Cathode Active Material Research Articles

An active and Cr-tolerant high-entropy La0.7Sr0.3FeO3-δ based cathode for solid oxide fuel cells

The development of high active and stable cathode materials is one of the main challenges of intermediate temperature solid oxide fuel cells (SOFCs). Herein, a high-entropy Fe-based perovskite oxide La0.7Sr0.3Fe0.3Ni0.3Co0.3Mo0.1O3-δ (LSFNCM) is synthesized by self-propagation combustion based on La0.7Sr0.3FeO3-δ (LSF) and the electrochemical properties are systematically tested. The symmetric half-cell with the LSFNCM cathode has a high catalytic activity with a polarization impedance of 0.12 Ω·cm2 at 800 °C, and also shows outstanding CO2 resistance and chromium resistance owing to the entropy stabilization strategy. After 50h of treatment in a 10% CO2 environment, the polarization impedance of the LSF electrode increases by 8.89 Ω·cm2, while that of the LSFNCM electrode only increases by 1.81 Ω·cm2. Additionally, after being treated for 24h in a chromium vapor environment, the polarization impedance of the LSF electrode increases by 5.95 Ω·cm2, whereas that of the LSFNCM electrode only increases by 0.44 Ω·cm2. Moreover, the single cell with LSFNCM cathode exhibits the maximum power density of 932.82 mW/cm2 and the polarization impedance of 0.34 Ω·cm2 at 800 °C with humidify hydrogen as fuel. Our results indicate that high-entropy perovskite oxide LSFNCM is an active and Cr-tolerant promising cathode for SOFCs.

Influence of green solvents on the recovery of cathode active materials from electrode scraps: A comparative study

Direct recycling of cathode materials from spent Li-ion batteries (LIBs) or electrode scraps necessitates the efficient recovery of active materials from the aluminum foil. The variability in electrode types and recovery processes across previous studies complicates the comparative assessment of the recovery performance of green solvents. In this study, we evaluated the performance of three green solvents—triethyl phosphate (TEP), dihydrolevoglucosenone (Cyrene), and propylene carbonate (PC)—in recovering valuable active materials from industrial-grade cathode scraps. Using ultrasonication, we developed a standardized, energy-efficient recovery process that eliminated the need for conventional stirring and achieved complete cathode delamination from the aluminum foil. Furthermore, we successfully recovered the used green solvents after the process, ensuring their reuse and supporting a circular economy. The recovered materials retained their original morphology, chemical composition, and crystalline structure; however, the presence of surface impurities varied significantly depending on the green solvent used. These impurities had a considerable impact on the electrochemical performance of the recovered materials. TEP and PC yielded high-purity active materials and aluminum foils suitable for reuse or direct recycling, while Cyrene resulted in substantial residues of PVDF/solvent, requiring additional post-processing. Additionally, the recyclability of these green solvents was influenced by their solubility power for PVDF. This study provides valuable insights into the green solvent-based recycling process, laying the groundwork for future sustainable practices in LIB recycling.

Suppression of Transition Metal Dissolution in Mn-Rich LayeredOxide Cathodes with Graphene Nanocomposite Dry Coatings

Abstract The growing demand for lithium-ion batteries (LIBs) and the reliance on scarce metals in cathode active materials (CAMs) have prompted a search for sustainable alternatives. However, the performance of Mn-rich CAMs formulated with less Co suffer from transition metal dissolution (TMD).
TMD can be suppressed by applying a thin film of carbon or oxide to the CAM but the assumed need for a continuous film necessitates bottom-up coating methods. This has been a challenge for LIB production as well as limiting material choices. Here we show that particulate coatings can also suppress TMD, allowing for scalable, material-independent, dry coating methods. Dry coating the Mn-rich CAM surfaces with graphene encapsulated nanoparticles (GEN) (1 wt\%) suppresses TMD while nearly doubling the cycle life and improving rate capacities up to 42\% under stressful conditions. The ability to suppress TMD is attributed to the unique chemical and electronic properties of the GEN produced by plasma enhanced chemical vapor deposition. The method is general and could provide a scalable path to CAM with less Co.

Elucidating the Limit of Lithium Difluorophosphate Electrolyte Additive for High‐Voltage Li/Mn‐Rich Layered Oxide || Graphite Li Ion Batteries

Li/Mn‐rich layered oxide (LMR) cathode active materials offer remarkably high specific discharge capacity (>250 mAh g−1) from both cationic and anionic redox. The latter necessitates harsh charging conditions to high cathode potentials (>4.5 V vs Li|Li+), which is accompanied by lattice oxygen release, phase transformation, voltage fade, and transition metal (TM) dissolution. In cells with graphite anode, TM dissolution is particularly detrimental as it initiates electrode crosstalk. Lithium difluorophosphate (LiDFP) is known for its pivotal role in suppressing electrode crosstalk through TM scavenging. In LMR || graphite cells charged to an upper cutoff voltage (UCV) of 4.5 V, effective TM scavenging effects of LiDFP are observed. In contrast, for an UCV of 4.7 V, the scavenging effects are limited due to more severe TM dissolution compared an UCV of 4.5 V. Given the saturation in solubility of the TM scavenging agents, which are LiDFP decomposition products, e.g., PO43− and PO3F2−, higher concentrations of the LiDFP as “precursor” cannot enhance the amount of scavenging species, they rather start to precipitate and damage the anode.

Super Chloride Ionic Conductivity in CsSnCl3‐Based Perovskite Compound and Its Application for Solid‐State Chloride Batteries

A CsSnCl3‐based solid electrolyte in which 5% of Sn sites are occupied by Y ions, CsSn0.95Y0.05Cl3.05 (CSYC), is developed using a one‐step mechanical ball‐milling method. CSYC exhibits a stable cubic perovskite crystal structure and a high chloride ion conductivity of 4.9 mS cm−1. The relative density of a CSYC pellet following cold pressing without heat treatment is 97.5%. The high relative density and ionic conductivity are considered to originate from the high mechanical plasticity of the pellets, as evidenced by a low Young's modulus of 8.2 GPa. An all‐solid‐state chloride ion battery cell using CSYC as the electrolyte, BiCl3 as the active cathode material, and Sn as the anode is confirmed to operate at room temperature. The cell shows a large initial discharge capacity of 178 mAh g−1, ≈70% utilization, and good capacity retention with a reversible capacity of 100 mAh g−1 after 40 cycles. The mechanical plasticity of CSYC is considered to be a major contributor to its high ionic conductivity and good battery cycling performance.

3-Electrode Setup for the Operando Detection of Side Reactions in Li-Ion Batteries: The Quantification of Released Lattice Oxygen and Transition Metal Ions from NCA

Detecting parasitic side reactions is paramount for developing stable cathode active materials (CAMs) for Li-ion batteries. This study presents a method for the quantification of released lattice oxygen and transition metal ions (TMII+ ions). It is based on a 3-electrode cell design employing a Vulcan carbon-based sense electrode (SE) that is held at a controlled voltage against a partially delithiated lithium iron phosphate (LFP) counter electrode (CE). At this SE, reductive currents can be measured while polarizing a CAM working electrode (WE), here a LiNi0.80Co0.15Al0.05O2 (NCA), against the same LFP CE. In voltammetric scans, we show how the SE potential can be selected to specifically detect a given side reaction during CAM charge/discharge, allowing, e.g., to discriminate between lattice oxygen and dissolved TMs. Furthermore, it is shown via online electrochemical mass spectrometry (OEMS) that O2 reduction in the here-used LP47 electrolyte consumes ∼2.3 electrons/O2. Using this value, the lattice oxygen release deduced from the 3-electrode setup upon charging of the NCA WE is in good agreement with OEMS measurements up to NCA potentials >4.65 VLi. At higher potentials, the contributions from the reduction of TMII+ ions can be quantified by comparing the integrated SE current with the O2 evolution from OEMS.

Cycling Aging in Different State of Charge Windows in Lithium-Ion Batteries with Silicon-Dominant Anodes

Reducing the capacity utilization of silicon-containing anodes and choosing the optimal full-cell voltage window improve the lifetime significantly. In this study, we investigate how different voltage windows affect the aging modes with a common 50% cycling depth. First, the cyclic stability, the anode potentials, and the polarization increase are analyzed for the different voltage windows using 70 wt% microscale silicon anodes and NCA cathodes with a lithium metal reference electrode to investigate the electrode-specific characteristics. Further, the underlying aging modes are quantified in the post-mortem analysis. Finally, the anode thickness increase is quantified using a dilatometer setup for different anode lithiations. In contrast to the literature, the highest voltage window is most beneficial for the lifetime since high anode delithiation potentials and high surface increases are avoided. The anode potential at the end-of-discharge, the charge-averaged full-cell potentials, and the resistance increase are a function of the state of health (SoH). The common underlying main aging mechanism is the loss of lithium inventory, followed by the loss of anode active material. In contrast, the loss of cathode active materials only plays a minor role.

Progressive degradation behavior and mechanism of lithium-ion batteries subjected to minor deformation damage

Minor deformation damage poses a concealed threat to battery performance and safety. This study delves into the progressive degradation behavior and mechanisms of lithium-ion batteries under minor deformation damage induced by out-of-plane compression. The effects of varying initial states of charge and loading speed on battery degradation are also analyzed. It has been observed that a deformation damage degree as low as 3.1 % can cause a significant transient capacity reduction up to 6.3 %. More transient capacity reduction can occur at higher initial state of charges and loading speed. Additionally, the investigation reveals that the capacity decay rate between the normal cell and cells experiencing deformation damage degree of <4.7 % is almost similar, with a maximum difference of merely 1.887 mAh/cycle and a minimum difference of 0.001 mAh/cycle, both observed over 3000 cycles. Non-destructive and destructive analysis methods are used to investigate degradation behaviors of the cells experiencing minor deformation dagame. It is found that such progressive degradation is primarily driven by the loss of active lithium ions, followed by the loss of cathode and anode active materials. It is anticipated that the findings will offer theoretical underpinnings for advancements in battery damage assessment, early failure prediction, and facilitation of loss adjustment and compensation by insurance agencies.

Flotation separation of lithium–ion battery electrodes predicted by a long short-term memory network using data from physicochemical kinetic simulations and experiments

Anode and cathode active materials from spent lithium–ion batteries may be recovered and potentially used in new batteries to promote recycling and resource circulation. Froth flotation was applied to pristine active materials and the black mass obtained from pretreated spent batteries. Flotation kinetics was simulated with the use of computational fluid dynamics and surface chemistry. Bubble surface coverage and entrainment in the flotation kinetics model were selected and optimized by systematic fitting to experimental data. Entrainment influences the recovery and grade of the active materials. The optimized flotation kinetics model was used for generating additional data that, along with the fitted data, were used to train a deep learning neural network. The trained network was validated using anode–cathode and black mass flotation experiments, and its predictions showed a maximum residual error of 0.18 ± 0.11 recovery. The simulation framework was developed into a desktop application that predicts the flotation behavior of active materials. It provides information for estimating results following operational and physicochemical changes and for optimizing flotation processes. Finally, recovered anode active materials from black mass were selected for coin cell tests. The coulombic efficiency of these coin cells was initially lower (86.8 %) than that of cells made with pristine graphite particles (98.4 %).

Comparative environmental and economic assessment of emerging hydrometallurgical recycling technologies for Li-ion battery cathodes

The growing demand for electric vehicles has led to a growing concern for battery recycling, particularly for critical raw materials. However, there is insufficient investigation into the environmental and economic impacts of hydrometallurgical recycling methods. In this study we explored emerging hydrometallurgical technologies in economic and environmental perspective to establish conceptual routes to recover Co, Ni and Mn oxides from waste LiNi0.33Mn0.33Co0.33O2 cathode materials from spent Li-ion batteries. After, life cycle assessment and costing techniques were utilized to compare the environmental and economical performances of each conceptual route. Recovery efficiency of metal oxides through each route was also considered as a key factor. Results suggested that deep eutectic solvent-based leaching produces the highest impact under many impact categories while electrolysis-based leaching showed the least. Under purification technologies assessed, ion-exchange based purification showed significantly lower impact under many categories except stratospheric ozone depletion. Solvent based purification has been identified as the worst technology for purification. Hydroxide based calcination has been identified as the most environmentally sustainable calcination method compared to oxalate calcination. The route consists with inorganic leaching, ion-exchange based purification and hydroxide calcination showed the lowest environmental impact (emission effect at 33.8 kg CO2 eq), with lower economic impact ($ 119) and the highest recovery efficiency (78 %) per 1 kg of cathode active materials. However, using electrolysis-based leaching can slightly increase the impacts with lower recovery efficiency (75 %) and better economic performance ($104/kg of cathode active materials). Terrestrial ecotoxicity was identified to be the most affected impact category for the recovery processes. It is recommended that technologies like deep eutectic solvent-based leaching, solvent extraction and environmentally sustainable technologies like supercritical fluid extraction need further studies prior to industrial applications.

S@FeS2 Core-Shell Cathode Nanomaterial for Preventing Polysulfides Shuttling and Forming Solid Electrolyte Interphase in High-Rate Li-S Batteries.

Lithium-sulfur (Li-S) battery is a potential next-generation energy storage technology over lithium-ion batteries for high capacity, cost-effective, and environmentally friendly solutions. However, several issues including polysulfides shuttle, low conductivity and limited rate-capability have hampered its practical application. Herein, a new class of cathode active material with perfect core-shell structure is reported, in which sulfur is fully encapsulated by conductivity-enhancing FeS2 (named as S@FeS2), for high-rate application. Surface-stabilized S@FeS2 cathode exhibits a stable cycling performance under 2 - 20 times higher rates (1-2 C, charged in 30-60min) than standard rates (e.g., 0.1-0.5C, charged in 2-10h), without polysulfides shuttle event. Surface analysis results reveal the unprecedented formation of a stable solid electrolyte interphase (SEI) layer on S@FeS2 cathode, which is distinguished from other sulfur-based cathodes that are not able to form the SEI layer. The data suggest that the prevention of polysulfides shuttling is owing to the surface protection effect of FeS2 shell and the SEI layer formation overlying core-shell S@FeS2. This unique and potential material concept proposed in the present study will give insight into designing a prospective fast charging Li-S battery.

Strong Magnetic Exchange Interactions and Delocalized Mn-O States Enable High-Voltage Capacity in the Na-Ion Cathode P2-Na0.67[Mg0.28Mn0.72]O2.

The increased capacity offered by oxygen-redox active cathode materials for rechargeable lithium- and sodium-ion batteries (LIBs and NIBs, respectively) offers a pathway to the next generation of high-gravimetric-capacity cathodes for use in devices, transportation and on the grid. Many of these materials, however, are plagued with voltage fade, voltage hysteresis and O2 loss, the origins of which can be traced back to changes in their electronic and chemical structures on cycling. Developing a detailed understanding of these changes is critical to mitigating these cathodes' poor performance. In this work, we present an analysis of the redox mechanism of P2-Na0.67[Mg0.28Mn0.72]O2, a layered NIB cathode whose high capacity has previously been attributed to trapped O2 molecules. We examine a variety of charge compensation scenarios, calculate their corresponding densities of states and spectroscopic properties, and systematically compare the results to experimental data: 25Mg and 17O nuclear magnetic resonance (NMR) spectroscopy, operando X-band and ex situ high-frequency electron paramagnetic resonance (EPR), ex situ magnetometry, and O and Mn K-edge X-ray Absorption Spectroscopy (XAS) and X-ray Absorption Near Edge Spectroscopy (XANES). Via a process of elimination, we suggest that the mechanism for O redox in this material is dominated by a process that involves the formation of strongly antiferromagnetic, delocalized Mn-O states which form after Mg2+ migration at high voltages. Our results primarily rely on noninvasive techniques that are vital to understanding the electronic structure of metastable cycled cathode samples.

Conductive Li2S‐NbSe2 Cathode Material Capable of Bidirectional Self‐Activation for High‐Performance All‐Solid‐State Lithium Metal Batteries

AbstractAll‐solid‐state lithium metal batteries (ASSLBs) offer an alternative route to safe and high energy density power sources. Sulfur‐based cathodes with high theoretical specific capacity and low cost are crucial for advancing ASSLBs. However, the electronic insulation and sluggish kinetics of sulfide materials like Li2S severely limit battery performance. Herein, the strategy is proposed that a highly electronic conductive Li2S‐NbSe2 material enhances the electrochemical performance through bidirectional self‐activation. The chemical interaction between Li2S and NbSe2 induces NbSe2‐xSx and Li2Se derivatization, serving as the basis for activation. The carrier transport properties, chemical evolution and self‐activation mechanism of Li2S‐NbSe2 during the oxidation–reduction process are revealed. The chemical activation of NbSe2‐xSx is explored to accelerate the electrochemical processes by modifying the conductivity of sulfur species and the conversion pathways without insulating Li2S and S aggregation. Therefore, ASSLBs using Li2S‐NbSe2 as cathode active material achieve an electrode‐level energy density of 394 Wh kg−1 and a power density of 524 W kg−1 at 1 C (4.35 mA cm−2) and 25 °C. The capacity retention after 100 cycles at 0.5 C is ≈99.3% with almost no degradation. This work provides new options and insights for the rational design and development of chalcogenide cathode active materials for high‐performance ASSLBs.

Life Cycle of LiFePO4 Batteries: Production, Recycling, and Market Trends.

Significant attention has focused on olivine-structured LiFePO4 (LFP) as a promising cathode active material (CAM) for lithium-ion batteries. This iron-based compound offers advantages over commonly used Co and Ni due to its lower toxicity abundance, and cost-effectiveness. Despite its current commercial use in energy storage technology, there remains a need for cost-effective production methods to create electrochemically active LiFePO4. Consequently, there is ongoing interest in developing innovative approaches for LiFePO4 production. While LFP batteries exhibit significant thermal stability, cycling performance, and environmental benefits, their growing adoption has increased battery disposal rates. Improper disposal practices for waste LFP batteries result in environmental degradation and the depletion of valuable resources. This review comprehensively examines diverse synthesis approaches for generating LFP powders, encompassing conventional methodologies alongside novel procedures. Furthermore, it conducts an in-depth assessment of the methodologies employed in recycling waste LFP batteries. Moreover, it emphasizes the importance of LFP cathode recycling and investigates pretreatment techniques to enhance understanding. Additionally, it provides valuable insights into the recycling process of used LFP batteries, aiming to raise awareness regarding the market for retired LFP batteries and advocate for the enduring sustainability of lithium-ion batteries.

Review on the Polymeric and Chelate Gel Precursor for Li-Ion Battery Cathode Material Synthesis.

The rapid design of advanced materials depends on synthesis parameters and design. A wide range of materials can be synthesized using precursor reactions based on chelated gel and organic polymeric gel pathways. The desire to develop high-performance lithium-ion rechargeable batteries has motivated decades of research on the synthesis of battery active material particles with precise control of composition, phase-purity, and morphology. Among the most common methods reported in the literature to prepare precursors for lithium-ion battery active materials, sol-gel is characterized by simplicity, homogeneous mixing, and tuning of the particle shape. The chelate gel and organic polymeric gel precursor-based sol-gel method is efficient to promote desirable reaction conditions. Both precursor routes are commonly used to synthesize lithium-ion battery cathode active materials from raw materials such as inorganic salts in aqueous solutions or organic solvents. The purpose of this review is to discuss synthesis procedure and summarize the progress that has been made in producing crystalline particles of tunable and complex morphologies by sol-gel synthesis that can be used as active materials for lithium-ion batteries.

Exploring Gas‐Solid Phase Diagrams: Novel Methods for Oxyfluorination of Mn3O4 and Mn2O3 with Molecular Fluorine

AbstractFluorinated, manganese‐redox cation‐disordered rocksalts are promising candidates for high‐performance cobalt‐free Li‐ion cathode active material. A need for reactive fluorinated precursors was however identified. While manganese oxyfluorides are promising precursor candidates, none stable at room temperature was reported prior to 2023. The key to their recent synthesis by reacting molecular fluorine with MnO was a procedure to continuously scan the temperature axis in search of activation temperatures. In line with this philosophy of continuous exploration of the chemical space, two experimental procedures are reported to scan the stoichiometry axis of a gas‐solid phase diagram in search of transitions and intermediate compounds. Their application to F2 ‐ Mn3O4 and F2 ‐ Mn2O3 phase diagrams resulted in the discovery of two new ranges of stable manganese oxyfluorides of respective compositions MnO1.33‐0.13xFx with x&lt;0.5 and MnO1.5‐0.22xFx with x&lt;1.

Cradle-to-gate life cycle assessment of cylindrical sulfide-based solid-state batteries

Abstract Purpose Solid-state batteries (SSBs) are a current research hotspot, as they are safer and have a higher energy density than state-of-the-art lithium-ion batteries (LIBs). To date, their production only occurs on a laboratory scale, which provides a good opportunity to analyze the associated environmental impacts prior to industrialization. This paper investigates the environmental impacts of the production of cylindrical SSB, to identify environmental hotspots and optimization potentials. Methods Here, an attributional cradle-to-gate life cycle assessment (LCA) is performed, focusing on SSBs that use a NMC811/lithium germanium phosphorous sulfide (LiGPS) composite cathode, a sulfide-based solid separator electrolyte, and a lithium metal anode. The life cycle impact assessment (LCIA) is performed in Umberto 11 using the Environmental Footprint 3.1 method with primary and literature data and the Evoinvent 3.9 database for background data. Results and discussion The results show climate change impacts of 205.43 kg CO2 eq./kwh (for the base case), with hotspots primarily attributable to the electrolyte and cathode production, and more specifically to the LiPS and LiGPS synthesis as well as to the cathode active material. Additionally, the scenario analysis shows that an upscaling of the LiPS and LiGPS synthesis reduces environmental impacts across all assessed impact categories. In addition, it was shown that the use of an in situ anode further improves the overall environmental performance, while the use of alternative cathode active materials, such as NMC622 and LFP did not lead to any improvements, at least with reference to the storage capacity. Conclusion The article highlights the environmental hotspots of sulfide-based SSB production, namely electrolyte and catholyte synthesis. The results show that upscaling the synthesis reduces the environmental impact and that cells with higher energy density show a favorable environmental performance. However, SSBs are still in the development stage and no final recommendation can be made at this time.

Superionic lithium argyrodite-type sulfide electrolyte with optimized composite cathode fabrication enabling stable All-Solid-State Batteries

All-solid-state batteries (ASSBs) are promising candidates for next-generation energy storage devices. However, several key aspects especially superionic solid electrolytes (SEs) and carefully designed electrode configurations still remain a challenge for the development of high performance ASSBs. Herein, a halogen-rich lithium argyrodite, Li5.5PS4.5Cl0.8Br0.7 (LPSCB) with optimized synthesis condition is successfully prepared. Electrochemical impedance spectroscopy and X-ray diffraction illustrate that annealing temperature affects Li-ion dynamics, which guides the formation of LPSCB with a high room-temperature ionic conductivity of 10.7 mS cm−1. Furthermore, LiNi0.9Co0.05Mn0.05O2 with ZrO2 dual-functional coating layer (ZrO2@NCM) was introduced as cathode active materials (CAMs) to guarantee high-energy-density composite cathode. Correspondingly, a better understanding of the optimization of composite cathode design based on the superionic LPSCB is well elucidated and fast ion/electron transport is achieved by revealing the effect of different CAM fractions in the cathodes on the rate and cycling performance. Specifically, ASSBs with 60 wt.% and 80 wt.% CAM deliver high discharge capacity of 1.1 and 1.95 mAh cm−2 at −20 °C and 60 °C, with corresponding capacity retention of 86.4 % and 69.7 % after 100 and 150 cycles, respectively. This work demonstrates the necessity of customizing CAM fractions depending on the desired applications of ASSBs, and provides an effective cathode modification strategy toward the development of sulfide-based ASSBs with excellent electrochemical performance.

Characterization of Lithium-Ion Batteries from Recycling Perspective towards Circular Economy

Recycling processes of lithium-ion batteries used in electric and hybrid vehicles are widely studied today. To perform such recycling routes, it is necessary to know the composition of these batteries and their components. In this work, three pouch and three cylindrical LIBs were discharged, dismantled, and characterized, having their compositions known and quantified. The dismantling was performed using scissors, pliers, and a precision cutter equipment. The organic liquid electrolyte was quantified via mass loss after it evaporated at 60 °C for 24 h. The separators were analyzed using Fourier-transform infrared spectroscopy (FTIR), and the cathode and anode active materials were analyzed using a scanning electronic microscope coupled to an energy-dispersive spectroscope (SEM-EDS), X-ray diffraction (XDR), and energy-dispersive X-ray fluorescence spectrometry (EDXRF). All LIBs were identified by type (NCA, NMC 442, NMC 811, LCO, and two LFP batteries), and a preliminary economic evaluation was conducted to understand their potential economic value (in USD/t). Both results (characterization and preliminary economic evaluation) were considered to discuss the perspective of recycling towards a circular economy for end-of-life LIBs.

Coating Robust Layers on Ni-Rich Cathode Active Materials while Suppressing Cation Mixing for All-Solid-State Lithium-Ion Batteries.

This study focused on addressing the challenges associated with the incompatibility between sulfide solid electrolytes and Ni-rich cathode active materials (CAMs) in all-solid-state lithium-ion batteries. To resolve these issues, protective layers have been explored for Ni-rich materials. Lithium lanthanum titanate (LLTO), a perovskite-type material, is recognized for its excellent chemical stability and ionic conductivity, which render it a potential protective layer in CAMs. However, traditional methods of achieving the perovskite structure involve temperatures exceeding 700 °C, resulting in challenges such as LLTO agglomeration, secondary phase formation between LLTO and CAM, and cation mixing within the CAM. In this study, a rapid technique known as flash-light sintering (FLS) was employed to fabricate a uniform and pure perovskite protective layer without inducing cation mixing within the CAM. The LLTO-coated LiNi0.8Co0.1Mn0.1O2 (NCM811) with FLS treatment demonstrated minimal cation mixing and formed a fully covered dense layer. This resulted in a high initial capacity and effectively addressed the incompatibility issues between the sulfide electrolytes and CAM. The rapid FLS method not only streamlines the fabrication of LLTO-coated NCM811 but also provides opportunities for its broader application to materials that were previously deemed impractical because of high sintering temperatures.