High-performance Anode Materials Research Articles

Sustainable conversion of vine shoots and pig manure into high-performance anode materials for sodium-ion batteries

Sodium-ion batteries (SIBs) are considered promising candidates for future grid energy storage, with hard carbons emerging as key commercial anode materials. This study presents a novel approach to synthesize N-doped hard carbons via co-hydrothermal treatment of vine shoots and pig manure and subsequent thermal annealing of the resulting hydrochar. This method enhances the development of micro- and ultra-microporosity in the synthesized hard carbons, with nitrogen, and to a lesser extent phosphorus and sulfur, introduced as doping elements. Furthermore, the incorporation of hydrochloric acid during the hydrothermal step promotes biomass hydrolysis, leading to increased mesoporosity and the formation of microsphere clusters. In the realm of electrochemical performance, an investigation into various ester- and ether-based electrolytes has revealed NaPF6 in diglyme as the best formulation, thanks to its thinner and more stable solid electrolyte interface (SEI). Using this electrolyte, the best-performing electrode showed an initial Coulombic efficiency (ICE) of 73 %, with reversible capacities of 239, 180, 86, and 57 mAh g−1 at 0.1, 1, 5, and 10 A g−1, respectively. In addition, the electrode exhibited a remarkable capacity retention of 88 % after 250 cycles as well as a compatible behavior when paired with a NVPF-based cathode.

Interfacial post-heterojunction construction in Mn-doped NiS2 for realizing fast and stable sodium storage

Sodium-ion batteries (SIBs) are considered as ideal energy storage devices. However, sluggish kinetics and mechanical instability of electrode materials hinder the development of SIBs in practical application. It is necessary to design a high-performance anode material for fast and stable sodium storage. Herein, Mn-doped NiS2 with a post-heterojunction (M−NS/C-2) is prepared. The electrochemical performance is improved by the synergistic effect of Mn-doping and post-heterojunction interface construction. On the one hand, Mn-doping enlarges the lattice spacing of NiS2 to accommodate sodium ions, moreover, the stacked morphology with interlamellar void influenced by doping provides a structural buffer and dominant pseudo-capacity. On the other hand, Cu7.2S4 is formed in ether electrolyte for the reaction of polysulfide and copper current collector, which grafts active material onto the copper current collector, reinforcing mechanical supporting. Further, the post-heterojunction interface formation between NiS2 and Cu7.2S4 in the cyclic process can be promoted by Mn-doping, boosting electron transfer to facilitate rapid kinetics. Thus, M−NS/C-2 displays good rate performance (497.9 mAh/g even at 10 A/g) and superior cycling stability (390.4 mAh/g after 20,000 cycles at 10 A/g with 0.0013 % attenuation per cycle). The M−NS/C-2|| Na3V2(PO4)3 full cell shows cyclic performance of 241.5 mAh/g after 100 cycles at 1 A/g.

A Strategy for Anode Recovery and Upgrading by In Situ Growth of Iron-Based Oxides on Microwave-Puffed Graphite.

Faced with the increasing volume of retired lithium-ion batteries (LIBs), recycling and reusing the spent graphite (SG) is of great significance for resource sustainability. Here, a facile method for transforming the SG into a carbon framework as well as loading Fe2O3 to form a composite anode with a sandwich structure is proposed. Taking advantage of the fact that the layer spacing of the spent graphite naturally expands, impurities and intercalants are eliminated through microwave thermal shock to produce microwave-puffed graphite (MPG) with a distinct three-dimensional structure. Based on the mechanism of microwave-induced gasification intercalation, a Fe2O3-MPG intercalation compound (Fe2O3-MPGIC) anode material was constructed by introducing iron precursors between the framework layers and subsequently converting them into Fe2O3 through annealing. The Fe2O3-MPGIC anode exhibits a high reversible capacity of 1000.6 mAh g-1 at 200 mA g-1 after 100 cycles and a good cycling stability of 504.4 mAh g-1 at 2000 mA g-1 after 500 cycles. This work can provide a reference for the feasible recycling of SG and development of high-performance anode materials for LIBs.

Insight into graphene/boron arsenide heterostructure used for high-performance lithium-ion battery anode materials: The first principles study

Two-dimensional (2D) van der Waals (vdW) heterostructures demonstrate potential applications in Lithium-ion batteries (LIBs) characterized by their elevated energy storage capacity and extended operational longevity as anode materials. The structures and electronic properties of graphene/boron arsenide (Gr/BAs) heterostructures, along with the adsorption and migration of lithium (Li) atoms within the structures, are methodically analyzed through first-principles studies underpinned by density functional theory. Our calculations indicate the metallic Gr/BAs heterostructures have the structural stability, where their mechanical strength is confirmed from the elastic constant. Its diffusion barrier of Li atoms (0.25 eV) is superior among similar anode materials. The Li atoms' diffusion coefficient within the Gr/BAs heterostructure at 300 K (1.27 × 10−10 m2/s) exceeds that observed in Gr (2.0×10−11 m2/s). Besides, the presence of Gr assists in maintaining the open-circuit voltage (OCV) of Gr/BAs heterostructures in the range of 0-1 V. The theoretical specific capacity of proposed heterostructure reaches 920 mAh/g. The present calculations suggest that the Gr/BAs heterostructure could serve effectively as an anode in LIBs due to its excellent electrical conductivity, small diffusion barriers and appropriate open-circuit voltage.

A novel nickel cobalt sulfide-indium (hydroxy) sulfide [NiCo2S4@In(OH)xSy] composites for LAGP-based all-solid-state lithium-ion capacitors

Metal sulfides have attracted the attention of researchers as electrode materials in energy storage systems because of their superior electrochemical performance. In this study, we synthesized a nickel cobalt sulfide@indium(hydroxy) sulfide nanoarchitecture (NiCo2S4@In(OH)xSy) using a one-step hydrothermal method and investigated its potential as a high-performance anode material for lithium-ion capacitors (LICs). The volume expansion of sulfides during charge-storage can be reduced by fabricating suitable ternary sulfide composites. This unique composite highlights the importance of –OH bonding for better charge kinetics. The NiCo2S4@In(OH)xSy composite nanoarchitecture as an anode can achieve a high specific capacity of 1277 mA h g−1 at 0.1 A/g, high rate capability, and long cycling performance. Furthermore, the all-solid-state LIC device fabricated using NiCo2S4@In(OH)xSy as anode, activated carbon as cathode, and LAGP (Li1.5Al0.5Ge1.5P3O12)-based solid-state electrolyte/separator can deliver a high energy density of 172.4 Wh kg−1 at 423.5 W kg−1 and 70.6 Wh kg−1 even at a high power density of 8470 W kg−1.

What drives the heterogeneous interdiffusion in the Li-Si interfacial region of Si anodes: the Li flux or the Si flux?

The electrochemical reaction in silicon (Si) electrode, accompanying with tremendous volume expansion, causes rapid capacity fade of Li-ion batteries. The Li-ion concentration gradient and structural distribution uniformity influence the inhomogeneous expansion, and the kinetic mechanism of lithiation and interfacial morphology evolvement remains debated. The present study focuses on the dynamics of Li-Si interdiffusion at Si/Li interfaces with various Si-facet orientations and phases using a machine-learning potential. We find that the Si flux from bulk Si to Li-Si interface regions controls the length of Li-Si interdiffusion region. The lithiation length in different Si/Li interface systems exhibits the order of amorphous-Si > crystalline-Si(110) > crystalline-Si(100) > crystalline-Si(111), which agrees with the experimental trend. Our atomic simulations further reveal that the key factor determining the Li-Si interdiffusion is the difference of on-site Si atomic energies between the bulk Si and the Li-Si interface regions. We propose that the large interdiffusion extent is due to a low thermodynamics barrier. Our findings provide insights for the development of high-performance Si anode materials.

Synthesized nanosphere ZnSe and reduced graphene oxide as anode materials for sodium-ion batteries: Analysis on phase transition and storage mechanism

Zinc selenide (ZnSe), a metal chalcogenide, is an attractive anode material for sodium-ion batteries, exhibiting high theoretical capacity (371.4 mAhg−1) and numerous redox sites. However, volume expansion and low stability during the charge/discharge processes present challenges. This study aimed to solve these inherent problems and synthesize a high-performance anode material by growing nano sized ZnSe on surface of reduced graphene oxide (rGO). ZnSe has two crystal structures, namely zinc-blende and wurtzite, and undergoes a transformation from wurtzite to the zinc-blende phase during sodium ion storage. This study conducted X-ray diffraction analysis of the electrode after the galvanostatic charge/discharge test and performed cyclic voltammetry analysis to investigate the transformation process. In addition, real-time monitoring of Nyquist plot and phase transition was performed to investigate the mechanisms of sodium ion storage. The ZnSe-rGO, exhibiting conversion reactions, shows cycle performance of 316.14 mAhg−1 at a current density of 0.5 Ag−1 after 1000 cycles. The evaluation of anode materials and analysis of their storage mechanism can facilitate sodium-ion batteries research.

Dealloying induced Porous Bi anodes for rechargeable magnesium-ion batteries

Alloy-type anodes have attracted extensive attention in magnesium-ion batteries (MIBs) due to their low reaction potentials and high theoretical specific capacities. However, the kinetically sluggish Mg insertion/extraction and diffusion in electrode materials, as well as the huge volume changes resulting in the capacity decay limit their further development. Herein, a series of porous-Bi (P-Bix) anodes are fabricated through a facile dealloying strategy based on the Sn100-xBix (x = 1, 5, 10, 43, at.%) precursor alloys. Among them, the P–Bi10 anode delivers a high discharge specific capacity (376.0 mAh g−1 at 500 mA g−1), greatly improved rate capability (363.3 mAh g−1 at 1000 mA g−1) and good cycling stability even at 2000 mA g−1 (104.0 mAh g−1 after 1000 cycles). Furthermore, operando X-ray diffraction (XRD) is performed to unveil the magnesiation/demagnesiation mechanisms of the P–Bi5 and P–Bi10 anodes, indicating a simple two-phase reaction process. Additionally, the P–Bi10 anode displays good compatibility with conventional Mg salt electrolytes such as Mg(TFSI)2. Our findings could provide useful information on design of high-performance alloy-type anode materials for MIBs.

In situ synthesis of vertical graphene on porous Si microparticle composite for high-performance anode material

Silicon is capable of delivering a high theoretical specific capacity (4200 mAh g-1) in lithium-ion batteries. However, silicon has poor electrical conductivity, huge volume expansion (∼300%), and unstable solid electrolyte interface (SEI) film, especially for micron-sized silicon particles. We proposed and prepared a novel vertical carbon (VG) coating on a porous silicon (p-Si) microparticle structure, which effectively alleviated the volume expansion and inhibited the interface reaction. The synthesized porous silicon p-Si@VG composite exhibited significant enhanced cycling stability and an excellent reversible capacity of 1563 mAh g-1 (capacity retention of 48.6%) after 200 cycles. The vertical carbon nanosheet structure constructed a three-dimensional conductive network. Therefore, the p-Si@VG composite showed better rate capability and higher lithium-ion diffusion rates. This work is expected to promote the application of micron Si-based composites in lithium-ion batteries.

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.

In situ anchoring in carbon matrix of Bi2O2CO3 as a high-performance anode material for Li-ion batteries

In situ anchoring in carbon matrix of Bi2O2CO3 as a high-performance anode material for Li-ion batteries

A soft carbon materials with engineered composition and microstructure for sodium battery anodes

Sodium-ion batteries (SIBs) have advantages in high sodium resources, providing powerful supplement to the current energy storage system. However, the lack of low-cost and high-performance anode materials still limits its practical application. Herein, a soft carbon anode derived from petroleum coke was successfully synthesized by engineering its composition and microstructure through resin and sodium phosphate compositing with optimal heat treatment process, delivering significant merits over existing composite anode in term of price density, initial Coulombic efficiency (ICE) and carbon yield. Resin helps to increase micropores and inhibit graphitization. Na3PO4 contributes to expand layer spacing and increase reversible groups, meanwhile facilitates the cross-linking of graphite microcrystalline and provides additional sodium supplement with improved ICE and conductivity. Through the synergistic effect by the additives, the optimized sample (P-ONH-1200) exhibits a superior reversible charge specific capacity of 311.9 mAh g−1 with high cycling stability, ICE (90.7 %) in SIBs, and high carbon yield (70 %). It also gains rate performance of 209.7 mAh g−1 at 4 C with 98 % retention after 1000 cycles. The full cell with Na3V2(PO4)3 (NVP) cathode at 1.05 N/P ratio exhibits an excellent stability with a capacity retention of 70 % after 500 cycles at 1 C. It provides a model reference for the microstructure regulation of petroleum coke and a revenue for preparation high-performance soft carbon anode for SIBs.

Atomically Engineered Encapsulation of SnS2 Nanoribbons by Single-Walled Carbon Nanotubes for High-Efficiency Lithium Storage.

Rechargeable lithium-ion batteries are integral to contemporary energy storage, yet current anode material systems struggle to meet the increasing demand for extended range capabilities. This work introduces a novel composite anode material composed of one-dimensional 2H-phase tin disulfide (SnS2) nanoribbons enclosed within cavities of single-walled carbon nanotubes (SnS2@SWCNTs), achieved through precise atomic engineering. Employing aberration-corrected transmission electron microscopy, we precisely elucidated the crystal structure of SnS2 within the confines of the SWCNTs. This deliberate design effectively addresses the inherent limitations of SnS2 as a lithium-ion anode material, including its low electrical conductivity, considerable volume expansion effects, and unstable solid electrolyte interface membrane. Testing confirmed that SnS2 transforms into the Li5Sn2 alloy phase after full lithiation and back to SnS2 after delithiation, showing excellent reversibility. The composite also benefits from edge effects, improving lithium storage through stronger binding and lower migration barriers, which were supported by calculations. This pioneering work advances high-performance anode materials for applications.

Silicene/BN heterostructure as high-performance anode material for Mg-ion batteries

Finding a suitable anode material is a key part of the development of Mg-ion batteries (MIBs) to commercialize. In this work, an outstanding Silicene/BN heterostructure was discovered as a candidate anode material for MIBs by using first-principles calculations. The mixed sp2/sp3 orbital hybridization of silicon atoms makes Silicene monolayer easy to adsorb Mg atoms. The introduction of BN monolayer can effectively buffer the structural deformation and improve the electrochemical performances. Compared to pristine Silicene, the Silicene/BN heterostructure exhibited higher structural stability and Mg adsorption capacity. The diffusion of Mg ions in the heterostructure interlayer was easier with a low barrier of 0.160 eV than that on the Silicene monolayer. A comparable low open circuit voltage (0.112 V) was also observed. These results indicated the potential of Silicene/BN heterostructure as a high-performance anode material for MIBs.

Preparation of high-performance anode materials for sodium-ion batteries using bamboo waste: Achieving resource recycling

Bamboo exhibits various excellent properties and is widely used in construction. However, appropriate disposal of the bamboo waste generated in a green manner is difficult. To realize resource recycling, we used a simple treatment method to prepare waste bamboo as a negative electrode material exhibiting considerable electrochemical properties for sodium-ion batteries. The electrochemical properties of high-temperature calcination materials considerably improved after impurity removal treatment using an acid solution, which was performed to eliminate the influence of impurities on electrochemical properties. However, the materials still could not meet commercial requirements. A simple pre-oxidation modification treatment enabled the introduction of O atoms into the carbon skeleton to expand the layer spacing, improved the transport kinetics of Na+ in the carbon skeleton, and further increased the platform capacity of the pre-oxidation material. The preoxidative high-temperature co-treated materials exhibited a specific charge capacity close to 280 mAh g−1 at a 0.1 C rate and a capacity attenuation of almost zero after 100 cycles, and showing a specific charge capacity of more than 150 mAh g−1 at a 2 C rate test. In the context of sustainable development, this study makes waste bamboo become a candidate of low-cost negative electrode material for sodium-ion batteries.

Pristine and defective 2D SiCN substrates as anode materials for sodium-ion batteries

Exploring more high-performance anode materials for sodium-ion batteries (SIBs) can smoothly help to build a more sustainable, cleaner, and reliable energy system. This study systematically investigates the potential of 2D pristine SiCN (p-SiCN) and defective (d-SiCN) substrate as candidate materials for SIBs anodes using first-principles computational method. The computational results reveal that the p-SiCN possesses excellent thermal stability and structural cyclical performance, good conductivity, high theoretical specific capacity (1486 mAh·g−1), low diffusion barrier (0.177 eV), and appropriate open-circuit voltage (0.340 V), which allows the p-SiCN substrate more suitable as a potential anode material for SIBs. Furthermore, by investigating the effects of intentionally designed defects on p-SiCN, it is observed that the adsorption energy and diffusion barrier of the Na atom on the d-SiCN substrate increase. Our work demonstrates that investigating the effect of defects on p-SiCN can better explore the properties of anode materials, thus further optimizing the battery performances.

Two-Dimensional TOD-Graphene in a Honeycomb–Kagome Lattice: A High-Performance Anode Material for Potassium-Ion Batteries

Two-Dimensional TOD-Graphene in a Honeycomb–Kagome Lattice: A High-Performance Anode Material for Potassium-Ion Batteries

WITHDRAWN: Novel design of Sn4P3@NxC electrodes and their electrochemical properties

Tin phosphide (SnxPy) is recognized as one of the most promising anode materials for lithium-ion batteries due to its exceptionally high theoretical capacity. However, its application is hampered by significant volume expansion during charge-discharge cycles and inferior electrical conductivity. Proper structural design placs a pivotal role in addressing these challenges, paving the way for high-performance anode materials. This study introduces a nitrogen-doped carbon-coated Sn4P3 nanosphere with a core-shell structure, employing dopamine as the nitrogen source. This innovative approach, utilizing template removal and solid-phase phosphorization, results in both the core and shell acting as active materials, thereby enhancing the volumetric energy density of the electrode. The internal voids within the shell layer mitigate volume expansion during charge-discharge cycles, while the presence of the nitrogen-doped carbon layer maintains the material's stability throughout cycling and improves its electrical conductivity. Electrochemical performance tests confirm the outstanding energy storage capability of this material, with an initial Coulombic efficiency reaching up to 73.6 %. Furthermore, it maintains a stable capacity of 585 mAh g^-1 after 1200 cycles at a current density of 2 A g^-1. This research offers a design paradigm for the development of novel energy storage materials.

β12-Borophene/Graphene Heterostructure as a High-Performance Anode Material for Li-Ion Batteries.

In the world of two-dimensional (2D) materials, various Borophene allotropes have gained significant attention for their remarkable specific capacity. However, the instability of monolayers has challenged experimental investigations of innovative approaches. Due to this limitation, in this work, graphene was investigated as a sublayer with the aim of providing stability to the β12-borophene monolayer. This study delves into the potential of a novel β12-borophene/graphene (β12-B/G) van der Waals (vdW) heterostructure using Quantum Espresso software based on vdW-corrected density functional theory. Our investigation includes exploring thermal and dynamical stability, adsorption energy, open circuit voltage, specific capacity, and diffusion barrier energy properties. Impressively, the calculated specific capacity reached 907 mAh/g, outperforming other 2D materials and heterostructures. The combination of a graphene layer not only ensures dynamical stability but also provides the adsorption energy of lithiumon the β12-borophene layer, simultaneously decreasing the diffusion barrier energy in comparison with the β12-borophene monolayer. The calculated open circuit voltage falls in the range 0.08-1.09 V, rendering it suitable for an overall average commercial voltage. For the borophene layer, the computed diffusion barrier energies are approximately 0.52 and 0.78 eV. Collectively, these findings underscore the potential of theβ12-B/G heterostructure as an advanced anode material for lithium-ion batteries.

High-Performance Anode Material Based on Zinc Naphthalocyanine/Graphene Composite.

Transition metal oxides are a potential anode material owing to their high theoretical capacity. Nonetheless, their large volume changes and low electrical conductivities lead to poor cycling performance and rate capabilities. In this article, an effective strategy is proposed and developed for preparing a ZnO/N-doped graphene composite (ZnNc/GO-5). The key point of this strategy is to use zinc tetra tert-butyl-naphthalocyanine (ZnNc) as a codoped source of N atoms and zinc ions, and graphene oxide (GO) which is combined with ZnNc by π-π deposition as a carbon matrix. After calcination, ZnO microcrystals coated with N-doped graphene are obtained. The unique features of the composite and synergistic effect between N-doped reduced graphene oxide and ZnO microcrystals enable good electrochemical performance by the composites when used in lithium-ion batteries. As an anode material, the as-synthesized ZnNc/GO-5 composite delivers a high first capacity of 1942.9 mAh g-1 and excellent cyclic stability of 861.4 mAh g-1 after 150 cycles at 100 mA g-1. This strategy may offer a new method of designing the anode materials of lithium-ion batteries and promote the practical use of organic molecules in next-generation lithium-ion batteries.