Quasi-Solid-State Electrolyte Induced by Metallic MoS2 for Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are a promising high-energy-density technology for next-generation energy storage but suffer from an inadequate lifespan. The poor cycle life of Li-S batteries stems from their commonly adopted catholyte-mediated operating mechanism, where the shuttling of dissolved polysulfides results in active material loss on the sulfur cathode and surface corrosion on the lithium anode. Here, we report in situ formation of a quasi-solid-state electrolyte (QSSE) on the metallic 1T phase molybdenum disulfide (MoS2) host that extends the lifetime of Li-S batteries. We find that the metallic 1T phase MoS2 host is able to initiate the ring-opening polymerization of 1,3-dioxolane (DOL), forming an integrated QSSE inside batteries. Nuclear magnetic resonance analysis reveals that the QSSE consists of ∼13% liquid DOL in a solid polymer matrix. The QSSE efficiently mediates sulfur redox reactions through dissolution-conversion chemistry while simultaneously suppressing polysulfide shuttling. Therefore, while ensuring high sulfur utilization, it avoids degradation of both electrodes, as well as the concomitant electrolyte consumption, leading to enhanced cycling stability. Under a practical lean electrolyte condition (electrolyte-to-sulfur ratio = 2 µL mg-1), Li-S pouch cell batteries with the QSSE demonstrate a capacity retention of 80.7% after 200 cycles, much superior to conventional liquid electrolyte cells that fail within 70 cycles. The QSSE also enables Li-S pouch cell batteries to operate across a wider temperature range (5 to 45 °C), together with improved safety under mechanical damage.

Sub-millisecond lithiothermal synthesis of graphitic meso-microporous carbon.

Porous carbons with concurrently high specific surface area and electronic conductivity are desirable by virtue of their desirable electron and ion transport ability, but conventional preparing methods suffer from either low yield or inferior quality carbons. Here we developed a lithiothermal approach to bottom-up synthesize highly meso-microporous graphitized carbon (MGC). The preparation can be finished in a few milliseconds by the self-propagating reaction between polytetrafluoroethylene powder and molten lithium (Li) metal, during which instant ultra-high temperature (>3000 K) was produced. This instantaneous carbon vaporization and condensation at ultra-high temperatures and in ultra-short duration enable the MGC to show a highly graphitized and continuously cross-coupled open pore structure. MGC displays superior electrochemical capacitor performance of exceptional power capability and ultralong-term cyclability. The processes used to make this carbon are readily scalable to industrial levels.

Understanding and Optimizing Capacitance Performance in Reduced Graphene-Oxide Based Supercapacitors.

Reduced graphene-oxide (RGO)-based electrodes in supercapacitors deliver high energy/power capacities compared to typical nanoporous carbon materials. However, extensive critical analysis of literature reveals enormous discrepancies (up to 250 F g-1 ) in the reported capacitance (variation of 100-350 F g-1 ) of RGO materials synthesized under seemingly similar methods, inhibiting an understanding of capacitance variation. Here, the key factors that control the capacitance performance of RGO electrodes are demonstrated by analyzing and optimizing various types of commonly applied electrode fabrication methods. Beyond usual data acquisition parameters and oxidation/reduction properties of RGO, a substantial difference of more than 100% in capacitance values (with change from 190 ± 20 to 340 ± 10 F g-1 ) is found depending on the electrode preparation method. For this demonstration, ≈40 RGO-based electrodes are fabricated from numerous distinctly different RGO materials via typically applied methods of solution (aqueous and organic) casting and compressed powders. The influence of data acquisition conditions and capacitance estimation practices are also discussed. Furthermore, by optimizing electrode processing method, a direct surface area governed capacitance relationship for RGO structures is revealed.

DFT Simulation-Based Design of 1T-MoS2 Cathode Hosts for Li-S Batteries and Experimental Evaluation.

The main challenge in lithium sulphur (Li-S) batteries is the shuttling of lithium polysulphides (LiPSs) caused by the rapid LiPSs migration to the anode and the slow reaction kinetics in the chain of LiPSs conversion. In this study, we explore 1T-MoS2 as a cathode host for Li-S batteries by examining the affinity of 1T-MoS2 substrates (pristine 1T-MoS2, defected 1T-MoS2 with one and two S vacancies) toward LiPSs and their electrocatalytic effects. Density functional theory (DFT) simulations are used to determine the adsorption energy of LiPSs to these substrates, the Gibbs free energy profiles for the reaction chain, and the preferred pathways and activation energies for the slow reaction stage from Li2S4 to Li2S. The obtained information highlights the potential benefit of a combination of 1T-MoS2 regions, without or with one and two sulphur vacancies, for an improved Li-S battery performance. The recommendation is implemented in a Li-S battery with areas of pristine 1T-MoS2 and some proportion of one and two S vacancies, exhibiting a capacity of 1190 mAh/g at 0.1C, with 97% capacity retention after 60 cycles in a schedule of different C-rates from 0.1C to 2C and back to 0.1C.

Defected vanadium bronzes as superb cathodes in aqueous zinc-ion batteries.

There is a growing need for fast, efficient, safe, and low-cost energy storage. Aqueous zinc-ion batteries (AZIBs) may be able to address this need, but suffer from fast capacity fade and poor ion diffusion kinetics due to unstable structures and non-optimised interspacing of layered cathode materials. Herein, we propose a structural engineering strategy by synergistically inducing anionic defects and cationic groups within vanadium bronze structures to improve kinetics and boost capacity. The materials discovered and used as the cathodes in AZIBs showed a high capacity of 435 mA h g-1 at a current density of 0.2 A g-1 and excellent stability with 95% capacity retention after 1500 cycles at 10 A g-1. This combined experimental and computational study systemically indicated that rapid Zn2+ storage was achieved from both a highly porous structure and enlarged d-spacing combined with improved electron conductivity as determined by density of states calculations. The modification of vanadium bronze-type cathodes achieved by controlled pre-intercalated species and tailored oxygen deficiency opens up an avenue for the realization of superior material design, whose feasibility is proved in this work.

Promotion of Proangiogenic Secretome from Mesenchymal Stromal Cells via Hierarchically Structured Biodegradable Microcarriers.

Adipose-derived mesenchymal stromal cells (AdMSC) release numerous soluble factors capable of stimulating angiogenesis. Improved methods for delivering these cells to maximize their potency are now sought that ideally they retain viable cells in the target tissue while promoting the secretion of angiogenic factors. Substrate surface topography is a parameter that can be used to manipulate the behavior of AdMSC but challenges exist with translating this parameter into materials compatible with minimally invasive delivery into tissues for in situ delivery of the angiogenic secretome. The current study investigates three compositions of hierarchically structured, porous biodegradable microcarriers for the culture of AdMSC and the influence of their surface topographies on the angiogenic secretome. All three compositions perform well as cell microcarriers in xeno-free conditions. The attached AdMSC retain their capacity for subsequent trilineage differentiation. The secretome of AdMSC attached to the microcarriers consists of multiple proangiogenic factors, including significantly elevated levels of vascular endothelial growth factor, which stimulates angiogenesis in vitro. The unique properties of hierarchically structured, porous biodegradable microcarriers investigated in this study offer a radically transformative approach for achieving targeted in vivo delivery of AdMSC and enhancing the potency of their proangiogenic activity to induce neovascularization in ischemic tissue.

Size-Related Electrochemical Performance in Active Carbon Nanostructures: A MOFs-Derived Carbons Case Study.

Metal-organic framework-derived carbon nanostructures have generated significant interest in electrochemical capacitors and oxygen/hydrogen catalysis reactions. However, they appear to show considerably varied structural properties, and thus exhibit complex electrochemical-activity relationships. Herein, a series of carbon polyhedrons of different sizes, between 50 nm and µm, are synthesized from zeolitic imidazolate frameworks, ZIF-8 (ZIF-derived carbon polyhedrons, ZDCPs) and their activity is studied for capacitance and the oxygen reduction reaction (ORR). Interestingly, a well-correlated performance relationship with respect to the particle size of ZDCPs is evidenced. Here, the identical structural features, such as specific surface area (SSA), microporosity, and its distribution, nitrogen doping, and graphitization are all strictly maintained in the ZDCPs, thus allowing identification of the effect of particle size on electrochemical performance. Supercapacitors show a capacity enhancement of 50 F g-1 when the ZDCPs size is reduced from micrometers to ≤200 nm. The carbonization further shows a considerable effect on rate capacitance-ZDCPs of increased particle size lead to drastically reduced charge transportability and thus inhibit their performance for both the charge storage and the ORR. Guidelines for the capacitance variation with respect to the particle size and SSA in such carbon nanostructures from literature are presented.

Design of 3D Graphene-Oxide Spheres and Their Derived Hierarchical Porous Structures for High Performance Supercapacitors.

Graphene-oxide (GO) based porous structures are highly desirable for supercapacitors, as the charge storage and transfer can be enhanced by advancement in the synthesis. An effective route is presented of, first, synthesis of three-dimensional (3D) assembly of GO sheets in a spherical architecture (GOS) by flash-freezing of GO dispersion, and then development of hierarchical porous graphene (HPG) networks by facile thermal-shock reduction of GOS. This leads to a superior gravimetric specific capacitance of ≈306 F g-1 at 1.0 A g-1 , with a capacitance retention of 93% after 10 000 cycles. The values represent a significant capacitance enhancement by 30-50% compared with the GO powder equivalent, and are among the highest reported for GO-based structures from different chemical reduction routes. Furthermore, a solid-state flexible supercapacitor is fabricated by constructing the HPG with polymer gel electrolyte, exhibiting an excellent areal specific capacitance of ≈220 mF cm-2 at 1.0 mA cm-2 with exceptional cyclic stability. The work reveals a facile but efficient synthesis approach of GO-based materials to enhance the capacitive energy storage.