Lithium-ion Battery Cathode Research Articles

High‐Voltage Spinel Cathode Materials: Navigating the Structural Evolution for Lithium‐Ion Batteries

AbstractHigh‐voltage LiNi0.5Mn1.5O4 (LNMO) spinel oxides are highly promising cobalt‐free cathode materials to cater to the surging demand for lithium‐ion batteries (LIBs). However, commercial application of LNMOs is still challenging despite decades of research. To address the challenge, the understanding of their crystallography and structural evolutions during synthesis and electrochemical operation is critical. This review aims to illustrate and update the fundamentals of crystallography, phase transition mechanisms, and electrochemical behaviors of LNMOs. First, we outline the research history of LNMO and its development into a LIB cathode material. Then we review the structural basics of LNMOs including the classic and updated views of the crystal polymorphism, interconversion between the polymorphs, and structure‐composition relationship. Afterwards, the phase transition mechanisms of LNMOs that connect structural and electrochemical properties are comprehensively discussed from fundamental thermodynamics to operando dynamics at intra‐ and inter‐particle levels. In addition, phase evolutions during overlithiation as well as thermal‐/electrochemical‐driven phase transformations of LNMOs are also discussed. Finally, we offer recommendations for the further development of LNMOs as well as other complex materials to unlock their full potential for future sustainable and powerful batteries.This article is protected by copyright. All rights reserved

Revealing the origin of enhanced structural stability for nickel-rich LiNi0.83Co0.11Mn0.06O2 cathodes in situ modified with multifunctional polysiloxane

Multifunctional polysiloxane (MPS) layer is elaborately constructed on the surface of LiNi0.83Co0.11Mn0.06O2 (NCM83) particles via in situ hydrolysis-polycondensation of tetraethyl orthosilicate. Impressively, optimal NCM83 (NCM83-2) electrode covered with average 7 nm-thickness of fresh MPS layer delivers improved capacity retention ratio of 81.8 % after 150 cycles at 25 °C and retains the value of 78.7 % after 200 cycles at 60 °C and 1.0 C. Moreover, NCM83-2 electrode presents lower polarization degree with sluggish growth of the capacity platform. The significant advantages of NCM83-2 can be interpreted by the fact that the MPS layer effectively mitigates microcracks generation by inhibiting phase transition and lattice oxygen loss. Moreover, the MPS protective layer suppresses the thickening of cathode electrolyte interphase film and boosts the structural stability of NCM83 electrode to optimize electrochemical properties. Therefore, this strategy may provide promising enlightenments for preserving structural integrity and improving interfacial stability of nickel-rich cathodes for lithium-ion batteries.

Lithium-Ion Conductive Coatings for Nickel-Rich Cathodes for Lithium-Ion Batteries.

Nickel (Ni)-rich cathodes are among the most promising cathode materials of lithium batteries, ascribed to their high-power density, cost-effectiveness, and eco-friendliness, having extensive applications from portable electronics to electric vehicles and national grids. They can boost the wide implementation of renewable energies and thereby contribute to carbon neutrality and achieving sustainable prosperity in the modern society. Nevertheless, these cathodes suffer from significant technical challenges, leading to poor cycling performance and safety risks. The underlying mechanisms are residual lithium compounds, uncontrolled lithium/nickel cation mixing, severe interface reactions, irreversible phase transition, anisotropic internal stress, and microcracking. Notably, they have become more serious with increasing Ni content and have been impeding the widespread commercial applications of Ni-rich cathodes. Various strategies have been developed to tackle these issues, such as elemental doping, adding electrolyte additives, and surface coating. Surface coating has been a facile and effective route and has been investigated widely among them. Of numerous surface coating materials, have recently emerged as highly attractive options due to their high lithium-ion conductivity. In this review, a thorough and comprehensive review of lithium-ion conductive coatings (LCCs) are made, aimed at probing their underlying mechanisms for improved cell performance and stimulating new research efforts.

Deep eutectic solvent with acidity, reducibility, and coordination capability for recycling of valuable metals from spent lithium-ion battery cathodes

The substantial increase in spent lithium-ion batteries (SLIB) has resulted in serious environmental impacts that require attention and appropriate intervention. In this study, we designed a DES composed of ethylene glycol (EG) and hydroxylamine hydrochloride (NH2OH·HCl) with appropriate acidity, remarkable reductive property and strong coordination capability for the efficient one-step leaching of cobalt ions and lithium ions from LiCoO2 (LCO). Following leaching at a modest temperature of 80 °C for 8 h, the solubility of LiCoO2 reaches an 83.3 mg g−1 (much higher than previous works), accompanied by remarkably high leaching efficiencies of up to 99.7 % for lithium and 88.0 % for recovery of cobalt. Notably, this approach significantly enhances the solubility of the LiCoO2 while upholding leaching efficiency. Importantly, this study achieves a one-step separation of lithium and cobalt, avoiding metal co-precipitation and simplifying the separation procedure. Furthermore, the residual components within the system can be reclaimed and recycled. This work provides an efficient and sustainable route for the recovery of precious metals from lithium-ion batteries, characterized by its cost-effectiveness and straightforward processing.

Boron- and calcium-interspersed cathode-electrolyte interphases on Ni-rich layered oxide cathodes for advanced performance lithium-ion batteries

Although Ni-rich layered oxides (Ni-rich NCM) have become the preferred cathode materials in the electric vehicle market, their unsustainable cycling behavior arising from the extremely high reactivity at the interface has become a formidable challenge. To alleviate this problem, we propose modifying the cathode-electrolyte interphase (CEI) of Ni-rich L-NCM cathodes by incorporating B/Ca functional groups. Dual-functionalized CEI layers are prepared by heating boric acid (H3BO3) and calcium oxide (CaO) in a one-step process. Islands of B- and Ca-functionalized CEI layer are observed at the Ni-rich L-NCM cathode, and the thickness is controlled to approximately 2.4 nm. The B-functional group not only lowers the concentration of residual lithium but also compensates for the longer Li+ migration distance by providing a desirable pathway based on ion-hopping sites. The Ca functional groups increase the mechanical rigidity of the Ni-rich L-NCM cathode, which inhibits the appearance of microcracks. In terms of its cycling behavior, the capacity retention of the cell with the B/Ca-incorporated Ni-rich L-NCM cathode improves markedly (72.4%), whereas the bare Ni-rich L-NCM material only retains 44.3% of its capacity after 100 cycles.

Enhanced cycling stability in 4.6 V LiCoO2 for high energy density lithium-ion batteries through Al and Y co-doping

For the first time, this work investigates the synergetic impact of yttrium (Y) and aluminium (Al) co-doping on the electrochemical properties of 4.6 V LiCoO2 (LCO) cathode for high energy density lithium-ion batteries. The optimized LCO demonstrates an impressive initial discharge capacity of 208.6 mAh g−1 in the voltage range of 3-4.6 V, along with superior structural stability, retaining over 86% of its initial capacity even after 125 cycles at the current of 100 mA g−1 that is far higher than the capacity retention of 40% for the pristine LCO under the same condition. Thanks to the synergistic effect, Al in Co layers enhances the bonds of Al/Co-O to stabilize oxygen in the LCO crystal structure while Y serves “pillar” in Li layers, migrated from the initial Co layers during cycling process, effectively curtail the formation and expansion of interlayer cracking, which contributes to the long-term cycle stability of LCO under high voltage. Most importantly, Al/Y co-doping is a facile process compatible with the existing industrial infrastructure for LCO mass production, and thus it can be scaled up readily for commercial applications. Al/Y co-doped LCO is assembled into commercial-level pouch cells with graphite anode, achieves an extremely high energy density of 750 Wh/L, and exhibits a superior cycling stability and obtains a capacity retention of 88.2% at 25 °C after 800 cycles with the high cutoff voltage of 4.55 V.

Stochastic reconstruction and performance prediction of cathode microstructures based on deep learning

The effective properties of lithium-ion battery (LIB) cathode are determined by both the volume fractions of constituents and the morphological features of microstructure. However, it is difficult to establish an accurate quantitative relationship between the macroscopic effective properties and microstructural features. Deep learning techniques, due to their exceptional nonlinear fitting capabilities, have been widely applied in various complex fields. Our study presents a generation scheme of numerous three-dimensional (3D) digital microstructures of cathode, using a deep convolutional neural network (CNN)-based stochastic reconstruction algorithm combining with the scanning electron microscope (SEM) images. The reconstructed samples are substituted with the corresponding finite element (FE) models, and the effective mechanical and electrochemical properties are assessed through the FE-based homogenization theory. Finally, the generated cathode samples and their effective properties are used to train the 3D CNN for performance prediction. This study demonstrates that the deep learning approaches can accurately and rapidly reconstruct the microstructure of cathode and predict their effective properties. Furthermore, the established framework can be extended to other heterogeneous materials.

Mixed crystal FeFx submicron spheres loaded on fluorinated graphene as cathode materials for Lithium-Ion batteries

Iron fluoride (FeF3 and FeF2) is a potential candidate for the next generation of lithium-ion battery (LIBs) cathode materials due to their high theoretical specific capacity and low cost. However, previous studies have reported that the poor conductivity of FeF3 and FeF2 prevents their theoretical specific capacity from being effectively realized. Herein, fluorinated graphene loaded FeFx (FeFx@FG) submicron sphere was synthesized using graphene oxide and utilized as cathode materials for LIBs. Characterization by X-ray diffraction and transmission electron microscopy confirmed that the synthesized FeFx (x = 2 and 3) contains mixed FeF3 and FeF2crystals. The mixed crystal structure enables the FeFx@FG submicron sphere composite to display two steps in the electrochemical reaction when FeF3 and FeF2 discharge cooperatively, leading to excellent discharge performance. In addition, since the FG prepared by acid thermal method has good conductivity, it can significantly improve the FeFx conductivity and specific capacity when being connected to FG via C-F bond. The electrochemical tests show that the initial discharge capacity of FeFx@FG is as high as 394.24 mAh/g at the rate of 0.2C in the range of 1.5–4.0 V at 25 °C and display an excellent discharge capacity retention rate after the first discharge process, showing great potential of the mixed crystalline iron fluoride cathode in the field of lithium-ion batteries.

Unveiling the vacancy-mediated charge kinetics and capacity fading mechanism in Mn-based cathode for lithium-ion battery

In the recent past, Li2MnSiO4 (LMS) has been considered a promising cathode material for high energy density lithium-ion batteries (LIBs). Extraction of the maximum amount of Li from the host LMS and reversibility of Li insertion and extraction is still challenging, probably because of poor conductivity and, thereby, poor Li-kinetics. To improve the Li-diffusion and ionic conductivity, oxygen vacancies (OVs) in pristine LMS (LMS180) have been created, and then their impact on the Li-reactivity of LMS is studied. The quantity of OVs is determined by X-ray photoelectron spectroscopy (XPS) and calculated to be 6.8% in LMS180 heated at 300 ºC in Ar (LMSA300) and ∼ 8.2% in LMS180 heated at 500° C in Ar (LMSA500), subsequently it is supported and validate by the electron paramagnetic response (EPR) and high-resolution transmission electron microscopy (HR-TEM). The best sample, i.e., LMSA500, exhibits a total conductivity of 8.06×10−6 S/cm, resulting in an initial charge capacity of 292 (±5) mAh/g at 10 mA/g. The OVs are found to facilitate the facile lithium-ion movement by providing the lowest migration energy. Furthermore, knowing the impacts of OVs presence in LMS and their effect on Li-diffusion enables us to address traditional capacity fading processes in LMS.

Hydrogen Reduction Behavior of NCM-based Lithium-ion Battery Cathode Materials

As the demand for lithium-ion batteries for electric vehicles is increasing, it is important to recover valuable metals from waste lithium-ion batteries. In this study, the effects of gas flow rate and hydrogen partial pressure on hydrogen reduction of NCM-based lithium-ion battery cathode materials were investigated. As the gas flow rate and hydrogen partial pressure increased, the weight loss rate increased significantly from the beginning of the reaction due to the reduction of NiO and CoO by hydrogen. At 700 °C and hydrogen partial pressure above 0.5 atm, Ni and Li2O were produced by hydrogen reduction. From the reduction product and Li recovery rate, the hydrogen reduction of NCM-based cathode materials was significantly affected by hydrogen partial pressure. The Li compounds recovered from the solution after water leaching of the reduction products were LiOH, LiOH·H2O, and Li2CO3, with about 0.02 wt% Al as an impurity.

Comparison Study of a Thermal-Driven Microstructure in a High-Ni Cathode for Lithium-Ion Batteries: Critical Calcination Temperature for Polycrystalline and Single-Crystalline Design.

High-Ni layered oxide cathodes are promising candidates for lithium-ion batteries due to their high energy density. However, their cycle stability is compromised by the poor mechanical durability of the particle microstructure. In this study, we investigate the impact of the calcination temperature on microstructural changes, including primary particle growth and pore evolution, using LiNi0.88Mn0.08Co0.04O2 (N884), with an emphasis on the critical calcination temperature for polycrystalline and single-crystal designs in high-Ni cathodes. As the calcination temperature increases, the primary particles undergo a rectangular growth pattern while the pore population decreases. Beyond a certain critical temperature (in this case, 850 °C), a sudden increase in primary particle size and a simultaneous rapid reduction in the pore population are observed. This sudden microstructure evolution leads to poor cycle retention in N884. In contrast, single-crystal particles, free of grain boundaries, synthesized at this critical temperature exhibit superior cycle retention, underscoring the significance of microstructural design over crystalline quality for achieving long-term cyclability. Our study sheds light on the interplay between calcination temperature and microstructural evolution, proposing the critical temperature as a key criterion for single-crystal synthesis.

Characteristics of graphite obtained by recycling lithium - iron phosphate batteries

Based on both the economic and environmental points of view, processing used lithium-ion batteries (LIBs) is of great importance. The valuable components contained in LIB (cathode, anode and current collectors) generate high interest in solving the problem of resource deficiency and reducing environmental destruction due to overexploitation. The starting anode material extracted from a used lithium iron phosphate battery is a mixture of graphite, acetylene carbon black, and polymer binder. Reusing this material in lithium batteries without additional cleaning is impractical owing to poor electrochemical characteristics and the presence of impurities. To achieve effective regeneration, the recycled anode material is first treated in a nitric acid solution to remove copper foil and lithium ions with electrolyte interaction products formed during battery operation. The next step is heat treatment of the material, which allows the removal of acetylene soot and polymer glue binder. The tests showed sufficiently high values of the specific capacity of recycled graphite (~330 mA h g-1 at 0.1 C), which are comparable to commercial materials and meet the requirements of reuse.

Novel synthesis of FeF3·0.33H2O@hollow acetylene black nanosphere and its long-life electrochemical properties as a cathode for lithium-ion batteries

Iron (III) fluoride (FeF3), characterized by high voltage and high specific capacity and emerges as a promising candidate for the forthcoming generation of cathode materials in lithium-ion batteries. This study employs a novel methodology by introducing Fe3+ sources into hollow acetylene black particles through a vacuum impregnation method. This innovative approach results in the synthesis of a composite material comprising FeF3∙0.33H2O encapsulated within hollow acetylene black nanospheres, denoted as the FeF3∙0.33H2O @hollow acetylene black nanosphere composite material (FF@HCN). The composite exhibits a shell composed of highly graphitized carbon and a core containing FeF3∙0.33H2O particles in the range of 10–20 nm. The proportion of active materials is 75.56 %. The acetylene black has chain-like structure and high specific surface area, significantly enhances the material's conductivity, contributing 74.4 % to the pseudocapacitance at a scan rate of 1 mV s−1. The cavity graphite shell plays a crucial role in restricting the expansion and pulverization decay of FeF3∙0.33H2O nanoparticles, thereby markedly improving the cycle stability. The initial capacity of the FF@HCN composite is 224.4 mAh g−1, and after 1000 cycles at 0.1 C, it maintains a capacity of 162.3 mAh g−1, resulting in a capacity retention rate of 72.3 % and decay per cycle of 0.027 %.

Rest in phase transition: Should charging habits in next generation EVs be adapted?

Nickel-rich cathode materials are a popular cathode for high energy lithium ion batteries in the current and next generation of electric vehicles. While nickel-rich cathodes offer high energy density, their cycle-life is compromised due to several factors directly related to their (de)lithiation behavior. At high state of charge the nickel-rich cathode experiences a hexagonal-hexagonal transition which is accompanied by drastic changes in the unit cell parameters. This phenomenon is detrimental for cycle-life of a battery cell. This work elucidates on the effect of storing LiNi0.8Mn0.1Co0.1O2‖Graphite cells at 95 % state of charge corresponding to the above-mentioned transition for 10 h every six cycles. The results are compared to cells cycled without a rest at high state of charge and cells cycled to 100 % state of charge. Analysis of the obtained cycling data shows that resting lithium ion cells based nickel-rich cathode based cells is detrimental leading to higher impedance growth and capacity decay than cycling to 100 % state of charge.

Dual-type confinement strategy: Improving the stability of organic composite cathodes for Lithium-ion batteries with longer lifespan

Inclusive reports on organic cathodes are the key evidence of their superior performance for Lithium-ion batteries. However, it is still promising to simultaneously achieve a higher practical specific capacity and longer cycling life, owing to the crucial concern of the dissolution of active molecules in organic electrolytes. The introduction of porous carbon confinement and coating which can impart discharge capacity and cycling stability, is highly beneficial. Herein, we designed and prepared a novel composite cathode (designated as HKUST-1-C@DHAQ@TiO2) with small molecules (DHAQ) in porous carbon skeleton (HKUST-1-C) as core and TiO2 as shell. The unique dual-type confinement strategy offers short Li+/e- diffusion directions for redox reactions and superior structural stability during cycling without dissolution or decomposition of the components, resulting in excellent electrochemical performance. The HKUST-1-C@DHAQ@TiO2 cathode delivers significant specific capacity (209 mAh g−1, 0.1 A g−1), markable Coulombic efficiency (nearly 100 %), notable cycling stability (86 % retention for provided 200 cycles) and excellent rate capacity (138 mAh g−1 at 1.0 A g−1). The presented findings offer the deep understanding of redox reactions and organic cathode evolution mechanisms for the progress of smarter energy storage batteries.

Zr0.1Fe0.9V1.1Mo0.9O7 as Cathode for Lithium-Ion Battery

Abstract With the development of lithium-ion batteries, high capacity and high cycle stability have been the two main goals being pursued. Recent studies have shown that ZrV2O7 does not perform well in energy storage due to its low electrical conductivity and poor cycling stability. Elemental doping has proven to be an effective strategy for improving electrochemical performance. In this paper, we prepared Zr0.1Fe0.9V1.1Mo0.9O7(ZFVMO) and Zr0.1Fe0.9V1.1Mo0.9O7@c (ZFVMO@c) materials using a simple solid-phase sintering method and a fast microwave sintering method. Double ionic heterovalent substitution of Zr4+/V5+ in ZrV2O7 using Fe3+/Mo6+, Fe3+/Mo6+ gives it near-zero thermal expansion characteristics and excellent conductive properties. In electrochemical tests, the first discharge capacities of ZFVMO and ZFVMO@C are 2261 mA h g−1 and 727 mA h g−1, respectively, and the batteries were finally stabilized for 475 and 500 cycles. Compared to ZrV2O7, the electrochemical properties of ZFVMO are greatly improved.

Toward Cost-Effective High-Energy Lithium-Ion Battery Cathodes: Covalent Bond Formation Empowers Solid-State Oxygen Redox in Antifluorite-Type Lithium-Rich Iron Oxide

Toward Cost-Effective High-Energy Lithium-Ion Battery Cathodes: Covalent Bond Formation Empowers Solid-State Oxygen Redox in Antifluorite-Type Lithium-Rich Iron Oxide

Direct synthesis of a lithium carboxymethyl cellulose binder using wood dissolving pulp for high-performance LiFePO4 cathodes in lithium-ion batteries

Lithium carboxymethyl cellulose (CMC-Li) is a promising novel water-based binder for lithium-ion batteries. The direct synthesis of CMC-Li was innovatively developed using abundant wood dissolving pulp materials from hardwood (HW) and softwood (SW). The resulting CMC-Li-HW and CMC-Li-SW binders possessed a suitable degree of substitutions and excellent molecular weight distributions with an appropriate quantity of long- and short-chain celluloses, which facilitated the construction of a reinforced concrete-like bonding system. When used as cathode binders in LiFePO4 batteries, they uniformly coated and dispersed the electrode materials, formed a compact and stable conductive network with high mechanical strength and showed sufficient lithium replenishment. The prepared LiFePO4 batteries exhibited good mechanical stability, low charge transfer impedance, high initial discharge capacity (∼180 mAh/g), high initial Coulombic efficiency (99 %), excellent cycling performance (<3% loss over 200 cycles) and good rate capability, thereby outperforming CMC-Na and the widely used cathode binder polyvinylidene fluoride.

Glutamate Leaching of Spent Lithium-Ion Battery Cathode in Weak Acidic-Neutral Condition: New Insight on Kinetics and Dissolution Mechanism

ABSTRACT Organic acid leaching receives less attention than inorganic acids for Li-ion battery recycling process at the industrial scale due to the high consumption rate of the acids as leaching reagents. This paper reports an effective leaching of cobalt (Co) and lithium (Li) from spent battery cathode using low concentration of monosodium glutamate as lixiviants. More than 95% of Co and Li could be dissolved at leaching conditions MSG 0.1 M (18 g/L), pH 5, sodium sulfite 0.5 M as reductant, pulp density 20 g/L, room temperature and leaching time 6 h. Increasing the temperature to 80°C sped up the leaching process, where maximum recovery could be attained within 1 h. pH played a major role in the leaching efficiency (effective range pH 4–6). pH lower than 4 led to neutral and cationic glutamate species, which were ineffective in attracting cobalt ion. pH higher than 6 initiated the surface passivation by Co(OH)2. In the absence of a passivation layer, cobalt dissolution mechanism followed the chemical reaction-controlled model, while in the presence of the layer, the mechanism switched to diffusion through product layer. Kinetic studies demonstrated that aside from pH, the formation of passivation layer was hypothetically regulated by adjusting the other leaching parameters. Aside from the observation on kinetic study, the proposed leaching mechanism was supported by characterization (particle size analysis, SEM-EDS, FT-IR) results.

Effective upcycling of NMC 111 to NMC 622 cathodes by hydrothermal relithiation and Ni-enriching annealing

It is imperative that a sustainable approach to the recycling of lithium-ion batteries (LIBs)—in particular the spent NMC cathodes—which reach their end-of-life (EOL) is realized as 11 million metric tonnes are expected to reach EOL by 2030. The current recycling processes based on pyrometallurgy and hydrometallurgy are not fully sustainable options as they recover only the value metals. By contrast direct recycling that aims in regenerating EOL LIB cathodes without breaking down the active compound’s crystal structure offers the most sustainable option. In this paper the direct recycling of NMC cathodes is investigated in combination with their upcycling. Upcycling is going to be in growing demand since the first generation NMC 111 cathode chemistries evolve to higher energy/nickel-rich formulations. In this work, the baseline is established for direct recycling of low and high nickel NMC cathodes by analyzing the three key steps of chemical delithiation of pristine NMC cathode material, hydrothermal relithiation (4M LiOH for 4 h at 220 °C), and annealing (4 h at 850 °C) in order to set the ground for investigating the upcycling of NMC 111 to NMC 622. Upcycling is affected via the co-addition of pre-calculated excess NiSO4 and Li2CO3 salts during annealing, following the hydrothermal relithiation step. Use of NiSO4 that is commonly used as p-CAM provides a lower cost alternative to Ni(OH)2 as Ni source. Characterization revealed the upcycled material to have been endowed with the typical α-NaFeO2 layered structure and have surface morphology and composition similar to pristine NMC material. The upcycled NMC 622 cathode yielded good cycling stability (91.5% retention after 100 cycles) and >99% Coulombic efficiency albeit with certain polarization loss justifying further optimization studies.