02415nas a2200301 4500008004100000022001400041245011600055210006900171260000800240300001200248490000700260520140900267653002801676653002501704653002601729653002001755653002501775100002701800700001701827700001801844700001701862700001901879700002101898700001901919700002401938700002401962856012701986 2020 eng d a1613-681000aIn situ cross-linked nonaqueous polymer electrolyte for zinc-metal polymer batteries and hybrid supercapacitors0 aIn situ crosslinked nonaqueous polymer electrolyte for zincmetal cSEP a20025280 v163 a

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.

10anonaqueous electrolytes10apolymer electrolytes10apostlithium batteries10aSupercapacitors10azinc-metal batteries1 aVijayakumar, Vidyanand1 aGhosh, Meena1 aKurian, Maria1 aTorris, Arun1 aDilwale, Swati1 aBadiger, Manohar1 aWinter, Martin1 aNair, Jijeesh, Ravi1 aKurungot, Sreekumar uhttp://library.ncl.res.in/content/situ-cross-linked-nonaqueous-polymer-electrolyte-zinc-metal-polymer-batteries-and-hybrid02135nas a2200193 4500008004100000022001400041245009500055210006900150260000900219300001400228490000700242520146600249100001701715700002701732700001801759700001901777700002401796856012101820 2021 eng d a1477-922600aNaphthalene dianhydride organic anode for a `rocking-chair' zinc-proton hybrid ion battery0 aNaphthalene dianhydride organic anode for a rockingchair zincpro cMAR  a4237-42430 v503 a

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 `rocking-chair' 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.

1 aGhosh, Meena1 aVijayakumar, Vidyanand1 aKurian, Maria1 aDilwale, Swati1 aKurungot, Sreekumar uhttp://library.ncl.res.in/content/naphthalene-dianhydride-organic-anode-rocking-chair-zinc-proton-hybrid-ion-battery02084nas a2200229 4500008004100000022001400041245013800055210006900193260000800262300001400270490000600284520125800290100002701548700001701575700001801592700002401610700001701634700002301651700002501674700002401699856013101723 2021 eng d a2398-490200aSulfonated polyvinyl alcohol ionomer membrane favoring smooth electrodeposition of zinc for aqueous rechargeable zinc metal batteries0 aSulfonated polyvinyl alcohol ionomer membrane favoring smooth el cOCT a5557-55640 v53 aOne 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.1 aVijayakumar, Vidyanand1 aTorris, Arun1 aKurian, Maria1 aMathew, Megha, Mary1 aGhosh, Meena1 aKhairnar, Ajay, B.1 aBadiger, Manohar, V.1 aKurungot, Sreekumar uhttp://library.ncl.res.in/content/sulfonated-polyvinyl-alcohol-ionomer-membrane-favoring-smooth-electrodeposition-zinc-aqueous02682nas a2200253 4500008004100000022001400041245010100055210006900156260000900225300001400234490000600248520179900254653002602053653003302079653003102112653003302143653001802176100002102194700002302215700001802238700001702256700002402273856013102297 2022 eng d a2574-096200aAir-cathode interface-engineered electrocatalyst for solid-state rechargeable zinc-air batteries0 aAircathode interfaceengineered electrocatalyst for solidstate re cJUL  a8756-87680 v53 a

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.

10aair-cathode interface10abifunctional oxygen catalyst10aN-doped entangled graphene10asolid-state zinc-air battery10aspinel oxides1 aManna, Narugopal1 aSingh, Santosh, K.1 aKurian, Maria1 aTorris, Arun1 aKurungot, Sreekumar uhttp://library.ncl.res.in/content/air-cathode-interface-engineered-electrocatalyst-solid-state-rechargeable-zinc-air-batteries02326nas a2200229 4500008004100000022001400041245016800055210006900223260000800292490000700300520143400307653003201741653003001773653002301803100001801826700001701844700002701861700004001888700001701928700002401945856012701969 2022 eng d a2194-428800aInfluence of ice templating on oxygen reduction catalytic activity of metal-free heteroatom-doped mesoporous carbon derived from polypyrrole for zinc-air batteries0 aInfluence of ice templating on oxygen reduction catalytic activi cDEC0 v103 a

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.

10ametal-free electrocatalysts10aoxygen reduction reaction10azinc-air batteries1 aKurian, Maria1 aGhosh, Meena1 aVijayakumar, Vidyanand1 aPuthiyaveetil, Priyanka, Pandinhare1 aTorris, Arun1 aKurungot, Sreekumar uhttp://library.ncl.res.in/content/influence-ice-templating-oxygen-reduction-catalytic-activity-metal-free-heteroatom-doped02281nas a2200253 4500008004100000022001400041245009700055210006900152260000800221490000600229520140600235653002501641653002301666653001801689653002901707653003301736100001901769700001701788700004001805700001801845700001701863700002401880856012301904 2023 eng d a2366-748600aBinder-free and flexible VOPO4/CNT film as cathode for aqueous rechargeable Zn-metal battery0 aBinderfree and flexible VOPO4CNT film as cathode for aqueous rec cSEP0 v73 a

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 `F' 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.

10abinder-free cathodes10aflexible batteries10alayered VOPO410apolymer gel electrolytes10aself-standing flexible films1 aDilwale, Swati1 aBabu, Athira1 aPuthiyaveetil, Priyanka, Pandinhare1 aKurian, Maria1 aGhosh, Meena1 aKurungot, Sreekumar uhttp://library.ncl.res.in/content/binder-free-and-flexible-vopo4cnt-film-cathode-aqueous-rechargeable-zn-metal-battery02015nas a2200205 4500008004100000022001400041245018000055210006900235260000800304300001600312490000700328520121400335100001801549700002701567700002101594700002701615700001701642700002401659856012601683 2023 eng d a2050-748800aElectrode|electrolyte interface enhancement in quasi-solid-state zinc-air batteries through an anion conducting polymer electrolyte interlayer by in situ polymerization0 aElectrodeelectrolyte interface enhancement in quasisolidstate zi cJUL a14776-147870 v113 a

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).

1 aKurian, Maria1 aVijayakumar, Vidyanand1 aManna, Narugopal1 aKanheerampockil, Fayis1 aBhat, Suresh1 aKurungot, Sreekumar uhttp://library.ncl.res.in/content/electrodeelectrolyte-interface-enhancement-quasi-solid-state-zinc-air-batteries-through