Anode For Lithium-ion Batteries Research Articles

Advances in the Application of Graphene in Lithium-ion Batteries

The search for effective energy storage options has escalated due to the rising global energy demands and environmental concerns. Lithium-ion batteries (LIBs) emerge as a key technology. However, the performance of traditional LIBs still needs to be improved. Therefore, choosing new nanomaterials for the modification of LIBs has become an effective solution. Graphene, as a nanomaterial, is an excellent candidate material for modification. This paper delves into the application of graphene in enhancing the performance of LIBs. Graphene, with its superior electrical conductivity and substantial specific surface area, offers the potential to enhance the performance of both anode and cathode materials in LIBs. This can lead to significant improvements in the overall cycle life, energy density, and power density of these batteries. This work emphasizes the application of graphene in cathode and anode materials. In cathode materials, the layered structure of graphene enables lithium-ion with high theoretical capacity. Meanwhile, graphene helps improve the electron and lithium ion mobility of anode materials. Despite the promising developments, challenges such as lithium loading capacity and coulombic efficiency still remain. The continued exploration of graphene applications is expected to drive LIBs to unprecedented performance metrics. This is in line with the global quest for sustainable and efficient energy storage technologies.

Rational Synthesis of Spongy Fe3N@N-Doped Carbon Nanorods with Controlled Topography and Porosity for Enhanced Energy Storage Anodes in Lithium-Ion Batteries.

Iron nitrides with the merits of high theoretical capacities, cost-effectiveness, and good electronic/ionic conductivity have been recognized as attractive anode candidates for lithium-ion batteries (LIBs). Carbon compositing, pore engineering, and nanostructure construction have proved to be effective strategies to prepare high-performance metal nitride anodes for LIBs. Herein, we synthesized a series of Fe3N-embedded and N-doped carbon nanorods (Fe3N@NCNR) with a hierarchical porous system and controllable topography by metal-catalyzed graphitization-nitridization of the Fe(III)-triazole framework (Fe-MOF) and thermal evaporation of the triblock copolymer F127 template assembled in Fe-MOF via hydrogen bonding interaction, followed by the air oxidation and urea-assisted ammonolysis processes. The Fe3N@NCNR as anodes for LIBs display extraordinary lithium storage capabilities with a high reversible capacity of 830 mA h g-1 at 0.1 C, a good rate performance of 576 mAh g-1 at 5 C, and a long-term cycling stability of 742 mA h g-1 over 600 cycles at 1 C. Such outstanding performance benefits from the spongy carbon nanorods with rich macropores for rapid electronic/ionic transport and effective accommodation of electrode volume expansion, abundant N-doped meso-/microporous carbon for the additional storage of Li+ via capacitive effect, and the efficient utilization of Fe3N nanoparticles uniformly distributed through carbon nanorods. Importantly, this work introduces an effective strategy to construct superior performance nitride anodes from MOF surfactants based on hydrogen bonding-driven interface self-assembly and provides insight into the preparation of highly efficient nanoarchitectures for Li+ storage.

Machine learning descriptors for crystal materials: applications in Ni-rich layered cathode and lithium anode materials for high-energy-density lithium batteries

Lithium batteries have revolutionized energy storage with their high energy density and long lifespan, but challenges such as energy density limitations, safety, and cost still need to be addressed. Crystalline materials, including Ni-rich cathodes and lithium anodes, play pivotal roles in the performance of high-energy-density lithium batteries. Understanding the micro-scale behavior and degradation mechanisms of these materials is crucial for improving macro-scale battery performance. Simulation methods, particularly machine learning (ML) techniques, have become indispensable tools in elucidating these intricate processes because of great efficiency and acceptable accuracy. ML methods depend on descriptors, which bridge the gap between crystal structures and input matrices of models. These descriptors encode essential atomic-level details in crystal structures, enabling predictions of material properties and behaviors relevant to lithium batteries. This paper reviews and discusses the diverse array of descriptors employed in the simulation of crystalline materials for lithium batteries with high energy density. Case studies highlight the effectiveness of different descriptors in simulating cathode behaviors such as Li/Ni disordering, screening of stable LiNi0.8Co0.1Mn0.1O2 (NMC811) configurations, and lithium deposition behaviors at the anode interface. The discussed descriptors can also be applied to other crystalline cathode, anode, and electrolyte materials in lithium batteries and advance the development of lithium batteries with superior energy density.

A flexible porous polyimide/copper composite film toward high-mass-loading anodes in lithium-ion batteries

Conventional metal foil current collectors are essential for electronic conduction in lithium-ion batteries, but the planar structure limits the fast transporting of electron and the power density. Herein, a light, conductive, self-extinguishing, and flexible porous polyimide/copper composite film (PIF/Cu) derived from a polyimide foam was fabricated via hot pressing and electroless plating methods. The honeycomb structure was illustrated in PIF/Cu under a 3D X-ray tomography microscope, revealing the successful construction of a 3D conductive network. PIF/Cu-30 possessed an electronic conductivity of as high as 3.6 × 105 S m−1 at a bulk density of 0.26 g cm−3 and exhibited exceptional structural stability even after successive and harsh mechanical loads. Graphite with a mass load of 12 mg cm−2 was loaded into the PIF/Cu-30 to prepare the anode for cell assembly. The cells using PIF/Cu-30 achieved a better performance in capacity retention (98.2 %@60 cycles) than those using traditional Cu foils (55.1 %@60 cycles), which resulted from the fast transport of electrons and Li-ion through the 3D conductive networks in the porous PIF/Cu-30.

Photodiode-based focus monitoring in ultrashort-pulsed laser structuring of graphite anodes for lithium-ion batteries

In recent years, there has been an increased demand for elaborate monitoring techniques in laser material processing. This has been driven by the need for fast and cost-efficient quality assurance processes. At the same time, ultrashort-pulsed (USP) laser radiation has emerged as a promising technology for creating intricate microstructures in lithium-ion battery graphite anodes due to its high precision and negligible thermal impact. However, the integration of process monitoring in USP laser applications for graphite anode structuring is still unexplored. There is a lack of clarity on suitable sensors, observable parameters, and extractable process-relevant insights. The presented study addressed this gap by demonstrating the capability of state-of-the-art photodiode-based monitoring systems in collecting process-relevant data and deriving valuable insights. A sensor equipped with three photodiodes was employed to address these challenges. Exploratory data analysis and machine learning methodologies were leveraged to develop a data pipeline for processing the acquired information. The data were used to train convolutional neural networks that could accurately predict the focal position. At the same time, the limitations of traditional regression approaches could be shown. The findings advanced the understanding of the possibilities of process monitoring in USP laser applications and emphasized the significance of data-driven approaches in optimizing manufacturing processes.

Molecular Engineering Chemical Pre-lithiation Reagent with Low Redox Potential for Graphite Anode Enables High Coulombic Efficiency.

Graphite (Gr) is a low-cost and high-stability anode for lithium-ion batteries (LIBs). However, Gr anode exhibits an obstinate drawback of low initial Coulombic efficiency (ICE), owing to the active lithium loss for the solid electrolyte interphase (SEI) layer. Herein, a straightforward and effective chemical pre-lithiation strategy is proposed to compensate for the lithium loss. A molecular engineering phenanthrene-based lithium-arene complex (Ph-based LAC) reagent is designed by density functional theory (DFT) calculations. The engineering Ph-based reagent enhances the stability of the π-electron system and the electron-donating capacity, resulting in a reduced redox potential to facilitate lithium transfer. The electrochemical distinct of the Ph-based reagent is illustrated, the prelithiation process in a low Li-insertion platform, and the lithiation degree is controllable with the dipping time (ICE = 102%, 3min). Notably, a denser and homogeneous SEI layer has pre-formed to enhance the Li+ transport and interface stability. Moreover, the lithium-ion full batteries assemble with LiFePO4 and NCM811 cathode, which exhibits high ICE (96.5% and 90.3%) and energy density (310 and 333Whkg-1). These findings present a facile and controllable pre-lithiation strategy to compensate for the lithium of LIBs, providing new valuable insights into the design and optimization of battery manufacture.

Preparation of interconnected tin oxide nanoparticles on multi-layered MXene for lithium storage anodes

MXenes, a novel class of two-dimensional (2D) materials known for their excellent electronic conductivity and hydrophilicity, have emerged as promising candidates for lithium-ion battery anodes. This study presents a simple wet-chemical method for depositing interconnected SnO2 nanoparticles (NPs) onto MXene sheets. The SnO2 NPs act as both a high-capacity energy source and a spacer to prevent MXene sheets from restacking. The highly conductive MXene facilitates rapid electron and lithium-ion transport and mitigates the volume changes of SnO₂ during the lithiation/delithiation process by confining the SnO₂ NPs between the MXene layers. This composite anode, SnO2@MXene, leverages the high capacity of SnO2 and the structural and mechanical stability MXene provides. The SnO2@MXene anode exhibits superior electrochemical performance, with a high specific capacity of 678 mAh g− 1 at a current rate of 2.0 A g− 1 over 500 cycles, outperforming pristine MXenes and SnO2 nanoparticles.

Enhancing lithium storage performance of Carbon/SiOx composite via coating edge-nitrogen-enriched carbon

Silicon oxide (SiOx) exhibits promising potential as a lithium-ion battery anode. However, its practical application is impeded by low electrical conductivity and significant volumetric expansion. To overcome these limitations, we developed a novel co-precipitation and selectively etching approach that leveraged the nitrogen-retaining effect of ZnNCN to prepare an edge-nitrogen-enriched carbon/SiOx composite (NEC@LC-SiOx). This NEC@LC-SiOx showed enhanced electrical conductivity and reduced volumetric expansion. Our innovative approach effectively prevented excessive decomposition of nitrogen species, resulting in a high nitrogen doping content of 21.67 at.% while maintaining a stable structure and mitigated volume expansion during charging and discharging. Consequently, the prepared NEC@LC-SiOx exhibited excellent performance as an anode material for lithium-ion batteries, demonstrating a high reversible specific capacity of 802 mAh/g and outstanding rate capability. This work presents a novel strategy for designing high-performance SiOx anode materials.

Oxygen-containing groups assist in enhancing Li+/K+ storage: Balancing adsorption and intercalation mechanisms

Porous carbon nanosheets were prepared using a high-temperature solid-phase method and subsequently modified through oxidative acid treatment to introduce oxygen-containing groups. The application and performance of these nanosheets as anodes in lithium-ion and potassium-ion batteries were investigated. The results indicated that the oxidative acid treatment successfully enhanced the porous carbon nanosheets' capacity for storing Li+/K+. Electrochemical analysis revealed that the oxygen-containing groups balanced intercalation and surface storage behaviors, optimizing the nanosheets' storage performance. These modified porous carbon nanosheets (termed SN@PCNs) demonstrated significantly boosted reversible Li+ and K+ storage capacities, achieving 1038.1 mAh⋅g−1 and 371.7 mAh⋅g−1 at 0.1 A g−1, respectively, while maintaining capacities of 443.3 mAh⋅g−1 for Li+ and 153.9 mAh⋅g−1 for K+ at 5.0 A g−1. Furthermore, the study emphasized the significance of a balanced surface capacitance and solid-phase diffusion storage mechanism in attaining high storage capacity and cycle stability. Moderate oxidation and the introduction of oxygen-containing groups were identified as crucial factors in optimizing performance. Additionally, potassium adsorption storage exhibited an advantage over lithium adsorption storage, and the impact of oxygen-containing groups on potassium storage performance was even more pronounced.

Improved electrochemical properties of lithium-ion batteries prepared using oxygen plasma-treated needle coke-based anode materials

High-rate capacities and specific capacities are important indicators for evaluating lithium-ion battery (LIB) anodes. To improve the electrochemical properties of needle coke-based anode materials, oxygen plasma treatment was used. Various analyses were performed to assess the impact of the oxygen plasma treatments on the chemical, structural, and morphological properties of the needle coke samples. The oxygen plasma treatment effectively introduced oxygen functional groups (hydroxyl, ether, carbonyl, and carboxyl groups) without significant structural changes to the needle coke samples, and the O/C ratio increased to 0.23 after the plasma treatment. The synergistic effect of the increased oxygen content and the defects formed on the surface by plasma treatment improved the electrochemical properties of the needle coke-based anodes. The discharge capacity of the oxygen plasma-treated needle coke-based LIBs increased to a maximum of 20.48 %, and the retention rate was 74.51 % at 5 C with respect to 0.1 C. The oxygen plasma-treated needle coke material prepared via a simple method could have an important role in improving the rate capacities and specific capacities of LIBs.

Weakly solvated electrolyte enables the robust solid electrolyte interface on SiOx anodes for lithium-ion battery

Silicon oxide (SiOx) anodes are considered to be the promising alternative to graphite anodes for lithium-ion batteries. However, the traditional carbonate electrolyte fails to generate the effective solid electrolyte interface (SEI) on SiOx anodes to well adapt the large volume expansion of SiOx particles. Herein, a weakly solvated perfluorinated electrolyte with dual lithium salts was designed to match SiOx anodes. The perfluorinated solvent with weakened solvation ability and the strong coordination of Li+-DFOB− and Li+-TFSI− lead to an anion-dominated solvated shell, which induces the formation of inorganics-rich SEI. The high-strength bonds (Li-F, B-F, B-O, B-N et al.) enable high mechanical strength and rapid ion migration of the SEI film, thereby effectively accommodating the volume expansion of SiOx and avoiding continuous decomposition of the electrolyte. Furthermore, as designed electrolyte also shows excellent flame retardancy and high voltage stability. Consequently, the SiOx anode exhibits remarkably improved cycling performance in contrast to that in traditional carbonate electrolyte, maintaining 1073.7 mAh/g after 300 cycles at 1.0 A/g when paired with metal Li, and presents excellent compatibility with commercial cathodes including LiFePO4 and LiNi0.8Co0.1Mn0.1O2. This work provides a new inspiration and path for the design of electrolyte highly matched with silicon oxide anodes.

Effect of Various Carbon Coating Techniques on the Electrochemical Performance of Li4Ti5O12 Synthesized by Sol-Gel Method

This study aimed to prepare spinel carbon-coated Li4Ti5O12 (LTO/C) via sol-gel reaction and applied as a high-performance lithium-ion battery anode. The LTO powder was coated using various carbon sources, super P (SP), sugar and PVDF-assisted SP. The crystal structure, morphology, conductivity and electrochemical performance of the samples were examined using X-ray diffraction (XRD), Field Emission scanning electron microscopy (FESEM), Fourier Transform Infrared (FTIR) spectroscopy, Electrochemical Impedance Spectroscopy (EIS) and Cyclic Voltammetry/Charge-discharge (CV/CD), respectively. The XRD analysis results showed that the samples contain highly crystalline spinel LTO as the main phase and rutile as impurity. The FESEM image showed that SP covers the entire LTO surface more homogenous than sugar. However, sugar carbon makes roughness on the LTO surface. FTIR spectra showed that the coating using sugar and PVDF still contain hydrocarbon element. Electrochemical performance evaluations showed that SP carbon-coated-LTO possesses higher lithium diffusion and specific capacity than pure LTO, while sugar-coated-LTO shows the lowest specific capacity. Moreover, the SP carbon-coated-LTO sample high-rate capability has improved during full cell evaluation, delivering a discharge capacity of 249, 231, 211, 194, 58, and 23 mAhg-1 at the charge or discharge current density of 0.05, 0.1, 0.5, 1, 5, and 10 C, respectively.

A chronicle of titanium niobium oxide materials for high‐performance lithium‐ion batteries: From laboratory to industry

AbstractTitanium niobium oxide (TiNbxO2 + 2.5x) is emerging as a promising electrode material for rechargeable lithium‐ion batteries (LIBs) due to its exceptional safety characteristics, high electrochemical properties (e.g., cycling stability and rate performance), and eco‐friendliness. However, several intrinsic critical drawbacks, such as relatively low electrical conductivity, significantly hinder its practical applications. Developing reliable strategies is crucial to accelerating the practical use of TiNbxO2 + 2.5x‐based materials in LIBs, especially high‐power LIBs. Here, we provide a chronicle review of the research progress on TiNbxO2 + 2.5x‐based anodes from the early 1950s to the present, which is classified into early stage (before 2008), emerging stage (2008–2012), explosive stage (2013–2017), commercialization (2018), steady development (2018–2022), and new breakthrough stage (since 2022). In each stage, the advancements in the fundamental science and application of the TiNbxO2 + 2.5x‐based anodes are reviewed, and the corresponding developing trends of TiNbxO2 + 2.5x‐based anodes are summarized. Moreover, several future research directions to propel the practical use of TiNbxO2 + 2.5x anodes are suggested based on reviewing the history. This review is expected to pave the way for developing the fabrication and application of high‐performance TiNbxO2 + 2.5x‐based anodes for LIBs.

Modification mechanism of graphite anode in lithium-ion battery coated with ethylene tar pitch

Modification mechanism of graphite anode in lithium-ion battery coated with ethylene tar pitch

Electrochemical in-situ lithiated Li2SiO3 layer promote high performance silicon anode for lithium-ion batteries

Si anode is considered to be one of the most promising candidates for the next-generation lithium-ion batteries (LIBs). However, the severe volume variation of Si (> 300%) during the lithiation/delithiation process results in unstable interface and thus contributes to poor cycling stability. Moreover, the relatively low conductivity derived from the semiconductor nature of Si leads to inferior rate performance. Herein, Li2SiO3 layer with fast lithium-ions transport capability and high mechanical property was formed on Si surface in an in-situ electrochemical method. The relationships between the valence of SiOx and LixSiOy constituents were readily studied. Fortunately, the as-prepared Si@ES-LSO showed great potential to mitigate the expansion and high lithium-ions diffusion coefficient. When employed as anode materials for LIBs, the modified Si anode delivered a specific capacity of 2074.8 mAh g−1 at 1000 mA g−1 with a retention ratio of 98.9% after 100 cycles, demonstrating superior electrochemical performance. This work provides a facial and efficient strategy for the roadmap of Si anode application.

Efficient Synthesis of Flower-Ball Structured CuFeS2 as Advanced Anode Material for Lithium-Ion Batteries Across Wide Temperature Ranges.

Transition metal sulfides stand as potential anode candidates for lithium-ion batteries offering high capacity, redox reversibility, and safety. However, cycling-induced volume variations and slow kinetics hinder their application. Here, CuFeS2 with a flower-ball nanosheet structure is synthesized via a hydrothermal method, enhancing electrolyte infiltration, Li+ transport, and cycle life. CuFeS2 exhibits a large initial discharge specific capacity of 532.4 mAh g-1 at 500 mA g-1 with 95.7% initial Coulombic efficiency, retaining an impressive 90.5% (481.6 mAh g-1) of its initial capacity after 300 cycles. Remarkably, at 2000 mA g-1 for 700 cycles, it maintains a high specific capacity of 487.1 mAh g-1 with an 89.4% capacity retention rate. Moreover, it maintains excellent reversibility at both high temperature (60 °C) and low temperature (-25 °C) and demonstrates excellent electrochemical performance even under high loading conditions. Consequently, CuFeS2 holds immense promise as a lithium-ion battery anode material, offering fast charging, safety, high capacity, and long life.

Utilizing copper waste to develop silicon-carbon anode materi als for lithium-ion batteries

This study dedicated to a novel method for synthesizing silicon-carbon (Si/C) and silicon dioxide-carbon (SiO2/C) nanocomposite anodes for lithium-ion batteries, utilizing industrial copper slags from the Almalyk Mining and Metallurgical Complex as a cost-effective source of SiO2. The synthesized nanocomposites address key challenges in lithium-ion battery anodes, including the volumetric expansion of silicon and its low conductivity, by leveraging the high lithiation capacity of silicon combined with the structural stability and conductivity of carbon. Amorphous SiO3 was extracted from copper slags via ammonium fluoride (NH4F) treatment and subsequently reduced to metallurgical-grade silicon through carbothermal reduction. The resulting SiO2/C and Si/C composites were thoroughly characterized using SEM, XRD, and electrochemical analyses, demonstrating improved electrochemical performance, favorable particle size distribution, and stability. This approach not only reduces material costs but also promotes environmental sustainability by repurposing industrial waste, offering promising candidates for high-performance lithium-ion battery anodes.

Synthesis and electrochemical performance of novel high-entropy spinel oxide (FeCoMgCrLi)3O4

High-entropy oxides (HEOs) are attractive options for anode materials in lithium-ion batteries (LIBs) because of their impressive specific capacity and structural stability. The multi-element composition of HEOs endows them with diverse physicochemical properties. However, the role of different elements in the energy storage mechanism remains unclear, and the limited number of successfully synthesized high-entropy oxide systems currently hinders further development. Therefore, developing HEOs with different compositions and studying their electrochemical properties is of great significance. Using the glycine-nitrate solution combustion synthesis (SCS) method, we produced two new High Entropy Oxides (HEOs), namely (FeCoMgCr)3O4 and (FeCoMgCrLi)3O4, and assessed their electrochemical performance as LIBs anode materials. The studies indicate that the inclusion of lithium significantly enhances the lithium storing capabilities of the material system. Specifically, after undergoing two hundred cycles at a current density of 200 mA/g, (FeCoMgCrLi)3O4 exhibited a specific capacity of 658 mAh/g, which was considerably greater than the specific capacity of (FeCoMgCr)3O4, which was 306.9 mAh/g. This work enriches the spinel-type high-entropy oxide systems and proposes a new design strategy for HEOs as LIBs anode materials.

Mechanically Robust Polyimide Binder Realizes Stable and High Electrochemical Performance for Micro-Silicon Anodes in Lithium-Ion Batteries.

Silicon is regarded as a highly promising anode material for lithium-ion batteries, attributed to its substantial theoretical specific capacity. The practical implementation of Si-anodes is hindered by side reactions and significant volumetric changes, ~300% to 400%, occurring during the lithiation/delithiation processes. Pertinent binders can effectively mitigate the stress resulting from the volumetric exchange in Si-anodes. Herein, we developed a mechanically stable polyimide binder PI-CF3 and introduced trifluoromethyl and hydroxyl groups for commercial microparticular Si-anodes. With the highest Young's modulus of ~921.1 MPa, the binder presented the maximum resilience during the charging and discharging of Micro-Si, integrating the morphology, and reducing the degree to which the electrode disrupted ion and electric pathways. Moreover, -OH and -CF3 groups of the binder could potentially interact with the oxide layer at the surface of silicon through H-bonds resulting in a cross-linking network to improve interface stability. The as-prepared PI-CF3 binder with excellent intrinsic mechanical and electro-rich groups stabilizes the electrode structure and facilitates fast Li+ transportation. Consequently, at 0.6 Ag-1, the micro-Si anode produced an initial specific capacity of 1838 mAh g-1 at Si 0.66 mg cm-2. Besides, at Si 0.78 mg cm-2 specific capacity retained around 1219 mAh g-1 over 330 cycles.

Preparation of core-shell Si/C/graphene composite for high-performance lithium-ion battery anodes

One of the important objectives for the development of enhanced lithium-ion batteries is developing high-performance silicon-based anodes with durable operational capability. Herein, a three-dimensional graphene-decorated core-shell Si/C composite is fabricated by the in-situ polymerization of organic pyrrole molecule and pyrolysis process, in which the melamine formaldehyde resin is subtly used as three-dimensional porous framework to offer abundant loading area for the uniform dispersion of active silicon nanoparticles. Meanwhile, the core-shell structure deriving from polypyrrole in the composite can effectively buffer the volume change of silicon ingredient and avoid the direct contact with the electrolyte during the cycling process, leading to the improved structural stability and electrochemical performance. The outermost layer of graphene nanosheets is designed to enhance the electrical conductivity of the electrode. As a result, the synthesized Si/C/graphene composite exhibits a high capacity and excellent cycling performance. This work reveals that combining a three-dimensional carbon substrate with a core-shell structure might be a promising solution for anode materials with obvious volume transformation.