Hydroxide ion-conducting viologen–bakelite organic frameworks for flexible solid-state zinc–air battery applications

Rase, Deepak; Illathvalappil, Rajith; Singh, Himan Dev; Shekhar, Pragalbh; Leo, Liya S.; Chakraborty, Debanjan; Haldar, Sattwick; Shelke, Ankita; Ajithkumar, T. G.; Vaidhyanathan, Ramanathan

doi:10.1039/d2nh00455k

Cited by 7 publications

(15 citation statements)

References 54 publications

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“…We calculated the diffusion coefficients inside the COF using the Z' versus 𝜔 −1/2 plot. [39,40] The low-frequency spectrum of the impedance plot yielded the characteristic linear fits (Figure S23 and Table S3, Supporting Information), from which the diffusion coefficients were estimated to be 7.67 × 10 −6 cm 2 s −1 for the Zn 2+ ions and 1.40 × 10 −5 cm 2 s −1 for the I 3 − with 3 m ZnSO 4 (aq) and 3 m ZnSO 4 + 0.2 m ZnI 2 (aq), respectively. Notably, the magnitude of the ionic conductivity is much higher for the redox electrolyte system than the electronic one (10 −3 vs 10 −6 S cm −1 ).…”

Section: Electrochemical Performance Of Cof Through Coin Cell Configu...mentioning

confidence: 99%

Made to Measure Squaramide COF Cathode for Zinc Dual‐Ion Battery with Enriched Storage via Redox Electrolyte

Kushwaha,

Jain,

Shekhar

et al. 2023

Advanced Energy Materials

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Aqueous rechargeable batteries are promising grid‐scale energy storage devices because of their affordability, operational safety, and environmental benignity. Among these, Zn‐ion batteries (ZIBs) have unfolded new horizons. Designing superior cathodes for ZIBs is crucial. Covalent organic frameworks (COFs) can be made redox active with a high storage surface. Here, for the first time, a chelating COF with redox‐active ZnI2 in a ZnSO4(aq) electrolyte is combined. Including iodide harvests an approximately threefold enhancement in capacity from 208 to 690 mAh g−1 at 1.5 A g−1, the highest among all the COF‐derived ZIBs. Remarkably, a charge–discharge curve at 1.3 V exhibits very limited dropout voltage and super‐flat platform, with a remarkable capacity of 600 mAh g−1 at 5 A g−1 stable up to 6000 cycles, confirming that the polyiodide generation and storage are sustainable. The COF's dual‐ion storage (Zn2+ and polyidode) delivers a ZIB with the highest energy density. Spectro‐electrochemical measurements coupled with X‐ray photoelectron spectroscopy unambiguously unveil the existence of multiple polyiodide species, with I3− and IO3− ions as the prominent species. The latter gets reduced at the COF electrode under an applied potential, leaving I3− as the major species stored on the COF. The prospect of COF‐polyiodide(aq) is a windfall for metal‐ion batteries.

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Section: Electrochemical Performance Of Cof Through Coin Cell Configu...mentioning

confidence: 99%

Made to Measure Squaramide COF Cathode for Zinc Dual‐Ion Battery with Enriched Storage via Redox Electrolyte

Kushwaha,

Jain,

Shekhar

et al. 2023

Advanced Energy Materials

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“…Despite these aforementioned advantages, materials that promote the high mobility and conductivity of hydroxide anions remain a significant challenge in AEMFCs because the large mass and slow diffusion of hydroxide ion sluggish the rate of conduction compared to proton. Additionally, the material used as a conductive electrolyte in AEMFCs must be highly alkaline stable as the cell operates under strongly basic conditions. , Covalent organic frameworks (COFs) belong to crystalline porous polymers with tailorable pore topologies . The reticular synthesis of covalent organic frameworks (COFs) provides a robust platform for the synthesis of specified channel architectures by the chemical (reactive) assembly of molecular building blocks .…”

Section: Introductionmentioning

confidence: 99%

Hydroxide Ion Conduction through Viologen-Based Covalent Organic Frameworks (vCOFs): An Approach toward the Advancement

Jhariat,

U.,

Warrier

et al. 2024

ACS Appl. Mater. Interfaces

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Alkaline fuel cells rely on the movement of hydroxide anions (OH − ) for their operation, yet these anions face challenges in efficient conduction due to their limited diffusion coefficient and substantial mass compared to proton (H + ) transport. Within the covalent organic framework structure, ordered channels offer a promising solution for the OH − ion transport. Herein, we synthesized a cationic covalent organic framework (vTAPA) via the solvothermalassisted Zincke reaction. vTAPA showcases excellent stability in harsh basic solution (12 M) and a wide range of pH. This framework facilitates OH − conduction through its one-dimensional network through the anion exchange process. We employed various tertiary ammonium salts (tetramethyl, tetraethyl, and tetrabutyl ammonium hydroxide) to exchange trapped anionic chloride ions inside the vTAPA structure with OH − ions. The density functional theory (DFT) study exhibited that the anion exchange process is very favorable, as the vTAPA framework offers preferable interaction sites for OH − ions. The impact of steric hindrance from these tertiary ammonium salts on the OH − conduction performance was extensively investigated. Butyl@vTAPA exhibited a high OH − ion conductivity of 1.05 × 10 −4 S cm −1 at 90 °C under 98% relative humidity (RH). Our uniquely designed cationic covalent organic frameworks (COF) created a platform for a preferential transport network of hydroxide ions, and this is the first report of directly used COFs for hydroxide ion conduction without any vigorous postsynthetic modification.

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“…16,24 Although there is a recent surge in the investigation of hydroxide-ion conducting polymers for energy storage, they are aimed mostly for use as supercapacitor electrolytes and fuel cell membranes, [25][26][27][28][29][30][31][32] to our knowledge, there is only one report on their utilization in ZABs. 33 However, there is no evidence that these porous hydroxide-ion conducting polymer electrolytes can support a RZAB.…”

Section: Introductionmentioning

confidence: 99%

Design enhancement in hydroxide ion conductivity of viologen–bakelite organic frameworks for a flexible rechargeable zinc–air battery

Rase,

Manna,

Kushwaha

et al. 2024

Chem. Sci.

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Hydroxide ion-conducting viologen–bakelite organic frameworks for flexible solid-state zinc–air battery applications

Abstract: Adaptable polymer-based solid-state electrolytes can be a game-changer to safe, lightweight flexible batteries. We present a robust Bakelite-type organic polymer covalently decked with viologen, triazine, and phenolic moieties. Its flexible...

Cited by 7 publications

References 54 publications

Made to Measure Squaramide COF Cathode for Zinc Dual‐Ion Battery with Enriched Storage via Redox Electrolyte

Made to Measure Squaramide COF Cathode for Zinc Dual‐Ion Battery with Enriched Storage via Redox Electrolyte

Hydroxide Ion Conduction through Viologen-Based Covalent Organic Frameworks (vCOFs): An Approach toward the Advancement

Design enhancement in hydroxide ion conductivity of viologen–bakelite organic frameworks for a flexible rechargeable zinc–air battery

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