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Iron-based hexacyanoferrate (Fe-HCF) are promising cathode materials for sodium-ion batteries (SIBs) due to their unique open-channel structure that facilitates fast ion transport and framework stability. However, practical implementation of SIBs has been hindered by low initial Coulombic efficiency (ICE), poor rate performance, and short lifespan. Herein, we report a coordination engineering to synthesize sodium-rich Fe-HCF as cathodes for SIBs through a uniquely designed 10-kg-scale chemical reactor. Our study systematically investigated the relationship between coordination surroundings and the electrochemical behavior. Building on this understanding, the cathode delivered a reversible capacity of 99.3 mAh g-1 at 5 C (1 C = 100 mA g-1), exceptional rate capability (51 mAh g-1 even at 100 C), long lifespan (over 15,000 times at 50 C), and a high ICE of 92.7%. A full cell comprising the Fe-HCF cathode and hard carbon (HC) anode exhibited an impressive cyclic stability with a high-capacity retention rate of 98.3% over 1,000 cycles. Meanwhile, this material can be readily scaled to the practical levels of yield. The findings underscore the potential of Fe-HCF as cathodes for SIBs and highlight the significance of controlling nucleation and morphology through coordination engineering for a sustainable energy storage system.
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Low-concentration ether electrolytes cannot efficiently achieve oxidation resistance and excellent interface behavior, resulting in severe electrolyte decomposition at a high voltage and ineffective electrode-electrolyte interphase. Herein, we utilize sandwich structure-like gel polymer electrolyte (GPE) to enhance the high voltage stability of potassium-ion batteries (PIBs). The GPE contact layer facilitates stable electrode-electrolyte interphase formation, and the GPE transport layer maintains good ionic transport, which enabled GPE to exhibit a wide electrochemical window and excellent electrochemical performance. In addition, Al corrosion under a high voltage is suppressed through the restriction of solvent molecules. Consequently, when using the designed GPE (based on 1 m), the K||graphite cell exhibits excellent cycling stability of 450 cycles with a capacity retention of 91%, and the K||FeFe-Prussian blue cell (2-4.2 V) delivers a high average Coulombic efficiency of 99.9% over 2200 cycles at 100 mA g-1. This study provides a promising path in the application of ether-based electrolytes in high-voltage and long-lasting PIBs.
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Biomass-derived materials generally exhibit uniform and highly-stable hierarchical porous structures that can hardly be achieved by conventional chemical synthesis and artificial design. When used as electrodes for rechargeable batteries, these structural and compositional advantages often endow the batteries with superior electrochemical performances. This review systematically introduces the innate merits of biomass-derived materials and their applications as the electrode for advanced rechargeable batteries, including lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, and metal-sulfur batteries. In addition, biomass-derived materials as catalyst supports for metal-air batteries, fuel cells, and redox-flow batteries are also included. The major challenges for specific batteries and the strategies for utilizing biomass-derived materials are detailly introduced. Finally, the future development of biomass-derived materials for advanced rechargeable batteries is prospected. This review aims to promote the development of biomass-derived materials in the field of energy storage and provides effective suggestions for building advanced rechargeable batteries.
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Today, rechargeable batteries are omnipresent and essential for our existence. In order to improve the electrochemical performance of electric fields, the introduction of electrolytes with fluorine (F)-based inorganic elemental compositions is a direction of exploration. However, most fluorocarbons have a high global warming potential and ozone depletion potential, which do not meet the sustainability requirements of the battery industry. Therefore, developing sustainable electrolytes is a viable option for future battery development. Although researchers have made much progress in electrolyte optimization, little attention has been paid to developing low-toxic and safe electrolytes. This review aims to elucidate the design principles and recent advances in this direction for solvents and salts. It concludes with a summary and outlook on future research directions for the molecular design of green electrolytes for practical high-voltage rechargeable batteries.
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Current potassium-ion batteries (PIBs) are limited in safety and lifetime owing to the lack of suitable electrolyte solutions. To address these issues, herein, we report an innovative non-flammable electrolyte design strategy that leverages an optimal moderate solvation phosphate-based solvent which strikes a balance between solvation capability and salt dissociation ability, leading to superior electrochemical performance. The formulated electrolyte simultaneously exhibits the advantages of low salt concentration (only 0.6â M), low viscosity, high ionic conductivity, high oxidative stability, and safety. Our electrolyte also promotes the formation of self-limiting inorganic-rich interphases at the anode surface, alongside robust cathode-electrolyte interphase on iron-based Prussian blue analogues, mitigating electrode/electrolyte side reactions and preventing Fe dissolution. Notably, the PIBs employing our electrolyte exhibit exceptional durability, with 80 % capacity retention after 2,000â cycles at high-voltage of 4.2â V in a coin cell. Impressively, in a larger scale pouch cell, it maintains over 81 % of its initial capacity after 1,400â cycles at 1â C-rate with high average Coulombic efficiency of 99.6 %. This work represents a significant advancement toward the realization of safe, sustainable, and high-performance PIBs.
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Ether-based electrolyte is beneficial to obtaining good low-temperature performance and high ionic conductivity in potassium ion batteries. However, the dilute ether-based electrolytes usually result in ion-solvent co-intercalation of graphite, poor cycling stability, and hard to withstand high voltage cathodes above 4.0â V. To address the aforementioned issues, an electron-withdrawing group (chloro-substitution) was introduced to regulate the solid-electrolyte interphase (SEI) and enhance the oxidative stability of ether-based electrolytes. The dilute (~0.91â M) chloro-functionalized ether-based electrolyte not only facilitates the formation of homogeneous dual halides-based SEI, but also effectively suppress aluminum corrosion at high voltage. Using this functionalized electrolyte, the K||graphite cell exhibits a stability of 700â cycles, the K||Prussian blue (PB) cell (4.3â V) delivers a stability of 500â cycles, and the PB||graphite full-cell reveals a long stability of 6000â cycles with a high average Coulombic efficiency of 99.98 %. Additionally, the PB||graphite full-cell can operate under a wide temperature range from -5 °C to 45 °C. This work highlights the positive impact of electrolyte functionalization on the electrochemical performance, providing a bright future of ether-based electrolytes application for long-lasting, wide-temperature, and high Coulombic efficiency PIBs and beyond.
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Aqueous rechargeable zinc-ion batteries (ARZBs) are impeded by the mutual problems of unstable cathode, electrolyte parasitic reactions, and dendritic growth of zinc (Zn) anode. Herein, a triple-functional strategy by introducing the tetramethylene sulfone (TMS) to form a hydrated eutectic electrolyte is reported to ameliorate these issues. The activity of H2 O is inhibited by reconstructing hydrogen bonds due to the strong interaction between TMS and H2 O. Meanwhile, the preferentially adsorbed TMS on the Zn surface increases the thickness of double electric layer (EDL) structure, which provides a shielding buffer layer to suppress dendrite growth. Interestingly, TMS modulates the primary solvation shell of Zn2+ ultimately to achieve a novel solvent co-intercalation ((Zn-TMS)2+ ) mechanism, and the intercalated TMS works as a "pillar" that provides more zincophilic sites and stabilizes the structure of cathode (NH4 V4 O10 , (NVO)). Consequently, the Zn||NVO battery exhibits a remarkably high specific capacity of 515.6â mAh g-1 at a low current density of 0.2â A g-1 for over 40â days. This multi-functional electrolytes and solvent co-intercalation mechanism will significantly propel the practical development of aqueous batteries.
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The rampant dendrites and hydrogen evolution reaction (HER) resulting from the turbulent interfacial evolution at the anode/electrolyte are the main culprits of short lifespan and low Coulombic efficiency of Zn metal batteries. In this work, a versatile protective coating with excellent zincophilic and amphoteric features is constructed on the surface of Zn metal (ZP@Zn) as dendrite-free anodes. This kind of protective coating possesses the advantages of reversible proton storage and rapid desolvation kinetics, thereby mitigating the HER and facilitating homogeneous nucleation concomitantly. Furthermore, the space charge polarization effect promotes charge redistribution to achieve uniform Zn deposition. Accordingly, the ZP@Zn symmetric cell manifests excellent reversibility at an ultrahigh cumulative plating capacity of 4700â mAh cm-2 and stable cycling at 80 % depth of discharge (DOD). The ZP@Zn//V6 O13 pouch cell also reveals superior cycling stability with a high capacity of 326.6â mAh g-1 .
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Recharging batteries operate at sub-zero temperature is usually limited by the slow ion diffusion and uneven charge distribution at low temperature. Here, we report a strategy to regulate electric field and thermal field simultaneously, creating a fast and uniform deposition surroundings for potassium ion in potassium metal batteries (PMBs). This regulation is achieved by using a highly ordered 1D nanoarray electrode which provides a dense and flat surface for uniforming the electric field and high thermal conductivity for reducing the temperature fluctuation. Consequently, this electrode could achieve high-areal capacity of 10â mAh cm-2 . Besides, the dependence of potassium nucleation on temperature is unveiled. Furthermore, a full-cell could steady operate with over 80 % of its room-temperature capacity at -20 °C. Those respectable performances demonstrate that this strategy is valid, potentially providing guidelines for the rational design of advanced electrodes toward PMBs.
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Ether-based electrolytes are promising for secondary batteries due to their good compatibility with alkali metal anodes and high ionic conductivity. However, they suffer from poor oxidative stability and high toxicity, leading to severe electrolyte decomposition at high voltage and biosafety/environmental concerns when electrolyte leakage occurs. Here, we report a green ether solvent through a rational design of carbon-chain regulation to elicit steric hindrance, such a structure significantly reducing the solvent's biotoxicity and tuning the solvation structure of electrolytes. Notably, our solvent design is versatile, and an anion-dominated solvation structure is favored, facilitating a stable interphase formation on both the anode and cathode in potassium-ion batteries. Remarkably, the green ether-based electrolyte demonstrates excellent compatibility with K metal and graphite anode and a 4.2â V high-voltage cathode (200 cycles with average Coulombic efficiency of 99.64 %). This work points to a promising path toward the molecular design of green ether-based electrolytes for practical high-voltage potassium-ion batteries and other rechargeable batteries.
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Although proton-ion batteries have received considerable attention owing to their reliability, safety, toxin-free nature, and low cost, their development remains in the early stages because of lacking proper electrolytes and cathodes for facilitating a high output voltage and stable cycle performance. We present a novel cathode based on active nitrogen centre, which provides a flat discharge plateau at 1â V with a capacity of 115â mAh g-1 and excellent stability. Moreover, a quasi-solid electrolyte was developed to overcome the issue of corrosion, broaden the potential window of the electrolyte, and prevent the active material from dissolving. While using the unique as-developed electrolyte, the newly designed cathode retained 89.67 % of its original capacity after 2000â cycles. Finally, we demonstrated the excellent cycle performance of the as-developed metal-free, flexible, soft-packed battery. Notably, even when a portion of the battery was cut off, it continued to function normally.
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In recent years, the increasing demand for high-capacity and safe energy storage has focused attention on zinc batteries featuring high voltage, high capacity, or both. Despite extensive research progress, achieving high-energy-density zinc batteries remains challenging and requires the synergistic regulation of multiple factors including reaction mechanisms, electrodes, and electrolytes. In this Review, we comprehensively summarize the rational design strategies of high-energy-density zinc batteries and critically analyze the positive effects and potential issues of these strategies in optimizing the electrochemistry, cathode materials, electrolytes, and device architecture. Finally, the challenges and perspectives for the further development of high-energy-density zinc batteries are outlined to guide research towards new-generation batteries for household appliances, low-speed electric vehicles, and large-scale energy storage systems.
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Conventional ether-based electrolytes exhibited a low polarization voltage in potassium-ion batteries, yet suffered from ion-solvent co-intercalation phenomena in a graphite anode, inferior potassium-metal performance, and limited oxidation stability. Here, we reveal that weakening the cation-solvent interactions could suppress the co-intercalation behaviour, enhance the potassium-metal performance, and improve the oxidation stability. Consequently, the graphite anode exhibits K+ intercalation behaviour (K||graphite cell operates 200â cycles with 86.6 % capacity retention), the potassium metal shows highly stable plating/stripping (K||Cu cell delivers 550â cycles with average Coulombic efficiency of 98.9 %) and dendrite-free (symmetric K||K cell operates over 1400â hours) properties, and the electrolyte exhibits high oxidation stability up to 4.4â V. The ion-solvent interaction tuning strategy provides a promising method to develop high-performance electrolytes and beyond.
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The development of new rechargeable battery systems could fuel various energy applications, from personal electronics to grid storage. Rechargeable aluminium-based batteries offer the possibilities of low cost and low flammability, together with three-electron-redox properties leading to high capacity. However, research efforts over the past 30 years have encountered numerous problems, such as cathode material disintegration, low cell discharge voltage (about 0.55 volts; ref. 5), capacitive behaviour without discharge voltage plateaus (1.1-0.2 volts or 1.8-0.8 volts) and insufficient cycle life (less than 100 cycles) with rapid capacity decay (by 26-85 per cent over 100 cycles). Here we present a rechargeable aluminium battery with high-rate capability that uses an aluminium metal anode and a three-dimensional graphitic-foam cathode. The battery operates through the electrochemical deposition and dissolution of aluminium at the anode, and intercalation/de-intercalation of chloroaluminate anions in the graphite, using a non-flammable ionic liquid electrolyte. The cell exhibits well-defined discharge voltage plateaus near 2 volts, a specific capacity of about 70 mA h g(-1) and a Coulombic efficiency of approximately 98 per cent. The cathode was found to enable fast anion diffusion and intercalation, affording charging times of around one minute with a current density of ~4,000 mA g(-1) (equivalent to ~3,000 W kg(-1)), and to withstand more than 7,500 cycles without capacity decay.
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The phase transition and lattice parameter evolution of O3 structure commonly occurs in O3-type sodium ion battery (SIB) cathodes, which might enlarge the voltage hysteresis and lower the energy efficiency. Given that the cost is one of the issues discouraging the application of SIBs in large-scale energy storage, here we focus on Co/Ni-free NaxCu0.18Fe0.3Mn0.52O2 (x = 0.8, 0.85, 0.9) and propose a convenient strategy to reduce the voltage hysteresis. It is found that when the Na content is 0.8, the highest energy efficiency of 95.4% after activation is achieved (2.5-4.0 V, 50 mA g-1, the 50th cycle), in addition to a satisfactory capacity retention (about 0.056% decay per cycle). The further characterizations reveal that Na0.8Cu0.18Fe0.3Mn0.52O2 owns a gentle O3-P3 phase transition process and does not undergo O3 phase lattice parameter evolution. The key point lies in the attainability of the O3/P3 composite of the material. This work will provide a simple strategy for the rational design of O3-type cathodes with a high energy efficiency and might offer inspiration to search for layered oxides with a higher O3/P3 critical Na content through element adjustments.
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Lithium sulfur (Li-S) batteries are attracting increasing interest for high-density energy storage. However, the practical application is limited by the rapid capacity fading over repeated charge/discharge cycles which is largely attributed to the formation and shuttling of soluble polysulfide species. To address these issues, we develop a hierarchical structure composite with triple protection strategy via graphene, organic conductor PEDOT, and nitrogen and phosphorus codoped biological carbon to encapsulate sulfur species (GOC@NPBCS). This unique hierarchical structure can effectively immobilize the sulfur species while at the same time improve the electrical conductivity and ensure efficient lithium ion transport to enable excellent Li-S battery performance. In particular, the biological carbon derived from natural bacteria features inherent nitrogen and phosphorus codoping with a strong absorption to lithium polysulfides, which can greatly suppress the dissolution and shuttling of polysulfides that are responsible for rapid capacity fading. With these synergistic effects, the GOC@NPBCS cathode exhibits exceptionally stable cycling stability (an ultralow capacity fading rate of 0.045% per cycle during 1000 cycles at the current rate of 5 C), high specific capacity (1193.8 mAh g-1 at 0.5 C based on sulfur weight), and excellent rate capability.
Asunto(s)
Bacterias/química , Carbono/química , Suministros de Energía Eléctrica , Litio/química , Conductividad EléctricaRESUMEN
Graphite as an anode for the potassium ion battery (PIBs) has the merits of low cost and potentially high energy density, while suffering from limited cycle time and inferior stability. Herein we, using a concentrated electrolyte, demonstrate that formation of a robust inorganic-rich passivation layer on the graphite anode could resolve these problems. Consequently, the PIBs with graphite anode could operate for over 2000â cycles (running time of over 17â months) with negligible capacity decay, and had a high area capacity over 7.36â mAh cm-2 with a high mass loading of 28.56â mg cm-2 . These unprecedented performances of graphite are comparable to that of traditional lithium-ion batteries, and may promote the rapidly development of high performance PIBs.
RESUMEN
Potassium ion-batteries (PIBs) have attracted tremendous attention recently due to the abundance of potassium resources and the low standard electrode potential of potassium. Particularly, the solid-electrolyte interphase (SEI) in the anode of PIBs plays a vital role in battery security and battery cycling performance due to the highly reactive potassium. However, the SEI in the anode for PIBs with traditional electrolytes is mainly composed of organic compositions, which are highly reactive with air and water, resulting in inferior cycle performance and safety hazards. Herein, a highly stable and effective inorganic SEI layer in the anode is formed with optimized electrolyte. As expected, the PIBs exhibit an ultralong cycle performance over 14 000 cycles at 2000 mA g-1 and an ultrahigh average coulombic efficiency over 99.9%.
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A potassium ion battery has potential applications for large scale electric energy storage systems due to the abundance and low cost of potassium resources. Dual graphite batteries, with graphite as both anode and cathode, eliminate the use of transition metal compounds and greatly lower the overall cost. Herein, combining the merits of the potassium ion battery and dual graphite battery, a potassium-based dual ion battery with dual-graphite electrode is developed. It delivers a reversible capacity of 62 mA h g-1 and medium discharge voltage of ≈3.96 V. The intercalation/deintercalation mechanism of K+ and PF6- into/from graphite is proposed and discussed in detail, with various characterizations to support.
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A carbon thin film/carbon foam core/sheath structure was synthesized by chemical vapor deposition (CVD) on carbonized melamine foam. It has a specific capacitance of 310â F g-1 at a current density of 1â A g-1 and shows outstanding electrochemical performance in both aqueous and water-in-salt electrolytes. Electrochemical analysis by cyclic voltammetry and galvanostatic charge/discharge testing revealed a large capacitive contribution up to more than 90 % of its total capacitance. The core/sheath structure has advantages in ion transport and a high degree of utilization of the electrode surface, and the synthetic process provides a way to coat carbon thin film on any substrate by nickel-catalyzed CVD.