Energy Storage Materials 62 (2023) 102943

Contents lists available at ScienceDirect

Energy Storage Materials

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

Combining electrochemical, molecular simulation and operando techniques

to investigate the stability of electrodes and organic electrolytes used
in EDLCs
Raissa Venâncio a, Rafael Vicentini a, Manuel J. Pinzón C． a, Débora A. Corrêa a, b,
André N. Miranda a, Adriana C. Queiroz c, Francisco Tadeu Degasperi d, Leonardo J.A. Siqueira b,
Leonardo M. Da Silva e, *, Hudson Zanin a, *
a
Advanced Energy Storage Division, Center for Innovation on New Energies, University of Campinas, Av. Albert Einstein 400, Campinas, SP 13083-852, Brazil
b
Department of Chemistry, Laboratory of Hybrid Materials, Federal University of São Paulo, Rua São Nicolau 210, Diadema, SP 09913-030, Brazil
c
Institute of Chemistry, St. Josué de Castro, University of Campinas, Campinas, SP 13083-970, Brazil
d
Department of Materials, Process, and Electronic Components, Technology School of São Paulo, Av. Tiradentes 615, São Paulo, SP 01101-010, Brazil
e
Department of Chemistry, Laboratory of Fundamental and Applied Electrochemistry, Federal University of Jequitinhonha e Mucuri’s Valley, Rodovia MGT 367, km 583,
5000, Alto da Jacuba, Diamantina, MG 39100-000, Brazil

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

Keywords: A comprehensive study involving Electrochemical, Mass Spectrometry, Raman & FT-IR operando analyses, and
Anomalous transport in electrolytes Molecular Dynamics Simulations is present to evaluate the stability of electrodes and electrolytes used in organic-
Residual gas analyses based EDLCs. In this sense, we present some directions to correctly determine the maximum stable cell voltage,
Raman operando
specific capacitance, energy, and power, as well as the equivalent series resistance. Multi-walled carbon nano­
Mass spectrometry operando
tubes and activated carbon electrodes are contrasting in symmetric devices filled with 1.0 M LiTFSI and TEABF4
Electrochemical stability
Electrolytes salts dissolved in AN, PC, and EC:DMC electrolyte. We observed anomalous transport caused by adsorption ef­
fects in the electrical double-layer in all electrochemical studies due to the defective nature of the ionic channels
in the presence of displacement of finite-sized charge carriers. This behavior is unequivocally verified from the
impedance analysis using a double-channel transmission line model representing the macrohomogenous
behavior of the electrochemical system. The residual gas analysis suggested a maximum stable voltage of 3 V to
avoid electrolyte degradation. The carbon-based electrodes remain stable in all cases, as evidenced by the Raman
& FT-IR operando studies. We verified that the AC/TEABF4-PC/AC system is auspicious for further studies aiming
to develop EDLC prototypes with high specific capacitance, energy, and power characteristics. The derivative
analysis method involving the galvanostatic findings permitted us to verify the different dynamics regarding the
charge-storage process in macro and microporous structures as a function of the applied current. Computational
simulations indicated that [TEA]+ has a high affinity for the carbon electrodes, which is related to the higher
electrochemical stability of TEABF4-PC.

1. Introduction
Supercapacitors have drawn attention due to their capacity for fast
charge accumulation through an electrical double layer at the electrode/
electrolyte interface, long-term life cycling, reliability, and material
flexibility for potential supplies [1–4]. In order to expand their appli­
cability, the energy density has to be improved by optimizing the cell
configuration, which implies that its performance relies mainly on the
electrolyte choice (e.g., aqueous, organic, ionic liquid, and solid-state)
and the active surface area of the electrode applied in these systems.
However, these devices’ electrochemical stability depends mainly on
the ion/solvent and ion/pore interaction of its main components, and
the incompatibility among such materials can accelerate the aging
process and decrease the overall performance. So, it is essential to un­
derstand the mechanism related to the charge-discharge processes at the
electrode/electrolyte interfaces that limit the supercapacitor operation
leading to the early cell aging induced by contaminations, in­
compatibility between the system components, and erroneous

* Corresponding authors.
E-mail addresses: lsilvamorais@hotmail.com (L.M. Da Silva), hzanin@unicamp.br (H. Zanin).

https://doi.org/10.1016/j.ensm.2023.102943
Received 17 March 2023; Received in revised form 1 August 2023; Accepted 25 August 2023
Available online 26 August 2023
2405-8297/© 2023 Elsevier B.V. All rights reserved.
R. Venâncio et al.
experimental conditions (e.g., excessive-high voltages, high tempera­
tures, etc.) [5–7].
The use of ill-defined conditions accelerates the gas evolution due to
component degradation which increases the internal cell pressure,
causing a blockage of the active electrode area with lowering the
capacitance retention.
One approach to avoid these possible issues is applying electro­
chemistry combined with operando techniques that evaluate which kind
of gasses are evolving, at what voltage conditions they emerged, and
which device component is mainly responsible for the gas evolution. At
first glance, the Tafel plot analysis might evaluate the irreversible
faradaic reactions quantitatively and relate them to the degradation
phenomena in EDLCs. Nevertheless, the Online Electrochemical Mass
Spectroscopy (OEMS) technique can unequivocally quantify and qualify
the evolved gaseous species, following the ionization steps, ions sepa­
ration based on their mass/charge ratio, and ion detection. The entire
test is performed under vacuum conditions to avoid intermediate re­
actions between the ions themselves, and this analysis is done in
conjunction with floating time [8–11].
In the past few years, the state-of-the-art regarding the effects of
electrolyte degradation in the aging process of energy storage devices by
applying the OEMS technique has been frequently discussed. The latter
elucidates the crucial effects of temperature [12,13], pressure [14], test
cell setup [15–18], different cathode materials [19,20], SEI formation
[21–23], or electrolytes nature [24]. In, several of these works are car­
ried out in batteries or pseudocapacitive-based devices analyzed by ex &
in-situ techniques, performed by cycling, storing, or floating time tests.
Only a few studies were focused on the interfacial mechanisms of the
EDLC aging process by operando analysis.
In this context, some previous experiments [25,26] were carried out
for EDLCs using AC/1 M TEABF4-ACN/AC. This study proved that the
modification in the electrodes resulted from the polymerization of
acetonitrile which caused the blocking of micro and macropores, then
causing capacitance losses, carbon corrosion, and electrolyte decom­
position. The carbon oxidation resulted from the adsorption of in-situ
generated functional groups. In addition, it was reported a hybrid
LTO/1 M LiBF4-PC/AC system using a floating range of 2.7 to 3.5 V. At
high voltages, contamination by water due to oxidative decomposition
was noticed due to the presence of some functional groups. The diffusion
of H2O from the carbon electrode to the LTO accelerated the solvent
hydrolysis process at low voltages. At the same time, H2 generation is
persistent as long as the LTO remains charged. This study allowed
optimizing the system, changing the solvent by one more resistant to
hydrolysis, thus leading to greater cell cyclability, and operating voltage
(3.3 V).
In addition, in the context of non-aqueous solutions, Hanh et al. [27]
analyzed the irreversibility of the reactions through a pressure variation
test. They concluded that this pressure fluctuation was related to solvent
stability issues. However, the occurrence of faradaic currents was pri­
marily due to the formation of decomposition products of soluble elec­
trolytes as the gas evolved [28]. It was inferred from this analysis that
these parasitic reactions can provide pseudocapacitances at the expense
of some prejudice toward the device. The gas evolution can further in­
crease the general impedance of the cell with the formation of gaseous
pockets in different parts of the capacitors, thus introducing severe
ohmic losses. The decomposition of the functional groups present on the
electrode surface, water-splitting, and corrosion processes depend on
the applied voltage that affects the nature of the evolved gas. Some
strategies were considered to mitigate the aging effects of ECs, such as
the addition of stabilizers in the electrolytes, surface treatment of the
electrodes (mainly pure carbon), variation of the salt concentration, and
the adequacy of the viscosity of the electrolytes that affect the ionic
conductivity and diffusion of the species [29,30].
Kötz et al. [14] elucidated how the balance stability of the EDLC is
dependent on the solvent properties, by comparing acetonitrile (ACN),
γ-butyrolactone (GBL), and propylene carbonate (PC) evolved gases
2
Energy Storage Materials 62 (2023) 102943
during the cycling electrochemical tests. In this sense, they identified
that ACN produces more soluble residual gases that stay trapped in the
system increasing the Faradaic leakage current, as the PC favors the
gasses secondary reactions. In the same direction, Azais et al. [31]
described that the composition, and structure of the carbon-based
electrodes, as the electrolyte purity are crucial requirements for good
cell cyclability by an ex-situ analysis of the supercapacitors before and
after the floating test.
In an innovative way, Hahn et al. [27] investigated through OEMS
the reaction products of a carbon-based EDLC filled with 1.0 M of
TEABF4-PC during charge and discharge up to its working voltage
window (WVW). They found that solvent reduction produces propene
and hydrogen gases, as its oxidation is responsible for CO2 products. The
latter presented a slight appearance delay due to its high soluble ability,
i.e., the CO2 is dissolved into the pores. So, the stability of PC with
ammonium-based salts was already discussed by the literature, but there
is still some lack of information about the effects of the different pores
structures (e.g., micro-, meso, and macropores), and ion-ion/ion-pore
interactions on the importance of the passivation of PC in
carbon-based systems that could be improved by combining different
operando analyses with different electrochemical tests.
In this sense, different from the above-mentioned studies, the present
work validates the alternative (or hybrid) operando-electrochemical
methodology for studying organic-based EDLCs whose electrochemical
details were previously reported by our research group [32]. In this
study, the electrochemical findings (e.g., CV, CA, GCD, and mostly EIS)
and Molecular Dynamics simulation analysis were constrasted to
describe the ion-pore interactions. At the same time, we bring different
operando techniques to observe through a unique adapted cell the indi­
vidual ion-pore interactions (Raman) and ion-ion dynamics (FTIR &
RGA) under abusive voltage conditions. This novel combined/hybrid
methodology allowed us to observe the charge-storage behavior in
different perspectives. In this sense, it was possible to identify the
different SC components involved in the ’overall deactivation mecha­
nism’ present in in real-devices, thus prevent failures, and adressing
safety concerns and improve the overall’s system efficiency.
With that in mind, we decipher the influence of the applied voltage
on degradation processes by making use of combined Electrochemical,
Mass Spectrometry, FT-IR & Raman operando analyses, as well as Mo­
lecular Dynamics simulations. To detect charge transport anomalies in
the porous/defective ionic channels, we simulated the impedance data
using a theoretical approach based on the so-called macrohomogenous
model using its double-channel transmission line representation. The
dynamics involving the charge-storage process were investigated from
the differential analysis involving the galvanostatic (GCD) data using the
methodology recently proposed by some of the present authors. As
model systems, we used symmetrically assembled supercapacitors using
two different salts (TEABF4 and LiTFSI), three solvents (ACN, PC, and
EC:DMC), and two types of carbon materials (e.g., AC and MWNCTs).
2. Methodological section
2.1. Experimental details
2.1.1. Electrode fabrication
Commercial multiwalled carbon nanotubes (MWCNT) with a 95%
purity from CNT Co. Ltd was solubilized in 400 mL of deionized water
with sodium dodecyl sulfate (SDS, from Synth, 90%) at a 1:8.6 mass
ratio, respectively. The suspension was stabilized using an ultrasonic
processor (80 W) in two steps of 15 min. Then, the homogenized mixture
was filtered under a vacuum (p = 460 mbar) using a 0.22-µm pore size
PTFE membrane. The buckypaper (BP) carbon-based electrode material
was washed with deionized water and isopropyl alcohol until SDS was
removed and pH neutralized. The BP was separated from the PTFE filter
and dried at 60 ◦ C. Afterward, the electrodes were cut into 10 mm discs
with 2.3 mg, and vacuum dried at 120 ◦ C for 24 h.
R. Venâncio et al. Energy Storage Materials 62 (2023) 102943

Fig. 1. Molecular representation of supercapacitor built with planar graphite electrodes and the structure of the ions in ionic liquids.

For the highly porous carbon-based supercapacitors, an ink solution voltammetry (CV) experiments at a low scan rate of 10 mV s− 1 for the
was prepared with activated carbon (Kuraray Co. Ltd., Japan), Black voltage range of 2.0 to 3.2 V, with single-step chronoamperometry (SSC)
Pearls (Cabot,), and polyvinylidene fluoride (PVDF) with an 8:1:1 mass at 0.0 V for 30 s to pre-conditioning the cell, and then obtain the results
ratio, and then solubilized in N-Methylpyrrolidone (NMP). This sus­ during 5 min for different voltages in the 2.0–3.2 V interval. To complete
pension was mixed for 24 h and used to coat an etched aluminum foil the analyses, electrochemical impedance spectroscopy (EIS) experi­
using the doctor blade method. The resulting carbon films were dried at ments at different voltages were accomplished using a sinusoidal
80 ◦ C for 2 h and vacuum dried at 120 ◦ C for 24 h. Finally, the electrodes perturbation function with amplitude of 10 mV (peak-to-peak) in the
were cut into 16 mm discs with an average loading mass of 3.0 mg. frequency range of 10 kHz to 10 mHz.
For the OEMS test, the MWCNT and AC electrodes were cut into 10 Once identified the WVW value, the galvanostatic charge-discharge
mm discs with a mass loading of ~5 mg. (GCD) tests were applied by using different gravimetric currents of
0.02, 0.05, 0.1, 0.2, and 1.1 A g− 1 to measure the distributed specific
2.1.2. Cell assembly capacitance, according to Eq. (1):
All procedure was executed in an Mbraun glove box under Ar at­
dQ I
mosphere with < 0.1 ppm of H2O and O2, to prevent contamination. The Cdistr. = =4× , (1)
dU m(dU/dt)
solvents acetonitrile (Sigma-Aldrich, >99%), propylene carbonate
(Sigma-Aldrich, >99%), and dimethyl carbonate solvent (Sigma- where m is the total active mass, I is the applied current, and dU/dt is the
Aldrich, >99%) were dried for 72 h using a 3− Å molecular sieve. voltage-time curve derivative. The GCD findings were used to calculate
Ethylene carbonate (Sigma-Aldrich, 99%) was melted at 70 ◦ C for 30 the specific energy, power, and maximum power as follows [33]:
min. Further, it was mixed with DMC in a 50:50 proportion. Then, a 1.0
( )
M concentration of TEABF4-AN, TEABF4-PC, LiTFSI-AN, LiTFSI-PC, and CU 2 103
E= , (2)
LiTFSI-EC:DMC (1:1) electrolyte solutions were prepared, and 80 µL of 2h 3600
the electrolyte was used to soak a 50-µm cellulosic paper (TF-4850)
separating the carbon-based electrodes assembled in a CR2032 standard E
P= , (3)
coin cell. t

Uc2
2.1.3. Electrochemical analyses Pmax = (4)
Different electrochemical tests using CV, SSC, GCD, and EIS tech­ 4Rs
niques were performed with a Biologic® potentiostat to determine the
where RS is the equivalent series resistance (ESR) obtained from EIS
best (maximum) working voltage window (WVW), the specific capaci­
spectra [34]. From these findings, we construct the Ragone plot from the
tance, power, and energy, as well as the distributed capacitance in time
iterative (numerical) process involving the power (PL) and energy (EL)
domain. As described elsewhere [32], we intercalated cyclic
values as reported previously [33] using Eq. (5):

3
R. Venâncio et al.
( √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ )
Emax PL
EL = 1+ 1− , (5)
2 Pmax
where EL and PL are the energy and power delivered to the load.
2.1.4. Analysis of the evolved gases in the electrochemical cell
In order to collect the evolved gasses generated in the electro­
chemical cell from the oxidative degradation of chemical species, we
assembled a carbon-based symmetrical coin cell with 80 µL of 1.0 M of
TEABF4-PC, LiTFSI-PC, and LiTFSI-EC:DMC. The cell was properly
closed under a high vacuum (see Fig. S1) and polarized at abusive
voltages using a Biologic© SP-150 potentiostat. In this sense, SSC ex­
periments were conducted from 0 to 4.8 V, in steps of 0.4 V, with an
acquisition time of 5 min. At the same time, the evolved gasses inside the
cell were directed to a Pfeiffer Quadrupole Mass Spectrometer (QMS-
200) analyzer with a Faraday detector coupled to an ultra-high vacuum
(UHV) stainless steel chamber kept at 6 μbar.
2.1.5. Raman operando analyses
The operando Raman analysis was performed using a Renishaw
microscopy coupled to the electrochemical cell. This analysis used a
two-electrode symmetrical opto-electrochemical cell filled with 60 µL of
the particular electrolytes (e.g., 1.0 M of LiTFSI-PC, LiTFSI-EC:DMC, and
TEABF4-PC). This cell contains a quartz window allowing the Raman
laser to pass through it. The cell was connected to a VersaSTAT®
potentiostat from AMETEK. SSC experiments were carried out for 5 min
where different voltages from 0 to 4.8 V, separated in steps of 0.4 V,
were applied. At the same time, the Raman spectra were obtained with a
785-nm laser wavelength acquired at 10% power laser (3.2 mW), and
45 s of exposition time (one accumulation).
2.1.6. FT-IR operando analysis
The FT-IR operando analysis was acquired using a model Cary 620
spectrometer from Agilent in the mid-IR range (e.g., 4000–400 cm− 1)
using a Globar source, with a spectral resolution of 16 cm− 1 and 256
scans accumulated by a DLATGS detector. A two-electrode symmetrical
cell was used in the transmittance mode. This electrochemical device
was filled with a 30-µL 1.0 M of TEABF4-PC to establish ionic contact
with the porous carbon paper electrodes (Toray). This cell contains a
ZnSe window allowing the FT-IR laser to pass through it. The cell was
connected to a model VersaSTAT® potentiostat from AMETEK. SSC
experiments were carried out for 5 min where different voltages from
0 to 4.8 V were applied in steps of 0.4 V, as shown in Fig. S2. A Math­
ematica® routine code was used to analyze specific regions of the FTIR
spectra. The spectra’s background was normalized and the integral
above the wavenumber region was calculated.
2.2. Computational details
Atomistic molecular dynamics simulations were employed to inves­
tigate three supercapacitors built with TEABF4 or LiTFSI species con­
taining propylene carbonate (PC) considering a given applied voltage
Table 1
Electrochemical data extracted from coin cells filled with 1.0 M of LiTFSI-AN, TEABF4-AN, LiTFSI-PC, TEABF4-PC, and LiTFSI-EC:DMC, using symmetrical mesoporous
MWCNT electrodes. These data were obtained by combining CV at 10 mV s− 1, 5 min of SSC, EIS of 10 kHz to 10 mHz between 2.2 to 3.2 V, and GCD at 0.1 – 1.1 A g− 1
for each specified WVW of supercaps.
Electrolyte LiTFSI-AN LiTFSI-PC
WVW (V) 2.5 2.5
ESR (Ω) 3.1 ± 0.1 3.2 ± 0.8
Phase angle 85.8 ± 0.7 87.2 ± 0.2
Pmax (kW kg− 1) 27.5 28.6
Emax (Wh kg− 1) 0.61 0.74
C (F g− 1) 11.2 ± 1.0 13.6 ± 2.0
Capacitance retention (%) 87 74
4
Energy Storage Materials 62 (2023) 102943
(ΔΨ = 3.0 V). The electrolyte was confined between two planar-carbon
electrodes as shown in Fig. 1. All the configurations were generated
using the PACKMOL [35] and FFTOOL [36]. The distance between the
two electrodes along the z-axis was set up to reproduce the bulk density
of the electrolytes. All simulations were performed using the Large-scale
Atomic/Molecular Massively Parallel Simulator (LAMMPS) [37]. The
potential models to describe inter and intramolecular interactions of the
ions were taken from CL&AP force field [38]. The force field for pro­
pylene carbonate was taken from OPLS [39]. The simulations were
performed using the constant potential method (CPM) implemented in
the LAMMPS package [40]. A vacuum slab of 20 nm was added in the
z-direction to mimic 2D periodic boundary conditions, and the
Yeh-Berkovitz condition for slab correction was used [41]. The simula­
tions were conducted in the canonical ensemble (NVT) with a time step
of 2 fs, and the Nosé-Hoover thermostat [42] at 300 K. The systems were
first equilibrated for 10,000 ps at zero constant charge on each elec­
trode. The equilibrated structures at zero charge were submitted to an
applied voltage of 3 V for at least 2000 ps, which was enough to charge
the electrodes completely. The trajectories obtained have been used to
analyze the electric and structural properties of the supercapacitors.
3. Results and discussion
3.1. Electrochemical analysis
We analyzed the electrochemical response of five symmetric coin
cells using mesoporous MWCNT electrodes filled with 1.0 M of LiTFSI-
AN, TEABF4-AN, LiTFSI-PC, TEABF4-PC, and LiTFSI-EC:DMC electro­
lytes. These organic electrolytes have highly conductive salts with large
ions. It is of fundamental interest to properly determine the super­
capacitor parameters such as WVW, ESR, and specific capacitance,
among other parameters [32–34,43]. Thus, by combining CV, SSC, GCD,
and EIS experiments as described elsewhere [32–34,43], we extracted
the different data from Fig. S1 (Please check on the supplementary
section), and summarized them in Table 1.
As seen in Table 1, all lithium ammonium-based SCs reached a sta­
bility region up to 2.5 V. We can assume that the LiTFSI presents limited
stability independent of the solvent used in this work. This is directly
related to the large anion size and low charge density that reduces the
electrolyte stability [44]. On the other hand, when we look at the
electrode/electrolyte interaction, it is noticed that the ESR for the
carbonate-based solvents is higher than for acetonitrile-based SCs. This
is an effect of the strongest dipole moment of the cyclic carbonates (PC
and EC) that binding with the high coordinate Li+ ion, making it difficult
for the ion to lose its solvation shell, i.e., when polarized, they occupied
a negative low state-of-charge affecting the specific capacitance, thus
enhancing the equivalent series resistance. This effect is softened when
we used the linear carbonate DMC that improves ion dissociation. As a
result, the specific power and energy delivered by the EC:DMC-based
electrolyte device is more significant for the applied gravimetric cur­
rents in the range of 0.025 to 1.08 A g− 1 (Please see Figs. S3 and S4).
Different from the previous data, the quaternary ammonium-based
LiTFSI-EC:DMC TEABF4-AN TEABF4-PC
2.5 2.7 3.0
1.9 ± 0.1 1.4 ± 0.6 1.4 ± 0.3
86.5 ± 0.2 82.7 ± 0.5 85.8 ± 0.4
47.8 71.2 86.7
0.60 0.51 0.98
10.9 ± 0.6 8.0 ± 1.04 12.5 ± 1.7
83 57 89
R. Venâncio et al.
Fig. 2. (a) Cyclic voltammetry at 10 mV s− 1 using different maximum voltages, (b) Single-step chronoamperometry at different voltages, Nyquist (c) and Bode (d)
impedance plots at different voltages, and (e) Galvanostatic charge-discharge curves at 0.02 A g− 1 at different voltages. Voltage range: 2.0 to 3.4 V. System: AC/
TEABF4-PC/AC.
supercapacitors presented different levels of dissociation with the sol­
vents, showing higher voltage values with the akylcarbonates higher
than 2.6 V and lower ESR values.
In summary, these data suggested that the TEABF4-based SCs pre­
sented lower ESR and higher WVW, except for TEABF4-AN, demon­
strating the lowest specific capacitance, energy, and capacitance
retention due to the AN sensibility to environmental variations. On the
contrary, LiTFSI-PC exhibited the highest specific capacitance at the
expense of lower capacitance retention. The main reason for this
behavior is the lower charge field in the electrode surface resulting from
the distortion of the electronic cloud of the solvent bounded with Li+
[45].
To further analyze the electrochemical performance in a
commercial-like device, we assembled a supercapacitor with a high
surface area electrode composed of activated carbon using the most
promising electrolyte system (e.g., TEABF4-PC). These electrochemical
findings are gathered in Fig. 2. We also took this opportunity to explain
to the reader how to correctly evaluate the WVW values. Please, check
Fig. S5, which shows the data obtained for MWCNT and AC electrodes
with the TEABF4-PC electrolyte to facilitate the understanding of the
adopted experimental approach to determine the WVW values.
The CV tests were performed at 10 mV s− 1 since the voltammetric
profile is directly affected at fast scan rates leading to misinterpretation
of the obtained findings. Therefore, slow scan rates are mandatory for
this type of analysis. As shown in Fig. 2(a), the voltammograms pre­
sented a quasi-rectangular shape, evidencing a capacitive behavior.
However, as the voltage increases up to 3.2 V, the current plateau that
5
Energy Storage Materials 62 (2023) 102943
represents the capacitive response stabilizes at low values, and when it
reaches the maximum voltage dramatically increases forming the well-
known faradaic current exponential tail due to the undesired irrevers­
ible reactions (e.g., electrolyte degradation and/or corrosion processes).
This Tafel-like process is predicted by Butler-Volmer’s reaction model,
which describes the faradaic contribution to the overall current during
the anodic scan. While a pure capacitive current is represented by Eq.
(6), the coupled (faradaic + capacitive) current is represented by Eq. (7)
[46]:
[ ( )]
− ΔUc
IC = CEDL ν 1 − exp , (6)
RESR CEDL ν
[ ( )] [ ]
− ΔU αa F(U − U0 )
I = IC + IF = CEDL ν 1 − exp + I0(a) exp , (7)
RESR CEDL ν RT
where I0(a) is the anodic exchange current density measured at U = U0
(OER), αa is the anodic charge-transfer coefficient, R is the universal gas
constant, and T is the absolute temperature.
To complement that, the SSC tests were applied at the same poten­
tials used in the CV analysis. Here, the plot of current vs. time must be an
exponential decay for well-behaved capacitive systems, i.e., blocked
electrode interfaces. Moreover, the transient current tends to disappear
even after short polarization times (e.g., t ≈ 1− 20 s). In general, the
transient (capacitive) current in the presence of an irreversible faradaic
reaction has a non-transient component as represented by Eq. (8):
R. Venâncio et al.
Fig. 3. (a) Nyquist and (b) Bode plots obtained at 3.0 V for the AC/TEABF4/AC coin cell. The dotted line represents the experimental data while the continuous lines
are the simulated data using the double-channel TL model shown in (c).
[ ]
(− t) αa F(U − U0 )
I = I0 × exp + I0(a) exp , (8)
τ RT
where τ = RESRCEDL is the time constant, and I0 = Ustep/RESR.
In this sense, only the first term at the right-hand side of Eq. (8) must
be considered in the case of well-behaved (blocked) interfaces, as in the
case of EDLCs polarized in the stable working voltage window (WVW).
On the contrary, under abusive polarization conditions (e.g., U > WVW),
one has the presence of a faradaic process due to the irreversible
degradation of chemical species present in the coin cell. Under these
conditions, one has in SSC experiments the presence of an almost con­
stant faradaic current (current plateau) after the exponential decay of
the capacitive current.
From the practical viewpoint, in SSC experiments, when the
measured current showing an initial value (I0) is characterized by a
sudden decrease (I/I0 ≤ 0.01), we can consider the interface is effec­
tively blocked for charge-transfer, i.e., the presence of irreversible
faradaic processes can be ruled out [33]. On the contrary, when the I/I0
ratio is larger than 0.01 we must suspect that some faradaic reaction is
developing inside the coin cell. In practice, we must verify the presence
of an almost stationary (faradaic) current predicted by Butler-Volmer’s
reaction model at a given voltage. In this sense, it was seen in Fig. 2(b)
that all the SSC curves presented a negligible residual current lower than
1%. However, it is noticed an unusual behavior as we increase the
voltage beyond 3.2 V (brown line), there is a ~50 % increase in the
residual current value that evidenced the presence of an irreversible
oxidation process due to the application of an abusive voltage.
Therefore, to confirm the best (maximum) WVW value, the imped­
ance data were obtained for the symmetric coin cell, thus giving
essential information about the occurrence of faradaic reactions. With
that in mind, we applied the EIS analysis at the same voltages used in the
CV and SSC experiments, whose results are presented in Fig. 2(c & d). As
can be seen in the complex-plane plots, there is an occurrence of a
depressed semicircle at high frequencies, followed by an inclined line at
6
Energy Storage Materials 62 (2023) 102943
medium frequencies showing a phase angle close to − 42◦ The latter
findings are commonly found for porous electrodes (e.g., De Levie’s
model). Finally, at lower frequencies, a straight line almost parallel to
the imaginary axis with a phase angle close to − 80◦ was verified, con­
firming the presence of capacitance dispersion according to the so-called
CPE behavior.
Besides that, when we carefully analyze the magnification of Fig. 2(c
& d) we noticed that the phase angle shifts towards higher values (e.g.,
more capacitive behavior) when it reaches 3.0 V and then the magnitude
of the imaginary component of the impedance underwent a low
decrease, thus indicating the presence of a parasitic faradaic process.
The abusive voltages used in this study are exceptionally high for
supercapacitors composed of microporous carbon-based electrodes
(~2.7 nm) in the presence of large electrolyte ions (e.g., [TEA]+ and
[BF4]− ). However, it is an innate response from the EDL structure with
highly organized counterions and solvent molecules dipoles at the
charged interface, giving extra stability to the electrochemical system
[47–49]. In order to understand better this anomalous behavior that
occurs during the formation of the electrical double-layer in organic
electrolytes (AC/TEABF4), a double-channel transmission line (TL) model
blocked for charge transfer was applied to interpret the EIS spectra
obtained at 3.0 V, as shown in Fig. 3.
The applied double-channel TL model is composed of an impedance
(χ 1 = R/CPE1) that includes an ohmic resistance (R) in parallel to a
constant phase element (CPE1) to account for the anomalous charge
transport in the ionic conductor formed in the internal regions of the
porous/defective surface structures. In the present case, the time con­
stant τ = RCPE1 is a "special transport property", as previously demon­
strated by Bisquert’s group [50,51], i.e., the product RCPE1 represents a
single anomalous transport event instead of an unblocked interface. At the
same time, the impedance Z2 = Rcarbon represents the ohmic resistance
due to the grain-to-grain contacts (or electron hopping transport)
formed between the carbon particles composing the electrode material.
Finally, the electrode/solution interface is represented by a CPE3 to
R. Venâncio et al. Energy Storage Materials 62 (2023) 102943

Table 2 ( )1/2
Z3
EIS simulation findings obtained using the double-channel transmission line λ= (11)
model obtained at 3.0 V. χ 1 + Z2
1
RESR (mΩ g) Rion (kΩ g) Rcarbon (kΩ g) Qion (μF sα− g− 1) QEDL (F sβ− 1
g− 1)
1
11 1.23 1.11 212 26.74
Z3 (interface) = , (12)
q3 (jω)β
(α = 0.87) (β = 0.89)
From the above considerations, the electrode and electrolyte trans­
verse impedances (Z2 and χ 1, respectively) is given in Ω m− 1 unities,
include the capacitance dispersion under blocked electrode conditions. while the interface/parallel impedance (Z3) is given in unities of Ω m. As
The impedance model used in this work is a particular case of the generic predicted, the interface only presents a dispersive capacitance behavior
TL model developed by Bisquert’s group [50,51]. In fact, different when β < 1. In addition, the anomalous ionic transport requires that α <
particular cases can be obtained from the generic impedance model 1 [50,51]
considering the particular properties of the electrochemical system. The EIS simulation findings are summarized in Table 2. At first, the
The following transfer function gives the overall impedance of the TL results demonstrated a very low ESR value, which implies negligible
model used in this work: ohmic losses in the electrolyte present outside the pore channels. In
⎡ ⎤ addition, we verified almost identical ionic and electronic resistances for
( 2 ) ( )
χ Z2 ⎢ ⎥ 2 the different conducting phases (Rion ≈ Rele ). This behavior allied to the
Z = RESR + 1 ⎢L + 2λ( )⎥ + λ χ 1 + Z2 coth L , (9)
χ 1 + Z2 ⎣ L
sinh λ ⎦ χ 1 + Z2 λ so-called porous electrode behavior is the main cause of the high-
frequency depressed semicircle verified in the complex-plane plot [51].
Unfortunately, in several cases, instead of using the macro­
where RESR is equivalent series resistance and Z2 = Rcarbon. The theo­ homogeneous model applied to blocked electrodes, some authors incor­
retical length of the intermixed phases according to the macro-homogenous rectly apply modified versions of the Randles-Ershler (R-E) circuit model
impedance model can be roughly represented by L = m/ρA, where m is the containing the Warburg impedance. Obviously, the latter circuit does
active electrode mass, ρ is the apparent material density, and A is the not make sense in the case of EDLCs since there is not a faradaic
geometrical surface area. Despite its theoretical significance, this latter component to sustain the presence of the Nernst layer where the diffu­
parameter (L) is not commonly used in practical simulations. sion mass transport operates. The macrohomogeneous TL model and
The experimental (macroscopic) impedances are obtained in terms of some equivalent circuits containing the Warburg impedance degenerate,
the microscopic parameters as follows [50,51]: i.e., they predict the same impedance spectra. Therefore, the SSC find­
r1 ings not showing any mass-transport (Cottrell’s behavior) characteris­
χ 1 (ionic) = (10) tics can be used to confirm the LT model assumptions. Obviously, the
1 + r1 q1 (jω)α
physicochemical meanings behind the present LT and R-E circuit model

Fig. 4. (a) Cyclic voltammograms at different scan rates, (b) galvanostatic charge-discharge curves at different gravimetric currents, (c) distributed capacitance
obtained from numeric differentiation of the GCD data, and (d) Ragone plot obtained for the AC/TEABF4-PC/AC symmetric SC device.

7
R. Venâncio et al.
are entirely different, i.e., the misuse of the latter can lead to misinter­
pretation of the impedance data obtained for blocked EDLCs.
The present findings suggest that pure electrostatic adsorption is
happening. The surface excesses (Γ) are strictly controlled by the applied
electric field in the presence of ion-ion and ion-electrode interactions, i.
e., we can rule out the presence of irreversible faradaic reactions at 3.0
V. The coin cell operates by simultaneous transport of electronic and
ionic charge carriers in the closely mixed (interconnected) electronic-
ionic phases to maintain the local electroneutrality conditions. Howev­
er, the presence of irregular paths for the ionic charge transport with
different tortuosity degrees incurs the so-called anomalous (non-Fick­
ian) transport, which is generically characterized by the dispersive
exponent present in the RCPE circuit element (α = 0.87). On the con­
trary, regular (Fickian) transports must be characterized by unitary ex­
ponents [5,52].
These EIS findings permitted us to elucidate the non-ideal charge
transport mechanism in the presence of adsorption processes at the elec­
trode/solution interface which induces a pronounced frequency (or
capacitance) dispersion (β = 0.89). Overall, the present impedance find­
ings confirm that the carbon-based SCs using organic solvents have
excellent electrochemical stability, good charge-storage performance, as
well as a well-defined blocked condition even for the high voltage of 3.0 V.
Afterward, we evaluated the device’s performance by combining the
CV and GCD techniques. Fig. 4(a) shows the CV curves obtained at
different scan rates using a working voltage window of 3.0 V. As can be
seen, CVs are characterized by a capacitive (rectangular) shape with
negligible distortion at their borders at the higher scan rates. At the same
time, the triangular GCD profiles obtained for current densities in the
0.02− 10 A g− 1 range demonstrated an excellent capacitive response
with a negligible ohmic drop caused by the ESR, i.e., the ohmic resis­
tance present ’outside’ the pore structures.
By charging and discharging the coin cell at low and high gravimetric
currents, we observed the effect of frequency on the specific capaci­
tance, energy, and power characteristics. Combined with EIS data, the
present study using CV and GCD clarifies the intrinsic complex behavior
impressed by the adsorption process at the electrode/solution interface
coupled with the non-ideal charge transport process in porous/defective
Fig. 5. (a & f) Chronoamperometry test using symmetric electrodes. (a) MWCNT buckypaper and (f) AC electrodes soaked with ~80 µL of TEABF4-PC electrolyte.
Mass-to-charge ionic signals of (b & g) CO (m/z = 28), (c & h) CO2 (m/z = 44), (d & i) H2 (m/z = 2), and (e & j) O2(m/z = 32). Voltage steps of 0.4 V for 5 min. For
each measurement, the background signal was subtracted.
8
Energy Storage Materials 62 (2023) 102943
electrode materials [53]. We can further expand the GCD study to gain
more information about the complex charge-storage process in coin cells
using the concept of a “distributed capacitance” recently proposed by
some of the present authors [5,46], as shown in Fig. 4(c) (see Eq. (1)). In
this sense, it is possible to verify the dynamic aspects related to the ionic
charge transport as a function of the polarization time. Generally, during
the discharge, only after a given time is that a voltage plateau, corre­
sponding to the overall access of the electrochemically active surface (e.
g., inner and outer surface areas), can be observed. At reduced polari­
zation times, the lower capacitances can be ascribed to the so-called
outer/external surface areas mainly composed of mesopores and
larger micropores. On the contrary, at longer polarization times, the
entire surface area is accessed, and a capacitance plateau is expected. In
principle, a small capacitance oscillation at the plateau region indicates
a complex scenario due to the presence of pronounced tortuosity effects
(e.g., anomalous charge transport) into reduced micropores.
Fig. 4(c) shows the distributed capacitance (Cdistr) as a function of the
normalized discharging time (t/tmax) at different gravimetric currents
(0.02 to 10 A g− 1). The curves profiles indicate that the overall active
surface area is not entirely accessed by the ionic species at higher
applied currents. This behavior can be understood considering the
hysteresis imposed by the finite-sized ionic species with different
mobility. From left to right, Fig. 4(c) also shows an asymptotic increase
of the capacitance until ca. 10% of the normalized discharging time,
where ions only have access to the outer/external surface areas [5]. In
the next stage of the charge-storage process, the ions progressively ac­
cess the narrow micropores which increase the capacitance to its
maximum value, i.e., in this case, the ions have fully accessed all regions
of the electrochemically active surface area. Besides that, it is interesting
to notice that the charge-storage process exhibited a strong dependence
on the applied gravimetric current with a capacitive plateau in the range
of ca. 25− 85 F g− 1. A strong capacitance reduction was observed at 10 A
g− 1. This behavior indicates the electrode structure composed of mi­
cropores allied to the presence of finite-sized ionic species incur pro­
nounced “steric effects” which preclude the rapid access of the ionic
species in the internal surface areas when a high charge flow (e.g.,
gravimetric current) is applied to the symmetric coin cell.
R. Venâncio et al.
During polarization conditions, each type of electrode material can
exhibit different accessibility considering the particular ion size and
solvent used in the electrolyte. When considering a pure ion diffusion
process, the electric field does not affect the ion transport. However, in
practical cases, the migration process caused by the applied electric field
necessarily induces a coupled “local diffusion” due to the unequal
mobility exhibited by the cationic and anionic species, as predicted by
Nernst’s theory of electrolyte transport under the concept of an “internal
electric field”. As a result, the local electric field and the chemical po­
tential gradients simultaneously affect the overall charge transport in
electrolytes. In this context, the rapidity that the charging and dis­
charging processes are accomplished necessarily affects the degree of
accessibility of the inner/internal surface regions present in narrow
micropores by the ionic species.
After analyzing the charge storage process, we evaluated the device’s
energy and power capabilities using Eqs. (3) and (5). These findings are
presented in Fig. 4(d). As expected, the assembled symmetric SCs
exhibited a high-power capability and moderate values for the specific
energy.
3.2. Residual gas analysis using in situ mass spectrometry
In order to better understand the charge-storage process in SCs and
the stability of cell components, we also evaluated the gas evolution in
the symmetrical cells under operando conditions. The mass spectra were
taken under polarization conditions using the electrochemical cell
shown in Fig. S1 and described in the experimental section. The working
electrodes were assembled at the bottom of the cell, and the counter
electrodes at the top, were both embedded by the electrolyte where a
membrane was used to avoid the electrolyte being sucked by the mass
spectrometer high-vacuum chamber that works at 1 μbar. Only gases
such as CO, CO2, O2, and H2 are sucked into the analyzing chamber, and
Fig. 6. Raman spectra as a function of the applied voltage in symmetric cells using (a) MWCNT & (d) AC electrodes in 1.0 M TEABF4-PC electrolyte. Raman operando
spectra analyses of (b & e) peak intensities and (c & f) AD/AG ratios and shift position of D-peak as a function of cell voltage are also shown.
9
Energy Storage Materials 62 (2023) 102943
the mass-to-charge ratio signals were collected during the experiments.
Since the TEABF4-PC electrolyte performed better regarding the charge-
storage properties, we directed our analysis to this particular system.
Fig. 5 shows the TEABF4-PC system performance as the voltage in­
creases. Fig. 5(a & e) shows data from the cell as the voltage is held
constant for 5 min at different values. The voltage was increased in steps
of 0.4 V and we tracked the transient current response (e.g., chro­
noamperometry test). In these cases, the voltage was kept at almost
constant values at longer polarization times sustained by irreversible
faradaic reactions after the capacitive transient. In both cases, the
TEABF4-PC mass spectra showed that CO2, CO, and H2 started to evolve
at 3.0 V. Negligible gas evolution at a lower voltage was also detected. In
principle, the origin of CO2, CO, and H2 signals may be from the elec­
trode and/or electrolyte oxidation (faradaic) processes. However, ac­
cording to Raman operando spectra analyses, electrolyte degradation is
the source of these gaseous substances (Please see Fig. 6 and further
discussion). Also, we verified that the peak intensities in the Raman
spectra increased as a function of the electrolyte decomposition voltage.
Thus the primary source of the evolved gases is due to oxidation of PC
(Please see Fig. S8, where all chemical formulas are presented).
The oxidative degradation of PC direct interacts with hydrogen
species forming, preferably, CO and CO2 signals at high voltages, as
shown below. It is interesting to notice that the level of CO evolved is
much higher than CO2, indicating constant partial oxidation of the
electrolyte for MWCNT but not to AC electrode materials. Probably the
oxidation of the oxygenated functional groups present in AC favors the
CO2 formation. Please see Fig. S9, whose findings suggest that AC has
much higher oxygen functional groups than MWCNTs. These functional
groups are the leading cause of CO and CO2 formation, but should
contribute less than oxidative electrolyte degradation. These functional
groups mainly comprise hydroxyl (C-OH), carbonyl (C=O), and quinone
groups, preferably originating the CO signals. At the same time, the CO2
R. Venâncio et al.
gas may derivate from the oxidation of carboxyl (COOH), lactone, and
anhydride groups as follows [54–56]:
C = O + 3H2 O→CO + 2H3 O+ + 2e−
COOH + 5H2 O→COOH + 3H3 O+ + 3e−
COOH + 2H2 O→2H3 O+ + CO2
It is interesting to observe that tiny amounts of CO2, CO, and H2
gasses can escape from the cell, causing oscillations in the mass spectra
obtained for the MWCNT-based cell. In other words, the peaks ascribed
to CO2, CO, and H2 do not follow the dU/dt abrupt changes verified in
the chronoamperometry tests (see Fig. 5(a)). For certain internal pres­
sure, a small amount of gas passes through the PTFE cell membrane, and
current peaks can be detected as the gas reaches the mass spectrometer
detector. For AC-based cells, that does not happen, indicating that in the
experimental setup, the evolved gasses gradually escape from the cell as
they are produced in more quantities. As we change the cell voltage, we
remove the background signal of the gasses in the mass detector
chamber to better correlate the gas signals to the applied voltage in the
symmetric cells.
Nevertheless, the fast increase of the residual current in Fig. 5(f)
suggests the presence of pore-clogging by the products of electrolyte
degradation is more evident than in the MWCNT-based cell (Fig. 5(a)),
this corroborates with the AC morphology that is mostly composed of
-micro and mesopores.
Fig. 7. FT-IR spectra as a function of the applied voltage in symmetric cells using carbon paper electrode in 1.0 M TEABF4-PC electrolyte. (a) Vibrational assignments
from TEABF4 and PC, (b) 3D spectra shift as a function of the applied voltage, and (c-g) (left) bands intensity in specific wavenumber ranges and (right) area under
spectra bands in the selected ranges as a function of voltage.
10
Energy Storage Materials 62 (2023) 102943
3.3. Raman operando spectroscopy analysis
We applied the Raman operando technique to better understand SC
components’ degradation mechanisms. Raman technique is a powerful
tool for analyzing electrode degradation processes. We analyzed here
the degradation of MWCNT and AC electrodes under similar conditions.
Fig. 6 contrasts Raman operando spectra and data from (a-d) MWCNT
and (e-g) AC electrodes in 1.0 M of TEABF4-PC cells. Raman spectra are
presented as a function of the applied voltage exceeding the electrolyte
stability range.
The presence of the D-band originates from breaking the symmetry
breathing at A1g mode of the carbon ring as it interacts with a defect. Its
appearance and shifts are associated with the longitudinal optical
excitation phonon [57–59]. The G-band is the vibration mode of E2g
symmetry related to the sp2 hybridization [57,60,61]. Moreover, the
Raman bands in the 500− 1000 cm− 1 interval comprise the primary vi­
brations modes of the electrolytes and are fully described in supple­
mentary data (Please see Table S1 to S3).
The AD/AG intensity ratio shows similar values (Please see Fig. 6(c &
f)) as the voltage was scanned from 0 to 4.8 V, indicating minimal/
negligible degradation of MWCNT and AC electrodes in that specific
cycle and environment. These findings suggest that CO, CO2, and H2
mainly originate from electrolyte decomposition, as previously dis­
cussed using mass spectrometry analysis. All findings demonstrate that
both MWCNT and AC electrodes are highly stable in the present
electrolyte.
R. Venâncio et al.
Raman analyses also evidenced that the D-peak positions exhibit a
blue shift (please see Fig. 6(c & f)), meaning that the ion adsorption and
polarization affect the local electrical field with a symmetry break
involving the breathing mode of the carbon ring. In this sense, it can be
proposed that the adsorbed ions at the electrode/solution interface built
local electrical charge excesses that interact with the electrode Fermi
level. Since AC is more defective by nature, the presence of such charge
excesses can be more pronounced compared to MWCNT electrodes. It is
worth mentioning that the maximum Raman shift observed for the D-
band in MWCNT is ~1 cm− 1, while for AC the corresponding value is ≈
18 cm− 1 at 4.8 V.
After polarization at 3 V, the Raman signal’s intensity reduces due to
light scattering and absorption due to collisions with ions from the
electrolyte. The strong local electrical field causes a considerable in­
crease in ion concentration at the electrode and electrolyte interfaces (e.
g., surface excesses), forming a turbulent (non-isotropic) media for the
radiation. This phenomenon that is commonly found in organic com­
pounds is called fluorescence. The latter blocks the laser from reaching
the electrode, leading to more scattering and absorption processes. The
chosen wavelengths in Raman experiments are then crucial to diminish
the influence of fluorescence [62–68].
3.4. FT-IR operando analysis
FT-IR operando spectroscopy was used to further investigate the
electrolyte degradation mechanisms. A cell containing TEABF4-PC
electrolyte was electrochemically tested from 0 to 4.8 V by expanding
the voltage window in steps of 0.4 V. In this way, we followed the
vibrational assignments of the electrolyte as a function of the applied
potential. As could be seen in Fig. 7(a,b), typical TEABF4 [69–74] and PC
[75–78] bands can be seen in the spectra. Fig. 7(c–g) shows regions of
the spectra as a function of voltage in detail, the peak area can be found
in Fig. S6 at supplementary data. In this case, all spectra had the back­
ground normalized to investigate the absorbance intensity. In addition,
it was calculated the area under the bands in order to compare the
changes in spectra over time.
As seen in Fig. 7(b), most of the changes in the spectra start to occur
after 3 V, which agrees with the previous electrochemical tests followed
by mass spectroscopy. After 3 V, the intensity of most of the bands
increased significantly. This effect can be explained similarly to the
Raman spectroscopy experiment, i.e., at high voltages, there is the po­
larization of the electrolyte, which then leads to a high concentration of
ions all over the working electrode. This effect contributes to the incre­
ment of the IR absorbance, which causes the enhancement of the elec­
trolyte’s band signals. Shifts in these bands were also observed. When a
11
Energy Storage Materials 62 (2023) 102943
shift occurs, it means that the vibration mode of the bond is affected. For
instance, it can represent the weakening of the bond strength by the
presence of an ion causing electrolyte polarization. In this experiment,
two prominent bands showed shifts (e.g., 1690 cm− 1 and 2500 cm− 1
(Please see Fig. 7(c,d)) representing the vibration of the C=O groups in PC
and a complex vibration of TEABF4-PC, respectively. The effect of po­
larization and ion accumulation at the electrode/solution interface will be
further discussed in the molecular dynamics (MD) simulation section.
Besides the changes in the absorbance intensity and bands’ shifts,
new bands can be detected when a high voltage is applied to the device.
In Fig. 7(e) a new band emerges at ~880 cm− 1, which can be related to
the epoxide group (-C-O-C- ring) present in the propylene oxide (PO)
[79]. PO is a product of the oxidative decomposition of PC (Please see
the reaction scheme below), thus confirming the hypothesis of electro­
lyte degradation at high voltages. CO2 is also produced in the oxidative
reaction and can be seen in the spectrum at 2340 cm− 1 (Fig. 7(f)). A wide
band also appears in the 3100− 3300 cm− 1 interval (Fig. 7(g)). The latter
can be ascribed to the O-H stretch mode of carboxylic acids (R-COOH),
which is another product of the PC decomposition [80]. The vibrations
mode that appears in the FT-IR spectra is consistent with the results
shown in the residual gas analysis section, it is seen that in an oxidative
atmosphere with the TEABF4 as a catalyst, the cyclic structure breaks in
carbon-based modes resulting in the gasses found in Fig. 5. In this way,
we propose the following degradation mechanism reactions of the pro­
pylene carbonate.
3.5. Atomistic picture by molecular dynamics simulations
Molecular Dynamics simulations of 1.0 M of TEABF4-PC and LiTFSI-
PC electrolytes confined into graphite electrodes were performed to gain
some insights at the atomistic level. Fig. 8(a) shows the charge accu­
mulated on the electrodes at an applied voltage of 3.0 V during the
simulation time. Specific areal capacitances (C = Q/ΔV⋅A, where Q is
the total charge accumulated on electrode, ΔV is the applied potential,
and A is the electrode area) SCs, resulting in 2.37 μF cm− 2 and 1.45 μF
cm− 2 for LiTFSI-PC and TEABF4-PC, respectively, following the experi­
mental trend (Please see Table 1). Following the charging times (τ)
obtained by fitting a monoexponential function to the charge curves
(Fig. 8(a)), the charging process in LiTFSI-PC is slightly faster, which
might be linked with the planar electrode used here. In such a perfectly
flat surface, the solvated Li+ cations can be close to the electrode surface
without losing their solvation shell, which can be the root of this fast-
charging process. Also, we recall that the simulations were performed
with the same applied voltage (3.0 V), which is above the one used in the
experimental section (2.5 V).
R. Venâncio et al. Energy Storage Materials 62 (2023) 102943

Furthermore, looking at the molecular number trend curve (Please species get closer to the electrode surface, but the vast majority of these
see Fig. 8(b–e)), at zero charge potential, there is a considerable amount ionic species depart from the surface, going toward the second layer of
of Li+ ions close to the electrode surface, incurring in the peaks around cations solvated by PC according to the peak at ≈ 0.75 nm in the
0.3 and 13.25 nm. Upon the application of the voltage, some of the Li+ negative electrode polarized at 3 V (Please see Fig. 8(b)). This comes

Fig. 8. (a) Accumulated charges calculated for the simulations of LiTFSI-PC and TEABF4-PC electrolytes confined between symmetric planar graphite electrodes
using an applied voltage of 3 V. The lines are the best-fit curves obtained by fitting the function Q(t) = Q(1 − exp(− t/τ)) to the charges accumulated on the electrode.
Number density profile of (b-c) LiTFSI – PC and (d-e) TEABF4 – PC at applied voltages of 0 and 3 V. The electrode positions are identified at z = 0 and z = 13.7 nm in
LiTFSI, and at 0 and 11.7 nm in TEABF4. The density profile of PC was divided by 4 to allow for the visualization of all density profiles together.

12
R. Venâncio et al.
Fig. 9. Representative snapshots extracted from the MD simulations of LiTFSI in PC (a) and TEABF4 in PC (b) close to the electrode surfaces. Carbon atoms of
graphite are represented in violet, [Li]+ (pink) and [TEA]+ cation in gray/blue/white spheres. [TFSI]− and [BF4]− anions are in silver/cyan/yellow/blue/red and
orange/cyan, respectively.
from the strong Li-OPC interaction and the repulsion between the
negative electrode and the oxygen atoms (negatively charged) of PC,
causing the rearrangement of PC molecules adsorbed on the electrode
surface. Note that the red spheres in Fig. 9(a) form a thicker layer close
to the negative electrode than the positive one. Electrostatic repulsion
between TFSI and the negative electrode also happens to cause the an­
ions’ departure toward the electrolyte’s bulk region.
In the positive electrode, Li+ ions drag the coordinating PC molecules
towards the bulk region, whereas TFSI anions adsorb onto the carbon
surface to screen the positive charge present in the electrode (Fig. 9(a)).
In the case of TEABF4–PC (Please see Fig. 8(d,e)), the three electro­
lyte components can be adsorbed on the surface of the electrode at zero
charge potential. Upon applying the voltage (3 V), the main change at
the electrode-electrolyte interface is the desorption of [BF4]− anions
from the negative electrode. Considering the smaller charge accumu­
lated on the electrodes with TEABF4–PC, the electrostatic repulsion
between the positive electrode and [TEA]+ species is insufficient to
overcome the attractive Lennard-Jones’s interactions between the
electrode and the ethyl chains of [TEA]+. This finding suggests that
carbon-based electrodes are coated by a [TEA]+ layer, as shown in Fig. 9
(b), which might be responsible for the higher electrochemical stability
of TEABF4-PC electrolyte compared to LiTFSI–PC, as observed experi­
mentally. The layer of [TEA]+ on the positive electrode is pushed toward
the bulk phase of the electrolyte when the applied voltage is high, for
instance, 4.8 V.
4. Conclusions
A comprehensive study has been presented regarding the stability
analysis of some organic electrolytes in EDLCs by electrochemical, mass
spectrometry, and Raman and FTIR operando analyses techniques. The
use of best characterization practices becomes obvious to correctly
determine the stability voltage window, as well as the specific capaci­
tance and ESR in symmetric coin cell devices. The present study high­
lights some important experimental details to determine the specific
energy and power characteristics in EDLCs correctly. In particular, we
have analyzed the LiTFSI and TEABF4 salts dissolved in AN, PC, and EC:
DMC. As verified, the AC/TEABF4-PC/AC systems performed best,
strongly supporting further studies to optimize the specific capacitance,
energy, and power characteristics to develop bench-scale EDLC
prototypes.
13
Energy Storage Materials 62 (2023) 102943
It was clearly verified from the simulation of the impedance findings
that ion accumulation at the electrode/solution interface can induce the
appearance of anomalous charge transport in the defective/tortuous
ionic channels. At the same time, the residual gas analysis suggested a
maximum stability voltage of 3 V for the organic electrolyte, which was
confirmed by the Raman operando studies that evidence high electrode
stability for both AC and MWCNT materials while the FT-IR analysis
highlighted the solvent degradation effect in the evolved gas from abuse
conditions. The experimental analysis agrees with the computational
simulation that described the higher stability as related to the high af­
finity of [TEA]+ by the carbon surfaces of the electrode.
CRediT authorship contribution statement
Raissa Venâncio: Conceptualization, Methodology, Investigation,
Validation, Writing – original draft, Visualization. Rafael Vicentini:
Methodology, Validation, Investigation. Manuel J. Pinzón C． ．: Inves­
tigation. Débora A. Corrêa: Formal analysis, Writing – original draft.
André N. Miranda: Investigation, Validation. Adriana C. Queiroz:
Methodology. Francisco Tadeu Degasperi: Methodology, Writing –
review & editing. Leonardo J.A. Siqueira: Formal analysis, Writing –
review & editing. Leonardo M. Da Silva: Writing – review & editing.
Hudson Zanin: Writing – review & editing, Resources, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors are very grateful to the financial support from the Bra­
zilian funding agencies CNPq (301486/2016–6), FAPESP (2014/02
163–7, 2017/11958–1, 2018/20756–6, 2019/18125–0 2020/149
68–0). L.M. Da Silva wishes to thank FAPEMIG (APQ-01745–21) and
CNPq (PQ-2 grant: 303248/2021–1). The authors gratefully acknowl­
edge the support from Shell and the strategic importance of the support
given by ANP (Brazil’s National Oil, Natural Gas and Biofuels Agency)
through the R&D levy regulation. D.A.C and L. J. A. S. are also grateful
for the infrastructure provided by the “Centro Nacional de Process
R. Venâncio et al.
amento de Alto Desempenho em São Paulo (CENAPAD-SP)”, and Santos
Dumont supercomputer at LNCC. A special thanks to CNPEM Sirius for
beamline time.
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.ensm.2023.102943.
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