Journal of

Materials Chemistry A
View Article Online
PAPER View Journal | View Issue

An “electronegative” bifunctional coating layer:

Published on 10 September 2019. Downloaded by Shanghai University on 6/22/2024 9:35:56 AM.

Cite this: J. Mater. Chem. A, 2019, 7,

simultaneous regulation of polysulfide and Li-ion
22463 adsorption sites for long-cycling and “dendrite-
free” Li–S batteries†
Qian Lu, ‡a Xiaohong Zou,‡a Ran Ran,a Wei Zhou, a
Kaiming Liao *a
and Zongping Shao ab

Received 23rd July 2019
Accepted 10th September 2019
DOI: 10.1039/c9ta07999h
rsc.li/materials-a
Lithium–sulfur (Li–S) batteries are of great interest due to their high theoretical energy density and
potentially low cost. However, two of the key issues hindering their commercialization are the
polysulfide shuttling and Li-dendrite growth, which result in severe capacity decay and serious safety
hazards. Herein, liquid-phase delaminated birnessite (HxMnO2+x) nanosheets along with graphene and
carbon nanotubes are utilized for the first time to create an “electronegative” coating layer for Li–S
batteries to suppress the polysulfide shuttling and Li-dendrite growth. The as-prepared coating layer
enables stable cycling of the Li–S battery with a low capacity decay rate of 0.04% per cycle over 1000
cycles at 1C. In addition, a Li-symmetrical cell with the coating layer shows suppressed dendrite growth
even after being cycled over 1000 hours at 1 mA cm
2. This excellent performance is ascribed, in part, to
the synergistic effect of the chemical and electrostatic interactions among polysulfides, Li ions, and
[MnO2+x]x
ions, resulting in a homogeneous Li-ion flux distribution and a mitigated polysulfide shuttling.
The proposed concept of an “electronegative” bifunctional coating layer illustrates a simple and effective
way to develop highly stable and safe Li–S batteries.

Introduction
The widespread use of electric vehicles and the quickly
expanding demand for grid-scale energy storage in recent
years have triggered intensive research activities on innovative
rechargeable energy storage systems that are characterized by
low cost, high energy density and long durability.1–4 Recently,
lithium–sulfur (Li–S) batteries have received much attention
because of the high theoretical specic energy density of sulfur
cathodes (1675 mA h g
1), which are inexpensive, non-toxic
and naturally abundant.5–8 However, two dominant chal-
lenges should be addressed before the widespread commer-
cialization of these batteries: (1) the “polysulde shuttling”
challenge, in which the highly soluble polysulde intermedi-
ates (Li2Sx, 4 # x # 8) can easily diffuse through the porous
separator to react with the Li metal anode, leading to the loss
a
State Key Laboratory of Materials-Oriented Chemical Engineering, College of
Chemical Engineering, Nanjing Tech University, Nanjing 210009, China. E-mail:
kaimingliao@njtech.edu.cn
b
WA School of Mines: Minerals, Energy and Chemical Engineering (WASM-MECE),
Curtin University, Perth, WA 6845, Australia
† Electronic supplementary information (ESI) available: SEM images; TEM
images; XPS data; EIS data; nitrogen adsorption/desorption isotherms; and
additional photographs. See DOI: 10.1039/c9ta07999h
‡ Q. L. and X. Z. contributed equally to this work.
of active sulfur and poor cycling stability,7,9–14 and (2) the “Li
dendrite” challenge, in which a non-homogeneous Li-ion
distribution in the electrolyte generates Li dendrites upon
cycling. The highly reactive Li dendrites readily react with the
electrolyte solvent, inducing the rapid depletion of the elec-
trolyte.15–17 Moreover, the Li dendrites can penetrate the
separator in Li–S batteries, causing internal short circuits and
sometimes catastrophic res.16,18
Many efforts have been made in response to the two main
challenges mentioned above. To address the rst challenge, i.e.,
the polysulde “shuttling”, two main approaches have been
highlighted: (1) a physisorption approach, in which the poly-
suldes were conned in the pores of carbon materials (e.g.,
highly ordered mesoporous carbons, hollow carbon spheres,
graphene foam, MOF-derived carbon, and carbon nanotubes)
by tuning their pore size,19–25 and (2) a chemisorption approach,
in which the polysuldes could anchor on the surface of polar
materials (e.g., heteroatom-doped carbon, MXenes, VN, C3N4,
MnO2, Ti4O7, and RuO2) by the formation of chemical
bonds.26–34 In general, the physisorption approach is not strong
enough to conne the polysuldes over long-term cycling
because of the weak interaction between polysuldes and polar
materials compared to the interactions formed in the chemi-
sorption approach.35 Consequently, as reported in previous
studies, developing chemisorptive sulfur host cathodes or

This journal is © The Royal Society of Chemistry 2019 J. Mater. Chem. A, 2019, 7, 22463–22474 | 22463

Journal of Materials Chemistry A
functional coating layers through the rational selection of polar
materials is the main approach to alleviate the “shuttling effect”
of polysuldes in Li–S batteries.36–38 To address the second
challenge, i.e., the dangerous Li dendrites, two primary
attempts have been made with the purpose of suppressing Li-
dendrite growth: (1) a “chemical-pretreatment” strategy, in
which an ionically conductive protective layer is created on the
Li anode by pretreating highly reactive Li metal in a special
solution (e.g., GeCl4–THF, polyphosphoric acid, and [C3mPyr+]
Published on 10 September 2019. Downloaded by Shanghai University on 6/22/2024 9:35:56 AM.
[FSI
] ionic liquid) before battery assembly,39–41 and (2) a “Li-ion
ux regulation” strategy, in which a protective layer containing
a polar material (e.g., C3N4, oxidized PAN nanobers, and pol-
ydopamine) that has strong interactions with Li ions enables
homogeneous Li-ion ux during its deposition process.42–44
Compared with the “chemical-pretreatment” method, the “Li-
ion ux regulation” approach is better at achieving dendrite-
free lithium deposition. This effect may result from the
following: (1) in the case of the “chemical-pretreatment”
strategy, due to the high reactivity of metallic Li, all the proce-
dures must be conducted in an inert atmosphere or under
vacuum conditions, thus increasing the fabrication cost; (2)
these “chemical-pretreatment” strategies generally design the
protective layer as a mechanical barrier to suppress Li
dendrites, but the fundamental behaviour of dendrite growth
does not change.45
Considering these points, we propose and demonstrate
a novel 3 mm-thick bifunctional membrane that consists of
electronegative HxMnO2+x nanosheets entangled with graphene
and carbon nanotubes to create highly stable and safe Li–S
batteries by suppressing the polysulde shuttling and Li-
dendrite growth simultaneously. The electronegative Hx-
MnO2+x nanosheets were delaminated from the protonic bir-
nessite in tetramethylammonium hydroxide (TMAOH) solution
under stirring. The delaminated, electronegative HxMnO2+x
nanosheets with a thickness of 3 nm can fundamentally
suppress dendrite growth by altering the Li-ion ux distribu-
tion. Moreover, the synergistic improvement in polysulde
chemisorption with the HxMnO2+x-based coating layer resulting
from the combination of graphene and carbon nanotubes was
also conrmed. As a result, a highly stable cycling performance
(1000 cycles) and greatly reduced dendrite formation (1000
hours) were observed for both Li–S batteries and Li-symmetrical
cells.
Experimental section
Materials synthesis
Synthesis of HxMnO2+x nanosheets. HxMnO2+x nanosheets
were prepared by a liquid-phase delamination process.46 In
detail, a 400 mL mixed solution of 1 mol L
1 H2O2 and
0.6 mol L
1 NaOH was quickly poured into a 200 mL 0.3 mol L
1
Mn (NO3)2 solution under vigorous stirring at room tempera-
ture, and the obtained mixed solution was aged for 8 h at room
temperature. Then, the obtained suspension was ltered and
washed several times with deionized water. Aer that, 4 g of the
obtained powder was hydrothermally reacted for 24 h at 150  C
in a 100 mL Teon-lined stainless-steel autoclave, and the
22464 | J. Mater. Chem. A, 2019, 7, 22463–22474
View Article Online
Paper
obtained sample was named Na-birnessite. Subsequently, 2 g
Na-birnessite was added to 1000 mL 0.1 mol L
1 HCl solution
under stirring for 5 days, and the obtained sample was named
protonic birnessite. Finally, the resulting protonic birnessite
(0.5 g) was added to 0.5 wt% TMAOH solution, and stirred for 10
days. Aer centrifugation at 8000 rpm for 15 min, the obtained
golden solution was further centrifuged at 12 000 rpm and
washed several times with deionized water to remove residual
TMA+. Finally, the HxMnO2+x nanosheet powder was obtained
by lyophilization.
Synthesis of the EB-PP separator. The EB-PP was prepared by
a facile vacuum ltration method. In a typical synthesis process,
HxMnO2+x nanosheets, graphene and CNTs in a mass ratio of
1 : 2 : 2 were added into 50 mL NMP (N-methyl pyrrolidone)
solution. Aer high-power ultrasonication for 30 min, the as-
obtained ink-like solution was deposited onto one side of
a commercial separator (Celgard 2400) by vacuum ltration
with a mass loading of 0.2 mg cm
2. Then, the EB-PP was dried
at 60  C for 30 min in a vacuum oven. For comparison,
a modied G-PP separator was also fabricated using the same
procedure as that used for preparing the EB-PP separator except
for replacing HxMnO2+x nanosheets with graphene, and a CNT-
PP separator was also prepared by the same method with CNTs
only.
Synthesis of the sulfur cathode. To prepare the cathode,
sublimed sulfur (S) and Vulcan XC-72 (VC) were mixed in a mass
ratio of 7 : 3, and then the mixture was heated at 155  C for 12 h
in a sealed vessel to prepare the sulfur/carbon composites (70%
S@VC). Then, the mixture of 70%S@VC, super P, and LA132
(70%S@VC : super P : LA132 ¼ 8 : 1 : 1) was dispersed in
isopropanol/water (vol ¼ 3/1) solution to form a dark slurry. The
slurry was vigorously ground for 20 min, and then coated onto
Al foil using an applicator. Finally, the as-obtained sulfur
cathode was dried in a vacuum oven at 60  C for 12 h, and
punched into circular disks to further assemble coin cells. The
sulfur loadings in the 70%S@VC cathode are 1.8 mg cm
2 and
3.5 mg cm
2.
Materials characterization
XPS spectra were recorded using a PHI5000 Versa Probe with an
Al Ka X-ray source. SEM images and TEM images were observed
with a Hitachi S-4800 and Tecnai G2 F30 S-TWIN, respectively.
Raman spectra were obtained using a Horiba LabRAM HR
spectrometer with a 514 nm excitation laser. The specic
surface areas and pore size distributions were measured from
nitrogen adsorption–desorption isotherms at 77 K with a BEL-
SORP II instrument using the Brunauer–Emmett–Teller (BET)
equation and the Barrett–Joyner–Halenda (BJH) method (with
the data from the adsorption branch), respectively. Powder X-
ray diffraction (XRD) patterns were collected with a Rigaku
Smart Lab operating at 40 kV and 40 mA. Zeta potentials were
measured using a Zetasizer Nano ZS90.
Electrochemical tests
CR2025 coin cells with lithium as the anode and 70%S@VC as
the cathode were assembled in a glovebox lled with argon to
This journal is © The Royal Society of Chemistry 2019

Paper
evaluate the electrochemical performance of PP, G-PP and EB-
PP separators, respectively. 1 M bis(tri-uoromethane) sulfoni-
mide lithium (LiTFSI, 99%, Sigma-Aldrich) and 1 wt% LiNO3
(99%, Aladdin) in a mixed solvent of 1,3-dioxolane (DOL, 99%,
Sigma-Aldrich) and 1,2-dimethoxyethane (DME, 99.5%, Sigma-
Aldrich) (vol/vol ¼ 1 : 1) was used as the electrolyte. The
amount of electrolyte was 40 mL for each battery. The galvano-
static discharge/charge proles of the batteries were recorded
using a LAND CT2001A battery test station (5 V, 10 mA) in
Published on 10 September 2019. Downloaded by Shanghai University on 6/22/2024 9:35:56 AM.
a voltage window between 1.7 and 2.8 V (vs. Li+/Li). AC imped-
ances were obtained using a PARSTAT 2273 at open-circuit
potential over a frequency range from 100 kHz to 100 mHz
with an amplitude of 10 mV. Symmetric Li|Li batteries was
constructed using two 14 mm pieces of lithium foil and tested at
a current density of 1 mA cm
2 for 1 h per cycle.
Polysulde adsorption tests
The 0.5 M polysulde (Li2S6) solution was prepared by dissolv-
ing sublimed sulfur (99.5%, Aladdin) and Li2S powder (99.9%,
Alfa Aesar) (mole ratio ¼ 5 : 1) into a mixed solvent of 1, 3-
dioxolane (DOL, 99%, Sigma-Aldrich) and 1,2-dimethoxyethane
(DME, 99.5%, Sigma-Aldrich) (vol/vol ¼ 1 : 1), followed by
magnetic stirring at 50  C for 12 h. Then, the as-prepared Li2S6
solution was diluted with DME (vol/vol ¼ 1 : 1) for the adsorp-
tion test (36 mL 0.5 M Li2S6 solution added to 6 mL DME/DOL
solution). CNTs, graphene and HxMnO2+x nanosheets with the
same mass (5 mg) and the same specic area (CNTs: 2.3 mg,
graphene: 1.2 mg, and HxMnO2+x: 5 mg) were used as the
sorbent, respectively.
Fig. 1 Schematic diagram of Li–S batteries without and with a functional coating layer.
This journal is © The Royal Society of Chemistry 2019
View Article Online
Journal of Materials Chemistry A
Results and discussion
Fig. 1 shows a schematic diagram of a Li–S battery with
a conventional polypropylene separator (denoted as PP) and an
electronegative bifunctional separator (denoted as EB-PP). A
conventional non-polar porous polypropylene lm (Celgard
2400) separator is usually used in Li–S batteries. However, the
soluble polysulde intermediates could easily shuttle to the
lithium surface, thus leading to the loss of active sulfur and
consumption of bulk lithium. Moreover, the inhomogeneous
Li-ion ux in the PP separator induced uncontrollable Li-
dendrite growth. In contrast, the EB-PP separator with electro-
negative HxMnO2+x nanosheets entangled with graphene and
carbon nanotubes could anchor the polysuldes by the forma-
tion of S–O bonds and tune the Li-ion ux distribution via
electrostatic adsorption,47,48 thus simultaneously alleviating the
polysulde shuttling at the cathode and suppressing Li-
dendrite growth at the anode. The layer-by-layer structure of
graphene and HxMnO2+x nanosheets with cross-linked carbon
nanotubes (CNTs) is favourable for the transmission of elec-
trons owing to a well-built conductive network, thus reusing
soluble polysuldes.30
Benetting from a liquid-phase delamination approach,
MnO2 nanosheets with electronegative –OH groups can be
prepared (denoted as HxMnO2+x). The synthesis procedure is
schematically illustrated in Fig. S1.† In detail, Na-type birnessite
was pre-synthesized based on a hydrothermal treatment
procedure similar to a previous report49 and then treated with
a 0.1 M HCl solution for several days at room temperature to
J. Mater. Chem. A, 2019, 7, 22463–22474 | 22465

Journal of Materials Chemistry A
trigger the extraction of Na ions. The resultant protonic bir-
nessite with a lamellar structure was then submerged in
0.5 wt% TMAOH solution to achieve delamination. In this step,
the large diameter TMA+ ions intercalated into the inter-
lamination of the protonic birnessite, leading to the expansion
of the lattice distance along the c-axis. The increase in lattice
distance weakened the van der Waals force of interlamination.
As a result, the HxMnO2+x nanosheets could be easily delami-
nated from the protonic birnessite even under continuous
Published on 10 September 2019. Downloaded by Shanghai University on 6/22/2024 9:35:56 AM.
electromagnetic stirring at room temperature. Digital photo-
graphs of the delaminated product suspension and product
powder with a uffy appearance are shown in Fig. S2,† indi-
cating the potential for large-scale production.
The morphology and topography of the delaminated
samples were examined by scanning electron microscopy
(SEM), transmission electron microscopy (TEM), and atomic
force microscopy (AFM). Fig. S3 and S4† show SEM images of
Na-type birnessite and protonic birnessite, revealing that the
lamellar structure of the birnessite can be preserved aer
treatment with hydrochloric acid. Fig. S5† shows the SEM
images of the product aer liquid-phase delamination, dis-
playing the delaminated HxMnO2+x with a graphene-like nano-
sheet structure. Representative TEM images further revealed
the nanosheet texture of the obtained HxMnO2+x, conrming
successful delamination of protonic birnessite (Fig. 2a and S6a–
c†). In addition, d-spacing values of 0.64 nm and 0.24 nm were
observed by high-resolution TEM (HR-TEM, Fig. 2b), corre-
sponding to the (001) and (200) crystal planes of HxMnO2+x
nanosheets, respectively.50,51 According to the HR-TEM images
in Fig. 2c and S6d and e,† the as-prepared HxMnO2+x nano-
sheets had a thickness of 3 nm (4 atomic layers). The
selected area electron diffraction (SAED, inset of Fig. 2c) pattern
conrmed the delaminated HxMnO2+x nanosheets with the
Fig. 2 (a) TEM image and (b and c) high-resolution TEM images of HxMnO2+x nanosheets (the inset in (c) shows the SAED pattern). (d) AFM image
of HxMnO2+x nanosheets and the corresponding height profile. (e) Tyndall effect of HxMnO2+x nanosheets. (f) Zeta potential of HxMnO2+x
nanosheets dispersed in ethanol.
22466 | J. Mater. Chem. A, 2019, 7, 22463–22474
View Article Online
Paper
birnessite structure. The AFM topographical image and the
corresponding height prole revealed that the thickness of an
individual delaminated nanosheet of HxMnO2+x was approxi-
mately 3.5 nm (Fig. 2d), agreeing with the observation from HR-
TEM images. It is well known that most of the well-dispersed
colloidal particles are in a charged state.49 As shown in
Fig. 2e, the observed Tyndall effect conrmed the formation of
well-dispersed HxMnO2+x in aqueous solution, which may be
due to the potential electronegative or electropositive nature of
the HxMnO2+x nanosheet. To determine the charge state of the
delaminated HxMnO2+x nanosheets, zeta potential measure-
ment was carried out in ethanol dispersion media similar to
previous reports.46,49 As seen, the zeta potential of HxMnO2+x
nanosheets dispersed in ethanol is approximately
15 mV
(Fig. 2f), conrming the electronegative nature of the delami-
nated HxMnO2+x nanosheets in ethanol solvent. This may result
from the fact that HxMnO2+x readily releases protons to produce
[MnO2+x]x
based on the dissociation reaction (HxMnO2+x /
xH+ + [MnO2+x]x
).
The successful formation of birnessite-structured HxMnO2+x
nanosheets from the delamination of protonic birnessite (acid-
treated Na-type birnessite) was conrmed by powder X-ray
diffraction (XRD). The XRD patterns of the Na-type birnessite,
protonated birnessite and delaminated birnessite (HxMnO2+x
nanosheets) are shown in Fig. 3a. The diffraction pattern of Na-
type birnessite is well indexed to the standard birnessite phase
(JCPDS 00-043-1456). Aer proton exchange of the interlayer
Na+ ions (Fig. 3b), the shiing of diffraction peaks (c-axis
direction) occurs at 2q angles of 12.4 and 24.9 , correspond-
ing to the (001) and (002) facets, which indicates the successful
protonation of Na-type birnessite.52,53 Compared with that of
protonic birnessite, the broader full width at half maximum
(FWHM) of the HxMnO2+x X-ray diffraction peak indicates that
This journal is © The Royal Society of Chemistry 2019
 View Article Online

Paper Journal of Materials Chemistry A

Published on 10 September 2019. Downloaded by Shanghai University on 6/22/2024 9:35:56 AM.

Fig. 3 The powder X-ray diffraction patterns of the H+-birnessite, Na+-birnessite, and HxMnO2+x nanosheets in the 2q range of 10–90 (a) and
10–30 (b), respectively. (c) Nitrogen adsorption–desorption isotherms of the HxMnO2+x nanosheets and the corresponding pore size distri-
bution. (d) Na 1s, (e) Mn 2p3/2, and (f) O 1s XPS analysis of the HxMnO2+x nanosheets. FTIR spectra (g) and Raman spectra (h) of the HxMnO2+x
nanosheets.

the layer thickness is reduced, which is important evidence for
successful delamination aer the TMA+ intercalated into the
interlamination of the protonic birnessite.54 The microstructure
of HxMnO2+x nanosheets was further explored using N2
adsorption/desorption isotherms. As shown in Fig. 3c, Hx-
MnO2+x nanosheets have a high BET (Brunauer–Emmett–Teller)
specic surface area of 120 m2 g
1. The high specic surface
area could provide more anchoring sites for the adsorption of
polysuldes and Li ions. Additionally, the pore size distribution
obtained from the adsorption branch (inset in Fig. 3c) indicated
the existence of mesopores in the HxMnO2+x nanosheets, which
was also proven by HR-TEM in Fig. S6f.†
To gain further insights into HxMnO2+x nanosheets, X-ray
photoelectron spectroscopy (XPS) measurements were con-
ducted to determine the surface chemical compositions. The
XPS survey spectra of the delaminated HxMnO2+x nanosheets
are shown in Fig. S7,† proving the existence of Na, Mn, and O
elements with atomic contents of 0.8%, 30.8%, and 68.4%,
respectively. Note that the atomic ratio of O and Mn is slightly
higher than 2 : 1, which is ascribed to the interlaminar water
and the supercial hydroxyl groups, agreeing well with the
proposed formula of HxMnO2+x. Owing to the ultrathin struc-
ture of HxMnO2+x, the atomic contents obtained from XPS
approached the actual atomic contents; thus the chemical
formula could be indexed to H0.22MnO2.22. Fig. 3d shows the
XPS Na 1s spectra of the delaminated HxMnO2+x nanosheets
with one peak at a binding energy of 1071.4 eV, conrming that
a few sodium ions remained in the interlamination of protonic
birnessite. The XPS Mn 2p3/2 spectra of the HxMnO2+x nano-
sheets are shown in Fig. 3e, and the nanosheets are mainly
composed of Mn4+ (642.6 eV) in the bulk, Mn3+ (641.6 eV) near
the surface, and two satellite peaks of Mn4+ at higher binding
energies of 643.6 and 644.7 eV.47,50,55–57 The XPS O 1s spectra
reveal four oxygen environments, including bonds of Mn–O,
Mn–OH, and adsorbed H2O* and CO2* (Fig. 3f);50,58 the content
of Mn–OH near the surface reaches 35%, and these hydroxyl
groups on the surface of HxMnO2+x provide additional evidence
for the negative charges on HxMnO2+x nanosheets. To further
prove the existence of the hydroxyl groups, FTIR spectra of the
HxMnO2+x nanosheet were obtained between 400 and

This journal is © The Royal Society of Chemistry 2019 J. Mater. Chem. A, 2019, 7, 22463–22474 | 22467

Journal of Materials Chemistry A
4000 cm
1 as shown in Fig. 3g. The broad bands at 3410 cm
1
and 1650 cm
1 refer to the stretching and bending vibrations of
the hydroxyl groups, and the broad band range from 400 to
800 cm
1 is assigned to the Mn–O stretching vibrations of the
MnO6 octahedra.58,59 The FTIR results indicated the existence of
hydroxyl groups for HxMnO2+x nanosheets, agreeing well with
the XPS O 1s result. Fig. 3h shows the Raman spectra of the
HxMnO2+x nanosheets, which could be divided into three
ranges: 250–450 cm
1, 450–550 cm
1, and 550–700 cm
1, cor-
Published on 10 September 2019. Downloaded by Shanghai University on 6/22/2024 9:35:56 AM.
responding to the overlapping characteristic peaks of MnOOH,
the metal–oxygen chain of Mn–O–Mn in the MnO6 octahedral
lattice and the Mn–O stretching mode of the MnO6 octahedra,
respectively.60,61 These Raman results are consistent with the
XPS results for the mixed valence state of Mn and the existence
of hydroxyl groups. Then, the prepared electronegative Hx-
MnO2+x nanosheet was used to build a functional coating layer
for Li–S batteries.
To build a coating layer, with the delaminated HxMnO2+x
nanosheets on the surface of the commercial PP separator
serving as a functional coating layer to suppress the polysulde
shuttling and regulate the Li+ ux distribution, vacuum ltra-
tion, an extremely suitable method that allows the self-assembly
of 2D nanosheets, was applied.62 For the fabrication, the as-
obtained HxMnO2+x nanosheets, together with commercial
graphene and CNTs at a mass ratio of 1 : 2 : 2, were rst well
mixed in NMP solution by ultrasound probe sonication. Then,
the as-obtained ink-like solution was vacuum ltered to deposit
it onto one side of the commercial PP separator with a specic
weight of 0.2 mg cm
2. The as-obtained modied separator
was named EB-PP. As shown in Fig. 4a, the commercial
Fig. 4 SEM images recorded at the surface of (a) PP and (b and c) EB-PP. (d) SEM image recorded at the edge of the EB-PP. Digital photographs
of EB-PP under (e) full folding conditions and (f) recovering conditions. (g) SEM image and the corresponding EDX mapping images of the EB-PP.
22468 | J. Mater. Chem. A, 2019, 7, 22463–22474
View Article Online
Paper
separator PP with a large number of open-system holes was
used in this study as a control experiment. Aer vacuum
ltration, according to the SEM images shown in Fig. 4b, a at
and tightly packed HxMnO2+x nanosheet/graphene coating layer
on the surface of the PP separator was constructed. Fig. 4c
shows the SEM image of the EB-PP separator, which conrms
that the created coating layer is of high quality without any
obvious holes. Usually, the thickness of the coating layer is an
important parameter to determine the volumetric energy
density. According to the cross-sectional SEM image of the EB-
PP separator shown in Fig. 4d, the functional coating layer has
a thickness of 3 mm, which is much thinner than that in most
of the previous reports (as listed in Table S2†). The graphene
and HxMnO2+x nanosheets in the functional coating layer
showed the ideal layer-by-layer structure, and the CNTs served
as conductive networks crossing all the coating layers. For
comparison, the graphene modied (denoted as G-PP) sepa-
rator was also prepared by replacing HxMnO2+x nanosheets with
graphene, showing a similar surface SEM image to that of the
EB-PP separator in Fig. S8.†
The thermal and exural properties of EB-PP were also
investigated. As shown in Fig. S9,† aer being placed on a hot
plate and heated at 120  C for 10 min, the EB-PP lm retained
the original geometrical shape, while the pristine PP lm began
to curl. The improved thermal stability of the EB-PP is very
helpful for improving the safety of Li–S batteries in practical
applications.63 The EB-PP also showed good mechanical exi-
bility because its original geometrical shape was restored aer
being bent to an angle of 180 (Fig. 4e and f). To obtain further
information about the distribution of HxMnO2+x nanosheets
This journal is © The Royal Society of Chemistry 2019
 View Article Online

Paper Journal of Materials Chemistry A

inside the EB-PP layer, elemental mapping of the surface and
cross-section was conducted. As shown in Fig. 4g and S10,†
elements carbon, manganese, and oxygen were uniformly
distributed in the coating layer both over the surface and across
the interior, demonstrating a uniform distribution of HxMnO2+x
in the coating layer.
To evaluate the benets of the functional separator in Li–S
batteries, CR2025-type coin cells were assembled from the EB-
PP separator and a 70%S@VC (S : Vulcan XC-72 ¼ 7 : 3)
Published on 10 September 2019. Downloaded by Shanghai University on 6/22/2024 9:35:56 AM.
and S13,† for the batteries before cycling, only one semicircle in
the EIS was observed for the Li–S batteries with the EB-PP
separator compared to two semicircles for the cell with the
conventional PP separator and G-PP separator. In the EIS
spectrum of a conventional Li–S battery with a PP separator and
a G-PP separator, the semicircle that appeared in the high
frequency range is usually ascribed to the charge-transfer
resistance (dened as Rct), and the second semicircle in the
middle frequency is attributed to the reaction between poly-

cathode (XRD and SEM images are shown in Fig. S11 and S12†)
with 70 wt% sulfur loading and were then subjected to elec-
trochemical evaluation. A comparison was made with the
conventional cell with an unmodied PP separator and a G-PP
separator. Electrochemical impedance spectroscopy (EIS) char-
acterization was rst conducted to explore the electrochemical
behaviour of the fresh and cycled batteries. As shown in Fig. 5a
suldes and Li-metal (dened as Rf).30,64 The appearance of
a second semicircle with PP and G-PP separators suggests the
appearance of a Li2S/Li2S2 solid lm on the surface of the
metallic Li anode (dened as Rf).30,35,64,65 The lm resulted from
the reaction between the metallic lithium lm and the poly-
sulde intermediates that were produced by self-discharge and
that migrated from the cathode to the anode. The lower value of

Fig. 5 (a) Characterization of Li–S batteries assembled with PP and EB-PP using EIS spectra collected before and after cycling. (b) Rate
performance and coulombic efficiency of the Li–S batteries with PP, G-PP and EB-PP at varied current rates with a sulfur loading of 1.8 mg cm
2.
Comparison of the cycling performance and coulombic efficiency of the Li–S batteries with PP, G-PP and EB-PP at (c) 0.2C and (d) 0.5C rates. (e)
Long cycling stability and coulombic efficiency of the Li–S battery with EB-PP at a 1C rate.

This journal is © The Royal Society of Chemistry 2019 J. Mater. Chem. A, 2019, 7, 22463–22474 | 22469

Journal of Materials Chemistry A
Rf for the G-PP separator (6.34 U) compared to that for the PP
separator (16.41 U) meant that the graphene-modied separator
could slightly mitigate the “shuttle effect” by the physisorption
of polysuldes. Surprisingly, the battery with the EB-PP sepa-
rator shows a single semicircle corresponding to charge-
transfer resistance, which means that the HxMnO2+x nano-
sheets play an important role in the inhibition of the shuttle
effect. Aer 60 charge–discharge cycles at 0.2C, the batteries
showed an Rct of 15.61 U, which is comparable to that (18.17 U)
Published on 10 September 2019. Downloaded by Shanghai University on 6/22/2024 9:35:56 AM.
for the fresh cell with the EB-PP separator, and no additional
semicircle in the intermediate frequency range appeared, indi-
cating that the polysuldes were well preserved at the cathode
side. In contrast, the battery with the PP separator shows similar
Rf values of 16.41 U and 15.69 U before and aer 60 cycles,
respectively. Similar values of Rf indicate that the substantial
self-discharge caused by the shuttling of polysuldes is
remarkable for fresh cells. Aer 60 cycles, the improved values
of both Rct and Rf are shown in Fig. S13† for the battery with the
G-PP separator compared to the fresh cell, which demonstrates
the inferior trapping ability of graphene for polysuldes. The
detailed tting parameters and equivalent circuit are shown in
Table S1 and Fig. S14,† respectively. The EIS spectra suggest the
high efficiency of the HxMnO2+x coating layer for suppressing
the diffusion of polysuldes from the cathode to the anode side.
For the conventional cells with the unmodied PP separator
and modied G-PP separator, the rst semicircle was enlarged,
indicating an increase in charge-transfer resistance aer
cycling, while the second semicircle still existed or even
increased.
The electrochemical performance of the Li–S batteries with
EB-PP, G-PP and PP separators was further studied and
compared via the rate and cycling performance. As shown in
Fig. 5b, the capacities of batteries with EB-PP and G-PP sepa-
rators were improved at 0.2C for the rst few cycles. A discharge
capacity of 950 mA h g
1 (25th cycle) at 0.2C is observed for the
batteries with the EB-PP separator and over 885 mA h g
1 (25th
cycle) for the batteries with the G-PP separator, while the
capacity with the typical unmodied PP separator decreased
quickly. This result indicates the effectiveness of the modied
coating layer in improving the performance of Li–S batteries,
despite their ultrathin properties (3 mm). Moreover, the
batteries with EB-PP showed a good rate performance, as
demonstrated by high discharge capacities of 742, 630, and
515 mA h g
1 at current densities of 0.5, 1, and 2C, respectively.
Comparatively, the discharge capacities with the G-PP separator
were 725, 568, and 420 mA h g
1 at current densities of 0.5, 1,
and 2C, respectively, while the cell with the coating layer-free
conventional PP separator demonstrated much lower capac-
ities of 585 mA h g
1 (0.5C), 504 mA h g
1 (1C), and
387 mA h g
1 (2C). The corresponding discharge/charge proles
are displayed in Fig. S15,† showing the two typical discharge/
charge platforms of Li–S batteries. The specic area and
conductivity of graphene are far higher than those of HxMnO2+x
nanosheets. By partially replacing the graphene with the Hx-
MnO2+x nanosheets in the modied separator (G-PP versus EB-
PP), the discharge capacities were improved at various current
densities. This result strongly supports the excellent trapping
22470 | J. Mater. Chem. A, 2019, 7, 22463–22474
View Article Online
Paper
ability of HxMnO2+x nanosheets for polysuldes, agreeing with
the results of electrochemical impedance spectroscopy.
According to Fig. 5c, the batteries with the EB-PP functional
separator also had better cycling stability than the other two
types of batteries (with the conventional PP separator or the G-
PP functional separator), and they retained a high capacity of
980 mA h g
1 (500 mA h gcathode
1, based on the mass of the
cathode and coating layer) aer 100 cycles at 0.2C compared to
the cell with the G-PP functional separator, which retained
780 mA h g
1 (398 mA h gcathode
1). In contrast, the batteries
with the PP separator showed an inferior cycling stability for
a low capacity of 295 mA h g
1 (165 mA h gcathode
1) aer 60
cycles at 0.2C. These results conrm that HxMnO2+x nanosheets
could effectively suppress the shuttling of polysuldes, agreeing
with the results of EIS analysis. The corresponding discharge/
charge proles with these three separators are displayed in
Fig. S16.† In addition, the battery with the CNT-PP separator
exhibited inferior cycling performance at 0.5C, similar to the
battery with the PP separator (Fig. S17†). The cycling perfor-
mance of the Li–S battery with the EB-PP separator was further
evaluated at 0.5C and 1C. As shown in Fig. 5d, for the battery
with the EB-PP separator, the capacity is gradually improved in
the rst 100 cycles at 0.5C, which is related to the activation
process for ion transport in the coating layer.35,66–68 The capacity
reached 718 and 675 mA h g
1 at the 100th and 300th cycles,
respectively, showing excellent cycling performance. In
contrast, the battery with the PP separator exhibited a sharp
decay in capacity. Furthermore, aer 200 cycles, an internal
short circuit caused by a lithium dendrite occurred for the PP
separator. The long cycling stability continued at 1C, as shown
in Fig. 5e. The battery with the EB-PP separator showed an
ultrastable cycling capability with a low capacity decay of
0.040% and a high average coulombic efficiency of 99.8% for
1000 cycles. These results demonstrated that the functional
coating layer could not only improve the capacity but also
enhance the lifespan of the Li–S battery. To demonstrate the
practical application of the HxMnO2+x modied separator,
a battery with a high sulfur mass loading of approximately
3.5 mg cm
2 was also assembled, showing an ultrastable cycling
performance (Fig. S18†). Furthermore, the batteries with and
without the HxMnO2+x-based coating layer were also compared
by immersing the cycled cathode and separator (aer 100 cycles
at 0.5C) in DME solution for one hour. As shown in Fig. S19,†
the solution containing the cycled electrode and separator
harvested from the battery with EB-PP was colorless. By
contrast, a yellow color was observed for the solution when
adding the cycled electrode and separator harvested from the
battery with PP. Based on the above observations, we believe
that the content of polysuldes on EB-PP is reduced, demon-
strating that the HxMnO2+x-based coating layer provides an
efficient polysulde-trapping shield for Li–S batteries.
Based on the previous analysis, the highly stable cycling
performance of Li–S batteries with EB-PP separators is attrib-
uted to the strong chemical interaction between the HxMnO2+x
nanosheets in the coating layer and the polysulde intermedi-
ates. The adsorption effect of HxMnO2+x nanosheets, CNTs, and
graphene for polysuldes was rst visually distinguished by an
This journal is © The Royal Society of Chemistry 2019

Paper
adsorption test. The same mass of these three materials was
added into three individual solutions of Li2S6 in DME to
monitor the colour change. As shown in Fig. 6a, the excellent
capability of HxMnO2+x nanosheets for the adsorption of Li2S6
was demonstrated by the complete change from a yellow Li2S6
solution to a colourless solution. In contrast, the other two
solutions, which had CNTs or graphene, retained their original
colour, even though the specic surface areas of CNTs (265 m2
g
1) and graphene (534 m2 g
1) were much larger than that of
Published on 10 September 2019. Downloaded by Shanghai University on 6/22/2024 9:35:56 AM.
the as-prepared HxMnO2+x nanosheets (120 m2 g
1) (the corre-
sponding adsorption/desorption isotherms are shown in
Fig. S20†). In addition, the polysulde adsorption capability of
HxMnO2+x, CNTs and graphene with normalized specic area
was investigated. As shown in Fig. S21,† the same specic area
of these three materials exhibited different adsorption capa-
bilities and followed the order HxMnO2+x > CNTs or graphene.
To directly investigate the chemical interaction of poly-
suldes with HxMnO2+x nanosheets, Li2S6 was employed as the
representative polysulde species, and X-ray photoelectron
spectroscopy (XPS) was applied as a useful tool to analyse the
chemical interaction between polysuldes and HxMnO2+x. For
comparison, the characteristic peaks of the polysulde were rst
obtained. According to Fig. 6b (top), the XPS S 2p spectrum of
the pristine Li2S6 demonstrated two peaks of S 2p3/2 at 161.4 and
163.0 eV that corresponded to terminal sulfur (ST
1) and
bridging sulfur (SB0) atoms, respectively.32,47,50,69 The inset in
Fig. 6d is the XPS Li 1s spectrum of Li2S6, where the single peak
of Li 1s at 55.2 eV is ascribed to the bond between Li and S in
Li2S6.29 To exploit the interaction between polysuldes and Hx-
MnO2+x nanosheets, the powdery HxMnO2+x nanosheets were
added to a Li2S6 solution with stirring. Then, the remaining
solid, named HxMnO2+x@Li2S6, was collected and subjected to
XPS characterization. Fig. 6b (bottom) displays the XPS S 2p
spectrum of HxMnO2+x@Li2S6. Two new peaks, located at 167.7
and 166.1 eV, appeared, which were ascribed to the formation of
Fig. 6 (a) Sealed vials of the Li2S6 solution after contact with different
sample powders. XPS S 2p spectra of (b) raw Li2S6 (top) and Hx-
MnO2+x@Li2S6 (bottom). (c) Results of the Mn 2p3/2 XPS analysis of
HxMnO2+x before and after contact with Li2S6. (d) XPS Li 1s spectra of
HxMnO2+x@Li2S6 and raw Li2S6 (inset).
This journal is © The Royal Society of Chemistry 2019
View Article Online
Journal of Materials Chemistry A
thiosulfate and sulte, respectively.47,50,57 The two newly formed
sulfur environments are caused by the surface redox reaction
between Li2S6 and –O/–OH on the surface of HxMnO2+x nano-
sheets with the creation of O–S and O]S bonds (Fig. S22†).18,47
As the results of TEM, AEM and BET show, the ultrathin struc-
ture of the delaminated HxMnO2+x nanosheet could provide
abundant active sites for the adsorption of polysuldes and Li
ions. In addition, aer mixing HxMnO2+x with polysuldes, the
contribution of Mn3+ located at 641.6 eV signicantly increased
from 14.3 to 31.6%, and two additional Mn 2p3/2 peaks of Mn2+
appeared at 640.6 and 639.9 eV, suggesting the partial reduction
of Mn4+ and Mn3+ (Fig. 6c). The decrease in the oxidation state of
manganese in HxMnO2+x@Li2S6 is indicative of the oxidation of
Li2S6 to thiosulfate. In other words, a surface redox reaction
between the HxMnO2+x nanosheets and Li2S6 was realized.
To further explore the electrostatic interaction between
electronegative HxMnO2+x nanosheets and electropositive Li+
ions, the XPS spectrum of the Li 1s of HxMnO2+x@Li2S6 was
obtained. As expected, the Li 1s peak at 53.8 eV for Hx-
MnO2+x@Li2S6 was negatively shied by approximately 1.4 eV
compared with that of pure Li2S6 (55.2 eV, inset in Fig. 6d),
which indicates an electron transfer from the HxMnO2+x nano-
sheets to Li+ ions.31,70 According to our previous analysis, the
shi in the binding energy is mainly attributed to the electro-
static interaction between electronegative HxMnO2+x and elec-
tropositive Li+ ions. In addition, the three additional peaks at
51.2, 49.7 and 48.2 eV were ascribed to Mn4+ 3p, Mn3+ 3p and
Mn2+ 3p, respectively.71 From the aforementioned zeta potential
measurement (Fig. 2f), in conjunction with the XPS analyses,
the electrostatic interaction between the HxMnO2+x nanosheets
and the Li+ ions was veried, thus allowing homogeneous Li-ion
ux on the surface of the Li anode.
Lithium dendrite growth upon cycling also severely impedes
practical application of Li–S batteries. Inspired by the electro-
static interaction between the HxMnO2+x nanosheets and the Li+
ions, symmetric Li|Li cells with PP and EB-PP separators were
assembled. During cycling, 1 mA h cm
2 of active lithium was
reversibly deposited between the two symmetric electrodes at
a current density of 1 mA cm
2. As shown in Fig. 7a and b, the
battery with the EB-PP separator exhibits an excellent cycling
performance over 1000 hours and a much lower polarization
voltage (within 100 mV) over 1000 hours. In contrast, the battery
with the PP separator shows a larger polarization voltage, and
a gradual increase in polarization voltage is observed aer
cycling for 250 hours, which can be attributed to the inhomo-
geneous plating and stripping of Li+ ions, thus forming Li
dendrites and impeding Li-ion ow. More importantly, at the
initial plating and stripping stage, the nucleation overpotential
of the Li electrode in the Li symmetric cell with the EB-PP
separator (38.7 mV) is much lower than that of the PP sepa-
rator (88.3 mV), demonstrating that the functional coating layer
can signicantly lower the Li deposition barrier (Fig. S23†). The
reason could be attributed to the homogeneous ux of Li ions at
the Li anode/electrolyte interface inducing uniform reduction of
Li ions on the Li surface during the deposition step (Li+ + e
¼
Li). To elucidate the intrinsic nature of the functional coating
layer, the morphologies of Li-metal electrodes disassembled
J. Mater. Chem. A, 2019, 7, 22463–22474 | 22471

Journal of Materials Chemistry A
Published on 10 September 2019. Downloaded by Shanghai University on 6/22/2024 9:35:56 AM.
Fig. 7 Voltage–time profiles of Li plating/stripping with (a) PP and (b) EB-PP. Digital photographs and SEM images of the Li metal anodes
disassembled from the Li symmetrical cells with (c and e) PP and (d and f) EB-PP after long-term repetitive cycling.
from the Li symmetrical cells using a PP separator and an EB-PP
separator aer long cycling were carefully investigated. As shown
in the digital photographs (Fig. 7c and d), the Li metal surface
with the PP separator turns black aer repetitive cycling for 600
hours, while the Li metal surface with the EB-PP separator still
has a metallic lustre even aer being cycled for 1000 hours. The
SEM images of the Li metal electrodes using the PP separator
and EB-PP separator are shown in Fig. 7e and f and S24† for
comparison. For the symmetric cell with the PP separator, the
obvious rod-like Li dendrites and mossy Li with a loosely stacked
porous structure are formed aer 600 hours of cycling. In
contrast, for the symmetric cell with the EB-PP separator,
a uniform and at surface without obvious Li dendrites is
observed on the surface of the lithium electrode, which looks
similar to the fresh lithium electrode in Fig. S25.†
The superior suppression ability towards Li dendrites comes
from the synergistic effect between electronegative HxMnO2+x in
the separator and the electrolyte. The battery without the Hx-
MnO2+x modied separator showed uncontrolled growth of Li
dendrites arising from inhomogeneous Li electrodeposition and
could repeatedly break the SEI lms, which were generated from
the side reactions between metallic lithium and electrolyte.72,73
Therefore, the rapid consumption of electrolyte and active Li and
the formation of electrochemically inert dead Li could induce
a large polarization of Li metal-based batteries.72,74 Aer using the
HxMnO2+x modied separator, the inhomogeneous distribution
of Li ions in the electrolyte could redistribute on the functional
electronegative HxMnO2+x modied separator based on electro-
static interactions between them, thus enabling a homogeneous
Li-ion ux distribution on the anode that can fundamentally alter
dendrite formation during the Li deposition process.75,76 In
addition, stable SEI lms on the surface of Li metal could further
prevent the consumption of electrolyte and active Li. Therefore,
22472 | J. Mater. Chem. A, 2019, 7, 22463–22474
View Article Online
Paper
a “dendrite-free” Li–S battery with a long cycle life could be
achieved using this electronegative functional separator.
Conclusions
In summary, delaminated electronegative HxMnO2+x nano-
sheets with a thickness of 3.5 nm were successfully prepared
and used for the rst time in combination with graphene and
CNTs as a bifunctional coating layer for Li–S batteries. A thin
and lightweight coating layer with a thickness of 3 mm and
a mass loading of 0.2 mg cm
2 was created through vacuum
ltration. Compared to traditional modied separators in
previous reports, the HxMnO2+x-based electronegative coating
layer can simultaneously regulate polysulde and Li+ adsorp-
tion sites, thus enabling suppressed polysulde shuttling and
homogeneous Li-ion ux to achieve a long cycle life and
“dendrite-free” Li–S batteries. The interactions among poly-
suldes, Li ions and HxMnO2+x nanosheets were investigated by
XPS, conrming the occurrence of chemisorption and electro-
static interactions. As a proof of concept, the Li–S batteries
assembled with the proposed coating layer displayed excellent
performance, including cycling stability (decay rate of 0.04%
per cycle) and long cycle life (over 1000 cycles at 1C). Addi-
tionally, Li-symmetrical cells with the proposed coating layer
showed fundamentally suppressed dendrite growth even aer
being cycled over 1000 hours. These results demonstrated that
the proposed coating layer is promising for practical Li–S
batteries, hence encouraging more research on the fabrication
of other electronegative nanosheet families as bifunctional
coating layers.
Conflicts of interest
There are no conicts to declare.
This journal is © The Royal Society of Chemistry 2019

Paper
Acknowledgements
Z. Shao and K. Liao are thankful for the funding support
provided by the National Key R&D Program of China (No.
2018YFB0905400). K. Liao is thankful for the funding support
provided by the National Natural Science Foundation of China
(No. 51802152) and the Natural Science Foundation of Jiangsu
Province of China (No. BK20170974).
Published on 10 September 2019. Downloaded by Shanghai University on 6/22/2024 9:35:56 AM.
Notes and references
1 M. Du, K. Liao, Q. Lu and Z. Shao, Energy Environ. Sci., 2019,
12, 1780–1804.
2 Q. Lu, J. Yu, X. Zou, K. Liao, P. Tan, W. Zhou, M. Ni and
Z. Shao, Adv. Funct. Mater., 2019, 29, 1904481.
3 X. Wu, Y. Xu, Y. Hu, G. Wu, H. Cheng, Q. Yu, K. Zhang,
W. Chen and S. Chen, Nat. Commun., 2018, 9, 4573.
4 W. Ni and L. Shi, J. Vac. Sci. Technol., A, 2019, 37, 040803.
5 A. Manthiram, Y. Q. Fu and Y.-S. Su, Acc. Chem. Res., 2013,
46, 1125–1134.
6 R. Xu, J. Lu and K. Amine, Adv. Energy Mater., 2015, 5,
1500408.
7 P. G. Bruce, S. A. Freunberger, L. J. Hardwick and
J. M. Tarascon, Nat. Mater., 2011, 11, 19–29.
8 H. Yuan, H.-J. Peng, J.-Q. Huang and Q. Zhang, Adv. Mater.
Interfaces, 2019, 6, 1802046.
9 Y. X. Yin, S. Xin, Y. G. Guo and L. J. Wan, Angew. Chem., Int.
Ed., 2013, 52, 13186–13200.
10 Y. Yang, G. Zheng and Y. Cui, Chem. Soc. Rev., 2013, 42,
3018–3032.
11 A. Manthiram, S. H. Chung and C. Zu, Adv. Mater., 2015, 27,
1980–2006.
12 Y. Zhu, S. Wang, Z. Miao, Y. Liu and S. L. Chou, Small, 2018,
14, e1801987.
13 Y. Mao, G. Li, Y. Guo, Z. Li, C. Liang, X. Peng and Z. Lin, Nat.
Commun., 2017, 8, 14628.
14 S.-H. Chung and A. Manthiram, Adv. Funct. Mater., 2014, 24,
5299–5306.
15 X. Zou, Q. Lu, Y. Zhong, K. Liao, W. Zhou and Z. Shao, Small,
2018, 14, 1801798.
16 W. Chen, T. Lei, C. Wu, M. Deng, C. Gong, K. Hu, Y. Ma,
L. Dai, W. Lv, W. He, X. Liu, J. Xiong and C. Yan, Adv.
Energy Mater., 2018, 8, 1702348.
17 F. Wu, Y.-X. Yuan, X.-B. Cheng, Y. Bai, Y. Li, C. Wu and
Q. Zhang, Energy Storage Materials, 2018, 15, 148–170.
18 J. Liu, T. Qian, M. Wang, J. Zhou, N. Xu and C. Yan, Nano
Lett., 2018, 18, 4598–4605.
19 Y. Zhong, Q. Lu, Y. Zhu, Y. Zhu, W. Zhou, S. Wang and
Z. Shao, Adv. Sustainable Syst., 2017, 1, 1700081.
20 Q. Lu, Y. Zhong, W. Zhou, K. Liao and Z. Shao, Adv. Mater.
Interfaces, 2018, 5, 1701659.
21 G. Zhou, L. Li, D. W. Wang, X. Y. Shan, S. Pei, F. Li and
H. M. Cheng, Adv. Mater., 2015, 27, 641–647.
22 S. Bai, X. Liu, K. Zhu, S. Wu and H. Zhou, Nat. Energy, 2016,
1, 16094.
23 Y. He, S. Bai, Z. Chang, Q. Li, Y. Qiao and H. Zhou, J. Mater.
Chem. A, 2018, 6, 9032–9040.
This journal is © The Royal Society of Chemistry 2019
View Article Online
Journal of Materials Chemistry A
24 S. H. Chung and A. Manthiram, Adv. Mater., 2014, 26, 7352–
7357.
25 S. H. Chung and A. Manthiram, J. Phys. Chem. Lett., 2014, 5,
1978–1983.
26 Y. Song, W. Zhao, L. Kong, L. Zhang, X. Zhu, Y. Shao, F. Ding,
Q. Zhang, J. Sun and Z. Liu, Energy Environ. Sci., 2018, 11,
2620–2630.
27 Y. Zhong, S. Wang, Y. Sha, M. Liu, R. Cai, L. Li and Z. Shao, J.
Mater. Chem. A, 2016, 4, 9526–9535.
28 Z. Sun, J. Zhang, L. Yin, G. Hu, R. Fang, H. M. Cheng and
F. Li, Nat. Commun., 2017, 8, 14627.
29 K. Liao, P. Mao, N. Li, M. Han, J. Yi, P. He, Y. Sun and
H. Zhou, J. Mater. Chem. A, 2016, 4, 5406–5409.
30 W. Kong, L. Yan, Y. Luo, D. Wang, K. Jiang, Q. Li, S. Fan and
J. Wang, Adv. Funct. Mater., 2017, 27, 1606663.
31 Q. Pang, D. Kundu, M. Cuisinier and L. F. Nazar, Nat.
Commun., 2014, 5, 4759.
32 Q. Lu, Y. Sun, K. Liao, X. Zou, I. Hamada, W. Zhou, M. Ni and
Z. Shao, Electrochim. Acta, 2019, 298, 421–429.
33 Z. Li, J. Zhang and X. W. Lou, Angew. Chem., Int. Ed., 2015, 54,
12886–12890.
34 X. Liang, Y. Rangom, C. Y. Kwok, Q. Pang and L. F. Nazar,
Adv. Mater., 2017, 29, 1603040.
35 X. Ni, T. Qian, X. Liu, N. Xu, J. Liu and C. Yan, Adv. Funct.
Mater., 2018, 28, 1706513.
36 M. Li, C. Wang, L. Miao, J. Xiang, T. Wang, K. Yuan, J. Chen
and Y. Huang, J. Mater. Chem. A, 2018, 6, 5862–5869.
37 W. Chen, T. Lei, W. Lv, Y. Hu, Y. Yan, Y. Jiao, W. He, Z. Li,
C. Yan and J. Xiong, Adv. Mater., 2018, 30, 1804084.
38 Z. Chang, Y. He, H. Deng, X. Li, S. Wu, Y. Qiao, P. Wang and
H. Zhou, Adv. Funct. Mater., 2018, 28, 1804777.
39 K. Liao, S. Wu, X. Mu, Q. Lu, M. Han, P. He, Z. Shao and
H. Zhou, Adv. Mater., 2018, 30, 1705711.
40 N. W. Li, Y. X. Yin, C. P. Yang and Y. G. Guo, Adv. Mater.,
2016, 28, 1853–1858.
41 A. Basile, A. I. Bhatt and A. P. O'Mullane, Nat. Commun.,
2016, 7, 11794.
42 Y. Guo, P. Niu, Y. Liu, Y. Ouyang, D. Li, T. Zhai, H. Li and
Y. Cui, Adv. Mater., 2019, e1900342, DOI: 10.1002/
adma.201900342.
43 Z. Liang, G. Zheng, C. Liu, N. Liu, W. Li, K. Yan, H. Yao,
P. C. Hsu, S. Chu and Y. Cui, Nano Lett., 2015, 15, 2910–2916.
44 Y. He, H. Xu, J. Shi, P. Liu, Z. Tian, N. Dong, K. Luo, X. Zhou
and Z. Liu, Energy Storage Materials, 2019, DOI: 10.1016/
j.ensm.2019.04.026.
45 F. Ding, W. Xu, G. L. Graff, J. Zhang, M. L. Sushko, X. Chen,
Y. Shao, M. H. Engelhard, Z. Nie, J. Xiao, X. Liu, P. V. Sushko,
J. Liu and J. G. Zhang, J. Am. Chem. Soc., 2013, 135, 4450–
4456.
46 Z. H. Liu, K. Ooi, H. Kanoh, W. P. Tang and T. Tomida,
Langmuir, 2000, 16, 4154–4164.
47 X. Liang, C. Hart, Q. Pang, A. Garsuch, T. Weiss and
L. F. Nazar, Nat. Commun., 2015, 6, 5682.
48 X.-Q. Zhang, X. Chen, L.-P. Hou, B.-Q. Li, X.-B. Cheng,
J.-Q. Huang and Q. Zhang, ACS Energy Lett., 2019, 4, 411–416.
49 S. Guo, H. Yu, P. Liu, X. Liu, D. Li, M. Chen, M. Ishida and
H. Zhou, J. Mater. Chem. A, 2014, 2, 4422–4428.
J. Mater. Chem. A, 2019, 7, 22463–22474 | 22473

Journal of Materials Chemistry A
50 L. Ni, Z. Wu, G. Zhao, C. Sun, C. Zhou, X. Gong and G. Diao,
Small, 2017, 13, 1603466.
51 N. Yu, H. Yin, W. Zhang, Y. Liu, Z. Tang and M.-Q. Zhu, Adv.
Energy Mater., 2016, 6, 1501458.
52 Z. Sun, D. Shu, C. Lv, Q. Zhang, C. He and S. Tian, J. Alloys
Compd., 2013, 569, 136–143.
53 X. Duan, J. Yang, H. Gao, J. Ma, L. Jiao and W. Zheng,
CrystEngComm, 2012, 14, 4196–4204.
54 H. Zhao, S. Chen, X. Quan, H. Yu and H. Zhao, Appl. Catal., B,
Published on 10 September 2019. Downloaded by Shanghai University on 6/22/2024 9:35:56 AM.
2016, 194, 134–140.
55 L. Ni, G. Zhao, G. Yang, G. Niu, M. Chen and G. Diao, ACS
Appl. Mater. Interfaces, 2017, 9, 34793–34803.
56 X. Song, G. Chen, S. Wang, Y. Huang, Z. Jiang, L. X. Ding and
H. Wang, ACS Appl. Mater. Interfaces, 2018, 10, 26274–26282.
57 X. Wang, G. Li, J. Li, Y. Zhang, A. Wook, A. Yu and Z. Chen,
Energy Environ. Sci., 2016, 9, 2533–2538.
58 J. Liu, X. Ge, X. Ye, G. Wang, H. Zhang, H. Zhou, Y. Zhang
and H. Zhao, J. Mater. Chem. A, 2016, 4, 1970–1979.
59 Y. Zhang, Z. Hu, Y. An, B. Guo, N. An, Y. Liang and H. Wu, J.
Power Sources, 2016, 311, 121–129.
60 Z. Pan, Y. Qiu, J. Yang, F. Ye, Y. Xu, X. Zhang, M. Liu and
Y. Zhang, Nano Energy, 2016, 26, 610–619.
61 T. Lin, L. Yu, M. Sun, G. Cheng, B. Lan and Z. Fu, Chem. Eng.
J., 2016, 286, 114–121.
62 B. Yao, J. Zhang, T. Y. Kou, Y. Song, T. Y. Liu and Y. Li, Adv.
Sci., 2017, 4, 1700107.
63 Y. Yang and J. Zhang, Adv. Energy Mater., 2018, 8, 1801778.
22474 | J. Mater. Chem. A, 2019, 7, 22463–22474
View Article Online
Paper
64 K. Shen, H. Mei, B. Li, J. Ding and S. Yang, Adv. Energy Mater.,
2018, 8, 1701527.
65 M. He, L. X. Yuan, W. X. Zhang, X. L. Hu and Y. H. Huang, J.
Phys. Chem. C, 2011, 115, 15703–15709.
66 L. Luo, S.-H. Chung and A. Manthiram, J. Mater. Chem. A,
2016, 4, 16805–16811.
67 L.-B. Xing, K. Xi, Q. Li, Z. Su, C. Lai, X. Zhao and R. V. Kumar,
J. Power Sources, 2016, 303, 22–28.
68 C. Zhang, Y. Lin and J. Liu, J. Mater. Chem. A, 2015, 3, 10760–
10766.
69 K. Cao, H. Liu, Y. Li, Y. Wang and L. Jiao, Energy Storage
Materials, 2017, 9, 78–84.
70 W. Chen, T. Lei, T. Qian, W. Lv, W. He, C. Wu, X. Liu, J. Liu,
B. Chen, C. Yan and J. Xiong, Adv. Energy Mater., 2018, 8,
1702889.
71 K. Natarajan, M. Saraf and S. M. Mobin, Nanoscale, 2018, 10,
13250–13260.
72 Y. He, Z. Chang, S. Wu, Y. Qiao, S. Bai, K. Jiang, P. He and
H. Zhou, Adv. Energy Mater., 2018, 8, 1802130.
73 Y. He, Y. Qiao, Z. Chang and H. Zhou, Energy Environ. Sci.,
2019, 12, 2327–2344.
74 C. Li, S. Liu, C. Shi, G. Liang, Z. Lu, R. Fu and D. Wu, Nat.
Commun., 2019, 10, 1363.
75 C.-Z. Zhao, P.-Y. Chen, R. Zhang, X. Chen, B.-Q. Li,
X.-Q. Zhang, X.-B. Cheng and Q. Zhang, Sci. Adv., 2018, 4,
eaat3446.
76 L. Chen, W. Li, L. Z. Fan, C. W. Nan and Q. Zhang, Adv. Funct.
Mater., 2019, 1901047, DOI: 10.1002/adfm.201901047.
This journal is © The Royal Society of Chemistry 2019