RESUMO
Charge compensation from cationic and anionic redox couples accompanying Na+ (de)intercalation in layered oxide cathodes contributes to high specific capacity. However, the engagement level of different redox couples remains unclear and their relationship with Na+ content is less studied. Here we discover that it is possible to take full advantage of the high-voltage transition metal (TM) redox reaction through low-valence cation substitution to tailor the electronic structure, which involves an increased ratio of Na+ content to available charge transfer number of TMs. Taking NaxCu0.11Ni0.11Fe0.3Mn0.48O2 as the example, the Li+ substitution increases the ratio to facilitate the high-voltage TM redox activity, and further F-ion substitution decreases the covalency of the TM-O bond to relieve structural changes. As a consequence, the final high-entropy Na0.95Li0.07Cu0.11Ni0.11Fe0.3Mn0.41O1.97F0.03 cathode demonstrates â¼29% capacity increase contributed by the high-voltage TMs and exhibits excellent long-term cycling stability due to the improved structural reversibility. This work provides a paradigm for the design of high-energy-density electrodes by simultaneous electronic and crystal structure modulation.
RESUMO
Sodium-ion batteries (SIBs) have been considered as one of the most promising secondary battery techniques for large-scale energy storage applications. However, developing appropriate electrode materials that can satisfy the demands of long-term cycling and high energy/power capabilities remains a challenge. Herein, a fluorine modulation strategy is reported that can trigger highly active exposed crystal facets in anatase TiO2- x Fx , while simultaneously inducing improved electron transfer and Na+ diffusion via lattice regulation. When tested in SIBs, the optimized fluorine doped TiO2- x Fx nanocrystals exhibit a high reversible capacity of 275 mA h g-1 at 0.05 A g-1 , outstanding rate capability (delivering 129 mA h g-1 at 10 A g-1 ), and remarkable cycling stability with 91% capacity retained after 6000 cycles at 2 A g-1 . Importantly, the optimized TiO2- x Fx nanocrystals are dominated by pseudocapacitive Na+ storage, which can be attributed to the fluorine induced surface and lattice regulation, enabling ultrafast electrode kinetics.
RESUMO
Oxidative anion insertion into graphite in an aqueous environment represents a significant challenge in the construction of aqueous dual-ion batteries. In dilute aqueous electrolytes, the oxygen evolution reaction (OER) dominates the anodic current before anions can be inserted into the graphite gallery. Herein, we report that the reversible insertion of Mg-Cl superhalides in graphite delivers a record-high reversible capacity of 150â mAh g-1 from an aqueous deep eutectic solvent comprising magnesium chloride and choline chloride. The insertion of Mg-Cl superhalides in graphite does not form staged graphite intercalation compounds; instead, the insertion of Mg-Cl superhalides makes the graphite partially turbostratic.
RESUMO
Anodes involving conversion and alloying reaction mechanisms are attractive for potassium-ion batteries (PIBs) due to their high theoretical capacities. However, serious volume change and metal aggregation upon potassiation/depotassiation usually cause poor electrochemical performance. Herein, few-layered SnS2 nanosheets supported on reduced graphene oxide (SnS2 @rGO) are fabricated and investigated as anode material for PIBs, showing high specific capacity (448 mAh g-1 at 0.05 A g-1 ), high rate capability (247 mAh g-1 at 1 A g-1 ), and improved cycle performance (73% capacity retention after 300 cycles). In this composite electrode, SnS2 nanosheets undergo sequential conversion (SnS2 to Sn) and alloying (Sn to K4 Sn23 , KSn) reactions during potassiation/depotassiation, giving rise to a high specific capacity. Meanwhile, the hybrid ultrathin nanosheets enable fast K storage kinetics and excellent structure integrity because of fast electron/ionic transportation, surface capacitive-dominated charge storage mechanism, and effective accommodation for volume variation. This work demonstrates that K storage performance of alloy and conversion-based anodes can be remarkably promoted by subtle structure engineering.
RESUMO
Amorphous metal oxides (AMOs) have aroused great enthusiasm across multiple energy areas over recent years due to their unique properties, such as the intrinsic isotropy, versatility in compositions, absence of grain boundaries, defect distribution, flexible nature, etc. Here, the materials engineering of AMOs is systematically reviewed in different electrochemical applications and recent advances in understanding and developing AMO-based high-performance electrodes are highlighted. Attention is focused on the important roles that AMOs play in various energy storage and conversion technologies, such as active materials in metal-ion batteries and supercapacitors as well as active catalysts in water splitting, metal-air batteries, and fuel cells. The improvements of electrochemical performance in metal-ion batteries and supercapacitors are reviewed regarding the enhancement in active sites, mechanical strength, and defect distribution of amorphous structures. Furthermore, the high electrochemical activities boosted by AMOs in various fundamental reactions are elaborated on and they are related to the electrocatalytic behaviors in water splitting, metal-air batteries, and fuel cells. The applications in electrochromism and high-conducting sensors are also briefly discussed. Finally, perspectives on the existing challenges of AMOs for electrochemical applications are proposed, together with several promising future research directions.
RESUMO
Plating battery electrodes typically deliver higher specific capacity values than insertion or conversion electrodes because the ion charge carriers represent the sole electrode active mass, and a host electrode is unnecessary. However, reversible plating electrodes are rare for electronically insulating nonmetals. Now, a highly reversible iodine plating cathode is presented that operates on the redox couples of I2 /[ZnIx (OH2 )4-x ]2-x in a water-in-salt electrolyte. The iodine plating cathode with the theoretical capacity of 211â mAh g-1 plates on carbon fiber paper as the current collector, delivering a large areal capacity of 4â mAh cm-2 . Tunable femtosecond stimulated Raman spectroscopy coupled with DFT calculations elucidate a series of [ZnIx (OH2 )4-x ]2-x superhalide ions serving as iodide vehicles in the electrolyte, which eliminates most free iodide ions, thus preventing the consequent dissolution of the cathode-plated iodine as triiodides.
RESUMO
The electrochemical performance of most transition metal oxides based on the conversion mechanism is greatly restricted by inferior cycling stability, rate capability, high overpotential induced by the serious irreversible reactions, low electrical conductivity, and poor ion diffusivity. To mitigate these problems, highly porous Mn3 O4 micro/nanocuboids with in situ formed carbon matrix (denoted as Mn3 O4 @C micro/nanocuboids) are designed and synthesized via a one-pot hydrothermal method, in which glucose plays the roles of a reductive agent and a carbon source simultaneously. The carbon content, particle size, and pore structure in the composite can be facilely controlled, resulting in continuous carbon matrix with abundant pores in the cuboids. The as-fabricated Mn3 O4 @C micro/nanocuboids exhibit large reversible specific capacity (879 mAh g-1 at the current density of 100 mA g-1 ) as well as outstanding cycling stability (86% capacity retention after 500 cycles) and rate capability, making it a potential candidate as anode material for lithium-ion batteries. Moreover, this facile and effective synthetic strategy can be further explored as a universal approach for the synthesis of other hierarchical transition metal oxides and carbon hybrids with subtle structure engineering.
RESUMO
The deposition of volatilized Na+ on the surface of the cathode during sintering results in the formation of surface residual alkali (NaOH/Na2 CO3 NaHCO3 ) in layered cathode materials, leading to serious interfacial reactions and performance degradation. This phenomenon is particularly evident in O3-NaNi0.4 Cu0.1 Mn0.4 Ti0.1 O2 (NCMT). In this study, a strategy is proposed to transform waste into treasure by converting residual alkali into a solid electrolyte. Mg(CH3 COO)2 and H3 PO4 are reacted with surface residual alkali to generate the solid electrolyte NaMgPO4 on the surface of NCMT, which can be labeled as NaMgPO4@NaNi0.4 Cu0.1 Mn0.4 Ti0.1 O2 -X (NMP@NCMT-X, where X indicates the different amounts of Mg2+ and PO4 3- ). NaMgPO4 acts as a special ionic conductivity channel on the surface to improve the kinetics of the electrode reactions, remarkably improving the rate capability of the modified cathode at a high current density in the half-cell. Additionally, NMP@NCMT-2 enables a reversible phase transition from the P3 to OP2 phase in the charge-discharge process above 4.2 V and achieves a high specific capacity of 157.3 mAh g-1 and outstanding capacity retention in the full cell. The strategy can effectively and reliably stabilize the interface and improve the performance of layered cathodes for Na-ion batteries (NIBs).
RESUMO
Dual-ion battery (DIB) is an up-and-coming technology for the energy storage field. However, most of the current cathodes are still focused on the graphite hosts, which deliver a limited specific capacity. In this work, we demonstrated for the first time that H2PO4- can be used as the charge carrier for Na3V2(PO4)3 under an aqueous electrolyte, which enabled the V3+/V4+ and V4+/V5+ multielectron reactions in the Na3V2(PO4)3 electrode. The fabricated aqueous DIB delivers a high average voltage of â¼0.75 V (vs Ag/AgCl) and a high capacity of 280.7 mA h g-1. Moreover, the formed V5+-based novel cathode exhibits a capacity of 170.2 mA h g-1 in an organic sodium-ion battery. This study may open a new direction for fabricating high-voltage electrodes through the design of DIBs.
RESUMO
The formation of the soluble polysulfides (Na2S n , 4 ≤ n ≤ 8) causes poor cycling performance for room temperature sodium-sulfur (RT Na-S) batteries. Moreover, the formation of insoluble polysulfides (Na2S n , 2 ≤ n < 4) can slow down the reaction kinetics and terminate the discharge reaction before it reaches the final product. In this work, coffee residue derived activated ultramicroporous coffee carbon (ACC) material loading with small sulfur molecules (S2-4) as cathode material for RT Na-S batteries is reported. The first principle calculations indicate the space confinement of the slit ultramicropores can effectively suppress the formation of polysulfides (Na2S n , 2 ≤ n ≤ 8). Combining with in situ UV/vis spectroscopy measurements, one-step reaction RT Na-S batteries with Na2S as the only and final discharge product without polysulfides formation are demonstrated. As a result, the ultramicroporous carbon loaded with 40 wt% sulfur delivers a high reversible specific capacity of 1492 mAh g-1 at 0.1 C (1 C = 1675 mA g-1). When cycled at 1 C rate, the carbon-sulfur composite electrode exhibits almost no capacity fading after 2000 cycles with 100% coulombic efficiency, revealing excellent cycling stability and reversibility. The superb cycling stability and rate performance demonstrate ultramicropore confinement can be an effective strategy to develop high performance cathode for RT Na-S batteries.
RESUMO
Potassium-ion batteries (PIBs) are one of the emerging energy-storage technologies due to the low cost of potassium and theoretically high energy density. However, the development of PIBs is hindered by the poor K+ transport kinetics and the structural instability of the cathode materials during K+ intercalation/deintercalation. In this work, birnessite nanosheet arrays with high K content (K0.77 MnO2 â 0.23H2 O) are prepared by "hydrothermal potassiation" as a potential cathode for PIBs, demonstrating ultrahigh reversible specific capacity of about 134 mAh g-1 at a current density of 100 mA g-1 , as well as great rate capability (77 mAh g-1 at 1000 mA g-1 ) and superior cycling stability (80.5% capacity retention after 1000 cycles at 1000 mA g-1 ). With the introduction of adequate K+ ions in the interlayer, the K-birnessite exhibits highly stabilized layered structure with highly reversible structure variation upon K+ intercalation/deintercalation. The practical feasibility of the K-birnessite cathode in PIBs is further demonstrated by constructing full cells with a hard-soft composite carbon anode. This study highlights effective K+ -intercalation for birnessite to achieve superior K-storage performance for PIBs, making it a general strategy for developing high-performance cathodes in rechargeable batteries beyond lithium-ion batteries.
RESUMO
Highlighted by the safe operation and stable performances, titanium oxides (TiO2) are deemed as promising candidates for next generation lithium-ion batteries (LIBs). However, the pervasively low capacity is casting shadow on desirable electrochemical behaviors and obscuring their practical applications. In this work, we reported a unique template-assisted and two-step atomic layer deposition (ALD) method to achieve TiO2@Fe2O3 core-shell nanotube arrays with hollow interior and double-wall coating. The as-prepared architecture combines both merits of the high specific capacity of Fe2O3 and structural stability of TiO2 backbone. Owing to the nanotubular structural advantages integrating facile strain relaxation as well as rapid ion and electron transport, the TiO2@Fe2O3 nanotube arrays with a high mass loading of Fe2O3 attained desirable capacity of ~520 mA h g-1, exhibiting both good rate capability under uprated current density of 10 A g-1 and especially enhanced cycle stability (~450 mA h g-1 after 600 cycles), outclassing most reported TiO2@metal oxide composites. The results not only provide a new avenue for hybrid core-shell nanotube formation, but also offer an insight for rational design of advanced electrode materials for LIBs.
RESUMO
Metal sulfides are promising anode materials for sodium-ion batteries due to their large specific capacities. The practical applications of metal sulfides in sodium-ion batteries, however, are still limited due to their large volume expansion, poor cycling stability, and sluggish electrode kinetics. In this work, a two-dimensional heterostructure of CoSx (CoS and Co9S8) quantum dots embedded N/S-doped carbon nanosheets (CoSx@NSC) is prepared by a sol-gel method. The CoSx quantum dots are in situ formed within ultrafine carbon nanosheets without further sulfidation, thus resulting in ultrafine CoSx particle size and embedded heterostructure. Meanwhile, enriched N and S codoping in the carbon nanosheets greatly enhances the electrical conductivity for the conductive matrix and creates more active sites for sodium storage. As a result, the hybrid CoSx@NSC electrode shows excellent rate capability (600 mAh g-1 at 0.2 A g-1 and 500 mAh g-1 at 10 A g-1) and outstanding cycling stability (87% capacity retention after 200 cycles at 1 A g-1), making it promising as an anode material for high-performance sodium-ion batteries. A CoSx@NSC//Na0.44MnO2 full cell is demonstrated, and it can deliver a specific capacity of 414 mAh g-1 (based on the mass of CoSx@NSC) at a current density of 0.2 A g-1.