@article {46761, title = {In situ cross-linked nonaqueous polymer electrolyte for zinc-metal polymer batteries and hybrid supercapacitors}, journal = {Small}, volume = {16}, year = {2020}, month = {SEP}, pages = {2002528}, type = {Article}, abstract = {

This work reports the facile synthesis of nonaqueous zinc-ion conducting polymer electrolyte (ZIP) membranes using an ultraviolet (UV)-light-induced photopolymerization technique, with room temperature (RT) ionic conductivity values in the order of 10(-3)S cm(-1). The ZIP membranes demonstrate excellent physicochemical and electrochemical properties, including an electrochemical stability window of \>2.4 V versus Zn|Zn(2+)and dendrite-free plating/stripping processes in symmetric Zn||Zn cells. Besides, a UV-polymerization-assisted in situ process is developed to produce ZIP (abbreviated i-ZIP), which is adopted for the first time to fabricate a nonaqueous zinc-metal polymer battery (ZMPB; VOPO4|i-ZIP|Zn) and zinc-metal hybrid polymer supercapacitor (ZMPS; activated carbon|i-ZIP|Zn) cells. The VOPO(4)cathode employed in ZMPB possesses a layered morphology, exhibiting a high average operating voltage of approximate to 1.2 V. As compared to the conventional polymer cell assembling approach using the ex situ process, the in situ process is simple and it enhances the overall electrochemical performance, which enables the widespread intrusion of ZMPBs and ZMPSs into the application domain. Indeed, considering the promising aspects of the proposed ZIP and its easy processability, this work opens up a new direction for the emergence of the zinc-based energy storage technologies.

}, keywords = {nonaqueous electrolytes, polymer electrolytes, postlithium batteries, Supercapacitors, zinc-metal batteries}, issn = {1613-6810}, doi = {10.1002/smll.202002528, Early Access Date = JUL 2020}, author = {Vijayakumar, Vidyanand and Ghosh, Meena and Kurian, Maria and Torris, Arun and Dilwale, Swati and Badiger, V. Manohar and Winter, Martin and Nair, Jijeesh Ravi and Kurungot, Sreekumar} } @article {47419, title = {Naphthalene dianhydride organic anode for a {\textquoteleft}rocking-chair{\textquoteright} zinc-proton hybrid ion battery}, journal = {Dalton Transactions}, volume = {50}, year = {2021}, month = {MAR }, pages = {4237-4243}, type = {Article}, abstract = {

Rechargeable batteries consisting of a Zn metal anode and a suitable cathode coupled with a Zn2+ ion-conducting electrolyte are recently emerging as promising energy storage devices for stationary applications. However, the formation of high surface area Zn (HSAZ) architectures on the metallic Zn anode deteriorates their performance upon prolonged cycling. In this work, we demonstrate the application of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA), an organic compound, as a replacement for the Zn-metal anode enabling the design of a {\textquoteleft}rocking-chair{\textquoteright} zinc-proton hybrid ion battery. The NTCDA electrode material displays a multi-plateau redox behaviour, delivering a specific discharge capacity of 143 mA h g(-1) in the potential window of 1.4 V to 0.3 V vs. Zn|Zn2+. The detailed electrochemical characterization of NTCDA in various electrolytes (an aqueous solution of 1 M ZnOTF, an aqueous solution of 0.01 M H2SO4, and an organic electrolyte of 0.5 M ZnOTF/acetonitrile) reveals that the redox processes leading to charge storage involve a contribution from both H+ and Zn2+. The performance of NTCDA as an anode is further demonstrated by pairing it with a MnO2 cathode, and the resulting MnO2||NTCDA full-cell (zinc-proton hybrid ion battery) delivers a specific discharge capacity of 41 mA h g(total)(-1) (normalized with the total mass-loading of both anode and cathode active materials) with an average operating voltage of 0.80 V.

}, issn = {1477-9226}, doi = {10.1039/d0dt04404k}, author = {Ghosh, Meena and Vijayakumar, Vidyanand and Kurian, Maria and Dilwale, Swati and Kurungot, Sreekumar} } @article {47603, title = {Sulfonated polyvinyl alcohol ionomer membrane favoring smooth electrodeposition of zinc for aqueous rechargeable zinc metal batteries}, journal = {Sustainable Energy \& Fuels}, volume = {5}, year = {2021}, month = {OCT}, pages = {5557-5564}, type = {Article}, abstract = {One of the failure mechanisms of aqueous rechargeable zinc metal batteries (AZMBs) involves high surface area zinc (HSAZ)/dendrite-like deposits over the Zn-metal anode during long-term cycling. Negatively charged (anionic) polymeric ionomer electrolyte membranes and separators are known for suppressing the dendrite-/HSAZ-induced failure of AZMBs. However, the preparation of cost-effective and non-fluorinated ionomers from cheap and environmentally friendly polymers is essential to leverage the feasibility of AZMBs. The current work demonstrates the potential of an ionomer electrolyte membrane (P-AS-C-Zn) made by the crystallization-induced physical cross-linking of sulfonated poly (vinyl alcohol) (PVS) and poly (vinyl alcohol) (PVA) as a dendrite-/HSAZ-inhibiting separator for AZMBs. The P-AS-C-Zn membranes exhibited excellent Zn plating/stripping behavior with a stable voltage vs. time profile beyond 1100 h, compared to their neutral PVA-C-Zn counterpart without any ionomer character (cell failure at close to 280 h). Applying the optimized P-AS-C-Zn membrane in a MnO2||Zn full cell helps retain about 50\% of the initial capacity close to 600 cycles in the absence of extra manganese salt in the electrolyte, which is indeed promising.}, issn = {2398-4902}, doi = {10.1039/d1se00865j}, author = {Vijayakumar, Vidyanand and Torris, Arun and Kurian, Maria and Mathew, Megha Mary and Ghosh, Meena and Khairnar, Ajay B. and Badiger, Manohar V. and Kurungot, Sreekumar} } @article {48174, title = {Air-cathode interface-engineered electrocatalyst for solid-state rechargeable zinc-air batteries}, journal = {ACS Applied Energy Materials}, volume = {5}, year = {2022}, month = {JUL }, pages = {8756-8768}, type = {Article}, abstract = {

Solid-state rechargeable zinc-air batteries (ZABs) are gaining interest as a class of portable clean energy technology due to their advantages such as high theoretical energy density, intrinsic safety, and low cost. It is expected that an appropriately triple-phase boundary (TPB) engineered, bifunctional oxygen reaction (OER and ORR) electrocatalyst at the air- electrode of ZABs can redefine the performance characteristics of these systems. To explore this possibility, an electrode material consisting of manganese- cobalt-based bimetallic spinel oxide (MnCo2O4)-supported nitrogen-doped entangled graphene (MnCo2O4/NEGF) with multiple active sites responsible for facilitating both OER and ORR has been prepared. The porous 3D graphitic support significantly affects the bifunctional oxygen reaction kinetics and helps the system display a remarkable catalytic performance. The air electrode consisting of the MnCo2O4/NEGF catalyst coated over the gas diffusion layer (GDL) ensures the effective TPB, and this feature works in favor of the rechargeable ZAB system under the charging and discharging modes. As an important structural and functional attribute of the electrocatalyst, the porosity and nitrogen doping in the 3D conducting support play a decisive aspect in controlling the surface wettability (hydrophilicity/hydrophobicity) of the air electrode. The fabricated solid-state rechargeable ZAB device with the developed electrode displayed a maximum peak power density of 202 mW cm(-2), which is significantly improved as compared to the one based on the Pt/C + RuO2 standard catalyst pair (124 mW cm(-2)). The solid-state device which displayed an initial charge-discharge voltage gap of only 0.7 V at 10 mA cm(-2) showed only a small increment of 86 mV after 50 h.

}, keywords = {air-cathode interface, bifunctional oxygen catalyst, N-doped entangled graphene, solid-state zinc-air battery, spinel oxides}, issn = {2574-0962}, doi = {10.1021/acsaem.2c01266}, author = {Manna, Narugopal and Singh, Santosh K. and Kurian, Maria and Torris, Arun and Kurungot, Sreekumar} } @article {48356, title = {Influence of ice templating on oxygen reduction catalytic activity of metal-free heteroatom-doped mesoporous carbon derived from polypyrrole for zinc-air batteries}, journal = {Energy Technology}, volume = {10}, year = {2022}, month = {DEC}, type = {Article}, abstract = {

The development of highly active, cost-effective, and durable, noble metal-free oxygen reduction electrocatalysts is inevitable for the full-fledged implementation of fuel cells and zinc-air batteries. This work reports the synthesis of heteroatom (N, P, S)-doped metal-free mesoporous carbon-based electrocatalyst derived from polypyrrole by combining the ice templating, freeze-drying, and carbonization processes. The correlation between the structure and electrochemical activity of the polypyrrole-derived carbon-based electrocatalyst in the presence and absence of ice templating is investigated. The optimized electrocatalyst, aided by the ice-templating and freeze-drying step, shows an onset and half-wave potential (E-1/2) of 0.94 and 0.78 V vs reversible hydrogen electrode, respectively, in an alkaline electrolyte (0.1 m KOH). Later, the application of the optimized electrocatalyst is demonstrated in a primary zinc-air battery (ZAB) cell. The results prove that the ZAB device performance based on the homemade catalyst is on par with that of the state-of-the-art Pt/C cathode. The catalyst performance is correlated with the heteroatom doping and the enhanced porosity of the sample benefitted from ice templating. Ultimately, this work depicts a facile and rational synthesis of a truly metal-free electrocatalyst for the primary ZABs that can be a potential replacement for state-of-the-art systems.

}, keywords = {metal-free electrocatalysts, oxygen reduction reaction, zinc-air batteries}, issn = {2194-4288}, doi = {10.1002/ente.202200840}, author = {Kurian, Maria and Ghosh, Meena and Vijayakumar, Vidyanand and Puthiyaveetil, Priyanka Pandinhare and Torris, Arun and Kurungot, Sreekumar} } @article {48692, title = {Binder-free and flexible VOPO4/CNT film as cathode for aqueous rechargeable Zn-metal battery}, journal = {Advanced Sustainable Systems}, volume = {7}, year = {2023}, month = {SEP}, type = {Article}, abstract = {

Aqueous rechargeable Zn-metal batteries (AZMBs) are promising energy storage aids due to their inherent safety, low cost, and competent performance, with prospects in stationary and portable applications. In this regard, one of the critical requirements is developing electrodes that can adapt to mechanical deformation without compromising the charge storage performance. The current work demonstrates the development of a binder-free and mechanically flexible composite cathode film (VP/fCNT-F, where {\textquoteleft}F{\textquoteright} stands for the film) based on VOPO4 (VP) and functionalized carbon nanotubes (fCNTs). The VP/fCNT-F film processing involves simple vacuum filtration of the composite obtained from the in-situ reaction of the fCNTs and the VP precursor in an aqueous medium. The functionalization of carbon nanotube (CNT) is important for the homogenous dispersion of VP and fCNT. The VP/fCNT-F electrode is used as a monolithic electrode in AZMB cells in combination with both liquid and quasi-solid-state gel polymer electrolytes. Besides, the utility of the VP/fCNT-F electrode in a flexible battery configuration is also demonstrated. Interestingly, in both the coin-cell and flexible configurations, the VP/fCNT-F electrode delivers a comparable discharge capacity of 90 and 78 mAh g(-1), respectively (at 0.1 A g(-1)), validating the advantage of the binder-free VP/fCNT-F electrode for AZMBs.

}, keywords = {binder-free cathodes, flexible batteries, layered VOPO4, polymer gel electrolytes, self-standing flexible films}, issn = {2366-7486}, doi = {10.1002/adsu.202300141}, author = {Dilwale, Swati and Babu, Athira and Puthiyaveetil, Priyanka Pandinhare and Kurian, Maria and Ghosh, Meena and Kurungot, Sreekumar} } @article {48676, title = {Electrode|electrolyte interface enhancement in quasi-solid-state zinc-air batteries through an anion conducting polymer electrolyte interlayer by in situ polymerization}, journal = {Journal of Materials Chemistry A}, volume = {11}, year = {2023}, month = {JUL}, pages = {14776-14787}, type = {Article}, abstract = {

This work introduces a novel concept of electrode|electrolyte interface enhancement using an ultraviolet (UV) light-assisted in situ polymerization strategy to improve the performance of quasi-solid-state zinc-air batteries (ZABs). The suitability of the UV polymerization strategy to process a mechanically stable OH- conducting anion exchange polymer electrolyte membrane (AEPEM) reinforced by a glass fiber (GF) separator is also reported. The in situ polymerized ionomer-skin/interlayer (a thin anion-conducting polymer coating over the air-cathode of ZAB) acts as a buffer layer to narrow down the performance gap generally observed between ZABs possessing quasi-solid-state electrolytes and standard liquid electrolytes, respectively. For instance, when combined with the in situ polymerization strategy, a rechargeable ZAB (rZAB) based on an AEPEM-GF composite membrane delivered a high power density of 140 mW cm(-2), higher than that of the one without an in situ polymerized ionomer interlayer (120 mW cm(-2)). Notably, in a flexible rZAB configuration, this new strategy resulted in enhanced rate capability and cycling stability for 14 h at an operating current density of 2 mA cm(-2).

}, issn = {2050-7488}, doi = {10.1039/d3ta02320f}, author = {Kurian, Maria and Vijayakumar, Vidyanand and Manna, Narugopal and Kanheerampockil, Fayis and Bhat, Suresh and Kurungot, Sreekumar} }