Alternative Anode Material Research Articles

Molten salt assisted synthesis of Si/C nanocomposite derived from palygorskite and sodium alginate for electrochemical lithium storage.

Silicon/carbon (Si/C) nanocomposites are considered as one of the most promising anode materials for lithium-ion batteries due to their high capacity and suitable lithiation potential. However, the complex and time-consuming preparation processes of silicon-based nanocomposites and the unexpected silicon carbide generated during high treatment make it difficult to achieve high-performance Si/C nanocomposites for practical applications. Herein, a silicon/carbon nanocomposite is successfully prepared through a facile and eco-friendly molten salt assisted precarbonization-reduction method using palygorskite (PAL) and sodium alginate as raw materials. Based on physical characterizations, it is demonstrated that the sodium alginate plays a key role in the successful preparation of Si/C nanocomposite, which not only boosts uniform embedding of PAL nanoparticles in the carbon matrix but also releases molten sodium salt to suppress the formation of unexpected SiC. When used as an alternative anode material for lithium-ion battery applications, the as-obtained Si/C composite delivers a high reversible specific capacity of 1362.7 mA h g-1 with an initial Coulombic efficiency of 70.3% at a current density of 200 mA g-1 and excellent long-term cycling stability. The findings here provide a facile and eco-friendly molten salt assisted precarbonization-reduction method for high-performance silicon/carbon anode materials.

Fast kinetics for lithium storage rendered by Li3VO4 nanoparticles/porous N-doped carbon nanofibers

Li3VO4 (LVO) has been recognized as an alternative anode material for lithium-ion batteries (LIBs) because of its appropriate lithium storage potential and capacity merits. However, its practical application is seriously hindered by slow reaction kinetics stemming from poor electronic conductivity. Herein, Li3VO4/porous N-doped carbon nanofibers (LVO/PNC NFs) are firstly designed and fabricated via an electrospinning method, utilizing the thermal decomposition characteristics of polylactic acid (PLA). The porous N-doped carbon nanofibers provide efficient electrolyte diffusion paths and facilitate ion transport. In addition, LVO nanoparticles are uniformly dispersed along the nanofibers to effectively inhibit particle aggregation. The obtained LVO/PNC NFs are evaluated as anodes for LIBs and deliver high reversible capacity of 768 mAh g−1 after 300 cycles at 0.2 A g−1, along with excellent rate capability (average capacity of 355 mAh g−1 at 8 A g−1 after 6 periodic rate testing) and long cycling life (286 mAh g−1 after 2000 cycles at 4 A g−1). The special porous nanofiber represents an effective strategy for improving the electronic conductivity, inhibiting particle aggregation, and ensuring rapid ion/charge transport towards advanced energy storage technologies.

High-performance flexible CoFe2O4/N-doped carbon nanofiber composite anode materials for sodium-ion batteries

Graphite is traditionally used as an anode material but is unsuitable for use in sodium-ion batteries because it has a low specific capacity and poor safety characteristics, it is therefore necessary to develop alternative anode materials. Flexible CoFe2O4 nanoparticle/N-doped carbon nanofiber films were prepared by electrospinning and calcination. The advantages of this process included inexpensive starting materials, easy preparation, and suitability for commercialization. The inherent shortcomings of CoFe2O4, such as poor electronic conductivity and large changes in volume, were mitigated via elemental doping and the formation of composites with high-quality carbon materials. Nitrogen-doped carbon nanofibers with large specific surface areas and superior mechanical properties were used as the supporting skeleton of the material. These nanofibers limited the volume expansion of CoFe2O4 throughout the cycling process and increased the ion diffusion velocity in the material. The optimal integration of nanoscale CoFe2O4 particles, which possess a higher theoretical specific capacity, with a nitrogen-doped carbon nanofiber conductive framework featuring a crosslinked three-dimensional structure facilitated the infiltration of the electrolyte into the electrode. This integration reduced the diffusion distance of sodium ions and effectively reduced the volume expansion of the material, as well as damage to the material during the electrochemical reaction. After 200 cycles at a current density of 0.1 A g−1, it provided a high sodium storage capacity of 365.7 mA h g−1. The capacity was maintained at 176.3 mA h g−1 even at a high current density of 2 A g−1. Exhibits good cycle stability.

Ni-Doped SFM Double-Perovskite Electrocatalyst for High-Performance Symmetrical Direct-Ammonia-Fed Solid Oxide Fuel Cells.

Ammonia has emerged as a promising fuel for solid oxide fuel cells (SOFCs) owing to its high energy density, high hydrogen content, and carbon-free nature. Herein, the electrocatalytic potential of a novel Ni-doped SFM double-perovskite (Sr1.9Fe0.4Ni0.1Mo0.5O6-δ) is studied, for the first time, as an alternative anode material for symmetrical direct-ammonia SOFCs. Scanning and transmission electron microscopy characterization has revealed the exsolution of Ni-Fe nanoparticles (NPs) from the parent Sr2Fe1.5Mo0.5O6 under anode conditions, and X-ray diffraction has identified the FeNi3 phase after exposure to ammonia at 800 °C. The active-exsolved NPs contribute to achieving a maximal ammonia conversion rate of 97.9% within the cell's operating temperatures (550-800 °C). Utilizing 3D-printed symmetrical cells with SFNM-GDC electrodes, the study demonstrates comparable polarization resistances and peak power densities of 430 and 416 mW cm-2 for H2 and NH3 fuels, respectively, with long-term stability and a negligible voltage loss of 0.48% per 100 h during ammonia-fed extended galvanostatic operation. Finally, the ammonia consumption mechanism is elucidated as a multistep process involving ammonia decomposition, followed by hydrogen oxidation. This study provides a promising avenue for improving the performance and stability of ammonia-based SOFCs for potential applications in clean energy conversion technologies.

Unveiling Potential of Gallium Ferrite (GaFeO3) as an Anode Material for Lithium-Ion Batteries.

Lithium-ion batteries (LIBs) serve as the backbone of modern technologies with ongoing efforts to enhance their performance and sustainability driving the exploration of new electrode materials. This study introduces a new type of alloy-conversion-based gallium ferrite (GFO: GaFeO3) as a potential anode material for Li-ion battery applications. The GFO was synthesized by a one-step mechanochemistry-assisted solid-state method. The powder X-ray diffraction analysis confirms the presence of an orthorhombic phase with the Pc21 n space group. The photoelectron spectroscopy studies reveal the presence of Ga3+ and Fe3+ oxidation states of gallium and iron atoms in the GFO structure. The GFO was evaluated as an anode material for Li-ion battery applications, displaying a high discharge capacity of ∼887 mA h g-1 and retaining a stable capacity of ∼200 mA h g-1 over 450 cycles, with a Coulombic efficiency of 99.6 % at a current density of 100 mA g-1. Cyclic voltammetry studies confirm an alloy-conversion-based reaction mechanism in the GFO anode. Furthermore, density functional theory studies reveal the reaction mechanism during cycling and Li-ion diffusion pathways in the GFO anode. These results strongly suggest that the GFO could be an alternative anode material in LIBs.

Lead Zirconate Titanate As an Anode for Li-Ion Batteries

Graphite, a successfully commercialized anode for lithium-ion batteries (LIBs), faces multipronged challenges, including an unsustainable supply chain and sluggish rate capabilities, underscoring the necessity of alternative anode materials for LIBs. Herein, the potential of lead zirconate titanate (PZT) as an anode material for LIBs has been investigated. Synthesis of bulk PZT materials was accomplished through a solid-state reaction, and the electrochemical performance of PZT anodes was investigated. The electrochemical characterization reveals that diffusion-controlled intercalation is the predominant charge storage mechanism in the PZT anode. Overall, the electrochemical performance of PZT indicates that it could be an alternative anode material for LIBs.

Antimony nanoparticles encapsulated in interconnected nitrogen-doped carbon nanospheres for high performances PIBs

Antimony (Sb) has attracted significant attention as an anode material for potassium-ion batteries (PIBs) due to its high theoretical capacity and suitable working voltage. However, the severe volume variations of Sb during potassiation/depotassiation process lead to sluggish kinetics and poor cyclic stability for PIBs. In this study, Sb nanoparticles are confined within interconnected N-doped carbon nanospheres (Sb@NC) through an effective carbothermal reduction process. The potassium storage performances and mechanism are elucidated through electrochemical tests combined with ex-XRD analysis. When used as an anode for PIBs, the optimized Sb@NC-2 anode exhibits excellent cycle stability of 463.0 mAh g−1 at 200 mA g−1 over 100 cycles and superior rate capability of 113.4 mAh g−1 at a high current density of 2 A g−1. Besides, a full cell comprising an Sb@NC-2 anode and a PTCDA cathode is also tested to validate the practical feasibility of the anode. Furthermore, Density Functional Theory (DFT) calculations demonstrate that N-doped carbon can enhance the adsorption of K+ and improve the kinetics of electrochemical reactions. Therefore, the unique yolk-shell structure in this study effectively restricts volume expansion and aggregation of Sb particles while facilitating rapid electron/ion transfer. These findings provide a potential alternative anode material for advanced PIBs.

Electrolysis of CuCl/HCl aqueous system in Cu–Cl thermochemical cycle for green hydrogen production: Investigations on alternative to platinum anode

The ICT-OEC Cu–Cl cycle is a six-step thermochemical copper-chlorine (Cu–Cl) closed-loop cycle to produce green hydrogen via water splitting. One of the critical steps in this cycle involves the electrolysis of CuCl to generate copper (Cu) and cupric chloride (CuCl2). Using platinum as the anode material in this system is economically disadvantageous and expensive. Consequently, this work investigates the feasibility of alternative anode materials to replace platinum. Mixed Metal Oxide (MMO) coated on Ti mesh (MMO mesh) and Pt coated on Ti mesh (Pt mesh) were evaluated as suitable anode alternatives to pure Pt sheet based on their performance metrics at different voltages. The integration of MMO mesh for a 100-h Time on Stream (TOS) study at a mini-pilot scale demonstrated promising current density and efficiency values. However, performance variations were observed over prolonged operation, potentially due to changes in membrane resistance. After 100 h, the MMO mesh remained undamaged, indicating its durability for extended use. Characterization studies revealed the electrodeposited copper to have a dendritic structure with an FCC phase. The findings suggest that MMO mesh and Pt mesh are viable alternatives to platinum at operating voltages above 0.7 V in this system.

Interfacial engineering in SnO2-embedded graphene anode materials for high performance lithium-ion batteries

Tin dioxide is regarded as an alternative anode material rather than graphite due to its high theoretical specific capacity. Modification with carbon is a typical strategy to mitigate the volume expansion effect of SnO2 during the charge process. Strengthening the interface bonding is crucial for improving the electrochemical performance of SnO2/C composites. Here, SnO2-embedded reduced graphene oxide (rGO) composite with a low graphene content of approximately 5 wt.% was in situ synthesized via a cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal method. The structural integrity of the SnO2/rGO composite is significantly improved by optimizing the Sn–O–C electronic structure with CTAB, resulting a reversible capacity of 598 mAh g−1 after 200 cycles at a current density of 1 A g−1. CTAB-assisted synthesis enhances the rate performance and cyclic stability of tin dioxide/graphene composites, and boosts their application as the anode materials for the next-generation lithium-ion batteries.

Effects of the oxyfluorination of needle coke-based anode materials on the capacities and stabilities of lithium-ion batteries

Needle cokes have emerged as an alternative anode material to graphite due to their high rate performance and cost advantages. Herein, we introduced oxygen and fluorine functional groups to increase the capacity and increase the cycling stability, respectively. Oxyfluorination was used to simultaneously introduce these two heterogeneous elements, and their effective introduction was quickly confirmed at room temperature. Compared with those of pristine needle coke-based lithium-ion batteries, the capacities of the lithium-ion batteries based on oxyfluorinated needle cokes increased by 17.9%, and the cycling stabilities of the modified batteries exceeded 92%. Therefore, introducing oxygen and fluorine functional groups into needle cokes through oxyfluorination is a viable strategy for producing anode materials for lithium-ion batteries with high rates and capacities.

Structural modeling of high-entropy oxides battery anodes using x-ray absorption spectroscopy

High-entropy oxides (HEOs) are single phase solid solutions where five or more metals share the same sublattice, giving rise to unexpected features in various fields of applications. Recently, HEOs have emerged as an alternative conversion electrode anode material for next-generation Li-ion batteries, where the combination of several different elements in a single solid solution can synergistically act to overcome some of its main drawbacks, improving performance. Due to their chemical complexity, x-ray absorption spectroscopy (XAS) emerges as an appropriate technique to study the electronic (x-ray absorption near edge structure, XANES) and local structure (extended x-ray absorption fine structure, EXAFS) of these compounds as a function of cycling. This work aims to highlight the capabilities of XAS as an element-specific probe to understand a material’s structure at the atomistic level through EXAFS modeling of (MgFeCoNiCuZn)O high-entropy system and how to extract valuable information about the bond distance, number of near neighbors, and local disorder, which are crucial to a full understanding of the electrochemical reaction mechanisms of such battery electrodes.

Empowering lithium-ion batteries: The potential of 2D o-Al2N2 as an exceptional anode material through DFT analysis

Finding an appropriate new anode material with high electrochemical performance for lithium-ion batteries (LIBs) is considered one of the significant challenges for both the academic and industrial research communities. Herein, we propose to explore the efficiency of a newly designed two-dimensional (2D) material, named orthorhombic dialuminium dinitride (o-Al2N2), as an alternative anode material for LIB systems through first-principles calculations and ab initio molecular dynamics (AIMD) simulations. The obtained results show that orthorhombic-Al2N2 exhibits a high specific capacity of 1144.2913 mAhg−1, an operating voltage around 0.575 V, and a low kinetic diffusion barrier of 0.26 eV. These results prove the suitability of the o-Al2N2 monolayer as a promising anode material for LIBs with high structural stability, strong binding energy towards lithium adsorbent, fast lithium diffusion, and a high theoretical capacity. These features rank the 2D o-Al2N2 monolayer among the best choices for the anode part of the next-generation rechargeable LIBs.

Biochar-Derived Anode Materials for Lithium-Ion Batteries: A Review

Highly portable nanoelectronics and large-scale electronics rely on lithium-ion batteries (LIBs) as the most reliable energy storage technology. This method is thought to be both environmentally friendly and cost-effective. We provide a study of a low-cost, abundant, and renewable supply of carbon-based biomass with potential uses in LIBs. Renewable feedstocks have received significant attention in recent decades as promising tools for efficient and alternative anode materials for LIBs. Researchers can synthesise carbon-rich biochar through the pyrolytic process of biomass. Depending on the synthetic process, precise surface chemistry, and textural qualities such as specific surface area and porosity, this material can be customised to favour application-specific properties with a preferred application. In this research, we look at the performance of biochar in LIBs, its properties, and the biomass supply, and we discuss the prospects for these biomass-derived materials in energy storage devices.

Exploring Lead Zirconate Titanate, the Potential Advancement as an Anode for Li-Ion Batteries.

Graphite, widely adopted as an anode for lithium-ion batteries (LIBs), faces challenges such as an unsustainable supply chain and sluggish rate capabilities. This emphasizes the urgent need to explore alternative anode materials for LIBs, aiming to resolve these challenges and drive the advancement of more efficient and sustainable battery technologies. The present research investigates the potential of lead zirconate titanate (PZT: PbZr0.53Ti0.47O3) as an anode material for LIBs. Bulk PZT materials were synthesized by using a solid-state reaction, and the electrochemical performance as an anode was examined. A high initial discharge capacity of approximately 686 mAh/g was attained, maintaining a stable capacity of around 161 mAh/g after 200 cycles with diffusion-controlled intercalation as the primary charge storage mechanism in a PZT anode. These findings suggest that PZT exhibits a promising electrochemical performance, positioning it as a potential alternative anode material for LIBs.

Harnessing the Potential of Zn Powder Anodes: Innovations and Future Directions in Aqueous Zinc‐Ion Batteries

AbstractThe pursuit of alternative anode materials featuring inexpensive, efficient, and adaptable is shaping the future of rechargeable zinc‐ion batteries. The Zn powder anodes stand out among contenders due to their cost‐effectiveness, exceptional processability, and adjustability. However, their widespread use is hampered by significant challenges, including volume expansion and dendrite growth. To counter these issues, a gamut of optimization strategies for Zn powder anodes has been explored and developed. This review systematically encapsulates these research findings, offering a comprehensive understanding of various enhancement methods, such as three‐dimensional printing, in‐situ surface engineering, scalable electrostatic self‐assembly, and epoxy oligomer binding. These methodologies are discussed in detail in the context of their unique synthesis methods and underlying mechanisms. The paper concludes by outlining prospective research trajectories aimed at further optimizing the use of Zn powder anodes in aqueous zinc‐ion batteries, thereby illuminating potential avenues for future exploration and development.

Sulfur-Defect-Induced TiS1.94 as a High-Capacity and Long-Life Anode Material for Zinc-Ion Batteries.

Aqueous zinc-ion batteries (ZIBs) are competitive among the elective candidates for electrochemical energy storage systems, but the intrinsic drawbacks of zinc metal anodes such as dendrites and corrosion severely hinder their large-scale application. Developing alternative anode materials capable of high reversibility and stability for storing Zn2+ ions is a feasible approach to circumvent the challenge. Herein, a sulfur-defect-induced TiS1.94 (D-TiS1.94) as a promising intercalation anode material for ZIBs is designed. The abundant Zn2+-storage active sites and lower Zn2+ migration barrier induced by sulfur defects endow D-TiS1.94 with a high capacity for Zn2+-storage (219.1 mA h g-1 at 0.05 A g-1) and outstanding rate capability (107.3 mA h g-1 at 5 A g-1). In addition, a slight volume change of 8.1% is identified upon Zn2+ storage, which favors a prolonged cycling life (50.3% capacity remaining in 1500 cycles). More significantly, the D-TiS1.94||ZnxMnO2 full battery demonstrates a high discharge capacity of 155.7 mA h g-1 with a capacity retention of 59.8% in 400 cycles. It has been estimated that the high-capacity, low-operation voltage, and long-life D-TiS1.94 can be a promising component of the ZIB anode material family, and the strategy proposed in this work will provide guidance to the defect engineering of high-performance electrode materials toward energy storage applications.

Carbon Covering Method to Enhance the Storage Capacity of Materials Belonging to the Conversion and Alloy Storage Types

AbstractDriven by the development of energy storage systems (EESs), finding alternative anode materials forlithium‐ion batteries to replace the general carbon materials is becoming a hot research topic in the world. Using the metal oxides, metal sulfides, metal phosphides, metal selenides belonging to the conversion type and Sn, Sb, Bi, Ge, P and Si belonging to the alloy storage type seems to be a preferred option. Nevertheless, the demerits such as volume expansion and bad conductivity of alternative materials restrict their practical application. Carbon covering is an efficacious strategy to deal with the aforementioned issues because it can restrict the volume expansion and improve the conductivity of the composite materials effectively. This present review paper comprehensively describes the suitable carbon resources and preparation methods for expanding the practical applications of materials belonging to the conversion type and ally type in fabrications of negative electrodes.

Regulating Lithium Nucleation at the Electrolyte/Electrode Interface in Lithium Metal Batteries

AbstractLithium (Li) metal has emerged as a viable alternative anode material to address the current energy density shortfalls in Li batteries. However, its integration into widespread implementation remains somewhat constrained due to the substandard reversibility issues and safety concerns arising from erratic Li deposition. To effectively tackle these obstacles, considerable endeavors have been exerted to modulate the morphology of Li deposition. Nevertheless, it is exceedingly challenging for Li nuclei that tend to dendritic growth thermodynamically to transform into dense Li morphologies during their growth process. Therefore, it is crucial to understand what influences the formation process of Li nuclei and how to improve the state of Li nuclei. Herein, Li nucleation mechanisms involving mass transport across the solid electrolyte interface from electrolyte to electrode and electrode interfacial reactions are elucidated. Inspired by the understanding of Li nucleation, the corresponding design principles, including enhancing and homogenizing mass transport, stabilizing solid electrolyte interface film, and regulating surface interaction/selection, are summarized for optimizing Li nucleation and further inducing dendrite‐free Li deposition. In light of the competition among these design principles, a perspective on the existing challenges and opportunities for further promoting the application of Li metal batteries is proposed.

Carbon enhanced cementitious coatings: Alternative anode materials for impressed current cathodic protection systems intended for reinforced concrete

AbstractIn this study, the functionality of self‐formulated carbon‐based conductive coatings (CBCCs) with incorporation of graphite as the anode in an impressed current cathodic protection system is studied. The anode materials are tested and evaluated for long‐term durability and performance by an accelerated durability test method. The results show that the functional time is highly dependent on the acceleration factor, and thus the charge passed through the material during testing, as well as the material composition. From the results, there are also indications that the addition of graphene into the CBCC matrix has a positive effect on the homogeneity of the material, but without any major influence on the conductivity and performance.

Understanding of Polyacrylic Acid as Binder for High Silicon Containing Anodes and Ni-Rich Cathodes

With the increased demand on electric vehicles, portable devices and energy storage systems, a great attention is being drawn to improve the energy density of lithium-ion batteries (LiBs) [1]. The commercial LiBs anodes are usually consisted of graphite-based material, which limits the energy density due to its relatively low theoretical capacities. Silicon (Si) has been recognized as an alternative anode material with its high theoretical capacity, natural abundance, and low discharge potential. Despite the above-mentioned advantages, Si undergoes a substantial volume expansion (300% approximately) during the battery operation [2]. There are some approaches to mitigate the adverse of expansion, whereas the cost and scalability of these techniques are the bottlenecks to solve this issue [3]. In this work, we focus on maintaining the structural integrity, along with the coordination of Li as functional binder which could be an effective solution to the abovementioned challenges.In addition to the energy density and capacity targets, considering more environmentally friendly approaches is also one of the key topics for battery manufacturing. Aqueous processing of the anodes is already state-of-the-art whilst, the cathode has its own challenges to be overcome. Ni-rich transition oxide active materials, such as LiNi0.8MN0.1Co0.1 (NMC811), are attractive for high-capacity target applications. Due to the high reactive surface of the active material, during the slurry processing, NMC811 reacts with water, which leads to Li+/H+ exchange [4]. Thus, the slurry results in high pH which can corrode the aluminum foil current collector and cause poor capacity due to Li loss. The advantage of using polyacrylic acid (PAA) is to employ COOH, in which the leached Li+ can bond to the backbone. Hence, the pH of slurry is maintained on desirable coating range and the capacity loss can be reduced due to the proposed aqueous processing.In this study, we explore the utilization of a well-known polymer, polyacrylic acid, as binder for both negative and positive electrodes. On the anode, PAA is functionalized with Li+ and used LiPAA prior to electrode production. It is highly crucial to observe how the dynamics of Si and LiPAA impacts the anode performance during the cycling. To comprehend this, post mortem, scanning electron microscopy (SEM) was performed to detect the positioning and concentration of Si on pristine and cycled anodes. On the cathode side, the focus is to utilize the leached Li+ during the slurry processing by having PAA as binder. This technique has been already successfully implemented by our group on the research pilot scale [5]. The idea is to make pH stable slurry without using any additional acid, in conjunction with creating in situ functional binder (LiPAA). Deep understanding of functional binders is to serve as a guide for the rational design of Si-electrode and aqueous NMC811 cathodes for LiBs.