Conjugated Microporous Polymers with Bipolar and Double Redox‐Active Centers for High‐Performance Dual‐Ion, Organic Symmetric Battery

Abstract

Redox‐active conjugated microporous polymers (RCMPs) have received remarkable interest in electrochemical energy‐storage systems in view of their porous structure and tunable redox nature. This work presents an effective strategy to construct RCMPs with bipolar and double redox‐active centers by integrating copper (II) tetraaminephthalocyanine (CuTAPc) and 1,4,5,8‐naphthalenetetracarboxylic dianhydride (NTCDA) units into the RCMPs (CuPcNA‐CMP). As expected, CuPcNA‐CMP has potential application in the half cells of dual‐ion batteries (lithium based DIBs, LDIBs), asymmetric DIBs (graphite based DIBs, ADIBs), and symmetric DIBs (all organic DIBs, SDIBs). Among them, LDIBs show a high reversible capacity (202.4 mAh g−1 at 0.2 A g−1) and excellent rate capability (86.1 mAh g−1 at 5 A g−1). And ADIBs also show a high reversible capacity (245.3 mAh g−1 at 0.1 A g−1), long cycle stability with capacity retention of 89% after 500 cycles, and good rate performance (125.1 mAh g−1 at 5 A g−1). In addition, SDIBs show high initial charge/discharge capacities of 269.4/198.5 mAh g−1 at 0.05 A g−1 and a high cell voltage of 2.5 V. Meanwhile, the mechanism of CuPcNA‐CMP on hosting both anions (PF6−) and cations (Li+) is investigated by detailed experimental analysis and density functional theory studies.

A novel conjugated porous polymer based on triazine and imide as cathodes for sodium storage

“…10 On the other hand, organic electrode materials have attracted more and more attention because of their flexibility, which can accommodate the large ions without volume changes during ion intercalation/extraction. [10][11][12][13][14][15] Among them, polymers containing carbonyl groups have the advantages of good redox reversibility and high capacity for carbonyl groups 8,10,11,[16][17][18][19][20][21][22][23] but also the merits of insolubility for polymers. [24][25][26][27] Beside of these virtues, as one kind of such polymers, polyimides are superior in large abundance and high stability as well.…”

Quinone‐Amine Polymer Nanoparticles Prepared through Facile Precipitation Polymerization as Ultrafast and Ultralong Cycle Life Cathode Materials for Lithium‐Ion Batteries

“…The relationship between peak current (i) and voltage scan rate (v) is described as i = av b , where a and b are positive variables. [55] A b approaching 0.5 represents a diffusion-controlled process, while it implies a surface capacitance-dominated process if b is close to 1. In this work, the b-values of three redox peaks are all close to 1 (0.93, 0.91, and 0.95 as shown in Figure S11b, Supporting Information), suggesting a surface capacitancedominated behavior during the charge/discharge processes of the PQANP-3 electrode.…”

Recent research on emerging organic electrode materials for energy storage

“…(C) Polymerized PTCDA monomers with different short alkyl chains [30] . (D) The truxenone-based covalent organic framework material [31] . (E) The conjugated microporous polymers material [32] .…”

“…Covalent organic framework materials have a tunable chemical structures, which they can be used in different batteries for various purposes. Yang et al [31] reported a truxenone-based covalent organic framework (COF-TRO) material [Figure 3D] in all-solid-state lithium-ion batteries as the cathode. The material showed a capacity of 268 mAh g -1 , and 99.9% capacity retention after 100 cycles at a 0.1 C rate.…”