RESUMEN
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.
RESUMEN
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.
RESUMEN
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.
RESUMEN
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.
RESUMEN
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.
RESUMEN
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.
RESUMEN
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.
RESUMEN
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.
RESUMEN
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 1.14â10-5 S cm-1.
RESUMEN
Lithium-sulfur batteries (LSBs) are considered as promising candidates in the next generation of high energy density devices. However, the serious shuttle effect, irreversible dendrite growth of Li metal anode, and the potential safety hazard impede the practical application of LSBs. Herein, a novel homogeneous Janus membrane based on functionalized MOFs crosslinked by aramid nanofibers is designed and synthesized to simultaneously solve the above challenges in quasi-solid-state LSBs. The aramid nanofibers with good mechanical properties and thermal stability act as a homogeneous scaffold to crosslink the MOF particles with different ligands on both sides and this Janus membrane upgrades the stability and safety on both the cathode and anode. Specifically, the amino ligand-decorated MOFs contribute to homogenize Li-ion flux and stabilize the lithium anode, and the sulfonic ligand-decorated MOFs effectively suppress the shuttle effect by the dual effects of chemical adsorption and electrostatic repulsion. The quasi-solid-state LSBs assembled with this homogeneous Janus membrane deliver excellent rate performance and cycling stability. Moreover, it exhibits a high initial capacity of 923.4 mAh g-1 at 1 C at 70 °C, and 697.3 mAh g-1 is retained after 100 cycles, indicating great potential for its application in high-safety LSBs.
RESUMEN
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 imigration. 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 (the longest cycle life reported until now) 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.
RESUMEN
Synaptic transistors require sufficient retention (memory) performances of current signals to exactly mimic biological synapses. Ion migration has been proposed to achieve high retention characteristics but less attention has been paid to polymer-based solid-state electrolytes (SSEs) for organic synaptic transistors (OSTRs). Here, OSTRs with water-processable polymer-based SSEs, featuring ion migration-controllable molecular bridges, which are prepared by reactions of poly(4-styrenesulfonic acid) (PSSA), diethylenetriamine (DETA), and lithium hydroxide (LiOH) are demonstrated. The ion conductivity of PSSA:LiOH:DETA (1:0.4:X, PLiD) films is remarkably changed by the molar ratio (X) of DETA, which is attributed to the extended distances between the PSSA chains by the DETA bridges. The devices with the PLiD layers deliver noticeably changed hysteresis reaching an optimum at X = 0.2, leading to the longest retention of current signals upon single/double pulses. The long-term potentiation test confirms that the present OSTRs can gradually build up the postsynaptic current by gate pulses of -2 V, while the long-term depression can be adjusted by varying the depression gate pulses (≈0.2-1.2 V). The artificial neural network simulations disclose that the present OSTRs with the ion migration-controlled PLiD layers can perform synaptic processes with an accuracy of ≈96%.
RESUMEN
High ionic conductivity solid-state electrolytes are essential for powerful solid-state lithium-ion batteries. With density functional theory andab initiomolecular dynamics simulations, we investigated the crystal structures of Li3YBr6and Li3LaBr6. The lowest energy configurations with uniform distribution of lithium ions were identified. Both materials have wide electrochemical stability windows (ESW): 2.64 V and 2.57 V, respectively. The experimental ESW for Li3YBr6is 2.50 V. Through extrapolating various temperature diffusion results, the conductivity of Li3YBr6was obtained at room temperature, approximately 3.9 mS cm-1, which is comparable to the experimental value 3.3 mS cm-1. Li3LaBr6has a higher conductivity, a 100% increase compared with Li3YBr6. The activation energies of Li3YBr6and Li3LaBr6through the Arrhenius plot are 0.26 eV and 0.24 eV, respectively, which is also close to the experimental value of 0.30 eV for Li3YBr6. This research explored high ionic conductivity halide materials and will contribute to developing solid-state lithium-ion batteries.
RESUMEN
Zinc dendrite, active iodine dissolution, and polyiodide shuttle caused by the strong interaction between liquid electrolyte and solid electrode are the chief culprits for the capacity attenuation of aqueous zinc-iodine batteries (ZIBs). Herein, mullite is adopted as raw material to prepare Zn-based solid-state electrolyte (Zn-ML) for ZIBs through zinc ion exchange strategy. Owing to the merits of low electronic conductivity, low zinc diffusion energy barrier, and strong polyiodide adsorption capability, Zn-ML electrolyte can effectively isolate the redox reactions of zinc anode and AC@I2 cathode, guide the reversible zinc deposition behavior, and inhibit the active iodine dissolution as well as polyiodide shuttle during cycling process. As expected, wide operating voltage window of 2.7 V (vs Zn2+/Zn), high Zn2+ transference number of 0.51, and low activation energy barrier of 29.7 kJ mol-1 can be achieved for the solid-state Zn//Zn cells. Meanwhile, high reversible capacity of 127.4 and 107.6 mAh g-1 can be maintained at 0.5 and 1 A g-1 after 3 000 and 2 100 cycles for the solid-state Zn//AC@I2 batteries, corresponding to high-capacity retention ratio of 85.2% and 80.7%, respectively. This study will inspire the development of mineral-derived solid electrolyte, and facilitate its application in Zn-based secondary batteries.
RESUMEN
This review article delves into the growing field of solid-state batteries as a compelling alternative to conventional lithium-ion batteries. The article surveys ongoing research efforts at renowned Swiss institutions such as ETH Zurich, Empa, Paul Scherrer Institute, and Berner Fachhochschule covering various aspects, from a fundamental understanding of battery interfaces to practical issues of solid-state battery fabrication, their design, and production. The article then outlines the prospects of solid-state batteries, emphasizing the imperative practical challenges that remain to be overcome and highlighting Swiss research groups' efforts and research directions in this field.
RESUMEN
Realizing rechargeable cells with practical energy and power density requires electrodes with high active material loading, a remaining challenge for solid-state batteries. Here, we present a new strategy based on ionogel-derived solid-state electrolytes (SSEs) to form composite electrodes that enable high active material loading (>10 mg/cm2, ~9 mA/cm2 at 1C) in a scalable approach for fabricating Li-ion cells. By tuning the precursor and active materials composition incorporated into the composite lithium titanate electrodes, we achieve near-theoretical capacity utilization at C/5 rates and cells capable of stable cycling at 5.85 mA/cm2 (11.70 A/g) with over 99% average Coulombic efficiency at room temperature. Finally, we demonstrate a complete polymeric solid-state cell with a composite anode and a composite lithium iron phosphate cathode with ionogel SSEs, which is capable of stable cycling at a 1C rate.
RESUMEN
The lack of stable solid-state electrolytes (SSEs) with high-ionic conductivity and rational design of electrode/electrolyte interfaces remains challenging for solid-state lithium batteries. Here, for the first time, a high-performance solid-state lithium-oxygen battery is developed based on the Li-ion-conducted hydrogen-bonded organic framework (LHOF) electrolyte and the core-shell HOF-DAT@CNT cathode with a few layers of HOF-DAT on surface of carbon nanotubes. Benefiting from the abundant dynamic hydrogen bonding network in LHOF-DAT SSEs, fast Li+ ion transport (2.2 × 10-4 S cm-1), a high Li+ transfer number (0.88), and a wide electrochemical window of 5.05 V are achieved. Symmetric batteries constructed with LHOF-DAT SSEs exhibit a stably cycled duration of over 1400 h, which mainly stems from the jumping sites that promote a uniformly high rate of Li+ flux and the hydrogen-bonding network structure that can relieve the structural changes during Li+ transport. LHOF-DAT SSEs-based Li-O2 batteries exhibit high specific capacity (10335 mAh g-1), and stable cycling life up to 150 cycles. Moreover, the solid-state lithium metal battery with LHOF-DAT SSEs endow good rate capability (128.8 mAh g-1 at 1 C), long-term discharge/charge stability (210 cycles). The design of LHOF-DAT SSEs opens an avenue for the development of novel SSEs-based solid-state lithium batteries.
RESUMEN
Parlous structure integrity of the cathode and erratic interfacial microdynamics under high potential take responsibility for the degradation of solid-state lithium metal batteries (LMBs). Here, high-voltage LMBs have been operated by modulating the polymer electrolyte intrinsic structure through an intermediate dielectric constant solvent and further inducing the gradient solid-state electrolyte interphase. Benefiting from the chemical adsorption between trimethyl phosphate (TMP) and the cathode, the gradient interphase rich in LiPFxOy and LiF is induced, thereby ensuring the structural integrity and interface compatibility of the commercial LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode even at the 4.9 V cutoff voltage. Eventually, the specific capacity of NCM811|Li full cell based on TMP-modulated polymer electrolyte increased by 27.7% from 4.5 to 4.9 V. Such a universal screening method of electrolyte solvents and its derived electrode interfacial manipulation strategy opens fresh avenues for quasi-solid-state LMBs with high specific energy.
RESUMEN
Flexible zinc-air batteries are leading power sources for next-generation smart wearable electronics. However, flexible zinc-air batteries suffer from the highly-corrosive safety risk and limited lifespan due to the absence of reliable solid-state electrolytes (SSEs). Herein, a single-anion conductive SSE with high-safety is constructed by incorporating a highly amorphous dual-cation ionomer into a robust hybrid matrix of functional carbon nanotubes and polyacrylamide polymer. The as-fabricated SSE obtains dual-penetrating ionomer-polymer networks and hierarchical ionic highways, which contribute to mechanical robustness with 1200 % stretchability, decent water uptake and retention, and superhigh ion conductivity of 245â mS â cm-1 and good Zn anode reversibility. Remarkably, the flexible solid-state zinc-air batteries delivers a high specific capacity of 764â mAh â g-1 and peak power density of 152â mW â cm-2 as well as sustains excellent cycling stability for 1050 cycles (350â hours). This work offers a new paradigm of OH- conductors and broadens the definition and scope of OH- conductors.
RESUMEN
Solid-state lithium (Li) metal batteries, represent a significant advancement in energy storage technology, offering higher energy densities and enhanced safety over traditional Li-ion batteries. However, solid-state electrolytes (SSEs) face critical challenges such as lower ionic conductivity, poor stability at the electrode-electrolyte interface, and dendrite formation, potentially leading to short circuits and battery failure. The introduction of additives into SSEs has emerged as a transformative approach to address these challenges. A small amount of additives, encompassing a range from inorganic and organic materials to nanostructures, effectively improve ionic conductivity, drawing it nearer to that of their liquid counterparts, and strengthen mechanical properties to prevent cracking of SSEs and maintain stable interfaces. Importantly, they also play a critical role in inhibiting the growth of dendritic Li, thereby enhancing the safety and extending the lifespan of the batteries. In this review, the wide variety of additives that have been investigated, is comprehensively explored, emphasizing how they can be effectively incorporated into SSEs. By dissecting the operational mechanisms of these additives, the review hopes to provide valuable insights that can help researchers in developing more effective SSEs, leading to the creation of more efficient and reliable solid-state Li metal batteries.