Materials For Lithium-ion Batteries Research Articles

Exploring Electrolyte Adsorption on the Different Types of Layered Cathode Surfaces in Lithium-Ion Batteries via a Universal Neural Network Potential Method.

LiNi x Mn y Co z O2 (NCM) is a promising cathode material for lithium-ion batteries. Their long-term stability and impedance growth as cycles are strongly influenced by the properties of the cathode electrolyte interface (CEI), formed by the reaction between the electrolyte and electrode surface. Understanding of these interactions at the atomic level of the NCM electrode surface and electrolyte will provide a new strategic approach for the design of a highly functional CEI layer. In this study, we explored the influence of Ni content in transition metal layers on surface energies under different synthetic conditions and terminations using a density functional theory (DFT) validated universal neural network potential (UNNP) method. Furthermore, we investigated the adsorption of ethylene carbonate (EC) and dimethyl carbonate (DMC) on the most favorable NCM surfaces. EC and DMC displayed similar adsorption energy trends; however, differences were observed in the preferred configurations, which can affect the formation of the CEI.

Rational synthesis of vertical graphene supported TiN@N-Li4Ti5O12 as advanced high-rate electrodes for lithium-ion batteries

The Li4Ti5O12 (LTO) is demonstrated to be one of the most promising anode materials for lithium-ion batteries (LIBs) to provide safe and high-power density cells but suffer from poor electrical conductivity. In this study, we present a TiN-decorated N-LTO on a vertical graphene (VG) array (TiN@N-LTO) as a potential anode material for lithium-ion batteries (LIBs). The use of atomic layer deposition (ALD) enables the formation of a thin layer of LTO on VG, with precise control over the thickness. The VG serves as highly conductive channels, facilitating the transfer of electrons. Moreover, the introduction of nitrogen heteroatoms into the LTO under an active N2 plasma atmosphere has been shown to enhance its intrinsic conductivity, which is achieved by reducing the bandgap and expanding the diffusion pathways of ions. Concurrently, a small number of metallic TiN are formed and deposited on the surface of N-LTO, thereby further improving its conductivity. COMSOL simulations and DFT calculations demonstrate that the introduced TiN acts as a "conductive bridge", improving the charge distribution of LTO electrodes and enhancing the Li+ transport rate. The TiN@N-LTO exhibits a high rate performance (169.51, 131.61 and 101.08 mAh/g at 0.2, 2 and 20 C, respectively) and remarkable cycling stability (a capacity retention of 99.6% after 5000 cycles at 10 C).

Aluminum particles as anode material for lithium ion batteries: effect of particle sizes on the electrochemical behaviours

This study presents a preliminary investigation on using pristine aluminum particles as anodes for lithium-ion battery. The microstructural characteristics of aluminum particle samples with sizes from 100 nm (0.1 μm) to 70 µm were analyzed by the SEM and XRD methods. The electrochemical behaviors of the aluminum particles were examined by the cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD) measurements. The obtained results demonstrated the distinct lithiation/delithiation features of the aluminum electrodes at the potential couple of around 0.25 V/0.50 V vs. Li/Li+. Moreover, the GCD results also revealed the strong impact of the particle size on the initial capacity and galvanostatic discharge/charge potential profiles of electrode samples. However, aluminum electrodes with the large-sized particles showed dramatical capacity decay after certain cycles, and stabilized at around the specific capacity of 50 mAh g-1 and exhibited capacitive charge/discharge behavior. In contrast, the nano-sized particles aluminum electrodes possessed stable electrochemical performance upon cycling, but with low initial capacities. The results in this work will enrich the knowledge of the aluminum-based anode for LIBs in future works.

In situ anchoring of FeNi nanoparticles into three-dimensional nitrogen-doped carbon framework as a self-supporting electrode for high-performance lithium storage

Constructing free-standing electrodes with superior lithium storage capacity and good mechanical performance are fascinating for next-generation lithium-ion batteries (LIBs). Nevertheless, their practical application is hindered by complicated synthesis procedures and high cost. Herein, a highly stable, self-supporting and flexible electrode material for LIBs was constructed by encapsulating spherical FeNi nanoparticles into one-dimensional N-doped carbon fiber film (FeNi/N- CFM) using the electrospinning technique and subsequent heat treatment. The FeNi/N-CFM can be directly used as anode materials for LIBs without conductive additive, current collector and binder. The synergistic effect of uniformly dispersed small FeNi nanoparticles and three-dimensional (3D) conductive network constructed by CF framework effectively improves the utilization rate of active materials, enhances the transport of both electrons and lithium ions, facilitates the electrolyte penetration, and promotes the lithium-ion storage kinetics and stability, thus leading to a greatly enhanced electrochemical performance. Benefiting from the unique architectural feature and flexibility, the FeNi/N-CFM composites employed as binder-free electrodes for LIBs exhibit good lithium storage performance (an initial discharge capacity of 1031.5 mA h g−1 and a reversible capacity of 481.3 mA h g−1 at 100 mA g−1 after 100 cycles), rate capacity (305.1 mA h g−1 at 1000 mA g−1) and outstanding reversibility (coulombic efficiency of around 100 % after 100 cycles). Furthermore, this work also provides a facile and effective pathway to design and fabricate free-standing electrodes.

Core–shell Fe2O3@MnO2 nanoring composites as anode materials for high-performance lithium-ion batteries

Core–shell Fe2O3@MnO2 nanoring composites as anode materials for high-performance lithium-ion batteries

Harnessing MBene termination for superior anode interfaces in Li/Ca-ion batteries

The elevation of two-dimensional (2D) transition metal borides, specifically MBenes, as anode materials for lithium-ion batteries (LIBs) and calcium-ion batteries (CIBs) can be achieved through strategic functionalization with appropriate groups. Utilizing a first-principles approach, we conducted an in-depth investigation into the electrochemical properties of chlorine-terminated V2B (V2BCl2) as a candidate anode material for LIBs and CIBs. V2BCl2 exhibits metallic behavior, as demonstrated by band structure analysis, which endows it with exceptional conductivity due to the free electron surface of the system, thereby embodying ideal anode characteristics. The dynamic and thermal stability of the system was assessed through comprehensive phonon dispersion analyses and ab-initio molecular dynamics (AIMD) calculations. High net charge transfer rates of Li/Ca ions towards the monolayer, augmented electron localization function (ELF) near system atoms, and the presence of ionic bonds between Ca/Li and the V2BCl2 monolayer contribute to the enhanced conductivity observed in these anode systems. This is corroborated by metrics such as the projected crystal orbital Hamiltonian population (-pCOHP), low diffusion energy barriers (< 0.35 eV) facilitating rapid charging mechanisms, and low open circuit voltages (< 0.32 V) ensuring robust battery performance stability. Furthermore, V2BCl2 exhibits notable specific storage capacities of 875.67 mAh g−1 for Ca ions and 1167.75 mAh g−1 for Li ions, surpassing the benchmarks set by recent MBene systems. These promising results strongly advocate for V2BCl2 as a viable candidate for anode material in both LIB and CIB applications, highlighting its potential significance in advancing battery technology.

A Review of Mexican Contributions to Li2CuO2 and its Chemical Modifications as Cathode Materials for Lithium-Ion Batteries

Abstract. Over the past few decades, battery research has primarily focused on reducing costs and increasing energy density. There have been significant efforts to identify alternative cathode materials that could replace cobalt-based ones, with the goal of finding more environmentally friendly and cost-effective options. In this context, copper-based cathodes have emerged as promising candidates. The appeal of copper-based cathodes lies in their relatively high abundance, particularly in Mexico, their high theoretical energy density, and the potential to enhance their properties by altering their chemical structure. In recent years, numerous research initiatives in Mexico have aimed to make Li2CuO2 cathodes a viable option. This review examines the recent advances and future perspectives of these efforts, with a particular emphasis on the latest attempts to modify the synthesis route and incorporate multiple dopants to create synergistic effects. Resumen. Durante las últimas décadas, la investigación sobre baterías se ha enfocado principalmente en la disminución de costos y el incremento de la densidad energética. Se han realizado importantes esfuerzos para identificar materiales catódicos alternativos que podrían reemplazar a los materiales basados en cobalto, con el objetivo de encontrar opciones rentables y con menor impacto al medio ambiente. En este contexto, los materiales catódicos basados en cobre se han convertido en candidatos prometedores. El interés por los cátodos basados en cobre radica en su abundancia relativamente alta, particularmente en México, su alta densidad energética teórica y la cualidad de mejorar sus propiedades alterando su estructura química. En los últimos años, numerosas propuestas de investigación en México han tenido como objetivo hacer de los cátodos de Li2CuO2 una opción viable. Este resumen recopila los avances recientes y las perspectivas a futuro de estos esfuerzos, con especial énfasis en los últimos intentos de modificar la ruta de síntesis y, a su vez, incorporar múltiples dopantes para crear efectos sinérgicos.

Enhanced Cyclic Performance of Lithium-Ion Battery Based on Anthraquinone/SBA-15 Composite Cathode Prepared via Ultra-Sonication

In this study, novel organic/inorganic composites were fabricated by blending anthraquinone (AQ) with SBA-15 molecular sieve in varying ratios via ultrasonication, characterized structurally using XRD, SEM, and BET methods, and analyzed electrochemically as cathode materials for lithium-ion batteries via galvanostatic discharge/charge and electrochemical impedance spectroscopy. The composite with a 2:1 ratio of AQ and SBA-15 achieved a specific discharge capacity of 144.5 mAh/g at 0.2 C, which decreased to 63.3 mAh/g after 50 cycles, 8% higher than that of the pure AQ. The initial discharge platform of the composite was 2.28 V, which decreased to 2.10 V after 50 cycles, 50 mV higher than that of the pure AQ. This is because the loading of anthraquinone particles by the SBA-15 pore size structure facilitated the stabilization of the active materials, hindered the solubility of AQ in the electrolyte, and enhanced the cycling stability of the battery.

Effect of Rare Earth Ion Doping on the Performance of Lithium-Rich Cathode Materials for Lithium-Ion Batteries

Lithium-rich layered oxide cathode materials have the advantages of a high voltage and a high specific capacity. Their commercial applications have however been impeded by some disadvantages such as low initial coulombic efficiency and low cycle life. To overcome these issues, rare earth ion-doped lithium-rich layered oxide cathode materials are investigated in this work. The irreversible release of O2- in Li2MnO3 is suppressed by rare earth ions doping, which enhanced the initial coulombic efficiency of the materials. Meanwhile, the rare-earth ion radius used for doping is larger than the Mn4+ radius, which enlarges the (003)-crystalline plane spacing, resulting in a significant enhancement of the rate performance of the material.

High-Performance Polyimide Covalent Organic Frameworks for Lithium-Ion Batteries: Exceptional Stability and Capacity Retention at High Current Densities.

Organic polymers are considered promising candidates for next-generation green electrode materials in lithium-ion batteries (LIBs). However, achieving long cycling stability and capacity retention at high current densities remains a significant challenge due to weak structural stability and low conductivity. In this study, we report the synthesis of two novel polyimide covalent organic frameworks (PI-COFs), COF-JLU85 and COF-JLU86, by combining truxenone-based triamine and linear acid anhydride through polymerization. These PI-COFs feature layers with pore channels embedded with 18 carbonyl groups, facilitating rapid lithium-ion diffusion and enhancing structural stability under high current densities. Compared to previously reported organic polymer materials, COF-JLU86 demonstrates the excellent performance at high current densities, with an impressive specific capacity of 1161.1 mA h g-1 at 0.1 A g-1, and outstanding cycling stability, retaining 1289.8 mA h g at 2 A g-1 after 1500 cycles and 401.1 mA h g-1 at 15 A g-1 after 10000 cycles. Additionally, in-situ infrared spectroscopy and density functional theory (DFT) calculations provide mechanistic insights, revealing that the high concentration of carbonyl redox-active sites and the optimized electronic structure contribute to the excellent electrochemical performance.

DFT investigation on effectiveness of Beryllium-doped and defective graphene for anode material in lithium-ion batteries

Lithium-ion batteries employing graphite as the anode material are now widely used in powering electronic gadgets like, mobile phones, laptops, electronic watches and calculators and also to provide required power to run engine of electric vehicles. However, storage capacity, open circuit voltage, energy density and battery life are the major considerations on which researchers are trying different alternatives to achieve better performance of the battery. In this research, Beryllium-doped and defective graphenes have been investigated by employing the ab initio DFT method. It has been found that graphene with a defect and Be–doped graphene with defects can serve as an efficient materials for anode in Li-ion batteries.

Exploring the Electrochemical Superiority of V2O5/TiO2@Ti3C2-MXene Hybrid Nanostructures for Enhanced Lithium-Ion Battery Performance.

The use of vanadium(V)-based materials as electrode materials in electrochemical energy storage (EES) devices is promising due to their structural and chemical variety, abundance, and low cost. V-based materials with a layered structure and high multielectron transfer in the redox reaction have been actively explored for energy storage. Our current work presents the structural and electrochemical properties of a vanadium-based composite with TiO2@Ti3C2 MXene, referred to as VM. This composite is obtained through the in situ thermal decomposition of the VO2(OH)/Ti3C2mixture, which is achieved by solution mixing and drying. The material structure is confirmed using various characterization tools, which establish an orthorhombic V2O5 nanostructure compositing with nanocrystalline TiO2@Ti3C2. VM with 5 wt % MXene, referred to as VM5, can achieve 460 mAhg-1 at a current density of 0.1 Ag1- and 290 mAhg-1 at 1 Ag1-, with an average coulombic efficiency of 98.5%. The presence of the V2O5/TiO2 (nanocrystals) heterojunction attached with Ti3C2 sheets contributed to reduced charge transfer resistance. The cyclic stability shows a capacity retention of 62% over 500 cycles at 1 Ag1- (4C rate, where 1C equals 0.25 Ag1-) with a 0.22 capacity drop with each cycle. Dunn's approach to examining the charge storage mechanism demonstrates 72% contribution of the surface-dominant capacitive process and 28% of the diffusion-controlled intercalation process at 0.4 mVs-1, suggesting a potential high-performance pseudocapacitive hybrid electrode material for lithium-ion batteries.

Synthesis of C@Si composite materials for lithium battery anode using Chinese rose as carbon source

As a promising anode for lithium-ion batteries (LIBs), silicon (Si) has been studied due to its high specific capacity. However, significant volume change during charge-discharge process has seriously impeded its practical application. Compounding with carbon is one of the methods to solve this problem. In this paper, biomass carbon is prepared by high temperature carbonization of Chinese rose petals. Different mass ratios of Si nanoparticles are embedded in the biomass carbon to produce C@Si composites. The as-prepared C@Si composites are assembled into LIBs to investigate their electrochemical performance. As an anode material for LIBs, the manufactured C@Si composite material (Si-25 wt%) manifests a stable cycling performance (524 mAh•g−1 at 0.1 A•g−1 after 100 cycles), a long cycle life (581 mAh•g−1 at 1 A•g−1 after 400 cycles) and excellent rate capability. And its initial coulombic efficiency at the current density of 1 A•g−1 (99.62 %) is much larger than that of pure nano-Si (29.45 %). The electrochemical impedance spectroscopy (EIS) results indicate that the C@Si composite materials can behave as an ideal capacitor. This study reveals the possibility of changing flower petals to carbon material and the potential applications in the field of LIBs.

Nanosizing strategy to fabricate uniformly dispersed NiO/Ni/lignin porous carbon composites for high lithium storage

Nickel oxide is considered a promising anode material for lithium-ion batteries. Nevertheless, its performance is hindered by significant volume expansion and low electrical conductivity, particularly at larger particle sizes, which lead to a notable decrease in lithium storage capacity and rate performance. To address these challenges, we introduce a nanocomposite strategy to synthesise nickel oxide and lignin-derived porous carbon composites (LPC/Ni/NiO). Through in situ polymerization, lignin macromolecules form a uniform 3D network with nickel carbonate, which, during the subsequent carbonisation process, results in the formation of nickel oxide within a conductive carbon network. This approach reduces the nickel oxide to nanosize and enhances the composite's electrical conductivity, effectively integrating the buffering framework of porous carbon with the high storage capacity of nickel oxide. As a result, the LPC/Ni/NiO composite exhibited significantly improved lithium storage capacity. Notably, when employed as an anode material in lithium-ion half-cells, the optimized composite maintained an excellent specific capacity of 1065 mAh/g after 100 cycles at a current density of 0.2 A/g. It also shown exceptional rate performance, delivering a specific discharge capacity of 505 mAh/g at a current density of 2 A/g, with stable cycling performance. The electrochemical reaction process was further validated using in ex-situ EIS. This study offers valuable insights into scalable synthesis methods for oxide nanocomposites, highlighting their potential as promising anode materials for lithium-ion batteries.

Three-dimensional porous structure CoP/N-doped carbon nanospheres as anode for enhanced lithium storage performance

Transition metal phosphides (TMPs) with high theoretical capacities and safe operating voltage are recognized as prospective anode materials for lithium-ion batteries (LIBs). While, the huge volume expansion and low conductivity of TMPs still restrict their applications. Engineering nanostructured composites consisting of TMPs and conductive carbon-based materials is of great importance to improve electrochemical performance. Herein, a novel and facile pyrolysis-oxidation-phosphidation approach is designed to fabricate porous nanospheres composing of CoP nanoparticles and N-doped carbon substrate. The abundant pores in CoP/N-C provide ample active sites for lithium storage and facilitate Li+ transport. The introduction of N-doped carbon substrate enhances the electrical conductivity, allowing CoP to maintain its structure during cycling. The CoP/N-C anode achieves remarkable cycle performance, maintaining an extremely stable cycle life over 2000 cycles at 5 A g−1. More importantly, the full cell consisting of CoP/N-C and LiFePO4 also exhibits a prominent cycling durability with a capacity retention of 96.5 % at 0.1 A g−1 after 150 cycles. This work proposes a simple and feasible structural engineering strategy, which can provide a new way for optimizing the electrochemical performance of conversion-type anode materials.

Enhancement of LiFePO4 cathodic material through incorporation of reduced graphene oxide via a simple two-step procedure

The aim of the present work is the improvement of LiFePO4 (LFP) as cathodic material for Lithium Batteries (LIBs) by controlled incorporation of graphene oxide (GO) and its subsequent reduction during LFP synthesis. The electrochemical performance of the samples is analysed after reduction treatment of GO in different steps of the synthesis. The purpose of the reduction is to provide LFP particles with higher conductivity through a uniform conductive carbon coating that facilitates the migration of Li+ ions in the cathode for charge-discharge process. These electrochemical measurements revealed an initial discharge capacity of 70.19 mAh g−1 for LFP without GO, 141.3 mAh g−1 and 154.3 mAh g−1 with GO added in heat-treatment and solvothermal step, at 0.5C rate, respectively. Additionally, the cycling stability of the samples with GO improves the corresponding one obtained for pristine LFP. At 0.5C rate cycle-life, the LFP with GO combined with raw materials during solvothermal synthesis, attained capacity retention of 99 % after 100 cycles, decreasing to values of 88 % and 87 % for LFP with GO incorporated just before thermal treatment and LFP without GO. These results indicate that the LFP with GO incorporated initially in the synthesis improves rate capability of the material, reaching reversible capacity of 158.5 mAh g−1 at 0.1C, 154.4 mAh g−1 at 0.2C, 151.3 mAh g−1 at 0.5C, 122.7 mAh g−1 at 1C and 112.6 mAh g−1 at 2C. The improvement in electrochemical behaviour can be attributed to the optimization of the synthesis process that provides a well-crosslinked interior of the composite and, therefore, a stable conductive network which has an associated higher diffusion coefficient.

Discharging of Ramsdellite MnO2 Cathode in a Lithium-Ion Battery.

We report an application of our unbiased Monte Carlo approach to investigate thermodynamic and electrochemical properties of lithiated manganese oxide in the ramsdellite phase (R-MnO2) to uncover the mechanism of lithium intercalation and understand charging/discharging of R-MnO2 as a cathode material in lithium-ion batteries. The lithium intercalation reaction was computationally explored by modeling thermodynamically significant distributions of lithium and reduced manganese in the R-MnO2 framework for a realistic range of lithium molar fractions 0 < x < 1 in Li x MnO2. We employed interatomic potentials and analyzed the thermodynamics of the resultant grand canonical ensemble. We found ordered or semiordered phases at x = 0.5 and 1.0 in Li x MnO2, verified by configurational entropy changes and simulated X-ray diffraction patterns of partially lithiated R-MnO2. The radial distribution functions show the preference of lithium for homogeneous distributions across the one-dimensional 2 × 1 ramsdellite channels accompanied by alternating reduced/oxidized manganese ions. The occupation of the interstitial sites in the channels is correlated with the calculated voltage profile, showing a sharp voltage drop at x = 0.5, which is explained by the energy penalty of shifting lithium ions from stable tetrahedral to unstable octahedral sites. To facilitate this work, our in-house software, Knowledge Led Master Code (KLMC) was extended to support massive parallelism on high-performance computers.

Unveiling Potential of Gallium Ferrite (GaFeO3) as an Anode Material for Lithium-Ion Batteries.

Lithium-ion batteries (LIBs) serve as the backbone of modern technologies with ongoing efforts to enhance their performance and sustainability driving the exploration of new electrode materials. This study introduces a new type of alloy-conversion-based gallium ferrite (GFO: GaFeO3) as a potential anode material for Li-ion battery applications. The GFO was synthesized by a one-step mechanochemistry-assisted solid-state method. The powder X-ray diffraction analysis confirms the presence of an orthorhombic phase with the Pc21 n space group. The photoelectron spectroscopy studies reveal the presence of Ga3+ and Fe3+ oxidation states of gallium and iron atoms in the GFO structure. The GFO was evaluated as an anode material for Li-ion battery applications, displaying a high discharge capacity of ∼887 mA h g-1 and retaining a stable capacity of ∼200 mA h g-1 over 450 cycles, with a Coulombic efficiency of 99.6 % at a current density of 100 mA g-1. Cyclic voltammetry studies confirm an alloy-conversion-based reaction mechanism in the GFO anode. Furthermore, density functional theory studies reveal the reaction mechanism during cycling and Li-ion diffusion pathways in the GFO anode. These results strongly suggest that the GFO could be an alternative anode material in LIBs.

Micron silicon-oxide-carbon coated with TiOx(OH)y layer as better performance anode for lithium-ion batteries

Micron-silicon based material is a promising anode material for high performance lithium batteries due to its ultra-high specific capacity. However, the volume expansion exceeds 300 % during charging and discharging, resulting in the collapse of the electrode structure and a rapid decline in electrochemical performance. Coating the surface of silicon-based materials with flexible ionic conductors is an effective method to maintain their high capacity and suppress swelling. Here, to further improve the electrochemical performance of silicon-based materials, we have deposited a titanate-type ionic conductor layer on a micron-sized silicon-carbon oxide (SiOX-C) material to synthesize the SiOX-C@TiOx(OH)y material. The TiOx(OH)y layer not only exhibits the elastic properties of a superpolymer to mitigate swelling strain, but also has a fast capacitance effect to improve its rate performance. In addition, the interfacial charge transport of SiOX-C@TiOx(OH)y is enhanced due to the structural diversity of the TiOx(OH)y layer. For the above mechanisms, the SiOX-C@TiOx(OH)y has a specific capacity of 278.3 mAh g−1 under high current of 3500 mA g−1. Meanwhile, the SiOX-C@TiOx(OH)y with the capacity retention of 67 % is achieved at 2000 mA g−1 after 100 cycles.

Impact of Mn/Ni and Li/(Mn+Ni) ratios on phase equilibrium and electrochemical performance of the high voltage spinel LiNi0.5Mn1.5O4

LiNi0.5Mn1.5O4 (LNMO) emerges as a promising spinel-type positive electrode material for lithium-ion batteries (LIBs) due to its low cost and high operating voltage (4.8 V vs. Li+/Li), attributed to the Ni4+/Ni3+/Ni2+ redox couples, which contribute to high energy density, a crucial requirement for next-generation LIBs. In this study, we investigate the influence of Mn/Ni and Li/(Mn + Ni) ratios on the phase equilibrium and electrochemical performance of LNMO positive electrode materials. A series of 18 samples were synthesized using a two-stage solid-state method with varying Mn/Ni and Li/(Mn + Ni) ratios and annealing under different atmospheres. These synthesis conditions have major impact on the composition and level of purity of LNMO phases, as well as on the nature of the impurities themselves. Mn excess significantly enhances the electrochemical performance, with superior discharge capacity, coulombic efficiency, and capacity retention for the Mn-rich sample with Li/(Mn + Ni) = 0.50. A comprehensive structural analysis combining synchrotron X-ray and neutron powder diffraction gives an in-depth characterization of these samples with a clear differentiation between the global Mn content within samples and that within the LNMO phase.