Anode Material For Li-ion Batteries Research Articles

Simple Solution Plasma Synthesis of Ni@NiO as High-Performance Anode Material for Lithium-Ion Batteries Application.

Pursuing of straightforward and cost-effective methods for synthesizing high-performance anode materials for lithium-ion batteries is a topic of significant interest. This study elucidates a one-step synthesis approach for a conversion composite using glow discharge in a nickel formate solution, yielding a composite precursor comprising metallic nickel, nickel hydroxide, and basic nickel salts. Subsequent annealing of the precursor facilitated the formation of the Ni@NiO composite, exhibiting exceptional electrochemical properties as anode material in Li-ion batteries: a capacity of approximately 1000 mAh g-1, cyclic stability exceeding 100 cycles, and favorable rate performance (200 mAh g-1 at 10 A g<M-.1). Comparative analysis across various methods for synthesizing NiO-based materials underscored the superiority of the Ni@NiO composite. Furthermore, an assessment of resource costs demonstrated the cost-effectiveness and scalability of the approach in terms of resource consumption per Ah. Lastly, the integration of a Ni@NiO anode with an NMC532 cathode in a full battery highlights Ni@NiO's potential for conversion anodes, achieving a practical gravimetric energy density of 92 Wh kg-1.

Coral-shaped AlSi anode materials for Li-ion batteries enabled by THF-based electrolyte

This research aims to implement a strategy of using a controlled acidic etching on AlSi alloy particles to partially remove Al and preserve a porous Si framework as anode materials. The etched AlSi materials with different Al/Si weight ratios have been investigated in lithium-ion batteries. Microstructural analysis shows the evolution of the AlSi material during selective wet etching, highlighting the preservation of coral-shaped Si nanostructures with an Al-rich core. Lower Al/Si ratios result in increased surface area and pore volume, which is favorable for improving lithium-ion diffusion and accommodating volume expansion during cycling. Evaluation of electrochemical performance in different electrolytes proves the importance of electrolyte selection for AlSi anodes. The tetrahydrofuran-based (THF-based) electrolyte stabilizes electrochemical reactions, resulting in superior specific capacity, cycle life, and Coulombic efficiency compared to the carbonate-based electrolyte with fluoroethylene carbonate additive. Rate performance analysis shows excellent high-rate capability with stable capacity retention at 3C, particularly in Al53Si47 and Al10Si90 materials. Electrochemical impedance spectroscopy measurements emphasize the critical role of porous structure and electrolytes in sustaining low resistance and enhancing cycle life performance. Selective aluminum etching and the THF-based electrolyte effectively mitigate the breakdown and subsequent reformation of the solid electrolyte interphase, resulting in superior efficiency and extended lifespan.

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

Enhanced electrochemical performance of MgFeO4 spinel as anode materials for Lithium-ion batteries through manganese doping

Existing graphite anode materials are reaching their limits, and iron-based AB2O4 spinel materials are considered as potential anodes for Li-ion batteries owing to their significant theoretical capacities. In this work, novel nanocrystalline MgFe2-xMnxO4 (x = 0, 0.1, 0.2, and 0.3) spinel ferrites were evaluated as anode materials for high-capacity Li-ion batteries. The Mn-doped MgFe2-xMnxO4 (x = 0, 0.1, 0.2, and 0.3) spinel ferrites were synthesized through a facile sol-gel synthesis method coupled with an annealing process. Their crystal structure, morphology, and purity were examined via X-ray diffraction (XRD), Raman spectroscopy, and scanning electron microscopy (SEM). The X-ray diffraction analyses with Rietveld refinement of the synthesized ferrites reveal pure cubic structure with a characteristic Fd3̅m space group for all prepared samples. This was confirmed by Raman spectroscopy by revealing five spinel Raman active modes. The SEM images showed interconnected nanosized particles for all compositions, which led to a porous morphology. Their electrochemical proprieties as anode materials for Li-ion batteries were examined by cyclic voltammetry and galvanostatic charge-discharge tests. For all compositions, the cyclic voltammetry plots demonstrate the conversion type for the Li-ion storage mechanism. At an applied current density of 150 mA g−1, the compositions x = 0, 0.1, 0.2, and 0.3 show initial discharge/charge capacities of 1235/712, 1187/680, 1542/938, and 1239/768 mAh g−1, respectively. After 100 operational cycles, their galvanostatic charge/discharge capacities remain 529/534, 612/606, 642/663, and 700/700 mAh g−1. However, the compositions x = 0.2 and 0.3 exhibit excellent cycling stability during 100 cycles, even at higher rates. As a result, the Mn doping led to enhanced specific capacity and cycling stability of the MgFe2O4 spinel. The optimized compositions with x = 0.2 and 0.3 are, thus, proposed as promising anodes materials compositions for Li-ion batteries.

Structural modeling of high-entropy oxides battery anodes using x-ray absorption spectroscopy

High-entropy oxides (HEOs) are single phase solid solutions where five or more metals share the same sublattice, giving rise to unexpected features in various fields of applications. Recently, HEOs have emerged as an alternative conversion electrode anode material for next-generation Li-ion batteries, where the combination of several different elements in a single solid solution can synergistically act to overcome some of its main drawbacks, improving performance. Due to their chemical complexity, x-ray absorption spectroscopy (XAS) emerges as an appropriate technique to study the electronic (x-ray absorption near edge structure, XANES) and local structure (extended x-ray absorption fine structure, EXAFS) of these compounds as a function of cycling. This work aims to highlight the capabilities of XAS as an element-specific probe to understand a material’s structure at the atomistic level through EXAFS modeling of (MgFeCoNiCuZn)O high-entropy system and how to extract valuable information about the bond distance, number of near neighbors, and local disorder, which are crucial to a full understanding of the electrochemical reaction mechanisms of such battery electrodes.

A DFT modeling of 4-cyclohexene-1,3-dione embedded in covalent triazine framework as a stable anode material for Li-ion batteries

Developing porous organic anode materials with outstanding electrical conductivity and high capacity is crucial to enhancing the performance of Li-ion batteries (LIBs). Herein, 4-cyclohexene-1,3-dione-functionalized covalent triazine framework (CYC-CTF0) monolayer as a new anode material in LIBs was explored through density functional theory calculations. The monolayer demonstrates good thermal, mechanical, and cycling stability and has a strong affinity for Li-ions to bind to the C=O and C=N redox-active sites. The adsorption of Li-ions transforms the CYC-CTF0 monolayer from being semiconducting to becoming metallic, reflecting its high electrical conductivity. Remarkably, the lattice undergoes a minimal expansion of 1.1 % throughout the charging and discharging process, suggesting an extended cycle life. The unit cell of the monolayer can be fully loaded with four Li-ions at different adsorption sites, exhibiting a specific theoretical capacity of 585.41 mAh g−1 and a low open-circuit voltage of 0.12 V. Moreover, the adsorbed Li-ions display a low diffusion energy barrier of 0.17 eV, enabling effective rates of charging and discharging. Our findings reveal the unique characteristics of the CYC-CTF0 monolayer as a promising anode material in LIBs.

Redox Mechanisms upon the Lithiation of Wadsley-Roth Phases.

The Wadsley-Roth family of transition metal oxide phases are a promising class of anode materials for Li-ion batteries due to their open crystal structures and their ability to intercalate Li at high rates. Unfortunately, most early transition metal oxides that adopt a Wadsley-Roth crystal structure intercalate Li at voltages that are too high for most battery applications. First-principles electronic structure calculations are performed to elucidate redox mechanisms in Wadsley-Roth phases with the aim of determining how they depend on crystal structure. A comparative study of two very distinct polymorphs of Nb2O5 reveal two redox mechanisms: (i) an atom-centered redox mechanism at early stages of Li intercalation and (ii) a redox mechanism at intermediate to high Li concentrations involving the bonding orbitals of metal-metal dimers formed by edge-sharing Nb cations. Our study motivates several design principles to guide the development of new Wadsley-Roth phases with superior electrochemical properties.

Solid-state lithium batteries composed of hematite and oxide electrolyte

As Li-ion battery anode materials, two types of hematite (Fe2O3(big), Fe2O3(ultrafine)) were evaluated by using liquid electrolyte and oxide-based solid electrolyte. Although the anode using Fe2O3(ultrafine) with larger specific surface area showed a high initial reversible capacity in the liquid-electrolyte cell, there was a steep capacity decay in the cycling test. In the solid-electrolyte cell, we obtained very low reversible capacities of 40 mA h g−1 for the anode using Fe2O3(big) with smaller specific surface area. In contrast, the capacity of Fe2O3(ultrafine) anode was as high as 400 mA h g−1 at the 20th cycle. This is the first demonstration of charge–discharge reactions for Fe2O3 anode in oxide-based solid-state batteries. The Fe2O3(ultrafine) particles were dispersed relatively uniformly between solid electrolyte in the active layer, suggesting that the contact area between Fe2O3 and solid electrolyte becomes large. Consequently, Fe2O3(ultrafine) could benefit from larger contact area delivering the suitable reaction site for Li+ to improve the anode performance.

Investigation of N C and B C bilayers as anode materials for Li-ion batteries by first-principles calculations.

The best choice today for a realistic method of increasing the energy density of a metal-ion battery is to find novel, effective electrode materials. In this paper, we present a theoretical investigation of the properties of hitherto unreported two-dimensional B C and N C bilayer systems as potential anode materials for lithium-ion batteries. The simulation results show that N C bilayer is not suitable for anode material due to its thermal instability. On the other hand B C is stable, has good electrical conductivity, and is intrinsically metallic before and after lithium intercalation. The low diffusion barrier (0.27 eV) of Li atoms shows a good charge and discharge rate for B C bilayer. Moreover, the high theoretical specific capacity (579.57 mAh/g) connected with moderate volume expansion effect during charge/discharge processes indicates that B C is a promising anode material for Li-ion batteries.

Sulphonated coal tar pitch as a carbon source to develop the storage capacity of Fe2O3@C materials

Utilizing metal oxides as substitutes for carbon anodes is imperative in advancing LIBs. Recently, the researchers regarding to the Fe2O3 have become very popular owing to its advantages such as a high theoretical capacity (1007 mAh g−1), cost-effectiveness and sustainability. In our present studies, the Fe2O3@SCTPC (Fe2O3 nanosphere coated by carbons which are obtained by the carbonizations using the sulphonated coal tar pitches) materials are firstly and successfully fabricated by a one-step hydrothermal method using the Fe(NO3)3·9 H2O and sulphonated coal tar pitches (SCTPs). An intriguing observation is that the nanosphere Fe2O3 is encapsulated by carbons with a core-shell structure. This specific core-shell structure effectively mitigates the volume expansion of Fe2O3, and exhibits a notable enhancement in conductivity. Thanks to this unique structure, the Fe2O3@SCTPC electrode has a maximum capacity of 1106.74 mAh g−1 after 100 cycles at a current density of 0.1 A g−1 and a high reversible specific capacity of 373.5 mAh g−1 after 500 cycles at a current density of 2 A g−1, when it is used as an anode material for Li-ion battery. These results suggest that adjusting the structures of carbons is crucial to develop the potential storage capacity of the covered Fe2O3.

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.

In Situ Integration of a Flame Retardant Quasisolid Gel Polymer Electrolyte with a Si-Based Anode for High-Energy Li-Ion Batteries.

Silicon (Si) stands out as a promising high-capacity anode material for high-energy Li-ion batteries. However, a drastic volume change of Si during cycling leads to the electrode structure collapse and interfacial stability degradation. Herein, a multifunctional quasisolid gel polymer electrolyte (QSGPE) is designed, which is synthesized through the in situ polymerization of methylene bis(acrylamide) with silica-nanoresin composed of nanosilica and a trifunctional cross-linker in cells, leading to the creation of a "breathing" three-dimensional elastic Li-ion conducting framework that seamlessly integrates an electrode, a binder, and an electrolyte. The silicon particles within the anode are encapsulated by buffering the QSGPE after cross-linking polymerization, which synergistically interacts with the existing PAA binder to reinforce the electrode structure and stabilize the interface. In addition, the formation of the LiF- and Li3N-rich SEI layer further improves the interfacial property. The QSGPE demonstrates a wide electrochemical window until 5.5 V, good flame retardancy, high ionic conductivity (1.13 × 10-3 S cm-1), and a Li+ transference number of 0.649. The advanced QSGPE and cell design endow both nano- and submicrosized silicon (smSi) anodes with high initial Coulombic efficiencies over 88.0% and impressive cycling stability up to 600 cycles at 1 A g-1. Furthermore, the NCM811//Si cell achieves capacity retention of ca. 82% after 100 cycles at 0.5 A g-1. This work provides an effective strategy for extending the cycling life of the Si anode and constructing an integrated cell structure by in situ polymerization of the quasisolid gel polymer electrolyte.

Versatile multi-lithiophilic metal oxide nano seeds embedded in hollow carbon nanospheres via electrostatically functional template for dendrite-free lithium metal anodes

Lithium metal anodes, which are promising candidates for anode materials in Li-ion batteries, are highly regarded for their combination of high energy density and low electrochemical potential, making them a compelling option for next-generation anodes. However, the growth of dendritic Li during the charging and discharging processes, along with the resulting decrease in stability and efficiency, poses a significant obstacle to the commercialization of Li metal anodes. To address the challenges associated with Li metal anodes, we propose the use of hollow carbon incorporating zinc oxide (ZnO) and magnesium oxide (MgO) as anode materials. ZnO has high lithiophilicity, enabling selective reactions with Li ions, and MgO exhibits a low nucleation overpotential. By placing these two substances inside the hollow carbon structure, stable Li growth can occur within the hollow carbon, enabling the formation of a reliable Li metal anode. Furthermore, to simplify and precisely synthesize the proposed structure, polystyrene-b-polyacrylic acid was introduced. Metals such as Zn and Mg can be uniformly attached to the hollow carbon through the carboxylic group of acrylic acid. The synthesized structure exhibited significantly improved Li storage performance compared to that of hollow carbon. It demonstrated superior metrics, achieving a Coulombic efficiency of 99.8% over 350 cycles. The introduction of Zn and Mg with distinct properties effectively enhanced the internal storage performance of Li in hollow carbon.

Low diffusion barrier in black phosphorene/graphdiyne heterostructure for ultrafast Li-ion battery anode

Black phosphorene (BlackP) with low diffusion barriers has been extensively researched as one of the new Li-ion batteries (LIBs) anode materials. Nevertheless, the poor mechanical properties and elastic stiffness of BlackP obviously limit its practical application. Thus, owing to the excellent mechanical properties and good elastic stiffness exhibited by Graphdiyne (GDY), the BlackP/GDY Van der Waals (vdW) heterostructure was investigated in our study to overcome those disadvantages on the basis of the density functional theory (DFT). Our results suggest that the BlackP/GDY vdW heterostructure has favorable mechanical properties and high thermodynamic stability with a small lattice mismatch, which is owing to the synergistic effect existed in BlackP and GDY. Besides, the adsorption energy of Li adsorption on the BlackP/GDY vdW heterostructure evidently enhanced along with the changing of the heterostructure from semiconductor to metallic. Moreover, the maximum theoretical storage capacity (384.703 mA h/g) of the BlackP/GDY vdW heterostructure is larger than that of Graphite (372 mA h/g). Above all, the minimum diffusion barrier (0.083 eV) is extremely low, which is vital for achieving ultrafast charge and discharge rates. These favorable advantages suggest that the BlackP/GDY vdW heterostructure is a viable ultrafast LIBs anode material.

Multiwalled-Carbon-Nanotube-Modified Li2ZnTi3O8 as Anode with Improved Cycling Stability and Rate Capability for Lithium-Ion Batteries

Due to its better electronic conductivity and larger lithium intercalation capacity, a multiwalled-carbon-nanotube (MWCNT)-modified Li2ZnTi3O8 (LZTO) has significant potential for use as an anode material for Li-ion batteries. The rapid and affordable ball-mill-aided solid state approach is used to synthesize LZTO with MWCNT-modified Li2ZnTi3O8 (LZTO@MWCNTs). Electrochemical performance tests of the anode material were carried out using cyclic voltammetry (CV), galvanostatic charge-discharge measurement, and electrochemical impedance spectroscopy (EIS). The CV experiments reveal that the LZTO@MWCNT electrode has a lower anodic and cathodic peak potential difference (0.184 V) than the LZTO electrode (0.211 V) and LZTO@MWCNT electrode has better electrochemical reversibility than that of pristine electrode after five cycles utilizing the same procedure. LZTO@ MWCNTs anode material has a higher charge-discharge capacity than LZTO anode material at 0.1–5 C rates. After 100 cycles, the initial discharge capacities of LZTO@MWCNT electrode are 227 and 142 mAh g−1 at the 1C–5C rate, respectively, whereas the initial discharge capacities of LZTO electrode are only144 and 28 mAh g−1 in the same condition. The charge transfer and SEI resistance of the LZTO anode are 19.31 and 62.74 ohms, respectively, after 30 cycles at 1C, according to the EIS data. Additionally, the values for the LZTO@MWCNTs anode are 7.93 and 12.06 ohms for charge transfer and SEI resistance, respectively.

Functionalized MBenes as promising anode materials for high-performance alkali-ion batteries: a first-principles study

The discovery of novel electrode materials based on two-dimensional (2D) structures is critical for alkali metal-ion batteries. Herein, we performed first-principles computations to investigate functionalized MXenes, Mo2BT2 (T = O, S), which are also regarded as B-based MXenes, or named as MBenes, as potential anode materials for Li-ion batteries and beyond. The pristine and T-terminated Mo2BT2 (T = O, S) monolayers reveal metallic character with higher electronic conductivity and are thermodynamically stable with an intrinsic dipole moment. Both Mo2BO2 and Mo2BS2 monolayers exhibit high theoretical Li/Na/K storage capacity and low ion diffusion barriers. These findings suggest that functionalized Mo2BT2 (T = O, S) monolayers are promising for designing viable anode materials for high-performance alkali-ion batteries.

Dilithium pyridine-2, 5-dicarboxylate as potential anode material for Li-ion battery

Amongst various small molecules with different functional groups, conjugated carbonyls are the most promising materials for lithium storage at low potential. This work reports lithium storage in dilithium pyridine-2, 5-dicarboxylate small molecule. We show here that dilithium pyridine-2, 5-dicarboxylate reversibly stores 2 mol of Li-ion per molecule, giving a reversible capacity of 307 mAh/g at an average voltage of 1.0 V. The capacity retention after 500 cycles at 1C rate is 69 %. This material shows impressive rate performance with a capacity retention of 140 mAh/g at 5C rate. The inclusion of electronegative nitrogen in the benzene ring helps in improving the storage performance compared to lithium terephthalate. Further ex-situ studies demonstrate possible mechanism for reversible lithium storage. Our findings showcase that the deliberately engineered organic electrode material facilitates the development of high capacity lithium-ion battery.

A Fast-Charge Graphite Anode with a Li-Ion-Conductive, Electron/Solvent-Repelling Interface.

Graphite has been serving as the key anode material of rechargeable Li-ion batteries, yet is difficultly charged within a quarter hour while maintaining stable electrochemistry. In addition to a defective edge structure that prevents fast Li-ion entry, the high-rate performance of graphite could be hampered by co-intercalation and parasitic reduction of solvent molecules at anode/electrolyte interface. Conventional surface modification by pitch-derived carbon barely isolates the solvent and electrons, and usually lead to inadequate rate capability to meet practical fast-charge requirements. Here we show that, by applying a MoOx-MoNx layer onto graphite surface, the interface allows fast Li-ion diffusion yet blocks solvent access and electron leakage. By regulating interfacial mass and charge transfer, the modified graphite anode delivers a reversible capacity of 340.3 mAh g-1 after 4000 cycles at 6 C, showing promises in building 10-min-rechargeable batteries with a long operation life.

Large-Scale Synthesis of Highly Porous CuO/Cu2O/Cu/Carbon Derived from Aerogels for Lithium-Ion Battery Anodes.

In this work, an effective strategy for the large-scale fabrication of highly porous CuO/Cu2O/Cu/carbon (P-Cu-C) has been established. Cu-cross-linked aerogels were first continuously prepared using a continuous flow mode to form uniform beads, which were transformed into P-Cu-C with a subsequent pyrolysis process. Various pyrolysis temperatures were used to form a series of P-Cu-C including P-Cu-C-250, P-Cu-C-200, P-Cu-C-350, and P-Cu-C-450 to investigate suitable pyrolysis conversion processes. The obtained P-Cu-C series were utilized as anodes of lithium-ion batteries, in which P-Cu-C-250 exhibited a higher reversible gravimetric capacity, excellent rate capability, and superior cycle stability. The enhanced behavior of P-Cu-C-250 was benefitted from the synergistic interaction between uniformly dispersed CuO, Cu2O, Cu nanoparticles, and highly graphitized carbon with a large surface area and highly porous structure. More importantly, the preparation of P-Cu-C-250 could be scaled up by taking advantage of the continuous flow synthesis mode, which may provide pilot- or industrial-scale applications. The large-scale fabrication proposed here may give a universal method to fabricate highly porous metal oxide-carbon anode materials for electrochemical energy conversion and storage applications. Porous CuO/Cu2O/Cu/carbon derived from Cu-crosslinked aerogels was used as Li-ion battery anode materials, exhibiting a high reversible areal capacity, large gravimetric capacity, superior cycling performance, and excellent rate capacity. A continuous preparation method is established to ensure the product scaled up.

Reutilization of Silicon-Cutting Waste via Constructing Multilayer Si@SiO2@C Composites as Anode Materials for Li-Ion Batteries.

The rapid development of the photovoltaic industry has also brought some economic losses and environmental problems due to the waste generated during silicon ingot cutting. This study introduces an effective and facile method to reutilize silicon-cutting waste by constructing a multilayer Si@SiO2@C composite for Li-ion batteries via two-step annealing. The double-layer structure of the resultant composite alleviates the severe volume changes of silicon effectively, and the surrounding slightly graphitic carbon, known for its high conductivity and mechanical strength, tightly envelops the silicon nanoflakes, facilitates ion and electron transport and maintains electrode structural integrity throughout repeated charge/discharge cycles. With an optimization of the carbon content, the initial coulombic efficiency (ICE) was improved from 53% to 84%. The refined Si@SiO2@C anode exhibits outstanding cycling stability (711.4 mAh g-1 after 500 cycles) and rate performance (973.5 mAh g-1 at 2 C). This research presents a direct and cost-efficient strategy for transforming photovoltaic silicon-cutting waste into high-energy-density lithium-ion battery (LIB) anode materials.