Research Article

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“Sauna” Activation toward Intrinsic Lattice Deficiency

in Carbon Nanotube Microspheres for High-Energy and
Long-Lasting Lithium–Sulfur Batteries
Yongguang Zhang, Gaoran Li, Jiayi Wang, Dan Luo, Zhenghao Sun, Yan Zhao,
Aiping Yu, Xin Wang,* and Zhongwei Chen*

energy needs.[1] Recently, lithium–sulfur

Lithium–sulfur (Li–S) battery technology offers one of the most promising (Li–S) batteries emerged as a prom-
replacement strategies for conventional lithium-ion batteries, but for several ising energy storage system candidate.
The main reasons lie in the high spe-
serious obstacles remain, such as the notorious polysulfide shuttling and
cific capacity, natural abundance, and
their sluggish reaction kinetics. In this work, it is demonstrated that these environmental compatibility of sulfur.[2]
problems can be significantly ameliorated via intrinsic lattice defect engi- However, the widespread application of
neering in carbon-based sulfur host materials. Specifically, porous carbon Li–S batteries has been limited by some
nanotube microspheres (ePCNTM) are developed through a scalable spray intractable technical challenges, particu-
drying method, followed by a critical water-steam etching under high tem- larly the notorious shuttle effect of lithium
polysulfide (LPS) intermediates, and the
perature. Such “sauna” activation constructs abundant intrinsic topological
intrinsically sluggish reaction kinetics of
defects in the carbon lattice, endowing ePCNTM with enhanced sulfur sulfur redox reactions.[3]
adsorbability and catalytic activity in sulfur redox reactions. In addition, To overcome these obstacles, sulfur
the interwoven and highly porous architecture renders favorable conduc- host materials have been developed to
tivity, homogeneous sulfur distribution, and massive host–guest interactive stockpile sulfur and alleviate LPS shut-
surfaces. As a result, the ePCNTM-based sulfur electrodes achieve excellent tling. Carbon-based materials have been
generally investigated as a multifunctional
cyclability with an ultralow capacity attenuation rate of 0.046% per cycle upon sulfur scaffold, owing to the high conduc-
500 cycles, excellent rate capability up to 3 C, and decent areal capacity reten- tivity, low cost, and good structural tailor-
tion of 3.2 mAh cm−2 after 50 cycles under raised high sulfur loading. Thus, ability.[4] The good electrical conductivity
this synergistic approach, combining composite nanostructuring and intrinsic of carbon enables fast electron transport
defect engineering, yields highly competitive Li–S batteries, which is also for electrochemical process, while the
large surface area and high porosity pro-
expected to inform advanced material development in related energy fields.
vide physical confinement for LPS. How-
ever, carbon materials suffer from low
binding capability to LPS, resulting in
1. Introduction limited constraint of shuttle effect, which causes low coulombic
efficiency during cycling and fast capacity fading.[5] Given this,
High-efficiency and inexpensive energy storage systems have the modification of carbon lattice structure has been proposed
been always actively pursued to meet the world’s increasing as valid strategy to strengthen the sulfur adsorbability and thus

Prof. Y. Zhang, Z. Sun, Y. Zhao Dr. G. Li

School of Materials Science and Engineering MIIT Key Laboratory of Advanced Display Materials and Devices
State Key Laboratory of Reliability and Intelligence Institute of Optoelectronics and Nanomaterials
of Electrical Equipment School of Materials Science and Engineering
Hebei University of Technology Nanjing University of Science and Technology
Tianjin 300130, China Nanjing 210094, China
Prof. Y. Zhang, J. Wang, Dr. D. Luo, Prof. X. Wang Prof. A. Yu, Prof. Z. Chen
South China Academy of Advanced Optoelectronics Department of Chemical Engineering
International Academy of Optoelectronics at Zhaoqing University of Waterloo
South China Normal University Waterloo N2L 3G1, Canada
Guangzhou 510006, China E-mail: zhwchen@uwaterloo.ca
E-mail: wangxin@scnu.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.202100497.

DOI: 10.1002/aenm.202100497

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improve the sulfur hosting effect. Typically, heteroatomic (such
as N, P, S, and B) doping has been extensively developed to
endow the carbon lattice with higher chemical polarity due to
the different electronegativity between carbon and the doping
atoms.[6] Such enhancement of polarity tends to chemically and
more strongly bind LPS via the polar–polar interaction. Nazar
et al. reported g-C3N4 with 53.5% concentration of accessible
pyridinic-nitrogen polysulfide adsorption sites demonstrated
a strong Li+–Nδ− interaction to anchor LPS.[7] S-doped carbon
aerogel was developed by Yang et  al., which exhibit higher
binding energy with LPS compared with the bare carbon sur-
face, thereby strengthening the sulfur confinement against the
sulfur loss upon cycling.[8]
Despite the progress in heteroatomic defect engineering, the
intrinsic carbon defects, namely the topological transformation
of basic C6 lattice units in to C5, C7, C8, etc., and their impli-
cation on sulfur electrochemistry has been rarely reported. In
fact, similar lattice engineering has been somewhat imple-
mented in electrocatalysis field and gained positive feedbacks.
Wang et al. revealed that the carbon defects could localize the
surface charge on the defective active sites, which enhanced the
activity for oxygen electrocatalysis.[9] Higher oxygen reduction
reaction activity was also found at the edge carbon sites over
the ones in the basal plane, suggesting the superiority of defec-
tive carbon electrocatalysts.[10] In view of the considerable simi-
larities between sulfur and oxygen electrochemical conversions,
the intrinsic carbon defect engineering is expected as a prom-
ising strategy for the improvement of sulfur reactions.
In this work, we developed a synergistic strategy of com-
bining composite nanostructuring and defect engineering
to address the above-mentioned problems in Li–S batteries.
Through the high-throughput, simple, and cost-effective spray-
drying method, unique interwoven microspherical assemblies
were obtained, which was further projected to a “sauna” acti-
vation to yield the water-steamed porous carbon nanotube
microspheres (ePCNTM). The construction of massive intrinsic
lattice defects was verified by a series of morphological and
spectral characterizations, which enabled stronger chemical
sulfur immobilization, facilitated Li+ transportation, and cata-
lyzed sulfur conversions. As a result, effective shuttle inhibition
and fast reaction kinetics can be realized, contributing to high-
efficiency Li–S batteries based on ePCNTM as the sulfur host.
Such synergistic lattice and architectural design also provides a
feasible way to achieve electrochemically active electrode even
under raised sulfur areal loadings, which is of great importance
for high-energy-density Li–S battery commercialization.
2. Results and Discussion
The synthesis of ePCNTM was schematically presented in
Figure S1, Supporting Information. The homogeneous disper-
sion of carbon nanotube (CNT) and commercial SiO2 nano-
sphere (≈300 nm diameter, Figure S2, Supporting Information)
in DI water were first prepared. This precursor solution was
subject to spray drying at 200  °C to yield the quasi-spherical
micrometric CNT/SiO2 composite. After that, the SiO2 was
etched away by hydrofluoric acid (HF) to obtain the porous
carbon nanotube microspheres (PCNTM), while a subsequent
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“sauna” activation was carried out by exposing PCNTM to
water-steam-contained argon gas at 800 °C for certain minutes
(10, 20, and 40 min) to achieve ePCNTM (denoted as ePCNTM-
10, -20, and -40, respectively). As shown in Figure 1a, the water-
steam etching was designed to partially destroy the intact lattice
and generate the intrinsic defects, which is attributed to the
reaction between H2O vapor and CNT under high temperature
to produce CO and H2, leaving behind carbon vacancies.
The SEM images in Figure S3, Supporting Information,
show uniform CNT/SiO2 microspheres resulting from spray
drying process, where the CNTs intertwine and tightly confine
the SiO2 spheres into a hybrid quasi-microsphere. After the
SiO2 removal, the porous structure is clearly visible in PCNTM
as shown in Figure  1b. Through the SEM result, it can be
observed that the “sauna” activation imposes few morpholog-
ical impacts on PCNTM, as the porous and spherical architec-
ture is still intact after the water-steam etching (Figure 1c). The
homogeneity of the synthesized products can be verified by the
SEM images with a scale bar of 10 µm in Figure S4, Supporting
Information, which show the uniform size distribution for both
PCNTM and ePCNTM-20. It is worth noting that the morpho-
logical characters of PCNTM can be maintained within a cer-
tain range of etching degree (ePCNTM-10 and ePCNTM-20),
but as the etching time extends, the porous spherical struc-
ture collapses for ePCNTM-40 as shown in Figure S5,
Supporting Information. Given this, the ePCNTM-20 is
speculated as a promising specimen that simultaneously car-
ries the activation and morphological merits. To further observe
the microstructure, TEM characterization was conducted with
the result shown in Figure S6, Supporting Information. The
cross-linked CNTs are bent and wound into a quasi-spherical
structure, and the pore structure left after removing the SiO2
template is also clearly visible for ePCNTM-20. In this archi-
tecture, the CNT is expected to guarantee an excellent electrical
conductivity, while the porous structure provides ample space
for sulfur storage and can alleviate the dramatic volume change
during charging and discharging.
Apart from that, aberration-corrected high-resolution trans-
mission electron microscopy (AC-HRTEM) was further per-
formed for PCNTM and ePCNTM-20 as shown in Figure 1d–g.
The boundary of the CNT changes from smooth (Figure  1d)
to rough (Figure  1e) after the etching process, indicating that
the “sauna” activation increases the surface roughness and
porosity, which is beneficial to the exposure of active interfaces.
More importantly, PCNTM witnesses a high degree of graphiti-
zation with clearly visible ordered carbon interplanar spacing
for the CNT shells (Figure  1f), while contrastively, obvious
disordered surface amorphization can be noticed in ePCNTM
(Figure 1g). Similar effect can be also observed from the Aberra-
tion-corrected scanning transmission electron microscopy (AC-
STEM) as shown in Figure S7, Supporting Information. Such
lattice variation can be also confirmed by the fast Fourier trans-
form (FFT) results in selected areas (insets in Figure 1d,e). The
PCNTM (blue frame) presents typical diffraction spots repre-
senting the (002) plane of carbon, demonstrating the good lat-
tice ordering of CNT. By contrast, the FFT result of ePCNTM-20
(purple frame) presents a ring-like diffraction pattern, which
is characteristic of relatively low crystallinity and reveals a dis-
order carbon lattice structure.
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Figure 1.  a) Schematic diagram of PCNTM and ePCNTM. SEM images of b) PCNTM and c) ePCNTM-20; TEM images of d) PCNTM and e) ePCNTM-
20; inset: FFT images for framed areas; AC-HRTEM images of f) PCNTM and g) ePCNTM-20.

To further study the lattice deficiency, the Electron Energy
Loss Spectroscopy (EELS) spectra were recorded as shown in
Figure 2a. The peak at around 285 eV is associated with the tran-
sition of the unoccupied anti-bonding π*-states of sp2 carbon,
while the one at around 295  eV is assigned to the transitions
of anti-bonding σ*-states of sp3 carbon (labeled as σ*).[11] After
etching, the σ* peak changes from sharp to broad, indicating
the generation of a large number of intrinsic carbon defects
along with the considerable decrease of graphitic carbon struc-
ture. Such variation of carbon structure can be also perceived
from the XPS spectra before and after water-steam etching
(Figure  2b). Typical peaks can be deconvoluted referring to
287.2, 285.4, and 284.8 eV, respectively, which corresponds to the
CO/CO, Csp3 and Csp2.[12] It can be noted that the Csp2
to Csp3 content ratio undergoes a decrease from PCNTM to
ePCNTM-20 (3.36 vs 2.98), suggesting the damage of graphitic
carbon structure and the increase of intrinsic lattice defects
after the water-steam activation. In view of this, EPR charac-
terization was performed to inspect the defective character for
all the prepared samples. As shown in Figure  2c, all the sam-
ples exhibit certain resonance signal at g  = 2.003, suggesting
the existence of unpaired electrons in both pristine and etched
carbon structures. However, a continuous increase of the EPR
peak intensity can be noticed long with the increase of etching
time, which is an evidential indicator of the accumulation of
carbon defects. The defects are dominated by the form of
point defect as revealed by the positron annihilation lifetime
spectroscopy (PALS) as shown in Figure S8 and Table S1, Sup-
porting Information. Apart from that, the Raman spectra were
also collected to study the defect content variation under dif-
ferent etching time. As shown in Figure  2d, all the samples
show two typical Raman peaks at 1337 and 1564 cm−1 ascribed
to D band and G band, respectively. The corresponding inten-
sity ratio (ID/IG) is a good describer of the structural deficiency
in carbon lattice. It is noted that a continuous increase of
ID/IG can be noticed alongside the prolonged etching time, indi-
cating the increasing damage to the CNT surface. Nevertheless,
the relatively low value as well as the limited growth of ID/IG
suggest that the water-steam etching considerably preserves
the intrinsic CNT structure, which is beneficial to maintain
high electrical conductivity as shown in Table S2, Supporting
Information. These results collectively confirm the successful
surface amorphization and defect construction in ePCNTM,
which should be attributed to the water-gas generation reaction
during the water-steam etching. Under high-temperature, such
reaction breaks the CC bonds to form carbonic oxide and
hydrogen that discharges with the tail gases, leaving abundant
lattice defects in the ePCNTM product. The resulting intrinsic

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Figure 2.  a) EELS spectra, and b) XPS spectra of PCNTM and ePCNTM-20; c) EPR spectra, d) Raman spectra, e) N2 adsorption–desorption isotherms,
and f) pore size distribution of PCNTM, ePCNTM-10, ePCNTM-20 and ePCNTM-40.
and topological defects in carbon lattice are expected to alters
the geometrical and electronic structures, which may positively
impact the sulfur reaction behaviors thereon.
In view of the potential enhancement in porosity by the
water-steam etching, the porous textures of different samples
were investigated by N2 adsorption–desorption test. Figures 2e
and  2f show the isotherm curves and the corresponding pore
size distributions, respectively. Typically, the PCNTM exhibits
a specific surface area of 72.9 m2 g−1 and hierarchical pore size
distribution with strong pore size concentration at around 1.6
and 4.2 nm. What is noteworthy is that the water-steam etching
basically maintains the pore size distribution profile, but with
a continuous enhancement in surface area, which is mainly
contributed by the enrichment in micropore range. The BET
surface areas of ePCNTM-10, -20, and -40 are 78.1, 102.5, and
115.1 m2 g−1, respectively. This result is in accordance with the
SEM and TEM observations, and confirms the positive effect on
porosity through the defect construction. Such improvement
could favor the sulfur accommodation and its physical confine-
ment against the shuttle effect, and also expose abundant inter-
faces for sulfur reactions.
The influence of intrinsic carbon lattice defects on sulfur
electrochemistry was investigated by density functional theory
(DFT) calculations. The DOS patterns of defective carbon lattice
with 0–5 C atom loss (denoted as C, C-VC1, C-VC2, C-VC3, C-VC4
and C-VC5) are shown in Figure S9, Supporting Information.
The defective carbons maintain the conductor nature as con-
firmed by the almost zero bandgap and the high conductivity
mentioned above. The chemical interactions between LPS and
defective carbon are presented in Figure  3a, which shows the
geometrically stable configurations of Li2S6, as a representative
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LPS, adsorbed on different defective sites. The corresponding
adsorption energies are summarized in Figure  3b. Clearly,
the defective surfaces exhibit enhanced binding energies with
Li2S6 over their non-defective counterpart. The Li2S6 adsorp-
tion on the defective carbon with 5 atom loss demonstrates
a binding energy up to −1.62  eV, which is even comparable
to those achieved by some metal compounds. Such improve-
ment is likely due to that the carbon deficiency can induce the
formation of partially positive C atoms in the remaining lat-
tice,[13] which tends to accept electrons more preferentially from
LPS than the perfect carbon according to the Lewis acid–base
interaction principle.[2b] Apart from the static adsorption, the
Li2S decomposition behavior, which is considered as a critical
kinetic-limiting process in Li–S electrochemistry, was also the-
oretically studied. Figure  3c compares the energy barriers for
Li2S decomposition on various defective carbon surfaces, with
the corresponding energy profiles and configurations presented
in Figure  3d–i. Notably, the perfect carbon lattice suffers from
the highest energy barrier of 1.3  eV for Li2S decomposition,
while on the defective carbon, such barrier can be reduced to
varied extents. The defective configuration with four C atoms
loss delivers the lowest Li2S decomposition barrier of 0.84  eV
among these samples. These calculation results strongly dem-
onstrate that the intrinsic carbon defects are capable of more
effectively confining LPS and catalyzing the sulfur conversion
reactions, thus is promising to promote a stable and fast sulfur
electrochemistry when serving as the multifunctional sulfur
host.
For the experimental validation of the above-mentioned
effects, the cyclic voltammetry (CV) files of symmetric cells
were collected as shown in Figure 4a. It can be clearly observed
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Figure 3.  a) Configurations and b) binding energies for Li2S6 adsorption on a series of defective carbon sites; c) energy barriers of Li2S decomposition
on a series of defective carbon sites and d–i) the corresponding energy profiles.

that the ePCNTM-20 cell exhibits two pairs of redox peaks at
−0.32/0.32  V and −0.6/0.6  V in the CV curves, while contras-
tively, the PCNTM and CNT cells undergo considerable sup-
pression on the peak intensity aside from the serious enlarge-
ment of overpotential to form fusiform CV curves. This obvious
comparison strongly indicates the significantly facilitated
sulfur redox conversions by the carbon lattice defective design.
In addition, the CV profile of the ePCNTM-20 cell maintains
quite well upon several cycles (Figure 4b), suggesting the good
electrochemical reversibility of sulfur reactions thereon. The
facilitation of sulfur reactions by the defect engineering can
be also perceived from the EIS spectra in Figure  4c, where
the ePCNTM-20 cell reveals the smallest internal impedance
among these samples. In concert with the theoretical studies
above, the Li2S redox behaviors were split and respectively
examined. Figure 4d shows the Li2S precipitation profiles under
potentiostatic discharging at 2.05 V (vs Li/Li+). A much higher
deposition capacity (189.1 mAh g−1, vs 52.1 and 154.6 mAh g−1
for CNT and PCNTM respectively) and faster current rising can
be observed in the case of ePCNTM-20, indicating the much
more facile reduction of LPS and the nucleation/growth of Li2S
compared with those on CNT and PCNTM surfaces. Further-
more, The SEM image of ePCNTM-20 microsphere after Li2S
deposition (denoted as ePCNTM-20@Li2S) are observed as

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Figure 4.  a,b) CV and c) EIS profiles of different symmetric cells; d) Li2S deposition profiles and e) LSV curves of Li2S oxidation with f) the corresponding
Tafel plots on different host surfaces; g) UV–vis spectra and optical images (inset) of LPS solution after adsorption by different samples; h) S 2p XPS
spectra of Li2S6 and LPS@ePCNTM-20 composites.
shown in Figure S10, Supporting Information. The uniform
and porous Li2S thin films can be observed coating on the sur-
face of ePCNTM-20, which demonstrates that the ePCNTM-20
can facilitate and uniformize the Li2S deposition. On the other
hand, the Li2S oxidization process was investigated by LSV tech-
nique as shown in Figure 4e. The ePCNTM-20 enables a much
smaller onset potential and a stronger current response for Li2S
oxidization compared with those on PCNTM and CNT surfaces.
Meanwhile, the corresponding Tafel plots in Figure 4f also dem-
onstrate the smallest Tafel slope (76 mV dec−1) in ePCNTM-20
scenario, suggesting the fastest conversion kinetics. These
results strongly confirm the excellent catalytic effect on the
sulfur redox reactions by the carbon defect engineering, which
is consistent with the theoretical prediction above.
Apart from that, the LPS adsorption effect was verified by
immersing the same mass of different host materials in 5 mm
Li2S6 solution. The inset of Figure 4g shows the typical brownish
color of the blank LPS solution, while the most significant
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discoloration is observed after adsorption by ePCNTM-20 for
12 h. Correspondingly, the UV–vis spectrum of the superna-
tant in the case of ePCNTM-20 also demonstrate the weakest
absorbance intensity among these samples, signifying the most
LPS adsorbed by the adsorbent. These results consistently con-
firm the highest LPS adsorbability of ePCNTM-20 attributed to
the defective structure. The underlying chemical interactions
between LPS and ePCNTM-20 was probed by XPS analysis.
Figure  4h shows the S 2p spectra of Li2S6 before and after
adsorption by ePCNTM-20. Two pairs of typical S 2p peaks at
160.4/161.6 and 162.7/163.9 eV can be observed in the spectrum
of bare Li2S6, which can be assigned to the terminal (ST−1) and
bridging sulfur (SB0) in Li2S6 configuration, respectively. After
adsorption, the LPS@ePCNTM-20 composite witness a consid-
erable shift for these peaks toward higher binding energy (BE)
region, accompanied by the emergence of two new broad peaks
at high BE range corresponding to the thiosulfate and sulfate
species. These variations suggest the reduction of electron
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Figure 5.  a) CV curves of S/ePCNTM-20 electrode; b) cycle performances of different electrodes at 0.2 C, c) charge–discharge profiles of S/ePCNTM-20
electrode at different cycles; d) rate performances, e) long-term cycling behaviors at 1 C, and f) EIS plots of different electrodes; g) cycling performance
and h) voltage profile of S/ePCNTM-20 electrode under raised sulfur loadings.

cloud density of S atoms due to the electron transfer between
LPS and ePCNTM-20, which further confirms the chemical
sulfur confinement effect on ePCNTM-20 surface.
Based on the above results, the actual effects of carbon lat-
tice defects on Li–S battery performance were examined in
coin cell configuration. To this end, sulfur composite based on
the as-developed defect-rich ePCNTM-20 was first prepared as
the cathode materials. The composite was obtained through
the typical melt-impregnation method. Figure S11, Supporting
Information, shows the XRD pattern of PCNTM, ePCNTM-20,
and the S-loaded S/ePCNTM-20 composite. Compared with
PCNTM, the relatively weaker XRD intensity with still distinct
peak of graphitic carbon at 26° in ePCNTM-20 pattern confirm
the partial amorphization and defect construction via the water-
steam etching, which echoes with previous results. Meanwhile,
the sharp and characteristic peaks of sulfur (JCPDS 08-0247)
in the composite confirms the successful sulfur impregnation.
The TGA result determines a sulfur content of 74.2  wt.% in
S/ePCNTM-20 (Figure S12, Supporting Information), and the
EDS mapping also demonstrates the uniform sulfur distribu-
tion therein (Figure S13, Supporting Information). Other sulfur
composites including S/CNT and S/PCNTM were also pre-
pared for comparison.
The obtained Li–S coin cells were evaluated first by CV
measurement. As shown in Figure  5a, the S/ePCNTM-20
electrode exhibits clearly two peaks during the cathodic scan-
ning. The peak at around 2.34 V relates to the reduction of ele-
ment sulfur into high-order LPS (e.g., Li2S8, Li2S6, and Li2S4),
while the other one at around 2.02  V is contributed by the
further reductive conversion into the insoluble Li2S2 and Li2S.
Accordingly, the overlapped peaks upon anodic scanning can
be assigned to the inverse oxidization processes into element
sulfur. By comparison, the S/ePCNTM-20 delivers clearly much
higher current, sharper peaks, and smaller overpotentials com-
pared with those in the CV profiles of S/CNT and S/PCNTM
electrodes (Figure S14, Supporting Information), suggesting the
significantly improved reaction kinetics. Figure S15a–c, Sup-
porting Information, shows the CV curves at different sweeping
rates to evaluate the Li+ diffusion behaviors in different cells.
The corresponding correlation between the peak intensity (at
various peaks marked as A, B, and C) versus the square root of
scanning rate were linearly fitted in Figure S15d–f, Supporting

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Information. According to the Randles–Sevick equation,[14] the
Li+ diffusion coefficient positively relates to the slope of fitted
line when the other parameters are assumed constant. It is
notable that the S/ePCNTM-20 electrode exhibits consistently
much higher slopes at all the peaks, indicating the higher Li+
diffusion rate compared with those in the other two electrodes.
Such improvement in Li+ diffusion property could also benefit
the sulfur reaction kinetics and effectively improve the rate per-
formance of the batteries.
Figure  5b demonstrates the cycling behavior of different
electrodes at 0.2 C. Clearly, the S/ePCNTM-20 electrode
exhibits the best cycling performance, with a high coulombic
efficiency and discharge capacity of 1067 mAh g−1 after
100 cycles. The post-cycling SEM image was collected as shown
in Figure S16, Supporting Information. It can be noted that the
ePCNTM-20 basically maintains the microspherical architec-
ture in rich porosity after 100 cycles, demonstrating the good
structural integrity that accounts for its good cyclic stability.
The charge–discharge profiles of S/ePCNTM-20 electrode in
Figure  5c are consistent with the CV result, showing two dis-
charge plateaus and a long charge plateau. Such voltage pro-
file maintains well upon the gravimetric cycling over 100 cycle
with limited capacity loss. Figure 5d compares the rate perfor-
mance of different electrodes. S/ePCNTM-20 exhibits the best
rate capability with much higher capability of 785 mAh g−1 at
3.0 C compared with those of S/CNT (363 mAh g−1) and S/
PCNTM (573 mAh g−1) electrodes. Meanwhile, a highly revers-
ible capacity of 1178 mAh g−1 can be recovered after the C-rate
is switched back to 0.2 C. Owing to strong sulfur confine-
ment and effective catalyzation effect, a remarkable long-term
cyclic stability of S/ePCNTM-20 electrode can be achieved,
with a 0.046% per cycle capacity fading rate after 500 cycles
at 1.0 C (Figure 5e). It should be noted that the obtained elec-
trochemical performance of S/ePCNTM-20 electrode is highly
competitive among other CNT-based sulfur cathodes (Table S3,
Supporting Information). The EIS spectra in Figure  5f com-
pare the electrochemical resistance among different electrodes.
All the EIS curves show a semicircle, which corresponds to the
charge-transfer impedance (Rct), and a linear part assigned to
the Warburg resistance. Clearly, the S/ePCNTM-20 electrode
delivers the smallest Rct compared with those of S/CNT and
S/PCNTM electrode, consistently demonstrate the facilitated
sulfur reaction by the defective design. Hence, ePCNTM-20
could be considered as the promising choice as the sulfur host
material in Li–S batteries.
Given this, S/ePCNTM-20 electrode was employed for high-
loading battery evaluation to explore the potential of the as-
developed defective design for practical application. A series
of sulfur loadings were applied from 2.9 to 6.5  mg cm−2 as
shown in Figure 5g,h. Attributed to the effective sulfur immo-
bilization and catalyzation by the intrinsic carbon defects,
decent cycling performance can be achieved for all the elec-
trodes at 0.1 C. The areal capacity gradually enhances along
with the increase of sulfur loading, leading to a favorable areal
capacity retention of 3.2 mAh cm−2 after 50 cycles under a
sulfur loading of 6.5  mg cm−2, which is comparable to that
of the commercial Li-ion batteries. The typical two-plateau
discharge profile can be still achievable even under the high
loading of 6.5  mg cm−2, further indicating the good reaction
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kinetics realized by the ePCNTM design. All above results
demonstrate the great promise of the intrinsic carbon lattice
defect engineering in the development of high-performance
and practically viable Li–S batteries.
3. Conclusion
In summary, an intrinsic carbon defect engineering was
employed to address the key challenges of shuttle effect and
sluggish kinetics in Li–S batteries. The unique nanostruc-
turing in terms of both morphology and lattice character was
developed via the facile and scalable spray drying method fol-
lowed by a critical “sauna” activation. The product delivers
a porous quasi-microspherical architecture assembled by
intertwined CNT with intrinsic atomic deficiency in carbon
lattice. The defect-rich CNT is endowed with stronger sulfur
immobilization and higher catalytic activity to sulfur reac-
tions compared with its pristine counterpart in intact lattice,
which is consistently confirmed by a series of computational,
spectral, and electrochemical results. When applied as sulfur
host material, the as-developed ePCNTM enables high sulfur
utilization, reversible redox conversions, and fast reaction
kinetics, contributing to excellent cyclability and rate capa-
bility, as well as decent high-loading performance of the
Li–S cells.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was supported by Natural Science Foundation of Hebei
Province of China (B2020202052, B2019202277); State Key Laboratory
of Reliability and Intelligence of Electrical Equipment (No. EERI_
PI2020007), Hebei University of Technology, China; Outstanding Youth
Project of Guangdong Natural Science Foundation (2021B1515020051);
the Program for the Outstanding Young Talents of Hebei Province,
China (YG.Z.); Chunhui Project of Ministry of Education of the
People’s Republic of China (No. Z2017010); Department of Science
and Technology of Guangdong Province (No. 2020B0909030004,
2019JC01L203); Guangdong Innovative and Entrepreneurial Team
Program (No. 2016ZT06C517); Science and Technology Program of
Guangzhou (No. 2019050001); Science and Technology Program
of Zhaoqing (No. 2019K038); and Yunnan Expert Workstation
(202005AF150028). The authors also thank the support from Natural
Sciences and Engineering Research Council of Canada, University of
Waterloo, and Waterloo Institute for Nanotechnology.
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
Research data are not shared.
© 2021 Wiley-VCH GmbH
www.advancedsciencenews.com
Keywords
carbon defects, carbon nanotubes, electrochemical performance, Li–S
batteries, water-steam etching
Received: February 10, 2021
Revised: April 4, 2021
Published online: May 3, 2021
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