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Article
Ultramicroporous N-Doped Activated Carbon Materials for
High Performance Supercapacitors
Taylan Karakoç, Housseinou Ba, Lai Truong Phuoc, Dominique Bégin, Cuong Pham-Huu * and Sergey N. Pronkin *

Institute of Chemistry and Processes for Energy, Environment and Health (ICPEES)—UMR-7515-25 Rue
Becquerel, CEDEX 2, 67087 Strasbourg, France; taylan.karakoc@etu.unistra.fr (T.K.); hba@blackleaf.fr (H.B.);
ltruongphuoc@unistra.fr (L.T.P.); dominique.begin@unistra.fr (D.B.)
* Correspondence: cuong.pham-huu@unistra.fr (C.P.-H.); sergey.pronkin@unistra.fr (S.N.P.)

Abstract: Porous carbon electrode materials are utilized in supercapacitors with very fast
charge/discharge and high stability upon cycling thanks to their electrostatic charge storage mecha-
nism. Further enhancement of the performance of such materials can be achieved by doping them
with heteroatoms which alter the kinetics of charge/discharge of the adsorbed species and result in
pseudocapacitance phenomena. Here, microporous N-doped activated carbons were synthesized
by thermochemical activation process. The structure and composition of the final material were
adjusted by tuning the synthesis conditions and the choice of precursor molecules. In particular,
N-doped activated carbons with a controlled specific surface area in the range of 270–1380 m2 /g
have been prepared by KOH-activation of sucrose/ammonium citrate mixture. By adjusting the
composition of precursors, N-doping was varied from ca. 1.5 to 7.3 at%. The role of the components
and synthesis conditions on the composition and structure of final products has been evaluated.
The N-doped activated carbon with optimized structure and composition has demonstrated an
outstanding performance as electrode material for aqueous electrolyte supercapacitors. The specific
capacitance measured in a 3-electrode cell with 0.75 mg/cm2 loading of optimized activated carbon
in 1M H2 SO4 changed from 359 F/g at 0.5 A/g charging rate to 243 F/g at 20 A/g. Less than 0.01%
of capacitance loss has been detected after 1000 charging/discharging cycles.

Citation: Karakoç, T.; Ba, H.; Phuoc, Keywords: EDLC; activated carbon; N-doped carbon
L.T.; Bégin, D.; Pham-Huu, C.;
Pronkin, S.N. Ultramicroporous
N-Doped Activated Carbon Materials
for High Performance
1. Introduction
Supercapacitors. Batteries 2023, 9, 436.
https://doi.org/10.3390/
Supercapacitors are one of electrochemical energy storage devices (EESD), with per-
batteries9090436
formance characteristics complementary to batteries. Namely, in comparison to Li-ion
batteries, supercapacitors are characterized by high power density and charging cyclability,
Academic Editor: Hao Liu
but lower energy density [1,2]. Carbon materials are among the most commonly used
Received: 18 July 2023 electrode materials for supercapacitors, in particular in electrical double layer capacitors
Revised: 10 August 2023 (EDLC), relying on the charging of an interfacial electrical double layer as a mechanism
Accepted: 19 August 2023 of charge storage [3,4]. The advantages of carbon materials are their high electrical con-
Published: 24 August 2023 ductivity, electrochemical stability, and controlled variability of materials structure and
composition [3,5]. Carbon materials can be synthesized with wide variety of structures [6,7]:
from 0D (carbon nanodots and carbon quantum dots [8]), to 1D (carbon nanotubes and
nanofibres), 2D (graphene-type carbons [9]), to numerous porous 3D carbons, for exam-
Copyright: © 2023 by the authors. ple, activated carbons (AC). For EDLC electrodes, the carbon materials with high specific
Licensee MDPI, Basel, Switzerland. surface area (SSA) are of high interest, AC in particular [10].
This article is an open access article
AC is the group of carbon materials with outstandingly high SSA, close to the theoreti-
distributed under the terms and
cal maximum for a closely packed sp2- carbon sheet (single graphene layer) of 2680 m2 /g.
conditions of the Creative Commons
Considering the typical value of the surface-specific interfacial capacitance of carbon ma-
Attribution (CC BY) license (https://
terials Cs ≈ 5–10 µF/cm2 [11], one may expect the mass specific capacitance of carbon
creativecommons.org/licenses/by/
electrodes in the range Cg ≈ 150–300 F/g.
4.0/).

Batteries 2023, 9, 436. https://doi.org/10.3390/batteries9090436 https://www.mdpi.com/journal/batteries

Batteries 2023, 9, 436 2 of 17

High SSA is provided by the open porous structure of AC with a predominant contri-
bution of micropores (diameter d < 2 nm). The porous structure is formed by thermal or
thermochemical activation of carbon precursors at high temperature (600–900 ◦ C) under
inert atmosphere.
As it has been thoroughly discussed in a number of reviews from the last
decade [3,12–16], AC materials can be prepared from the wide range of carbon-rich pre-
cursors, including relatively cheap and abundant bio-wastes (domestic, agricultural, or
agro-industrial). The electrochemical characteristics of AC materials, in particular their spe-
cific capacitance and stability, are influenced by the properties of AC, namely its chemical
composition, SSA and porosity, and electrical conductivity. These properties are strongly
varied depending on the choice of precursor and preparation conditions, which have to
be optimized for the case of each particular type of precursor. The bio-sourced precursors
have a complex composition, mostly containing sugars (sucrose and polysaccharides), cel-
lulose, hemicellulose, and lignin [12,17]. In order to understand the correlation between the
properties of AC and the conditions of its preparation, a simple chemically pure precursor
model is used, such as glucose, sucrose, or cellulose. In particular, sucrose has been used as
a precursor for the AC electrode materials for electrocatalysis [18] and EDLC supercapaci-
tors [15]. It has been demonstrated [19] that AC materials with high SSA > 2000 m2 /g can
be prepared by the KOH thermochemical activation of sucrose under inert atmosphere.
This work presents a two-step synthesis of N-doped activated carbon (AC-N) prepared
by the conventional approach with thermochemical activation by KOH as the final step.
We intended to study the influence of the addition of ammonium citrate to the sucrose
precursor on the properties of a final AC material. Citric acid is known to efficiently catalyze
the hydrothermal carbonization of bio-waste precursors [20–22] through an esterification
reaction with carbohydrates [23]. By using ammonium salt of citric acid, we intended
to introduce N-heteroatoms into the carbon matrix of the final AC material. N-doped
carbon materials are intensively studied as electrode materials for energy storage devices,
namely Li-S and Li-ion batteries [24]. A systematic increase of the capacitance of carbon
electrodes of supercapacitors with an increase in N-content (in the range 2–7 at.%) in
various electrolytes has been demonstrated [25,26]. Outstanding mass specific capacitance
above 800 F/g has been reported for N-doped mesoporous carbon prepared by the hard
template method [27]. However, the variety of the nature of N-heteroatoms imbedded
into the carbon structure complicates the general prediction of an optimal composition of
N-doped carbon.
In the present work, we demonstrate that by using ammonium citrate and sucrose
as initial precursors, N-doped AC materials with high SSA and performance as EDLC
electrodes can be obtained. The origins of high capacitance and the role of different
components of the synthesis are evaluated and discussed.

2. Materials and Methods

2.1. Synthesis of AC-N
First, 10 g of D(+)-Sucrose C12 H22 O11 (Acros Organics, 99+% purity for analysis, CAS:
57-50-1) was mixed with 10 g of anhydrous ammonium citrate (NH4 )3 Cit (Sigma, ≥97%
purity, CAS: 3458-72-8), and finely grinded in a coffee grinder. The solid powder was then
put into an oven at 160 ◦ C in air for 4 h. The resulting solid intermediate was grinded once
again and mixed with a concentrated aqueous solution containing 10 g of KOH (Acros
Organics, extra pure, ca. 85%, flakes, CAS: 1310-58-3). The slurry mixture was dried
again at 160 ◦ C for 4 h. Dried KOH-impregnated intermediate was loaded into a tubular
reactor kept under Ar flow (10 ccm. min−1 ). The temperature was raised to the annealing
temperature of 700 ◦ C/800 ◦ C/900 ◦ C within 3 h, and then kept at the set temperature
for 1 h. The product was then left to cool down under the flow of Ar. The final product
was washed with 2M HCl and ultrapure water, filtered, and dried in the oven overnight
at 80 ◦ C.
Batteries 2023, 9, 436 3 of 17

The reference samples were also synthesized by using 10 g of pure sucrose without
any other additive, and 10 g of sucrose and 10 g of citric acid (Chem-Lab, 99.5–101%, CAS:
5949-29-1). All other conditions of synthesis were the same as described above.
All aqueous solutions in this work were prepared by using ultrapure water
(18.2 Mohm.cm, TOC < 2 ppb) produced by the Ultra PureLab Chorus (Veolia) device.

2.2. Physicochemical Characterization of AC-N

Scanning electron microscopy (SEM) measurements were done in ICPEES by using a
Zeiss 2600F microscope with a resolution of 5 nm. The carbon samples were deposited on
a conductive carbon tape. X-ray diffraction (XRD) measurements were performed by a
Bruker D-8 Advance diffractometer with Cu Kα source (λ = 1.54184 Å). Attenuated total
reflection Fourier-transformed IR (ATR-FTIR) measurements were done by a Thermosci-
entific Nivolet iS10 IR spectrometer equipped by an ATR Smart Orbit setup. Surface area
determination by Brunauer-Emmett-Teller theory (BET) measurements were done using
an ASAP 2420 Micrometric analyzer measuring N2 physisorption isotherm at 77 K after
degassing the samples at 150 ◦ C for 12 h. Raman spectra were recorded using a LabRAM
HORIBA ARAMIS spectrometer with a CDD detector and laser line from 532 nm/100 mW
(YAG) Laser Quantum MPC600 PSU. X-ray photoelectrons spectroscopy (XPS) measure-
ments were done using a Multilab 2000 Thermoelectron spectrometer with Al Kα source
(λ = 1486.6 eV).
For 2-point conductivity measurements, a controlled amount of power was placed
in a vertical narrow calibrated glass tube (inner diameter d = 0.61 cm). The lower end of the
tube was blocked by Cu foil. The powder was blocked in the tube from above by another
glass rod with Cu contact at the end (d ≈ 0.61 cm). Thus, the cross-section of the contact
was A = 14 πd2 = 0.29 cm2 . No extra pressure was applied on the power except the weight
of the glass rod (8.1 g). The volume of the powder V between 2 contacts was precisely
measured. Conductivity of the powder was measured by Ohm’s law by passing a constant
current and measuring voltage between 2 Cu contacts. The dependence of conductivity on
frequency was measured by measuring impedance between 2 contacts by applying 7 mV
voltage modulation with frequencies f from 106 to 10−1 Hz.

2.3. Electrochemical Measurements

2.3.1. Preparation of Electrodes
Ink Preparation
Inks were prepared by adding a desired amount of active material in a glass vial and
the required volume of MilliQ water (resistivity of 18.2 MΩ·cm at 25 ◦ C, Total of organic
compound (TOC) ≤ 1 ppb) to obtain a 2 g/L concentrated ink. All the inks were prepared
by usually weighting 10.0 mg of activated carbon powder in the vial and adding 5000 µL
of MilliQ water with a 0.5–5.0 mL micropipette. The ink was then shaken and sonicated in
an ultrasonication bath for 20 min.

Ink Deposition on Glassy Carbon Rod

The active material was deposited by drop casting onto the surface of a glassy carbon
rod electrode of 6 mm radius. The total deposited volume of ink was 75 µL divided
by 5 deposition steps of 15 µL, in which the electrode was dried for 10 min in an oven
programmed at 80 ◦ C between each step. The loading of active material was approximated
to 0.75 mg/cm2 . A final deposition of 15 µL Nafion 0.5 wt. % in a mixture of lower aliphatic
alcohols and water was added and dried to act as a binder.

2.3.2. Electrochemical Measurements

A 3-electrode cell inside a Faraday cage was used for the electrochemical tests. A
100 mL 1M H2 SO4 electrolyte was poured in the cell, followed by the addition of a platinum
wire with a coil end counter electrode in the compartment separated by a fritted and a mer-
cury/mercurous sulfate electrode (MSE) in saturated K2 SO4 in the compartment separated
 wire with a coil end counter electrode in the compartment separated by a fritted and a
mercury/mercurous sulfate electrode (MSE) in saturated K2SO4 in the compartmen
separated by Luggin capillary. The solution in the cell was then purged for at least 30 min
under N2 gas. The glassy carbon rod electrode with active material—the working
Batteries 2023, 9, 436 electrode—was placed in a holder and then placed inside the electrochemical4cell of 17in order

to only have contact with the surface of the electrode. The N2 gas was flushing above the
electrolyte to keep a controlled atmosphere without O2. The electrodes were connected to
by Luggin capillary. The solution in the cell was then purged for at least 30 min under N2
a SP-300 Potentiostat from BioLogic (Grenoble, France).
gas. The glassy carbon rod electrode with active material—the working electrode—was
placed in a holder and then placed inside the electrochemical cell in order to only have
3. Results
contact with the surface of the electrode. The N2 gas was flushing above the electrolyte
3.1. to keep a controlled
Synthesis atmosphere without O2 . The electrodes were connected to a SP-300
of AC-N Samples
Potentiostat from BioLogic (Grenoble, France).
Figure 1 summarizes the different synthesis steps, i.e., precursors nature and
temperature,
3. Results for the preparation of AC-N samples. The synthesis was carried out through a
3.1. Synthesis
two-step process:of AC-N Samples
polycondensation at 160 °C in air for 4 h, and thermochemical activation
by KOHFigureat various temperatures
1 summarizes under synthesis
the different Ar for 1 h. Thei.e.,
steps, samples synthesized
precursors by tem-
nature and this process
perature, for the preparation of AC-N samples. The synthesis was carried
are denoted as AC-N-xxx, where xxx is the temperature of the activation step. For out through
a two-steptwo
comparison, process:
otherpolycondensation at 160 ◦ C in air
samples were synthesized, for 4 h, and thermochemical
differentiating acti-
from AC-N samples only
vation by KOH at various temperatures under Ar for 1 h. The samples synthesized by
by the composition of the precursors. Namely, the AC-800 sample was synthesized
this process are denoted as AC-N-xxx, where xxx is the temperature of the activation step.
from
pureForsucrose, and the
comparison, two AC-C-800 sample
other samples was synthesized
were synthesized, from sucrose
differentiating and samples
from AC-N citric acid with
a 1:1only
molar mixture.
by the Bothofthese
composition samples Namely,
the precursors. were activated
the AC-800 bysample
KOH was
at 800 °C under iner
synthesized
atmosphere.
from pure sucrose, and the AC-C-800 sample was synthesized from sucrose and citric acid
with a 1:1 molar mixture. Both these samples were activated by KOH at 800 ◦ C under
inert atmosphere.

Figure 1. The
Figure scheme
1. The schemeofof2-step
2-step synthesis
synthesis ofof AC-N
AC-N samples.
samples.

Polycondensationof
Polycondensation of precursors
precursors results
resultsin in
foam-like darkdark
foam-like solidsolid
intermediate product.product
intermediate
TheThe ATR-FTIR spectra
ATR-FTIR spectra ofof
solid intermediates
solid preparedprepared
intermediates are shown are
in Figure
shown2. The
inproposed
Figure 2. The
compositions of polycondensation intermediates are given in Figure 3.
proposed compositions of polycondensation intermediates are given in Figure 3.
Batteries 2023, 9, 9,
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17

Figure
Figure
Figure 2.
2.2. ATR-FTIR
ATR-FTIR
ATR-FTIR spectra
spectra
spectra of
ofof intermediate
intermediate
intermediate products
products prepared
prepared
products prepared by
byby polycondensation
polycondensation
polycondensation of
ofof precursors
precursors
precursors
mixture
mixtureatat160
160 ◦ C: pure
°C: pure sucrose
sucrose (black
(black spectrum),
spectrum), sucrose
sucrose + + citric
citric acidacid mixture
mixture (red (red spectrum),
spectrum), sucrose
mixture at 160 °C: pure sucrose (black spectrum), sucrose + citric acid mixture (red spectrum),
sucrose + ammonium
+ ammonium
sucrose citrate
citrate mixture
+ ammonium mixture (green spectrum).
(green spectrum).
citrate mixture (green spectrum).

Figure
Figure 3. Proposed structure ofof
intermediates formed by polycondensation of sucrose (A), sucrose-
Figure 3.3. Proposed
Proposedstructure
structure ofintermediates
intermediatesformed
formedby
bypolycondensation
polycondensationofofsucrose
sucrose(A),
(A),sucrose-
sucrose-
citric acid
citric acid(B), and
(B), sucrose-ammonium
and sucrose-ammonium citrate (C).
citrate (C).
citric acid (B), and sucrose-ammonium citrate (C).
TheThethermal
The thermaltransformation
thermal transformationof
transformation ofof sucrose
sucrose
sucrose close
close toto
close toits
its itsmelting
melting melting temperature
temperature
temperature (186 (186
◦ C)
(186 °C)
°C)
results
results
results in its partial
in its decomposition
in its partial decomposition
partial decomposition with
with thewith the formation
the formation
formation of
of glucose glucose
of glucose and
and fructose, fructose,
and fructose, and its
and its
and its polycon-
polycondensation
polycondensation
densation with formation withwithformation
formation ofofa amixture
of a mixture mixture ofofoligo-
of oligo- oligo-
and and
andpolysaccharides
polysaccharides
polysaccharides [28]. [28].[28].Indeed,
Indeed, Indeed,
the IR
the
the IRIRspectra
spectra of theofproduct
spectra ofthe theproduct
product
of sucroseofofsucrose
sucrose polycondensation
polycondensation
polycondensation (first step(first ofstep
(first step
the ofofthethesynthesis),
synthesis), synthesis),
Figure 2,
Figure
Figure
shows 2,2,
ashows
showsaνastrong
strong strong
band νOH band
bandcentered
νcentered centered
at around atataround
around
3340 cm33401 , acm
−3340 cm,−1a, adoubled
−1
doubled peak ofpeak
doubled νpeak ofofνaround
νC-Hatat
C-H
OH OH C-H at
around
around 2930
− 1
2930 cmcm
−1 ,
−1and
, and a set
a setof peaks
of peaks in inthe 1200–1400
the 1200–1400 −
2930 cm , and a set of peaks in the 1200–1400 cm range, which are attributed to νC-O-C1 cmcm
−1 range,
−1 range, which
which areare attributed
attributed toto
νC-O-C stretching.
νstretching.
C-O-C stretching. The
The set set of
Theofsetpeaks peaks
of peaks in
in the the
in the range
range range 1600–1780
1600–1780
1600–1780 cm −
cmcm can
−1
1 can
−1 be attributed
canbebeattributed to ν
attributedtotoννC=O C=O and
C=O and
and
νC=C
ννC=C stretching
C=Cstretching
stretching andandandassociated
associated
associated totothe
tothe formation
the formation
formation ofofof
5-hydroxymethylfurfural
5-hydroxymethylfurfural
5-hydroxymethylfurfural (5-HMF),
(5-HMF),
(5-HMF), one
one
one
ofofthe
of the
thebyproducts
byproducts
byproducts ofof sucrose
of sucrose
sucrose polycondensation
polycondensation[29]. [29].
TheThe
Theaddition
addition
addition ofof citric
of citricacid
citric acid
acid totosucrose
to sucrose
sucrose during
during
during itsits
thermal
its thermal
thermal treatment
treatment
treatment has a strong
has
has aastrong
strong influence
influence
influence
onon
onthetheprocess
the process
process ofofsucrose
of sucrose
sucrose decomposition
decomposition
decomposition and and
and polycondensation.
polycondensation. It It
has
Ithas
hasbeen
been
been proposed
proposed
proposed [30,31]
[30,31]
[30,31]
that ◦ C,
that citric acid acts as a catalyst of sucrose hydrolysis at temperatures close to 100°C,
that citric
citricacidacidactsacts as asa catalyst
a catalyst ofofsucrose
sucrose hydrolysis
hydrolysis at attemperatures
temperatures close
close to 100
to 100 °C,
accelerating
acceleratingthe
accelerating the formation
theformation
formationof of glucose
ofglucose and
glucoseand fructose,
andfructose,
fructose,as as well
aswell as
wellas 5-HMF,
as5-HMF, which,
5-HMF, which, in
which, in turn,
in turn, triggers
turn, triggers
triggers
thetheformation
formation ofof
ofoligosaccharides
oligosaccharides already
already atat
at100 100°C. ◦ C.
Further
Furtherincrease increaseofof ofthe thesynthesis
synthesis
the formation oligosaccharides already 100 °C. Further increase the synthesis
temperature
temperature toto170
to 170 ◦C
°C°C results
results inin
inananesterification
esterification reaction
reaction between
between thethealcohol
alcohol group
group ofof
of
temperature 170 results esterification reaction between the alcohol group
Batteries 2023, 9, 436 6 of 17

saccharides and the carboxylic group of citric acid. This process results in cross-linking
of polysaccharides chains and the formation of a strong adhesive solid [30,31]. In the IR
spectrum (Figure 2), one can observe a strong band at 1720 cm−1 , which can be attributed
to νC=O stretching in ester and, perhaps, carbonyl fragments. A strong band that appears
at 1165 cm−1 is attributed to νRC-O-CR stretching in aliphatic ether fragments, while peaks
related to the presence of alcohol groups (νOH at 3400 cm−1 and νC-OH at 1020 cm−1 ) are
significantly weaker than in the case of the product of pure sucrose polycondensation.
The IR spectra of polycondensation intermediate produced from sucrose and ammo-
nium citrate mixture show several differences compared to one from sucrose and citric
acid intermediate. The peaks related to alcohol groups (νOH at 3400 cm−1 and νC-OH at
1020 cm−1 ) are much weaker in the case of sucrose—ammonium citrate mixture. Also, in
this case, new IR bands are observed: a strong and broad band centered at 3210 cm−1 , and a
peak at 1350 cm−1 , as well as a broad shoulder at 1580 cm−1 . These bands can be attributed
to νN-H and νC-N , and δH-N-H in primary amines/amides, respectively, indicating that
ammonium is at least partially transformed to amine/amides (primary or secondary) in
polycondensation products (Figure 3C). We note that the vibrations νN-H and δH-N-H in
ammonium citrate are also detected close to the peaks observed in the polycondensation
product, and, thus, the presence of ammonium in the product cannot be excluded.
After thorough grounding of the polycondensation product, it was mixed with KOH
solution and then dried at 160 ◦ C in air. This procedure is expected to eliminate any
remaining ammonium salt within the polycondensation product via the formation of
gaseous ammoniac. The dried product was again grounded and then pyrolyzed at 700 ◦ C,
800 ◦ C, or 900 ◦ C in argon for thermochemical activation of the carbon.
The structure and composition of these prepared samples was characterized as de-
scribed in the next section. The synthesis conditions and some characteristics of the studied
samples are summarized in Table 1.

Table 1. Summary of the conditions of samples AC samples studied in the work, and some of
their characteristics.

ρ,
Activation Cg, F/g (2 A/g,
Sample Name Precursors SSA, m2 /g x(O), x(N), at.% kOhm.
Temperature, ◦ C 1 M H2 SO4 )
cm
AC-800 Sucrose 800 10 30.4/- 0.61 3.2
Sucrose +
AC-C-800 800 130 15.9/- 0.30 75
Citric acid
AC-N-700 Sucrose + (NH4 )3 Cit 600 271 11.8/7.3 19.5 44.2
AC-N-800 Sucrose + (NH4 )3 Cit 700 776 10.8/3.3 0.19 320.9
AC-N-900 Sucrose + (NH4 )3 Cit 800 1379 8.6/1.5 0.009 208.4

3.2. Physicochemical Characterization of AC Samples

Typical SEM images of the AC-N samples are given in Figure S1. The SEM images
demonstrate irregular porous structure typical for AC materials. No clear difference in the
structure of samples activated at different temperatures was detected. Also, we did not
detect any visible difference in terms of structures between AC-N and AC-C-800 samples,
prepared from sucrose and citric acid mixtures. The SEM resolution allows only evidencing
the presence of macropores. For more detailed understanding of the porosity of the sample,
a BET study has been done (see Figure 4).
The increase in the activation temperature results in an increase in SSA of the as-
synthesized AC-N samples. High SSA values and diameter distribution demonstrates the
formation of a large contribution of micropores with d ≤ 2 nm, that is confirmed by the Type
I of observed isotherm. In the case of AC-N-800, we also observed the formation of a small
amount of mesopores with d ≈ 10–20 nm, while for the AC-N-900 sample, the distribution
of the sizes of mesopores is much broader. However, the contribution of mesopores is very
low, as attested by the absence of hysteresis of the isotherms.
Batteries 2023, 9, x FOR PEER REVIEW 7 of 18
Batteries 2023, 9, 436 7 of 17

Figure 4. 4.
Figure BET isotherms
BET isotherms(A)
(A)and
andpore
porediameter
diameter distribution (B) of
distribution (B) of AC-N
AC-Nsamples.
samples.

In general,
The increasethesein theresults are in temperature
activation agreement with studies
results in ofanthe porousinstructure
increase SSA of of thebio-
as-
char-derived
synthesized activated
AC-N carbon
samples. High onSSA
activation
valuestemperature
and diameter [19,32]: an increase
distribution in activation
demonstrates the
temperature
formation of a at
large up to 800 ◦ Cof
leastcontribution results in a higher
micropores withBETd ≤ surface areaisofconfirmed
2 nm, that the sampleby duethe
to the opening of micropores formed at lower temperature. An
Type I of observed isotherm. In the case of AC-N-800, we also observed the formation of increase of activation
◦ C results in the general widening of pores: the relative contribution
a temperature
small amount aboveof 700
mesopores with d≈10–20 nm, while for the AC-N-900 sample, the
of ultramicropores (diameter
distribution of the sizes of mesopores d ≈ 0.3–0.4 nm) decreases
is much broader. with higherthe
However, temperature
contribution andof
longer activation time, while the relative contribution of micropores with d ≈ 0.8–2.0 nm
mesopores is very low, as attested by the absence of hysteresis of the isotherms.
increases [32]. The BET surface area of the AC-N-800 sample is significantly higher than
In general, these results are in agreement with studies of the porous structure of bio-
that of AC-C-800. It shows that thermal decomposition of the cross-linked product of
char-derived activated carbon on activation temperature [19,32]: an increase in activation
polycondensation of sucrose and ammonium citrate addition results in a more porous
temperature at least
structure than in theup to of
case 800sucrose
°C results in a higher
and citric BET surface area
acid, demonstrating of theofsample
the effect due to
the presence
theof opening of micropores formed at lower
N-containing groups in polycondensation intermediate. temperature. An increase of activation
temperature
Figure 5above
shows N1s 700 XPS
°C spectra
resultsofin AC-Nthe samples
generalafterwidening of pores:
KOH activation. the relative
Deconvolution
contribution of ultramicropores (diameter d ≈ 0.3–0.4 nm)
of N1s XPS spectra of AC-N samples demonstrates that N-heteroatoms are incorporated decreases with higher
to
temperature and longer activation time, while the relative contribution
the carbon structure in various forms: pyrrolic N, pyridinic, amines/amides, quaternary of micropores with
d ≈N0.8–2.0
(Q-N),nmandincreases
NOx . Due [32].toThe
theBET surface
variety area
of the of the
types ofAC-N-800 samplethere
N-heteroatoms, is significantly
is certain
higher than that
incertitude of AC-C-800.
in peaks It shows
deconvolution, that thermal
making decomposition
difficult the precise analysisof the cross-linked
of the ratio of
different
product of types. However, certain
polycondensation qualitative
of sucrose and conclusions
ammoniumcan be drawn,
citrate addition as described
results in below.
a more
N-pyrrolic is the predominant type of N-heteroatom, and its ratio
porous structure than in the case of sucrose and citric acid, demonstrating the effect of the slightly decreases
with anofincrease
presence in activation
N-containing groupstemperature. Also, theintermediate.
in polycondensation ratio of remaining amine/amide-
N slightly
Figure decreases,
5 shows while N1s the XPSratio of more
spectra of thermally stable N-pyridinic
AC-N samples after KOH and,activation.
perhaps
Deconvolution of N1s XPS spectra of AC-N samples demonstrates that N-heteroatoms of
Q-N, increases. In general, as the activation temperature increases, the concentration are
heteroatoms (N
incorporated to and theO)carbon
decreases. The pyrolysis
structure of polycondensation
in various forms: pyrrolic intermediate results
N, pyridinic,
in a decomposition of N- and O-containing functional groups, which starts at ca. 600 ◦ C [33].
amines/amides, quaternary N (Q-N), and NOx. Due to the variety of the types of N-
The decomposition results in the formation of gaseous products, such as CO2 and NH3
heteroatoms, there is certain incertitude in peaks deconvolution, making difficult the
and/or NOx . The formation of gaseous products is one of the processes responsible for the
precise analysis of the ratio of different types. However, certain qualitative conclusions
development of the open porous structure of the final carbon product. In particular, the
can be drawn,
formation of as described
ammonia viabelow.
decomposition of amine/amide groups of polycondensation
intermediate results in higher BET surface area due to chemical etching of carbon by
gaseous ammonia, which above 700 ◦ C, reacts with carboxylic groups and the carbon
skeleton, forming more thermally stable pyrrolic, pyridinic, and Q-nitrogen groups [34,35].
Indeed, XPS results show that the AC-N-800 sample is more reduced (contains less oxygen)
compared to AC-800 and AC-C-800 prepared without using N-containing precursors. The
certain ratio of amine/amide N-heteroatoms remains, even at 900 ◦ C, even though this
Batteries 2023, 9, 436 8 of 17

Batteries 2023, 9, x FOR PEER REVIEW 8 of 18

ratio, as expected, decreases with temperature due to transformation of amines and amides
to more stable forms of N-heteroatoms.

Figure 5. N1s −XPS spectra

N1s−XPS AC−Nsamples
spectra of AC−N samples (in
(in red) with peak deconvolution
deconvolution (in
(incorresponding
corresponding
colors). The results of deconvolution
deconvolution are
are given
given in
in the
thetable
tableinsert.
insert.

The decomposition
N-pyrrolic of N- and O-containing
is the predominant functional groups
type of N-heteroatom, and itsresults in the formation
ratio slightly decreases
of unsaturated C-C bonds, i.e., an increase in the relative population of sp 2 -carbon, and in
with an increase in activation temperature. Also, the ratio of remaining amine/amide-N
graphitization
slightly decreases,of the remaining
while the ratio carbon
of morestructure. The Raman
thermally spectra of AC-N
stable N-pyridinic and AC-C-
and, perhaps Q-
800increases.
and AC-800 − 1
N, Insamples
general,showas the D- activation
and G-bandtemperature
at 1344 and 1593 cm ,the
increases, respectively (Figure
concentration of
S2), which is usual for disordered graphitic structures. The full
heteroatoms (N and O) decreases. The pyrolysis of polycondensation intermediate results width at half maximum
(FWHM)
in values of G-band
a decomposition of N- for AC-N-700,
and O-containing AC-N-800,
functionalandgroups,
AC-N-900 samples
which startsareataccounted
ca. 600 °C
for 117, 103, and 81 cm −1 , demonstrating a systematic decrease in the FWHM with an
[33]. The decomposition results in the formation of gaseous products, such as CO2 and
increase in activation temperature. It has been shown that G-band FWHM is inversely
NH3 and/or NOx. The formation of gaseous products is one of the processes responsible
proportional to the average size of ordered sp2 -domain La , [36,37]. Using the empirical
for the development of the open porous structure of the final carbon product. In particular,
correlation equation for pyrolyzed nanographites [37], the La of AC-N-700, AC-N-800, and
the formation of ammonia via decomposition of amine/amide groups of polycondensation
AC-N-900 can be estimated as 4.2 nm, 4.9 nm, and 6.4 nm, respectively, i.e., 10–20 graphitic
intermediate results in higher BET surface area due to chemical etching of carbon by
layers. Thus, one can conclude that the La of AC-N samples is slightly increasing with
gaseous ammonia, which above 700 °C, reacts with carboxylic groups and the carbon
an increase in activation temperature. The values of FWHM of AC-800, AC-C-800, and
skeleton, forming more thermally stable pyrrolic, pyridinic, and Q-nitrogen groups
AC-N-800 samples are close, indicating that the activation temperature is a determining
[34,35].
factor forIndeed,
the size XPSof results show that the AC-N-800 sample is more reduced (contains less
sp2 -domains.
oxygen) compared to AC-800
Two-point conductivity of AC-N and AC-C-800 prepared
samples increases without using
approximately by twoN-containing
orders of
precursors. The certain ratio ◦ of amine/amide N-heteroatoms
magnitude with every 100 C increase of activation temperature. The resistivity remains, even at 900 °C, ofeven
the
though
AC-N-700 thissample
ratio, ρas≈expected,
19.5 kOhm.cm decreases withtotemperature
is close the typical one duefor to activated
transformation
carbons.of
amines and amides to more stable forms of N-heteroatoms.
The resistivity of samples AC-N-800 and AC-N-900 are 194 and 9.2 Ohm.cm, respectively.
The
For all decomposition
three samples, theofvalueN- and ofO-containing
resistivity was functional
found togroups results in the formation
be frequency-independent in
of
the range 10 –10 Hz. It suggests that for the AC-N-700 sample, theofelectron
unsaturated − 2 C-C 6 bonds, i.e., an increase in the relative population sp2-carbon, and in
transport
graphitization
via direct continuousof the remaining
pathway carbon structure. Theconductivity
is the predominant Raman spectra of AC-N and
mechanism, while AC-C-
the
800 and AC-800
contributions ofsamples show D- and
other mechanisms G-band at
(electrons 1344 and
hopping and1593 cm , respectively
−1
tunneling between carbon(Figure
S2), which
clusters, is usual for
interfacial disorderedare
polarization) graphitic structures.
negligible [33]. TheTherelatively
full widthhigh at half maximum
resistivity of
(FWHM)
the AC-N-700 values of G-band
sample for AC-N-700,
can be explained by theAC-N-800, and AC-N-900
small concentration and narrowsamples size are
of
accounted for 117, 103, and 81 cm −1, demonstrating a systematic decrease in the FWHM
continuous electron pathways, which is in agreement with the above assumption of smaller
with
La of an
theincrease
AC-N-700 in sample.
activation temperature.
Considering thatIt the
hasestimated
been shown sizethat 2 domains
of spG-band FWHM in theis
inversely
AC-N-800proportional
sample is only to the average
slightly largersize
thanof ordered sp -domainthe
that of AC-N-700,
2 La,strong
[36,37].increase
Using theof
conductivity
empirical with activation
correlation equationtemperature
for pyrolyzed could be related to
nanographites thethe
[37], strong
La of increase
AC-N-700, in AC-
the
2 domains.
concentration
N-800, of ordered
and AC-N-900 canspbe estimated as 4.2 nm, 4.9 nm, and 6.4 nm, respectively, i.e.,
10–20 graphitic layers. Thus, oneAC-C-800,
The conductivity of AC-800, can conclude and AC-N-800
that the Lsamples
a of AC-N is in good correlation
samples is slightly
with the reduction state of the carbon, as characterized
increasing with an increase in activation temperature. The values of FWHM by x(O) at.%. One may argue
of AC-800,
that the decomposition
AC-C-800, and AC-N-800ofsamples O-containing fragments
are close, indicatingof polycondensation intermediatesis
that the activation temperature
a determining factor for the size of sp2-domains.
Two-point conductivity of AC-N samples increases approximately by two orders of
magnitude with every 100 °C increase of activation temperature. The resistivity of the AC-
 Batteries 2023, 9, 436 9 of 17

and the formation of C-C unsaturated bonds is the main mechanism of appearance of
sp2 -domains, which are, in turn, responsible for electronic conductivity. The transformation
of N-amine/amide and N-pyrollic to N-pyridinic and Q-N may also be expected to increase
conductivity, as in the last two forms, N-heteroatoms are included to the π-electrons conju-
gated network. Also, the thermal decomposition of an intermediate with N-heteroatoms
results in a more reduced carbon state, and, as a result, a higher conductivity.

3.3. Electrochemical Properties of AC Samples

Figure 6A shows the stable CV curves of AC-N samples measured in 1 M H2 SO4 at
20 mV/s. The CV curves of AC-N-800 and AC-N-900 samples contain a pair of broad
reversible redox peaks centered around 0.70–0.80 V RHE, conventionally attributed to
the reversible surface redox transition of O-containing groups (quinone-hydroquinone
Batteries 2023, 9, x FOR PEER REVIEW type [10]), and/or N-containing groups (for example N-pyrrolic) (Figure 7). The integral
10 of 18
mass specific capacitance calculated from the CV curves measured at 20 mV/s is 55 F/g,
284 F/g, and 197 F/g for AC-N-700, AC-N-800, and AC-N-900 samples, respectively.

Figure 6. Electrochemical
Figure 6. Electrochemicalcharacterization ofAC
characterization of AC−N samplesinin
−N samples 1M1M
H2H2SO
SO 4. Stable CVs at 20 mV/s
4 . Stable CVs at 20 mV/s
(A);(A);
frequency
frequency dependence of a capacitive component of total impedance C C”
dependence of a capacitive component of total impedance 00 (B);(B); Nyquist
Nyquist plots
plots of of
impedance (C) (right side graph is a zoom of the left side plots).
impedance (C) (right side graph is a zoom of the left side plots).
 Figure 6. Electrochemical characterization of AC−N samples in 1M H2SO4. Stable CVs at 20 mV/s
Batteries 2023, 9, 436 10 of 17
(A); frequency dependence of a capacitive component of total impedance C” (B); Nyquist plots of
impedance (C) (right side graph is a zoom of the left side plots).

Figure 7. Surface redox reactions responsible for surface fast pseudocapacitance phenomena in
Figure 7. Surface redox reactions responsible for surface fast pseudocapacitance phenomena in AC-
AC-N-800 and AC-N-900 samples.
N-800 and AC-N-900 samples.
It is most surprising to observe that the capacitance of the AC-N-900 sample is ca.
30% It smaller
is mostcompared
surprising to observe
to the AC-N-800 that the capacitance
sample, of thetwice
despite the nearly AC-N-900
as highsample
SSA of is ca.
30%thesmaller
former. compared
The SSA ofto thethe AC-N-800
carbon samplessample,
can bedespite
used to the nearly
estimate thetwice as high SSA of
corresponding
thespecific
former. The capacitance
surface SSA of theCcarbon
s , whichsamples can besamples
for the studied used towasestimate µF/cm2
the15corresponding
16, 41, and
for AC-N-700,
specific surfaceAC-N-800, andCAC-N-900.
capacitance Thethe
s, which for values of Cs samples
studied for AC-N-700
wasand16, AC-N-900
41, and 15areµF/cm2
just slightly higher than C ≈ 10–12 µF/cm 2 , expected for 3D carbon electrodes with high
for AC-N-700, AC-N-800, and AC-N-900. The values of Cs for AC-N-700 and AC-N-900
s
while the value of Cs of the AC-N-800 sample
areSSA
just[11],
slightly higher than Cs ≈ 10–12 µF/cm2, expected is a few times higher; one would
for 3D carbon electrodes with
expect the value Cg ≈ 95 F/g for pure double-layer capacitance for carbon electrode with
high SSA [11],2 while the value of Cs of the AC-N-800 sample is a few times higher; one
SSA = 776 m /g and with a corresponding Cs ≈ 10–12 µF/cm2 .
The difference in the electrochemical properties of AC-N samples can be correlated
to their different surface and bulk composition. It has been previously reported that the
capacitance of various carbon electrode materials can be significantly improved by their
surface functionalization [38], resulting in better wettability of pores. In the case of N-
doped carbons, the additional contribution to interfacial capacitance can be attributed to
pseudocapacitance related to the redox transitions of N-heteroatoms. As mentioned earlier,
a nearly linear increase of Cg with x(N)%at. was reported for PAN-derived carbons [26],
and attributed to a pseudocapacitance reaction involving N-pyridinic. Outstandingly high
mass specific capacitance Cg > 800 F/g (in H2 SO4 at 1 A/g) was reported for N-doped
mesoporous carbon, and explained by redox reactions involving pyrrolic and pyridinic
N-heteroatoms [27]. These redox reactions result in the exchange of 1 H+ between carbon
electrode and electrolyte, and, thus, contribute the charge of 1e- per one N-heteroatom
(Figure 8B). The additional mass specific capacitance contribution related to the pseudoca-
pacitance reaction involving N-heteroatoms CN-PS (in F/g) for 1 V range can be estimated as:

F · xN
CN−PS = = xN ·8041 (1)
MC

where xN is an atomic ratio of N-heteroatoms active in the pseudocapacitance reaction.

In order to evaluate the nature of active N-heteroatoms, it is useful to compare the
oxidation potentials of various N-containing organic aromatic molecules; see Table 2. The
comparison of oxidation potential of aniline, pyrrole, and pyridine shows that N-amine
and N-pyrrolic heteroatoms can be oxidized at lower potentials and thus, are more likely
to contribute to pseudocapacitance than N-pyridinic.
 additional mass specific capacitance contribution related to the pseudocapacitance reaction
involving N-heteroatoms CN-PS (in F/g) for 1 V range can be estimated as:
𝐹 ∙𝑥
𝐶 = = 𝑥 ∙ 8041 (1)
𝑀
Batteries 2023, 9, 436
where xN is an atomic ratio of N-heteroatoms active in the pseudocapacitance reaction.11 of 17

Batteries 2023, 2023,

Batteries 9, x FOR
9, x PEER REVIEW
FOR PEER REVIEW 12 of 12
18 of 18

Batteries 2023, 9, x FOR(A)PEER REVIEW (B) 12 of 18

Batteries 2023, 9, x FOR PEER REVIEW 12 of 18
Batteries
Batteries 2023,2023,
2023,
Batteries 9, xx FOR
9, FOR
9, x PEER
FOR Figure
PEERPEER
REVIEW
REVIEW8. 8.
Evolution
REVIEW
Figure Evolutionofofspecific
specific capacitance with cycling
capacitance with cyclingatat2 A/g
2 A/g (A);
(A); dependence
dependence of specific
of specific 12 of
12
capaci-of12
18of 18
18
TableTable
capacitance on2.the
Selected ofN-containing
2. Selected N-containing aromatic organic
aromatic molecules
organic and
molecules the
andredox potential
the redox of their
potential oxidation
of their oxidation
tance on the raterate charge/discharge,
of charge/discharge, measured
measured in
in 1M 1M H2SO
H2 SO 4 (B).
(B).
4[39],[40].
(in bold red),red),
(in bold estimated as E1/2
estimated asof oxidation
E1/2 wave,
of oxidation V SCE
wave, V SCE [39],[40].
Table 2. Selected N-containing aromatic organic molecules and the redox potential of their oxidation
InTable (in2.bold
order Selected
to red),N-containing
evaluate the nature
estimated as aromatic organic
E1/2ofofactive molecules
N-heteroatoms,
oxidation wave, V SCE and itthe
is redox
[39],[40].usefulpotential of theirthe
to compare oxidation
TableTable
Table
(in
2. bold2. Selected
2.
Table Selected
red),
Selected N-containing
N-containing
2. N-containing
Selected
estimated as E aromatic
1/2 aromatic
N-containing of
aromatic oxidationorganic
organic
aromatic
organic molecules
molecules
organic
wave, V
molecules molecules
SCE
and andredox
and the
the
[39],[40].
the redox
andredox
the potential
potential
redox
potential of their
of their
potential
of their oxidation
oxidation
of their
oxidation oxidation
oxidationAniline
potentials of various
1.14 V N-containing
V 1-Naphtalamine organic0.88aromatic
V molecules;
1-Aminoantharcenesee Table 2. The 0.75 V
(in (in Aniline
(in bold
bold red),red),
red),
bold 1.14 as
estimated
estimated as
estimated EE1/2
asof
1/2
1-Naphtalamine
of oxidation
oxidation
E1/2 wave,
wave,
of oxidation V
wave, 0.88
V SCE
SCE V [39],[40].
[39],[40].
[39],[40].
V SCE 1-Aminoantharcene 0.75 V
(in bold red),
comparison of estimated E1/2 of oxidation
oxidationaspotential wave,
of aniline, V SCE [39,40].
pyrrole, and pyridine shows that N-amine
Aniline 1.14 V 1-Naphtalamine 0.88 V 1-Aminoantharcene 0.75 V
and N-pyrrolic
Anilineheteroatoms
1.14 V can be oxidized at lower
1-Naphtalamine 0.88potentials
V and thus, are more likely
1-Aminoantharcene 0.75 V
Aniline
Aniline 1.14
1.14 VV V V 1-Naphtalamine
1-Naphtalamine1- 0.88
0.88 VV V V 1-Aminoantharcene 1-
1-Aminoantharcene 0.75 V
V V
to contribute
Aniline Aniline 1.14
to pseudocapacitance
1.14 1-Naphtalamine
than N-pyridinic. 0.880.88 1-Aminoantharcene 0.75 V0.75 0.75
Naphtalamine Aminoantharcene

Pyrrole
Pyrrole 1.24 V
1.24 V 1H-Indole
1H-Indole 1.16 V
1.16 V
Pyrrole 1.24 V 1H-Indole 1.16 V
Pyrrole
Pyrrole 1.24 VV
1.24 1H-Indole
1H-Indole 1.16 VV
1.16
Pyrrole
Pyrrole 1.24 V
Pyrrole 1.24 V V
1.24 1H-Indole
1H-Indole
1H-Indole 1.16 V
1.16 V V
1.16

Pyridine
Pyridine2.26 V2.26 V Quinoline
Quinoline 2.14 V
2.14 V
Pyridine 2.26 V Quinoline 2.14 V
Pyridine 2.26 V Quinoline 2.14 V
Pyridine 2.26 V Quinoline 2.14 V
Pyridine
Pyridine 2.26 V
Pyridine2.26 V V
2.26 Quinoline
Quinoline
Quinoline 2.14 V
2.14 V V
2.14

Considering
Considering that that
for the forAC-N-800
the AC-N-800 sample, sample,the total ratioratio
the total of N-heteroatoms
of N-heteroatoms is 3.3isat.%
3.3 at.%
Considering that for the AC-N-800 sample, the total ratio of N-heteroatoms is 3.3 at.%
and ca.
and 71%
ca.
and ca. 71% Considering of
71% these
of atoms
these are
atoms N-amine
are N-amine or N-pyrrolic,
or N-pyrrolic,
xN =x N =x 2.34%, and
N = 2.34%, C
andN-PSC=N-PS
CN-PS = 188 F/g188 = F/g
188 for
F/gat.%
for
of these atoms that arefor the AC-N-800
N-amine sample, the
or N-pyrrolic, total ratioand
2.34%, of N-heteroatoms is 3.3
this Considering
sample,
this sample, which thatcan
which forcanthe AC-N-800
well account
well account sample,
for the
for the difference
total ratio
difference
the ofbetween
between N-heteroatoms
C g (284
C F/g)
g (284 isF/g)
3.3 at.%
and the
and the
for this sample,
and ca.
Considering
Considering which
71%
Considering canthat
ofthat
these
that for
for well
atoms
the
the
for account
are
AC-N-800
AC-N-800
theN-amine forsample,
N-amine
AC-N-800 thesample,
sample, difference
or N-pyrrolic,
theother
the total
totalbetween
ratio
ratio
theother
total xratio
of
of Cof
g (284
N = 2.34%, F/g)
and
N-heteroatoms
N-heteroatoms
N-heteroatoms and
CN-PS is the
is=3.3
188
3.3 F/g for
at.%
isat.%
3.3
and expected
expected ca.
expected 71%
double doubleofdouble
these
layer layer atoms
capacitance
layer
capacitance are
capacitance
(95 (95 F/g).
F/g). (95
On orF/g).
OnN-pyrrolic,
the the
On
other the xhand,
hand, N = 2.34%,
hand,
AC-N-900 and
AC-N-900
AC-N-900 Ccontains
N-PS =
contains 188
contains
1.5 F/g
1.5
at.% forat.%
at.%
1.5 at.%
and
and this
ca.
ca.
and 71%sample,
71%
ca. of
of
71% these
ofwhich
these atoms
atoms
these can
atomsarewell
are account
N-amine
N-amine
are N-amine or
or for the
N-pyrrolic,
N-pyrrolic,
or difference
N-pyrrolic,x
x N=
N = between
2.34%,
2.34%,
x and
and
N = 2.34%, CCN-PS
C
andg (284 F/g) and the
N-PSC== 188
188
N-PS = F/g
F/g
188 for
for
F/g for
this
of sample,
N-heteroatoms, which
of N-heteroatoms,
of N-heteroatoms, only can
only
58% well
58%
only
of ofaccount
which
58% ofare
which which for
are
N-amine the
N-amine difference
are N-amine
or theor between
N-pyrrolic,
or N-pyrrolic,
N-pyrrolic, and, C
and,g
thus, (284
thus,
and, F/g)
xNF/g)x
thus,
N =and
= 0.87%, 0.87%,
xN =1.5the
0.87%,
this
this expected
sample,
sample,
this sample, double
which
which which layer
can
can capacitance
well
well
can account
account
well account(95
for
for F/g).
the
the
for On
difference
difference
the other
difference hand,
between
between AC-N-900
betweenC
C (284
gg (284
C g (284
contains
F/g) and
and
F/g) the
the
and at.%
the
expected
and and CN-PS
and Cdouble
=N-PS
70 =F/g
70 layer
are
F/g capacitance
significantly
are significantly (95
lowerF/g).
lower Oncompared
compared thetoother hand,
to AC-N-800.
to AC-N-900 contains 1.5 at.%
CN-PSof
expected
expected
= 70
expected
F/g
N-heteroatoms,
double
double
are
layer
double
significantly
layer only
capacitance
layer 58%lower
capacitance
capacitanceof(95
(95 compared
which
F/g).
F/g).
(95 are
Onlow
On
F/g). N-amine
the
the other
other
Oncapacitance
the orAC-N-800.
AC-N-800.
hand,
hand,
other N-pyrrolic,
AC-N-900
AC-N-900
hand, AC-N-900and, thus,
contains
contains xN at.%
1.5
1.5
contains =at.%
0.87%,
1.5 at.%
of N-heteroatoms,
However,
However, However, one
one= still only
still
one
hasare 58%
has
still to of
has which
explain
to
to significantly explain
explain the low are
the N-amine
low
the
capacitance or
capacitance N-pyrrolic,
oftotheof theof and,
AC-N-700
the
AC-N-700 thus,
AC-N-700
sample, xsample,
sample,N = 0.87%,
which which which
of
of and
of C N-PS
N-heteroatoms,
N-heteroatoms,
N-heteroatoms, 70 F/g
only
only 58%
58%
only of
of
58% which
which
of lower
are
are
which compared
N-amine
N-amine
are N-amine or
or AC-N-800.
N-pyrrolic,
N-pyrrolic,
or and,
and,
N-pyrrolic, thus,
thus,
and, xx
thus,
NN= =x0.87%,
0.87%,
N = 0.87%,
and more
has Cthan
has more=than
70 than
F/g
doubleare significantly
doubletotal x(N)
total lower
compared
x(N) tocompared
compared to AC-N-800, to74%
AC-N-800.
tocapacitance
AC-N-800, 74% of which
74% are N-amine and and
theofAC-N-700
which aresample,
N-amine and
N-PS
has more double total x(N) compared AC-N-800, of which are N-amine
andand
and C N-PS
N-PS
N-pyrrolic, CHowever,
CHowever,
==N-PS
N-pyrrolic, 70
70
andF/g
=F/g
70
one are
yet
and
one
are
F/g
still
a
yet
still
has
lowera
has
significantly
significantly
are toC
lower
to
significantlyexplain
explain lower
lower
s value.
C s
lower
the
the
compared
compared
low
According
value.
low
compared tomeasurements
to
capacitance
According the AC-N-800.
AC-N-800.
the of
of
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AC-N-800.
the AC-N-700
of sample,
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of which
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AC-N-800, 74% ofofconductivity,
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AC-N-700
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sample one
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has to
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explain
x(N) tocompared
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lower lowerlow
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capacitance
low
AC-N-800,
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concentration of
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74% the
the
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the AC-N-700
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We We
has
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has more than
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than yettotala lower
total x(N)
x(N)
total C s value. According the measurements of conductivity, the
compared
compared to
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AC-N-800, 74%
74% of which
of which areare
are N-amine
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N-pyrrolic,
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only Cs x(N)
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to 74%
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AC-N-700
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pseudocapacitance phenomena. concentration
phenomena. of orderedof
N-heteroatoms
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disordered
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carbon
may speculate
AC-N-700
AC-N-700 sample
sample thatsignificantly
has
has only N-heteroatoms
significantly lower incorporated
concentration of to graphitic
ordered domains
graphitic are
domains. capable
We to
mayAC-N-700
speculate
structure
structureare sample
that
arguably
are only
arguablyhas
inactive too, lower
significantly
N-heteroatoms
inactive due
too, lower
due concentration
thetoconcentration
toincorporated
lack of the
the lack ofof
to ordered
of
graphitic
possibility
the graphitic
ordered
domainsgraphitic
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possibility domains.
are domains.
capable
of stabilizing We
the extra
the We
toextra
may
may contribute
speculate
speculate
may speculate to
that
that pseudocapacitance
only
only
that N-heteroatoms
N-heteroatoms
only N-heteroatoms phenomena.
incorporated
incorporated
incorporated N-heteroatoms
toof
to graphitic
graphitic
to domains
domains
graphitic of
domainsdisordered
are capable
are capable
areaniline,carbon
capableto to
to
contribute
charge added
charge to by
added pseudocapacitance
redox
by redoxtransition.
transition. phenomena.
Indeed,Indeed, comparison N-heteroatoms
comparison oxidation
of of potentials
oxidation disordered
potentialsof carbon
of aniline,
Batteries 2023, 9, 436 12 of 17

AC-N-700 sample has significantly lower concentration of ordered graphitic domains. We

may speculate that only N-heteroatoms incorporated to graphitic domains are capable
to contribute to pseudocapacitance phenomena. N-heteroatoms of disordered carbon
structure are arguably inactive too, due to the lack of the possibility of stabilizing the extra
charge added by redox transition. Indeed, comparison of oxidation potentials of aniline,
1-naphtylamine, and 1-aminoantracene (Table 2) clearly shows that the addition of an
aromatic ring to the conjugated π-electron network facilitates the oxidation of amine. The
same trend can be seen by comparison of oxidation potentials of pyrrole and 1H-indole,
and pyridine and quinoline. Thus, it is reasonable to suggest that N-heteroatoms included
into the extended conjugated π-electron network (conductive graphitic domain) are more
active in the pseudocapacitance phenomenon than isolated N-heteroatoms.
In summary, we suggest that the high pseudocapacitance of carbon requires simulta-
neous high content of both graphitic domains and N-pyrrolic heteroatoms, like N-doped
mesoporous carbons in Ref. [27], or, in a lesser extent, sample AC-N-800 in the present
study. For the preparation of N-doped AC materials, 800 ◦ C appears to be an optimal
activation temperature, as in the products of activation at lower temperature, the major-
ity of N-heteratoms are not linked to the conductive graphitic domains, and at higher
temperature, N-heteroatoms are gradually transformed to less active N-pyridinic and
Q-N heteroatoms.
Impedance spectroscopy is a valuable tool to have a deeper insight on the dependence
of interfacial capacitance on the rate of charging of the interface. The Nyquist plots of
AC-N samples are shown in Figure 6C. The observed curves can be qualitatively fitted
by an equivalent circuit depicted in the inset. It must be noted that this equivalent circuit
serves only for qualitative explanation of the impedance behavior and for the comparison
between similar carbon materials. The impedance of the complex porous system is properly
described by models based on the transmission line concept [41].
This circuit in Figure 6C can be interpreted as follows: R1 is a resistance of the elec-
trolyte, C1 is the interfacial capacitance of the outer surface of carbon deposit, C2 is the
interfacial capacitance of the surface of large open pores easily accessible for the electrolyte,
R2 is the resistance of the electrolyte inside of these pores, R3 -Q is an impedance of smaller
pores, which are the branches of the bigger open pores. Q is a constant phase element (CPE)
with a as the CPE constant. In the case of the impedance of a pore, the value of a depends
on the relative values of the length of small pores lp and AC penetration depth λ, namely a
= 0.5 for lp > λ, and a ≈ 1 for lp < λ. The value of λ can be estimated by Equation (2) [42]:
s
1 σd p
λ= (2)
2 2ω Cs

where σ is the conductivity of the electrolyte, dp is the pore diameter, ω = 2πf is the angular
frequency, and Cs is the surface specific capacitance. According to Equation (3), for thinner
pores, the modulation penetration depth is shorter, and the pore-specific impedance (i.e.,
a = 0.5) is observed already at lower modulation frequencies.
The parameters of the fitting of experimental Nyquist diagrams are given in Table S1.
The EIS diagrams of AC-N-900 can be well fitted by the circuit depicted in Figure 7 with
a = 0.9. It demonstrates the open porous structure of the sample with wide and short pores,
easily accessible for electrolytes for a whole range of utilized frequencies. Also, the value of
capacitive component of total impedance C00 :

1
C 00 = − (3)
Im( Z )·ω

where Z is a total impedance, which remains nearly constant up to the intermediate range
of frequencies f ≈ 10 Hz (Figure 6B). At higher frequencies, the decrease with the slope
−1 of log C00 —log f is observed, which is an indication of the influence of resistance of the
electrolyte in pores.
Batteries 2023, 9, 436 13 of 17

In contrast to AC-N-900, the EIS diagrams of AC-N-700 can be fitted only with a = 0.5,
demonstrating that the narrow pores are longer, and lp > λ even for low frequency (0.1 Hz).
In the case of AC-N-800, the best fit was obtained with a = 0.90; However, it appears that
the fit is not correct at a low frequencies range, as AC penetration depth becomes deeper,
and narrower and longer pores are engaged to the charge storage. The fit for the AC-N-800
sample is only possible assuming the value of a varying with applied frequency, which is
an indication of the non-uniform size of the pores. The C00 component decrease observed
already at low frequencies with the slope ca. −0.75 indicates the limitation related to both
resistance of the electrolyte, and the AC penetration depth dependence of frequency.
In summary, EIS analysis confirms the assumption of the fact that the diameter of the
pores is increasing as activation temperature increases (from AC-N-700 to AC-N-900), and
thus, the pores are getting more open, facilitating the accessibility of the electrolyte (lower
R2 and R3 ), and penetration of the AC-signal.
Figure 8A shows the dependence of mass specific capacitance of AC-N samples on the
number of charge/discharge cycles applied at 2 A/g. All samples demonstrated excellent
stability within the 1000 cycles. It is important to note that the capacitance of the AC-
N-900 sample significantly increased in the first hundred charging cycles. This increase
in capacitance can be attributed to improving the accessibility of inner pore volumes of
AC-N-900 by potential cycling. Indeed, the surface AC-N-900 sample is most reduced,
compared to other AC-N samples, and, arguably, less hydrophilic. Also, the surface of
ordered graphitic domains, of which AC-N-900 has the highest content, is hydrophobic.
Thus, originally the volume of micropores of AC-N-900 can be less accessible compared
to other AC-N samples, despite a larger average diameter, suggested earlier. However,
periodic oxidative polarization of the carbon electrode results in the partial oxidation of
the carbon surface, its improved hydrophilicity, and better accessibility of pores. We note
that the impedance measurements discussed above were performed after the stability tests
completed by 1000 charge/discharge cycles.
Figure 8B shows the dependence of specific capacitance on the charging rate. These
measurements were also performed after 1000 charging cycles. As expected, all samples
demonstrated a decrease in specific capacitance, as the charging rate increases from 0.5 A/g
to 20 A/g. However, the loss of capacitance systematically depends on the activation tem-
perature: it is 93%, 32%, and 19.5% for AC-N-700, AC-N-800, and AC-N-900, respectively.
This observation is in agreement with the assumption of wider pores of the AC-N-900
sample, and their easier accessibility for electrolyte species, compared to AC-N-800 and
AC-N-700 samples.

4. Discussion
The addition of ammonium citrate to sucrose precursor for the synthesis of activated
carbon results in a significant change in the structure and properties of the final product. The
cross-linked polycondensation intermediate formed from ammonium citrate and sucrose
(Figure 2C) contains amide and imide groups, which are decomposed above 600 ◦ C [43]
nitrogen groups and the formation of more stable aromatic N-containing fragments of the
carbon matrix. These phenomena result in a significantly higher surface area of AC-N-
800 synthesized with ammonium citrate compared to AC-C-800, synthesized with citric
acid additive. Moreover, AC-N-800 has lower oxygen content x(O), and higher electrical
conductivity. An increase in activation temperature results in a decrease in the remaining
content of N-heteroatoms.
All synthesized AC samples are electrically conductive, demonstrating constant elec-
trical resistance in the frequency range 10−1 –106 Hz. This is an indication that, already after
activation at 700 ◦ C, the continuous network of conductive sp2 -carbon domains is devel-
oped. An increase in the activation temperature from 700 to 800 and to 900 ◦ C results in ca.
100-times increase in the conductivity of carbon samples. The FWHM of Raman spectra
G-band of these samples indicates a slight increase in the average size of ordered graphitic
domains; however, the main factor responsible for the strong increase in conductivity is
Batteries 2023, 9, 436 14 of 17

assumed to be a strong increase in the concentration of ordered graphitic domains with

activation temperature. It is important to note that the estimated size of these domains
remains relatively small, so that no graphitic domains are detected by XRD, and thus,
even after activation at 900 ◦ C, the final structure can be characterized as a disordered
graphitic structure.
The samples prepared from the sucrose and ammonium citrate mixture after activation
at 800 and 900 ◦ C (AC-N-800 and AC-N-900) demonstrate excellent properties as EDLC
electrode materials. In particular, the AC-N-800 sample demonstrates very high mass- and
surface-specific capacitances, Cg = 320 F/g and Cs = 41.4 µF/cm2 , respectively, in 1M H2 SO4
at 2A/g. Such an unusually high Cs value is arguably related to the combination of two
factors: the presence of a relatively high surface concentration of N-pyrrolic heteroatoms,
responsible for fast redox surface transitions (Figure 8), and the high concentration of
ordered small graphitic domains, facilitating the redox reactions. The lower content of
both graphitic domains (AC-N-700 sample) and N-pyrollic heteroatoms (AC-N-900 sample)
resulted in lower specific capacitance.
It has to be mentioned that outstandingly high capacitance (≈ 600 F/g) in concentrated
H2 SO4 has been observed for commercial AC CH900-20 (Kuraray Co., Tokyo, Japan), with
no N-heteroatoms and predominantly amorphous structure [44]. The observed capacitance
was attributed to the intercalation of H+ to the extent of the formation of a stoichiometric
C6 H composition. However, this process was strongly limited by the kinetic of charge
transfer and solid-state diffusion of H+ , and high intercalation extent required several hours
of charging.
In order to evaluate the contribution of mass transport-controlled processes into the
charge capacitance, the CVs of AC-N-800 were measured with different potential sweep
rates w from 1000 to 0.5 mV/s (Figure S3A,B). The dependence of CV currents on the
sweep rate is close to linear, at least for rates not very high w < 200 mVs/(Figure S3C),
demonstrating a negligible contribution of mass transport-controlled processes to the
charge of CV curves at these conditions. At higher sweep rates, the dependence deviates
from linear as the time of single sweep becomes comparable with the RC constant of the
cell (ca. 0.5 s). Following the deconvolution method suggested earlier [27], the fast charging
contribution to capacitance CDL was estimated by extrapolating C(w) vs. w−1/2 dependence
to w→ ∞ (w−1/2 → 0); see Figure S3D:

C(w) = CDL + kw−1/2 (4)

Thus, by estimating that the capacitance related to fast charging is ca. 93% of the
total capacitance measured at 20 mV/s, this confirms negligible contribution of any mass
transport-controlled process to charge capacitance at these conditions. We can conclude
that the kinetics of pseudocapacitance reaction involving H+ addition/elimination from
the carbon network is strongly facilitated by the presence of N-heteroatoms.
An increase in the activation temperature from 800 to 900 ◦ C results in the widening
of the pores and better accessibility of the pores for electrolyte species, and lower pores
resistance. The full accessibility of pores inner volume requires a few hundreds of potential
cycling in order to improve the hydrophilicity of the carbon surface, which is too reduced
and too hydrophobic after thermochemical activation at 900 ◦ C. After the cycling, the
easy accessibility of pores inner volume of AC-N-900 is indicated by the lower decrease of
capacitance when the charging rate is increased from 0.5 A/g to 20 A/g, and by the results
of the fitting of EIS spectra. For the AC-N-900 sample, the EIS diagram was qualitatively
described by the model, assuming that all pores are available for charge storage even at high
charging rates (high modulation frequencies f ). On the other hand, the AC-N-700 sample
demonstrated the strongest decrease in capacitance with an increase in charging rate, and
the capacitance is limited by the depth of penetration of potential modulation, even at low
charging rates (low frequencies). The AC-N-800 sample also shows a stronger dependence
of capacitance on the charging rate. Nevertheless, this sample demonstrates the highest
Batteries 2023, 9, 436 15 of 17

specific capacitance in the wide range of charging currents due to the simultaneously
relatively high content of N-pyrrolitic heteroatoms and ordered graphitic domains.

5. Conclusions
We have demonstrated that the addition of ammonium citrate to sucrose has a strong
influence on the structure and composition of resulting AC material, and on its electrochem-
ical properties. The N-doped AC with electrochemical properties offering high performance
as an EDLC electrode material has been synthesized. In particular, the AC-N-800 sample,
prepared by activation at 800 ◦ C, demonstrated mass specific capacitance of 320 F/g at
2 A/g in 1M H2 SO4 . We attributed the higher capacitance of the AC-N-800 sample to the
higher content of N-heteroatoms, in particular N-pyrrolic and N-amine heteroatoms, which
are arguably more active in the redox pseudocapacitive reaction than N-pyridinic and Q-N
heteroatoms. The ratio of N-pyridinic and Q-N heteratoms increases with the activation
temperature increase, resulting in lower capacitance of the AC-N-900 sample, despite its
higher SSA compared to AC-N-800. On the other hand, the low capacitance of the AC-
N-700 sample, which also contains a high ratio of N-pyrrolic and N-amine heteroatoms,
shows that only N-heteroatoms included in the ordered graphitic domains are active in the
pseudocapacitance phenomena. The latter can be explained by the facilitated stabilization
of an extra charge by the conjugated π-electrons network of the graphitic domain.
The improvement of the performance of N-doped AC electrode materials, prepared
by the described two-step thermal activation method, can arguably be achieved by further
optimization of the synthesis conditions. In particular, the ratio between ammonium
citrate and sucrose precursor is expected to have an influence on the atomic ratio of N-
heteroatoms in the resulting AC material. The study of electrochemical properties of
AC-N materials in organic electrolytes is expected to demonstrate the influence of the
hydrophilicity/hydrophobicity of the materials on their electrochemical properties. Finally,
a detailed analysis of electrochemical impedance of AC-N electrode materials with variable
electrode loading will provide a better understanding of the influence of carbon porosity
on its electrochemical performance. These studies are currently being performed as a
follow-up of the present work.

Supplementary Materials: The following supporting information can be downloaded at: https:
//www.mdpi.com/article/10.3390/batteries9090436/s1, Figure S1: Typical SEM images of AC-N-700
(A), AC-N-800 (B) and AC-N-900 (C) samples; Table S1: Parameters of the fit of Nyquist diagrams
by equivalent circuit in Figure 6; Figure S2: Raman spectra of AC-N samples (A) and AC-N-800,
AC-C-800, and AC-800 samples (B); Figure S3: CV curves of AC-N-800 sample in 1M H2 SO4 measured
at different sweep rates (A,B); dependence of CV current at direct sweep at −0.15 V MSE on sweep
rate (C); dependence of integrated mass specific capacitance on w−1/2 .
Author Contributions: Conceptualization, C.P.-H. and S.N.P.; methodology H.B., L.T.P.; experimental
work T.K. (vast majority of the work), D.B., L.T.P. and S.N.P.; data analysis, T.K., D.B. and S.N.P.
project administration and funding C.P.-H., S.N.P. and D.B.; manuscript preparation T.K., S.N.P. and
C.P.-H. All authors have read and agreed to the published version of the manuscript.
Funding: This work is funded by the INFINE ANR (France) project ANR-21-CE08-0025-01.
Data Availability Statement: The raw experimental data for the results discussed in the present
paper can be provided by the authors of the manuscript on demand.
Acknowledgments: The authors are grateful to the staff of ICPEES for performing and assisting
in the materials characterization: Sécou Sall helped with ATR-FTIR experiments, Fabrice Vigneron
helped with BET measurements, Thierry Dintzer performed SEM imaging, Vasiliki Papaefthymiou
performed XPS measurements and guided data analysis. Fréderic Antoni (ICube, Strasbourg) guided
Raman experiments.
Conflicts of Interest: The authors declare no conflict of interest.
Batteries 2023, 9, 436 16 of 17

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