Regulating the Inner Helmholtz Plane with a High Donor Additive for Efficient Anode Reversibility in Aqueous Zn‐Ion Batteries

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 24, 2023

The performance of aqueous Zn ion batteries (AZIBs) is highly dependent on inner Helmholtz plane (IHP) chemistry. Notorious parasitic reactions containing hydrogen evolution (HER) and dendrites both originate from abundant free H2 O random deposition inside active IHP. Here, we report a universal high donor number (DN) additive pyridine (Py) with only 1 vol. % addition (Py-to-H2 volume ratio), for regulating molecule distribution Density functional theory (DFT) calculations molecular dynamics (MD) simulation verify that incorporated Py could tailor Zn2+ solvation sheath exclude molecules IHP effectively, which in favor preventing decomposition. Consequently, even at extreme conditions such as depth discharge (DOD) 80 %, the symmetric cell based can sustain approximately 500 h long-term stability. This efficient strategy DN additives furnishes promising direction designing novel electrolytes promoting practical application AZIBs, despite inevitably introducing trace organic additives.

Language: Английский

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Electrolyte‐Wettability Issues and Challenges of Electrode Materials in Electrochemical Energy Storage, Energy Conversion, and Beyond

Advanced Science, Journal Year: 2023, Volume and Issue: 10(17)

Published: April 21, 2023

Abstract The electrolyte‐wettability of electrode materials in liquid electrolytes plays a crucial role electrochemical energy storage, conversion systems, and beyond relied on interface process. However, most do not have satisfactory for possibly reaction. In the last 30 years, there are lot literature directed at exploiting methods to improve electrodes, understanding basic mechanisms materials, exploring effect its conversion, performance. This review systematically comprehensively evaluates storage performance used supercapacitors, metal ion batteries, metal‐based fuel cells water splitting as well capacitive deionization systems. Finally, challenges approaches improving characterization techniques electrolyte‐wettability, applied special environment other systems with electrodes electrolytes, which gives future possible directions constructing interesting meet demand high performance, also discussed.

Language: Английский

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Dendrite-Free and Highly Stable Zn Metal Anode with BaTiO₃/P(VDF-TrFE) Coating

ACS Energy Letters, Journal Year: 2023, Volume and Issue: 8(7), P. 2886 - 2896

Published: June 2, 2023

Aqueous rechargeable Zn metal batteries have garnered increasing attention due to their high theoretical capacity, safety, and low cost. However, commercialization has been impeded by the rapid cycling deterioration caused side reactions dendrite growth on anodes. The present work explores a dielectric organic–inorganic film with hydrophobic surface circumvent these problems suppress zinc anode. Dielectric BaTiO3/P(VDF-TrFE) (BTO/PVT) coating demonstrated promote uniform deposition inhibit growth. also regulates Zn-ion desolvation process at interfaces is crucial in preventing water from harming anode surface, leading dendrite-free little formation of byproducts. resulting BTO/PVT@Zn long lifespan 3000 h an average Coulombic efficiency 99.6% 1 mA cm–2. In addition, BTO/PVT@Zn||NH4V4O10 full cell shows good rate capability lifespan.

Language: Английский

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Dextran: A Multifunctional and Universal Electrolyte Additive for Aqueous Zn Ion Batteries

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(37)

Published: Aug. 13, 2023

Abstract The aqueous Zn ion battery (ZIB) is a potentially sustainable energy storage device. However, its performance still far from satisfactory. Herein, it demonstrated that branched sugar, dextran, widely used in eyedrop products to relieve irritated eyes, multifunctional and universal electrolyte additive enable high‐performance ZIBs. Experimental theoretical results reveal dextran has four functions: forming surface protective layer minimize side reactions, facilitating stepwise [Zn(H 2 O) 6 ] 2+ desolvation, preferably adsorbing on Zn(0002) planes supply desolvated homogenizing electric field. These functions are universally observed Zn(CF 3 SO ) , ZnSO 4 Zn(ClO ZnCl electrolytes. As demonstrations for practical applications, anodes deliver Coulombic efficiency of 99.97% after 3400 cycles an with 50 mg mL ‒1 cumulative plating capacity mAh cm ‒2 at 5 mA . Zn//V O full cells low negative/positive electrode ratio 2.18 can be stably cycled over 138 1 A g Pouch work under mechanical bending conditions. Zn//polyaniline cycle steadily 3000 0.5 −10 °C. Dextran shows excellent potential as low‐cost non‐toxic safe reliable

Language: Английский

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Covalent Organic Framework with 3D Ordered Channel and Multi-Functional Groups Endows Zn Anode with Superior Stability

Nano-Micro Letters, Journal Year: 2024, Volume and Issue: 16(1)

Published: Jan. 4, 2024

Abstract Achieving a highly robust zinc (Zn) metal anode is extremely important for improving the performance of aqueous Zn-ion batteries (AZIBs) advancing “carbon neutrality” society, which hampered by uncontrollable growth Zn dendrite and severe side reactions including hydrogen evolution reaction, corrosion, passivation, etc. Herein, an interlayer containing fluorinated zincophilic covalent organic framework with sulfonic acid groups (COF-S-F) developed on (Zn@COF-S-F) as artificial solid electrolyte interface (SEI). Sulfonic group (− SO 3 H) in COF-S-F can effectively ameliorate desolvation process hydrated ions, three-dimensional channel fluoride (-F) provide interconnected channels favorable transport ions ion-confinement effects, endowing Zn@COF-S-F dendrite-free morphology suppressed reactions. Consequently, symmetric cell stably cycle 1,000 h low average hysteresis voltage (50.5 mV) at current density 1.5 mA cm −2 . Zn@COF-S-F|MnO 2 delivers discharge specific capacity 206.8 mAh g −1 1.2 A after 800 cycles high-capacity retention (87.9%). Enlightening, building SEI metallic surface targeted design has been proved effective strategy to foster practical application high-performance AZIBs.

Language: Английский

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Dielectric–Metallic Double-Gradient Composition Design for Stable Zn Metal Anodes

ACS Energy Letters, Journal Year: 2023, Volume and Issue: 8(4), P. 2042 - 2050

Published: April 4, 2023

The commercial implementation of aqueous Zn-ion batteries is being impeded by the rampant dendrite growth and exacerbated side reactions on Zn metal anodes. Herein, a 60 nm artificial protective layer with spatial dielectric–metallic gradient composition (denoted as GZH) developed via HfO2 cosputtering. In this design, top high permittivity low electronic conductivity effectively suppresses hydrogen evolution. intermediate Zn-rich oxide region promotes dendrite-free deposition reinforces contact between sputtered layer. This design allows stable battery operation at currents. Symmetric cells Zn-GZH exhibit voltage separation over 500 h 10 mA cm–2 cutoff capacity 5 mAh cm–2. When paired vanadate cathode, full-cell delivers retention around 75% after 2000 cycles. concept may apply to other batteries.

Language: Английский

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Bifunctional Interphase with Target‐Distributed Desolvation Sites and Directionally Depositional Ion Flux for Sustainable Zinc Anode

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(25)

Published: April 18, 2023

Aqueous zinc batteries (AZBs) feature high safety and low cost, but intricate anodic side reactions dendrite growth severely restrict their commercialization. Herein, ethylenediaminetetraacetic acid (EDTA) grafted metal organic framework (MOF-E) is proposed as a dually-functional interphase for sustainable Zn anode. Specifically, the target-distributed EDTA serves an ion-trapped tentacle to accelerate desolvation ionic transport by powerful chemical coordination, while MOFs offer suitable channels induce oriented deposition. As result, MOF-E fundamentally suppresses guides horizontally arranged deposition with (002) preferred orientations. The Zn|MOF-E@Cu cell exhibits markedly improved Coulombic efficiency of 99.7 % over 2500 cycles, MOF-E@Zn|KVOH (KV12 O30-y ⋅ nH2 O) yields steady circulation 5000 [email protected] at 8 A g-1 .

Language: Английский

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Tailoring desolvation strategies for aqueous zinc-ion batteries

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: 17(14), P. 4819 - 4846

Published: Jan. 1, 2024

This review provides a comprehensive overview detailing the advancements in desolvation strategies pertaining to aqueous zinc-ion batteries (AZIBs) performances, addressing applications and working mechanisms of AZIBs.

Language: Английский

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Regulating the Inner Helmholtz Plane with a High Donor Additive for Efficient Anode Reversibility in Aqueous Zn‐Ion Batteries

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(21)

Published: March 24, 2023

Abstract The performance of aqueous Zn ion batteries (AZIBs) is highly dependent on inner Helmholtz plane (IHP) chemistry. Notorious parasitic reactions containing hydrogen evolution (HER) and dendrites both originate from abundant free H 2 O random deposition inside active IHP. Here, we report a universal high donor number (DN) additive pyridine (Py) with only 1 vol. % addition (Py‐to‐H volume ratio), for regulating molecule distribution Density functional theory (DFT) calculations molecular dynamics (MD) simulation verify that incorporated Py could tailor 2+ solvation sheath exclude molecules IHP effectively, which in favor preventing decomposition. Consequently, even at extreme conditions such as depth discharge (DOD) 80 %, the symmetric cell based can sustain approximately 500 h long‐term stability. This efficient strategy DN additives furnishes promising direction designing novel electrolytes promoting practical application AZIBs, despite inevitably introducing trace organic additives.

Language: Английский

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Maximizing Electrostatic Polarity of Non‐Sacrificial Electrolyte Additives Enables Stable Zinc‐Metal Anodes for Aqueous Batteries

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 16, 2023

Abstract Although additives are widely used in aqueous electrolytes to inhibit the formation of dendrites and hydrogen evolution reactions on Zn anodes, there is a lack rational design principles systematic mechanistic studies how select suitable additive regulate reversible plating/stripping chemistry. Here, using saccharides as representatives, we reveal that electrostatic polarity non‐sacrificial critical descriptor for their ability stabilize anodes. Non‐sacrificial found continuously modulate solvation structure ions form molecular adsorption layer (MAL) uniform deposition, avoiding thick solid electrolyte interphase due decomposition sacrificial additives. A high renders sucrose best hydrated 2+ desolvation facilitates MAL formation, resulting cycling stability with long‐term cycle life thousands hours. This study provides theoretical guidance screening optimal high‐performance ZIBs.

Language: Английский

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