Constructing Atomic Fe and N Co-doped Hollow Carbon Nanospheres with a Polymer Encapsulation Strategy for High-Performance Lithium-Sulfur Batteries with Accelerated Polysulfide Conversion.

As competitive next-generation rechargeable batteries, lithium-sulfur batteries (LSBs) suffer from the shuttle effect and the sluggish kinetics of intermediate polysulfides during charge and discharge processes, adversely affecting their electrochemical performances and actual applications. Herein, we demonstrate a polymer encapsulation strategy to synthesize atomic Fe and N co-doped hollow carbon nanospheres (Fe-NHC) with Fe-Nx sites for modifying commercial PP separator of LSBs to suppress the shuttle effect and promote the kinetics of intermediate polysulfides. Benefiting from the excellent structural design, the doped-N with positive charges could effectively adsorb negatively charged soluble polysulfides, help attract the soluble polysulfides to the Fe atoms and boost the catalytic transformation of the soluble polysulfides. Additionally, such a thin carbon shell could provide a short mass diffusion pathway and hence promote the adsorption and the catalytic conversion. Therefore, the battery with the Fe-NHC/PP separator delivers outstanding cycling and rate performances. At the large current density of 1 C, the specific capacity is 1079 mA h g-1 and maintains a low loss of 0.076 % per cycle within 500 cycles. Even at a harsh current density of 4 C, a high capacity of 824 mA h g-1 is still achieved, indicating the advantage of the Fe-NHC/PP separator in LSBs.

Mesoporous Yolk-Shell Structured Organosulfur Nanotubes with Abundant Internal Joints for High-Performance Lithium-Sulfur Batteries by Kinetics Acceleration.

Although organosulfur compounds can protect lithium anodes, participate in the redox reaction, and suppress the shuttle effect, the sluggish electrochemical dynamics of their bulk structure and the notorious shuttle effect of covalent long-chain sulfurs largely impede their actual applications. Herein, sulfurized carbon nanotube@aminophenol-formaldehyde (SC@A) with covalently linked short-chain sulfurs is firstly synthesized by in situ polymerization of aminophenol-formaldehyde (AF) on the surface of carbon nanotubes (CNTs) followed by acetone etching and inverse sulfurization processes, forming mesoporous yolk-shell organosulfur nanotubes with abundant internal joints between the yolk of CNTs and the shell of sulfurized AF for the first time. In situ Raman spectra, in situ XRD patterns, and ex situ XPS spectra verify that the covalent short-chain sulfurs bring about a reversible solid-solid conversion process of sulfur, thoroughly avoiding the shuttle effect. The mesoporous yolk-shell structure with abundant internal joints can effectively accommodate the volume change, fully expose active sites and efficiently improve the transport of electrons and lithium ions, thus highly promoting the solid-solid electrochemical reaction kinetics. Therefore, the SC@A cathode exhibits a superior specific capacity of 841 mAh g-1 and a capacity decay of 0.06% per cycle within 500 cycles at a large current density of 5.0 C.

Achieving High Lithium Storage Capacity and Long-Term Cyclability of Novel Cobalt Germanate Hydroxide/Reduced Graphene Oxide Anodes with Regulated Electrochemical Catalytic Conversion Process of Hydroxyl Groups.

To develop ternary transition-metal germanate anodes with superior lithium storage performances for lithium-ion batteries, a novel capacity counterbalance approach in one compound is designed by introducing an electrocatalytic conversion-type component with a positive cycling trend to compensate the negative cycling trend of the GeO2 component. Novel cobalt germanate hydroxide (CGH) nanoplates chemically bonded on reduced graphene oxide (RGO) sheets are thus synthesized with a mild one-pot hydrothermal approach, constructing maximal face-to-face contact interfaces with interfacial bonds to boost the electrochemical conversion reactions. Furthermore, the hydroxyl groups (Co-OH) of CGH nanoplates are regulated by thermal annealing treatments, thus controlling the capacity contribution resulting from the electrocatalytic conversion reaction of LiOH to exactly offset the capacity fading of GeO2. The results on the CGH electrodes at different cycling potentials confirm the stepwise electrochemical reactions of Co, GeO2, and LiOH. The equilibrium of these electrochemical reactions ensures a stable cycling capacity without obvious fluctuations. Consequently, the optimal CGH/RGO hybrid anode delivers a reversible capacity as high as 1136 mA h g-1 at 0.1 A g-1 until 100 cycles. It also exhibits a long cyclability with a retained capacity of 560 mA h g-1 at 1 A g-1 until 1000 cycles. This work demonstrates a general and efficient capacity counterbalance method to highly boost lithium storage performances in terms of high capacity and long-term cyclability.

Layered Birnessite Cathode with a Displacement/Intercalation Mechanism for High-Performance Aqueous Zinc-Ion Batteries.

Mn-based rechargeable aqueous zinc-ion batteries (ZIBs) are highly promising because of their high operating voltages, attractive energy densities, and eco-friendliness. However, the electrochemical performances of Mn-based cathodes usually suffer from their serious structure transformation upon charge/discharge cycling. Herein, we report a layered sodium-ion/crystal water co-intercalated Birnessite cathode with the formula of Na0.55Mn2O4·0.57H2O (NMOH) for high-performance aqueous ZIBs. A displacement/intercalation electrochemical mechanism was confirmed in the Mn-based cathode for the first time. Na+ and crystal water enlarge the interlayer distance to enhance the insertion of Zn2+, and some sodium ions are replaced with Zn2+ in the first cycle to further stabilize the layered structure for subsequent reversible Zn2+/H+ insertion/extraction, resulting in exceptional specific capacities and satisfactory structural stabilities. Additionally, a pseudo-capacitance derived from the surface-adsorbed Na+ also contributes to the electrochemical performances. The NMOH cathode not only delivers high reversible capacities of 389.8 and 87.1 mA h g-1 at current densities of 200 and 1500 mA g-1, respectively, but also maintains a good long-cycling performance of 201.6 mA h g-1 at a high current density of 500 mA g-1 after 400 cycles, which makes the NMOH cathode competitive for practical applications.