Cathode Materials For Lithium-ion Batteries Research Articles

Structural stability and enhanced electrochemical performance of Co-free Li-rich layered Mn-based Li1.2Mn0.6Ni0.2O2 cathodes via F doping at the O site of lithium-ion batteries

Structural stability and enhanced electrochemical performance of Co-free Li-rich layered Mn-based Li1.2Mn0.6Ni0.2O2 cathodes via F doping at the O site of lithium-ion batteries

Linker length-dependent lithium storage of pyrene-4,5,9,10-tetraone-based conjugated organic polymer cathodes

Linker length-dependent lithium storage of pyrene-4,5,9,10-tetraone-based conjugated organic polymer cathodes

Constructing Targeted Strong Nb4d-O2p-Li2s Configurations to Obtain Excellent Energy Density and Long Life for Li-Rich Cathodes.

The Li-rich Mn-based cathode materials (LMRs) deliver excellent energy density and exhibit low cost, which are considered as the most promising cathode materials for the next generation lithium-ion batteries. However, the irreversible redox reaction of the oxygen atoms directly leads to release oxygen and intensifies phase transformation. Besides, the local stress and strain will be generated due to the unit-cell volume difference between R-3m and C2/m phases, which continuously aggravates the collapse of secondary particles. Herein, the strong Nb4d-O2p-Li2s configurations at the Li1 sites of the TM-layer in the C2/m phase and secondary particles with the radial arrangement of refined primary particles are designed to inhibit oxygen release and relieve lattice stress by Nb2O5 treatment. Meanwhile, the preferential growth of the active {010} planes is presented to obtain an excellent transmission rate of Li+. As a result, the designed LMR delivers remarkable electrochemical properties with high discharge capacity and initial coulomb efficiency of 276 mAh g-1 and 85 % at 0.1 C, outstanding cycling retention rate of 81 % after 300 cycles. This novel crystal structure combining oxygen coordination regulation and micro-nano scale design provides inspiration for the design of high-performance LMRs.

Lithium extraction from geothermal brine using γ-MnO2: A case study for Tuzla geothermal power plant

Geothermal brines contain high concentrations of ions and form a source of various valuable elements. The isolation of the elements from their water systems is a great challenge when the gradual depletion of ores in mining is considered. Attempts have been made for a long time to isolate valuable elements from aqueous mixtures prepared in the laboratory. However, those studies might not reflect the complexity of natural systems and might yield results that deviate significantly from the performance in real field systems. In this study, sorption is used to extract lithium ions from a representative field, Tuzla Geothermal Power Plant (TGPP) Turkey, using a mini-pilot reactor introduced to the reinjection well of the plant. Electrolytic manganese dioxide (γ-MnO2), a relatively inexpensive material widely used as the cathode material in lithium-ion batteries, was employed as a sorbent material for lithium. The sorption/desorption performance of the novel γ-MnO2 was investigated under various conditions. Sorption is performed at 360K and 2bars. The maximum sorption performance was obtained at 1 h in Tuzla GPP. The desorption experiments were performed in acidic solutions. The concentration of Li+ in the desorption solution was found to be 25mg/L on average when 10g of γ-MnO2 was dispersed into 30mL of the acidic aqueous solution. The first desorption solution was used consecutively for collecting more Li+ions through the desorption of fresh brine-treated powder samples (cumulative desorption). By repeating this process four times consecutively, 230mg/L of Li+ was obtained in the desorption solution. Moreover, the reusability of the γ-MnO2 sorbent was examined. The sorbent powder showed almost 40% performance efficiency compared to virgin powder under the conditions employed in this study. The use of electrolytic γ-MnO2 sorbent for lithium adsorption was found to be a promising process for practical use in the separation of lithium from geothermal brines.

Preparation of Single-Crystal Li-Rich Mn-Based Layered Oxides with Excellent Electrochemical Performance via Simple Stepwise High-Temperature Sintering.

Li-rich Mn-based layered oxides have attracted extensive attention in lithium-ion battery cathode materials due to their high specific capacity, wide operating voltage, and low cost. However, the large-scale production of single-crystal Li-rich Mn-based layered oxides remains a significant challenge. Herein, the morphology, structure, and electrochemical properties of a series of samples (Li1.2Ni0.13Co0.13Mn0.54O2) prepared by the solid-state method and the molten-salt flux method were assessed. Single-crystal particles exactly could be prepared by potassium chloride (KCl), but its electrochemical performance was inferior and the molten-salt flux method was too complicated for industry. Surprisingly, we found that water washing and annealing processes could enhance the cycling performance. Furthermore, single-crystal Li1.2Ni0.13Co0.13Mn0.54O2 with a particle size of 536 nm was successfully prepared by simple stepwise sintering (950 °C for 7 h, 1000 °C for 1 h, and 850 °C for 2 h), which delivered a specific capacity of 274.9 mAh·g-1 between 2.0 and 4.8 V at 0.1 C with 77.4% initial Coulombic efficiency and 82.1% capacity retention after 100 cycles at 0.1 C. This study may provide theoretical guidance for the industrial production of single-crystal Li-rich Mn-based layered oxides.

Highly Conductive Two-Dimensional FeTHBQ/Graphene Nanocomposite as the Cathode Material for Lithium-Ion Batteries.

Constructing high-performance coordination polymer (CP) cathodes for lithium-ion batteries based on the redox reactions of both high-potential transition metal ions and high-capacity organic ligands has attracted extensive attention. However, CP cathodes suffer from structural degradation, low electrical conductivity, and sluggish diffusion kinetics, resulting in poor cycling stability and inferior rate capability. Herein, the ultrafine FeTHBQ (THBQ = tetrahydroxy-1,4-benzoquinone) CP nanoparticles in situ grew on both sides of graphene nanosheets to form the uniform two-dimensional (2D) FeTHBQ/Graphene nanocomposite with a sandwich structure via a one-pot solvothermal method. The highly conductive graphene skeleton promotes the electronic conduction and structural stability for the 2D FeTHBQ/Graphene nanocomposite. Besides, compared with bulk FeTHBQ, the primary FeTHBQ nanoparticles in the FeTHBQ/Graphene nanocomposite have smaller particle sizes with larger specific surface areas. This not only shortens the Li+ diffusion distance in the FeTHBQ crystal but also benefits Li+ transfer between the electrolyte and the electrode. In the FeTHBQ/Graphene nanocomposite, the active material of FeTHBQ manifested multiple redox centers of transition metal ions (Fe3+/Fe2+) and carbonyls (C═O/C-O-) in THBQ ligands. Owing to the enhancements of structural stability, electronic conduction, and Li+ diffusion kinetics, the 2D FeTHBQ/Graphene nanocomposite presented a high lithium-ion storage capacity of 217.2 mA h g-1 at 50 mA g-1, a fast rate capability of 79.1 mA h g-1 at 5000 mA g-1, and a stable cycling performance of 87.2 mA h g-1 at 500 mA g-1 after 100 cycles. This work sheds light on the great opportunity for optimizing the electrochemical performances of CP-based functional electrode materials by combining with conductive substrates.

Enhanced electrochemical properties of Al2O3-coated LiNiPO4 cathode materials for lithium-ion batteries

Enhanced electrochemical properties of Al2O3-coated LiNiPO4 cathode materials for lithium-ion batteries

Defect Chemistry in High-Voltage Cathode Materials for Lithium-Ion Batteries.

High-voltage cathodes (HVCs) have emerged as a paramount role for the next-generation high-energy-density lithium-ion batteries (LIBs). However, the pursuit of HVCs comes with inherent challenges related to defective structures, which significantly impact the electrochemical performance of LIBs. The current obstacle lies in the lack of a comprehensive understanding of defects and their precise effects. This perspective aims to provide insights into defect chemistry for governing HVCs. The classifications, formation mechanisms, and evolution of defects are outlined to explore the intricate relationship between defects and electrochemical behavior. The pressing need for cutting-edge characterization techniques that comprehensively investigate defects across various temporal and spatial scales is emphasized. Building on these fundamental understandings, engineering strategies such as composition tailoring, morphology design, interface modification, and structural control to mitigate or utilize defects are thoroughly discussed for enhanced HVCs performance. These insights are expected to provide vital guidelines for developing high-performance HVCs for next-generation high-energy lithium-ion batteries.

Cracking Mechanism and Inhibition Strategies of Polycrystalline NCM Electrode Particles.

Developing a high-energy-density cathode material (LiNi1-x-yCoxMnyO2, NCM) for lithium-ion batteries is crucial to the electric vehicle and energy storage industries. However, the continuous insertion/extraction of Li+ generates diffusion-induced stress, causing NCM particles to crack or even pulverize, leading to battery capacity loss and limiting its wider commercial application. Current experimental studies are primarily postmortem examinations, and it is difficult to capture the particle cracking evolution. Simulation studies frequently ignore or simplify anisotropic volume contraction, demonstrating an insufficient understanding of the cracking mechanism of NCM polycrystalline particles, and cracking prevention strategies still need improvement. Therefore, we develop an anisotropic polycrystalline fracture phase-field model (AP-FPFM) that focuses on the anisotropic volume contraction of primary particles and precisely generates grain boundary distribution, coupling with Li+ diffusion, mechanical stress, and particle cracking. We employ AP-FPFM to demonstrate the behavior and mechanism of NCM polycrystalline particle cracking and illustrate the necessity and importance of anisotropic volume contraction to understand particle cracking. Furthermore, we explore the effects of average primary particle size, secondary particle size, and core-shell structure modulation on crack initiation and propagation and propose strategies to inhibit or migrate NCM polycrystalline particle cracking. This work provides theoretical support for revealing the cracking mechanism of anisotropic polycrystalline NCM particles and supplying optimization strategies to suppress particle cracking and improve the mechanical stability.

Modification study of Mg/W-doped LiNi0.9Mn0.1O2 layered oxide cathode materials for lithium-ion batteries

Modification study of Mg/W-doped LiNi0.9Mn0.1O2 layered oxide cathode materials for lithium-ion batteries

Promoting homogeneous tungsten doping in LiNiO2 through a grain boundary phase induced by excessive lithium

Promoting homogeneous tungsten doping in LiNiO2 through a grain boundary phase induced by excessive lithium

Local electronic structure modulation via S substitution enables fast-discharging capability for Li-rich Mn-based oxides cathodes

Local electronic structure modulation via S substitution enables fast-discharging capability for Li-rich Mn-based oxides cathodes

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.

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.

Synthesis and Electrochemical Performance Enhancement of Li2MnSiO4 Cathode Material for Lithium‐Ion Batteries via Mn‐Site Ni Doping

AbstractIn exploring the potential of Li2MnSiO4 as a cathode material for lithium‐ion batteries (LIBs), the key challenges often involve enhancing electronic conductivity and lithium‐ion diffusion rates. To address these issues, this paper proposes the combination of solid‐state doping and a two‐step calcination process to successfully prepare the Li2Mn1−xNixSiO4 series of cathode materials, where Ni substitutes Mn at different doping amounts (x = 0, 0.02, 0.04, 0.06, 0.08). The use of chemically equivalent Ni2+ ions to replace Mn2+ ions is an effective method. Since the ionic radius of Ni2+ is smaller than that of Mn2+, this substitution can create more voids in the lattice structure. These increased voids provide smoother channels for the transport of electrons and lithium ions, thereby improving the material's electrical conductivity. At a Ni doping amount of 0.06, the material exhibits optimal electrochemical performance, achieving a discharge capacity of 155 mAh g−1 at 0.1 C, significantly superior to undoped lithium manganese silicate. The doping of Mn sites with Ni significantly improves the conductivity and lithium‐ion diffusion capabilities of Li2MnSiO4, revealing the tremendous potential of doping strategies in optimizing the performance of LIBs cathode materials.

A novel coating layer of mesoporous silica on LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode material for advanced lithium-ion batteries

A novel coating layer of mesoporous silica on LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode material for advanced lithium-ion batteries

Nickel‐Manganese‐Based Layered Oxide for Sodium Ion Battery Cathode Materials

Sodium‐ion batteries (SIBs) have demonstrated significant potential as alternatives to conventional lithium‐ion batteries (LIBs) for modern grid and mobile energy storage applications, due to the abundant natural resources and low cost of sodium. Layered transition metal oxides (LTMOs) have attracted focused research attentions due to their high specific capacities, energy densities as well as the compatible preparation processes with those of LIBs cathode materials. Among these, Ni/Mn‐based LTMOs (NMLOs) are particularly noteworthy for their cost‐effectiveness and superior electrochemical performance, such as excellent capacity retention, voltage stability, high operating voltage and rate capability. In this review, we briefly introduce the synthesis methods of NMLOs, discuss the challenges, and summarize the solutions. The insights presented may contribute to the development of NMLOs based SIBs.

Diammonium Hydrogen Citrate-Assisted Spray Pyrolysis Synthesis of Nanostructured LiCoPO4 Microspheres as High-Voltage Cathode Material for Lithium-Ion Batteries.

Nanostructured LiCoPO4 (LCP) microspheres were successfully synthesized by one-step spray pyrolysis, adding an appropriate amount of diammonium hydrogen citrate (DHC) additive to the precursor solution. Comprehensive physical characterization confirmed that the obtained LCPs exhibited a desirable orthorhombic olivine structure with nanostructured morphology and a significant increase in specific surface area. This enhancement was attributed to the dispersion effect due to the carboxyl group and the evolution of the ammonium group of DHC during the pyrolysis process. The resultant LCP delivered a high initial discharge capacity of 132 mA h g-1 with 63.3% capacity retention (vs 103 mA h g-1 and 37.1% of bare-LCP) after 50 cycles at 0.1 C using the conventional electrolyte. Moreover, the electrochemical performance showed additional enhancement when a fluorinated electrolyte was introduced, resulting in initial and 50th discharge capacities of 141 and about 100 mA h g-1, respectively, at 0.1 C.