Anode Material For Lithium-ion Batteries Research Articles

Study on the synthesis mechanism of new α-FeOOH@3DGF material and its lithium storage performance

A new self-supporting material contained nanorods α-FeOOH and three-dimensional skeleton graphene foam (3D Graphene Foam, 3DGF) was prepared by hydrothermal method. The growth mechanism and phase change rules of nanorods α-FeOOH@3DGF were studied to obtain the electrochemical lithium storage performance. The results showed that growth mechanism of nanorods α-FeOOH was accompanied by the consumption of nanoparticles β-FeOOH. If the hydrothermal time reached to 12 h, the nanoparticle β-FeOOH phase completely disappeared with only rod-shaped α-FeOOH@3DGF single phase obtained. Rod-shaped α-FeOOH@3DGF was used as anode material of lithium-ion batteries and the reversible specific capacity remained at about 305 mAh·g−1 after charging and discharging 250 times at 500 mA·g−1, with significantly cycling stability compared with that of the monomaterial α-FeOOH.

The Effect of Silicon Nanoparticle Size on Cycle and Calendar Life

Lithium-ion batteries are now ubiquitous in modern electronics, electric vehicles, and many other applications. As the battery industry continues to push for better, longer lasting batteries, many have turned to using a different anode material that would provide higher-energy density and require less frequent charges. While graphite is the tried-and-true anode material for lithium-ion batteries, a silicon anode battery could provide up to ten times higher theoretical energy density than graphite. However, there are a lot of challenges standing in the way between silicon anode batteries and commercialization—the large volume expansion of silicon (around 200-300% expansion, compared to graphite at 10%) and the unstable solid-electrolyte-interface (SEI) of silicon results in anodes that mechanically degrade and calendar age faster than their graphite counterparts.Previous research has demonstrated that plasma-enhanced chemical vapor deposition (PECVD) silicon nanoparticles with a hydrophilic coating such as polyethylene oxide (PEO) results in silicon anodes with good cycle life [1, 2, 3, 4]. In this system, smaller particle sizes typically yielded better cyclability than larger particle sizes, which is contrary to conventional wisdom that more surface area is detrimental as it allows for more SEI formation and side reactions. However, since silicon anodes experience large volume changes during cycling, the surface area might not be the dominant contribution to capacity fade. Larger silicon particles result in larger total expansions of the electrode, which causes more mechanical damage like cracks to form, exposing fresh surface area to electrolyte and SEI formation.This research investigates the performances of PEO-coated PECVD Si electrodes with nanoparticles ranging from 3 to 27 nm in diameter. We measure the cycle life at a rate of 0.333C, as well as the calendar lifetimes of each electrode. We characterize each electrode with SEM imaging, tortuosity measurements, and electrochemical impedance spectroscopy to understand the differences in microstructure that contribute to capacity fade and impedance rise.

Ab Initio Tomography Analysis of Lithium Incorporation and Diffusion in Multidomain Silicon Suboxide Anode Materials

Silicon is considered a promising anode material to supplant conventional graphite materials in lithium-ion batteries due to its higher theoretical energy-storage capacity compared to graphite. However, the widespread application of Si anodes has been hindered because the capacity of Si anodes decreases rapidly as the charge/discharge cycle proceeds. The controlled incorporation of oxygen into Si is often considered as a feasible approach for employing Si as an anode material in the form of silicon suboxide. Silicon suboxide exhibits a lower energy capacity compared to pure Si, but offers enhanced stability against volume expansion. Consequently, silicon suboxide materials have been commercialized by blending them with graphite. However, the blending ratio of silicon suboxide with graphite is limited to low levels due to its poor first-cycle efficiency, so-called initial Coulombic efficiency. In-depth understanding of the lithium interaction characteristics within multidomain silicon suboxide is indispensable for optimizing the electrochemical performance of silicon suboxide anode materials for lithium-ion batteries. In this study, we investigate the domain-dependent thermodynamic and kinetic properties of lithium atoms within systematically designed multidomain silicon suboxide models composed of Si, SiO2, and Si/SiO2 interface by performing a series of computational simulations combined with a unique tomography-like sampling scheme. We find that the Si/SiO2 interfacial region exhibits preferential thermodynamics and kinetics for lithiation and can serve as a critical lithium transport channel during charge-discharge cycles, while the SiO2 domain is likely to be excluded from lithiation due to its high resistance to lithium diffusion. Consequently, a significant fraction of lithium is expected to be trapped at the Si/SiO2 interface during the discharge process, which ultimately contributes to a low initial Coulombic efficiency. This theoretical understanding suggests that the formation of continuously connected lithium-transportable Si/SiO2 interfacial channels surrounding the Si domains, along with a well-structured shallow SiO2 framework through the use of appropriate synthesis methods, is essential for maximizing the electrochemical performance of silicon suboxide anode materials. Our theoretical approach offers new insights into the atomistic characteristics of silicon suboxide during lithiation/delithiation processes, ultimately enabling the identification of the origin of low ICE and strategies for addressing it.References(1) Chae, S.; Lim, H.-K.; Lee, S. Energy Landscapes for Lithium Incorporation and Diffusion in Multidomain Silicon Suboxide Anode Materials. ACS Applied Materials & Interfaces 2023, 15 (49), 57059-57069. DOI: 10.1021/acsami.3c12846. Figure 1

Scalable Synthesis of Bulk TiO2 Hybrids and Its Li-Storage Properties in “Rocking-Chair” Type Full-Cell Assembly with LiNi0.5Mn1.5O4 Cathode

TiO2 as an anode material in lithium-ion batteries (LIB) has abolished hurdles like irreversibility, cycling stability, rate capability, and energy density, which are vital for electrochemical performance. Conventionally, time-consuming and complex techniques like solvothermal methods are employed to synthesize TiO2. We herein open a new avenue towards a simple, scalable, and eco-friendly synthesis of bulk TiO2 anatase/bronze hybrids from sodium meta-titanate through a facile mechano-chemical and ion-exchange process under different temperature conditions (400, 450, and 500 °C). Structural and morphological features are analyzed through various characterization techniques such as XRD, FE-SEM, HR-TEM, and XPS. The bronze phase’s high reversibility, low redox potential, high current rate performance, and high power capability of the anatase phase make the hybrid attractive for fabricating high power and high energy density Li-ion power packs. The Li insertion/extraction properties are studied in half-cell assembly (Li/TiO2), where all three TiO2 hybrids exhibited promising results with an initial discharge capacity >165 mAh g-1 at a current rate of 0.05 A g-1 along with a capacity retention >90% after 100 cycles. A “rocking-chair” type full-cell configuration with high voltage LiNi0.5Mn1.5O4 cathode is fabricated, in which LNMO/TiO2-400 °C displayed a discharge capacity of ~88 mAh g-1 at a current rate of 0.05 A g-1. Moreover, the full cell exhibited a capacity retention of >70% after 100 cycles with a maximum energy density of 192.75 Wh kg-1. Figure 1

(Invited) The Role of Carbon in Enabling Stable Solid State Batteries

Carbonaceous materials are widely used as the anode materials in rechargeable lithium-ion batteries. In that context, they serve as the host for lithium ions. Their structural stability and limited volume changes underpin the long-term stability of the batteries. In solid-state batteries, however, their roles have evolved. With the focus on raising cell energy density and the promise of stable operation of lithium metal due to the absence of organic solvent, carbon has not been widely studied as an anode material. Unfortunately, the promise of lithium metal has encountered significant challenges: it chemical reacts with virtually all known solid state electrolytes; lithium also grows dendrites which can eventually lead to shorting; the stripping of lithium is also often inhomogeneous which had led to void formation at the interface. To address these challenges, carbonaceous materials have been reintroduced.In this talk, we overview several applications of carbonaceous materials in solid state batteries. We have shown that graphite can be engineered as a 3D host for lithium deposition. Lithiated graphite becomes lithiophilic with low nucleation barrier for lithium metal deposition. The voids between the graphite particles can accomodate lithium metal. As a result, the critical current density and cycling stability of both full cells and symmetric cells have greatly improved. We note that in this context, the anode is essentially a graphite electrode that experiences intentional overlithiation.In a second application, we show that carbon can serve as an effective interlayer between lithium and the solid electrolyte. This interlayer reduces the side reaction between lithium and the electrolyte, thus greatly improving the cycle life and coulombic efficiency. It is rather surprising that upon lithiation, the interlayer enables lithium transport and preferential lithium deposition at the carbon/lithium interface, rather than the carbon/electrolyte interface. This desirable outcome is observed despite the fact that the interlayer itself is electrically conducting. We studied a wide variety of carbon materials in terms of surface area, crystal structure, and defect density. With the optimized carbon material, critical current densities of over 30 mA/cm2 have been observed. The mechanism of lithium transport will be discussed along with the design criteria for using carbon as an effective mixed electron and ion conductor.

Deciphering the Impact of Current, Composition, and Potential on the Lithiation Behavior of Graphite in Silicon-Graphite Anodes

Graphite is the most used anode material for current-generation lithium-ion batteries due to its beneficial cycle life, availability and reasonable rate capability. Still, the modest capacity of 372 mAhg-1 represents a bottleneck in the pursuit of high-energy density anodes. Enabling much higher theoretical capacities of 3600 mAhg-1 [1], silicon represents a promising candidate as anode material for next generation batteries. However, the alloying-based lithiation mechanism of silicon is accompanied by a large volumetric change of up to 300% upon cycling, leading to fast degradation due to electrode pulverization, continuous SEI formation and extensive electrolyte consumption. Even though shallow cycling of silicon anodes has been demonstrated in laboratory scale cells [2], the mixing of silicon with graphite is considered the most viable approach to lift energy density while maintaining appropriate cycle life.Due to the fundamentally different kinetics and potentials of Li insertion and extraction of both materials, the development of silicon-graphite composite electrodes is not straightforward. One of the key questions for optimization is how the incorporation of silicon impacts the (de)lithiation behavior of graphite as a function of the silicon:graphite mass ratio, operating current and electrode potential. While lithiation of graphite in composite electrodes of 15 wt% silicon has been shown to occur in a similar manner as pure graphite, higher fractions of silicon are expected to exert more stress on the graphite and represent kinetic barriers for Li diffusion. This study presents results from in-situ X-ray diffraction experiments (XRD) of silicon-graphite/Li half cells conducted at the European Synchrotron Radiation Facility (ESRF). Serving as a reference, the current-dependent (de)lithiation behavior of a pure graphite/Li half cell has been thoroughly investigated and systematically compared to the (de)lithiation behavior of two selected silicon-graphite composite anodes (silicon:graphite ratio of 30:70 and 70:30, respectively) exposed to the same formation cycle and C-rate protocol. An optimized and novel measurement setup was used, based on a perforated current collector of the anode, providing a complete picture of the graphite in-plane and interplanar structural changes as well as the evolution of semicrystalline silicon peaks which would usually be obscured by the current collector signal.By correlating the electrochemical features (voltage curve and differential capacity plot) with the in-situ diffraction data, it was possible to identify and assign the occurrence and absence of dilute-stage and ordered graphite intercalation compounds (GICs) for the respective electrodes, yielding an in-depth insight into the graphite state of charge upon (de)lithiation and how it is influenced by the silicon content and applied C-rate.As expected, the silicon is (de)lithiated within the entire potential range, whereas graphite is most electrochemically active at potentials lower than 260 mV. In both composite electrodes, graphite attains a lower lithiation degree compared to pure graphite. This is because the high theoretical capacity of silicon results in high specific currents, ultimately challenging the rate capability of graphite. Moreover, the high delithiation overpotential encountered in the composite electrodes results in a highly asymmetrical lithiation/delithiation behavior of graphite. Also, graphite lithiation is less uniform in the composite anodes, indicated by the coexistence of dilute GICs upon (de)lithiation, compared to pure graphite where dilute phases are fully consumed (formed) as (de)lithiation progresses. Surprisingly, the in-situ XRD studies did not reveal signs of structural degradation and strain of graphite as a result of mechanical interaction with silicon. Instead, the volume change of graphite is well correlated with the amorphization of crystalline, unreacted silicon and the volume evolution of silicon crystallites upon charge-discharge.To mitigate the observed effects, the work suggests nanostructuring and advanced electrode architectures towards higher utilization and more homogeneous lithiation of graphite. Overall, the study provides a demonstration of a suitable operando cell for studies of anodes for Li-based systems, and aids the rational design of silicon-graphite composite anodes.

Influence of Cycling in Different State-of Charge Windows on Lifetime and Electrode Expansion of Microscale Silicon-Dominant Lithium-Ion Batteries

Silicon (Si) is a promising active anode material for next-generation lithium-ion batteries due to its high theoretical electrochemical capacity of 3579 mAh/gSi (Li15Si4) and low costs using microscale Si particles.1,2 However, the wide usage of Si as an active anode material is hindered due to its lower lifetime compared to graphite anodes. The degradation in silicon-containing batteries can be suppressed by partial lithiation strategies,2,3,4 with applications for automotive cells leading to improved lifetime.5 However, the lifetime problem still exists in partially lithiated microscale Si particles with lower volume expansion2,3 with ≈200 cycles for one-third silicon utilization, i.e., 1200 mAh/gSi 2. Moreover, we confirmed in our previous study6 as reported by Wetjen et al.4 and Haufe et al.2 that lower cell discharge cut-off voltages and thus higher silicon delithiation potentials versus Li+/Li led to accerlated aging and should be avoided.Thus, the motivation for this study is to avoid these high anode delithiation potentials by operating the cells in a high full cell state of charge (SoC) and to investigate the influence of different SoC windows on lifetime with laboratory 182.1 ± 0.7 mAh/gNCA Swagelok T-cells comprising a microscale silicon-dominant anode and a NCA cathode. The electrode-specific aging is monitored with the lithium metal reference electrode based on the anode and cathode potentials and pulse tests. To investigate the aging in different SOC regimes, three cycling conditions were chosen in the low (LV), middle (MV) and high voltage (HV) window and compared to cells cycled between 2.8 and 4.2 V as full voltage6. The voltage window of LV, MV and HV were chosen to represent cycling between 0-50%, 25-75%, and 50-100% SOC, respectively. Formation and checkups were the same for all cells with 2.80 V to 4.20 V. After reaching the end-of-life criterion of 55% state of health (SoH), the cells were disassembled and anode and cathodes were re-assembled in half-cells for a post-mortem analysis to reveal loss of lithium inventory (LLI) and loss of active material of the anode LAMAn, and the cathode LAMCat of the respective full-cells. Complementary to the electrochemical aging, dilatometer measurements7 were conducted to quantify the electrode expansion for the different silicon anode SoC windows since particle decoupling is expected to be one of the major aging mechanisms for microscale silicon2, which is expected for high electrode expansions.For the electrochemical results, the lifetime can be drastically increased from ≈230 to ≈560 equivalent full cycles (EFCs) for operating the full cell in the HV compared to the FV window, as shown in Fig. 1a. One EFCs is defined as the total charge throughput for charging and discharging one cycle normalized to the capacity of the initial checkup cycle. Over aging, the full cell degradation correlates very well with the end of discharge potential of the silicon anodes. Moreover, the electrode-specific pulse results show strong anode degradation while the cathode remains intact. The post-mortem results reveal LLI as most dominenat aging mode, which was very similar for all voltage windows. The HV cells showed both the highest LAMNE and LAMPE, whereas LAMNE was more dominant compared to LAMPE. The silicon amorphization was the lowest for the LV anodes and the highest for the HV anodes at the same SoH. The dilatometer results show that the silicon electrode expansion is the lowest for the low lithiation, i.e., LV, and the highest for the highest lithiation, i.e., HV. From the dilatometry results, we conclude that the mechanical electrode stability does not limit lifetime.Our results demonstrate that lifetime can be significantly improved by a factor of ≈2.4 based on the EFCs if operating cells with silicon dominant anodes in high SoCs and that low SoCs should be avoided. Acknowledgments: S. F. gratefully acknowledges the financial support from the BMBF (Federal Ministry of Education and Research, Germany) under the auspices of the ExZellTUM III project (grant number 03XP0255). The authors want to thank our student worker, Maximilian Reichl, for the fabrication of the NCA coatings. We also thank Wacker Chemie AG for kindly providing the microscale silicon material.

Aluminum doped non-stoichiometric titanium dioxide as a negative electrode material for lithium-ion battery: In-operando XRD analysis

Lithium-ion batteries (LIB) with titanium dioxide as anode material emerged as one of the most energy-storage systems. In this study, we investigate aluminum-doped non-stoichiometric titanium dioxide synthesized using sol-gel method and subsequent reduction treatment. Different analysis techniques, such as X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) tests are conducted for the analysis of material and performance of the battery. The XRD results affirmed that the sample consisted of pure titanium-dioxide phases with no other precipitated phases, such as aluminum oxide (α-Al2O3 or γ-Al2O3). XPS analysis evident that aluminum was successfully incorporated into the titanium-dioxide lattice and the presence of Ti3+ and oxygen vacancy signals confirmed its non-stoichiometric nature. TEM images implies that doping and its extent did not significantly affect the size and morphology of the nanoscale particles. The selected area electron diffraction shows that the sample consisted of a mixture of the anatase and rutile phases. The best-performing electrode was found to be the one composed of 1 % aluminum-doped non-stoichiometric titanium dioxide. After 200 charge-discharge cycles, the battery maintained a capacity of 195 mAh/g, retaining 97.5 % of its reversible capacity. Cyclic stability test under high current condition shows that the capacity remained at 157 mAh/g without any noticeable decay after 750 charge-discharge cycles at a 1 C rate. This material exhibited the lowest impedance and the highest lithium-ion diffusion rate. Additionally, in situ synchrotron-based XRD indicates coexistence of three phases such as a new reversible intermediate phase LiTiO2, a partially irreversible intermediate phase Li0.55TiO2, and the anatase phase. The analysis results indicated that the peak intensities and angular shifts were associated with the phase changes that occurred during charge and discharge of the electrochemical processes. The interaction mechanism study between lithium ions and the lattice of mixed phase (anatase, rutile) identified the occurrence of non-uniform stress resulting from lithium-ion insertion in the rutile phase, in addition to the irreversible reactions in both the rutile and anatase phases. Through the synergistic effect of heteroatom doping and oxygen vacancy treatment, the conductivity of titanium dioxide is enhanced, leading to improved performance in capacity, impedance, cycle life, and rate as an anode material in LIBs.

High Loading Micro-Si anode with Oxidation Controlled Carbon Nanotube Scaffolds: Towards Pouch Cell Fabrication in Industrial Level

Silicon (Si) emerges as a promising anode material for lithium-ion batteries (LiB) due to its ultrahigh theoretical capacity and cost-effectiveness. However, the large-scale fabrication of high-loading Si anodes remains rarely documented. Herein, we developed large-scale oxidation-controlled carbon nanotube (CNT) scaffolds with high electrical conductivity by regulating oxidation conditions. The oxidation-controlled CNTs are self-assembled into an interwoven network, facilitating their incorporation with micro-Si particles and a polymer binder to form a stable aqueous slurry. We investigated the feasibility of scalable electrode coating through rheological analysis, revealing the viscoelastic slurry suitable for industrial-scale shear-coating. Utilizing the bar-coating method, we fabricated a large-scale electrode (30 cm x 40 cm) and confirmed the uniformity of the electrode layer via statistical quality control charts, demonstrating scalability for industrial production. In terms of electrochemical performance, the optimized Si anode surpassed previously reported Si-based anodes, exhibiting a high areal capacity of 3.9 mAh cm−2 and exceptional capacity retention (94 %) after 50 cycles. Finally, we validated the development of the Si anode, nearing industrial-level standards with exceptional pouch cell performance. The oxidation-controlled CNT scaffolds not only enable scalable coating of electrode materials but also effectively mitigate the expansion of micro-Si particles by uniformly covering the Si surface.

Preparation and corrosion resistance of β-Al2O3–MgAl2O4 multiphase materials for synthesising Li-ion battery cathode materials

The sagger, primarily composed of aluminum-silicon, serves as an essential vessel in the sintering process of ternary lithium battery anode materials (LiNixCoyMn1-x-yO2, LNCM). However, the acidic oxide SiO2 in the sagger material readily reacts with Li2O in the cathode material, forming substances such as LiAlO2 or LiAlSiO4, resulting in volume expansion, which makes the sagger spalled and damaged. In this study, β-Al2O3–MgAl2O4 multiphase materials with excellent alkali resistance were prepared using the high-temperature solid-state method. The effects of anhydrous sodium carbonate content and heat treatment temperature on the properties of the composites were investigated, and the thermal shock resistance of the specimens was evaluated by the water-rapid-cooling method, as well as the LNCM corrosion resistance of the specimens was evaluated by the static crucible method. The results showed that the overall performance of the specimens was the best at a anhydrous sodium carbonate content of 6 wt%, with a compressive strength of 57.50 MPa and a flexural strength of 42.49 MPa after firing at 1600 °C for 4 h. The strength retention of the specimens was 33.21 % after one thermal shock at a thermal shock temperature of 900 °C. The specimens showed excellent resistance to erosion as there were no obvious erosion traces on the surface of the specimens after undergoing five cycles of erosion.

Batch-Scale Synthesis and Interfacially Enhanced Stability of Silicon Suboxide-Based Anodes toward High-Performance Lithium-Ion Batteries.

SiOx anode materials are among the most promising candidates for next-generation high-energy-density lithium-ion batteries (LIBs). However, their commercial application is hindered by poor conductivity, low initial Coulombic efficiency (ICE), and an unstable solid electrolyte interface. Developing cost-effective SiOx anodes with high electrochemical performance is crucial for advanced LIBs. To tackle these issues, this study utilized APTES as a silicon source and carbon nanotubes (CNTs) as additives to prepare a T-SiOx/C/CNTs composite material with N doping and in situ carbon coating using a "molecular assembly combined with controlled pyrolysis" strategy under mild conditions. The in situ carbon coating, formed by the pyrolysis of organic groups on the molecular precursor, effectively protects the inner SiOx active material. The introduced CNTs enhance electron migration and improve the rigidity of the carbon coating layer. The prelithiated T-SiOx@C/CNTs electrode achieves an ICE of 91.6%, with a specific capacity of 622 mAh g-1 after 400 cycles at 1 A g-1 and 475.8 mAh g-1 after 800 cycles. Full cell tests with commercial NCM811 cathodes further demonstrate the potential of T-SiOx@C/CNTs as a highly promising anode material. This work provides some insights into the rational design of advanced anode materials for LIBs, paving the way for their future development and application.

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.

Theoretical design of graphene/tungsten dichalcogenide (Gr/WX2, X=S, Se) heterostructures used for anode materials of LIBs from DFT calculations

2D van der Waals heterostructures are highly promising for Lithium-ion batteries (LIBs), offering excellent energy capacity and extended lifespan when used as anodes. In this study, we systematically investigate the geometrical structures and electronic properties of graphene/tungsten dichalcogenide (Gr/WX2, X=S, Se) heterostructures, focusing on lithium (Li) atom adsorption and movement in these materials using first-principles calculations through density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. Our results reveal that the Gr/WX2 heterostructures possess excellent structural stability, with mechanical strength validated by their elastic constants. The diffusion barriers of Li atoms in Gr/WS2 and Gr/WSe2 heterostructures are competitive compared with other anode materials. Additionally, the Li diffusion coefficients at 300 K for Gr/WS2 and Gr/WSe2 are also surpassing those observed in pristine Gr. Furthermore, Gr effectively lowers the average open-circuit voltage (OCV) of Gr/WX2 heterostructures to optimal levels, with Gr/WS2 at 0.29V and Gr/WSe2 at 0.25V. The Gr/WS2 and Gr/WSe2 heterostructures after adsorption of Li exhibit remarkable thermal stability at 300K, maintaining their structural integrity throughout the simulation period. Our research provides comprehensive theoretical guidance for the practical development and application of Gr/WX2 heterostructures as anode materials in LIBs.

Polyvinylpyrrolidone-assisted sol–gel synthesis of efficient Li2TiSiO5/C composite anodes for Li-Ion batteries

This study presents the process of developing an effective anode material for lithium-ion batteries (LIBs) by usage of Li2TiSiO5 coated with a thin layer of carbon (LTSO/C). The material was prepared through a sol–gel method, where varying amounts of polyvinylpyrrolidone (PVP) were used as a carbon source during the synthesis process. The physicochemical analysis of the LTSO/C samples indicates that as the amount of PVP used during sol–gel synthesis increases, the particle diameter of LTSO decreases. Furthermore, the analysis shows that a thin amorphous carbon layer is deposited on the LTSO surfaces, along with additional carbon networks between the LTSO particles. Based on the electrochemical analysis conducted to optimize the amount of PVP during synthesis, the resulting LTSO/C composite electrode synthesized with 1 g of PVP exhibits a specific capacity of 274.5 mAh·g−1 at 0.1C after 150 cycles, which is quite close to the theoretical capacity. In addition, this LTSO/C electrode demonstrates exceptional electrochemical performance when operated at high rates, surpassing a discharge capacity of 170 mAh g−1 up to 2C. Therefore, the LTSO/C is an excellent choice for high-performance anode material in LIBs.

Adsorption and diffusion behavior of lithium atom on boron-doped armchair graphene nanoribbon- A dispersion-corrected DFT study

In this paper, we study the relevance of considering dispersion interactions in DFT calculations to determine the adsorption behavior of lithium atom(s) on boron-doped armchair graphene nanoribbons. Our findings suggest that substitutional doping with boron atoms makes the AGNR electron-deficient which results in charge transfer from Li to the AGNR. Li atom binds more strongly to B-doped AGNR than pristine AGNR. A stronger Li-C interaction prevents the clustering of Li atoms, thus, inhibiting dendrite growth. The maximum storage capacity of B-doped AGNR reaches to 1261 mAh/g. B-doped AGNR offers a lower diffusion barrier of 0.19 eV to Li atom as compared to pristine AGNR. From the analysis of density of states, it is observed that the semiconducting nature of both pristine and B-doped AGNRs turns into metallic after the adsorption of lithium atom. Our results show that B-doped AGNR can be used as a potential anode material of lithium-ion batteries.

Mitigating the capacity fading of silicon nanoparticles through double carbon coatings and cobalt doping

Silicon (Si) is considered a highly promising anode material for lithium-ion batteries (LIBs), attributing to its suitable working potential and high specific capacity. Nevertheless, the enormous volume expansion during the lithiation, poor electron conductivity, and low lithium-ion (Li+) diffusion rate limit the application of Si anodes. Here, we design a novel single carbon layer and carbon nanotubes (CNT) coated Si nanoparticle (Si NP@C@CNT composites), in which the single carbon layer derived from citric acid separates between Si nanoparticle (Si NP), effectively avoiding the aggregation of Si NP, while the external carbon framework (CF) composed of CNT boosts the electrical contact between Si NP. Such micro-morphology structure can reduce the stresses during lithiation and promote the formation of stable solid electrolyte interface. Besides, the metallic cobalt (Co) and CNT can effectively enhance electrode conductivity and promote rapid electron transfer. The electrochemical testing results indicate that Si NP@C@CNT anode presents faster electrochemical reaction kinetics with excellent cycle stability (1055.1 mAh g−1 after 300 cycles at 0.5 A g−1) and rate performance (809.9 mAh g−1 at 5 A g-1). The special capacities and capacity retention of Si NP@C@CNT composites are 885.3 mAh g−1 and 85.9 % after 1000 cycles at 1 A g−1. In addition, the constructed full-cell NCM811// Si NP@C@CNT shows well reversible capacity. This research provides a novel idea for Si -based anode with excellent cycling stability, high electron transfer and fast Li+ diffusion ability for LIBs.

Sequencing-Dependent Impact of Carbon Coating on Microstructure Evolution and Electrochemical Performance of Pre-lithiated SiO Anodes: Enhanced Efficiency and Stability via Pre-Coating Strategy.

Silicon monoxide (SiO) has attracted considerable interest as anode material for lithium-ion batteries (LIBs). However, their poor initial Coulombic efficiency (ICE) and conductivity limit large-scale applications. Prelithiation and carbon-coating are common and effective strategies in industry for enhancing the electrochemical performance of SiO. However, the involved heat-treatment processes inevitably lead to coarsening of active silicon phases, posing a significant challenge in industrial applications. Herein, the differences in microstructures and electrochemical performances between prelithiated SiO with a pre-coated carbon layer (SiO@C@PLi) and SiO subjected to carbon-coating after prelithiation (SiO@PLi@C) are investigated. A preliminary carbon layer on the surface of SiO before prelithiation is found that can suppress active Si phase coarsening effectively and regulate the post-prelithiation phase content. The strategic optimization of the sequence whereprelithiation and carbon-coating processes of SiO exert a critical influence on its regulation of microstructure and electrochemical performances. As a result, SiO@C@PLi exhibits a higher ICE of 88.0%, better cycling performance and lower electrode expansion than SiO@PLi@C. The pouch-type full-cell tests demonstrate that SiO@C@PLi/Graphite||NCM811 delivers a superior capacity retention of 91% after 500 cycles. This work provides invaluable insights into industrial productions of SiO anodes through optimizing the microstructure of SiO in prelithiation and carbon-coating processes.

MoS2/SnS heterostructure composite for high-performance lithium-ion battery anodes

Layered metal sulfides are potential anode materials for lithium-ion batteries (LIBs) because their unique structure makes them suitable for Li+ de-intercalation. As a typical 2D layered material, MoS2 is a potential anode material for LIBs due to the weak van der Waals forces between the layers, which facilitates the de-intercalation of Li+ and supports multiple Li+. However, when MoS2 is used as anodes for LIBs material, rapid capacity decay hinders the application. Coupling two different materials to form a heterogeneous structure is an effective way to solve the above problems. In this work, one-pot hydrothermal method is proposed to construct MoS2/SnS heterostructure composites. The electrochemical properties are significantly enhanced, which could be attributed to the presence of heterogeneous structures, leading to increase the electrode charge transfer rate and interfacial reaction kinetics. The results show that the discharge capacity of the MoS2/SnS-1.5 electrode is about 1492.1 mAh/g at 500 mA/g. Furthermore, assembled MoS2@SnS-1.5||LiCoO2 full cell displays a high discharge capacity of 226.1 mAh/g after 50 cycles at 500 mA/g. This facile method provides the application value of layered metal sulfides as LIBs anode materials.

Preparation of WSi@SiOx/Ti3C2 from photovoltaic silicon waste as high-performance anode materials for lithium-ion batteries

Preparation of WSi@SiOx/Ti3C2 from photovoltaic silicon waste as high-performance anode materials 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.