RESUMEN
Layered oxide cathode materials may undergo irreversible oxygen loss and severe phase transitions during high voltage cycling and may be susceptible to transition metal dissolution, adversely affecting their electrochemical performance. Here, to address these challenges, we propose synergistic doping of nonmetallic elements and in situ electrochemical diffusion as potential solution strategies. Among them, the distribution of the nonmetallic element fluorine within the material can be regulated by doping boron, thereby suppressing manganese dissolution through surface enrichment of fluorine. Furthermore, in situ electrochemical diffusion of fluorine from the surface into the bulk of the materials after charging reduces the energy barrier of potassium ion diffusion while effectively inhibiting irreversible oxygen loss under high voltage. The modified K0.5Mn0.83Mg0.1Ti0.05B0.02F0.1O1.9 layered oxide cathode exhibits a high capacity of 147 mAh g-1 at 50 mA g-1 and a long cycle life of 2200 cycles at 500 mA g-1. This work demonstrates the efficacy of synergistic doping and in situ electrochemical diffusion of nonmetallic elements and provides valuable insights for optimizing rechargeable battery materials.
RESUMEN
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.
RESUMEN
In the past few decades, great efforts have been made to develop advanced transition metal dichalcogenide (TMD) materials as metal-ion battery electrodes. However, due to existing conversion reactions, they still suffer from structural aggregation and restacking, unsatisfactory cycling reversibility, and limited ion storage dynamics during electrochemical cycling. To address these issues, extensive research has focused on molecular modulation strategies to optimize the physical and chemical properties of TMDs, including phase engineering, defect engineering, interlayer spacing expansion, heteroatom doping, alloy engineering, and bond modulation. A timely summary of these strategies can help deepen the understanding of their basic mechanisms and serve as a reference for future research. This review provides a comprehensive summary of recent advances in molecular modulation strategies for TMDs. A series of challenges and opportunities in the research field are also outlined. The basic mechanisms of different modulation strategies and their specific influences on the electrochemical performance of TMDs are highlighted.
RESUMEN
Carbon has been widely used as an electrode material in commercial metal-ion batteries (MIBs) because of its desirable electrical, mechanical, and physical properties. Still, traditional carbon electrodes suffer from limited mechanical stability and electrochemical performance in MIBs. Drawing inspiration from biological species, the carbon allotropes, such as fullerenes, carbon nanotubes, and graphene, can be engineered into mechanically robust, highly conductive frameworks with enhanced ion storage and transport capabilities for MIBs. Here, we present an assortment of bio-inspired carbon electrodes that have enhanced the cycling stability, capacity retention, and overall performance of MIBs. In addition, mimicking the structure and functionality of biological systems has led to the development of flexible MIBs whose performance does not degrade even when stretched, bent, or twisted. Finite element analysis (FEA) is a useful guide in identifying such bio-inspired carbon frameworks because it can simulate and analyze potential failure scenarios, such as stress build-up or structural collapse in MIBs. This review highlights through several examples that there is much scope for improving carbon-based electrode materials through bio-inspired designs for practical high-performance MIBs.
RESUMEN
Solid-state potassium metal batteries (SPMBs) are promising candidates for the next generation of energy storage systems for their low cost, safety, and high energy density. However, full SPMBs are not yet reported due to the K dendrites, interfacial incompatibility, and limited availability of suitable solid-state electrolytes. Here, stable SPMBs using a new iodinated solid polymer electrolyte (ISPE) are presented. The functional ions reconstruct ion transport channels, providing efficient potassium ion transport. ISPE shows a combination of high ionic conductivity, superior interfacial compatibility, and electrochemical stability. In situ alloying and iodinated interlayer increase K metal compatibility for prolonged cycling with low polarization. Moreover, the ISPE enables SPMBs with Prussian blue cathode stable operation at a high voltage of 4.5 V, a superior rate capability, and long-term cycling over 3000 cycles (4.2 V vs K+/K) with an ultra-high coulombic efficiency of 99.94%. More importantly, a classic solid-state potassium metal pouch cell achieves 4.2 V stable cycling over 800 cycles with a high retention of 93.6%, presenting a new development strategy for secure and high-performance rechargeable solid-state potassium metal batteries.
RESUMEN
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.
RESUMEN
The manganese-based layered oxides as a promising cathode material for potassium ion batteries (PIBs) have attracted considerable interest owing to their simple synthesis, high specific capacity, and low cost. However, due to the irreversible phase transition and the Jahn-Teller distortion of the Mn3+ , its application in potassium ion batteries is limited, leading to slow potassium ion kinetics and severe capacity attenuation. Here, entropy-tuning by changing the content of cathode material composition is proposed to address the above challenges. Compared to low and high entropy variants of K0.45 Mnx Co(1- x )/4 Mg(1- x )/4 Cu(1- x )/4 Ti(1- x )/4 O2 , where x = 0.8, 0.6, and 0.4, the medium entropy K0.45 Mn0.6 Co0.1 Mg0.1 Cu0.1 Ti0.1 O2 shows more balanced electrochemical properties in the PIBs. Benefiting from entropy-tuned suppression of the Jahn-Teller distortion of the Mn3+ , the K0.45 Mn0.6 Co0.1 Mg0.1 Cu0.1 Ti0.1 O2 can achieve a high K+ ion transport rate and alleviated volume variation while retaining high specific capacity. Accordingly, the medium entropy K0.45 Mn0.6 Co0.1 Mg0.1 Cu0.1 Ti0.1 O2 cathode in the full cell exhibits a high capacity of 100 mAh g-1 at 50 mA g-1 , delivers superior rate capability (65.8 mAh g-1 at 500 mA g-1 ) and cycling stability (67.8 mAh g-1 after 350 cycles at 100 mA g-1 ). The entropy-tuning strategy is expected to open new avenues in designing PIB cathode materials and beyond.
RESUMEN
High degrees of freedom (DOF) for K+ movement in the electrolytes is desirable, because the resulting high ionic conductivity helps improve potassium-ion batteries, yet requiring support from highly free and flammable organic solvent molecules, seriously affecting battery safety. Here, we develop a K+ flux rectifier to trim K ion's DOF to 1 and improve electrochemical properties. Although the ionic conductivity is compromised in the K+ flux rectifier, the overall electrochemical performance of PIBs was improved. An oxidation stability improvement from 4.0 to 5.9 V was realized, and the formation of dendrites and the dissolution of organic cathodes were inhibited. Consequently, the K||K cells continuously cycled over 3,700 h; K||Cu cells operated stably over 800 cycles with the Coulombic efficiency exceeding 99%; and K||graphite cells exhibited high-capacity retention over 74.7% after 1,500 cycles. Moreover, the 3,4,9,10-perylenetetracarboxylic diimide organic cathodes operated for more than 2,100 cycles and reached year-scale-cycling time. We fabricated a 2.18 Ah pouch cell with no significant capacity fading observed after 100 cycles.
RESUMEN
We study the early time carrier drift dynamics in CsPbI3 nanocrystal thin films with a sub 25 ps time resolution. Prior to trapping, carriers exhibit band-like transport characteristics, which is similar to those of traditional semiconductor solar absorbers including Si and GaAs due to optical phonon and carrier scattering at high temperatures. In contrast to the popular polaron scattering mechanism, the CsPbI3 nanocrystal thin film demonstrates the strongest optical phonon scattering mechanism among other inorganic-organic hybrid perovskites, Si, and GaAs. This ultrafast dynamics study establishes a foundation for understanding the fundamental carrier drift properties that drive perovskite nanocrystal optoelectronics.
RESUMEN
The relative natural abundance of potassium and potentially high energy density has established potassium-ion batteries as a promising technology for future large-scale global energy storage. However, the anodes' low capacity and high discharge platform lead to low energy density, which impedes their rapid development. Herein, we present a possible co-activation mechanism between bismuth (Bi) and tin (Sn) that enhances K-ion storage in battery anodes. The co-activated Bi-Sn anode delivered a high capacity of 634 mAh g-1, with a discharge plateau as low as 0.35 V, and operated continuously for 500 cycles at a current density of 50 mA g-1, with a high Coulombic efficiency of 99.2%. This possible co-activation strategy for high potassium storage may be extended to other Na/Zn/Ca/Mg/Al ion battery technologies, thus providing insights into how to improve their energy storage ability.
RESUMEN
Amorphous polymer-derived silicon-oxycarbide (SiOC) ceramics have a high theoretical capacity and good structural stability, making them suitable anode materials for lithium-ion batteries. However, SiOC has low electronic conductivity, poor transport properties, low initial Couloumbic efficiency, and limited rate capability. Therefore, there is an urgent need to explore an efficient SiOC-based anode material that could mitigate the abovementioned limitations. In this study, we synthesized carbon-rich SiOC (SiOC-I) and silicon-rich SiOC (SiOC-II) and evaluated their elemental and structural characteristics using a broad spectrum of characterization techniques. Li-ion cells were fabricated for the first time by pairing a buckypaper composed of carbon nanotubes with SiOC-I or SiOC-II as the anode. When mixed with graphene nanoplatelets, the SiOC-II/GNP composites exhibited improved electrochemical performance. High specific capacity (average specific capacity of 744 mAh/g at a 0.1C rate) was achieved with the composite anode (25 wt % SiOC-II and 75% GNP), which was much better than that of monolithic SiOC-I, SiOC-II, or GNPs. This composite also exhibited excellent cycling stability, achieving 344 mAh/g after 260 cycles at a 0.5C rate and high reversibility. The enhanced electrochemical performance is attributed to better electronic conductivity, lower charge-transfer resistance, and short ion diffusion length. Due to their superior electrochemical performance, SiOC/GNP composites with CNT buckypaper as a current collector can be considered a promising anode material for LiBs.
RESUMEN
Instability at the solid electrolyte interface (SEI) and uncontrollable growth of potassium dendrites have been pressing issues for potassium-ion batteries. Herein, a self-supporting electrode composed of bismuth and nitrogen-doped reduced graphene oxide (Bi80 /NrGO) is designed as an anode host for potassium-metal batteries. Following the molten potassium diffusion into Bi80 /NrGO, the resulting K@Bi80 /NrGO exhibits unique hollow pores that provide K+ -diffusion channels and deposition space to buffer volume expansion, thus maintaining the electrode structure and SEI stability. The K@Bi80 /NrGO also provides a controlled electric field that promotes uniform K+ flux, abundant potassiophilic N sites, and Bi alloying active sites, collectively enabling precise nucleation and selective deposition of potassium to achieve dendrite-resistant anodes. With the K@Bi80 /NrGO-based optimized electrodes, the assembled K@Bi80 /NrGO symmetrical cells can sustain stable cycling over 3000 h at a current density of 0.2 mA cm-2 . Full cells with a Prussian blue cathode and K@Bi80 /NrGO anode exhibit high stability (with no degradation for 1960 cycles at 1000 mA g-1 ) with 99% Coulombic efficiency. This work may lead to the design of anodes with the triple attributes of precise nucleation, smooth diffusion, and dendrite inhibition, ideal for developing stable potassium-metal anodes and beyond.
RESUMEN
Aqueous electrolytes are highly important for batteries due to their sustainability, greenness, and low cost. However, the free water molecules react violently with alkali metals, rendering the high-capacity of alkali-metal anodes unusable. Here, water molecules are confined in a carcerand-like network to build quasi-solid aqueous electrolytes (QAEs) with reduced water molecules' freedom and matched with the low-cost chloride salts. The formed QAEs possess substantially different properties than liquid water molecules, including stable operation with alkali-metal anodes without gas evolution. Specifically, the alkali-metal anodes can directly cycle in a water-based environment with suppressed growth of dendrites, electrode dissolution, and polysulfide shuttle. Li-metal symmetric cells achieved long-term cycling over 7000 h (and over 5000/4000 h for Na/K symmetric cells), and all the Cu-based alkali-metal cells exhibited a Coulombic efficiency of over 99%. Full metal batteries, such as Li||S batteries, attained high Coulombic efficiency, long life (over 4000 cycles), and unprecedented energy density among water-based rechargeable batteries.
RESUMEN
The crystal phase structure of cathode material plays an important role in the cell performance. During cycling, the cathode material experiences immense stress due to phase transformation, resulting in capacity degradation. Here, we show phase-engineered VO2 as an improved potassium-ion battery cathode; specifically, the amorphous VO2 exhibits superior K storage ability, while the crystalline M phase VO2 cannot even store K+ ions stably. In contrast to other crystal phases, amorphous VO2 exhibits alleviated volume variation and improved electrochemical performance, leading to a maximum capacity of 111 mAh g-1 delivered at 20 mA g-1 and over 8 months of operation with good coulombic efficiency at 100 mA g-1. The capacity retention reaches 80% after 8500 cycles at 500 mA g-1. This work illustrates the effectiveness and superiority of phase engineering and provides meaningful insights into material optimization for rechargeable batteries.
RESUMEN
Electrolyte anions are critical for achieving high-voltage stable potassium-metal batteries (PMBs). However, the common anions cannot simultaneously prevent the formation of 'dead K' and the corrosion of Al current collector, resulting in poor cycling stability. Here, we demonstrate cyclic anion of hexafluoropropane-1,3-disulfonimide-based electrolytes that can mitigate the 'dead K' and remarkably enhance the high-voltage stability of PMBs. Particularly, even using low salt concentration (0.8 M) and additive-free carbonate-based electrolytes, the PMBs with a high-voltage polyanion cathode (4.4 V) also exhibit excellent cycling stability of 200 cycles with a good capacity retention of 83%. This noticeable electrochemical performance is due to the highly efficient passivation ability of the cyclic anions on both anode and cathode surfaces. This cyclic-anion-based electrolyte design strategy is also suitable for lithium and sodium-metal battery technologies.
RESUMEN
It remains challenging to capture and investigate the drift dynamics of primary hot carriers because of their ultrashort lifetime (â¼200 fs). Here we report a new mechanism for secondary hot carrier (â¼25 ps) generation in monolayer transition metal dichalcogenides such as WS2 and WSe2, triggered by the Auger recombination of trions and biexcitons. Using ultrafast photocurrent spectroscopy, we measured and characterized the photocurrent stemming from the Auger recombination of trions and biexcitons in WS2 and WSe2. A mobility of 0.24 cm2 V-1 s-1 and a drift length of â¼3.8 nm were found for the secondary hot carriers in WS2. By leveraging interactions between exciton complexes, we envision a new mechanism for generating and controlling hot carriers, which could lead to efficient devices in photophysics, photochemistry, and photosynthesis.
RESUMEN
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.
RESUMEN
Hexagonal boron nitride (h-BN) and exfoliated nanosheets (BNNs) not only resemble their carbon counterparts graphite and graphene nanosheets in structural configurations and many excellent materials characteristics, especially the ultra-high thermal conductivity, but also offer other unique properties such as being electrically insulating and extreme chemical stability and oxidation resistance even at elevated temperatures. In fact, BNNs as a special class of 2-D nanomaterials have been widely pursued for technological applications that are beyond the reach of their carbon counterparts. Highlighted in this article are significant recent advances in the development of more effective and efficient exfoliation techniques for high-quality BNNs, the understanding of their characteristic properties, and the use of BNNs in polymeric nanocomposites for thermally conductive yet electrically insulating materials and systems. Major challenges and opportunities for further advances in the relevant research field are also discussed.
Asunto(s)
Grafito , Nanocompuestos , Compuestos de Boro , Conductividad TérmicaRESUMEN
Potassium-ion batteries (PIBs) have attracted tremendous attention because of their high energy density and low-cost. As such, much effort has focused on developing electrode materials and electrolytes for PIBs at the material levels. This review begins with an overview of the high-performance electrode materials and electrolytes, and then evaluates their prospects and challenges for practical PIBs to penetrate the market. The current status of PIBs for safe operation, energy density, power density, cyclability, and sustainability is discussed and future studies for electrode materials, electrolytes, and electrode-electrolyte interfaces are identified. It is anticipated that this review will motivate research and development to fill existing gaps for practical potassium-based full batteries so that they may be commercialized in the near future.
RESUMEN
Large-scale low-cost synthesis methods for potassium ion battery (PIB) anodes with long cycle life and high capacity have remained challenging. Here, inspired by the structure of a biological cell, biomimetic carbon cells (BCCs) were synthesized and used as PIB anodes. The protruding carbon nanotubes across the BCC wall mimicked the ion-transporting channels present in the cell membrane, and enhanced the rate performance of PIBs. In addition, the robust carbon shell of the BCC could protect its overall structure, and the open space inside the BCC could accommodate the volume changes caused by K+ insertion, which greatly improved the stability of PIBs. For the first time, a stable solid electrolyte interphase layer is formed on the surface of amorphous carbon. Collectively, the unique structural characteristics of the BCCs resulted in PIBs that showed a high reversible capacity (302 mAh g-1 at 100 mA g-1 and 248 mAh g-1 at 500 mA g-1), excellent cycle stability (reversible capacity of 226 mAh g-1 after 2100 cycles and a continuous running time of more than 15 months at a current density of 100 mA g-1), and an excellent rate performance (160 mAh g-1 at 1 A g-1). This study represents a new strategy for boosting battery performance, and could pave the way for the next generation of battery-powered applications.