Enabling selective zinc-ion intercalation by a eutectic electrolyte for practical anodeless zinc batteries

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 27, 2023

Two major challenges hinder the advance of aqueous zinc metal batteries for sustainable stationary storage: (1) achieving predominant Zn-ion (de)intercalation at oxide cathode by suppressing adventitious proton co-intercalation and dissolution, (2) simultaneously overcoming Zn dendrite growth anode that triggers parasitic electrolyte reactions. Here, we reveal competition between Zn2+ vs intercalation chemistry a typical using ex-situ/operando techniques, alleviate side reactions developing cost-effective non-flammable hybrid eutectic electrolyte. A fully hydrated solvation structure facilitates fast charge transfer solid/electrolyte interface, enabling dendrite-free plating/stripping with remarkably high average coulombic efficiency 99.8% commercially relevant areal capacities 4 mAh cm-2 function up to 1600 h 8 cm-2. By concurrently stabilizing redox both electrodes, achieve new benchmark in battery performance anode-free cells retain 85% capacity over 100 cycles 25 °C. Using this eutectic-design electrolyte, | |Iodine full are further realized 86% retention 2500 cycles. The approach represents avenue long-duration energy storage.

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 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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Selection criteria for electrical double layer structure regulators enabling stable Zn metal anodes

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(4), P. 1721 - 1731

Published: Jan. 1, 2023

Combined with experimental and theoretical studies, we revealed a critical criterion that gives priority to the SEI-forming capability of additives for developing effective EDL structure regulators.

Language: Английский

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Reunderstanding aqueous Zn electrochemistry from interfacial specific adsorption of solvation structures

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(7), P. 2910 - 2923

Published: Jan. 1, 2023

Reunderstanding the faradaic reaction mechanism at electrode/electrolyte interface from specific adsorption of solvation structures towards advanced aqueous Zn–Mn batteries.

Language: Английский

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Highly Reversible Zinc Metal Anodes Enabled by Solvation Structure and Interface Chemistry Modulation

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(36)

Published: Aug. 9, 2023

Abstract Aqueous Zn−ion batteries (AZIBs) promise appealing advantages including safety, affordability, and high volumetric energy density. However, rampant parasitic reactions dendrite growth result in inadequate Zn reversibility. Here, a biocompatible additive, L‐asparagine (Asp), low‐cost aqueous electrolyte, is introduced to address these concerns. Combining substantive verification tests theoretical calculations, it demonstrated that an Asp‐containing ZnSO 4 electrolyte can create robust nanostructured solid‐electrolyte interface (SEI) by simultaneously modulating the 2+ solvation structure optimizing metal‐molecule interface, which enables dense deposition. The optimized supports excellent reversibility achieving dendrite‐free plating/stripping over 240 h at utilization of 85.5% symmetrical cell average 99.6% Coulombic efficiency for 1600 cycles asymmetrical cell. Adequate full‐cell performance with poly(3,4‐ethylenedioxythiophene) intercalated vanadium oxide (PEDOT‐V 2 O 5 ) cathode, delivers areal capacity 4.62 mAh cm −2 holds 84.4% retention 200 under practical conditions ultrathin anode (20 µm) low negative/positive ratio (≈2.4). This engineering strategy provides new insights into regulating anode/electrolyte interfacial chemistries toward high‐performance AZIBs.

Language: Английский

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Manipulating Electric Double Layer Adsorption for Stable Solid‐Electrolyte Interphase in 2.3 Ah Zn‐Pouch Cells

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: March 31, 2023

Abstract Constructing a reliable solid‐electrolyte interphase (SEI) is imperative for enabling highly reversible zinc metal (Zn 0 ) electrodes. Contrary to conventional “bulk solvation” mechanism, we found the SEI structure dominated by electric double layer (EDL) adsorption. We manipulate EDL adsorption and Zn 2+ solvation with ether additives (i.e. 15‐crown‐5, 12‐crown‐4, triglyme). The 12‐crown‐4 medium on leads layer‐structured inner inorganic ZnF x /ZnS outer organic C−O−C components. This endows high rigidness strong toughness 100 cm 2 Zn||Zn pouch cell exhibit cumulative capacity of 4250 mAh −2 at areal‐capacity 10 . More importantly, 2.3 Ah 0.25 V O 5 ⋅ n H delivers recorded energy density 104 Wh L −1 runs >70 days under harsh conditions low negative/positive electrode ratio (2.2 : 1), lean electrolyte (8 g ), high‐areal‐capacity (≈13 ).

Language: Английский

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An extended substrate screening strategy enabling a low lattice mismatch for highly reversible zinc anodes

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 25, 2024

Aqueous zinc batteries possess intrinsic safety and cost-effectiveness, but dendrite growth side reactions of anodes hinder their practical application. Here, we propose the extended substrate screening strategy for stabilizing verify its availability (d

Language: Английский

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Facet‐Termination Promoted Uniform Zn (100) Deposition for High‐Stable Zinc‐Ion Batteries

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(31)

Published: June 27, 2023

Abstract Reversibility, usually evaluated by Coulombic efficiency (CE) and limited dendrite growth, has become the major roadblock toward widespread commercialization of zincion batteries. Tailoring Zn deposition behavior is vital to prevent growth. In this work, facet‐terminator serine introduced modulate interface obstruct rampant growth (100) plane. The cation (Ser + ) revealed preferentially adsorb onto electrode/electrolyte interface, suppressing interfacial parasitic reaction. Theoretical analysis postmortem/operando experimental techniques indicate that Ser bestows (100)‐dominated morphology zinc anodes, enabling a highly reversible dendrite‐free anode. These features endow anode with long cyclic life more than 800 h for Zn//Zn batteries high average 99.8% at 5 mA cm −2 mAh Zn//Cu When assembling commercial V 2 O , full battery delivers capacity 345.1 g −1 A retention 74.1% over 2000 cycles.

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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Solvation Modulation Enhances Anion‐Derived Solid Electrolyte Interphase for Deep Cycling of Aqueous Zinc Metal Batteries

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)

Published: July 31, 2023

Stable Zn anodes with a high utilization efficiency pose challenge due to notorious dendrite growth and severe side reactions. Therefore, electrolyte additives are developed address these issues. However, the always consumed by electrochemical reactions over cycling, affecting cycling stability. Here, hexamethylphosphoric triamide (HMPA) is reported as an additive for achieving stable of anodes. HMPA reshapes solvation structures promotes anion decomposition, leading in situ formation inorganic-rich solid-electrolyte-interphase. More interestingly, this decomposition does not involve HMPA, preserving its long-term impact on electrolyte. Thus, symmetric cells survive ≈500 h at 10 mA cm-2 mAh or ≈200 40 rate 85.6 %. The full Zn||V2 O5 exhibit record-high cumulative capacity even under lean condition (E/C ratio=12 μL mAh-1 ), limited supply (N/P ratio=1.8) areal (6.6 ).

Language: Английский

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