Cathode Materials For Li-ion Batteries Research Articles

Regulating electronic structure of anionic oxygen by Ti4+ doping to stabilize layered Li-rich oxide cathodes for Li-ion batteries

Abstract Layered Li-rich oxide cathodes enable to activate lattice oxygen anions redox in the charge compensation process and provide superior high specific capacity over 250 mAh/g due to their unique configuration, and thus attracting great attentions as promising cathode candidates for Li-ion batteries. However, how to better stabilize the bulk lattice oxygen framework and surface structure, and slow down the release of oxygen, is still major bottleneck to develop high performance Li-rich materials. Transition metal ions with outer d0 electronic configuration have distortable configuration, which can accommodate the local structure and chemical environment of the material, and then improve structural stability. Herein this work, the d0 transition metal Ti4+ is used as doping element to improve the chemical and structural stability, capacity retention and lithium ion diffusion kinetics of Li-rich material. The role of Ti in the material modification is revealed through synchrotron-based soft X-ray absorption spectroscopy, XRD, XPS and electrochemical tests. The improvement in structural stability can be attributed to that Ti doping can adjust the hybridization of O2p and TM3d to regulate the local electronic structure of both bulk lattice oxygen and surface oxygen vacancies. It is hoped that this work should shed light on the development of high-performance cathode materials for Li-ion Batteries.

Isovalent Co-Substitution of Iron and Titanium into Single-Crystal NMC622

Abstract Substitutional Li[Ni0.6Mn0.2Co0.2]O2 oxides (known as NMC622) were made by all-dry synthesis with Fe and Ti substituting Co and Mn, respectively. The substitutions were performed in three series, Fe substitution for Co, Ti substitution for Mn, and Fe and Ti co-substitution for Co and Mn, according to the formula Li(Ni0.6Mn0.2-yCo0.2-xFexTiy)O2. The resulting oxides were evaluated as cathode materials for Li-ion batteries. Fe-substitution for Co resulted in increased intersite mixing, resulting in increased polarization and capacity fade. Ti-substitution for Mn also resulted in increased intersite mixing, but the mixing was due to Ti3+ in the Li-layer. As a result, Ti-substituted NMCs had improved capacity retention and reduced polarization. These effects were independent of each other, so that Ti could partially offset the negative aspects of Fe-substitution. Additionally, layered Mn-free Li(Ni0.6Ti0.2Co0.2)O2 (NTC622) was produced as an endmember of this series for the first time with low intersite mixing and superior electrochemical performance in comparison to previous reports. These results demonstrate benefits of all-dry Ti-substitution in NMC and the all-dry synthesis method as an avenue towards new cathode composition discovery.

Substituting Na for Excess Li in Li1+x(Ni0.6Mn0.4)1-xO2 Materials

Abstract NMC640, a series of Li1+x(Ni0.6Mn0.4)1-xO2 materials, are important Co-free mid-Ni cathode materials for Li-ion batteries, offering high energy density and better cost-efficiency than Ni-rich counterparts. These materials require excess Li compared to stoichiometric composition to improve the electrochemical performance in terms of rate capability and cycling stability. Although lithium-to-transition metal ratios up to 1.15 can be used to optimize the performance, less than 80% of this lithium is electrochemically active during cycling up to a 4.4 V upper cut off. This study explores whether some percentage of the inactive Li can be replaced by sodium to make these materials more cost-effective and bring potential improvements in electrochemical performance. Various amounts of excess Li were substituted by sodium in the structure. The results show that sodium can be integrated into the layered oxide structure without forming any impurity phases and effectively decreases the cation mixing observed in these layered structures. However, this does compromise cycling stability and rate capability. Na tends to occupy Li sites rather than transition metal sites, resulting in electrochemical instability and capacity loss. Even though excess Li is not electrochemically active, it cannot be effectively replaced by sodium without compromising battery performance of Li1+x(Ni0.6Mn0.4)1-xO2 materials.

Imaging inter - and intra-particle features in crystalline cathode materials for Li-ion batteries using nano-focused beam techniques at 4th generation synchrotron sources

Imaging inter - and intra-particle features in crystalline cathode materials for Li-ion batteries using nano-focused beam techniques at 4th generation synchrotron sources

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 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.

Design of Linear-Polymer-Coated Graphene Nanosheets with π-Conjugated Structure and Multi-Active-Center for Long-Lifespan and High-Rate Li-Storage Performance.

Organic material holds immense potential for Li-ion batteries (LIBs) due to their eco-friendly nature, high structural designability, abundant sources, and high theoretical capacity. However, the limited redox-active sites, low electronic conductivity, sluggish ionic diffusion, and high solubility hinder their practical application. Here, we reported the use of a linear polymer called poly(naphthalenetetracarboxylic dianhydride-pyrene-4,5,9,10-tetraone)-coated graphene nanosheets (NPT/rGO) as a cathode material for LIBs. The NPT polymer has a rotation angle of approximately 63° between each plane, which helps in exposing the active sites and preventing structural pulverization during cycling. The highly conjugated skeleton of the polymer, along with graphene, forms a synergistic effect through a π-π interaction. This combination enhances the conductivity and restricts solubility. Additionally, the linear structure of NPT and the two-dimensional rGO substrates work together to enhance charge transfer and ion diffusion rates, resulting in faster reaction kinetics. Consequently, NPT/rGO exhibits excellent electrochemical performance in terms of high capacity, superior cyclic stability, and good rate capability for LIBs. Moreover, through the combination of experimental investigations and theoretical simulations, a multiple electron reaction mechanism, an efficient Li-ion storage behavior, and a reversible dynamic evolution have been revealed. This study introduces a rational molecular design approach to enhance the electrochemical performance of polyimide derivatives, thereby contributing to the advancement of cutting-edge organic electrode materials for LIBs.

A novel morphology of high voltage LiMn1.5Ni0.5O4 cathode material with niobium-doping

Spinel LiMn1.5Ni0.5O4 (LMNO) is one of the promising cathode materials for the next generation Li-ion batteries due to its voltage platform. However, the dissolution of the transition metal at high voltage is the biggest obstacle that LMNO suffers from. In this study, we successfully suppressed transition metal dissolution in LMNO by the morphology control from regular octahedron to spherical. Niobium was integrated as a dopant, which restricted the growth of (111) crystal face, and increased the indices of crystal faces by homogenizing the surface energy. By changing to a smaller surface area with spherical morphology, the contact area with the electrolyte was reduced, thus suppressing the dissolution of the Mn ion. Consequently, the niobium-doped LMNOexhibited superior rate performance, capacity retention with 74.1% at 1C after 500 cycles in half-cell, and thermal stability compared to pristine LMNO.

Hydrothermal synthesis of αILiVOPO4 as a cathode material for Li-ion batteries

This paper presents the synthesis of a novel cathode material, αI-LiVOPO4, featuring a porous multilayered lamellar structure, achieved through the hydrothermal method. Initially, αI-LiVOPO4·2 H2O was synthesized by maintaining a reaction kettle at 160 °C for 40 h. Subsequently, the parent compound underwent dehydration at various temperatures for 2 h to yield αI-LiVOPO4. The dehydration process was investigated through thermogravimetric analysis. Analysis via powder X-ray diffraction confirmed the crystallization of the product into the αI-LiVOPO4 phase. TEM and EDS analyses revealed an irregular porous structure with uniform distribution of elements. The electrochemical performance of αI-LiVOPO4 was evaluated through constant current charge-discharge tests within a voltage range of 3–4.5 V. Results demonstrated an initial capacity of 106.9 mAh·g–1 at 0.05 C, with a capacity retention of 100.9 mAh·g–1 after the 50th cycle. Additionally, cyclic voltammetry indicated favorable cycling performance and minimal polarization at elevated voltages.

Improved ACOM pattern matching in 4D-STEM through adaptive sub-pixel peak detection and image reconstruction

The technique known as 4D-STEM has recently emerged as a powerful tool for the local characterization of crystalline structures in materials, such as cathode materials for Li-ion batteries or perovskite materials for photovoltaics. However, the use of new detectors optimized for electron diffraction patterns and other advanced techniques requires constant adaptation of methodologies to address the challenges associated with crystalline materials. In this study, we present a novel image-processing method to improve pattern matching in the determination of crystalline orientations and phases. Our approach uses sub-pixel adaptive image processing to register and reconstruct electron diffraction signals in large 4D-STEM datasets. By using adaptive prominence and linear filters, we can improve the quality of the diffraction pattern registration. The resulting data compression rate of 103 is well-suited for the era of big data and provides a significant enhancement in the performance of the entire ACOM data processing method. Our approach is evaluated using dedicated metrics, which demonstrate a high improvement in phase recognition. Several features are extracted from the registered data to map properties such as the spot count, and various virtual dark fields, which are used to enhance the handling of the results maps. Our results demonstrate that this data preparation method not only enhances the quality of the resulting image but also boosts the confidence level in the analysis of the outcomes related to determining crystal orientation and phase. Additionally, it mitigates the impact of user bias that may occur during the application of the method through the manipulation of parameters.

Reducing Voltage Hysteresis in Li-Rich Sulfide Cathodes by Incorporation of Mn.

Conventional intercalation-based cathode materials in Li-ion batteries are based on charge compensation of the redox-active cation and can only intercalate one mole of electron per formula unit. Anion redox, which employs the anion sublattice to compensate charge, is a promising way to achieve multielectron cathode materials. Most anion redox materials still face the problems of slow kinetics and large voltage hysteresis. One potential solution to reduce voltage hysteresis is to increase the covalency of the metal-ligand bonds. By substituting Mn into the electrochemically inert Li1.33Ti0.67S2 (Li2TiS3), anion redox can be activated in the Li1.33-2y/3Ti0.67-y/3Mn y S2 (y = 0-0.5) series. Not only do we observe substantial anion redox, but the voltage hysteresis is significantly reduced, and the rate capability is dramatically enhanced. The y = 0.3 phase exhibits excellent rate and cycling performance, maintaining 90% of the C/10 capacity at 1C, which indicates fast kinetics for anion redox. X-ray absorption spectroscopy (XAS) shows that both the cation and anion redox processes contribute to the charge compensation. We attribute the drop in hysteresis and increase in rate performance to the increased covalency between the metal and the anion. Electrochemical signatures suggest the anion redox mechanism resembles holes on the anion, but the S K-edge XAS data confirm persulfide formation. The mechanism of anion redox shows that forming persulfides can be a low hysteresis, high rate capability mechanism enabled by the appropriate metal-ligand covalency. This work provides insights into how to design cathode materials with anion redox to achieve fast kinetics and low voltage hysteresis.

Revisit of Polyaniline as a High-Capacity Organic Cathode Material for Li-Ion Batteries.

Polyaniline (PANI) has long been explored as a promising organic cathode for Li-ion batteries. However, its poor electrochemical utilization and cycling instability cast doubt on its potential for practical applications. In this work, we revisit the electrochemical performance of PANI in nonaqueous electrolytes, and reveal an unprecedented reversible capacity of 197.2 mAh g-1 (244.8 F g-1) when cycled in a wide potential range of 1.5 to 4.4 V vs. Li+/Li. This ultra-high capacity derives from 70% -NH- transformed to =NH+- during deep charging/discharging process. This material also demonstrates a high average coulombic efficiency of 98%, an excellent rate performance with 73.5 mAh g-1 at 1800 mA g-1, and retains 76% of initial value after 100 cycles, which are among the best reported values for PANI electrodes in battery applications.

Exploring the Molecular-Scale Structures at Solid/Liquid Interfaces of Li-Ion Battery Materials: A Force Spectroscopy Analysis with Sparse Modeling.

In this study, we clarify the liquid structure formed at the interface between LiCoO2 (LCO), the cathode material of Li-ion batteries, and propylene carbonate (PC), which is used as a solvent in the electrolyte, on a molecular scale. We apply sparse modeling-based modal analysis to force spectroscopy data measured by frequency modulation atomic force microscopy (FM-AFM) and show that each component in the FM-AFM force curve, such as oscillatory solvation force, background, and noise, can be automatically decomposed. Moreover, by combining detailed force curve analysis with solid/liquid interface simulations based on first-principles calculation, we have identified that there are distinct damped vibrational modes in the force curves at the LCO/PC interface with a period of about 0.57 nm and those with shorter periods, which likely correspond to the solvation forces associated with bulk-state PC molecules and those with PC molecules in "lying down" orientations.

Valence study of Li(Ni0.5Mn0.5)1−xCoxO2 and LiNi1−xCoxO2 : The role of charge transfer and charge disproportionation

The series of LiMO2 (M: transition metal) materials are highly relevant as cathode materials of Li-ion batteries. The stability of such systems remains an important factor for their usability in batteries, and depends strongly on the electronic configuration of the transition-metal ions. In particular, the promising class of multi-transition-metal systems exhibits complicated valence states due to intermetallic charge transfer and charge disproportionation. Here we perform a systematic study on the valence of the transition-metal ions using x-ray absorption spectroscopy on the M−L2,3 edges and O-K edges. In Li(Ni0.5Mn0.5)1−xCoxO2 we established that the valence is Co3+ and Ni0.52+Mn0.54+ throughout the whole series. Meanwhile, in LiNi1−xCoxO2 we found that the Ni displays a behavior consistent with a charge disproportionated negative charge transfer system, and that with increased concentration of Co3+, the disproportionation signal decreases. Since the number of O 2p holes also gets reduced, we infer that the material will also become more unstable. Published by the American Physical Society 2024

Homogenous coating of Li+ conductive Li5AlO4 on single-crystalline nonstoichiometric Li1.04Ni0.92Al0.04O2 for rechargeable lithium-ion batteries

Cobalt-free, nickel-rich LiNi1-xAlxO2 (x ≤ 0.1) is an attractive cathode material because of high energy density and low cost but suffers from severe structural degradation and poor rate performance. In this study, we propose a molten salt-assisted synthesis in combination with a Li-refeeding induced aluminum segregation strategy to prepare Li5AlO4-coated single-crystalline slightly Li-rich Li1.04Ni0.92Al0.04O2. The symbiotic formation of Li5AlO4 from reaction between molten lithium hydroxide and doped aluminum in the bulk ensures a high lattice matching between the Ni-rich oxide and the homogenous conductive Li5AlO4 that permits high Li+ conductivity. Benefiting from mitigated undesirable side reactions and phase evolution, the Li5AlO4-coated single-crystalline Li1.04Ni0.92Al0.04O2 delivers a high specific capacity of 220.2 mA h g−1 at 0.1 C and considerable rate capability (182.5 mA h g−1 at 10 C). Besides, superior capacity retention of 90.8% is obtained at 1/3 C after 100 cycles in a 498.1 mA h pouch full cell. Furthermore, the particulate morphology of Li1.04Ni0.92Al0.04O2 remains intact after cycling at a cutoff voltage of 4.3 V, whereas slightly Li-deficient Li0.98Ni0.97Al0.05O2 features intragranular cracks and irreversible lattice distortion. The results highlight the value of molten salt-assisted synthesis and Li-refeeding induced elemental segregation strategy to upgrade Ni-based layered oxide cathode materials for advanced Li-ion batteries.

Determining effects of doping lithium nickel oxide with tungsten using Compton scattering

X-ray Compton scattering experiments along with parallel first-principles computations were carried out on LiNiO2 to understand the effects of W doping on this cathode material for Li-ion batteries. By employing high-energy x rays exceeding 100 keV, an insight is gained into the fate of the W valence electrons, which are adduced to undergo transfer to empty O 2p energy bands within the active oxide matrix of the cathode. The substitution of W for Ni is shown to increase the electronic conductivity and to enhance the total magnetization per Ni atom. Our study demonstrates that an analysis of line shapes of Compton scattered x rays in combination with theoretical modeling can provide a precise method for an atomic level understanding of the nature of the doping process.

Efficient and environmentally friendly separation and recycling of cathode materials and current collectors for lithium-ion batteries by fast Joule heating

Spent Li-ion batteries(LIBs) cathodes possess high recycling value. To improve subsequent recovery efficiency and product purity, separating the cathode materials from the aluminum foil is critical. However, traditional separation methods are characterized by high energy consumption, low recycling efficiency, and environmental pollution. This research presents a novel method that involves injecting Joule heat directly into the aluminum foil in the air, resulting in the melting and slight thermal decomposition of the PVDF binder, which reduces its adhesive properties. Owing to the difference in thermal expansion coefficients between the binder and aluminum foil, an instantaneous thermal stress was generated at the interface of the cathode materials and aluminum foil, resulting in a peeling force. This method enabled a rapid and efficient separation of lithium iron phosphate (LFP) and ternary Li-ion (NCM) battery cathode materials. The optimal separation conditions, separation mechanism, and properties of the recovered products were investigated thoroughly using high-speed camera imaging, temperature rise calculations, and microscopic characterization. This chemical-free method avoids the generation of wastewater and gas emissions. Under optimal experimental parameters, the separation efficiency and purity of cathode material reached 99 % and 99.7 %, respectively. Additionally, this method preserves both the structural integrity of the aluminum foil and the crystalline structure of the cathode materials, offering a new pathway for sustainable recycling of end-of-life LIBs.

Revealing the Nanoscopic Corrosive Degradation Mechanism of Nickel-Rich Layered Oxide Cathodes at Low State-of-Charge Levels: Corrosion Cracking and Pitting.

Ni-rich layered oxides have received significant attention as promising cathode materials for Li-ion batteries due to their high reversible capacity. However, intergranular and intragranular cracks form at high state-of-charge (SOC) levels exceeding 4.2 V (vs. Li/Li+), representing a prominent failure mechanism of Ni-rich layered oxides. The nanoscale crack formation at high SOC levels is attributed to a significant volume change resulting from a phase transition between the H2 and H3 phases. Herein, in contrast to the electrochemical crack formation at high SOC levels, another mechanism of chemical crack and pit formation on a nanoscale is directly evidenced in fully lithiated Ni-rich layered oxides (low SOC levels). This mechanism is associated with intergranular stress corrosion cracking, driven by chemical corrosion at elevated temperatures. The nanoscopic chemical corrosion behavior of Ni-rich layered oxides during aging at elevated temperatures is investigated using high-resolution transmission electron microscopy, revealing that microcracks can develop through two distinct mechanisms: electrochemical cycling and chemical corrosion. Notably, chemical corrosion cracks can occur even in a fully discharged state (low SOC levels), whereas electrochemical cracks are observed only at high SOC levels. This finding provides a comprehensive understanding of the complex failure mechanisms of Ni-rich layered oxides and provides an opportunity to improve their electrochemical performance.

New exploration of water-soluble lithium polyacrylate/xanthan gum composite binder for Li-rich Mn-based cathode materials

Li-rich Mn-based oxides are considered promising cathode materials of Li-ion batteries with high specific capacity and operating voltage. However, Li-rich materials suffer from a high initial irreversible capacity loss and severe voltage attenuation during cycling. In this work, lithium polyacrylate (LiPAA) was crosslinked with xanthan gum (XG) to form a water-soluble binder for Li[Li0.2Co0.13Ni0.13Mn0.54]O2 electrode. The capacity retention was 78.3 % after 100 cycles at 0.2 C. LiPAA provided additional Li+ ions during cycling, while XG firmly bound to the surface of the active particles. Cost-effective binders provide a facile mean to improve the electrochemical performance of Li-rich cathode materials.

Improving performance of cathode NMC-811 by CeO2-coating for Li-ion battery

The high energy density layered oxide LiNi0.8Mn0.1Co0.1O2 (NMC811) holds great promise as a cathode material for future Li-ion batteries. However, its application in electric vehicles is hindered by issues such as inadequate cycle performance and rate capability. Additionally, the corrosion caused by the electrolyte poses limitations on high voltage operation. In this study, Cerium Oxide (CeO2) was used to coat NMC811 using wet chemical method followed by heat treatment. Distilled water was used to dissolve Ce salt instead of ethanol so that it can reduce coating costs and is more environmentally friendly. XRD analysis showed no significant change in the hexagonal crystal structure of NMC811 material but the appearance of small CeO2 peaks in patterns. Electrochemical test of CeO2 coated NMC811 exhibited 18% and 9% higher cyclic and rate performance, respectively in comparison to pristine material.