Cathode Materials For Lithium-ion Batteries Research Articles

Water Effect on the Electronic Properties and Lithium-Ion Conduction in a Defect-Engineered LiFePO4 Electrode

Defect-engineering accelerates the conduction of lithium ions in the cathode materials of lithium-ion batteries. However, the effects of defect-engineering on ion conduction and its mechanisms in humid environments remain unclear in the academic discourse. Here, we report on the effect of vacancy defects on the electronic properties of and Li-ion diffusion in a LiFePO4 material in humid environments. The research findings indicate that vacancy defects reduce the lattice constant and unit cell volume of LiFePO4. Additionally, the water molecules occupy the Li-ion vacancies, leading to an increase in the lattice constant of LiFePO4. The computational results of the electronic properties show that the introduction of water molecules induces a transition in LiFePO4 from a semiconductor to a metallic behavior, with a transfer of 0.38 e of charge from the water molecules to LiFePO4. Additionally, the migration barrier for Li ions in the H2O + LiFePO4 system is found to be 0.50 eV, representing an 11.1% increase compared to the pristine LiFePO4 migration barrier. Our findings suggest that water molecules impede the migration of Li ions and provide important insights into the effect of defect-engineering on electronic properties and ion conduction under humid conditions.

Computational and Machine Learning‐Assisted Discovery and Experimental Validation of Conjugated Sulfonamide Cathodes for Lithium‐Ion Batteries

AbstractConjugated sulfonamides (CSAs) stand out for their propitious electroactivity and notable stability in ambient conditions, making them suitable candidates for high‐potential cathode materials in lithium‐ion batteries (LIBs). This study employs a combination of machine learning, semi‐empirical quantum mechanics, and density functional theory methods to evaluate a large library of 11 432 CSA molecules, focusing on material properties crucial for application in batteries, such as synthetic complexity, redox potential, gravimetric charge capacity, and energy density. After applying the thresholds for the synthetic complexity score at 2.62 and the redox potential at 3.25 V versus Li/Li+, we identify 50 CSA molecules that are easy to synthesize and suitable for the positive electrode in LIBs. By ranking on the basis of redox potential, 13 CSA molecules having potentials greater than 3.50 V versus Li/Li+ are identified. Through further investigations using molecular dynamics simulations on these reactant molecules and their lithiated products, a molecule is singled out for synthesis and electrochemical evaluation. This molecule, lithium (2,5‐dicyano‐1,4‐phenylene)bis((methylsulfonyl)amide)(Li2‐DCN‐PDSA), demonstrates a redox potential surpassing those previously reported within the class of CSA molecules. Moreover, the study explores the quantitative structure‐property relations of CSAs, yielding insights for the development of CSA‐based LIB cathode materials, informed by the comprehensive data assembled.

Classification of cathode materials for lithium-ion batteries of new energy electric vehicles based on safety and dynamic performance

The severe environmental pollution caused by fossil fuels has driven the demand for new energy vehicles. The choice of cathode materials for lithium-ion batteries is a major difficulty to be overcome in the development of new energy vehicles. Based on the performance characteristics of new energy vehicle batteries in actual use, this paper classifies the six most widely used cathode electrode materials in the new energy vehicle market. Firstly, the temperature data of power batteries with different cathode materials in the overcharge experiment and acupuncture experiment were collected to characterize the safety performance of power batteries. Then the maximum specific discharge capacity and operating voltage data of the battery were collected, and the maximum specific discharge energy of the battery was calculated to study the dynamic performance of the vehicle. After that, the safety performance and dynamic performance of each index is compared. Finally, according to the safety performance and dynamic performance of the corresponding power battery, the six cathode materials are divided into three types: power type, safety type, and balanced type. According to the classification results, it can be concluded that the design of balanced cathode materials with both safety and dynamic performance is the best development route for future new energy vehicle batteries.

Dual Modification Strategy for Enhanced Cycling and Rate Performance of Ni-Rich Cathode Materials in Lithium-Ion Batteries.

A great challenge in the commercialization process of layered Ni-rich cathode material LiNixCoyMn1-x-yO2 (NCM, x ≥ 80%) for lithium-ion batteries is the surface instability, which is exacerbated by the increase in nickel content. The high surface alkalinity and unavoidable cathode/electrolyte interface side reactions result in significant decrease for the capacity of NCM material. Surface coating and doping are common and effective ways to improve the electrochemical performance of Ni-rich cathode material. In this study, an in situ reaction is induced on the surface of secondary particles of NCM material to construct a stable lithium sulfate coating, while achieving sulfur doping in the near surface region. The synergistic modification of lithium sulfate coating and lattice sulfur doping significantly reduced the content of harmful residual lithium compounds (RLCs) on the surface of NCM material, suppressed the side reactions between the cathode material surface and electrolyte and the degradation of surface structure of the NCM material, effectively improved the rate capability and cycling stability of the NCM material.

Effect of Mo6+ induced valence changes of transition metal ions in Mn-rich layered cathode materials on electrochemical performance

Layered cathode materials for lithium-ion batteries have been extensively investigated; however, comparatively scant attention has been paid to Mn-rich layered cathode materials. Herein, LiNi0.5Mn0.5O2 cathode materials are doped to investigate the effect of doping elements on the electrochemical properties of Mn-rich layered cathodes. XRD (X-ray diffraction), XPS (X-ray photoelectron spectroscopy), and SQUID (superconducting quantum interference device) results reveal that Mo doping affects the electrochemical properties of the cathode materials by changing the valence state of transition metal ions. Due to the Mo6+ ions doping, a large proportion of Mn3+ ions present in LiNi0.5Mn0.5O2 were converted to Mn4+ ions, which alleviated the Jahn-Teller effect and reduced the elongated Mn-O octahedra, thus increasing the Li layer spacing and facilitating Li+ diffusion. Therefore, 1 % Mo-doped cathode exhibits a significantly improved Li-ion diffusion coefficient and superior rate performance with a specific discharge capacity of 103 mAh·g−1 at 5C. Meanwhile, the cathode materials significantly improve cycling performance due to the reduction in the amount of Mn3+. The current study provides guidelines for the modification of Mn-rich layered cathodes in the future.

Synthesis, intercalation reactions, and electrochemical studies for VO2/PEO/Chitosan

VO2 obtained by hydrothermal synthesis from V2O5 was used as a matrix to obtain hybrid compounds containing different proportions of polyethylene oxide and chitosan. The XRD results demonstrate that monoclinic VO2 was obtained, and hybrid compounds showed variation in the displacement of the lamella peak, indicating an intercalation of polymers into the matrix. The stretching and vibration bands show a variation towards higher wavelength values of the hybrid compounds, which indicates that the intercalation of the polymers occurred into the matrix. The UV–Vis spectra show the absorptions that can be attributed to the transitions of each material. Absorption in the visible region decreases for hybrid compounds in relation to VO2. The hybrid compounds presented lower bandgap values compared to VO2. From cyclic voltammetry, it was possible to observe anodic and cathodic peaks linked to the redox process of the VIV/VIII pair for both VO2 and VO2/polymers, which is derived from the insertion/disinsertion process of lithium ions, where the hybrid compound presented a different voltammetric profile compared to VO2. The total charge curves as a function of the number of cycles demonstrate better cycling stability and a greater total charge of the hybrid compounds compared to VO2. These results demonstrate that hybrid compounds have potential as cathode materials for lithium-ion batteries.

Anionic-surfactant-assisted synthesis of Ni0.8Co0.1Mn0.1(OH)2 as precursors of high-performance cathode materials for lithium-ion batteries

A facilitated anionic-surfactant-assisted method is developed to synthesize hierarchical microstructure Ni0.8Co0.1Mn0.1(OH)2 precursors. The anionic surfactant β-styrylphosphonic acid could directionally regulate the growth and the arrangement of the precursor nanosheets, where the primary nanosheets could maintain layered growth and ordered arrangement. The cathode material of the LiNi0.8Co0.1Mn0.1O2 synthesized from the above precursors exhibits best electrochemical performances and its capacity retention rates could reach 93 % (164.5 mAh g−1) after 100 cycles and 84.3 % (149.0 mAh g−1) after 300 cycles. Meanwhile, the detailed atomic arrangements on the crystal facets of cathodes are investigated both via first-principles calculations and transmission electron microscopy (TEM) analysis, and this research reveals that the crystal facet structures of cathode materials determine the electrochemical properties significantly.

Functionalized porous conductive carbon layer improves the low-temperature performance of LiFePO4 cathode material for lithium-ion batteries

Lithium iron phosphate (LiFePO4) has been successfully utilized due to its stable structure, low cost, and higher safety. Nevertheless, the sluggish diffusion kinetics and low electrical conductivity have suppressed the rate capacity and long-term cyclability at lower temperature, causing significant capacity degradation problems. Herein, to address such issues, a well-designed 3D porous structure LFP@NS is synthesized via the sol-gel method combined with a high-temperature calcination route. Furthermore, the nitrogen and sulfur in thiourea can be induced to enter the carbon matrix, resulting in generating more defects and active sites. Simultaneously, N,S co-doped carbon matrix can form successive migration channels for lithium-ion, which can promote the diffusion kinetics and electrical conductivity. The as-prepared LFP@NS-2 sample provides 158.5 mAh g−1 discharge capacity in the room temperature (RT) and 101.3 mAh g−1 (in −20 °C) at 1C, and exhibits remarkable cyclic performance (122.3 mAh g−1 after 2000 circles at 10C in the RT). Furthermore, to investigate the practical application in low temperature, coupled with a graphite (Gr) anode, the LFP@NS-2||Gr full battery releases 100.1mAh g−1 at 1C in −20 °C. Therefore, this work has a far-reaching implication for designing the high-performance LIBs electrode materials for practical application at low temperature.

Biometabolically Derived Selenium Nanoparticles Armed with Protein Protective Suit toward High-Performance Li-Se Batteries.

Selenium (Se) serves as a burgeoning high-energy-density cathode material in lithium-ion batteries. However, the development of Se cathode is strictly limited by low Se utilization and inferior cycling stability arising from intrinsic volume expansion and notorious shuttle effect. Herein, a microbial metabolism strategy is developed to prepare "functional vesicle-like" Se globules via Bacillus subtilis subsp. from selenite in sewage, in which Se nanoparticles are armed with a natural biological protein membrane with rich nitrogen and phosphorus, achieving the eco-efficient conversion of trash into treasure (selenite, SeO3 2- → Selenium, Se). The appealing-design "functional vesicle-like" Se globules are beneficial to accommodate volume changes of Se in electrochemical reactions, confining polyselenides via chemisorption, and enhancing mechanical strength of electrode by associated bacteria debris, realizing comprehensive utilization of microorganism. By conceptualizing "functional vesicle-like" Se globules, rather than artificial Se-host composites, as cathode for lithium-selenium batteries, it exhibits outstanding cycling stability and improved rate performance. This strategy opens the door to design smart electrode materials with unattainable structure that cannot be achieved by traditional approaches, achieving eco-efficient conversion of pollutants into energy-storage nanomaterials, which will be a promising research field for interdisciplinary of energy, biology, and environment.

Decoding Li+/H+ ion exchange route toward low-temperature synthesis of layered oxide cathode materials for lithium-ion batteries

Decoding Li+/H+ ion exchange route toward low-temperature synthesis of layered oxide cathode materials for lithium-ion batteries

Conversion of cobalt from spent LIBs to Co3O4 electrode material for application in supercapacitors

ABSTRACT The cathode material of lithium-ion batteries (LIBs) is endowed with valuable metals, such as cobalt. The improper treatment of these batteries pollutes the environment and causes enormous resource waste. Therefore, the recovery of valuable metals from spent LIBs has attracted widespread attention. In this study, Co3O4 electrode materials were prepared by a simple homogeneous precipitation method and heat treatment using a leaching solution of spent LIBs-positive electrode material as the cobalt source. The crystal structure and morphology of the products were examined at different annealing temperatures, and their electrochemical performance was analyzed. The results show that low-temperature annealing contributes to grain refinement. The Co3O4 material prepared at 300°C annealing temperature has a rod-like structure with distinct pores and a specific surface area of 58.98 m2 g−1. Furthermore, electrochemical performance testing reveals that Co3O4 prepared at 300°C displays the best electrochemical performance as an electrode material, with a specific capacitance of 97.93 F g−1 and a cycle retention rate of 79.12% after 500 charge–discharge cycles. These findings demonstrate the feasibility of recycling valuable metal cobalt from spent LIBs cathode materials to produce Co3O4 materials for use as supercapacitor electrode materials, opening up new avenues for the recycling and utilisation of spent LIBs.

Advancing Lithium-Ion Batteries' Electrochemical Performance: Ultrathin Alumina Coating on Li(Ni0.8Co0.1Mn0.1)O2 Cathode Materials.

Ni-rich Li(NixCoyMnz)O2 (x ≥ 0.8)-layered oxide materials are highly promising as cathode materials for high-energy-density lithium-ion batteries in electric and hybrid vehicles. However, their tendency to undergo side reactions with electrolytes and their structural instability during cyclic lithiation/delithiation impairs their electrochemical cycling performance, posing challenges for large-scale applications. This paper explores the application of an Al2O3 coating using an atomic layer deposition (ALD) system on Ni-enriched Li(Ni0.8Co0.1Mn0.1)O2 (NCM811) cathode material. Characterization techniques, including X-ray diffraction, scanning electron microscopy, and transmission electron microscopy, were used to assess the impact of alumina coating on the morphology and crystal structure of NCM811. The results confirmed that an ultrathin Al2O3 coating was achieved without altering the microstructure and lattice structure of NCM811. The alumina-coated NCM811 exhibited improved cycling stability and capacity retention in the voltage range of 2.8-4.5 V at a 1 C rate. Specifically, the capacity retention of the modified NCM811 was 5%, 9.11%, and 11.28% higher than the pristine material at operating voltages of 4.3, 4.4, and 4.5 V, respectively. This enhanced performance is attributed to reduced electrode-electrolyte interaction, leading to fewer side reactions and improved structural stability. Thus, NCM811@Al2O3 with this coating process emerges as a highly attractive candidate for high-capacity lithium-ion battery cathode materials.

Doping Effects on Ternary Cathode Materials for Lithium-Ion Batteries: A Review.

The ongoing advancements in lithium-ion battery technology are pivotal in propelling the performance of modern electronic devices and electric vehicles. Amongst various components, the cathode material significantly influences the battery performance, such as the specific capacity, capacity retention and the rate performance. Ternary cathode materials, composed of nickel, manganese, and cobalt (NCM), offer a balanced combination of these traits. Recent developments focus on elemental doping, which involves substituting a fraction of NCM constituent ions with alternative cations such as aluminum, titanium, or magnesium. This strategic substitution aims to enhance structural stability, increase capacity retention, and improve resistance to thermal runaway. Doped ternary materials have shown promising results, with improvements in cycle life and operational safety. However, the quest for optimal doping elements and concentrations persists to maximize performance while minimizing cost and environmental impact, ensuring the progression towards high-energy-density, durable, and safe battery technologies.

Beyond the Conventional Leaching: Exploring Pyruvic Acid-Based Deep Eutectic Solvents for Sustainable Recycling of Spent Lithium-Ion Battery Cathode Material

Beyond the Conventional Leaching: Exploring Pyruvic Acid-Based Deep Eutectic Solvents for Sustainable Recycling of Spent Lithium-Ion Battery Cathode Material

The enhancement and impact of Se doping on the electrochemical properties of LiMn2O4 cathode material for aqueous Li-ion batteries

Spinel LiMn2O4 is a promising cathode material for lithium-ion batteries. However, due to the Jahn-Teller effect and Mn dissolution, its capacity decreases seriously in the cycle process, which hinders its wider application. In the course of our research, we discovered that a modest infusion of Se-doping is capable of significantly augmenting the oxygen vacancy within the material, improve the conductivity of the LiMn2O4 material and promotes superior battery performance. Moreover, due to Se-doped the average valence state of Mn is raised, which effectively mitigates the Jahn-Teller effect. The optimized sample exhibits high capacity, long cycle life, and superior rate capability, with an initial discharge specific capacity of 101.0 mAh·g−1 at 7 C and capacity retention of 87.3 % after 200 cycles. The maximum specific discharge capacity of the full battery during the cycle was 97.9 mAh·g−1, the capacity retention rate after 200 cycles was 78.2 %, and the maximum energy density during the cycle is 145.1 Wh·Kg−1, which was nearly twice that of the single lithium-ion battery in this paper. The effect of Se-doped on the properties of LiMn2O4 cathode materials provides a new idea for the development of high-performance spinel lithium manganese oxide cathode materials.

Synergetic recycling of permanent magnet and Li-ion battery cathode material for metals recovery

Rare earth elements (REEs)-based (NdFeB) magnets and lithium−ion batteries (LIBs) are critical for a low−carbon economy. Their production depends on critical elements like REEs, Li, Co and Ni. Recycling of these products have been explored separately as a potential solution. Conventional methods for recycling NdFeB magnets and LIBs face challenges like high energy consumption, lengthy processing, excessive reagent usage, and waste generation. In this study, a novel synergetic recycling methodology is proposed to minimize these challenges. The idea is based on using waste ferrous sulfate solution generated during magnet leaching as a reducing and leaching reagent for battery recycling thereby eliminating the need for additional reagents for oxidation of iron in NdFeB and reduction of cathode material in LIBs. The magnet is leached in diluted H2SO4 at 70 °C followed by double sulfate precipitation for REEs with Na2SO4. The REE-depleted but acidic ferrous solution is then used for reductive leaching of cathode material at 90 °C. The overall recovery rates of REEs, Li, Co, Ni, and Mn in this process are >95%. The iron from magnet material is recovered as crystalline and easily-filterable iron compound that can be converted to goethite and used as a byproduct. This synergetic approach not only reduces reagent consumption and waste generation aligning with the principles of circular economy but also offers improved efficiency, resource conservation, and environmental sustainability.

LiMn0.8Fe0.2PO4 as a promising cathode material in solid-state lithium batteries: Structural and electrical characterization

In this study, the synthesis, structural characterization, and electrical property analysis of LiMn0.8Fe0.2PO4 (LM8F) and its carbon-composite variant (LM8F-10%C) as potential cathode materials for solid-state lithium batteries were reported. Employing high-energy ball milling (HEBM) followed by calcination, LM8F was synthesized using ammonium dihydrogen phosphate, lithium carbonate, manganese(II) acetate tetra-hydrate, and iron(III) phosphate as precursors. The introduction of glucose as a carbon source aimed at the formation of a carbon-coated composite to enhance the electrical conductivity of the material. Structural and morphological characteristics of the synthesized materials were elucidated through X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and field emission scanning electron microscopy (FeSEM). The XRD results confirmed the olivine and orthorhombic structure of the synthesized material, highlighting its suitability for use as a cathode in solid-state lithium batteries. Electrical properties were assessed using an LCR meter to examine the impact of carbon coating on electrochemical performance. The findings demonstrated that the inclusion of carbon significantly improved the electrical conductivity, potentially leading to enhanced battery performance. This work contributes to the development of high-performance cathode materials for solid-state lithium batteries, paving the way for future advancements in energy storage technologies.

Enhanced structural stability and durability in lithium-rich manganese-based oxide via surface double-coupling engineering

Lithium-rich manganese-based oxides (LRMOs) exhibit high theoretical energy densities, making them a prominent class of cathode materials for lithium-ion batteries. However, the performance of these layered cathodes often declines because of capacity fading during cycling. This decline is primarily attributed to anisotropic lattice strain and oxygen release from cathode surfaces. Given notable structural transformations, complex redox reactions, and detrimental interface side reactions in LRMOs, the development of a single modification approach that addresses bulk and surface issues is challenging. Therefore, this study introduces a surface double-coupling engineering strategy that mitigates bulk strain and reduces surface side reactions. The internal spinel-like phase coating layer, featuring three-dimensional (3D) lithium-ion diffusion channels, effectively blocks oxygen release from the cathode surface and mitigates lattice strain. In addition, the external Li3PO4 coating layer, noted for its superior corrosion resistance, enhances the interfacial lithium transport and inhibits the dissolution of surface transition metals. Notably, the spinel phase, as excellent interlayer, securely anchors Li3PO4 to the bulk lattice and suppresses oxygen release from lattices. Consequently, these modifications considerably boost structural stability and durability, achieving an impressive capacity retention of 83.4% and a minimal voltage decay of 1.49 mV per cycle after 150 cycles at 1 C. These findings provide crucial mechanistic insights into the role of surface modifications and guide the development of high-capacity cathodes with enhanced cyclability.

Enhanced electrochemical performance of a cost-effective Sm2O3-coated spinel LiNi0.5Mn1.5O4 cathode for high-voltage lithium-ion batteries

Spinel LiNi0.5Mn1.5O4 (LNMO) has gained significant attention as a promising cathode material for lithium-ion batteries due to its high working voltage (>4.7 V) and energy density. However, challenges such as electrolyte decomposition-induced material interface erosion and transition metal dissolution under high operating voltage hinder its commercial use. In this study, a thin and uniform Sm2O3 layer has been successfully deposited on the surface of LNMO using a wet chemical method. A comprehensive investigation of surface morphology, crystal structure, and electrochemical performance of the modified LNMO is conducted. The results demonstrate that the Sm2O3 surface modification acts as a robust multifunctional protective layer, effectively shielding against hydrofluoric acid-induced chemical attack and enhancing the migration efficiency of lithium ions. Notably, the capacity retention rate of LNMO@Sm2O3 (3 wt%) remains up to 88 % after 280 cycles, significantly surpassing the uncoated counterpart. The coated material exhibits a capacity of 114 mAh g−1 even under 10 C rate conditions. Moreover, the AC impedance values and manganese dissolution of the modified material in the organic electrolyte are considerably lower than those of the uncoated counterpart. Theoretical calculations strongly support the experimental findings, revealing higher Mn vacancy formation energy and density of states at the Fermi energy level for the Sm2O3-modified electrodes. This research contributes to the field of surface modification and paves the way for further enhancements in the electrochemical performance of other high-voltage manganese-based lithium-ion batteries (LIBs).

Enhanced mechanical and surface chemical stability in cobalt-free, high-nickel cathode materials for lithium-ion batteries

Cobalt-free, high-nickel cathode materials are essential for the sustainable evolution of energy storage technologies, reducing the dependence on resources with significant environmental and social implications and simultaneously improving the efficiency and cost effectiveness of batteries. This paper introduces a cobalt-free, high-nickel cathode material called 0.01B-LiNi0.98Mg0.01Zr0.01O2 (NMZB) developed using a novel blend of elements to enhance mechanical and surface chemical stability. Detailed evaluations confirmed the successful integration of Mg, Zr, and B into the particles, with Mg and Zr primarily located within the particle interior and B predominantly on the surface. This unique elemental configuration significantly improves the stability of the bulk phase and surface structure of the material. In addition, the refinement of primary particles within NMZB further enhances its mechanical stability. As a result, NMZB exhibits exceptional electrochemical stability, achieving 90.5 % capacity retention after 200 cycles at a 1C rate. This compositional strategy incorporates a high nickel content into layered materials while eliminating cobalt, which is crucial for advancing the development of cost effective and high-performance lithium-ion battery technology.