Lithium-ion Battery Cathode Research Articles

Mechanical failure modeling for cathode sheets

The mechanical integrity of the cathode is critical for the operation and safety of lithium-ion batteries (LIBs). This study presents a comprehensive exploration of the progression and underlying mechanisms of failure within LIB cathodes, employing a combination of experimental and numerical methodologies. First, shear and 180° peel tests are designed and conducted to calibrate the parameter values governing the interface between the aluminium (Al) foil and the active layer, leveraging cohesive zone modeling (CZM). Furthermore, based on finite element modeling (FEM) and extended finite element modeling (XFEM), failure criteria and damage models are introduced to simulate the damage behavior of both Al foils and active layer. Notably, XFEM computes the initiation and expansion of the crack in cathode. The numerical simulation demonstrates a good correlation with the experimental observations, effectively delineating the failure process of the cathode. Moreover, a parametric analysis is conducted to study the influence of the active layer and interface on cathode failure. It reveals that as the failure strain of the active layer increases, the failure strain of the cathode rises, ultimately converging with the failure strain of an isolated Al foil. However, the failure strain of cathode decreases and then increases with increasing interface peel strength. At a peel strength of 304 N/m, the stress distribution within the active layer and the interface is more uniform compared to the lower peel strength scenarios. Besides, the interface stress transfer behavior leads to the failure of the Al foil in early. The results enhance our understanding of the failure process and mechanisms in LIB electrodes and thus provide guidance for the design and fabrication of cathode.

Embedment of Molybdenum Disulfide in Electrospun Fibers as an Integrated Cathode for Lithium-Ion Batteries

As an important component of LIBs, the electrode material plays a crucial role in determining the lithium (Li) storage performance in LIBs. In this study, MoS2 nano-flowers were synthesized using a one-pot hydrothermal method. The resulting MoS2 nano-flower, along with PAN, were used as raw materials for electrospinning. After annealing treatment, MoS2/(carbon nanofibers) CNFs nano-composites coated with carbon fibers were formed. The CNFs coating exhibited electrical conductivity and enhanced structural stability of the MoS2 due to the stabilizing effect of the carbon fibers. Additionally, electrochemical tests, including CV and GCD, indicated that the optimal capacity and cycling stability were achieved when the MoS2 content was 10%. The results indicated that the charge/discharge capacity of MoS2/CNFs-10% at a current density of 100 mA/g was ~650 mAh/g. After the cycling current returned to 100 mA/g, the current recovery was ~600 mAh/g, thereby indicating outstanding cycling stability. Accordingly, our fabrication technique and new insight could both widen design strategy of multicomponent composite electrode materials and promote the practical applications of the latest emerging transition metal sulfides in next-generation high-performance lithium-ion batteries.

Effect of La3+ Doping on the Electrical Properties of LiCoO2 Cathodes for Lithium-Ion Batteries

Effect of La3+ Doping on the Electrical Properties of LiCoO2 Cathodes for Lithium-Ion Batteries

Research Progress of Lithium Iron Phosphate in the Cathode of Lithium-Ion Battery

Lithium-ion batteries (LIBs) have been a new candidate for various industries. Unlike other types of lead-acid batteries, LIBs have a very high energy density, power density, and nominal voltage, making them a beneficial choice of battery for many electronic devices like electric vehicles. The role of cathode material in the battery is to start the electrochemical reaction, and the rate capacity is highly dependent on the ion-diffusion rate at the cathode. This makes the cathode the most critical component in the battery. Therefore, it is essential to have excellent cathode material to perform its function. Lithium iron phosphate has always been a desirable cathode material due to its stable structure, high safety, and low cost. By choosing the appropriate material, high capacity and performance can be achieved. By modifying the material through different strategies, LFP has the potential to exceed its theoretical capacity and be applied in the broader field of the electronics industry. First, this article focuses on a comparison of different cathode materials and explains why LFP is superior. Then, it will introduce the synthesis methods, including solid-state, hydrothermal, and sol-gel methods. Finally, it will discuss ways to modify LFP, including nanostructured LFP, carbon coating, and doping. This paper aims to serve as a guide and reference for research in the battery industry.

Progress in the Application of LiMnPO4 Nanomaterials in Lithium-ion Battery Cathode

Lithium-ion batteries (LIBs) have become vital in today's energy storage systems, especially for electric cars and portable gadgets. High energy density, extended cycle life, and quick charging times are features of lithium batteries. Compared to conventional batteries, they are lightweight, ecologically benign, and have a low self-discharge rate. LiMnPO4 nanomaterials have garnered significant interest among various cathode materials due to their superior thermal stability, safety, and high operating voltage. The main topics of this paper are the structural characteristics, production techniques, and performance improvements of LiMnPO4 nanoparticles as LIBs cathodes. The basic operating principles of LIBs were covered in this article, with particular attention paid to the redox reactions occurring at the electrodes, the unique olivine structure of LiMnPO4, and how these factors affect electrochemical performance. The efficiency of many synthesis methods, such as spray pyrolysis, sol-gel, solid-state, hydrothermal, and solvothermal processes, in yielding superior LiMnPO4 nanoparticles is assessed. Additionally, surface modifications through ion doping and carbon coating are reviewed to highlight their roles in enhancing conductivity and stability. This article aims to provide ideas for developing high-performance LiMnPO4 cathode materials to affect LIBs' development positively. This article aims to provide ideas for developing high-performance LiMnPO4 cathode materials to influence LIBs' development positively.

Oxygen vacancies-enriched spent lithium-ion battery cathode materials loaded catalytic membrane for effective peracetic acid activation and organic pollutants degradation

Advanced oxidation processes combined with membrane filtration technique offer a promising approach for pollution mitigation and catalyst recovery. Herein, a waste ternary lithium-ion battery cathode material of LiNixCoyMnzO2 (LNCM) loaded polytetrafluoroethylene (PTFE) membrane was synthesized for peracetic acid (PAA) activation (LNCM-PTFE/PAA) and 2,4,6-trichlorophenol (TCP) degradation. Such a novel membrane, with a catalyst loading of 10 mg (0.796 mg/cm2) of LNCM achieved 96.4 % removal of TCP (2 mg/L) within 20 min in neutral pH. The redox cycles of surface metals (such as Co3+/Co2+, Ni3+/Ni2+, and Mn4+/Mn3+/Mn2+) in spent LNCM efficiently enhance charge transfer and mediated PAA activation. And intrinsic oxygen vacancies in LNCM facilitated PAA adsorption and its cleavage. The resulting carbon-centered radicals (R-C•, CH3C(O)OO•) and 1O2 are identified as the primary reactive species that collaboratively participate in TCP degradation. Quantitative structure-activity relationship analysis demonstrated a substantial reduction in product toxicity. The successful practical application of the LNCM-PTFE/PAA membrane was exemplified by treating chlorophenol industrial wastewater. This study presents a new LNCM-PTFE/PAA catalytic membrane for high-efficiency water treatment and a novel perspective for green utilization of waste LNCM.

Thermal characteristics of LiMnxFe1-xPO4 (x = 0, 0.6) cathode materials for safe lithium-ion batteries

Lithium-ion batteries have recently gained attention as energy storage devices due to their high energy densities and various applications. Layered Ni-Mn-Co-based cathode materials are widely used for their high energy density; however, their high cost necessitates the exploration of alternatives. Consequently, olivine-type LiMnxFe1-xPO4 materials are gaining popularity and are being increasingly adopted. While the synthesis methods and electrochemical properties of these materials have been extensively studied, thermal analyses remain limited. In this study, we investigated the thermal properties of olivine-type LiMnxFe1-xPO4 by combining thermal analysis, structural analysis, and computational calculations to evaluate the safety of lithium-ion batteries. Our results show that the formation energy of LiMn0.6Fe0.4PO4 is more stable than that of LiFePO4. As temperature increases, LiFePO4 decomposes at 350 °C, whereas LiMn0.6Fe0.4PO4 begins to decompose at 450 °C. The P-O bond plays a crucial role in the thermal stability of these materials; as the temperature rises, the thermal stability of the PO4 group diminishes, leading to structural decomposition. To enhance thermal stability, it is recommended to experiment with doping small amounts of various elements at the P site. This paper provides valuable insights for the design and development of thermally stable olivine-structured cathodes for lithium-ion batteries.

Green low-melting mixture solvents/ionic liquids-based carbon materials and lithium-ion batteries recycling leachate unexpectedly cause water pollution from dissolved organic matter

Low-melting mixture solvents (LoMMSs) and ionic liquids (ILs) are regarded as green solvents for the recovery of lithium-ion batteries (LIBs) cathode with high sustainability. Unexpectedly, we find for the first time that the release of LoMMSs- or ILs-based carbon materials and LIBs recycling leachate into water can lead to significant pollution from dissolved organic matter (DOM). Moreover, COD, NH4–N and total P concentration in river from Jingjinji Region is relatively high due to the high concentration of DOM. This work would provide us a hint that the application of so-called green LoMMSs and ILs in materials preparation and LIBs recovery should be treated with high caution in order to minimize DOM pollution for the rivers in Jingjinji Region.

High-entropy doping for high-voltage LiCoO2 with enhanced electrochemical performances

Lithium cobalt oxide (LiCoO2), as a pioneering layered oxide cathode material for lithium-ion batteries (LIBs), possesses exceptional theoretical specific capacity and cycling stability, positioning it as a leading candidate for commercial LIB applications. Boosting the upper-limit of charge voltage of LiCoO2 is a promising strategy to increase the capacity of batteries, vital for advancing energy storage solutions from portable electronics to electric vehicles. Nevertheless, hybrid redox reactions at high voltages speed up oxygen evolution, electrolyte decomposition, and irreversible phase transitions, ultimately causing rapid capacity fading.To address these challenges, we present a novel approach to enhance the structural stability and electrochemical performances of LiCoO2 cathode via La-Al-Mg-Y high-entropy doping. This strategy significantly improves the high-voltage cycling stability of the cathode material by retaining 72.5 % of its initial capacity after 500 cycles at 5 C under 4.6 V. Furthermore, the structural change caused by the phase transition between the O3 and H1-3 phases is remarkably suppressed. This advancement in LIB cathode technology paves the way for the development of high performance batteries and it is crucial for meeting the growing demand for sustainable energy storage.

Alternatives assessment of polyvinylidene fluoride-compatible solvents for N-methyl pyrrolidone substitution in lithium-ion battery cathodes

Lithium-ion batteries (LIBs) are central to electrification yet, to increase the efficiency and scalability of electric systems, energy storage technologies must integrate sustainability concepts into their design. Notably, the incumbent LIB technology uses the reprotoxic solvent N-methyl pyrrolidone (NMP) to dissolve polyvinylidene fluoride (PVdF) as a binder. This solvent, of concern to human and ecological health, must be replaced with less toxic alternatives. Accordingly, the objective of this study was to determine which potential solvents, compatible with PVdF binder within the cathode processing of LIBs, could replace NMP. This study followed the U.S. National Research Council’s Framework to Guide Selection of Chemical Alternatives, and thus assembled and compared data concerning ecological and human hazards, performance, and cost. Five solvents were assessed as alternatives to NMP, derived from an analysis of 948 cells of data (708 cells of hazard data, 54 cells of performance data, and 186 cells of cost data). Triethyl phosphate (TEP) and N-N’-dimethylpropyleneurea (DMPU) are found to exhibit reprotoxic properties, and dimethylsulfoxide (DMSO) raised concerns in all three data categories studied. The most promising alternatives to NMP were dihydrolevoglucosenone (Cyrene) and γ-valerolactone (GVL). With demand for sustainable energy storage growing, the results of this study aim to guide research and innovation of LIB technologies while avoiding regrettable substitutions in developing NMP-free LIBs.

How dispersed LLZTO enhances ionic conductivity in LiFePO4 composite cathodes for solid-state batteries

To improve the ionic conductivity of the LiFePO4 cathode for high-performance solid-state lithium-ion batteries, we incorporated the chemically stable and ion-conductive Li6.75La3Zr1.75Ta0.25O12 (LLZTO) into the cathode. We discovered that the impact of this incorporation on enhancing conductivity was influenced by how well the LLZTO particles were dispersed. A solid-state battery constructed with the LiFePO4 cathode without any LLZTO incorporated exhibited an initial capacity of 146 mAh g−1 at 0.2C, with a retention of 26 % after 100 cycles of charge-discharge. When the cathode was incorporated with LLZTO particles in their original agglomerated state, the initial capacity remained similar to the pristine one, but the retention decreased to <20 %. However, when LLZTO was well-dispersed during incorporation, the initial capacity increased to 160 mAh g−1, and retention improved to over 95 %. The difference in the effectiveness of incorporating dispersed and agglomerated LLZTO on the electrochemical performance has been clarified to be mainly related to the polarization of Li+ during transport in the cathodes. This was elucidated by numerical simulations based on finite element analysis, which revealed that incorporating LLZTO agglomerates leads to a deficiency of Li+ transport in specific regions within the LiFePO4 cathode and non-uniform Li+ transport through LLZTO, resulting in reduced overall cathode conductivity and battery performance.

Enhancing Chemomechanical Stability and High-Rate Performance of Nickel-Rich Cathodes for Lithium-Ion Batteries through Three-in-One Modification

Ni-rich cathode, recognized for high specific capacities and cost-effectiveness, are deemed promising candidates for high-energy Li-ion batteries. However, these cathodes display notable structural instability and experience severe strain propagation during rapid charging and extended cycling under high voltage, hindering their widespread commercialization. To tackle this chemo-mechanical instability without compromising energy and power density, we propose an efficient modification strategy involving hexavalent metal cation-induced three-in-one modification to reconstruct the nanoscale surface phase. This strategy includes uniform W-doping, integration of cation-mixed phases, and Li2WO4 nanolayers on the surface of Ni-rich cathode microspheres. W-doping strengthen the bond to oxygen, thereby enhancing structural stability and suppressing oxygen loss linked to a layered-to-rock salt phase transition during deep delithiation process. Additionally, establishing a cation-mixing domain with an optimal thickness on the cathode surface enhances Li⁺ diffusivity and alleviates particle structural degradation. Moreover, Li2WO4 nanolayers reduce electrolyte side reactions and act as a damping medium against cycling stresses. Importantly, detailed investigations into structural changes before and after modification at varying current rates were conducted to better comprehend the rate-dependent degradation mechanism. These findings yield valuable mechanistic insights into the high-rate utilization of a viable Ni-rich cathode, ensuring prolonged service life in electric vehicles.

Systematic electrochemical analysis of high-capacity NMC-88 and NMC-83 cathodes for lithium-ion batteries

Systematic electrochemical analysis of high-capacity NMC-88 and NMC-83 cathodes for lithium-ion batteries

Balancing Layered Ordering and Lattice Oxygen Stability for Electrochemically Stable High-Nickel Layered Cathode for Lithium-ion Batteries

Despite the high-capacity nature of high-nickel cathode materials, achieving their practical implementation is challenging due to the susceptibility of atomic arrangement to calcining conditions. Extensive studies have enlightened the correlation between layered ordering and calcining conditions; nevertheless, the alterations in the electronic structure of lattice oxygen remain obscure. In this study, by comparing cathode materials with varying degrees of layered ordering, achieved through adjustments in calcination temperature and lithium equivalent, it is shown that although layered ordering increases, it compromises the electronic structure, creating a labile lattice oxygen environment. Fine structural analysis reveals that a higher local Li/O ratio in highly ordered cathode subsequently alters the band structure by narrowing the band gap between Ni 3d and O 2p, which enhances transition metal–oxygen covalency, and reduces the oxygen vacancy formation energy, adversely affecting cyclability. In highly ordered cathode, the tendency of lattice oxygen to reside within a Li-enriched environment arises from the changes in the favorability of non-paired antisite defects contingent upon the calcination temperature and lithium equivalent. This research underscores the need to balance layered ordering and lattice oxygen stability, offering important insights for the future design of high-nickel cathodes.

Mechanisms of Thermal Decomposition in Spent NCM Lithium-Ion Battery Cathode Materials with Carbon Defects and Oxygen Vacancies.

Resource recovery from retired electric vehicle lithium-ion batteries (LIBs) is a key to sustainable supply of technology-critical metals. However, the mainstream pyrometallurgical recycling approach requires high temperature and high energy consumption. Our study proposes a novel mechanochemical processing combined with hydrogen (H2) reduction strategy to accelerate the breakdown of ternary nickel cobalt manganese oxide (NCM) cathode materials at a significantly lower temperature (450 °C). Particle refinement, material amorphization, and internal energy storage are considered critical success factors for the accelerated decomposition of NCM cathode materials. In our proposed approach, NCM cathode materials can develop active sites with carbon defects (Cv) and oxygen vacancies (Ov), which improve the reduction and breakdown of H2. The adsorbed H2 on the surface of NCM decomposes into H* and combines with oxygen to form OH species, which can be facilitated by Ov via the enhanced charge transfer. The introduced Cv can enhance H2 cracking and generate *C-H species to promote the thermal decomposition of NCM. The presence of defects proves to foster the preferential reduction of Mn(IV) by H2, leading to a lower activation energy for the NCM decomposition (from 139 to 110 kJ/mol) with less H2 consumption. Life cycle assessment suggests a reduction of 4.42 kg CO2 eq for the recycling of every 1.0 kg of retired batteries. This study can promote material circularity and minimize the environmental burden of mining technology-critical metals for a low-carbon transition.

A Hybrid Modelling Approach Coupling Physics-based Simulation and Deep Learning for Battery Electrode Manufacturing Simulations

Lithium-ion battery (LIB) performance is significantly influenced by its manufacturing process. Manufacturing of an optimized electrode can incur high production costs such as high energy consumption, high scrap rates and emissions. This is due to the process that consists of a series of manufacturing steps presenting a complex interrelationship, thus limiting the understanding of performance as a function of manufacturing parameters. While several empirical and computational methods are employed for optimization, they are demanding in terms of resources such as materials or computational effort. By leveraging Deep Learning (DL), we can enhance our understanding of the complex manufacturing processes and accelerate its optimization. We propose a data-driven supervised DL methodology to complement physics-based LIB cathode manufacturing simulations. The trained DL-based predictive model integrates well into the manufacturing simulation framework to forecast cathode slurry microstructures. The DL model demonstrates robust predictive performance for LIB NMC-111 and LiFePO4–based slurries and slurries for a solid-state battery NMC-622/argyrodite composite electrode preparation. While the current work is focused on the cathode slurry process, the proposed methodology has potential for application to drying and calendering steps. This approach will be helpful in streamlining lab-scale electrode manufacturing, and reducing errors, waste and resource consumption.

Fulgide Derivatives as Photo-Switchable Coatings for Cathodes of Lithium Ion Batteries - A DFT Study.

Photo-switchable coatings for lithium ion batteries (LIB) can offer the possibility to control the diffusion processes from the electrode materials to the electrolyte and thus, for example, reducing the energy loss in the fully charged state. Fulgide derivatives, as known photo-switches, are investigated concerning their use as coating for vanadium pentoxide, a potential cathode material for LIB. With the help of Density Functional Theory calculations, two fulgide derivatives are characterized with respect to their photophysics, their aggregation behaviour on the cathode material and the ability to form self-assembled monolayers (SAM). Furthermore, the two states of the photo-switchable coating are tested with respect to lithium diffusion from the cathode material, passing the SAM and entering the electrolyte. We found a difference for the energy barriers depending on the state of the photo-switch, preferring its closed form. This behaviour can be used to prevent the loss of charge in batteries of portable devices.

The Development and Prospect of Stable Polyanion Compound Cathodes in LIBs and Promising Complementers.

Cathode materials are usually the key to determining battery capacity, suitable cathode materials are an important prerequisite to meet the needs of large-scale energy storage systems in the future. Polyanionic compounds have significant advantages in metal ion storage, such as high operating voltage, excellent structural stability, safety, low cost, and environmental friendliness, and can be excellent cathode options for rechargeable metal-ion batteries. Although some polyanionic compounds have been commercialized, there are still some shortcomings in electronic conductivity, reversible specific capacity, and rate performance, which obviously limits the development of polyanionic compound cathodes in large-scale energy storage systems. Up to now, many strategies including structural design, ion doping, surface coating, and electrolyte optimization have been explored to improve the above defects. Based on the above contents, this paper briefly reviews the research progress and optimization strategies of typical polyanionic compound cathodes in the fields of lithium-ion batteries (LIBs) and other promising metal ion batteries (sodium ion batteries (SIBs), potassium ion batteries (PIBs), magnesium ion batteries (MIBs), calcium ion batteries (CIBs), zinc ion batteries (ZIBs), aluminum ion batteries (AIBs), etc.), aiming to provide a valuable reference for accelerating the commercial application of polyanionic compound cathodes in rechargeable battery systems.

Improving the Cycle Stability of LiNiO2 through Al3+ Doping and LiAlO2 Coating.

In this study, we addressed the poor cycling and rate performance of LiNiO2, a material with ultrahigh nickel content considered a strong contender for high-energy-density lithium-ion battery cathodes. We introduced nano-Al2O3 during the lithiation process to achieve dual modified material through bulk phase element doping and in situ LiAlO2 coating. Comparison revealed notable improvements in the modified materials. In particular, LiNi0.99Al0.01O2 maintained a capacity retention rate of 73.1% after 300 cycles in a long-cycle test at 0.5C current density, outperforming the undoped material. In rate performance tests, the doped samples consistently exhibited higher discharge-specific capacities than that of the undoped counterpart. Notably, at a high current density of 5C, LiNi0.99Al0.01O2 exhibited a discharge-specific capacity of 101.75 mAh g-1. The results indicate that an appropriate amount of Al doping can effectively stabilize the layered structure of the cathode material and delay the irreversible phase transition from H2 to H3. Further, Al doping facilitates the formation of a LiAlO2 coating on the surface of the particles. This coating acts as a fast-ion conductor, enhancing the transport of lithium ions and reducing the erosion of the active material by the electrolyte.

Comprehensive study on lithium-ion battery cathode LiNixCoyMn1-x-yO2 as an air electrode for protonic ceramic fuel cells

The protonic ceramic fuel cells (PCFCs) exhibits a remarkable high-energy conversion efficiency and significant application potential at low temperatures. In this context, the layered ternary lithium-ion batteries (LIB) material, LiNixCoyMn1-x-yO2 (LNCM), is explored as a potential cathode for PCFCs. Utilizing density functional theory (DFT) calculations, we have conducted a comprehensive analysis of oxygen vacancies, hydration energy, density of states, and other pertinent properties to evaluate these ternary materials. Both theoretical and experimental findings suggest that LiNi0.5Co0.2Mn0.3O2 (LNCM523) may offer the optimal performance as a PCFCs cathode. Notably, after calcination in air at 700 °C for 100 h, LNCM523 displayed no phase transition or the emergence of new phases. The impedance of LNCM523, measured on a BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb) electrolyte, is 0.225 Ω cm2 at 650 °C. At this temperature, the peak power density of the single cell reaches 355 mW cm−2. Moreover, during a 100-h stability test conducted at 550 °C, the output performance of the single cell remained unaltered. In electrolysis mode, at 650 °C and 1.3 V, the current density for electrolysis water attained 1.75 A cm−2. Based on these promising results, LNCM emerges as a viable cathode candidate for PCFCs.