High Structural Stability and Reaction Mechanism of Porous Carbon Nanobox Encapsulated Monodisperse CoP Nanoparticles for High‐Performance Lithium‐Ion Battery

Abstract

Transition metal phosphides (TMPs) are perplexed by the low electronic/ionic conductivity, volume variations, and unstable reaction interfaces. To tackle these issues, herein, we have proposed a low‐temperature phosphorization strategy by reactions between Co‐based metal‐organic frameworks (MOF) and sodium dihydric hypophosphite to encapsulate monodisperse CoP nanoparticle (∼12 nm) into MOF‐derived hollow and porous carbon nanobox (CoP@PCB). Compared to bare CoP, such CoP@PCB electrode has shown remarkable electrochemical performance, which is highly ascribed to its robust structural feature, pre‐reserved voids, monodisperse CoP nanoparticles, and stable reaction interfaces, as well as fast reaction kinetics. Moreover, the good electrochemical properties of CoP@PCB//LiFePO4 full cells have demonstrated practical possibility. The formation of Co and Li3P as discharged products has corroborated the redox conversion reaction mechanism, as assessed by in‐situ X‐ray diffractions. The favorable function of the carbon shell in boosting both electronic conductivity and lowering diffusion energy barriers has been confirmed by theoretical calculations, demonstrating an important synergistic effect.

State‐of‐the‐Art Two‐Dimensional Metal Phosphides for High Performance Lithium‐ion Batteries: Progress and Prospects

“…monophosphorus MPs (M/P = 1) FeP [49,50] CoP [37,51] 912 894 structure (Figure 2c). Due to its unique spatial structure, CoP synthesized by CVD method shows ultrathin porous nanosheet with a high ratio (200) of crystalline plane.…”

“…The high theoretical capacity of 2D MPs is partly attributed to phosphorus component, which possesses the extremely high capacity (2596 mAh g À 1 ). [32][33][34][35][36][37] Moreover, the main group metal can form alloy (e. g. In 3 Li 13 , Li 4.4 Ge and Li 4.4 Sn) with lithium to contribute high capacity. [38,39] Not only that, the high conductivity of metal endows MPs higher electron transport ability.…”

“…reported Ni 2 P nanosheets by Ni template method and used them as anode, [47] which achieved good lithium storage performance. The high theoretical capacity of 2D MPs is partly attributed to phosphorus component, which possesses the extremely high capacity (2596 mAh g −1 ) [32–37] . Moreover, the main group metal can form alloy (e. g. In 3 Li 13 , Li 4.4 Ge and Li 4.4 Sn) with lithium to contribute high capacity [38,39] .…”

3D Porous N and S Co-doped CNT Microspheres with Highly Dispersed CoP Nanoparticles: Toward an Efficient Bifunctional Electrocatalyst for Zn-Air Batteries

“…Peaks at 786.7, 784.1, and 803.1 eV are associated with satellite peaks [45,46]. The P 2p spectrum could be divided into three peaks observed at 129.6, 130.1, and 134.4 eV, corresponding to P 2p 3/2 , P 2p 1/ 2 , and the P-O bonding originating from the surface oxidation of CoP due to air exposure, respectively (Figure 5(c)) [47][48][49]. Thermogravimetric analysis (TGA) was conducted to confirm the loading mass of CoP in the composite microsphere, and the corresponding data is shown in Figure S7.…”