Anode Material For Lithium-ion Batteries Research Articles

The Effect of TiO2 on the Electrochemical Performance of Sb2O3 Anodes for Li-Ion Batteries

Antimony (Sb) and its composites have been recognized as potentially good anode materials for lithium-ion batteries (LIBs) due to their relatively high theoretical capacity of 660 mAh g−1 and to their low cost. However, Sb-based anodes suffer from a high-volume change during the lithiation/delithiation process that results in capacity fading and anode degradation after prolonged charge/discharge cycles. To address this issue, Sb2O3/TiO2 nanocomposite electrodes can be synthesized and used as anodes for LIBs with high capacity and good electrochemical stability. In the present work, TiO2@Sb2O3 composites with different (TiO2:Sb2O3) ratios of 0:1, 1:1, 1:4 and 3:1 were synthesized and directly used as anode materials for LIBs. The electrochemical performance of the TiO2/Sb2O3 composite anode with different ratios of TiO2 to Sb2O3 was evaluated by galvanostatic charge/discharge, rate performance and cyclic voltammetry. The 3:1 (TiO2:Sb2O3) composite anode delivered the highest capacity compared to those of the TiO2, SbO3, 1:1 (TiO2:Sb2O3) and 1:4 (TiO2:Sb2O3) electrodes. The TiO2@Sb2O3 composite anode with a 3:1 ratio exhibited a stabilized capacity of 536 mAh g−1 after 100 cycles at 100 mA g−1 and showed excellent rate performance, with current densities between 50 and 500 mA g−1. The improved electrochemical performance was attributed to the synergistic effect of TiO2 (i.e., the coating of Sb2O3 with TiO2) on reducing the volume change of the Sb anode material after prolonged charge/discharge cycles and on maintaining a stable interface between the electrolyte and the composite electrode material.

Hierarchical porous microrod In2O3@C@Ti3C2TX composite anode for high-performance lithium-ion batteries

In2O3, employed as an anode, demonstrates exceptional capacity in lithium-ion batteries (LIBs). Nonetheless, its propensity for significant volume expansion results in internal fracturing and reorganization. Two-dimensional double transition metal carbides and nitrides (MXenes), characterized by unique out-of-plane metal atom ordering, exhibit promising electrical properties due to their chemical versatility and intricate structure. However, MXenes' tendency to aggregate or stack into lamellar structures impedes their practical energy storage application. To address these issues, a hierarchical porous microrods In2O3@C@Ti3C2TX (HPMR-In2O3@C@Ti3C2TX) composite anode material was synthesized through electrostatic self-assembly of MIL-68 (In) and Ti3C2TX, followed by carbonization. This synthesis produced continuous one-dimensional microrods with hierarchical porous channels in HPMR-In2O3@C, offering a substantial specific surface area, numerous Li+ storage sites, and enhanced charge transfer rates. Moreover, the interlayer space within Ti3C2TX acts as an electrolyte reservoir, facilitating comprehensive electrochemical reactions and accommodating volume changes during charge-discharge cycles. Consequently, the HPMR-In2O3@C@Ti3C2TX anode exhibited remarkable properties, including a high initial discharge specific capacity of 1406 mAh g-1 at 0.1 C, outstanding cycling performance, and superior rate performance. This research presents a promising direction for the advancement of high-performance anode materials for lithium-ion batteries.

Comprehensive Investigation of the Crystal Structure of Cation-Disordered Li3VO4 as a High-Rate Anode Material: Unveiling the Dichotomy between Order and Disorder.

This study investigates mechanochemical synthesis and cation-disordering mechanism of wurtzite-type Li3VO4 (LVO), highlighting its promise as a high-performance anode material for lithium-ion batteries and hybrid supercapacitors. Mechanochemical treatment of pristine LVO using a high-energy ball mill results in a "pure cation-disordered" LVO phase, allowing for meticulous analysis of cation arrangement. The X-ray and neutron diffraction study demonstrates progressive loss of order in LVO crystal with increasing milling duration. High-resolution transmission electron microscopy reveals disrupted lattice fringes, indicating cationic misalignment. Pair-distribution function analysis confirms loss of cation arrangements and the presence of short-range order. Combination of these multiple analytical techniques achieves a comprehensive understanding of cation regularity and clearly demonstrates order/disorder dichotomy in cation-disordered materials, ranging from short (<8 Å) to middle-long range (8-30 Å), using an integrated superstructure model of the cation-disordered LVO crystals. Electrochemical testing reveals that mechanochemically treated LVO exhibits superior rate capability, with a 70% capacity retention at a high current density of 50C-rate. Lithium diffusion coefficient measurements demonstrate enhanced lithium-ion mobility in the mechanochemically treated LVO, attributed to cation-disordering effect. These findings provide valuable insights into mechanochemical cation-disordering in LVO, presenting its potential as an efficient anode material for lithium-ion-based electrochemical energy storage.

Computational Insights into the Influence of Surface Functionalization Groups on Zirconium Carbide MXenes as Anode Materials for Lithium-Ion Batteries

Computational Insights into the Influence of Surface Functionalization Groups on Zirconium Carbide MXenes as Anode Materials for Lithium-Ion Batteries

Dual carbon protected ultrafine SnO2 nanoparticles with Sn–C interface for robust lithium storage

Stannic oxide (SnO2)-based lithium-ion batteries (LIBs) have garnered tremendous attention due to their high theoretical capacity and suitable lithium ion insertion potential. However, their widespread applications have been hindered by severe electrode degradation caused by substantial volume expansion of SnO2. In this study, we embedded amorphous carbon encapsulated ultrafine SnO2 nanoparticles on hollow macroporous carbon (AC@SnO2/HMC) as a superior anode material for LIBs. The unique Sn–C interface and dual carbon protection layers effectively mitigated SnO2 nanoparticle agglomeration and volume expansion, reinforcing the cycling stability. Additionally, the capacitive contribution from amorphous carbon significantly improved the reversible capacity and rate capability. As such, the resulting AC@SnO2/HMC electrode exhibited high capacity (1828 mAh g−1 after 200 cycles at 0.1 A g−1), excellent rate capability (1017.6 mAh g−1 at 1 A g−1), and outstanding cycling performance (792.1 mAh g−1 after 880 cycles at 2 A g−1), surpassing previously reported SnO2-based anodes. Furthermore, the AC@SnO2/HMC-based Li-ion full cell demonstrated a remarkable capacity of 566.3 mAh g−1 at 0.2 A g−1 after 200 cycles. This study offers valuable insights into the development of advanced SnO2-based anodes for LIBs and beyond, highlighting their potential for future advancements in battery technology.

A Novel Spinel High-Entropy Oxide (Cr0.2Mn0.2Co0.2Ni0.2Zn0.2)3O4 as Anode Material for Lithium-Ion Batteries

In this study, we synthesized spinel high-entropy oxide (HEO) (Cr0.2Mn0.2Co0.2Ni0.2Zn0.2)3O4 nanoparticles by a simple solution combustion method. These particles were investigated for their performance as anodes in lithium-ion batteries. The reversible capacity is 132 mAh·g−1 after 100 cycles at a current density of 100 mA·g−1, 107 mAh·g−1 after 1000 cycles at a current density of 1 A g−1, and 96 mAh·g−1 rate capacity at a high current density of 2 A g−1. The outstanding cycle stability under high current densities and remarkable rate performance can be attributed to the stable structure originating from the high entropy of the material.

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.

Deciphering the degradation mechanisms of nano-Si and micro-SiO anodes in lithium-ion battery full-cells using distribution relaxation times analysis

Silicon (Si) and silicon monoxide (SiO) have attracted great interest as next-generation anode materials for lithium-ion batteries (LiBs) due to their high energy density. However, their commercialization has been hindered by rapid capacity fading, which stems from mechanical degradation (e.g., cracking and delamination) and the aggressive formation of solid electrolyte interphase (SEI) layer. While understanding these degradation mechanisms in batteries necessitates in-operando measurement techniques, very few non-destructive analytical methods have been documented in literature. This paper highlights the effectiveness of combined electrochemical impedance spectroscopy (EIS) and distribution of relaxation times (DRT) techniques in performing systematic characterization of LiNi0.6Mn0.2Co0.2O2 (NMC)/nano-Si and NMC/micro-SiO full-cells. The systematic design of experiments enabled the separate deconvolution of anode and cathode aging using symmetrical cells. This approach offered a clear understanding of the overall degradation mechanisms in the full-cells. The major impedance sources in the NMC/nano-Si full-cell were anode contact impedance, resulting from mechanical degradation of Si, and cathode charge transfer impedance, due to significant lithium loss and consequently deeper extraction of lithium ions in NMC. In contrast, micro-SiO anodes exhibited less electrode-level degradation, as evidenced by SEM images and relatively stable impedance behaviors during extended cycling, which strongly corroborate its superior capacity retention (66 % at 300th cycle) compared to that of nano-Si anode in full-cells (26.5 % at 300th cycle).

Carbon-Based 3D Architectures as Anodes for Lithium-Ion Battery Systems.

Graphite, with its exceptional cyclic performance, continues to dominate as the preferred anode material for lithium-ion batteries. However as high-energy application gains momentum, there is growing demand for higher capacities that alloying/de alloying and conversion type anode materials can offer. Despite their potential, these materials are plagued by challenges such as volumetric fluctuations, low conductivities, and poor cyclic stability. Carbon nanostructures, on the other hand, show tremendous promise with their low volume expansion, high ion diffusion rates, and excellent conductivity. Nevertheless, their limited areal and volumetric densities restrict their widespread utilization. To address these limitations, various strategies such as doping, composite formation, and structural modification have been proposed. This article provides a succinct overview of carbon nanomaterials and their electrochemical performance as 3D carbon-based anodes, along with a comprehensive analysis of the strategies employed to overcome associated challenges while evaluating their potential prospects in the field.

A Novel Gelatin Binder with Helical Crosslinked Network for High-Performance Si Anodes in Lithium-Ion Batteries.

Silicon(Si) is a promising anode material for lithium-ion batteries, but its large volume expansion during cycling poses a challenge for the binder design. In this study, a novel gelatin binder is designed and prepared with a helical crosslinked network structure. This gelatin binder is prepared by enzymatic crosslinking and immersion in Hofmeister salt solution, which induces the formation of network and helical secondary structures. The helical crosslinked network structure can be analogous to a spring group system to effectively dissipate the stress and strain caused by the Si expansion. The gelatin binder is further partially carbonized by low-temperature pyrolysis, which improves its conductivity and stability. The Sianode with the optimized gelatin binder exhibits high initial coulombic efficiency, excellent rate performance, and long-term cycling stability. This study provides an innovative approach for the preparation of high-performance Si anodes, namely by controlling the molecular configuration of the binder to significantly improve the cycle stability, which can also be applied to other high-capacity anode materials that suffer from large volume changes during cycling.

A Hybrid Structure to Improve Electrochemical Performance of SiO Anode Materials in Lithium-Ion Battery.

The wide utilization of lithium-ion batteries (LIBs) prompts extensive research on the anode materials with large capacity and excellent stability. Despite the attractive electrochemical properties of pure Si anodes outperforming other Si-based materials, its unsafety caused by huge volumetric expansion is commonly admitted. Silicon monoxide (SiO) anode is advantageous in mild volume fluctuation, and would be a proper alternative if the low initial columbic efficiency and conductivity can be ameliorated. Herein, a hybrid structure composed of active material SiO particles and carbon nanofibers (SiO/CNFs) is proposed as a solution. CNFs, through electrospun processes, serve as a conductive skeleton for SiO nanoparticles and enable SiO nanoparticles to be uniformly embedded in. As a result, the SiO/CNF electrochemical performance reaches a peak at 20% the mass ratio of SiO, where the retention rate reaches 73.9% after 400 cycles at a current density of 100 mA g-1, and the discharge capacity after stabilization and 100 cycles are 1.47 and 1.84 times higher than that of pure SiO, respectively. A fast lithium-ion transport rate during cycling is also demonstrated as the corresponding diffusion coefficient of the SiO/CNF reaches ~8 × 10-15 cm2 s-1. This SiO/CNF hybrid structure provides a flexible and cost-effective solution for LIBs and sheds light on alternative anode choices for industrial battery assembly.

A Novel Biogenic Silicon-Based Anode Material for Lithium-Ion Batteries: A Review

A Novel Biogenic Silicon-Based Anode Material for Lithium-Ion Batteries: A Review

A novel Cu-MOF@Si/C prepared by the pulse discharge and hydrothermal method as an anode material for lithium-ion battery

Metal-organic framework (MOF) composite materials have attracted significant interest owing to their customizable shape and porosity. However, the widespread use of MOFs in lithium-ion batteries is limited because of its low ionic conductivity and charging capacity. In this study, Si nanospheres are synthesized using the pulse-discharge method. Subsequently, a composite of Cu-MOF-coated Si nanospheres (Cu-MOF@Si) is developed via a solvothermal process using MOF-199 as the precursor. This is followed by the synthesis of a novel Cu-MOF@Si/C composite via thermal decomposition. Cu-MOF@Si/C composites have been employed as anode materials in lithium-ion batteries. After undergoing 300 charge and discharge cycles at a rate of 100 mA g−1, the composite exhibited a capacity of 725.4 mAh g−1 and an initial Coulombic efficiency of 96.86 %. In addition, the battery showed an excellent rate performance and maintained a high discharge capacity even at current densities of 0.2, 0.5, 1.0, and 2.0 C. These findings suggest that the conductive network formed during the annealing of the Cu-MOF@Si/C composite is vital for enhancing the ionic conductivity and mitigating the expansion of Si nanoparticles during battery cycling.

Tailoring Alkalized and Oxidized V2CTx as Anode Materials for High-Performance Lithium Ion Batteries.

V2CTx MXenes have gained considerable attention in lithium ion batteries (LIBs) owing to their special two-dimensional (2D) construction with large lithium storage capability. However, engineering high-capacity V2CTx MXenes is still a great challenge due to the limited interlayer space and poor surface terminations. In view of this, alkalized and oxidized V2CTx MXenes (OA-V2C) are envisaged. SEM characterization confirms the accordion-like layered morphology of OA-V2C. The XPS technique illustrates that undergoing alkalized and oxidized treatment, V2CTX MXene replaces -F and -OH with -O groups, which are more conducive to pseudocapacitive properties as well as Na ion diffusion, providing more active sites for ion storage in OA-V2C. Accordingly, the electrochemical performance of OA-V2C as anode materials for LIBs is evaluated in this work, showing excellent performance with high reversible capacity (601 mAh g-1 at 0.2 A g-1 over 500 cycles), competitive rate performance (222.2 mAh g-1 and 152.8 mAh g-1 at 2 A g-1 and 5 A g-1), as well as durable long-term cycling property (252 mAh g-1 at 5 A g-1 undergoing 5000 cycles). It is noted that the intercalation of Na+ ions and oxidation co-modification greatly reduces F surface termination and concurrently increases interlayer spacing in OA-V2C, significantly expediting ion/electron transportation and providing an efficient way to maximize the performance of MXenes in LIBs. This innovative refinement methodology paves the way for building high-performance V2CTx MXenes anode materials in LIBs.

Modeling and simulation of chemo-elasto-plastically coupled battery active particles

AbstractAs an anode material for lithium-ion batteries, amorphous silicon offers a significantly higher energy density than the graphite anodes currently used. Alloying reactions of lithium and silicon, however, induce large deformation and lead to volume changes up to 300%. We formulate a thermodynamically consistent continuum model for the chemo-elasto-plastic diffusion-deformation behavior of amorphous silicon and it’s alloy with lithium based on finite deformations. In this paper, two plasticity theories, i.e. a rate-independent theory with linear isotropic hardening and a rate-dependent one, are formulated to allow the evolution of plastic deformations and reduce occurring stresses. Using modern numerical techniques, such as higher order finite element methods as well as efficient space and time adaptive solution algorithms, the diffusion-deformation behavior resulting from both theories is compared. In order to further increase the computational efficiency, an automatic differentiation scheme is used, allowing for a significant speed up in assembling time as compared to an algorithmic linearization for the global finite element Newton scheme. Both plastic approaches lead to a more heterogeneous concentration distribution and to a change to tensile tangential Cauchy stresses at the particle surface at the end of one charging cycle. Different parameter studies show how an amplification of the plastic deformation is affected. Interestingly, an elliptical particle shows only plastic deformation at the smaller half axis. With the demonstrated efficiency of the applied methods, results after five charging cycles are also discussed and can provide indications for the performance of lithium-ion batteries in long term use.

Ultrahigh rate and cycling properties of Li2CuTi3O8 anode derived from HKUST-1 copper source for high-performance lithium-ion batteries

Rational design and preparation of titanium-based anode materials with superior fast charge and discharge are a key focuses of the lithium-ion batteries research. Herein, a novel and facile synthesis of uniformly carbon-coated Li2CuTi3O8 (LCuTO) nanoparticles with excellent high-rate lithium storage properties is presented using HKUST-1 with pore structure and active metal sites as a copper source. The well-designed LCuTO@HKUST with carbon bridges between the particles and the carbon layer on the outer surface offers high electronic conductivity for fast charge and discharge. The LCuTO@HKUST exhibits extraordinary lithium storage performance: high capacity (251.8 mAh/g after 1000 cycles at a current density of 1.0 A/g), a superior high-rate capability (160.3 mAh/g after 500 cycles at 3.0 A/g and 138.1 mAh/g after 500 cycles at 5.0 A/g), and excellent cycle reversibility and cycle stability under various current densities. In addition, the lower Li+ migration barrier in LCuTO@HKUST demonstrated by density functional theory (DFT) calculations is beneficial to the long-cycle stability and high-rate performance. The proposed preparation method and the strategy of using the MOF as a metal source for lithium-ion battery anode materials provide a new approach for advanced fast charge–discharge energy storage applications.

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.

NiCo Nanoparticles Encapsulated in Nitrogen-Doped Carbon Tubes as Anode Materials for High-Performance Lithium-Ion Batteries

NiCo Nanoparticles Encapsulated in Nitrogen-Doped Carbon Tubes as Anode Materials for High-Performance Lithium-Ion Batteries

Fabrication of a Stable and Highly Effective Anode Material for Li-Ion/Na-Ion Batteries Utilizing ZIF-12.

Transition metal selenides (TMSs) are receiving considerable interest as improved anode materials for sodium-ion batteries (SIBs) and lithium-ion batteries (LIBs) due to their considerable theoretical capacity and excellent redox reversibility. Herein, ZIF-12 (zeolitic imidazolate framework) structure is used for the synthesis of Cu2Se/Co3Se4@NPC anode material by pyrolysis of ZIF-12/Se mixture. When Cu2Se/Co3Se4@NPC composite is utilized as an anode electrode material in LIB and SIB half cells, the material demonstrates excellent electrochemical performance and remarkable cycle stability with retaining high capacities. In LIB and SIB half cells, the Cu2Se/Co3Se4@NPC anode material shows the ultralong lifespan at 2000 mAg-1, retaining a capacity of 543 mAhg-1 after 750 cycles, and retaining a capacity of 251 mAhg-1 after 200 cycles at 100 mAg-1, respectively. The porous structure of the Cu2Se/Co3Se4@NPC anode material can not only effectively tolerate the volume expansion of the electrode during discharging and charging, but also facilitate the penetration of electrolyte and efficiently prevents the clustering of active particles. In situ X-ray difraction (XRD) analysis results reveal the high potential of Cu2Se/Co3Se4@NPC composite in building efficient LIBs and SIBs due to reversible conversion reactions of Cu2Se/Co3Se4@NPC for lithium-ion and sodium-ion storage.

Theoretical prediction on Irida-graphene monolayer as promising anode material for lithium-ion batteries

With the growing interest in energy storage technologies, the demand for alternative rechargeable batteries has become increasingly urgent. We evaluate the feasibility of a two-dimensional (2D) material, Irida-graphene (IG) monolayer, as an anode for lithium-ion batteries (LIBs) through first-principles calculations. IG monolayer, after Li adsorption, exhibits metallic property, suggesting the good electrical conductivity. Additionally, in comparison with IG bilayer, IG monolayer possesses low diffusion barriers (0.19–0.24 eV), high theoretical capacity (1115.8mA h/g), and low average open circuit voltage (0.317 V). Furthermore, under the influence of solvent effects, the adsorption performance becomes even more stable, and the theoretical capacity increases. These intriguing findings make IG monolayer great potentials for the anode of LIBs.