Encapsulation of Red Phosphorus in Carbon Nanocages with Ultrahigh Content for High-Capacity and Long Cycle Life Sodium-Ion Batteries

Liu, Weili; Du, Lei; Ju, Shunlong; Cheng, Xueyi; Wu, Qiang; Hu, Zheng; Xia, Guanglin

doi:10.1021/acsnano.1c00924

Cited by 67 publications

(38 citation statements)

References 53 publications

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“…[37] However, much more extensive structural models are likely required to correctly describe alkali-metal insertion in a-P. In terms of composite materials, the encapsulation of P 4 molecules in carbon nanotubes [38] and the interaction of small phosphorus clusters with pristine graphene [39] have been studied with DFT; building on such ideas, much larger-scale ML-based simulations of a-P segments in carbon nanofibers (>10 nm in diameter), such as those experimentally characterized in ref. [35], could be envisioned in the future.…”

Section: Introductionmentioning

confidence: 99%

Cluster Fragments in Amorphous Phosphorus and their Evolution under Pressure

2021

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such as "ab initio" molecular dynamics (AIMD). ML-based interatomic potentials, therefore, are beginning to be applied to a range of challenging materials-science research questions, such as the modeling of phase-change memory materials, [12][13][14] catalysts, [15] or battery materials. [16] Recently, a number of "general-purpose" ML potentials have been reported, which can accurately describe a broad range of atomic configurations and materials properties-including silicon, [17] carbon, [18] aluminum, [19,20] and the binary Ga-As system. [21] The hope for such potentials is to enable "off-the-shelf" use without further modification: for example, the aforementioned silicon ML potential has been used to study complex structural transitions under pressure [22] or unusual mechanical properties of amorphous silicon (a-Si). [23] The starting point for the present study is a general-purpose Gaussian approximation potential (GAP) ML model for bulk and nanostructured phosphorus-which was shown to be flexible enough to be applicable to the pressure-induced liquidliquid phase transition from the molecular fluid to the network liquid, whilst also accurately describing the crystalline allotropes and the layered structure of phosphorene. [24] This GAP is now set to facilitate even more challenging studies on more extended length or time scales, and the exploration of other structurally complex phases for which it has not been explicitly "trained", such as amorphous phosphorus (a-P).Research interest in a-P has grown because of emerging applications in batteries. [25][26][27][28] As a commercially available anode material, red phosphorus provides a large cation-storage ability with high theoretical capacities by forming binary X-P compounds (X = Li, Na, K), but it suffers from low conductivity and a large volumetric change during cycling. [29] As discussed in ref. [30], these issues can be ameliorated by creating composites of a-P and carbonaceous materials: on the one hand, increasing electronic conductivity; [31,32] on the other hand, minimizing the mechanical stress induced by volume changes. [30,33] The structure and properties of phosphorus itself are clearly important for battery applications: for example, experimental work showed that the size of a-P particles in phosphoruscarbon composite anodes has an effect on the electrochemical performance, [34] and in situ transmission electron microscopy (TEM) revealed images of red phosphorus segments within a carbon nanofiber. [35] Computationally, structurally ordered phases have been studied with density-functional theory (DFT; Amorphous phosphorus (a-P) has long attracted interest because of its complex atomic structure, and more recently as an anode material for batteries. However, accurately describing and understanding a-P at the atomistic level remains a challenge. Here, it is shown that large-scale molecular-dynamics simulations, enabled by a machine-learning (ML)-based interatomic potential for phosphorus, can give new insights into the atomic structure of a-P and how...

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Section: Introductionmentioning

confidence: 99%

Cluster Fragments in Amorphous Phosphorus and their Evolution under Pressure

2021

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“…Although the theoretical capacity of red phosphorus (RP) reaches as high as 2596 mAh/g, its practical application as anode for SIBs is still limited by its inherent low electronic conductivity (10 −14 S/cm). In this regard, RP NPs has been tried to be encapsulated into the conductive and networked carbon nanocages (CNC) to prepare the RP@CNC composite [102] . Based on DFT calculations (Figure 12A), the adsorption energy of P nucleated in micropores (−0.78 eV) was higher than that in carbon layers without micropores (−0.66 eV), suggesting that the micropores of CNCs were more beneficial for the nucleation and growth of P. Besides, an electric field could be established from the carbon layer to RP that a charge accumulation zone was formed at the interface between the carbon layer and RP, while a charge depletion zone on the RP plate, and thus the high loading of RP (85.3 wt%) on CNC could be achieved.…”

Section: Application Of 3d‐carbon In Sibs Electrode Materialsmentioning

confidence: 99%

“…In this regard, RP NPs has been tried to be encapsulated into the conductive and networked carbon nanocages (CNC) to prepare the RP@CNC composite. [102] Based on DFT calculations (Figure 12A), the adsorption energy of P nucleated in micropores (À 0.78 eV) was higher than that in carbon layers without micropores (À 0.66 eV), suggesting that the micropores of CNCs were more beneficial for the nucleation and growth of P. Besides, an electric field could be established from the carbon layer to RP that a charge accumulation zone was formed at the interface between the carbon layer and RP, while a charge depletion zone on the RP plate, and thus the high loading of RP (85.3 wt%) on CNC could be achieved. This result has been confirmed by EDS and TGA, and the content is higher than any other reported RP-carbon-based composite as SIBs anode so far.…”

Section: Alloying Materialsmentioning

confidence: 99%

3D Carbon Networks: Design and Applications in Sodium Ion Batteries

2021

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As the key component of a new generation for low‐cost energy storage systems, sodium‐ion batteries (SIBs) have attracted enormous attention and research due to its promising potentiality in large‐scale electrochemical energy storage. For practical application of SIBs, carbonaceous materials have been considered to be one of the best choices for electrodes in virtue of their abundant reserves, low cost, easy availability, and environmental friendliness. 3D carbon network (3D‐carbon) is of particular interests, which has displayed outstanding features, including abundant active sites, interconnected multi‐level pore structures, high electronic conductivity, and excellent mechanical stability. Herein, we review the structural advantages of 3D‐carbon and its preparation methods, and then discuss recent progress in 3D carbon materials and their composites for SIBs. The superior functionalities of 3D‐carbon are emphasized as support templates or encapsulation shell membranes. Finally, we summarize and outline the challenges and future prospects of 3D‐carbon in SIBs.

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“…Various electrocatalysts have been explored [ 5 ] even though platinum (Pt) still represents the state‐of‐the‐art electrocatalyst for acid HER as before. [ 6 ] Noble metal‐free catalysts, [ 7 ] metal‐free catalysts, [ 8 ] heteroatom‐doped carbon materials, [ 9 ] have exhibited decent activities in HER. Nevertheless, there is still a great difference between the activities of those catalysts and the most advanced Pt‐based catalysts.…”

Section: Introductionmentioning

confidence: 99%

Superfast Synthesis of Densely Packed and Ultrafine Pt–Lanthanide@KB via Solvent‐Free Microwave as Efficient Hydrogen Evolution Electrocatalysts

Nie

Zhang

Wang

et al. 2021

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At present, it is still a great challenge to synthesize refractory Pt‐based electrocatalysts with excellent active specific surface area, specific activity, and stability by a simple method. Here, a superfast and solvent‐free microwave strategy is reported to synthesize refractory ultrafine (≈3 nm) Pt–lanthanide@Ketjen Black (PtM@KB, M = La, Gd, Tb, Er, Tm, and Yb) alloy with densely packed as efficient hydrogen evolution electrocatalysts in a domestic microwave oven for the first time. The optimized Pt61La39@KB delivers excellent hydrogen evolution reaction (HER) activity with a low overpotential of 38 mV (10 mA cm−2) and a high TOF value of 44.13 s−1 (100 mV) in 0.5 m H2SO4, and performs well in 1.0 m KOH. This method can also be used to grow catalysts on carbon cloth (CC) directly. PtLa@CC shows an overpotential of 99 mV (1000 mA cm−2) in 0.5 m H2SO4 and can maintain activity after 500 h. Theoretical calculations reveal the enhanced stability and activity owing to the higher vacancy formation energy of Pt atoms and the optimized value of ΔGH*. Solvent‐free microwave strategy constitutes a significant insight into the development of refractory electrocatalyst with ultrafine size and highly dense, which can also work well at high current densities.

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Encapsulation of Red Phosphorus in Carbon Nanocages with Ultrahigh Content for High-Capacity and Long Cycle Life Sodium-Ion Batteries

Cited by 67 publications

References 53 publications

Cluster Fragments in Amorphous Phosphorus and their Evolution under Pressure

Cluster Fragments in Amorphous Phosphorus and their Evolution under Pressure

3D Carbon Networks: Design and Applications in Sodium Ion Batteries

Superfast Synthesis of Densely Packed and Ultrafine Pt–Lanthanide@KB via Solvent‐Free Microwave as Efficient Hydrogen Evolution Electrocatalysts

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