Carbon 167 (2020) 896e905

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Facile regulation of carbon framework from the microporous to low-

porous via molecular crosslinker design and enhanced Na storage
Fei Xu a, b, *, Haojie Han a, Yuqian Qiu a, En Zhang b, Hlib Repich a, Changzhen Qu a,
Huiwu Yu a, Hongqiang Wang a, **, Stefan Kaskel b, ***
a
School of Materials Science and Engineering, Northwestern Polytechnical University and Shaanxi Joint Laboratory of Graphene (NPU), Xi’an, 710072, PR
China
b
Technische Universita€t Dresden, Bergstrasse 66, 01062, Dresden, Germany

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

Article history: Rational manipulation of the carbon framework from the microporous to nonporous via a molecular
Received 13 April 2020 design approach is interesting but challenging. Herein, we report a versatile strategy for transforming the
Received in revised form microporous carbon framework to the low porous one by an elaborate molecular crosslinker design in
22 May 2020
the polystyrene (PS) precursor. Direct coupling of benzene rings in PS via Scholl reaction yields hyper-
Accepted 27 May 2020
Available online 27 May 2020
crosslinked PS-derived carbon with low porous framework, while insertion of methylene crosslinker into
PS via a solvent knitting strategy leads to microporous carbon framework. The results show that
methylene crosslinker functions as molecular-scale soft templates for facilitating micropores, whereas
Keywords:
Carbon microporosity regulation
direct linking PS chains promotes aromatization and mitigates micropore formation during the pyrolysis.
Low porous carbon The distinct carbon frameworks derived from similar precursor and pyrolysis condition provide an
Hypercrosslinking intriguing platform for structure-property relationship study, as preliminarily exemplified by the
Porous polystyrene application in Na ion storage. The low-porosity carbon shows higher initial Coulombic efficiency and
Crosslinker superior capacity thanks to its low surface area and enhanced Na insertion into pseudo-graphitic
Na ion storage microcrystal structure. The present protocol opens up new avenues towards flexible carbon frame-
work porosity manipulation at molecular level and would trigger further efforts for low-porosity carbons
in energy storage.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction
Exploring advanced carbon materials is of fundamental impor-
tance for the development of current state-of-the-art electro-
chemical energy storage/conversion devices, benefitting from their
intriguing characteristics such as tailored pore structures, controlled
surface functionalities and excellent conductivity [1e10]. Depend-
ing on the application requirements, delicate control over the
porosity present in carbon materials is essential for boosting elec-
trochemical energy storage performances. For example, reducing
micropores with low specific surface area and defects helps to
* Corresponding author. School of Materials Science and Engineering, North-
western Polytechnical University and Shaanxi Joint Laboratory of Graphene (NPU),
Xi’an, 710072, PR China.
** Corresponding author.
*** Corresponding author.
E-mail addresses: feixu@nwpu.edu.cn (F. Xu), hongqiang.Wang@nwpu.edu.cn
(H. Wang), stefan.kaskel@tu-dresden.de (S. Kaskel).
increase the first-cycle Coulombic efficiency and is also beneficial for
plateau intercalation capacity in Li/Na ion batteries [6,11e14]. While
constructing copious micropores with high specific surface area is
necessary for accumulating sufficient ions to enhance electrical
double layer capacitances, and the meso- and macropores for rapid
ion diffusion/transport [4,15e20]. Therefore, substantial effort has
been devoted to tailor the porosity in carbon materials at different
length scales ranging from micropores to macropores for potential
performance breakthroughs.
Significant advances have been made in engineering the
porosity at meso- and/or macropore scale in the past two decades,
especially with the development of templating strategies. For
example, macropores (>50 nm) can be constructed by using large-
size templates such as silica, polymer beads or colloidal crystals;
mesopores (2e50 nm), especially those with ordered structures,
can be readily fabricated via self-assembly involving block co-
polymers as soft templates via microphase separation, or by the use
of nanocasting with mesoporous silica templates [21,22]. However,

https://doi.org/10.1016/j.carbon.2020.05.081
0008-6223/© 2020 Elsevier Ltd. All rights reserved.
 F. Xu et al. / Carbon 167 (2020) 896e905
research on efficient strategies for control over the microporosity
(<2 nm) within carbon frameworks largely lags behind. This is
because the microporous characteristics are either governed by the
types of precursors or directed through carbonization/activation
conditions. For a given precursor, the use of chemical or physical
activation can achieve developed microporosity with high surface
area, whereas extremely increasing the carbonization temperature
(e.g. 1000
C or higher) could give rise to the decrease of micro-
porosity to some extent [14,23e25]. However, the high tempera-
ture treatment raises cost, and the carbon materials with distinct
micropososities either from different origins or pyrolysis conditions
also show concurrent change in surface chemistry, conductivity and
other microstructures, restricting systematic structural-property
investigation. Consequently, readily manipulating the carbon
framework from the microporous to nonporous on a given type of
precursor and pyrolysis condition is quite difficult, if not impossible
to achieve. Our previous work shows that it is possible to switch
carbon frameworks from the microporosity to non- or low-porosity
[26,27]. However, the reported protocols only worked for special
carbon precursors of conjugated polymers, which limit the flexi-
bility in molecular design and are of high cost for some conjugated
polymers. It is thus in high demand to develop versatile methods
for adjusting carbon framework between the microporous and
nonporous using novel precursors, which should not only possess
low cost for potential large-scale production, but also enable a
flexible molecular design possible.
Herein, we report a versatile molecular crosslinker design strat-
egy to manipulate the carbon framework microporosity using low-
cost polystyrene (PS) resins as raw materials. Hypercrosslinking of
styrenic polymers has been prevalent in designing porous polymer
and corresponding carbons with tremendous micropores or hier-
archical pore structures in the past several years [28e35]. However,
to the best of our knowledge, constructing low-porosity or nonpo-
rous carbons from hypercrosslinking strategy remains scarce,
probably associated with the intrinsic properties of crosslinkers.
Encouragingly, by elaborate design of crosslinker molecular struc-
ture between PS chains, we demonstrate that the transformation
from the microporous to nonporous frameworks can be accom-
plished in PS-derived carbons. Specifically, low-porosity carbon
derived from hypercrosslinked PS (LPCHP) was obtained by direct
coupling pendant benzene rings on the PS chains using the Scholl
reaction [36,37]; whereas microporous carbon (MICHP) was con-
structed with methylene (-CH2-) crosslinker between benzene rings
via a solvent knitting crosslinking strategy (Scheme 1) [38,39]. Un-
der a relatively low carbonization temperature of 800
C, LPCHP
Scheme 1. Schematic illustration of the synthesis process of LPCHP (Low porosity) and MICHP (Microporosity) via hypercrosslinking and carbonization of PS with distinct
crosslinkers.
897
exhibits low surface area of 5 m2 g1, while the surface area of MICHP
is up to 387 m2 g1. The -CH2- crosslinker probably acts as molecular-
scale soft organic template for producing micropores, while direct
linking PS chains via benzene rings with sp2 carbon is beneficial for
aromatization and suppressing micropore formation. As prelimi-
narily exemplified by the application in Na ion storage, LPCHP with
low porosity is able to enhance initial Coulombic efficiency (ICE) and
boost Na ion insertion into graphite-like microcrystal structure,
allowing superior reversible capacity and rate capability.
2. Experimental
2.1. Materials synthesis
Preparation of PS. PS was synthesized by the bulk polymeriza-
tion. Prior to use, monomer styrene was passed through a column
filled with Al2O3 to remove the inhibitor. 15 mL of styrene and 0.15 g
of azodiisobutyronitrile as initiator were placed into a 50 mL flask.
The reaction was first heated to 60
C with magnetic stirring for 6 h
under nitrogen atmosphere and then the temperature was elevated
to 90
C for 2 h without stirring. After cooling to room temperature,
15 mL of toluene was added to dissolve the PS completely, followed
by adding excess of ethanol to precipitate PS from the solution. The
PS was isolated by filtration and then dried at 30
C for 24 h.
Preparation of hypercrosslinked PS. The hypercrosslinked PS with
direct linking of benzene rings on the PS chains (or self-
crosslinking, HPP-S) was prepared using the Scholl coupling reac-
tion. Specifically, 0.4 g of PS and 50 mL of CH2Cl2 were placed into a
two-neck flask equipped with a reflux condenser and a moisture-
removing trap. The mixture was stirred at room temperature to
completely dissolve the PS. Then anhydrous AlCl3 catalyst (1.5 g)
was added and the reaction was heated to reflux with stirring for
24 h. After cooling to room temperature, the mixture was quenched
with 40 mL of HCl-H2O mixed solution (v/v ¼ 1:3), and the solid
product was filtered off, washed several times with a mixed solu-
tion of HCl and acetone. Further purification was carried out by
Soxhlet extraction with ethanol for 48 h. The polymer was obtained
as a pale yellow solid (~0.36 g) by drying in a vacuum oven at 70
C
for 24 h.
The hypercrosslinked PS with -CH2- crosslinker (HPP-CH2) was
synthesized by solvent knitting strategy [38]. Specifically, 0.4 g of
PS was dissolved in 20 mL of CH2Cl2 under nitrogen atmosphere in
a three-neck flask equipped with a reflux condenser. Subsequently,
anhydrous AlCl3 was added to the pre-cooled solution (0
C) under
vigorous stirring, allowing reacting at 0
C for 4 h, and then 30
C
898 F. Xu et al. / Carbon 167 (2020) 896e905
for 8 h, 40
C for 12 h, 60
C for 12 h and finally 80
C for 24 h. After
cooling to room temperature, the mixture was quenched with
40 mL of HCl-H2O (v/v ¼ 1:3), and the solid product was filtered off,
washed several times with a mixed solution of HCl and acetone.
Further purification was done by Soxhlet extraction with ethanol
for 48 h and the product was finally dried in a vacuum oven at 70
C
for 24 h. The HPP-CH2 was obtained as a dark brown solid (~0.53 g).
Preparation of hypercrosslinked PS-derived carbons. The as-
prepared hypercrosslinked PSs were carbonized at 800
C for 3 h
in nitrogen gas flow (100 mL min1) with a heating rate of 5
C min1,
thus obtaining the resulting carbons with distinct microporosity.
2.2. Materials characterizations
Fourier transform infrared (FT-IR) spectra were recorded using a
Thermo Scientific iS50 Spectrometer (wavenumber range 4000-
500 cm1). Solid-state 13C CP/MAS NMR spectra were performed on
an Agilent 600 M spectrometer with a spinning rate of 8 kHz. N2 and
CO2 adsorption and desorption isotherms were measured on a
Micromeritics ASAP 2020 analyzer at 77 K and 273 K, respectively.
The Brunauere-Emmette-Teller method is used to determine the
surface area (SBET), and pore size distribution is analyzed through a
density functional theory (DFT) model assuming a slit pore geom-
etry from N2 adsorption and desorption isotherm. Total pore volume
was obtained at relative pressure P/P0 ¼ 0.995. Thermogravimetric-
Mass spectrum (TG-MS) analysis was performed from room tem-
perature to 800
C with a heating rate of 10
C min1 under argon
atmosphere. Transmission electron microscope (TEM) in-
vestigations were carried out using a JEOL JEM-2100F with acceler-
ating voltage of 200 kV. The field-emission scanning electron
microscopy (FE-SEM) images were collected on a FEI Talos F200X
field-emission scanning electron microscope. X-ray diffraction
(XRD) patterns were measured on a X’Pert PRO MPD (Cu Ka radia-
tion, 0.154 nm) at room temperature. Raman spectra were per-
formed on a Renishaw inVia Laser Micro-Raman Spectrometer
excited by a 532 nm He-Ne laser with a laser spot size of 1 mm and a
laser power of 10%. X-ray photoelectron spectroscopy (XPS) mea-
surements were carried out on an ESCALAB 250 Spectrometer.
2.3. Na ion storage measurements
The electrochemical Na ion storage performances were all
tested in CR2032 type coin cells, which were assembled in an Ar-
filled glovebox with oxygen and water content below 0.1 ppm.
For preparing the electrode, 80 wt% of the as-obtained carbon
samples, 10 wt% of Super P as conductive agent and 10 wt% of
polyacrylic acid as binder were mixed with distilled water to form a
homogeneous slurry. Then the slurry was coated onto Cu foils using
a doctor blade. After drying at 80
C for 12 h, the electrode was cut
into a circle disk with diameter of 10 mm. After further drying at
80
C until a constant weight, the mass loading was obtained in the
range of 0.7e1.0 mg cm2. The as-prepared carbon electrode and
metallic Na serve as working and counter electrode, respectively,
with a glass fiber as separator. The electrolyte was a solution of 1 M
NaClO4 in a solvent mixture of ethylene carbonate (EC) and
dimethyl carbonate (DMC) (1:1 by volume) with 5 wt% fluoro-
ethylene carbonate (FEC) additive. The half cells were discharged
and charged within a potential window of 0.01e2.0 V using LAND
CT2001A battery testing system. The cyclic voltammogram (CV,
scan rate from 0.1 to 0.9 mV s1) and electrochemical impedance
spectroscopy (EIS, frequency range from 100 kHz to 0.01 Hz)
measurements were performed on a CHI electrochemical work-
station. In-situ Raman spectra were collected on a Renishaw inVia
Raman spectroscope combined with a CV measurement under the
scan rate of 1 mV s1 within a potential window of 0.01e2.0 V using
a home-made coin cell setup. All the electrochemical measure-
ments were conducted at room temperature.
3. Results and discussion
3.1. Preparation and structural characterization
As one of the five general resins in the world, PS is promising as
the carbon precursor due to its low-cost and easy availability.
However, linear PS with thermoplastic property will be burnt off
completely during carbonization process and thus cannot be used
as carbon precursor directly [30,35,40]. To address this problem,
hypercrosslinking strategy confers excellent carbonizability to the
PS-based precursors with tremendous micropores or hierarchical
pore structures in the resulting carbons [28,30,31]. The intrinsic
property of crosslinker plays an important role in determining the
nanomorphology of carbons, for instance, carbonyl crosslinker
shows the nanostructure inheritability, while the methylene
crosslinker leads to the collapse of nanonetwork structure with
only micropores [31]. Further exploration of novel crosslinking
chemistry to tune the pore structure, such as the development of
low-porosity carbons, is highly desirable but remains scarce. We
found that by using different crosslinking chemistry of Scholl re-
action and solvent knitting strategy, the resulting PS-derived car-
bons can be controlled with low porous and microporous
structures, respectively, as discussed below.
To well compare the crosslinking reactions, the same linear PS,
CH2Cl2 solvent and AlCl3 catalyst were used in both cases, and the
main difference is the reaction temperature. For the solvent knit-
ting strategy, a gradient heating procedure is applied to enable the
formation of -CH2- crosslinker between benzene rings of PS chains.
Briefly, at lower temperature, CH2Cl2 firstly reacts with AlCl3 to
form CH2Cl2$AlCl3 with weakening interaction between the chlo-
rine atom and the methylene. Subsequent stepwise rise in tem-

perature leads to the formation of CH2þ 2þ
2 and AlCl4 , and then CH2
will react with the benzene rings of PS by substituting its hydrogen
atoms [38], thus forming hypercrosslinked polymer HPP-CH2. For
the Scholl reaction, it is a Lewis acid-catalyzed coupling of aromatic
CAr-CAr via eliminating two hydrogen atoms in benzene rings of PS
chains through direct heating to reflux [36,37], thus yielding HPP-S.
HPP-CH2 shows a dark brown color, similar to the conventional
-CH2- crosslinked polymers [41]; whereas the color of HPP-S is pale
yellow (Fig. S1). Further solid-state UVeVis spectra interpret the
different colors (Fig. S2). HPP-S shows a peak centered at 388 nm
while HPP-CH2 displays a broader peak at 420 nm, probably due to
steric hindrance of coupled benzene rings with deviation from
sharing the same plane in HPP-S and the local p-p conjugation in
HPP-CH2 [42]. However, both crosslinked PS samples are non-
conjugated polymers. Different from HPP-S, HPP-CH2 shows a
weight increase after crosslinking due to the insertion of additional
-CH2- crosslinker. From the Fourier transform infrared (FTIR)
spectroscopy (Fig. 1a), both polymers show the asymmetric
stretching nas(-CH2-) and oscillations in plane no(-CH2-) vibrations
from the PS backbone. However, a slight red shift was observed for
HPP-CH2 (2853 and 740 cm1 for nas and no, respectively), as
compared to that of HPP-S (2866 and 756 cm1, respectively), due
to the conjugation effect with p-p interaction of CAr-CH2-CAr. We
also attempted to figure out the structural difference via the 13C CP/
MAS NMR spectra (Fig. S3). However, the result is quite close
probably due to the similar electronic cloud density of aliphatic/
aromatic carbons in crosslinked PS, and thus the low resolution of
solid-state 13C CP/MAS NMR is incapable of figuring out their fine
structures. After crosslinking, both HPPs consist of aggregated
nanoparticles interconnected in different directions, forming a
three-dimensional network (Fig. 1c and d). Inside the nanoparticle,
 F. Xu et al. / Carbon 167 (2020) 896e905
Fig. 1. (a) FTIR spectroscopy of HPP-S and HPP-CH2; (b) N2 adsorption-desorption isotherms of HPP-S, HPP-CH2 and PS; SEM images of (c) HPP-S, (d) HPP-CH2. (A colour version of
this figure can be viewed online.)
there are abundant nanopores, as verified by the sharp increase of
nitrogen uptake at low relative pressure in nitrogen adsorption-
desorption isotherms (Fig. 1b). The gradual rise of adsorption
amount without a plateau at high relative pressure indicates the
presence of meso- and macropores, which are derived from
compact and loose aggregation of these nanoparticles. Such a hi-
erarchical pore structure can be also revealed by the DFT pore size
distribution curves (Fig. S4). Therefore, HPP-S and HPP-CH2 exhibit
SBET of 691 and 628 m2 g1, respectively, while the surface area of PS
without crosslinking is as low as 0.68 m2 g1 (Fig. 1b). These results
also indicate the successful implementation of hypercrosslinking
reactions.
After carbonization at 800
C, the as-obtained carbons MICHP and
LPCHP both show compact layered structure with smooth surface
(Fig. 2a and b), different from their precursory nanostructures. This
result demonstrates the nanomorphology collapses upon carbon-
ization using either -CH2- crosslinker or self-crosslinking in PS, in
agreement with the reported literatures where -CH2- crosslinker did
not have the nanostructure inheritability [31]. High resolution
transmission electron microscopy (HRTEM) images of both carbon
samples reveal amorphous graphite-like microcrystal structure
899
(Fig. 2c and d). Their selected area electron diffraction (SAED) patterns
show dispersing diffraction rings, further verifying the amorphous
structure. However, it can be observed that LPCHP exhibits slightly
sharper diffraction rings than MICHP, in line with the relatively clearer
curved layers in HRTEM image of LPCHP, indicating higher content of
graphitic-like nanodomain structure.
The microstructures of both carbons were also examined by
XRD, Raman spectroscopy and XPS. The XRD patterns with hump
peaks of (002) and (100) diffractions suggest amorphous structure,
in agreement with the observation from HRTEM images. Never-
theless, a close analysis shows that the center of (002) peak in
LPCHP shifts slightly to a higher diffraction angle of 24.8
(Fig. 2e),
indicating a decreased interlayer distance with relatively more or-
dered graphitic-like structure [23]. The empirical R value was
calculated to evaluate the graphitization degree of amorphous
carbons, based on the ratio of the (002) intensity and background at
the equivalent peak according to the previous studies [43,44]. As
listed in Table S1, LPCHP exhibits larger R value of 3.2 than MICHP
(3.0) and a slight lower d spacing, revealing its increased graphi-
tization degree. Fig. 2f displays the typical Raman spectra, which
could be fitted with combinations of D2, D, A, G bands. The D-band
900 F. Xu et al. / Carbon 167 (2020) 896e905
Fig. 2. SEM images of (a) LPCHP and (b) MICHP; HRTEM images of (c) LPCHP and (d) MICHP, and the inset in (c) and (d) is the corresponding SAED images; (e) XRD and (f) Raman
spectra of LPCHP and MICHP. (A colour version of this figure can be viewed online.)
is ascribed to the defect-induced mode, while the G-band is iden-
tified as the graphitic mode. The integrated intensity ratio of D-
band over G-band (ID/IG) decreases slightly for LPCHP in compari-
son to MICHP (Table S2), indicating a relatively less intrinsic
defective site in pseudographitic carbon planes of LPCHP [26]. On
this account, LPCHP demonstrates enhanced sp2 graphitic carbon
content of 52.7% and reduced sp3 C of 15.3%, compared to MICHP
with 50.3% and 23.7% of sp2 and sp3 carbon, respectively, as
determined by XPS measurement (Fig. 3c and Figs. S5 and S6). The
remaining is the C bonding with O. Both samples show similar O
content from either XPS or combustion elemental analysis
(Table S3), and the O functionalities are mainly COOR, C-O and C¼O
(Fig. S7). Our finding indicates the crosslinker structure can influ-
ence the graphitic-like microcrystal structure. However, the dif-
ference is actually quite low because both samples are essentially
amorphous carbons. The micropores can be also regarded as
structural defects in randomly distributed microcrystallites of
amorphous carbons. The obvious distinction is the microporosity in
the carbon framework, as shown below.
The pore structures of both carbons were determined from N2
adsorption-desorption isotherms (Fig. 3a). For LPCHP, the isotherm
exhibits little adsorption amount, indicative of its low-porosity
framework, whereas MICHP demonstrates a steep increase of
adsorption amount at low relative pressure (P/P0), indicating a
microporous framework. The SBET of MICHP is up to 387 m2 g1 with
microporous surface area of 308 m2 g1 and pore size of 0.5 nm
(Fig. 3b and Fig. S8), whereas LPCHP exhibits a surprisingly low SBET
of 5 m2 g1. CO2 adsorption was also performed to verify whether
there are ultramicropores that could not be detected by N2 adsorp-
tion. Likewise, LPCHP has much less uptake than MICHP (Fig. S9),
further confirming the low microporosity in LPCHP. It is known that
micropores with high surface area in carbon frameworks are the
main places for adsorbing ions to build electrical double layer
capacitance [7,32]. As expected, LPCHP with low porosity and
surface area displays much lower capacitance of 31 F g1; while the
capacitance of MICHP is up to 154 F g1 (Fig. S10). We also use the
conventional pathway to construct -CH2- crosslinker in PS by
Friedel-Crafts reaction with formaldehyde dimethyl ether (FDA)
crosslinker and FeCl3 catalyst. The resulting carbon also displays a
microporous framework with similar N2 adsorption-desorption
behavior (Fig. S11), further confirming that -CH2- crosslinker is
responsible for the microporosity in the resulting carbons.
To further track the structural evolution of HPPs during
carbonization, thermogravimetric analysis (TG) and TG coupled
with mass spectroscopy (TG-MS) tests were employed to identify
the chemical species released during pyrolysis. From the TGA
(Fig. S12), HPP-S exhibits enhanced thermal stability with higher
carbonization yield of 42% than HPP-CH2 of 33%, demonstrating
that more non-carbon elements and carbon-containing com-
pounds were burnt off for HPP-CH2 [27]. Considering the same PS
backbone but only additional -CH2- crosslinker in HPP-CH2, it can
be concluded that -CH2- species in this case probably function as
soft-template-like sacrificial component for the generation of mi-
cropores in MICHP. From the TG-MS result (Fig. 3d), HPP-CH2 ex-
hibits much stronger cumulative intensity of CH4 produced around
540
C in comparison to HPP-S. In addition, CO2 produced from
HPP-CH2 shows higher cumulative intensity at lower decomposi-
tion temperature than that from HPP-S. The intensive production of
CH4 and lower temperature of CO2 evolution can be ascribed to the
thermal decomposition of -CH2- crosslinker in HPP-CH2. The
temperature-dependent pore structure evolution was tested
(Figs. S13 and S14). During pyrolysis process, the sintering and
collapse of nanonetwork morphology occurred, coupled with
gradual elimination of micropores. Thus, the SBET decreases for both
samples more or less. However, there is a sharp decrease from 666
to 21 m2 g1 for HPP-S when increasing the pyrolysis temperature
from 400 to 600
C, while HPP-CH2 still retains a SBET of 368 m2 g1
at 600
C (Fig. S14). Thus, it can be inferred that the microporous
 F. Xu et al. / Carbon 167 (2020) 896e905
Fig. 3. (a) N2 adsorption-desorption isotherms of LPCHP and MICHP; (b) the DFT pore size distribution curves for LPCHP and MICHP; (c) the proportion of sp2 and sp3 carbon species
in LPCHP and MICHP; (d) cumulative intensity of CH4 and CO2 generated in the pyrolysis process of HPP-S and HPP-CH2 under the Ar atmosphere measured by TG-MS technique; (e)
schematic illustration of the carbonization process for LPCHP and MICHP. (A colour version of this figure can be viewed online.)
framework can be associated with the decomposition of -CH2-
based species above 400
C, leaving many defective micropores
within the as-formed carbon framework or more disordered
packing of turbostratic carbon sheets. For the HPP-S, once the
scission occurs between the crosslinked benzene rings with
elevating pyrolysis temperature, polycyclic aromatic carbon planes
could be formed at the active sites via aromatization and further
formation of graphitic-like nanodomains without substantial
micropore generation. A possible scheme illustration is thus pro-
vided in Fig. 3e for the formation of distinct microporous structures.
In contrast to the conventional templating strategy, templates and
carbon precursors are usually two incompatible materials [45], thus
generally meso- and/or macropores were constructed due to the
difficulty in building uniform nano-interface. Our proposed concept
of integration of the precursor and template in one material with
molecular-scale interface may also offer opportunity for tailoring
the micropores via molecular design. It is also worth noting that the
crosslinking chemistry could be implemented with waste PS, which
is one source for causing so-called “white pollution”, and thus is
helpful for coping with plastic waste reuse.
3.2. Na ion storage performances
Na-ion batteries (SIBs) are emerging as one of the most
intriguing alternatives to Li-ion batteries (LIBs), thanks to the nat-
ural abundance of Na with cost advantage [46e48]. Nevertheless, a
major obstacle to the commercial development is the lack of suit-
able anode materials. This is because the commercial LIBs anode,
graphitic carbons, does not work well for SIBs due to the large and
highly ionized Na ion or thermodynamic issues with sluggish ki-
netics. Hard carbons are regarded as one of the most promising
anodes benefitting from their graphitic-like nanodomain and
901
nanovoids with expanding interlayer distance and numerous
nanopores for Na ion storage [5,6]. Although promising, hard car-
bons with copious micropores and defects typically exhibit lower
ICE and fast capacity fading, mainly derived from the uncontrolla-
ble electrolyte decomposition and ineffective formation of solid
electrolyte interface (SEI) on the large surface area. Recent studies
suggested that low-surface-area hard carbons help to increase the
ICE and enable high capacity and good stability. However, the
majority of these low-porosity carbon materials were obtained
either by changing the pyrolysis conditions or using different ori-
gins [14,23,49,50], giving rise to concurrent change in surface
chemistry, conductivity and other microstructures. Intriguingly, the
present distinct carbon frameworks of MICHP and LPCHP were
obtained from analogous PS and same pyrolysis condition, offering
great opportunities to clarify the essential role of structural effect
on Na ion storage.
The electrochemical performances were evaluated using
CR2032 half cells versus Na metal as a counter electrode in the
potential window of 0.01e2.0 V. Both samples show irreversible
capacity loss in the initial discharge-charge curves (Fig. S15), due to
the decomposition of electrolyte for SEI formation. However, LPCHP
exhibits an initial discharge capacity of 270 mA h g1 and reversible
charge capacity of 143 mA h g1, corresponding to an ICE of 53%,
higher than that (32%) of MICHP (Fig. 4a). With continuous cycling,
the Coulombic efficiency of LPCHP increases to 86% in the second
cycle and afterward nearly to 99% (Fig. 4d) after 10 cycles. This is in
contrast to a lower Coulombic efficiency of 71% in the second cycle
and then 91% after the following 10 cycles for MICHP. These results
demonstrate the importance of reducing microporosity and surface
area in mitigating undesirable electrolyte decomposition for
effective formation of SEI and thus boosting ICE [26]. Cross-section
SEM analysis shows that the electrode thickness of LPCHP remains
902 F. Xu et al. / Carbon 167 (2020) 896e905
Fig. 4. (a) Histograms of ICE for LPCHP and MICHP at 0.02 A g1; (b) galvanostatic discharge-charge curves of the second cycle for LPCHP and MICHP at 0.02 A g1; (c) the plateau
capacity for the second and after two-hundred cycle; (d) cycling performances of LPCHP and MICHP at 0.02 A g1; (e) rate performances from 0.02 to 2 A g1 and back to 0.02 A g1
with 5 cycles at each current density for LPCHP and MICHP, except 7 cylces at the beginning 0.02 A g1. (A colour version of this figure can be viewed online.)
stable, while MICHP exhibits a huge change after 10 cycles
(Fig. S16), indicating the efficient formation of SEI without exces-
sive side reactions for low-porosity carbon LPCHP. LPCHP also dis-
plays a superior ICE in comparison to those of reported carbons
(Table S4). Further work should be focused on improvement of ICE
in LPCHP by decreasing the intrinsic defects in amorphous struc-
ture and optimization of testing conditions.
The discharge-charge curves exhibit typical hard carbon be-
haviors, displaying two distinct regions: a slope region and a
plateau one [49]. The LPCHP with the low-porosity framework
shows higher discharge capacities than MICHP (Fig. 4b). During 200
cycles, LPCHP shows excellent stability with little decay and a ca-
pacity of 194 mA h g1 is obtained. Rate capability was investigated
by applying stepwise current densities from 0.02 to 2 A g1 (Fig. 4e
and Fig. S17). Evidently, LPCHP delivers superior rate performances
with reversible capacities of 180, 156, 134, 112, 93, 74, 78 and
62 mA h g1 at 0.02, 0.05, 0.1, 0.2, 0.5, 0.8, 1 and 2 A g1, respec-
tively. Moreover, the capacities almost recovered after returning to
various low current densities, demonstrating the robustness of the
low-porosity structure in LPCHP. Inversely, MICHP displays lower
capacities at each rate, i.e., only 133 and 36 mA h g1 at 0.02 and
2 A g1, respectively. LPCHP also exhibits outstanding capacity
retention of 79% over 1000 cycles at 0.1 A g1 with Coulombic ef-
ficiency close to 100% except the initial several cycles (Fig. S18),
indicating its good durability. From these results, it can be inferred
that the low-porosity structure is responsible for higher ICE, larger
capacity and rate capability; while the micropores seem to play less
contribution to the performance [11,50]. What is the underlying
role to determine the Na ion storage performances with distinct
microporous frameworks? Further analysis was carried out below.
Although there is still controversy for assigning the slope and
plateau capacity in hard carbons, one prevalent explanation is that
the slope-potential region is related to Na ion adsorption while
plateau-potential region is ascribed to Na ion intercalation into
graphitic-like nanodomains, i.e., adsorption-intercalation mecha-
nism [11e14,49]. To provide some evidence to reveal the possible
mechanism, in-situ Raman spectroscopic technique was applied
(Fig. 5a). It was previously reported that the insertion of Li or Na
ions into graphitic layers of hard carbons will lead to redshift of the
G-band in Raman spectra, owing to the electron occupation in the
p* antibonding band that weakens the C-C bonds [26,51]. In the
sodiation process, the position of the G-band remains almost un-
changed (1600 cm1) in the sloping potential region. This indicates
the adsorption process with no intercalation into the graphitic-like
nanodomains. When further discharging to 0.01 V, a slight redshift
of the G-band to 1590 cm1 was observed, suggesting partially ions
insertion into pseudo-graphitic layers [52e54]. In addition, ID/IG
ratio rises from 2.19 to 3.21 when potential decreases from 2.0 to
0.1 V, due to the increasing disorders upon adsorption of Na ions
[55,56]. Then a significant rise to 3.72 was observed when further
discharging to 0.01 V, which was probably caused by the Na ion
intercalation with the formation of graphite intercalation com-
pounds [57]. During the charging process, ID/IG ratio decreases,
indicative of the desodiation with reversible recovery of the
structure. Further analysis shows that capacity contribution from
the plateau region is higher in LPCHP than that of MICHP, especially
the difference become more intense upon further cycling (Fig. 4c).
Considering the slightly increased graphitic-like nanodomains of
LPCHP than that of MICHP and the result from in-situ Raman
spectra, the higher plateau capacity is thus ascribed to Na ion
intercalation. The capacity contribution from sloping region could
be associated with the adsorption of Na ions. Despite the surface
area of MICHP (387 m2 g1) is 77 times higher than that of LPCHP
(5 m2 g1), the sloping capacity from Na ion adsorption is almost
similar. Thus, our results indicate that the micropores hardly
accommodate or foster the Na ion adsorption, consistent with some
reported results [11,50]. The adsorption could be occurred on the
defective sites or nanovoids between the turbostratic nano-
domains. Based upon the analysis, a possible scheme for Na ion
storage was provided (Fig. 5c).
To further clarify kinetics and diffusivity of Na ions, CV mea-
surements under different scan rates were carried out (Figs. 6a and
 F. Xu et al. / Carbon 167 (2020) 896e905 903

Fig. 5. (a) Raman spectra collected in operando mode during discharge and charge process under the potential window of 0.01e2.0 V; (b) intensity ratio of D-band and G-band
calculated from in-situ Raman spectra; (c) possible schematic illustration of the mechanism for Na ion storage. (A colour version of this figure can be viewed online.)

S19a). Based on the equation, log(i) ¼ blog(v) þ log(a), where i is the (Fig. 6b). When the b value is 0.5, the capacity is a diffusion-
peak current, v the scan rate, a and b the adjustable constants, the b dominated process; while the value of 1 represents a capacitive-
value can be obtained from the slope of the log(i)-log(v) plots controlled process [48,58]. The calculated b values are 0.53 for

Fig. 6. (a) CV curves for LPCHP with scan rates from 0.1 mV s1 to 0.9 mV s1; (b) logarithm peak current versus logarithm scan rate plots of peak 2 for LPCHP and MICHP;
separation of capacitive (pink region) and diffusion-controlled (blue region) contribution at 0.1 mV s1 for (c) LPCHP and (d) MICHP; (e) comparison of diffusion-controlled
proportion calculated from CV curves for LPCHP and MICHP. (A colour version of this figure can be viewed online.)
904 F. Xu et al. / Carbon 167 (2020) 896e905
LPCHP and 0.73 for MICHP, suggesting that the Na ion storage
process in this region is mainly controlled by a diffusion process in
LPCHP. To quantify the ratio, the current response i at a fixed po-
tential is separated for capacitive (pseudocapacitive)-controlled
process (k1v) and diffusion-controlled reaction (k2v1/2), according to
the equation i(V) ¼ k1v þ k2v1/2. Fig. 6c displays typical contribution
from diffusion process (blue region) and pseudocapacitive process
(pink region) for LPCHP. An obviously higher diffusion-controlled
process up to 90% at 0.1 mV s1 was obtained, in line with the
result of the b value calculated above. For comparison, a lower
diffusion contribution of 70% at 0.1 mV s1 for MICHP was obtained
(Fig. 6d). The low porosity in LPCHP gives rise to diffusion process
during the electrochemical process. With increasing the scan rate,
the diffusion contribution for both carbons reduces (Fig. 6e and
Fig. S20). However, LPCHP always shows higher diffusion contri-
bution than MICHP (Fig. 6e). Generally, diffusion process is the main
bottleneck to achieve a high capacity [59]. Especially at high rate,
the diffusion process decreases significantly leading to depression
of capacity, because of the restricted ion diffusion ability. LPCHP
always exhibits higher diffusion contribution than MICHP no
matter the low or high scan rate, indicating its superior ion diffu-
sion process. All these intriguing discoveries demonstrate that our
molecular crosslinker design strategy is an effective way to
decrease the microporosity in carbon frameworks, thus enhancing
the plateau Na ion storage capacity and boosting the ICE. The
enhancement of low-potential plateau capacity in anode material is
crucial for increasing the voltage of the full cell and thus further
improving the energy density of devices.
4. Conclusions
In summary, we have successfully established a facile molecular
crosslinker design strategy to regulate the microporosity of carbon
frameworks based on PS resins. The crosslinker structure plays a
crucial role in determining the framework microporosity in
resulting carbons. Methylene crosslinker in PS results in micropo-
rous framework while the direct linking of PS is beneficial for the
formation of low-porosity carbon framework. Such intriguing re-
sults offer a protocol for manipulating the framework porosity of
amorphous carbon via flexible molecular design at relatively low
carbonization temperature. When used as anode material for Na
ion storage, low-porosity carbon displays higher ICE, larger
reversible capacity and superior rate performance, as compared
with microporous carbon. Taking into account of flexible molecular
design, low-cost PS and distinct performances, we think our find-
ings will have a major impact on carbon materials field and also on
the progress on well-defined carbons for energy storage requiring
low microporous structure. It is envisioned that further fine
structural tuning can be realized by exploring novel crosslinker
chemistry coupled with sophisticated styrenic-based polymers
design with controlled chain length, configuration/topology and
functionality (such as block copolymer self-assembling, star-shape,
brush-like and ladder-like structures), which are underway.
CRediT authorship contribution statement
Fei Xu: Conceptualization, Supervision, Writing - original draft,
Writing - review & editing. Haojie Han: Methodology, Investiga-
tion, Data curation. Yuqian Qiu: Methodology, Investigation, Data
curation. En Zhang: Methodology, Investigation, Data curation.
Hlib Repich: Methodology, Investigation, Data curation. Changz-
hen Qu: Methodology, Investigation, Data curation. Huiwu Yu:
Methodology, Investigation, Data curation. Hongqiang Wang:
Conceptualization, Project administration, Supervision. Stefan
Kaskel: Conceptualization, Supervision, Validation.
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.
Acknowledgement
This work was supported by the National Natural Science Foun-
dation of China (51972270, 51702262, 51872240, 51911530212,
51672225, 21603175 and 61805201), the Natural Science Foundation
of Shaanxi Province (2020JZ-07), the Key Research and Develop-
ment Program of Shaanxi Province (2019TSLGY07-03), the Funda-
mental Research Funds for the Central Universities (3102019JC005,
3102019ghxm004), the Research Fund of the State Key Laboratory of
Solidification Processing, NPU, China (2019-QZ-03), and the Top
International University Visiting Program for Outstanding Young
scholars of Northwestern Polytechnical University. We would like to
thank the Analytical & Testing Center of Northwestern Polytechnical
University for XPS characterizations. S. Kaskel acknowledges sup-
port by the DFG (KA 1698/27-1). F. Xu acknowledges support by the
Alexander von Humboldt Foundation.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.carbon.2020.05.081.
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