Accelerating the Rate-Determining Steps of Sulfur Conversion Reaction for Lithium-Sulfur Batteries Working at an Ultrawide Temperature Range.

Wide operation temperature is the crucial objective for an energy storage system that can be applied under harsh environmental conditions. For lithium-sulfur batteries, the "shuttle effect" of polysulfide intermediates will aggravate with the temperature increasing, while the reaction kinetics decreases sharply as the temperature decreasing. In particular, sulfur reaction mechanism at low temperatures seems to be quite different from that at room temperature. Here, through in situ Raman and electrochemical impedance spectroscopy studies, the newly emerged platform at cryogenic temperature corresponds to the reduction process of Li2S8 to Li2S4, which will be another rate-determining step of sulfur conversion reaction, in addition to the solid-phase conversion process of Li2S4 to Li2S2/Li2S at low temperatures. Porous bismuth vanadate (BiVO4) spheres are designed as sulfur host material, which achieve the rapid snap-transfer-catalytic process by shortening lithium-ion transport pathway and accelerating the targeted rate-determining steps. Such promoting effect greatly inhibits severe "shuttle effect" at high temperatures and simultaneously improves sulfur conversion efficiency in the cryogenic environment. The cell with the porous BiVO4 spheres as the host exhibits excellent rate capability and cycle performance under wide working temperatures.

In-situ synthesis Fe3C@C/rGO as matrix for high performance lithium-sulfur batteries at room and low temperatures.

People have been focusing on how to improve the specific capacity and cycling stability of lithium-sulfur batteries at room temperature, however, on some special occasions such as cold cities and aerospace fields, the operating temperature is low, which dramatically hinders the performance of batteries. Here, we report an iron carbide (Fe3C)/rGO composite as electrode host, the Fe3C nanoparticles in the composite have strong adsorption and high catalytic ability for polysulfide. The rGO makes the distribution of Fe3C nanoparticles more disperse, and this specific structure makes the deposition of Li2S more uniform. Therefore, it realizes the rapid transformation and high performance of lithium-sulfur batteries at both room and low temperatures. At room temperature, after 100 cycles at 1C current density, the reversible specific capacity of the battery can be stabilized at 889 ± 7.1 mAh/g. Even at -40 °C, in the first cycle battery still emits 542.9 ± 3.7 mAh/g specific capacity. This broadens the operating temperature for lithium-sulfur batteries and also provides a new idea for the selection of host materials for sulfur in low-temperature lithium-sulfur batteries.

Synthesis of Low-Cost and High-Performance Dual-Atom Doped Carbon-Based Materials with a Simple Green Route as Anodes for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are promising alternatives to replace lithium-ion batteries as future energy storage batteries because of their abundant sodium resources, low cost, and high charging efficiency. In order to match the high energy capacity and density, designing an atomically doped carbonous material as the anode is presently one of the important strategies to commercialize SIBs. In this work, we report the preparation of high-performance dual-atom-doped carbon (C) materials using low-cost corn starch and thiourea (CH4N2S) as the precursors. The electronegativity and radii of the doped atoms and C are different, which can vary the embedding properties of sodium ions (Na+) into/on C. As sulfur (S) can effectively expand the layer spacing, it provides more channels for embedding and de-embedding Na+. The synergistic effect of N and S co-doping can remarkably boost the performance of SIBs. The capacity is preserved at 400 mAh g -1 after 200 cycles at 500 mA g-1; more notably, the initial Coulombic efficiency is 81%. Even at a high rate of high current of 10 A g-1, the cell capacity can still reach 170 mAh g-1. More importantly, after 3000 cycles at 1 A g-1, the capacity decay is less than 0.003% per cycle, which demonstrates its excellent electrochemical performance. These results indicate that high-performance carbon materials can be prepared using low-cost corn starch and thiourea.

Thin Nano Cages with Limited Hollow Space for Ultrahigh Sulfur Loading Lithium-Sulfur Batteries.

Owning to its various advantages, the lithium-sulfur battery is one of the research hot spots for new energy storage systems. Diverse hollow structures with specific morphologies have been used as the sulfur host materials to adsorb or/and catalyze the polysulfides, and can in particular concurrently inhibit the volume expansion during electrochemical processes in lithium-sulfur batteries. However, hollow space with a large volume will restrict the performance of the cell under high sulfur area loading, which is a very important indicator for the practical applications of the lithium-sulfur battery. Here, we report a nano thin cage cobalt acid zinc (ZnCo2O4) with limited hollow space as the cathode catalyst for lithium-sulfur batteries, which greatly reduces the electrode volume occupied by the hollow structure. The hollow volume of these thin cages is much smaller than those of the normally reported hollow materials in the literatue. The electrochemical performance of lithium-sulfur batteries with ZnCo2O4 thin cages could greatly improve due to the unique structure and the synergistic adsorption/catalytic effect of Zn/Co sites, especially at an ultrahigh S area load. Under a high S loading of 8 mg cm-2, the cell could keep a reversible capacity of 600 mAh g-1 after 500 cycles. Even at a sulfur loading of 10 mg cm-2, the cell still releases a discharge capacity of 1000 mAh g-1 which is equivalent of an area capacity of 10 mAh cm-2. This work provides a feasible way to develop lithium sulfur batteries with a high area sulfur load. This idea provides a possible solution to develop a Li-S battery at high area S loading and move one step closer to the practical applications.

Tuning Redox Active Polyoxometalates for Efficient Electron-Coupled Proton-Buffer-Mediated Water Splitting.

We present strategies to tune the redox properties of polyoxometalate clusters to enhance the electron-coupled proton-buffer-mediated water splitting process, in which the evolution of hydrogen and oxygen can occur in different forms and is separated in time and space. By substituting the heteroatom template in the Keggin-type polyoxometalate cluster, H6 ZnW12 O40 , it is possible to double the number of electrons and protonation in the redox reactions (from two to four). This increase can be achieved with better matching of the energy levels as indicated by the redox potentials, compared to the ones of well-studied H3 PW12 O40 and H4 SiW12 O40 . This means that H6 ZnW12 O40 can act as a high-performance redox mediator in an electrolytic cell for the on-demand generation of hydrogen with a high decoupling efficiency of 95.5 % and an electrochemical energy efficiency of 83.3 %. Furthermore, the H6 ZnW12 O40 cluster also exhibits an excellent cycling behaviour and redox reversibility with almost 100 % H2 -mediated capacity retention during 200 cycles and a high coulombic efficiency >92 % each cycle at 30 mA cm-2 .

Multifunctional Ion-Sieve Constructed by 2D Materials as an Interlayer for Li-S Batteries.

For Li-S batteries, the interlayer between the separator and sulfur cathode preventing lithium polysulfide (LiPS) travel across the membrane is a research hotspot. The good blocking ability for LiPSs indicates that these interlayers can promote the electrochemistry performance with high S loading. However, most of these interlayers are just used as a simple blocking wall. Such a blocking wall, for example, the lower Li+ ion conductivity, would often reduce the electrochemical performance, especially under large current density. Here, we report a multifunctional ion-sieve made by three two-dimensional (2D) sheets, graphitic carbon nitride (g-C3N4), boron nitride (BN), and graphene. A g-C3N4 sheet which possesses orderly channels with a size of 3 Å in the crystalline structure can effectively prevent polysulfides from passing through but allow lithium ions to pass freely, whereas a BN sheet acts as an excellent catalyst for sulfur redox, and graphene acts as an extended collector, which can promote the conductivity of the sulfur electrode region. Benefiting from the synergistic effect among these 2D materials, the ion-sieve interlayer makes the Li-S battery show excellent performance at a large rate with both high sulfur loadings and high sulfur content. In addition, the host materials are not necessary in these cells. The ion-sieve liberated a discharge capacity of about 600 mA h g-1 after 500 cycles at 1 C, and the capacity attenuation was less than 0.01% per cycle with a 6 mg cm-2 areal S-loading (pure S as the active material). The reversible capacity could be maintained at more than 400 mA h g-1 at 2 C, which amounts to an area current density of 26.88 mA cm-2.

Enhanced Adsorptions to Polysulfides on Graphene-Supported BN Nanosheets with Excellent Li-S Battery Performance in a Wide Temperature Range.

For Li-S batteries, the catalysis for S redox reaction is indispensable. A lot of multifunctional sulfur electrode support materials with have been investigated widely. However, most of these studies were carried out at room temperature, and the interaction between different components in the matrix is not often paid enough attention. Here, we report a graphene supported BN nanosheet composite in which the synergistic effect between BN and graphene greatly enhanced the adsorption for polysulfides, thus leading to excellent performance in a wide temperature range. When used as a host material of sulfur, it can make the Li-S battery apply to a wide range of temperatures, from -40 to 70 °C, delivering a high utilization of sulfur, an excellent rate capability, and outstanding cycling life. The capacity can stabilized at 888 mAh g-1 at 2 C after 300 cycles with a capacity attenuation of <0.04% per cycle at 70 °C, and the battery can deliver a capacity above 650 mAh g-1 at -40 °C.

Strategies to Explore and Develop Reversible Redox Reactions of Li-S in Electrode Architectures Using Silver-Polyoxometalate Clusters.

Investigations of the Ag (I)-substituted Keggin K3[H3AgIPW11O39] as a bifunctional Lewis acidic and basic catalyst are reported that explore the stabilization of Li2Sn moieties so that reversible redox reactions in S-based electrodes would be possible. Spectroscopic investigations showed that the Li2Sn-moieties can be strongly adsorbed on the {AgIPW11O39} cluster, where the Ag(I) ion can act as a Lewis acid site to further enhance the adsorption of the S-moieties, and these interactions were investigated and rationalized using DFT. These results were used to construct an electrode for use in a Li-S battery with a very high S utilization of 94%, and a coulometric capacity of 1580 mAh g-1. This means, as a result of using the AgPOM, both a high active S content, as well as a high areal S mass loading, is achieved in the composite electrode giving a highly stable battery with cycling performance at high rates (1050 and 810 mAh g-1 at 1C and 2C over 100 to 300 cycles, respectively).

Co4N Nanosheet Assembled Mesoporous Sphere as a Matrix for Ultrahigh Sulfur Content Lithium-Sulfur Batteries.

High utilization and loading of sulfur in cathodes holds the key in the realization of Li-S batteries. We here synthesized a Co4N mesoporous sphere, which was made up of nanosheets, via an easy and convenient method. This material presents high affinity, speedy trapping, and absorbing capacity for polysulfides and acts as a bifunctional catalysis for sulfur redox processes; therefore it is an ideal matrix for S active material. With such a mesoporous sphere used as a sulfur host in Li-S batteries, extraordinary electrochemistry performance has been achieved. With a sulfur content of 72.3 wt % in the composite, the Co4N@S delivered a high specific discharge capacity of 1659 mAh g-1 at 0.1 C, almost reaching its theoretic capacity. Also, the battery exhibited a large reversible capacity of about 1100 mAh g-1 at 0.5 C and 1000 mAh g-1 at 1 C after 100 cycles. At a high rate of 2 C and 5 C, after 300 cycles, the discharge capacity finally stabilized at 805 and 585 mAh g-1. Even at a 94.88% sulfur content, the cathode can still deliver an extremely high specific discharge capacity of 1259 mAh g-1 with good cycle performance.