3D Covalent Polyoxovanadate‐Organic Framework as an Anode for High‐Performance Lithium‐Ion Batteries

Abstract

Polyoxometalates (POMs), as a unique class well‐defined metal‐oxo clusters with excellent multielectron redox properties, have attracted extensive attention in the field of energy storage and conversion, but it is still challenging to achieve their highly uniform and stable monodispersed. In this study, for the first time, polyoxovanadate (POV) is used, (NH4)2[VIV3VV3O10{NH2C(CH2O)3}3] (tris‐V6O19), as nodes and successfully obtain a 3D covalent polyoxovanadate‐organic framework through a green hydrothermal synthesis method, termed POF‐1. Total scattering atomic pair distribution function analysis confirms that POF‐1 has a noninterpenetrated diamond‐like framework, fully exposing the monodispersed tris‐V6O19, effectively utilizing the active components of VIV/VV and enhancing surface mass transfer. Notably, POF‐1 demonstrates exceptional performance in lithium‐ion batteries, achieving a high reversible capacity of 887.4 mAh g−1 at 0.1 A g−1 and retaining over 92% capacity at 1 C during 1000 cycles. Electrochemistry mechanism and density functional theory calculations reveal that V centers in tris‐V6O19 and carbonyls (C═O) in BDOEB linkers are the main active sites, with each POF‐1 fragment capable of storing up to 14 Li+. This study opens a new pathway for the efficient and green synthesis of new 3D well‐defined POM‐organic frameworks, and shows great application prospect in the field of energy storage.

3D Porous Metal–Organic Skeleton Based on Polyoxometalate Nanoclusters as an Anode in a Lithium-Ion Battery

“…It is noteworthy that the actual capacitance value is much higher than the theoretical specific capacitance, which may be due to the capacitance contribution of the BAS-MOF-1 channel. The theoretical capacity value (about 329 mA h g –1 ) of BAS-11 determined from 2 Mo 5+ and 16 Mo 6+ ions in BAS-11 is reduced to Mo 4+ and possible lithiation/delithiation sites for two HPO 4 – and six N coordination with Li in the protonated btb ligands, with maximum of n = 42 and Q BAS‑MOF‑1 = 329 mAh g –1 . , …”

“…Polyoxometalates (POMs) are suitable candidates for energy storage due to their electronic sponge characteristics, structural diversity, and electrochemical stability. − Since the Sonoyama group first attempted to use Keggin phosphomolybdate as the anode material for Li-ion batteries (LIBs), the related properties of many POM-based compounds have been intensively reported. − However, most POMs suffer from limited specific surface area, high solubility in electrolytes, and relatively weak conductivity, restricting their practical utilization in LIBs. Integration of POM units with metal–organic frameworks (MOFs) to form POM-based MOFs (POMOFs) is an effective method to get over the above defects. − POMOF materials possess improved specific surface area, enhanced stability, and accelerated electron conversion efficiency and exhibit excellent electrochemical storage performance due to their combination of the merits of MOF and POMs.…”

Bridging Component Strategy in Phosphomolybdate-Based Sensors for Electrochemical Determination of Trace Cr(VI)

“…32 Therefore, it is urgent to develop a kind of economy and efficient electrocatalyst for the fast and sensitive determination of trace Cr(VI). Polyoxometalates (POMs) as a subset of transition metaloxo clusters with distinctive structural features and regulable redox activity have excellent electron transport capacity 36,37 and can undergo gradual multielectron redox without any structural changes. 38,39 Thus, POMs showcase great application potential in the territory of electrochemical sensing.…”

“…Polyoxometalates (POMs) as a subset of transition metal-oxo clusters with distinctive structural features and regulable redox activity have excellent electron transport capacity , and can undergo gradual multielectron redox without any structural changes. , Thus, POMs showcase great application potential in the territory of electrochemical sensing . As a unique member of the POM family, the fully reduced phosphomolybdate {M­[P 4 Mo V 6 O 31 ] 2 } n – (M­{P 4 Mo 6 } 2 , M represents the metal ion) is composed of two ring-like [P 4 Mo V 6 O 31 ] 12 – half-units ({P 4 Mo 6 }) and one sandwich metal ion .…”

Fabrication of porous polyimide as cathode for high performance lithium-ion battery

“…[9][10][11] Despite showing advantages of high theoretical capacities and tuneable properties, small organic carbonyl molecules exhibit poor cycle performance due to their high solubility in electrolytes. [12][13][14] One efficient way is to polymerize these carbonyl molecules units to give a stable framework and an electroactive functional group to minimize the solubility. [15][16][17] Polyimide (PI), an organic carbonyl material, is well known as an engineering plastic with its amazing physical features, such as thermal stability, mechanical strength and flexibility.…”