Batteries & Supercaps最新文献

Li-CO₂ batteries offer a revolutionary energy storage solution, combining high specific energy with the utilization of greenhouse CO₂. Although promising for applications on Earth and Mars, the limited cycle life and significant overpotentials from stable discharge products, Li₂CO₃ and amorphous carbon, hinder the practicalization of Li-CO₂ batteries. To address these, a unique freestanding core-shell metal–organic framework-derived heterojunction catalyst, Fe₃O₄/Co₃O₄, embedded in electrospun nitrogen-doped carbon nanofibers for the Li-CO_2Mars batteries, is designed. It eliminates the need for insulating binders, toxic solvents and ensures uniformly distributed composite catalysts across the nanofibers. The electrochemical performance of Fe₃O₄/Co₃O₄/N-doped carbon fiber (FCo/NCF)-based Li-CO_2Mars coin cells operated in the simulated Mars’ atmosphere achieves a cycling life of 120 cycles at a current density of 50 μA cm⁻², with a limited discharge/charge capacity of 0.1 mAh cm⁻², and delivers a full discharge capacity of 6.8 mAh cm⁻² outperforming the conventional catalysts. In situ and first-principle studies demonstrate that enhanced CO₂ adsorption and improved reversibility, driven by the bifunctional catalytic activity of FCo/NCF, lead to exceptional electrochemical performance of Li-CO_2Mars batteries. A prototype of Li-CO_2Mars pouch cell is also developed, operating with an average efficiency of ≈68%, advancing the scalable development of Li-CO_2Mars batteries for diverse applications.

During fast charging, metallic lithium can form on the negative graphite electrode, compromising both cycle life and safety. After deposition, plated lithium can re-intercalate within graphite, be disconnected or chemically oxidized. To better understand these reactions and their kinetics, operando measurements on cells with electrochemical performances close to commercial ones are essential. Herein, a dedicated pouch-cell design is developed to follow the dynamic of lithium using ⁷Li nuclear magnetic resonance (NMR) spectroscopy. These developments provide ⁷Li NMR spectra every 6 min leading to a good temporal resolution. The dynamics of lithium is investigated for various charging scenarios and temperatures within NMC 811/graphite pouch cells with industry-standard electrodes. Introduction of an original method allows assessing the mass of plated lithium formed in operando mode, offering insights on the competition between graphite lithiation, plating, and reintercalation processes. Interestingly, the lithium deposition occurs mainly during the constant-current step and early stage of the constant-voltage (CV) step, and lithium reintercalation, oxidation, or disconnection during the subsequent CV hold, highlighting the interest of reducing the current during fast-charge scenario. Comparison with three-electrode monolayer pouch cells provides an onset of plating located between −100 and –150 mV versus Li.

Efficient mass transport is critical for tubular flow battery performance and for its eventual scale-up; yet the influence of design parameters like electrode fiber filling density, internal membrane volume, and electrode structure remains largely unexplored. Herein, a tubular all-vanadium flow battery with a fibrous 4 mg cm⁻¹ electrode filling density and a 0.238 cm internal diameter (ID) membrane is fed with dilute vanadium electrolyte at varying flow rates, and its mass transfer coefficient is calculated. The filling densities are increased to 8 and 16 mg cm⁻¹, where the 4 mg cm⁻¹ shows the highest mass transfer coefficient, 2.64 × 10⁻⁶ cm s⁻¹. Decreasing the internal membrane diameter to 0.144 and 0.116 cm while restraining the 4 mg cm⁻¹ filling density reveals the 0.238 cm diameter results in the largest mass transfer coefficient. Comparing a solid electrode to the 4 mg cm⁻¹, 0.238 cm ID electrode, the solid electrode reports the highest mass transfer coefficient, 2.56 × 10⁻⁵ cm s⁻¹. These findings surprisingly demonstrate that fibrous electrodes, despite their higher total surface area, do not inherently lead to improved mass transfer performance in tubular flow batteries, rather, it is the amount of available surface area and the uniformity in electrolyte flow, seen in the solid graphite electrode, that is critical for mass transfer.

Manganese-based Prussian blue analog (MnPBA) shows great potential as a high energy density and low-cost cathode material for sodium-ion batteries (SIBs) due to its electrochemical activity, high redox potential, low-cost raw materials, and facile synthesis. However, its practical application is severely challenged by the high water content (>10 wt%) in the framework and the Jahn–Teller effect from high-spin Mn³⁺, leading to poor reversibility and rapid capacity decay during cycling. Herein, Cu-substituted MnPBA samples (CuMnPBAs) are successfully synthesized under high-concentration chelation conditions, which reduced the water content and alleviated the Jahn–Teller effect from Mn³⁺. Accordingly, the optimal 25% Cu-substituted MnPBA (CuMnPBA-25) exhibits a significantly reduced water content of 7.6% and excellent cyclability, maintaining 81.2 mAh g⁻¹ at 1 C after 700 cycles. Furthermore, the CuMnPBA-25/hard carbon (HC) pouch cell exhibits superb capacity retention of 80.9% after 280 cycles. This research provides new insights into the development of highly stable PBAs for practical applications in SIBs.

Lithium-ion batteries (LIBs) have drawn significant attention in the electric vehicle industry, and activated carbon-based anodes are widely recognized as a cost-effective alternative to conventional anode materials. However, the application of these anode materials is significantly limited by the formation of an unstable solid–electrolyte interface (SEI). This study introduces nutmeg shell waste-derived activated carbon (ACNM) as a viable anode material for LIBs with a particular focus on the role of SEI in determining their electrochemical behavior and battery performance. The hierarchical pore structure in ACNM is achieved through systematic optimization of synthesis parameters, ensuring a balance between surface area and the stability of the SEI. The combination of micropores and mesopores in ACNM effectively minimizes extensive SEI formation and associated capacity loss. The potential of ACNM for LIB anode applications is validated by fabricating anode half cells that exhibit a maximum specific capacity of 610 mAh g⁻¹. The half cells also show good cycling performance with significant rate capability. Using scanning electrochemical microscopy, the local electrochemical activity and formation of the SEI layer are investigated. This study highlights the suitability of ACNM for anode applications in LIBs and the importance of SEI engineering for next-generation LIBs.

Garnet-type Li_6.4La₃Zr_1.4Ta_0.6O₁₂ solid-state electrolytes (SSEs) have attracted considerable attention for solid-state lithium metal batteries (SSLMBs) due to their high ionic conductivity, wide electrochemical window, and excellent stability towards lithium. However, poor interfacial contact hinders charge transport and increases impedance. Herein, introducing only 1.0 wt% BiBr₃ into molten lithium at 280 °C in situ forms a mixed ion–electronic conductor (MIEC) of Li₃Bi and LiBr, significantly enhancing wettability. Thanks to its uniqueness, the modified symmetric cell achieves a remarkably low interfacial resistance (15.7 Ω cm²) compared to pristine lithium (1280.3 Ω cm²). Furthermore, lithiophilic Li₃Bi with high ionic conductivity improves the interfacial adhesion and regulates the Li nucleation. Meanwhile, the lithiophobic LiBr, with high interfacial energy against Li, enables effective suppression of the growth of Li dendrites by promoting the lateral growth of deposited Li metal. Therefore, it achieves a high critical current density (1.4 mA cm⁻²) and stable cycling over 1100 h, at 0.1 mA cm⁻² at room temperature. When paired with a LiFePO₄ cathode, the cell retains 91.6% of its initial capacity after 300 cycles at 0.5 C, demonstrating excellent cycling stability. These findings suggest that the incorporation of 1.0 wt% BiBr₃ effectively constructs a superlithiophilic interface on garnet electrolyte, offering a simple and effective strategy for high-performance SSLMBs.

There has been growing interest in aqueous batteries, which are considered safer and more cost-effective compared to Li-ion batteries. Among them, aqueous Sn-ion batteries have emerged as promising alternatives because of their high specific capacity and wide voltage window. Despite these numerous advantages, in aqueous-based electrolytes, significant variations in metal growth behavior with temperature lead to severe performance degradation, necessitating a fundamental investigation into the underlying mechanisms to develop high-performance aqueous batteries capable of operating across a wide temperature range. Therefore, this study for the first time examines the temperature-dependent Sn metal plating and stripping behavior in aqueous Sn-ion batteries. The results indicate that, at low temperatures, uneven pits are formed during stripping, leading to a rough and nonuniform surface. These pits serve as nucleation sites for deposition during plating, further exacerbating surface irregularities. In contrast, at high temperatures, stripping occurs uniformly along the grain boundaries and grain surfaces, resulting in a smooth and homogeneous surface. Similarly, plating under high-temperature conditions leads to uniform Sn deposition. In contrast, the corrosion tests reveal that pits form on the electrode surface under high-temperature conditions, leading to deterioration. These findings are expected to contribute to the development of high-performance aqueous Sn-ion batteries.

All-solid-state batteries (ASSBs) with sulfide electrolytes are promising for next-generation battery systems owing to their superior safety and favorable electrochemical properties. However, interfacial instability between the oxide cathode and sulfide electrolyte induces undesirable side reactions, degrading cell performance. This study develops a sulfurized LiNbO₃ coating to stabilize this interface. While conventional LiNbO₃ coatings reduce interfacial side reactions, their limited compatibility with sulfide electrolytes, due to Li-ion chemical potential differences, hinders ion transport. The sulfurized LiNbO₃ coating improves compatibility, acting as a buffer that reduces the Li-ion potential gradient and enhances interfacial conductivity. The coating effectively suppresses side reactions, lowering cathode degradation and interfacial resistance. A simple and cost-effective sulfur treatment process is used, where sulfur sublimation at 300 °C forms a sulfurized outer layer on the coating. Electrochemical evaluations of the coating reveal significant capacity, rate capability, and cyclic performance improvements over conventional LiNbO₃ coatings. These findings underscore sulfur treatment as an effective method for stabilizing interfaces and enabling smooth Li-ion transport, highlighting the advantages of the sulfurized LiNbO₃ coating method. Overall, sulfurized LiNbO₃ coatings offer scalable solutions to interfacial challenges in sulfide-based ASSBs, thereby promoting improved performance and commercialization of solid-state battery systems.

In this study, conductive, fluorine and antimony codoped tin oxide nanoparticles (FATO-NPs) are highlighted as a possible alternative for conductive carbon additives in fluoride ion batteries, successfully circumventing oxidative side reactions. Since good cyclability with high and stable discharge capacities is achieved with both types of conductive additive at a high stack pressure of 180 MPa, it is concluded that conductive carbon is well-suited for high-voltage fluoride ion batteries, contrary to prior assumptions. However, FATO-NP-based cathodes outperform those based on conductive carbon at lower stack pressures of 50 MPa, emphasizing the importance of avoiding carbon fluorination at low stack pressures.

Li–CO₂/O₂ batteries hold tremendous promises for energy storage and conversion systems, attributed to their high theoretical energy density and economic viability. Nevertheless, their widespread application is hindered by high overpotential and compromised cycling stability. Herein, ruthenium (Ru)-doped copper-based metal organic frameworks (HKUST) octahedral particles (Ru@HKUST) are synthesized as the cathode catalyst for Li–CO₂/O₂ batteries. The Ru@HKUST matrix rich in free channels provides unimpeded gas permeation and substantial adsorption spaces for CO₂/O₂. A synergistic interaction between HKUST and Ru significantly enhances the kinetic conversion of Li₂CO₃ upon cycles, thereby markedly boosting the capacity and extending the cycle life of Li–CO₂/O₂ batteries. A high discharge capacity of 19 437 mAh g⁻¹ is achieved at 2 V cutoff voltage in the Li–CO₂/O₂ cell with Ru@HKUST under a constant current density of 200 mA g⁻¹. The cells exhibit a superior catalytic efficiency with reduced charge plateaus of 4.1 V for over 100 cycles at a fixed capacity of 1000 mAh g⁻¹, demonstrating excellent electrochemical properties and paving the way for advanced battery technology.