Stabilizing zinc deposition through solvation sheath regulation and preferential adsorption by electrolyte additive of lithium difluoro(oxalato)borate

Zhou, Weijun; Chen, Minfeng; Quan, Yuhui; Ding, Jun; Cheng, Hanlin; Han, Xiang; Chen, Jizhang; Liu, Bo; Shi, Siqi; Xu, Xinwu

doi:10.1016/j.cej.2023.141328

Cited by 16 publications

(7 citation statements)

References 64 publications

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“…Consequently, the adsorption of DR80 onto the surface of the zinc anode becomes notably more facile compared to Zn atoms and H 2 O molecules, providing further confirmation of the earlier speculation regarding the adsorption of DR80 onto the zinc anode. The charge–density difference analysis further highlights the chemisorption of DR80 on Zn through the polar sulfonic acid groups, as evidenced by the overlapping of electron clouds at the atomic level in Figure S18. , As a result, the potential mechanism behind the synergistic effect of DR80 in modulating the electrochemical performance of AZIBs is elucidated in Figure k. In the pristine electrolyte, zinc ions are solvated as [Zn(H 2 O) 6 ] 2+ , as illustrated in Figure j.…”

Section: Resultsmentioning

confidence: 99%

“…This interaction hinders the approach of SO 4 2− ions to Zn 2+ , thereby impeding their participation in the formation of the inner solvated shell. 38 The properties of the electrolyte directly influence the electrochemical reaction rate, electrode material stability, and electrochemical performance of AZIBs, and the addition of DR80 is bound to have an impact on the intrinsic properties of the electrolyte. The contact angle of the electrolyte on the surface of the zinc foil was analyzed, as depicted in Figure 1b,c.…”

Section: Resultsmentioning

confidence: 99%

“…As depicted in Figure S3, the representative peak at 983 cm –1 due to the SO 4 2– stretching vibration in the ZnSO 4 electrolyte undergoes a noticeable peak shift upon the addition of DR80, indicating the interaction between zinc ions and DR80 molecules. This interaction hinders the approach of SO 4 2– ions to Zn 2+ , thereby impeding their participation in the formation of the inner solvated shell …”

Section: Resultsmentioning

confidence: 99%

“…Consequently, the Zn ions tend to horizontally diffuse and accumulate on the electrode tips, leading to the gradual formation of zinc dendrites. 38 In contrast, the Zn ions within the ZnSO 4 -DR80 electrolyte exhibit a three-dimensional diffusion behavior after a nucleation process of ∼100 s. This observation confirms that the DR80 adsorbed on the surface of the Zn electrode facilitates the guided diffusion of Zn ions, resulting in more uniform and smoother zinc deposition. Linear sweep voltammetry is a reliable method for measuring the HER as it competes with Zn deposition.…”

Section: Acsmentioning

confidence: 96%

“…The charge−density difference analysis further highlights the chemisorption of DR80 on Zn through the polar sulfonic acid groups, as evidenced by the overlapping of electron clouds at the atomic level in Figure S18. 16,38 As a result, the potential mechanism behind the synergistic effect of DR80 in modulating the electrochemical performance of AZIBs is elucidated in Figure 4k. In the pristine electrolyte, zinc ions are solvated as [Zn(H 2 O) 6 ] 2+ , as illustrated in Figure 4j.…”

Section: Acsmentioning

confidence: 99%

See 4 more Smart Citations

Transforming Dye Molecules into Electrochemical Allies: Direct Red 80 as a Dual-Functional Electrolyte Additive for Dendrite-Free Aqueous Zinc-Ion Batteries

Wang,

Guo,

et al. 2023

ACS Appl. Mater. Interfaces

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Despite the numerous advantages of abundant zinc resources, low redox potential, and affordability, aqueous zinc-ion batteries (AZIBs) currently face limitations due to dendritic growth and side reactions. This study explores the use of low-cost and efficient anionic dyes, specifically Direct Red 80 (DR80) as dual-functional electrolyte additives to enhance the electrochemical performance of AZIBs and facilitate the reuse of dye wastewater. Experimental and theory calculation results all demonstrate that the DR80 molecules readily adsorb onto the surface of the zinc anode, creating a stable and robust solid electrolyte interphase layer. This layer acts as a protective barrier, effectively mitigating H + attacks and reducing both hydrogen evolution and corrosion reactions. Additionally, it covers any initial protrusions on the zinc anode, preventing the occurrence of the "tip-effect" phenomenon and limiting access of water to the zinc anode, thereby minimizing water decomposition. Moreover, the sulfonic acid groups of DR80 molecules displace some water molecules in [Zn(H 2 O) 6 ] 2+ , disrupting the original solvent sheath and reducing water decomposition. Especially, using the DR80 additive, the Zn/Zn cell reaches an impressive cycle life of 1500 h at 2 mA cm −2 @1 mAh cm −2 . Given the low cost and widespread availability, this additive shows great potential in the future practical implementation of AZIBs.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Acsmentioning

confidence: 96%

Section: Acsmentioning

confidence: 99%

See 3 more Smart Citations

Transforming Dye Molecules into Electrochemical Allies: Direct Red 80 as a Dual-Functional Electrolyte Additive for Dendrite-Free Aqueous Zinc-Ion Batteries

Wang,

Guo,

et al. 2023

ACS Appl. Mater. Interfaces

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Regulating Electrode/Electrolyte Interface with Additives towards Dendrite‐Free Zinc‐Ion Batteries

Cao,

Sun,

Zhang

et al. 2024

ChemElectroChem

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Aqueous zinc‐ion batteries (AZIBs) are highly promising for grid‐scale energy storage due to their high‐safety and low‐cost characteristics. Nevertheless, the progress in AZIBs has been impeded due to challenges encompassing corrosion, hydrogen evolution reaction, and the formation of dendrites on Zn anodes. These issues arise from the decomposition of active water molecules in the Zn2+ solvation structure in the electrolyte. Various strategies have been proposed to regulate the electrode/electrolyte interface to effectively address these problems. In spite of remarkable headway, an inadequacy of comprehensive studies addressing the mechanisms and evolutionary dynamics of the electrode/electrolyte interface is evident within scientific literature. This overview aims to provide a comprehensive overview of the strategies for regulating the electrode/electrolyte interface, focusing on dendrite‐free and side reactions‐suppressed AZIBs. These strategies include the introduction of metal ion additives, inorganic additives, surfactant additives, polymer additives and organic additives. Furthermore, a detailed examination is made on the effects and underlying mechanisms associated with modifying the electrolyte at the interface between the electrode and electrolyte. Moreover, an appraisal is provided on the performance metrics of diverse strategies and prospective research directions are recommended as well.

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Achieving Dendrite‐Free and By‐Product‐Free Aqueous Zn‐Ion Battery Anode via Nicotinic Acid Electrolyte Additive with Molecule‐Ion Conversion Mechanism

Liang,

Wu,

et al. 2024

Small

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The widespread adoption of aqueous Zn ion batteries is hindered by the instability of the Zn anode. Herein, an elegant strategy is proposed to enhance the stability of Zn anode by incorporating nicotinic acid (NA), an additive with a unique molecule‐ion conversion mechanism, to optimize the anode/electrolyte interface and the typical ZnSO4 electrolyte system. Experimental characterization and theoretical calculations demonstrate that the NA additive preferentially replaces H2O in the original solvation shell and adsorbs onto the Zn anode surface upon conversion from molecule to ion in the electrolyte environment, thereby suppressing side reactions arising from activated H2O decomposition and stochastic growth of Zn dendrites. Simultaneously, such a molecule‐to‐ion conversion mechanism may induce preferential deposition of Zn along the (002) plane. Benefiting from it, the Zn||Zn symmetric battery cycles stably for 2500 h at 1 mA cm−2, 1 mAh cm−2. More encouragingly, the Zn||AC full batteries and the Zn||AC full batteries using NA electrolyte and Zn||VO2 full batteries also exhibit excellent performance improvements. This work emphasizes the role of variation in the form of additives (especially weak acid‐based additives) in fine‐tuning the solvation structure and the anode/electrolyte interface, hopefully enhancing the performance of various aqueous metal batteries.

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Stabilizing zinc deposition through solvation sheath regulation and preferential adsorption by electrolyte additive of lithium difluoro(oxalato)borate

Cited by 16 publications

References 64 publications

Transforming Dye Molecules into Electrochemical Allies: Direct Red 80 as a Dual-Functional Electrolyte Additive for Dendrite-Free Aqueous Zinc-Ion Batteries

Transforming Dye Molecules into Electrochemical Allies: Direct Red 80 as a Dual-Functional Electrolyte Additive for Dendrite-Free Aqueous Zinc-Ion Batteries

Regulating Electrode/Electrolyte Interface with Additives towards Dendrite‐Free Zinc‐Ion Batteries

Achieving Dendrite‐Free and By‐Product‐Free Aqueous Zn‐Ion Battery Anode via Nicotinic Acid Electrolyte Additive with Molecule‐Ion Conversion Mechanism

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