Chemical Engineering Journal 421 (2021) 129707

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Chemical Engineering Journal

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Laser-induced micro-explosion to construct hierarchical structure as

efficient polysulfide mediators for high-performance
lithium-sulfur batteries
Chao Zhou a, *, Ming Li b, Min Hong a, Nantao Hu a, *, Zhi Yang a, Liying Zhang a, Yafei Zhang a, *
a
Key Laboratory of Thin Film and Microfabrication Technology (Ministry of Education), School of Electronics, Information and Electrical Engineering, Shanghai Jiao
Tong University, Dong Chuan Road No.800, Shanghai 200240, China
b
State Key Laboratory of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050,
China

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

Keywords: Rational design and scalable construction of sulfur cathodes with high areal capacity and suppressed shuttle
Laser-induced effect are challenging for real Li-S application. Herein, laser-induced micro-explosive techniques were firstly
ZnO nanoparticles demonstrated as high-efficient polysulfide mediator for Li-S batteries, in which unique hierarchical structure
Shuttle effect
(nitrogen-doped porous carbon (LNPCs) skeletons uniformly decorated with metal oxide nanoparticles) were
Catalytic conversion
Li-S batteries
designed and constructed. The as-assembled nitrogen-doped porous carbons decorated with ZnO nanoparticles
(LNPCs-ZnO) hybrids cathode perform exceptionally high discharge capacity of 1184.9 mAh g− 1 at 0.5C and
excellent rate discharge capacity of 716.1 mA h g− 1 at 3C, as well as a remarkable cycling performance (a low-
capacity decay rate of 0.31% per cycle at 0.5C upon 1000 cycles). Moreover, impressive areal sulfur loading up to
6.7 mg cm− 2 leads to a high initial areal capacity of 6.36 mAh cm− 2 and excellent cycling stability at 0.2C. The
DFT calculations propose that the intrinsic interaction and the rapid catalytical effects play the key role in
suppressing the shuttling effect of LiPSs. This work provides new insights for novel structure design and opens up
a potential route to construct Li-S batteries with high areal sulfur loadings for their practical applications.

1. Introduction the above-mentioned issues, multifarious strategies have been devel­

Lithium-sulfur batteries (Li-S batteries) have been deemed as one of
the most prospective devices for the next-generation energy storage
systems owing to their ultrahigh theoretical specific capacity (1675 mA
h g− 1), [1] remarkable energy density (2600 W h kg− 1), [2] low cost [3]
and less contamination. [4] However, there are many issues which still
plagued the wide practical applications, 1) intrinsic insulating nature of
element sulfur [5] and final discharge products of Li2S2/Li2S result in
sluggish reaction kinetics;[6] 2) soluble LiPS intermediates formed
during discharge process and diffusion between cathode and anode,
those intermediates dissolved in the ether electrolyte and formed
obvious concentration fluctuation, resulting in “shuttle effect”;[7] 3)
insulated Li2S layer is easily formed on the surface of the Li metal anode
during discharge process, leading to the S element and Li metal anode
irreversible loss, which further causes the irreversible capacity attenu­
ation, large polarization and poor cycling stability. [8] In order to solve
oped to restrain polysulfide shuttling [8].
Carbonaceous materials, such as meso- /microporous carbon, [9,10]
carbon nanotubes, [11–13] carbon fibers, [14–16] carbon sphere,
[17,18] grapheme [10b], [19–21] and reduced graphene oxide [22–25],
have been widely used as the sulfur host materials. These carbon-based
materials can not only provide large pore volume and substantially
boost the electronic conductivity of the sulfur-based cathode but also
can further alleviate the diffusion of polysulfide in the electrode system.
[26–31] However, the weak trapping ability and fast capacity decay can
result from the feeble Van der Waals bond energy between nonpolar
carbonaceous materials and polar polysulfides. [32] Although hetero­
atom (such as N, S, F, P, and B elements) doping into the carbon struc­
ture can produce polar sites and enhance the adsorbing interaction with
polysulfide, it does not substantially improve the polysulfide trapping
ability over long cycling due to the weak chemisorption. [33–39]
Alternatively, polar inorganic nanomaterials, including metal oxides,

* Corresponding authors.
E-mail addresses: chaozhou0721@sjtu.edu.cn (C. Zhou), hunantao@sjtu.edu.cn (N. Hu), yfzhang@sjtu.edu.cn (Y. Zhang).

https://doi.org/10.1016/j.cej.2021.129707
Received 15 January 2021; Received in revised form 20 March 2021; Accepted 3 April 2021
Available online 15 April 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
C. Zhou et al.
[40–42] metal sulfides, [26,43–48] metal phosphides, [49–51] metal
nitrides, [52–54] and metal carbides [55–57], etc., have widely been
demonstrated that adequate functional polar groups had strong inter­
action with LiPSs and blocked the LiPSs diffusion. In this respect, con­
structing 3D porous carbonaceous hosts with polar inorganic
nanomaterials is preferable in addressing the long cycling life and pol­
ysulfide shuttle issues. In light of recent research work, it was demon­
strated that ZnO NPs had an excellent LiPSs anchoring ability and
superior binding energy with LiPSs. [58–60] For example, Kumar et al.
[59] proposed a novel interconnected conductive frameworks with
strongly coupled zinc oxide (ZnO) nanowires and macroporous nickel
foam to obtain an areal sulfur loading of 3 mg cm− 2 and a reversible
discharge capacity of 776 mA h g− 1 at 1C after 200 cycles. Shi et al. [60]
developed free-standing electrode materials combined with reduced
graphene oxide (rGO)-sulfur hybrid aerogel and atomic layer deposition
(ALD) ZnO coatings for Li-S battery, and a discharge capacity of 998 mA
h g− 1 at 0.2C was achieved. Despite the wide varieties of polar nano­
materials have been investigated, the rate performance and polysulfide
trapping ability are still not satisfactory with a high areal sulfur loading
due to the poor electronic conductivity and low specific surface area of
metal oxides. [29,61,62] Moreover, it is imperative to open up a novel
path to overcome the above-mentioned problems.
Since laser-induced graphene was firstly reported in 2014, [63] it has
been aroused warm research interest in the field of energy storage giving
credit to their high surface area, [64] superior electronic conductivity,
[63,64] and excellent thermal stability. [63,65] These excellent physical
and chemical properties make them proverbially studied in the field of
Li-ion battery, [66] Na-ion battery, [67] etc. The Li/Na-ion battery
based on pristine LIG or heteroatom-doped LIG exhibits excellent elec­
trochemical performances. To further enhance the discharge capacity
and rate performance of LIG-based Li/Na-ion battery, transition-metal
oxides [68] and transition-metal sulfide [69] have been introduced to
form hybrids with LIG or heteroatom-doped LIG hybrid frameworks. In
our previous work, [68] biomass gelatin solutions and manganese (II)
phthalocyanine were used as precursors to construct 3D laser-induced
MnO/Mn3O4/N-doped-graphene hybrid framework on copper foils
through a simple one-step laser-inducing process, showing exceptionally
reversible capacity of 992 mAh g− 1 at 0.2 A g− 1. Although great pro­
gresses have been made in the field of Li/Na-ion batteries, most of these
researches are focusing on the electrical conductivity and reversible
capacity optimization. However, some problems still exist in terms of
cycle stability and rate performance. Until now, few works are evolving
in unique laser-induced heteroatom-doped porous carbon/ transition
metal oxides hybrids through a one-step laser-induced micro-explosive
technique for Li-S battery and it is difficult to rationally design a
unique polar-non-polar structure with excellent conductivity and high
specific surface area to strongly trap polysulfide as well as long-term
cycling stability.
Herein, a facile laser-induced micro-explosive strategy was demon­
strated to rationally design a novel 3D porous cathode configuration for
Li-S batteries based on N-doped porous carbon hierarchical frameworks,
which are simultaneously decorated with polysulfide-confining ZnO
NPs, hereafter referred to as LNPCs-ZnO. The gel coatings, containing
poly (amic acid) (PAA), glycine, and Zn(NO3)2, were cast onto the sur­
face of glass slides, followed by undergoing graphitization during the
micro-explosive process via a facile laser irradiation at room tempera­
ture. As a result, unique 3D porous architectural LNPCs-ZnO hybrid
frameworks were obtained. As a cathode in Li-S batteries, the unique
structure of LNPCs-ZnO hybrid frameworks not only exhibited high
reversible capacity, but also alleviated polysulfide shuttling effect and
greatly improved cycling stability. Moreover, giving credit to the high
specific surface area and high electronic conductivity of these unique
structures, high sulfur utilization and high-rate performance of Li-S
battery were achieved. This study will indeed provide a new direction
to construct unique 3D porous hybrid frameworks applied in Li-S bat­
tery-based devices, which holds great potentials for next-generation
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Chemical Engineering Journal 421 (2021) 129707
high-performance wearable and portable devices.
2. Experimental section
2.1. Preparation of 3D porous LNPCs-ZnO hybrid frameworks
The LNPCs-ZnO hybrid frameworks were prepared by using the same
laser scribing method proposed in our previous works. [68,86] Typi­
cally, 40 mmol Zn(NO3)2⋅6H2O and 40 mmol glycine were dissolved in
10 mL Dimethylacetamide (DMAc) solution with continuous magnetic
stirring at 65 ◦ C to form a uniform solution. And then 10 mL poly (amic
acid) (PAA) solution was also added into the as-obtained solution. PAA
was prepared by the same method that had been described in our pre­
vious work. The mixture solution was magnetically stirred for 2 h to
form a homogeneous solution. [86] The PAA solutions containing Zn
(NO3)2⋅6H2O and glycine were then cast onto the surface of slides. The
thickness of the gel coating contained PAA, glycine, and Zn(NO3)2 was
controlled at 100 μm through the scraper. Subsequently, the coating was
cured on slides upon evaporation at 80 ℃ for 12 h, followed by laser
direct writing under ambient conditions using a CO2 laser cutter plat­
form, which employed an infrared wave laser with a laser power of 25
W, a wavelength of 10.6 μm (Trotec Speedy 100), and a beam size of
laser was ~ 100 μm. In this experiment, the laser power and scan rate
were fixed at 4.8 W and 35 cm/s, respectively, during laser induction. In
order to remove the unreacted precursors and by-products of LNPCs-
ZnO hybrids, the LNPCs-ZnO hybrids were alternately washed with
ethanol and deionized water three times and then dried in the vacuum
oven at 60 ◦ C for 12 h. For comparison, LNPCs were prepared with a
similar method without Zn moieties.
2.2. Preparation of LNPCs-ZnO/S cathode
LNPCs-ZnO/S cathode was achieved by a feasible melt-diffusion
method. [49] Briefly, LNPCs-ZnO hybrid frameworks were mixed and
ground with sublimed sulfur powder at a different weight ratio of 3:7,
2:8, and 1:9, respectively. The obtained composites were transferred
into a 10 mL Teflon-lined autoclave and then followed by maintaining
the temperature at 155 ◦ C for 12 h under argon atmospheres. For
comparison, LNPCs/S was also obtained via a similar procedure, apart
from LNPCs was used as the host material instead of LNPCs-ZnO.
2.3. Preparation of Li2S6 solution and adsorption test
In this experiment, the Li2S6 solution was chosen as the representa­
tive of polysulfides. To prepare the Li2S6 solution, Li2S and sulfur
powders with a molar ratio of 1:5 were added into a certain amount of
1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) solution (1 : 1, v/
v) under vigorous stirring at 60 ◦ C for 24 h in the glove-box filled with
Ar. The concentration of the as-obtained Li2S6 solution was 5 mmol L-1.
Before the polysulfides adsorption test, all the LNPCs and LNPCs-ZnO
hybrids were dried at 60 ◦ C under vacuum for 12 h. The LNPCs and
LNPCs-ZnO hybrids with equal weight (10 mg) were immersed in a 2 mL
Li2S6 solution undergoing static adsorption for 12 h, respectively. The
color variation of supernatant with time can be observed and the
adsorption capability of LNPCs and LNPCs-ZnO to Li2S6 was tested by
UV–vis spectroscopy. The blank Li2S6 solution was used as the reference.
2.4. Material characterization
The morphologies of the above-mentioned materials were charac­
terized by FE-SEM analysis (Carl Zeiss Ultra55). TEM, HRTEM and EDX
mapping were all performed on a JEOL 2010HT microscope operating at
200 keV. X-ray photoelectron spectroscopy (XPS) was performed on a
Kratos Axis Ultra DLD and fitted with XPS peak 4.1 software. The
structural information of the samples was conducted on XRD, utilizing
Cu Kα as a radiation source and 40 kV as working voltage. Raman
C. Zhou et al.
spectra were measured by a Renishaw in Via Reflex Raman spectrometer
with a 532 nm laser. The UV–Vis absorption spectra were obtained from
a Perkin-Elmer Lambda 950 UV–Vis–NIR spectrophotometer. N2
adsorption–desorption isotherms were obtained at 78 K using a Quan­
tachrome Autosorb-3B surface analyzer relying on the Brunauer-
Emmett-Teller (BET) method. The pore size distributions were ac­
quired according to the Barrett-Joyner-Halenda (BJH) method. The
sulfur content in these hybrids was performed by thermogravimetric
Analysis (TGA) from 30 to 500 ◦ C with a programmed heating rate of
5 ◦ C/min under nitrogen atmospheres.
2.5. Li2S nucleation measurements
The mixture of S and Li2S at a molar ratio of 7:1 was added in 1 M
lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in a solvent of DOL/
DME (1:1, v/v) with stirring at 60 ◦ C for 24 h in glovebox. 20 µL Li2S8
(0.5 mol/L) catholyte was added onto LNPCs-ZnO, while 20 µL 1.0 M
LiTFSI (DME/DOL, v/v = 1:1) electrolyte onto Li anode. The assembly
cell was galvanostatically discharged to 2.06 V at a current of 0.112 mA
and then kept potentiostatically at 2.05 V for Li2S nucleation and growth
until the current dropped below 10-5 A.
2.6. Electrochemical measurements
The detailed electrochemical performance of the LNPCs/S, and
LNPCs/S cathodes was measured using a CR2025 coin cell, assembled in
an Ar-filled glove box (H2O＜0.1 ppm and O2＜0.1 ppm). The cathode
and Li metal anode were separated by a Celgard 3501 separator. The
electrolyte used in this work was 1 M lithium bis-
trifluoromethanesulfonyl imide (LiTFSI) dissolved in DME/DOL (1:1 in
volume) with 1.0 wt% LiNO3 as the additive, and the electrolyte/sulfur
ratio was controlled as about 10 μL mg− 1. The cathode slurry was pre­
pared by mixing the LNPCs/S or LNPCs-ZnO/S cathode, super P, and
polyvinylidene fluoride (PVDF) binder with a mass ratio of 8:1:1 in N-
methylpyrrolidone (NMP) and magnetic stirred for 2 h to form a ho­
mogeneous dispersion. Then, the as-obtained slurry was uniformly cast
onto carbon-coated aluminum (Al) foil through using a doctor blade and
dried under vacuum oven at 60 ◦ C overnight. Subsequently, the ob­
tained electrode foil was punched into disks with a diameter of 12 mm,
where the areal sulfur mass loading is around 2.4–6.7 mg cm− 2. Cyclic
voltammetry (CV) plots and electrochemical impedance spectroscopy
(EIS) were conducted on a CHI-760E electrochemical workstation
(Shanghai Chenhua Instrument Co. Ltd., China). CV plots were per­
formed at a potential range of 1.7–2.8 V with the scan rate from 0.05 to
1 mV s− 1. EIS curves were implemented under open circuit potential
with a frequency ranging from 105 to 10-2 Hz at 5 mV amplitude. The
galvanostatic charge–discharge (GCD) and rate performance were car­
ried out using Land Battery Measurement System with the potential
from 1.6 to 2.8 V at room temperature. Shuttle current tests were con­
ducted similar to the previous work based on S. R. Narayanan method.
[87,88] LiNO3-free electrolyte was chosen to avoid Lithium anode
passivation. For the measurement, the sulfur cathodes were fully acti­
vated under a current density of 0.05C. Then, the voltage of the cells was
charged to 2.7 V and leave the cell under open circuit potential for 5
min. Subsequently, the test was switched to potentiostatic mode for 60
mins to offset the drop voltage at voltage stages of 2.6 V until steady-
state value reached. This steady-state current is the value of the shut­
tle current. The redox current tests of symmetric batteries and Li2S
nucleation tests are shown in Supporting Information.
2.7. Theoretical calculation
ZnO crystal structure with lattice parameters of a = b = 3.249 Å, c =
5.205 Å was built. The studied (0 0 2) plane was then cleaved from the
unit cell. Further, the cleaved plane was increased to five atomic layers
and 3 × 3 super-cell, comprised of a total of 54 atoms, and a vacuum
3
Chemical Engineering Journal 421 (2021) 129707
layer of 15 Å was added in the Z direction to avoid slab interlayer
possible interaction as shown in Figure A larger surface area was
generated to provide favorable adsorption locations for Li2Sx species
(These Li2Sx species include S8, Li2S, Li2S2, Li2S4, Li2S6, and Li2S8).
An all-electron method with the generalized gradient approximation
(GGA) was exploited to execute the spin-polarized DFT computations.
The model of Perdew-Burke-Ernzerhof (PBE) functional in the DMol3
Code was implemented.1-4 Also, the double numerical plus polarization
(DNP) basis set was used. A convergence criterion of 10-5 a.u. on the
total energy, maximum force of 0.002 a.u-1, and maximum displacement
of 0.005 Å were used for self-consistent field (SCF) calculations. The
binding energy (E) was defined by the following equation:
Ebinding = E(ZnO (0 0 2)/Li2Sx))-E(ZnO -E(Li2Sx) (2)
(0 0 2)
where the E(ZnO (0 0 2)/Li2Sx)), E(ZnO (0 0 2), E(Li2Sx) are, respectively, the
total energies of the selected (0 0 2) surface, the ZnO NPs, and the Li2Sx
(1 ≤ x ≤ 8) molecule adsorbed on the surface.
3. Results and discussion
The construction workflow of LNPCs-ZnO hybrid frameworks for Li-S
batteries are schematically demonstrated in Fig. 1. For the purpose of
directly obtaining the LNPCs-ZnO hybrid frameworks, the precursor
solution containing PAA, glycine, and Zn(NO3)2 was cast onto the sur­
face of slides (Fig. 1(a)). The thickness of the gel coating was fixed at
100 μm through the scraper. A solid coating attached on slides was able
to be formed via evaporation of DMAc at 120 ◦ C for 2 h. The solid
coating atop slides was used as the precursor for laser irradiation. During
this process, the extremely high local temperature (＞2500 oC) was
generated, [31,32] while the coatings were undergoing graphitization
during the micro-explosive process, which facilitated the metal oxides to
undergo homogeneous nucleation process on the surface of the laser-
induced porous carbons, and consequently forming transitional metal
oxides/N-doped pore carbon hybrid frameworks (Fig. 1(b)). However,
the obtained hybrid frameworks have abundant internal voids, which
can effectively encapsulate more active sulfur and absorb/store the
electrolyte. To fabricate the LNPCs-ZnO/80S cathodes, a facile melt-
diffusion method was used to infuse the sulfur powder into an internal
void. As a result, the long-chain sulfur particles were uniformly
dispersed and anchoring on the surface of laser-induced pore carbons.
Based on the LNPCs-ZnO/80S cathodes, the Li-S battery was facilely
assembled (Fig. 1(c)). For comparison, LNPCs hybrid frameworks
without Zn moieties were also constructed with a similar method.
To clarify the morphologies and structure features of LNPCs and
LNPCs-ZnO hybrid frameworks, the FESEM and HRTEM images were
collected. As shown in Fig. 2(a) and Figure S1 (Supporting Information),
the as-constructed LNPCs-ZnO hybrid frameworks were combined with
an inter-connected porous network by laser induction micro-explosion
techniques under focusing conditions using PAA, glycine, and Zn
(NO3)2 as the precursor, and the porous network with diameters of ＜
100 nm. In contrast, when only using PAA and glycine as the precursor,
the structure of LNPCs hybrid frameworks has changed significantly. As
shown in Fig. 2(d), the LNPCs hybrid frameworks have a more homo­
geneous distribution of nanopores and macropores distributed
throughout the composites. Being consistent with the FESEM results, the
TEM image also revealed that ZnO nanoparticles with 5–10 nm were
uniformly anchored on the surfaces of LNPCs. Moreover, the HRTEM
indicated that the ZnO nanoparticles were well crystallized with a
marked lattice fringe spacing of ~ 0.26 nm, corresponding to the (0 0 2)
lattice plane (JCPDS no.79–0207) (Figure S1(d), Supporting Informa­
tion). [70] Fig. 2(e) displays the TEM images of the LNPCs hybrid
frameworks for comparison. The TEM image demonstrates that the
fabricated LNPCs hybrid frameworks are composed of nanopores/mes­
opores and hierarchical structures. At higher magnifications, it can be
clearly observed that the nanopores/ mesopores are uniformly
C. Zhou et al.
Fig. 1. Schematic illustration of the construction of LNPCs-ZnO hybrid frameworks for Li-S batteries.
distributed on the LNPCs hybrid frameworks (Fig. 2(f)).
Raman spectroscopy of the LNPCs and LNPCs-ZnO hybrid frame­
works was carried out, as shown in Fig. 2(g). The three typical peaks
located at around 1350, 1580, and 2650 cm− 1 clearly correspond to the
D band arising from sp3-type disordered carbon and lattice defects, G
band arising from sp2-type ordered graphitic carbon and 2D band
resulting from second-order zone-boundary phonons, respectively. [68]
In comparison with LNPCs, LNPCs-ZnO hybrid frameworks can be
formed after adding Zn(NO3)2 as a micro-explosive initiator into PAA
and glycine solutions. For LNPCs-ZnO hybrid frameworks, characteristic
peaks at 318 and 437 cm− 1 are ascribing to the bending vibration of Zn-
O, suggesting the formation of ZnO nanoparticles. [71] Fig. 2(h) shows
the XRD patterns of LNPCs and LNPCs-ZnO hybrid frameworks. Both of
the LNPCs and LNPCs-ZnO hybrids show the obvious two broad pro­
nounced diffraction peaks at 2θ ≈ 26.3◦ , and 43.2◦ , which can agree well
with the (0 0 2) and (0 0 4) diffraction peaks of graphitic structure of
graphene (JCPDS 75–1621), respectively. [68,72,73] For LNPCs-ZnO
hybrid frameworks, apart from the broad peak of LNPCs, sharp peaks
at 2θ ≈ 31.7, 34.4, 36.2, 47.4, 56.4, 62.6, and 67.6◦ are observed, cor­
responding to the (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), and (1 1 2)
planes of ZnO (JCPDS no.79–0207). [74,75] These results further
demonstrate the existence of ZnO nanoparticles in LNPCs-ZnO hybrid
frameworks. Moreover, the chemical states and surface compositions of
the elements in the LNPCs and LNPCs-ZnO hybrids fabricated with and
without addition of Zn(NO3)2 were analyzed by XPS. As depicted in
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Chemical Engineering Journal 421 (2021) 129707
Figure S2 (Supporting Information), the full survey XPS spectrum of
LNPCs-ZnO hybrid frameworks reveals the presence of C 1 s (285.2 eV),
[76] O 1 s (532.1 eV), [23] N 1 s (398.2 eV), [29] and Zn 2p (1021.2 eV
and 1045.1 eV). [77,78] The deconvoluted XPS spectra of LNPCs-ZnO
hybrid frameworks at C 1 s region (Figure S2(b), Supporting Informa­
tion) show four main peaks at 284.8, 285.4, 286.2, and 289.4 eV,
respectively, corresponding to C–C, C-N/C-O, C-N/C-O, and O-C = O.
[76] The C–C bond reveals that the LNPCs-ZnO hybrids have abundant
carbon frameworks. In the meantime, oxygen-containing functional
groups may play an important role in capturing polysulfide. The high-
resolution O 1 s spectrum in Figure S2(c) (Supporting Information)
can be deconvoluted into four main peaks of Zn-O (530.9 eV), [77] C-O
(531.4 eV), [23] C = O (532.7 eV), [23] and O-C = O (533.8 eV). [23]
Figure S2(d) (Supporting Information) shows the N 1 s spectra, and three
prominent peaks can be distinguished at 398.3, 399.3, and 401.3 eV,
which correspond to Pyridinic N, Pyrrolic N, and Graphitic N, respec­
tively. [29,34] Graphitic N can benefit for improving the conductivity of
the LNPCs-ZnO hybrid frameworks. [29,79] Pyrrolic N and Pyridinic N
can bring about a large amount of functional and active site, and provide
multiple channels which further facilitate the electrolyte-ion diffusion.
[34] It’s suggested that the nitrogen-containing moieties can help
improving the electrochemical performance. [68] The Zn state spectrum
of LNPCs-ZnO hybrid frameworks shows two prominent peaks at 1021.2
eV and 1045.1 eV (Figure S2(d), Supporting Information), correspond­
ing to Zn 2p1/2 and Zn 2p3/2, respectively. [58,78] All these results
C. Zhou et al. Chemical Engineering Journal 421 (2021) 129707

Fig. 2. Morphology and structure of LNPCs-ZnO and LNPCs hybrid frameworks. (a) FESEM images of LNPCs-ZnO with porous structure. (b) TEM image showing the
ZnO nanoparticles (dark color) and the background porous carbon-based materials. (c) HRTEM image of few-layer graphene with different interlayer distances ZnO
with 0.26 nm interlayer distance, respectively. (d) FESEM images of LNPCs with porous structure. (e) TEM image showing the nanopores/mesopores and hierarchical
structure of carbon-based materials. (f) HRTEM image of porous carbon with different pore diameters. (g) Raman spectroscopy of LNPCs and LNPCs-ZnO sample
showing the coexistence of nitrogen-doped graphene, ZnO nanoparticles, in comparison to the LNPCs from glycine. (h) XRD pattern of LNPCs and LNPCs-ZnO hybrids
showing characteristic peaks of nitrogen-doped graphene, and ZnO. (i) Nitrogen adsorption and desorption isotherms of LNPCs-ZnO hybrid frameworks.

strongly confirm that the unique structure of LNPCs-ZnO hybrid
frameworks has been formed via this simple method. To further inves­
tigate the porous structure of LNPCs and LNPCs-ZnO hybrid frameworks,
nitrogen adsorption–desorption isotherms and corresponding pore-size
distribution are shown in Fig. 2(i) and Figure S4 (Supporting Informa­
tion). The LNPCs-ZnO hybrid framework possesses the largest specific
surface area of 704.2 m2 g− 1 (with pore sizes below 2 nm), whereas
LNPCs has a value of 879.6 m2/g (with pore sizes ＜15 nm) (Figure S4,
Supporting Information). The huge specific surface area of LNPCs-ZnO
hybrids provides abundant reaction interface and facilitates the
dispersion of sulfur, thus further increasing the electrochemical capacity
of the cathode. [80] The pore volume resulting from interspace between
adjacent hierarchical structures can mitigate the volume expansion,
further improving the cycling stability. To estimate the weight content
of ZnO in LNPCs-ZnO hybrid frameworks, the ICP-AES of the composite
was tested (Table S1, Supporting Information). Based on the ICP-AES
result, the weight fraction of ZnO was about 4.33%.
To investigate the performance of Li-S battery with the unique
structure as the sulfur host, firstly the sulfur can be securely infiltrated
into the LNPCs-ZnO hybrid frameworks through a typical molten
method, resulting in substantial sulfur loading of 71.3–87.6 wt% in the
LNPCs-ZnO hybrid frameworks (Fig. 3(a)). In order to confirm that the
sulfur powder was successfully diffused into the mesopores and micro­
pores of LNPCs-ZnO and LNPCs matrix, the XRD characterization was
carried out to measure pristine sulfur, LNPCs-ZnO/80S and LNPCs/80S
hybrids, respectively. As shown in Fig. 3(b), the additional sharp char­
acteristic peaks of LNPCs-ZnO/80S and LNPCs hybrids are well indexed
to the typical peaks of orthorhombic crystalline sulfur (JCPDS no.
08–0247), [81,82] demonstrating that the sulfur particles have been
encapsulated into the mesopores and micropores of LNPCs-ZnO and
LNPCs matrix successfully. What’s more, compared to the diffraction
peaks of pristine crystalline sulfur, the peak intensity of the LNPCs-ZnO/
80S and LNPCs/80S was drastically weakened. This indicates that the
crystalline sulfur formation has been suppressed efficiently due to the
long-chain of S8 and most of the sulfur particles have been successfully
encapsulated within the pores of LNPCs-ZnO hybrids. To further

5
C. Zhou et al.
Fig. 3. (a) TGA curves of LNPCs-ZnO/70S, LNPCs-ZnO/80S, and LNPCs-ZnO/90S in N2 atmosphere. (b) XRD pattern of pristine sulfur, LNPCs-ZnO/80S and LNPCs/
80S hybrids. (c) XPS survey spectrum of LNPCs-ZnO/80S and LNPCs/80S hybrids. d-f) High-resolution XPS spectra of LNPCs-ZnO/80S with emphasis on C 1 s (d), Zn
2p (e) and S 2p (f) regions. (g) HAADF image of LNPCs-ZnO/80S hybrids. The corresponding EDX mapping of C (h), O (i), N (j), Zn (k), and S (l).
examine the surface compositions of the LNPCs-ZnO/80S hybrids, XPS
spectrum was performed (Fig. 3(c)). For comparison, XPS data of LNPCs
were also collected (Figure S4, Supporting Information). The XPS
spectra of LNPCs/80S and LNPCs-ZnO/80S hybrids in Fig. 3(c) and
Figure S6 (Supporting Information) confirm the presence of C, N, O, Zn,
and S elements. The C 1 s XPS spectrum in Fig. 3(d) reveals the coex­
istence of four major peaks at 284.7, 285.7, 286.7, and 289.4 eV, which
can be attributed to C–C/C–H, C-N/C-O/C-S, C-N/C-O, and O = C-O,
respectively. [26,29] The characteristic peaks of Zn 2p1/2 and Zn 2p3/2
are observed at 1045.9 and 1022.3 eV in high-resolution Zn 2p spectra
(Fig. 3(e)), which can be attributed to Zn2+ in ZnO. [58,78] Intriguingly,
compared to those of the LNPCs-ZnO hybrids, the Zn 2p peaks in the
LNPCs-ZnO/80S hybrids show a slight shift to higher binding energy,
suggesting strong interactions between ZnO and sulfur. [58] In accor­
dance with the above results, two prominent peaks centered at 165.1
and 163.9 eV, which are assigned to the S 2p1/2 and S 2p3/2 for S or S8 in
the composite of LNPCs-ZnO/80S (Fig. 3(f)). [83] Moreover, two weaker
peaks appear at 161.7 and 168.7 eV, verifying that S2-/S2- 2 and S-O
bonding in sulfate, respectively. [28] The binding energy of the S 2p3/2
peak is lower than that of elemental sulfur (164.0 eV), further con­
firming the possible existence of Zn-S interactions. [78] Figure S7
(Supporting Information) shows the high-resolution N 1 s spectra. Three
prominent peaks correspond, respectively, to the Pyridinic N, Pyrrolic N,
and N-oxide, which can be distinguished at 398.3, 400.2, and 402.7 eV.
[44,84] It is expected that the coexistence of N-doped heteroatoms and
ZnO NPs in the LNPCs-ZnO/80S hybrid can not only facilitate electro­
chemical reaction but also provide more efficient electroactive sites for
trapping the intermediates Li2Sx through strong chemical adsorption,
while inhibiting the shuttling effect. [84] The typical TEM image of
6
Chemical Engineering Journal 421 (2021) 129707
LNPCs-ZnO/80S and corresponding elemental mapping images of C, O,
N, Zn, and S are illustrated in Fig. 3(g-l) exhibiting that all the elements
are uniformly distributed in the interest area of composite indicating
that the LNPCs-ZnO hybrid had successfully accommodated sulfur.
To evaluate the electrochemical performance of the Li-S batteries
based on the LNPCs-ZnO/80S as the cathode, standard coin cells were
assembled and studied. LNPCs/80S cathode was also prepared for
comparison. The initial five cyclic voltammetry (CV) curves of LNPCs-
ZnO/80S cathode shown in Fig. 4(a) exhibit no obvious peak shifts
and peak current changes, demonstrating the excellent reversibility and
low-capacity decay of such electrochemical system with LNPCs/ZnO.
The two representative reduction peaks locate at ~ 2.3 V and ~ 2.08 V,
which are corresponded to the electrochemical transformation from S8
to long-chain polysulfides and then further reduction to insoluble short-
chain Li2S2 and Li2S, respectively, while the two oxidation peaks around
2.38 V and 2.34 V versus Li/Li+ are due to the reverse oxidation process
from Li2S/Li2S2 to Li2S8 and then to S8. In contrast, the initial five CV
profiles of the Li-S battery with the LNPCs/80S cathode (Figure S8
(Supporting Information)) indicate that the oxidation/reduction peaks
are deformed and integral areas decreased, which suggests a poor
cycling stability and sluggish kinetic process. Figure S9(a) (Supporting
Information) shows the initial curves of LNPCs-ZnO/80S and LNPCs/
80S cathodes, it is obvious to note that the reduction peaks of the LNPCs-
ZnO/80S cathode are positively shifted slightly and the oxidation peaks
shift to the negative position, suggesting that ZnO NPs can improve the
polysulfide redox kinetics and cell polarization decreases. [77] Figure S9
(b) (Supporting Information) compares the first cycle charge–discharge
voltage curves of the Li-S batteries with LNPCs/80S and LNPCs-ZnO/80S
cathodes at 0.5C rate within a voltage window of 1.7–2.8 V versus Li+/
C. Zhou et al.
Fig. 4. Electrochemical performance of the LNPCs-ZnO/80S cathode. a) CV curves of the LNPCs-ZnO/80S at a scan rate of 0.1 mV s− 1. b) Galvanostatic char­
ge–discharge profiles of LNPCs-ZnO/80S cathodes at 1st,20th, 100th, 500th, and 1000th cycles. c) The rate performances of the Li-S batteries based on the LNPCs-
ZnO/80S or LNPCs/80S cathodes at various C-rates. d) Galvanostatic charge–discharge profiles of LNPCs-ZnO/80S cathodes at 0.2, 0.5, 1, 2, and 3C.e) Cycling
performance of the Li-S batteries with LNPCs-ZnO/80S or LNPCs/80S cathodes at 0.5C for 1000 cycles and corresponding coulombic efficiency.
Li. The LNPCs-ZnO/80S cathode shows two typical discharge plateaus at
around 2.3 and 2.1 V, and two obvious charge plateaus at around 2.38
and 2.34 V, which are well consistent with the result of CV profiles. From
Figure S9(b), it is obvious that the initial specific capacity of the LNPCs-
ZnO/80S cathode (1184.9 mAh g− 1 at 0.5C) is much higher than that of
the LNPCs/80S cathode (840.6 mAh g− 1 at 0.5C). This is a representa­
tive signal that polysulfide has been confined in the cathode porous
zone, polysulfides dissolution is efficiently restrained and further
significantly inhibiting polysulfides shuttling effect. Fig. 4(b) shows the
GCD curves of the LNPCs-ZnO cathode with a sulfur content of 80% and
at current densities of 0.5C (1C = 1675 mAh g− 1) after the 1st, 20th,
100th, 500th, and 1000th cycles. Two typical discharge plateaus can be
clearly observed, corresponding to a typical multistep change of S8. The
discharge voltage plateau, at 2.35 V, implies the reduction of S8 to Li2S8;
the corresponding discharge capacity (QH) is often used to assess the
polysulfides trapping efficiency and the degree of polysulfides genera­
tion. [85] Importantly, the QH in the 500 cycles was 79.1% of that in the
initial cycle, indicating that the LNPCs-ZnO hybrid frameworks can be
suppressed the active sulfur loss efficiently. And the lower discharge
plateau, at 2.05 V, indicates the transformation from polysulfides to
Li2S2/Li2S, which contributes to the main discharge capacity (70%).
Notably, the discharge plateaus of LNPCs-ZnO cathode display longer
and flatter with a higher capacity and a lower polarization (△V = 0.23
V) than LNPCs (△V = 0.31 V) cathode (Figure S10 (Supporting Infor­
mation)), and only 29.5% fading is observed within 1000 cycles, sug­
gesting a high polysulfides trapping ability of the ZnO NPs and LNPCs,
and improved electrochemical reaction kinetic. The rate capabilities of
the LNPCs-ZnO/80S and LNPCs/80S cathodes were further investigated
under stepwise current densities from 0.2 to 3C (Fig. 4(c)). The LNPCs-
ZnO/80S cathode delivered average reversible capacities of 1224.2,
1093.5, 960.6, 851, and 716.1 mAh g− 1 at current densities of 0.2, 0.5,
1, 2 and 3C, respectively. Furthermore, after the high current densities,
the LNPCs-ZnO/80S cathode exhibiting excellent capacity reversibility
and the discharge capacity recovers to 1169.1 mAh g− 1 at 0.2C. In
contrast, the rate performance of LNPCs/80S cathode is inferior to that
of LNPCs-ZnO/80S cathode, the capacity gaps between these two
7
Chemical Engineering Journal 421 (2021) 129707
cathodes increased as the current density increased, and the discharge
capacities of only 328.5 mAh g− 1 was remained for LNPCs/80S cathode
at 3C. The corresponding GCD profiles of the LNPCs-ZnO/80S and
LNPCs/80S cathode at different current densities are shown in Fig. 4(d)
and Figure S11 (Supporting Information). Although the polarization
increased at high charge/discharge current densities, the profiles still
showed two discharge plateaus and remained favorable reversibility. To
further verify the ZnO NPs on the improvement of the electrochemical
kinetics process during cycling, the electrochemical impedance spec­
troscopy (EIS) before/after cycling is tested (Figure S10, Supporting
Information). As shown in Figure S12 (Supporting Information), the
LNPCs-ZnO/80S cathode before cycling (20.57 Ω.cm2) exhibits higher
electrolyte resistance (Rs) compared with LNPCs/80S cathode (18.32
Ω.cm− 2), which is mainly caused by the low electronic conductive ZnO
NPs that increased the resistance of the whole electrode. However, it can
be seen that the charge transfer resistance (Rct) value of LNPCs-ZnO/80S
cathode is 58.4 Ω, which are obviously lower than that of LNPCs/80S
cathode (74.3 Ω). More importantly, Rs of the LNPCs-ZnO/80S (62 Ω)
after 1000th cycling is much smaller than that of LNPCs/80S (89.7 Ω),
suggesting that the ZnO NPs facilitates Li-ion diffusion between elec­
trolyte and electrode surface. In the low-frequency region, the slope of
the line reflected ion diffusion rates in the electrode materials. Before
cycling, the slope lines of LNPCs-ZnO/80S and LNPCs/80S show similar
in Figure S12 (Supporting Information). After 1000th cycling, the slope
of the LNPCs/80S cathode decreased, suggesting a lower ion diffusion
coefficient of the hybrid frameworks. In contrast, LNPCs-ZnO/80S
cathode still has a big slope. In short, the outstanding performance of
LNPCs-ZnO/80S cathode are originated from the high conductivity of
3D hybrid frameworks, polar ZnO NPs and N-doped porous carbons
framework structures, which can efficiently trap the polysulfides,
further inhibiting shuttling effects.
The cycling stabilities of the Li-S battery based on LNPCs-ZnO/80S
and LNPCs/80S cathode at 0.5C with the sulfur loading of 3.4 mg
cm− 2, are shown in Fig. 4(e). The initial discharge capacity of the Li-S
battery with LNPCs-ZnO/S cathode is as high as 1155.8 mAh g− 1 (cor­
responding to areal capacity of 3.07 mAh cm− 2), which slowly decrease
C. Zhou et al. Chemical Engineering Journal 421 (2021) 129707

to 760.7 mAh g− 1 (areal capacity: 2.11 mAh cm− 2) after 1000 cycles
with an average capacity decay rate of 0. 31% per cycle and high-
capacity retention of 70.5%, and with a superior Coulombic efficiency
of nearly 100%. In striking contrast, the Li-S battery with LNPCs/S
cathode delivers an initial discharge capacity of 841.6 mAh g− 1 (areal
capacity: 2.26 mAh cm− 2), and drastically falls to 393.3 mAh g− 1 (areal
capacity: 1.06 mAh cm− 2) after 1000 cycles with a Coulombic efficiency
as high as 104.3% and with a high-capacity decay rate of 0.54% per
cycle. It ascertains that LNPCs/S as a cathode show inferior cycle sta­
bility, and the poor electrochemical performance can be contributed to
few polar functional groups on the surface of LNPCs hybrid frameworks,
which cannot promote LiPS trapping efficiently, and hence the conver­
sion reaction of LiPS is sluggish. On the contrary, due to the stable and
high conductivity of LNPCs-ZnO/S frameworks and strong chemical
interaction between LiPSs and ZnO NPs, this unique structure demon­
strates that the polar ZnO NPs on the surface of high conductive N-doped
porous carbons has suitable functional sites to effectively inhibit the
shuttling effect. In order to further demonstrate the superior capture
mechanism of such electrochemical performance improvement, LNPCs-
ZnO/S and LNPCs/S cells are disassembled. Post-cycling SEM
(Figure S13 and Figure S14, Supporting Information) characterization of
cathodes and lithium anodes provides additional evidence to verify the
excellent long-term cycling performance (after 1000 cycles at 0.5C).
Compared with the cycled LNPCs/S electrode (Figure S13(a) and (b))
with cracks covered on the surface, the morphologies of the cycled
LNPCs-ZnO/S electrodes (Figure S13(c) and (d)) display smooth surface
and still maintains its original 2D hierarchical porous structure without
any obvious pulverization or size variation as cycled before. Compared
to the sulfur cathode, the introduction of ZnO NPs has a more profound
influence on the lithium anode (Figure S14). It is clearly revealed that
the lithium anode based on the LNPCs-ZnO/80S cathode (Figure S14(c)
and (d)) shows no cracks or dendrites but a smooth surface can be
observed. In sharp contrast, lithium anodes display heavy pitting
corrosion and obvious dendrites on the surface of the LNPCs/80S based
anode (Figure S14(a) and (b)). In brief, even after long cycling at high
current density, the lithium anode surface does not unveil a seriously
damaged surface, demonstrating that the novel LNPCs-ZnO/80S cathode
can effectively block the notorious polysulfide shuttling to alleviate
lithium anode surface corrosion and further mitigate the anode cracks
problem, thus benefiting to the superior long-term cycle stability and
high sulfur utilization.
To further investigate the chemical conversion of LiPS on the surface
of LNPCs-ZnO and LNPCs, XPS spectra (Figure S15, Supporting Infor­
mation) were performed after 1000th charge/discharge process at 0.5C.

Fig. 5. (a) Cycling performance and the corresponding Coulombic efficiency of the Li-S battery based on the LNPCs-ZnO/S cathode at 1and 2C with a sulfur loadings
3.4 mg cm− 2. (b) Cycling performance and the corresponding coulombic efficiency of the Li-S battery based on the LNPCs-ZnO/S cathode at 0.2C with 3.4, 5.3, and
6.7 mg cm− 2 sulfur loadings, respectively. (c) Charge and discharge GITT curves at 0.2C. (d) CV curves of the symmetrical cells with the LNPCs and LNPCs-ZnO
electrodes in electrolytes with and without 0.5 M Li2S6 at a scan rate of 5 mV s− 1 (voltage range: –0.8 to 0.8 V). Fitting of current vs. time curve on different
surfaces: (e) LNPCs, and (f) LNPCs-ZnO. The cells were discharged galvanostatically at 0.1 mA to 2.06 V and kept potentiostatically at 2.05 V until the current was
below 10-5 A. (g) Schematic representation of flexible Li-S pouch cell employing a LNPCs-ZnO/S cathode. (h) Cycling performance of pouch cell at different folding
angles and the corresponding pictures of LEDs lighten up by pouch cell.

8
C. Zhou et al.
At the fully-discharged state of 1.7 V (Figure S15(c)), the obvious
characteristic peak located at 161.4 and 162.5 eV, which are attributed
to the fully transformation of LiPSs into lithium sulfide (Li2S2/Li2S).
Furthermore, it is obviously noted that the peak of the lithium sulfide
species gradually decreases after the subsequent fully-charged state of
2.8 V (Figure S15(d)). Besides, the peak of the S-S bond obviously in­
creases. Intriguingly, compared to those of the LNPCs-ZnO hybrids, the
peak of the lithium sulfide in the LNPCs/80S hybrids show incomplete
conversion (Figure S15(b)), suggesting the presence of ZnO can effec­
tively promote the reversible oxidation of lithium sulfide to LiPSs.
For the LNPCs-ZnO/80S cathode, the cycling performances of Li-S
batteries at a larger current density of 1 and 2C were further detected,
respectively (Fig. 5(a)). Clearly, the LNPCs-ZnO/80S cathodes show
high reversible specific capacities of 952.9 mAh g− 1 (1C) and 858.9 mAh
g− 1 (2C), which is 25.9% and 39.3% higher than that of LNPCs/80S
cathode (705.3 mAh g− 1 at 1C and 521.6 mAh g− 1 at 2C), respectively.
The corresponding areal capacities are as high as 2.81 (1C) and 2.53
mAh cm− 2 (2C) for the LNPCs-ZnO/80S cathode, which are much higher
than those of the LNPCs/80S cathode (2.07 mAh cm− 2 at 1C and 1.54
mAh cm− 2 at 2C) (Figure S16, Supporting Information). The unique
structure of the LNPCs-ZnO hybrids makes the battery to achieve better
cycling stability with a discharge capacity of 725.9 mAh g− 1 at 1C (2.14
mAh cm− 2) and 525 mAh g− 1 at 2C (1.54 mAh cm− 2) after 500 cycles,
exceeding those of 310.9 mAh g− 1 at 1C (0.91 mAh cm− 2) and 116.6
mAh g− 1 at 2C (0.34 mAh cm− 2) in LNPCs/80S cathode, respectively.
The Coulombic efficiencies of LNPCs-ZnO/80S cathodes at 1 and 2C
both are near 100%. By comparison experiments, it’s found that the
excellent cycling stability is obtained by LNPCs-ZnO/80S cathodes,
which may be mainly ascribed to high-efficiency conductive networks
and superior structural stability. The ZnO NPs anchoring on the surface
of LNPCs provides more active sites for trapping polysulfides and pro­
motes polysulfides fast diffusion. [58,77,78] Moreover, considering the
high sulfur loading and high reversible capacity of the LNPCs-ZnO/S
cathode, the cycling stability of Li-S battery assembled with the sulfur
loading of 3.4, 5.3, and 6.7 mg cm− 2 at 0.5C is investigated. As shown in
Fig. 5(b), with the sulfur loading of 3.4, 5.3, and 6.7 mg cm− 2 at 0.2C,
the Li-S battery exhibits initial areal capacities of 2.93, 5.01, and 6.36
mAh cm− 2, respectively. After 200 cycles, the reversible areal capacities
maintain at 2.45, 3.85, and 4.71 mAh cm− 2, achieving a capacity
retention of 74–84%. Even when the sulfur loading increases up to 6.7
mg cm− 2, the high reversible areal capacity of 4.71 mAh cm− 2 is still
retained after 200 cycles. Such a high areal capacity of the LNPCs-ZnO/S
cathode can be contributed to its unique structures, in which the 3D
conductive networks facilitates rapid electronic/ionic transport, and the
high specific surface area offers multiple void spaces, which provides
more storage space for sulfur and further beneficial to improve sulfur
utilization. To the best of our knowledge, even under high areal sulfur
loading and high-rate charging-discharging state, this high electro­
chemical performance of LNPCs-ZnO/S cathodes was superior to many
previously reported TMO-based cathodes materials (Tables S3 and S4
Supporting Information), highlighting the great potential of as-prepared
LNPCs-ZnO hybrid frameworks for next-generation high-performance
Li-S batteries. Because the electrode material has a strong trapping
ability to polysulfides, it can effectively suppress polysulfide shuttles.
According to previous literature reports, shuttle current can be used as
one of the important parameters to evaluate the degree of shuttle.
Figure S17 compares the shuttle behavior of LNPCs/80S and LNPCs-
ZnO/80S cathodes. As can be seen from FigureS17, the LNPCs-ZnO/
80S cathode shows a smaller shuttle current compared with the
LNPCs/80S cathode, indicating that the LNPCs-ZnO hybrid frameworks
have a strong trapping ability to suppress polysulfide shuttling effect.
Figure S18 compares the cycling performance of the Li-S battery based
on the LNPCs-ZnO/S cathode at 0.5C with 5, 10, and 15 μL/mg E/S ratio,
respectively. As can be seen from Figure S18, the E/S ratio of 15 μL/mg
shows a better cycling stability compared with the 5 and 10 μL/mg.
However, the energy density of lithium-sulfur batteries under this N/P
9
Chemical Engineering Journal 421 (2021) 129707
ratio is significantly lower than other ratios, only 141 Wh/kg can be
achieved (Figure S18(b), Supporting Information).
To investigate the reaction kinetics of the LPSs transformation
behavior for the LNPCs-ZnO/80S and LNPCs/80S cathodes, CV mea­
surements were carried out between 1.7 and 2.8 V at various scan rate
from 0.05 to 1 mV s− 1 and the relationship of peak current versus (v/
s)0.5 are displayed in Figure S20 (Supporting Information). As shown in
Figure S20 (a) and (d), LNPCs-ZnO/80S and LNPCs/80S cathodes show
two representative reduction peaks and two oxidation peaks for all scan
rates. Notably, because of the diffusion process of LiPS, a linear rela­
tionship between the peak current and the square root of scan rate can
be determined by diffusion coefficient of Li ions (DLi+) according to the
classical Randles-Sevcik equation:
Ip = 2.69*105n1.5AD0.5
Li CLiv
0.5
(1)
where Ip is the peak current, n is the charge transfer number, A is the
area of active electrode, DLi is the lithium ion diffusion coefficient, CLi is
the concentration of lithium ions in the electrolyte, and v is the scan rate.
Therefore, the slope of curves (Ip/V0.5) can reflect the lithium-ion
diffusion rate, which provides critical information about the kinetics
of polysulfides conversion, because n, A, and CLi in the battery are un­
changed. Clearly, the LNPCs-ZnO/80S cathode exhibits larger slopes
(bIA = 8.07, bIC1 = -4.57, bIC2 = -5.94) as compared with the LNPCs/80S
cathode (bIA = 6.92, bIC1 = -3.40, bIC2 = -5.75). The resulting DLi in
peaks IA, IC1, and IC2 are 4.56*10-8, 1.46*10-8, 2.47*10-8 cm2/s for
LNPCs-ZnO/80S and 3.36*10-8, 8.10*10-9, 2.32*10-8 cm2/s for LNPCs/
80S, respectively. In addition, galvanostatic inter-mittent titration
technique (GITT) was also conducted to determine the Li+ diffusion
coefficients. Fig. 5(c) shows the GITT profiles for both LNPCs and
LNPCs-ZnO. It shows an obvious lower polarization between the
discharge and charging plateau for the LNPCs-ZnO, which should be
related to the promotion of redox kinetics by ZnO NPs. Apparently, the
Li+ diffusion coefficients (DLi+) of LNPCs-ZnO hybrid frameworks
(8.47*10-8 cm2/s) are larger than LNPCs (9.79*10-8 cm2/s). Those result
are consistent with the above CV curve calculation results. Above all, it
clearly indicates that the faster diffusion process of LiPS is mainly
related to the introduction of ZnO NPs anchoring on the LNPCs frame­
works, which can strong adsorb LiPSs and facilitate the sulfur redox
reactions for further enhancing the Li storage performance.
In addition, the power-law formula i = avb was used to analyze the
reaction kinetics. The values of b can be easily calculated from the slope
of the linear plots of log(sweep rate) - log(peak current). In Figure S20
(c), the fitted b-values of the LNPCs-ZnO/80S are determined to be 0.62,
0.60, and 0.58, respectively, but the LNPCs/80S (Figure S20(f)) shows
lower b values (0.47, 0.53, and 0.52, respectively) than those of the
LNPCs-ZnO/80S. Those results suggest that the reversible conversion
kinetics of polysulfides can be significantly enhanced by LNPCs-ZnO/
80S electrode. Further research reveal that the b values corresponding
to IC1 of LNPCs-ZnO/80S and LNPCs/80S are significantly greater than
that of IC2, which is indicated that the conversion kinetics of S8 → Li2S6/
Li2S4 (solid–liquid conversion) are faster than Li2S6/Li2S4 → Li2S2/Li2S
(liquid–solid conversion). Importantly, the sluggish Li reaction kinetics
on the surface of the LNPCs frameworks can be enhanced by ZnO NPs.
To further demonstrate the enhanced redox kinetics catalyzed by
ZnO, redox current in combination with Li2S nucleation experiments
were carried out. The redox current curves were collected by the CV
measurements of symmetric cells with loading LNPCs-ZnO (or LNPCs)
on steel mesh simultaneously serving as the working and counter elec­
trodes and Li2S6 solution (0.5 M) served as the electrolyte at a scan rate
of 50 mV/s in the voltage range from − 0.8 to 0.8 V. As shown in Fig. 5
(d), LNPCs-ZnO electrode presents two pairs of pronounced redox peaks
located at − 0.42, 0.03, 0.42, and − 0.03 V, demonstrating the reversible
conversion of the Li2S6 in electrochemical process. In contrast, the
symmetric cell with LNPCs electrode only deliver the unobvious redox
peaks with the lower current response than the case of the LNPCs-ZnO
C. Zhou et al. Chemical Engineering Journal 421 (2021) 129707

electrode. It further implies that the outstanding catalytic ability of ZnO
toward LiPS redox. In parallel, Li2S precipitation experiments are driven
by loading LNPCs-ZnO and LNPCs on carbon fiber paper (CFP),
respectively. It is observed that a sharp nucleation peak appears earlier
in the LNPCs-ZnO cell (Fig. 5(f)) than in the LNPCs cell (Fig. 5(e)). More
importantly, a large capacity of 175 mAh gs− 1 (Fig. 5(f)) indicates that
LNPCs-ZnO can induce more nucleation of Li2S than LNPCs (116 mAh
gs− 1), suggesting the accelerated Li2S precipitation in the presence of
ZnO. Above all, ZnO NPs anchoring on the LNPCs frameworks can
efficiently address the LiPSs shuttle and enhance LiPS conversion ki­
netics, which would be beneficial to modifying sulfur utilization and
showing excellent reversible capacity and superior rate capability of
LNPCs-ZnO/80S cathode-based Li-S battery.
To further demonstrate the practical application of as-designed
LNPCs-ZnO electrodes, a flexible Li-S was assembled as pouch cells
(Fig. 5(g)). As expected, 41 red light diode (LED) array of “SJTU” letters
were lightened up by pouch cells (Fig. 5(h)). To show the great me­
chanical flexibility, different folding angles for pouch cells were tested.
As shown in Fig. 5(h), the pouch cells were subjected to bending
deformation and almost no change in brightness was observed even
when bending at an angle of nearly 180◦ . Furthermore, the electro­
chemical performance was also monitored to show the cycle stability in
various folding angles at 0.2C (Fig. 5(h)). The capacity loss was negli­
gible even at the folding angles of 180◦ . Moreover, the areal capacity of
pouch cells decreased a little from initial 3.23 to 2.47 mAh cm− 2 after
400 cycles. The favorable electrochemical performance of the LNPCs-
ZnO based Li-S pouch cells could be attributed to the excellent cycling
stability as well as the effective suppression of polysulfide shuttling,
highlighting their practical use in flexible energy systems.
To shed light on the catalysis process from the perspective of mo­
lecular or atomic scales, the density functional theory (DFT) calculations
were conducted to elucidate how LiPSs were activated during catalysis
and the binding energy between ZnO NPs (or LNPCs) and long-chain
Li2Sn (n = 4, 6, 8)/S8. As aforementioned, ZnO (0 0 2) facet (shown in
Figure S21(a)) was selected as the representative plane for modeling
because of its larger surface area and provided favorable adsorption
locations for Li2Sx species. The binding energies (Eb) of Li2Sn/S8 (mo­
lecular structures are shown in Figure S21 (b)) with ZnO and LNPCs
were implemented by a DMol3 Code in the framework of DFT. Fig. 6(a)
reveals the binding geometric configurations between ZnO and various
sulfur species, with the corresponding Eb values marked. In the
adsorption structure (Fig. 6(a)), the most favorable binding sites of
Li2Sn/S8 are S atoms which tend to bond with the Zn atoms on ZnO
(0 0 2), in which the S-Zn distance is 2.93 Å. Clearly, the Eb values be­
tween the (0 0 2) facet of ZnO and S8, Li2S, Li2S2, Li2S4, Li2S6, and Li2S8
species are − 3.94, − 6.91, − 5.52, − 4.34, − 3.84 and − 5.21 eV, respec­
tively. As shown in Fig. 6(a), the Eb value for Li2S8 remarkably reaches
− 5.21 eV, which is one of the best-reported values for ZnO-based sys­
tems. When the molecular length of LiPSs further decreased, the corre­
sponding Eb values decrease to the lowest value of − 3.84 eV for Li2S6.
After that, the Eb values gradually increase to − 6.91 eV for Li2S, which
could be interpreted by the strong interaction between the ZnO surface

Fig. 6. Theoretical calculation and adsorption test of LNPCs-ZnO with Li2Sn/S8. (a) The trends of binding energies for various polysulfides molecular with (0 0 2)
plane of ZnO. (b) UV–visible spectra of the Li2S6 solution after exposure to LNPCs, and LNPCs-ZnO, respectively. Insets are the digital photograph of the Li2S6 and
polysulfides trapping ability by LNPCs, and LNPCs-ZnO before and after one week. (c) Free Gibbs energy curves for the reduction of LiPSs on the LNPCs (black line)
and ZnO (red line). Insets are the optimized adsorption geometries of intermediate species on the LNPCs and ZnO. Li2S decomposition on LNPCs (d) and ZnO (f) and
Li2S decomposition path on ZnO. (g) Schematic of the capture and catalytic mechanism of the LiPSs on the surface of LNPCs-ZnO in electrochemical process.

10
C. Zhou et al.
and short-chain polysulfides owing to similar polarity. On the other
hand, the corresponding Eb values of S8, Li2S, Li2S2, Li2S4, Li2S6, and
Li2S8 species on LNPCs surface are − 0.43, − 1.32, − 1.27, − 0.90, − 0.98,
and − 1.07 eV, respectively (Figure S22, Supporting Information). Ac­
cording to the above DFT results, a higher Eb values of ZnO to LiPSs
indicates a stronger chemical anchoring of LiPSs.
In order to further evaluate the adsorption ability of LiPSs on the
surface of ZnO, the LiPSs adsorption test using LNPCs and LNPCs-ZnO
hybrid frameworks with the 5 mmol Li2S6 in DOL/DME (1:1, v/v) are
showing in Fig. 6(b). Interestingly, after a short static test of one day,
LNPCs-ZnO almost decolorizes while the LNPCs sample in which still
retained yellow. Moreover, even after one week of the static adsorption
test, the color of the LNPCs-ZnO-containing solution changes to almost
transparent compared to the LNPCs in which the color of Li2S6 is still
retained. These results indicated that the LNPCs-ZnO-based cathode has
a strong absorbing capacity on polysulfides. To further verify the strong
Li2S6 adsorption ability of LNPCs and LNPCs-ZnO, the corresponding
ultraviolet–visible (UV–vis) spectroscopy was also measured. As can be
seen from Fig. 6(b), the absorption peak of Li2S6 solution in the 410–420
nm region are disappeared obviously after adding LNPCs-ZnO, and in
contrast, obvious absorbance is seen for those exposed to LNPCs. As
theoretical and experimental results substantially reveal that LNPCs-
ZnO is an ideal cathode material, ZnO NPs can be considered as a type
of polar matrix and can provide strong chemical interaction with LiPS,
which can effectively confine LiPSs shuttling and further improve the
rate and cycle performances of Li-S battery.
Fig. 5(c) shows the calculated Gibbs free energies of the stepwise
intermediates including S8, Li2S, Li2S2, Li2S4, Li2S6, and Li2S8 species on
the LNPCs and ZnO during the polysulfide transformation reaction. The
reduction from Li2S2 to Li2S has the largest positive Gibbs free energy in
the whole discharging process, indicating that the rate-controlling step
and the sluggish sulfur redox reaction in the Li-S battery. And the value
on ZnO (0.67 eV) is much lower than LNPCs (1.12 eV), suggesting that
the presence of ZnO on LNPCs enables the reduction from Li2S2 to Li2S is
thermodynamically more favorable than pristine LNPCs. In addition, the
Li2S oxidation process during the inverse charging process play an
important role for studying reaction kinetics in electrochemical process.
As shown in Fig. 6(d) and (e), the calculated Li2S decomposition energy
barrier of ZnO surface (1.51 eV) is far lower than the case of LNPCs
(2.49 eV). Such a low energy barrier confirms that the ZnO NPs on
LNPCs can efficiently catalyze the breaking of the Li-S bond and enhance
delithiation reaction kinetics during the electro-chemical process.
Benefiting from merits of the transition metal oxides in terms of
effective confinement, catalysis and diffusion, the Li-S batteries assem­
bled with LNPCs-ZnO/S cathodes show excellent electrochemical per­
formance. As illustrated in Fig. 6(h), the polar ZnO NPs in LNPCs-ZnO
electrode exhibits strong capture ability of soluble polysulfides, which
effective suppress polysulfide shuttling outside of cathode. Conse­
quently, sulfur utilization during charge–discharge processes is
improved and cycling stability is ultimately extended. Moreover, the
catalytic effect of multifunctional ZnO NPs can promote fast conversion
from polysulfides to Li2S, high areal sulfur loading is able to undergo
complete redox reactions and regulatable Li2S deposition sites, which
facilitate the fast polysulfides conversion kinetics, high areal capacity,
and superior cycling stability of Li-S batteries.
4. Conclusion
In summary, a laser-induced metal oxide/N-doped porous carbons
hybrid framework was firstly demonstrated for high-performance Li-S
batteries. As a cathode in Li-S batteries, the unique structure of LNPCs-
ZnO hybrid frameworks not only provides adequate internal voids, but
also greatly improves the conductivity of the cathode. In addition, these
unique structures could efficiently suppress the shuttle effects due to the
superior trapping ability of LiPSs by ZnO NPs, which can endow ZnO
NPs and its hybrid frameworks with an impressive ability to significantly
11
Chemical Engineering Journal 421 (2021) 129707
enhance the cycle life and rate performance of the Li-S battery. Conse­
quently, the LNPCs-ZnO/S cathode with 80 wt% of sulfur (areal sulfur
loading of 3.4 mg cm− 2) delivers a high initial discharge capacity of
1155.8 mAh g− 1 at 0.5C with a Coulombic efficiency of 99.7%.
Furthermore, the LNPCs-ZnO/80S cathode can operate at 0.5C over
1000 cycles with 70.5% capacity retention and shows superior rate
performance up to 3C. Even when the areal sulfur loading reaches up to
6.7 mg cm− 2, the LNPCs-ZnO/S cathode exhibits high initial areal ca­
pacity of 6.36 mAh cm− 2 and excellent cycling stability at 0.2C. In
addition, the adsorption test and DFT calculations demonstrate that the
intrinsic interaction between LiPSs/S8 and ZnO NPs is the main factor to
inhibit the shuttle effect of LiPSs. This study will indeed provide a new
direction to construct various 3D porous hybrid frameworks to be
applied in the next-generation high-performance wearable and portable
devices.
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.
Acknowledgements
The financial supports from the National Natural Science Foundation
of China (no. 61574091), China Postdoctoral Science Foundation
(2020M681300), Shanghai Sailing Program (18YF1427800) and the
Foundation for SMC Excellent Young Teacher in Shanghai Jiao Tong
University were gratefully acknowledged. The analysis supports from
the Instrumental Analysis Center of Shanghai Jiao Tong University and
the Center for Advanced Electronic Materials and Devices of Shanghai
Jiao Tong University were also acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2021.129707.
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