Journal of Energy Chemistry 64 (2022) 451–462

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Journal of Energy Chemistry

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

Anion effect on Li/Na/K hybrid electrolytes for Graphite//NCA

(LiNi0.8Co0.15Al0.05O2) Li-ion batteries
Aiman Jrondi a, Georgios Nikiforidis a,b, Mérièm Anouti a,b,⇑
a
Laboratoire PCM2E, Université de Tours, Faculté des sciences et technologie, Parc de Grandmont, 37200 Tours, France
b
LE STUDIUM Institute for Advanced Studies, 45000 Orléans, France

a r t i c l e i n f o a b s t r a c t

Article history: The electrolyte is an essential component of a battery system since it is responsible for the conduction of
Received 23 March 2021 ions between the electrodes. In the quest for cheaper alternatives to common organic electrolytes for
Revised 1 May 2021 lithium-ion batteries (LIB), we formulated hybrid electrolytes comprising a mixture of Na, K, and Li alka-
Accepted 4 May 2021
line salts with ethylene carbonate (EC), ethyl methyl carbonate (EMC), and lithium hexafluorophosphate
Available online 14 May 2021
(LiPF6), giving a total salt concentration of 1.5 M; we determined their physicochemical properties and
investigated their electrochemical behavior on a nickel cobalt aluminum oxide (NCA) cathode and gra-
Keywords:
phite (Gr) anode. The electrolytes demonstrated a melting transition peak (Tm), eutectic behavior, and
Hybrid electrolyte
Alkali salts
ionic conductivities (~13 mS cm
1) close to those of a commercial LIB electrolyte (SE, EC/EMC + 1 M
NCA//Li cell LiPF6) and activation energies of ca. 3 kJ mol
1. The half-cell coin cells revealed high coulombic efficiency
Li-ion battery (99%), specific capacity (175 mAh g
1 at C/10), and capacity retention (92% for NaCF3SO3) for the NCA
cathode and a moderate performance (coulombic efficiency of 98% for 20 cycles) on the graphite anode
after the formation of the SEI layer. The hybrid electrolytes were cycled at 25 °C in a Gr//NCA cell yielding
specific capacities of ca. 225 mAh g
1 at a C/5 rate, corroborating that the anion plays a key role and high-
lighting their potential for energy storage applications.
Ó 2021 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published
by ELSEVIER B.V. and Science Press. All rights reserved.

1. Introduction
The difficulty of integrating renewable energy, such as wind and
solar, into the power grid is that it is unpredictable and intermit-
tent. To compensate for its uncertainty and fluctuation, and to
modernize the current grid, battery energy storage systems (BESS)
are pivotal, as they allow the energy output to be stored and dis-
tributed upon demand. The energy can then be used for a wide
range of applications, including transportation, portable, and sta-
tionary backup power [1]. The prevalent battery technology for
such applications is based on lithium-ion chemistry; lithium-ion
batteries (LIBs) have a long-cycle life (>500 cycles), high energy
density (up to 300 Wh kg-1), and moderate cost (US$127 per
kWh) [2]. Nonetheless, they require further development to sus-
tain their advantage against other electrochemical energy storage
systems (i.e., supercapacitors [3], Na-ion [4,5], NaS [6], LiS [7],
and redox flow batteries [8]), lower their cost and improve their
efficiency and safety. The major hurdles of LIBs are ascribed to
the degradation of the electrolyte and electrode materials, which
⇑ Corresponding author.
E-mail address: meriem.anouti@univ-tours.fr (M. Anouti).
affects the safety and lifespan of the batteries, and the high cost
of the electrodes’ raw materials (e.g., alkali (Li) and transition met-
als (Co, Ni)) [9].
In this vein, advances in material and electrolyte design are
indispensable. Batteries consist of three main components: anode
(negative electrode), cathode (positive electrode), and electrolyte.
The anode material of choice is lamellar graphite, with a high
reversible capacity (372 mAh g
1) and a low volume expansion
(<10%) [10]. At high operating voltages, solvent reduction and inor-
ganic salt decomposition occur at the anode-electrolyte interface,
resulting in the formation of a surface film, commonly referred to
as the solid electrolyte interface (SEI) [11]. This passivation layer
is critical for battery longevity and performance as it allows
lithium ions access to graphite while acting as a barrier for further
electrolyte reduction [12].
At the cathode, layered transition metal oxides are adopted in
electric vehicle batteries (i.e., Tesla [6]), portable electronics [13],
and stationary power [14], namely NCA (Li(Ni1
x
yCoxAly)O2) and
NMC (Li1+a(NixMnyCoz)1
aO2), with working potentials reaching
up to 5 V vs. Li/Li+ [11,15–17]. These materials exhibit good elec-
trochemical performance (i.e., reversible specific capacities nearing
200 mAh g
1) on account of their enhanced structure crystallinity

https://doi.org/10.1016/j.jechem.2021.05.004
2095-4956/Ó 2021 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.
A. Jrondi, G. Nikiforidis and Mérièm Anouti
and, in turn, improved cyclability [18–20]. Nevertheless, degrada-
tion phenomena in nickel-rich cathodes remain an issue when they
are exposed to high oxidation potentials (i.e., >4.9 V). Such events
affect the cycling stability, inducing gradual phase transformations
(i.e., layered R3̅m to rock-salt Fm3̅m), transition metal (TM) disso-
lution, and electrolyte reactions with TMs in high oxidation states
(e.g., electrolyte oxidation with highly active Ni4+) [21]. Electrolyte
oxidation reactions at the cathode-electrolyte interface (CEI) [22]
have also been linked to cell impedance increase and performance
deterioration [23]. Structural changes due to rock-salt phase trans-
formation have been known to release oxygen, exacerbating these
oxidation reactions at the cathode surface [24]. Therefore, surface
modification to produce self-limiting CEIs by chemical coating of
NCA particles (e.g., TiO2, MnO2, ZrO2) has been widely adopted as
an efficient method to prevent and suppress side reactions with
the electrolyte [25,26].
Alternatively, the understanding and enhancement of the
oxidative stability of electrolyte solvents as a function of elec-
trolyte composition (e.g., salt concentration) has been the subject
of numerous studies [27,28] as an approach to hamper such reac-
tions. Electrolytes are integral components of batteries; their con-
ductivities and electrochemical windows dictate the extent of
operating potentials, electrode utilization, and power density of
the batteries, hence their capacities, charging rates, and perfor-
mance. The standard composition adopted by most commercial
LIBs includes ethyl carbonate (EC) in conjunction with a linear
alkyl carbonate or ester to lower the viscosity of the solution
and, finally, a lithium salt, commonly 1 M lithium hexafluorophos-
phate (LiPF6) [15]. The concentration range of LiPF6 is optimized to
ensure good thermal stability, transport properties, and electro-
chemical performance for alkyl carbonate salt solvent mixtures
at 1 M < C < 1.5 M [29–31]. Searching for alternatives to common
organic electrolytes, and taking into account the fact that their
oxidative stability depends on the coupling between anion and sol-
vents, herein we propose a series of hybrid electrolytes (HE) com-
prising a mixture of alkaline salts (e.g., Li, Na, K) at a total salt
concentration of 1.5 M and compare them against a standard com-
mercial electrolyte (SE) composed of ethylene carbonate (EC):
ethyl methyl carbonate (EMC) 1:1 wt/wt and 1 M LiPF6. Sodium
ions (Na+,
2.71 vs. SHE for Na/Na+) and potassium ions (K+,

2.93 vs. SHE for K/K+) have a lower reduction potential than
lithium ions (Li+,
3.04 vs. SHE for Li/Li+), yet, they are widely used
in electrochemical energy storage devices due to their abundance
and low cost [1,32]. The addition of Na+ and K+ cations in Li-
based electrolytes has been demonstrated before and does not
pose an issue at low reduction potentials due to the formation of
the SEI layer (or on the lithium metal [33–35]). The SEI (protective
film on the graphite or Li) constitutes a barrier to the subsequent
degradation of Na+ cations and solvents. In alkylcarbonate based
electrolytes, the potential of solvated Na+ and K+ ions shift depend-
ing on the nature of the Li-(SEI) surface quality and electrolyte
composition. In-situ Tof-SIMS (i.e., Time-of-Flight Secondary Ion
Mass Spectrometry) from Stark et al. [36] has shown that Na blocks
the accelerated dendrite growth and yields a dimpled and
dendrite-free morphology. Xu et al also demonstrated that the
addition of Na+ to a carbonate-based electrolyte (i.e., 1 mol L-1
lithium difluoro(oxalato)borate/ethylene carbonate/dimethyl car-
bonate) could reduce electrode polarization and favor Li deposi-
tion/stripping cycling [37].
The effect of anion composition on the lithium salts is high-
lighted in its importance in determining the lithium transference
number and ionic conductivities [38]. The anion radius affects
the transference number and promotes or demotes the migration
of Li+ in the carbonate electrolyte [39].
Electrochemical stability under high voltage conditions can be
achieved either thermodynamically, through electrolyte design
452
Journal of Energy Chemistry 64 (2022) 451–462
via the selection of intrinsically stable components, or kinetically
via the passivation layer formation in the first cycles. We anticipate
that the addition of Na+ and K+ will better polarize the interface at
high potentials, as they are more resistant to oxidation than Li+.
With the smaller desolvation energies of Na and K, we expect a
beneficial kinetic effect on the electrode–electrolyte interface’s
charge transfer reactions. This assumption is supported by previ-
ous work. For instance, a study on propylene carbonate revealed
that despite the larger ionic radius of Na+ (1.02 Å) and K+ (1.38
Å) than that of Li+’s (0.76 Å), the former delivered smaller Strokes’
radii because of their weaker Lewis acidity, which enables them to
exhibit faster mobility and smaller ionic diffusion activation
energy in the electrolyte [40]. In addition, it has been proven that
the diffusion coefficient of K+ is about three times larger than that
of Li+, as investigated by ab initio molecular dynamics simulations
[41]. What’s more, a fluorinated LiF/NaF hybrid interphase derived
from an electrolyte-soaking approach exhibited improved ionic
conductivity, high mechanical strength, and extended dendrite-
free cycling of metallic Li in Li symmetrical cells [42].
In this study, we investigated the comparative effect of Li+, Na+,
and K+ cations and their counter-anions on the physicochemical
behavior of the electrolytes. The anions selected in the alkali salts
were tetrafluoroborate (BF-4), trifluoromethanesulfonate (CF3SO-3),
and methanesulfonate (CH3SO-3). BF-4 is not uncommon in LIBs; it
has often been implemented as an additive [43,44], while CF3SO-3
and CH3SO-3 anions have been used in both Li and other battery sys-
tems (i.e., zinc and vanadium redox flow batteries [45–47]). We
first determined the ionic conductivity and thermal stability of
the electrolytes. Then, we examined the cycling behavior of
NCA//Li, Gr//Li half-cells, and the Gr//NCA cell with SE and HE at
25 °C by cyclic voltammetry and galvanostatic charge–discharge
cycling.
2. Experimental
2.1. Chemical compounds and electrolyte formulation
All electrolyte components were battery-grade and used as
received. Ethylene carbonate, EC, (99.9%), and ethyl methyl carbon-
ate, EMC, (99.9%) were purchased from Sigma Aldrich. Lithium
hexafluorophosphate salt (LiPF6, Sigma Aldrich, battery grade),
KBF4 (Sigma Aldrich, 99.99%), NaBF4 (Sigma Aldrich, >98%), NaCF3-
SO3 (Sigma Aldrich, 98%), and KCH3SO3 (Sigma Aldrich, >98%) were
used without prior treatment. KCF3SO3 and NaCH3SO3 salts were
formulated by equimolar acid-base neutralization of the corre-
sponding acids with concentrated aqueous KOH or NaOH solutions.
The obtained salts were then dried to eliminate residual water and
stored in a glovebox.
For the standard electrolyte (SE), a binary solvent mixture of EC/
EMC with a mass ratio of 1/1 was formulated in the glove box at
25 °C (MBraun) and mixed with 1.0 M LiPF6. The quantity of alkali
salt (i.e., LiPF6, NaBF4, NaCH3SO3, NaCF3SO3, KBF4, KCH3SO3 and
KCF3SO3) added in the EC/EMC + 1 M LiPF6, standard electrolyte
(SE), was 0.5 M. For simplification, we will identify the electrolytes
formulated by the added salt in the following manner: SE + 0.5 M
KBF4 is noted as ‘‘KBF004 and SE + 0.5 M LiPF6, as ”LiPF006 . The water
content of each solution was less than 20 ppm, determined by
using an 831 Karl-Fisher Coulometer (Metrohm). The electrolytes
were prepared using a Sartorius 1602 MP balance with ± 10-4 g
accuracy inside an argon-filled MBraun glovebox, at 25 °C, with
less than 5 ppm moisture content.
2.2. Physicochemical characterization
The ionic conductivity of the electrolytes was measured
from
20 °C to 100 °C with a 10-slot (WTSH 10) multichannel
A. Jrondi, G. Nikiforidis and Mérièm Anouti
conductivity meter (BioLogic), based on a frequency response ana-
lyzer (MCM 10), and connected to a Peltier-based cooling system.
Simultaneous measurements were performed using sealed cells
with Pt parallel electrodes protecting the samples from air expo-
sure. The conductometer was calibrated using standard KCl solu-
tions. The thermal stability of electrolyte solutions was
investigated by differential scanning calorimetry (DSC) using a
Perkin-Elmer DSC-4000 at a heating rate of 5 °C min
1 from

60° C to 250 °C under nitrogen flow (20 ml min
1).
2.3. Electrochemical characterization
The half-cell tests were performed in standard CR2032-type
coin cells, where the active mass (NCA or graphite) was used as
the working electrode, and a piece of lithium metal foil (0.5 mm
thick, Alfa Aesar) was the counter and reference electrode. Glass
microfiber filter paper (WhatmanTM GF/C) was employed as the
separator. Full-cell tests were performed in CR2032-type coin cells
with graphite and NCA as working and counter electrodes, respec-
tively. All the cells were assembled in an Ar-filled glove box
(MBraun, H2O < 0.1 ppm, O2 < 0.1 ppm) and sealed by a press
(Shenzhen Teensky Technology Co., Shenzhen, China). All elec-
trodes and separators were dried under vacuum at 80 °C for 12 h
and placed in the glovebox without exposure to ambient air. The
NCA and graphite electrodes were acquired from TCI chemicals.
The weight ratios of conductive carbon black (CB), Polyvinylidene
fluoride (PVDF), and active material were 90:5:5 for graphite
(porosity of 43%, a surface mass of 3.45 mg cm
2, and 96.25% of
active material) and 80:10:10 for NCA (viz. active mass of 11 mg/
cm2). The graphite electrodes were equilibrated with NCA elec-
trodes (N/P = 1.2).
Cyclic voltammetry (CV) and electrochemical impedance spec-
troscopy (1 MHz-10 Hz, 10 mV amplitude) curves were performed
on a VMP3 potentiostat (Biologic Science Instrument, France).
The galvanostatic charge/discharge was measured using a VMP
multichannel potentiostat (Biologic Science Instrument, France).
Finally, the spatial distributions of electrostatic potentials of the
Table 1
Structure, Van der Waals volume (VdW), dipolar moment, and partial negative charge of the anions under study.
Anions CH3SO-3
Structure
VDW volume (Å)3 69.4
Electrostatic potential
HOMO, LUMO orbitals HOMO:
0.58
(Hartree) LUMO:
0.48
Dipolar moment l = 4.509
(Debye)
Partial negative charge of anion
0.576
Quantum chemical calculations were performed using the Gaussian 09 W package. Orbital molecular optimization for HOMO LUMO was obtained with B3PW91/6-31G (d)
and calculated with a larger basis set 6–311++G (d, p).
Journal of Energy Chemistry 64 (2022) 451–462
investigated anions were calculated using Density Functional The-
ory (DFT) with the B3LYP functional- and 6–311 + G(d) basis set
(Mopac software).
3. Results and discussion
3.1. Electrolyte formulation and characterization
Given that the proposed anions are associated with alkali met-
als, they can be either solvated or polarized. They react in a differ-
ent way subject to the extent of the association. Here, we mix two
different salts (AB and XY) with two common linear carbonate sol-
vents (EC, EMC). For instance, if AB = LiPF6 and XY = KCH3SO3, we
obtain four types of associations (AB, AY, BX, and XY) and eight
possible solvation complexes (A(EC)n, A(EMC)n, X(EC)n, X(EMC)n,.
Y(EMC)n, Y(EC)n, B(EMC)n, and Y(EC)n,). The formation of quater-
nary systems (two salts with two solvents) is highly complex and
can lead to high conductivities and improved electrochemical
behavior.
Table 1 displays the Van der Waals (VdW) volume, partial
charge, electrostatic potential, and HOMO, LUMO energy levels of
the anions investigated in this study. The VdW volume is defined
as the space occupied by a molecule, which is impenetrable to
other molecules with normal thermal energies [48]. Here the low-
est VdW volume is reported for BF4. The low (red) and high (blue)
electrostatic potentials indicate the electron-rich and deficient
regions. The F atom, due to its electronegativity and weak polarity
stemming from the presence of seven electrons in its outermost
electron orbital [49], withdraws electrons in the vicinity; still, it
does not contribute to the highest occupied molecular orbital
(HOMO) and lowest occupied molecular orbital (LUMO) due to
the strong C-F bond that induces localized electronic states ener-
getically far below the delocalized HOMO [50]. CF3SO-3 and CH3SO-3
display similar properties (e.g., HOMO, LUMO, and VdW) differing
from those of BF-4, the latter exhibiting a lower LUMO energy level,
indicative of a high electron affinity. Ab initio calculations of
CF3SO-3 BF-4 PF-6
85.0 49.9 74.9
HOMO:
0.52 HOMO:
0.66 HOMO:
0.66
LUMO:
0.49 LUMO: 0.02 LUMO:
0.18
l = 4.865 apolar apolar

0.433
0.239
0.479
453
A. Jrondi, G. Nikiforidis and Mérièm Anouti
halogens and BF-4 as their super halogen building block have
revealed high electron affinities[51].
3.1.1. Ionic conductivity of electrolytes
Ionic conductivity (r) is the property most prone to optimiza-
tion during the formulation of electrolytes. Fig. 1 displays a com-
parison of the conductivities of the hybrid electrolytes with the
standard electrolyte at 60 °C. The hybrid electrolytes SE + 0.5 M
KBF4 (‘‘KBF004 ), SE + 0.5 M NaCH3SO3 (”NaCH3SO003 ) and SE + 0.5 M
NaBF4 (‘‘NaBF004 ) show comparable r to SE (i.e., ~14 mS cm
1) at
60 °C, with the lowest recorded conductivity for the NaCF3SO3 salt,
reaching 10 mS cm
1. Since the conductivity is associated with the
anions’ charge, BF-4, being the least charged anion, exhibits the
most conducting properties in the presence of the most polarizable
cation (K+) at 60 °C followed by the standard electrolyte (Fig. 1). In
contrast, the mobility of large anions such as CF3SO-3 is more slug-
gish, as denoted by the VdW volume (Table 1), and leads to low
Fig. 1. Conductivity (r) of the standard electrolyte (1 M LiPF6 in EC/EMC (1:1, wt))
and its homologue hybrid electrolytes, SE + 0.5 M AB salt at 60 °C.
Fig. 2. Ionic conductivity (r) vs. temperature for hybrid electrolytes (a) (Li/K) and (b) (Li/Na)-based salts. Both graphs include SE (1 M LiPF6 in EC/EMC: 1:1, wt) as
comparison.
454
Journal of Energy Chemistry 64 (2022) 451–462
conductivities in the presence of Na+. The polarity of the species
plays no role in electrolytic media where the induced dipoles, by
solvation (or polarized interfaces such as electrodes), are more
relevant.
Fig. 2 compares the r of the hybrid electrolytes based on the Li/
K-salt (Fig. 2a) and Li/Na-salt (Fig. 2b) within a 120 °C temperature
range (viz.
20 to 100 °C). The SE exhibits an ionic conductivity of
22.34 mS cm
1 at 100 °C, while ‘‘KCF3SO003 and ”NaCH3SO003 conduc-
tivities are ca. 16.60 and 14.89 mS cm
1, respectively. The 33% salt
increase, either Na or K, leads to cluster formation of the alkali ions
present with the EC/EMC molecules and decreases the electrolyte
conductivity at high temperatures. At low temperatures (viz.

20 °C), the hybrid electrolytes yield similar r values to the SE,
with the relative deviation of the conductivity is less than 5%
between
20 and 5 °C. The trend of increased ionic conductivities
with elevated temperatures for cyclic and linear carbonate binary
solutions with Li salt reported in the literature [52] is also evi-
denced here.
The plots of Fig. 2 adopt a non-Arrhenius behavior and are mod-
eled by the Vogel-Tamman-Fulcher model (VTF, Fig. 3 a-d) [53],
yielding a goodness of fit (R2) of ca. 0.999 for the HEs. Table 2 sum-
marizes r and the ideal glass transition temperature, T0, which is
defined as the temperature where the ion mobility tends to zero.
The activation energy, Ea, represented by parameter B, is related
to the free volume required for Li+ ions transportation through
the electrolyte and corresponds to the slope of the VTF plots
[54]. T0 ranged between 155 and 187 K at
80 °C. The activation
energy measurements exhibit a maximum deviation of
0.7 kJ mol
1 from the standard electrolyte. A low Ea value of ca.
2.5 KJ mol
1 was found in the case of CH3SO-3 anions for Na as
opposed to 2.9 KJ mol
1 for K, while for the case of CF3SO3, the
opposite trend was observed (i.e., Ea KCF3SO3 < Ea NaCF3SO3). This
can be explained by the ionic association between sodium cations
(Na+) and sulfonate ions (SO-3), whose partial charges are different
in the case of CF3SO-3 (-0.576) and CH3SO-3 (-0.433), as indicated in
Table 1. Overall, the results summarized in Table 2 indicate the via-
bility of HEs for LIB application with respect to ionic conductivity.
Ionic conductivity is associated with (i) the solvation of ions,
which is linked to the size and charge density of the cation and
the nature of the solvent, and (ii) the ionic associations between
cation and anion, which hinder the diffusion of the cation by the
interactions of Li+, Na+ or K+ with the counter-anion. These interac-
A. Jrondi, G. Nikiforidis and Mérièm Anouti Journal of Energy Chemistry 64 (2022) 451–462

Fig. 3. Arrhenius and VTF plots showing the ionic conductivity (r) as a function of temperature for hybrid electrolytes (a, b) Na and (c, d) K-based salts.

Table 2 with different LiPF6 concentrations (0.25–3 M) in EC and EMC have

Comparison of the VTF-parameters of the ionic conductivity between SE and derived indicated that the reactivity of the electrolyte increases with
electrolytes at 25 °C. R2 describes the goodness of fit. higher salt concentrations [55,56]. Fig. 4 shows the DSC profiles
Electrolyte r(mS cm
1) T0 (K) Ea (R  B)KJ mol
1 R2 of the SE and its hybrid electrolytes where for most systems, a
melting transition peak (Tm) and eutectic behavior are evident.
SE 9.01 158.8 3.2 0.998
LiPF6 7.55 187.3 2.6 0.999 Yet, the onset temperature of the endothermic evaporation peaks
NaBF4 8.14 161.7 3.1 0.997 varies. This behavior is attributed primarily to EMC (Tm EMC = 107
KBF4 8.82 163.7 3.1 0.998 °C), whose interaction with alkali cations and counter anion delays
NaCF3SO3 5.50 155.7 3.5 0.997
KCF3SO3 7.60 167.8 2.7 0.999
NaCH3SO3 9.99 166.6 2.5 0.991
KCH3SO3 7.80 163.4 2.9 0.999

tions can be collaborative or competitive. In essence, the ionic con-

ductivity depends on cation, anion, and solvent interactions, which
in turn, rely on temperature. The ionic conductivity at 25 °C follows
the order ‘‘NaCH3SO003 < SE < ”KBF004 < ‘‘NaBF004 < ”KCH3SO003 < ‘‘KCF3SO003
< ”LiPF006 < ‘‘NaCF3SO003 . At elevated temperatures (80 °C), there is an
inversion, LiPF6 1.5 M becomes the most conductive (Fig. 2), prob-
ably because the temperature lowers the ionic interactions and
boosts the diffusion of Li+ ions. In the latter case, there is a high
molecular association between the carbonates and the salt,
prompting the alkali salts to move in a more coupled manner.

3.1.2. Thermal properties

The formulated electrolytes were measured by differential
scanning calorimetry (DSC) to delineate the role of the added salt Fig. 4. DSC thermograms of a LIB standard electrolyte (1 M LiPF6 in EC/EMC
in the thermal properties of the electrolytes. Typical DSC studies (1:1, wt) together with its homologue hybrid electrolytes SE + 0.5 M AB salt.

455
A. Jrondi, G. Nikiforidis and Mérièm Anouti
the evaporation process. EC has been reported to show an exother-
mic decomposition peak between 205 and 250 °C [57].
The presence of a eutectic diagram in the EC/EMC mixture
stems from the interactions between the two solvents, which pre-
vent their crystallization (Tc = -14 °C for EMC and 36 °C for EC). In
turn, the eutectic equilibrium and its coordinates are affected by
the nature and the concentration of the salts present. For instance,
the electrolyte containing CF3SO-3 anion for both Na and K metals
boils at 150 and 161 °C, respectively; this is the highest tempera-
ture amongst all hybrid electrolytes, followed by KBF4 (the
endothermic peak could be due to the polymorphic transition of
KBF4 from the orthorhombic to the cubic phase [58]) and NaBF4.
These electrolytes evaporate later than the SE (149 °C), validating
their superior thermal stability. On the other hand, the hybrid elec-
trolytes with CF3SO-3, reveal no evaporation peak. Here, the broad
endothermic peaks corresponding to eutectic melting lie between
65 and 115 °C.
There are two elements to consider with thermal stability at
increasing temperatures. Firstly, solvent evaporation is lowered
by interactions due to ion solvation (Raoult’s law [59]). Secondly,
thermal degradation of the LiPF6 salt, known for its deleterious
effects in the presence of traces of water on the electrolytes by
thermal decomposition, i.e., PF-6 + H+ ?HF + PF5. When considering
the solvent evaporation and thus vapor pressure, the 1.5 M LiPF6
mixture is more stable. Nevertheless, taking into account the
chemical behaviour of the latter, the electrolytes with Na and K-
based salts with anions other than PF-6 display superior thermal
and chemical stability.
3.2. Electrochemical performance of Li, Na, and K-based electrolytes on
the NCA //Li system
3.2.1. NCA activation step in the presence of alkali salt additives
The use of alkaline salt mixtures in standard battery electrolytes
decreases the conductivity (i.e., hinders the transport properties of
Li+). Yet, we anticipate that they wild better polarize the interface
at high potentials as they are more resistant to oxidation. To this
end, the electrochemical performance of NCA//Li cells was first
investigated by cyclic voltammetry at 25 °C in coin cells, at a scan
rate of 0.05 mV s
1, equivalent to a C/10 rate. A slow scan rate can
delineate the cation mixing effect on the phase transformations
during the charge–discharge process. Fig. 5a shows the first three
cyclic voltammetry cycles in a solution containing 1.5 M LiPF6
(SE + 0.5 M LiPF6). It allows a qualitative analysis of the potentials
at which chemical reactions accompany electron transfer in the
NCA electrode. The first cycle corresponds to an irreversible activa-
tion process of the NCA lamellar structure [60], viz. inner structural
arrangements accompanying the departure of oxygenated species
and the SEI film formation at the anode during the first cycle
Fig. 5. Cyclic voltammetry of a NCA//Li half-cell at 25 °C and a scan rate of 0.05 mV s
1 in a solution containing EC/EMC and 1.5 M LiPF6. Snapshot of the initial galvanostatic
charge profiles of NCA//Li half-cells in the presence of Na-salt (b) and K-salt (c).
456
Journal of Energy Chemistry 64 (2022) 451–462
[61]. From the first CV cycle, we can see that all the nickel is oxi-
dized at 4.5 V vs. Li/Li+, in line with reports attesting that at poten-
tials of 4.5 V, Ni4+ ions would not oxidize any further [20].
After the activation occurring in the first cycle, the CVs embody
a sequential rearrangement of the lattice since Li is extracted dur-
ing oxidation and reinserted during reduction. The pairs of redox
peaks in the CV curves (cycle 2 and 3) stem from the oxidation
of Ni from Ni3+ to Ni4+, involving the phase transitions from hexag-
onal to monoclinic (H1 M M) and monoclinic to hexagonal
(M M H2), and hexagonal (H2) to hexagonal (H3) during lithium
extraction [62]. The three prominent redox peaks of the CV in
Fig. 5a were previously assigned to phase transfer among four dif-
ferent phases of LiNiO2-based cathode materials during cycling
[63]. No significant change in cycles 2 and 3 was observed, suggest-
ing good stability of the NCA cathode during the lithiation and
delithiation process in the presence of hybrid electrolytes. The
good superposition of the different peaks during the successive
cycles demonstrates good reversibility of the NCA material’s elec-
trochemical process in the HEs, which in turn implies an absence
of capacity loss and activation within the operating potential
range, viz. 3.0–4.5 V. H1 exhibits the highest oxidation and reduc-
tion peaks, indicating that the Li is extracted from the Ni4+ rich
phase surface of the electrode, boosting the electronic conductivity
(i.e., smaller cation mixing in favor of higher electrochemical activ-
ity[64]). The potential difference (DE) between the main redox
couple (H1 M M) in the CV indicates the polarization degree [65].
The DE value found here (110 mV) is in line with other reported
values of NCA//Li systems [66], suggesting that in concentrated
solutions, there is high diffusion of Li + cations in the NCA.
NCA cathodes mediate electrochemical reactions via intercala-
tion, where Li+ are extracted from/reinserted into the original
structure with minimum structural changes [67]. The NCA activa-
tion process allows the material to cross the energy gap necessary
for its restructuring by reducing the energy barrier required to pro-
duce the conductive R2 phase (i.e., increased electronic conductiv-
ity due to the formation of Ni4+ ions [60]). This process is
demonstrated by the initial increase in potential (within 0.25
mAh g
1 of the charge capacity) followed by a relaxation and sta-
bilization of the potential (0.25–1.5 mAh g
1) once the energy bar-
rier for the activation is reached. The nature of the electrolyte
affects the activation rate and stabilization potential (i.e., peak
broadening) of NCA. The magnitude of this initial overvoltage has
been reported to reflect the amount of water-induced surface spe-
cies on NCA [68]. Fig. 5b and c show the initial stage of the galvano-
static curve of the NCA activation and confirm that the addition of
salt, whatever its nature, does not accentuate the energy barrier,
which remains below 4.39 V vs. Li/Li+ before stabilizing
at ~ 4.05 V (Fig. 5b and c). The stabilization plateau is lower for
the Na salts (Fig. 5b) than for K (Fig. 5c). When lithium salt is added
A. Jrondi, G. Nikiforidis and Mérièm Anouti Journal of Energy Chemistry 64 (2022) 451–462

(+LiPF6), two activation peaks are present. We will, therefore,
essentially retain that the activation process is not disturbed by
the addition of salts beyond 1 M and that both Na and K are rather
favorable towards this step.
3.2.2. Comparative galvanostatic characterization of electrolytes
containing alkali salt additives in NCA//Li half-cells
Previous reports have shown that nickel-rich cathodes possess
high specific capacity and discharge voltage but suffer from severe
cycling degradation, attributed to rapid volume contraction during
the structural transformation from H2 to H3 [69]. The galvanostatic
cycling of NCA//Li half cells was carried out at 25 °C and different
C-rates for 20 cycles. All cells containing the hybrid electrolytes (K
and Na) exhibited similar charge–discharge profiles between 3 and
4.5 V, typical of the delithiation/lithiation profile of NCA cathodes
[70,71], suggesting a similar charge–discharge mechanism.
For the hybrid electrolytes containing NaCF3SO3 salt (Fig. 6a),
the capacity obtained in the first cycle at C/20 reaches 221 mAh
g
1 and 191 mAh g
1 during charge and discharge, respectively.
The dissimilar specific capacities found here indicate that during
the first cycle (formation of the cathode electrolyte interphase
(CEI) layer), more lithium ions are consumed during charge, and

Fig. 6. Voltage specific capacity profiles of the NCA//Li half-cells at cycle 1 and 20 for hybrid electrolytes containing (a, c) Na and (b, d) K salts together with the standard
electrolyte. Current rate is C/20, and the operating temperature is 25 °C.

Table 3
Comparison of the electrochemical performance of the NCA//Li half-cell in the presence of SE and HE at 25 °C.

E + 0.5 M (APF6) QCycle 1 QCycle 20 EDcycle 1(Wh kg
1) EDcycle 20 gC (%)

(A = Li, Na, K) (mAh.g
1) (mAh.g
1) (Wh kg
1)
E = 1.0 M LiPF6
Li E 168 154 636 583 99.5
LiPF6 187 177 708 670 98.4
Na BF4 159 168 602 636 99.3
CH3SO3 177 159 670 602 99.4
CF3SO3 191 175 723 662 99.3
K BF4 133 115 503 435 98.9
CH3SO3 183 175 693 662 99.2
CF3SO3 162 145 613 598 98.5

The discharge specific capacity (Q) is measured for a C/10 rate. ED: energy density. gC: average Coulombic efficiency at C/10.

457
A. Jrondi, G. Nikiforidis and Mérièm Anouti
along with the high potentials, lead to lower discharge capacity. All
Na hybrid electrolytes show superior capacity in both the 1st and
20th cycle compared to the SE (Fig. 6b), validating that in the pres-
ence of these hybrid electrolytes, Li+ can efficiently extract/insert
from/in the NCA cathode. For the best performing HE (NaCF3SO3),
the capacity retention was ca. 92% at the end of the 20th cycle, con-
sistent with the one recorded for the SE (91.6%), and lower when
compared to 1.5 M LiPF6. The effect of a higher LiPF6 concentration
(1 vs. 1.5 M) has been previously reported [72]; here, we propose
to use cheaper alkali salts (e.g., NaBF4 and KBF4) than LiPF6[15]
to achieve comparable LIB performances.
A summary of the results for the rest of the electrolytes is given
in Table 3. The positive correlation of the addition of Na salt in the
SE with capacity from Table 3, together with the unchanged dis-
charge profiles of NCA in most HEs (apart from KBF4), indicate that
the lamellar structure of NCA is adequately protected by this alkali
salt at high potentials (i.e., 4.5 V vs. Li/Li+) as opposed to the SE (i.e.,
the direct contact between Co, Ni and 1 M LiPF6 gives rise to disso-
lution of these transition metals and in turn to capacity fade of NCA
Fig. 7. Cycling performance of the NCA//Li half-cells in different hybrid electrolytes containing (a) Na and (b) K salts on top of the standard electrolyte (SE), EC/EMC + 1 M
LiPF6. The operating temperature is 25 °C.
Scheme 1. Comparative HOMO and LUMO energy levels of CF3SO3,CH3SO-3 BF-4 and PF-6 anions. The values are extracted from Table 1.
458
Journal of Energy Chemistry 64 (2022) 451–462
[73] whilst higher LiPF6 concentrations could provide stronger oxi-
dation resistance as suggested by previous studies [72]).
Similar findings were recorded for the case of K-based hybrid
electrolytes except for ‘‘KBF004 which shows poor cycling (Fig. 6c).
The best performing, HE contains ”KBF004 ‘‘KCH3SO003 and yields a
capacity of 230 mAh g
1 and 180 mAh g
1 during charge and dis-
charge, respectively, with a capacity retention of 93% (Fig. 6d).
The NCA//Li half cells were tested at four different C-rates (e.g.,
C/20, C/10, C/5, and 1C, Fig. 7a and b). As expected, higher C-rates
(1C) moderated the cell’s capacity to 100 mAh g
1 (e.g., ‘‘NaCF3SO3-
”, ‘‘NaCH3SO3” and ‘‘KCH3SO3”) and even to 50 mAh g
1 for both
electrolytes KCH3SO3BF-4. The performance of the HEs containing
NaCF3SO3, NaCH3SO3, and KCH3SO3 was superior to the SE for all
C-rates. The galvanostatic results of the NCA//Li cells indicate that
the addition of the aforementioned alkali salts improves the capac-
ity of the cell by an average of 10%. Likewise, the coulombic effi-
ciency (gC) remained at 99% (Table 3), while the specific energy
density based on the average operating voltage of the cell
remained between 600 and 670 Wh Kg
1.
A. Jrondi, G. Nikiforidis and Mérièm Anouti
In general, the stability of the electrolyte is associated with the
highest occupied molecular orbital (HOMO) for the oxidation pro-
cess and the lowest unoccupied molecular orbital (LUMO) energy
levels for the reduction. From Scheme 1, we note that PF-6 and
BF-4 exhibit the lowest HOMO energy (
0.66 Hartree
17.96 eV),
indicative of high oxidation stability that arises from the high elec-
tronegativity of the fluorine atom. These HOMO levels however,
don’t explain the performances observed on the NCA cathode
(Fig. 7). Additionally, taking into account the potential reduction
of anions on the Li metal, the CF3SO3 anion exhibits the lowest
LUMO, making it more susceptible to reduction than the other
three anions (e.g., BF4, CH3SO3, and LiPF6). These anion potential
windows do not justify the observed performance. Therefore, there
is no correlation between the intrinsic oxidation–reduction stabil-
ity of salts and the electrolyte’s performance; this stability is linked
to the solvent after the solvation of ions.
3.2.3. Comparative galvanostatic characterization of electrolytes
containing alkali salt additives in Gr//Li half-cells
During the operation of LIBs, a solid electrolyte interphase (SEI)
layer forms on the graphite surface by the reductive decomposition
of carbonate solvents. Hence, the electrochemical properties of gra-
phite (Gr) in the hybrid electrolytes were investigated by con-
structing Gr//Li half cells using lithium metal as the counter
electrode.
Fig. 8. Voltage specific capacity profiles of the Gr//Li half-cells at cycle 1 and 20 in the presence of hybrid electrolytes containing (a) Na and (b) K salts and compared against
SE. Current rate is C/20, and the operating temperature is 25 °C.
Fig. 9. Cycling performance of the Gr//Li half-cells at room temperature in hybrid electrolytes containing (a) Na and (b) K salts on top of the standard electrolyte (SE).
459
Journal of Energy Chemistry 64 (2022) 451–462
The Li+ insertion is regarded as a ‘‘charging process” where dur-
ing the first cycle (at C/20, Fig. 8a and 8b), the SEI is formed, fol-
lowed by lithium de-insertion (discharge). The electrolyte
containing excess Li (1.5 M LiPF6) exhibits the highest charge
capacity, ca. 350 mAh g
1, and the best cycling behavior (upon
20 cycles, Fig. 9), followed by ‘‘KCH3SO003 and SE with 310 and 300
mAh g
1, respectively. After the formation of the SEI layer, the
Gr//Li half-cells show high coulombic efficiency, over 98%, for the
remaining 20 cycles. It should be noted that high C-rates restrict
(C/1) the capacity to values under 100 mAh g
1 except for the case
of SE and 1.5 M LiPF6. Here, the Li+ intercalation into the 3D stacked
structure and the coexistence of two-phase lithiated graphite [74]
is enhanced and stabilized with an excess amount of lithium salt
[75,76]. Comparable performance to that of SE is apparent for the
”NaCH3SO003 , where a capacity of 309 mAh g
1 at a C/10 rate was
observed after 20 cycles (i.e., 97% capacity retention). The results
of the rate capability are summarized in Table 4, along with the
gC values.
3.2.4. Performance of electrolytes containing alkali salt additives in
Gr//NCA full-cells
When characterizing a material in a half-cell configuration, one
cannot neglect the lithium metal’s surface changes during cycling
and propagating salt deposits, mainly when the electrolyte con-
tains cations other than Li+. To mitigate this issue, we compiled
A. Jrondi, G. Nikiforidis and Mérièm Anouti Journal of Energy Chemistry 64 (2022) 451–462

Gr//NCA full cells and carried out galvanostatic charge–discharge rates. The discharge capacity remained over 150 mAh g
1 when the
measurements at 25 °C for the HE. Voltage-capacity profiles for cell was discharged in 1 hour for NaBF4 and KBF4 HE.
the HE containing NaBF4 and KBF4, respectively, are illustrated in The capacities shown in Fig. 10 are greater than those obtained
Fig. 10. The cycling protocol commenced with the SEI layer forma- in the half-cell configuration (Table 4), indicating that Na+ and K+
tion at a slow rate (C/20) followed by ramping through different C- are not beneficial to the Li metal anode when in contact with the
HE (possibly creating a poor electrode/electrolyte interface at these
concentrations) leading to poor overall cell performance. To this
Table 4 end, reducing the amount of extra salt could promote a better
Comparison of the electrochemical performance of the Gr//Li half-cell in the presence
interface. A recently formulated electrolyte with 1 M LiPF6 and
of SE and HE at 25 °C.
0.02 M NaPF6 yielded low overpotentials on Li symmetric cells
E + 0.5 M (APF6) QCycle 1 QCycle 20 gC (%) [77], stemming from an isolating and self-healing electrostatic
E = 1.0 M LiPF6 (mAh.g
1) (mAh.g
1)
shield of Na+.
(A = Li, Na, K)
The NCA//Gr full-cells were cycled at different C-rates up to 1C
Li SE 332 329 98.50
(Fig. 11a and 11b) for Na-based and K-based HE, respectively. HEs
LiPF6 395 376 98.89
Na BF4 316 310 98.31 containing KBF4, NaBF4, KCH3SO3, and 1.5 M LiPF6 exhibited supe-
CH3SO3 316 309 98.41 rior performance to that of the standard electrolyte throughout all
CF3SO3 332 329 98.3 C-rates and good capacity retention (viz. 85–92%, Table 5). Other
K BF4 290 298 99.3 than the initial SEI formation cycle, the cells’ coulombic efficiencies
CH3SO3 362 360 98.2
were high, remaining between 98 to 99.5% for most of the HEs, and
CF3SO3 119 nw* nw*
are in line with SE values. The HE containing KCH3SO3 reaches an
The discharge specific capacity (Qdischarge) is measured for a C/10 rate. * Not energy density of 777 Wh kg
1 after 40 cycles, the highest of all
working. ED: Energy density. gC: Average Coulombic efficiency at C/10.
investigated samples and more than double when compared to

Fig. 10. Voltage specific capacity profiles of the NCA//Gr cell in hybrid electrolytes containing (a) 1 M LiPF6 (EC/EMC) + 0.5 M NaBF4 and (b) 1 M LiPF6 (EC/EMC) + 0.5 M KBF4
at 25 °C. The current rate C/20 represents the initial formation cycle.

Fig. 11. Cycling performance of the Gr//NCA cells under different hybrid electrolytes containing (a) Na and (b) K salts and compared against SE. Operating temperature is
25 °C.

460
A. Jrondi, G. Nikiforidis and Mérièm Anouti Journal of Energy Chemistry 64 (2022) 451–462

Table 5
Comparison of the electrochemical performance of the Gr//NCA cell in the presence of SE and HE at 25 °C.

E + 0.5 M (APF6) QCycle 4 (C/5) QCycle 40 EDcycle 4 EDcycle 40 gC (%)

(A = Li, Na, K) mAh.g
1 (C/5) Wh kg
1 Wh kg
1
E = 1.0 M LiPF6 mAh.g
1 (DE = 3.7 V) (DE = 3.7 V)
Li E 125 104 462 384 98.50
LiPF6 160 157 592 580 99.20
Na BF4 182 179 673 662 99.11
CH3SO3 46 36 170.2 133 97.67
K BF4 187 173 691.9 640 98.3
CH3SO3 190 210 703 777 98.9
CF3SO3 152 95 562 351 99.8

The discharge specific capacity (Qdischarge) is measured for a C/5 rate. ED: energy density. gC: average Coulombic efficiency at C/5.

the SE. KBF4 and KCF3SO3 yielded slightly lower efficiencies,
between 92 and 95%. The results obtained with the Gr//NCA full
cell suggest that these hybrid electrodes with mixed alkali salts
are suitable for operation in this system at room temperature. On
the contrary, the HE with KCF3SO3, and NaCH3SO3 exhibit low
specific capacities. These results do not reflect the classification
observed in the half Gr//Li cells and corroborate the deleterious
role of lithium metal, which does not make it possible to account
for the actual performance of materials when they are in the pres-
ence of Na+ and K+ (particularly at such concentrations) while
specifying that the counterion plays a non-negligible role in this
effect.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
The authors would like to thank ‘‘La Région Centre Val de Loire”
for financial support through the Obama project under the Lavoi-
sier regional program.

4. Conclusion
In this study, we have synthesized and tested a series of hybrid
electrolytes comprising a mixture of alkali salts (Li, Na, K) at a total
salt concentration of 1.5 M for LIB applications. Their ionic conduc-
tivity at 60 °C is between 10 and 15 mS cm
1 and follows the order:
NaCH3SO3 <SE<KBF4 <NaBF4 <KCH3SO3 <KCF3SO3 <LiPF6 <NaCF3SO3.
The majority of the HEs demonstrated a melting transition peak
(Tm) and eutectic behavior, with the onset of the endothermic
evaporation peak varying due to their interaction with EMC.
Molecular simulations revealed that the CF3SO-3 and CH3SO-3 anions
display similar properties (e.g., HOMO, LUMO, and VdW) as
opposed to BF-4. The activation energies of the Na and K salt homo-
logues depend strongly on the nature of the anions, reaching val-
ues of 3.2 kJ mol
1 with a maximum deviation of ± 0.5 kJ mol
1.
Upon assembling coin cells with the proposed HEs, half-cell studies
confirmed the NCA activation, which displayed adequate cyclabil-
ity (20 cycles), high coulombic efficiency (99%), and high capacity
retention (e.g., 92% for NaCF3SO3) compared to a standard com-
mercial electrolyte, signifying that the lamellar structure of NCA
is adequately protected by the alkali salts at high potentials
(4.5 V vs. Li/Li+). In addition, after the formation of the SEI layer,
the Gr//Li half-cells exhibited high coulombic efficiency (>98%)
for 20 cycles but showed moderate resilience to high current rates,
suggesting that the coexistence of two-phase lithiated graphite is
solely stabilized with an excess amount of lithium salt. Since only
the Li+ ions are intercalated in the insertion materials (Gr and
NCA), the counterions have no role in the insertion mechanism.
Aside from the HE with KCF3SO3, and NaCH3SO3, the performance
of the Gr//NCA full cell with the HEs is typical for this battery sys-
tem (i.e., 40 cycles, four different C-rates, capacity retention of 90%,
coulombic efficiency of 98%), validating the suitability of these
electrolytes for battery applications. The conclusion of this work
is therefore that the cations (Li, Na, or K) added to Li+ (standard
electrolyte) do not disturb or improve the performance during
intercalation of Li+ cations in NCA and graphite, but improve the
thermal stability, conductivity, and potentially the cost of elec-
trolytes because Na and K salts are more accessible and cheaper.
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