ABSTRACT
Niobate Li+ -storage anode materials with shear ReO3 crystal structures have attracted intensive attention due to their inherent safety and large capacities. However, they generally suffer from limited rate performance, cyclic stability, and temperature adaptability, which are rooted in their insufficient interlayer spacings. Here, sodium niobate (NaNb13 O33 ) micron-sized particles are developed as a new anode material owning the largest interlayer spacing among the known shear ReO3 -type niobates. The large interlayer spacing of NaNb13 O33 enables very fast Li+ diffusivity, remarkably contributing to its superior rate performance with a 2500 to 125 mA g-1 capacity percentage of 63.2%. Moreover, its large interlayer spacing increases the volume-accommodation capability during lithiation, allowing small unit-cell-volume variations (maximum 6.02%), which leads to its outstanding cyclic stability with 87.9% capacity retention after as long as 5000 cycles at 2500 mA g-1 . Its cyclic stability is the best in the research field of niobate micron-sized particles, and comparable to that of "zero-strain" Li4 Ti5 O12 . At a low temperature of -10 °C, it also exhibits high rate performance with a 1250 to 125 mA g-1 capacity percentage of 65.6%, and even better cyclic stability with 105.4% capacity retention after 5000 cycles at 1250 mA g-1 . These comprehensively good electrochemical results pave the way for the practical application of NaNb13 O33 in high-performance Li+ storage.
ABSTRACT
Perovskite-type oxides are widely used for energy conversion and storage, but their rate-inhibiting phase transition and large volume change hinder the applications of most perovskite-type oxides for high-rate electrochemical energy storage. Here, it is shown that a cation-deficient perovskite CeNb3 O9 (CNO) can store a sufficient amount of lithium at a high charge/discharge rate, even when the sizes of the synthesized particles are on the order of micrometers. At 60 C (15 A g-1 ), corresponding to a 1 min charge, the CNO anode delivers over 52.8% of its capacity. In addition, the CNO anode material exhibits 96.6% capacity retention after 2000 charge-discharge cycles at 50 C (12.5 A g-1 ), indicating exceptional long-term cycling stability at high rates. The excellent cycling performance is attributed to the formation of atomic short-range order, which significantly prevents local and long-range structural rearrangements, stabilizing the host structure and being responsible for the small volume evolution. Moreover, the extremely high rate capacity can be explained by the intrinsically large interstitial sites in multiple directions, intercalation pseudocapacitance, atomic short-range order, and cation-vacancy-enhanced 3D-conduction networks for lithium ions. These structural characteristics and mechanisms can be used to design advanced perovskite electrode materials for fast-charging and long-life lithium-ion batteries.
ABSTRACT
Cu2Nb34O87 with an inverse opal morphology is fabricated, showing highly-ordered macropores with sizes of â¼170 nm and walls with thicknesses of 20-30 nm. This first-reported Cu2Nb34O87 nanomaterial exhibits good Li+-storage properties, including a large capacity, safe operating potential, large initial coulombic efficiency, high rate performance and good cycling stability.
ABSTRACT
In this work, we revisited the stability of the Cr4+/Cr3+ redox couple in a sodium superionic conductor (NASICON)-type compound, Na2TiCr(PO4)3. Experimental results showed that the Na2TiCr(PO4)3 compound exhibited a specific capacity of 49.9 mA h g-1 at 20 mA g-1, about 80% of its theoretical capacity of 62.2 mA h g-1 with one Na+ insertion/deinsertion per formula Na2TiCr(PO4)3. The redox couple was found to be stable against cycling with some 90.3% capacity retention after 300 cycles within the voltage range between 2.5 and 4.7 V. With a wider voltage range between 2.5 and 5.0 V, the capacity retention was about 76.6% after 1000 cycles, indicating the redox couple is stable against overvoltage. In addition, the effect of Ti/Cr ratio on the reversibility of the redox couple was studied by varying x in Na1+xTi2-xCrx(PO4)3 (where x = 0.6, 0.8, 1.0, 1.2, 1.4, 2.0). It was confirmed that x = 1 is optimal for balancing the electrode stability and the capacity. The obtained optimal content of Cr in the compound provides useful guidance for designing new Cr-based NASICON-type cathode materials. Furthermore, in situ X-ray diffraction (XRD) analysis of compound Na2TiCr(PO4)3 indicated a two-phase sodium-ion storage mechanism, which is different from the previously reported one-phase mechanism. Rietveld refinement XRD analysis showed a small volume change of the compound during cycling (about 2.6%), indicating good structural stability.
ABSTRACT
Highly Li+-conductive HfNb24O62 is explored as a new intercalation-type niobium-based oxide anode material for superior Li+ storage. HfNb24O62 owns a Wadsley-Roth shear structure with a large unit-cell volume, leading to a large Li+ diffusion coefficient. HfNb24O62 shows a large capacity, safe operating potential, high rate performance and good cyclability.
ABSTRACT
Conductive Nb12O29 hierarchical microspheres with nanosheet shells were synthesized based on a hydrothermal process and a high-temperature hydrogen reduction treatment. The obtained materials demonstrated comprehensively good electrochemical properties, including a significant pseudocapacitive contribution, safe operating potential, high reversible capacity, superior initial coulombic efficiency, increased rate capability, and durable cycling stability.
ABSTRACT
M-Nb-O compounds are advanced anode materials for lithium-ion batteries (LIBs) due to their high specific capacities, safe operating potentials, and high cycling stability. Nevertheless, the found M-Nb-O anode materials are very limited. Here, Mg2Nb34O87 is developed as a new M-Nb-O material. Mg2Nb34O87 porous microspheres (Mg2Nb34O87-P) with primary-particle sizes of 30-100 nm are fabricated based on a solvothermal method. Mg2Nb34O87 has an open 3 × 4 × ∞ Wadsley-Roth shear structure and a large unit-cell volume, leading to its largest Li+ diffusion coefficients among all the developed M-Nb-O anode materials. In situ X-ray diffraction analyses reveal its high structural stability and intercalating characteristic. These architectural, conductivity, and structural advantages in Mg2Nb34O87-P lead to its most significant intercalation pseudocapacitive contribution (87.7% at 1.1 mV s-1) among the existing M-Nb-O anode materials and prominent rate capability (high reversible capacities of 338 mAh g-1 at 0.1C and 230 mAh g-1 at 10C). Additionally, this new material exhibits a safe operating potential (â¼1.68 V), an ultrahigh initial Coulombic efficiency (94.8%), and an outstanding cycling stability (only 6.9% capacity loss at 10C over 500 cycles). All of these evidences indicate that Mg2Nb34O87-P is an ideal anode material for high-energy, safe, fast-charging, and stable LIBs.