Zinc Phosphides as Outstanding Sodium-Ion Battery Anodes

Abstract

To design a high-performance sodium-ion battery anode, binary zinc phosphides (ZnP2 and Zn3P2) were synthesized by a facile solid-state heat treatment process, and their Na storage characteristics were evaluated. The Na reactivity of ZnP2 was better than that of Zn3P2. Therefore, a C-modified ZnP2-based composite (ZnP2-C) was fabricated to achieve better electrochemical performance. To investigate the electrochemical reaction mechanism of ZnP2-C during sodiation/desodiation, various ex situ analytical techniques were employed. During sodiation, ZnP2 in the composite was transformed into NaZn13 and Na3P phases, exhibiting a one-step conversion reaction. Conversely, Zn and P in NaZn13 and Na3P, respectively, were fully recombined to the original ZnP2 phase during desodiation. Owing to the one-step conversion/recombination of ZnP2 in the composite during cycling, the ZnP2-C showed high electrochemical performance with a highly reversible capacity of 883 mA h g–1 after 130 cycles with no capacity deterioration and a fast C-rate capability of 500 mA h g–1 at 1 C and 350 mA h g–1 at 3 C.

Urchin‐Type Architecture Assembled by Cobalt Phosphide Nanorods Encapsulated in Graphene Framework as an Advanced Anode for Alkali Metal Ion Batteries

“…Transition metal phosphides (TMPs) have been regarded as one class of burgeoning anode competitors for rechargeable batteries due to their high theoretical capacities, vivid electrochemical activity, and low operating potentials [8–12] . However, as a kind of conversion‐type electrode, most of the TMPs exhibited unsatisfactory energy storage life due to the occurrence of large volume variation during discharge/charge processes [13] .…”

Manganese Tetraphosphide (MnP4) as a High Capacity Anode for Lithium‐Ion and Sodium‐Ion Batteries

“…The obtained electrochemical performance of MnP 4 /G20 electrode was superior to those of previously reported various phosphorus‐rich metal phosphide nanocomposites synthesized by a high energy milling as anodes for SIBs (Figure 6d; and Table S4, Supporting Information). [ 14,23,33,43–48 ] In addition, by changing the cut‐off potential from 0.01–2.0 V to 0.01–1.0 V (vs Na/Na + ), the cycle performance of MnP 4 and MnP 4 /G20 electrodes could be further improved without a significant reduction of specific capacity (Figure S6, Supporting Information) due to the relatively low sodiation/desodiation potential of MnP 4 electrode (Figure S3, Supporting Information).…”

Advances in metal phosphides for sodium‐ion batteries

“…There are a large number of other transition MPs formed through the alloying of transition metals (i.e., V, Ti, W, Zn, Mo, etc.) with phosphorus to form MPs (MP x ) with various compositions, structures, properties, and reaction mechanism 141–150 …”