Facile Method for Cross-Linking Aromatic Polyamines to Engender beyond Lithium Ion Cathodes for Dual-Ion Batteries

Abstract

Numerous recent reports on organic-based batteries indicate an emerging interest in dual-ion batteries with polyaminebased cathodes, which are associated with outstanding rate capabilities, high specific capacities, and optimal operation voltages demonstrated by materials of this type. One of the most important and urgent tasks for this research field is the design of polyaminebased materials with advanced performance, as well as the development of methods for their preparation. In this work, a facile cross-linking approach for chemical modification of polymeric aromatic amines, which refines their cathode performance for dual-ion batteries, is presented. The precursor polymers NPDPA and PHTPA were exposed to an additional oxidative polymerization step with ferric chloride to obtain cross-linked (CL) CL-NPDPA and CL-PHTPA materials, respectively. The study of their electrochemical properties in lithium half-cells revealed improved capacities and cycling stabilities for cross-linked polymers, especially for CL-PHTPA; the values of 112.5, 102.6, and 81.1 mAh g −1 were reached under galvanostatic charging and discharging at current densities of 0.1, 1, and 10 A g −1 , respectively, thus indicating decent capacities and impressive rate capabilities. The capacity retention of 98 and 36% after 100 and 15 000 cycles, respectively, measured at a current density of 10 A g −1 showed the decent operational stability of lithium batteries. Furthermore, encouraging energy densities of 415, 425, and 211 Wh kg −1 were achieved for CL-PHTPA, while it was applied as a cathode for Na, K, and Mg half-cells, indicating the promise of polyamine materials and the presented cross-linking approach for the development of alternative battery chemistries.

Organic Electrode Materials for Dual‐Ion Batteries

“…Recently, polyimide‐based materials have attracted wide attention as cathode for DIBs. Obrezkov et al [104] . presented a simple cross‐linking method to modify the polymeric aromatic amine to improve its performance.…”

“…Recently, polyimide-based materials have attracted wide attention as cathode for DIBs. Obrezkov et al [104] presented a simple cross-linking method to modify the polymeric aromatic amine to improve its performance. As for the Synthesis steps, First, synthesize Bis-(4-brormophenyl) amine (Hyperbranched Polydiphenylamine, PHTPA) precursor through oxidative polymerization, then realizing the additional oxidative polymerization by exposing the precursor polymers to ferric chloride.…”

p‐Type Redox‐Active Organic Electrode Materials for Next‐Generation Rechargeable Batteries

“…To circumvent such a solubility issue, hyper-cross-linked polymers [120][121][122] and micro/mesoporous covalent organic frameworks (COFs) have been studied. [70,[123][124][125] In particular, synthesizing COFs effectively suppressed the dissolution of active materials in the electrolyte due to high molecular weight and tight intermolecular interactions, leading to high cycle stability.…”

Hypercrosslinked Phenothiazine Polymer as a Low-Cost and Durable Organic Cathode for Rechargeable Lithium Batteries

“…However, organic electrodes have two notable drawbacks such as poor conductivity compared to inorganic materials and the tendency to leach out during the battery operation. , Former is compensated by making their composites with high amounts of conductive additives like carbon black, nanotubes, etc., and the general solution for the latter is forming their larger-molecular-weight analogues (i.e., polymers). , Particularly, extended (hypercrosslinked, ladder type, etc.) polymers produced from conjugated monomers are interesting to overcome both shortcomings thanks to their electron-rich and poorly/nonsoluble backbone. − …”