Promising Anode Material For Lithium-ion Batteries Research Articles

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.

Empowering lithium-ion batteries: The potential of 2D o-Al2N2 as an exceptional anode material through DFT analysis

Finding an appropriate new anode material with high electrochemical performance for lithium-ion batteries (LIBs) is considered one of the significant challenges for both the academic and industrial research communities. Herein, we propose to explore the efficiency of a newly designed two-dimensional (2D) material, named orthorhombic dialuminium dinitride (o-Al2N2), as an alternative anode material for LIB systems through first-principles calculations and ab initio molecular dynamics (AIMD) simulations. The obtained results show that orthorhombic-Al2N2 exhibits a high specific capacity of 1144.2913 mAhg−1, an operating voltage around 0.575 V, and a low kinetic diffusion barrier of 0.26 eV. These results prove the suitability of the o-Al2N2 monolayer as a promising anode material for LIBs with high structural stability, strong binding energy towards lithium adsorbent, fast lithium diffusion, and a high theoretical capacity. These features rank the 2D o-Al2N2 monolayer among the best choices for the anode part of the next-generation rechargeable LIBs.

First-principles prediction of one-dimensional conductive metallic organic polymers as ultrahigh energy density anode for lithium-ion batteries.

Metal-Organic Polymers (MOPs) have attracted growing attention for lithium-ion battery (LIB) applications due to their merits in orderly ionic transportation and robust structure stability in electrochemical reactions. However, they suffer from poor electronic conductivity. In this work, we apply first-principles density functional theory to explore the potential of three one-dimensional (1D) electrically conductive C6H2S4TM (TM = Fe, Co, and Ni) MOPs with the π-d conjugated coordination as anode materials for Li+ ions storage. Our theoretical results reveal that these 1D MOPs possess a superior theoretical capacity of over 748 mA h g-1. In particular, the 1D C6H2S4Ni MOP shows an exceptional theoretical specific capacity of 1110 mA h g-1 based on the three-electron transferring reaction, which significantly outperforms the traditional graphite-based anode material in LIBs. Moreover, the resonant charge transfer between Ni metal and ligand within the 1D C6H2S4Ni MOP reduces the diffusion energy barrier of the Li atoms when they migrate on the surface of the MOP. The ultrahigh theoretical specific capacity of the C6H2S4Ni MOP predicts that it can be a promising anode material for LIBs.

3D porous structure Fe3O4@SnO2/MXene composites with enhanced electrochemical performance for lithium ion battery anode

The low theoretical capacity of the commercial graphite electrodes used in lithium-ion batteries (LIBs) necessitates the development of novel anode materials with higher rate performance, reversible specific capacities, long cycle lives, and low costs. In this work, three-dimensional porous structure Fe3O4 nanosphere with extremely thin SnO2 coatings are prepared by a method of getting twice the result with half the effort. And it was uniformly dispersed in an MXene flexible conductive matrix to fabricate a 3D porous heterogeneous Fe3O4@SnO2/MXene composite to act as an anode material for LIBs. The 3D porous heterojunction structure integrates the advantages of Fe3O4@SnO2 and MXene, achieving rapid electron and ion transport at the interface and the effective release of structural stress. The introduction of MXene markedly enhances the conductibility of the materials, limits the expansion of Fe3O4 during the Li+ insertion/removal process, and inhibits its aggregation. The Fe3O4@SnO2/MXene anode exhibits excellent electrochemical performance (1609 mAh g−1 over 200 cycles at 100 mA g−1 and 626.1 mAh g−1 over 900 cycles at 1000 mA g−1). These findings demonstrate that the Fe3O4@SnO2/MXene composite is a promising anode material for LIBs.

High-Performance Li-Organic Batteries Based on Conjugated and Nonconjugated Schiff-Base Polymer Anode Materials.

In recent years, organic materials have been increasingly studied as anode materials in lithium-ion batteries (LIBs) due to their remarkable advantages, including abundant raw materials, low prices, diverse structures, and high theoretical capacity. In this paper, three types of aromatic Schiff-base polymer materials have been synthesized and examined as anode materials in LIBs. Among them, the polymer [C6H4N = CHC6H4CH=N]n (TTD-PDA) has a continuous conjugated backbone (label as conjugated polymer), while polymers [(CH2)2N=CHC6H4CH=N]n (TTD-EDA) and [C6H4N=CH(CH2)3CH=N]n (GA-PDA) have discontinuous conjugated back-bones (label as nonconjugated polymer). The organic anodes based on TTD-PDA, TTD-EDA, and GA-PDA for LIBs are discovered to represent high reversible specific capacities of 651, 492, and 416 mAh g-1 at a current density of 100 mA g-1 as well as satisfactory rate capabilities with high capacities of 210, 90, and 178 mAh g-1 and 105, 57, and 122 mAh g-1 at current densities of 2 and 10 A g-1, indicating that these Schiff-base polymers are all promising anode materials for LIBs, which broadens the design of organic anode materials with high specific capacity, superior rate performance, and stable cycling stability.

Phosphorus-doped TiO2 mesoporous nanocrystals for anodes in high-current-rate lithium ion batteries

Limited by the intrinsic low electronic conductivity and inferior electrode kinetics, the use of TiO2 as an anode material for lithium ion batteries (LIBs) is hampered. Nanoscale surface-engineering strategies of morphology control and particle size reduction have been devoted to increase the lithium storage performances. It is found that the ultrafine nanocrystal with mesoporous framework plays a crucial role in achieving the excellent electrochemical performances due to the surface area effect. Herein, a promising anode material for LIBs consisting of phosphorus-doped TiO2 mesoporous nanocrystals (P-TMC) with ultrafine size of 2–8 nm and high specific surface area (234.164 m2 g–1) has been synthesized. It is formed through a hydrothermal process and NaBH4 assisted heat treatment for anatase defective TiO2 (TiO2–x) formation followed by a simple gas phosphorylation process in a low-cost reactor for P-doping. Due to the merits of the large specific surface area for providing more reaction sites for Li+ ions to increase the storage capacity and the presence of oxygen vacancies and P-doping for enhancing material’s electronic conductivity and diffusion coefficient of ions, the as-designed P-TMC can display improved electrochemical properties. As a LIB anode, it can deliver a high reversible discharge capacity of 187 mAh g–1 at 0.2 C and a good long cycling performance with ∼82.6% capacity retention (101 mAh g–1) after 2500 cycles at 10 C with an average capacity loss of only 0.007% per cycle. Impressively, even the current rate increases to 100 times of the original rate, a satisfactory capacity of 104 mAh g−1 can be delivered, displaying good rate capacity. These results suggest the P-TMC a viable choice for application as an anode material in LIB applications. Also, the strategy in this work can be easily extended to the design of other high-performance electrode materials with P-doping for energy storage.

In-situ construction of Ti3C2TX/Ni-HHTP heterostructure as anode for lithium-ion batteries

Pursuing anode materials with high specific capacity and long cycle stability is critical for advanced lithium-ion batteries (LIBs). Metal-organic frameworks (MOFs) with high specific surface area, regular pore channels, and multiple active sites are promising anode materials for LIBs. However, the poor electronic conductivity limits their application in LIBs. Thus, introducing some conducting materials is necessary. MXene, known for its excellent electronic conductivity in electrochemical energy storage systems, is an ideal candidate. Herein, a heterostructure composite material (Ti3C2TX/Ni-HHTP) that combines the advantages of both MOFs and MXene has been synthesized via an in-situ growth method, the composite exhibits regular pore channels, enhanced electronic conductivity, and excellent stability. When it is used as an anode material in LIBs, the composite presents satisfying rate performance and cycling stability. The initial discharge capacity of the Ti3C2TX/Ni-HHTP electrode exhibits 424.4 mA h g−1 at 0.5 A g−1 and remains at 390.2 mA h g−1 after 800 cycles with a capacity retention rate of 92.0%. This design strategy provides valuable insights into constructing MOF hybrid materials with enhanced electronic conductivity for various electrochemical applications.

Synergistic Engineering of Architecture and Composition in Bimetallic Selenide@Carbon Hybrid Nanotubes for Enhanced Lithium‐ and Sodium‐Ion Batteries

AbstractDeveloping sustainable and affordable anode materials that are capable of delivering high performance in both lithium‐ion batteries (LIBs) and sodium‐ion batteries (SIBs) remains a significant challenge. Bimetallic selenide@carbon hybrids are considered as one of the most promising anode materials in LIBs and SIBs due to their high electronic conductivity, high specific capacity, and fast reaction kinetics. Herein, a series of bimetallic selenide@carbon hybrid nanotubes are successfully prepared as anodes of LIBs or SIBs based on the dual regulation of component and micro‐nanostructure. The selenization strategy plays a key important role in determining the composition, microstructure, and electrochemical energy storage properties of anode materials. As a consequence, the ZnSe/CoSe2@NPC NTs(I)‐600 exhibit a reversible capacity of 1328.3 mAh g−1 at 0.1 A g−1 and superior rate capability (269.1 mAh g−1 at 10 A g−1) towards Li+ storage. Meanwhile, ZnSe/CoSe2@NPC NTs(II)‐700 achieve 354.1 mAh g−1 at 0.1 A g−1 and ultralong cycling stability (97.6% of capacity retention after 40 000 cycles at 10 A g−1) used as anode materials in SIBs. This study provides a feasible strategy to fabricate selenide‐based composites as anode materials for high‐performance LIBs and SIBs via architecture engineering and composition tailoring.

Lithium-ion insertion properties of one-dimensional layered rhenium phosphide

Metal phosphides have aroused great interest among the electrochemical community due to their stunning performance, including good electrical conductivity, high theoretical capacity, and considerable cycling stability. In this work, we synthesized and utilized Re6P13 for the first time as a promising anode material for lithium-ion batteries (LIBs). High-purity Re6P13 needle-like crystals were successfully grown by a chemical vapor transport method. Surface modification of Re6P13 by conductive carbon results in Re6P13 @C composite electrode, exhibiting a high specific capacity of 1265 mAh g−1 at 0.1 A g−1. The calculated band structure of Re6P13 reveals a highly symmetric point path that is beneficial for achieving high electrical conductivity and good structural flexibility. These features further empower the Re6P13 @C composite anodes with good cycling life (775 mAh g−1 at 1 A g−1 after 100 cycles) and rate performance (558 mAh g−1 at 20 A g−1). This work suggests that Re6P13 compounds with needle-like structures are promising anode materials for LIBs.

Graphene aerogel encapsulated Co3O4 open-ended microcage anode with enhanced performance for lithium-ion batteries

Prussian blue analogues are receiving a great deal of attention on the field of energy storage materials. They can provide abundant active sites for the diffusion of various ions and their stable framework structure brings excellent cycling stability to the electrode. Despite this, their worse capacity retention and cycle life and the complexity of their electrochemical reaction mechanisms restrict their practical applications as the anode of lithium-ion batteries (LIBs) seriously. In this work, graphene aerogel encapsulated Co3O4 open-ended microcage (Co3O4 microcages@GA) is synthesized via simply etching and hydrothermal methods. While applied as the anode for LIBs, the reversible capacity remained at 1439 mAh/g after 200 cycles (1 A/g), furthermore, even at a high current density of 10 A/g, the samples still reached a great capacity of 575.2 mAh/g. The excellent electrochemical performance may be attributed to the enhancing conductivity of the material by the addition of graphene aerogel. Moreover, the enlarged surface area provided by the hollow cage structure also increases the reactive active sites, which is conducive to improving the reaction kinetics of the material so as to speed up the reaction and make the reaction more complete. The simple preparation method and the synergistic effect of reduced graphene oxide(rGO) and open-ended microcage structure give the material an ultra-high capacity retention rate and stability. Thus, Co3O4 microcages@GA has the potential as a promising anode material for LIBs.

Semi-hydrogenated SiB: A promising anode material for lithium-ion and sodium-ion batteries

Design and development of new high-performance electrode materials are of great importance to improve the energy density in energy storage devices such as lithium-ion batteries (LIBs), and sodium-ion batteries (NIBs). In this work, we introduce semi hydrogenated SiB (H-SiB) as an effective anode material for LIBs and NIBs using first-principles calculations. The electronic properties of H-SiB indicate semiconducting behavior before lithiation and metallic behavior after lithiation. A theoretical capacity of 1343 and 671.7 mAh.g−1is predicted for LIBs and NIBs, respectively, which proves that H-SiB can be an incredible electrode material among 2D materials. Meanwhile, the calculated low diffusion barrier heights in combination with low open-circuit voltages and enhanced electronic conductivity after Li/Na ions intercalation processes confirm a remarkably beneficial effect on the rate of charging and discharging process in H-SiB based batteries. Our findings reveal that Li/Na ions on the H-SiB surface (300–500 K) can be stable and diffuse freely, the signature of the ultra-fast Li ion diffusivity on the substrate. These results altogether suggest that the H-SiB as a flexible electrode could be a promising anode material for LIBs.

Rational Construction of Self‐Standing Layered Polyhedral Co3O4/CoS2 Heterostructure Materials Boosting Superior Lithium Storage Performance

AbstractThe increasing demands of electric vehicles and portable electronics have stimulated enhanced investigations on lithium‐ion batteries (LIBs) with high capacity, increased rate capability, and long cycle stability. Transition metal oxides (TMOs) are regarded as the most promising anode materials for LIBs due to their higher theoretical capacity. However, the low conductivity and poor rate‐capability of the TMOs have seriously restricted their further development in the LIBs. Herein, layered polyhedral cobalt oxide (Co3O4)/cobalt disulifde (CoS2) with heterostructure is directly grown on carbon cloth (CC) via a facile hydrothermal method and one‐step sulfuration process for use as an anode. The heterostructures can effectively enhance the charge transfer capability due to the interfacial effect between Co3O4 and CoS2. Due to the decrease of the diffusion barrier on the nanocrystalline surface, the electrical conductivity of the material is significantly increased, the ionic diffusion resistance is significantly reduced, and the interface electron transfer increases. The Co3O4/CoS2//CC can deliver a high capacity (1545.8 mAh g−1 at 2 A g−1) and outstanding cycling life (493 mAh g−1 after 300 cycles). This method provides a new idea and choice for the application of heterogeneous anode materials for LIBs.

NiO/nitrogen-oxygen co-doped carbon nanoflower composites based on covalent organic frameworks for lithium-ion battery anodes

Designing novel NiO/porous carbon nanocomposites is an effective strategy to improve poor conductivity and rapid capacity fading of NiO in lithium-ion batteries (LIBs). Covalent organic frameworks (COFs) are attractive materials for LIBs as they have large specific surface areas, well-ordered structure, and controllable pore size. Here, we designed a COFTpPa nanoflower as templates for the preparation of porous carbon and a carrier for NiO to obtain NiO/nitrogen-oxygen co-doped carbon nanoflower (NiO/NCF) composites. NiO nanostructures have a smaller volume effect, and the coating of carbon nanoflowers can further buffer the volume expansion of NiO nanostructures, which effectively slow down the capacity decay. In addition, the NCF derived from COFTpPa provide a larger specific surface area and more pores, which not only increases the capacity of nanocomposites but also improves the electrical conductivity of the electrodes. When applied to the anode of LIBs, NCF and NiO/NCF exhibit excellent performance (with first-cycle capacities of 1038.2 and 1685.9 mAh g−1, respectively, and high first coulomb efficiencies of 61.5 % and 60.9 %, respectively). The designed NiO/NCF nanocomposites is a promising anode material for LIBs.

Carbon-based materials and their composites as anodes: A review on lithium-ion batteries

Nowadays, providing powerful and green energy sources is one of the main challenges for a cleaner environment. Rechargeable lithium-ion batteries (LIBs), as effective energy storage devices, have gained lots of attention because of their relatively low self-discharge rate, high energy density, and rapid response. Since the efficiency of LIBs is significantly dependent on electrode materials; attention has been paid to the design of various electrodes.  carbon materials with their special structural, electrical, and mechanical properties are considered promising anode materials in LIBs. However, more research is still needed to identify suitable carbonaceous materials to improve the properties of anodes. In this regard, transition metals and silicon as high-capacity anodes can combine with carbon to develop LIBs. In this review, the employed carbonaceous materials and their composites as well as their outlook for LIB anodes have been investigated.

Ultrafast Lithium‐Ion Batteries with Long‐Term Cycling Performance Based on Titanium Carbide/3D Interconnected Porous Carbon

AbstractCarbon‐based materials are a new class of highly conductive materials that have shown cutting‐edge performance in energy storage. However, the lack of a rational design for three‐dimensional (3D) structures continues to limit its performance in lithium‐ion batteries (LIBs). Herein, we report a 3D layered titanium carbide (TiC) prepared by a facile one‐pot carbonization treatment. This as‐prepared TiC anode has unique continuous 3D architecture, embedded with nanodots and surface oxygenated defects that can provide fast electron and ionic transportation, as well as multiple electrochemical sites for the intercalation/deintercalation of lithium ions in LIBs, resulting in fast rate capability and excellent cycle life of LIBs, for instance, the LIBs consisting of 3D TiC exhibits a specific capacity of 225 mAh g−1 at 10 A g−1 after 10,000 cycles with a capacity retention of 95%. Our findings reinvent carbon‐based materials, specifically TiC, as promising anode materials for LIBs.

One-pot synthesis of MnO-loaded mildly expanded graphite composites as high-performance lithium-ion battery anode materials

Improving the properties of conventional graphite anode materials has been an important research topic for enhancing the performances of lithium-ion batteries (LIBs). Herein, we develop a facile one-pot approach to mildly expand graphite (MEG) and simultaneously load MnO onto the as-prepared MEG to synthesize MnO@MEG composites as high-performance anode materials for LIBs. With the improved porous structure and electrical conduction network, both the MEG and MnO components of the composite exhibit well-defined electrochemical properties and alleviated volume changes upon charge/discharge, synergistically enhancing the electrochemical performances for our composites. With a high active material content and high mass loading for the testing electrode, the optimized MnO@MEG composite shows a high capacity (437.77 mAh g−1 at 0.1 C), a high rate capability (capacity retains 71.93% at 1 C vs. 0.1 C), and a high cycling stability (capacity retains 73.17% and 68.13% after charge/discharge at 0.5 C and 1 C, respectively, for 50 cycles), significantly outperforming its pristine graphite counterpart and previously reported similar MnO composites with other carbon materials, thereby standing for a practically promising anode material for LIBs. Broadly, the one-pot approach developed in the present work can be extended for producing other graphite-based composites for other energy-related technologies.

Submicro-sized and partially etched V2AlxCTz as an anode for lithium-ion storage

Vanadium-based MXenes are prospective as anode materials in energy-storage devices including lithium-ion batteries (LIBs) but limited by their charge-discharge capacities. Herein, partially-etched V2AlxCTz with the average particle size of ~400 nm was synthesized using 40 wt% HF or mixed NaF+HCl solutions as etchants, respectively. V2AlxCTz etched by 40 wt% HF for 96 h at room temperature (RT) has more exceptional charge-discharge performances against mixed NaF+HCl solutions, with an average reversible capacity of ~450 mAh g−1 at 0.1 A g−1 in the 120 cycles and ~301.2 mAh g−1 at 0.5 A g−1 after 200 cycles in LIBs. The effect of etchants on electrochemical performances and lithium-ion (Li-ion) storage mechanism of V2AlxCTz was discussed comprehensively. Additionally, a Li-ion full cell using LiFePO4 as cathode has exhibited excellent electrochemical performance (150.4 mAh g−1 at 0.1 C). This work illustrates that partially-etched V2AlxCTz with the submicro-sized distribution is also a promising anode material for LIBs.

Fabrication of Mesoporous Graphene@Ag@TiO2 Composite Nanofibers Via Electrospinning as Anode Materials for High-Performance Li-Ion Batteries

Nanosized TiO2 has been actively developed as a low-cost and environment-friendly anode material for lithium-ion batteries (LIBs), but its poor electronic conductivity seriously restricts its practical applications. This drawback is addressed in this work by the fabrication of one-dimensional mesoporous graphene@Ag@TiO2 composite nanofibers as anode materials for high-performance LIBs. The materials were prepared via electrospinning combined with annealing treatment, and the effects of graphene addition on the microstructure and electrochemical performance of the resulting mesoporous graphene@Ag@TiO2 nanofibers were investigated in detail. Ag@TiO2 nanofibers with the optimal amount of graphene displayed a maximum initial discharge capacity of [Formula: see text] at [Formula: see text] and retained a discharge capacity of [Formula: see text] at [Formula: see text] after 100 cycles. These results reflect the excellent cycling stability of the material. The average specific discharge capacity of the nanofibers ([Formula: see text] at [Formula: see text] was two-fold higher than that of samples without graphene, and their discharge capacity returned to [Formula: see text] (approximately [Formula: see text] for other nanofibers) when the current density was recovered to the initial value ([Formula: see text]. Electrochemical impedance spectroscopic measurements confirmed that the conductivity of the electrode was [Formula: see text], which is higher than that of bare mesoporous Ag@TiO2 ([Formula: see text]). Thus, one-dimensional mesoporous graphene@Ag@TiO2 nanofibers can be regarded as a promising anode material for LIBs.

Structure design of CuO/Cu2O@C heterostructure polyhedron accumulated by hollow microspheres for high-performance lithium storage

In this work, CuO/Cu2O@C heterostructure polyhedron accumulated by hollow microspheres was obtained through a etching-pyrolysis-oxidation strategy. CuO/Cu2O@C composites, utilized for lithium-ion batteries (LIBs) anodes, exhibited excellent initial discharge specific capacity (1053 mAh g−1 at 0.05 A g−1, initial Coulombic efficiency (ICE) is 70%) and long-cycle life (510 mAh g−1 after 1000 cycles at 1 A g−1). Even after cycle of various current densities (0.05–5 A g−1) for 70 cycles, discharge capacity backtracked to 663 mAh g−1 at 0.05 A g−1. Furthermore, energy storage behavior of CuO/Cu2O@C coexisting with diffusion and capacitance during the cycle was investigated by CV tests at different scanning rate. These exceptional electrochemical performances were ascribed to hollow spherical structure, cross-linked porous carbon network, and the synergy between the two components of CuO and Cu2O, making CuO/Cu2O@C polyhedron one of the promising anode materials for LIBs.

Metal-organic frameworks-derived CoMOF-D@Si@C core-shell structure for high-performance lithium-ion battery anode

Silicon (Si) is considered as the most promising candidate for anode materials in the next-generation lithium-ion batteries (LIBs). Regulating the morphology and structure of Si plays a vital role in alleviating the volume expansion and improving electronic conductivity. Herein, an ingenious core-shell structure (denoted as CoMOF-D@Si@C) is synthesized by depositing Si uniformly on the pyrolytic metal-organic frameworks (MOFs) via chemical vapor deposition (CVD) method and then encapsulated with a carbon shell. The CoMOF-D@Si@C exhibits excellent rate capability and cycle performance, which delivers a high-rate capability of ~957 mAh g−1 at 10 A g−1 and a reversible capacity of 1493 mAh g−1 after 400 cycles. In particular, the capacity is maintained at 648 mAh g−1 after 1200 cycles at a high current density of 4 A g−1 with a rapid increase of the Coulombic efficiency (CE) to 99.8% after only 5 cycles and the average CE (99.7%) in the whole cycling at 4 A g−1. Profiting from the outer carbon shell, uniform Si deposition and inner porous pyrolytic MOF structure, this architecture can maintain structural stability and provide constructive conductivity during cycling processes. The superior electrochemical performance of the CoMOF-D@Si@C composite makes it a promising anode material for LIBs.