Lithium–sulfur (Li–S) batteries are regarded as one of the most promising next-generation electrochemical cells. However, shuttling of lithium polysulfide intermediates and sluggish kinetics in random deposition of lithium sulfide (Li 2 S) have significantly degraded their capacity, rate and cycling performance. Herein, few-layered MoS 2 nanosheets enriched with sulfur vacancies are anchored inside hollow mesoporous carbon (MoS 2−x /HMC) via S–C bonding and proposed as a novel functional mediator for Li–S batteries. Ultrathin MoS 2 sheets with abundant sulfur vacancies have strong chemical affinity to polysulfides and in the meantime catalyze their fast redox conversion with enhanced reaction kinetics as proved by experimental observations and first-principles density functional theory (DFT) calculations. At a current density of 1C, the MoS 2−x /HMC-S composite cathode exhibits a high initial capacity of 945 mA h g −1 with a high retained capacity of 526 mA h g −1 and a coulombic efficiency of nearly 100% after 500 cycles. The present work sheds light on the design of novel functional electrodes for next-generation electrochemical cells based on a simple yet effective vacancy engineering strategy.
more »
« less
Oxygen-deficient titanium dioxide as a functional host for lithium–sulfur batteries
The shuttling of polysulfides with sluggish redox kinetics has severely retarded the advancement of lithium–sulfur (Li–S) batteries. In this work oxygen-deficient titanium dioxide (TiO 2 ) has been investigated as a novel functional host for Li–S batteries. Experimental and first-principles density functional theory (DFT) studies reveal that oxygen vacancies help to reduce polysulfide shuttling and catalyze the redox kinetics of sulfur/polysulfides during cycling. Consequently, the resulting TiO 2 /S composite cathode manifests superior electrochemical properties in terms of high capacity (1472 mA h g −1 at 0.2C), outstanding rate capability (571 mA h g −1 at 2C), and excellent cycling properties (900 mA h g −1 over 100 cycles at 0.2C). The present strategy offers a viable way through vacancy engineering for the design and optimization of high-performance electrodes for advanced Li–S batteries and other electrochemical devices.
more »
« less
- Award ID(s):
- 1803256
- NSF-PAR ID:
- 10121548
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 7
- Issue:
- 17
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 10346 to 10353
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
The shuttling of polysulfides and uncontrollable growth of lithium dendrites remain the most critical obstacles deteriorating the performance and safety of lithium–sulfur batteries. The separator plays a key role in molecule diffusion and ion transport kinetics; thus, endowing the separator with functions to address the two abovementioned issues is an urgent need. Herein, a protein-based, low-resistance Janus nanofabric is designed and fabricated for simultaneously trapping polysulfides and stabilizing lithium metal. The Janus nanofabric is achieved via combining two functional nanofabric layers, a gelatin-coated conductive nanofabric (G@CNF) as a polysulfide-blocking layer and a gelatin nanofabric (G-nanofabric) as an ion-regulating layer, into a heterostructure. The gelatin coating of G@CNF effectively enhances the polysulfide-trapping ability owing to strong gelatin–polysulfide interactions. The G-nanofabric with exceptional wettability, high ionic conductivity (4.9 × 10 −3 S cm −1 ) and a high lithium-ion transference number (0.73) helps stabilize ion deposition and thus suppresses the growth of lithium dendrites. As a result, a Li/Li symmetric cell with the G-nanofabric delivers ultra-long cycle life over 1000 h with very stable performance. Benefiting from the synergistic effect of the two functional layers of the Janus nanofabric, the resulting Li–S batteries demonstrate excellent capacity, rate performance and cycling stability ( e.g. initial discharge capacity of 890 mA h g −1 with a decay rate of 0.117% up to 300 cycles at 0.5 A g −1 ).more » « less
-
Li–S batteries have attracted great attention for their combined advantages of potentially high energy density and low cost. To tackle the capacity fade from polysulfide dissolution, we have developed a confinement approach by in situ encapsulating sulfur with a MOF-derived CoS 2 in a carbon framework (S/Z-CoS 2 ), which in turn was derived from a sulfur/ZIF-67 composite (S/ZIF-67) via heat treatment. The formation of CoS 2 was confirmed by X-ray absorption spectroscopy (XAS) and its microstructure and chemical composition were examined through cryogenic scanning/transmission electron microscopy (Cryo-S/TEM) imaging with energy dispersive spectroscopy (EDX). Quantitative EDX suggests that sulfur resides inside the cages, rather than externally. S/hollow ZIF-67-derived CoS 2 (S/H-CoS 2 ) was rationally designed to serve as a control material to explore the efficiency of such hollow structures. Cryo-STEM-EDX mapping indicates that the majority of sulfur in S/H-CoS 2 stays outside of the host, despite its high void volumetric fraction of ∼85%. The S/Z-CoS 2 composite exhibited highly improved battery performance, when compared to both S/ZIF-67 and S/H-CoS 2 , due to both the efficient physical confinement of sulfur inside the host and strong chemical interactions between CoS 2 and sulfur/polysulfides. Electrochemical kinetics investigations revealed that the CoS 2 could serve as an electrocatalyst to accelerate the redox reactions. The composite could provide an areal capacity of 2.2 mA h cm −2 after 150 cycles at 0.2C and 1.5 mA h cm −2 at 1C. This novel material provides valuable insights for further development of high-energy, high-rate and long-life Li–S batteries.more » « less
-
Rechargeable lithium–sulfur batteries have emerged as a viable technology for next generation electrochemical energy storage, and the sulfur cathode plays a critical role in determining the device performance. In this study, we prepared functional composites based on polypyrrole-coated MnO 2 nanotubes as a highly efficient sulfur host (sulfur mass loading 63.5%). The hollow interior of the MnO 2 nanotubes not only allowed for accommodation of volumetric changes of sulfur particles during the cycling process, but also confined the diffusion of lithium polysulfides by physical restriction and chemical adsorption, which minimized the loss of polysulfide species. In addition, the polypyrrole outer layer effectively enhanced the electrical conductivity of the cathode to facilitate ion and electron transport. The as-prepared MnO 2 -PPy-S composite delivered an initial specific capacity of 1469 mA h g −1 and maintained an extremely stable cycling performance, with a small capacity decay of merely 0.07% per cycle at 0.2C within 500 cycles, a high average coulombic efficiency of 95.7% and an excellent rate capability at 470 mA h g −1 at the current density of 3C.more » « less
-
more » « less
Abstract The shuttling of polysulfides is the most detrimental contribution to degrading the capacity and cycle stability of lithium‐sulfur (Li−S) batteries. Adding a carbon interlayer to prevent the polysulfides from migrating is feasible, and a rational design of the structures and surface properties of the carbon layer is essential to increasing its effectiveness. Herein, we report a hierarchical porous carbon (HPC) created by carbonization of bis(phenoxy)phosphazene and in‐situ doping of triple heteroatoms into the carbon lattice to fabricate an effective polysulfide‐trapping interlayer. The generated carbon integrates the advantages of a hierarchical porous structure, a high specific area and rich dopants (N, O and P), to yield chemisorption and physical confinement for polysulfides and fast ion‐transport synergistically. The HPC interlayer significantly improves the electrochemical performance of Li−S batteries, including an exceptional discharge capacity of 1509 mA h/g at 0.06 C and a high capacity retention of 83.7 % after 250 cycles at 0.3 C. This work thus proposes a facile in‐situ synthesis of heteroatom‐doped carbon with rational porous structures for suppressing the shuttle effect.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c9ta01598a
