Corrosion Of Zinc Research Articles

Quasi Solid Polyzwitterion- Polyacrylamide Electrolytes for Rechargeable Zinc-Ion Battery

Zinc-ion batteries have attracted significant attention due to their low cost, rechargeability, and superior safety features. In fact, the use of aqueous electrolytes negatively affects battery performance due to the solid electrolyte interface (SEI), creating zinc corrosion, hydrogen evolution reaction (HER), and dendrite formation. To address these challenges, quasi-solid electrolytes (QSE) based on polyacrylamide-poly (3-(1-vinyl-3-imidazolio) propanesulfonate) (PAM/PVIPS) have been developed. PAM stands out as matrix QSE due to its excellent flexibility and electrochemical stability. PVIPS offers a well-defined pathway for ion transportation caused by cationic and anionic groups in structure. Clearly, the asymmetrical zinc cell with PAM/PVIPS QSE effectively reduces the overpotential profile, prolongs the stabilized zinc plating/stripping and enhances ionic conductivity, compared to PAM QSE. Additionality, the performance of Zn||δ-MnO2 is also enhanced with PAM/PVIPS QSE, yielding the specific capacity value of 65 mAh g-1, which is superior to the pristine PAM QSE (56 mAh g-1).

Unlocking self-discharge: Unveiling the mysteries of electrode-free Zn-MnO2 batteries with advanced in situ techniques in mild acid aqueous electrolytes

We introduce a novel approach to Zinc-MnO2 battery architecture utilizing a 3D network of carbon nanofibers as both current collector and electrode material, promising enhanced performance and longevity for large-scale energy storage. Employing mild aqueous electrolytes, we address the challenge of managing self-discharge, crucial for short-term energy storage. Advanced coupled characterization techniques, including in-situ EQCM (Electrochemical Quartz Crystal Microbalance) and high-resolution optical microscopy, elucidate self-discharge mechanisms across over multiple length scales. Findings reveal that the self-discharge is mainly at the zinc electrode due to concomitant dissolution of Zinc (corrosion) and HER (Hydrogen Evolution Reaction) phenomena. Interestingly, the corrosion current was estimated irrespective of charging protocol and remains consistent, indicating the independence of zinc corrosion kinetics from the length scale. Finally, the morphology of the zinc layer appears to be critical, suggesting that self-discharge is primarily a chemical process. This innovative design strategy offers the potential for high-performance Zinc-MnO2 batteries with extended cycle life to meet the requirements of large-scale energy storage applications.

Severe plastic deformation of Zn and Zn-based alloys

There has been much research on zinc and its alloys for being used in different industries and applications, mainly due to their low cost, availability, good wear resistance and mechanical properties. Moreover, zinc alloys have emerged as the latest advancement in the field of biodegradable metals, offering a more sustainable option with their moderate corrosion rate when compared to other biodegradable metals like magnesium and iron-based alloys. Nevertheless, mechanical properties of zinc alloys typically fall below the necessary levels for use in load-bearing implant applications. In this regard, severe plastic deformation serves as a distinctive technique to enhance the mechanical characteristics of zinc-based alloys, all while keeping the chemical composition intact. In addition to mechanical properties, and as is discussed in this article, SPD can affect other properties of Zn alloys, including biological and corrosion behavior. Over the past few years, extensive studies have been conducted to explore how various SPD processes impact the properties of zinc and its alloys. In this study, the main effects of SPD on the microstructure, mechanical properties, superplastic behavior, and corrosion of zinc and zinc allots together with the underlying mechanisms are reviewed.

Tunable zinc corrosion rate by laser surface modification for implants with controllable degradation direction

Tunable zinc corrosion rate by laser surface modification for implants with controllable degradation direction

Expermintal Research of Electrochemical Behaviour of Zinc in Ammonium Chloride Solutions

A present study was investigated “Experimental Research of Electrochemical Behaviour of Zinc in Ammonium Chloride Solutions.” The study was investigated by the electrochemical corrosion of sine is a problem of high significance both in the fundamental and applied fields of electrochemistry. Hence investigations were undertaken to study the corrosion of zinc in storage systems, the electrodeposition and characterisation of sine and the electrodeposition and characterisation of Siti nickel alloy. Results was shows that Potential-pH diagram for zinc in ZnClg/ NH₄Cl electrolyte, as used in Laclanche’s cell. When the surface composition of polished zinc. A freshly polished Zn surface was immersed in 0.5M NH₄Cl for 45 seconds and then analysed for energy measurements by ESCA. The composition of the modified zinc surface is summarised in table-1, When the binding energy was scanned in a narrow range of 1021 to 1010 eV, the participation of Zn 2PI electrons in the bond formation was confirmed. The investigations on the zinc- NH₄Cl system were hence carried out with the following specific objectives: IC4 find out the structure and nature of the species formed un the surface of sine when introduced in NH₄Cl solutions.

Correction: Influence of Plastic Deformation and Hydroxyapatite Coating on Structure, Mechanical, Corrosion, Antibacterial and Cell Viability Properties of Zinc Based Biodegradable Alloys

Correction: Influence of Plastic Deformation and Hydroxyapatite Coating on Structure, Mechanical, Corrosion, Antibacterial and Cell Viability Properties of Zinc Based Biodegradable Alloys

Galvanic Corrosion Behavior of Zn and Al Couples in NaCl Solution

Multi-materialization is being promoted in automotive structural materials, and fuel economy is being improved by replacing steel with aluminum and other lightweight metallic materials. Automotive steel is often galvanized for corrosion protection, and galvanic corrosion of aluminum and zinc in an atmospheric environment is a very important issue in evaluating automotive durability. Zinc is usually considered to be an anode when combined with aluminum, but its galvanic corrosion behavior can be complicated by environmental conditions because the corrosion potentials of the two are relatively close. Therefore, the objective of this study is to investigate the galvanic corrosion behavior of the couples consisting of zinc and aluminum under corrosive environmental conditions.The galvanic couple used in this study was fabricated from AA1050 Al and zinc plates. The width and length of both plates are 10 mm and 15 mm, respectively. After connecting lead wires to each plate, both plates were embedded in epoxy resin. To fabricate coplanar galvanic couples in this study, both plates were placed separately along the surface from a gap size of 500 um. The surfaces of the galvanic pairs were polished with SiC paper to JIS 2000 grit and cleaned with EtOH. The test solutions used in this study were aqueous NaCl solutions of various concentrations from 0.01 to 2 M, prepared with Milli-Q water and reagent grade chemicals. Galvanic currents and corrosion potentials were measured to investigate the galvanic corrosion behavior of the couples after 72 hours of galvanic corrosion experiments in the test solutions.The results of the galvanic corrosion test showed that the immersion potentials of the galvanic couples were lower at higher NaCl concentrations. The galvanic current decreased with immersion time, finally reaching about 1 uA in all NaCl solutions. The results of the electrochemical impedance measurements for galvanic couples in various NaCl concentrations showed that the impedance gradually increased with immersion time. It was also found that the impedance can be expressed as an electrical equivalent circuit consisting of two time constants, and that the impedance increases at intermediate frequencies between 0.1 and 1 Hz, which is thought to correspond to the dissolution reaction of Zn. This was the same trend as the behavior of the galvanic current. These results suggest that prolonged immersion reduces the galvanic current and the dissolution rate of zinc due to the passivation of the A1050 surface and the suppression of cathodic reactions.

Potential-Dependent BDAC Adsorption on Zinc Enabling ‘Selective’ Suppression of Zinc Corrosion for Energy Storage Applications

Utility-scale zinc (Zn) batteries are a promising solution to address the problem of intermittency of renewable energy sources[1],[2]; however, Zn-metal anodes in these batteries suffer from capacity loss due to spontaneous corrosion of the Zn especially when high-surface area anode configurations are employed[3]. Additionally, Zn dendrites are known to form during battery charging which limits the cycle-life of these batteries. Electrolyte additives have been explored that prevent the aforementioned issues[4],[5], but these too come at a cost, i.e., surface-blocking additives polarize the electrode surface leading to loss in the voltaic and energy efficiencies of the battery. In this presentation, a novel electrolyte additive, benzyldimethylhexadecylammonium chloride (BDAC), will be presented for its ability to suppresses corrosion of Zn in a mildly acidic (pH = 3) electrolyte. An attribute of BDAC distinct from previously studied additives is that it ‘selectively’ suppresses corrosion when the Zn electrode is held near its mixed potential; however, during high-rate Zn deposition (charging) or stripping (discharging), BDAC is essentially deactivated and thus does not appreciably polarize the electrode surface. This selective corrosion suppression behavior is explored using slow-scan cyclic voltammetry, which reveals a hysteretic response. The response implies a current-dependent BDAC adsorption mechanism in which BDAC reaches higher surface coverages when the partial currents at the Zn surface are low (e.g., at or near the corrosion mixed potential), but BDAC coverage is reduced considerably when the Zn deposition-stripping rates are increased. Numerical simulations of the BDAC diffusion-adsorption process are used to corroborate this model. Ramifications of our approach to the selective suppression of Zn dendrites will also be discussed.

Protection against Atmospheric Corrosion of Zinc in Marine Environment Rich in H2S Using Self-Assembled Monolayers Based on Sargassum fluitans III Extract

The self-assembled monolayers (SAMs) process is one of the techniques used for the production of ultra-thin layers. The present work is therefore devoted to the study of the inhibition of zinc corrosion in a marine environment rich in H2S by SAMs based on Sargassum fluitans III. The protective effect of crude extracts of Sargassum fluitans on the surface of zinc using the SAMs process was evaluated by gravimetry and impedance on two different sites after three months of exposure. The formation of SAMs was characterized by FTIR, and the corrosion products formed on the surfaces were analyzed by XRD. The results obtained show that SAMs based on Sargassum fluitans III effectively inhibit zinc corrosion.

Emerging strategies for the improvement of modifications in aqueous rechargeable zinc–iodine batteries: Cathode, anode, separator, and electrolyte

AbstractAqueous rechargeable zinc–iodine batteries have gained traction as a promising solution due to their suitable theoretical energy density, cost‐effectiveness, eco‐friendliness, and safety features. However, challenges such as the polyiodide shuttle effect, low iodine cathode conductivity, zinc anode dendritic growth, and the requirement for efficient separators and electrolytes hinder their commercial prospects. Hence, this review highlights recent progress in refining the core optimization strategies of zinc–iodine batteries, focusing on enhancements to the cathode, anode, separator, and electrolyte. Cathode improvements involve the addition of inorganic, organic, and hybrid materials to counteract the shuttle effect and boost redox kinetics, where these functional materials also are applied in anode modifications to curb dendritic growth and enhance cycling stability. Meanwhile, cell separator design approaches that effectively block polyiodide shuttle while promoting uniform zinc deposition are also discussed, while electrolyte innovations target zinc corrosion and polyiodide dissolution. Ultimately, the review aims to map out a strategy for developing zinc–iodine batteries that are efficient, safe, and economical, aligning with the demands of contemporary energy storage.

Comparative electrochemical and thermodynamic study of cold-rolled steel, Al alloy AA5754, and Zn corrosion in fluoride and chloride solutions

This study investigates the effects of fluoride and chloride ions on the corrosion of cold-rolled steel, aluminium alloy AA5754, and zinc, using ammonium bicarbonate as a buffer at pH 4 and compares electrochemical findings with thermodynamic calculations of E-pH diagrams. The distinct electrochemical behaviours of fluoride and chloride ions were confirmed, with fluoride-induced corrosion leading to the significant complex formation on cold-rolled steel and AA5754, the latter leading to a narrowing of the Al passive region. However, a comprehensive analysis of all ionic species in the solution (F−, Cl−, NH4+ and HCO3−) and their complex equilibria reveals that zinc's corrosion is primarily influenced by the overall ionic strength of the solution and further complexation with the buffering agent at higher pH levels, should these conditions occur during corrosion. In addition, this analysis also highlights the subtle differences in the stabilization effects of open circuit potential on cold-rolled steel and AA5754. The results underscore the importance of considering the overall solution equilibrium in thermodynamic analyses and provide a foundation for further research on the role of F- and Cl- ions in zirconium conversion coatings.

Bili leaf extract: Green corrosion inhibitor for zinc in hydrochloric acid-experimental and theoretical study

The primary goal of this study was to examine whether Bili leaf extract (BLE) (Aegle marmelos leaf) could inhibit zinc corrosion in an acidic environment, specifically in 0.05–0.10 M HCl solutions. The corrosion rate was examined using PDP (Potentiodynamic Polarization), EIS (Electrochemical Impedance Spectroscopy), and weight loss techniques. The research attains notable inhibition efficiencies of 99.0 %, 83.4 %, and 78.95 % in weight loss, PDP, and EIS respectively, at a concentration of 2.0 g/L BLE and a temperature of 303 K. The influence of temperature (ranging from 303 to 333 K) on the corrosion behaviour was examined upon the addition of BLE. As the concentration of BLE increased, the corrosion rate(CR) of Zn decreased, and a similar reduction was observed with decreasing temperature. Adsorption of BLE onto the metal surface followed by Langmuir and Freundlich adsorption isotherm models. The activation parameters of BLE and its negative Gibbs free energy indicate spontaneous adsorption rates. Tafel polarization measurements showed that BLE acts as a mixed-type corrosion inhibitor, meaning it influences anodic and cathodic reactions. FT-IR spectroscopy is employed to determine the functional groups of BLE. Atomic Force Microscopy(AFM)/Energy Dispersive X-ray (EDX)/Scanning Electron Microscopy (SEM) images of the zinc surface verified a significant reduction in surface inhomogeneities when BLE was present. The quantum parameters obtained through DFT(Density Functional Theory)/MD (Molecular Dynamics) demonstrated excellent agreement with the experimental findings.

In-situ physical/chemical cross-linked hydrogel electrolyte achieving ultra-stable zinc anode-electrolyte interface towards dendrite-free zinc ion battery

Hydrogen evolution reaction (HER), zinc corrosion, and dendrites growth on zinc metal anode are the major issues limiting the practical applications of zinc-ion batteries. Herein, an in-situ physical/chemical cross-linked hydrogel electrolyte (carrageenan/polyacrylamide/ZnSO4, denoted as CPZ) has been developed to stabilize the zinc anode-electrolyte interface, which can eliminate side reactions and prevent dendrites growth. The in-situ CPZ hydrogel electrolyte improves the reversibility of zinc anode due to eliminating side reactions caused by active water molecules. Furthermore, the electrostatic interaction between the SO4−· groups in CPZ and Zn2+ can encourage the preferential deposition of zinc atoms on (002) crystal plane, which achieve dendrite-free and homogeneous zinc deposition. The in-situ hydrogel electrolyte offers a streamlined approach to battery manufacturing by allowing for direct integration into the battery. Subsequently, the Zn//Zn half battery with CPZ hydrogel electrolyte can enable an ultra-long cycle over 5500 h at a current density of 0.5 mA cm−2, and the Zn//Cu half battery reach an average coulombic efficiency of 99.37%. The Zn//V2O5-GO full battery with CPZ hydrogel electrolyte demonstrates 94.5% of capacity retention after 2100 cycles. This study is expected to open new thought for the development of commercial hydrogel electrolytes for low-cost and long-life zinc-ion batteries.

Engineering zinc slurry anodes for high-performance primary alkaline batteries

The anode in Zn alkaline batteries is complex, comprised of zinc powder, gelled electrolyte, and additives, including surfactants. Optimizing the performance of these anodes means improving material utilization and suppressing corrosion of the electroactive zinc, which translates in real cells to higher energy density and longer shelf life. A challenge with optimizing these anodes has been in isolating the performance of the zinc slurry from the rest of the cell components in traditional, high-throughput cell-build studies. In this work, we use a combination of ex-situ and in-situ platforms to understand the effects of Zn content, KOH weight percent in the electrolyte, surfactant type and surfactant level on anode behavior. This is done by using electrochemical techniques including electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), potentiodynamic polarization (PDP), and constant current (galvanostatic) discharge (CCD). The results of these experiments were combined with a systematic design of experiments (DoE) matrix, allowing for optimized slurries to be realized and tested in-situ in commercially representative cells. This work can aid in intelligently designing zinc slurries for deployment in commercial products.

Influence of Plastic Deformation and Hydroxyapatite Coating on Structure, Mechanical, Corrosion, Antibacterial and Cell Viability Properties of Zinc Based Biodegradable Alloys

AbstractZinc (Zn)-based biodegradable alloys have been at the forefront of absorbable biomaterial research in recent years due to their high biocompatibility and corrosion rates. The arc melting process was used to produce the Zn–1Cu–1Ag biodegradable alloy. The influence of different plastic deformation rates on the microstructure of the material was examined after the cold rolling at deformation rates of 47% and 61%. The undeformed and deformed alloys have been hydroxyapatite-coated using the electrophoretic deposition process to improve its surface, corrosion, and bioactivity properties. Optical, XRD, SEM, and EDS examinations were used to analyze the samples’ uncoated, coated, and rolled-unrolled forms. The nucleation of the (Ag, Cu)Zn4 secondary phase was formed during the rolling process. Hardness and compression tests were used to determine the mechanical properties of cast and rolled alloys, and in vitro corrosion tests were carried out in simulated body fluid. Antimicrobial and cell viability tests are executed to demonstrate the biocompatibility of the deformed and HA-coated Zn–1Cu–1Ag alloy. The mechanical properties were improved after the rolling process, with the highest results found in 47% of the rolled samples exhibiting a compressive strength of 412.65 ± 0.5 MPa and 61% of the rolled samples exhibiting a hardness value of 88.1 ± 0.5 HV. The samples that were rolled (61%) and coated with hydroxyapatite (HA) exhibited the highest level of corrosion resistance. The antimicrobial tests revealed that the rolled and HA coated Zn1Cu1Ag groups exhibited greater inhibition rates (47 and 61%) compared to the other groups when tested against E. coli. The HA-coated groups exhibited good cell viability ratios, with the maximum viability seen in the rolled and HA-coated group at 47%. Graphical Abstract

Oligopeptide‐Induced Multifunctional Interface Layer with Protonated Hydrophobic Behavior and Strong Affinity for Highly Stable Zinc Anode

AbstractZinc‐ion batteries (ZIBs) have attracted wide attention due to their low redox potential, high capacity, and intrinsic safety. However, key issues such as zinc dendrite growth, corrosion, and passivation on zinc anode detrimentally affect the electrochemical performance. Herein, as proof of a concept of oligopeptide, glutathione with functional groups including –NH2 and −SH is introduced as an electrolyte additive to construct a multifunctional electrode–electrolyte interface layer on the zinc anode. A protonated amino group (NH3+) is formed, which prevents the adsorption of water molecules on the Zn anode, building a hydrophobic interface layer and thus attenuating corrosion. Moreover, the strong interaction between the −SH and the zinc allows glutathione molecules to be tightly anchored to the electrode surface, constructing a robust interface layer. Consequently, a long cycling life of nearly 3000 h at 1 mA cm−2 for the Zn||Zn symmetric battery is achieved, and a stable cycling life of 1600 h is demonstrated at 3 mA cm−2. Furthermore, Zn||activated carbon (AC) hybrid capacitor with the glutathione‐containing electrolyte runs stably for nearly 28 000 cycles at 5 A g−1, among the best results of reported Zn hybrid capacitors.

In-situ constructed interface buffer layer enabled highly reversible Zn Deposition/Stripping for long-lifespan aqueous zinc metal anodes

Despite the advantages of high capacity, high safety and low cost, zinc anodes also face the inherent problems of dendritic growth, corrosion and passivation, vastly limiting the development and application of aqueous zinc ion batteries (AZIBs). Here, the epigallocatechin gallate (EGCG) was used as a hydroxyl-rich natural electrolyte additive for AZIBs. During charge–discharge process, the EGCG can be preferentially adsorbed on the zinc anode, and act as an interface buffer layer to weaken the direct contact between active water molecule and zinc anode. Based on this effect, the interface buffer layer is helped to inhibit the water-induced side reactions of hydrogen evolution, zinc corrosion and passivation, and lower the polarization overpotential, contributing to highly reversible Zn deposition/stripping behavior. As a result, the Zn||Zn symmetric batteries can maintain a stable cycling for more than 1500 h at 1.0 mA cm−2 and 1.0 mAh cm−2. Furthermore, the assembled Zn||MnO2 full batteries still delivered high capacity retention of 98.02 % after 400 cycles at 1.0 A/g. This finding enriches the design thoughts for the development of high-efficiency and practical AZIBs.

A Rational Approach to Suppress Hydrogen Evolution Reaction and its Concurrent Zinc Corrosion in Zinc-air Batteries: A Uniform Dispersion of Carbon Nanodots in the Electrolyte

Abstract Zinc-air batteries (ZABs) have garnered tremendous attention due to their higher theoretical energy density, cost-free fuel from the atmosphere, ease of fabrication, and environmental friendliness. However, the poor kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) happening at the air-cathode, the hydrogen evolution reaction (HER), and its concurrent zinc corrosion occurring at the anode contribute to the failures of ZABs. While various electrocatalysts are developed to accelerate ORR and OER, the strategies explored to mitigate the issues of anode involve modification of either the zinc anode or the electrolyte. Though the modification of the anode or the electrolyte suppresses HER, it affects the oxygen reactions taking place at the air-cathode. Herein, HER and its concurrent zinc corrosion are suppressed by uniform dispersion of carbon nanodots in the native electrolyte. In addition, this rational approach accelerates both the ORR and OER. The carbon nanodots are prepared electrochemically and characterized using absorption and emission spectroscopy and microscopic studies. Subsequently, carbon nanodots are uniformly dispersed in 6 M KOH (CNF) and used as the electrolyte. The CNF suppresses HER by increasing the overpotential and impedes the zinc corrosion.

Phytic Acid Customized Hydrogel Polymer Electrolyte and Prussian Blue Analogue Cathode Material for Rechargeable Zinc Metal Hydrogel Batteries.

Zinc anode deterioration in aqueous electrolytes, and Zn dendrite growth is a major concern in the operation of aqueous rechargeable Zn metal batteries (AZMBs). To tackle this,the replacement of aqueous electrolytes with a zinc hydrogel polymer electrolyte (ZHPE) is presented in this study. This method involves structural modifications of the ZHPE by phytic acid through an ultraviolet (UV) light-induced photopolymerization process. The high membrane flexibility, high ionic conductivity (0.085Scm-1), improved zinc corrosion overpotential, and enhanced electrochemical stability value of ≈2.3V versus Zn|Zn2+ show the great potential of ZHPE as an ideal gel electrolyte for rechargeable zinc metal hydrogel batteries (ZMHBs). This is the first time that the dominating effect of chelation of phytic acid with M2+ center over H-bonding with water is described to tune the gel electrolyte properties for battery applications. The ZHPE shows ultra-high stability over 360h with a capacity of 0.50mAhcm-2 with dendrite-free plating/stripping in Zn||Zn symmetric cell. The fabrication of the ZMHB with a high-voltage zinc hexacyanoferrate (ZHF) cathode shows a high-average voltage of ≈1.6V and a comparable capacity output of 63mAhg-1 at 0.10Ag-1 of the current rate validating the potential application of ZHPE.

Zwitterionic Organic Multifunctional Additive Stabilizes Electrodes for Reversible Aqueous Zn‐Ion Batteries

AbstractAqueous zinc‐ion batteries (AZIBs) exhibit significant potential for grid energy storage due to their low cost and safety. However, the commercial applications of AZIBs face challenges, particularly in the anode, such as zinc dendrites, hydrogen evolution reaction (HER), and zinc corrosion. In this study, a protonated triglycine (ggg) as a multifunctional electrolyte additive for AZIBs is employed. This ggg molecule can dissociate as zwitterion (both anion and cation) in mildly acidic ZnSO4 electrolytes. The NH3+ cation in ggg molecule can adsorb on the surface of the zinc anode, regulating the deposition of Zn2+ and slowing down the side reactions, and the spontaneously dissociated ggg anions will combine with Zn2+ to regulate the solvated Zn2+ chemistry in the electrolyte, establishing the electrostatic interaction via the strong adsorption ability to Zn2+. Theoretical calculations indicate that ggg molecule demonstrates a strong affinity toward Zn2+, enabling the reconstruction of Zn(H2O)62+ and facilitating subsequent de‐solvation processes. As a result, Zn||Zn symmetric cells in ZnSO4/0.2 mM ggg electrolyte exhibited an extended cycling lifetime of ≈4500 h. Furthermore, the Zn||MnO2 full battery demonstrated enhanced capacity and cycling performance with the addition of ggg molecule. This study provides valuable insights into constructing a highly reversible electrolyte for AZIBs.