Self-Templated Formation of Fluffy Graphene-Wrapped Ni₅P₄ Hollow Spheres for Li-Ion Battery Anodes with High Cycling Stability

Abstract

Transition-metal phosphides have gained great importance in the field of energy conversion and storage such as electrochemical water splitting, fuel cells, and Li-ion batteries. In this study, a rationally designed novel fluffy graphene (FG)wrapped monophasic Ni 5 P 4 (Ni 5 P 4 @FG) is in-situ-synthesized using a chemical vapor deposition method as a Li-ion battery anode material. The porous and hollow structure of Ni 5 P 4 core is greatly helpful for lithium-ion diffusion, and at the same time, the cilia-like graphene nanosheet shell provides an electron-conducting layer and stabilizes the solid electrolyte interface formed on the Ni 5 P 4 surface. The Ni 5 P 4 @FG sample shows a high reversible capacity of 739 mAh g −1 after 300 cycles at a specific current density of 500 mA g −1 . The high capacity, superior cycling stability, and improved rate capability of Ni 5 P 4 @FG are ascribed to its unique hierarchical structure. Moreover, the present efficient fabrication methodology of Ni 5 P 4 @FG has potential to be developed as a general method for the synthesis of other transition-metal phosphides.

Phosphorus/Phosphide‐Based Materials for Alkali Metal‐Ion Batteries

“…Impressively, the serious volume changes would induce the continuous generation and broken of solid electrolyte interface (SEI) layers, [ 39 , 40 ] thus consuming the electrolyte and degrading the cyclic stability and Coulumbic efficiency (CE). [ 41 , 46 ] To resolve these pressing issues, the promising strategies included the hybridization of phosphorus‐ and phosphide‐based materials with conductive materials (e.g., carbonaceous materials and conductive polymers) and constructing unique micro‐ and nanostructures, [ 42 , 49 ] which can boost the electron transfer, provide enough space for volume changes and enhance the entire structural integrity of electrode.…”

“…However, similar to pure phosphorus, phosphides suffered from low electrical conductivity and significant volume expansion. Hybridizing phosphides with carbonaceous materials can solve the above issues, and the adopted carbonaceous materials include graphene, [ 49 ] carbon nanotubes (CNTs), [ 50 ] and porous carbon matrices. [ 51 ] For instance, Zhao et al.…”

Deciphering the lithium storage chemistry in flexible carbon fiber‐based self‐supportive electrodes

“…These studies showed that the conversion reaction process can be expressed as follows: MP + xLi + + e ─ → Li 3 P + M (where M represents transition metals). [25][26][27] However, the in-depth mechanistic contribution of the CFC was not emphasized. 17,28 Compared to CoP, nickel phosphides have also been utilized as electrode materials for energy storage devices.…”

Sulfide-Fixed Intrinsic Porous NiCoP for Boosting High Capacitance and Long-Term Stability

“…2,3 BTMPs have the advantages of high conductivity, earth-abundant reserves, and good physicochemical properties. 4,5 However, the lack of high activity and unstable structure of BTMPs are the main obstacles to their practical applications in energy storage fields. Many efforts have been devoted to improving their activity and stability, including (1) modulation of active sites through heteroatom doping and vacancy engineering 6−8 and (2) multicomponent and multidimensional structure design of nanocomposites and morphology.…”

“…Binary transition metal phosphides (BTMPs) consisting of phosphorus with d and f metals are widely used in electrocatalysis, photocatalysis, and electrochemistry. , BTMPs have the advantages of high conductivity, earth-abundant reserves, and good physicochemical properties. , However, the lack of high activity and unstable structure of BTMPs are the main obstacles to their practical applications in energy storage fields. Many efforts have been devoted to improving their activity and stability, including (1) modulation of active sites through heteroatom doping and vacancy engineering − and (2) multicomponent and multidimensional structure design of nanocomposites and morphology. − These conventional methods are usually cumbersome and do not have significant effects.…”