Anode For Lithium-ion Batteries Research Articles

Innovative Tin and hard carbon architecture for enhanced stability in lithium-ion battery anodes

Tin (Sn), with a theoretical capacity of 994 mAh g-1, is a promising anode material for lithium-ion batteries (LIBs). However, fundamental limitations like large volume expansion during charge-discharge cycle and confined electronic conductivity limit its practical utility. Here, we report a new material design and manufacturing method of LIB anodes using Sn and Hard Carbon (HC) architecture, which is produced by Physical Vapor Deposition (PVD). A bilayer HC/Sn anode structure is deposited on a carbon/copper sheet as a function of deposition time, temperature, and substrate heat treatment. The developed anodes are used to make cells with a lithium-ion electrolyte using a specific fabrication process. The morphology, atomic structure, conductivity, and electrochemical performance of the developed HC/Sn anodes are studied with SEM, TEM, XPS, and electrochemical techniques. At a discharge rate of 0.1C, the Snheated + HC anode performs exceptionally well, offering a capacity of 763 mAh g-1. It is noteworthy that it achieves a capacity of 342 mAh g-1 when fast charging at 5C, demonstrating exceptional rate capability. The Snheated + HC anode maintains >97 % Coulombic efficiency of its capacity after 3000 cycles at a rate of 0.1C after 3000 cycles 730.5 mAh g-1 recorded, demonstrating an impressive cycle life. The novel material design approach of the Snheated + HC anode, which has a multi-layered structure and HC acting as a barrier against volumetric expansion and improving electronic conductivity during battery cycling, is perceived as influential in uplifting anode's performance.

Small‐Molecule Polycyclic Aromatic Hydrocarbons as Exceptional Long‐Cycle‐Life Li‐Ion Battery Anode Materials

The growing demand for cost‐effective and sustainable energy‐storage solutions has spurred interest in novel anode materials for lithium‐ion batteries (LIBs). In this study, the potential of small‐molecule polycyclic aromatic hydrocarbons (SMPAHs) as promising candidates for LIB anodes is explored. Through a comprehensive experimental approach involving electrode fabrication, material characterization, and electrochemical testing, the electrochemical performance of SMPAHs, including naphthalene, biphenyl, 9,9‐dimethylfluorene, phenanthrene, p‐terphenyl, and pyrene (Py), is thoroughly investigated. In the results, the impressive cycle stability, high specific capacity, and excellent rate capability of the SMPAH electrode are revealed. Additionally, a direct contact prelithiation strategy is implemented to enhance the initial Coulombic efficiency (ICE) of SMPAH anodes, yielding significant improvements in the ICE and cycle stability. Computational simulations provide valuable insights into the electrochemical behavior and lithium‐storage mechanisms of SMPAHs, confirming their potential as effective anode materials. The simulations reveal favorable lithium adsorption sites, the predominant storage mechanisms, and the dissolution mechanism of Py through computational calculations. Overall, in this study, the promise of SMPAHs is highlighted as sustainable anode materials for LIBs, advancing energy‐storage technologies toward a greener future.

In situ multilevel covalent crosslinking binder with high ionic conductivity for high-performance Si anodes

Silicon (Si) anode has emerged as a promising material for high-energy-density lithium-ion batteries (LIBs), thanks to its high theoretical capacity. However, the commercial application of Si anodes is hindered by inadequate cycling performance and poor interfacial stability, stemming from unfavorable stress conditions. In this study, a multiple crosslinking binder with high ionic conductivity is proposed combining high mechanical strength and high adhesion to current collector and active Si particles by coupling poly(acrylic acid), polyvinyl alcohol, and polyethylene glycol. The designed polymer binder not only efficiently dissipates the inner stress with its multiple crosslinked networks, but also establishes a fast lithium-ion conduction pathway to facilitate the electrode reaction kinetic. The resultant Si anode using the designed binder exhibits significantly improved cycling stability and superior rate performance. This work presents a straightforward yet highly effective method to alleviate the detrimental stress incurred by high-capacity anodes in high-energy LIBs.

Unveiling the Interplay Between Silicon and Graphite in Composite Anodes for Lithium-Ion Batteries.

Si provides an effective approach to achieving high-energy batteries owing to its high energy density and abundance. However, the poor stability of Si requires buffering with graphite particles when used as anodes. Currently, commercial lithium-ion batteries with Si/graphite composite anodes can provide a high energy density and are expected to replace traditional graphite-based batteries. The different lithium storage properties of Si and graphite lead to different degrees of lithiation and chemical environments for this composite anode, which significantly affects the performance of batteries. Herein, the interplay between Si and graphite in mechanically mixed Si/graphite composite anodes is emphasized, which alters the lithiation sequence of the active materials and thus the cycling performance of the battery. Furthermore, performance optimization can be achieved by changing the intrinsic properties of the active materials and external operating conditions, which are summarized and explained in detail. The investigation of the interplay based on Si/graphite composite anodes lays the foundation for developing long-life and high-energy batteries. The abovementioned experimental methods provide logical guidance for future research on composite electrodes with multiple active materials.

The future of carbon anodes for lithium-ion batteries: The rational regulation of graphite interphase

The future of carbon anodes for lithium-ion batteries: The rational regulation of graphite interphase

Micron silicon-oxide-carbon coated with TiOx(OH)y layer as better performance anode for lithium-ion batteries

Micron-silicon based material is a promising anode material for high performance lithium batteries due to its ultra-high specific capacity. However, the volume expansion exceeds 300% during charging and discharging, resulting in the collapse of the electrode structure and a rapid decline in electrochemical performance. Coating the surface of silicon-based materials with flexible ionic conductors is an effective method to maintain their high capacity and suppress swelling. Here, to further improve the electrochemical performance of silicon-based materials, we have deposited a titanate-type ionic conductor layer on a micron-sized silicon-carbon oxide (SiOX-C) material to synthesize the SiOX-C@TiOx(OH)y material. The TiOx(OH)y layer not only exhibits the elastic properties of a superpolymer to mitigate swelling strain, but also has a fast capacitance effect to improve its rate performance. In addition, the interfacial charge transport of SiOX-C@TiOx(OH)y is enhanced due to the structural diversity of the TiOx(OH)y layer. For the above mechanisms, the SiOX-C@TiOx(OH)y has a specific capacity of 278.3 mAh g−1 under high current of 3500 mA g−1. Meanwhile, the SiOX-C@TiOx(OH)y with the capacity retention of 67% is achieved at 2000 mA g−1 after 100 cycles.

Oxygen vacancy modulated Ti2Nb10O29 anodes for high-rate lithium storage

Ti2Nb10O29 (TNO) is a prospective anode for lithium-ion batteries (LIBs) because of its high theoretical capacity, high energy density, and safer operating voltage. However, the lower conductivity and slower lithium-ion diffusion characteristic lead to performance degradation and accelerated capacity degradation. In this work, we developed a novel and simple urea-assisted heat treatment method to enrich oxygen vacancies in TNO anodes. Oxygen vacancy introduction leads to the formation of Ti3+ and Nb4+ and the optimization of electronic structure, which provide more active sites for ion insertion and accelerate electron transport and migration. The optimized sample (TNO-M) demonstrates excellent high-rate capacity and cyclic stability. Specifically, the reversible capacity is 155.4 mAh/g at 10C. A capacity retention ratio of 97.87 % can be maintained after 200 cycles at 1C. Even after 500 cycles at 5C, TNO-M can still deliver a high capacity of 156.4 mAh/g. The strategy of developing high-capacity and high-rate anodes provides a new inspiration for the applications of fast charging of energy-dense LIBs.

Enhancing lithium-storage properties through amino functionalization in two-dimensional lamellar carbon-supported mesoporous SiO2 nanospheres

Currently, common two-dimensional (2D) carbon materials composited with Si-based materials as anode for lithium-ion batteries exhibit excellent electrochemical properties. In this study, we describe the one-step synthesis of amino-functionalized mesoporous silica (SiO2) nanospheres through self-assembly. Morphology modulation and amino group grafting were performed simultaneously without secondary modification. Using tartaric acid and melamine as dual carbon sources, the 2D lamellar structure was constructed using the dehydration condensation reaction, with the mesoporous SiO2 nanospheres uniformly intercalated within the carbon sheets. The composites were securely bonded by chemical bonding, effectively addressing the issue of structural collapse often encountered in silica–carbon composites. Ultimately, the lamellar SiO2@NC composite exhibited stable capacity of 539.5 mAh g−1 after 500 cycles at 1 A g−1. This strategy is simple and effective, compared to the complex processes typically associated with 2D carbon materials synthesis, and can be potentially extended to applications in catalysis, adsorption, and separation within diverse fields.

Electrospun metal-organic framework materials derived bimetallic oxides as high-efficiency anodes for lithium-ion battery

Energy devices are receiving more and more attention, and this is especially true for lithium-ion batteries. Moreover, applying novel nanostructures in multicomponent systems is a very effective way to promote the development of energy storage systems. This study synthesizes a nitrogen-doped carbon nanofiber encapsulating MOF-derived bimetallic oxide nanomaterial by combining electrospinning and MOF materials. Nitrogen-doped carbon nanofibers are porous and highly conductive, providing structural stability, a practical pathway for lithium ion diffusion, and an essential channel for rapid charge transfer during cycling. The bimetallic oxides derived from the MOF materials provide sufficient space for fast reaction sites and mitigate volume expansion during cycling. When the composite material FNO@NCNFs is used as the anode material for lithium batteries, its reversible capacity is maintained at 1105.4 mAh g−1 after 100 cycles at a current density of 0.1 A g−1. Its capacity reaches 748.5 mAh g−1 after 900 cycles at a current density of 1 A g−1, and at the same time, it exhibits excellent cycling stability, with the coulombic efficiency remaining above 98 %. The material also exhibits a small ion transfer resistance and good rate performance. The structural design approach based on combining MOFs with electrospinning in this study will provide new insights into the design and development of materials for advanced energy storage applications.

Multi-dimensional carbon modification strategy for lithium-ion battery anodes: Carbon-covered TiP2O7 supported by 3D carbon skeleton

Carbon coating is a beneficial method for improving surface capacitive behavior, electron transfer kinetics and cyclic stability of three-dimensional lattice lithium-embedded anode materials. Herein, we adopt one-step pyrolysis to achieve carbon-covered TiP2O7 supported by a three-dimensional carbon skeleton utilizing phytic acid and glucose as carbon sources. The two-dimensional amorphous carbon layer on TiP2O7 surface improves the initial Coulombic efficiency and rate capacity by inhibiting the irreversible embedding of lithium ions and reducing the interfacial charge transfer impedance. The three-dimensional carbon skeleton not only forms a conductive pathway between the carbon-covered TiP2O7, but also its large specific surface area, randomly oriented and defective carbon layer provide extra lithium storage sites and capacitive contribution. In addition, the specific capacity of the TiP2O7/C composite is still as high as 314.5 mA h g−1 after 1000 cycles at 1 A g−1. A TiP2O7/C//LiFePO4 full cell delivers a high energy density of 273.96 Wh kg−1 at 0.153 kW kg−1, and retains 114.43 Wh kg−1 even at the power density of 4.086 kW kg−1. The multi-dimensional carbon modification strategy has improved the electrochemical performance of TiP2O7-based anode materials, providing a model for synthesizing other high-performance anode materials.

Comparative Investigation of Water-Based CMC and LA133 Binders for CuO Anodes in High-Performance Lithium-Ion Batteries.

Transition metal oxides are considered to be highly promising anode materials for high-energy lithium-ion batteries. While carbon matrices have demonstrated effectiveness in enhancing the electrical conductivity and accommodating the volume expansion of transition metal oxide-based anode materials in lithium-ion batteries (LIBs), achieving an optimized utilization ratio remains a challenging obstacle. In this investigation, we have devised a straightforward synthesis approach to fabricate CuO nano powder integrated with carbon matrix. We found that with the use of a sodium carboxymethyl cellulose (CMC) based binder and fluoroethylene carbonate additives, this anode exhibits enhanced performance compared to acrylonitrile multi-copolymer binder (LA133) based electrodes. CuO@CMC electrodes reveal a notable capacity ~1100 mA h g-1 at 100 mA g-1 following 170 cycles, and exhibit prolonged cycling stability, with a capacity of 450 mA h g-1 at current density 300 mA g-1 over 500 cycles. Furthermore, they demonstrated outstanding rate performance and reduced charge transfer resistance. This study offers a viable approach for fabricating electrode materials for next-generation, high energy storage devices.

Stress-Relieving Carboxylated Polythiophene/Single-Walled Carbon Nanotube Conductive Layer for Stable Silicon Microparticle Anodes in Lithium-Ion Batteries.

Stress-relieving and electrically conductive single-walled carbon nanotubes (SWNTs) and conjugated polymer, poly[3-(potassium-4-butanoate)thiophene] (PPBT), wrapped silicon microparticles (Si MPs) have been developed as a composite active material to overcome technical challenges such as intrinsically low electrical conductivity, low initial Coulombic efficiency, and stress-induced fracture due to severe volume changes of Si-based anodes for lithium-ion batteries (LIBs). The PPBT/SWNT protective layer surrounding the surface of the microparticles physically limits volume changes and inhibits continuous solid electrolyte interphase (SEI) layer formation that leads to severe pulverization and capacity loss during cycling, thereby maintaining electrode integrity. PPBT/SWNT-coated Si MP anodes exhibited high initial Coulombic efficiency (85%) and stable capacity retention (0.027% decay per cycle) with a reversible capacity of 1894 mA h g-1 after 300 cycles at a current density of 2 A g-1, 3.3 times higher than pristine Si MP anodes. The stress relaxation and underlying mechanism associated with the incorporation of the PPBT/SWNT layer were interpreted by quasi-deterministic and quantitative stress analyses of SWNTs through in situ Raman spectroscopy. PPBT/SWNT@Si MP anodes can maintain reversible stress recovery and 45% less variation in tensile stress compared with SWNT@Si MP anodes during cycling. The results verify the benefits of stress relaxation via a protective capping layer and present an efficient strategy to achieve long cycle life for Si-based anodes for next-generation LIBs.

Metallic MoS2 grown on CNT as high performance anodes for lithium-ion batteries

To mitigate the structural collapse of MoS2 during charging and discharging, MoS2-CNT composites were fabricated as anodes for lithium-ion batteries (LIBs). Hydroxylation CNT was incorporated to provide growth sites for MoS2 nanosheets, thereby enhancing their overall dispersion. This structure effectively improves the stability during cycling compared to MoS2/CNT, and to some extent improves the structural collapse of MoS2. As a result, the initial discharge capacity of the MoS2-CNT anode was 1194 mAh g−1 and the sustained capacity was 774 mAh g−1 after 200 cycles at 0.5 A g−1.

Effect of Sulfur Modification on Structural and Electrochemical Performance of Pitch-Based Carbon Materials for Lithium/Sodium Ion Batteries.

Coal tar pitch (CTP) has become an ideal choice in the preparation of anode precursors for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) because of its abundant carbon content, competitive pricing and adjustable structure properties. In this paper, sulfurized pitch-based carbon (SPC-800) was obtained by allowing CTP to react with sulfur at 350 °C and subsequently achieve carbonization at 800 °C. SPC-800 was more disordered and had a larger layer spacing than carbonized CTP (PC-800). Upon utilization as an anode for LIBs, SPC-800 possessed a higher reversible specific capacity (478.1 mAh g-1 at 0.1 A g-1), while utilization in SIBs displayed a capacity of 220.9 mAh g-1 at 20 mA g-1. This work is an important guide to the design of high-performance anodes suitable for use with both LIBs and SIBs.

Construction of ternary Sn/SnO2/nitrogen-doped carbon superstructures as anodes for advanced lithium-ion batteries

Construction of ternary Sn/SnO2/nitrogen-doped carbon superstructures as anodes for advanced lithium-ion batteries

Co(OH)2 derived from in-situ conversion of metal Co confined within a spongy porous carbon for high-performance lithium-ion battery anode

Fabricating Co(OH)2/C composites is considered as an efficient solution to poor conductivity and significant volume expansion issues of Co(OH)2 anode during cycle, but the easy conversion of Co(OH)2 into cobalt oxides during thermal treatment process limits structural design of materials and selection of carbon precursors, hence constricting the diversified design and structural optimization of the Co(OH)2/C composites. Herein, a distinctive method is demonstrated to embed Co(OH)2 nanoparticles (NPs) into a porous carbon (PC), which involves in-situ conversion of the metallic Co NPs confined within a spongy PC into Co(OH)2 NPs by simple H2O2 treatment under hydrothermal conditions. The as-prepared composite is referred as Co(OH)2@PC. This method avoids the conversion of Co(OH)2 into cobalt oxides during preparation of Co(OH)2/C. Moreover, the findings verify that the rational combination of porous carbon and nanoscale Co(OH)2 NPs endows Co(OH)2@PC with enhanced conductivity, improved Li+ diffusion coefficient, high capacitive contribution, stable structure and a LiF-rich SEI layer during cycle. As a result, the Co(OH)2@PC exhibits outstanding electrochemical performance, displaying 815.8 and 543.4 mAh g−1 after 120 cycles at 0.2 and 1.0 A g−1, respectively. This work may broaden the way for diversified design and structural optimization of Co(OH)2/C anodes of lithium-ion batteries.

The Green Synthesis of Nanostructured Silicon Carbides (SiCs) from Sugarcane Bagasse Ash (SCBA) as Anodes in Lithium-Ion (Li-Ion) Batteries: A Review Paper

Silicon is a promising anode material for the increased performance of lithium-ion batteries because of its high elemental composition and specific capacity. The application of silicon on a commercial scale is restricted due to the limitation of volume expansion. Silicon is also expensive, making it difficult for large-scale commercialisation. Different methods were used to address these issues, including a sintering process and the sol–gel method, to form silicon carbide (SiC), a hard chemical compound containing silicon and carbon. The silicon carbide anode not only acts as a buffer for volume expansion but also allows for better infiltration of the electrolyte, increasing charge and discharge capacity in the battery. Like silicon, silicon carbides can be costly. The development of renewable energy systems is very important, especially in the development of energy storage systems that are not only efficient but also cost-friendly. The cost of the energy storage devices is lowered, making them easily accessible. Silicon carbides can be synthesised from sugarcane, which is the fibrous waste that remains after juice extraction. This could be beneficial, as we could never run out of such a resource, and it offers low carbon with a high surface area. Silicon carbides can be synthesised by carbothermal reduction of silica from sugarcane bagasse. This review provides a comprehensive understanding of silicon carbides and synthetic processes. The innovative use of waste to synthesise materials would reduce costs and comply with Sustainable Development Goals (SDGs) 7 (affordable and clean energy) and 13 (climate action).

Tin nanoparticles decorated on banana-peel-derived carbon as a stable and high-rate-performance anode for lithium-ion batteries

Tin nanoparticles decorated on banana-peel-derived carbon as a stable and high-rate-performance anode for lithium-ion batteries

Construction of 2D/1D rGO/H2Ti3O7 composite as anode for high performance lithium-ion batteries

Ultrafine one-dimensional (1D) H2Ti3O7 nanowires were prepared by a hydrothermal reaction with high concentration of KOH as base source. Then 2D/1D rGO/H2Ti3O7 architecture was constructed and investigated as the anode material for lithium-ion batteries. Benefiting from the addition of rGO nanosheets and the retention of ultrafine 1D H2Ti3O7 nanowires, the rGO/H2Ti3O7 electrode presented superior electrochemical performance with excellent rate capability, long cycling stability and high capacity in half cells. It delivered high reversible capacities of 274 mAh g−1 at 0.1 A g−1 and 163 mAh g−1 at 1 A g−1, as well as a long-term cycling performance (259.3 mAh g−1 at 0.2 A g−1 after 1000 cycles). The excellent electrochemical performance of the composite can be attributed to the unique architecture with smaller diameter of 1D H2Ti3O7 nanowires and conductive rGO nanosheets to shorten the transmission distance of electrons and Li+ and improve the electrical conductivity in rGO/H2Ti3O7 composite.

Preparation and electrochemical properties of nitrogen-doped starch hard carbon anode materials for lithium-ion battery

Here, we report the synthesis of hard carbon materials (CSHs) made from corn starch and their application as an anode in lithium-ion batteries. The study shows that the microstructure and electrochemical properties of CSHs are affected by nitrogen doping. It is found that nitrogen is embedded in the carbon layer with graphite nitrogen, pyridyl nitrogen, and pyrrole nitrogen, so that the surface morphology was changed and reduced the disorder of the materials. The electrochemical test results show that the introduction of nitrogen elements can increase the reversible capacity of the material, with the first discharge capacity reaching above 426.35 mAh g−1, and the rate performance also improves. When melamine and pre-carbonized corn starch are carbonized at a mass ratio of 1:9, the obtained material has a reversible capacity of 122.04 mAh g−1 at a rate of 2 C. During the carbonization process, the nitrogen in melamine is doped into the carbon materials, improving the electrochemical performance of the material.