Covalent Attachment of Anderson‐Type Polyoxometalates to Single‐Walled Carbon Nanotubes Gives Enhanced Performance Electrodes for Lithium Ion Batteries

Abstract

Single-walled carbon nanotubes (SWNTs) covalently functionalized with redox-active organo-modified polyoxometalate (POM) clusters have been synthesized and employed as electrode materials in lithium ion batteries. The Anderson cluster [MnMo6 O24 ](9-) is functionalized with Tris (NH2 C(CH2 OH)3 ) moieties, giving the new organic-inorganic hybrid [N(nC4 H9 )4 ]3 [MnMo6 O18 {(OCH2 )3 CNH2 }2 ]. The compound is then covalently attached to carboxylic acid-functionalized SWNTs by amide bond formation and the stability of this nanocomposite is confirmed by various spectroscopic methods. Electrochemical analyses show that the nanocomposite displays improved performance as an anode material in lithium ion batteries compared with the individual components, that is, SWNTs and/or Anderson clusters. High discharge capacities of up to 932 mAh g(-1) at a current density of 0.5 mA cm(-2) can be observed, together with high long-term cycling stability and decreased electrochemical impedance. Chemisorption of the POM cluster on the SWNTs is shown to give better electrode performance than the purely physisorbed analogues.

Dawson‐Type Polyoxomolybdate Anions (P2Mo18O626−) Captured by Ionic Liquid on Graphene Oxide as High‐Capacity Anode Material for Lithium‐Ion Batteries

“…In this temperature range, the GO‐IL and GO‐IL‐P 2 Mo 18 nanocomposite show weight losses of 36.86 and 21.45 wt %, respectively, which is associated with the thermal degradation of organic groups such as −COOH, −OH, and so on. Assuming that the weight losses of the organic groups are the same in the GO‐IL and GO‐IL‐P 2 Mo 18 , the content of P 2 Mo 18 in the GO‐IL‐P 2 Mo 18 nanocomposite can be estimated to be approximately 46.72 wt % …”

“…Our group first studied a nanocomposite of pyrene‐modified POMs and SWNTs, and its application as an LIB anode material showed improved charge‐transfer efficiency . Later, we reported the preparation of Anderson covalently functionalized SWNTs, and electrochemical analyses indicated that the resultant nanocomposite had a high discharge capacity of up to 932 mAh g −1 at a current density of 0.5 mA cm −2 with excellent stability . Li et al.…”

Covalent Photosensitizer–Polyoxometalate‐Catalyst Dyads for Visible‐Light‐Driven Hydrogen Evolution

“…[31] POM-organo-functionalization critically relies on stable cluster architectures that can be deployed in chemicallyd emanding reaction environments. [36] Here, we show how the covalenta ttachment of 2,2'-bipyridine to Anderson anionsa nd subsequent coordination of iridium complexes gives accesst op hotosensitizer-HER-catalyst dyadsc apableo fs ustained visible-light-drivenh ydrogen evolution. [36] Here, we show how the covalenta ttachment of 2,2'-bipyridine to Anderson anionsa nd subsequent coordination of iridium complexes gives accesst op hotosensitizer-HER-catalyst dyadsc apableo fs ustained visible-light-drivenh ydrogen evolution.…”

The Anderson–Evans polyoxometalate: From inorganic building blocks via hybrid organic–inorganic structures to tomorrows “Bio-POM”

“…The activated proton allowed grafting of tris-NH 2 , tris-CH 3 and tris-CH 2 CH 3 ligands that cap a tetrahedral cavity instead of the heteroatom by covalently binding to two μ 3 -O atoms and one μ 2 -O atom on the planar Anderson-Evans surface giving the single-sided χ-isomer [190]. The formed product allows in theory further post-functionalization (Figure 7, C3) as observed with δ-isomers (section 5.2).…”

“…The following paragraphs looks into some interesting hybrid tris-functionalized compounds in terms of structure and crystal packing with a special emphasis on the Mn III Mo 6 system. -CH2OH (S, χ-isomer) nr [190] Mn III Mo6…”