Stable Zinc Research Articles

Separator functionalization realizing stable zinc anode through microporous metal-organic framework with special functional group

Separator functionalization realizing stable zinc anode through microporous metal-organic framework with special functional group

Zincophilic Sites Enriched Hydrogen‐Bonded Organic Framework as Multifunctional Regulating Interfacial Layers for Stable Zinc Metal Batteries

AbstractTo construct an efficient regulating layer for Zn anodes that can simultaneously address the issues of dendritic growth and side reactions is highly demanded for stable zinc metal batteries (ZMBs). Herein, we fabricate a hydrogen‐bonded organic framework (HOF) enriched with zincophilic sites as a multifunctional layer to regulate Zn anodes with controlled spatial ion flux and stable interfacial chemistry (MA‐BTA@Zn). The framework with abundant H‐bonds helps capture H2O and remove the solvated shells on [Zn(H2O)6]2+, leading to suppressed side reactions. The HOF layer also helps form electrolyte‐philic surfaces and expose Zn (002) crystal planes which benefit for rapid conduction and uniform deposition of Zn2+, and weakened sides reactions. Additionally, the electrochemically active zincophilic sites (C=O, −NH2 and triazine groups) favor the targeted guidance and penetration of Zn2+ and provide advantageous sites for uniform Zn deposition. High Young's modulus of the HOF layer further contributes to a high interfacial flexibility and stability against Zn plating‐associated stress. The MA‐BTA@Zn symmetric cells thereby obtain a substantially extended battery life over 1000 h at 4 mA cm−2. The MA‐BTA@Zn||Cu half‐cell demonstrates a highly reversible Zn stripping/plating process over 1500 cycles with impressive average Coulombic efficiency (CE) of 99.5 % at 10 mA cm−2.

Stable Zinc Metal Battery Development: Using Fibrous Zirconia for Rapid Surface Conduction of Zinc Ions With Modified Water Solvation Structure.

The two most critical technical issues in Zn-based batteries, dendrite formation, and hydrogen evolution reaction, can be simultaneously addressed by introducing negatively charged fibrous ZrO2 as a separator. Electron redistribution between ZrO2 and Zn2+ ions renders the ZrO2 surface a preferred adsorption site for Zn2+ ions, making surface conduction the primary ion-transport mode. Surface conduction enables fibrous ZrO2 to exhibit a 6.54 times higher single-Zn-ion conductivity than that of conventional glass fiber, minimizing the concentration gradient of Zn2+ and suppressing dendrite formation. Additionally, strong Zr─O─Zn bonding stabilizes the Zn2+ ions with fewer solvated H2O molecules (≈2), preventing water molecules from approaching the electrode surface, as evidenced by a 58.8% decrease in the hydrogen evolution rate. Consequently, the cycling stability of a fibrous-ZrO2-based Zn/Zn symmetric cell (3000h at 1mAhcm-2 and 5mAcm-2) is approximately ten times greater than that of the conventional variant. Furthermore, a fibrous-ZrO2-based Zn-I2 full cell exhibits a notably high energy density (271.4Whkg-1) as well as a long lifespan (≈5000 cycles) at an ultrahigh current density (4Ag-1).

Interlayer expanded magnesium vanadium bronze for high capacity stable aqueous zinc batteries and method for proton contribution calculation

Magnesium vanadium bronze, MgV6O16·6H2O, is demonstrated as a cathode material for aqueous zinc batteries. Its remarkable electrochemical performance is attributed to the hydrated magnesium pillar layer, which enhances zinc ion diffusion into the structure, yielding a high initial discharge capacity of 298 mAh g−1 and capacity retention above 97 % after 300 cycles. Zinc ions and protons are co-intercalated into the MgV6O16·6H2O structure, while zinc hydroxide sulfate forms on the surface during the discharge process. Ex-situ X-ray diffraction results and elemental analyses confirm the zinc and proton co-intercalation reaction within the MgV6O16·6H2O structure during cycling, providing detailed insights into the electrochemical mechanisms. These findings demonstrate the potential of MgV6O16·6H2O as a high-energy cathode material for aqueous zinc batteries and offer a comprehensive understanding of the zinc ion and proton co-intercalation mechanism in the MgV6O16·6H2O structure.

Stable and reversible zinc metal anode with fluorinated graphite nanosheets surface coating

Stable and reversible zinc metal anode with fluorinated graphite nanosheets surface coating

Achieving dendrite-free zinc deposition by large-size anion-reinforced solvated structures for highly reversible zinc anode

The electrochemical instability of zinc anode caused by surface side reactions and irregular zinc deposition severely hinders the practical application of aqueous zinc ion batteries (AZIBs). In this work, diethylenetriaminepentaacetic acid, pentasodium salt (DTPA) was used as a novel electrolyte additive to modulate the electrochemical stability of Zn anode. The DTPA anion can strongly coordinate with Zn2+, thus enabling the formation of a unique large-size anion-enhanced solvation structure of electrolyte. In this, not only the generation of by-products on Zn anode can be effectively inhibited, but more importantly, the deposition kinetics of Zn2+ can be well regulated to induce even and stable zinc deposition. In addition, DTPA is more prone to chemically adsorbed on the surface of Zn anode than H2O, contributing to the resistance of electrochemical corrosion. Synergistically, the Zn anode demonstrates excellent cycling stability (3850 h at 1 mA cm−2, 1 mAh cm−2, and 500 h at 10 mA cm−2, 10 mAh cm−2), enhanced coulombic efficiency (99.83% upon 3500 cycles at 5 mA cm−2, 1 mAh cm−2), and high reversibility of 1050 h even at a stringent discharge depth of 80%. Particularly, the full cell assembled with NaV3O8·1·5H2O (NaVO) cathode can also operate stably for 1800 cycles at 2 A g−1 with a high capacity retain of 90.8%. This work may pave a new route to achieve high-performance AZIBs by regulating the deposition process of Zn2+ based on large-size anion-enhanced solvation structure of electrolyte.

Biomimetic Quasi‐Skin‐Capillary Structure Engineering of Ionic‐Electronic Conducting Full‐Chain Networks for Stable Zinc Powder Anodes

Biomimetic Quasi‐Skin‐Capillary Structure Engineering of Ionic‐Electronic Conducting Full‐Chain Networks for Stable Zinc Powder Anodes

WN-CoS2 nanoparticles encapsulated into carbon nanotubes enable a stable and high-performance rechargeable zinc air battery

The battery performance associated with longevity are the priorities for the industrialization of rechargeable zinc air battery (ZAB). Herein, we have reported the construction of WN-CoS2 heterostructure enveloped by nitrogen and phosphorus co-doped carbon nanotubes (WN-CoS2@NPCNT). WN-CoS2@NPCNT performs a superior oxygen evolution reaction (OER) catalytic activity of 279 mV overpotential to reach 10 mA cm−2, lowered by 85 mV with relative to CoS2@NCNT attributing to the heterostructure efficiently modulating the electronic structure of active sites. Besides, the half-wave potential reaches 0.875 V vs. RHE for WN-CoS2@NPCNT under oxygen reduction reaction (ORR) condition, corresponding to a 3.2-time higher kinetic current density compared to commercial Pt/C. Due to the exceptional bifunctionality, the battery performance is 205 mW cm−2 for WN-CoS2@NPCNT, 1.54 times higher than commercial counterpart, Pt/C + IrO2. Impressively, the battery performance sustains for 1000 h for WN-CoS2@NPCNT stemming from the confinement effect caused by NPCNT. In addition, the all-solid-state ZAB shows a high-power density of 55 mW cm−2.

Electric Field Regulator Constructed by Magnetron Sputtering for Dendrite‐Free and Stable Zinc Metal Anode

AbstractRechargeable aqueous zinc‐ion batteries (AZIBs) are considered to be one of the most promising devices in the next generation of energy storage systems. However, the uncontrolled growth of Zn dendrites during electroplating leads to rapid battery failure, which hinders the wide application of AZIBs. In this work, an Fe metal interface (FMI) with electric field regulation is designed on the Zn metal anode using a magnetron sputtering technology. The FMI layer with nanosheet array not only uniforms the surface electric field, but also adjusts the surface Zn2+ ion distribution to inhibit 2D diffusion. The strong orientation relationships of the FMI layer enhance the reversibility of Zn plating/stripping, improving the structural stability of the interface layer. Consequently, FMI@Zn symmetric cell exhibits ultra‐stable lifespan for over 6000 h (Cumulative plated capacity, CPC = 15 Ah cm−2) with a low voltage hysteresis of 46.4 mV and high Coulombic efficiency of 99.8% at 5 mA cm−2. Even at the large current density of 40 mA cm−2, the CPC reaches 19.7 Ah cm−2. The proposed electric field regulation strategy reveals a promising prospect for designing highly stable Zn anode, which also applies to other metal anodes in energy storage systems.

Agar-Activated Carbon Cathode with Optimized Redox Electrolyte for High-Energy and Stable Aqueous Zinc Hybrid Battery–Capacitor

Agar-Activated Carbon Cathode with Optimized Redox Electrolyte for High-Energy and Stable Aqueous Zinc Hybrid Battery–Capacitor

Organic molecular intercalation regulated hydrated vanadate cathodes with improved electrochemical properties and fast kinetics for aqueous zinc-ion batteries

Due to the large hydrated zinc ion radius resulting from the stable solvation structure with six water molecules in electrolyte, the interlayer spacing of most vanadium-based materials fails to meet the requirements for efficient insertion and extraction of Zn2+. Therefore, it is crucial to optimize and reconstruct the VO layer structure in order to achieve rapid and stable zinc storage. In this paper, composites of phenylalanine methyl ester (PM) inserted hydrated V2O5 (PMVO) are prepared using a one-step hydrothermal method. With the increase of PM insertion, the electrochemical properties initially exhibit enhancement followed by subsequent decline. Notably, PMVO-1.6 presents exceptional electrochemical performance, including a high capacity of 464 mAh g−1 at 0.1 A g−1, excellent rate capability with 220 mAh g−1 at 7 A g−1, and superior cycling stability with 97.5 % capacity retention after 1000 cycles at 4 A g−1. The incorporation of PM not only serves as stable structural pillars, but also reduces the solubilization of vanadium, facilitates the diffusion kinetics of hydrated zinc ions, and enhances the surface pseudo-capacitance effect.

Weakening the Space Charge Layer Effect Through Tethered Anion Electrolyte and Piezoelectric Effect Toward Ultra-Stable Zinc Anode.

The space charge layer (SCL) dilemma, caused by mobile anion concentration gradient and the rapid consumption of cations, is the fundamental reason for the generation of zinc dendrites, especially under high-rate discharge conditions. To address the issue, a physical (PbTiO3)/chemical (AMPS-Zn) barrier is designed to construct stable zinc ion flow and disrupt the gradient of anion concentration by coupling the ferroelectric effect with tethered anion electrolyte. The ferroelectric materials PbTiO3 with extreme-high piezoelectric constant can spontaneously generate an internal electric field to accelerate the movement of zinc ions, and the polyanionic polymer AMPS-Zn can repel mobile anions and disrupt the anions concentration gradient by tethering anions. Through numerical simulations and analyses, it is discovered that a high Zn2+ transference number can effectively weaken the SCL, thus suppressing the occurrence of zinc dendrites and parasitic side reactions. Consequently, an asymmetric cell using the PbTiO3@Zn demonstrates a reversible plating/stripping performance for 2900h, and an asymmetric cell reaches a state-of-the-art runtime of 3450h with a high average Coulombic efficiency of 99.98%. Furthermore, the PbTiO3@Zn/I2 battery demonstrated an impressive capacity retention rate of 84.0% over 65000 cycles by employing a slender Zn anode.

Zincophilic Sites Enriched Hydrogen-bonded Organic Framework as Multifunctional Regulating Interfacial Layers for Stable Zinc Metal Batteries.

To construct an efficient regulating layer for Zn anodes that can simultaneously address the issues of dendritic growth and side reactions is highly demanded for stable zinc metal batteries (ZMBs). Herein, we fabricate a hydrogen-bonded organic framework (HOF) enriched with zincophilic sites as a multifunctional layer to regulate Zn anodes with controlled spatial ion flux and stable interfacial chemistry (MA-BTA@Zn). The framework with abundant H-bonds helps capture H2O and remove the solvated shells on [Zn(H2O)6]2+, leading to suppressed side reactions. The HOF layer also helps form electrolyte-philic surfaces and expose Zn (002) crystal planes which benefit for rapid conduction and uniform deposition of Zn2+, and weakened sides reactions. Additionally, the electrochemically active zincophilic sites (C=O, -NH2 and triazine groups) favor the targeted guidance and penetration of Zn2+ and provide advantageous sites for uniform Zn deposition. High Young's modulus of the HOF layer further contributes to a high interfacial flexibility and stability against Zn plating-associated stress. The MA-BTA@Zn symmetric cells thereby obtain a substantially extended battery life over 1000 h at 4 mA cm-2. The MA-BTA@Zn||Cu half-cell demonstrates a highly reversible Zn stripping/plating process over 1500 cycles with impressive average Coulombic efficiency (CE) of 99.5% at 10 mA cm-2.

Motional Resistance as Highly Selective Descriptor to Probe Dynamic Formation of Surface Films on Zinc Anode

AbstractZinc anodes are expected as a promising alternative to lithium‐based anodes in energy storage systems due to their low cost, high theoretical capacity, and environmental friendliness. However, the development of efficient and stable zinc anode requires a fundamental understanding of the interfacial processes occurring during zinc deposition and dissolution cycling. In this study, we employed electrochemical quartz crystal microbalance (EQCM) analysis to investigate the potential‐dependent formation and decomposition of surface films on zinc metal anodes in sulfate‐based aqueous electrolytes. Changes in frequency and motional resistance served as complementary descriptors, with motional resistance being a highly selective indicator for probing dynamic surface film formation driven by side reactions at the zinc anode. While the frequency change provided the overall changes in the mass of both zinc metal and surface films, changes in the motional resistance selectively reflected the amount and nature of the visco‐elastic interface that comprise the surface films. The two descriptors provide quantitative and complementary means to discover the complex interfacial processes such as the formation of surface visco‐elastic films, guiding to the development of more stable and efficient zinc‐based electrochemical systems.

An organic-inorganic composite coating with excellent protection and ion regulation effects for highly stable zinc anodes

Aqueous zinc ion batteries (AZIBs) have received a number of attention because of their high safety, low cost, environmental friendliness, and favorable specific volume capacity. However, the cycle stability of AZIBs is hindered mainly by the undesired dendrite growth and side reactions of zinc anode. Herein, aiming at the issues we prepared an organic-inorganic coating composed of polyvinyl butyral and modified zeolite (Mzeolite). The composite coating combines the barrier effect of polymer and the ion migration regulation effect of zeolite, thus protecting the Zn anode and develop a uniform Zn2+ deposition simultaneously. With the modification of the composite coating on the Zn anode, the symmetric cell displays an outstanding lifespan of more than 2500 h, and the asymmetric cell also provides 974 reversible Zn plating/stripping cycles (1 mA cm−2, 1 mAh cm−2) with an average coulombic efficiency (CE) of 99.4 %. Moreover, the assembled full cell with modified Zn anode also shows an extremely long lifespan over 8000 cycles at 5 A g−1. The exceptional electrochemical performances indicate that the design of the composite coating holds great potential in the protection of Zn anode.

In-situ construction of solid electrolyte interphase for stable zinc anode via synergy of electrochemical reduction and chemical precipitation

Aqueous zinc ion batteries (ZIBs) feature high theoretical capacity, low cost, and high safety, but they suffer from moderate reversibility arising from electrolyte decomposition, Zn corrosion/passivation, and dendrite growth. To address this issue, an effective strategy is to construct a functional solid electrolyte interface (SEI) in situ. However, this is substantially challenging owing to the severe hydrogen evolution reaction (HER) and a lack of substances that can be decomposed to form SEI in the aqueous electrolytes. Herein, we propose the fabrication of a stable SEI in situ via a synergistic electrochemical reduction-chemical precipitation approach. By chemically capturing the hydroxide ions (OH−) from HER, fatty acid methyl ester ethoxylate (FMEE), as an aqueous electrolyte additive, undergoes ester group hydrolysis following by a combination with Zn2+ to form insoluble fatty acid-zinc, enabling intelligent growth of a SEI on the Zn anode surface. As a result, the enhanced Zn anode exhibits a prolonged cycling life of up to 2700 h at 1 mA/cm2 and 1 mAh/cm2. The Zn-V2O5 full cell with the designed electrolyte demonstrates excellent rate capability and significantly improved cycling stability. This study presents a simple and practical strategy for in-situ formation of SEI in aqueous electrolytes, advancing the development of high-performance aqueous batteries.

Interfacial Engineering of Polymer Membranes with Intrinsic Microporosity for Dendrite-Free Zinc Metal Batteries.

Metallic zinc has emerged as a promising anode material for high-energy battery systems due to its high theoretical capacity (820 mAh g-1), low redox potential for two-electron reactions, cost-effectiveness and inherent safety. However, current zinc metal batteries face challenges in low coulombic efficiency and limited longevity due to uncontrollable dendrite growth, the corrosive hydrogen evolution reaction (HER) and decomposition of the aqueous ZnSO4 electrolyte. Here, we report an interfacial-engineering approach to mitigate dendrite growth and reduce corrosive reactions through the design of ultrathin selective membranes coated on the zinc anodes. The submicron-thick membranes derived from polymers of intrinsic microporosity (PIMs), featuring pores with tunable interconnectivity, facilitate regulated transport of Zn2+-ions, thereby promoting a uniform plating/stripping process. Benefiting from the protection by PIM membranes, zinc symmetric cells deliver a stable cycling performance over 1500 h at 1 mA/cm2 with a capacity of 0.5 mAh while full cells with NaMnO2 cathode operate stably at 1 A g-1 over 300 cycles without capacity decay. Our work represents a new strategy of preparing multi-functional membranes that can advance the development of safe and stable zinc metal batteries.

Interfacial Engineering of Polymer Membranes with Intrinsic Microporosity for Dendrite‐free Zinc Metal Batteries

Metallic zinc has emerged as a promising anode material for high‐energy battery systems due to its high theoretical capacity (820 mA h g‐1), low redox potential for two‐electron reactions, cost‐effectiveness and inherent safety. However, current zinc metal batteries face challenges in low coulombic efficiency and limited longevity due to uncontrollable dendrite growth, the corrosive hydrogen evolution reaction (HER) and decomposition of the aqueous ZnSO4 electrolyte. Here, we report an interfacial‐engineering approach to mitigate dendrite growth and reduce corrosive reactions through the design of ultrathin selective membranes coated on the zinc anodes. The submicron‐thick membranes derived from polymers of intrinsic microporosity (PIMs), featuring pores with tunable interconnectivity, facilitate regulated transport of Zn2+‐ions, thereby promoting a uniform plating/stripping process. Benefiting from the protection by PIM membranes, zinc symmetric cells deliver a stable cycling performance over 1500 h at 1 mA/cm² with a capacity of 0.5 mAh while full cells with NaMnO2 cathode operate stably at 1 A g‐1 over 300 cycles without capacity decay. Our work represents a new strategy of preparing multi‐functional membranes that can advance the development of safe and stable zinc metal batteries.

Stable Interlayer Zinc Plating/Stripping in the Maxwell-Wagner Effect-Enhanced Interface.

Zinc metal batteries have recently emerged as a promising stable and reversible anode aqueous battery. However, due to the serious dendrite problem and hydrogen evolution problem of the zinc metal anode, the practical application of the zinc metal battery is limited. Here, we propose Y2O3 as an effective coating, which inhibits hydrogen evolution and side reactions by physical isolation and simultaneously prevents dendrite growth by ensuring a uniform Zn-ion flux and fast transport channels generated by Maxwell-Wagner polarization, thus improving the stability of batteries. Meanwhile, in situ/ex situ characterizations and different simulations are conducted to investigate in detail the effect of Maxwell-Wagner polarization on the performance of Zn metal batteries. The symmetric Y2O3@Zn anode system exhibits a stable electroplating/stripping performance over 780 h and enables the Zn battery to achieve a Coulombic efficiency of up to 99.81% over 1000 cycles by reducing side reactions. The Y2O3@Zn||MnO2 full cell delivers a high energy density of 301.42 Wh kg-1 at a power density of 205.04 W kg-1. The work provides insights into the reversibility and stability of zinc anodes and provides a promising way to promote the practical application of Zn metal batteries.

Selection of Negative Charged Acidic Polar Additives to Regulate Electric Double Layer for Stable Zinc Ion Battery

HighlightsNegative charged acidic polarity (NCAP) has been unveiled as the guideline for selecting additives to regulate electric double layer (EDL) for Zn-ion batteries.NCAP glutamate has been verified to regulate EDL structure with synergetic effects, including preferential adsorption on Zn anode and reconstruction of hydrated Zn-ion clusters.Adding NCAP additives, Zn|Cu half-cell achieves a high Coulombic efficiency of 99.83% for 2000 cycles, and NH4V4O10|Zn full cell realizes a high-capacity retention of 82.1% for 3000 cycles.