Graphene-Based Three-Dimensional Hierarchical Sandwich-type Architecture for High-Performance Li/S Batteries

Abstract

A multiwalled carbon nanotube/sulfur (MWCNT@S) composite with core-shell structure was successfully embedded into the interlay galleries of graphene sheets (GS) through a facile two-step assembly process. Scanning and transmission electron microscopy images reveal a 3D hierarchical sandwich-type architecture of the composite GS-MWCNT@S. The thickness of the S layer on the MWCNTs is ~20 nm. Raman spectroscopy, X-ray diffraction, thermogravimetric analysis, and energy-dispersive X-ray analysis confirm that the sulfur in the composite is highly crystalline with a mass loading up to 70% of the composite. This composite is evaluated as a cathode material for Li/S batteries. The GS-MWCNT@S composite exhibits a high initial capacity of 1396 mAh/g at a current density of 0.2C (1C = 1672 mA/g), corresponding to 83% usage of the sulfur active material. Much improved cycling stability and rate capability are achieved for the GS-MWCNT@S composite cathode compared with the composite lacking GS or MWCNT. The superior electrochemical performance of the GS-MWCNT@S composite is mainly attributed to the synergistic effects of GS and MWCNTs, which provide a 3D conductive network for electron transfer, open channels for ion diffusion, strong confinement of soluble polysulfides, and effective buffer for volume expansion of the S cathode during discharge.

Leaf‐Like Graphene‐Oxide‐Wrapped Sulfur for High‐Performance Lithium–Sulfur Battery

“…However, RGO or G does not have the abundant functional groups that can bind sulfur and its discharge products. In addition, similar with previous reports about porous‐carbon/S composites,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 the sulfur content in the GO/S and RGO/S (or G/S) composites and sulfur loading on the electrode is still low 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44. In addition, some efforts34 have been made to mix high conductivity carbon nanotube (CNT) with GO to improve the conductivity of GO.…”

“…However, one of the most salient problems of GO also arises from the functional groups on the surface that lead to poor electronic conductivity 46. Therefore, the achieved rate performances in most previous reports about GO/S composites are generally below the rate of 2 C (1 C = 1675 mA g −1 ) 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35. On the contrary, reduced GO (RGO) or graphene (G) with higher electronic conductivity was also employed to prepare RGO/S or G/S composites for improving rate performance 36, 37, 38, 39, 40, 41, 42, 43, 44.…”

“…However, the insulating nature of sulfur (S) and its reaction products (i.e., Li 2 S), the large volume expansion from S to Li 2 S, along with the dissolution of lithium polysulfide intermediates (i.e., Li 2 S x , 4 ≤ x ≤ 8) into liquid electrolyte and the consequent shuttling effect between the anode and cathode, makes it generally display poor rate ability, limited cycle life and severe self‐discharge 1, 2, 3, 4, 5, 6, 7. Therefore, a variety of strategies have been pursued to circumvent the sulfur cathode problems, including optimization of organic electrolytes8, 9 and fabrication of sulfur‐conductive polymer composites10, 11 and sulfur–carbon‐based composites 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, 44, 45. Among these approaches, porous‐carbon/sulfur composites12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 are more attractive because porous carbon can i...…”

“…Very recently, many efforts have been made to develop graphene oxide/sulfur (GO/S) composites cathode for Li–S battery,25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35 because GO consists of a basal plane decorated mostly with epoxide and hydroxyl groups, in addition to carbonyl and carboxyl groups, which are located on the edges. Zhang and co‐workers successfully demonstrated that these functional groups on the surface of GO play an important role for immobilizing the sulfur and its discharge products 25.…”

“…Furthermore, GO network can also accommodates the volume change of the electrode during the Li–S electrochemical reaction. Then, more and more researches have focused on GO/S composites and modified GO/S composites, and further improvements in cyclability of Li–S battery have been achieved by smartly designing GO/S composites in recent years 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35. However, one of the most salient problems of GO also arises from the functional groups on the surface that lead to poor electronic conductivity 46.…”