Application of Li6.4La3Zr1.45Ta0.5Mo0.05O12/PEO Composite Solid Electrolyte in High-Performance Lithium Batteries.

Replacing the flammable liquid electrolytes with solid ones has been considered to be the most effective way to improve the safety of the lithium batteries. However, the solid electrolytes often suffer from low ionic conductivity and poor rate capability due to their relatively stable molecular/atomic architectures. In this study, we report a composite solid electrolyte, in which polyethylene oxide (PEO) is the matrix and Li6.4La3Zr1.45Ta0.5Mo0.05O12 (LLZTMO) and Li6.4La3Zr1.4Ta0.6O12 (LLZTO) are the fillers. Ta/Mo co-doping can further promote the ion transport capacity in the electrolyte. The synthesized composite electrolytes exhibit high thermal stability (up to 413 °C) and good ionic conductivity (LLZTMO-PEO 2.00 × 10-4 S·cm-1, LLZTO-PEO 1.53 × 10-4 S·cm-1) at 35 °C. Compared with a pure PEO electrolyte, whose ionic conductivity is in the range of 10-7~10-6 S·cm-1, the ionic conductivity of composite solid electrolytes is greatly improved. The full cell assembled with LiFePO4 as the positive electrode exhibits excellent rate performance and good cycling stability, indicating that prepared solid electrolytes have great potential applications in lithium batteries.

Phonon Engineering in Solid Polymer Electrolyte toward High Safety for Solid-State Lithium Batteries.

Extensively-used rechargeable lithium-ion batteries (LIBs) face challenges in achieving high safety and long cycle life. To address such challenges, ultrathin solid polymer electrolyte (SPE) is fabricated with reduced phonon scattering by depositing the composites of ionic-liquid (1-ethyl-3-methylimidazolium dicyamide, EMIM:DCA), polyurethane (PU) and lithium salt on the polyethylene separator. The robust and flexible separator matrix not only reduces the electrolyte thickness and improves the mobility of Li+, but more importantly provides a relatively regular thermal diffusion channel for SPE and reduces the external phonon scattering. Moreover, the introduction of EMIM:DCA successfully breaks the random intermolecular attraction of the PU polymer chain and significantly decreases phonon scattering to enhance the internal thermal conductivity of the polymer. Thus, the thermal conductivity of the as-obtained SPE increases by approximately six times, and the thermal runaway (TR) of the battery is effectively inhibited. This work demonstrates that optimizing thermal safety of the battery by phonon engineering sheds a new light on the design principle for high-safety Li-ion batteries.

Amphiphilic Polymer Electrolyte Blocking Lattice Oxygen Evolution from High-Voltage Nickel-rich Cathodes for Ultra-Thermal Stabile Batteries.

Ni-rich cathodes have been intensively adopted in Li-ion batteries to pursuit high energy density, which still suffering irreversible degradation at high voltage. Some unstable lattice O2- species in Ni-rich cathodes would be oxidized to singlet oxygen 1O2 and released at high volt, which lead to irreversible phase transfer from the layered rhombohedral (R) phase to a spinel-like (S) phase. To overcome the issue, the amphiphilic copolymers (UMA-Fx) electrolyte were prepared by linking hydrophobic C-F side chains with hydrophilic subunits, which could self-assemble on Ni-rich cathode surface and convert to stable cathode-electrolyte interphase layer. Thereafter, the oxygen releasing of polymer coated cathode was obviously depressed and substituted by the Co oxidation (Co3+→Co4+) at high volt (>4.2V), which could suppressed irreversible phase transfer and improve cycling stability. Moreover, the amphiphilic polymer electrolyte was also stable with Li anode and had high ion conductivity. Therefore, the NCM811//UMA-F6//Li pouch cell exhibited outstanding energy density (362.97 Wh/kg) and durability (cycled 200 times at 4.7V), which could be stalely cycled even at 120℃ without short circuits or explosions.

Molecule Crowding Strategy in Polymer Electrolytes Inducing Stable Interfaces for All-Solid-State Lithium Batteries.

All-solid-state lithium batteries with polymer electrolytes suffer from electrolyte decomposition and lithium dendrites because of the unstable electrode/electrolyte interfaces. Herein, a molecule crowding strategy is proposed to modulate the Li+ coordinated structure, thus in situ constructing the stable interfaces. Since 15-crown-5 possesses superior compatibility with polymer and electrostatic repulsion for anion of lithium salt, the anions are forced to crowd into a Li+ coordinated structure to weaken the Li+ coordination with polymer and boost the Li+ transport. The coordinated anions prior decompose to form LiF-rich, thin, and tough interfacial passivation layers for stabilizing the electrode/electrolyte interfaces. Thus, the symmetric Li-Li cell can stably operate over 4360 h, the LiFePO4||Li full battery presents 97.18% capacity retention in 700 cycles at 2 C, and the NCM811||Li full battery possesses the capacity retention of 83.17% after 300 cycles. The assembled pouch cell shows excellent flexibility (stand for folding over 2000 times) and stability (89.42% capacity retention after 400 cycles). This work provides a promising strategy to regulate interfacial chemistry by modulating the ion environment to accommodate the interfacial issues and will inspire more effective approaches to general interface issues for polymer electrolytes.

Fluorine-Doped Li7La3Zr2O12 Fiber-Based Composite Electrolyte for Solid-State Lithium Batteries with Enhanced Electrochemical Performance.

Garnet-based electrolytes with high ionic conductivity and excellent stability against lithium metal anodes are promising for commercial applications in solid-state lithium batteries (SSLBs). However, the further development of SSLBs is inhibited by issues such as low ionic conductivity and uncontrolled lithium dendrite growth. Herein, we report the synthesis of fluorine-doped Li7La3Zr2O12 (LLZO-F0.2) fibers by electrospinning and the subsequent calcination at high temperatures. The solid composite electrolyte with LLZO-F0.2 exhibits an ionic conductivity of 5.37 × 10-4 S cm-1 and a high lithium-ion transference number of 0.61 at room temperature. Meanwhile, it exhibits lower resistance and more uniform lithium metal stripping and deposition in symmetric cells. The full cell with LiFePO4 cathode exhibits excellent rate capability and cycling stability for 800 cycles at 0.5 C with a discharge specific capacity retention of 97.7%. This fluorine-doped fibrous garnet-type electrolyte provides a viable option for preparing high-performance SSLBs.

Operando Study Insights into Lithiation/Delithiation Processes in a Poly(ethylene oxide) Electrolyte of All-Solid-State Lithium Batteries by Grazing-Incidence X-ray Scattering.

Poly(ethylene oxide) (PEO)-based composite electrolytes (PCEs) are considered as promising candidates for next-generation lithium-metal batteries (LMBs) due to their high safety, easy fabrication, and good electrochemical stability. Here, we utilize operando grazing-incidence small-angle and wide-angle X-ray scattering to probe the correlation of electrochemically induced changes and the buried morphology and crystalline structure of the PCE. Results show that the two irreversible reactions, PEO-Li+ reduction and TFSI- decomposition, cause changes in the crystalline structure, array orientation, and morphology of the PCE. In addition, the reversible Li plating/stripping process alters the inner morphology, especially the PEO-LiTFSI domain radius and distance between PEO-LiTFSI domains, rather than causing crystalline structure and orientation changes. This work provides a new path to monitor a working battery in real time and to a detailed understanding of the Li+ diffusion mechanism, which is essential for developing highly transferable and interface-stable PCE-based LMBs.

Formation and Detriments of Residual Alkaline Compounds on High-Nickel Layered Oxide Cathodes.

High-nickel layered oxides LiNixM1-xO2 (x ≥ 0.9) have emerged as promising cathode materials for automotive batteries due to their high energy density and lower cost. However, the formation and accumulation of surface alkaline compounds during storage hinder their mass production and commercialization. Here, a validated chemical method is employed to deconvolute and quantify the evolution of each residual lithium compound in four representative cathodes during ambient-air storage, viz., LiNiO2 (LNO), LiNi0.95Co0.05O2 (NC), LiNi0.95Mn0.05O2 (NM), and LiNi0.95Al0.05O2 (NA). Furthermore, the activation energy of the reaction between water and the cathode is determined by measuring the leached LiOH concentration at various temperatures. While residual lithium and time-of-flight secondary-ion mass spectrometry measurements collectively reveal that the air stability overall follows the trend of NM > NA ≈ NC > LNO, the aged NM exhibits the highest charge-transfer resistance and the worst electrochemical performance among the cathodes. In situ, X-ray diffraction and scanning transmission electron microscopy unveil that the aged NM is plagued by a large area of resistive spinel-like M3-xLixO4 phases, leading to aggravated particle reaction heterogeneity. Finally, a one-step recalcination method is demonstrated effective in fully restoring the degraded cathodes. This work provides insights into overcoming air sensitivity issues of high-Ni cathodes.

Stability of Li1.3Al0.3Ti1.7(PO4)3-Based Composite Electrolytes against Lithium Anodes Enhanced by Uniform Surface Coating of Two-Dimensional Graphene-like C3N4 on Particle Surfaces.

All-solid-state lithium (Li) batteries have attracted considerable interest due to their potential in high energy density as well as safety. However, the realization of a stable Li/solid-state electrolyte (SSE) interface remains challenging. Herein, two-dimensional graphene-like C3N4 (g-C3N4) as a coating layer on Li1.3Al0.3Ti1.7(PO4)3 (LATP) electrolyte (LATP@CN) has been applied to construct the stable Li/SSE interface. The g-C3N4 layer is uniformly coated on the LATP surface using the in situ calcination method, which not only enhances the dispersibility of LATP particles in poly(ethylene oxide) (PEO) through the interaction between surface functional groups but also suppresses the side reactions between Li and LATP. The coating layer can effectively improve the interfacial stability. As a result, the conductivity and stability of the obtained composite solid-state electrolytes (CSEs) against Li are enhanced. The Li∥CSEs∥Li symmetric cells stably cycle for 670 and 600 h at 0.1 and 0.2 mA cm-2, respectively. The Li∥CSEs∥LiFePO4 cells stably cycle more than 100 times at 0.1 and 0.2 C with a capacity retention rate of about 86% and 88%, respectively. This work inspires a new strategy to avoid the reactions between LATP and Li.

In Situ Polymer Gel Electrolyte in Boosting Scalable Fibre Lithium Battery Applications.

The poor interfacial stability not only deteriorates fibre lithium-ion batteries (FLBs) performance but also impacts their scalable applications. To efficiently address these challenges, Prof. Huisheng Peng team proposed a generalized channel structures strategy with optimized in situ polymerization technology in their recent study. The resultant FLBs can be woven into different-sized powering textiles, providing a high energy density output of 128 Wh kg-1 and simultaneously demonstrating good durability even under harsh conditions. Such a promising strategy expands the horizon in developing FLB with particular polymer gel electrolytes, and significantly ever-deepening understanding of the scaled wearable energy textile system toward a sustainable future.

Designing the Interface Layer of Solid Electrolytes for All-Solid-State Lithium Batteries.

Li1.3Al0.3Ti1.7(PO4)3 (LATP) is one of the most attractive solid-state electrolytes (SSEs) for application in all-solid-state lithium batteries (ASSLBs) due to its advantages of high ionic conductivity, air stability and low cost. However, the poor interfacial contact and slow Li-ion migration have greatly limited its practical application. Herein, a composite ion-conducting layer is designed at the Li/LATP interface, which a MoS2 film is constructed on LATP via chemical vapor deposition, followed by the introduction of a solid polymer (SP) liquid precursor to form a MoS2@SP protective layer. This protective layer not only achieves a lower Li-ion migration energy barrier, but also adsorbs more Li-ion, which is able to promote interfacial ion transport and improve interfacial contacts. Thanks to the improved migration and adsorption of Li-ion, the Li symmetric cell containing LATP-MoS2@SP exhibits a stable cycle of more than 1200 h at 0.1 mA cm-2. More remarkably, the capacity retention of the full cell assembled with LiFePO4 cathode is as high as 86.2% after 400 cycles at 1 C. This work provides a design strategy for significantly improving unstable interfaces of SSEs and realizing high-performance ASSLBs.

Reviving Cost-Effective Organic Cathodes in Halide-Based All-Solid-State Lithium Batteries.

The evolution of inorganic solid electrolytes has revolutionized the field of sustainable organic cathode materials, particularly by addressing the dissolution problems in traditional liquid electrolytes. However, current sulfide-based all-solid-state lithium-organic batteries still face challenges such as high working temperatures, high costs, and low voltages. Here, we design an all-solid-state lithium battery based on a cost-effective organic cathode material phenanthrenequinone (PQ) and a halide solid electrolyte Li2ZrCl6. Thanks to the good compatibility between PQ and Li2ZrCl6, the PQ cathode achieved a high specific capacity of 248 mAh g-1 (96 % of the theoretical capacity), a high average discharge voltage of 2.74 V (vs. Li+/Li), and a good capacity retention of 95 % after 100 cycles at room temperature (25 °C). Furthermore, the interactions between the high-voltage carbonyl PQ cathode and both sulfide and halide solid electrolytes, as well as the redox mechanism of the PQ cathode in all-solid-state batteries, were carefully studied by a variety of advanced characterizations. We believe such a design and the corresponding investigations into the underlying chemistry give insights for the further development of practical all-solid-state lithium-organic batteries.

Lithium-Ion Conductive Coatings for Nickel-Rich Cathodes for Lithium-Ion Batteries.

Nickel (Ni)-rich cathodes are among the most promising cathode materials of lithium batteries, ascribed to their high-power density, cost-effectiveness, and eco-friendliness, having extensive applications from portable electronics to electric vehicles and national grids. They can boost the wide implementation of renewable energies and thereby contribute to carbon neutrality and achieving sustainable prosperity in the modern society. Nevertheless, these cathodes suffer from significant technical challenges, leading to poor cycling performance and safety risks. The underlying mechanisms are residual lithium compounds, uncontrolled lithium/nickel cation mixing, severe interface reactions, irreversible phase transition, anisotropic internal stress, and microcracking. Notably, they have become more serious with increasing Ni content and have been impeding the widespread commercial applications of Ni-rich cathodes. Various strategies have been developed to tackle these issues, such as elemental doping, adding electrolyte additives, and surface coating. Surface coating has been a facile and effective route and has been investigated widely among them. Of numerous surface coating materials, have recently emerged as highly attractive options due to their high lithium-ion conductivity. In this review, a thorough and comprehensive review of lithium-ion conductive coatings (LCCs) are made, aimed at probing their underlying mechanisms for improved cell performance and stimulating new research efforts.

Constructing Nano-Interlayer Inhibiting Interfacial Degradation toward High-Voltage PEO-Based All-Solid-State Lithium Batteries.

The interfacial instability between PEO-based solid electrolyte (SPE) and high-voltage cathode materials inhibits the longevity of high-energy-density all-solid-state polymer lithium metal batteries (ASSPLBs). Herein, for the first time it is demonstrated, that contact loss caused by gas generation from interfacial side reactions between the high-voltage cathode and solid polymer electrolyte (SPE) can also arise in ASSPLBs. To alleviate the interfacial side reactions, a LiNb0.6Ti0.5O3 (LNTO) layer is well coated on LiNi0.83Co0.07Mn0.1O2 (NCM83), denoted as (CNCM83). The LNTO layer with low electronic conductivity reduces the decomposition drive force of SPE. Furthermore, Ti and Nb in the LNTO layer spontaneously migrate inside the NCM83 surface to form a strong Ti/Nb─O bond, stalling oxygen evolution in high-voltage cathodes. The interfacial degradation phenomena, including SPE decomposition, detrimental phase transition and intragranular cracks of NCM83, and void formation between cathode and SPE, are effectively mitigated by the LNTO layer. Therefore, the growth rate of interfacial resistance (RCEI) decreases from 37.6 Ω h-0.5 for bare NCM83 to 2.4 Ω h-0.5 for CNCM83 at 4.2 V. Moreover, 4.2 V PEO-based ASSPLBs achieve impressive cyclability with high capacity retention of 135 mAh g-1 (75%) even after 300 cycles at 0.5 C.

In Situ Electrochemical Atomic Force Microscopy: From Interfaces to Interphases.

The electrochemical interface formed between an electrode and an electrolyte significantly affects the rate and mechanism of the electrode reaction through its structure and properties, which vary across the interface. The scope of the interface has been expanded, along with the development of energy electrochemistry, where a solid-electrolyte interphase may form on the electrode and the active materials change properties near the surface region. Developing a comprehensive understanding of electrochemical interfaces and interphases necessitates three-dimensional spatial resolution characterization. Atomic force microscopy (AFM) offers advantages of imaging and long-range force measurements. Here we assess the capabilities of AFM by comparing the force curves of different regimes and various imaging modes for in situ characterizing of electrochemical interfaces and interphases. Selected examples of progress on work related to the structures and processes of electrode surfaces, electrical double layers, and lithium battery systems are subsequently illustrated. Finally, this review provides perspectives on the future development of electrochemical AFM.

Hidden Negative Issues and Possible Solutions for Advancing the Development of High-Energy-Density in Lithium Batteries: A Review.

This review article discusses the hidden or often overlooked negative issues of large-capacity cathodes, high-voltage systems, concentrated electrolytes, and reversible lithium metal electrodes in high-energy-density lithium batteries and provides some feasible solutions that can realize the construction of realistic rechargeable batteries with higher energy densities. Similar objective discussion of the negative aspects of lithium-air batteries, multi-valent shuttles, anion shuttles, sulfur cathode systems, and all-solid ceramic batteries can help fabricate more realistic batteries.

A Functional Air-Stable Li9.8GeP1.7Sb0.3S11.8I0.2 Superionic Conductor for High-Performance All-Solid-State Lithium Batteries.

Solid-state electrolytes (SSEs) based on sulfides have become a subject of great interest due to their superior Li-ion conductivity, low grain boundary resistance, and adequate mechanical strength. However, they grapple with chemical instability toward moisture hypersensitivity, which decreases their ionic conductivity, leading to more processing requirements. Herein, a Li9.8GeP1.7Sb0.3S11.8I0.2 (LGPSSI) superionic conductor is designed with a Li+ conductivity of 6.6 mS cm-1 and superior air stability based on hard and soft acids and bases (HSAB) theory. The introduction of optimal antimony (Sb) and iodine (I) into the Li10GeP2S12 (LGPS) structure facilitates fast Li-ion migration with low activation energy (Ea) of 20.33 kJ mol-1. The higher air stability of LGPSSI is credited to the strategic substitution of soft acid Sb into (Ge/P)S4 tetrahedral sites, examined by Raman and X-ray photoelectron spectroscopy techniques. Relatively lower acidity of Sb compared to phosphorus (P) realizes a stronger Sb-S bond, minimizing the evolution of toxic H2S (0.1728 cm3 g-1), which is ∼3 times lower than pristine LGPS when LGPSSI is exposed to moist air for 120 min. The NCA//Li-In full cell with a LGPSSI superionic conductor delivered the first discharge capacity of 209.1 mAh g-1 with 86.94% Coulombic efficiency at 0.1 mA cm-2. Furthermore, operating at a current density of 0.3 mA cm-2, LiNbO3@NCA/LGPSSI/Li-In cell demonstrated an exceptional reversible capacity of 117.70 mAh g-1, retaining 92.64% of its original capacity over 100 cycles.

In-Situ Construction of Electronically Insulating and Air-Stable Ionic Conductor Layer on Electrolyte Surface and Grain Boundary to Enable High-Performance Garnet-Type Solid-State Batteries.

Lithophobic Li2CO3/LiOH contaminants and high-resistance lithium-deficient phases produced from the exposure of garnet electrolyte to air leads to a decrease in electrolyte ion transfer ability. Additionally, garnet electrolyte grain boundaries (GBs) with narrow bandgap and high electron conductivity are potential channels for current leakage, which accelerate Li dendrites generation, ultimately leading to short-circuiting of all-solid-state batteries (ASSBs). Herein, a stably lithiophilic Li2ZO3 is in situ constructed at garnet electrolyte surface and GBs by interfacial modification with ZrO2 and Li2CO3 (Z+C) co-sintering to eliminate the detrimental contaminants and lithium-deficient phases. The Li2ZO3 formed on the modified electrolyte (LLZTO-(Z+C)) surface effectively improves the interfacial compatibility and air stability of the electrolyte. Li2ZO3 formed at GBs broadens the energy bandgaps of LLZTO-(Z+C) and significantly inhibits lithium dendrite generation. More Li+ transport paths found in LLZTO-Z+C by first-principles calculations increase Li+ conductivity from 1.04×10-4 to 7.45×10-4 S cm-1. Eventually, the Li|LLZTO-(Z+C)|Li symmetric cell maintains stable cycling for over 2000 h at 0.8 mA cm-2. The capacity retention of LiFePO4|LLZTO-(Z+C)|Li battery retains 70.5% after 5800 ultralong cycles at 4 C. This work provides a potential solution to simultaneously enhance the air stability and modulate chemical characteristics of the garnet electrolyte surface and GBs for ASSBs.

Elucidating the Role of Electrochemically Formed LiF in Discharge and Aging of Li-CFx Batteries.

Fifty years after its introduction, the lithium-carbon monofluoride (Li-CFx) battery still has the highest cell-level specific energy demonstrated in a practical cell format. However, few studies have analyzed how the main electrochemical discharge product, LiF, evolves during the discharge and cell rest periods. To fill this gap in understanding, we investigated molecular-level and interfacial changes in CFx electrodes upon the discharge and aging of Li-CFx cells, revealing the role of LiF beyond that of a simple discharge product. We reveal that electrochemically formed LiF deposits on the surface of the CFx electrode and subsequently partially disperses into the electrolyte to form a colloidal suspension during cell aging, as determined from galvanostatic electrochemical impedance spectroscopy (EIS), solid-state 19F nuclear magnetic resonance (NMR), dynamic light scattering (DLS), and operando optical light microscopy measurements. Electrochemical LiF formation and LiF dispersion into the electrolyte are distinct competing rate processes that each affect the cell impedance differently. Using knowledge of LiF dispersion and saturation, an in-line EIS method was developed to compute the depth of discharge of CFx cells beyond coulomb counting. Solid-state 19F NMR measurements quantitatively revealed how LiF and CF moieties evolved with discharge. Covalent CF bonds react first, followed by a combination of covalent and ionic CF bonds. Quantitively correlating NMR and electrochemical measurements reveals not only how LiF formation affects cell impedance but also that CF bonds with the most ionic character remain unreacted, which limits realization of the full theoretical specific capacity of the CFx electrode. The results reveal new insights into the electrochemical discharge mechanism of Li-CFx cells and the unique role of LiF in cell discharge and aging, which suggest pretreatment strategies and methods to improve and measure the performance of Li-CFx batteries.

Wide Temperature Electrolytes for Lithium Batteries: Solvation Chemistry and Interfacial Reactions.

Improving the wide-temperature operation of rechargeable batteries is crucial for boosting the adoption of electric vehicles and further advancing their application scope in harsh environments like deep ocean and space probes. Herein, recent advances in electrolyte solvation chemistry are critically summarized, aiming to address the long-standing challenge of notable energy diminution at sub-zero temperatures and rapid capacity degradation at elevated temperatures (>45°C). This review provides an in-depth analysis of the fundamental mechanisms governing the Li-ion transport process, illustrating how these insights have been effectively harnessed to synergize with high-capacity, high-rate electrodes. Another critical part highlights the interplay between solvation chemistry and interfacial reactions, as well as the stability of the resultant interphases, particularly in batteries employing ultrahigh-nickel layered oxides as cathodes and high-capacity Li/Si materials as anodes. The detailed examination reveals how these factors are pivotal in mitigating the rapid capacity fade, thereby ensuring a long cycle life, superior rate capability, and consistent high-/low-temperature performance. In the latter part, a comprehensive summary of in situ/operational analysis is presented. This holistic approach, encompassing innovative electrolyte design, interphase regulation, and advanced characterization, offers a comprehensive roadmap for advancing battery technology in extreme environmental conditions.

Dry-processed technology for flexible and high-performance FeS2-based all-solid-state lithium batteries at low stack pressure.

All-solid-state lithium batteries (ASSLBs) are considered promising energy storage systems due to their high energy density and inherent safety. However, scalable fabrication of ASSLBs based on transition metal sulfide cathodes through the conventional powder cold-pressing method with ultrahigh stacking pressure remains challenging. This article elucidates a dry process methodology for preparing flexible and high-performance FeS2-based ASSLBs under low stack pressure by utilizing polytetrafluoroethylene (PTFE) binder. In this design, fibrous PTFE interweaves Li6PS5Cl particles and FeS2 cathode components, forming flexible electrolyte and composite cathode membranes. Beneficial to the robust adhesion, the composite cathode and Li6PS5Cl membranes are tightly compacted under a low stacking pressure of 100 MPa which is a fifth of the conventional pressure. Moreover, the electrode/electrolyte interface can sustain adequate contact throughout electrochemical cycling. As expected, the FeS2-based ASSLBs exhibit outstanding rate performance and cyclic stability, contributing a reversible discharged capacity of 370.7 mAh g-1 at 0.3C after 200 cycles. More importantly, the meticulous dQ/dV analysis reveals that the three-dimensional PTFE binder effectively binds the discharge products with sluggish kinetics (Li2S and Fe) to the ion-electron conductive network in the composite cathode, thereby preventing the electrochemical inactivation of products and enhancing electrochemical performance. Furthermore, FeS2-based pouch-type cells are fabricated, demonstrating the potential of PTFE-based dry-process technology to scale up ASSLBs from laboratory-scale mold cells to factory-scale pouch cells. This feasible dry-processed technology provides valuable insights to advance the practical applications of ASSLBs.