Subscriber access provided by BIU Pharmacie | Faculté de Pharmacie, Université Paris V

Article
Highly Efficient Polysulfide Trapping and Ion
Transferring within Hierarchical Porous Membrane
Interlayer for High-Energy Lithium-Sulfur Batteries
Shuting Wang, Xiangcun Li, Yue Zhang, Wenji Zheng, Yan Dai, and Gaohong He
ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.0c00629 • Publication Date (Web): 24 Apr 2020
Downloaded from pubs.acs.org on April 24, 2020

Just Accepted

“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W.,

Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the
course of their duties.
Page 1 of 22 ACS Applied Energy Materials

1
2
3
4
5 Highly Efficient Polysulfide Trapping and Ion Transferring within Hierarchical
6
7
Porous Membrane Interlayer for High-Energy Lithium-Sulfur Batteries
8
9
10 Shuting Wang, Xiangcun Li,* Yue Zhang, Wenji Zheng, Yan Dai, Gaohong He
11
12 State Key Laboratory of Fine Chemicals, Department of Chemical Engineering
13
14 Dalian University of Technology
15
16 Linggong Road 2#, Dalian 116024, China
17
18 E-mail: lixiangcun@dlut.edu.cn
19
20
21
22 Abstract
23
24 Inserting an interlayer between the sulfur cathode and the separator has been considered as one
25
26 of the most promising solutions to suppress the shuttle effect of soluble polysulfide intermediates
27
28 (LiPSs) for lithium-sulfur (Li-S) batteries. However, the previously reported CNT or carbon
29
30 composite-based interlayers can be easily blocked with the LiPSs adsorption and impede the
31
32 transmission of lithium ions due to lacking of rationally designed porous structure. Here we report a
33
34 hierarchical porous Fe3C-C/CNT membrane interlayer with rapid ion-transport macropores and
35
36 hierarchical polysulfide-trapping mesopores via a convenient and scalable phase-inversion approach
37
38 for high-energy-density Li–S batteries. The rationally designed porous structure of Fe3C-C/CNT
39
40 interlayers significantly provide a fine environment for fast transportation of Li+ ions and electrons,
41
42 and simultaneously effectively restrain the shuttle effect by chemical adsorption energy of the Fe3C
43
44 nanoparticles toward soluble LiPSs. As a result, due to the self-supporting Fe3C-C/CNT interlayer,
45
46 batteries with high sulfur loading (7.06 mg cm-2) and a low ratio of electrolyte to sulfur (5.7 μL
47
48 mg-1) can exhibit an high areal capacity up to 4.32 mA h cm-2, achieving high gravimetric specific
49
50 energy (1560 W h kg-1) and volumetric specific energy (1694 W h L-1). This facile approach of
51
52 membrane interlayer fabrication and structural design provides a promising future for the practical
53
54 applications of Li-S batteries.
55
56 Keywords: Li-S batteries; Membranes; Carbon nanotubes; Phase inversion; Electrochemistry
57
58
59
60
1

ACS Paragon Plus Environment

 ACS Applied Energy Materials Page 2 of 22

1
2
3
4
5 Introduction
6
7 The ever-increasing energy storage requirements cannot be satisfied by lithium-ion batteries with
8
9 conventional intercalation cathodes.1-2 Lithium-sulfur batteries have induced extensive interesting
10
11 for promising rechargeable battery systems due to their extremely high energy density (2600 W h
12
13 kg−1) and theoretical specific capacity (1675 mA h g−1) 3. Besides, sulfur is an abundant natural
14
15 resource, with low price and nontoxicity.4 However, the commercialization of lithium-sulfur
16
17 batteries is still limited by some major obstacles, including the insulating nature of sulfur, low
18
19 utilization efficiency of active material as well as the poor cyclability and low coulombic efficiency
20
21 due to the dissolution and shuttle effect of LiPSs.5-10
22
23 To alleviate the above issues, extensive studies including metal oxides, metal sulfides, carbon
24
25 composites, polymers, and other host materials have been carried out.11-15 One of the most promising
26
27 solutions is to insert an interlayer between the sulfur cathode and the separator, which can effectively
28
29 reutilize the sulfur species and prevent LiPSs from diffusing to the anode side in order to improve
30
31 the energy storage properties of Li-S batteries.8, 10, 16 Carbon materials, with high electrical
32
33 conductivity, large surface area and chemical stability, are good choices for interlayers.2, 10
34
35 Therefore, porous carbon paper, 17-19 carbon aerogels,20-22 carbon nanotubes (CNTs),23-25 reduced
36
37 graphene oxides,26-28 and various carbon composites,29-31 have been developed and inserted between
38
39 the sulfur cathode and separator as a physical barrier against diffusion of LiPSs while guaranteeing
40
41 pathways for electrons. In addition, transition metal compounds, such as Fe2O3,32 TiO2-TiN,33
42
43 MoS2,27 Fe3C,34 with catalytic performance or a mass of LiPSs trapping sites were also introduced to
44
45 these carbon materials. However, these CNTs or carbon composite-based interlayer can be easily
46
47 clogged by LiPSs for high-sulfur-loading cathodes and impede the transmission of lithium ions due
48
49 to lacking of rationally designed porous structures. Moreover, these porous structures are also
50
51 essential for transportation of electrolyte and accommodation of sulfur species.23, 35 Therefore, the
52
53 reported Li-S battery interlayers can be only suitable for the low-sulfur-loading battery cathodes (< 3
54
55 mg cm-2), which is far away from commercialization. In addition, these carbon materials are often
56
57 prepared in a lab-scale with high cost and complex fabrication procedures, which is difficult to
58
59 achieve large-scale and far-ranging production. Accordingly, it is greatly anticipated to develop a
60
2

ACS Paragon Plus Environment

Page 3 of 22 ACS Applied Energy Materials

1
2
3
4
5 facile method to prepare interlayers with high-sulfur-trapping ability and rationally designed porous
6
7 structure to address the above mentioned issues in the meantime.
8
9 In this work, we prepared a scalable Fe3C-C/CNT membrane interlayer via a convenient phase
10
11 inversion method for simultaneously inhibiting the shuttle effect of soluble LiPSs and facilitating Li+
12
13 ion transportation. As a multifunctional interlayer, the hierarchical porous networks comprised of
14
15 CNT cores and crosslinked carbon shell achieves a high-efficient LiPSs accommodation ability
16
17 through the tapping effect of the Fe3C nanoparticles in the carbon membrane towards LiPSs, and
18
19 meanwhile the patterned pathways significantly promote Li+ and electrolyte transportation. With the
20
21 self-supporting Fe3C-C/CNT as interlayer, batteries with high sulfur loading (7.06 mg cm-2) and a
22
23 low ratio of electrolyte to sulfur (5.7 μL mg-1) can exhibit an areal capacity of 4.32 mA h cm-2,
24
25 achieving high gravimetric specific energy (1560 W h kg-1) and volumetric specific energy (1694 W
26
27 h L-1), thus demonstrating a promising strategy towards realizing applications of high-energy-density
28
29 Li-S batteries.
30
31 Results and discussion
32
33 Phase-inversion is known as an important membrane fabrication method because it shows good
34
35 ability to template porous structures in membranes and definite potential for scalable
36
37 preparation.36-40 However, how to design ideal interlayer materials by using this convenient method
38
39 has not been reported. Hence, we fabricated monolithic porous polymer membranes and their
40
41 free-standing carbonized membrane interlayer for Li-S batteries by the facile phase-inversion
42
43 method for the first time. As shown in Figure S1, the homogeneous slurry composed of
44
45 polyacrylonitrile (PAN), CNTs, FeCl3·6H2O (1:2:1) and N,N-dimethylformamide (DMF, solvent)
46
47 was scraped on a glass plate for preparation of a liquid layer with a thickness of ~200μm by an
48
49 automatic membrane casting machine. The polymer membrane was prepared by immersing the glass
50
51 plate with liquid layer into nonsolvent (water bath). The immersion induced phase separation
52
53 immediately with penetration of water into the liquid layer, forming polymer-lean and polymer-rich
54
55 phases to template patterned and hierarchical pores respectively. Simultaneously, porous networks
56
57 with the CNT as cores and the PAN polymer coating as crosslinked shells were constructed in the
58
59 membrane. After peroxidation and carbonization, the self-supporting Fe3C-C/CNT membrane
60
3

ACS Paragon Plus Environment

 ACS Applied Energy Materials Page 4 of 22

1
2
3
4
5 interlayer with patterned ion-transporting pathways and porous polysulfide-trapping networks were
6
7 obtained.
8
9 Figure 1a shows Fe3C-C/CNT membrane interlayer for inhibiting shuttle effect of LiPSs and
10
11 facilitating Li+ ion transportation simultaneously. Due to the unique porous frameworks and the
12
13 doped Fe3C nanoparticles in the crosslinked carbon shell, the hierarchical porous networks can
14
15 high-efficiently accommodate LiPSs via strong chemical absorption. Remarkably, Li+ ions can react
16
17 directly with the LiPSs adsorbed in the porous networks due to the high electrical conductivity of the
18
19 interconnecting CNT networks crosslinked by carbon shell, while the patterned channels can ensure
20
21 high-speed transmission of Li+ ions and electrolyte, accompanying adsorption of LiPSs. Figure 1b
22
23 and c show the optical photograph of the scalable-prepared Fe3C-C/CNT membranes, which can be
24
25 further cut into small carbon pieces for LiPSs adsorption and work as an interlayer in Li-S
26
27 batteries.41 Figure 1d shows the cross-section scanning electron microscopy (SEM) image of
28
29 Fe3C-C/CNT membrane of about 60µm in thickness (Figure S2a), and the patterned channels are
30
31 obvious. The high-resolution SEM images in Figure 1e and f show the hierarchical porous channel
32
33 walls, and the porous networks are constructed with CNTs as skeleton and Fe3C-doped carbon
34
35 coating as crosslinked carbon shell. The patterned channels and porous interconnecting framework
36
37 can provide an environment for electrochemical redox reaction of sulfur species within electrolyte,
38
39 and meanwhile it can also effectively facilitate the transportation of Li+ ions and electrolyte, thus
40
41 decrease the use of electrolyte and electrolyte/sulfur (E/S) ratio and reduce the charge transfer
42
43 resistance, which are crucial for LIPSs adsorption and fast Li+ transmission. Besides construction of
44
45 the porous frameworks, the addition of CNT is also critical to the formation of porous structure in
46
47 the membrane surface (Figure S2 b, c). This can be further improved by the control experiments that
48
49 distinct dense layers are obtained for both pure C and Fe3C-C membranes without the addition of
50
51 CNT (Figure S3 and Figure S4). For phase inversion membranes, solvent / non-solvent
52
53 compatibility and exchange rate are important factors affecting membrane structure. When the
54
55 casting solution contains only PAN without any additives, the exchange of solvent and non-solvent
56
57 is very rapid, so the top surface finally appears as a dense layer. As the degree of exchange deepens,
58
59 the polymer-lean phase droplets composed of a small amount of DMF, water, and PAN are dispersed
60
4

ACS Paragon Plus Environment

Page 5 of 22 ACS Applied Energy Materials

1
2
3
4
5 in the continuous polymer-rich phase. The polymer-lean phase continues to grow, generating crystal
6
7 nuclei, forming a sub-layer finger-like macroporous structure. At the interface of solution and glass
8
9 plate, the phase separation rate slows down, the polymer-rich phase nucleates, and the lean phase
10
11 only aggregates to a certain extent, thus the sponge pores are finally formed (Figure S3). The
12
13 thermodynamic stability can be changed by metal salt ions, the force between the iron salt and the
14
15 solvent is greater than the force between the iron salt and the polymer when FeCl3 is added. In
16
17 addition, the concentration difference caused by the addition of iron salts makes the increase of the
18
19 osmotic pressure in the membrane and induces the agglomeration of polymer and growth of finger
20
21 pores. The pore structure of the Fe3C-C membrane is more regular, but the dense layer still exists
22
23 (Figure S4). Therefore, as a substance with poor solvent and non-solvent compatibility, when CNTs
24
25 are added to the casting solution at twice the mass of PAN, they will cause the polymer to be
26
27 difficult to form a dense layer in a short time, thus a porous top surface is formed.
28
29 The structure of Fe3C-C/CNT membrane can greatly increase the specific surface area and
30
31 pore volume. Nitrogen isothermal adsorption-desorption measurements of the materials are provided
32
33 (Figure S5) and the Brunauer-Emmett-Teller (BET) surface area and pore volume of Fe3C-C/CNT
34
35 membrane are 104.35 m2 g-1 and 0.28 cm3 g-1, much larger than those of Fe3C-C (28.36 m2 g-1, 0.039
36
37 cm3 g-1) and pure C (1.48 m2 g-1, 0.0037 cm3 g-1) membranes (Table S1). Furthermore, the addition
38
39 of CNT results in a higher degree of graphitization, which can be demonstrated by the X-ray
40
41 diffraction (XRD, Figure S6) peaks in accordance with the standard data for graphite C
42
43 (PDF#26-1079) and the lower value of ID/IG in Raman spectrum (Figure 1g). The lower intensity
44
45 ratio of the D band to G band (ID/IG) commonly represents the higher graphitization degree, which
46
47 means better electrical conductivity and thus accelerating electrochemical conversion of sulfur
48
49 species.4 The XRD diffraction peaks in accordance with the standard XRD data for Fe3C
50
51 (PDF#35-0772) can prove that the Fe element is present in the material after carbonization in the
52
53 form of Fe3C, which also leads to a reducing of ID/IG indicated by comparison of pure C and Fe3C-C.
54
55 The transmission electron microscopy (TEM) images reveal homogeneous distributed CNTs (Figure
56
57 S7 a-c), and the doped Fe3C nanoparticles have a lattice distance 0.211 nm, in agreement with the
58
59 (211) plane of Fe3C (Figure S7 d).42 Furthermore, the content of Fe3C can be obtained from the
60
5

ACS Paragon Plus Environment

 ACS Applied Energy Materials Page 6 of 22

1
2
3
4
5 calculation of thermogravimetry (TGA) in air (Figure S8). The inflection point at about 350℃
6
7 corresponds to the oxidation of Fe3C to Fe2O3. The platform in the TGA curve after 600℃ means the
8
9 mass fraction of Fe2O3 is 10.07%, which is the resulting product, corresponding to the Fe3C content
10
11 of 7.54%.37
12
13 The blocking effects and adsorption ability of Fe3C-C/CNT interlayer for LiPSs can be
14
15 characterized through Figure 1h-j. To intuitively reveal the adsorption effects of interlayers, Li2S6
16
17 was selected as the representative LiPSs.43 The polysulfide solution was obtained by adding Li2S6
18
19 into colorless electrolyte and eventually displays a yellow color. Figure 1h shows the polysulfide
20
21 solution before and after pure C, Fe3C-C and Fe3C-C/CNT materials soaked for 24 h, respectively.
22
23 The color of the solution with pure C interlayer soaked was close to the untreated Li2S6 solution and
24
25 of the solution with Fe3C-C interlayer soaked was lighter, while the solution with Fe3C-C/CNT
26
27 interlayer soaked was completely transparent and colorless, confirming the strong adsorption
28
29 capability of Fe3C-C interlayer to LiPSs. As shown in Figure 1i, the left side of the U-type unit for
30
31 permeation experiment was equipped with polysulfide solution and the right side was equipped with
32
33 pure electrolyte. In the permeation experiment with Fe3C-C/CNT interlayer, LiPSs were unable to
34
35 pass through the interlayer, demonstrating the obvious blocking effect of Fe3C-C/CNT interlayer as
36
37 an ion sieve on LiPSs. Furthermore, adsorption ability for polysulfides was also tested by UV-vis
38
39 measurement (Figure 1j). The characteristic peak of S62- is located approximately 310nm and the
40
41 peak intensities decrease remarkably owing to the adsorption of Li2S6 by the carbon materials.44
42
43
Figure 1.
44
45
46 Figure 2a shows the cycle voltammetry (CV) curves of cells with and without Fe3C-C/CNT
47
48 interlayer at 0.1 mV s-1 in the voltage range of 1.7-2.8V. The sulfur loading of the resulting cathodes
49
50 is about 1.5 mg cm-2. There are two distinct cathodic peaks at about 2.32 and 2.02 V of the cell with
51
52 Fe3C-C/CNT interlayer, the former can be attributed to the transformation from sulfur to LiPSs
53
54 (Li2Sn, 4 ≤ n ≤ 8) and the latter attributed to the subsequent reduction to short-chain LiPSs (Li2Sn, 3
55
56 ≤ n ≤ 4), Li2S2 and Li2S. In the anodic scan, an obvious oxidation peak at about 2.30 V is
57
58 corresponding to the transformation of short-chain to long-chain LiPSs.3 Compared to the cell
59
60 without interlayer, the cathodic peaks and anodic peaks of the cell with Fe3C-C/CNT interlayer show
6

ACS Paragon Plus Environment

Page 7 of 22 ACS Applied Energy Materials

1
2
3
4
5 positive shifts and a negative shift respectively, evidencing the reduction of electrode polarization.
6
7 The negative shift of anodic peak suggests that Fe3C-C/CNT interlayer could facilitate the oxidation
8
9 of short-chain LiPSs to long-chain, increasing the utilization of sulfur.45 Notably, both the cathodic
10
11 peaks and anodic peak belonging to the cell with Fe3C-C/CNT interlayer are much stronger and
12
13 sharper than the cell without interlayer. The higher peak currents can also indicate that the
14
15 polysulfide redox reaction kinetics of the Li-S cell can be promoted significantly by Fe3C-C/CNT
16
17 interlayer. Figure 2b exhibits typical charge-discharge curves of the batteries with Fe3C-C/CNT
18
19 interlayer and without interlayer at a low current density of 0.1 C. Each discharge curve has two
20
21 plateaus at approximately 2.3 and 2.0 V, which are consistent with the CV curves. The plateau
22
23 voltage gap (△E) determined from the profiles is related to electrode polarization.45-46 The plateau
24
25 voltage gap of the cell with Fe3C-C/CNT interlayer (△E = 0.1330 V) is much lower than the cell
26
27 without interlayer (△E = 0.2145 V), which is due to the high electrical conductivity. Figure 2c and
28
29 Figure S9 a, b show rate performance of the cells with Fe3C-C/CNT interlayer and without
30
31 interlayer, the charged and discharged curves at different current rates, ranging from 0.1 C to 2 C.
32
33 Similar to the cycling performance results, the capacity of the cell with Fe3C-C/CNT interlayer
34
35 outperforms that of the cell without interlayer across all tested current rates. As the current rate
36
37 increasing from 0.1 C to 2 C, the specific capacity of the cell with Fe3C-C/CNT interlayer decreases
38
39 from 1126.4 mA h g−1 to 846.6 mA h g−1, corresponding to a capacity retention of 63.6%. In
40
41 comparison, the capacity of the cell without interlayer is 842.3 mA h g−1 at 0.1 C rate initially, and
42
43 313.5 mA h g−1 at 2 C, only retaining 37.2%. When the current rate becomes to 0.1 C again, the
44
45 capacity of the cell with Fe3C-C/CNT interlayer is recovered by approximately 88.8%. Furthermore,
46
47
there is no significant change in the voltage plateaus and △E at different rates for the cell with
48
49
Fe3C-C/CNT interlayer. On the contrary, as the current rate increases, the voltage plateau of the cell
50
51
without interlayer is shortened, the discharge voltage is lowered, and the charging voltage is
52
53
increased, so that △E is significantly increased.
54
55
The cycling stability and coulombic efficiency (CE) of the cells with Fe3C-C/CNT interlayer
56
57
58
demonstrate the superior performance intuitively. After 100 cycles at a current rate of 0.2 C (Figure
59
60
2d), the cell with Fe3C-C/CNT interlayer exhibits a high discharge capacity of 870.2 mA h g−1 with

ACS Paragon Plus Environment

 ACS Applied Energy Materials Page 8 of 22

1
2
3
4
5 an excellent CE of 98.3%. The discharge capacity is about 52% of the theoretical capacity of sulfur,
6
7 while the discharge capacity of the battery without interlayer is 595.7 mA h g−1, only 35.5%. The
8
9 difference in battery performance is more pronounced at higher current rates of 0.5 C and 1 C
10
11 (Figure S9 c, d). As for the cells without interlayer, not only the initial capacity is lower, but also
12
13 the capacity fades very fast. On the contrary, the cells with Fe3C-C/CNT interlayer remain the
14
15 discharge capacity of 798.2 mA h g−1 at 0.5 C rate and 751.5 mA h g−1 at 1 C rate. It shows a
16
17 capacity retention of 76.8% and 78.6%, which means that the capacity fading rate is approximately
18
19 0.1% per cycle during the 200 cycles, while keeping a coulombic efficiency of 96.3% and 96.6% at
20
21 0.5 and 1 C rate, respectively. The result shows that the performance of the cells with Fe3C-C/CNT
22
23 interlayer is obviously superior to the cells without interlayer.
24
25 The addition of Fe3C-C/CNT interlayer bring about the running of the cells with higher sulfur
26
27 loadings from 3.00 to 7.06 mg cm-2 at 0.2 C (Figure 2e, f). When the sulfur loading rises from 3.00
28
29 to 3.90 mg cm-2, the change of specific capacity is inconspicuous, so the areal capacity increases
30
31 obviously, which is from 2.76 to 3.59 mA h cm-2. After that, as the sulfur loading rises, the specific
32
33 capacity decreases, but the areal capacity still increases. In addition, since the positive electrode
34
35 adopts the structure of Al foil coated with ordinary C/S slurry, more activation cycles are required
36
37 for the high-sulfur-loading electrodes. For the cell with a sulfur loading of 7.06 mg cm-2, the areal
38
39 capacity reaches to 4.32 mA h cm-2 after 40 cycles, at a low ratio of electrolyte to sulfur (E/S) of 5.7
40
41 μL mg-1. After 100 cycles, 3.81 mA h cm-2 is remained, corresponding to a capacity retention of
42
43 88%. It is calculated that when the sulfur loading is 5.75 mg cm-2, the gravimetric specific energy
44
45 can even reach up to 1560 W h kg-1 and still maintain 1190 W h kg-1 after 100 cycles, corresponding
46
47 to the volumetric specific energy of 1694 W h L-1 and 1554 W h L-1. In addition to the blocking and
48
49 adsorbing efficiency for LiPSs, the Li+ ions transport efficiency is another factor which determines
50
51 the electrochemical performance. According to the Randles-Sevcik equation, the diffusion
52
53 coefficients of Li+ (𝐷Li + ) can be calculated from the slope of the linear fitting curve between the
54
55
peak current and the square root of the scan rate (Figure 2g, h). 47-49 It is evident that the peak value
56
57
at different rates of each peak for the cell with Fe3C-C/CNT interlayer is more than three times
58
59
higher than the cell without interlayer (Figure S10). Accordingly, the diffusion coefficients of
60
8

ACS Paragon Plus Environment

Page 9 of 22 ACS Applied Energy Materials

1
2
3
4
5 lithium ions for Fe3C-C/CNT interlayer are much higher than no interlayer. As summarized in Table
6
7 S2, 𝐷Li + for the cell with Fe3C-C/CNT interlayer are 1.7873×10-8, 6.9464×10-8 and 1.4334×10-7
8
9 cm2 s-1, coincided to peak A, B and C, respectively, while for the cell without interlayer are only
10
11 8.6366×10-9, 1.7829×10-8 and 4.0630×10-8 cm2 s-1, indicating decrease in the concentration
12
13 polarization and further increase in electrochemical kinetics due to the addition of Fe3C-C/CNT
14
15 interlayer. Figure 2i shows that about 50 light-emitting diodes can be lighted by two cells with a
16
17 sulfur loading of approximately 3.0 mg cm-2, showing that Li-S cells with Fe3C-C/CNT interlayer
18
19 are promising for the future practical applications due to their scalable production and favorable
20
21 performance of the membranes.
22
23 Figure 2.
24
25
26 To further elucidate the reason for the good performance of Fe3C-C/CNT interlayer, we took
27
28 X-ray photo-electron spectroscopy (XPS) before and after cycling. The cycled Fe3C-C/CNT
29
30 membrane for XPS measurement is from the cell that is at totally discharged state after 200 cycles.
31
32 The deconvoluted C 1s spectrum shows distinguishable peaks assigned to C-C/C=C, C-O/C-N and
33
34 C-O/C=N at 284.2, 285.3, and 288.5 eV, respectively (Figure 3a).39, 50 The high-resolution N 1s
35
36 spectrum reveals three types of peaks at 398.06, 400.43 and 402.3 eV indexed to pyridinic N,
37
38 pyrrolic N, and quaternary N (Figure 3b). Quaternary N and pyridinic N are formed from nitrogen
39
40 atoms substituting the carbon atoms within the six-membered rings. Quaternary N, which is
41
42 connected with three carbon atoms, can offer extra free electrons to lead to a higher electrical
43
44 conductivity of the carbon material. Pyridinic N, which is not only contributing to the π-conjugated
45
46 system but also has a pair of p-electrons, can enhance the affinity for Li+. Pyrrolic N, which replaces
47
48 a carbon atom in a five-membered ring, is conducive to both conductivity and adsorption capacity,
49
50 but its contribution is less than the former two. 50-54 With comparison, cycled peaks have positive
51
52 shifts (Figure 3c), indicating that N-doped carbon materials can effectively adsorb LiPSs. The
53
54 high-resolution spectrum of Fe 2p is resolved into three peaks of Fe-C bindings at 709.75, 714.8 and
55
56 723.8 eV, corresponding to Fe 2p3/2, satellite Fe 2p3/2 and Fe 2p1/2 of Fe3C (Figure 3d).43 According
57
58 to Figure 3e, there are two new peaks appearing at 709.1 and 718.8 eV near the peaks of Fe 2p3/2
59
60 and Fe 2p1/2, which are assigned to Fe-S. Figure 3f shows eight peaks because every kind of S has
9

ACS Paragon Plus Environment

 ACS Applied Energy Materials Page 10 of 22

1
2
3
4
5 two different sites of S 2p3/2 and S 2p1/2.55 The S 2p doublet located at the highest binding energy is
6
7 corresponding to the sulfur in the product of the oxidation reaction of polysulfides in contact with air
8
9 during the test.39 The nearby S 2p doublet is assigned to highly oxidized SOx originating from the
10
11 lithium bis(trifluoromethanesulfonyl)imide electrolyte salt. The S 2p3/2 peaks of the bridging S
12
13 bonded to Fe (SB-Fe) is positioned at 163.96 eV and the terminal S bonded to Fe (ST-Fe) is
14
15 positioned at 162.52 eV. 46 Compared to the binding energy of 163.1 and 161.7 eV of SB and ST of
16
17 LiPS itself, when SB and ST are bonded to Fe, the electron density decreases, so there are positive
18
19 chemical shifts of 0.86 and 0.82 eV, respectively.56 The synergistic effect of Fe-S and Li-N enables
20
21 Fe3C-C/CNT interlayer to effectively adsorb LiPSs.
22
23 Figure 3
24
25
26 To substantiate the polysulfide adsorbing ability, Fe3C-C/CNT interlayer after cycling is also
27
28 studied through the SEM images (Figure 4a-c). Sulfur species is adsorbed in the hierarchical porous
29
30 networks, while the patterned channels still retain favorable structure, which can avoid blocking the
31
32 transport of Li+ ions. It can also be seen that though the sulfur loading increases, the patterned
33
34 channels are still well preserved and unobstructed. As shown in EDX analysis (Figure S11 a-c,
35
36 Figure S12), the sulfur species trapped in the hierarchical porous networks increase with the
37
38 increase of sulfur loading, in line with the SEM images. Due to good electrical conductivity of the
39
40 interlayer, Li+ ions can also react directly with the sulfur species adsorbed in the porous networks.
41
42 Furthermore, Figure S11 d-g shows SEM images and EDX mapping of the cycled anode of the cell
43
44 with and without Fe3C-C/CNT interlayer, respectively. The cycled Li foil of the cell with
45
46 Fe3C-C/CNT interlayer offers a smooth SEI layer, and there is almost no sulfur species on the
47
48 surface. In contrast, the SEI layer is rough for the cell without interlayer, with visible flake-like
49
50 precipitates, and the existence of S on the surface of cycled Li foil is obvious. These differences
51
52 suggest that the addition of Fe3C-C/CNT interlayer can favorably reduce shuttle effect and suppress
53
54 the polysulfide shuttle to induce formation of a highly stable SEI on the surface of Li anode.57
55
56 Nyquist plots are obtained from EIS to provide further insight into the electrochemical kinetics
57
58 (Figure 4d).47, 58-60 The semicircles in the high frequency region are corresponding to the interfacial
59
60 charge-transfer resistance, Rct. The cell without interlayer has a high Rct of 35.2 Ω. After the
10

ACS Paragon Plus Environment

Page 11 of 22 ACS Applied Energy Materials

1
2
3
4
5 insertion of Fe3C-C/CNT interlayer, the Rct decreases to 7.2 Ω because the interlayer provides
6
7 conductive pathways for charge transfer. In the low frequency region, the slopes of liner fit between
8
9 the negative square root of the frequency (ω-0.5) and Z1 are inversely to the values of 𝐷Li + , which
10
11 means that the lower slope corresponds to higher 𝐷Li + ( Figure 4e ). The slope of the cell with
12
13 Fe3C-C/CNT interlayer is 0.58, while of the cell without interlayer is 1.95, which is in agreement
14
15 with the calculation results of 𝐷Li + .
16
17
Figure 4.
18
19
20 Conclusions
21
22 In this study, a scalable Fe3C-C/CNT membrane interlayer is introduced via a convenient phase
23
24 inversion process for promoting Li-S battery performance. The self-supporting membrane interlayer
25
26 shows a high electrical conductivity and diffusion coefficients of Li+ ions, as well as low charge
27
28 transfer resistance, thanks to the coexistence of Fe3C nanoparticles, patterned channels, crosslinked
29
30 CNT frameworks and nitrogen-containing functional groups. Fe3C-C/CNT interlayer can selectively
31
32 sieve Li+ ions while blocking and adsorbing LiPSs, effectively suppressing the shuttle effect,
33
34 reducing the polarization of the electrode, and protecting the Li anode. Therefore, cycling stability,
35
36 specific capacity and areal capacity were enhanced obviously. By varying the ratio of the
37
38 components, the phase inversion nonsolvent system and the doping elements, it is believe that the
39
40 properties of the self-supporting CNT/C materials can be adjusted for cathode optimization and
41
42 anode protection of Li-S batteries, and for other energy storage devices.
43
44
45
46
Experiments
47
48
49 Preparation of membranes
50
51 Fe3C-C/CNT membranes were fabricated by a convenient phase-inversion process with subsequent
52
53 carbonization, the detailed experimental description have been provided in our previous work.39 The
54
55 contents of FeCl3·6H2O and polyacrylonitrile (PAN) in N, N-Dimethylformamide (DMF) were
56
57 constant with the previous work except for the addition 1 g of carbon nanotubes (CNT, Deke
58
59 Daojin, > 95%). Considering the enhancement of mechanical performance, asymmetric membranes
60
11

ACS Paragon Plus Environment

 ACS Applied Energy Materials Page 12 of 22

1
2
3
4
5 of FeCl3/PAN/CNT prepared by the phase-inversion method were preoxidized at 250℃ for 2 h in air
6
7 with a ramp rate of 2℃ min-1. Fe3C-C/CNT membranes were finally obtained via the carbonization
8
9 in Ar at 900℃ for 1 h (5℃ min−1). Fe3C-C and pure C membrane were fabricated by the same
10
11 procedure except the mixture solution were CNT-free or both CNT-free and FeCl3·6H2O free.
12
13 Characterizations
14
15 The structures and morphology were obtained from scanning electron microscopy (SEM, Nova
16
17 Nano SEM 450) and transmission electron microscope (TEM, Thermo Scientific TF30). The
18
19 elemental compositions were detected by an energy dispersive X-ray spectroscopy (EDX) analyzer
20
21 attached to Nova Nano SEM 450. Nitrogen sorption experiments (Quantachrome iSorb HP2) were
22
23 realized at 77.35 K. The samples were degassed at 300℃ for 5 h. The XRD, Raman spectra,
24
25 thermogravimetric analyzer and XPS analysis were similar to the previous study. For the polysulfide
26
27 adsorption study, C, Fe3C-C or Fe3C-C/CNT (50 mg, respectively) were added to the solution
28
29 consisting of Li2S6 (50 μL) and electrolyte (10 mL, 1M LiTFSI-DOL : DME (1:1) + 1% LiNO3), and
30
31 the samples were allowed to stand for 12 hours to observe the color change. The remaining solution
32
33 was also detected by Ultraviolet-visible absorption spectroscopy (UV-vis, Persee TU-1900).
34
35 Fe3C-C/CNT exhibited the resistance towards polysulfides by the U-type permeation device, with
36
37 the same component to the adsorption experiments and pure electrolyte in the left and right side,
38
39
respectively.
40
41
Electrochemical measurements
42
43
CR2025 coin-type cells assembled in an argon-filled glovebox according to our previous study
44
45
were used to test the electrochemical properties of Fe3C-C/CNT.39 For comparison, Li-S cells
46
47
without interlayer were also prepared with the same cathodes. The cycle performance of coin cells
48
49
was tested in galvanostatic mode at various current rates on a LAND CT2001A multichannel battery
50
51
test system within a voltage range of 1.7-2.8 V. The cells were pre-cycled for three cycles at a low
52
53
current rate of 0.1 C before the cycling performance test because both sulfur and interlayer need time
54
55
to get into connect with electrolyte in order to become electrochemically active. The abnormal
56
57
coulombic efficiency (>100%) in initial cycles are on account of the reduction of LiNO3 in the
58
59
electrolyte from NO3− to NO2−. The cyclic voltammetry (CV) measurements were conducted at
60
12

ACS Paragon Plus Environment

Page 13 of 22 ACS Applied Energy Materials

1
2
3
4
5 different scan rates (0.03, 0.05, 0.1, 0.15 and 0.2 mV s-1) within the above voltage window, from
6
7 which the diffusion coefficients of Li+ were calculated. The electrochemical impedance spectroscopy
8
9 (EIS) measurements were obtained over a frequency range of 100 kHz to 10 mHz with an AC
10
11 voltage amplitude of 10 mV at the open-circuit voltage of the cells. Both CV and EIS measurements
12
13 were carried out on Solartron 1470E electrochemical workstation.
14
15
16
17
18 Supporting Information
19
20 This material is available free of charge via the Internet at http://pubs.acs.org.
21
22 Structure parameters of the membranes (Tab. S1), Li+ diffusion coefficients (Tab. S2), Fabrication
23
24 process of the membrane (Fig. S1), SEM images (Fig. S2), SEM images of C membranes (Fig. S3),
25
26 SEM images of Fe3C-C membrane (Fig. S4), Adsorption-desorption curves (Fig. S5), XRD
27
28 spectrum (Fig. S6), TEM images (Fig. S7), TGA analysis (Fig. S8), Electrochemical properties (Fig.
29
30 S9), Linear fittings (Fig. S10), SEM and EDX mappings (Fig. S11), Membranes after cycling (Fig.
31
32 S12).
33
34 Conflict of Interest
35
36 The authors declare no conflict of interest.
37
38
39
40 Acknowledgments
41
42 X. L. and G. H. acknowledge the funding support from Natural Science Foundation of China
43
44 (21476044, 21676043, 21506028, 21706023, 21978035, 21706023), Fundamental Research Funds
45
46 for the Central Universities (DUT18JC14), Dalian Innovation Funding supporting (2019J12SN68),
47
48 Project funded by China Postdoctoral Science Foundation (2018M631167), and Changjiang Scholars
49
50 Program (T2012049).
51
52
53
54
55
56
57
58
59
60
13

ACS Paragon Plus Environment

 ACS Applied Energy Materials Page 14 of 22

1
2
3
4
5 References
6
7 (1) Li, T.; Bai, X.; Gulzar, U.; Bai, Y. J.; Capiglia, C.; Deng, W.; Zhou, X.; Liu, Z.; Feng, Z.; Proietti
8
Zaccaria, R. A Comprehensive Understanding of Lithium–Sulfur Battery Technology. Adv. Funct. Mater.
9
10 2019, 29, 1901730.
11 (2) Zhang, J.; Huang, H.; Bae, J.; Chung, S.-H.; Zhang, W.; Manthiram, A.; Yu, G. Nanostructured Host
12 Materials for Trapping Sulfur in Rechargeable Li-S Batteries: Structure Design and Interfacial Chemistry.
13
14 Small Methods 2018, 2, 1700279.
15 (3) Seh, Z. W.; Sun, Y.; Zhang, Q.; Cui, Y. Designing High-Energy Lithium–Sulfur Batteries. Chem. Soc.
16 Rev. 2016, 45, 5605-5634.
17
18 (4) Li, Z.; Xiao, Z.; Wang, S.; Cheng, Z.; Li, P.; Wang, R. Engineered Interfusion of Hollow Nitrogen‐
19 Doped Carbon Nanospheres for Improving Electrochemical Behavior and Energy Density of Lithium–
20 Sulfur Batteries. Adv. Funct. Mater. 2019, 29, 1902322.
21
(5) Cheng, Z.; Pan, H.; Zhong, H.; Xiao, Z.; Li, X.; Wang, R. Porous Organic Polymers for Polysulfide
22
23 Trapping in Lithium–Sulfur Batteries. Adv. Funct. Mater. 2018, 28, 1707597.
24 (6) Choi, J.-W.; Kim, J.-K.; Cheruvally, G.; Ahn, J.-H.; Ahn, H.-J.; Kim, K.-W. Rechargeable
25 Lithium/Sulfur Battery with Suitable Mixed Liquid Electrolytes. Electrochim. Acta 2007, 52, 2075-2082.
26
27 (7) Manthiram, A.; Fu, Y.; Su, Y.-S. Challenges and Prospects of Lithium–Sulfur Batteries. Acc. Chem.
28 Res. 2012, 46, 1125-1134.
29 (8) Peng, H. J.; Huang, J. Q.; Cheng, X. B.; Zhang, Q. Review on High‐Loading and High‐Energy
30
31 Lithium–Sulfur Batteries. Adv. Energy Mater. 2017, 7, 1700260.
32 (9) Manthiram, A.; Fu, Y.; Chung, S.-H.; Zu, C.; Su, Y.-S. Rechargeable Lithium–Sulfur Batteries. Chem.
33 Rev. 2014, 114, 11751-11787.
34
(10) Shi, H.; Lv, W.; Zhang, C.; Wang, D. W.; Ling, G.; He, Y.; Kang, F.; Yang, Q. H. Functional
35
36 Carbons Remedy the Shuttling of Polysulfides in Lithium–Sulfur Batteries: Confining, Trapping,
37 Blocking, and Breaking Up. Adv. Funct. Mater. 2018, 28, 1800508.
38 (11) Evers, S.; Nazar, L. F. New Approaches for High Energy Density Lithium–Sulfur Battery Cathodes.
39
40 Acc. Chem. Res. 2012, 46, 1135-1143.
41 (12) Yang, Y.; Yu, G.; Cha, J. J.; Wu, H.; Vosgueritchian, M.; Yao, Y.; Bao, Z.; Cui, Y. Improving the
42 Performance of Lithium–Sulfur Batteries by Conductive Polymer Coating. ACS Nano 2011, 5,
43
44 9187-9193.
45 (13) Liu, Y.; Li, X.; Shen, W.; Dai, Y.; Kou, W.; Zheng, W.; Jiang, X.; He, G. Multishelled Transition
46 Metal-Based Microspheres: Synthesis and Applications for Batteries and Supercapacitors. Small 2019,
47
15, 1804737.
48
49 (14) Zhang, J.; Shi, Y.; Ding, Y.; Peng, L.; Zhang, W.; Yu, G. A Conductive Molecular Framework
50 Derived Li2s/N,P-Codoped Carbon Cathode for Advanced Lithium-Sulfur Batteries. Adv. Energy Mater.
51 2017, 7, 1602876.
52
53 (15) Liu, B.; Bo, R.; Taheri, M.; Di Bernardo, I.; Motta, N.; Chen, H.; Tsuzuki, T.; Yu, G.; Tricoli, A.
54 Metal–Organic Frameworks/Conducting Polymer Hydrogel Integrated Three-Dimensional Free-Standing
55 Monoliths as Ultrahigh Loading Li–S Battery Electrodes. Nano Lett. 2019, 19, 4391-4399.
56
57 (16) Jeong, Y. C.; Kim, J. H.; Nam, S.; Park, C. R.; Yang, S. J. Rational Design of Nanostructured
58 Functional Interlayer/Separator for Advanced Li–S Batteries. Adv. Funct. Mater. 2018, 28, 1707411.
59 (17) Su, Y.-S.; Manthiram, A. Lithium–Sulphur Batteries with a Microporous Carbon Paper as a
60
14

ACS Paragon Plus Environment

Page 15 of 22 ACS Applied Energy Materials

1
2
3
4
5 Bifunctional Interlayer. Nat. Commun. 2012, 3, 1166.
6
(18) Zhang, K.; Li, Q.; Zhang, L.; Fang, J.; Li, J.; Qin, F.; Zhang, Z.; Lai, Y. From Filter Paper to Carbon
7
8 Paper and toward Li–S Battery Interlayer. Mater. Lett. 2014, 121, 198-201.
9 (19) Zu, C.; Su, Y.-S.; Fu, Y.; Manthiram, A. Improved Lithium–Sulfur Cells with a Treated Carbon
10 Paper Interlayer. Phys. Chem. Chem. Phys. 2013, 15, 2291-2297.
11
12 (20) Wutthiprom, J.; Phattharasupakun, N.; Sawangphruk, M. Designing an Interlayer of Reduced
13 Graphene Oxide Aerogel and Nitrogen-Rich Graphitic Carbon Nitride by a Layer-by-Layer Coating for
14 High-Performance Lithium Sulfur Batteries. Carbon 2018, 139, 945-953.
15
(21) Liu, M.; Yang, Z.; Sun, H.; Lai, C.; Zhao, X.; Peng, H.; Liu, T. A Hybrid Carbon Aerogel with Both
16
17 Aligned and Interconnected Pores as Interlayer for High-Performance Lithium–Sulfur Batteries. Nano
18 Research 2016, 9, 3735-3746.
19
(22) Shi, H.; Zhao, X.; Wu, Z.-S.; Dong, Y.; Lu, P.; Chen, J.; Ren, W.; Cheng, H.-M.; Bao, X.
20
21 Free-Standing Integrated Cathode Derived from 3d Graphene/Carbon Nanotube Aerogels Serving as
22 Binder-Free Sulfur Host and Interlayer for Ultrahigh Volumetric-Energy-Density Lithiumsulfur Batteries.
23 Nano Energy 2019, 60, 743-751.
24
25 (23) Su, Y.-S.; Manthiram, A. A New Approach to Improve Cycle Performance of Rechargeable
26 Lithium–Sulfur Batteries by Inserting a Free-Standing Mwcnt Interlayer. Chem. Commun. 2012, 48,
27 8817-8819.
28
(24) Kim, H. M.; Hwang, J.-Y.; Manthiram, A.; Sun, Y.-K. High-Performance Lithium–Sulfur Batteries
29
30 with a Self-Assembled Multiwall Carbon Nanotube Interlayer and a Robust Electrode–Electrolyte
31 Interface. ACS Appl. Mater. Interfaces 2016, 8, 983-987.
32
(25) Kim, J. H.; Seo, J.; Choi, J.; Shin, D.; Carter, M.; Jeon, Y.; Wang, C.; Hu, L.; Paik, U. Synergistic
33
34 Ultrathin Functional Polymer-Coated Carbon Nanotube Interlayer for High Performance Lithium–Sulfur
35 Batteries. ACS Appl. Mater. Interfaces 2016, 8, 20092-20099.
36 (26) Vizintin, A.; Lozinšek, M.; Chellappan, R. K.; Foix, D.; Krajnc, A.; Mali, G.; Drazic, G.; Genorio,
37
38 B.; Dedryvère, R. m.; Dominko, R. Fluorinated Reduced Graphene Oxide as an Interlayer in Li–S
39 Batteries. Chem. Mater. 2015, 27, 7070-7081.
40 (27) Tan, L.; Li, X.; Wang, Z.; Guo, H.; Wang, J. Lightweight Reduced Graphene Oxide@ Mos2
41
Interlayer as Polysulfide Barrier for High-Performance Lithium–Sulfur Batteries. ACS Appl. Mater.
42
43 Interfaces 2018, 10, 3707-3713.
44 (28) Wang, X.; Wang, Z.; Chen, L. Reduced Graphene Oxide Film as a Shuttle-Inhibiting Interlayer in a
45
Lithium–Sulfur Battery. J. Power Sources 2013, 242, 65-69.
46
47 (29) Zhang, Z.; Wang, G.; Lai, Y.; Li, J. A Freestanding Hollow Carbon Nanofiber/Reduced Graphene
48 Oxide Interlayer for High-Performance Lithium–Sulfur Batteries. J. Alloys Compd. 2016, 663, 501-506.
49 (30) Huang, J.-Q.; Xu, Z.-L.; Abouali, S.; Garakani, M. A.; Kim, J.-K. Porous Graphene Oxide/Carbon
50
51 Nanotube Hybrid Films as Interlayer for Lithium-Sulfur Batteries. Carbon 2016, 99, 624-632.
52 (31) Peng, H. J.; Huang, J. Q.; Zhao, M. Q.; Zhang, Q.; Cheng, X. B.; Liu, X. Y.; Qian, W. Z.; Wei, F.
53 Nanoarchitectured Graphene/Cnt@ Porous Carbon with Extraordinary Electrical Conductivity and
54
55 Interconnected Micro/Mesopores for Lithium‐Sulfur Batteries. Adv. Funct. Mater. 2014, 24, 2772-2781.
56 (32) Zheng, C.; Niu, S.; Lv, W.; Zhou, G.; Li, J.; Fan, S.; Deng, Y.; Pan, Z.; Li, B.; Kang, F.; Yang, Q.-H.
57 Propelling Polysulfides Transformation for High-Rate and Long-Life Lithium–Sulfur Batteries. Nano
58
Energy 2017, 33, 306-312.
59
60 (33) Zhou, T.; Lv, W.; Li, J.; Zhou, G.; Zhao, Y.; Fan, S.; Liu, B.; Li, B.; Kang, F.; Yang, Q.-H.
15

ACS Paragon Plus Environment

 ACS Applied Energy Materials Page 16 of 22

1
2
3
4
5 Twinborn Tio 2–Tin Heterostructures Enabling Smooth Trapping–Diffusion–Conversion of Polysulfides
6
Towards Ultralong Life Lithium–Sulfur Batteries. Energy Environ. Sci. 2017, 10, 1694-1703.
7
8 (34) Huang, J.-Q.; Zhang, B.; Xu, Z.-L.; Abouali, S.; Akbari Garakani, M.; Huang, J.; Kim, J.-K. Novel
9 Interlayer Made from Fe3c/Carbon Nanofiber Webs for High Performance Lithium–Sulfur Batteries. J.
10 Power Sources 2015, 285, 43-50.
11
12 (35) Liu, X.-M.; dong Huang, Z.; woon Oh, S.; Zhang, B.; Ma, P.-C.; Yuen, M. M.; Kim, J.-K. Carbon
13 Nanotube -Based Composites as Electrode Material for Rechargeable Li-Ion Batteries: A Review.
14 Compos. Sci. Technol. 2012, 72, 121-144.
15
(36) Yang, X.; Chen, Y.; Wang, M.; Zhang, H.; Li, X.; Zhang, H. Phase Inversion: A Universal Method
16
17 to Create High-Performance Porous Electrodes for Nanoparticle-Based Energy Storage Devices. Adv.
18 Funct. Mater. 2016, 26, 8427-8434.
19
(37) Shen, W.; Kou, W.; Liu, Y.; Dai, Y.; Zheng, W.; He, G.; Wang, S.; Zhang, Y.; Wu, X.; Fan, S.; Li,
20
21 X. Fe3c-Doped Asymmetric Porous Carbon Membrane Binder-Free Integrated Materials as High
22 Performance Anodes of Lithium-Ion Batteries. Chem. Eng. J. 2019, 368, 310-320.
23 (38) Kou, W.; Chen, G.; Liu, Y.; Guan, W.; Li, X.; Zhang, N.; He, G. Patterned Macroporous Fe3C/C
24
25 Membrane-Induced High Ionic Conductivity for Integrated Li–Sulfur Battery Cathodes. J. Mater. Chem.
26 A 2019, 7, 20614-20623.
27 (39) Kou, W.; Li, X.; Liu, Y.; Zhang, X.; Yang, S.; Jiang, X.; He, G.; Dai, Y.; Zheng, W.; Yu, G.
28
Triple-Layered Carbon-SiO2 Composite Membrane for High Energy Density and Long Cycling Li-S
29
30 Batteries. ACS Nano 2019, 13, 5900-5909.
31 (40) Li, X.; Zhang, Y.; Wang, S.; Liu, Y.; Ding, Y.; He, G.; Zhang, N.; Yu, G. Hierarchically Porous
32
C/Fe3C Membranes with Fast Ion-Transporting Channels and Polysulfide-Trapping Networks for
33
34 High-Areal-Capacity Li-S Batteries. Nano Lett 2020, 20, 701-708.
35 (41) Yang, X.; Chen, Y.; Wang, M.; Zhang, H.; Li, X.; Zhang, H. Phase Inversion: A Universal Method
36 to Create High‐Performance Porous Electrodes for Nanoparticle‐Based Energy Storage Devices. Adv.
37
38 Funct. Mater. 2016, 26, 8427-8434.
39 (42) Bateer, B.; Wang, L.; Zhao, L.; Yu, P.; Tian, C.; Pan, K.; Fu, H. A Novel Fe 3 C/Graphitic Carbon
40 Composite with Electromagnetic Wave Absorption Properties in the C-Band. RSC Adv. 2015, 5,
41
60135-60140.
42
43 (43) Zhou, J.; Liu, X.; Zhou, J.; Zhao, H.; Lin, N.; Zhu, L.; Zhu, Y.; Wang, G.; Qian, Y. Fully Integrated
44 Hierarchical Double-Shelled Co 9 S 8@ Cnt Nanostructures with Unprecedented Performance for Li–S
45
Batteries. Nanoscale Horiz. 2019, 4, 182-189.
46
47 (44) Wang, L.; Yang, Z.; Nie, H.; Gu, C.; Hua, W.; Xu, X.; Chen, X. a.; Chen, Y.; Huang, S. A
48 Lightweight Multifunctional Interlayer of Sulfur–Nitrogen Dual-Doped Graphene for Ultrafast,
49 Long-Life Lithium–Sulfur Batteries. J. Mater. Chem. A 2016, 4, 15343-15352.
50
51 (45) Park, S. K.; Lee, J. K.; Kang, Y. C. Yolk–Shell Structured Assembly of Bamboo‐Like Nitrogen‐
52 Doped Carbon Nanotubes Embedded with Co Nanocrystals and Their Application as Cathode Material
53 for Li–S Batteries. Adv. Funct. Mater. 2018, 28, 1705264.
54
(46) Balach, J.; Jaumann, T.; Klose, M.; Oswald, S.; Eckert, J.; Giebeler, L. Functional Mesoporous
55
56 Carbon‐Coated Separator for Long‐Life, High‐Energy Lithium–Sulfur Batteries. Adv. Funct. Mater.
57 2015, 25, 5285-5291.
58
(47) Zhu, X.; Ouyang, Y.; Chen, J.; Zhu, X.; Luo, X.; Lai, F.; Zhang, H.; Miao, Y.-E.; Liu, T. In Situ
59
60 Extracted Poly (Acrylic Acid) Contributing to Electrospun Nanofiber Separators with Precisely Tuned
16

ACS Paragon Plus Environment

Page 17 of 22 ACS Applied Energy Materials

1
2
3
4
5 Pore Structures for Ultra-Stable Lithium–Sulfur Batteries. J. Mater. Chem. A 2019, 7, 3253-3263.
6
(48) Wu, K.; Hu, Y.; Shen, Z.; Chen, R.; He, X.; Cheng, Z.; Pan, P. Highly Efficient and Green
7
8 Fabrication of a Modified C Nanofiber Interlayer for High-Performance Li–S Batteries. J. Mater. Chem.
9 A 2018, 6, 2693-2699.
10 (49) Zhuang, T. Z.; Huang, J. Q.; Peng, H. J.; He, L. Y.; Cheng, X. B.; Chen, C. M.; Zhang, Q. Rational
11
12 Integration of Polypropylene/Graphene Oxide/Nafion as Ternary ‐ Layered Separator to Retard the
13 Shuttle of Polysulfides for Lithium–Sulfur Batteries. Small 2016, 12, 381-389.
14 (50) Reddy, A. L. M.; Srivastava, A.; Gowda, S. R.; Gullapalli, H.; Dubey, M.; Ajayan, P. M. Synthesis
15
of Nitrogen-Doped Graphene Films for Lithium Battery Application. ACS Nano 2010, 4, 6337-6342.
16
17 (51) Huang, J.-Q.; Zhang, B.; Xu, Z.-L.; Abouali, S.; Garakani, M. A.; Huang, J.; Kim, J.-K. Novel
18 Interlayer Made from Fe3C/Carbon Nanofiber Webs for High Performance Lithium–Sulfur Batteries. J.
19
Power Sources 2015, 285, 43-50.
20
21 (52) Sheng, Z.-H.; Shao, L.; Chen, J.-J.; Bao, W.-J.; Wang, F.-B.; Xia, X.-H. Catalyst-Free Synthesis of
22 Nitrogen-Doped Graphene Via Thermal Annealing Graphite Oxide with Melamine and Its Excellent
23 Electrocatalysis. ACS Nano 2011, 5, 4350-4358.
24
25 (53) Song, J.; Gordin, M. L.; Xu, T.; Chen, S.; Yu, Z.; Sohn, H.; Lu, J.; Ren, Y.; Duan, Y.; Wang, D.
26 Strong Lithium Polysulfide Chemisorption on Electroactive Sites of Nitrogen ‐ Doped Carbon
27 Composites for High‐Performance Lithium–Sulfur Battery Cathodes. Angew. Chem. Int. Ed. 2015, 54,
28
4325-4329.
29
30 (54) Peng, H. J.; Hou, T. Z.; Zhang, Q.; Huang, J. Q.; Cheng, X. B.; Guo, M. Q.; Yuan, Z.; He, L. Y.;
31 Wei, F. Strongly Coupled Interfaces between a Heterogeneous Carbon Host and a Sulfur ‐ Containing
32
Guest for Highly Stable Lithium‐Sulfur Batteries: Mechanistic Insight into Capacity Degradation. Adv.
33
34 Mater. Interfaces 2014, 1, 1400227.
35 (55) Pang, Q.; Tang, J.; Huang, H.; Liang, X.; Hart, C.; Tam, K. C.; Nazar, L. F. A Nitrogen and Sulfur
36 Dual‐Doped Carbon Derived from Polyrhodanine@ Cellulose for Advanced Lithium–Sulfur Batteries.
37
38 Adv.Mater. 2015, 27, 6021-6028.
39 (56) Liang, X.; Hart, C.; Pang, Q.; Garsuch, A.; Weiss, T.; Nazar, L. F. A Highly Efficient Polysulfide
40 Mediator for Lithium–Sulfur Batteries. Nat. Commun. 2015, 6, 5682.
41
(57) Wu, F.; Lv, H.; Chen, S.; Lorger, S.; Srot, V.; Oschatz, M.; van Aken, P. A.; Wu, X.; Maier, J.; Yu,
42
43 Y. Natural Vermiculite Enables High‐Performance in Lithium–Sulfur Batteries Via Electrical Double
44 Layer Effects. Adv. Funct. Mater. 2019, 29, 1902820.
45
(58) Choi, Y.-J.; Chung, Y.-D.; Baek, C.-Y.; Kim, K.-W.; Ahn, H.-J.; Ahn, J.-H. Effects of Carbon
46
47 Coating on the Electrochemical Properties of Sulfur Cathode for Lithium/Sulfur Cell. J. Power Sources
48 2008, 184, 548-552.
49 (59) Song, S.; Shi, L.; Lu, S.; Pang, Y.; Wang, Y.; Zhu, M.; Ding, D.; Ding, S. A New Polysulfide
50
51 Blocker-Poly (Acrylic Acid) Modified Separator for Improved Performance of Lithium-Sulfur Battery. J.
52 Membr. Sci. 2018, 563, 277-283.
53 (60) Gao, F.; Tang, Z. Kinetic Behavior of Lifepo4/C Cathode Material for Lithium-Ion Batteries.
54
Electrochim. Acta 2008, 53, 5071-5075.
55
56
57
58
59
60
17

ACS Paragon Plus Environment

 ACS Applied Energy Materials Page 18 of 22

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43 Figure 1. (a) Fe3C-C/CNT membrane interlayer with hierarchical porous networks and patterned
44 channels for high-efficient polysulfide trapping and facilitated Li+ diffusion. (b, c) Photos of
45
Fe3C-C/CNT membrane and the corresponding circular membrane plate for Li-S battery interlayer.
46
47 SEM images of Fe3C-C/CNT membrane with (d) patterned channels and (e) hierarchical porous
48 networks. (f) SEM image of the hierarchical porous networks with CNT cores and Fe3C-doped
49 carbon coating as the crosslinked shell. (g) Raman spectra of different membranes. (h) Li2S6 solution
50
51 adsorption with different membrane fragments for 24 h. (i) U-type permeation device with
52 Fe3C-C/CNT membrane as an interlayer. (j) UV-vis spectrum of the Li2S6 solution before and after
53 membrane adsorption.
54
55
56
57
58
59
60
18

ACS Paragon Plus Environment

Page 19 of 22 ACS Applied Energy Materials

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30 Figure 2. (a) CV curves of Li-S batteries with and without Fe3C-C/CNT interlayer at a scan rate of
31
0.1 mV s-1. (b) Galvanostatic charge-discharge profiles of cells with and without Fe3C-C/CNT
32
33 interlayer at 0.1 C. (c) Rate performance of cells at different current densities from 0.1 to 2 C. (d)
34 Cycling stability of cells at 0.2 C for 100 cycles. (e)Specific capacities and (f) areal capacities of the
35 cells with Fe3C-C/CNT interlayer and different S loadings at 0.2 C. CV curves of cells (g) with
36
37 Fe3C-C/CNT interlayer and (h) without interlayer at different scan rates. (i) Photo of about 50 red
38 light-emitting diodes lighted by two cells with a sulfur loading of 3.0 mg cm-2.
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
19

ACS Paragon Plus Environment

 ACS Applied Energy Materials Page 20 of 22

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25 Figure 3. High resolution XPS spectra of (a) C 1s, (b) N 1s before cycling, (c) N 1s after cycling, (d)
26 Fe 2p before cycling, (e) Fe 2p after cycling, and (f) S 2p after cycling of Fe3C-C/CNT membrane
27
28 interlayer.
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
20

ACS Paragon Plus Environment

Page 21 of 22 ACS Applied Energy Materials

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40 Figure 4. SEM images of Fe3C-C/CNT interlayer after 100 cycles at 0.2 C with different sulfur
41
42 loading in the electrodes: (a1-a3) 1.5 mg cm-2, (b1-b3) 3.0 mg cm-2, (c1-c3) 7.0 mg cm-2. (d) EIS
43 spectra of cells with and without Fe3C-C/CNT interlayer and (e) relationships between Z1 and ω-0.5
44 in a low-frequency region.
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
21

ACS Paragon Plus Environment

 ACS Applied Energy Materials Page 22 of 22

1
2
3
4
5
6
7 Graphical abstract
8
9
10 We report a scalable yet flexible Fe3C-C/CNT membrane interlayer for inhibiting shuttle effect of LiPSs
11 and facilitating Li+ ion transportation simultaneously. Li-S batteries with high S loading of 7.06 mg cm-2
12 and the self-supporting membrane as an interlayer can delivere a high areal-capacity capacity of 4.32mAh
13
14 cm-2 at a low E/S ratio of 5.7 μl mg-1. The multifunctional membrane interlayer with high gravimetric
15 specific energy (1560 W h kg-1) and volumetric specific energy of (1694 W h L-1) under lean electrolyte
16 condition reveal its great potential in practical application of Li-S batteries.
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
22

ACS Paragon Plus Environment