Emerging organic electrode materials for aqueous proton batteries

Wu, Zhenzhen; Yang, Pan; Wang, Shouyue; Li, Sheng; Zhang, Shanqing

doi:10.1016/j.trechm.2022.09.007

Cited by 11 publications

(7 citation statements)

References 46 publications

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“…The cycle numbers and the retention rate of fabricated device outstrip the reported state-of-the-art APB devices (Fig. 5g) 31,34,39,55,57,[59][60][61][62][63] . More information about the energy/power density, electrochemical kinetics and low-temperature capability of the soft-package APB is provided in Fig.…”

Section: Resultsmentioning

confidence: 57%

“…5d shows the GCD profiles of the soft-package APB based on the mass of PPHZ anode, which can deliver a large specific capacity of 184.7 mAh g -1 at a loading density of 1 A g -1 , far superior to previously reported APB devices (Fig. 5e) 35,39,[55][56][57][58] . Additionally, the soft-package APB was subsequently subjected to repeated charging-discharging cycles.…”

Section: Resultsmentioning

confidence: 74%

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A long-range planar polymer with efficient π-electron delocalization for superior proton storage

Wang

Shi

et al. 2023

Preprint

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Due to the unique "Grotthus mechanism", aqueous proton batteries (APBs) are promising energy devices with intrinsic safety and sustainability. Although polymers with tunable molecular structures are expected as ideal electrode materials, their unsatisfactory proton-storage redox behaviors hinder the practical application in APB devices. Herein, a novel planar phenazine (PPHZ) polymer with a robust and extended imine-rich skeleton based on phenazine units is synthesized and used for APB application for the first time. The long-range planar configuration achieves ordered molecular stacking and reduced conformational disorder, while the high conjugation with strong π-electron delocalization optimizes energy bandgap and electronic properties, enabling to the polymer with ultra-low proton diffusion barriers (≤ 0.12 eV), high redox activity and superior electron affinity. As such, the PPHZ polymer as an electrode material exhibits fast, stable and unrivaled proton-storage redox behaviors with a record capacity of 254.5 mAh g-1 in aqueous acidic electrolyte, which is the highest value among all proton-inserted organic electrodes. Dynamic in-situ monitoring techniques confirm the high redox reversibility upon proton uptake/removal, and the corresponding protonation pathways are elucidated by multiple theoretical calculations. Moreover, a soft-packaged APB cell using PPHZ electrode exhibits an ultralong lifespan over 30,000 cycles, further verifying its promising application prospect.

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Section: Resultsmentioning

confidence: 57%

Section: Resultsmentioning

confidence: 74%

A long-range planar polymer with efficient π-electron delocalization for superior proton storage

Wang

Shi

et al. 2023

Preprint

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“…[1][2][3] Until now, OEMs have been used in several battery chemistries, such as Li-ion, Na-ion, Mg-ion, and proton batteries, owing to their versatile characteristics. [4][5][6][7][8][9] Among OEMs, semiconducting polymers are emerging as promising candidates for cathode materials thanks to their high capacity and redox reversibility. [10][11][12][13][14][15] In particular, poly(1,4-anthraquinone) (P14AQ, Figure 1) has demonstrated excellent electrochemical performance and high stability.…”

Section: Introductionmentioning

confidence: 99%

Poly(1,4-anthraquinone) as an organic electrode material: Interplay of the electronic and structural properties due to the unusual lone-pair-π conjugation

Zhang,

de Silva

2024

Preprint

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Organic semiconductors with lone-pair-π conjugation offer a promising yet enigmatic route to advanced electrode materials for rechargeable batteries. This study employs molecular dynamics and electronic structure simulations to explore the relationship between structural and electronic properties of poly(1,4-anthraquinone) (P14AQ), which exhibits this unusual conjugation mechanism. The results indicate that P14AQ is resistant to structural disorder, always maintaining an appreciable conjugation length within its polymer chain. It also shows restrained volume changes during battery cycling when lithium, magnesium, and hydrogen cations are intercalated. These results rationalize the reported good performance of P14AQ as an organic cathode material. Our analysis offers fundamental insights into the role of lone-pair-π conjugation in organic semiconductors and paves the way for the development of new material based on this unorthodox design paradigm.

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“…Phenazine active unit shows a lower redox potential (~0.2 V vs. NHE in 1 M H 2 SO 4 ) [29] and a proton-storage capability that makes it as a suitable anode in proton-based batteries. [46] Recently, Minjie Shi et al [29] demonstrated an improved proton-storage capability of a rod-like diquinoxalinophenazine (DPZ) compared to the phenazine monomer (PZ) in a 1 M H 2 SO 4 owing to the enhanced structural stability of the DPZ, sustaining 300 cycles at 3 C, whereas the phenazine small molecule dissolved after 100 cycles. Another promising strategy to increase the structural stability of redox organic compounds is to develop conjugated (micro)porous polymers (C(M or P)Ps) and covalent organic framework (COFs).…”

Section: Introductionmentioning

confidence: 99%

“…In the particular case of phenazine‐based compounds, their π‐conjugated aromatic structure containing N heteroatoms with a lone pair of electrons attracted the interest of the scientific community. Phenazine active unit shows a lower redox potential (∼0.2 V vs. NHE in 1 M H 2 SO 4 ) [29] and a proton‐storage capability that makes it as a suitable anode in proton‐based batteries [46] . Recently, Minjie Shi et al [29] .…”

Section: Introductionmentioning

confidence: 99%

Hybrid based on Phenazine Conjugated Microporous Polymer as a High‐Performance Organic Electrode in Aqueous Electrolytes

Alván

Grieco

Patil

et al. 2023

Batteries & Supercaps

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Incorporating redox active units in a 3D porous network is an encouraging strategy to enhance electrochemical performance of organic electrode materials. Herein, a new hybrid composed by phenazine-based conjugated microporous polymer (IEP-27-SR, stand for IMDEA Energy Polymer number 27) and singlewalled carbon nanotubes (SWCNTs) and graphene oxide (RGO) is synthesized, fully characterized and tested electrochemically in different aqueous electrolyte conditions, i. e., at various pH values (1-12) and also with different charge carriers (H + in acidic, and Li + , Na + , K + in neutral and alkaline electrolytes).Although the IEP-27-SR is found to be very versatile showing very good electrochemistry both in alkaline and acidic solution, it exhibits best specific capacity, redox kinetics and cycle stability in acidic electrolyte. Then encouragingly, when IEP-27-SR is combined with an activated carbon (AC) counter electrode to construct a proof-of-the-concept device, the IEP-27-SR//AC demonstrates high specific capacity (168 mAh g À 1 at 2 C), impressive rate performance (96 mAh g À 1 at 60 C) and ultralong cycle stability (76 % capacity retention over 28800 cycles at 10 C; 2690 h) in 1 M H 2 SO 4 .

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Emerging organic electrode materials for aqueous proton batteries

Cited by 11 publications

References 46 publications

A long-range planar polymer with efficient π-electron delocalization for superior proton storage

A long-range planar polymer with efficient π-electron delocalization for superior proton storage

Poly(1,4-anthraquinone) as an organic electrode material: Interplay of the electronic and structural properties due to the unusual lone-pair-π conjugation

Hybrid based on Phenazine Conjugated Microporous Polymer as a High‐Performance Organic Electrode in Aqueous Electrolytes

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