Electrodes For Lithium-ion Batteries Research Articles

Neural Network-Based Modeling of Diffusion-Induced Stress in a Hollow Cylindrical Nano-Electrode of Lithium-Ion Battery

Abstract Understanding the interaction between mechanical deformation and mass transport, such as diffusion-induced stress, is crucial in the development of advanced battery materials and electrochemical devices. Mathematical modeling and solving the coupling problems have played important roles in advancing the understanding of the interaction between mechanical deformation and mass transport. As the complexity of mathematical modeling continues to increase, numerical methods used to solve the related coupling problems are likely to encounter significant challenges. This work explores the feasibility of designing a neural network specifically for solving diffusion-induced stress in the electrode of lithium-ion battery via deep learning techniques. A loss function is constructed from the spatiotemporal coordinates of sampling points within the solution domain, the overall structure of the system of partial differential equations, boundary conditions, and initial conditions. The distributions of stress and lithium concentration in a hollow-cylindrical nanoelectrode are obtained. The high degree of conformity between the numerical results and those from finite element method is demonstrated.

Mechanical deformation in lithium-ion battery electrodes: modelling and experiment

Abstract Models that can accurately describe deformation and stress in lithium-ion batteries are required to inform new device designs that can better withstand mechanical fatigue. Developing such models is particularly challenging because (i) there is a need to capture several different materials including, active materials, binders, current collectors and separators, and (ii) the length scales of interest are highly disparate (ranging from a few microns, relevant to active material particles, up to centimeters, relevant to whole devices). In this study we present a continuum mechanical model that resolves individual active material particles of a nickel-manganese-cobalt-oxide cathode, and predicts the mechanical response of the cathode coating as a whole. The model is validated by comparison with experimental tests which mimic industrial-scale electrode calendaring, and then a parametric study is conducted to provide insight into the roles of the material and geometric properties of the electrode's constituents on the cathode's overall behavior.

Iodine and nitrogen co-doped carbon flower materials for the anode electrode of lithium-ion batteries

Iodine and nitrogen co-doped carbon flower materials for the anode electrode of lithium-ion batteries

Self-Charging Power System Empowered by Bismuth Halide Perovskite-Based Hybrid Nanogenerator and Lithium-ion Battery.

Halide perovskite, renowned for its multifunctional properties, shows considerable promise for realizing self-charging power systems. In this study, a lead-free methylammonium bismuth iodide (MA3Bi2I9) perovskite is used to create a self-charging power unit (SPU). This involves constructing a hybrid piezoelectric-triboelectric nanogenerator (Hybrid-TENG) and utilizing MA3Bi2I9 for energy storage as an anode in a lithium-ion battery (LIB). Initially, MA3Bi2I9 nanorods are synthesized and composited with a polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene polymer. The dielectric and mechanical properties of composite films having perovskite loading content are investigated. The optimized Hybrid-TENG exhibits superior performance, generating a voltage of 537V, current density of 13.2µAcm- 2, and maximum power density of 3.04mWcm-2, which can be attributed to the high piezoelectric coefficient of MA3Bi2I9 nanorods (≈20.6pmV-1). A MA3Bi2I9 thin film, serving as an electrode in LIB, demonstrates a high specific capacity of 2378.9mAhcm-3 (578.8mAhg-1) with a capacity retention of ≈87.5% over 100 cycles, underscoring its stable performance. Furthermore, a Hybrid-TENG is employed to charge the MA3Bi2I9-based LIB, thus realizing an SPU for driving portable electronics. This study highlights the promising potential of perovskites for developing efficient nanogenerators and LIBs, paving the way for sustainable energy solutions in small-scale electronics.

Research on Quantitative Diagnosis of Dendrites Based on Titration Gas Chromatography Technology

Lithium plating can cause capacity fade and thermal runaway safety issues in lithium-ion batteries. Therefore, accurately detecting the amount of lithium plating on the surface of the battery’s negative electrode is crucial for battery safety. This is especially crucial in high-energy-density applications such as battery energy storage systems or in electric vehicles (EVs). Early detection of lithium plating is crucial for evaluation of reliability and longevity. It also serves as a method for early diagnostics in practical industrial applications or infrastructure, such as EV transportation. This can enhance its impact on customers. This study validates the effectiveness of titration gas chromatography (TGC) technology in quantitatively detecting lithium plating on graphite negative electrodes in lithium-ion batteries. The results show that it can detect a minimum of 2.4 μmol of metallic lithium. Compared with the heating direct current resistance and reference electrode methods, which can be used to perform only qualitative dendrite detection, TGC has a wider range of detection. Compared with the nuclear magnetic resonance (NMR) method with higher quantitative detection accuracy, the maximum difference between the detection results of the two methods was only 7.2%, but the TGC method had lower cost and higher implementation convenience. In summary, among various dendrite detection methods, the TGC method can not only realize the effective quantitative detection of lithium plating, but also comprehensively consider its detection range, implementation convenience, cost, and detection accuracy, indicating that it is suitable for engineering applications and has the prospect of realizing large-scale quantitative detection of lithium plating in lithium-ion batteries.

Nitrogen-Doped Titanium Niobium Oxides Coated with N/S-Codoped Carbon as an Integrated Electrode for Lithium-Ion Batteries

Nitrogen-Doped Titanium Niobium Oxides Coated with N/S-Codoped Carbon as an Integrated Electrode for Lithium-Ion Batteries

Precycling Strategy in Suitable Voltage to Improve the Stability of Interfacial Film and Suppress the Decline of LiNi0.6Mn0.2Co0.2O2 Cathode at Elevated Temperatures.

Layered ternary oxide LiNixMnyCo1-x-yO2 is a promising cathode candidate for high-energy lithium-ion batteries (LIBs). However, the capacity of LIBs is significantly restricted by several factors, including the repeated dissolution-regeneration of the interfacial film at high temperatures, the dissolution of transition metals, and the increase of impedance. Herein, a new precycling strategy in suitable voltage scope at room temperature is proposed to construct a uniform, thermally stable, and insoluble cathode-electrolyte interface (CEI), which helps to maintain stable cycling performances at high temperatures. Specifically, after 5 precycles in the range of 3.85-4.3 V at room temperature, a CEI layer containing numerous inorganic components and oligomers is formed on the surface of LiNi0.6Mn0.2Co0.2O2. Subsequently, the harmful side reactions are effectively suppressed, endowing the cell with an excellent capacity retention of 84.67% after 50 cycles at 0.5C and 55 °C, much higher than that of 65.61% under the conventional film-forming process conditions. This work emphasizes the crucial role of the precycling strategy in regulating the characteristics of CEI layer on the surface of cathode electrode, opening up a new avenue for the high-temperature application of positive electrodes of LIBs.

Optimizing Structural Patterns for 3D Electrodes in Lithium-Ion Batteries for Enhanced Fast-Charging Capability and Reduced Lithium Plating

The most common pattern types for anode structuring, in particular the line, grid, and hexagonal-arranged hole pattern were evaluated in a comparable setup in full-cells and symmetrical cells. The cells with structured electrodes were compared to reference cells with unstructured anodes of similar areal capacity (4.3 mAh cm−2) and the onset of lithium plating during fast-charging was determined in situ by differential voltage analysis of the voltage relaxation and ex situ by post-mortem analysis. Furthermore, electrochemical impedance spectroscopy measurements on symmetrical cells were used to determine the ionic resistance of structured and unstructured electrodes of similar areal capacity. All cells with structured electrodes showed lower ionic resistances and an onset of lithium plating shifted to higher C-rates compared to cells with unstructured electrodes. The structure patterns with capillary structures, i.e., lines and grids, showed significant reduced lithium plating during fast-charging and a higher rate capability compared to reference cells with unstructured electrodes and cells with hole structured electrodes. The continuous rewetting of the electrode with liquid electrolyte by capillary forces and the reduced ionic resistance of the 3D electrode are identified as key factors in improving overall battery performance. The data of the studied cells were used to calculate the resulting energy and power densities of prospective commercial pouch cells and potential pitfalls in the comparison to cells with unstructured electrodes were identified.

High-Area-Capacity Cathode by Ultralong Carbon Nanotubes for Secondary Binder-Assisted Dry Coating Technology.

Thick electrodes with high mass loading and increased content of active materials are critical for achieving higher energy density in contemporary lithium-ion batteries (LIBs). Nonetheless, producing thick electrodes through the commonly used slurry coating technology remains a formidable challenge. In this study, we have addressed this challenge by developing a dry electrode technology by using ultralong multiwalled carbon nanotubes (MWCNT) as a conductive additive and secondary binder. The mixing process of electrode compositions and the fibrillation process of the polytetrafluoroethylene (PTFE) binder were optimized. The resulting LiCoO2 (LCO) electrode exhibited a remarkable mass loading of 48 mg cm-2 and an active material content of 95 wt %. Notably, the thick LCO electrode demonstrated a superior mechanical strength and electrochemical performance. After 100 cycles at a current density of 1/3 C, the electrode still exhibited a capacity retention of 91% of its initial capacity. This dry electrode technology provides a practicable and scalable approach to the powder-to-film LIB electrode manufacturing process.

Controlled Growth Lateral/Vertical Heterostructure Interface for Lithium Storage.

Artificial heterostructures with structural advancements and customizable electronic interfaces are fundamental for achieving high-performance lithium-ion batteries (LIBs). Here, we propose a design idea for a covalently bonded lateral/vertical black phosphorus (BP)-graphdiyne oxide (GDYO) heterostructure achieved through a facile ball-milling approach. Lateral heterogeneity is realized by the sp2-hybridized mode P-C bonds, which connects the phosphorus atoms at the edges of BP with the carbon atoms of the terminal acetylene in GDYO. The vertical connection of the heterojunction of BP and GDYO is connected by P-O-C bond. Experimental and theoretical studies demonstrate that BP-GDYO incorporates interfacial and structural engineering features, including built-in electric fields, chemical bond interactions, and maximized nanospace confinement effects. Therefore, BP-GDYO exhibits improved electrochemical kinetics and enhanced structural stability. Moreover, through ex- and in-situ studies, we clarified the lithiation mechanism of BP-GDYO, highlighting that the introduction of GDYO inhibits the shuttle/dissolution effect of phosphorus intermediates, hinders volume expansion, provides more reactive sites, and ultimately promotes reversible lithium storage. The BP-GDYO anode exhibits lithium storage performance with high-rate capacity and long-cycle stability (602.6 mAh g-1 after 1000 cycles at 2.0 A g-1). The proposed interfacial and structural engineering are universal and represents a conceptual advance in building high-performance LIBs electrode. This article is protected by copyright. All rights reserved.

Application of nanotechnology in the battery of electric vehicles

Application of nanotechnology in the battery of electric vehicles

Development of a feasible and scalable manufacturing method for PTFE-based solvent-free lithium-ion battery electrodes

Conventional wet-electrode manufacturing encounters challenges in producing thicker electrodes due to issues related to solvent evaporation. This study introduces a novel method for fabricating solvent-free dry electrodes using polytetrafluoroethylene (PTFE) as a binder, representing a significant advancement in electrode manufacturing processes. By eliminating the use of solvents, this method not only addresses these challenges but also offers a scalable and practical solution for mass production. The process is meticulously structured into sequential unit operations, each specifically tailored for a distinct function, utilizing the distinctive fibrillation properties of PTFE. Intermediate product specifications for each phase are clearly defined, accompanied by a comprehensive analysis of both physical and electrochemical performances. This analysis highlights the influence of varying PTFE contents and properties on the microstructure of the dry electrode. Notably, the study achieves a significant breakthrough with an electrode formulation of NCM811/PTFE/carbon black (CB)/carbon nanotube (CNT) = 96/2.0/1.8/0.2, which demonstrates exceptional discharge rate capability of 80 % at a 0.5 C-rate (5 mA/cm2) under the demanding parameters of 10 mAh/cm2 and 3.8 g/cc. This approach not only enhances the microstructural properties of dry electrodes but also paves the way for environmentally friendly and efficient electrode manufacturing for future energy storage applications.

Rate-dependent damage and failure behavior of lithium-ion battery electrodes

The mechanical properties and failure behavior of composite electrodes are critical to understanding the internal short circuits and ensuring the crush safety of lithium-ion batteries used in electric transportation. This study provides a comprehensive experimental investigation into the strain rate–dependent tensile/compressive behavior and failure mechanism of both anode and cathode, covering a range from quasi-static to dynamic conditions. A universal testing machine equipped with an industrial camera was used to assess the mechanical properties and observe the deformation process of the electrodes under quasi-static conditions. Additionally, a split Hopkinson bar system, coupled with a high-speed camera, was utilized to evaluate the mechanical properties and capture the deformation process of the electrodes under dynamic loading. The detailed deformation and failure modes of the electrodes were revealed by a combination of post-mortem characterization and images from high-speed cameras. The experimental results demonstrate a significant strain rate effect on the tensile and compressive mechanical behavior and failure mechanism of both anode and cathode. The rate dependence of tensile/compressive strength and failure strain were discussed, and the underlying mechanism for strain rate sensitivity was analyzed. The results and conclusions from this study provide an important foundation for the detailed modeling and failure prediction of lithium-ion batteries under impact loading. Further, these findings facilitate the safety design of electric vehicles by informing to enhance crash safety.

Phase Evolution of Multi-Metal Dichalcogenides With Conversion-Alloying Hybrid Mechanism for Superior Lithium Storage.

Traditional lithium-ion battery (LIB) anodes, whether intercalation-type like graphite or alloying-type like silicon, employing a single lithium storage mechanism, are often limited by modest capacity or substantial volume changes. Here, the kesterite multi-metal dichalcogenide (CZTSSe) is introduced as an anode material that harnesses a conversion-alloying hybrid lithium storage mechanism. Results unveil that during the charge-discharge processes, the CZTSSe undergoes a comprehensive phase evolution, transitioning from kesterite structure to multiple dominant phases of sulfides, selenides, metals, and alloys. The involvement of multi-components facilitates electron transport and mitigates swelling stress; meanwhile, it results in formation of abundant defects and heterojunctions, allowing for increased lithium storage active sites and reduced lithium diffusion barrier. The CZTSSe delivers a high specific capacity of up to 2266mA h g-1 at 0.1 A g-1; while, maintaining a stable output of 116mA h g-1 after 10000 cycles at 20 A g-1. It also demonstrates remarkable low-temperature performance, retaining 987mA h g-1 even after 600 cycles at -40°C. When employed in full cells, a high specific energy of 562Wh kg-1 is achieved, rivalling many state-of-the-art LIBs. This research offers valuable insights into the design of LIB electrodes leveraging multiple lithium storage mechanisms.

Liquid Metal Electrode Ink for Printable Lithium‐Ion Batteries

Recent advancements have significantly improved the flexibility of lithium‐ion batteries (LIBs). The battery electrode contains a reaction layer and a current collector layer. Flexible battery electrodes, in which these layers are integrated, are fabricated in a single process, simplifying the electrode fabrication process. However, to date, integrated electrodes have lower conductivity than conventional two‐layer electrodes, and the process that maintains conductivity has not been simplified. This study proposes a liquid metal electrode ink that simultaneously plays the role of the reaction and current collector layers with high conductivity and can be formed in a single process via printing. It employs a gallium‐based liquid metal as a liquid current collector, embedded with Li4Ti5O12 or Li2TiS3 as active materials. These liquid metal electrodes exhibit a high electronic conductivity of 104 S cm−1 and can be fabricated without requiring the lengthy postprocessing time associated with conventional inks. Moreover, the ink can be applied directly to various insulating and nonflat curved substrates, demonstrating its charge–discharge performance, even when bent to a 1 mm radius to maintain flexibility. Liquid metal‐based electrode inks simplify the LIB fabrication process, contributing to efficient production methods for electrodes in future LIBs.

Quenching-Induced Ultrathin LiF-Rich Interphases on LiNi0.8Co0.1Mn0.1O2 Cathode

Nickel-rich layered oxides (NCM) are a promising contender material for the cathode electrode of high-energy lithium-ion batteries (LIBs) due to their large reversible capacity and high operating voltage. However, the poor surface/interfacial stability and the dissolution of transition metal ions hinder the commercial application of NCM. To create an artificial cathode electrolyte interphase (CEI) with LiF-rich inorganic phase on the NCM surface, a practical and efficient way of quenching the NCM powder from high temperature in 1,1,2,2-Tetrafluoroethyl 2,2,2-trifluoroethyl ether (HFE) was devised. With this artificial CEI film, the side reactions between NCM and electrolytes are inhibited, and the dissolution of TM ions is retarded. The quenched-NCM achieved fantastic cycling performance and suppressed voltage decay. Our research offers an efficient and worthy approach for improving the surface/interfacial stabilization of nickel-rich cathode materials for high-energy-density LIBs.

Microstructure evolution and mechanical analysis of lithium battery electrode in calendering deformation zone

Microstructure evolution and mechanical analysis of lithium battery electrode in calendering deformation zone

Is silicon worth it? Modelling degradation in composite silicon–graphite lithium-ion battery electrodes

The addition of silicon into graphite lithium-ion battery anodes has the potential to increase cell energy density. However, understanding the complex degradation behaviour in these composite systems remains a research challenge. Here, we developed a coupled electrochemical–mechanical model of a composite silicon/graphite electrode, including stress-driven crack formation and solid electrolyte interphase layer growth for each material, validated with experimental degradation data from an LG M50T cell. The model reveals self-limiting loss of silicon due to decreasing stress in the silicon as the silicon activity shifts to a lower state-of-charge. Higher C-rates can lead to lower degradation due to lower phase utilisation as voltage cut-offs are reached earlier. Increasing silicon content can reduce the stress in the silicon by distributing reaction current density over more material. Using this model, we explored whether the extra capacity from silicon is generally ‘worth’ the faster degradation compared to graphite-only electrodes. The model shows if you use the silicon, you lose it, as the higher initial capacity is rapidly lost with regular high depth-of-discharge events. However, silicon does have value if it enables full graphite utilisation without range anxiety; if high depth-of-discharge events are minimised then graphite’s superior longevity can be utilised while exploiting silicon’s high specific capacity. The model is integrated into PyBaMM (an open-source physics-based modelling platform); providing the research community and industry with the capability to reproduce our results and further explore the dynamic lifetime behaviour of composite electrodes.

Two-dimensional analysis on interfacial solvation structure of ionic liquid electrolyte on a hydrogen-terminated Si electrode by atomic force microscopy

Abstract Ionic liquids (ILs) have been intensively studied as a new electrolyte for lithium-ion batteries (LIBs). Structural analysis of interfaces between an IL-based electrolyte and a LIB electrode would provide beneficial information for improving LIBs. In this study, we investigated the interfacial structures between an IL, 1-methyl-1-propyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (Py13-TFSI), and an H-terminated Si(111) electrode in the presence and absence of Li-salt by frequency modulation atomic force microscopy (FM-AFM) utilizing a quartz tuning fork sensor. Two-dimensional frequency shift mapping imaging of the solvation structure at the interface showed that the layered solvation structure was only observed in the absence of Li salts in the ILs, which was in good agreement with our previous studies performed on the IL/lithium titanate interfaces. Combined with the electrochemical measurements, the partial disappearance of the layered solvation structure in the Li-salt-doped IL was strongly suggested to be due to the Li-ion insertion/extraction at the IL/Si interface.

Reaction Mechanism and Performance of Innovative 2D Germanane-Silicane Alloys: SixGe1- xH Electrodes in Lithium-Ion Batteries.

The adjustable structures and remarkable physicochemical properties of 2D monoelemental materials, such as silicene and germanene, have attracted significant attention in recent years. They can be transformed into silicane (SiH) and germanane (GeH) through covalent functionalization via hydrogen atom termination. However, synthesizing these materials with a scalable and low-cost fabrication process to achieve high-quality 2D SiH and GeH poses challenges. Herein, groundbreaking 2D SiH and GeH materials with varying compositions, specifically Si0.25Ge0.75H, Si0.50Ge0.50H, and Si0.75Ge0.25H, are prepared through a simple and efficient chemical exfoliation of their Zintl phases. These 2D materials offer significant advantages, including their large surface area, high mechanical flexibility, rapid electron mobility, and defect-rich loose-layered structures. Among these compositions, the Si0.50Ge0.50H electrode demonstrates the highest discharge capacity, reaching up to 1059 mAh g-1 after 60 cycles at a current density of 75 mA g-1. A comprehensive ex-situ electrochemical analysis is conducted to investigate the reaction mechanisms of lithiation/delithiation in Si0.50Ge0.50H. Subsequently, an initial assessment of the c-Li15(SixGe1- x)4 phase after lithiation and the a-Si0.50Ge0.50 phase after delithiation is presented. Hence, this study contributes crucial insights into the (de)lithiation reaction mechanisms within germanane-silicane alloys. Such understanding is pivotal for mastering promising materials that amalgamate the finest properties of silicon and germanium.