Carbon-based material has been regarded as one of the most promising electrode materials for potassium-ion batteries (PIBs). However, the battery performance based on reported porous carbon electrodes is still unsatisfactory, while the in-depth K-ion storage mechanism remains relatively ambiguous. Herein, we propose a facile “in situ self-template bubbling” method for synthesizing interlayer-tuned hierarchically porous carbon with different metallic ions, which delivers superior K-ion storage performance, especially the high reversible capacity (360.6 mAh·g−1@0.05 A·g−1), excellent rate capability (158.6 mAh·g−1@10.0 A·g−1) and ultralong high-rate cycling stability (82.8% capacity retention after 2,000 cycles at 5.0 A·g−1). Theoretical simulation reveals the correlations between interlayer distance and K-ion diffusion kinetics. Experimentally, deliberately designed consecutive cyclic voltammetry (CV) measurements, ex situ Raman tests, galvanostatic intermittent titration technique (GITT) method decipher the origin of the excellent rate performance by disentangling the synergistic effect of interlayer and pore-structure engineering. Considering the facile preparation strategy, superior electrochemical performance and insightful mechanism investigations, this work may deepen the fundamental understandings of carbon-based PIBs and related energy storage devices like sodium-ion batteries, aluminum-ion batteries, electrochemical capacitors, and dual-ion batteries.
Sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) have been considered as attractive alternatives for next-generation battery systems, which have promising application potential due to their earth abundance of potassium and sodium, high capacity and suitable working potential, however, the design and application of bi-functional high-performance anode still remain a great challenge up to date. Bismuth sulfide is suitable as anode owing to its unique laminar structure with relatively large interlayer distance to accommodate larger radius ions, high theoretical capacity and high volumetric capacity etc. In this study, dandelion-like Bi2S3/rGO hierarchical microspheres as anode material for PIBs displayed reversible capacity, and 206.91 mAh·g−1 could be remained after 1,200 cycles at a current density of 100 mA·g−1. When applied as anode materials for SIBs, 300 mAh·g−1 could be retained after 300 cycles at 2 A·g−1 and its initial Coulombic efficiency is as high as 97.43%. Even at high current density of 10 A·g−1, 120.3 mAh·g−1 could be preserved after 3,400 cycles. The Na3V2(PO4)3@rGO//Bi2S3/rGO sodium ion full cells were successfully assembled which displays stable performance after 60 cycles at 100 mA·g−1. The above results demonstrate that Bi2S3/rGO has application potential as high performance bi-functional anode for PIBs and SIBs.
Multicomponent metal sulfide materials with a yolk–shell structure and a single phase were studied for the first time as anode materials for sodium-ion batteries. Yolk–shell-structured Fe–Ni–O powders with a molar ratio of iron and nickel components of 1/1 were prepared via one-pot spray pyrolysis. The prepared Fe–Ni–O powders were transformed into yolk–shell-structured (Fe0.5Ni0.5)9S8 solid-solution powders via a sulfidation process. The initial discharge and charge capacities of the (Fe0.5Ni0.5)9S8 powders at a current density of 1 A·g−1 were 601 and 504 mA·h·g−1, respectively. The discharge capacities of the (Fe0.5Ni0.5)9S8 powders for the 2nd and 100th cycle were 530 and 527 mA·h·g−1, respectively, and their corresponding capacity retention measured from the 2nd cycle was 99%. The (Fe0.5Ni0.5)9S8 powders had high initial discharge and charge capacities at a low current density of 0.1 A·g−1, and the reversible discharge capacity decreased slightly from 568 to 465 mA·h·g−1 as the current density increased from 0.1 to 5.0 A·g−1. The synergetic effect of the novel yolk–shell structure and the multicomponent sulfide composition of the (Fe0.5Ni0.5)9S8 powders resulted in excellent sodium-ion storage performance.
Sodium-ion batteries (SIBs) have been attracting considerable attention as a promising candidate for large-scale energy storage because of the abundance and low-cost of sodium resources. However, lack of appropriate anode materials impedes further applications. Herein, a novel self-template strategy is designed to synthesize uniform flowerlike N-doped hierarchical porous carbon networks (NHPCN) with high content of N (15.31 at.%) assembled by ultrathin nanosheets via a self-synthesized single precursor and subsequent thermal annealing. Relying on the synergetic coordination of benzimidazole and 2-methylimidazole with metal ions to produce a flowerlike network, a self-formed single precursor can be harvested. Due to the structural and compositional advantages, including the high N doping, the expanded interlayer spacing, the ultrathin two-dimensional nano-sized subunits, and the three-dimensional porous network structure, these unique NHPCN flowers deliver ultrahigh reversible capacities of 453.7 mAh·g−1 at 0.1 A·g−1 and 242.5 mAh·g−1 at 1 A·g−1 for 2,500 cycles with exceptional rate capability of 5 A·g−1 with reversible capacities of 201.2 mAh·g−1. The greatly improved sodium storage performance of NHPCN confirms the importance of reasonable engineering and synthesis of hierarchical carbon with unique structures.
The low specific capacity and sluggish electrochemical reaction kinetics greatly block the development of sodium-ion batteries (SIBs). New high-performance electrode materials will enhance development and are urgently required for SIBs. Herein, we report the preparation of supersaturated bridge-sulfur and vanadium co-doped MoS2 nanosheet arrays on carbon cloth (denoted as V-MoS2+x/CC). The bridge-sulfur in MoS2 has been created as a new active site for greater Na+ storage. The vanadium doping increases the density of carriers and facilitates accelerated electron transfer. The synergistic dual-doping effects endow the V-MoS2+x/CC anodes with high sodium storage performance. The optimized V-MoS2.49/CC gives superhigh capacities of 370 and 214 mAh·g−1 at 0.1 and 10 A·g−1 within 0.4−3.0 V, respectively. After cycling 3,000 times at 2 A·g−1, almost 83% of the reversible capacity is maintained. The findings indicate that the electrochemical performances of metal sulfides can be further improved by edge-engineering and lattice-doping co-modification concept.
A three-dimensional flower-like NiCo2S4 formed by two-dimensional nanosheets is synthesized by a facile hydrothermal method and utilized as the anode for sodium-ion batteries. Studies have shown that materials can achieve the best performance under the ether-based electrolyte system with voltage ranging from 0.3 to 3 V, which could effectively avoid the dissolution of polysulfides and over-discharge of the material. Here, sodium storage mechanism and charge compensation behaviors of this ternary metal sulfide are comprehensively investigated by ex situ X-ray diffraction. Moreover, ex situ Raman spectra, ex situ X-ray photoelectron spectroscopy and transmission electron microscopy measurements are used to related tests for the first time. Additionally, quantitative kinetic analysis unravels that sodium storage partially depends on the pseudocapacitance mechanism, resulting in good specific capacity and excellent rate performance. The initial discharge capacity is as high as 748 mAh·g−1 at a current density of 0.1 A·g−1 with the initial coulomb efficiency of 94%, and the capacity can still maintain at 580 mAh·g−1 with the Coulomb efficiency close to 100% after following 50 cycles. Moreover, by the long cycle test at a high current density of 2 A·g−1, the capacity can still reach at 376 mAh·g−1 after over 500 cycles.
Aqueous Zinc-ion batteries (ZIBs), using zinc negative electrode and aqueous electrolyte, have attracted great attention in energy storage field due to the reliable safety and low-cost. A composite material comprised of VO2·0.2H2O nanocuboids anchored on graphene sheets (VOG) is synthesized through a facile and efficient microwave-assisted solvothermal strategy and is used as aqueous ZIBs cathode material. Owing to the synergistic effects between the high conductivity of graphene sheets and the desirable structural features of VO2·0.2H2O nanocuboids, the VOG electrode has excellent electronic and ionic transport ability, resulting in superior Zn ions storage performance. The Zn/VOG system delivers ultrahigh specific capacity of 423 mAh·g−1 at 0.25 A·g−1 and exhibits good cycling stability of up to 1,000 cycles at 8 A·g−1 with 87% capacity retention. Systematical structural and elemental characterizations confirm that the interlayer space of VO2·0.2H2O nanocuboids can adapt to the reversible Zn ions insertion/extraction. The as-prepared VOG composite is a promising cathode material with remarkable electrochemical performance for low-cost and safe aqueous rechargeable ZIBs.
Sodium-ion batteries (SIBs) have great promise for sustainable and economical energy-storage applications. Nevertheless, it is a major challenge to develop anode materials with high capacity, high rate capability, and excellent cycling stability for them. In this study, FeSe2 clusters consisting of nanorods were synthesized by a facile hydrothermal method, and their sodium-storage properties were investigated with different electrolytes. The FeSe2 clusters delivered high electrochemical performance with an ether-based electrolyte in a voltage range of 0.5–2.9 V. A high discharge capacity of 515 mAh·g–1 was obtained after 400 cycles at 1 A·g–1, with a high initial columbic efficiency of 97.4%. Even at an ultrahigh rate of 35 A·g–1, a specific capacity of 128 mAh·g–1 was achieved. Using calculations, we revealed that the pseudocapacitance significantly contributed to the sodium-ion storage, especially at high current rates, leading to a high rate capability. The high comprehensive performance of the FeSe2 clusters makes them a promising anode material for SIBs.
Carbon coating has been a routine strategy for improving the performance of Si-based anode materials for lithium-ion batteries. The ability to tailor the thickness, homogeneity and graphitization degree of carbon-coating layers is essential for addressing issues that hamper the real applications of Si anodes. Herein, we report the construction of two-dimensional (2D) assemblies of interconnected Si@graphitic carbon yolk-shell nanoparticles (2D-Si@gC) from commercial Si powders by exploiting oleic acid (OA). The OA molecules act as both the surface-coating ligands for facilitating 2D nanoparticle assembly and the precursor for forming uniform and conformal graphitic shells as thin as 4 nm. The as-prepared 2D-Si@gC with rationally designed void space exhibits excellent rate capability and cycling stability when used as anode materials for lithium-ion batteries, delivering a capacity of 1,150 mAh·g−1 at an ultrahigh current density of 10 A·g−1 and maintaining a stabilized capacity of 1,275 mAh·g−1 after 200 cycles at 4 A·g−1. The formation of yolk-shell nanoparticles confines the deposition of solid electrolyte interphase (SEI) onto the outer carbon shell, while simultaneously providing sufficient space for volumetric expansion of Si nanoparticles. These attributes effectively mitigate the thickness variations of the entire electrode during repeated lithiation and delithiation, which combined with the unique 2D architecture and interconnected graphitic carbon shells of 2D-Si@gC contributes to its superior rate capability and cycling performance.
Porous Si can be synthesized from diverse silica (SiO2) via magnesiothermic reduction technology and widely employed as potential anode material in lithium ion batteries. However, concerns regarding the influence of residual silicon oxide (SiOx) component on resulted Si anode after reduction are still lacked. In this work, we intentionally fabricate a cauliflower-like silicon/silicon oxide (CF-Si/SiOx) particles from highly porous SiO2 spheres through insufficient magnesiothermic reduction, where residual SiOx component and internal space play an important role in preventing the structural deformation of secondary bulk and restraining the expansion of Si phase. Moreover, the hierarchically structured CF-Si/SiOx exhibits uniformly-dispersed channels, which can improve ion transport and accommodate large volume expansion, simultaneously. As a result, the CF-Si/SiOx-700 anode shows excellent electrochemical performance with a specific capacity of ~1,400 mA·h·g−1 and a capacity retention of 98% after 100 cycles at the current of 0.2 A·g−1.
Porous graphitic carbon nanorings (PGCNs) are proposed by smart catalytic graphitization of nano-sized graphene quantum dots (GQDs). The as-prepared PGCNs show unique ring-like morphology with diameter around 10 nm, and demonstrate extraordinary mesoporous structure, controllable graphitization degree and highly defective nature. The mechanism from GQDs to PGCNs is proven to be a dissolution-precipitation process, undergoing the procedure of amorphous carbon, intermediate phase, graphitic carbon nanorings and graphitic carbon nanosheets. Further, the relationship between particles size of GQDs precursor and graphitization degree of PGCNs products is revealed. The unique microstructure implies PGCNs a broad prospect for energy storage application. When applied as negative electrode materials in dual-carbon lithium-ion capacitors, high energy density (77.6 Wh·kg−1) and super long lifespan (89.5% retention after 40,000 cycles at 5.0 A·g−1) are obtained. The energy density still maintains at 24.5 Wh·kg−1 even at the power density of 14.1 kW·kg−1, demonstrating excellent rate capability. The distinct microstructure of PGCNs together with the strategy for catalytic conversion from nanocarbon precursors to carbon nanorings opens a new window for carbon materials in electrochemical energy storage.