Materials For Lithium-ion Batteries Research Articles

Bio-Inspired Self-Healing Silicon Anodes: Harnessing Tea Polyphenols to Enhance Lithium-Ion Battery Performance.

This study introduces an anode material for lithium-ion batteries, achieved by integrating tea polyphenols (TP) with the widely utilized polyacrylic acid (PAA) binder. The composite material capitalizes on the intrinsic self-healing properties of TP, enhancing the anode's durability and adhesiveness without the need for additional organic synthesis. The incorporation of TP has been demonstrated to significantly elevate ionic conductivity and expedite lithium ion diffusion, thereby reducing interfacial resistance and decelerating the rate of capacity fade due to electrolyte decomposition and silicon particle expansion. Employing a comprehensive analytical toolkit, including Fourier transform infrared spectroscopy, thermogravimetric analysis, peel strength measurements, and density functional theory calculations, we elucidated the physicochemical properties of the Si@PAA-TP anode. The anode's electrochemical performance was systematically assessed through galvanostatic charge-discharge, cyclic voltammetry, and electrochemical impedance spectroscopy, with scanning electron microscopy providing insights into postcycling mechanical property alterations. This research advances a cost-effective, high-performance adhesive strategy for silicon anodes and contributes to the development.

Facile One-Pot Synthesis of Fe3O4 Nanoparticles Composited with Reduced Graphene Oxide as Fast-Chargeable Anode Material for Lithium-Ion Batteries.

To address the rapidly growing demand for high performance of lithium-ion batteries (LIBs), the development of high-capacity anode materials should focus on the practical perspective of a facile synthetic process. In this work, iron oxide nanoparticles (Fe3O4 NPs) in situ grown on the surface of reduced graphene oxide (rGO), denoted as Fe3O4 NPs@rGO, were prepared through a facile one-pot synthesis under the wet-colloidal conditions. The synthesized Fe3O4 NPs showed that uniform Fe3O4 NPs, with a size of around 9 nm, were distributed on the rGO surfaces. When applied as an anode material for LIBs, the Fe3O4 NPs@rGO anode revealed a high reversible capacity of 1191 mAh g-1 at 1.0 A g-1 after 200 cycles. It also exhibited excellent rate performance, achieving 608 mAh g-1 at a current density of 5.0 A g-1 over 500 cycles, with improved electronic and ionic conductivities due to the rGO template. This suggested that practically available anode materials can be developed through our one-pot synthesis by in situ growing the Fe3O4 NPs.

Structurally-constrained wrinkled NiO nanomembranes for high-performance lithium and sodium storage

In light of its exceptional capacity and safety features, nickel oxide (NiO) has emerged as a highly promising electrode material for advanced lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs), which operate through conversion mechanisms, meeting the growing demand for high-efficiency rechargeable batteries. To address the capacity degradation challenges associated with NiO anodes, we present an innovative approach involving the fabrication of wrinkled NiO nanomembranes through magnetron sputtering deposition followed by thermal treatment. This distinctive three-dimensional, ultra-thin architecture integrates nanostructural and microstructural features that effectively reduce ionic diffusion distances and mitigate dimensional fluctuations during cycling, thereby markedly enhancing the electrochemical performance and reliability. Specifically, for lithium storage, these wrinkled NiO nanomembranes achieve an impressive reversible specific capacity of 773 mA h g−1 at 100 mA g−1, with excellent rate capability of 468 mA h g−1 at 5000 mA g−1 and long-term cycling performance, maintaining 523 mA h g−1 at 500 mA g−1 even after 1000 cycles. Likewise, for sodium storage, they exhibit a substantial reversible capacity of 288 mA h g−1 at 50 mA g−1 and retain 202 mA h g−1 at 200 mA g−1 after 100 cycles. These findings underscore the promising application of wrinkled NiO nanomembranes as robust anodic materials for high-performance LIBs and SIBs.

Achieving high-rate capacity pitch-based carbon as anode materials for lithium-ion battery

Achieving high-rate capacity pitch-based carbon as anode materials for lithium-ion battery

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.

Li decorated graphdiyne nanosheets: A theoretical study for an electrode material for nonaqueous lithium batteries

In this work, Density Functional Theory (DFT) is used to study pristine and defective GDY. We investigate the effect of Li atom adsorption on the electronic and structural properties of this 2D material. In both cases, the Li atom is located at the corner of the triangular‐like pore (H1), but with a slight shift for the defective system. In the perfect system, the Li‐C bond distances range from 2.289 Å to 2.461 Å, while in the defective case, they range from 2.237 Å to 3.184 Å. In the perfect case, the GDY‐Li system becomes metallic and the Li 2s states are stabilized. Charge transfer to the surfaces occurs near the vicinity of the Li atom. The C vacancy generates new C=C bonds similar to double bonds, enhancing the interaction with Li through strong conjugation. After Li adsorption, the sum of bond order for all the C atoms increases in both structures, from 0.4% to 6%. The Li storage capacity without significant restructuring is six Li atoms. When the atom concentration increases, the OCV values for Li decrease from 0.93 V to 0.23 V. For defective GDY, the specific capacity is 788 mAhg‐1, which is slightly higher than for pristine case.

Defect Chemistry in High-Voltage Cathode Materials for Lithium-Ion Batteries.

High-voltage cathodes (HVCs) have emerged as a paramount role for the next-generation high-energy-density lithium-ion batteries (LIBs). However, the pursuit of HVCs comes with inherent challenges related to defective structures, which significantly impact the electrochemical performance of LIBs. The current obstacle lies in the lack of a comprehensive understanding of defects and their precise effects. This perspective aims to provide insights into defect chemistry for governing HVCs. The classifications, formation mechanisms, and evolution of defects are outlined to explore the intricate relationship between defects and electrochemical behavior. The pressing need for cutting-edge characterization techniques that comprehensively investigate defects across various temporal and spatial scales is emphasized. Building on these fundamental understandings, engineering strategies such as composition tailoring, morphology design, interface modification, and structural control to mitigate or utilize defects are thoroughly discussed for enhanced HVCs performance. These insights are expected to provide vital guidelines for developing high-performance HVCs for next-generation high-energy lithium-ion batteries.

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.

High-precision analysis of toxic metals in lithium-ion battery materials across various complex media

BackgroundPresent regulations regarding the management and recycling of spent Lithium-ion batteries (LIBs) are inadequate, which may lead to the pollution of lithium (Li) and heavy metals in water and soil during the informal disposal of such batteries. To comprehend the distribution of toxic metals within spent LIBs and contaminated environmental media, precise analytical methods for toxic metals in these materials are crucial. However, due to the chemical complexity of LIBs materials (e.g., lithium iron phosphate, graphite, separators, and electrolytes), there is still a lack of research on developing and validating analytical techniques for toxic metals in LIB materials across various environmental media. ResultsThis study establishes a comprehensive and highly precise analytical method for assessing toxic metal constituents in LIBs across various complex media, including sewage, soil, and biological matrices. We assessed the selection of digestion solutions for different LIB materials and identified the most suitable internal standard elements in the mass spectrometric analysis workflow. The devised digestion schemes for all components of LIBs are as follows: aqua regia for all cathode materials (excluding LiMn0.6Fe0.4PO4 (LMFP)), nitric acid for diaphragm materials, aqua regia with hydrofluoric acid for the anode material Li4Ti5O12 (LTO), and NaOH fusion for graphite and LMFP. LiPF6 electrolyte can be directly dissolved in ultrapure water. By employing this method, the analysis of cathode materials of LIBs within diverse environmental matrices (sewage, soil, plants, animals) yields recovery rates ranging from 83.6 % to 115.5 %. Furthermore, this research reveals the remarkable accumulation of Li and heavy metals in anode (graphite) of spent LIBs. SignificanceThis is the first to develop and validate analytical techniques for toxic metals in LIB materials across various environmental media, incorporating both acid digestion and alkaline fusion techniques. This methodology offers comprehensive support for conducting environmental risk assessments of spent LIBs. Using this method, the research elucidates the occurrence characteristics of toxic metals within different parts of commercial spent LIBs, providing valuable insights to enhance recycling efforts and facilitate risk management of spent LIBs.

Investigating the impact of acetylenic linkage in C20 fullerene: Utilization in optoelectronic devices and as anode material

This study delves into the diverse characteristics of C80 fulleryne, derived from the incorporation of acetylenic linkages into each chain of the smallest fullerene, C20. Utilizing advanced theoretical computations, we confirm the stability of C80 fulleryne. Notably, its possession of a finite energy gap (0.743 eV) categorizes it as a semiconductor. Further enlightenment into its structural stability, bonding and reactivity stems from an exploration of different energy components, topological descriptors of electron density and chemical reactivity parameters. C80 fulleryne can act as radical scavenger owing to its higher electron affinity (5.5 eV). Spectral analysis revealed the C80 fulleryne’s absorption within the near-infrared region and its intriguing optical transparency with negligible loss in specific regions of the electromagnetic spectrum. Additionally, our investigation scrutinized the viability of C80 fulleryne as an anode material in Lithium-ion batteries. The presence of low adsorption energy (−1.693 eV) and significant amount of Bader charge transfer (0.917 e) between Li-ion and C atoms of C80 fulleryne confirms that Li-ion gets chemisorbed on the C80 fulleryne. Remarkably, this cage acts as a storehouse to host 12 Li ions, precisely one for each of its constituent pentagons within the C80 fulleryne structure, bearing a theoretical capacitance of 335 mAhg−1.

Sustainable Synthesis of a Carbon-Supported Magnetite Nanocomposite Anode Material for Lithium-Ion Batteries

Transition metal oxide magnetite (Fe3O4) is recognized as a potential anode material for lithium-ion batteries owing to its high theoretical specific capacity, modest voltage output, and eco-friendly character. It is a challenging task to engineer high-performance composite materials by effectively dispersing Fe3O4 crystals with limited sizes in a well-designed supporting framework following sustainable approaches. In this work, the naturally abundant plant products sodium lignosulfonate (Lig) and sodium cellulose (CMC) were selected to coprecipitate with Fe3+ ions under mild hydrothermal conditions. The Fe-Lig/CMC intermediate sediment with an optimized microstructure can be directly converted to the Lig/CMC-derived carbon matrix-supported Fe3O4 nanocomposite sample (Fe3O4@LigC/CC). Compared with the controlled Fe3O4@LigC material, the Fe3O4@LigC/CC nanocomposite provides superior electrochemical performance in the anode, which has inspiring specific capacities of 820.6 mAh g−1 after 100 cycles under a current rate of 100 mA·g−1 and 750.5 mAh g−1 after 250 cycles, as well as more exciting rate capabilities. The biomimetic sample design and synthesis protocol closely follow the criteria of green chemistry and can be further developed in wider scenarios.

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.

Cracking Mechanism and Inhibition Strategies of Polycrystalline NCM Electrode Particles.

Developing a high-energy-density cathode material (LiNi1-x-yCoxMnyO2, NCM) for lithium-ion batteries is crucial to the electric vehicle and energy storage industries. However, the continuous insertion/extraction of Li+ generates diffusion-induced stress, causing NCM particles to crack or even pulverize, leading to battery capacity loss and limiting its wider commercial application. Current experimental studies are primarily postmortem examinations, and it is difficult to capture the particle cracking evolution. Simulation studies frequently ignore or simplify anisotropic volume contraction, demonstrating an insufficient understanding of the cracking mechanism of NCM polycrystalline particles, and cracking prevention strategies still need improvement. Therefore, we develop an anisotropic polycrystalline fracture phase-field model (AP-FPFM) that focuses on the anisotropic volume contraction of primary particles and precisely generates grain boundary distribution, coupling with Li+ diffusion, mechanical stress, and particle cracking. We employ AP-FPFM to demonstrate the behavior and mechanism of NCM polycrystalline particle cracking and illustrate the necessity and importance of anisotropic volume contraction to understand particle cracking. Furthermore, we explore the effects of average primary particle size, secondary particle size, and core-shell structure modulation on crack initiation and propagation and propose strategies to inhibit or migrate NCM polycrystalline particle cracking. This work provides theoretical support for revealing the cracking mechanism of anisotropic polycrystalline NCM particles and supplying optimization strategies to suppress particle cracking and improve the mechanical stability.

Enhancing Electrochemical Performance of Si@CNT Anode by Integrating SrTiO3 Material for High-Capacity Lithium-Ion Batteries

Silicon (Si) has attracted worldwide attention for its ultrahigh theoretical storage capacity (4200 mA h g−1), low mass density (2.33 g cm−3), low operating potential (0.4 V vs. Li/Li+), abundant reserves, environmentally benign nature, and low cost. It is a promising high-energy-density anode material for next-generation lithium-ion batteries (LIBs), offering a replacement for graphite anodes owing to the escalating energy demands in booming automobile and energy storage applications. Unfortunately, the commercialization of silicon anodes is stringently hindered by large volume expansion during lithiation–delithiation, the unstable and detrimental growth of electrode/electrolyte interface layers, sluggish Li-ion diffusion, poor rate performance, and inherently low ion/electron conductivity. These present major safety challenges lead to quick capacity degradation in LIBs. Herein, we present the synergistic effects of nanostructured silicon and SrTiO3 (STO) for use as anodes in Li-ion batteries. Si and STO nanoparticles were incorporated into a multiwalled carbon nanotube (CNT) matrix using a planetary ball-milling process. The mechanical stress resulting from the expansion of Si was transferred via the CNT matrix to the STO. We discovered that the introduction of STO can improve the electrochemical performance of Si/CNT nanocomposite anodes. Experimental measurements and electrochemical impedance spectroscopy provide evidence for the enhanced mobility of Li-ions facilitated by STO. Hence, incorporating STO into the Si@CNT anode yields promising results, exhibiting a high initial Coulombic efficiency of approximately 85%, a reversible specific capacity of ~800 mA h g−1 after 100 cycles at 100 mA g−1, and a high-rate capability of 1400 mA g−1 with a capacity of 800 mA h g−1. Interestingly, it exhibits a capacity of 350 mAh g−1 after 1000 lithiation and delithiation cycles at a high rate of 600 mA hg−1. This result unveils and sheds light on the design of a scalable method for manufacturing Si anodes for next-generation LIBs.

An Effective Strategy on Synthesizing a Stable SiOx-Based Anode for High Density Lithium-Ion Batteries.

Silicon oxides (SiOx) have received extensive attention as a promising anode candidate for next-generation lithium-ion batteries (LIBs). However, their commercial applications have been seriously hindered by low conductivity, large volume expansion, and unstable solid-electrolyte interface (SEI) layer, which result in low initial coulombic efficiency, poor rate performance, and short cycling lifespan. In this work, we demonstrated a simple way to prepare a series of SiOx materials with lithium fluoride (LiF) modified. When the mass ratio of SiOx and LiF equaled 1 : 0.15, the long-term cycling capacity retention could be greatly improved from 30.1 % to 76.5 % after 300 cycles. The result was primarily because of the enhancement of electrons and Li+-ions transport and the stability of the SEI layer due to LiF addition. However, excess LiF addition could hinder the diffusion of Li+-ions. This study presented the great potential of LiF modified on SiOx anode materials for LIBs.

Modification study of Mg/W-doped LiNi0.9Mn0.1O2 layered oxide cathode materials for lithium-ion batteries

Modification study of Mg/W-doped LiNi0.9Mn0.1O2 layered oxide cathode 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.

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