Cathode Materials For Li-ion Batteries Research Articles

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.

Pomegranate-like α-MoO3-x/C nanospheres as a stable and high-performance Li-ion intercalation host

Orthorhombic MoO3 (α-MoO3) is extensively investigated as a cathode material in Li-ion batteries with high capacity. However, suffering from the irreversible structural transformation and rapid capacity decline during discharge-charge process are still annoyed issues for α-MoO3 based electrodes. Herein, novel pomegranate-like oxygen-deficient α-MoO3/C (α-MoO3-x/C) nanospheres are prepared. The α-MoO3-x/C nanosphere is comprised of ultrafine α-MoO3-x subunits and porous graphitic carbon framework. Interlayer expansions caused by different contents of oxygen vacancies are realized in α-MoO3-x via a controllable oxidation process. When evaluated as the Li-ion intercalation host, the α-MoO3-x/C containing appropriate oxygen vacancies is found to be optimal with remarkable rate capability (230.0 mAh g−1 at 1 C, 54.5 mAh g−1 at 50 C) and long lifetime (69.6% retention after 3000 cycles at 10 C). Electrochemical test shows that the behavior of Li-ion intercalation in the intralayers of α-MoO3-x/C is suppressed effectively and becomes reversible. The structure evolutions during Li-ion intercalation/deintercalation process are investigated by ex situ X-ray diffraction, which reveals that α-MoO3-x/C undergoes lattice breathing rather than structural collapse compared with pure α-MoO3. Moreover, α-MoO3-x/C exhibits enhanced pseudocapacitance and improved Li-ion transport kinetics than pure α-MoO3. These unique features render α-MoO3-x/C an advanced intercalation host for Li-ions.

Performance improvement of Li-rich Mn-based materials with the submicron-sized single-crystal morphology and cationic doping

Lithium-rich manganese-based cathode materials (LRMCs) can be regarded as one of the most potential cathode materials for the next-generation high-energy Li-ion batteries due to the extra oxygen redox, which can greatly increase the actual output energy density of LRMCs. Nevertheless, the structure degradation and inevitable loss of oxygen will be triggered by the irreversible oxygen redox, which will cause a significant decline in cyclic performance and limited initial Coulombic efficiency, thus restricting their industrial applicability. Herein, the LRMCs with the submicron-sized single-crystal morphology and sodium doping are prepared by molten salt treatment with NaCl. On one hand, the submicron-sized single-crystal cathode effectively reduces the diffusion path for Li+ due to the smaller particle dimensions. On the other hand, Na+ doping expands the Li slab spacing, promoting the transport of Li+. The results show that the as-prepared material can purposefully alleviate oxygen release, improve structure stability, and increase the Li+ diffusion rate for the pristine LRMCs. Moreover, the as-prepared material in this study exhibits a higher reversible capacity of 282.8 mAh g−1 at 0.1 C and displays good cyclic performance, retaining a capacity rate of 80.9% after 200 cycles at 1 C. Therefore, this study offers a potential exploration for designing LRMCs with high energy density and excellent cyclic performance, which are achieved through building submicron-sized single-crystal morphology and introducing cationic doping.

Structure and Charge Regulation Strategy Enabling Superior Cycling Stability of Ni-Rich Cathode Materials.

Ni-rich layered oxides LiNixCoyMn1-x-yO2 (NCMs, x > 0.8) are the most promising cathode candidates for Li-ion batteries because of their superior specific capacity and cost affordability. Unfortunately, NCMs suffer from a series of formidable challenges such as structural instability and incompatibility with commonly used electrolytes, which seriously hamper their practical applications on a large scale. Herein, the Al/Ta codoping modification strategy is proposed to improve the performance of the LiNi0.83Co0.1Mn0.07O2 cathode, and the as-prepared Al/Ta-modified LiNi0.83Co0.1Mn0.07O2 delivers exceptional cycling stability with a capacity retention of 97.4% after 150 cycles at 1C and an excellent rate performance with a high capacity of 143.2 mAh g-1 even at 3C. Based on the experimental study, it is found that the structural stability of NCM is strengthened due to the regulated coordination of oxygen by introducing a robust Ta-O covalent bond, which prevents the layered structure from collapsing. Moreover, the reconstructed rock-salt-like surface is capable of effectively inhibiting interfacial side reactions as well as the overgrowth of the cathode-electrolyte interface. Theoretically, the energy of Li/Ni mixing is significantly increased with the introduction of Al and Ta elements in Al/Ta codoped NCM, leading to inhibited adverse phase transition during cycling. A feasible pathway for designing and developing advanced Ni-rich cathode materials for Li-ion batteries is provided in this work.

Enhancement of the electrochemical performance of LiNi0.5Mn1.5O4 cathode materials for Li-ion battery by Mo-F co-doping

Enhancement of the electrochemical performance of LiNi0.5Mn1.5O4 cathode materials for Li-ion battery by Mo-F co-doping

Characterization of ultrafast-laser ablation of micro-structures in Li-ion battery anode and cathode materials: Morphology, rate, and efficiency

Characterization of the rate and quality of ultrafast-laser ablation of Li-ion battery (LIB) electrode materials is presented for a collection of common and next-generation electrodes. Laser ablated micro-structures on the surface of LIB electrodes have been shown to provide dramatic enhancement of high-rate capability and electrode wetting. However, industrial adoption is hampered by a lack of data enabling informed choice of laser parameters and predicting process throughput. This work bridges this gap by providing characterization of the ablation process at more laser parameters (laser fluence and number of pulses used) than are currently available in the literature. Further, we expand on previous graphite and lithium iron phosphate (LFP) ablation work by extending ablation characterization to new LIB materials, providing high data resolution and adopting new characterization metrics which are relevant for industrial application of this technology. Ablated pores are characterized by their ablated depth, volume, and how the depth and volume ablation rate changes as a function of pore depth. Finally, we provide a detailed characterization of the morphology of laser ablated micro-structures which informs how material and laser parameters affect the quality of laser-processed electrodes.

Why the Synthesis Affects Performance of Layered Transition Metal Oxide Cathode Materials for Li-Ion Batteries.

The limited cyclability of high-specific-energy layered transition metal oxide (LiTMO2) cathode materials poses a significant challenge to the industrialization of batteries incorporating these materials. This limitation can be attributed to various factors, with the intrinsic behavior of the crystal structure during the cycle process being a key contributor. These factors include phase transition induced cracks, reduced Li active sites due to Li/Ni mixing, and slower Li+ migration. In addition, the presence of synthesis-induced heterogeneous phases and lattice defects cannot be disregarded as they also contribute to the degradation in performance. Therefore, gaining a profound understanding of the intricate relationship among material synthesis, structure, and performance is imperative for the development of LiTMO2. This paper highlights the pivotal role of structural play in LiTMO2 materials and provides a comprehensive overview of how various control factors influence the specific pathways of structural evolution during the synthesis process. In addition, it summarizes the scientific challenges associated with diverse modification approaches currently employed to address the cyclic failure of materials. The overarching goal is to provide readers with profound insights into the study of LiTMO2.

Enhancing the Stability of 4.6 V LiCoO2 Cathode Material via Gradient Doping.

LiCoO2 (LCO) can deliver ultrahigh discharge capacities as a cathode material for Li-ion batteries when the charging voltage reaches 4.6 V. However, establishing a stable LCO cathode at a high cut-off voltage is a challenge in terms of bulk and surface structural transformation. O2 release, irreversible structural transformation, and interfacial side reactions cause LCO to experience severe capacity degradation and safety problems. To solve these issues, a strategy of gradient Ta doping is proposed to stabilize LCO against structural degradation. Additionally, Ta1-LCO that was tuned with 1.0 mol% Ta doping demonstrated outstanding cycling stability and rate performance. This effect was explained by the strong Ta-O bonds maintaining the lattice oxygen and the increased interlayer spacing enhancing Li+ conductivity. This work offers a practical method for high-energy Li-ion battery cathode material stabilization through the gradient doping of high-valence elements.

Enabling High-Performance Layered Li-Rich Oxide Cathodes by Regulating the Formation of Integrated Cation-Disordered Domains.

Layered Li-rich oxide cathode materials are capable of offering high energy density due to their cumulative cationic and anionic redox mechanism during (de)lithiation process. However, the structural instability of the layered Li-rich oxide cathode materials, especially in the deeply delitiated state, results in severe capacity and voltage degradation. Considering the minimal isotropic structural evolution of disordered rock salt oxide cathode during cycling, cation-disordered nano-domains have been controllably introduced into layered Li-rich oxides by co-doping of d0-TM and alkali ions. Combining electrochemical and synchrotron-based advanced characterizations, the incorporation of the phase-compatible cation-disordered domains can not only hinder the oxygen framework collapse along the c axis of layered Li-rich cathode under high operation voltage but also promote the Mn and anionic activities as well as Li+ (de)intercalation kinetics, leading to remarkable improvement in rate capability and mitigation of capacity and voltage decay. With this unique layered/rocksalt intergrown structure, the intergrown cathode yields an ultrahigh capacity of 288.4mAhg-1 at 0.1C, and outstanding capacity retention of ≈90.0% with obviously suppressed voltage decay after 100 cycles at 0.5, 1, and 2C rate. This work provides a new direction toward advanced cathode materials for next-generation Li-ion batteries.