Cathode Materials For Lithium-ion Batteries Research Articles

Assumption on the optimization direction of positive electrode materials and new methods for recycling electrode materials in lithium-ion batteries

Abstract With the increasing scarcity of non-recyclable resources such as international fossil energy and coal industries, representatives from various countries at the Paris Summit advocated the strategy of “carbon neutrality, carbon peaking” and promoted the use of recyclable resources, namely electricity. There are many ways to generate electricity, such as solar power, hydroelectric power, thermal power, tidal power and wind power. However, the method of mobile storage of electricity is relatively single - using batteries. The most widely used mobile battery currently is lithium-ion battery. This research will focus on the different choices of cathode materials for lithium-ion batteries, analysing and comparing their performance, functional stability, lifespan, capacity, price, and working conditions under extreme temperatures. At the same time, in-depth analysis will be conducted on existing electrode material recycling methods. Finally, the development direction of electrode materials with economic benefits and promising development prospects, as well as recycling methods that are more in line with economic benefits and increase resource utilization, are proposed.

Electronic structure and delithiation mechanism of vanadium and nickel doped Li2MnPO4F cathode material for lithium-ion batteries

This study calculates the energy band structure and density of states of Lithium manganese fluorophosphate (Li2MnPO4F, a lithium transition metal phosphate compounds) using the first-principles plane-wave pseudopotential approach within the density-functional theory. The model of Li2M0.5Mn0.5PO4F (M = V, Ni) with transition metal doped Mn sites is constructed by using the CASTEP module. The calculation findings indicate that the transition metal doping can regulate the energy band structure of the intrinsic system, and Li2MnPO4F makes the band gap decrease, and the volume increase with the Li ions of being deintercalated, and the electrons can be readily stimulated from the valence band to the conduction band. The findings indicate that Li2MnPO4F is a favorable cathode material for high-voltage lithium ion batteries (LIBs). The introduction of vanadium (V) and nickel (Ni) doping reduces the band gap, facilitating an easier excitation of electrons from the valence band to the conduction band. This study provides a theoretical study of new cathode materials for high performance LIBs.

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.

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

Rare earth element (REE)-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 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 highly 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 high-grade goethite that can be 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.

Application of cathode materials in lithium ion phosphate battery and its modification

Abstract Lithium ion batteries have been widely used in various fields, such as electric vehicles, due to their excellent electrochemical performance. Especially, introducing some functional materials into batteries can further improve battery performance. This research analyses the application of lithium-ion phosphate as the cathode materials of the batteries, with a particular focus on the structural characteristics and various indices of the modification of lithium iron phosphate battery cathode materials. The electrode material is systematically described, highlighting its advantages, disadvantages, and application range while emphasizing its crucial role in different electrochemical performance such as energy density and recyclability. In addition, the relationship between the electrochemical performance and structure properties of cathode materials in LiFePO4 is summarized by placing emphasis on nanoparticle characteristics, interface environment effects, and electrode structures. This research also presents a series of achievements in modifying lithium iron phosphate cathode materials. And it identifies areas that require improvement and looks forward to future challenges and developments in lithium-ion battery cathode materials.

Efficient separation of cathode materials from aluminum foil by novel low-melting mixture solvent based on choline chloride-xylitol system

Lithium-ion batteries (LIBs) are important energy devices with significant growth and expansion that result in large amounts of metal waste. However, the separation of the cathode materials from aluminum (Al) foil during the recycling of spent LIBs is still challenging due to their strong bonding by polyvinylidene fluoride (PVDF). Herein, a novel low-melting mixture solvent (LoMMS) based on the choline chloride-xylitol system with ow-toxicity, cost-effectiveness, and environmental friendliness was developed for separating the cathode materials from Al foil in LIBs. Under the optimal treatment conditions of a molar ratio of choline chloride to xylitol of 2:1, a reaction temperature of 140 °C, a reaction time of 20min, and solid-liquid ratio of 16g/L separation efficiency cathode material reached a maximum of 94.92%. The mechanistic analysis revealed that the high separation efficiency can be attributed to strong hydrogen bonding provided by choline chloride and xylitol in LoMMS, disrupted PVDF molecular bonding and resulted in deactivation and successful separation of cathode material particles from the aluminum foil. Additionally, scanning electron microscopy examination revealed no changes in the morphologies of the cathode materials, useful for their restoration and reutilization. Overall, the proposed LoMMS method with low-cost and eco-friendly aspects has great potential for recycling spent LIB cathode materials.

Synthesis and Electrochemical Performance of Na and F Elements Co-Doped LiFePO4/C as a Cathode Material for High-Rate Lithium-Ion Batteries and the Mechanism of Modification

Synthesis and Electrochemical Performance of Na and F Elements Co-Doped LiFePO4/C as a Cathode Material for High-Rate Lithium-Ion Batteries and the Mechanism of Modification

Synthesis Pathway of Layered-Oxide Cathode Materials for Lithium-Ion Batteries by Spray Pyrolysis.

We report the synthesis of LiCoO2 (LCO) cathode materials for lithium-ion batteries via aerosol spray pyrolysis, focusing on the effect of synthesis temperatures from 600 to 1000 °C on the materials' structural and morphological features. Utilizing both nitrate and acetate metal precursors, we conducted a comprehensive analysis of material properties through X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Our findings reveal enhanced crystallinity and significant oxide decomposition within the examined temperature range. Morphologically, nitrate-derived particles exhibited hollow, spherical shapes, whereas acetate-derived particles were irregular. Guided by high-temperature X-ray diffraction (HT-XRD) data, the formation of a layered LCO oxide structure, with distinct spinel Li2Co2O4 and layered oxide LCO phases was shown to emerge at different annealing temperatures. Optimally annealed particles showcased well-defined layered structures, translating to high electrochemical performance. Specifically, nitrate-based particles annealed at 775 °C for 1 h demonstrated initial discharge capacities close to 179 mAh/g, while acetate-based particles, annealed at 750 °C for 3 h, achieved 136 mAh/g at a 0.1C discharge rate. This study elucidates the influence of synthesis conditions on LCO cathode material properties, offering insights that advance high throughput processes for lithium-ion battery materials synthesis.

Design of double layer cathode electrode for improving the safety and stability of lithium-ion batteries

LiNi0.8Co0.1Mn0.1O2 (NCM) is a widely used cathode material for lithium-ion batteries (LIBs). However, the poor cycle performance and safety issue remains a huge challenge for its practical applications. Here we show a simple double layer strategy to improve the electrochemical characteristics and safety performance. NCM was coated by LiFePO4 (LFP), a safe cathode material with long cycle stability, exhibited more excellent cycling stability and similar rate properties at room temperature (called NCM/LFP). Under 45 ℃, the NCM/LFP (6:1)||graphite pouch cell shows excellent 83% capacity retention after 600 cycles at 1C, which compared to the sharp attenuation of pristine NCM. Furthermore, NCM/LFP (6:1)||graphite cell could pass the nail penetration tests and the thermal runaway temperature (TTR) delayed by 193℃, which proved the double layer design has better safety performance. The current work might pave an avenue for cathode materials, as a sustainable solution to high energy density LIBs for applications.

A Comprehensive Review on Reductive Recycling of Cathode Materials of Spent Lithium-Ion Batteries.

The prosperity of the lithium-ion battery market is inevitably accompanied by the depletion of corresponding resources and the accumulation of spent batteries in a dialectical manner. Spent lithium-ion batteries are harboring the characteristics of hazardous waste and high-value resources, so efficient recycling is of great significance. The cathode material is considered as an interesting target for repurposing. Despite some important reviews give commendable emphasis to recycling technologies, there is still a dearth of exploration of recycling mechanisms. This deficiency of awareness highlights the need for further research and development in this area. This review aims to systematically review and thoroughly discuss the reduction reaction mechanism of each method regarding different cathode materials. And systematically digest the selection of reducing agent and the effect of reduction reaction on material regeneration are systematically digested, as well as the impact of the reduction reaction on the regeneration of materials. This review emphasizes the importance of balancing efficiency, economic and environmental benefits in reuse technologies. Finally, the review proposes an outlook on the opportunities and challenges facing the reuse of key materials for next-generation spent batteries aimed at promoting the green and sustainable development of lithium-ion batteries, circular economy and ecological balance.

Multiple-functional LiTi2(PO4)3 modification improving long-term performances of Li-rich Mn-based cathode material for advanced lithium-ion batteries

Li-rich layered oxides with high energy densities have become one kind of promising cathode for advanced lithium-ion batteries, however some issues are severely hindering their practical applications. To address these challenges, fast ion conductive LiTi2(PO4)3 (LTPO) is employed to modify the typical Li-rich cathode Li1·2Mn0·56Ni0·17Co0·07O2 (LMNCO) via a sol-gel process combined with a two-step annealing treatment in this work. Serving as a physical separator, LTPO coating effectively depresses the side reactions at cathode-electrolyte interface and the transition-metal dissolution from LMNCO active material under harsh electrochemical environment. Meanwhile, LTPO layer with high ion conductivity could facilitate the interfacial Li+ diffusion during charge/discharge process. In addition, partial Ti4+ ions doped into LMNCO effectively elevate the oxygen electronegativity and restrain the excessive oxidization of lattice oxygen, thus stabilizing the crystal structure and alleviating the stress-strain propagation upon cycling. Electrochemical characterization results demonstrate that the LTPO-modified LMNCO cathode exhibits a superior capacity retention of 86.5 % after 400 cycles at room temperature and that of 73.7 % even under an elevated temperature of 45 °C after 250 cycles under 1C. This study provides a facile strategy for the surface modification of Li-rich layered-structure oxides, which also sheds light in enhancing electrochemical performances for various cathode materials.

New Insight into Bulk Structural Degradation of High-Voltage LiCoO2 at 4.55 V.

The aggravated mechanical and structural degradation of layered oxide cathode materials upon high-voltage charging invariably causes fast capacity fading, but the underlying degradation mechanisms remain elusive. Here we report a new type of mechanical degradation through the formation of a kink band in a Mg and Ti co-doped LiCoO2 cathode charged to 4.55 V (vs Li/Li+). The local stress accommodated by the kink band can impede crack propagation, improving the structural integrity in a highly delithiated state. Additionally, machine-learning-aided atomic-resolution imaging reveals that the formation of kink bands is often accompanied by the transformation from the O3 to O1 phase, which is energetically favorable as demonstrated by first-principles calculations. Our results provide new insights into the mechanical degradation mechanism of high-voltage LiCoO2 and the coupling between electrochemically triggered mechanical failures and structural transition, which may provide valuable guidance for enhancing the electrochemical performance of high-voltage layered oxide cathode materials for lithium-ion batteries.

Boosting the Electrochemical Performance of Primary and Secondary Lithium Batteries with Mn-Doped All-Fluoride Cathodes.

Transition metal fluorides are potentially high specific energy cathode materials of next-generation lithium batteries, and strategies to address their low conductivity typically involve a large amount of carbon coating, which reduces the specific energy of the electrode. In this study, MnyFe1-yF3@CFx was generated by the all-fluoride strategy, converting most of the carbon in MnyFe1-yF3@C into electrochemical active CFx through a controllable NF3 gas phase fluorination method, while still retaining a tightly bound graphite layer to provide initial conductivity, which greatly improved the energy density of the composite. This synergistic effect of nonfluorinated residual carbon (∼11%) and Mn doping ensures the electrochemical kinetics of the composite. The loading mass of the active substance had been increased to 86%. The theoretical and actual discharge capacity of MnyFe1-yF3@CFx composite was up to 765 mAh g-1 (pure FeF3 is 712 mAh g-1) and 728 mAh g-1, respectively. The discharge capacity at the high-voltage (3.0 V) platform was more than three times higher than that of the non-Mn-doped composite (FeF3@CFx).

Promoted production of aromatic hydrocarbons in biomass catalytic pyrolysis over the coupled catalysts of carbon-reduced waste lithium battery cathode materials and HZSM-5

Inexpensive catalyst sources are of great importance in the conversion of biomass to economically valuable monocyclic aromatic hydrocarbons, and transition metals (Co, Ni, Fe and Mn) rich in catalytic effects in massive waste lithium battery cathode materials are not effectively reutilized currently. For this reason, the feasibility of employing the valuable metal oxides in the carbon-reduced waste lithium battery cathode materials (waste LiFePO4 batteries, LFP, and waste LiNixCoyMn1–x–yO2 batteries, NCM) with HZSM-5 as coupled catalysts in the rape straw catalytic pyrolysis to produce aromatic hydrocarbons was explored. The carbon-reduced waste lithium battery cathode materials performed well at 5 wt% carbon loading, and the content of active components Fe2O3 (SLFPC-5) and NiO (SNCMC-5) used for the reduction of large molecular oxygenates in biomass pyrolysis gas was increased by water leaching treatment. SLFPC-5 demonstrated superior bond-cutting performance, while SNCMC-5 exhibited strong deoxygenation performance. The selectivity of monocyclic aromatic hydrocarbons (MAHs) catalyzed by SLFPC-5/HZSM-5 and SNCMC-5/HZSM-5 was as high as 63.69 % and 79.19 %, with BTX yields of 14.58 wt% and 16.68 wt% respectively. This coupled catalytic system offers a low-cost source of catalysts for biomass catalytic pyrolysis and broadens the possibility of high-value recycling of wasted lithium batteries.

Facile synthesis of LiFePO4/Cu composite as enhanced cathode material for lithium-ion battery by a solid-state grinding method

Lithium iron phosphate (LiFePO4, LFP) is a frequently utilized cathode material for lithium-ion batteries. However, its practical applications are constrained by its relatively low ionic and electronic conductivities. To address this issue, it is possible to utilize highly conductive metallic coatings to enhance the material's electronic conductivity. Herein, LiFePO4 with Cu composites (LFP/Cu) as cathode was synthesized by a simple solid-state process via one-step grinding in the presence of CuNO3 and ascorbic acid. The discharge capacity of the LFP/Cu cathode with 0.75 wt% Cu was found to be 160.9 mA h g−1 at 0.1 C, representing a close approximation of its theoretical capacity and a notable enhancement compared to pure LFP (145.9 mA h g−1). Furthermore, it demonstrates excellent stability with a capacity retention of 136.5 mA h g−1 after 100 cycles at 2 C, as well as good rate performance. The electrochemical impedance spectra demonstrate that the incorporation of copper results in a further reduction in the resistance of LFP/Cu compared to pure LFP. The incorporation of copper particles into lithium iron phosphate has been shown to enhance its electronic conductivity, thereby further enhancing its electrochemical performance. In this study, we present a facile and cost-effective room-temperature synthesis method for the preparation of LiFePO4/Cu composites with improved electrochemical properties. This work provides a promising avenue for the design of cathode materials in lithium-ion batteries.

Boosting interface compatibility of high-voltage LiNi0.5Mn1.5O4 cathode materials with an ionic-conductive Li0.33La0.56TiO3 coating

High voltage LiNi0.5Mn1.5O4 (LNMO) is a crucial cathode material for lithium-ion batteries (LIBs) aiming at high energy densities. However, its performance is hindered by the dissolution of transition metal ions and the instability of the cathode electrolyte interface (CEI) film at elevated voltages. To address these issues, we report a solvothermal method to prepare LNMO coated with Li+-conductor Li0.33La0.56TiO3 (LNMO@LLTO). Our study reveals that the LLTO coating not only enhances ion diffusion at the interface, minimizing the Li+ concentration gradient, and acts as a barrier against Mn-ion dissolution. This coating minimizes side reactions, mitigates structural degradation, and promotes the formation of a stable and balanced CEI film that incorporates LLTO, thus ensuring the long-term cycle stability. When compared to bulk LNMO, the LNMO@LLTO cathode demonstrates superior performance, maintaining reversible capacities of 111.4 and 102.2 mAh·g−1 after 500 cycles at 2 and 5C at 25 °C, respectively. Even at 60 °C, the LNMO@LLTO maintains a high capacity of 94.3 mAh·g−1 with minimal electrochemical polarization after 200 cycles at 2C. This simple preparation technique, together with its performance promotion, offers new insights into the development of high voltage cathode materials for high energy density LIBs.

Recent advances of cobalt-free and nickel-rich cathode materials for lithium-ion batteries

Recent advances of cobalt-free and nickel-rich cathode materials for lithium-ion batteries

Fast lithium-ion conductor LiTi2(PO4)3 coating modified LiNi0.8Co0.15Al0.05O2 as cathode material for lithium-ion batteries

Fast lithium-ion conductor LiTi2(PO4)3 coating modified LiNi0.8Co0.15Al0.05O2 as cathode material for lithium-ion batteries

The dual modification of La and Zr of Ni-rich cathodes for improved cycling stability at elevated voltage and temperature

Nickel-rich layered oxides are regarded as a promising cathode material for next-generation lithium-ion batteries (LIBs) with advanced power capabilities. However, their poor cycling performance, especially under high voltage and temperature conditions, has seriously limited their large-scale application. In this work, a simple and effective strategy is proposed to enhance the structural and interface stability of Ni-rich materials by La4NiLiO8 coating and Zr doping. The interfacial side reactions and intergranular microcracks of the modified material are inhibited, which is helpful in improving the electrochemical performance. Therefore, the initial capacity of dual modification of La and Zr of Ni-rich cathode is 196.4 mA h g−1 at 4.5 V and exhibits excellent cycling performance with a capacity retention of 82.1 % after 200 cycles. Moreover, at 50 °C, the initial capacity of the modified material is 239.0 mA h g−1, and the capacity retention is 63.1 % after 100 cycles, representing a significant improvement of 94.8 % over the unmodified sample.

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.