NH4 + Pre-Intercalation and Mo Doping VS2 to Regulate Nanostructure and Electronic Properties for High Efficiency Sodium Storage.

Sodium-ion hybrid capacitors (SIHCs) have attracted much attention due to integrating the high energy density of battery and high out power of supercapacitors. However, rapid Na+ diffusion kinetics in cathode is counterbalanced with sluggish anode, hindering the further advancement and commercialization of SIHCs. Here, aiming at conversion-type metal sulfide anode, taking typical VS2 as an example, a comprehensive regulation of nanostructure and electronic properties through NH4 + pre-intercalation and Mo-doping VS2 (Mo-NVS2) is reported. It is demonstrated that NH4 + pre-intercalation can enlarge the interplanar spacing and Mo-doping can induce interlayer defects and sulfur vacancies that are favorable to construct new ion transport channels, thus resulting in significantly enhanced Na+ diffusion kinetics and pseudocapacitance. Density functional theory calculations further reveal that the introduction of NH4 + and Mo-doping enhances the electronic conductivity, lowers the diffusion energy barrier of Na+, and produces stronger d-p hybridization to promote conversion kinetics of Na+ intercalation intermediates. Consequently, Mo-NVS2 delivers a record-high reversible capacity of 453 mAh g-1 at 3 A g-1 and an ultra-stable cycle life of over 20 000 cycles. The assembled SIHCs achieve impressive energy density/power density of 98 Wh kg-1/11.84 kW kg-1, ultralong cycling life of over 15000 cycles, and very low self-discharge rate (0.84 mV h-1).

Mn2+ Ions Capture and Uniform Composite Electrodes with PEI Aqueous Binder for Advanced LiMn2O4-Based Battery.

The electrode deterioration and capacity decay caused by the dissolution of transition metal ions have been criticized for a long time. The branched polyethyleneimine (PEI) was employed as a functional binder for spinel lithium manganese oxide (LiMn2O4, LMO) and layer structure lithium cobalt oxide (LiCoO2, LCO) to resolve the problem. Due to the chelation reaction of amine groups, PEI polymer binder can effectively absorb soluble transition metal ions, which is beneficial to reduce the loss of active materials. For PEI-based cathode, the uniform distribution of key components is achieved by the rapid curing process of water, which endow PEI-based cathode with a higher Li+ diffusion coefficient and improved electrochemical reaction kinetics. In addition, the fixed binder coating is favorable to protecting the active materials from parasitic reaction with the lithium hexafluorophosphate (LiPF6)-based electrolyte. Therefore, the PEI-based cell shows superior rate capability and long-term cycle performance. Functional binders of this study provide a simple and effective strategy to achieve higher capacity and longer cycle stability for transition metal oxide electrodes.

Suppressed shuttling effect of polysulfides using three-dimensional nickel hydroxide polyhedrons for advanced lithium-sulfur batteries.

In this work, controlled-size hollow polyhedron assembled by crumpled nickel hydroxide (Ni(OH)2) nanosheets from silicon dioxide (SiO2)-covered zeolitic imidazole framework-67 (ZIF-67@SiO2) is prepared via a template-sacrificed method. It is found that SiO2 plays an essential role in keeping intact polyhedrons and suppressing particle growth. Benefiting from structural and compositional advantages, the Ni(OH)2@S electrode exhibits high specific capacity, excellent rate performance, and stable cycle life at 1C with a small capacity decay of 0.067% per cycle. The Ni(OH)2 hollow polyhedrons can accommodate the volume expansion to maintain the integrity of the electrode and suppress the shuttling effect of polysulfides via abundant hydroxyl groups. Hence, this strategy is beneficial to anticipate the material for large-scale applications.

Nickel Hollow Spheres Concatenated by Nitrogen-Doped Carbon Fibers for Enhancing Electrochemical Kinetics of Sodium-Sulfur Batteries.

The high energy density of room temperature (RT) sodium-sulfur batteries (Na-S) usually rely on the efficient conversion of polysulfide to sodium sulfide during discharging and sulfur recovery during charging, which is the rate-determining step in the electrochemical reaction process of Na-S batteries. In this work, a 3D network (Ni-NCFs) host composed by nitrogen-doped carbon fibers (NCFs) and Ni hollow spheres is synthesized by electrospinning. In this novel design, each Ni hollow unit not only can buffer the volume fluctuation of S during cycling, but also can improve the conductivity of the cathode along the carbon fibers. Meanwhile, the result reveals that a small amount of Ni is polarized during the sulfur-loading process forming a polar Ni-S bond. Furthermore, combining with the nitrogen-doped carbon fibers, the Ni-NCFs composite can effectively adsorb soluble polysulfide intermediate, which further facilitates the catalysis of the Ni unit for the redox of sodium polysulfide. In addition, the in situ Raman is employed to supervise the variation of polysulfide during the charging and discharging process. As expected, the freestanding S@Ni-NCFs cathode exhibits outstanding rate capability and excellent cycle performance.

Cobalt nanoparticles embedded into free-standing carbon nanofibers as catalyst for room-temperature sodium-sulfur batteries.

Room-temperature sodium-sulfur (RT Na-S) batteries are seriously limited because of poor conductivity of sulfur and sluggish reaction kinetics of polysulfide intermediates. Here, we design a free-standing film, constructed from Co nanoparticles onto nitrogen-doped porous carbon nanofibers (Co@NPCNFs), to load sulfur for RT Na-S batteries. Experiment result shows that Co as catalyst can enable the rapid sodium intercalation and fast reduction reaction of the polysulfides during cycling. Hence, the prepared Co@NPCNFs/S cathode exhibits a remarkable capacity of 906 mAh g-1 at 0.1 C and long cycling life up to 800 cycles with a slow capacity decay of 0.038% per cycle at 1 C.

Design and Construction of Sodium Polysulfides Defense System for Room-Temperature Na-S Battery.

Room-temperature Na-S batteries are facing one of the most serious challenges of charge/discharge with long cycling stability due to the severe shuttle effect and volume expansion. Herein, a sodium polysulfides defense system is presented by designing and constructing the cathode-separator double barriers. In this strategy, the hollow carbon spheres are decorated with MoS2 (HCS/MoS2) as the S carrier (S@HCS/MoS2). Meanwhile, the HCS/MoS2 composite is uniformly coated on the surface of the glass fiber as the separator. During the discharge process, the MoS2 can adsorb soluble polysulfides (NaPSs) intermediates and the hollow carbon spheres can improve the conductivity of S as well as act as the reservoir for electrolyte and NaPSs, inhibiting them from entering the anode to make Na deteriorate. As a result, the cathode-separator group applied to room-temperature Na-S battery can enable a capacity of ≈1309 mAh g-1 at 0.1 C and long cycling life up to 1000 cycles at 1 C. This study provides a novel and effective way to develop durable room-temperature Na-S batteries.

A labyrinth-like network electrode design for lithium-sulfur batteries.

The volume expansion of sulfur and the dissolution of polysulfides into the electrolyte are the key issues to be solved in the development of lithium-sulfur batteries. In this work, a labyrinth electrode material design is presented to overcome these difficulties in lithium-sulfur batteries. The shell of NiO-Co3O4 hollow spheres as the "wall" to prevent the polysulfide dissolution cross-links into a labyrinth network as a sulfur host. The 3D labyrinth network not only provides enough inner space to load sulfur but also adapts to its large volume expansion during lithiation and delithiation. In addition, the polar NiO-Co3O4 shells can promote the chemical adsorption of polysulfides, while NiO-Co3O4 shells can promote the conversion of polysulfides into Li2S. With this unique design, the 3D labyrinth-like NiO-Co3O4@S electrode presents a good electrochemical performance, delivering high capacity with a stable cycling life of up to 200 cycles at 1C and the attenuation rate of each cycle is only 0.1%.

Rechargeable K-Se batteries based on metal-organic-frameworks-derived porous carbon matrix confined selenium as cathode materials.

In this work, porous carbon matrix derived from metal-organic frameworks is synthesized by a facile carbonation process for confining element selenium. The Se/nitrogen-doped porous carbon composite is applied as the cathode for rechargeable K-Se batteries for the first time. The abundant and hierarchical porous structure is advantageous in overcoming the volume expansion problem caused by polyselenides during discharge-charge process. The in-situ nitrogen-doped porous carbon enhances electronic conductivity of the cathode composite material. The electrochemical result shows that the as-obtained Se/nitrogen-doped porous carbon composite with Se content of 53% delivers good rate capacity with coulombic efficiency of nearly ∼90% and a reversible cycling capacity of 327 mA h g-1 at 0.2 C, maintaining about 130 mA h g-1 even after 100 cycles.

Self-Supported FeCo2S4 Nanotube Arrays as Binder-Free Cathodes for Lithium-Sulfur Batteries.

Inhibiting the shuttle effect, buffering the volume expansion, and improving the utilization of sulfur have been the three strategic points for developing a high-performance lithium-sulfur (Li-S) battery. Driven by this background, a flexible sulfur host material composed of FeCo2S4 nanotube arrays grown on the surface of carbon cloth is designed for a binder-free cathode of the Li-S battery through two-step hydrothermal method. Among the rest, the interconnected carbon fiber skeleton of the composite electrode ensures the basic electrical conductivity, whereas the FeCo2S4 nanotube arrays not only boost the electron and electrolyte transfer but also inhibit the dissolution of polysulfides because of their strong chemical adsorption. Meanwhile, the hollow structures of these arrays can provide a large inner space to accommodate the volume expansion of sulfur. More significantly, the developed composite electrode also reveals a catalytic action for accelerating the reaction kinetic of the Li-S battery. As a result, the FeCo2S4/CC@S electrode delivers a high discharge capacity of 1384 mA h g-1 at the current density of 0.1 C and simultaneously exhibits a stable Coulombic efficiency of about 98%.

Improving the Performance of Hard Carbon//Na3V2O2(PO4)2F Sodium-Ion Full Cells by Utilizing the Adsorption Process of Hard Carbon.

Hard carbon has been regarded as a promising anode material for Na-ion batteries. Here, we show, for the first time, the effects of two Na+ uptake/release routes, i.e., adsorption and intercalation processes, on the electrochemical performance of half and full sodium batteries. Various Na+-storage processes are isolated in full cells by controlling the capacity ratio of anode/cathode and the sodiation state of hard carbon anode. Full cells utilizing adsorption region of hard carbon anode show better cycling stability and high rate capability compared to those utilizing intercalation region of hard carbon anode. On the other hand, the intercalation region promises a high working voltage full cell because of the low Na+ intercalation potential. We believe this work is enlightening for the further practical application of hard carbon anode.