Electrolyte additive of sorbitol rendering aqueous zinc-ion batteries with dendrite-free behavior and good anti-freezing ability

Quan, Yuhui; Yang, Ming; Chen, Minfeng; Zhou, Weijun; Han, Xiang; Chen, Jizhang; Liu, Bo; Shi, Siqi; Zhang, Peixin

doi:10.1016/j.cej.2023.141392

Cited by 50 publications

(14 citation statements)

References 57 publications

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“…Further, the C1s X-ray photoelectron spectroscopy (XPS) of the Zn foil after soaking in ZSO + LAA and ZSO electrolytes all shows three apparent peaks of C=O (288.3 eV), C–O (285.3 eV), and C–C/C=C (283.6 eV) (Figure b), whereas the intensity of these three peaks on the Zn surface is greatly increased in the ZSO + LAA electrolyte, especially for the C=O and C–C/C=C, demonstrating that the LAA anions can be firmly adsorbed on the Zn surface. And the zinc anode surface with the ZSO + LAA electrolyte exhibits a smaller contact angle of 63.5° than that with the ZSO electrolyte (Figure S2), which can be ascribed to the good affinity between LAA and Zn metal, and the improved wettability can decrease the barrier for the nucleation of Zn deposition . As a result, a H 2 O-resistive passivation layer composed of LAA anions is formed, which can not only prevent the contact of H 2 O/Zn but also facilitate the Zn 2+ ion diffusion on the anode surface.…”

Section: Resultsmentioning

confidence: 99%

“…And the zinc anode surface with the ZSO + LAA electrolyte exhibits a smaller contact angle of 63.5°than that with the ZSO electrolyte (Figure S2), which can be ascribed to the good affinity between LAA and Zn metal, and the improved wettability can decrease the barrier for the nucleation of Zn deposition. 43 As a result, a H 2 O-resistive passivation layer composed of LAA anions is formed, which can not only prevent the contact of H 2 O/Zn but also facilitate the Zn 2+ ion diffusion on the anode surface. As demonstrated in chronoamperogram (CA) curves of Figure 2c, after applying −100 mV, the current density response in the ZSO electrolyte shows a gradually increasing trend in 300 s, attributing to the uncontrollable 2D Zn 2+ diffusion, which can easily cause dendrite growth on the Zn surface.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Reconstructing the Anode Interface and Solvation Shell for Reversible Zinc Anodes

Zhang

Cao

Chanajaree

et al. 2023

ACS Appl. Mater. Interfaces

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The attractive advantages of the Zn metal anode and water-based electrolyte, such as inherent safety and low cost, endow the zinc-ion batteries (ZIBs) with great potential in the future energy storage market. However, the severe surface side reactions and dendrites affect the service lifespan and electrochemical performance of ZIBs. Herein, a bifunctional electrolyte additive, L-ascorbic acid sodium (LAA), has been added into ZnSO 4 (ZSO) electrolyte (ZSO + LAA) to settle the above issues of ZIBs. On the one hand, the LAA additive tends to adsorb on the Zn anode surface to generate a H 2 O-resistive passivation layer, which can effectively isolate the H 2 O corrosion and regulate the Zn 2+ ion 3D diffusion, thus inducing a uniform deposition layer. On the other hand, the strong adsorption capacity between LAA and Zn 2+ can transform the solvated [Zn(H 2 O) 6 ] 2+ into [Zn(H 2 O) 4 LAA], thus reducing the coordinated H 2 O molecules and further suppressing side reactions. With this synergy effect, the Zn/Zn symmetric battery with the ZSO + LAA electrolyte can deliver a cycle life of 1200 h under 1 mA cm −2 , and the Zn/Ti battery also presents an ultrahigh Coulombic efficiency of 99.16% under 1 mA cm −2 , greatly superior to the batteries with the ZSO electrolyte. Additionally, the effectiveness of the LAA additive can be further verified in the Zn/MnO 2 full battery and pouch cell.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Reconstructing the Anode Interface and Solvation Shell for Reversible Zinc Anodes

Zhang

Cao

Chanajaree

et al. 2023

ACS Appl. Mater. Interfaces

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“…Further, the chronoamperometric curves of Zn||Zn symmetric cells with ZSO–0.05Ga and ZSO electrolytes at −200 mV are shown in Figure c. The gradual increase in current density in the first 100 s in the ZSO electrolyte is attributed to uncontrollable 2D diffusion, leading to surface dendrite growth. , The ZSO–0.05Ga electrolyte is gradually equilibrated within 60 s and achieves rapid three-dimensional (3D) diffusion on the Zn surface, which is attributed to the rapid construction of a protective layer and the adjustment of the solvation mechanism by the Ga additive on the surface, resulting in a dendrite-free zinc anode …”

Section: Resultsmentioning

confidence: 99%

“…The gradual increase in current density in the first 100 s in the ZSO electrolyte is attributed to uncontrollable 2D diffusion, leading to surface dendrite growth. 51,52 The ZSO−0.05Ga electrolyte is gradually equilibrated within 60 s and achieves rapid three-dimensional (3D) diffusion on the Zn surface, which is attributed to the rapid construction of a protective layer and the adjustment of the solvation mechanism by the Ga additive on the surface, resulting in a dendrite-free zinc anode. 53 The change of the solvated structure from [Zn(H 2 O) 6 ] 2+ to [(Zn(H 2 O) 3 Ga)] 2+ in the 2 M ZSO electrolyte by the Ga additive will be directly reflected in its electrochemical performance.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Low-Cost Electrolyte Additive Enables an Ultra-stable and Dendrite-Free Zn Anode

Dai,

Rajendran,

Cao

et al. 2023

Energy Fuels

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With their cost-effectiveness and superior safety features, zincion batteries (ZIBs) have emerged as highly promising energy storage systems. However, severe Zn dendrites and harmful side reactions exist on the Zn surface during cycling, resulting in poor coulombic efficiency (CE) and cycling stability. Herein, the above problems have been solved by adding sodium gluconate (Ga) additive in a 2 M ZnSO 4 (ZSO) electrolyte (ZSO− 0.05Ga). On the one hand, the Ga additive is adsorbed on the surface of the Zn metal anode to form a protective layer, which effectively reduces the corrosion reaction and induces uniform deposition. On the other hand, the strong adsorption capacity between Ga and Zn 2+ in the electrolyte can change the solvation structure of Zn 2+ , thereby effectively inhibiting the generation of side reactions. Thus, a Zn||Zn symmetric battery with a ZSO−0.05Ga electrolyte can be cycled stably for more than 2700 h at a current density of 1 mA cm −2 ; the Zn||Cu half-battery has an ultrahigh stability of 500 cycles; and the average charge−discharge efficiency reaches 99.2%. In addition, the Ga additive greatly improves the cycle stability of the Zn||AC battery (89.3% after 1000 cycles at 1 A g −1 ). This electrolyte additive with co-regulation functions of the solvation shell and interface adsorption effect provides an idea for improving the stability of the Zn anode for further application of ZIBs.

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“…[4] Among them, Zn dendrite growth induced by inhomogeneous Zn 2+ flux can pierce the separator and cause the short circuit of battery. [5] These parasitic reactions, including Zn corrosion and hydrogen evolution reaction (HER) caused by the thermodynamic instability of Zn metal in a mildly acidic electrolyte, can persistently destroy the interfacial stability between ZMA and electrolyte, leading to inferior Zn utilization and a short cycle lifespan. [6] Beyond that, H 2 O molecules escaping from the Zn 2+ solvated sheath exhibit higher reactivity than H 2 O molecules in the bulk electrolyte, which can exacerbate the parasitic reactions on the ZMA surface.…”

Section: Introductionmentioning

confidence: 99%

Reshaping Inner Helmholtz Layer and Electrolyte Structure via Multifunctional Organic Molecule Enabling Dendrite‐Free Zn Metal Anode

Liu

Jiang

Xie

et al. 2023

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The dendrite growth and parasitic reactions that occur on Zn metal anode (ZMA)/electrolyte interface hinder the development of aqueous zinc ion batteries (AZIBs) in next‐generation renewable energy storage systems. Fortunately, reconstructing the inner Helmholtz layer (IHL) by introducing an electrolyte additive, is viewed as one of the most promising strategies to harvest the stable ZMA. Herein, (4‐chloro‐3‐nitrophenyl) (pyridin‐4‐yl) methanone (CNPM) with quadruple functional groups is introduced into the ZnSO4 electrolyte to reshape the interface between ZMA and electrolyte and change the solvation structure of Zn2+. Density functional theory (DFT) calculations manifest that the ─C═O, ─Cl, ─C═N─, and ─NO2 functional groups of CNPM interact with metallic Zn simultaneously and adsorb on the ZMA surface in a parallel arrangement manner, thus forming a water‐poor IHL and creating well‐arranged ion transportation channels. Furthermore, theoretical calculations and experimental results demonstrate that CNPM absorbed on the Zn anode surface can serve as zincophilic sites for inducing uniform Zn deposition along the (002) plane. Benefiting from the synergistic effect of these functions, the dendrite growth and parasitic reactions are suppressed significantly. As a result, ZMA exhibits a long cycle life (2900 h) and high coulombic efficiency (CE) (500 cycles) in the ZnSO4+CNPM electrolyte.

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Electrolyte additive of sorbitol rendering aqueous zinc-ion batteries with dendrite-free behavior and good anti-freezing ability

Cited by 50 publications

References 57 publications

Reconstructing the Anode Interface and Solvation Shell for Reversible Zinc Anodes

Reconstructing the Anode Interface and Solvation Shell for Reversible Zinc Anodes

Low-Cost Electrolyte Additive Enables an Ultra-stable and Dendrite-Free Zn Anode

Reshaping Inner Helmholtz Layer and Electrolyte Structure via Multifunctional Organic Molecule Enabling Dendrite‐Free Zn Metal Anode

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