Ion Sieve: Tailoring Zn<sup>2+</sup> Desolvation Kinetics and Flux toward Dendrite-Free Metallic Zinc Anodes

Jiao, Shangqing; Fu, Jimin; Wu, Mingzai; Hua, Tao; Hu, Haibo

doi:10.1021/acsnano.1c08638

Cited by 140 publications

(82 citation statements)

References 63 publications

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“…The electrostatic attraction with carbonyl oxygen has a positive effect on reducing the Zn 2+ deposition barrier. [ 35 ] Since the main obstacle of charge‐transference migration usually stems from the Zn 2+ desolvation process, [ 46,47 ] the reduced E a of Zn@ZCO confirms the facilitated Zn 2+ desolvation kinetics in the process of Zn plating through the ZCO layer, leading to flat Zn deposition with decreased energy consumption. Theoretical calculations were performed by DFT to explore the reasons for the enhanced kinetic performance of Zn@ZCO.…”

Section: Resultsmentioning

confidence: 99%

Spontaneous Construction of Nucleophilic Carbonyl‐Containing Interphase toward Ultrastable Zinc‐Metal Anodes

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Multifunctional interfacial engineering on the Zn anode to conquer dendrite growth, hydrogen evolution, and the sluggish kinetics associated with Zn deposition is highly desirable for boosting the commercialization of aqueous zinc‐ion batteries. Herein, a spontaneous construction of carbonyl‐containing layer on a Zn anode (Zn@ZCO) is rationally designed as an ion redistributor and functional protective interphase. It has strong zincphilicity and dendrite suppression ability due to the significant interaction of the highly electronegative and highly nucleophilic carbonyl oxygen, favoring ion transport and homogenizing Zn deposition effectively. On the other side, the hydrogen bond formed by the proton acceptor of oxygen atom in ZCO regulates the Zn‐ion desolvation process at the interfaces, thus bounding water activity and then mitigating water‐induced parasitic reactions. Consequently, the Zn@ZCO anode exhibits an extended cycling lifespan of 5000 h (>208 days) with a dendrite‐free surface and negligible by‐products. More encouragingly, the effectiveness is also convincing in NH4V4O10‐based full‐cells with excellent rate performance and cyclic stability. The stabilized Zn anode enabled by the strategy of spontaneous construction of functional solid electrolyte interphase brings forward a facile and instructive approach toward high‐performance zinc‐storage systems.

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Section: Resultsmentioning

confidence: 99%

Spontaneous Construction of Nucleophilic Carbonyl‐Containing Interphase toward Ultrastable Zinc‐Metal Anodes

et al. 2022

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“…Undoubtedly, the CPE strategy shows a remarkable improvement and surpasses the performance of Zn//Cu cells in the latest reported works (Table S2, Supporting Information). [26][27][28][29][30][31][32][33][34][35][36][37][38][39] To demonstrate the feasibility and efficiency of the CPE in full cell, NVO nanofibers are used as the cathodes to pair with Zn metal anodes. [40] The Zn//NVO full cell demonstrates nearly no capacity decay over 5000 cycles at a high rate of 5 A g −1 as shown in Figure 5f, featuring decent capacity ≈100 mAh g −1 and CE of >99%.…”

Section: Efficacy Of the Designed Cpementioning

confidence: 99%

Diminishing Interfacial Turbulence by Colloid‐Polymer Electrolyte to Stabilize Zinc Ion Flux for Deep‐Cycling Zn Metal Batteries

et al. 2022

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volumetric capacity of 5855 mAh cm −3 ) of metallic Zn. [1] However, nonuniform Zn deposition aggravates formation of dendrites and leads to a low Coulombic efficiency (CE), resulting in battery performance deterioration. It is believed that regulated Zn 2+ distribution is beneficial to the uniform Zn plating. [1,2] Many works in the field of Zn anode realize uniform Zn 2+ distribution and improve Zn electrochemistry by constructing efficient Zn 2+ transport path. [1][2][3] However, we find that at deep cycling (high current densities and capacities), the interfacial turbulence is a severe problem that cannot be ignored to destroy the stability of Zn 2+ transport path. In details, the Zn 2+ ions flux distribution is affected by two factors: construction and stabilization of Zn 2+ transport path. Homogeneous Zn 2+ channels are helpful to realize uniform ion flux distribution; while Zn 2+ transport path would be destructed due to inevitable severe interfacial turbulence caused by fluidity of electrolyte and undesired H 2 evolution reaction (HER), which would lead to the disturbance of ion flux and uneven Zn deposition. In addition, the HER is usually accompanied by metal corrosion. [3] This not only consumes water in the electrolyte, but also the generated H 2 would result in swelling of the cell and even cell rupture. Meanwhile, the consumption of H + in water results in the accumulation of residual OH − ions, driving the corrosion reaction to form inactive Zn 4 SO 4 (OH) 6 •xH 2 O byproducts. [4,5] Moreover, the operation of ZMBs with high capacities is limited owing to the incomplete Zn discharging process because accumulated Zn leads to increased polarization of the battery; High current density can also cause an inhomogeneous electric field, incomplete metal stripping, and excessive polarization especially current and concentration polarization. [6,7] These issues can cause more serious interfacial instability and disturbance for deep-cycling batteries with high areal capacities and high current densities, significantly undermining the performance of ZMBs and plaguing their scale-up implementation. Aqueous deeply rechargeable Zn metal electrodes can only be achieved when the interfacial turbulence is rectified. Considering that free water molecules in electrolytes induce H 2 evolution and interfacial corrosion, highly concentrated The fluidity of aqueous electrolytes and undesired H 2 evolution reaction (HER) can cause severe interfacial turbulence in aqueous Zn metal batteries (ZMBs) at deep cycling with high capacities and current densities, which would further perturb ion flux and aggravate Zn dendrite growth. In this study, a colloid-polymer electrolyte (CPE) with special colloidal phase and suppressed HER is designed to diminish interfacial turbulence and boost deep Zn electrochemistry. Density functional theory calculations confirm that the quantitative migratory barriers of Zn 2+ along the transport pathway in CPE demonstrate much smaller fluctuations compared with normal aqueous electrolyte, indicating...

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“…To overcome these challenges initiated by Zn dendrites, various strategies have been developed, such as adjusting the coordination environment (highly concentrated electrolyte, , interface desolvation, − and F-rich interfacial layer), regulating the interfacial electric field (3D scaffold Zn anode − and high conductive layer − ), and promoting uniform Zn deposition (surface polar group, , zincophilic hosts, − electrostatic shield, , epitaxial electrodeposition, , and optimizing ion flux − ). For example, Sun’s group reported a Cu–Zn/Zn composite electrode with enhanced cycling property for 1500 cycles .…”

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confidence: 99%

Highly Reversible Zn Metal Anodes Enabled by Freestanding, Lightweight, and Zincophilic MXene/Nanoporous Oxide Heterostructure Engineered Separator for Flexible Zn-MnO₂ Batteries

et al. 2022

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Aqueous zinc (Zn)-ion batteries are regarded as promising candidates for large-scale energy storage systems because of their high safety, low cost, and environmental benignity. However, the dendrite issue of Zn anode hinders their practical application. Herein, a freestanding, lightweight, and zincophilic MXene/nanoporous oxide heterostructure engineered separator is designed to stabilize a Zn metal anode. The nanoporous oxides prepared by a one-step vacuum distillation technique afford the advantages of large surface area, high porosity, and homogeneous porous structure. The zincophilic MXene@oxides layer can homogenize the electric field distribution, facilitate ion diffusion kinetics, reduce local current density, and promote even Zn ionic flux, which will regulate uniform Zn deposition and suppress side reactions. Accordingly, dendrite-free Zn anodes with stable cyclability are achieved for over 500 h at an ultrahigh area capacity of 10 mAh cm −2 . Besides, flexible, long-lifespan, and high-rate N/S-doped three-dimensional MXene@MnO 2 ||Zn full cells are constructed with the engineered separator. Moreover, this strategy can be successfully extended to lithium, sodium, potassium, and magnesium metal batteries, indicating that separator regulation is a universal approach to overcome the challenges of metal batteries.

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Ion Sieve: Tailoring Zn²⁺ Desolvation Kinetics and Flux toward Dendrite-Free Metallic Zinc Anodes

Cited by 140 publications

References 63 publications

Spontaneous Construction of Nucleophilic Carbonyl‐Containing Interphase toward Ultrastable Zinc‐Metal Anodes

Spontaneous Construction of Nucleophilic Carbonyl‐Containing Interphase toward Ultrastable Zinc‐Metal Anodes

Diminishing Interfacial Turbulence by Colloid‐Polymer Electrolyte to Stabilize Zinc Ion Flux for Deep‐Cycling Zn Metal Batteries

Highly Reversible Zn Metal Anodes Enabled by Freestanding, Lightweight, and Zincophilic MXene/Nanoporous Oxide Heterostructure Engineered Separator for Flexible Zn-MnO₂ Batteries

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Ion Sieve: Tailoring Zn2+ Desolvation Kinetics and Flux toward Dendrite-Free Metallic Zinc Anodes

Cited by 140 publications

References 63 publications

Spontaneous Construction of Nucleophilic Carbonyl‐Containing Interphase toward Ultrastable Zinc‐Metal Anodes

Spontaneous Construction of Nucleophilic Carbonyl‐Containing Interphase toward Ultrastable Zinc‐Metal Anodes

Diminishing Interfacial Turbulence by Colloid‐Polymer Electrolyte to Stabilize Zinc Ion Flux for Deep‐Cycling Zn Metal Batteries

Highly Reversible Zn Metal Anodes Enabled by Freestanding, Lightweight, and Zincophilic MXene/Nanoporous Oxide Heterostructure Engineered Separator for Flexible Zn-MnO2 Batteries

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Ion Sieve: Tailoring Zn²⁺ Desolvation Kinetics and Flux toward Dendrite-Free Metallic Zinc Anodes

Highly Reversible Zn Metal Anodes Enabled by Freestanding, Lightweight, and Zincophilic MXene/Nanoporous Oxide Heterostructure Engineered Separator for Flexible Zn-MnO₂ Batteries