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Significantly Improved Long-cycle Stability in High-rate Li-S Batteries Enabled
by Coaxial Graphene Wrapping over Sulfur Coated Carbon Nanofibers
Songtao Lu, Yingwen Cheng, Xiaohong Wu, and Jie Liu
Nano Lett., Just Accepted Manuscript • DOI: 10.1021/nl400543y • Publication Date (Web): 20 May 2013
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4 Significantly Improved Long-cycle Stability in High-rate Li-S
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Batteries Enabled by Coaxial Graphene Wrapping over Sulfur
7 Coated Carbon Nanofibers
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10 Songtao Lu,1,2 Yingwen Cheng,1 Xiaohong Wu1,2 and Jie Liu1,*
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1 Department of Chemistry, Duke University, Durham NC 27708 United
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16 2. Department of Chemistry, Harbin Institute of Technology, Harbin,
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18 P.R.China 150001
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20 Abstract:
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22 Long-term instability of Li-S batteries is one of their major disadvantages
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compare to other secondary batteries. The reasons for the instability include dissolution
25 of polysulfide intermediates and mechanical instability of the electrode film caused by
26 volume changes during charging/discharging cycles. In this paper, we report a novel
27 graphene-sulfur-carbon nanofibers (G-S-CNFs) multilayer and coaxial nanocomposite for
28 the cathode of Li-S batteries with increased capacity and significantly improved long-
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cycle stability. Electrodes made with such nanocomposites were able to deliver a
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31 reversible capacity of 694 mAh g-1 at 0.1C and 313 mAh g-1 at 2C, which are both
32 substantially higher than electrodes assembled without graphene wrapping. More
33 importantly, the long-cycle stability was significantly improved by graphene wrapping.
34 The cathode made with G-S-CNFs with a initial capacity of 745 mAh g-1 was able to
35 maintain ~273 mAh g-1 even after 1500 charge-discharge cycles at a high rate of 1C,
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37 representing an extremely low decay rate (0.043% per cycle after 1500 cycles). In
38 contrast, the capacity of an electrode assembled without graphene wrapping decayed
39 dramatically with a 10 times high rate (~0.40% per cycle after 200 cycles). These results
40 demonstrate that the coaxial nanocomposites are of great potential as the cathode for
41 high-rate rechargeable Li–S batteries. Such improved rate capability and cycle stability
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could be attributed to the unique coaxial architecture of the nanocomposite, in which the
44 contributions from graphene and CNFs enable electrodes with improved electrical
45 conductivity, better ability to trap soluble polysulfides intermediate and accommodate
46 volume expansion/shrinkage of sulfur during repeated charge/discharge cycles.
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The increasing energy demands and environmental crisis have stimulated intense
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5 research on the design of advanced energy storage systems for electrical vehicles (EVs)
6 and renewable energy productions.1-5 Among the current energy storage options,
7 rechargeable lithium-based batteries are widely used due to their high energy and power
8 densities as well as low maintenance cost.5 However, the performance of these batteries
9 is limited by the low capacity of conventional cathode materials (for example, ~150 mAh
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g-1 for layered oxides and ~170 mAh g-1 for LiFePO4).6,7 Therefore, considerable research
12 interests have focused on the exploration of novel cathode materials.8 Among these
13 materials, elemental sulfur has high theoretical specific capacity of 1672 mAh g-1 against
14 lithium and specific energy of 2600 Wh kg-1.7,9,10 As a cathode, sulfur could host two
15 lithium ions non-topotactically with the redox reaction of S8 + 16Li = 8Li2S, which lies ~
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2.2 V with respect to Li+/Li.11-14 Other advantages of sulfur include its naturally
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18 abundance, low cost (about $150 per ton) and low environmental impact. Hence, sulfur
19 based lithium batteries are of particular promises for next generation energy storage
20 systems. However, despite of these promises, several challenges exist for Li-S batteries
21 that hindered their commercial applications. Such challenges include the inherent low
22 electrical conductivity of sulfur (5×10-30 S cm-1), which results in limited active material
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utilization efficiency and rate capability; shuttling of high-order polysulfides between
25 cathode and anode and high solubility of polysulfide intermediates in the electrolyte, both
26 of which lead to limited cycle stability. Additionally, sulfur experiences severe
27 volumetric expansion/shrinkage during charge and discharge (~80%), which gradually
28 decreases the mechanical integrity and hence stability of the electrode over
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cycles.6,11,12,15-25
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31 Over the past decades, extensive research efforts have been devoted to develop
32 methods to improve the capacity and cycle stability of sulfur cathodes by introducing
33 mechanisms to improve the conductivity and prevent the polysulfide dissolution and
34 shuttling.6,17,23,24,26 Of these, one promising approach is to utilize sulfur composite
35 material with either carbon materials (such as graphene15,20,23,27,28, porous carbon10,11,22,
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37 CNFs6,19,26,29) or conductive polymers (such as PEDOT:PSS25). As a result, high specific
38 capacities exceeding 1000 mAh g-1 have been achieved under low discharge rates (~0.1C)
39 by several research groups.16,19,20,27,30-32 However, the long-cycle stability remains to be a
40 major problem, especially under high rates.21 In fact, most of published studies only
41 reported results from less than 200 cycles and most of them exhibited relatively high
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decay rates (>0.15% per cycle) .15,21,22,27,33,34 Besides, 200 cycles is far below the
44 technical target (1,000 cycles) of rechargeable batteries for EVs, which was set by the
45 United States Department of Energy in 2011.35 Recently, great work for long cycle test
46 was made by Cui et al. They demonstrated that sulphur-TiO2 yolk-shell nanoarchitesture
47 with internal void space can be cycled for 1000 cycles with a lower decay rate of 0.033%
48 per cycle.36 However, their sulphur mass loading is low (0.4-0.6 mg cm-2) and electrode
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50 fabrication process is complex. Hence, developing sulfur cathodes with improved long
51 cycle stability and high capacity is highly desired and critical for practical applications.
52 Here we report an approach to assemble graphene-sulfur-carbon nanofiber (G-S-
53 CNF) coaxial structured nanocomposite with sulfur sandwiched between graphene and
54 CNFs that can be used as cathode for Li-S batteries with significantly improved cycle
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stability and capacity. In our approach (Figure 1), sulfur was first coated uniformly on the
57 surface of CNF and then graphene was used to wrap around the whole structure. In this
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well designed structure, both CNFs and graphene serve as good conducting fillers to
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5 improve the overall conductance of the film. More importantly, graphene overcoated on S
6 limited the dissolution of polysulfide intermediate while CNF provided much needed
7 mechanical stability of the film. Working together, electrodes made with such composites,
8 without the use of any binder, was able to deliver a reversible specific capacity of 694
9 mAh g-1 at 0.1C and still maintained 313 mAh g-1 at 2C, demonstrating high-rate
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capability due to the highly conductive network formed by CNF and graphene.
12 Meanwhile, significantly improved long cycle stability at high charging rate was
13 achieved. For a G-S-CNFs electrode with initial capacitance of 745 mAh g-1, after 1500
14 charge-discharge cycles at a high rate of 1C, the electrode was able to deliver a specific
15 capacitance of ~273 mAh g-1, representing an extremely low decay rate (0.043% per
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cycle after 1500 cycles). Such improved rate capability and cycle stability could be
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18 attribute to the unique architecture of the nanocomposite, in which the synergistic
19 contribution from graphene and CNFs could enable electrodes with improved electrical
20 conductivity, better ability to trap soluble polysulfides intermediate and accommodate
21 volume expansion/shrinkage of sulfur during repeated charge/discharge cycles.
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43 Figure 1: Schematic illustration of the assembled G-S-CNFs multilayered coaxial
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nanocomposites for improving cathode performance. Note that in strong contrast to the S-
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46 CNFs composites that have sulfur in direct contact with the electrolyte and thus the
47 polysulfides could freely diffuse into the electrolyte, graphene wrapping could effectively
48 immobilize the polysulfides by confining them inside the sandwiched structure through
49 the entire charge-discharge process.
50 The G-S-CNFs multilayered coaxial nanocomposites were synthesized by a two-
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step approach. Prior the synthesis, CNFs were functionalized via refluxing in HNO3 to
53 introduce hydrophilic functionalities (hydroxyl and carboxyl radicals) on their external
54 surface. The functionalization is critical to ensure intimate interaction between sulfur and
55 CNFs. Uniform coatings of sulfur on CNF were achieved by the disproportionation
56 reaction of Na2S2O3 with HCl. The amount of sulfur coated onto CNFs could be readily
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tuned by controlling the concentration of precursors. Figure 2a and 2b compare the
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transmission electron microscopy (TEM) images of the CNFs before and after 50 wt% of
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5 sulfur coating. As can be seen, continuous and uniform tubular layer of sulfur was
6 successfully coated on CNFs after the reaction, forming a core-shell structure. On the
7 basis of the TEM examination, the diameter of CNFs increased from the initial 93.1 ±
8 13.5 nm to 116.5 ± 19.4 nm after sulfur coating, indicating the average thickness of the
9 sulfur shell is ~23 nm. A scanning electron microscopy (SEM) image acquired from the
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composite (Figure 1c) further revealed that the sulfur coating is uniform and no obvious
12 isolated sulfur particle was observed. The energy-dispersive X-ray spectroscopy (EDS) of
13 the composite (Figure 1c, inserted) clearly identified the existence of sulfur. The actual
14 percentages of sulfur in the composites were determined by thermo gravimetric analysis
15 (TGA) conducted under nitrogen environment (Figure 1d), which agrees well with the
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EDS quantification result and is similar as determined from the precursors.
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18 As a second step, graphene was wrapped around the S-CNFs composites by taking the
19 advantage of strong electrostatic attraction using a liquid process. Graphene used in this
20 work was synthesized via hydrazine reducing of graphene oxide. Briefly, appropriate
21 amount of graphene and S-CNFs were firstly dispersed together in nanopure water, which
22 was pre-adjusted with ammonium hydroxide to pH 10. Under this condition, both
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graphene sheets and sulfur coated on CNFs were negatively charged. The wrapping of
25 graphene to S-CNFs was realized by slowly decreasing the pH of the solution with
26 diluted HCl until pH~2. During this process the Zeta-potential of sulfur will slowly
27 become positive while the graphene sheets remain negative, and hence the positive-
28 negative charge attraction could direct the wrapping of graphene on the surface of S-
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CNFs composite.37,38 (Zeta potential of RGO and S-CNFs as a function of pH are shown
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31 in Figure S1 in the Supporting Information) A typical TEM image of the G-S-CNFs
32 coaxial nanocomposite shown in Figure 1e clearly revealed successful wrapping of
33 graphene on the external surface of S-CNFs. Further characterization with SEM (Figure
34 1f) also revealed that most of the S-CNFs were covered with graphene, indicating a very
35 efficient wrapping process.
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53 Figure 2: TEM images of (a) pristine CNFs and (b) CNFs with sulfur coating; (C) SEM
54 image of S-CNFs coaxial nanocomposite, inserted image is the EDS result that highlights
55 successful coating of sulfur; (d) TGA results of the S/CNFs nanocomposite with and
56 without graphene wrapping; (e) TEM and (f) SEM images of the G-S-CNFs
57 nanocomposite.
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After graphene wrapping, the G-S-CNFs coaxial nanocomposites were collected
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5 by vacuum filtration and they could form freestanding films after drying under ambient
6 condition without the need to add any binders. The sulfur content in the composite is ~33
7 wt% as determined by TGA measurement (Figure 1d). The cathodes for Li-S battery
8 testing were prepared by directly pressing a piece of the freestanding film (with a much
9 higher areal density of 2.0~3.0 mg/cm2 than similar studies11,19,20,22,25,30,39) onto a piece
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of nickel mesh. Unlike the conventional sulfur electrode preparation approach that
12 involves substantial amount of carbon additive and binder, such a binder-free strategy
13 used in this work could reduce the total weight of the electrode. The test batteries were
14 assembled as coin cells (type 2032), with a small piece of lithium foil used as the counter
15 electrodes. Figure 3a compares the 1st and 2nd charge-discharge profiles of cathodes
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assembled with or without graphene wrapping at 0.1C (where 1C corresponds to a current
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18 density of 1675 mA g-1) within 1.5 ~ 3.0V (vs Li+/Li). Both of these two electrodes have
19 similar sulfur content at 33 wt% to ensure comparable results. As can be seen, two
20 plateaus at 2.35 and 2.05V were clearly observed during the discharge process, which
21 correspond to the formation of long-chain lithium polysulfides (Li2Sx, 4≤x≤8) and short-
22 chain lithium polysulfides (such as Li2S2 and Li2S), respectively. Such discharge profile
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is typical for sulfur cathodes and agrees well with previous reports.18,39,40 On the basis of
25 the discharge results, the G-S-CNFs nanocomposites based cathode was able to deliver
26 1047 mAh g-1 (calculation based on the weight of S) in its first discharge process, which
27 is substantially higher than the 780 mAh g-1 of S-CNFs without graphene wrapping,
28 demonstrating improved capacity by graphene wrapping. With continued cycling, both of
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these electrodes experienced typical initial capacity fading as shown in Figure 3b.
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31 However, the graphene wrapped S-CNFs coaxial nanocomposites stabilized at high
32 capacities of ~694 mAh g-1 after the initial 10 cycles. In contrast, the control sample of S-
33 CNFs without graphene wrapping was only able to deliver a stable capacity of 207 mAh
34 g-1, which is only 30% of the cathode with graphene wrapping.
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45 Figure 3. Comparison of the (a)1st and 2nd charge-discharge profiles; (b) capacity as a
46 function of cycle numbers (50 cycles); and (c) capacity vs current density (0.1C, 0.5C, 1C
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48 and 2C) of the S-CNFs nanocomposite with (G-S-CNFs) and without (S-CNFs) graphene
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51 The effect of graphene wrapping on the rate capability of the S-CNFs
52 nanocomposite was studied by repeated charge-discharge tests conducted at increasing
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current densities from 0.1 C to 2 C and the results are compared in Figure 3c. As the
55 current increases, the capacity of the graphene wrapped S-CNFs nanocomposites
56 decreased slowly from the reversible 704mAh g-1at 0.1C to 429, 358 and 330 mAh g-1 at
57 0.5C, 1C and 2C, respectively. Importantly, a reversible capacity of 698 mAh g-1 was
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obtained when the current was switched back to 0.1 C, which is close to the initial
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5 capacity (704 mAh g-1) and indicating a highly reversible and efficient electrode enabled
6 by graphene wrapping. On the basis of these results, a capacity retention ratio of ~47%
7 was obtained when the current was increased from 0.1 C to 2 C. In strong contrast, the
8 cathode assembled without graphene wrapping exhibited not only much lower capacity at
9 the same discharge rate but also inferior capacity retention ratio of ~40% (from ~385
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mAh g-1 at 0.1 C to ~155 mAh g-1 at 2C). Additionally, when the current was switched
12 back to 0.1 C, the capacity of the control sample only showed a capacity of 218 mAh g-1,
13 which is 57% of the initial reversible capacity at the same rate and is much lower
14 compared with the cathode with graphene wrapping. The substantially higher capacity
15 and rate performance of G-S-CNFs nanocomposite could be attributed to its unique
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coaxial structure, in which sulfur was sandwiched between graphene and CNFs. As
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18 illustrated in Figure 1, the active material of sulfur in a S-CNFs cathode would be in
19 direct contact with the electrolyte and hence, during the charge-discharge process, the
20 soluble polysulfide intermediate could easily detach from the electrode to the electrolyte
21 and lead to decreased capacity. In contrast, graphene wrapped around the S-CNFs in a G-
22 S-CNFs cathode could efficiently immobilize the polysulfides and prevent their diffusion
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to the electrolyte, which could minimize the shuttling effect. At the same time, carbon
25 nanofibers are highly conductive and could provide mechanical support to the film during
26 charging and discharge process. Additionally, the graphene coated externally on the
27 surface of sulfur could interconnect and form conductive network to further increase the
28 conductivity of the electrode. Working together, the synergistic contribution from the
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inner carbon nanofibers and outer graphene could effectively not only improve the
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31 reaction kinetics by shorting the transport pathway for both electrons and ions, but also
32 accommodate the volume expansion and shrinkage of sulfur during charge-discharge
33 cycles, leading to significantly higher capacity and rate capability.
34 In order to clearly identify the effects of graphene wrapping on the cycle stability
35 of sulfur, the G-S-CNFs electrode was tested for 1500 cycles at a high rate of 1C. As
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37 shown in Figure S2 (supporting information), the charge-discharge profiles at increasing
38 cycles exhibited well-overlapped and flat plateaus, suggesting good stability and
39 reversibility of the electrode. Figure 4a compares the capacity of the electrode as a
40 function of cycle numbers. The electrode was able to deliver 1100 mAh g-1 during the 1st
41 discharge process. Despite the fact that capacity still fade rapidly during the first 10
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cycles, the electrode quickly stabilize and exhibited reversible and comparable capacity
44 of 375 mAh g-1 after 50 cycles.15,39,41 From the 50th cycle to the 1500th cycle, the capacity
45 of the G-S-CNFs nanocomposite decayed from 375 mAh g-1 to 273 mAh g-1 (27.2%
46 capacity loss over 1450 cycles), representing an extremely low decay rate of 0.043% per
47 cycle for 1500 cycles. At the same time, the coulombic efficiency remained at around
48 100%. On the basis of such superior cyclic stability, it is reasonable to conclude that the
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50 synergistic effect from graphene and CNFs could effectively improve the long cycle
51 stability of sulfur, likely through immobilization of the polysulfides intermediate and
52 provide better mechanical support to accommodate the volume changes during charge
53 and discharge. On the other hand, the control electrode made with S-CNFs without
54 graphene wrapping exhibited inferior stability (Figure 4b). In this case, the electrode was
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able to deliver an initial discharge capacity of 507 mA g-1. However, a rapid capacity
57 fade was observed after only ~ 120 cycles. Such observation of rapid capacity fade after
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the initially stabilized charge-discharge behavior is similar to silicon anode for Li-ion
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5 batteries and could be attributed to the stress induced by volume expansion/shrinkage
6 during charge-discharge, which eventually lead to cracking and pulverization of sulfur
7 and hence loss of electrical contact to CNFs.6,42,43 All these results show that the
8 nanoscale core-shell structure not only can immobilize polysulfide and minimize the
9 shuttling effect, but also accommodate the volume expansion effectively, avoiding
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cracking and pulverization even at a high charging/discharging rate of 1C.
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54 Figure 4: (a) Charge-discharge profiles at different cycle numbers as labeled for the G-S-
55 CNFs coaxial nanocomposites; Comparison of high-rate (1C) specific capacity and
56 coulombic efficiency as a function of cycle numbers for electrodes assembled with (b)
57 and without (c) graphene wrapping.
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5 In summary, a novel graphene-sulfur-carbon nanofibers coaxial nanocomposite
6 was designed and assembled as cathode for Li-S batteries with significantly improved
7 cycle stability and capacity in this paper. Owning to the unique sandwiched core-shell
8 architecture, electrodes made with such composites was able to demonstrate high specific
9 capacity, high retention ratio at increased charging/discharging rate and significantly
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improved long-cycle stability. The observed very slow decay at 1C (0.043% per
12 cycleafter 1500 cycles ) represents a significant step forward for Li-S batteries, which
13 exceeds the cycling target set by DOE in 2011. These results demonstrate that such
14 nanocomposite is of great potential for high-rate rechargeable Li–S batteries as the next
15 generation energy storage devices.
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18 Supporting Information. Experimental details for the material preparation,
19 characterization and device testing, along with additional supporting data. This material
20 is available free of charge via the Internet at http://pubs.acs.org.
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22 Corresponding Author
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*E-mail: [email protected]
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25 Acknowledgement: This work is in part supported by a research grant from the National
26 Science Foundation (NSF) and the Environmental Protection Agency (EPA) under NSF
27 Cooperative Agreement EF-0830093, Center for the Environmental Implications of
28 NanoTechnology (CEINT). Any opinions, findings, conclusions or recommendations
29 expressed in this material are those of the author(s) and do not necessarily reflect the
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views of the ARO, NSF or the EPA. This work has not been subjected to EPA review and
32 no official endorsement should be inferred. The authors also acknowledge the support
33 from Duke SMIF (Shared Materials Instrumentation Facilities). SL also acknowledges
34 support from Chinese government through China Scholarship Council.
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