72.1 68.4 58.6 58.4

Discharge capacity, mA h g–1 110.21 82.4 73.8 68.9 59.8 58.9
Capacity retention, % 99.0 98.6 97.6 98.2 97.9 98.1

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 56 No. 12 2020

1078 CHAITHRA MUNIVENKATAPPA et al.

the analogous active materials reported earlier [61]. At
10th cycles, the reversible discharge capacity is
99.0 mA h g–1 with capacity retention of 91%. After
500th cycle, there is a gradual decrease in the capacity
about 93.71 mA h g–1. The decline in the discharge
capacity is mainly because of dissolution of the LiCLN
and optimized over 1000 cycles [64]. Overall, the full cell
in positive potentials exhibits a quite stable capacity upon
cycling. The complete electrode cell reactions are in
aqueous medium is as predicted in Scheme 4.

At anode
Li
O
O
–Li+, +e

+Li+, –e

At cathode

LixFePO4 + Li+ + e Lix – 1FePO4

Overall cell reaction

Li
O
O
at anode
–Li+, +e
+ LixFePO4 Lix – 1FePO4 +
+Li+, –e
at cathode

Anode Cathode

Scheme 4. Overall cell reaction of LiCLN.

Kinetic parameters associated with redox reactions
can be evaluated by using Potentiostatic electrochem-
ical impedance technique. The Potentiostatic electro-
chemical impedance spectra with an open circuit
potential of –0.190 V for LiCLN in three electrode
system were recorded in the vicinity of CV peak poten-
tials and shown in Fig. 7.
The Nyquist plots of redox process obtained at six
different potential domains, i.e., three potential
domains for oxidation process and three potential
domains for the reduction process in the potential
range 0.05 to –1.0 V and frequency range of 100 kHz
to 5 mHz are characterized below.
Quantitatively, PEIS spectra are illustrated in two
parts: a linear line in the high frequency region which
is potential dependent, and a Warburg line with the
slope of 45° in the middle-low frequency region.
Figures 7a–7c shows the oxidation potential domain;
before oxidation potential domain, during oxidation
potential domain and after oxidation potential
domain. The impedance plot shows linear line with-
out any characteristic semicircle arc. The absence of
semi-circle in the high frequency region is mainly
attributed to a reduced form of solid electrolyte inter-
phase (SEI) where the migration of lithium ions takes
place via passivating layer indicating lower charge
transfer resistance [65]. In actual fact, SEI is usually
not occurring in aqueous sat. Li2SO4 electrolyte or
even though fit occurs, then it will be in the form of the
ultra-thin layer where its resistivity is of no conse-
quence [66]. The charge transfer resistance occurs due
to the electron-conductive properties of active materi-
als which show good stability of the chalcone material.
The presence of straight line with the slope of 45° at
middle-low frequency region indicates the diffusion-
controlled Warburg impedance due to the semi-
infinite diffusion at the aqueous electrolyte interface
[67]. Figures 7d–7f exhibits reduction potential pro-
files (Before reduction potential domain, during
reduction potential domain and after reduction poten-
tial domain). This type of Nyquist measurements
proves the formation of redox reaction, electron con-
duction and ion diffusion of lithiated chalcone.
The experimental Potentiostatic electrochemical
impedance spectra were fitted using the equivalent cir-
cuit as shown in Fig. 8 during both charge and dis-
charge process and the relationship between charge
voltage and kinetic parameters in saturated Li2SO4

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 56 No. 12 2020

 CHALCONE AS ANODE MATERIAL FOR AQUEOUS RECHARGEABLE LITHIUM-ION… 1079

(а) (b) (c)

7500 –0.54 V 54000
6000 –0.52 V
–0.8 V –0.5 V –0.4 V
–0.2 V

–Z '', Ω
5000 36000
–Z '', Ω

–Z '', Ω
0V
4000 300 –0.05 V
300
150
2500 18000
2000 150
0
0 150 300
150 300
0 2000 4000 6000 0 2500 5000 7500 0 18000 36000 54000
Z ', Ω Z ', Ω Z ', Ω

(d) (e) (f)

45000 7500
6000 –0.9 V
–0.62 V
30000 5000
–Z '', Ω

–Z '', Ω

–Z '', Ω
–0.1 V –0.64 V
–0.66 V
–0.3 V
–0.5 V
4000
–0.56 V 300
15000 2500 150
2000
0 150300

0 15000 30000 45000 0 2000 4000 6000 0 2500 5000 7500

Z ', Ω Z ', Ω Z ', Ω

Fig. 7. Nyquist plots to show the impedance response of lithiated chalcone anode material at different charge and discharge
potential range (a) before oxidation, (b) during oxidation, (c) after oxidation and (d) before reduction, (e) during reduction,
(f) after reduction of electrode material.

CPE Cdl

Rs Q

Rst ZW Rf

Fig. 8. The equivalent circuit for Nyquist plots at overall potential bias, which contains equivalent series resistance (Re), SEIre-
sistance (Rf), and charge transfer resistance (Rct).

solution were displayed in Tables 3, 4. The electrical
equivalent circuit has three main important compo-
nents i.e., resistive, capacitive, and inductive compo-
nents where the resistive component starts at the
region of stainless steel current collector, at the region
of electrode-electrolyte interfaces, and so on. The
double layer charging act as capacitive component and
the inductive components arise from the absorbent
character of the electrodes [68]. In the equivalent cir-
cuit shown in Fig. 8, Rs represent the ohmic resistance,
Rct is the charge transfer resistance, Q is the constant
phase element, Cdl is the double layer capacitance,
Rf is the resistance for Li+ migration through the sur-
face film and ZW is the Warburg impedance. This cir-
cuit consists of 2 Resistor-capacitor circuits in series
where, the ohmic resistance is serially connected to
the constant phase element which is in parallel with
the charge transfer resistance and Warburg imped-
ance. The charge transfer resistance related to the
slight polarization during cycling process and Warburg
impedance corresponds to the diffusion of lithium
ions into the bulk electrode and further serially con-
nected to the double layer capacitance where the sur-
face film resistance is parallel to it [69]. These results
confirm that the LiCLN provides the high conductiv-
ity and superior electron transport during the electro-
chemical reaction.

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 56 No. 12 2020

1080 CHAITHRA MUNIVENKATAPPA et al.

Table 3. PEIS parameters obtained by circuit fitting at charging potential bias

Potential, V Rs, Ohm Q, mF Rct, Ohm W, Ohm Cdl, mF Rf, Ohm
–0.8 1.64 0.8824 3.383E5 5.411E4 4.435E8 0.01001
–0.54 1.602 0.7584 64.1 0.0006671 0.007076 8496
–0.52 1.606 0.7506 6.308E4 1.08E4 0.003605 2.192
–0.50 1.602 0.7472 5.174E4 29.61 0.003814 2.867
–0.4 1.544 0.7404 3.049E–17 1.278E–19 1.358E16 6.558E–13
–0.2 1.59 0.8002 4057 0.0002554 0.002715 1.356E4
0.0 1.64 0.8824 3.383E5 5.411E4 4.435E8 0.01001
0.05 1.626 0.8629 0.07193 8.553E–6 0.0005615 5.445E4

Table 4. PEIS Parameters obtained by circuit fitting at discharging potential bias

Potential, V Rs, Ohm Q, mF Rct, Ohm W, Ohm Cdl, mF Rf, Ohm
–0.1 1.661 0.8954 7.067E5 2.487E–5 0.0004741 0.9778
–0.3 1.608 0.8118 1.148E4 0.0003494 0.001208 2.203E4
–0.5 1.574 0.7556 1.309E4 0.001547 2.406E4 3.251
–0.56 1.576 0.7512 4.274E4 21.02 0.007464 1.541
–0.62 1.881 0.7502 3.486E4 0.001579 0.001164 0.04653
–0.64 1.895 0.7541 2.991E4 0.0008475 0.001092 0.04764
–0.66 1.911 0.7562 3.122E4 0.004984 0.02482 7.543
–0.9 1.935 0.7924 7468 0.005091 0.001236 123

CONCLUSIONS
An efficient and eco-friendly protocol for the syn-
thesis of chalcone was carried out via Claisen–
Schmidt condensation of benzaldehyde and acetophe-
none in the presence of alumina sulfuric acid under
microwave method followed by lithiation using ball
milling technique. The CV measurements of lithiated
chalcones in aqueous electrolytes exhibited a good
reversibility during redox reactions. GCPL and PEIS
studies of lithiated chalcone revealed a good cycling
behavior due to good reversibility. Hence it can be an
interesting alternative organic based anode material
for future needs in energy fields.
ACKNOWLEDGMENTS
The authors acknowledge the funding support from the
Vision Group on Science and Technology-Government of
Karnataka. We thank Sri A. V. S. Murthy, Honorary Secre-
tary, Rashtreeya Sikshana Samiti Trust, Bangalore and
Dr. Snehalata G. Nadiger, Principal, NMKRV College for
Women, Bangalore for their continuous support and
encouragement.
CONFLICT OF INTEREST
The authors declare that they have no conflict of interest.
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