Anode For Lithium-ion Batteries Research Articles

Box-Behnken design for the synthesis optimization of mesoporous sulfur-doped carbon-based materials from birch waste: Promising candidates for environmental and energy storage application

The development of biomass-based carbon materials has accelerated the research interest in environmental (e.g., adsorbents for wastewater decontamination) and energy applications (e.g., batteries). In this paper, we developed a series of carbon materials (CMs) using a sulfur doping strategy to improve the physicochemical, adsorptive and energy storage properties of the aforementioned CMs. CMs were prepared and optimized using an experimental design denoted as the Box-Behnken design approach with three independent factors (i.e., the temperature of pyrolysis, zinc chloride: biomass ratio and sulfur: biomass ratio), and the responses were evaluated, namely the Specific Surface Area (SBET), mesopore area (AMeso) and micropore area (AMicro) with the help of Nitrogen Physisorption. According to the statistical analysis, under the studied conditions, the responses were mainly influenced by the pyrolysis temperature and ZnCl2 ratio, while the sulfur content did not give rise to any remarkable differences in the selected responses. The physicochemical characterization of the CMs suggested that very high Specific Surface Areas ranging from 1069 to 1925 m2 g−1 were obtained. The sulfur doping resulted in up to 7.33 wt% of sulfur in the CM structure, which yielded CMs with more defects and hydrophilic surfaces. When tested as adsorbents, CMs exhibited a very high adsorption capacity (190 – 356 mg g−1), and as anodes, they demonstrated a competitive Lithium Ion Battery (LIB) storage capacity, at least during the first five cycles (306 mAhg−1 at 1 C for CM9). However, further studies on long-term cyclability are required to prove the CM materials suitability in LIBs. This work extends our understanding of how pyrolysis and sulfur doping of biomass feedstock affects carbon materials' usability, final characteristics and potential to use in wastewater decontamination by adsorption and as anodes in LIBs.

A graded structure of silicon/carbon composite powder for highly stable lithium ion battery anode

Silicon has much higher theoretical specific capacity than traditional graphite materials (3579 mAh g−1vs. Graphite: 372mAh g−1). However huge volumetric expansion (∼300%) of silicon seriously reduces its cyclic stability as anode in lithium-ion batteries. Though reduce the size of silicon based composites to nanoscale and tuning their porosity have been extensively studied, above strategies reduce the vibration density of the anode material unsurprisingly, which is not conducive to the advantage of high volumetric capacity anode. In this work, we design a unique graded silicon/carbon powder to maintain excellent energy storage performance at high vibration density. The composite of graded structure is constructed by first particles and second particles. The construction strategy is proved to be adoptable to achieve cost effective production of high performance silicon/carbon composite anode for development of advanced lithium-ion battery. Under the premise of industrial powder materials’ production technologies, a graded structure silicon/carbon composite with optimized synthetic condition shows high-reversible capacity of 827.4 mAh g−1 at 200 mAh g−1 (equal to 1464.5 Ah L−1) and it capacity remains at 715.0 mAh g−1 after 800 cycles, with a capacity retention rate of 86.37%, which shows high cycle life.

Modulating functional groups of GO to improve the electrochemical performance of Si/rGO anode

Silicon (Si)-based materials show attractive potentials as the anode for lithium-ion batteries (LIBs) due to their high theoretical specific capacity. For the conventional silicon/reduced graphene oxide (Si/rGO) composites, the electrical conductivity, C/O ratio, and defect structure of reduced graphene oxide (rGO) significantly impact their electrochemical properties. Herein, we use three methods to prepare graphite oxide (GO) to adjust the percentage of functional groups, which further enhance the physicochemical properties of rGO and thus improve the electrochemical properties of Si/rGO. The GOs were synthesized through Hummers method (labeled as GO-1), Hummers method with H2O modulation (labeled as GO-2), and Hummers method with H2O and H3BO3 modulation (labeled as GO-3). Due the H2O promotes the production of hydroxyl and epoxy groups, and H3BO3 forms complexes with hydroxyl groups,the ratio of hydroxyl and epoxy groups in GO-1 to GO-3 is increased. After reduction process, the reduced rGO-3 exhibits a high C/O ratio, large structural defects, and excellent electrical conductivity. Because of the excellent properties of rGO-3, as an electrode material, Si/rGO-3 exhibits excellent electrochemical performance, with the highest reversible capacity of about 780.8 mAh/g after 150 cycles at 1 A/g and a good rate performance of 657.0 mAh/g at 5 A/g. This work proves that modulation of rGO from the GO with different oxygen-containing functional groups lead to enhanced ionic conductivity, cyclic stability, and rate capability of the Si/rGO electrodes.

Inorganic/organic composite binder with self-healing property for silicon anode in lithium-ion battery

Silicon (Si) has garnered significant attention as a high-capacity anode material in high-energy density lithium-ion batteries (LIBs). Nevertheless, the huge volume variation of Si (>300%) during cycling results in rapid capacity deterioration, thereby impeding its commercial application. To confront this challenge, inorganic binder has been identified as a highly promising solution for Si anode due to its high bonding strength. Despite its effectiveness, the inorganic binder's limited elasticity hinders the rejuvenation of the impaired electrode structure. Hence, we devised an elasticity and self-healing composite binder, incorporating both inorganic and organic binders. The inorganic lithium metasilicate not only offers ample adhesion sites to Si but also establishes a protective coating layer on SiNPs. Simultaneously, the organic poly (vinyl alcohol) featuring a low glass transition temperature (72 °C) furnishes elasticity and a self-healing framework. Consequently, the Si anode shows exemplary cycling and rate performances. Additionally, the Si||NCM811 full cell attains a reversible capacity of 1.86 mAh/cm2 with a capacity retention of 67% after 50 cycles, indicating the commercial application potential of the composite binder. This study thus explores design strategies for composite binders, paving the way for high-performance Si anode.

Synthesis of Organopolysilazane Nanoparticles as Lithium-Ion Battery Anodes with Superior Electrochemical Performance via the Two-Step Stöber Method.

The Stöber method, a widely utilized sol-gel technique, stands as a green and reliable approach for preparing nanostructures on a large scale. In this study, we employed an enhanced Stöber method to synthesize organopolysilazane nanoparticles (OPSZ NPs), utilizing polysilazane oligomers as the primary precursor material and ammonia as the catalytic agent. By implementing a two-step addition process, control over crucial parameters facilitated the regulation of the nanoparticle size. Generally, maintaining relatively low concentrations of organopolysilazane and catalyst while adjusting the water/acetonitrile ratio can effectively enhance the surface energy of the organopolysilazane, resulting in the uniform formation of small spherical particles. The average particle size of the synthesized OPSZ NPs is about 140 nm, which were monodispersed and characterized by scanning electron microscopy, transmission electron microscopy, and dynamic light scattering. Furthermore, the composition of OPSZ NPs after pyrolysis was confirmed as SiC2.054N0.206O1.631 with 5.44 wt % free carbon structure by X-ray diffraction and energy-dispersive X-ray spectroscopy. Notably, the electrochemical performance assessment of SiCNO NPs as potential electrode materials for lithium-ion batteries exhibited promising outcomes. Specifically, at 1 A g-1 current density, the specific capacity is 585.45 mA h g-1 after 400 cycles, and the minimum capacity attenuation per cycle is only 0.1076 mA h g-1 (0.0172% of the original capacity), which indicates excellent energy storage capacity and cycle stability. In summary, this research contributes to the development of advanced anode materials for next-generation energy storage systems, marking a stride toward sustainable energy solutions.

Black Phosphorus/PANI/Carbon Nanotube Composite as a Lithium-Ion Battery Anode

Black Phosphorus/PANI/Carbon Nanotube Composite as a Lithium-Ion Battery Anode

Reutilization of Silicon-Cutting Waste via Constructing Multilayer Si@SiO2@C Composites as Anode Materials for Li-Ion Batteries.

The rapid development of the photovoltaic industry has also brought some economic losses and environmental problems due to the waste generated during silicon ingot cutting. This study introduces an effective and facile method to reutilize silicon-cutting waste by constructing a multilayer Si@SiO2@C composite for Li-ion batteries via two-step annealing. The double-layer structure of the resultant composite alleviates the severe volume changes of silicon effectively, and the surrounding slightly graphitic carbon, known for its high conductivity and mechanical strength, tightly envelops the silicon nanoflakes, facilitates ion and electron transport and maintains electrode structural integrity throughout repeated charge/discharge cycles. With an optimization of the carbon content, the initial coulombic efficiency (ICE) was improved from 53% to 84%. The refined Si@SiO2@C anode exhibits outstanding cycling stability (711.4 mAh g-1 after 500 cycles) and rate performance (973.5 mAh g-1 at 2 C). This research presents a direct and cost-efficient strategy for transforming photovoltaic silicon-cutting waste into high-energy-density lithium-ion battery (LIB) anode materials.

Rationally designed capacitive enhanced three-dimensionally feather-like Co3O4/ZnCo2O4/NF composite as efficient anode for lithium-ion batteries

Rationally designed capacitive enhanced three-dimensionally feather-like Co3O4/ZnCo2O4/NF composite as efficient anode for lithium-ion batteries

Spray pyrolysis-derived W-doped MoSe2/rGO paper-like microspheres: optimization of microstructure and mesostructure for enhanced lithium storage

AbstractTwo-dimensional MoSe2 is a promising candidate for lithium-ion battery anodes. However, its conductivity and lithium storage volumetric effect still need to be optimized. In this work, W-doped MoSe2/rGO paper-like microspheres are successfully prepared through ultrasonic spray pyrolysis, achieving optimization at both the microstructure and mesostructure to enhance the lithium storage performance of the material. Firstly, by utilizing the similar two-dimensional structure between MoSe2 and rGO, self-assembly is achieved through spray pyrolysis, resulting in a well-defined van der Waals heterostructure at the interface on the microscale, enhancing the electron and ion transfer capability of the composite. Secondly, the mesoscale paper-like microsphere morphology provides additional volume expansion buffering space. Moreover, W-doping not only increases the interlayer spacing of MoSe2 (0.73 nm), thereby reducing the diffusion resistance of Li+, but also allow for the modulation of the energy band structure of the material. Density functional theory (DFT) calculations confirm that W-doped MoSe2/rGO exhibits the narrowest bandgap (0.892 eV). Therefore, the composite demonstrates excellent lithium storage performance, maintaining a specific capacity of 732.9 mAh·g−1 after 300 cycles at a current density of 1 A·g−1. Graphical abstract

Suppressing the damage of deposited Mn(II) ions to graphite anode in lithium‐ion batteries by electrolyte additive agent and positive material coating

AbstractSEM and EDS techniques are carried out to demonstrate the variation of morphology and chemical compound on the surface of graphite anode, which suggest a well‐accepted concept that the manganese ions have serious influence on the reversible capacity fade of graphite anode in lithium ion batteries. Based the main chemical compounds of the inorganic layer on the graphite surface, the evolution steps of graphite structure damaged by Mn ions are derived. Although the amount of deposited manganese ions is small, these play an important role in the catalytic decomposition of the electrolyte. Moreover, Raman analysis shows that the structure of the graphite anode becomes irregular at initial SEI formation cycles and tends to be stable at subsequent cycles. This structure variation is probably generated from the manganese ion deposition and the solid electrolyte interphase (SEI) film formation. According to the capacity tests, the cycling performance of NCM811/graphite lithium‐ion batteries could be improved 50% by FEC additive and B2O3 surface coating. FEC additive maybe benefit graphite forming a stable SEI film in the early stages of cycling to suppress the damage of Mn2+ ions, then improving the cycling performance.

Impact of LiAl Nucleation Kinetics on the Microstructural Evolution of Aluminum Foil Anodes in Lithium-ion Batteries

Aluminum foil anodes have the potential to significantly improve the energy density, safety, cost, and sustainability of Li-ion batteries (LIB). However, their adoption is limited by their notoriously poor cycle life, and the dramatic structural transformations of Al foil anodes during formation and cycling remain poorly understood. In this work, we investigate how the nucleation and growth kinetics of LiAl control the microstructural evolution and cycle life of Al foil anodes. First, we demonstrate the unique sensitivity of Al foil anodes to the cell design and cycling conditions and emphasize the necessity of electrochemical testing in practical full cells. Operando electrochemical impedance spectroscopy (EIS) is combined with scanning electron microscope (SEM) imaging of the lithiated foils to elucidate the relationships between LiAl nucleation kinetics and the resulting LiAl microstructure. Particularly, we investigate the effects of annealing the pristine foils, and controlling the overpotential and temperature during formation, showing that as-rolled foils lithiated at high overpotentials give a columnar LiAl microstructure. Finally, we show that uncontrolled LiAl nucleation during cycling quickly destroys this favorable columnar structure, and a significant improvement in cycle life of LiFePO4 || Al full cells is achieved by limiting the depth-of-discharge to <75%.

Impact of copper doping on the electrochemical response of MnSe2 as anode for lithium-ion battery

Impact of copper doping on the electrochemical response of MnSe2 as anode for lithium-ion battery

Study on modification of different amino silanes modified polyacrylic acid for ball milling silicon anode of lithium-ion batteries

Study on modification of different amino silanes modified polyacrylic acid for ball milling silicon anode of lithium-ion batteries

Synergistically enhanced LiF–rich protective layer for highly stable silicon anodes

Silicon (Si) is considered as one of the most promising anode materials with an extremely high specific capacity (3579 mAh/g), which is beyond the limit of conventional graphite anodes in lithium (Li) ion batteries (LIBs). However, large volume changes during the lithiation/delithiation process and formation of an unstable solid electrolyte interface (SEI) layer hinder the practical application of Si anodes. To address these issues, constructing a stable protective layer at the interface between anode and electrolyte is a desirable strategy. In this study, a LiF-rich SEI inducing protective layer (LPL) comprising aluminum fluoride (AlF3) and poly(acrylic acid) (PAA) is introduced onto Si anode to construct a stable LiF–rich SEI layer and mitigate the volume changes of the Si anodes during cycling. Owing to the synergetic effects of AlF3 and PAA, a LiF-rich SEI layer with robust physicochemical properties is uniformly formed on the Si anode. As a result, the LPL coated Si (LPL@Si) anodes exhibit outstanding electrochemical properties in Li metal cell tests. In addition, a full-cell prepared with the LPL@Si anode and LiNi0.8Co0.1Mn0.1O2 as a cathode exhibits an excellent cycling performance and mitigated volume changes, demonstrating the potential of this strategy to protect the Si anodes for the development of high-energy–density LIBs.

MXene as Promising Anode Material for High-Performance Lithium-Ion Batteries: A Comprehensive Review.

Broad adoption has already been started of MXene materials in various energy storage technologies, such as super-capacitors and batteries, due to the increasing versatility of the preparation methods, as well as the ongoing discovery of new members. The essential requirements for an excellent anode material for lithium-ion batteries (LIBs) are high safety, minimal volume expansion during the lithiation/de-lithiation process, high cyclic stability, and high Li+ storage capability. However, most of the anode materials for LIBs, such as graphite, SnO2, Si, Al, and Li4Ti5O12, have at least one issue. Hence, creating novel anode materials continues to be difficult. To date, a few MXenes have been investigated experimentally as anodes of LIBs due to their distinct active voltage windows, large power capabilities, and longer cyclic life. The objective of this review paper is to provide an overview of the synthesis and characterization characteristics of the MXenes as anode materials of LIBs, including their discharge/charge capacity, rate performance, and cycle ability. In addition, a summary of the potential outlook for developments of these materials as anodes is provided.

Recent Progress in Developing High-Performance Anode Materials for Next-Generation Sodium-Ion Batteries

Rechargeable lithium-ion batteries (LIBs) have attracted great attention due to their large-scale energy storage applications such as electric vehicles (EVs) and grid-scale energy storage systems (ESSs). The ongoing transition towards EVs has accelerated ever-increasing demand for LIBs that causes the shortage of lithium metal resources and their expensive price. Therefore, great efforts have been made to exploit an alternative system that replaces the conventional LIBs. While sodium-ion batteries (SIBs) can be the most evident alternatives to LIBs based on the natural abundance and low cost of sodium resources, the major scientific challenges reside in developing the new anode materials due to the poor performance of conventional LIB anodes in Na cells, such as graphite and silicon. This article reviews the potential of SIBs as promising alternatives to LIBs and recent progress in developing high-performance anode materials for SIBs. The strengths and drawbacks of recently developed anode materials have been discussed, including graphite, hard carbon, silicon, phosphorus, and other transition metal compounds such as oxides, phosphides, and sulfides.

Oxygen-rich vacancies in micro-caged NiMn2O4 derived from metal-organic frameworks enabling high-performance lithium-ion batteries

Transition metal oxides (TMOs) are increasingly attracting the interest of researchers with advantages of high theoretical capacity, abundant reserves, and ease of preparation. However, low coulombic efficiency, severe volume expansion, and poor electronic conductivity severely limit their application. The introduction of oxygen vacancies as well as morphology modulation is currently an effective solution to the above problems. Herein, we have synthesized a series of different MOF-derived NiMn2O4 (NMO) anodes for lithium-ion battery via the proposed hydrothermal synthesis method. Through the rational introduction of oxygen vacancies, all the synthesized 1,4-dicarboxybenzene-NiMn2O4 (BDC-NMO), 1,3,5-Benzenetricarboxylic acid-NiMn2O4 (BTC-NMO) and 1,2,4,5-Benzenetetracarboxylic acid-NiMn2O4 (PMA-NMO) electrodes achieved excellent cycle stability performance and rate performance. Meanwhile, BTC-NMO achieves superior cycling performance of 940 mAh g−1 after 250 cycles at 0.1 A g−1 compared to BDC-NMO and PMA-NMO electrodes, which was attributed to its hollow micro-cage structure, which could effectively shorten the Li+ diffusion path, alleviate volume expansion during the cycling and provide more Li+ reaction active sites. Theoretical calculations and experimental studies indicated that oxygen vacancies could enhance electronic conductivity, improve Li+ diffusion kinetics and promote the contribution of pseudo-capacitance. This strategy of regulating the electronic structure and reaction kinetics through oxygen vacancies and the hollow micro-cage structure design provides ideas for the commercialization path of TMOs as anodes for Li-ion battery.

In Situ Electrophoretic Decorated Cactus-Type Metallic-Phase MoS2 on CaMn2O4 Nanofibers for Binder-Free Next-Generation LIBs.

Ternary manganese-based oxides, such as CaMn2O4 (CMO) nanofibers fabricated via the electrospinning technique, have the potential to offer higher reversible capacity through conversion reactions in comparison to that of carbon-based anodes. However, its poor electrical conductivity hinders its usage in lithium-ion batteries (LIBs). Hence, to mitigate this issue, controlled single-step in situ decoration of highly conducting metallic-phase MoS2@CMO nanofibers has been achieved for the first time via the electrophoretic deposition (EPD) technique and utilized as a binder-free nanocomposite anode for LIBs. Further, the composition of MoS2@CMO nanofibers has also been optimized to attain better electronic and ionic conductivity. The morphological investigation revealed that the flakes of MoS2 nanoflowers are successfully and uniformly decorated over the CMO nanofibers' surface, forming a cactus-type morphology. As a binder-free nanocomposite LIB anode, CMOMS-7 (7 wt % MoS2@CMO) demonstrates a specific capacity of 674 mA h g-1 after 60 cycles at 50 mA g-1 and maintains a capacity of 454 mA h g-1 even after 300 cycles at 1000 mA g-1. Further, the good rate performance (102 mA h g-1 at 5000 mA g-1) of CMOMS-7 can be ascribed to the enhanced electrical conductivity provided by the metallic-phase MoS2. Moreover, the feasibility of CMOMS-7 is thoroughly investigated by using a full Li-ion cell incorporating a binder-free cathode of LiNi0.3Mn0.3Co0.3O2 (NMC). This configuration showcases an impressive energy density of 154 Wh kg-1. Thus, the hierarchical and aligned structure of CMO nanofibers combined with highly conductive MoS2 nanoflowers facilitates charge transportation within the composite electrodes. This synergistic effect significantly enhances the energy density of the conversion-based nanocomposites, making them highly promising anodes for advanced LIBs.

Insight of the evolution of structure and energy storage mechanism of (FeCoNiCrMn)3O4 spinel high entropy oxide in life-cycle span as lithium-ion battery anode

Recently, spinel high-entropy oxide (HEO) anode materials have garnered extensive attention for high-energy lithium-ion batteries due to their high specific capacity. Many studies have explored its energy storage mechanism, but few have paid attention to its characteristics in long cycle life. In this work, the whole life cycling performance of (FeCoNiCrMn)-HEO is presented and investigated for the first time. Distinct capacity trends are studied to divide the cycling life into three stages: activation, upgradation, and degradation. Ex situ morphological characterizations are conducted to reveal that the driving force of stage change is continuous particle fragmentation. As a result, refined particles promote conversion reaction reversibility and induce extra interfacial capacity, achieving 2831 mAh g−1 at 825 cycles. Density functional theory (DFT) calculations provide a deeper insight into the high entropy effect on the ultra-high extra interfacial capacity. However, continuous refinement brings about huge electrolyte interface-derived layers, which are also responsible for pre-decay and post-collapse. The view of the evolution of the lithium storage mechanism is explicitly presented and experimentally verified by high-energy ball milling and fluorinated vinyl carbonate (FEC). These above results can give practical solutions to design high specific capacity and long-life cycle stability HEO anode in the future.

Stabilizing Solid Electrolyte Interphase on Liquid Metal Via Dynamic Hydrogel-Derived Carbon Framework Encapsulation.

Eutectic gallium-indium liquid metal (EGaIn-LM), with a considerable capacity and unique self-healing properties derived from its intrinsic liquid nature, gains tremendous attention for lithium-ion batteries (LIBs) anode. However, the fluidity of the LM can trigger continuous consumption of the electrolyte, and its liquid-solid transition during the lithiation/de-lithiation process may result in the rupture of the solid electrolyte interface (SEI). Herein, LM is employed as an initiator to in situ assemble the 3D hydrogel for dynamically encapsulating itself; the LM nanoparticles can be homogeneously confined within the hydrogel-derived carbon framework (HDC) after calcination. Such design effectively alleviates the volume expansion of LM and facilitates electron transportation, resulting in a superior rate capability and long-term cyclability. Further, the "dual-layer" SEI structure and its key components, including the robust LiF outer layer and corrosion-resistant and ionic conductive LiGaOx inner layer are revealed, confirming the involvement of LM in the formation of SEI, as well as the important role of carbon framework in reducing interfacial side reactions and SEI decomposition. This work provides a distinct perspective for the formation, structural evolution, and composition of SEI at the liquid/solid interface, and demonstrates an effective strategy to construct a reliable matrix for stabilizing the SEI.