Structural phase transitions can be used to alter the properties of a material without adding any additional elements and are therefore of significant technological value. It was found that the hexagonal-SnS2 phase can be transformed into the orthorhombic-SnS phase after an annealing step in an argon atmosphere, and the thus transformed SnS shows enhanced sodium-ion storage performance over that of the SnS2, which is attributed to its structural advantages. Here, we provide the first report on a SnS@graphene architecture for application as a sodium-ion battery anode, which is built from two-dimensional SnS and graphene nanosheets as complementary building blocks. The as-prepared SnS@graphene hybrid nanostructured composite delivers an excellent specific capacity of 940 mAh g(-1)and impressive rate capability of 492 and 308 mAh g(-1) after 250 cycles at the current densities of 810 and 7290 mA g(-1), respectively. The performance was found to be much better than those of most reported anode materials for Na-ion batteries. On the basis of combined ex situ Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and ex situ X-ray diffraction, the formation mechanism of SnS@graphene and the synergistic Na-storage reactions of SnS in the anode are discussed in detail. The SnS experienced a two-structural-phase transformation mechanism (orthorhombic-SnS to cubic-Sn to orthorhombic-Na3.75Sn), while the SnS2 experienced a three-structural-phase transformation mechanism (hexagonal-SnS2 to tetragonal-Sn to orthorhombic-Na3.75Sn) during the sodiation process. The lesser structural changes of SnS during the conversion are expected to lead to good structural stability and excellent cycling stability in its sodium-ion battery performance. These results demonstrate that the SnS@graphene architecture offers unique characteristics suitable for high-performance energy storage application.
Potassium‐ion batteries (PIBs) are promising energy storage systems because of the abundance and low cost of potassium. The formidable challenge is to develop suitable electrode materials and electrolytes for accommodating the relatively large size and high activity of potassium. Herein, Bi‐based materials are reported as novel anodes for PIBs. Nanostructural design and proper selection of the electrolyte salt have been used to achieve excellent cycling performance. It is found that the potassiation of Bi undergoes a solid‐solution reaction, followed by two typical two‐phase reactions, corresponding to Bi ↔ Bi(K) and Bi(K) ↔ K5Bi4 ↔ K3Bi, respectively. By choosing potassium bis(fluorosulfonyl)imide (KFSI) to replace potassium hexafluorophosphate (KPF6) in carbonate electrolyte, a more stable solid electrolyte interphase layer is achieved and results in notably enhanced electrochemical performance. More importantly, the KFSI salt is very versatile and can significantly promote the electrochemical performance of other alloy‐based anode materials, such as Sn and Sb.
This work provides a feasible approach to overcome the durability bottlenecks of potassium-ion batteries (PIBs) through regulating dendrite growth and solidelectrolyte interphase formation. In operando synchrotron XRD studies suggested that Sn 4 P 3 anodes undergo a sequential conversion (P to K 3 P 11 , K 3 P) and alloying (Sn to KSn) reactions with a synergistic K-storage mechanism. We hope that this work inspires robust developments in exploring phosphorus-based anode materials in PIBs through materials design and manipulation of the salt/additive chemistry of the electrolytes.
As an emerging electrochemical energy storage device, potassium-ion batteries (PIBs) have drawn growing interest due to the resource-abundance and low cost of potassium. Graphite-based materials, as the most common anodes for commercial Li-ion batteries, have a very low capacity when used an anode for Na-ion batteries, but they show reasonable capacities as anodes for PIBs. The practical application of graphitic materials in PIBs suffers from poor cyclability, however, due to the large interlayer expansion/ shrinkage caused by the intercalation/deintercalation of potassium ions. Here, a highly graphitic carbon nanocage (CNC) is reported as a PIBs anode, which exhibits excellent cyclability and superior depotassiation capacity of 175 mAh g-1at 35 C. The potassium storage mechanism in CNC is revealed by cyclic voltammetry as due to redox reactions (intercalation/deintercalation) and double-layer capacitance (surface adsorption/desorption). The present results give new insights into structural design for graphitic anode materials in PIBs and understanding the double-layer capacitance effect in alkali metal ion batteries.
Solid-electrolyte interphase (SEI) is highly designable to restrain Zn dendrite growth and side reactions between Zn anode and water in rechargeable aqueous zinc-ion batteries (RAZBs), but it remains a challenge....
Owing to their high conductivity, crystalline Li 7-3x Ga x La 3 Zr 2 O 12 garnets are promising electrolytes for allsolid-state lithium-ion batteries. Herein, the influence of Ga doping on the phase, lithium-ion distribution, and conductivity of Li 7-3x Ga x La 3 Zr 2 O 12 garnets is investigated, with the determined concentration and mobility of lithium ions shedding light on the origin of the high conductivity of Li 7-3x Ga x La 3 Zr 2 O 12 . When the Ga concentration exceeds 0.20 Ga per formula unit, the garnet-type material is found to assume a cubic structure, but lower Ga concentrations result in the coexistence of cubic and tetragonal phases. Most lithium within Li 7-3x Ga x La 3 Zr 2 O 12 is found to reside at the octahedral 96h site, away from the central octahedral 48g site, while the remaining lithium resides at the tetrahedral 24d site. Such kind of lithium distribution leads to high lithium-ion mobility, which is the origin of the high conductivity; the highest lithium-ion conductivity of 1.46 mS/cm at 25 °C is found to be achieved for Li 7-3x Ga x La 3 Zr 2 O 12 at x = 0.25. Additionally, there are two lithium-ion migration pathways in the Li 7-3x Ga x La 3 Zr 2 O 12 garnets: 96h-96h and 24d-96h-24d, but the lithium ions transporting through the 96h-96h pathway determine the overall conductivity. Disciplines Engineering | Physical Sciences and Mathematics
Ultrathin 2D materials can offer promising opportunities for exploring advanced energy storage systems, with satisfactory electrochemical performance. Engineering atomic interfaces by stacking 2D crystals holds huge potential for tuning material properties at the atomic level, owing to the strong layer-layer interactions, enabling unprecedented physical properties. In this work, atomically thin Bi MoO sheets are acquired that exhibit remarkable high-rate cycling performance in Li-ion batteries, which can be ascribed to the interlayer coupling effect, as well as the 2D configuration and intrinsic structural stability. The unbalanced charge distribution occurs within the crystal and induces built-in electric fields, significantly boosting lithium ion transfer dynamics, while the extra charge transport channels generated on the open surfaces further promote charge transport. The in situ synchrotron X-ray powder diffraction results confirm the material's excellent structural stability. This work provides some insights for designing high-performance electrode materials for energy storage by manipulating the interface interaction and electronic structure.
Earth-abundant potassium is a promising alternative to lithium in rechargeable batteries, but a pivotal limitation of potassium-ion batteries is their relatively low capacity and poor cycling stability. Here, a high-performance potassium-ion battery is achieved by employing few-layered antimony sulfide/carbon sheet composite anode fabricated via one-step high-shear exfoliation in ethanol/water solvent. Antimony sulfide with few-layered structure minimizes the volume expansion during potassiation and shortens the ion transport pathways, thus enhancing the rate capability; while carbon sheets in the composite provide electrical conductivity and maintain the electrode cycling stability by trapping the inevitable by-product, elemental sulfur. Meanwhile, the effect of the exfoliation solvent on the fabrication of two-dimensional antimony sulfide/carbon is also investigated. It is found that water facilitates the exfoliation by lower diffusion barrier along the [010] direction of antimony sulfide, while ethanol in the solvent acts as the carbon source for in situ carbonization.
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