Effect of Cr2O3 Coating on LiNi1/3Co1/3Mn1/3O2 as Cathode for Lithium-Ion Batteries

Cr₂O₃ was applied to modify the surface of LiNi_1/3Co_1/3Mn_1/3O₂ cathode material by a novel facile route. X-ray diffraction (XRD), scanning electron microscopy and x-ray photoelectron spectroscopy were used to characterize the structure, shape and composite of the obtained samples. Transmission electron microscope images clearly show that the uniform coating layer thicknesses are about 40 nm and 45 nm for 1 wt.% and 2 wt.% Cr₂O₃, respectively. At the high concentration (3 wt.%), the coating layer becomes heterogeneously distributed. After coating with 1 wt.%, 2 wt.%, and 3 wt.% Cr₂O₃, the initial specific discharge capacities decrease to 159.3 mAh g^?1, 156.4 mAh g^?1, and 152.7 mAh g^?1 at 0.1 C, respectively. Despite an increasing charge transfer resistance for the Cr₂O₃ coating, a better rate capability and cycling ability have been obtained. High temperature-XRD (HT-XRD) data indicate that the thermal stability of the electrode material has also been obviously improved, which is especially helpful for LiNi_1/3Co_1/3Mn_1/3O₂ used as the cathode of lithium power batteries.     

Armoring LiNi1/3Co1/3Mn1/3O2 Cathode with Reliable Fluorinated Organic–Inorganic Hybrid Interphase Layer toward Durable High Rate Battery

Ternary layered oxide materials have attracted extensive attention as a promising cathode candidate for high‐energy‐density lithium‐ion batteries. However, the undesirable electrochemical degradation at the electrode–electrolyte interface definitively shortens the battery service life. An effective and viable approach is proposed for improving the cycling stability of the LiNi_1/3Co_1/3Mn_1/3O₂ cathode using lithium difluorophosphate (LiPO₂F₂) paired with fuoroethylene carbonate (FEC) as co‐additives into conventional electrolytes. It is found that the co‐additives can greatly reduce the interface charge transfer impedance and significantly extend the life span of LiNi_1/3Co_1/3Mn_1/3O₂//Li (NMC//Li) batteries. The developed cathode demonstrates exceptional capacity retention of 88.7% and remains structural integrity at a high current of 5C after 500 cycles. Fundamental mechanism study indicates a dense, stable fluorinated organic–inorganic hybrid cathode‐electrolyte interphase (CEI) film derived from LiPO₂F₂ in conjunction with FEC additives on the surface of NMC cathode material, which significantly suppresses the decomposition of electrolyte and mitigates the dissolution of transition metal ions. The interfacial engineering of the electrode materials stabilized by the additives manipulation provides valuable guidance for the development of advanced cathode materials.     

High‐Voltage LiNi0.45Cr0.1Mn1.45O4 Cathode with Superlong Cycle Performance for Wide Temperature Lithium‐Ion Batteries

Spinel LiNi_0.45Cr_0.1Mn_1.45O₄ synthesized by a scalable solution route combined by high temperature calcination is investigated as cathode for ultralong‐life lithium‐ion batteries in a wide operating temperature range. Scanning electron microscopy reveals homogeneous microsized polyhedral morphology with highly exposed {100} and {111} surfaces. The most highlighted result is that LiNi_0.45Cr_0.1Mn_1.45O₄ has extremely long cycle performance and high capacity retention at various temperatures (0, 25, 50 °C), indicating that Cr doping is a prospective approach to enable 5 V LiNi_0.5Mn_1.5O₄ (LNMO)‐based cathode materials with excellent cycling performances for commercial applications. After 1000 cycles, the capacity retention of LiNi_0.45Cr_0.1Mn_1.45O₄ is 100.30% and 82.75% at 0 °C and 25 °C at 1 C rate, respectively. Notably, over 350 cycles at 50 °C, the capacity retention of LiNi_0.45Cr_0.1Mn_1.45O₄ can maintain up to 91.49% at 1 C. All the values are comparable to pristine LNMO, which can be attributed to the elimination of Li_yNi_1?yO impurity phase, highly exposed {100} surfaces, less Mn³⁺ ions, and enhancement of ion and electron conductivity by Cr doping. Furthermore, an assembled LiNi_0.45Cr_0.1Mn_1.45O₄/Li₄Ti₅O₁₂ full cell delivers an initial discharge capacity of 101 mA h g^?1, meanwhile the capacity retention is 82.07% after 100 cycles.     

Synthesis and Surface Modification of LiCo1/3Ni1/3Mn1/3O2 for Lithium Battery Applications

In an attempt to prepare phase-pure LiCo_1/3Mn_1/3Ni_1/3O₂ compound, the sol–gel method with precursors containing different ratios of lithium and transition-metal ions such as Li:M = 1:1, 1.05:1, 1.10:1, 1.15:1, 1.20:1, and 1.25:1 has been deployed. Properties such as phase purity, perfect layeredness, good cation ordering, and acceptable charge–discharge behavior were observed only when LiCo_1/3Ni_1/3Mn_1/3O₂ was prepared using a Li:M ratio of 1.15:1.0, leading to the recommendation of this as the optimum precursor ratio to prepare active LiCo_1/3Ni_1/3Mn_1/3O₂ cathodes for batteries. Further, with a view to suppress the capacity fade behavior of native LiCo_1/3Mn_1/3Ni_1/3O₂ cathodes observed in high-voltage (4.6 V) regions, selected HF-scavenging metal oxide (Al₂O₃) or metal hydroxide [Al(OH)₃] was deployed as a surface modifier. Interestingly, LiCo_1/3Ni_1/3Mn_1/3O₂ cathode modified with Al(OH)₃ exhibited significantly improved electrochemical properties such as lower charge-transfer resistance (42 Ω), higher specific capacity (158 mAh/g), and excellent capacity retention (99%). This study demonstrates the superiority of Al(OH)₃ over Al₂O₃ in modifying the electrochemical properties of native LiCo_1/3Ni_1/3Mn_1/3O₂ cathodes, as desired for practical lithium battery applications.     

Understanding the Role of Alumina (Al2O3), Pentalithium Aluminate (Li5AlO4), and Pentasodium Aluminate (Na5AlO4) Coatings on the Li and Mn-Rich NCM Cathode Material 0.33Li2MnO3·0.67Li(Ni0.4Co0.2Mn0.4)O2 for Enhanced Electrochemical Performance

The active role of alumina, pentalithium aluminate (Li₅AlO₄, Li-aluminate), and pentasodium aluminate (Na₅AlO₄, Na-aluminate) as the surface protection coatings produced via atomic layer deposition on Li and Mn-rich NCM cathode materials 0.33Li₂MnO₃·0.67LiNi_0.4Co_0.2Mn_0.4O₂ is discussed. A notable improvement in the electrochemical behavior of the coated cathodes has been found while tested in Li-coin cells at 30 °C. Though all the coated cathodes demonstrate enhanced electrochemical cycling and rate performances, Na-aluminate coated cathodes exhibit exemplary behavior. Prolonged cycling and rate capability testing demonstrate that after more than 400 cycles at 1 C rate, the uncoated cathode delivers only 63 mAh g⁻¹, while those with alumina, Li-aluminate, and Na-aluminate coatings exhibit approximately two times higher specific capacities. The coated cathodes display steady average discharge potential and lower evolution of the voltage hysteresis during prolonged cycling compared to the uncoated cathode. Importantly, Na-aluminate coated cathode shows a lowering in gases (O₂, CO₂, H₂, etc.) evolution. Post-cycling analysis of the electrodes demonstrates higher morphological integrity of the coated cathode materials and lower transition metals dissolution from them. The coatings mitigate undesirable side reactions between the electrodes and the electrolyte solution in the cells.     

The Synthesis and Characterization of Cerium Carbonate Hydroxide Nanorods as an Anode for Lithium-Ion Batteries

Nanorods cerium carbonate hydroxide, CeCO₃OH, was synthesized through a low-temperature reaction route. The data of x-ray diffraction and scanning electron microscopy revealed that the as-prepared samples were CeCO₃OH nanorods. The diameters of the nanorods were in the range of 50–100 nm, and the lengths were around 300–500 nm. As an anode of a lithium ion battery, the charge–discharge capacity, cyclability and lithium-ion diffusion kinetics of CeCO₃OH nanorods were investigated. The calculated lithium ion diffusion coefficient was 1.36 × 10^?19 cm² s^?1. The initial discharge capacity was about 621.6 mA h g^?1 at 0.2 mA cm^?2 in 0.05–2.5 V. After 100 cycles, the discharge capacity stabilized at about 362 mA h g^?1 and the Coulombic efficiency was nearly 98%, indicating the potential application in anodes of lithium-ion batteries.     

Uniform and Multifunctional PEI-POSS/Carbon Encapsulation for High-Rate Performance and Surface Stabilization of Nickel-Rich Layered Cathodes in Lithium-Ion Batteries (Adv. Funct. Mater. 45/2023)

Graphene encapsulation is an attractive surface-coating technology that can simultaneously improve the rate capability and cycle stability of nickel-rich LiNi_xCo_yMn_1−x−yO₂ (NCM). Here, carbon encapsulation with the addition of polyethylenimine (PEI) and polyhedral oligomeric silsesquioxane (POSS), which can effectively suppress access to and generation of harmful factors in the electrolyte to maximize the rate performance and cycle stability of nickel-rich NCM, is described. The PEI-POSS/carbon layer not only facilitates electron and lithium-ion transport on the NCM surface but also inhibits side reactions with the electrolyte during repeated electrochemical reactions. In addition, it provides mechanical support that suppresses the formation of microcracks related to anisotropic volume change of nickel-rich NCM secondary particles and inhibits irreversible phase transitions on surface structures by mitigating electrolyte wettability. As a result, PEI-POSS/carbon-encapsulated NCM exhibits a higher rate capability (84 mAh g⁻¹ at 5 C) and cycle stability (93.5% for 100 cycles at 1 C) compared with bare NCM (0 mAh g⁻¹ at 5 C and 78.4% for 100 cycles at 1 C). In a cycle test at 45 °C, it achieves a capacity retention of 72.6% for 100 cycles at 1 C, which is a 323% improvement in performance over that of bare NCM (22.5%).     

A Rational Design for a High-Safety Lithium-Ion Battery Assembled with a Heatproof–Fireproof Bifunctional Separator

High-Ni-content LiNi_xCo_yMn_1−x−yO₂ is regarded as a feasible cathode material to meet the urgent requirement for high energy density batteries. However, such cathode has a poor safety performance because of reactive oxygen releasing at elevated temperatures. In pursuit of high-safety lithium-ion batteries, a heatproof–fireproof bifunctional separator is designed in this study by coating ammonium polyphosphate (APP) particles on a ceramic-coated separator modified with phenol-formaldehyde resin (CCS@PFR). The CCS@PFR separator acts as a thermal-supporting layer to inhibit the shrinkage of the separator at elevated temperatures, whereas the APP-coated layer functions as a fireproof layer, forming a dense polyphosphoric acid (PPA) layer above 300 °C. The PPA layer not only isolates the combustibles from the highly reactive oxygen released from the cathodes but also converts violent combustion reactions into mild stepwise exothermic reactions by carbonizing the combustibles in the batteries. Enabled with such a heatproof–fireproof bifunctional separator, LiNi_0.8Co_0.1Mn_0.1O₂|SiO_x−Gr full cells are constructed and these exhibit an excellent safety performance by not catching fire during a 30 s combustion test and surviving the 10 min high-temperature test above 300 °C. Additionally, an adiabatic rate calorimeter and nail penetration test are conducted with 3 Ah LiNi_0.8Co_0.1Mn_0.1O₂|SiO_x−Gr pouch cells to further verify the safety performance.     

Liberating the Electrolyte via In Situ Conversion of an Amide,Sulfonate-Containing Monomer Precursor for High-Temperature Graphite/NCM Batteries

High-temperature (HT) operation and storage performance of Li-ion batteries (LIBs) are essential for applications in electric vehicles, grid storage, or defense missions. Unfortunately, severe capacity fading is witnessed due to growing instability of the electrode/electrolyte interphase at HT. Herein, the study liberates the electrolyte from the task of film-formation. Instead, it takes advantage of the favorable solid-electrolyte interphase (SEI)-forming functional groups by priorly anchoring them on graphite surface. Specifically, via molecular design, unsaturated CC bond, together with amide and sulfonate groups, are concurrently involved, namely the lithium-2-acrylamido-2-methyl-1-propanesulfonate (Li-AMPS). Upon electrochemical cycle, the unsaturated CC bond in Li-AMPS turns into a radical that induces polymerization between CC bonds to construct a polymeric network. The presence of amide and sulfonate groups endows the SEI with nitrogen, sulfur-based reduction products OSO₂Li and Li₃N, etc. As such, the designed interphase makes the use of propylene carbonate-based electrolyte possible. By assembling full cells with the modified graphite and LiNi_0.5Co_0.2Mn_0.3O₂ (cathode loading of ≈18.5 mg cm⁻²), the capacity retention of the full cell has increased from 53.2% (with pristine graphite) to 77.8% after 300 cycles under 60 °C. A 2 Ah, 265 Wh kg⁻¹ pouch cell is also able to operate for 200 cycles at an extreme temperature of 80 °C with the modified graphite.     

Intercalated Electrolyte with High Transference Number for Dendrite‐Free Solid‐State Lithium Batteries

Solid‐state lithium (Li) batteries using solid electrolytes and Li anodes are highly desirable because of their high energy densities and intrinsic safety. However, low ambient‐temperature conductivity and poor interface compatibility of solid electrolytes as well as Li dendrite formation cause large polarization and poor cycling stability. Herein, a high transference number intercalated composite solid electrolyte (CSE) is prepared by the combination of a solution‐casting and hot‐pressing method using layered lithium montmorillonite, poly(ethylene carbonate), lithium bis(fluorosulfonyl)imide, high‐voltage fluoroethylene carbonate additive, and poly(tetrafluoroethylene) binder. The electrolyte presents high ionic conductivity (3.5 × 10^?4 S cm^?1), a wide electrochemical window (4.6 V vs Li⁺/Li), and high ionic transference number (0.83) at 25 °C. In addition, a 3D Li anode is also fabricated via a facile thermal infusion strategy. The synergistic effect of high transference number intercalated electrolyte and 3D Li anode is more favorable to suppress Li dendrites in a working battery. The solid‐state batteries based on LiFePO₄ (Al₂O₃ @ LiNi_0.5Co_0.2Mn_0.3O₂), CSE, and 3D Li deliver admirable cycling stability with discharge capacity 145.9 mAh g^?1 (150.7 mAh g^?1) and capacity retention 91.9% after 200 cycles at 0.5 C (92.0% after 100 cycles at 0.2 C) at 25 °C. This work affords a splendid strategy for high‐performance solid‐state battery.     

Kinetic Control of Long-Range Cationic Ordering in the Synthesis of Layered Ni-Rich Oxides

Deciphering the sophisticated interplay between thermodynamics and kinetics of high-temperature lithiation reaction is fundamentally significant for designing and preparing cathode materials. Here, the formation pathway of Ni-rich layered ordered LiNi_0.6Co_0.2Mn_0.2O₂ (O-LNCM622O) is carefully characterized using in situ synchrotron radiation diffraction. A fast nonequilibrium phase transition from the reactants to a metastable disordered Li_1−x(Ni_0.6Co_0.2Mn_0.2)_1+xO₂ (D-LNCM622O, 0 < x < 0.95) takes place while lithium/oxygen is incorporated during heating before the generation of the equilibrium phase (O-LNCM622O). The time evolution of the lattice parameters for layered nonstoichiometric D-LNCM622O is well-fitted to a model of first-order disorder-to-order transition. The long-range cation disordering parameter, Li/TM (TM = Ni, Co, Mn) ion exchange, decreases exponentially and finally reaches a steady-state as a function of heating time at selected temperatures. The dominant kinetic pathways revealed here will be instrumental in achieving high-performance cathode materials. Importantly, the O-LNCM622O tends to form the D-LNCM622O with Li/O loss above 850 °C. In situ XRD results exhibit that the long-range cationic (dis)ordering in the Ni-rich cathodes could affect the structural evolution during cycling and thus their electrochemical properties. These insights may open a new avenue for the kinetic control of the synthesis of advanced electrode materials.     

Effects of Synthesis and Spark Plasma Sintering Conditions on the Thermoelectric Properties of Ca3Co4O9+δ

Ca₃Co₄O_9+δ samples were synthesized by solid-state (SS) and sol–gel (SG) reactions, followed by spark plasma sintering under different processing conditions. The synthesis process was optimized and the resulting materials characterized with respect to their microstructure, bulk density, and thermoelectric transport properties. High power factors of about 400 μW/m·K² and 465 μW/m·K² (at 800°C) were measured for SS and SG samples, respectively. The improved thermoelectric performance of the SG sample is believed to originate from the smaller particle sizes and better grain alignment. The SG method is suggested to be a beneficial means of obtaining high-performance thermoelectric materials of Ca₃Co₄O_9+δ type.     

Effects of Ta2O5/Y2O3 Codoping on the Microstructure and Microwave Dielectric Properties of Ba(Co0.56Zn0.40)1/3Nb2/3O3 Ceramics

The effects of Ta₂O₅/Y₂O₃ codoping on the microstructure and microwave dielectric properties of Ba(Co_0.56Zn_0.40)_1/3Nb_2/3O₃-xA-xB (A = 0.045 wt.% Ta₂O₅; B = 0.113 wt.% Y₂O₃) ceramics (x = 0, 1, 2, 4, 8, 16, 32) prepared according to the conventional solid-state reaction technique were investigated. The x-ray diffraction (XRD) results showed that the main crystal phase in the sintered ceramics was BaZn_0.33Nb_0.67O₃-Ba₃CoNb₂O₉. The additional surface phase of Ba₈CoNb₆O₂₄ and trace amounts of Ba₅Nb₄O₁₅ second phase were present when Ta₂O₅/Y₂O₃ was added to the ceramics. The 1:2 B-site cation ordering was affected by the substitution of Ta⁵⁺ and Y³⁺ in the crystal lattice, especially for x = 4. Scanning electron microscopy (SEM) images of the optimally doped ceramics sintered at 1340°C for 20 h showed a compact microstructure with crystal grains in dense contact. Though the dielectric constant increased with the x value, appropriate addition would result in a tremendous modification of the Q × f and τ _f values. Excellent microwave dielectric properties (ε _r = 35.4, Q × f = 62,993 GHz, and τ _f  = 2.6 ppm/°C) were obtained for the ceramic with x = 0.4 sintered in air at 1340°C for 20 h.     

Achieving Thermodynamic Stability of Single-Crystal Co-Free Ni-Rich Cathode Material for High Voltage Lithium-Ion Batteries

Ni-rich layered cathode materials are progressively considered as the standard configuration of high-energy electric vehicles by virtues of their high capacity and eliminated “range anxiety.” However, the poor cyclic stability and severe cobalt supply crisis would restrain their wide commercial applicability. Here, a cost-effective single-crystal Co-free Ni-rich cathode material LiNi_0.8Mn_0.18Fe_0.02O₂ (NMF), which outperforms widely commercial polycrystalline LiNi_0.83Co_0.11Mn_0.06O₂ (MNCM) and single-crystal LiNi_0.83Co_0.11Mn_0.06O₂ (SNCM) is reported. Surprisingly, NMF can compensate for the reversible capacity loss under the designed conditions of high-temperature and elevated-voltage, achieving a competitive energy density compared with conventional MNCM or SNCM. Combining operando characterizations and density functional theory calculation, it is revealed that NMF cathode with improved dynamic structure evolution largely alleviates the mechanical strain issue commonly found in Ni-rich cathode, which can reduce the formation of intragranular cracks and improve the safety performance. Consequently, this new Co-free NMF cathode can achieve a perfect equilibrium between material cost and electrochemical performance, which not only reduces the production cost by >15%, but also demonstrates excellent thermal stability and cycling performance..     

水热法制备CoxMn1-xFe2O4纳米磁性粉体及磁性研究

用水热法成功合成了CoxMn1-xFe2O4纳米磁性颗粒粉体。样品物相用X射线衍射仪表征,形貌通过透射电镜(TEM)观测。CoxMn1-xFe2O4纳米粉体的平均尺寸和晶格常数从XRD计算得到,CoxMn1-xFe2O4纳米颗粒的晶格常数随着Co2+含量的增加而变小。所得样品的磁性用振动样品磁强计(VSM)测试,结果表明,所制备的CoxMn1-xFe2O4粉体在室温下的铁磁性、饱和磁化强度和矫顽力随着Co2+含量的增加而变大。     

The Unique Structural Evolution of the O3‐Phase Na2/3Fe2/3Mn1/3O2 during High Rate Charge/Discharge: A Sodium‐Centred Perspective

The development of new insertion electrodes in sodium‐ion batteries requires an in‐depth understanding of the relationship between electrochemical performance and the structural evolution during cycling. To date in situ synchrotron X‐ray and neutron diffraction methods appear to be the only probes of in situ electrode evolution at high rates, a critical condition for battery development. Here, the structural evolution of the recently synthesized O3‐phase of Na_2/3Fe_2/3Mn_1/3O₂ is reported under relatively high current rates. The evolution of the phases, their lattice parameters, and phase fractions, and the sodium content in the crystal structure as a function of the charge/discharge process are shown. It is found that the O3‐phase persists throughout the charge/discharge cycle but undergoes a series of two‐phase and solid‐solution transitions subtly modifying the sodium content and atomic positions but keeping the overall space‐group symmetry (structural motif). In addition, for the first time, evidence of a structurally characterized region is shown that undergoes two‐phase and solid‐solution phase transitions simultaneously. The Mn/Fe–O bond lengths, c lattice parameter evolution, and the distance between the Mn/FeO₆ layers are shown to concertedly change in a favorable manner for Na⁺ insertion/extraction. The exceptional electrochemical performance of this electrode can be related in part to the electrode maintaining the O3‐phase throughout the charge/discharge process.     

Flexible Films Derived from Electrospun Carbon Nanofibers Incorporated with Co3O4 Hollow Nanoparticles as Self‐Supported Electrodes for Electrochemical Capacitors

Flexible porous films are prepared from electrospun carbon nanofibers (CNFs) embedded with Co₃O₄ hollow nanoparticles (NPs) and are directly applied as self‐supported electrodes for high‐performance electrochemical capacitors. Uniform Co₃O₄ hollow NPs are well dispersed and/or embedded into each CNF with desirable electrical conductivity. These Co₃O₄‐CNFs intercross each other and form 3D hierarchical porous hybrid films. Benefiting from intriguing structural features, the unique binder‐free Co₃O₄ hollow NPs/CNF hybrid film electrodes exhibit high specific capacitance (SC), excellent rate capability and cycling stability. As an example, the flexible hybrid film with loading of 35.9 wt% Co₃O₄ delivers a SC of 556 F g^?1 at a current density of 1 A g^?1, and 403 F g^?1 even at a very high current density of 12 A g^?1. Remarkably, almost no decay in SC is found after continuous charge/discharge cycling for 2000 cycles at 4 A g^?1. This exceptional electrochemical performance makes such novel self‐supported Co₃O₄‐CNFs hybrid films attractive for high‐performance electrochemical capacitors.     

Elastic Interfacial Layer Enabled the High-Temperature Performance of Lithium-Ion Batteries via Utilization of Synthetic Fluorosulfate Additive

The key to producing high-energy Li-ion cells is ensuring the interfacial stability of Si-containing anodes and Ni-rich cathodes. Herein, 4-(allyloxy)phenyl fluorosulfate (APFS), a multi-functional electrolyte additive that forms a mechanical strain-adaptive solid electrolyte interphase (SEI) comprising LiF and polymeric species, and a thermally stable cathode–electrolyte interface containing S O and S F species. The radical copolymerization of vinylene carbonate (VC) with APFS via electrochemical initiation creates a spatially deformable polymeric SEI on the SiG-C (30 wt.% graphite + 70 wt.% SiC composite) anode, with large volume changes during cycling. Moreover, the APFS-promoted interfacial layers reduce Ni dissolution and deposition. Furthermore, APFS deactivates the Lewis acid PF₅, thereby inhibiting hydrolyses that produce unwanted HF. These results indicate that the combined use of VC with APFS allows capacity retentions of 72.5% with a high capacity of 143.5 mAh g⁻¹ in SiG-C/LiNi_0.8Co_0.1Mn_0.1O₂ full cells after 300 cycles at 45 °C.     

High-Performance All-Solid-State Batteries Enabled by Intimate Interfacial Contact Between the Cathode and Sulfide-Based Solid Electrolytes

All-solid-state batteries (ASSBs) are considered the ultimate next-generation rechargeable batteries due to their high safety and energy density. However, poor Li-ion kinetics caused by the inhomogeneous distribution of the solid electrolytes (SEs) and complex chemo-mechanical behaviors lead to poor electrochemical properties. In this study, LiNi_0.8Co_0.1Mn_0.1O₂ (NCM) (core) – Li₆PS₅Cl (LPSCl) SEs (shell) particles (NCM@LPSCl) are prepared by a facile mechano-fusion method to improve the electrochemical properties and increase the energy density of ASSBs. The conformally coated thin SEs layer on the surface of NCM enables homogeneous distribution of SEs in overall electrode and intimate physical contact with cathode material even under volume change of cathode material during cycling, which leads to the improvement in Li-ion kinetics without the increase in solid electrolyte content. As a result, an ASSBs employing NCM@LPSCl with 4 mAh cm⁻¹ specific areal capacity exhibits robust electrochemical properties, including the improved reversible capacity (163.1 mAh g⁻¹), cycle performance (90.0% after 100 cycles), and rate capability (discharge capacity of 152.69, 133.80, and 100.97 mAh g⁻¹ at 0.1, 0.2, and 0.5 C). Notably, ASSBs employing NCM@LPSCl composite show reliable electrochemical properties with a high weight fraction of NCM (87.3 wt%) in the cathode.