Single-ion-conducted covalent organic framework serving as Li-ion pump in polyethylene oxide-based electrolyte for robust solid-state Li-S batteries.

Poly(ethylene oxide) (PEO)-based electrolytes are widely used for building solid-state lithium-sulfur (Li-S) batteries but suffer from poor lithium-ion (Li+) transportation kinetics. Here, a lithium-sulfonated covalent organic framework (TpPa-SO3Li) was synthesized and functionalized as a Li+ pump in a PEO-based solid-state electrolyte to fabricate robust Li-S batteries. The designed TpPa-SO3, Li with its porous skeleton and abundant lithium sulfonate groups not only provided iontransport channels but also enhanced the fast migration of Li+. The PEO composite electrolyte containing 5 %-TpPa-SO3Li exhibited a notable ionic conductivity of 6.28 × 10-4 S cm-1 and an impressive Li+ transference number of 0.78 at 60 °C. As a result, Li-Li symmetric batteries with the optimized PEO/TpPa-SO3Li composite electrolyte stably cycled for 300 h, with a minimal overpotential of only 100 mV at 0.5 mA cm-2. Moreover, the customized solid-state Li-S batteries based on PEO/TpPa-SO3Li were stable for 600 cycles at 60 oC with a high Coulombic efficiency of approximately 98 %. This study provides a promising strategy for introducing covalent-organic-framework (COF)-based Li+ pumps to build robust solid-state Li-S batteries.

Phase-Transition-Promoted Interfacial Anchoring of Sulfide Solid Electrolyte Membranes for High-Performance All-Solid-State Lithium Battery.

Solvent-free manufacturing is crucial for fabricating high-performance sulfide-electrolyte-based all-solid-state lithium batteries (ASSLBs), with advantages including side reaction inhibition, less contamination, and practical scalability. However, the fabricated sulfide electrolytes commonly suffer from brittleness, limited ion transport, and unsatisfactory interfacial stability due to the uncontrolled dispersion of the sulfide particles within the polymer binder matrix. Herein, a "solid-to-liquid" phase transition strategy is reported to fabricate flexible Li6PS5Cl (LPSCl) electrolytes. The polycaprolactone (PCL)-based binder (PLI) with phase-transition characteristics fills the gap of LPSCl particles and tightly grafts on the particle surface via ion-dipole interaction, bringing a thin and compact electrolyte membrane (80 µm). The simultaneously high Li-ion conducting and electron insulating nature of PLI binder facilitates Li-ion transport and ensures good interfacial stability between electrolyte and anode. Consequently, the sulfide electrolyte membrane exhibits high ionic conductivity (8.5 × 10-4 S cm-1), enabling symmetric and full cells with 10 and 2.5 times longer cycling life compared with that of the cells with pristine LPSCl electrolyte, respectively. The demonstrated strategy is versatile and can be extended to ethylene vinyl acetate copolymer (EVA) that also brings enhanced electrochemical performance. The thin sulfide electrolyte with high interfacial stability potentially facilitates dendrite-free ASSLBs with high energy density.

In Situ Formation of Stable Dual-Layer Solid Electrolyte Interphase for Enhanced Stability and Cycle Life in All-Solid-State Lithium Metal Batteries.

All-solid-state lithium metal batteries have emerged as a promising solution to overcoming the energy density and safety challenges associated with conventional lithium-ion batteries. Solid polymer electrolytes, particularly those based on poly(vinylidene fluoride) (PVDF) and dimethylformamide (DMF), demonstrate significant potential. However, interfacial side reactions between residual DMF solvents and lithium metal present substantial challenges. In this study, we investigate the in situ formation of solid electrolyte interphase protective layers to mitigate these side reactions. By incorporating F-rich additives, such as fluoroethylene carbonate and lithium difluorophosphate, we successfully establish a dual-layer inorganic SEI structure characterized by an outer LiF layer and an inner Li2O layer. Consequently, our approach extends the cycle life of lithium symmetric batteries to 3000 h. Additionally, the Li||LiFePO4 solid-state battery demonstrates exceptional stability, enduring 400 cycles at a 1C rate with an impressive capacity retention of 84%. This strategic methodology effectively leverages the benefits of residual solvents, ensuring both enhanced battery efficiency and long-term operational stability for PVDF-based all-solid-state lithium metal batteries.

A Self-Healing, Flowable, Yet Solid Electrolyte Suppresses Li-Metal Morphological Instabilities.

Lithium metal (Li0) solid-state batteries encounter implementation challenges due to dendrite formation, side reactions, and movement of the electrode-electrolyte interface in cycling. Notably, voids and cracks formed during battery fabrication/operation are hot spots for failure. Here, a self-healing, flowable yet solid electrolyte composed of mobile ceramic crystals embedded in a reconfigurable polymer network is reported. This electrolyte can auto-repair voids and cracks through a two-step self-healing process that occurs at a fast rate of 5.6 µm h-1. A dynamical phase diagram is generated, showing the material can switch between liquid and solid forms in response to external strain rates. The flowability of the electrolyte allows it to accommodate the electrode volume change during Li0 stripping. Simultaneously, the electrolyte maintains a solid form with high tensile strength (0.28 MPa), facilitating the regulation of mossy Li0 deposition. The chemistries and kinetics are studied by operando synchrotron X-ray and in situ transmission electron microscopy (TEM). Solid-state NMR reveals a dual-phase ion conduction pathway and rapid Li+ diffusion through the stable polymer-ceramic interphase. This designed electrolyte exhibits extended cycling life in Li0-Li0 cells, reaching 12 000 h at 0.2 mA cm-2 and 5000 h at 0.5 mA cm-2. Furthermore, owing to its high critical current density of 9 mA cm-2, the Li0-LiNi0.8Mn0.1Co0.1O2 (NMC811) full cell demonstrates stable cycling at 5 mA cm-2 for 1100 cycles, retaining 88% of its capacity, even under near-zero stack pressure conditions.

Exploring Chemical and Electrochemical Limitations in Sulfide Solid State Electrolytes: A Critical Review on Current Status and Manufacturing Scope.

Lithium-ion batteries (LIBs) have gained recognition for their high energy density and cost-effectiveness. However, issues such as safety concerns, dendrite formation, and limited operational temperatures necessitate alternative solutions. A promising approach involves replacing flammable liquid electrolytes with non-flammable solid electrolytes (SEs). SEs represent a transformative shift in battery technology, offering stability, safety, and expanded temperature ranges. They effectively mitigate dendrite growth, enhancing battery reliability and lifespan. SEs also improve energy density, making them crucial for applications like portable gadgets, electric vehicles, and renewable energy storage. However, challenges such as ionic conductivity, chemical and thermal stability, mechanical strength, and manufacturability must be addressed. This review paper briefly identifies SE types, discusses their advantages and disadvantages, and explores ion transport fundamentals and all-solid-state batteries (ASSBs) production challenges. It comprehensively analyzes sulfide SEs (SSEs), focusing on recent advancements, chemical and electrochemical challenges, and potential future improvements. Electrochemical reactions, electrolyte materials, compositions, and cell designs are critically assessed for their impact on battery performance. The review also addresses challenges in ASSB production. The objective is to provide a comprehensive understanding of SSEs, laying the groundwork for advancing sustainable and efficient energy storage systems.

Porous Organic Cage-Based Quasi-Solid-State Electrolyte with Cavity-Induced Anion-Trapping Effect for Long-Life Lithium Metal Batteries.

Porous organic cages (POCs) with permanent porosity and excellent host-guest property hold great potentials in regulating ion transport behavior, yet their feasibility as solid-state electrolytes has never been testified in a practical battery. Herein, we design and fabricate a quasi-solid-state electrolyte (QSSE) based on a POC to enable the stable operation of Li-metal batteries (LMBs). Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC, the resulting POC-based QSSE exhibits a high Li+ transference number of 0.67 and a high ionic conductivity of 1.25 × 10-4 S cm-1 with a low activation energy of 0.17 eV. These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h. As a proof of concept, the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85% capacity retention after 1000 cycles. Therefore, our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems, such as Na and K batteries.

High Configuration Entropy Promises Electrochemical Stability of Chloride Electrolytes for High-Energy, Long-Life All-Solid-State Batteries.

Solid-state electrolytes (SSEs) with high ionic conductivity, stability, and interface compatibility are indispensable for high-energy-density and long-life all-solid-state batteries (ASSBs), yet there are scarce SSEs with sufficient ionic conductivity and electrochemical stability. In this study, with a high-entropy SSE (HE-SSE, Li2.9In0.75Zr0.1Sc0.05Er0.05Y0.05Cl6), we show the high configuration entropy has a thermodynamically positive relationship with the high-voltage stability. As a result, the ASSBs with HE-SSE and high-voltage cathode materials exhibit superior high-voltage and long-cycle stability, achieving 250 cycles with 81.4% capacity retention when charged to 4.8 V (vs. Li+/Li), and even 5000 cycles if charged to 4.6 V (vs. Li+/Li).  Experimental characterizations and density functional theory calculations confirm that the HE-SSE greatly suppresses the high-voltage degradation of SSE at the interface, promoting the high-voltage stability coordinately through high entropy and interface stability. The high entropy design offers a general strategy to simultaneously improve the high-voltage stability and ionic conductivity of SSEs, creating an avenue to building high-energy and long-life ASSBs.

Molecular Engineering of Poly(Ionic Liquid) for Direct and Continuous Production of Pure Formic Acid from Flue Gas.

Electrochemical CO2 reduction reaction (CO2RR) offers a promising approach to close the carbon cycle and reduce reliance on fossil fuels. However, traditional decoupled CO2RR processes involve energy-intensive CO2 capture, conversion, and product separation, which increases operational costs. Here, we report the development of a bismuth-poly(ionic liquid) (Bi-PIL) hybrid catalyst that exhibits exceptional electrocatalytic performance for CO2 conversion to formate. The Bi-PIL catalyst achieves over 90% Faradaic efficiency for formate over a wide potential range, even at low 15% v/v CO2 concentrations typical of industrial flue gas. The biphenyl in PIL backbone affords hydrophobicity while maintaining high ionic conductivity, effectively mitigating the flooding issues. The PIL layer plays a crucial role as a CO2 concentrator and co-catalyst that accelerates the CO2RR kinetics. Furthermore, we demonstrate the potential of Bi-PIL catalysts in a solid-state electrolyte (SSE) electrolyzer for the continuous and direct production of pure formic acid solutions from flue gas. Techno-economic analysis suggests that this integrated process can produce formic acid at a significantly reduced cost compared to the traditional decoupled approaches. This work presents a promising strategy to overcome the challenges associated with low-concentration CO2 utilization and streamline the production of valuable liquid fuels and chemicals from CO2.

Transient Phase-Mediated Li+ Transportation in the Lithium Lanthanum Titanate Solid-State Electrolyte.

The lithium lanthanum titanium oxide (LLTO) perovskite is one type of superior lithium (Li)-ion conductor that is of great interest as a solid-state electrolyte for all-solid-state lithium batteries. Structural defects and impurity phases formed during the synthesis of LLTO largely affect its Li-ion conductivity, yet the underlying Li+ diffusion mechanism at the atomic scale is still under scrutiny. Herein, we use aberration-corrected transmission electron microscopy to perform a thorough structural characterization of the LLTO ceramic pellet. We reveal a prevalent transient phase transition of (La, Ti)2O3 existing at the antiphase boundaries between single-crystalline LLTO domains. This transient phase exhibits a specific crystal orientation with the LLTO phase and shows a gradual structural transition to a tetragonal LLTO structure, which enables detailed crystallographic analysis to correlate their formation to the sintering process of LLTO powders into ceramic pellets. We also find that Li diffusion is retarded by this phase and correlated with the excess amount of La, which is corroborated by the theoretical evaluation of the atomistic mechanisms of Li diffusion across this phase.

Oriented Crystal Growth of Li0.33La0.557TiO3 Nanowire Induced by One-Dimensional Polymer Sheath toward Rapid Lithium-Ion Transfer.

Superionic conductor-based solid-state electrolytes with preferred crystal structures hold great promise for realizing ultrafast lithium-ion (Li+) transfer, which is urgently desired for all-solid-state lithium batteries. However, the precise control of crystal growth of superionic conductors is still challenging since the crystals always spontaneously grow to disordered structures with the lowest internal energy to ensure thermodynamic stability. Herein, a coaxial nanowire with a polyvinylpyrrolidone (PVP) sheath and a Li0.33La0.557TiO3 (LLTO) precursor core (PVP/LLTO-caNW) is prepared through coaxial electrospinning, followed by sintering into LLTO nanowire with an oriented crystal structure (LLTO-caNW). We demonstrate that the one-dimensional PVP sheath as a sacrificial layer generates uniform and the strongest adsorption ability on the (110) phase among different LLTO crystal planes, which induces the crystal to preferentially grow along the c-axis (the fastest Li+ transfer direction) during the nucleation and growth processes. As a result, the prepared LLTO-caNW displays an ultrahigh bulk ionic conductivity of 3.13 × 10-3 S cm-1, exceeding most LLTO crystals and approaching the theoretical conductivity. Meanwhile, the oriented crystal growth imparts to LLTO-caNW significantly reduced grain boundary resistance, and the grain-boundary conductivity reaches up to 1.09 × 10-3 S cm-1. This endows the composite solid electrolyte with high ionic conduction performance and superior cycle stability in the assembled all-solid-state lithium battery.

Dual Ionic Pathways in Semi-Solid Electrolyte based on Binary Metal-Organic Frameworks Enable Stable Operation of Li-Metal Batteries at Extremely High Temperatures.

The rapid development of the electronics market necessitates energy storage devices characterized by high energy density and capacity, alongside the ability to maintain stable and safe operation under harsh conditions, particularly elevated temperatures. In this study, a semi-solid-state electrolyte (SSSE) for Li-metal batteries (LMB) is synthesized by integrating metal-organic frameworks (MOFs) as host materials featuring a hierarchical pore structure. A trace amount of liquid electrolyte (LE) is entrapped within these pores through electrochemical activation. These findings demonstrate that this structure exhibits outstanding properties, including remarkably high thermal stability, an extended electrochemical window (5.25 V vs Li/Li+), and robust lithium-ion conductivity (2.04 × 10-4 S cm-1), owing to the synergistic effect of the hierarchical MOF pores facilitating the storage and transport of Li ions. The Li//LiFePO4 cell incorporating prepared SSSE shows excellent capacity retention, retaining 97% (162.8 mAh g-1) of their initial capacity after 100 cycles at 1 C rate at an extremely high temperature of 95 °C. It is believed that this study not only advances the understanding of ion transport in MOF-based SSSE but also significantly contributes to the development of LMB capable of stable and safe operation even under extremely high temperatures.

Synergistic Enhancement of Biaxial Stretching and Multilayer Composites in All-Solid-State Polymer Electrolytes.

As an important component of lithium-ion batteries, all-solid-state electrolytes should possess high ionic conductivity, excellent flexibility, and relatively high mechanical strength. All-solid-state polymer electrolytes (ASSPEs) based on polymers seem to be able to meet these requirements. However, pure ASSPEs have relatively low ionic conductivity, and the addition of inorganic fillers such as lithium salts will reduce their flexibility and mechanical strength. To address the above issues, in this paper, the solvent-free method was used to prepare a poly(vinylidenefluoride-co-hexafluoropropylene)/lithium bis(trifluoromethanesulfonyl) imide/poly(ethylene oxide) all-solid-state polymer electrolyte, which was then subjected to 4 × 4 magnification synchronous bidirectional stretching. Subsequently, it was multilayered with PEO-based composite polymer electrolytes to obtain multilayered composite polymer electrolytes (MCPEs). Bidirectional stretching provides superior in-plane and out-of-plane mechanical properties to MCPEs by inducing molecular chain orientation, which suppresses the growth of lithium dendrites. Concurrently, it facilitates the formation of the ß-crystal form of PVDF-HFP, thereby weakening the ion solvation effect and reducing the lithium-ion migration energy barrier. Multilayered compounding improves the interfacial contact between MCPEs and electrodes, thereby reducing the interfacial impedance. Experiments have demonstrated that the MCPEs prepared in this paper exhibit high ionic conductivity at room temperature (1.83 × 10-4 S cm-1), low interfacial resistance (547 Ω cm-2), excellent mechanical properties (26 MPa), and excellent cycling rate performance (a capacity retention rate of 90% after 110 cycles at 0.1 C), which can meet the performance requirements of lithium-ion batteries for ASSPEs.

Simultaneous Inhibition of Vanadium Dissolution and Zinc Dendrites by Mineral-Derived Solid-State Electrolyte for High-Performance Zinc Metal Batteries.

Designing solid electrolyte is deemed as an effective approach to suppress the side reaction of zinc anode and active material dissolution of cathodes in liquid electrolytes for zinc metal batteries (ZMBs). Herein, kaolin is comprehensively investigated as raw material to prepare solid electrolyte (KL-Zn) for ZMBs. As demonstrated, KL-Zn electrolyte is an excellent electronic insulator and zinc ionic conductor, which presents wide voltage window of 2.73 V, high ionic conductivity of 5.08 mS cm-1, and high Zn2+ transference number of 0.79. For the Zn//Zn cells, superior cyclic stability lasting for 2200 h can be achieved at 0.2 mA cm-2. For the Zn//NH4V4O10 batteries, stable capacity of 245.8 mAh g-1 can be maintained at 0.2 A g-1 after 200 cycles along with high retention ratio of 81 %, manifesting KL-Zn electrolyte contributes to stabilize the crystal structure of NH4V4O10 cathode. These satisfying performances can be attributed to the enlarged interlayer spacing, zinc (de)solvation-free mechanism and fast diffusion kinetics of KL-Zn electrolyte, availably guaranteeing uniform zinc deposition for zinc anode and reversible zinc (de)intercalation for NH4V4O10 cathode. Additionally, this work also verifies the application possibility of KL-Zn electrolyte for Zn//MnO2 batteries and Zn//I2 batteries, suggesting the universality of mineral-based solid electrolyte.

Ion Transport at Polymer-Argyrodite Interfaces.

Solid-state electrolytes, particularly polymer/ceramic composite electrolytes, are emerging as promising candidates for lithium-ion batteries due to their high ionic conductivity and mechanical flexibility. The interfaces that arise between the inorganic and organic materials in these composites play a crucial role in ion transport mechanisms. While lithium ions are proposed to diffuse across or parallel to the interface, few studies have directly examined the quantitative impact of these pathways on ion transport and little is known about how they affect the overall conductivity. Here, we present an atomistic study of lithium-ion (Li+) transport across well-defined polymer-argyrodite interfaces. We present a force field for polymer-argyrodite interfacial systems, and we carry out molecular dynamics and enhanced sampling simulations of several composite systems, including poly(ethylene oxide) (PEO)/Li6PS5Cl, hydrogenated nitrile butadiene rubber (HNBR)/Li6PS5Cl, and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)/Li6PS5Cl. For the materials considered here, Li-ion exhibits a preference for the ceramic material, as revealed by free energy differences for Li-ion between the inorganic and the organic polymer phase in excess of 13 kBT. The relative free energy profiles of Li-ion for different polymeric materials exhibit similar shapes, but their magnitude depends on the strength of interaction between the polymers and Li-ion: the greater the interaction between the polymer and Li-ions, the smaller the free energy difference between the inorganic and organic materials. The influence of the interface is felt over a range of approximately 1.5 nm, after which the behavior of Li-ion in the polymer is comparable to that in the bulk. Near the interface, Li-ion transport primarily occurs parallel to the interfacial plane, and ion mobility is considerably slower near the interface itself, consistent with the reduced segmental mobility of the polymer in the vicinity of the ceramic material. These findings provide insights into ionic complexation and transport mechanisms in composite systems, and will help improve design of improved solid electrolyte systems.

Cross-Linked Composite Solid Polymer Electrolyte Doped with Li6.4La3Zr1.4Ta0.6O12 for High Voltage Lithium Metal Batteries.

Composite solid polymer electrolytes (CSPEs) are safer alternatives to liquid electrolytes and excellent candidates for high-voltage solid-state batteries. However, interfacial instabilities between the electrodes and CSPEs are one of the bottlenecks in pursuing these systems. In this study, a cross-linked CSPE was synthesized based on polypropylene carbonate, polyethylene glycol methyl ether acrylate, polyethylene glycol diacrylate with additives including lithium bis(trifluoromethane)sulfonimide salt, and tantalum-doped lithium lanthanum zirconium oxide (LLZTO). Mass fractions of 10, 20, and 40% LLZTO were added to the CSPE matrix. In a symmetric cell, lithium plating and stripping revealed that the interface between the lithium metal anode and CSPE with 10% of the LLZTO (CSPE-10LLZTO) shows the most stable interface. The CSPE-10LLZTO sample demonstrated high flexibility and showed no degradation over 800 h of cycling at varying current densities. The ionic conductivity for the CSPE-10LLZTO sample at 40 °C was 6.4 × 10-4 S/cm. An all-solid-state full cell was fabricated with LiNi0.5Mn0.3Co0.2O2 as the cathode, CSPE-10LLZTO as the electrolyte and separator, and Li metal as the anode, delivering approximately 140 mAh/g of capacity. Differential scanning calorimetry measurements on CSPE-xLLZTO showed high miscibility and the elimination of crystallinity. Raman spectroscopy revealed uniformity in the structure. These findings demonstrate the capability of the CSPEs to develop high-voltage solid-state lithium metal batteries.

Design and Conformation of Separators for High-performance Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) are considered promising candidates for large-scale energy storage due to their high safety, low cost, and environmental friendliness. As a core component, separator plays a unique yet oftentimes overlooked role in providing electrochemical stability in AZIBs. This concept focuses on the exquisite structure-property relationship of separators, highlighting three forms of these components and their structural design requirements, i. e., traditional membranes, solid-state electrolytes, and electrode coatings. The mechanism by which separators influence the zinc anode and the cathode is discussed. The article also identifies the challenges and potential future directions for functional separators in the development of high-performance AZIBs.

Designing Cooperative Ion Transport Pathway in Ultra-Thin Solid-State Electrolytes toward Practical Lithium Metal Batteries.

Solid polymer electrolytes (SPEs) are promising for high-energy-density solid-state Li metal batteries due to their decent flexibility, safety, and interfacial stability. However, their development was seriously hindered by the interfacial instability and limited conductivity, leading to inferior electrochemical performance. Herein, we proposed to design ultra-thin solid-state electrolyte with long-range cooperative ion transport pathway to effectively increase the ionic conductivity and stability. The impregnation of PVDF-HFP inside pores of fluorinated covalent organic framework (CF3-COF) can disrupt its symmetry, rendering rapid ion transportation and inhibited anion immigration. The functional groups of CF3-COF can interact with PVDF-HFP to form fast Li+ transport channels, which enables the uniform and confined Li+ conduction within the electrolyte. The introduction of CF3-COF also enhances the mechanical strength and flexibility of SPEs, as well as ensures homogeneous Li deposition and inhibited dendrite growth. Hence, a remarkably high conductivity of 1.21×10-3 S cm-1 can be achieved. Finally, the ultra-thin SPEs with an extremely long cycle life exceed 9000 h can be obtained while the NCM523/Li pouch cell demonstrates a high capacity of 760 mAh and 96 % capacity retention after cycling, holding great promises to be utilized for practical solid-state Li metal batteries.

Missing-Linker Defect Functionalized Metal-Organic Frameworks Accelerating Zinc Ion Conduction for Ultrastable All-Solid-State Zinc Metal Batteries.

Solid-state polymer electrolytes (SPEs) are promising for high-performance zinc metal batteries (ZMBs), but they encounter critical challenges of low ionic conductivity, limited Zn2+ transference number (tZn2+), and an unstable electrolyte-electrode interface. Here, we present an effective approach involving a missing-linker metallic organic framework (MOF)-catalyzed poly(ethylene glycol) diacrylate (PEGDA)/polyacrylamide (PAM) copolymer SPE for single Zn2+ conduction and seamless electrolyte-electrode contact. The single-Zn2+ conduction is facilitated by the anchoring of the OTF- anions onto the unsaturated metal sites of missing-linker MOF, while the PEGDA and PAM chains in competitive coordination with Zn2+ ions promote rapid Zn ion transport. Our all-solid-state electrolyte simultaneously achieves a superior ionic conductivity of 1.52 mS cm-1 and a high tZn2+ of 0.83 at room temperature, alongside uniform Zn metal deposition (1000 cycles in symmetric cells) and high Zn plating/striping efficiencies (>99% after 600 cycles in asymmetric cells). Applications of our SPE in Zn//VO2 full cells are further demonstrated with a long lifespan of 2000 cycles and an extremely low-capacity degradation rate of 0.012% per cycle. This work provides an effective strategy for using a missing-linker MOF to catalyze competitively coordinating copolymers for accelerating Zn2+ ion conduction, assisting the future design of all-solid-state ZMBs.

Long-Life All-Solid-State Batteries Enabled by Cold-Pressed Garnet Composite Electrolytes with Enhanced Li+ Conduction.

Garnet Li7La3Zr2O12 (LLZO)-based solid-state electrolytes (SSEs) hold promise for realizing next-generation lithium metal batteries with high energy density. However, the high stiffness of high-temperature sintered LLZO makes it brittle and susceptible to strain during the fabrication of solid-state batteries. Cold-pressed LLZO exhibits improved ductility but suffers from insufficient Li+ conductivity. Here, we report cold-pressed Ta-doped LLZO (Ta-LZ) particles integrated with ductile Li6PS5Cl (LPSC) via a Li+ conductive Li-containing Ta-Cl structure. This configuration creates a continuous Li+ conduction network by enhancing the Li+ exchange at the Ta-LZ/LPSC interface. The resulting Ta-LZ/LPSC SSE exhibits Li+ conductivity of 4.42 × 10-4 S cm-1 and a low activation energy of 0.31 eV. Li symmetric cells with Ta-LZ/LPSC SSE demonstrate excellent Li dendrite suppression ability, with an improved critical current density of 5.0 mA cm-2 and a prolonged cycle life exceeding 600 h at 1 mA cm-2. Our finding provides valuable insights into developing cold-pressed ceramic powder electrolytes for high-performance all-solid-state batteries.

Spray-Flame Synthesis of NASICON-Type Rhombohedral (α) Li1+xYxZr2-x(PO4)3 [x = 0-0.2] Solid Electrolytes.

Since solid electrolytes have a broad electrochemical stability window, are exceptionally electrochemically stable against Li metal, and function as a physical separator to prevent dendrite growth, they are at the forefront of alternate possibilities, further increasing the stability and energy density of Li-ion batteries. NASICON-type electrolytes are a promising candidate due to their negligible moisture sensitivity, which results in outstanding stability and a lower probability of Li2CO3 passivity under the ambient atmosphere. However, one of the most promising representatives, Li1+xYxZr2-x(PO4)3 (LYZP), has multiple stable phases with significant variation in their corresponding Li-ion conductivity. In this paper, we have successfully synthesized the highly ionically conductive rhombohedral phase of LYZP via spray-flame synthesis. Two different solvent mixtures (e.g., 2-ethyl hexanoic acid/ethanol, propanol/propanoic acid) were chosen to explore the effect of precursor composition and combustion enthalpy on the phase composition of the nanoparticle. The as-synthesized nanoparticles from spray-flame synthesis consisted of the crystalline tetragonal zirconia (t-ZrO2) phase, while lithium, yttrium, and phosphate were present on the nanoparticles' surface as amorphous phases. However, a short annealing step (1 h) was sufficient to obtain the NASICON phase. Moreover, we have shown the gradual phase conversion from orthorhombic ß phase to rhombohedral α phase as the annealing temperature increased from 700 °C to 1300 °C (complete removal of ß phase). In this context, Y3+ doping was also crucial, along with the appropriate solvent mixture and annealing temperature, for obtaining the much-desired rhombohedral α phase. Further, 0.2 at% Y3+ doping was added to the solvent mixture of 2-ethyl hexanoic acid/ethanol, and annealing at 1300 °C for 1 h resulted in a high ionic conductivity of 1.14∙10-5 S cm-1.