Search Results (83)

In the wake of global energy transition and the “dual-carbon” goal, the rapid growth of electric vehicles has posed challenges for large-scale lithium-ion battery decommissioning. Retired batteries exhibit dual attributes of strategic resources (cobalt/lithium concentrations several times higher than natural ores) and environmental risks (heavy metal pollution, electrolyte toxicity). This paper systematically reviews pyrometallurgical and hydrometallurgical recovery technologies, identifying bottlenecks: high energy/lithium loss in pyrometallurgy, and corrosion/cost/solvent regeneration issues in hydrometallurgy. To address these, an integrated recycling process is proposed: low-temperature physical separation (liquid nitrogen embrittlement grinding + froth flotation) for cathode–anode separation, mild roasting to convert lithium into water-soluble compounds for efficient metal oxide separation, stepwise alkaline precipitation for high-purity lithium salts, and co-precipitation synthesis of spherical hydroxide precursors followed by segmented sintering to regenerate LiNi_1/3Co_1/3Mn_1/3O₂ cathodes with morphology/electrochemical performance comparable to virgin materials. This low-temperature, precision-controlled methodology effectively addresses the energy-intensive, pollutive, and inefficient limitations inherent in conventional recycling processes. By offering an engineered solution for sustainable large-scale recycling and high-value regeneration of spent ternary lithium ion batteries (LIBs), this approach proves pivotal in advancing circular economy development within the renewable energy sector. Full article

Zirconium, a critical rare metal with exceptional corrosion resistance and nuclear applications, is conventionally produced via the energy-intensive Kroll process. The electrolysis of ZrC_xO_y soluble anodes has been extensively investigated due to its advantages in having a short process flow and resulting in high-quality products. In particular, during the electrolysis of zirconium oxycarbide with a C:O molar ratio of 1:1, gaseous CO can be released, and no residual anodes are generated, which is extremely appealing. In this regard, this paper explores the feasibility of preparing zirconium metal through high-temperature vacuum reduction to produce zirconium oxycarbide using ZrO₂ as the raw material, followed by direct molten-salt electrolysis. Firstly, the reduction products were characterized using an X-ray diffractometer (XRD) and a scanning electron microscope (SEM). The results showed that under a vacuum of <10 Pa at 1750 °C, the reduction products mainly consisted of ZrC_xO_y and a small amount of ZrO₂, and they exhibited good electrical conductivity (0.0169 Ω·cm). Subsequently, the cyclic voltammetry test results of the reduction products revealed the reversible redox behavior of ZrC_xO_y. There were characteristic oxidation peaks at −0.53 V and −0.01 V (vs. Pt), corresponding to the formation of Zr²⁺ and Zr⁴⁺, respectively, and a reduction peak at −1.51 V, indicating the conversion from Zr²⁺ to Zr. Finally, β-zirconium metal with a purity of 99.2 ± 0.3 wt.% was obtained through potentiostatic electrolysis, and its quality met the R60704 grade specified in ASTM B551-12 (2021). This study offers a novel approach for the short-flow preparation of zirconium metal, which is conducive to expanding its applications. Full article

The “shuttle effect” caused by the shuttling of soluble long-chain polysulfides between the anode and cathode electrodes has persistently hindered lithium–sulfur batteries (LSBs) from achieving stable and high-capacity performance. Numerous materials have been explored to mitigate the adverse effects of this phenomenon, among which metal oxides and metal sulfides are regarded as promising solutions due to their strong adsorption capability toward lithium polysulfides (LiPSs). However, the poor electrical conductivity of the metal oxides and sulfides, coupled with their inherent morphological limitations, makes it challenging to sustainably suppress LiPS shuttling. In this study, we designed a heterostructured catalyst composed of a metal oxide–metal sulfide heterostructure integrated with carbon nanotubes (CNTs). This design addresses the low conductivity issue of metal oxides/sulfides while optimizing the material’s morphology, enabling persistent LiPSs adsorption. Furthermore, the composite successfully facilitates three-dimensional (3D) Li₂S deposition. The assembled battery exhibits stable and high-capacity performance, delivering an initial discharge capacity of 622.45 mAh g⁻¹ at 2C and retaining 569.5 mAh g⁻¹ after 350 cycles, demonstrating exceptional cycling stability. Full article

Despite their inherently lower energy density than lithium-ion batteries (LIBs), aqueous zinc metal batteries (AZMBs) have recently attracted interest as rechargeable energy storage devices due to their low cost and high operational and environmental safety. They are composed of metallic zinc as the anode, an aqueous zinc salt electrolyte and a cathode capable of (de)intercalating Zn²⁺ ions upon its (oxidation) reduction reaction. In this work, we studied a hybrid AZMB in which a dual-ion electrolyte containing both Zn²⁺ and Li⁺ ions was used in conjunction with a Li⁺ ion intercalation cathode, i.e., LiFePO₄ (LFP), one of the most common, reliable, and cheap cathodes for LIBs. In this study, we present evidence that, thanks to its insolubility in water, ethyl cellulose (EC) can be effectively utilized as a binder for cathode membranes in AZMBs. Furthermore, its solubility in alcohol provides a significant advantage in avoiding the use of toxic solvents, contributing to a safer and more environmentally friendly approach to the formulation process. Full article

We report the first synthesis of zwitterionic thiacalixarenes featuring imidazolium and sulfonate groups on the upper rim and alkyl (butyl or octyl) fragments on the lower rim of the platform. Despite their amphiphilic structure, these macrocycles exhibit limited water solubility. However, dynamic light scattering detected the formation of associates for derivatives with octyl moieties at a concentration of 0.1 mM. To develop stable materials for aqueous environments and to investigate the functionality of zwitterionic sulfonate-imidazolium groups along with the thiacalixarene platform, mixed organo-organic systems based on polydiacetylene polymer were created. Characterization of the modified polydiacetylene systems through various analytical methods revealed a significant colorimetric response to lead ions in aqueous media, surpassing that of the unmodified polydiacetylene polymer. Additionally, the modified polymers demonstrated efficacy in purifying aqueous media from lead ions, as evidenced by anodic stripping voltammetry (ASV) and microwave plasma atomic emission spectroscopy (MP AES). Full article

The bioavailability of dissolved copper (Cu) in seawater is influenced by the presence of natural organic matter. Changes in physicochemical conditions, such as pH, temperature, and salinity, can significantly affect the solubility and speciation of copper, thereby impacting the complexation of Cu(II)-binding organic ligands. The concentration of dissolved Cu in the coastal water of Mersing, Malaysia, was detected by anodic stripping voltammetry (ASV). The natural organic copper(II)-binding ligands (CuL) and their conditional stability constants (log K′) were determined by using the competitive ligand exchange–adsorptive cathodic stripping voltammetry method (CLE–AdCSV) in our samples. The in situ parameters, such as pH, temperature, salinity, and dissolved oxygen (DO), were found to be significantly different between sampling periods and indicated the different physical chemical conditions between the sampling periods. However, we found a consistent concentration of dissolved Cu throughout the water column between sampling periods. This suggests that the presence of a strong class of natural organic ligands (L₁) in Mersing’s coastal water maintains the dissolved Cu(II) ions in the water column and prevents the scavenging and precipitation processes under the seasonal variations. Full article

Epitaxial layers of water-soluble Sr₃Al₂O₆ were fabricated as sacrificial layers on SrTiO₃ (100) single-crystal substrates using the Pulsed Laser Deposition technique. This approach envisages the possibility of developing a new generation of micro-Solid Oxide Fuel Cells and micro-Solid Oxide Electrochemical Cells for portable energy conversion and storage devices. The sacrificial layer technique offers a pathway to engineering free-standing membranes of electrolytes, cathodes, and anodes with total thicknesses on the order of a few nanometers. Furthermore, the ability to etch the SAO sacrificial layer and transfer ultra-thin oxide films from single-crystal substrates to silicon-based circuits opens possibilities for creating a novel class of mixed electronic and ionic devices with unexplored potential. In this work, we report the growth mechanism and structural characterization of the SAO sacrificial layer. Epitaxial samarium-doped ceria films, grown on SrTiO3 substrates using Sr₃Al₂O₆ as a buffer layer, were successfully transferred onto silicon wafers. This demonstration highlights the potential of the sacrificial layer method for integrating high-quality oxide thin films into advanced device architectures, bridging the gap between oxide materials and silicon-based technologies. Full article

The effect of various atmospheric parameters on the corrosion mechanism of press-hardened steel (PHS) coated with Al-Si (AS) was studied. Quantitative models of the composition of soluble and stable corrosion products were developed. A high chloride concentration led to a localized corrosion due to the presence of cracks in the coating. Increased corrosion resistance of silicon-rich Al₈Fe₂Si and AlFe at the expense of the Al₅Fe₂ phase with low silicon content was shown. Under low-chloride-deposition conditions, the coating exhibited good corrosion resistance and provided sufficient protection to the underlying steel. The formation of more local anodes and cathodes under conditions of lower relative humidity led to a reduction in the depth of corrosion pits in the steel substrate. Constant high relative humidity and sulphate deposits on the surface were critical for the acceleration of steel corrosion in coating cracks. Full article

Polymer-based aqueous redox flow batteries (RFBs) are attracting increasing attention as a promising next-generation energy storage technology due to their potential for low cost and environmental friendliness. The search for new redox-active organic compounds for incorporation into polymer materials is ongoing, with anolyte-type compounds in high demand. In response to this need, we have synthesized and tested a range of new water-soluble redox-active s-tetrazine derivatives, including both low molecular weight compounds and polymers with different architectures. S-tetrazines are some of the smallest organic molecules that can undergo a reversible two-electron reduction in protic media, making them a promising candidate for anolyte applications. We have successfully modified linear polyacrylic acid and poly(N-isopropylacrylamide-co-acrylic acid) microgels with pendent 1,2,4,5-tetrazine groups. Electrochemical testing has shown that the new tetrazine-containing monomers and, importantly, the water-soluble redox polymers, both linear and microgel, demonstrate the chemical reversibility of the reduction process in an aqueous solution containing acetate buffer. This expands the range of water-soluble anodic materials suitable for water-based organic RFBs. The reduction potential value can be adjusted by changing the substituents in the tetrazine core. It is also worth noting that the choice of electrode material plays an important role in the kinetics of the tetrazine reaction: the use of carbon electrodes is particularly beneficial. Full article

An electrochemical investigation of 1,2- and 1,4-dihydroxybenzenes was carried out with platinum macro- and microelectrodes using square wave and cyclic voltammetry techniques. Furthermore, the effect of the two solvents—acetic acid and ethyl acetate—was compared. When using square wave voltammetry, signals only appeared at lower frequencies and only when the supporting electrolyte was in excess, as expected due to the relatively low permittivity of the used solvents. The behavior of hydroquinone and catechol did not differ significantly from that of their derivatives (dihydroxybenzaldehydes, dihydroxybenzoic acids and 2′,5′-dihydroxyacetophenone). When the cyclic voltammetric experiments using a microelectrode were extended to higher anodic potentials, electrode fouling was very significant in ethyl acetate after the potential region where steady-state oxidation to the corresponding quinone occurs. The substituent effect was not significant here either, which was proven by using different functional groups in different positions. In contrast, the position had a dramatic influence on the susceptibility to electropolymerization, as 1,2-dihydroxybenzenes—independent of the nature of the substituent on the benzene ring—deactivated the electrode, while 1,4-dihydroxybenzenes did not, possibly due to the different solubilities of the polymers formed from the primary oxidation product (quinones). A user-friendly analytical procedure is also proposed that uses an electropolymerization reaction and does not require frequent cleaning of the electrode via polishing, which is required usually especially with a microelectrode. Full article

As a unique form of TiO₂, TiO₂ nanotube arrays (TiO₂NTAs) have been widely used. TiO₂NTAs are usually prepared by Ti foil, with little research reporting its preparation by Ti mesh. In this paper, TiO₂NTAs are prepared on a Ti mesh surface via an anodic oxidation method in the F-containing electrolyte. The optimal parameters for the synthesis of TiO₂NTAs are as follows: the solvent is ethylene glycol and water; the electrolyte is NH₄F (0.175 mol/L); the voltage is 20 V; and the anodic oxidation time is 40 min without chemical polishing. However, there is a strange phenomenon where the nanotube arrays grow only at the intersection of Ti wires, which may be caused by chemical polishing, and the other areas, where TiO₂NTAs cannot be observed on the surface of Ti mesh, are covered by a dense TiO₂ film. New impurities (the hydrate of TiO₂ or other products) introduced by chemical polishing and attaching to the surface of the Ti mesh reduce the current of anodic oxidation and further inhibit the growth of TiO₂ nanotubes. Hence, under laboratory conditions, for commercially well-preserved Ti mesh, there is no necessity for chemical polishing. The formation of TiO₂NTAs includes growth and crystallization processes. For the growth process, F⁻ ions corrode the dense TiO₂ film on the surface of Ti mesh to form soluble complexes ([TiF₆]²⁻), and the tiny pores remain on the surface of Ti mesh. Given the basic photoelectrochemical measurements, TiO₂NTAs without chemical polishing have better properties. Full article

Titanium metal is primarily produced via the Kroll process, which is characterized by a semi-continuous production flow and a lengthy process cycle, resulting in high production costs. Researchers have explored alternative methods for titanium production, including molten salt electrolysis, such as the Fray–Farthing–Chen (FFC), Ono Suzuki (OS), and University of Science and Technology Beijing (USTB) processes, aiming to achieve more economical production. Among these, the USTB process, a representative of soluble anode electrolysis, has shown significant promise. However, controlling oxygen concentration in titanium produced by soluble anode electrolysis remains a challenge. This study proposes a novel approach to enhance deoxidation efficiency in soluble anode electrolysis for titanium production by introducing yttrium chloride (YCl₃) into the molten salt electrolyte. Thermodynamic analysis and experimental validation demonstrate that the theoretical deoxidation limit for titanium can reach below 100 ppm under Y/YOCl/YCl₃ equilibrium. We report the successful synthesis of titanium powder with an oxygen concentration of 6000 ppm from titanium-carbon-oxygen solid solution. Under optimized conditions, the purity of the titanium powder reached 99.42%, demonstrating a new approach for producing high-purity titanium. This method, based on soluble anode electrolysis, offers a potential alternative to the conventional Kroll process. The research elucidates the fabrication process and analytical methods for titanium-carbon-oxygen solid solution, and employs a combination of analytical techniques, including XRD, SEM-EDS, and ONH Analyzer, for characterization of the electrolytic product, encompassing phase analysis, microstructure, and oxygen concentration testing. Full article

With the development of electronic packaging technology toward miniaturization, integration, and high reliability, the diameter and pitch of solder joints continue to shrink. Adjacent solder joints are highly susceptible to electrochemical migration (ECM) due to the synergistic effects of high-density electric fields, water vapor, and contaminants. Dust has become one of the non-negligible causal factors in ECM studies due to air pollution. In this study, 0.2 mM/L NaCl and Na₂SO₄ solutions were used to simulate soluble salt in dust, and the failure mechanism of an Sn-58Bi solder ECM in the soluble salt in dust was analyzed by a water-droplet experimental method. It was shown that the mean failure time of the ECM of an Sn-58Bi solder in an NaCl solution (53 s) was longer than that in an Na₂SO₄ solution (32 s) due to the difference in the anodic dissolution characteristics in the two soluble salt solutions. XPS analysis revealed that the dendrites produced by the ECM process were mainly composed of Sn, SnO, and SnO₂, and there were precipitation products—Sn(OH)₂ and Na₂SO₄—attached to the dendrites. The corrosion potential in the NaCl solution (−0.351 V) was higher than that in the Na₂SO₄ solution (−0.360 V), as shown by a polarization test, indicating that the Sn-58Bi solder had better corrosion resistance in the NaCl solution. Therefore, an Sn-58Bi solder has better resistance to electrochemical migration in an NaCl solution compared to an Na₂SO₄ solution. Full article

Extracellular electron transfer (EET) is key to the success of microbial fuel cells (MFCs). Clostridium sp. often occurs in MFC anode communities, but its ability to perform EET remains controversial. We have employed Clostridium pasteurianum DSM 525 as a biocatalyst in a glycerol-fed MFC, designated MFC_DSM. We have also followed the EET of this biocatalyst in the presence of a mediator, namely soluble neutral red (NR), soluble methyl viologen (MV), neutral red film (FNR), or methyl viologen film (FMV). MFC_DSM provided power and current densities (j) of 0.39 μW·cm⁻² and 2.47 μA·cm⁻², respectively, which evidenced that the biocatalyst performs direct electron transfer (DET). Introducing 150.0 µM NR or MV into the MFC_DSM improved the current density by 7.0- and 3.7-fold (17.05 and 8.45 μA·cm⁻²), respectively. After 20 cyclic voltammetry (CV) cycles, the presence of FNR in the MFC_DSM anodic chamber provided an almost twofold higher current density (30.76 µA·cm⁻²) compared to the presence of NR in the MFC_DSM. Introducing MV or FMV into the MFC_DSM anodic chamber gave practically the same current density after 10 CV cycles. The MFC_DSM anodic electrode might interact with FMV weakly than with FNR, so FNR is more promising to enhance C. pasteurianum DSM 525 EET within MFC_DSM. Full article

As the core of modern energy technology, lithium-ion batteries (LIBs) have been widely integrated into many key areas, especially in the automotive industry, particularly represented by electric vehicles (EVs). The spread of LIBs has contributed to the sustainable development of societies, especially in the promotion of green transportation. However, the high demand for battery performance and safety in these fields has made the high viscosity, volatility, and potential leakage inherent in traditional organic liquid electrolytes a constraint on their further expansion. Especially at low temperature, the increased viscosity of the electrolyte, reduced solubility of lithium salts, crystallization or solidification of the electrolyte, increased resistance to charge transfer due to interfacial by-products, and short-circuiting due to the growth of anode lithium dendrites all affect the performance and safety of LIBs. Therefore, improving the safety performance of LIBs under low-temperature environments has become a focus of current research. This paper primarily reviews the progress made in utilizing different types of electrolytes in LIBs to enhance safety and optimize low temperature performance and discusses the current research progress as well as the future development direction of the field. Full article