Materials 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.

Fulgide Derivatives as Photo-Switchable Coatings for Cathodes of Lithium Ion Batteries - A DFT Study.

Photo-switchable coatings for lithium ion batteries (LIB) can offer the possibility to control the diffusion processes from the electrode materials to the electrolyte and thus, for example, reducing the energy loss in the fully charged state. Fulgide derivatives, as known photo-switches, are investigated concerning their use as coating for vanadium pentoxide, a potential cathode material for LIB. With the help of Density Functional Theory calculations, two fulgide derivatives are characterized with respect to their photophysics, their aggregation behaviour on the cathode material and the ability to form self-assembled monolayers (SAM). Furthermore, the two states of the photo-switchable coating are tested with respect to lithium diffusion from the cathode material, passing the SAM and entering the electrolyte. We found a difference for the energy barriers depending on the state of the photo-switch, preferring its closed form. This behaviour can be used to prevent the loss of charge in batteries of portable devices.

Unveiling BaTiO3-SrTiO3 as Anodes for Highly Efficient and Stable Lithium-Ion Batteries.

Amidst the swift expansion of the electric vehicle industry, the imperative for alternative battery technologies that balance economic feasibility with sustainability has reached unprecedented importance. Herein, we utilized Perovskite-based oxide compounds barium titanate (BaTiO3) and strontium titanate (SrTiO3) nanoparticles as anode materials for lithium-ion batteries from straightforward and standard carbonate-based electrolyte with 10% fluoroethylene carbonate (FEC) additive [1M LiPF6 (1:1 EC: DEC) + 10% FEC]. SrTiO3 and BaTiO3 electrodes can deliver a high specific capacity of 80 mA h g-1 at a safe and low average working potential of ≈0.6 V vs. Li/Li+ with excellent high-rate performance with specific capacity of ~90 mA h g-1 at low current density of 20 mA g-1 and specific capacity of ~80 mA h g-1 for over 500 cycles at high current density of 100 mA g-1. Our findings pave the way for the direct utilization of perovskite-type materials as anode materials in Li-ion batteries due to their promising potential for Li+ ion storage. This investigation addresses the escalating market demands in a sustainable manner and opens avenues for the investigation of diverse perovskite oxides as advanced anodes for next-generation metal-ion batteries.

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 Review of Perovskite-based Lithium-Ion Battery Materials

Lithium-ion batteries (Li-ion batteries or LIBs) have garnered significant interest as a promising technology in the energy industry and electronic devices for the past few decades owing to their superior energy and power density profiles, small size, long cycle life, low self-discharge rate, no memory effect, long-lasting power properties, and environmental friendly. The ongoing advancement of electrode and electrolyte materials has contributed significantly to enhancing and spreading the application of lithium-ion battery technology. Among the non-precious metal-based materials, perovskites have emerged as attention over the last decade, holding a prominent position in materials and energy. Due to their unique physical and chemical properties, these materials have garnered particular interest for their potential application in electrochemical energy devices. Perovskite oxides have piqued the interest of researchers as potential catalysts in Li-O₂ batteries due to their remarkable electrochemical stability, high electronic and ionic conductivity, and the ability to modify their properties through doping and element substitution. The purpose of this article is to provide an overview of recent developments in the application of perovskites as lithium-ion battery materials, including the exploration of novel compositions and structures, optimization of fabrication methods, and a deeper understanding of the fundamental mechanisms that can unveil the potential of perovskite materials.

First-principles study on the lithiation process of amorphous SiO anode for Li-ion batteries with Bayesian optimization.

Amorphous silicon monoxide (a-SiO), which contains Si atoms with various valence states, has attracted much attention as a high-performance anode material for lithium (Li) ion batteries (LIBs). Although current experiments have provided some information during charge/discharge cycles, further investigation of structural changes at the atomic scale is needed. To investigate the lithiation process of a-SiO using first-principles simulations and machine learning techniques, we developed a computational code employing Bayesian optimization to efficiently identify stable sites for Li insertion in the large search-space of amorphous models to reproduce the actual lithiation process and compared this approach to the conventional random scheme by applying it to an a-SiO model previously generated with neural network potentials. The lithiation process based on Bayesian optimization resulted in lower formation energies compared to the conventional random scheme, indicating a more stable structure. During lithiation, Li atoms tended to enter the silicon (Si) phase after the SiO2 phase, in agreement with experimental results. We analyzed the structural changes and observed significant differences in the structural evolution between the conventional and new schemes. Our study highlights the significant influence of the lithiation process on the structural transformation of a-SiO materials, which in turn affects the reversible capacity of the material. These findings will provide a framework for improving the performance and lifetime of a-SiO materials.

Synthesis Methods of Si/C Composite Materials for Lithium-Ion Batteries

Silicon anodes present a high theoretical capacity of 4200 mAh/g, positioning them as strong contenders for improving the performance of lithium-ion batteries. Despite their potential, the practical application of Si anodes is constrained by their significant volumetric expansion (up to 400%) during lithiation/delithiation, which leads to mechanical degradation and loss of electrical contact. This issue contributes to poor cycling stability and hinders their commercial viability, and various silicon–carbon composite fabrication methods have been explored to mitigate these challenges. This review covers key techniques, including ball milling, spray drying, pyrolysis, chemical vapor deposition (CVD), and mechanofusion. Each method has unique benefits; ball milling and spray drying are effective for creating homogeneous composites, whereas pyrolysis and CVD offer high-quality coatings that enhance the mechanical stability of silicon anodes. Mechanofusion has been highlighted for its ability to integrate silicon with carbon materials, showing the potential for further optimization. In light of these advancements, future research should focus on refining these techniques to enhance the stability and performance of Si-based anodes. The optimization of the compounding process has the potential to enhance the performance of silicon anodes by addressing the significant volume change and low conductivity, while simultaneously addressing cost-related concerns.

Synthesis of Monodisperse and Discrete Ultra-High Nickel LiNi0.97Co0.02Mn0.01O2 Octahedral Single Crystals via Single Crystal Intermediates for Li-Ion Batteries.

Micrometer-sized single crystal cathodes have garnered significant interest as promising cathode materials for lithium-ion batteries due to their ability to reduce surface area exposure to electrolytes and suppress side reactions, thereby enhancing electrochemical performance. One of the challenging issues with single crystal cathode materials is synthesizing monodisperse and discrete single crystals rather than agglomerated quasi-single crystals. However, conventional solid-state synthesis of most single crystals results in severe agglomeration and cation mixing, as it requires high temperatures to promote particle growth to several micrometers. In this study, a novel morphology-conserving reaction strategy that employs octahedron single crystal intermediates is introduced to synthesize discrete, monodisperse LiNi0.97Co0.02Mn0.01O2 octahedron single crystals. This scalable and cost-effective approach involves using rock-salt Ni0.97Co0.02Mn0.01O1+x octahedrons as single crystal intermediates, which are transformed in unreactive unary lithium salt melts (LiCl and Li2SO4) from spherical Ni0.97Co0.02Mn0.01(OH)2 obtained via coprecipitation. These intermediates are then subjected to a stoichiometric amount of Li precursor in a conventional solid-state synthesis to produce layered LiNi0.97Co0.02Mn0.01O2. This process is a morphology-conserving lithiation reaction, leading to the formation of discrete and monodisperse LiNi0.97Co0.02Mn0.01O2 octahedron single crystals. The resultant LiNi0.97Co0.02Mn0.01O2 single crystals demonstrate superior electrochemical performance, including stable capacity retention over 150 cycles, which surpasses that of typical quasi-single crystals produced through conventional methods. This is attributed to negligible crack formation during cycling, in contrast to significant cracking observed in conventional quasi-single crystals. This implies that single-crystal forms are preferred over agglomerated quasi-single crystal forms for enhancing cycle performance. These findings provide valuable insights into the industrial synthesis of discrete and monodisperse ultrahigh-nickel oxide cathode materials.

A Facile Two-Step Utilization of Sorghum Waste Derived Activated Carbon

Sorghum (Sorghum bicolor (L.) Moench) is an agricultural commodity that produces waste, including stems, during its cultivation. Sorghum stems can be used as an alternative precursor for forming activated carbon (AC) with a high surface area by utilizing ZnCl2 as an activator and followed by a pyrolysis process at 750 °C under N2 gas. In this study, AC from sorghum stems was sequentially used as an adsorbent for heavy metals in wastewater, as well as applied as an anode material for lithium-ion batteries. From the characterization analysis, the synthesized AC has an amorphous structure, a high carbon content of > 90%, and a surface area of 1189 m2/g. AC was applied to adsorb 10, 50, and 100 ppm of metal cobalt (Co) at 30 °C. The adsorption isotherm and kinetics of metal Co showed an adsorption capacity of around 28.2 mg/g. The Langmuir isotherm model also describes Co adsorption and follows the pseudo-first-order equation. As for the Li-ion anode material, the ACs material is fabricated on a cylindrical battery with LiNi0.8Co0.1Mn0.1O2 as the counter cathode material. The specific discharge capacity results are 104 mAh/g at the voltage window of 2.7-4.3 V. The sequential utilization of sorghum stem-derived activated carbon can improve the product’s sustainability, and such an approach is promising to be applied in other biomass-based waste treatments.Keywords: Activated carbon, adsorption, battery, biomass, sorghum

Structural stability and enhanced electrochemical performance of Co-free Li-rich layered Mn-based Li1.2Mn0.6Ni0.2O2 cathodes via F doping at the O site of lithium-ion batteries

Li-rich Mn-based Co-free layered oxides (LLOs) are promising cathode materials for lithium-ion batteries (LIBs). However, they exhibit capacity loss and low initial Coulombic efficiency. Herein, an F-doped Li1.2Mn0.6Ni0.2O1.9F0.10 material has been prepared by the high-temperature solid-state method, with numerous oxygen vacancies on the surface to accelerate Li + transport. The electrochemical performance of Li1.2Mn0.6Ni0.2O1.9F0.10 considerably improved after the treatment. A high-capacity retention of 86.9 % after 100 charge/discharge cycles at 1C was achieved for Li1.2Mn0.6Ni0.2O1.9F0.10. Results revealed that F doping replaces part of O2−, forming more force between the TM-F bonds (compared to the TM-O bond), which inhibits the cation mixing phenomenon. The layered structure stability of the material is improved after F doping, and the migration energy barrier of Li+ is reduced, which promotes the migration of Li+, thereby improving the electrochemical performance of Li1.2Mn0.6Ni0.2O2.

Constructing Targeted Strong Nb4d-O2p-Li2s Configurations to Obtain Excellent Energy Density and Long Life for Li-Rich Cathodes.

The Li-rich Mn-based cathode materials (LMRs) deliver excellent energy density and exhibit low cost, which are considered as the most promising cathode materials for the next generation lithium-ion batteries. However, the irreversible redox reaction of the oxygen atoms directly leads to release oxygen and intensifies phase transformation. Besides, the local stress and strain will be generated due to the unit-cell volume difference between R-3m and C2/m phases, which continuously aggravates the collapse of secondary particles. Herein, the strong Nb4d-O2p-Li2s configurations at the Li1 sites of the TM-layer in the C2/m phase and secondary particles with the radial arrangement of refined primary particles are designed to inhibit oxygen release and relieve lattice stress by Nb2O5 treatment. Meanwhile, the preferential growth of the active {010} planes is presented to obtain an excellent transmission rate of Li+. As a result, the designed LMR delivers remarkable electrochemical properties with high discharge capacity and initial coulomb efficiency of 276 mAh g-1 and 85 % at 0.1 C, outstanding cycling retention rate of 81 % after 300 cycles. This novel crystal structure combining oxygen coordination regulation and micro-nano scale design provides inspiration for the design of high-performance LMRs.

Very High-Capacity Li/Na-Ion battery anodes Enabled by Blue phosphorene and boron phosphide vdW heterostructure

The fascinating features of van der Waals heterostructure (vdWH) based electrodes and their potential to overcome the limiting properties of single-material systems have sparked a great deal of scientific attention. In this study, we investigate the potential of a blue phosphorene/boron phosphide (Blue-P/BP) vdWH as an anode material for both lithium-ion (Li-ion) and sodium-ion (Na-ion) batteries using first-principles calculations. We suggest that this vdWH could act as an effective anode material for metal-ion batteries, due to their high theoretical capacity and strong binding strength. Intriguingly, the theoretical specific capacity exhibits remarkable values, notably reaching 4510 mAhg−1 for Li and 3849 mAhg−1 for Na, which surpasses all capacities reported in the existing literature. Additionally, electronic structure calculations reveal a significant charge transfer that enhances the metallic characteristics, thereby increasing electrical conductivity. As we delve deeper into the electronic structure and calculate diffusion barriers and pathways, we observe that ionic diffusion (∼0.12/0.11 eV) is notably rapid compared to graphitic anodes (∼0.2 eV). We also found that intercalating Li/Na atoms in the Blue-P/BP vdWH results in low operating potentials of 0.38 V for Li and 0.34 V for Na. This research highlights the substantial enhancement of electrochemical performance of Blue-P/BP vdWH and holds great promise as high-power-density anode materials for Li/Na-ion batteries, facilitating rapid charge and discharge rates.

Ligand Stripped Vanadium (III) Trifluoride Nanocrystals with Churros Structure as Novel Anode Material in Lithium Ion Batteries

Ligand Stripped Vanadium (III) Trifluoride Nanocrystals with Churros Structure as Novel Anode Material in Lithium Ion Batteries

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.

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.

Highly Conductive Two-Dimensional FeTHBQ/Graphene Nanocomposite as the Cathode Material for Lithium-Ion Batteries.

Constructing high-performance coordination polymer (CP) cathodes for lithium-ion batteries based on the redox reactions of both high-potential transition metal ions and high-capacity organic ligands has attracted extensive attention. However, CP cathodes suffer from structural degradation, low electrical conductivity, and sluggish diffusion kinetics, resulting in poor cycling stability and inferior rate capability. Herein, the ultrafine FeTHBQ (THBQ = tetrahydroxy-1,4-benzoquinone) CP nanoparticles in situ grew on both sides of graphene nanosheets to form the uniform two-dimensional (2D) FeTHBQ/Graphene nanocomposite with a sandwich structure via a one-pot solvothermal method. The highly conductive graphene skeleton promotes the electronic conduction and structural stability for the 2D FeTHBQ/Graphene nanocomposite. Besides, compared with bulk FeTHBQ, the primary FeTHBQ nanoparticles in the FeTHBQ/Graphene nanocomposite have smaller particle sizes with larger specific surface areas. This not only shortens the Li+ diffusion distance in the FeTHBQ crystal but also benefits Li+ transfer between the electrolyte and the electrode. In the FeTHBQ/Graphene nanocomposite, the active material of FeTHBQ manifested multiple redox centers of transition metal ions (Fe3+/Fe2+) and carbonyls (C═O/C-O-) in THBQ ligands. Owing to the enhancements of structural stability, electronic conduction, and Li+ diffusion kinetics, the 2D FeTHBQ/Graphene nanocomposite presented a high lithium-ion storage capacity of 217.2 mA h g-1 at 50 mA g-1, a fast rate capability of 79.1 mA h g-1 at 5000 mA g-1, and a stable cycling performance of 87.2 mA h g-1 at 500 mA g-1 after 100 cycles. This work sheds light on the great opportunity for optimizing the electrochemical performances of CP-based functional electrode materials by combining with conductive substrates.

Tuning Work Function of Fe2N@C Nanosheets by Co Doping for Enhanced Lithium Storage.

Transition metal nitrides (TMNs) with high theoretical capacity and excellent electrical conductivity have great potential as anode materials for lithium-ion batteries (LIBs), but suffer from poor rate performance due to the slow kinetics. Herein, taking the Fe2N for instance, Co doping is utilized to enhance the work function of Fe2N, which accelerates the charge transfer and strengthens the adsorption of Li+ ions. The Fe2N nanoparticles with various Co dopants are anchoring on the surface of honeycomb porous carbon foam (named Cox-Fe2N@C). Co-doping can enlarge the work function of pristine Fe2N and thereby optimize the charging/discharging kinetics. The work function can be increased from 5.23eV (pristine Fe2N) to 5.67eV for Co0.3-Fe2N@C and 5.56eV for Co0.1-Fe2N@C. As expected, the Co0.1-Fe2N@C electrode exhibits the highest specific capacity (673mA h g-1 at 100mA g-1) and remarkable rate capability (375mA h g-1 at 5000mA g-1), outperforming most reported TMNs electrodes. Therefore, this work provides a promising strategy to design and regulate anode materials for high-performance and even commercially available LIBs.

Enhanced electrochemical properties of Al2O3-coated LiNiPO4 cathode materials for lithium-ion batteries

Enhanced electrochemical properties of Al2O3-coated LiNiPO4 cathode materials for lithium-ion batteries

Infiltration-driven performance enhancement of poly-crystalline cathodes in all-solid-state batteries

All-solid-state batteries (ASSBs) with adequately selected cathode materials exhibit a higher energy density and better safety than conventional lithium-ion batteries (LIBs). Ni-rich layered cathodes are benchmark materials for traditional LIBs owing to their high energy density. Recent studies have highlighted the advantages of using crack-free, single-crystalline cathode materials in ASSBs. In this study, a scalable infiltration sheet-type process was used to fabricate composite electrodes with different cathode-material morphologies for ASSBs. Typically, crack-free single-crystalline materials exhibit better retention performance and lower rate capability (i.e., slower kinetics in charge‒discharge processes) than polycrystalline cathode materials. Li6PS5Cl-infiltrated polycrystalline electrodes showed excellent retention performance and rate capability. Galvanostatic intermittent titration technique analysis and transmission electron microscopy of the single-crystalline electrode confirmed severe polarization and the presence of a rock-salt-structure layer in the cathode particles; these results indicated side reactions within the layered structure of the material. In contrast, composite electrodes consisting of polycrystalline cathode materials infiltrated with the solid electrolyte Li6PS5Cl showed excellent electrochemical performance owing to intimate electrode–electrolyte interfacial contact. The result from this study confirmed the critical influence of interface engineering and material morphology on the overall performance and stability of ASSBs and could facilitate the development of high-performance ASSBs in the future.

Recent Advancements of Graphene and Some Selected Graphene-Based Electrode Materials for Lithium-Ion Battery

Graphene is a two-dimensional monolayer of carbon atoms arranged in a hexagonal lattice consisting of sp2 hybridized conjugated carbon atoms and serves as a promising electrode material for lithium-ion batteries (LIBs) owing to its superior properties, including a high specific surface area (2630 m2g-1), a high theoretical capacity (744 mAhg-1), excellent electrical conductivity, and a wide electrochemical potential window. Despite having these superior properties, the restacking as well as the van der Waals forces of attraction among the graphene layers and the long path for Li-ion diffusion are factors that reduce the specific surface area and active site for Li-ion storage, which in turn influence the electrochemical performance of LIBs. The functionalization of graphene to porous graphene, graphene quantum dots, and graphene oxides, as well as the integration of graphene with other foreign materials such as transitional metal oxides, various heteroatoms (boron, nitrogen, sulfur, etc.), and covalent organic frameworks (COF), are the two main strategies that have been widely applied to improve the properties of graphene for Li-ion battery applications. In this review, recent works regarding the performance of graphene and graphenebased electrode materials for LIBs applications were reviewed and presented in detail. Moreover, various graphene fabrication techniques in terms of quality and quantity of graphene produced as well as the future overview of graphene and some selected graphene-based materials for LIBs applications have been assessed and summarized.