Confining Iodine into Metal‐Organic Framework Derived Metal‐Nitrogen‐Carbon for Long‐Life Aqueous Zinc‐Iodine Batteries

Advanced Materials, Год журнала: 2024, Номер 36(38)

Опубликована: Июль 31, 2024

Abstract Aqueous zinc–iodine batteries (AZIBs) are highly appealing for energy requirements owing to their safety, cost‐effectiveness, and scalability. However, the inadequate redox kinetics severe shuttling effect of polyiodide ions impede commercial viability. Herein, several Zn‐MOF‐derived porous carbon materials designed, further preparation iron–doped (Fe–N–C, M9) with varied Fe doping contents is optimized based on a facile self‐assembly/carbonization approach. M9, atomic coordinated nitrogen atoms, employed as an efficient cathode host AZIBs. Functional modifications hosts involving species levels investigated. The adsorption tests, in situ Raman spectroscopy, UV–vis results demonstrate capability charge‐discharge mechanism iodine species. Furthermore, experimental findings theoretical analyses have proven that conversion enhanced through physicochemical confinement effect. This study offers basic principles strategic design single‐atom dispersed high‐performance Flexible soft–pack battery wearable microbattery applications also implications future long‐life aqueous designs.

Язык: Английский

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Aqueous Electrolyte With Weak Hydrogen Bonds for Four‐Electron Zinc–Iodine Battery Operates in a Wide Temperature Range

Advanced Materials, Год журнала: 2024, Номер 36(32)

Опубликована: Июнь 4, 2024

Abstract In the pursuit of high‐performance energy storage systems, four‐electron zinc–iodine aqueous batteries (4eZIBs) with successive I − /I 2 + redox couples are appealing for their potential to deliver high density and resource abundance. However, susceptibility positive valence hydrolysis instability Zn plating/stripping in conventional electrolyte pose significant challenges. response, polyethylene glycol (PEG 200) is introduced as co‐solvent m ZnCl solution design a wide temperature electrolyte. Through comprehensive investigation combining spectroscopic characterizations theoretical simulations, it elucidated that PEG disrupts intrinsic strong H‐bonds water by global weak PEG–H O interaction, which strengthens O─H covalent bond intensifies coordination 2+ . This synergistic effect substantially reduces activity restrain hydrolysis, facilitating kinetics, mitigating 3 formation smoothening deposition. The 4eZIBs optimized hybrid not only superior cyclability low fading rate 0.0009% per cycle over 20 000 cycles close‐to‐unit coulombic efficiency but also exhibit stable performance range from 40 °C −40 °C. study offers valuable insights into rational electrolytes 4eZIBs.

Язык: Английский

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Urea Chelation of I⁺ for High-Voltage Aqueous Zinc–Iodine Batteries

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Янв. 7, 2025

The multielectron conversion electrochemistry of I–/I0/I+ enables high specific capacity and voltage in zinc–iodine batteries. Unfortunately, the I+ ions are thermodynamically unstable highly susceptible to hydrolysis. Current endeavors primarily focus on exploring interhalogen chemistry activate I0/I+ couple. However, practical working is below theoretical level. In this study, redox couple fully activated, efficiently stabilized by a chelation agent cost-effective urea conventional aqueous electrolyte. A record-high plateau 1.8 V vs Zn/Zn2+ has been realized. Theoretical calculations combined with spectroscopy studies electrochemical tests reveal that coordination between electron-deficient electron-rich O N atoms molecules favorable for inhibits self-disproportionation I+, which turn promotes rapid kinetics excellent reversibility I0/I+. Moreover, decreases water activity electrolyte forming hydrogen bonds further suppress hydrolysis I+. Accordingly, 419 mAh g–1 delivered at 1C, 147 retained after 10,000 cycles 5C. This work offers effective insights into formulating halogen-free electrolytes high-performance

Язык: Английский

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Toward High-Energy-Density Aqueous Zinc–Iodine Batteries: Multielectron Pathways

ACS Nano, Год журнала: 2024, Номер 18(42), С. 28557 - 28574

Опубликована: Окт. 9, 2024

Aqueous zinc–iodine batteries (ZIBs) based on the reversible conversion between various iodine species have garnered global attention due to their advantages of fast redox kinetics, good reversibility, and multielectron feasibility. Although significant progress has been achieved in ZIBs with two-electron I–/I2 pathway (2eZIBs), relatively low energy density hindered practical application. Recently, four-electron I–/I2/I+ electrochemistry (4eZIBs) shown a improvement density. Nonetheless, use 4eZIBs is challenged by poor reversibility polyiodide shuttling during I+ hydrolysis I2/I+ conversion. In this Review, we thoroughly summarize fundamental understanding two ZIBs, including reaction mechanisms, limitations, strategies. Importantly, provide an intuitive evaluation assess potential highlight critical impacts Zn utilization rate. Finally, emphasize cost issues associated electrodes propose closed-loop recycling routes for sustainable storage ZIBs. These findings aim motivate application advanced promote storage.

Язык: Английский

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Diatomic Catalysts for Aqueous Zinc‐Iodine Batteries: Mechanistic Insights and Design Strategies

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(49)

Опубликована: Сен. 13, 2024

Abstract There has been a growing interest in developing catalysts to enable the reversible iodine conversion reaction for high‐performance aqueous zinc‐iodine batteries (AZIBs). While diatomic (DACs) have demonstrated superior performance various catalytic reactions due their ability facilitate synergistic charge interactions, application AZIBs remains unexplored. Herein, we present, first time, DAC comprising Mn−Zn dual atoms anchored on nitrogen‐doped carbon matrix (MnZn−NC) loading, resulting AZIB with capacity of 224 mAh g −1 at 1 A and remarkable cycling stability over 320,000 cycles. The electron hopping along Mn−N−Zn bridge is stimulated via spin exchange mechanism. This process broadens Mn 3d xy band width enhances metallic character catalyst, thus facilitating transfer between intermediates. Additionally, increased occupancy within d‐orbital Zn elevates Zn's d‐band center, thereby enhancing chemical interactions MnZn−NC I‐based species. Furthermore, our mechanism demonstrates potential applicability other Metal‐Zn−NC DACs spin‐polarized atoms. Our work elucidates clear mechanistic understanding provides new insights into catalyst design AZIBs.

Язык: Английский

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Energetic Hypervalent Organoiodine Electrochemistry for Aqueous Zinc Batteries

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(36), С. 25108 - 25117

Опубликована: Авг. 27, 2024

Hypervalent organoiodine compounds have been extensively utilized in organic synthesis, yet their electrochemical properties remain unexplored despite theoretically high redox potential compared with inorganic iodine, which primarily relies on the I

Язык: Английский

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Oxygen Evolution Reaction of Amorphous/Crystalline Composites of NiFe(OH)_x/NiFe₂O₄

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Янв. 29, 2025

Orbital structures are strongly correlated with catalytic performance, whereas their regulation strategy is still in pursuit. Herein, the Fe 3d and O 2p orbital hybridization was optimized by controlling content of amorphous NiFe(OH)x (a-NiFe(OH)x), which grown situ on crystalline NiFe2O4 (c-NiFe2O4) using an ultrasonic reduction method. The results electron energy loss spectroscopy (EELS) X-ray absorption spectra (XAS) revealed that Fe-Oa a-NiFe(OH)x effectively strengthened jointing adjacent oxygen (Oc) c-NiFe2O4, further confirmed higher antibonding energies based density functional theory (DFT) calculations. resultant Oa-Fe-Oc at composite interface leads to balanced adsorption desorption energies. Accordingly, optimal strong 3d-O enhanced OER overpotential 150 mV, lower than pristine sample. This work represents a promising approach via introduction phase construct highly efficient catalysts.

Язык: Английский

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Boosting Reversible Four-Electron Redox in Aqueous Zn-Iodine Batteries with Two Halogen Ionic Additives and a N, F Codoped Carbon Cathode

ACS Applied Energy Materials, Год журнала: 2025, Номер 8(1), С. 601 - 610

Опубликована: Янв. 1, 2025

Recent interest has focused on aqueous zinc–iodine batteries (AZIBs), yet their practical application is hampered by limited capacity and energy density. To overcome these limitations, we report herein AZIBs with improved electrochemical performance incorporating two halogen-containing ionic additives (0.1 M ZnI2 0.1 ZnBr2) into the ZnSO4 electrolyte. Importantly, unlike previously reported approaches, nitrogen fluorine codoped porous carbon (N/F-PC) can be directly utilized as cathode material for without need preloading iodine. This allows full utilization of its rich structure, thereby promoting four-electron redox reaction (based iodine molecule) facilitating conversion between I– I+. Besides, bromide (Br–) introduced to activate species stabilizing I+ through formation interhalogen bonds. The resulting display distinct discharge plateaus at 1.55 1.15 V, corresponding reversible reactions among I–/I0/I+. In contrast, control electrolyte ZnBr2 additive exhibits only a single plateau V. Consequently, N/F-PC-based demonstrate large specific 452.6 mAh g–1 huge density 584.1 Wh kg–1, significantly outperforming conventional Zn-iodine based I–/I0. strategy presented in this study may pave way development high-energy-density storage devices.

Язык: Английский

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All‐Climate Energy‐Dense Cascade Aqueous Zn‐I₂ Batteries Enabled by a Polycationic Hydrogel Electrolyte

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 16, 2025

Abstract The practical development of aqueous zinc‐iodine (Zn‐I 2 ) batteries is greatly hindered by the low energy density resulting from conventional I 0 /I − conversion and limited temperature tolerance. Here, a temperature‐insensitive polycationic hydrogel electrolyte borax‐bacterial cellulose / p (AM‐ co ‐VBIMBr) (denoted as BAVBr) for achieving an energy‐dense cascade Zn‐I battery over wide range −50 to 50 °C designed. A comprehensive investigation, combining advanced spectroscopic investigation DFT calculations, has revealed that presence Br species in gel facilitates reaction /Br . Simultaneously, it activates high voltage + redox through interhalogen formation. Consequently, sequential highly reversible reactions involving , are achieved with assistance −NR 3 units BAVBr, effectively suppressing hydrolysis electrolyte. lead area capacity 0.76 mAh cm −2 at loading 1 mg or 760 g −1 based on mass iodine, demonstrating exceptional long‐term cycling stability °C. This study offers valuable insights into rational design electrolytes high‐energy batteries, specifically tailored wide‐temperature operation.

Язык: Английский

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Anion-Cation Synergy Enables Reversible Seven-Electron Redox Chemistry for Energetic Aqueous Zinc-Iodine Batteries

Nano Energy, Год журнала: 2025, Номер unknown, С. 110884 - 110884

Опубликована: Март 1, 2025

Язык: Английский

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