Charge-Transfer Complex-Based Artificial Layers for Stable and Efficient Zn Metal Anodes

ACS Energy Letters, Journal Year: 2023, Volume and Issue: 8(6), P. 2718 - 2727

Published: May 24, 2023

Herein, we report a charge-transfer complex electrolyte additive, 7,7,8,8-tetracyanoquinodimethane (TCNQ), with high Zn affinity, which was tightly adsorbed on the surface of anode to form dense and robust interfacial layer suppress activity H2O. As verified by comprehensive experimental computational analyses, this could construct Zn–Zn(TCNQ)2 Ohmic contact interface, guide rapid ion/electron transport, ameliorate electric field distribution, inhibit direct between active H2O anode, demonstrating dendrite-free facile plating/stripping kinetics. Consequently, Zn||Zn symmetrical cell exhibits reversibility over 1000 h at 20 mA cm–2 5 depth discharge (43%). Moreover, Zn||MnO2 full delivers capacity 143.3 g–1 2000 even after 4000 cycles retention 94.7% returning 100 g–1.

Language: Английский

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A Double‐Charged Organic Molecule Additive to Customize Electric Double Layer for Super‐Stable and Deep‐Rechargeable Zn Metal Pouch Batteries

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(8)

Published: Nov. 12, 2023

Abstract The electrochemical performance of aqueous zinc metal batteries (AZMBs) is highly dependent on the electric double layer (EDL) properties at Zn electrode/electrolyte interface. Herein, a novel reconfigured EDL constructed via double‐charged theanine (TN) additive for super‐stable and deep‐rechargeable AZMBs. Experiments theoretical computations unravel that positively charged TN not only serves as preferential anchor to form water‐poor Helmholtz plane onto anode, but also its anionic end could coordinate with 2+ tailor solvation structure in diffusion further reconstruct inner H‐bonds networks, thus effectively guiding uniform deposition suppressing water‐induced side reactions. Consequently, Zn//Zn cells acquire outstanding cycling stabilities nearly 800 h high depth discharge 80%. Moreover, Zn//VOX full deliver substantial capacity retention (94.12% after 1400 cycles 2 A g −1 ) under practical conditions. Importantly, designed 2.7 Ah pouch cell harvests recorded energy density 42.3 Wh Kg 79.5 L –1 , remarkable 85.93% 220 50 mA . This innovative design concept reshape chemistry would inject fresh vitality into developing advanced AZMBs beyond.

Language: Английский

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Alleviating Side Reactions on Zn Anodes for Aqueous Batteries by a Cell Membrane Derived Phosphorylcholine Zwitterionic Protective Layer

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: June 19, 2023

Aqueous zinc (Zn) ion batteries are attractive for next generation with high safety, yet their applications still hindered by the uncontrollable dendrite formation and side reactions on Zn anode. Here, a polyzwitterion protective layer (PZIL) was engineered polymerizing 2-methacryloyloxyethyl phosphorylcholine (MPC) in carboxymethyl chitosan (CMCS), which renders following merits: choline groups of MPC can preferentially adsorb onto metal to avoid reactions; charged phosphate chelate Zn2+ regulate solvation structure, further improving reaction inhibition; Hofmeister effect between ZnSO4 CMCS enhance interfacial contact during electrochemical characterization. Consequently, symmetrical battery PZIL keep stable more than 1000 hours under ultra-high current density 40 mA cm-2 . The confers Zn/MnO2 full Zn/active carbon (AC) capacitor cycling performance density.

Language: Английский

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Hydrated Eutectic Electrolyte Induced Bilayer Interphase for High‐Performance Aqueous Zn‐Ion Batteries with 100 °C Wide‐Temperature Range

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(11)

Published: Dec. 13, 2023

Abstract The practical implementation of aqueous zinc‐ion batteries (AZIBs) encounters challenges such as dendrite growth, parasitic reactions, and severe decay in battery performance under harsh environments. Here, a novel hydrated eutectic electrolyte (HEE) composed Zn(ClO 4 ) 2 ·6H O, ethylene glycol (EG), InCl 3 solution is introduced to effectively extend the lifespan AZIBs over wide temperature range from −50 50 °C. Molecular dynamics simulations spectroscopy analysis demonstrate that H O molecules are confined within liquid network through dual‐interaction, involving coordination with Zn 2+ hydrogen bonding EG, thus weakening activity free water extending electrochemical window. Importantly, cryo‐transmission electron microscopy techniques reveal HEE situ forms zincophobic/zincophilic bilayer interphase by dissociation‐reduction molecules. Specifically, zincophilic reduces energy barrier for nucleation, promoting uniform deposition, while zincophobic prevents active contacting surface, inhibiting side reactions. Furthermore, relationships between structural evolution interfacial chemistry at electrode/electrolyte further discussed this work. scalability design strategy can bring benefits operating range.

Language: Английский

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A robust gradient solid electrolyte interphase enables fast Zn dissolution and deposition dynamics

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 17(2), P. 680 - 694

Published: Dec. 5, 2023

A robust gradient rigid–soft coupling SEI layer on the Zn surface results in ultra-long cycling stability and high zinc utilization rate of AZIBs.

Language: Английский

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A Functional Janus Ag Nanowires/Bacterial Cellulose Separator for High‐Performance Dendrite‐Free Zinc Anode Under Harsh Conditions

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(47)

Published: Sept. 20, 2023

Aqueous zinc-ion batteries (AZIBs) offer promising prospects for large-scale energy storage due to their inherent abundance and safety features. However, the growth of zinc dendrites remains a primary obstacle practical industrialization AZIBs, especially under harsh conditions high current densities elevated temperatures. To address this issue, Janus separator with an exceptionally ultrathin thickness 29 µm is developed. This features bacterial cellulose (BC) layer on one side Ag nanowires/bacterial (AgNWs/BC) other side. High zincophilic property excellent electric/thermal conductivity AgNWs make them ideal serving as ion pump accelerate Zn2+ transport in electrolyte, resulting greatly improved conductivity, deposition homogeneous Zn nuclei, dendrite-free Zn. Consequently, Zn||Zn symmetrical cells exhibit stable cycle life over 1000 h 80 mA cm-2 are sustained 600 at 10 50 °C. Further, enables cycling stability aqueous capacitors (AZICs), scaled-up flexible soft-packaged batteries. study demonstrates potential functional separators promoting application batteries, particularly conditions.

Language: Английский

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All‐Round Ionic Liquids for Shuttle‐Free Zinc‐Iodine Battery

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(8)

Published: Jan. 5, 2024

Abstract The practical implementation of aqueous zinc‐iodine batteries (ZIBs) is hindered by the rampant Zn dendrites growth, parasite corrosion, and polyiodide shuttling. In this work, ionic liquid EMIM[OAc] employed as an all‐round solution to mitigate challenges on both anode iodine cathode side. First, EMIM + embedded lean‐water inner Helmholtz plane (IHP) inert solvation sheath modulated OAc − effectively repels H 2 O molecules away from surface. preferential adsorption metal facilitates uniform nucleation via a steric hindrance effect. Second, can reduce shuttling hindering dissolution forming ‐I 3 dominated phase. These effects holistically enhance cycle life, which manifested || symmetric cells Zn‐I full cells. ZIBs with EAc deliver capacity decay rate merely 0.01 ‰ per after over 18,000 cycles at 4 A g −1 , lower self‐discharge better calendar life than without additive.

Language: Английский

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Gel polymer electrolytes for rechargeable batteries toward wide-temperature applications

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 5291 - 5337

Published: Jan. 1, 2024

Design principles, engineering strategies, challenges, and opportunities of gel polymer electrolytes for rechargeable batteries toward wide-temperature applications are thoroughly reviewed.

Language: Английский

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Adaptive Ionization-Induced Tunable Electric Double Layer for Practical Zn Metal Batteries over Wide pH and Temperature Ranges

ACS Nano, Journal Year: 2023, Volume and Issue: 17(22), P. 23181 - 23193

Published: Nov. 13, 2023

The violent side reactions of Zn metal in aqueous electrolyte lead to sharp local-pH fluctuations at the interface, which accelerate anode breakdown; thus, development an optimization strategy accommodate a wide pH range is particularly critical for improving batteries. Herein, we report pH-adaptive electric double layer (EDL) tuned by glycine (Gly) additive with pH-dependent ionization, exhibits excellent capability stabilize anodes wide-pH electrolytes. It discovered that Gly-ionic EDL facilitates directed migration charge carriers both mildly acidic and alkaline electrolytes, leading successful suppression local saturation. worth mentioning regulation effect concentration on inner Helmholtz plane (IHP) structure electrodes clarified depth. revealed Gly additives without dimerization can develop orderly dense vertical adsorption within IHP effectively reduce repulsive force Zn2+ isolate H2O from surface. Consequently, they tunable superior electrochemical performance temperature, involving prodigious cycle reversibility 7000 h symmetric cells ZnSO4-Gly electrolytes extended lifespan 50 times KOH-Gly Moreover, powder||MnO2 pouch cells, high-voltage Zn||Ni0.8Co0.1Mn0.1O2 Zn||NiCo-LDH also deliver cycling reversibility. enables ultrahigh depth discharge (DOD) 93%. This work elucidates design compatible might cause inspiration fields practical multiapplication scenarios anodes.

Language: Английский

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Gradient‐Structured and Robust Solid Electrolyte Interphase In Situ Formed by Hydrated Eutectic Electrolytes for High‐Performance Zinc Metal Batteries

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(8)

Published: Jan. 26, 2024

Abstract The mechanically and electrochemically stable ionically conducting solid electrolyte interphase (SEI) is important for the stabilization of metal anodes. Since SEIs are originally absent in aqueous zinc batteries (AZMBs), it very challenging to suppress water‐induced side reactions dendrite growth Zn anodes (ZMAs). Herein, a gradient‐structured robust gradient SEI, consisting B,O‐inner F,O‐exterior layer, situ formed by hydrated eutectic homogeneous reversible deposition, demonstrated. Moreover, molar ratio acetamide salt modulated prohibit water activity hydrolysis BF 4 − as well achieve high ionic conductivity owing regulation solvation sheath 2+ . Consequently, allows Zn||Zn symmetric cells cycling lifespan over 4400 h at 0.5 mA cm −2 Zn||PANI full deliver capacity retention 73.2% 4000 cycles 1 A g −1 demonstrate operation low temperatures. This work provides rational design corresponding dendrite‐free even under harsh conditions.

Language: Английский

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