Anode Material Research Articles

Anti-Self-Discharge Capability of Zn-Halogen Batteries Through an Entrapment-Adsorption-Catalysis Strategy Built Upon Separator.

Aqueous Zn-halogen batteries (Zn-I2/Br2) suffer from grievous self-discharge behavior, resulting in irreversible loss of active cathode material and severe corrosion of zinc anode, which ultimately leads to rapid battery failure. Herein, an entrapment-adsorption-catalysis strategy is reported, leveraging Zn─Mn atom pairs-modified glass fiber separator (designated as ZnMn-NC/GF), to effectively mitigate the self-discharge phenomenon. The in situ Raman and UV experiments, along with theoretical calculations, confirmed the single-atom Mn sites are responsible for polyiodides adsorption, while Zn─Mn atom pairs facilitated the conversion of reaction intermediates. As a result, the utilization rate of cathode active species is enhanced through this ZnMn-NC/GF separator. The fully charged Zn-I2 battery assembled with ZnMn-NC/GF maintained a Coulombic efficiency (CE) of 90.1% after being left for 120 h, as well as a capacity retention rate of 95.3% after 30000 cycles at a current density of 5 A g-1. Additionally, the Zn-Br2 battery designed with ZnMn-NC/GF separator can withstand more serious self-discharge problems of bromine species, with an average discharge voltage platform of 1.75 V at 0.5 A g-1. The self-discharge problem of aqueous Zn-halogen batteries is significantly suppressed by this entrapment-adsorption-catalysis strategy, which can serve as a crucial reference for the advancement of high-performance aqueous Zn-halogen batteries.

Multifunctional Covalent Organic Frameworks for Zinc Metal Anodes

ABSTRACTAqueous zinc‐ion batteries (AZIBs) are one promising electrochemical energy storage system attributed to their high theoretical capacity, relatively low cost as well as high safety. Nevertheless, the formation for zinc dendrites at the anode side severely impedes their electrochemical performance. Covalent organic frameworks (COFs), as promising porous materials, possess some broad application prospects in advanced energy storage and conversion systems and they have demonstrated their versatility in settling the issues for zinc metal anodes. In this current review, the multifunctionality of COFs is reviewed. The overview toward zinc metal anodes is firstly overviewed. Then, multifunctional covalent organic frameworks toward stable zinc metal anodes is summarized. By construction of nanoporous structure, introduction of negative charges and utilization of zincophilic properties, COFs could act as protective layers for ZIBs. In addition, COFs have been utilized as the anode materials, separators and electrolytes in AZIBs. Finally, some perspective of COFs toward highly stable AZIBs are presented. This review could plat a platform for the application of the porous materials in advanced high‐energy‐density batteries.

Citric Acid as a Small Molecule Binder for Si-Based Li-Ion Battery Anode Materials

Abstract In this study, citric acid (CA) dissolved in propylene glycol (PG) was shown to be an effective binder/solvent system for Si-based anode materials in Li-ion batteries. In this system, PG serves both as a slurry solvent and provides viscosity to the slurry to inhibit the settling of active particles and for proper rheology during the coating process, while the small CA molecule serves as a binder/artificial solid electrolyte interphase. After 50 cycles, SiO/carbon black/CA electrodes had a higher capacity retention (93%) than conventional electrodes with lithium polyacrylate (LiPAA) polymeric binder (68%), due to superior maintenance of cohesion with active particles. This demonstrates that small molecules may be used as effective binders for Si-based anode materials when a slurry solvent is used that can take on the role of maintaining the slurry rheology.

Cyclically generated phase segregation synergizing with Si enhances lithium-ion storage capability.

Silicon-based materials has been focused as potential candidates for lithium-ion battery anodes due to their sufficient reserves and extremely high specific capacity. However, the drastic volume expansion during the cycling leads to material pulverization and instability of the solid-electrolyte interface resulting in the rapid capacity fading, which restricts their commercial application. In this study, an original synergistic effect resulting from the phase segregation of Mn-based metal organic framework (Mn-MOF) during cycling is proposed to modify silicon via a facile self-assembly method and investigated as an anode material in LIBs. The unique composite structure can effectively improve the reversibility of silicon and enhance lithium-ion storage capability. After 400 cycles, the Si@Mn-MOF composite exhibits a good electrochemical performance, achieving a high reversible capacity retention of 1234.4 mAh g-1 at a current density of 200 mA g-1.

Influence of surface chemistry on Li nucleation energetics on graphene-based surfaces.

Lithium metal is a promising high-capacity anode material for solid-state batteries, but it typically suffers from poor cyclability. Carbon scaffold hosts have the potential to improve this performance due to their high electronic conductivity and large surface area, which facilitates lithium-ion adsorption and desorption. Scaffold surface chemistry is known to significantly influence performance outcomes, but the details of these interactions are not fully understood. This study employs first-principles simulations to explore lithium transport and nucleation on graphene anodes with various surface chemistries. Using enhanced sampling techniques, abinitio molecular dynamics, and density functional theory calculations, we find that although surface chemistry has a minimal impact on lithium interfacial transport, it influences surface nucleation significantly. Both heteroatom dopants and intrinsic defects lower the nucleation barrier, creating a more favorable environment for lithium nucleation compared to pristine graphene. In addition, our results reveal a complex interplay between surface lithium concentration, lithium transport, and nucleation kinetics. These findings highlight the potential of surface modifications to precisely control nucleation processes on carbon-based anodes and provide design guidance for reducing dendrite formation and improving the cycle life of solid-state batteries.

Manganese‐Resorcin[4]arene‐Based Metal‐Organic Framework: Syntheses, Structures and Lithium‐Ion Battery Application

By employing a dodecarboxylic acid substituted resorcin[4]arene ligand (L), a new metal‐organic framework (MOF), [Mn6(L)(H2O)14]·DMA·5H2O (defined as Mn‐L) has been synthesized under solvothermal conditions. Mn‐L shows a 3D framework with abundant carboxyl groups, which result in the excellent electrochemical performance as anode materials in lithium ion batteries (LIBs). The activated Mn‐L maintains the specific capacities of 598 mAh/g at 100 mA/g after 150 runs and 420 mAh/g at 500 mA/g after 350 runs. The excellent rate capacity, cyclic stability enable Mn‐L to be prospective anode material for LIBs.mploying a dodecarboxylic acid substituted resorcin[4]arene ligand (L), a new metal‐organic framework (MOF), [Mn6(L)(H2O)14]·DMA·5H2O (defined as Mn‐L) has been synthesized under solvothermal conditions. Mn‐L shows a 3D framework with abundant carboxyl groups, which result in the excellent electrochemical performance as anode materials in lithium ion batteries (LIBs). The activated Mn‐L maintains the specific capacities of 598 mAh/g at 100 mA/g after 150 runs and 420 mAh/g at 500 mA/g after 350 runs. The excellent rate capacity, cyclic stability enable Mn‐L to be prospective anode material for LIBs.

Electrolysis of Liquefied Biomass for Sustainable Hydrogen and Organic Compound Production: A Biorefinery Approach

Liquefaction is an effective thermochemical process for converting lignocellulosic biomass into bio-oil, a hydrocarbon-rich resource. This study explores liquefied biomass electrolysis as a novel method to promote the electrocracking of organic molecules into value-added compounds while simultaneously producing hydrogen (H2). Key innovations include utilizing water from the liquefaction process as an electrolyte component to minimize industrial waste and incorporating carbon dioxide (CO2) into the process to enhance decarbonization efforts and generate valuable byproducts. The electrolysis process was optimized by adding 2 M KOH, and voltammetric methods were employed to analyze the resulting emulsion. The experimental conditions, such as the temperature, anode material, current type, applied cell voltage, and CO2 bubbling, were systematically evaluated. Direct current electrolysis at 70 °C using nickel electrodes produced 55 mL of H2 gas with the highest Faradaic (43%) and energetic (39%) efficiency. On the other hand, pulsed electrolysis at room temperature generated a higher H2 gas volume (102 mL) but was less efficient, showing 30% Faradaic and 11% energetic efficiency. FTIR analysis revealed no significant functional group changes in the electrolyte post-electrolysis. Additionally, the solid deposits formed at the anode had an ash content of 36%. This work demonstrates that electrocracking bio-oil is a clean, sustainable approach to H2 production and the synthesis of valuable organic compounds, offering significant potential for biorefinery applications.

Simple Synthesis and Sodium Storage Analysis of Ultra‐High Nitrogen‐Doped Core‐Shell Mesoporous Carbon Nanospheres

AbstractThe development of easily synthesized high‐performance anode materials is crucial for the current energy storage (ES) field. Considering the potential of nitrogen‐doped core‐shell mesoporous carbon materials, a simple micelle‐induced high‐temperature pyrolysis method is employed to synthesize ultra‐high nitrogen‐doped (21.1 wt.%) core‐shell mesoporous carbon nanospheres (CYMCS). This material exhibits excellent volume expansion resistance, achieves a high reversible sodium storage capacity of up to 283 mAh g−1 at a current density of 0.1 A g−1, and maintains stable cycling performance for over 10000 cycles at a high current density of 5 A g−1. Moreover, previous research has provided limited insights into the specific mechanisms behind the low initial coulombic efficiency (ICE) observed in CYMCS and other related porous materials. To address this, the study not only delves into the electrochemical performance of CYMCS but also provides a comprehensive analysis of the formation mechanisms of the solid electrolyte interphase (SEI) and the electrolyte decomposition process, revealing the connections between these processes and their impact on ICE. Overall, this research not only offers new insights into the synthesis and performance optimization of CYMCS materials for sodium storage applications but also provides valuable guidance for the design of related carbon materials and strategies to improve ICE.

In situ formed Organic Sodium Salt/rGO Nanocomposite as Anode Material for Sodium Ion Batteries.

Sodium-ion batteries (SIBs) are expected to be the next-generation large-scale energy storage technology. Organic anode materials are potential for efficient SIBs because they are not sensitive to the size of metal ions. Yet they still suffer from shortcomings such as low electrical conductivity, and solubility in electrolyte. Formation of nanocomposite with carbon materials is an efficient way to address these issues. Herein, we design a thiophene-based carboxylate compound STT, and the STT@rGO nanocomposite is also in situ formed as anode material for SIBs. The reduced graphene oxide (rGO) could improve conductivity and decrease the solubility of the anode material. Compared to the pristine STT electrode, STT@rGO delivers a reversible specific capacity of 178 mAh g-1, with a capacity retention rate of 86% after 1000 cycles. Moreover, full batteries are successfully assembled using the nanocomposite anode and the commercial cathode Na3V2(PO4)3, manifesting the potential applications of the nanocomposite as organic electrode materials.

Sucrose-anthracite composite supplemented by KOH&HCl washing strategy for high-performance carbon anode material of sodium-ion batteries

Sodium-ion batteries represent a promising alternative to lithium-ion batteries, necessitating research into cost-effective synthesis of high-performance anode materials. Herein, this work proposes a facile method combining sucrose-anthracite composites with KOH&HCl decontamination to produce soft/hard carbon hybrids. This approach enhances the structural stability of the material to optimize the carbon yield and increases the interlayer spacing and microcrystalline disorder. The presence of numerous defect sites and C=O active double bonds within the structure, coupled with the flaky morphology, results in an outstanding carbon anode material, exhibiting a high specific capacity of 272 mAh g−1 with excellent rate performance (229 mAh g−1 at 10 C). Furthermore, the material maintains 80 % capacity over 1300 cycles at a high current density of 10 C. The optimization in structure and morphology, along with enhanced electronic conductivity and ionic diffusion kinetics, also ensures that the capacity of the material is dominated by plateau capacity at any current density, which is beneficial for increasing the energy density of full battery configurations and holds promise for high-performance sodium-ion battery anode materials.

Sn@C Composite Architecture for Improved Stability and Performance in Lithium-Ion Battery Anodes

The theoretical capacity of metallic tin (Sn) is 994 mAh g−1, making it a promising anode material for lithium-ion batteries (LIBs). The cycling performance rapidly deteriorates due to the significant volume expansion and contraction during the lithium insertion/extraction process, which is the main limiting factor for the practical application of Sn-based anode materials in LIBs. We report a new material design and fabrication method for carbon-coated Sn solid sphere anodes, using amorphous carbon as the conductive and buffering matrix to form Sn@C composite materials. The size of the composite phases can be easily controlled by varying the carbon source ratio and reduction calcination temperature. The results show that the sample with a carbon source ratio of 1:4, reduced at 600 °C, exhibits excellent electrochemical performance. At a current density of 0.2 C, the discharge capacity reaches 994 mAh g−1 after 500 cycles. At a current density of 3 C, the capacity is maintained at 318 mAh g−1 after 1000 cycles. The synthesis of high-performance Sn-based anode materials through a simple and controllable method holds significant importance and value.

Cu3.21Bi4.79S9: Bimetal superionic strategy boosts ultrafast dynamics for Na-ion storage/extraction

Traditional metal sulfides used as anodes for sodium-ion batteries are hindered by sluggish kinetics, which limits their rate performance. Previous attempts to address this issue focused on nanostructured configurations with conductive frameworks. However, these nanomaterials often suffer from low packing density and the tendency for nanoparticles to agglomerate, posing significant challenges for practical applications. To overcome these limitations, this study presents a novel bimetal superionic anode material Cu3.21Bi4.79S9, which effectively resolves the conflict between sluggish kinetics and micrometer-scale particle size. By leveraging the vacancies created by free Cu and Bi atoms, this material forms rapid migration channels during sodium insertion and extraction, significantly reducing the migration barriers for sodium ions. The development of micrometer-scale Cu3.21Bi4.79S9 enables ultrafast charging-discharging capabilities, achieving a reversible capacity of 325.5 mAh g−1 after 4000 cycles at a high rate of 45 C (15 A g−1). This work marks a significant advancement in the field by offering a solution to the inherent trade-off between high capacity and rate performance in coarse-grained materials, reducing the need for reliance on nanostructured configurations for next-generation high-capacity anode materials.

Enhancing micro-scale SiOx anode durability: Electro-mechanical strengthening of binder networks via anchoring carbon nanotubes with carboxymethyl cellulose

With the increasing prevalence of lithium-ion batteries (LIBs) applications, the demand for high-capacity next-generation materials has also increased. SiOx is currently considered a promising anode material due to its exceptionally high capacity for LIBs. However, the significant volumetric changes of SiOx during cycling and its initial Coulombic efficiency (ICE) complicate its use, whether alone or in combination with graphite materials. In this study, a three-dimensional conductive binder network with high electronic conductivity and robust elasticity for graphite/SiOx blended anodes was proposed by chemically anchoring carbon nanotubes and carboxymethyl cellulose binders using tannic acid as a chemical cross-linker. In addition, a dehydrogenation-based prelithiation strategy employing lithium hydride was utilized to enhance the ICE of SiOx. The combination of these two strategies increased the CE of SiOx from 74% to 87% and effectively mitigated its volume expansion in the graphite/SiOx blended electrode, resulting in an efficient electron-conductive binder network. This led to a remarkable capacity retention of 94% after 30 cycles, even under challenging conditions, with a high capacity of 550 mA h g−1 and a current density of 4 mA cm−2. Furthermore, to validate the feasibility of utilizing prelithiated SiOx anode materials and the conductive binder network in LIBs, a full cell incorporating these materials and a single-crystalline Ni-rich cathode was used. This cell demonstrated a ∼27.3% increase in discharge capacity of the first cycle (∼185.7 mA h g−1) and exhibited a cycling stability of 300 cycles. Thus, this study reports a simple, feasible, and insightful method for designing high-performance LIB electrodes.

Three-Dimensional Array of Holey Graphene as a High-Performance Anode Material for Supercapacitors

Herein, a novel method is employed for the facile, and low-cost preparation of three-dimensional holey graphene (3DHG) starting from pristine graphite for supercapacitor applications. 3D nanopatterning of the holey graphene (HG), prepared via a jaggery-assisted ball mill exfoliation of graphite, is achieved here via heat treatment with urea, where the decomposition of urea causes more nanoholes on the graphene sheets. The structural and morphological analyses reveal the edge functionalization, less-defective nature, and extensive nanopores on graphene. Use of 3DHG as a supercapacitor electrode material is investigated and a high specific capacitance of 423 F/g (@3 A/g) is observed. The symmetric coin cell supercapacitor fabricated using the 3DHG delivers high energy density (7.5 Wh/kg), power density (106 W/kg), and long durability (100% capacitance retention after 8000 cycles). Furthermore, the asymmetric assembly with 3DHG as the anode material with HG cathode exhibits a higher cell voltage of 1.6 V, which diminishes the voltage limitation of aqueous electrolyte-based supercapacitors. The present study demonstrates exceptional supercapacitor performance of 3DHG architecture adequate for commercial energy storage applications.

Poly (acrylic acid)-Modified Silicon as an Active Material for Anodes in Advancing Lithium-ion Battery Performance

Poly (acrylic acid)-Modified Silicon as an Active Material for Anodes in Advancing Lithium-ion Battery Performance

Biomass-Derived Hard Carbon Materials for High-Performance Sodium-Ion Battery

Using biomass-derived hard carbon materials as anode materials for sodium-ion batteries has facilitated resource recycling and brought significant economic benefits. However, the main obstacles to the large-scale application of these materials are the low Coulombic efficiency and high irreversible capacity of hard carbon materials. This study used waste moso bamboo as a carbon source to prepare and pre-oxidize hard carbon through a stepped temperature sintering process. The introduction of oxygen atoms into the carbon layers has been shown to increase the spacing between the carbon layers, which facilitates the insertion of sodium-ions into them. Moreover, the presence of oxygen-containing groups increases the number of edge and vacancy defects in the carbon skeleton, thereby enhancing the actual capacity of the material. Studies have indicated that different pre-oxidation times have varying impacts on the electrochemical properties of hard carbon materials. This study used discarded moso bamboo as the raw material, and the optimal pre-oxidation duration of bamboo-based hard carbon was determined to be 4.5 h through a series of comparative experiments. A high-performance biomass-derived hard carbon material was prepared via a stepwise sintering process. It exhibited a specific capacity of 301.4 mAh·g−1 at 0.1 C and a first-cycle Coulombic efficiency of 87%.

A facile synthesis of MnSb2O6 anode material with enhanced Li-storage performance

A facile synthesis of MnSb2O6 anode material with enhanced Li-storage performance

SM‐Doped Ferric Molybdate Gives Oxygen Vacancies and Co‐Modified Carbon Nanotubes to Construct High‐Energy Supercapacitors

AbstractIn this paper, nanorods doped with Sm rare earth elements were successfully prepared by the hydrothermal method. In view of the formation of oxygen vacancies by replacing Fe3⁺ with Sm3⁺, it was found that the performance was excellent at the doping ratio of 0.5%, and the growth time was 12 h, and the specific capacity was as high as 1902 F/g at a current density of 1 A/g, and after 700 cycles, there was still 1892 F/g, and the capacitance was guaranteed. The holding rate is 99.1%. When the scanning rate is 10 mV/s, the surface control contributes 56.1% of the current, and when the scan rate is 140 mV/s, the contribution rate of pseudocapacitance behavior control increases to 75%, and the asymmetric device Sm–Fe2(MoO4)3//CNTs is constructed with modified carbon nanotube anode material at a current density of 1 A/g, with a specific capacity of 265 F/g, and the device has been tested for 4000 cycles under the condition of 3 A/g, and the capacitance retention rate is 93.8%. It exhibits a high energy density of 79.3 Wh/kg and a high power density of 760 W/kg. It provides a new idea for the development of supercapacitors.

One-step synthesis of Sb/SnO2@C hybrid nanocomposites as high-performance anode materials for lithium/sodium-ion batteries

One-step synthesis of Sb/SnO2@C hybrid nanocomposites as high-performance anode materials for lithium/sodium-ion batteries

Hydrothermal growth of vanadium pentoxide nanofibers on carbon nanofiber mat: An anodic material for solid-state asymmetric supercapacitors

Hydrothermal growth of vanadium pentoxide nanofibers on carbon nanofiber mat: An anodic material for solid-state asymmetric supercapacitors