Phytic Acid-Assisted Formation of Hierarchical Porous CoP/C Nanoboxes for Enhanced Lithium Storage and Hydrogen Generation

Abstract

Application of transition metal phosphides (TMPs) for electrochemical energy conversion and storage has great potential to alleviate the energy crisis. Although there are many methods to get TMPs, it is still immensely challenging to fabricate hierarchical porous TMPs with superior electrochemical performances by a simple, green, and secure approach. Herein, we report a facile method to synthesize the CoP/C nanoboxes by pyrolysis of phytic acid (PA) cross-linked Co complexes that are acquired from reaction of PA and ZIF-67. The PA can not only slowly etch ZIF-67 and gain a hollow structure but also act as a source of phosphorus to prepare CoP/C nanoboxes. The CoP/C nanoboxes deliver an ultrahigh specific capacity (868 mA h g −1 at 100 mA g −1 ) and excellent cycle stability (523 mA h g −1 after 1000 cycles at 500 mA h g −1 ) when used as anode materials for lithium-ion batteries. Moreover, when used as an electrocatalyst for hydrogen evolution reaction, the CoP/C nanoboxes exhibit ultralow overpotential, small Tafel slope, and excellent durability in acidic media.

Multifunctional Transition Metal‐Based Phosphides in Energy‐Related Electrocatalysis

“…Thereby, Co 0.6 Fe 0.4 P nanoframes presented better performance in both HER and OER as compared with that of Co 0.6 Fe 0.4 P nanocubes. Similar work could be found in hierarchical porous CoP/C nanoboxes, which used phytic acid as the etchant …”

“…Similar work could be found in hierarchical porous CoP/C nanoboxes, which used phytic acid as the etchant. [143] As a typical selective dissolving process, dealloying is a robust way to generate a nanoporous structure with tunable pore sizes and porosities. [144] In this regard, Chen's group fabricated the bicontinuous nanoporous cobalt phosphide (np-Co 2 P) by single-roller melt spinning and dealloying methods.…”

Virus‐Templated Nickel Phosphide Nanofoams as Additive‐Free, Thin‐Film Li‐Ion Microbattery Anodes

“…Over the last several decades, several classes of materials have emerged as possible conversion anodes for both micro-and macrobatteries, such as transition metal oxides, [10] carbides, [11] and sulfides. [12] In particular, metal phosphides have displayed strong performance in both lithium-ion [13][14][15] and sodium-ion [16][17][18][19] batteries, owing to their high capacity, good electronic conductivity, and naturally abundant constituent elements.Despite their technological promise, synthesis of metal phosphides has traditionally been challenging due to the flammability and toxicity of common phosphoruscontaining precursors. [20] Simultaneous control over nanostructure, crystal structure, and surface morphology remains imprecise, thereby impeding electrode design and incorporation into devices.…”

In Situ Growth of CoP3/Carbon Polyhedron/CoO/NF Nanoarrays as Binder‐Free Anode for Lithium‐Ion Batteries with Enhanced Specific Capacity

“…[27] For instance, Wang et al designed a handy-approach to prepare CoP/C nanoboxes by pyrolysis of phytic acid and zeolitic imidazolate frameworks-67 (ZIF-67) complexes. [28] The optimal structure of CoP/C nanoboxes improved the reaction kinetics and buffered the mechanical strain during the charge/discharge process, exhibiting high specific capacity of 868 mAh g −1 at 0.1 A g −1 with superior stability. Pan's group designed a novel shuttle-like FeP@C nanoporous structure using MIL-88 as precursor.…”