A COF‐Like N‐Rich Conjugated Microporous Polytriphenylamine Cathode with Pseudocapacitive Anion Storage Behavior for High‐Energy Aqueous Zinc Dual‐Ion Batteries

Abstract

Conducting polymers with good electron conductivity and rich redox functional groups are promising cathode candidates for constructing high-energy aqueous zinc batteries. However, the glaring flaw of activesite underutilization impairs their electrochemical performance. Herein, we report a poriferous polytriphenylamine conjugated microporous polymer (CMP) cathode capable of accommodating Cl − anions in a pseudocapativedominated manner for energy storage. Its specific 3D, covalent-organicframework-like conjugated network ensures high accessibility efficacy of N active sites (up to 83.2% at 0.5 A g −1 ) and distinct physicochemical stability (87.6% capacity retention after 1000 cycles) during repeated charging/discharging courses. Such a robust CMP electrode also leads to a zinc dual-ion battery device with a high energy density of 236 W h kg −1 and a maximum power density of 6.8 kW kg −1 , substantially surpassing most recently reported organic-based zinc batteries. This study paves the way for the rational design of advanced CMP-based organic cathodes for high-energy devices.

Porosity Design on Conjugated Microporous Poly(Aniline)S for Exceptional Mercury(II) Removal

“…To verify the success of the hybrid pore construction, we conducted the N 2 sorption isotherm to extract the porosity information. A deep increase in the sorption amount at a low relative pressure of 0–0.05 was observed in all cases (Figure a), suggesting that the rich microporosities or storage spaces were inherited to the CMPA-Ms . We further obtained insight into the pore structure by considering the pore size distribution (PSD) of the CMPA-M-2.…”

“…20,31,32 To verify the success of the hybrid pore construction, we conducted the N 2 sorption isotherm to extract the porosity information. A deep increase in the sorption amount at a low relative pressure of 0−0.05 was observed in all cases (Figure 2a), suggesting that the rich microporosities or storage spaces were inherited to the CMPA-Ms. 33 We further obtained insight into the pore structure by considering the pore size distribution (PSD) of the CMPA-M-2. Interestingly, the PSD of the CMPA-M-2, which was abundant in 6.80, 8.04, and 11.40 Å, as depicted in Figure 2b and Table S6, showed the combination of pores caused by three linkers of tris(4aminophenyl) amine (i.e., 6.05 and 11.40 Å, as highlighted in a blue strip), phenylenediamine (i.e., 7.05 Å, as highlighted in a light pink strip), and 1,4-diaminodiphenylamine (i.e., 8.37 Å, as highlighted in a red strip), strongly suggesting the existence of the hybrid hierarchic molecular pores (as highlighted in Figure 2b and illustrated in Figure 2c) in our CMPA-M-2 and thus the possibility to delicately tune the pore structure through our approach (we note that a slight difference between the pore size in CMPA-M-2 and CMPAs was caused by the interpenetration of linkers and cores during three-stage polymerization, which could be verified by the scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images discussed in Section S3.6 of the Supporting Information).…”

Manipulating Polymer Configuration to Accelerate Cation Intercalation Kinetics for High‐Performance Aqueous Zinc‐Ion Batteries

“…More importantly, the initial capacity remains 97% when current density is switched back to 0.3 A g -1 . Overall, P3Q-t displays superior electrochemical performance comparable to those of the state-of-the-art organic ZIB cathodes based on redox polymers (Figure 3d;Table S1, Supporting Information), [12,23,36,[44][45][46][47][48], e.g., PDBS (260 mA h g -1 at 0.1 A g -1 ), [12] t-CNTs-PA-PE (238 mA h g -1 at 0.2 A g -1 ), [44] PDA (126 mA h g -1 at 0.02 A g -1 ), [45] HqTp-COF (276 mA h g -1 at 0.125 A g -1 ), [46] Cu 3 (HHTP) 2 (228 mA h g -1 at 0.05 A g -1 ). [48] We further conducted the long-term GCD cycles for polymerbased ZIBs at the current density of 3 A g -1 (Figure 3e).…”

Ultrastable Conjugated Microporous Polymers Containing Benzobisthiadiazole and Pyrene Building Blocks for Energy Storage Applications

“…Therefore, CMPs displayed high capacity and long-term cycling stability when they were applied as material electrodes in electrochemical energy storage applications [ 56 , 57 , 58 , 59 , 60 ]. Hence, they are considered as one of the ideal candidates for catalysis, gas storage, and electrochemical energy storage [ 61 , 62 , 63 , 64 ].…”