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

Abstract

Phosphorus‐rich 6‐MnP4 nanoparticles are synthesized via high energy mechanical milling (HEMM) and their electrochemical properties as an anode for lithium‐ion batteries (LIBs) and sodium‐ion batteries (SIBs) are investigated focusing on the electrochemical activity and reaction mechanism. The 6‐MnP4 nanoparticles with a triclinic structure (P‐1) are successfully synthesized by HEMM and they are composed of 5 to 20 nm‐sized crystallites. During the lithiation process, the MnP4 phase undertakes the sequential alloying (MnP4 + 7 Li+ + 7 e− → Li7MnP4) and conversion (Li7MnP4 + 5 Li+ + 5 e− → Mn0 + 4 Li3P) reactions. On the other hand, the MnP4 nanoparticles are directly converted to Mn0 and Na3P without the formation of an intermediate Na–Mn–P alloy phase during sodiation process. The MnP4 electrode shows high initial discharge and charge capacity (1876 and 1615 mAh g−1 for LIBs, and 1234 and 1028 mAh g−1 for SIBs) and high initial Coulombic efficiency (86% for LIBs and 83% for SIBs), indicating a promising candidate for high capacity anodes. In addition, the long‐term cyclability and high rate capability of MnP4 can be further improved through the formation of MnP4/graphene nanocomposites and vanadium substituted Mn0.75V0.25P4 solid solutions.

Advances in metal phosphides for sodium‐ion batteries

“…Comparison of the electrochemical performance of advanced MPs (e.g., GeP 5 , 131 FeP 4 , 61 GeP 3 , 134 NiP 3 , 78 GeP, 155 Sn 4 P 3 , 156 CuP 2 , 94 MnP 4 , 157 FeP, 22 CoP, 125 SnP 3 , 158 SnP, 19 Zn 3 P 2 , 159 CoP 4 , 34 Ni 2 P, 85 MoP, 153 WP, 146 ZnP 2 , 149 Co 2 P, 160 Ni 5 P 4 , 89 CoP 3 , 26 Cu 3 P, 161 V 4 P 7 , 143 and Ni 12 P 5 88 )…”

Metal–organic framework‐derived phosphide nanomaterials for electrochemical applications

“…230 Also, it is known that TMPs have been widely studied because their intercalation potentials compared with Li/Li + are relatively low, while their theoretical capacities are high. However, its commercial applications have been impeded by low electrical conductivity and 225 TEM images of (F) hollow FeP@carbon nanocomposite (H-FeP@C) nanospheres and (G) the H-FeP@C@GR nanocomposite. (H) Cycling performance of all the samples.…”

“…In addition, the reasonably good rate capability and constant cyclability of MnP 4 can be advanced via the production of MnP 4 /graphene nanocomposites and vanadium‐substituted Mn 0.75 V 0.25 P 4 solid solutions (Figure 15A–E). 225 Furthermore, Park et al have successfully synthesized a carbon‐coated Na 3 V 1.96 Fe 0.04 (PO 4 ) 3 ‐Fe 2 P composite (NVFP‐FP/C) by using a one‐pot pyro‐synthesis method. As a cathode material, its excellent Na storage property for SIB is demonstrated.…”

“…Cycle performance of MnP 4 and MnP 4 /graphene (MnP 4 /G) electrodes for sodium‐ion batteries (SIBs) at a current density of (C) 50 mA g −1 and (D) 500 mA g −1 with activation of initial three cycles at 50 mA g −1 and (E) rate capability. Reproduced with permission: Copyright 2021, Wiley 225 . TEM images of (F) hollow FeP@carbon nanocomposite (H‐FeP@C) nanospheres and (G) the H‐FeP@C@GR nanocomposite.…”

Challenges and Design Strategies for Conversion-Based Anode Materials for Lithium- and Sodium-Ion Batteries

“…nanoparticles. Significantly high capacity of ~1600 and ~1028 mAh g -1 was delivered in LIBs and SIBs, respectively, by the conversion and alloying reaction forming metallic Mn and Li 3 P/Na 3 P phases [122].…”