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15 pages, 7017 KiB

Open AccessArticle

A Self-Growing 3D Porous Sn Protective Layer Enhanced Zn Anode

by Dezhi Kong, Qingwei Zhang, Lin Li, Huimin Zhao, Ruixin Liu, Ziyang Guo and Lei Wang

Batteries 2023, 9(5), 262; https://doi.org/10.3390/batteries9050262 - 06 May 2023

Viewed by 1633

Abstract

Aqueous zinc-ion batteries (ZIBs) have received much attention because of their high safety, low pollution, and satisfactory energy density (840 mAh g⁻¹), which is important for the research of new energy storage devices. However, problems such as short cell cycle life [...] Read more.

Aqueous zinc-ion batteries (ZIBs) have received much attention because of their high safety, low pollution, and satisfactory energy density (840 mAh g⁻¹), which is important for the research of new energy storage devices. However, problems such as short cell cycle life and low coulombic efficiency (CE) of zinc (Zn) anodes due to disorderly growth of Zn dendrites and side reactions of hydrogen corrosion have delayed the practical application of ZIBs. In this work, a new “self-growth” method is proposed to build a robust and homogeneous three-dimensional (3D) nanoporous structure of tin (Sn)-coated Zn anodes (ZSN) in just 10 min by a simple and fast reaction, which can largely raise the surface area of the electrode plate. The ZSN not only provides abundant Zn nucleation sites, but also reduces the corrosion current, thus alleviating the self-corrosion of the electrolyte, reducing the occurrence of hydrogen precipitation side reactions, and effectively inhibiting the growth of Zn dendrites during cycling. Thus, a symmetric cell with a ZSN anode can be stabilized with very low voltage hysteresis (30 mV) for 480 h of stable plating/stripping cycles and can operate well for 200 h even at high current densities of 10 mA cm⁻². Supercapacitors and button cells were assembled, respectively, to verify the performance of ZSN electrodes in different energy storage tools. The ZSN||AC supercapacitor exhibited superior capacity (75 mAh g⁻¹) and high reversibility (98% coulombic efficiency) at a current density of 2 A g⁻¹. With a MnVO (MVO) electrode as the cathode, the ZSN||MVO full cell presents excellent cycling stability with a capacity retention of 95.4% after 500 cycles at 2 A g⁻¹, which far exceeds that of the bare Zn cell. Full article

(This article belongs to the Special Issue Zn-Ion and Zn–Air Batteries: Materials, Mechanisms and Applications)

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10 pages, 2282 KiB

Open AccessArticle

Stabilizing a Zn Anode by an Ionic Amphiphilic Copolymer Electrolyte Additive for Long-Life Aqueous Zn-Ion Batteries

by Yu-E Liu and Xin Wang

Batteries 2023, 9(1), 25; https://doi.org/10.3390/batteries9010025 - 29 Dec 2022

Cited by 5 | Viewed by 2631

Abstract

The rampant growth of zinc dendrites and severe uncontrollable reactions have largely limited the industrialization of aqueous Zn-ion batteries. Electrolyte additive engineering was found to be a facile yet effective strategy in addressing these issues; however, traditional organic small molecule additives raise additional [...] Read more.

The rampant growth of zinc dendrites and severe uncontrollable reactions have largely limited the industrialization of aqueous Zn-ion batteries. Electrolyte additive engineering was found to be a facile yet effective strategy in addressing these issues; however, traditional organic small molecule additives raise additional safety and health risks and thus compromise the intrinsic advantage of aqueous batteries. In this study, we report a polyacrylonitrile-co-poly(2-acrylamido-2-methylpropanesulfonic acid) (PAN-co-PAMPS) copolymer with ionic and hydrophilicity PAMPS and non-ionic PAN, which acts as an electrolyte additive to regulate the Zn deposition in aqueous Zn-ion batteries. The hydrophilicity of PAMPS is designed to meet water solubility. Moreover, ionic PAMPS reacts with a Zn anode surface, chemically peels the surface, leaves a pre-polished anode surface, and removes heterogeneity and impurity of the metal surface. All these effects are beneficial for homogeneous zinc ion deposition and long-life battery. The PAN segments act as a water-shielding layer on a Zn anode to prevent its direct contact with H₂O. Consequently, the Zn|Zn symmetric cells with additive-containing electrolytes have a much longer life than those without additives (up to eight times) at a current density of 1 mA cm⁻² and a capacity of 1 mA h cm⁻². The assembled Zn|Cu cells and the Zn|V₂O₅ full batteries also display prominent electrochemical reversibility. The reactively acidic amphiphilic polymer provides not only an alternative strategy for the design of multi-functional electrolyte additives, but also constitutes an easy-to-operate way for advancing commercialization of aqueous zinc-storage devices. Full article

(This article belongs to the Special Issue Zn-Ion and Zn–Air Batteries: Materials, Mechanisms and Applications)

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12 pages, 2831 KiB

Open AccessArticle

Ag-Doping Effect on MnO₂ Cathodes for Flexible Quasi-Solid-State Zinc-Ion Batteries

by Yanxin Liao, Chun Yang, Qimeng Xu, Wenxuan Zhao, Jingwen Zhao, Kuikui Wang and Hai-Chao Chen

Batteries 2022, 8(12), 267; https://doi.org/10.3390/batteries8120267 - 02 Dec 2022

Cited by 3 | Viewed by 2064

Abstract

Rechargeable aqueous Zn/MnO₂ batteries are very potential for large-scale energy storage applications owing to their low cost, inherent safety, and high theoretical capacity. However, the MnO₂ cathode delivers unsatisfactory cycling performance owing to its low intrinsic electronic conductivity and dissolution issue. [...] Read more.

Rechargeable aqueous Zn/MnO₂ batteries are very potential for large-scale energy storage applications owing to their low cost, inherent safety, and high theoretical capacity. However, the MnO₂ cathode delivers unsatisfactory cycling performance owing to its low intrinsic electronic conductivity and dissolution issue. Herein, we design and synthesize a Ag-doped sea-urchin-like MnO₂ material for rechargeable zinc-ion batteries (ZIBs). Doping Ag was found to reduce charge transfer resistance, increase the redox activity, and improve the cycling stability of MnO₂. The unique sea-urchin-like structure maintains rich active sites for charge storage. As a result, the Ag-doped MnO₂-based ZIB presents a high reversible specific capacity to 315 mA h g⁻¹ at 50 mA g⁻¹, excellent rate performance, and a capacity retention of 94.4% when cycling over 500 cycles. An ex situ TEM test demonstrates the low-dissolution property of Ag-doped MnO₂. A flexible quasi-solid-state ZIB is successfully assembled using Ag-doped MnO₂ on graphite paper, which shows a stable specific capacity of 171 mA h g⁻¹ at 1 A g⁻¹ when cycled over 600 cycles. Our investigation demonstrates the significant role played by Ag doping in enhancing the ZIB performance of MnO₂, and gives some insight into developing advanced active materials by heteroatom doping. Full article

(This article belongs to the Special Issue Zn-Ion and Zn–Air Batteries: Materials, Mechanisms and Applications)

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19 pages, 8195 KiB

Open AccessArticle

Chitosan-Carboxymethylcellulose Hydrogels as Electrolytes for Zinc–Air Batteries: An Approach to the Transition towards Renewable Energy Storage Devices

by María Fernanda Bósquez-Cáceres, Lola De Lima, Vivian Morera Córdova, Anabel D. Delgado, José Béjar, Noé Arjona, Lorena Álvarez-Contreras and Juan P. Tafur

Batteries 2022, 8(12), 265; https://doi.org/10.3390/batteries8120265 - 30 Nov 2022

Cited by 7 | Viewed by 3389

Abstract

Biopolymers are promising materials as electrolytes with high flexibility, good performance, cost effectiveness, high compatibility with solvents, and film-forming ability. Chitosan (CS) and carboxymethylcellulose (CMC) can form an intermolecular complex, giving rise to hydrogels capable of absorbing ionic solutions. Citric acid (CA) is [...] Read more.

Biopolymers are promising materials as electrolytes with high flexibility, good performance, cost effectiveness, high compatibility with solvents, and film-forming ability. Chitosan (CS) and carboxymethylcellulose (CMC) can form an intermolecular complex, giving rise to hydrogels capable of absorbing ionic solutions. Citric acid (CA) is an effective biological chemical crosslinker that assists the formation of amide and ester bonds between CMC and CS, resulting in a structure with high ionic conductivity and good structural integrity. In this study, a chemical crosslinking strategy is used to synthesize electrolyte hydrogels for zinc–air batteries. The effects of crosslinking are studied on the structural and electrochemical performance of the membranes. The results show an improvement in the ionic conductivity with respect to the homologous electrolyte hydrogel systems reported, with a maximum of 0.19 S∙cm⁻¹ at 30 °C. In addition, the cyclic voltammetry studies showed a current intensity increase at higher CA content, reaching values of 360 mA∙cm⁻². Structural characterization suggests a higher thermal stability and a decrease in the degree of crystallinity caused by the polymers’ crosslinking. Finally, these membranes were tested in Zn–air batteries, obtaining power densities of 85 mW∙cm⁻². The proposed hydrogels show to be appropriate for energy zinc–air battery applications and present an alternative to support the sustainable energy transition. Full article

(This article belongs to the Special Issue Zn-Ion and Zn–Air Batteries: Materials, Mechanisms and Applications)

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12 pages, 5605 KiB

Open AccessArticle

SiO₂-Alginate-Based Gel Polymer Electrolytes for Zinc-Ion Batteries

by Peishu Tian, Xin Zhong, Caiting Gu, Zhe Wang and Fengwei Shi

Batteries 2022, 8(10), 175; https://doi.org/10.3390/batteries8100175 - 11 Oct 2022

Cited by 4 | Viewed by 2638

Abstract

Aqueous Zn-ion batteries (AZIBs) are quite promising energy sources. However, aqueous electrolytes present many challenges such as hydrolysis reactions, liquid leakage, Zn dendrites, and interfacial side reactions. To solve the above problems of aqueous electrolytes, in this study, a kind of SiO₂ [...] Read more.

Aqueous Zn-ion batteries (AZIBs) are quite promising energy sources. However, aqueous electrolytes present many challenges such as hydrolysis reactions, liquid leakage, Zn dendrites, and interfacial side reactions. To solve the above problems of aqueous electrolytes, in this study, a kind of SiO₂-sodium alginate gel polymer electrolyte (SiO₂-SA GPE) is prepared through a one-pot method. The SiO₂-SA GPE possessed high ionic conductivity of 1.144 × 10⁻² S·cm⁻¹ and perfect mechanical strength. The Zn//LiFePO₄ batteries assembled with SiO₂-SA GPE delivered a high discharge specific capacity of 89.9 mAh g⁻¹ (capacity retention = 74.9%) after 300 cycles at 1 C, which was much better than traditional liquid electrolytes (residual discharge capacity = 79.2 mAh g⁻¹). Results of the rate performance and long cycle life of AZIBs proved that SiO₂-SA GPE could effectively prevent zinc dendrites and side reactions, providing a feasible strategy for improving the performance of AZIBs. Full article

(This article belongs to the Special Issue Zn-Ion and Zn–Air Batteries: Materials, Mechanisms and Applications)

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11 pages, 2266 KiB

Open AccessEditor’s ChoiceArticle

Multi-Functional Potassium Ion Assists Ammonium Vanadium Oxide Cathode for High-Performance Aqueous Zinc-Ion Batteries

by Dan He, Tianjiang Sun, Qiaoran Wang, Tao Ma, Shibing Zheng, Zhanliang Tao and Jing Liang

Batteries 2022, 8(8), 84; https://doi.org/10.3390/batteries8080084 - 08 Aug 2022

Cited by 4 | Viewed by 2599

Abstract

Ammonium vanadium oxide (NH₄V₄O₁₀) is a promising layered cathode for aqueous zinc-ion batteries owing to its high specific capacity (>300 mA h g⁻¹). However, the structural instability causes serious cycling degradation through irreversible insertion/extraction of [...] Read more.

Ammonium vanadium oxide (NH₄V₄O₁₀) is a promising layered cathode for aqueous zinc-ion batteries owing to its high specific capacity (>300 mA h g⁻¹). However, the structural instability causes serious cycling degradation through irreversible insertion/extraction of NH₄⁺. Herein, a new potassium ammonium vanadate K_x(NH₄)_1−xV₄O₁₀ (named KNVO) is successfully synthesized by a one-step hydrothermal method. The inserted of K⁺ can act as structural pillars, connect the adjacent layers closer and partially reduce the de-insertion of NH₄⁺. Due to the multi-functional of K⁺, the prepared KNVO presents a high specific discharge capacity of 432 mA h g⁻¹ at a current density of 0.4 A g⁻¹, long cycle stability (2000 cycles, 94.2%) as well as impressive rate performance (200 mA h g⁻¹ at 8 A g⁻¹). Full article

(This article belongs to the Special Issue Zn-Ion and Zn–Air Batteries: Materials, Mechanisms and Applications)

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Review

Jump to: Research

20 pages, 4749 KiB

Open AccessReview

Two-Dimensional Materials for Dendrite-Free Zinc Metal Anodes in Aqueous Zinc Batteries

by Wen Xu, Minghui Zhang, Yanfeng Dong and Jingwen Zhao

Batteries 2022, 8(12), 293; https://doi.org/10.3390/batteries8120293 - 19 Dec 2022

Cited by 4 | Viewed by 2911

Abstract

Aqueous zinc batteries (AZBs) show promising applications in large-scale energy storage and wearable devices mainly because of their low cost and intrinsic safety. However, zinc metal anodes suffer from dendrite issues and side reactions, seriously hindering their practical applications. Two-dimensional (2D) materials with [...] Read more.

Aqueous zinc batteries (AZBs) show promising applications in large-scale energy storage and wearable devices mainly because of their low cost and intrinsic safety. However, zinc metal anodes suffer from dendrite issues and side reactions, seriously hindering their practical applications. Two-dimensional (2D) materials with atomic thickness and large aspect ratio possess excellent physicochemical properties, providing opportunities to rationally design and construct practically reversible zinc metal anodes. Here, we systematically summarize the recent progress of 2D materials (e.g., graphene and MXene) that can be used to enable dendrite-free zinc metal anodes for AZBs. Firstly, the construction methods and strategies of 2D materials/Zn hybrid anodes are briefly reviewed, and are classified into protecting layers on Zn foils and host materials for Zn. Secondly, various 2D material/Zn hybrid anodes are elaborately introduced, and the key roles played by 2D materials in stabilizing the Zn/Zn²⁺ redox process are specially emphasized. Finally, the challenges and perspectives of advanced 2D materials for advanced Zn anodes in next-generation AZBs are briefly discussed. Full article

(This article belongs to the Special Issue Zn-Ion and Zn–Air Batteries: Materials, Mechanisms and Applications)

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18 pages, 7175 KiB

Open AccessFeature PaperReview

The Gel-State Electrolytes in Zinc-Ion Batteries

by Fulong Hu, Maoyun Li, Guowei Gao, Huiqing Fan and Longtao Ma

Batteries 2022, 8(11), 214; https://doi.org/10.3390/batteries8110214 - 03 Nov 2022

Cited by 14 | Viewed by 5345

Abstract

Zinc-ion batteries (ZIBs) are receiving increasing research attention due to their high energy density, resource abundance, low-cost, intrinsic high-safety properties, and the appropriate plating/stripping voltage. Gel-state electrolytes possess merits of having a wide electrochemical window, good flexibility, superior water retainability, and excellent compatibility [...] Read more.

Zinc-ion batteries (ZIBs) are receiving increasing research attention due to their high energy density, resource abundance, low-cost, intrinsic high-safety properties, and the appropriate plating/stripping voltage. Gel-state electrolytes possess merits of having a wide electrochemical window, good flexibility, superior water retainability, and excellent compatibility with aqueous electrolytes, which makes them potential candidates for flexible batteries. However, the practical applications of ZIBs with gel-state electrolytes still have some issues of water content easily dropping, poor mechanical stability, and the interface problem. Therefore, the application of hydrogel-based, self-healing gel, gel polymer, thermos-reversible, and other additional functions of gel electrolytes in ZIBs are discussed in this review. Following that, the design of multi-functional gel-state electrolytes for ZIBs is proposed. Finally, the prospect and the challenges of this type of battery are described. Full article

(This article belongs to the Special Issue Zn-Ion and Zn–Air Batteries: Materials, Mechanisms and Applications)

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