Cathode Materials For Lithium-ion Batteries Research Articles

Synthesis and Properties of the LiMn2O4 Cathode Material for Lithium-ion Batteries

Spinel LiMn2O4 was synthesized by high-temperature solid-state method with lithium salt and manganese salt as raw materials, which were mixing with anhydrous ethanol as solvent under stirring, and calcining at high temperature in in the oxygen atmosphere. X-ray diffraction (XRD) and scanning electron microscope (SEM) showed that the size of lithium manganese particles with spinel structure was 80 to 200 nm, and the particle size distribution was uniform. The results showed that the prepared LiMn2O4 sample sintered at 700°C exhibited superior electrochemical performance when used as a cathode material for lithium-ion batteries with a voltage window of 2.5–4.8 V. The first charge-discharge specific capacity and first discharge capacity can reach 158.0 mAh‧g-1 and 138.4 mAh‧g-1, respectively, at 0.1 A‧g-1 current density, and the first Coulomb retention efficiency is 87.6%. The discharge specific capacity of the LiMn2O4 material can be maintained at 114 mAh‧g-1 when the test current density was returned to 0.1 A‧g-1 after 60 cycles.

Concerted Effect of Ion- and Electron-Conductive Additives on the Electrochemical and Thermal Performances of the LiNi0.8Co0.1Mn0.1O2 Cathode Material Synthesized by a Taylor-Flow Reactor for Lithium-Ion Batteries.

To address the issue that a single coating agent cannot simultaneously enhance Li+-ion transport and electronic conductivity of Ni-rich cathode materials with surface modification, in the present study, we first successfully synthesized a LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode material by a Taylor-flow reactor followed by surface coating with Li-BTJ and dispersion of vapor-grown carbon fibers treated with polydopamine (PDA-VGCF) filler in the composite slurry. The Li-BTJ hybrid oligomer coating can suppress side reactions and enhance ionic conductivity, and the PDA-VGCFs filler can increase electronic conductivity. As a result of the synergistic effect of the dual conducting agents, the cells based on the modified NCM811 electrodes deliver superior cycling stability and rate capability, as compared to the bare NCM811 electrode. The CR2032 coin-type cells with the NCM811@Li-BTJ + PDA-VGCF electrode retain a discharge specific capacity of ∼92.2% at 1C after 200 cycles between 2.8 and 4.3 V (vs Li/Li+), while bare NCM811 retains only 84.0%. Moreover, the NCM811@Li-BTJ + PDA-VGCF electrode-based cells reduced the total heat (Qt) by ca. 7.0% at 35 °C over the bare electrode. Remarkably, the Li-BTJ hybrid oligomer coating on the surface of the NCM811 active particles acts as an artificial cathode electrolyte interphase (ACEI) layer, mitigating irreversible surface phase transformation of the layered NCM811 cathode and facilitating Li+ ion transport. Meanwhile, the fiber-shaped PDA-VGCF filler significantly reduced microcrack propagation during cycling and promoted the electronic conductance of the NCM811-based electrode. Generally, enlightened with the current experimental findings, the concerted ion and electron conductive agents significantly enhanced the Ni-rich cathode-based cell performance, which is a promising strategy to apply to other Ni-rich cathode materials for lithium-ion batteries.

Analysis of Thermal Reduction of Mixture of Organic Components on Cathode Materials of Spent Ternary Lithium-Ion Battery

Analysis of Thermal Reduction of Mixture of Organic Components on Cathode Materials of Spent Ternary Lithium-Ion Battery

Fabricated and improved electrochemical properties of layered lithium-rich Co-free manganese-based Li1.2Mn0.6Ni0.2O2 cathode material for lithium-ion batteries

Fabricated and improved electrochemical properties of layered lithium-rich Co-free manganese-based Li1.2Mn0.6Ni0.2O2 cathode material for lithium-ion batteries

Electrochemical performance of Fe-doped modified high-voltage LiNiPO4 cathode material of lithium-ion batteries

Electrochemical performance of Fe-doped modified high-voltage LiNiPO4 cathode material of lithium-ion batteries

Mechanical properties modeling of cathode materials for lithium-ion batteries based on bond valence model

To clarify electrochemical-mechanical relation of cathode materials for lithium-ion batteries, a series of empirical mechanical property models based on the bond valence model are applied to estimate the hardness, bulk, shear, and Young’s moduli, Poisson’s ratio and fracture toughness of typical cathode materials, such as LiCoO2, LiNi1-x-yCoxMnyO2, LiNi0.80Co0.15Al0.05O2, LiMn2O4, and LiFePO4. The calculated results are in agreement with experimental values. The mechanical properties have been predicted for low Ni compounds LiNixCo1–2xMnxO2 (0 ≤ x ≤ 0.5), high Ni compounds LiNi0.8Mn0.2-xCoxO2 (x = 0, 0.1, 0.2), and free Co compounds LiNixMn1-xCo0O2 (x = 0.5, 0.6, 0.8). For LiCoO2 during lithiation and delithiation processes, the hardness and bulk modulus of LixCoO2 decrease nearly linearly with the decrease of Li concentration. The effects of Al doping on the mechanical properties of LiAlxCo1-xO2 are also revealed from the insights into the chemical bonds. The models are powerful for extensively predicting and tuning electrochemical-mechanical properties of cathode materials.

Resource Recovery of Spent Lithium-Ion Battery Cathode Materials by a Supercritical Carbon Dioxide System.

The increasing global market size of high-energy storage devices due to the boom in electric vehicles and portable electronics has caused the battery industry to produce a lot of waste lithium-ion batteries. The liberation and de-agglomeration of cathode material are the necessary procedures to improve the recycling derived from spent lithium-ion batteries, as well as enabling the direct recycling pathway. In this study, the supercritical (SC) CO2 was innovatively adapted to enable the recycling of spent lithium-ion batteries (LIBs) based on facilitating the interaction with a binder and dimethyl sulfoxide (DMSO) co-solvent. The results show that the optimum experimental conditions to liberate the cathode particles are processing at a temperature of 70 °C and 80 bar pressure for a duration of 20 min. During the treatment, polyvinylidene fluoride (PVDF) was dissolved in the SC fluid system and collected in the dimethyl sulfoxide (DMSO), as detected by the Fourier Transform Infrared Spectrometer (FTIR). The liberation yield of the cathode from the current collector reaches 96.7% under optimal conditions and thus, the cathode particles are dispersed into smaller fragments. Afterwards, PVDF can be precipitated and reused. In addition, there is no hydrogen fluoride (HF) gas emission due to binder decomposition in the suggested process. The proposed SC-CO2 and co-solvent system effectively separate the PVDF from Li-ion battery electrodes. Thus, this approach is promising as an alternative pre-treatment method due to its efficiency, relatively low energy consumption, and environmental benign features.

Recovery of Ni-Co-Mn Oxides from End-of-Life Lithium-Ion Batteries for the Application of a Negative Temperature Coefficient Sensor

This study demonstrates the current advancements in battery management systems (BMSs), emphasizing the need for precise temperature monitoring within battery packs to enhance safety and performance through efficient thermal management. The increased demand for lithium-ion batteries (LIBs) has driven the development of temperature sensors with improved accuracy and stability. In particular, Ni-Co-Mn-based spinel oxides are commonly used due to their stable negative temperature coefficient (NTC) behavior. However, challenges arise in manufacturing due to the high cost and uncertain supply of critical cathode components (e.g., Co, Ni, and Mn) for LIBs. This research focuses on developing spinel-type (Ni0.6Co0.4Mn2)O4 using recycled Ni-Co-Mn oxides obtained from end-of-life (EOL) LIBs, demonstrating temperature resistance behavior suitable for temperature sensing. The oxides are prepared through hydrometallurgy, oxalate synthesis, and post-heat treatment. Successful integration into spinel-type NTC thermistors suggests broader applications in various industrial fields. A systematic investigation into the synthesis and characterization of recovered Ni-Co-Mn oxides from EOL LIB cathode materials (Li(Ni0.33Co0.33Mn0.33)O2) is presented for NTC thermistor application. Thermogravimetric analysis-derivative thermogravimetry (TGA-DTG) identifies the optimal post-heat treatment temperature. The X-ray diffraction (XRD) patterns confirm a cubic spinel structure of the Ni-Co-Mn oxides, supported by scanning electron microscope (SEM) images showing a uniform microstructure. Also, energy dispersive X-ray spectroscopy (EDS) mapping confirms homogeneous element distribution. Recovered oxide pellets from the sintering process exhibit a single spinel structure, with X-ray photoelectron spectroscopy (XPS) analysis revealing changes in the valence states for Ni and Mn. Resistivity measurements demonstrate semiconductive behavior, which shows a B value (3376.92 K) suitable for NTC thermistor applications. This study contributes valuable insights to black powder recycling from EOL LIBs and its potential in temperature-sensitive electronic devices.

Transforming Residual Lithium Compounds on the LiNi0.8Mn0.1Co0.1O2 Surface into a Li-Mn-P-O-Based Composite Coating for Multifaceted Improvements.

LiNi0.8Mn0.1Co0.1O2 (NMC811) is the most promising cathode material for next-generation lithium-ion batteries (LIBs). However, the chemical instability of the material during air exposure leads to the formation of residual lithium compounds (RLCs: LiOH and Li2CO3) on the surface and inhibits its practical application. Here, we propose a chemical conversion process to remove RLCs by utilizing them and forming a hybrid coating layer on the surface of NMC811 that contains Li3PO4, LiMn2O4, and LiMnPO4 phases, yielding multifaceted benefits. The hybrid layer on the surface protects the material from undesirable side reactions. It improves the cycle life of NMC811 by retaining 80% of its initial capacity after 300 cycles and 66% after 500 cycles at a 0.5C rate in the operating voltage of 3.0-4.3 V. The process enables high-voltage (4.7 V vs Li+/Li) operation by stabilizing the electrode-electrolyte interface, reduces the degree of cationic disorder and the voltage polarization for phase transitions, improves Coulombic efficiency and ion diffusion kinetics, and minimizes the secondary particle crack formation over long-term cycling. In fact, the coating reduces the detrimental effects of RLCs, leaves the surface for better Li+ transport, and hence significantly improves the electrochemical performance of NMC811.

Enhanced thermal safety and rate capability of nickel-rich cathodes via optimal Nb-doping strategy

Nickel-rich layered oxides have garnered great attention as promising cathode materials in lithium-ion batteries for their high specific capacity, rate capability and comparatively lower cost. However, the long cycling with a high current scenario is still a critical challenge, resulting from the lattice cracks and high temperature which are induced by rapid Li-ions intercalation/extraction and local heat accumulation under component voltage. Besides the deterioration of electrochemical performance, these limitations further lead to the impairment of structure or even thermal runaway for nickel-rich layered oxides. Herein, considering the superiorities of niobium element with multilevel electron orbitals and suitable atomic radius, a strategy of nickel-rich material modified by niobium-doping is proposed. The incorporated niobium forms a strong niobium-oxygen bonding, which promotes structure stability, ions diffusivity, and electron conductivity of nickel-rich cathode (LiNi0.8Co0.1Mn0.1O2). Accordingly, the niobium-doping cathode deliver the specific capacities of 166.4 mAh g−1 and 151.02 mAh g−1 after 100 cycles at 1 C and 5 C (1C = 200 mAh g−1), especially with the capacity retention of 88.90 % and 89.06 %. Moreover, the niobium-doping cathode exhibit a more stable thermal safety with a reversibility around 76.75 % after 100 cycles at 1 C under 50 ℃, whereas is only 36.03 % for blank sample. Accompanied with exploring the stabilization for crystalline structure and superficial electronic structure, a generic approach to synthesize excellent Ni-rich cathode materials is identified, accelerating their endurance application in complicated scenes, particularly at high-temperature and high-rate operation conditions.

Bifunctional low molecular weight polyacrylic acid as aqueous binder and coating agent enables high performance LiMn2O4 cathode for lithium-ion batteries

LiMn2O4 is considered to be a promising cathode material for lithium-ion batteries due to its decent energy density, low price and environmental benignity. However, the problems of Mn dissolution, migration and deposition during the cycle, seriously affect its lifespan, especially at high temperature. In this study, we developed a strategy by which we killed two birds with one stone. A low molecular weight polyacrylic acid (PAA) mixed with sodium carboxymethyl cellulose (CMC) is applied as binder and coating agent for cathode particles at the same time. The conventional and environmental unfriendly polyvinylidene difluoride (PVDF)-N-methylpyrrolidone (NMP) system is replaced by the cheap and green aqueous binder with improved adhesive effect. Furthermore, the binder-based surface coating layer not only alleviates the side reaction between the electrolyte and the cathode particles, but also chelates the dissolved Mn2+ by the large amount of carboxyl groups in PAA molecules and so prevents the following migration and deposition of Mn2+. In the button half-cell with low molecular weight PAA based binder, the capacity retention reaches 94.1 % after 1000 cycles at room temperature and 92.0 % after 200 cycles at 60 degrees centigrade. Meanwhile, 18650-type cylindrical cells were prepared with this binder, which shows a great high temperature storage performance. After the cell was held at 60 degrees centigrade for 25 days at full charged state, the internal resistance increased by only 1.25mΩ, the voltage decreased by only 0.1 V, the residual capacity retention and recovery capacity retention reaches 85.6 % and 92.2 %. This work shows the great potential of the aqueous binder in dealing with the problem of Mn dissolution during the cycling of manganese-based cathode materials for lithium-ion batteries.

Identifying key determinants of discharge capacity in ternary cathode materials of lithium-ion batteries

Although lithium-ion batteries (LIBs) currently dominate a wide spectrum of energy storage applications, they face challenges such as fast cycle life decay and poor stability that hinder their further application. To address these limitations, element doping has emerged as a prevalent strategy to enhance the discharge capacity and extend the durability of Li-Ni-Co-Mn (LNCM) ternary compounds. This study utilized a machine learning-driven feature screening method to effectively pinpoint four key features crucially impacting the initial discharge capacity (IC) of Li-Ni-Co-Mn (LNCM) ternary cathode materials. These features were also proved highly predictive for the 50th cycle discharge capacity (EC). Additionally, the application of SHAP value analysis yielded an in-depth understanding of the interplay between these features and discharge performance. This insight offers valuable direction for future advancements in the development of LNCM cathode materials, effectively promoting this field toward greater efficiency and sustainability.

Li-doped transition metal high-entropy oxides (Li/TM-HEOs) as Li-Ion batteries cathodes: a first report on capacity fading and cycling stability

High-Entropy Oxides (HEOs) have gained significant attention for their wide range of compositions and potential applications across various sectors, including rechargeable batteries. This study explores the characterization of two distinct HEO systems as potential cathode materials for Lithium-ion batteries (LIBs). A series of rock salt structured HEOs with varying Li loadings (16Li/RS-HEO, 25Li/RS-HEO, 33Li/RS-HEO, and 41Li/RS-HEO) and a spinel-structured HEO with 16 mol% of Li loading (16Li/SP-HEO) were firstly synthesized through co-precipitation. Electrochemical analyses via cyclic voltammetry revealed stark differences in the behavior of these structures. The Li/SP-HEO sample displayed broad and strongly irreversible hysteresis cycles, while the Li/RS-HEO series manifested thin, narrow hysteresis cycles with single oxidation peaks between 0.5 V and 0.7 V. As the lithium content increases in the RS-HEO system, the cycling stability of the cell decreases, most likely due to the reduced ratio of transition metal cations to lithium ions. Although there was a noticeable decrease in capacity under higher current rates, the higher lithium loadings positively impact the cell capacity, albeit with notable capacity fading under higher current rates. Li-doped rock salt structured high entropy materials show potential for LIB cathodes in terms of high specific capacities; the observed stability issues at medium and high current densities indicate a rapid electrode degradation.

Stable surface lattice for prolonged cycle life of single-crystal lithium-rich layered oxide cathodes

Lithium-rich layered oxides (LLOs) have garnered significant attention due to their outstanding capacity. However, the severe capacity fading resulting from lattice deterioration initiated at the surface constrains the further advancement of LLOs. Here, we present a method to stabilize the surface lattice to enhance the capacity stability of LLOs. Specifically, we have engineered a nanometer-thin Gd-doped NiO rock-salt epitaxial layer on the surface of single-crystal LLOs, along with an atomic-level thickness LiGdO2coating layer. The dual-nanolayer protection strategy has successfully stabilized the surface structure of LLOs and suppressed electrode–electrolyte interface side reactions. As a result, the modified sample achieves a capacity retention rate of 93.4% after 500 cycles at 1C and 94.2% after 200 cycles at 0.2C. Our study underscores the importance of surface structure in achieving high cyclic stability in LLOs and provides an important approach for designing stable lithium-ion battery cathode materials.

Recycling of LiCoO2 from the cathode of a waste lithium battery via reduction in a molten salt

A new method for recycling and resynthesizing a lithium battery cathode material was developed. A LiCl-KCl molten salt was used as a medium. The raw materials were LiOH·H2O obtained by membrane electrolysis and Co2O3 obtained by carbothermal reduction, and the high-performance cathode material LiCoO2 was synthesized by molten salt method, and then placed into a battery for recycling. The specific reaction process and reaction kinetics for the LiCoO2 synthesis were studied by TG-DSC thermal analyses. The effects of different reaction conditions on the structure and morphology of the LiCoO2 were studied by XRD and SEM. The battery performance of the LiCoO2 was characterized with electrochemical analyses. The activation energies of the three endothermic reactions occurring in the synthetic process were calculated with the Kissinger method and were 34.212 kJ·mol−1, 168.53925 kJ·mol−1 and 221.26181 kJ·mol−1. The experimental battery prepared from a LiCoO2 sample calcined at 720 °C for 7 h showed first charge–discharge specific capacities of 150 mAh/g and 147 mAh/g, and the coulombic efficiency was 98%. The discharge specific capacity after 50 charge and discharge cycles was still 129 mAh/g. The battery showed good charge and discharge performance after rate cycling.

Preparation of layered high nickel cobalt-free LiNi0.8Mn0.17Fe0.03O2 cathode material for lithium-ion batteries

Preparation of layered high nickel cobalt-free LiNi0.8Mn0.17Fe0.03O2 cathode material for lithium-ion batteries

Enhancing performance and stability of LiNi0.8Co0.1Mn0.1O2 cathode via Na/Y dual doping for Lithium-Ion batteries

Nickel-rich layered oxide cathode materials face limitations in practical applications due to trade-offs between capacity and structural stability. As more Li+ is extracted during charging, the layered structure of nickel-rich materials becomes increasingly fragile. To address this, a double doping strategy with Na and Y is proposed in this study to enhance the strength of the layered structure. The research findings demonstrate that Na doping enlarges the spacing between Li layers in the crystal structure, while Y doping improves the reversibility of the H2-H3 phase transition but narrows the Li layer spacing in nickel-rich materials. Na and Y double doping, the advantages of Na in enlarging the Li layer, and Y in improving the H2-H3 phase transition can be harnessed simultaneously. This double doping strategy ensures that the laminar structure of the cathode material remains stable even when it is highly detached, effectively solving the trade-off between the capacity and structural stability of nickel-rich laminar cathode materials. The application in LiNi0.8Co0.1Mn0.1O2 shows that the capacity and cycle life of cathode materials can be significantly improved after Na/Y double doping. These findings open up opportunities for practical applications of nickel-rich cathode materials in lithium-ion batteries.

Mg/Ta dual-site doping of high-nickel layered cathode material LiNi0.9Co0.1O2 for extended cycling and thermal stability

Due to its high specific capacity and low cost, high-nickel layered oxide LiNi0.9Co0.1O2 has found promising application as the cathode materials for lithium-ion batteries. However, the crystallographic instability induced by Li+/Ni2+ anti-site exchange, the interfacial parasitic reactions and the microcracking caused by internal stress jointly contribute to the mechano-chemical failure of LiNi0.9Co0.1O2, leading to its fast capacity decay and high thermal stability concern. In this regard, a Mg/Ta dual-site doping strategy was proposed for LiNi0.9Co0.1O2, for which Mg2+ was doped in situ during the synthesis of cathode precursor, while Ta5+ ions were incorporated after the precursor synthesis. This novel synthesis approach leads to unique dual-site occupations of Mg2+ and Ta5+ in the 3a and 3b crystallographic sites respectively. The Mg2+ ions residing in 3a site can function as pillar ions by preventing the Li+/Ni2+ anti-site exchange and inhibiting layered to rock-salt phase transition. The Ta5+ ions occupying 3b site not only leads to the expanded lithium layer spacing but also creates interfacial protection and well-ordered microstructure in LiNi0.9Co0.1O2. Consequently, the dual-site-doped LiNi0.9Co0.1O2 outperforms the pristine and single-site-doped samples. For instance, its full cell shows a greatly enhanced cycling stability from 57.3 % to 90.5 % after 300 cycles at 1C/1C and well improved thermal stability from 205.2 °C to 225.6 °C, compared to the pristine sample. This Mg/Ta dual-site doping strategy provides a facile and practical way to improve the electrochemical and thermal performances of high-nickel layered cathode material LiNi0.9Co0.1O2.

Long-cycle-life Li2MnO3 thin-film cathode enabled by all-solid-state battery configuration

Li2MnO3 (LMO) is a key component in lithium-rich manganese-based oxides (LMROs) and has attracted great attention as a cathode for lithium-ion batteries (LIBs) due to its high theoretical capacity and cost-effectiveness. However, its severe capacity fading and discharge voltage decay during prolonged cycling greatly hinders its applications. In this study, an LMO film is prepared, followed by the fabrication and investigation of an LMO/LiPON/Li all-solid-state thin film lithium battery (LMO-TFLB). The results show that although the LiPON electrolyte deposition results in the formation of a disordered interface layer derived from the LMO layer, an LMO/LiPON interface with small interfacial resistance and good structural stability during cycling is obtained, allowing fast Li+ diffusion across the interface. Furthermore, in contrast to the half cell that uses liquid electrolyte (LMO-LIB), the LiPON electrolyte in the LMO-TFLB significantly aids in impeding the Mn dissolution to prevent active material loss. More importantly, although a structural transformation from a layered LMO phase to a spinel-like phase occurs in the cathode of the LMO-TFLB during cycling, the transformed spinel-like phase with a higher crystallinity than that in the LMO-LIB facilitates fast Li+ and electron transport to improve the LMO-TFLB's capacity. Consequently, the LMO-TFLB exhibits a long cycle life without any capacity loss after 1000 cycles, which outperforms that of the LMO-LIB (20% capacity retention after 450 cycles). This work demonstrates that all-solid-state battery configuration is highly promising for unlocking the full potential of LMROs cathode materials for LIBs.

The Influence of Cathode Degradation Products on the Anode Interface in Lithium-Ion Batteries.

Degradation of cathode materials in lithium-ion batteries results in the presence of transition metal ions in the electrolyte, and these ions are known to play a major role in capacity fade and cell failure. Yet, while it is known that transition metal ions migrate from the metal oxide cathode and deposit on the graphite anode, their specific influence on anode reactions and structures, such as the solid electrolyte interphase (SEI), is still quite poorly understood due to the complexity in studying this interface in operational cells. In this work we combine operando electrochemical atomic force microscopy (EC-AFM), electrochemical quartz crystal microbalance (EQCM), and electrochemical impedance spectroscopy (EIS) measurements to probe the influence of a range of transition metal ions on the morphological, mechanical, chemical, and electrical properties of the SEI. By adding representative concentrations of Ni2+, Mn2+, and Co2+ ions into a commercially relevant battery electrolyte, the impacts of each on the formation and stability of the anode interface layer is revealed; all are shown to pose a threat to battery performance and stability. Mn2+, in particular, is shown to induce a thick, soft, and unstable SEI layer, which is known to cause severe degradation of batteries, while Co2+ and Ni2+ significantly impact interfacial conductivity. When transition metal ions are mixed, SEI degradation is amplified, suggesting a synergistic effect on the cell stability. Hence, by uncovering the roles these cathode degradation products play in operational batteries, we have provided a foundation upon which strategies to mitigate or eliminate these degradation products can be developed.