Anode Material For Lithium-ion Batteries Research Articles

Research progress of carbon nanotubes as anode materials for lithium-ion batteries: a mini review

Research progress of carbon nanotubes as anode materials for lithium-ion batteries: a mini review

Preparation of hard carbon–coated and metal-modified silicon anode materials for lithium-ion batteries

Preparation of hard carbon–coated and metal-modified silicon anode materials for lithium-ion batteries

Revealing Asymmetric Phase Transformation of the BiVO4 Anodes for Potassium-Ion Batteries by In Situ Transmission Electron Microscopy.

Potassium-ion batteries (PIBs) have emerged as a promising alternative to lithium-ion batteries (LIBs), thanks to the cost-effectiveness of potassium resources and a favorable redox potential of approximately -2.936 V. The monoclinic BiVO4, known for its layered structure, shows noteworthy electrochemical properties when utilized as an anode material for both LIBs and sodium-ion batteries. However, the fundamental electrochemical reaction mechanisms of the BiVO4 anode during the potassium insertion/extraction processes remain unclear. Here, we constructed a BiVO4 anode PIB inside the transmission electron microscope (TEM) to explore the real-time potassiation/depotassiation behaviors of BiVO4 during electrochemical cycling. Utilizing the state-of-art in situ TEM technique, the BiVO4 nanorods are found to undergo an asymmetric phase transformation for the first time, where the pristine BiVO4 material is transformed into an amorphous KxBiVO4 phase after the first cycle. More interestingly, the anode materials near and far from the potassium source exhibit opposite volume-changing trends under the same voltage potential. Also, this phenomenon should be attributed to the mass flow of the unstable K-Bi alloy under the electric field. Our findings provide significant insights into the electrochemical mechanism of BiVO4 nanorods during the potassiation/depotassiation process, with the hope of assistance in designing anodes for high-performance PIBs.

New Suggestion of Highly Durable Electrode Design for Ordered Mesoporous Ni-Mn Binary Transition Metal Oxide Anode Material in Lithium-Ion Batteries.

Anode materials storing large-scale lithium ions gradually decrease electrochemical performance due to severe volume changes during cycling. Therefore, there is an urgent need to develop anode materials with high electrochemical capacity and durability, without deterioration arising due to the volume changes during the electrochemical processes. To date, mesoporous materials have received attention as anode materials due to their ability to mitigate volume expansion, offer a short pathway for Li+ transport, and exhibit anomalous high capacity. However, the nano-frameworks of transition metal oxide collapse during conversion reactions, demanding an improvement in nano-framework structure stability. In this study, ordered mesoporous nickel manganese oxide (m-NMO) is designed as an anode material with a highly durable nanostructure. Interestingly, m-NMO showed better cycle performance and higher electrochemical capacity than those of nickel oxide and manganese oxide. Operando small-angle X-ray scattering and ex situ transmission electron microscopic results confirmed that the binary m-NMO sustained a highly durable nanostructure upon cycling, unlike the single metal oxide electrodes where the mesostructures collapsed. Ex situ X-ray absorption spectroscopy proved that nickel and manganese showed different electrochemical reaction voltages, and thus undergoes sequential conversion reactions. As a result, both elements can act as complementary nano-propping buffers to maintain stable mesostructure.

Advances in Coating Materials for Silicon-Based Lithium-Ion Battery Anodes

Silicon anodes, which exhibit high theoretical capacity and very low operating potential, are promising as anode candidates that can satisfy the conditions currently required for secondary batteries. However, the low conductivity of silicon and the alloying/dealloying phenomena that occur during charging and discharging cause sizeable volume expansion with side reactions; moreover, various electrochemical issues result in inferior cycling performance. Therefore, many strategies have been proposed to mitigate these problems, with the most commonly used method being the use of nanosized silicon. However, this approach leads to another electrochemical limitation—that is, an increase in side reactions due to the large surface area. These problems can effectively be resolved using coating strategies. Therefore, to address the issues faced by silicon anodes in lithium-ion batteries, this review comprehensively discusses various coating materials and the related synthesis methods. In this review, the electrochemical properties of silicon-based anodes are outlined according to the application of various coating materials such as carbon, inorganic (including metal-, metal oxide-, and nitride-based) materials, and polymer. Additionally, double shells introduced using two materials for double coatings exhibit more complementary electrochemical properties than those of their single-layer counterparts. The strategy involving the application of a coating is expected to have a positive effect on the commercialization of silicon-based anodes.

Selectively Leaching Li from Anode Materials of Spent Lithium-Ion Battery by Using Water

Selectively Leaching Li from Anode Materials of Spent Lithium-Ion Battery by Using Water

Carbon matrix NiFeP/C nanoparticles anchored on Ti3C2Tx nanosheets as heterostructure high-performance anode for lithium-ion batteries

Engineered micro-nano heterogeneous architectures for transition metal phosphide (TMPs) anode materials in lithium-ion batteries (LIBs) provide multifunctional active components. These components synergistically interact to address pivotal challenges of pronounced volume expansion and sluggish reaction kinetics within the electrode. Consequently, this engineering design approach significantly enhances the overall battery performance. In this study, a self-assembled approach is employed to integrate hybridized NiFe-PBA nanocubes with two-dimensional (2D) monolayer MXene (Ti3C2Tx), producing a heterostructured NiFeP/C@Ti3C2Tx composite. In this meticulously engineered architecture, the interface between the outer MXene layer and NiFeP embedded within the carbon matrix exhibits several distinct superiorities, such as rapid interfacial ion migration, multidirectional migration pathways, and strong spatial adaptability. The resulting non-uniform phase structure effectively mitigates electrode expansion and enhances electronic conductivity. Consequently, the NiFeP/C@Ti3C2Tx-15 composite demonstrates distinct performance advantages over NiFeP/C without MXene. The composite achieves a specific capacity of 689.4 mAh g⁻¹ at 200 mA g⁻¹ over 300 cycles, double that of NiFeP/C. Furthermore, density functional theory (DFT) calculations validate the electronic conductivity facilitated by the heterointerface between MXene and NiFeP, substantiating the strategic significance of the heterostructure in advancing high-performance anode materials for lithium-ion batteries.

Tailoring the Li+ Intercalation Energy of Carbon Nanocage Anodes Via Atomic Al-Doping for High-Performance Lithium-Ion Batteries.

Graphitic carbon materials are widely used in lithium-ion batteries (LIBs) due to their stability and high conductivity. However, graphite anodes have low specific capacity and degrade over time, limiting their application. To meet advanced energy storage needs, high-performance graphitic carbon materials are required. Enhancing the electrochemical performance of carbon materials can be achieved through boron and nitrogen doping and incorporating 3D structures such as carbon nanocages (CNCs). In this study, aluminum (Al) is introduced into CNC lattices via chemical vapor deposition (CVD). The hollow structure of CNCs enables fast electrolyte penetration. Density functional theory (DFT) calculations show that Al doping lowers the intercalation energy of Li+. The Al-boron (B)-nitrogen (N-doped CNC (AlBN-CNC) anode demonstrates an ultrahigh rate capacity (≈300 mAhg-1 at 10 Ag-1) and a prolonged fast-charging lifespan (862.82 mAhg-1 at 5 Ag-1 after 1000 cycles), surpassing the N-doped or BN-doped CNCs. Al doping improves charging kinetics and structural stability. Surprisingly, AlBN-CNCs exhibit increased capacity upon cycling due to enlarged graphitic interlayer spacing. Characterization of graphitic nanostructures confirms that Al doping effectively tailors and enhances their electrochemical properties, providing a new strategy for high-capacity, fast-charging graphitic carbon anode materials for next-generation LIBs.

Carbon-encapsulated silicon ordered nanofiber membranes as high-performance anode material for lithium-ion batteries

Silicon have attracted much attention as a promising anode material for lithium-ion batteries due to the extremely high theoretical capacity. However, its practical application is limited by the huge volume expansion during the cycling process. To address this issue, carbon-encapsulated silicon ordered nanofiber membranes were designed through a modified electrospinning technology with a strong magnetic field. Compared with the conventional nanofiber membranes, the optimized M1200 Gs anode exhibited a high discharge capacity of 1603.1 mAh·g−1 at 0.1 A·g−1, a superior rate performance, and a robust cycling stability with a reversible capacity of 658.1 mAh·g−1 at 1 A·g−1 after 100 cycles. The improved electrochemical performance was confirmed to be highly correlated with the parallel structure of nanofibers, which help to facilitate the diffusion and transport of electrons and ions, realize the stress distribution and buffer the volume changes. This work provides unique insights into designing silicon-based anodes with novel structures for lithium-ion batteries.

Rational synthesis of vertical graphene supported TiN@N-Li4Ti5O12 as advanced high-rate electrodes for lithium-ion batteries

The Li4Ti5O12 (LTO) is demonstrated to be one of the most promising anode materials for lithium-ion batteries (LIBs) to provide safe and high-power density cells but suffer from poor electrical conductivity. In this study, we present a TiN-decorated N-LTO on a vertical graphene (VG) array (TiN@N-LTO) as a potential anode material for lithium-ion batteries (LIBs). The use of atomic layer deposition (ALD) enables the formation of a thin layer of LTO on VG, with precise control over the thickness. The VG serves as highly conductive channels, facilitating the transfer of electrons. Moreover, the introduction of nitrogen heteroatoms into the LTO under an active N2 plasma atmosphere has been shown to enhance its intrinsic conductivity, which is achieved by reducing the bandgap and expanding the diffusion pathways of ions. Concurrently, a small number of metallic TiN are formed and deposited on the surface of N-LTO, thereby further improving its conductivity. COMSOL simulations and DFT calculations demonstrate that the introduced TiN acts as a "conductive bridge", improving the charge distribution of LTO electrodes and enhancing the Li+ transport rate. The TiN@N-LTO exhibits a high rate performance (169.51, 131.61 and 101.08 mAh/g at 0.2, 2 and 20 C, respectively) and remarkable cycling stability (a capacity retention of 99.6% after 5000 cycles at 10 C).

Molecular dynamics study of mechanical stability of Ti4C3 MXene subjected to chirality, temperature, strain rate, and point-vacancy for Lithium-ion batteries

Two-dimensional Ti4C3 MXene has recently emerged as a promising electrode for Lithium-ion batteries (LIBs) because of its outstanding ion-transport abilities and high Li-absorbability. This study employed molecular dynamics simulation to explore the mechanical stability of Ti4C3 MXene subjected to various temperatures, strain rates, and vacancy concentrations. A slightly superior tensile strength and elasticity modulus have been observed along zigzag directions, measuring 148.14 GPa and 29.17 GPa, respectively. On the other hand, armchair-oriented Ti4C3 MXene shows a considerably greater fracture strain of 0.259 due to its strain-hardening tendency at lower temperatures. Elevated temperature decreases both fracture strength and fracture strain, which is opposite to the effect of strain rate. Armchair loading has been revealed to be more sensitive to strain rate than its counter direction. Unlike temperature and strain rate, point vacancy significantly deteriorates the elastic modulus of Ti4C3 MXene. Carbon vacancies are more probable than titanium vacancies, which have less formation energy. The atomistic deformation profile supports the predicted values of fracture strain from stress-strain behavior. This in-depth study offers a detailed understanding of the mechanical behavior of Ti4C3 MXene under diverse circumstances, which will aid further experimental study and be beneficial for adopting Ti4C3 as anode materials in LIBs.

VS2/ Blue Phosphorus composites for high speed lithium ions storage

Based on first-principles calculations, the potential of the H-VS2/Blue P heterojunction composite as a lithium-ion battery anode is systematically investigated. This heterojunction composite enhances the stability of the VS2 structure and increases its overall mechanical strength.The Young's modulus of the composite is 144.69 N/m, markedly exceeding that of the single layer. Furthermore, it modifies the electronic properties of the Blue P monolayer, converting it from an insulating to a metallic state.The H-VS2/Blue P heterojunction composite exhibits a high lithium adsorption energy of 4.34 eV and a low diffusion barrier of 0.15-0.19 eV, facilitating rapid lithium-ion migration during charge/discharge cycles. And the theoretical capacity of the heterojunction composite is up to 1211 mAh/g. The combination of elevated adsorption energy, low diffusion barrier, and high theoretical capacity indicates that the H-VS2/Blue P heterojunction composite is a highly promising anode material for lithium-ion batteries.

Chickpea shell biowaste-derived hard carbon as anode material for lithium-ion batteries

Chickpea shell biowaste-derived hard carbon as anode material for lithium-ion batteries

Nitrogen doping enhances pseudocapacitive lithium storage and ionic conductivity in Ti2Nb2O9 nanosheets

Titanium-niobium oxides (TixNbyO2x+2.5y) are promising anode materials for lithium-ion batteries due to their suitable lithium insertion potential, excellent rate performance, cycling stability, and considerable capacity based on multi-electron reactions. However, the intrinsic low electrical conductivity and rapid capacity decay during cycling limit their application. In this study, nitrogen-doped Ti2Nb2O9 nanosheets were synthesized using a chemical exfoliation method and the subsequent high-temperature phase transition. Meanwhile, introducing nitrogen atoms reduced the bandgap and increased the material's electrical conductivity. Thus, the lithium storage performance of the N-TNO electrode was improved with a reversible capacity of 348.1 mAh g−1.

Core-shell structure and high rate performance of Ce-doped Li4Ti5O12 for lithium-ion battery anode materials

Lithium titanate (LTO) can be a very promising anode material for lithium-ion batteries (LSBs) due to its inherent ability to inhibit the growth of lithium dendrites as well as its unique “zero-strain” properties. Unfortunately, the low electronic conductivity of LTO leads to serious shortcomings in higher electrochemical demands. In this work, the Ce3+-doped C@Li4Ti5-xCexO12 (x = 0, 0.1, 0.15 and 0.2) anode materials synthesized by the hydrothermal method using carbon spheres as templates showed more significant improvement in both structural and electrochemical properties. The results demonstrate that electronic conductivity, lithium-ion diffusion rate, discharge specific capacity, discharge rate capability, and significant improvement stability of C@Li4Ti5-xCexO12 (x = 0.1, 0.15 and 0.2) electrodes. Among them, C@Li4Ti4.85Ce0.15O12 electrode exhibits the highest initial discharge specific capacity (250.86 mAh/g) at 0.1C, which is 1.28-fold that of C@ Li4Ti5O12 (195.94 mAh/g), and initial discharge capacity from 205.96 mAh/g to 170.39 mAh/g after 500 cycles, corresponding to 82.7 % of the initial stable discharge capacity. The outstanding performance of C@Li4Ti4.85Ce0.15O12 can be attributed to the lower interfacial impedance, higher electronic conductivity, high oxygen vacancy concentration, and moderate amount of Ce3+ doping can enhance the electrochemical activity. In addition, carbon sphere surface defects shown to be effective in improving lithium-ion storage. This work demonstrates that Ce3+ doping is an effective method to improve the electrochemical performance of LTOs and provides a more effective guide for designing and optimizing anode electrode materials for lithium-ion batteries

Understanding the impact of porosity on Li-ion diffusion enhancement in micro-sized silicon particles for advanced batteries

Lithium-ion batteries (LIBs) require advanced and practical anode materials, such as porous silicon (PSi), which can meet these expectations due to their rapid Li-ion diffusion rates and structural relaxation. Several studies have focused on the structural design of PSi or its composites to improve Li-ion diffusion; however, no systematic and quantitative evaluations of the impact of porosity on Li-ion diffusion and battery performance have been reported. Therefore, to understand the impact of porosity on Li-ion diffusion, we developed micro-sized porous silicon (m-PSi) particles with various porosities via metal-assisted chemical etching (MACE) method using different concentrations of AgNO3 (0.02–0.08 M). Among the as-prepared samples, m-PSi-0.06 (prepared using 0.06 M AgNO3) with ∼70 % porosity achieved a maximum Li-ion diffusion rate of 2.35 × 10−9 cm2 s−1. This led to a high-rate capability, enhanced Li-ion storage, and better cyclic retention of 61.4 % compared to the non-porous micro-sized Si (m-Si) (5.8 %) sample at a current density of 0.1 A g−1. Furthermore, the optimal porosity of m-PSi-0.06 resulted in an impressive rate capability of 760 mAh g−1 at a high current density of 4 A g−1 with a recovery rate of 80 %. The improved efficiency of m-PSi-0.06 is attributed to its optimized mesoporosity, which ensures sufficient space for Li-ion storage and shortens the effective transmission path to accelerate Li-ion diffusion. Moreover, the mesopores provide a greater number of active sites for the reversible adsorption of Li ions, thereby improving the capacitive behavior of the anode. In contrast, the highly nanoporous m-PSi-0.08, with a pore diameter of 1–3 nm, impeded Li-ion movement and restricted diffusion. These results reveal that a high nano porosity hinders Li-ion diffusion, whereas an optimal mesoporosity ensures swift diffusion in m-PSi anodes. These insights could guide the design of Si-based anode materials for advanced LIBs.

Innovative Design of anode materials for Li-ion batteries: Bismuth oxide/sodium bismuth molybdate nanocomposites

Novel bismuth oxide/sodium bismuth molybdate nanocomposites (NCs), Bi2O3@NaBi(MoO4)2, were developed successfully via simple methods. Advanced analyses revealed that the NCs were composed of Bi2O3 and NaBi(MoO4)2 particles at the nanoscale, below 10 nm, in a combination of amorphous and crystalline forms. In this work, these NCs were utilized as lithium-ion battery anode materials for the first time, demonstrating exceptional electrochemical performances, including high capacity, superior capacity retention, high coulombic efficiency, excellent rate capacity, and pseudo-capacitance behavior. For instance, Bi2O3@NaBi(MoO4)2 NCs prepared at 1 h and 3 h of reaction time delivered a reversible charge capacity of 1052 and 1034 mAh g−1 after 200 cycles at current densities of 0.1 A g−1 with a capacity retention of 110 and 129 %, respectively. Notably, all the NCs anodes exhibited an excellent initial coulombic efficiency of above 80 %. Materials characterizations and electrochemical analysis revealed that the improved electrochemical properties of the NCs were attributed to their unique architectures, which featured nanostructures, molybdate components, and a small amount of amorphous phase. In addition, the significant capacity increase could be due to the electrochemical milling effect, the in situ formation of metallic particles, and the role of Mo metal in the NCs anodes as the catalysts for Li2O decomposition during cycling. It concluded that Bi2O3@NaBi(MoO4)2 NCs have great potential as advanced anodes for Li-ion storages.

In situ anchoring of FeNi nanoparticles into three-dimensional nitrogen-doped carbon framework as a self-supporting electrode for high-performance lithium storage

Constructing free-standing electrodes with superior lithium storage capacity and good mechanical performance are fascinating for next-generation lithium-ion batteries (LIBs). Nevertheless, their practical application is hindered by complicated synthesis procedures and high cost. Herein, a highly stable, self-supporting and flexible electrode material for LIBs was constructed by encapsulating spherical FeNi nanoparticles into one-dimensional N-doped carbon fiber film (FeNi/N- CFM) using the electrospinning technique and subsequent heat treatment. The FeNi/N-CFM can be directly used as anode materials for LIBs without conductive additive, current collector and binder. The synergistic effect of uniformly dispersed small FeNi nanoparticles and three-dimensional (3D) conductive network constructed by CF framework effectively improves the utilization rate of active materials, enhances the transport of both electrons and lithium ions, facilitates the electrolyte penetration, and promotes the lithium-ion storage kinetics and stability, thus leading to a greatly enhanced electrochemical performance. Benefiting from the unique architectural feature and flexibility, the FeNi/N-CFM composites employed as binder-free electrodes for LIBs exhibit good lithium storage performance (an initial discharge capacity of 1031.5 mA h g−1 and a reversible capacity of 481.3 mA h g−1 at 100 mA g−1 after 100 cycles), rate capacity (305.1 mA h g−1 at 1000 mA g−1) and outstanding reversibility (coulombic efficiency of around 100 % after 100 cycles). Furthermore, this work also provides a facile and effective pathway to design and fabricate free-standing electrodes.

Harnessing MBene termination for superior anode interfaces in Li/Ca-ion batteries

The elevation of two-dimensional (2D) transition metal borides, specifically MBenes, as anode materials for lithium-ion batteries (LIBs) and calcium-ion batteries (CIBs) can be achieved through strategic functionalization with appropriate groups. Utilizing a first-principles approach, we conducted an in-depth investigation into the electrochemical properties of chlorine-terminated V2B (V2BCl2) as a candidate anode material for LIBs and CIBs. V2BCl2 exhibits metallic behavior, as demonstrated by band structure analysis, which endows it with exceptional conductivity due to the free electron surface of the system, thereby embodying ideal anode characteristics. The dynamic and thermal stability of the system was assessed through comprehensive phonon dispersion analyses and ab-initio molecular dynamics (AIMD) calculations. High net charge transfer rates of Li/Ca ions towards the monolayer, augmented electron localization function (ELF) near system atoms, and the presence of ionic bonds between Ca/Li and the V2BCl2 monolayer contribute to the enhanced conductivity observed in these anode systems. This is corroborated by metrics such as the projected crystal orbital Hamiltonian population (-pCOHP), low diffusion energy barriers (< 0.35 eV) facilitating rapid charging mechanisms, and low open circuit voltages (< 0.32 V) ensuring robust battery performance stability. Furthermore, V2BCl2 exhibits notable specific storage capacities of 875.67 mAh g−1 for Ca ions and 1167.75 mAh g−1 for Li ions, surpassing the benchmarks set by recent MBene systems. These promising results strongly advocate for V2BCl2 as a viable candidate for anode material in both LIB and CIB applications, highlighting its potential significance in advancing battery technology.

Core–shell Fe2O3@MnO2 nanoring composites as anode materials for high-performance lithium-ion batteries

Core–shell Fe2O3@MnO2 nanoring composites as anode materials for high-performance lithium-ion batteries