Project description:Sodium ion capacitors (SICs) are designed to deliver both high energy and power densities at low cost. Electric double-layer capacitive cathodes are typically used in these devices, but they lead to very limited capacity. Herein, we apply a pseudocapacitive layered ferric vanadate (Fe-V-O) as cathode to construct non-aqueous SICs with both high energy and power densities. The Fe-V-O nanosheets cathode displays remarkable rate capability and cycling stability. The pseudocapacitive sodium storage mechanism of Fe-V-O, with over 83% of total capacity from capacitive contribution, is confirmed by kinetics analysis and ex situ characterizations. The capacitive-adsorption mechanism of hard carbon (HC) anode is demonstrated, and it delivers excellent rate capability. Based on as-synthesized materials, the assembled HC//Fe-V-O SIC delivers a maximum energy density of 194 Wh kg-1 and power density of 3,942 W kg-1. Our work highlights the advantages of pseudocapacitive cathodes for achieving both high energy and power densities in sodium storage devices.
Project description:With the increased application of batteries in powering electric vehicles as well as potential contributions to utility-scale storage, there remains a need to identify and develop efficient and sustainable active materials for use in lithium (Li)- and sodium (Na)-ion batteries. Organic cathode materials provide a desirable alternative to inorganic counterparts, which often come with harmful environmental impact and supply chain uncertainties. Organic materials afford a sustainable route to active electrodes that also enable fine-tuning of electrochemical potentials through structural design. Here, we report a bis-anthraquinone-functionalized s-indacene-1,3,5,7(2H,6H)-tetraone (BAQIT) synthesized using a facile and inexpensive route as a high-capacity cathode material for use in Li- and Na-ion batteries. BAQIT provides multiple binding sites for Li- and Na-ions, while maintaining low solubility in commercial organic electrolytes. Electrochemical Li-ion cells demonstrate excellent stability with discharge capacities above 190 mAh g-1 after 300 cycles at a 0.1C rate. The material also displayed excellent high-rate performance with a reversible capacity of 142 mAh g-1 achieved at a 10C rate. This material affords high power capabilities superior to current state-of-the-art organic cathode materials, with values reaching 5.09 kW kg-1. The Na-ion performance was also evaluated, exhibiting reversible capacities of 130 mAh g-1 after 90 cycles at a 0.1C rate. This work offers a structural design to encourage versatile, high-power, and long cycle-life electrochemical energy-storage materials.
Project description:Organic cathode materials are handled as promising candidates for new energy-storage solutions based on their transition-metal-free composition. Phenothiazine-based polymers are attractive owing to their redox potential of 3.5?V vs. Li/Li+ and high cycling stabilities. Herein, three types of poly(norbornene)s were investigated, functionalized with phenothiazine units through either a direct connection or ester linkages, as well as their crosslinked derivatives. The directly linked poly(3-norbornylphenothiazine)s demonstrated excellent rate capability and cycling stability with a capacity retention of 73?% after 10?000 cycles at a C-rate of 100?C for the crosslinked polymer. The polymer network structure of the crosslinked poly(3-norbornylphenothiazine) was beneficial for its rate performance.
Project description:Establishing energy storage systems beyond conventional lithium ion batteries requires the development of novel types of electrode materials. Such materials should be capable of accommodating ion species other than Li+, and ideally, these ion species should be of multivalent nature, such as Al3+. Along this line, we introduce a highly porous aerogel cathode composed of reduced graphene oxide, which is loaded with nanostructured SnO2. This binder-free hybrid not only exhibits an outstanding mechanical performance, but also unites the pseudocapacity of the reduced graphene oxide and the electrochemical storage capacity of the SnO2 nanoplatelets. Moreover, the combination of both materials gives rise to additional intercalation sites at their interface, further contributing to the total capacity of up to 16 mAh cm-3 at a charging rate of 2 C. The high porosity (99.9%) of the hybrid and the synergy of its components yield a cathode material for high-rate (up to 20 C) aluminum ion batteries, which exhibit an excellent cycling stability over 10,000 tested cycles. The electrode design proposed here has a great potential to meet future energy and power density demands for advanced energy storage devices.
Project description:Sodium-ion batteries operating at ambient temperature hold great promise for use in grid energy storage owing to their significant cost advantages. However, challenges remain in the development of suitable electrode materials to enable long lifespan and high rate capability. Here we report a sodium super-ionic conductor structured electrode, sodium vanadium titanium phosphate, which delivers a high specific capacity of 147?mA?h?g-1 at a rate of 0.1 C and excellent capacity retentions at high rates. A symmetric sodium-ion full cell demonstrates a superior rate capability with a specific capacity of about 49?mA?h?g-1 at 20 C rate and ultralong lifetime over 10,000 cycles. Furthermore, in situ synchrotron diffraction and X-ray absorption spectroscopy measurement are carried out to unravel the underlying sodium storage mechanism and charge compensation behaviour. Our results suggest the potential application of symmetric batteries for electrochemical energy storage given the superior rate capability and long cycle life.
Project description:Even though the energy density of O3-type layer-structured metal oxide cathode can fully reach the requirement for large-scale energy storage systems, the cycling lifespan still cannot meet the demand for practical application once it is coupled with a non-sodium-metal anode in full-cell system. Transition metal dissolution into the electrolyte occurs along with continuous phase transformation and accelerates deterioration of the crystal structure, followed by migration and finally deposition on the anode to form a vicious circle. Surface engineering techniques are employed to modify the interface between active materials and the electrolyte by coating them with a thin layer of AlPO4 ion conductor. This stable thin layer can stabilize the surface crystal structure of the cathode material by avoiding element dissolution. Meanwhile, it can protect the anode from increased resistance by suppressing the dissolution-migration-deposition process. This technique is a promising method to improve the lifetime for the future commercialization.
Project description:Rechargeable solid-state sodium-ion batteries (SSSBs) hold great promise for safer and more energy-dense energy storage. However, the poor electrochemical stability between current sulfide-based solid electrolytes and high-voltage oxide cathodes has limited their long-term cycling performance and practicality. Here, we report the discovery of the ion conductor Na3-xY1-xZrxCl6 (NYZC) that is both electrochemically stable (up to 3.8 V vs. Na/Na+) and chemically compatible with oxide cathodes. Its high ionic conductivity of 6.6 × 10-5 S cm-1 at ambient temperature, several orders of magnitude higher than oxide coatings, is attributed to abundant Na vacancies and cooperative MCl6 rotation, resulting in an extremely low interfacial impedance. A SSSB comprising a NaCrO2 + NYZC composite cathode, Na3PS4 electrolyte, and Na-Sn anode exhibits an exceptional first-cycle Coulombic efficiency of 97.1% at room temperature and can cycle over 1000 cycles with 89.3% capacity retention at 40 °C. These findings highlight the immense potential of halides for SSSB applications.
Project description:Metals fluorides (MFs) are potential conversion cathodes to replace commercial intercalation cathodes. However, the application of MFs is impeded by their poor electronic/ionic conductivity and severe decomposition of electrolyte. Here, a composite cathode of FeF2 and polymer-derived carbon (FeF2 @PDC) with excellent cycling performance is reported. The composite cathode is composed of nanorod-shaped FeF2 embedded in PDC matrix with excellent mechanical strength and electronic/ionic conductivity. The FeF2 @PDC enables a reversible capacity of 500 mAh g-1 with a record long cycle lifetime of 1900 cycles. Remarkably, the FeF2 @PDC can be cycled at a record rate of 60 C with a reversible capacity of 107 mAh g-1 after 500 cycles. Advanced electron microscopy reveals that the in situ formation of stable Fe3 O4 layers on the surface of FeF2 prevents the electrolyte decomposition and leaching of iron (Fe), thus enhancing the cyclability. The results provide a new understanding to FeF2 electrochemistry, and a strategy to radically improve the electrochemical performance of FeF2 cathode for lithium-ion battery applications.
Project description:The cathode materials of sodium-ion batteries (SIBs) have received considerable attention not only because of their abundant natural reserves and chemical properties similar to those of lithium-ion batteries but also their great potential in energy storage and conversion technologies. However, their low capacity and high diffusion barrier remain unsolved problems. In this work, we systematically studied the theoretical capacity and sodium ion diffusion barrier in a new family of layered transition metal compounds, named MX2 (M = Ti, V, Cr, Mn, and Fe; X = C, N, and O), as the cathode materials of SIBs. The results indicate that all 2H-phase MX2 materials possess a high theoretical capacity of over 300 mA h g-1. Moreover, it is found that the 2H-phase CrN2 exhibits a desirable sodium ion diffusion barrier, indicating high mobility of sodium ions. In addition, the layered CrN2 has a remarkable voltage window (3.1-3.8 V) and outstanding electrochemical performance arising from the charge transfer between Na and N atoms, which is induced by the large electronegativity of nitrogen. Our research provides a promising candidate for application in SIB cathode materials in the future.
Project description:Lithium-collaborating organic batteries (Li-[28]hexs) were investigated with [28]hexaphyrin(1.1.1.1.1.1) as an active electrode material. Each hexaphyrin of [28]Hex cathode ideally involved four electrons per unit cycle and performed a typical charge/discharge processes of Li-organic battery. Li-[28]Hex batteries set with fast charging rates showed reasonably stable charge and discharge performances over 200 cycles even though it caused incomplete (2~3 electrons) charge/discharge cycles due to failing the complete charging process. UV absorption changes of [28]hexaphyrin in CH2Cl2 were supplementary for the electrochemical oxidation, which performed a conversion from [28]hexaphyrin to [26]hexaphyrin.