Cathode Active Material Research Articles

Crystallization of Cathode Active Material Precursors from Tartaric Acid Solution.

In this study L-(+)-tartaric acid was used to extract metals from either pure cathode material (NMC111) or black mass from spent lithium-ion batteries. The leaching efficiencies of Li, Co, Ni, and Mn from NMC111 are > 87% at 70 °C, with an initial solid to liquid ratio of 17, and > 72.4±1.0% from black mass under corresponding conditions. The metals tend to form mixed phases in antisolvent crystallization and seeding has a minimal effect on the final solid composition. Impurities influence both crystal nucleation and growth. By controlling the antisolvent addition rate crystal growth can be promoted. The theoretical dielectric constant of the solution is shown to correlate excellently to the recovery efficiency across different antisolvents, where a value <52 results in over 95% total transition metal recovery efficiency. The correlation can be a powerful tool for quantitative prediction of optimal solvent composition for effective antisolvent crystallization.

Engineering Stable Decomposition Products on Cathode Surfaces to Enable High Voltage All‐Solid‐State Batteries

Sulfide solid electrolytes such as Li6PS5Cl hold high promise for solid state batteries due to their high ionic conductivity; however, their oxidation potential of ~2.5 V is not compatible with high voltage Ni‐rich cathodes such as LiNixCoyMn1−x−yO2 (x≥0.8). Here, we devise an effective, conformal and thin coating on the cathode active material guided by density functional theory, which suppresses the oxidative decomposition of Li6PS5Cl as shown by experiment. The nanometric coating on nickel‐rich NMC85 enabled capacity retention of 82% after 200 cycles (2.8‐4.3 V vs Li+/Li) using Li6PS5Cl as the solid electrolyte. In comparison, cells with an uncoated CAM only displayed 56% capacity retention. The coated‐NCM85 cells also demonstrate much better rate performance and higher capacity. The enhanced performance is due to the formation of a stable amorphous cathode‐electrolyte interphase accruing from the decomposition products of the LiPO2F2 precursor (as predicted by DFT), which protect the sulfide electrolyte from oxidation. The coating fabricated in this cost‐effective process showed superior performance to state‐of‐the‐art coatings such as LiNbO3. This work highlights the importance of rationally designing stable coating materials based on their potential decomposition products and confirms the suitability of a low‐cost and conformal coating to enable sulfide electrolyte‐based all‐solid‐state batteries.

Engineering Stable Decomposition Products on Cathode Surfaces to Enable High Voltage All-Solid-State Batteries.

Sulfide solid electrolytes such as Li6PS5Cl hold high promise for solid state batteries due to their high ionic conductivity; however, their oxidation potential of ~2.5 V is not compatible with high voltage Ni-rich cathodes such as LiNixCoyMn1-x-yO2 (x≥0.8). Here, we devise an effective, conformal and thin coating on the cathode active material guided by density functional theory, which suppresses the oxidative decomposition of Li6PS5Cl as shown by experiment. The nanometric coating on nickel-rich NMC85 enabled capacity retention of 82% after 200 cycles (2.8-4.3 V vs Li+/Li) using Li6PS5Cl as the solid electrolyte. In comparison, cells with an uncoated CAM only displayed 56% capacity retention. The coated-NCM85 cells also demonstrate much better rate performance and higher capacity. The enhanced performance is due to the formation of a stable amorphous cathode-electrolyte interphase accruing from the decomposition products of the LiPO2F2 precursor (as predicted by DFT), which protect the sulfide electrolyte from oxidation. The coating fabricated in this cost-effective process showed superior performance to state-of-the-art coatings such as LiNbO3. This work highlights the importance of rationally designing stable coating materials based on their potential decomposition products and confirms the suitability of a low-cost and conformal coating to enable sulfide electrolyte-based all-solid-state batteries.

Understanding of a Ni-Rich O3-Layered Cathode for Sodium-Ion Batteries: Synthesis Mechanism and Al-Gradient Doping.

O3-type NaNi0.8Mn0.1Co0.1O2 (NaNMC811) cathode active materials for sodium-ion batteries (SIBs), with a theoretical high specific capacity (∼187mAhg-1), are in the preliminary exploration stage. This study comprehensively investigates NaNMC811 from multiple perspectives. For the first time, the phase evolution ( - - ) during the solid-state synthesis is systemically investigated, which elucidates in-depth the mechanisms of the thermal sodiation process. Furthermore, an Al-gradient doping of NaNMC811 wassuccessfully implemented through Al2O3 coating on the cathode active material (CAM) precursor. The modified Al-NaNi0.8Mn0.1Co0.1O2 (Al-NaNMC811) exhibits excellent electrochemical dynamics and performance, maintaining a specific capacity above 100mAhg-1 after 100 cycles at 0.1 C (1.5-4.1 V) while providing a promising capacity retention of 63%. Additionally, the material demonstrates excellent rate capabilities, retaining a specific capacity of 107 mAh g-1 at 5 C. Compared to pristine NaNMC811, the modified Al-NaNMC811 is proven to have improved electrochemical kinetics with a higher Na+ diffusion coefficient due to dilated (003) interplanar spacing, and a more stable structure during the electrochemical charge-discharge processes, which is attributed to stronger Al-O bond energy. Understanding phase formations during the synthesis and comprehensive insight in the gradient doping for O3-type NaNMC811 CAMs guides further development of next-generation SIBsmaterials.

Suppressing high voltage chemo-mechanical degradation in single crystal nickel-rich cathodes for high-performance all-solid-state lithium batteries

Sulfide-based all-solid-state lithium batteries (SASSLBs) suffer from electrochemo.mechanical damage to Ni-rich oxide-based cathode active materials (CAMs), primarilycaused by severe volume changes, results in significant stress and strain cuase micro-cracks, and interfacial contact loss at potentials > 4.3 V(vs. Li/Li+). Quantifying micro-cracks and voids in cathode active materials (CAMs) can reveal the degradation mechanisms of Ni-rich oxide-based cathodes during electrochemical cycling. Nonetheless, the origin of electrochemical-mechanical damage remains unclear. Herein, We have developed a multifunctional PEG-based soft buffer layer (SBL) on the surface of carbon black (CB). This layer functions as a percolation network in the single crystal LiNi0.83Co0.07Mn0.1O2 and Li6PS5Cl composite cathode layer, ensuring superior ionic conductivity, reducing void formation and particle cracking, and promoting uniform utilization of the cathode active material in all-solid-state lithium batteries (ASSLBs). STEM-HAADF combined with nanoscale X-ray holo-tomography and plasma-focused ion beam scanning electron microscopy confirmed that the PEG-based SBL mitigated strain induced by reaction heterogeneity in the cathode. This strain produces lattice stretches, distortions, and the formation of curved transition metal oxide layers near the surface, contributing to structural degradation at elevated voltages. Consequently, ASSLBs with a LiNi0.83Co0.07Mn0.1O2 cathode containing LCCB-10 (CB/PEG mass ratio: 100/10) demonstrate a high areal capacity (2.53 mAh g–1/0.32 mA g–1) and remarkable rate capability (0.58 mAh g–1 at 1.4 mA g–1), with 88% capacity retention over 1000 cycles.

Systematic “Apple‐to‐Apple” Comparison of Single‐Crystal and Polycrystalline Ni‐Rich Cathode Active Materials: From Comparable Synthesis to Comparable Electrochemical Conditions

Systematic “Apple‐to‐Apple” Comparison of Single‐Crystal and Polycrystalline Ni‐Rich Cathode Active Materials: From Comparable Synthesis to Comparable Electrochemical Conditions

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.

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 (&gt;250 mAh g−1) from both cationic and anionic redox. The latter necessitates harsh charging conditions to high cathode potentials (&gt;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.

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

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.

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.

Investigation of the influence of fluorine on metal elution from cathodic active material liberated from spent lithium-ion batteries with a focus on the underwater electrical pulse method

Abstract As a promising candidate to separate the cathode materials and aluminum foils, the underwater electrical pulse method is an environmentally friendly method that can effectively liberate cathodic active material in a very short time. However, performing the electric pulse separation in aqueous media may cause the release of fluoridated elements, which may come from fluoridated components formed during battery cycles or due to the remaining electrolyte within the cathode particles. Thus, the purpose of this work is to study the solution obtained after pulse discharge in terms of fluoridated entities, to understand their effect on the elution of active cathodic materials. Herein, to investigate the potential source of F and its possible effects on metal extraction, leaching experiments were conducted in the presence of different fluoride concentrations with a solid/liquid ratio of 0.5g/L under circumneutral pH conditions (pH range: 5.7-7.5) using a spent nickel-cobalt-manganese lithium battery sample liberated by N-Methyl pyrrolidone. The results show that the amounts of F ions in solution increased with leaching time, with a maximum value close to 2.34 ppm F obtained after 2 h. It is worth noting that the presence of fluoride-ion can promote the elution of aluminum, as a maximum concentration of 1.85 ppm Al was observed at 2 h in the presence of 40 ppm F, whereas only about 0.32 ppm Al was detected in the case of fluoride-free solutions. Consequently, our results demonstrated that the amounts of transition metals (Ni, Mn, and Co) released towards liquid changed very little irrespective of the concentrations of dissolved fluoride, suggesting that the released F ions do not affect metals elution.

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.