Dendrite-free Zn electrodeposition triggered by interatomic orbital hybridization of Zn and single vacancy carbon defects for aqueous Zn-based flow batteries

Lee, Ju‐Hyuk; Kim, Riyul; Kim, Soohyun; Heo, Jiyun; Kwon, Hyeokjin; Yang, Jung Hoon; Kim, Hee‐Tak

doi:10.1039/d0ee00723d

Cited by 132 publications

(68 citation statements)

References 54 publications

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“…[ 29 ] Further studies on defective carbon hosts revealed defective zincophilic sites that can induce homogenous zinc plating. [ 34,35 ] Therefore, the strategy of tuning zincophilicity of the surface has been proposed to suppress zinc‐dendrite formation and boost electrochemical performance. [ 36–41 ] However, the detailed nucleation of zinc and the mechanism on zincophilic sites is not understood.…”

Section: Figurementioning

confidence: 99%

Mechanism for Zincophilic Sites on Zinc‐Metal Anode Hosts in Aqueous Batteries

Xie

Wang

et al. 2021

Advanced Energy Materials

308

207

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The zinc‐metal anode (ZMA) is a critical component of rechargeable Zn‐based batteries. Zinc‐dendrite formation on ZMA during cycling causes an internal short‐circuit, thereby limiting long‐term practical operation of batteries. A strategy of introducing zincophilic sites shows promise in suppressing dendrite growth. However, the mechanism is not understood. Here, a detailed study of the mechanism of zincophilic sites based on multiple in situ/ex situ techniques is reported. Using a carbon‐host as a model system with nitrogen sites as zincophilic sites and both ex situ near‐edge X‐ray absorption fine structure (NEXAFS) and in situ Raman spectra, it is shown that zinc ions are bonded with pyridine sites to form ZnN bonds. The ZnN bonds induce spacious nucleation of zinc on carbon‐hosts and suppress zinc‐dendrite formation. The host with zincophilic sites exhibits a homogenous Zn deposition, together with boosted electrochemical performance. This finding underscores the impact of nitrogen zincophilic sites in suppressing zinc‐dendrite formation. It is shown that bonding between zinc ions and zincophilic sites is the mechanism for zincophilic nucleation in the ZMA host. These findings are expected to be of immediate benefit to researchers in battery technologies and materials science.

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Section: Figurementioning

confidence: 99%

Mechanism for Zincophilic Sites on Zinc‐Metal Anode Hosts in Aqueous Batteries

Xie

Wang

et al. 2021

Advanced Energy Materials

308

207

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“…[8][9][10] Them ajor obstacle for developing advanced ZIBs with long cycle life lies in the suppression of Zn dendrite and byproducts derived from decomposition of active H 2 Om olecules belonging to solvation layer of Zn 2+ inside the electrolyte. [8] There are numerous strategies to alleviate or suppress the Zn dendrite under some mild test conditions,s uch as controlling oriented growth of specific crystal plane, [11,12] coating ap rotective layer on Zn surface, [13][14][15][16] depositing Zn nanostructure on 3D skeleton, [17][18][19][20] modulating electrolyte structure. [21][22][23][24][25][26][27][28] Mixing some additives (including solute or solvent) into the original electrolyte is asimple and affordable solution for restraining the growth of dendrite.…”

Section: Introductionmentioning

confidence: 99%

Simultaneous Regulation on Solvation Shell and Electrode Interface for Dendrite‐Free Zn Ion Batteries Achieved by a Low‐Cost Glucose Additive

et al. 2021

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Dendrite growth and by‐products in Zn metal aqueous batteries have impeded their development as promising energy storage devices. We utilize a low‐cost additive, glucose, to modulate the typical ZnSO4 electrolyte system for improving reversible plating/stripping on Zn anode for high‐performance Zn ion batteries (ZIBs). Combing experimental characterizations and theoretical calculations, we show that the glucose in ZnSO4 aqueous environment can simultaneously modulate solvation structure of Zn2+ and Zn anode‐electrolyte interface. The electrolyte engineering can alternate one H2O molecule from the primary Zn2+‐6H2O solvation shell and restraining side reactions due to the decomposition of active water. Concomitantly, glucose molecules are inclined to absorb on the surface of Zn anode, suppressing the random growth of Zn dendrite. As a proof of concept, a symmetric cell and Zn‐MnO2 full cell with glucose electrolyte achieve boosted stability than that with pure ZnSO4 electrolyte.

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“…An umber of approaches have been reported to enhance Zn electrode reversibility including,b uilding artificial solid/ electrolyte interphases, [7] introducing an electrolyte additive, [8] modifying current collectors, [9] developing functional gel electrolyte, [10] and controlling Zn deposition. [11] Highly concentrated Zn-based electrolytes have recently been proposed for high-performance aqueous batteries. [6a, 12] By decreasing the number of free water molecules in the electrolyte,t he water-induced H 2 evolution and corrosion reaction were suppressed.…”

Section: Introductionmentioning

confidence: 99%

Boosting Zinc Electrode Reversibility in Aqueous Electrolytes by Using Low‐Cost Antisolvents

et al. 2021

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Antisolvent addition has been widely studied in crystallization in the pharmaceutical industries by breaking the solvation balance of the original solution. Here we report a similar antisolvent strategy to boost Zn reversibility via regulation of the electrolyte on a molecular level. By adding for example methanol into ZnSO4 electrolyte, the free water and coordinated water in Zn2+ solvation sheath gradually interact with the antisolvent, which minimizes water activity and weakens Zn2+ solvation. Concomitantly, dendrite‐free Zn deposition occurs via change in the deposition orientation, as evidenced by in situ optical microscopy. Zn reversibility is significantly boosted in antisolvent electrolyte of 50 % methanol by volume (Anti‐M‐50 %) even under harsh environments of −20 °C and 60 °C. Additionally, the suppressed side reactions and dendrite‐free Zn plating/stripping in Anti‐M‐50 % electrolyte significantly enhance performance of Zn/polyaniline coin and pouch cells. We demonstrate this low‐cost strategy can be readily generalized to other solvents, indicating its practical universality. Results will be of immediate interest and benefit to a range of researchers in electrochemistry and energy storage.

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Dendrite-free Zn electrodeposition triggered by interatomic orbital hybridization of Zn and single vacancy carbon defects for aqueous Zn-based flow batteries

Abstract: Highly reversible aqueous zinc anodes are demonstrated via suppressing surface diffusion of Zn adatoms from strong orbital hybridization of the Zn adatoms and single vacancy defects.

Cited by 132 publications

References 54 publications

Mechanism for Zincophilic Sites on Zinc‐Metal Anode Hosts in Aqueous Batteries

Mechanism for Zincophilic Sites on Zinc‐Metal Anode Hosts in Aqueous Batteries

Simultaneous Regulation on Solvation Shell and Electrode Interface for Dendrite‐Free Zn Ion Batteries Achieved by a Low‐Cost Glucose Additive

Boosting Zinc Electrode Reversibility in Aqueous Electrolytes by Using Low‐Cost Antisolvents

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