Anode Material For Lithium-ion Batteries Research Articles

Construction of High-Performance Anode of Potassium-Ion Batteries by Stripping Covalent Triazine Frameworks with Molten Salt.

Covalent triazine frameworks (CTFs) are promising battery electrodes owing to their designable functional groups, tunable pore sizes, and exceptional stability. However, their practical use is limited because of the difficulty in establishing stable ion adsorption/desorption sites. In this study, a melt-salt-stripping process utilizing molten trichloro iron (FeCl3) is used to delaminate the layer-stacked structure of fluorinated covalent triazine framework (FCTF) and generate iron-based ion storage active sites. This process increases the interlayer spacing and uniformly deposits iron-containing materials, enhancing electron and ion transport. The resultant melt-FeCl3-stripped FCTF (Fe@FCTF) shows excellent performance as a potassium ion battery with a high capacity of 447 mAh g-1 at 0.1 A g-1 and 257 mAh g-1 at 1.6 A g-1 and good cycling stability. Notably, molten-salt stripping is also effective in improving the CTF's Na+ and Li+ storage properties. A stepwise reaction mechanism of K/Na/Li chelation with C═N functional groups is proposed and verified by in situ X-ray diffraction testing (XRD), ex-situ X-ray photoelectron spectroscopy (XPS), and theoretical calculations, illustrating that pyrazines and iron coordination groups play the main roles in reacting with K+/Na+/Li+ cations. These results conclude that the Fe@FCTF is a suitable anode material for potassium-ion batteries (PIBs), sodium-ion batteries (SIBs), and lithium-ion batteries (LIBs).

Recent advances in Sb-based anodes for Li/Na/K-ion batteries and all-solid-state Li-ion batteries

In recent decades, lithium-ion batteries (LIBs) have emerged as a primary focus in the energy-storage field owing to their superior energy and power densities. However, concerns regarding the depletion of non-abundant lithium resources have prompted the exploration and development of emerging energy-storage technologies, such as sodium- (SIBs) and potassium-ion batteries (PIBs). In addition, all-solid-state LIBs (ASSLIBs) have been developed to address the issues of flammability and explosiveness associated with liquid electrolytes. Among the various alloy-based anodes, antimony (Sb) anodes exhibit high energy densities owing to their high theoretical volumetric capacities that are attributable to their high densities. However, Sb anodes exhibit poor cyclabilities owing to excessive volume changes during cycling. To mitigate this issue, researchers have investigated the use of diverse solutions, including solid electrolyte interface control, structural control, and composite/alloy formation. Herein, we review and summarize Sb-based anode materials for LIBs, SIBs, PIBs, and ASSLIBs developed over the past five years (2018-present), focusing on their reaction mechanisms and multiple approaches used to achieve optimal electrochemical performance. We anticipate that this review will provide a comprehensive database of Sb-based anodes for LIBs, SIBs, PIBs, and ASSLIBs, thereby advancing relevant studies in the energy-storage-systems field.

ZIF-8-derived ultrasmall ZnO nanoparticles embedded in porous carbon nanocage as anode material for lithium-ion batteries

ZIF-8-derived ultrasmall ZnO nanoparticles embedded in porous carbon nanocage as anode material for lithium-ion batteries

Thermal plasma synthesis of Si-multi walled carbon nanotube nanocomposite as an anode for lithium-ion batteries

The Si-MWCNT (multi-walled carbon nanotube) nanocomposite, which is considered a promising replacement for graphite as an anode material for lithium-ion batteries, was prepared using a triple DC thermal plasma jet system. We used micron-size silicon powder and MWCNT powder as raw materials. We varied the main parameters by mixing silicon and MWCNTs or individually injected into the plasma jet and adjusting the mass ratio to 2:1 and 1:2. The location of injection for the raw materials played a critical role in the formation of Si-MWCNT nanocomposites as the temperature at the injection site has a significant impact on the vaporization of silicon and sublimation of carbon nanotubes. Additionally, it was influenced by efficient heat transfer of silicon and the structural change of MWCNT. As a result, the Si-MWCNT nanocomposite was easily produced under separate injection conditions, and silicon nanoparticles of 20 nm or less were attached to the surface of the MWCNT. We evaluated the electrochemical performance of the synthesized material by assembling a CR2032-type coin cell using it as an anode electrode material.

Preparation of SiO2 nanotubes and nanoparticles in the presence of L-tartaric acid by sol-gel method and their electrochemical performance for Li-ion batteries

Recently, SiO2 has attracted increasing attention as an anode material for lithium-ion batteries (LIBs) owing to its low cost and high theoretical specific capacity. However, its inherent poor conductivity limits its practical application. To address this issue, nanostructured material design is considered an effective solution. Herein, based on the traditional ammonium tartrate template-directed sol-gel method, we use low-cost and easily available L-tartaric acid in place of D, L-tartaric acid to prepare high-yield silica nanotubes (SNTs) with a thin wall (ca. 50 nm), small diameter (ca. 150 nm), rough surface and open ends, as well as tiny spongy-like silica nanoparticles (SNPs) by adjusting the feeding amount and feeding mode of NH4OH solution. The electrochemical characterization results suggest that the SNTs show better cyclability and rate performance than the SNPs, which maintain a reversible capacity of 741.3 mAh g−1 after 500 cycles at a current density of 0.4 A g−1 and deliver a high rate capacity of 819.4 mAh g−1 at a high current rate of 2 A g−1. The excellent electrochemical performance suggests that hollow one-dimensional hollow nanotubes are more efficient in improving the electrochemical performance of SiO2 than zero-dimensional nanoparticles, and SNTs with thin tube walls and rough surfaces are demonstrated to be fascinating and promising anode materials for LIBs.

The first-principles study of 2D monolayer T-Mo2C as promising anode material for Lithium-ion Batteries

The growing demand for renewable energy technologies emphasizes the necessity for advancements in anode materials to enhance the performance of lithium-ion batteries (LIBs). In this research, we employ first-principles calculations to investigate the properties of a T-Mo2C monolayer proposed as an anode material. Phonon dispersion calculations and ab initio molecular dynamics (AIMD) simulations are conducted to assess the dynamical stability and thermal characteristics of the T-Mo2C monolayer as an anode material. Remarkably low diffusion barriers of 0.029 eV (Li) and 0.01 eV (Na and K) have been identified, facilitating rapid ion mobility. Furthermore, a monolayer of metal ions (M = Li, Na, K) absorbed onto T-Mo2C is explored, revealing a high specific capacity of approximately 1314.37 mAh/g (Li), 262.87 mAh/g (Na), and 32.85 mAh/g (K). The average open circuit voltage is determined to be 0.08 V (Li), 0.68 V (Na), and 2.59 V (K). This research provides a comprehensive overview of T-Mo2C monolayer as a high-capacity anode material, emphasizing its significant contributions to advancing energy storage systems, particularly in the context of LIBs. The findings presented here pave the way for the development of efficient and sustainable energy storage solutions to meet the escalating demands of the renewable energy landscape.

Synthesizing Si/SiOC composites through different sol-gel reaction routes for lithium-ion battery anode materials

Silicon oxycarbide (SiOC) exhibits good retention and a reasonable specific capacity and is an alternative to silicon used as an anode material for high-performance lithium-ion batteries. However, SiOC generally shows a low Initial Coulombic Efficiency (ICE), wasting the lithium from the cathode. This work explores different sol-gel routes to synthesize SiOC from silanes and compares their performance. We found that the crushed bulk acid-catalyzed SiOC is simple and cost-effective but with excellent performance. Adding dimethyldimethoxysilane (DMDMS) by decreasing the oxygen content further enhances the battery performance. Building upon the excellent performance of SiOC, we further embed nano-silicon into SiOC. The Si/SiOC composites achieved a significantly higher specific capacity of 2185 mAhg−1 and an impressive ICE of 77 % with acceptable battery retention.

Encapsulating Antimony metal nanoparticles in hierarchical porous carbon skeleton as high-performance potassium- and lithium-ion batteries anodes

Metallic antimony (Sb) as alkaline metal battery anode material, being thoroughly researched for its high theoretical specific capacity, but there is still a huge expansion problem with repeated insertion/de-insertion., We reported a unique composite material that encapsulates Sb nanoparticles in hierarchical porous carbon skeletons (Sb@HPCs) in this work, to explore the effect of the hierarchical porous carbon structure on the electrochemical performance of the Sb@HPCs as potassium-ion batteries (KIBs) and lithium-ion batteries (LIBs) anode materials. The macropores could promote the penetration of electrolyte, thus reducing the internal impedance of the battery. The mesopores provide a short ion diffusion path and a large diffusion region, which plays a crucial role in facilitating rapid ionic migration in both KIBs and LIBs. The micropores in the electrode material contribute to a larger specific surface area, which provides more surface area for charge storage, thus enhancing the energy density of the material. Importantly, when the Sb@HPCs composite material is applied as anode material of KIBs, it exhibits an outstanding specific capacity of 360 mAh g−1 after 100 cycles at 100 mA g−1. In the LIBs, the specific capacity of the composite material is 595.2mAh g−1 after 100 cycles at a current density of 0.1 A g−1; even at a high current density of 1.0 A g−1, the specific capacity still maintains at 320.4 mAh g−1 after 800 cycles, indicating an excellent cycling stability. The development of hierarchical porous three-dimensional structure offers a practical solution to the capacity degradation issues of metal anode in KIBs/LIBs.

Enhanced reversible reaction of hexagonal SnS2@rGO as anode materials for lithium-ion batteries: Analysis of the morphological change mechanism

Tin-based materials have attracted attention as a promising anode material for lithium-ion batteries due to their high theoretical capacity and alloy metal characteristics. However, the structure tends to easily collapse with repetitive charging and discharging processes, leading to volume expansion. The conversion step in the SnS2 reaction mechanism is also sometimes considered irreversible. To address these challenges, this study synthesized layered hexagonal 2D structure-type SnS2 using the oleylamine as surfactant through a wet chemical process. Subsequently, SnS2@rGO was synthesized after compounding with reduced graphene oxide (rGO), utilizing a smaller amount of nanomaterials compared to rGO, showing optimal efficiency. The morphological changes in SnS2 and SnS2@rGO during the charging and discharging processes was revealed that pulverization occurred more slowly in SnS2@rGO compared to SnS2. We quantified the volume expansion rates of SnS2 and SnS2@rGO electrodes, demonstrating that rGO effectively reduces volume expansion. Additionally, an analysis of lithiation mechanism through a comprehensive analysis method using CV, ex-situ XRD, and ex-situ TEM demonstrated that SnS2@rGO enhanced Li+ storage characteristics compared to SnS2, resulting in more reversible chemical changes. rGO and bare SnS2 show poor capacities 307.23 mAh/g and 87.17 mAh/g after 120 cycles, respectively. However bare SnS2 anchored on the surface of rGO exhibits increased electrical conductivity and improved performance (711 mAh/g after 120 cycles), confirming that rGO plays an important role. SnS2@rGO showed enhanced cycling stability and discharge capacity as shown in the electrochemical testing.

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

As green anode materials with wide distribution, controllable cost, and diversified structure, carbon materials have received more attention. In this paper, iodine- and nitrogen-co-doped carbon flower materials were prepared. The flower-like structure of the material ensures the rapid diffusion of lithium ions, and the synergistic effect of iodine and nitrogen atoms improves the pore size distribution, the conductivity and the active sites of carbon materials realizing the high ion storage and the fast charge diffusion. As the anode material of lithium-ion batteries, the iodine- and nitrogen-co-doped carbon flower could have the capacitance of 410 mAh g[Formula: see text] at the current density of 0.1 A g[Formula: see text] after 150 cycles and 181 mAh g[Formula: see text] at the high current density of 2.0 A g[Formula: see text] after 1000 cycles. The results of electrochemical impedance spectroscopy, kinetics, and GITT show this material has fast charge transport kinetics and excellent rate performance.

In situ steam oxidation of nickel phosphide/carbon composite nanofibers as anode materials for lithium-ion batteries

The synthesis of self-standing nickel phosphide/carbon (NixP/C) composite nanofibers is accomplished through a one-pot electrospinning and in situ steam oxidation after the carbothermal reduction process. Control over the levels of in situ steam oxidizers in the forms of crystal water and nitrates in the precursor fibers is achieved by systematically adjusting the drying temperature before the high-temperature heat treatment. This led to structural modifications in the final products analyzed through comprehensive characterizations. Mechanistic insights into the in situ steam oxidation process are provided, emphasizing its potential in optimizing electrode materials. Electrochemical assessments reveal significantly improved performance in the sample prepared from the media with optimal content of oxidizers, attributed to a tailored surface oxide layer, electronic configuration, and microstructure, enabling enhanced reaction kinetics and minimizing volume expansion. This results in exceptional cycling stability and notable capacity retention during prolonged charge-discharge cycles. Thus, NixP/C achieves the highest initial charge capacity of 719.5 mAh g−1 with an initial Coulombic efficiency of 61% and maintains a high capacity of 590.7 mAh g−1 after 100 cycles at a current density of 0.1 A g−1.

Spontaneous Electrochemical Reconstruction of NiNb2O6@C for High-Rate Lithium-Ion Batteries

Niobium oxides are widely active in the arena of lithium-ion batteries due to their distinctive structure and rapid charging capability, nevertheless facing the serious challenge from their inherently low electrical conductivity. Herein, a molten salt method is proposed to prepare nickel niobate (NiNb2O6) anode materials for lithium-ion batteries, and a carbon coating derived from mesophase pitch is fabricated to construct NiNb2O6@C composites. Importantly, NiNb2O6@C undergoes spontaneous electrochemical reconstruction to generate metallic Ni and amorphous Nb2O5 during the initial charge/discharge cycle. The presence of the outer carbon layer not only serves as a uniform conductive coating to improve the conductivity and thereby deliver superior rate performance, but also effectively inhibits the stripping of Ni0 to guarantee a great cycling stability. The synergistic effects of the dual conductive interfaces, consisting of the carbon layer and the Mott-Schottky heterojunction between amorphous Nb2O5 and metallic Ni, culminate in exceptional electrochemical performance. Specifically, NiNb2O6@C-10% delivers impressive specific capacity of 436.3 mAh g−1 at 0.5C and conspicuous cycling stability, maintaining 86.3% capacity retention after 800 cycles at 10C. This work underscores the substantial potential of nickel niobate anode materials in advancing the development of next-generation lithium-ion batteries.

Elucidating the role of embedding dispersed cobalt sites in nitrogen-doped carbon frameworks in Si-based anodes for stable and superior storage

Unsatisfactory conductivity and volume effects have hindered the commercial application of silicon-based materials as advanced anode materials for high-performance lithium-ion batteries. Herein, nitrogen doped carbon silicon matrix composite with atomically dispersed Co sites (Si/Co-N-C) is obtained via the design of the frame structure loaded with nano-components and the multi-element hybrid strategy. Co atoms are uniformly fixed to the N-C frame and tightly packed with nanoscale silicon particles as an activation and protection building block. The mechanism of the N-C framework of loaded metal Co in the Si alloying process is revealed by electrochemical kinetic analysis and ex situ characterization tests. Impressively, the nitrogen-doped Co site activates the intercalation of the outer carbon matrix to supplement the additional capacity. The Co nanoparticles with high conductivity and support enhance the conductivity and structural stability of the composite, accelerating the Li+/Na+ diffusion kinetics. Density functional theory (DFT) calculation confirms that the hetero-structure Si/Co-N-C adjusts the electronic structure to obtain good lithium-ion adsorption energy, reduces the Li+/Na+ migration energy barrier. This work provides meaningful guidance for the development of high-performance metal/non-metal modified anode materials.

Topological Transformation of Hydrogen-Terminated Germanium to Germanium Nanosheets for Fast Lithium Storage.

Germanium has been recognized as a promising anode material for lithium-ion batteries (LIBs) due to its high theoretical capacity and excellent lithium-ion diffusivity. Nonetheless, it is challenging to enhance both the high-rate performance and long-term cycling stability simultaneously. This study introduces a novel heterostructure composed of germanium nanosheets integrated with graphene (Ge NSs@Gr). These nanosheets undergo an in situ phase transformation from a hydrogen-terminated multilayer germanium compound termed germanane (GeH) derived via topochemical deintercalation from CaGe2. This approach mitigates oxidation and prevents restacking by functionalizing the exfoliated germanane with octadecenoic organic molecules. The resultant germanium nanosheets retain their structural integrity from CaGe2 and present an exposed, active (111) surface that features an open crystal lattice, facilitating swift lithium-ion migration conducive to lithium storage. The composite material delivers a substantial reversible capacity of 1220 mA h g-1 at a current density of 0.2 C and maintains a capacity of 456 mA h g-1 even at an ultrahigh current density of 10 C over extended cycling. Impressively, a capacity of 316 mA h g-1 remains after 5000 cycles. The exceptional high-rate performance and durable cycling stability underscore the Ge NSs@Gr anode's potential as a highly viable option for LIBs.

Si@porous carbon fiber fabricated via wet spinning as a high-performance anode material for lithium-ion battery

Si/C composites are considered as attractive anode candidates for high-energy-density lithium-ion batteries and have been extensively researched. The carbon fiber (CF) fabricated by wet spinning is a well-established technology. However, there are scarce reports on Si/CF anodes fabricated by wet spinning. In this study, Si@porous carbon fiber (Si@PCF) composite were synthesized via wet spinning and subsequent thermal treatment. The porous carbon (PC) can effectively buffer the huge volume changes of Si nanoparticles during the charge-discharge process, promote the diffusion and transport of lithium ions, and compensate for the poor electronic conductivity of Si. The Si@PCF composite maintained a high capacity of 1178 mA h g−1 at 0.5 A g−1 after 100 cycles, suggesting potential for commercial application of the Si/PCF anode due to the excellent electrochemical performance and preparation technology suitable for large-scale production.

TPO12-graphene: A new two-dimensional metallic carbon with 4–5 ring for Lithium ion battery

For many decades, the stability of two-dimensional carbon structures involving connected 4–5 ring remained speculative. Recently, some of the planar carbon structures with connected 4–5 ring have showcased possible stability. In this work we present a new 4–5 ring carbon structure, belonging to Pmmm space group, having additional octagonal and dodecagonal rings to fill the space. The stability of this structure has been ensured in terms of its dynamical, thermal and mechanical stability. The electronic structure indicates that it is a non-magnetic metallic material. Moreover, the Fermi surface points to distinct electron and hole pockets in the first Brillouin zone. The quantum capacitance of the material suggests its use as anode in asymmetric supercapacitors. Besides its low optical absorption in visible range, its potential as an anode material for lithium-ion batteries is worth exploring. The storage capacity results of 558 mAh/g for the new material may be encouraging for its application as a lithium-ion battery anode material.

Mesoporous carbon hollow spheres with controllable pore structure for efficient lithium and aluminum ion storage

Mesoporous carbon hollow nanospheres (MCHS), synthesized via a block copolymer-mediated supramolecular self-assembly process, serve as both anode materials for lithium-ion batteries (LIBs) and cathode materials for aluminum-ion batteries (AIBs). By adjusting the carbonization temperature and the dosage of the pore extender, 1,3,5-trimethylbenzene (TMB), insights into the relationships among pore structure, crystal structure, and electrochemical properties of MCHS in Li/Al-ion batteries are gained. Their exceptional properties, including hierarchically porous structure, large surface area, tailored inner voids, mesoporous shells, and high electronic conductivity, contribute to high specific capacity, improved rate performances, and remarkable electrochemical stability. Crystallographic insights reveal that highly porous MCHS facilitate the intercalation of ionic lithium and aluminum species into the carbon crystal lattices while maintaining structural integrity. The appropriate mesopore size significantly impacts the storage of lithium or aluminum ions, with relatively larger mesopore sizes being more beneficial for aluminum ion storage compared to lithium ions. The optimal MCHS exhibit a stable discharge specific capacity of 330.8 mAh·g−1 after 800 cycles at a current density of 372 mA·g−1 (1C) in LIBs and 41.6 mAh·g−1 after 500 cycles at 74.4 mA·g−1 in AIBs.

Effects of cation substitution effects of dicarboxylic acid for energy storage applications

Organic materials (OMs) can accept alkali ions and function as energy storage systems, displaying several advantages such as low cost, ease of synthesis, and utilization of recyclable materials. Owing to their higher theoretical capacity, OMs exhibit a higher energy density, cheaper price, and easy recover than those of inorganic materials such as graphite, silicon, and metal oxides, respectively. This study reports the use of potassium 4-oxo-4H-pyran-2,6-dicarboxylic acid (K2CDA) and potassium 4-oxo-4H-pyran-2,6-dicarboxylic acid (K2CDO) as anode materials for potassium-ion batteries (KIBs) and lithium-ion batteries (LIBs). Although they share similar lightweight, carbonyl, and carboxylate functional groups, both materials display distinct reaction behaviors owing to differences in electronegative heteroatoms N and O. In this study, two alkaline salts (KFSI and LiFSI) have been discussed on the substitution effect of doping/ de-doping processes. K2CDA and K2CDO. Consequently, after 200 cycles, the K2CDA anodes deliver capacities of 310 (KFSI) and 485 (LiFSI) mAh g−1, respectively, at 0.1 C. The larger size of K+ compared with Li+ negatively impacts the performance of K2CDA. A similar trend is observed in the case of K2CDO in capacities of 220 (KFSI) and 405 mAh g‒1 (LiFSI), with 1.5 and 2.86 K+ ions participated in the corresponding redox reactions on the Fourier-transfer infrared spectroscopy analysis. The presence of N‒H in the K2CDA structure contributes to its superior performance and rate capability compared with K2CDO. In addition to the cation effect, the structural differences between K2CDA and K2CDO also influence their electrochemical activity.

Fabrication of heteroatom-doped cobalt oxide yolk–shell microsphere using recycled solution from waste materials and their excellent electrochemical properties as an anode material for lithium-ion batteries

Fabrication of heteroatom-doped cobalt oxide yolk–shell microsphere using recycled solution from waste materials and their excellent electrochemical properties as an anode material for lithium-ion batteries

Ice template-induced assembly coupled with carbonization strategy for preparation of sulfur-doped porous carbon nanosheets from lignite as high-capacity anode for lithium-ion batteries

Two-dimensional (2D) porous carbon nanosheets with heteroatom doping are promising anode materials for lithium-ion batteries (LIBs) due to their distinctive sheet-like structure and excellent electrical conductivity. Limited by high preparation costs and cumbersome preparation processes, the large-scale production of carbon nanosheets remains a major challenge. Herein, a series of sulfur-doped porous carbon nanosheets (SCNSs) are successfully synthesized through ice template-induced assembly coupled with a carbonization approach using aromatic ring fragments exfoliating from lignite as the precursor and K2SO4 as the sulfur source. The prepared SCNSs exhibit well-defined sheet-like structures, abundant hierarchical nanopores, large specific surface areas (∼1761 m2·g−1), and high sulfur doping contents (∼7.72 at%). Such unique microstructure characteristics of SCNSs not only provide favorable and efficient channels for the lithium-ions/electrons transportation but also offer sufficient available space or active sites for lithium-ions storage. When used as anode materials for LIBs, the SCNS-3 shows high reversible capacity (1620 mAh·g−1 at 0.05 A·g−1), excellent rate performance (315 mAh·g−1 at 2 A·g−1), and superior cycling stability (901 mAh·g−1 at 1 A·g−1 after 500 cycles). Lithium storage behavior analysis indicated that the capacitance enhancement in SCNSs anodes is primarily due to improved capacitive behavior. This study provides a novel and effective route for the large-scale production of sulfur-doped carbon nanosheets using aromatic ring fragments exfoliated from lignite, which demonstrates promising industrial application potential in LIBs anode materials.