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Journal ArticleDOI

Electrochemical Properties of Na0.66V4O10 Nanostructures as Cathode Material in Rechargeable Batteries for Energy Storage Applications.

TL;DR: In this article, the electrochemical performance of nanostructures of Na0.66V4O10 as cathode material for rechargeable batteries was reported, which showed a good cycling stability with specific discharge capacity (measured vs Na+/Na) between 80 (±2) and 30 (± 2) mAh g-1 at current densities of 3 and 50 mA g1, respectively.
Abstract: We report the electrochemical performance of nanostructures of Na0.66V4O10 as cathode material for rechargeable batteries. The Rietveld refinement of room-temperature X-ray diffraction pattern shows the monoclinic phase with C2/m space group. The cyclic voltammetry curves of prepared half-cells exhibit redox peaks at 3.1 and 2.6 V, which are due to two-phase transition reaction between V5+/4+ and can be assigned to the single-step deintercalation/intercalation of Na ion. We observe a good cycling stability with specific discharge capacity (measured vs Na+/Na) between 80 (±2) and 30 (±2) mAh g-1 at current densities of 3 and 50 mA g-1, respectively. The electrochemical performance of Na0.66V4O10 electrode was also tested with Li anode, which showed higher capacity but decayed faster than Na. Using density functional theory, we calculate the Na vacancy formation energies: 3.37 eV in the bulk of the material and 2.52 eV on the (100) surface, which underlines the importance of nanostructures.
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Journal ArticleDOI
TL;DR: In this paper, the performance of NVO as anode material in Li-ion and Na-ion batteries was investigated, and it was shown that the overall performance of the NVO anode is better than that of Na.

43 citations

Journal ArticleDOI
TL;DR: In this article, the authors developed hierarchically structured porous, conductive, and multifunctional N-doped carbon (N-C) nanofibers comprising homogeneously dispersed vanadium nitride quantum dots and hollow N-C nanocages as functional interlayers for advanced LSBs.
Abstract: The introduction of a functional interlayer between the cathode and anode in lithium–sulfur battery (LSB) technology results in significant improvements in electrochemical performance. Here, we developed hierarchically structured porous, conductive, and multifunctional N-doped carbon (N-C) nanofibers comprising homogeneously dispersed vanadium nitride quantum dots and hollow N-C nanocages as functional interlayers for advanced LSBs. The freestanding interlayer contains well-developed long-range channels and numerous interconnected hollow N-C nanocages derived from the metal–organic framework. Furthermore, the presence of a N-C framework and vanadium nitride quantum dots measuring several nanometers improves the redox reaction kinetics and provides numerous chemisorption sites for the effective trapping and reuse of lithium polysulfide. As a result, the assembled Li–S cell employing the unique nanostructured freestanding interlayer exhibits superior rate capability and stable cycling performance (decay rate of 0.02% per cycle at 0.5C) considering the high sulfur content (80 wt%) and loading (ca. 4 mg cm−2) in the sulfur electrodes. Even with an ultra-high sulfur loading of 11.0 mg cm−2, the Li–S cell delivered a stable areal capacity of 5.0 mA h cm−2 after 100 charge–discharge cycles at 0.05C. Thus, the uniquely nanostructured interlayer shows high potential for the development of advanced LSBs utilizing pure sulfur electrodes with realistic battery parameters.

36 citations

Journal ArticleDOI
TL;DR: Mechanistic studies, utilizing molecular dynamics and density functional theory calculations, were undertaken to provide a molecular level explanation of Ba cation segregation in double perovskite GdBaCo2O5+δ (GBCO) electrodes and proposed to control the degree of surface segregation by applying nanostructuring of the GBCO material in the form of nanoparticles.
Abstract: Mechanistic studies, utilizing molecular dynamics (MD) and density functional theory (DFT) calculations, were undertaken to provide a molecular level explanation of Ba cation segregation in double perovskite GdBaCo2O5+δ (GBCO) electrodes. The energy (γ) of the terminal surface having only Ba cations, indicated the surface to be the most stable (γ = 6.7 kJ mol-1A-2) as compared to the other surfaces. MD simulations elaborated on the cation disorder in the near surface region where Ba cations in the subsurface region were observed to migrate towards the surface. This led to a disruption in cation ordering with a propensity to form multiphases in the near surface region. In the near surface zone, oxygen anion diffusivity was observed to be reduced by an order of magnitude (D = 1.6 × 10-11 cm2 s-1 at 873 K) as compared to the bulk oxygen anion diffusivity value (D = 1.96 × 10-10 cm2 s-1 at 873 K). A novel idea was then proposed to control the degree of surface segregation of Ba cations by applying nanostructuring of the GBCO material in the form of nanoparticles. MD simulations elucidated that the near surface region having a high degree of cation disorder in the nanostructured GBCO may regain back the oxygen anion diffusivity value (D = 3.98 × 10-10 cm2 s-1, at 873 K) comparable to the bulk core region (D = 2.51 × 10-10 cm2 s-1, at 873 K). A proof of concept experiment was setup to test this hypothesis. The electrochemical performance of the electrode, fabricated using GBCO nanoparticles, was measured to improve by 15% as compared to the electrode synthesized with a bulk size GBCO material. This was attributed to the control in Ba-cation segregation, obtained on nanostructuring which resulted in higher oxygen anion transport in the near-surface region of the electrode material. XPS characterization of the surface of the nanostructured GBCO materials supported this assertion.

20 citations

Journal ArticleDOI
TL;DR: In this article , a short review highlights the intrinsic challenges and corresponding strategies for the extensively researched layered transition metal oxides, polyanionic compounds, and Prussian blue analogues.
Abstract: With the escalating demand for sustainable energy sources, the sodium-ion batteries (SIBs) appear as a pragmatic option to develop large energy storage grid applications in contrast to existing lithium-ion batteries (LIBs) owing to the availability of cheap sodium precursors. Nevertheless, the commercialization of SIBs has not been carried out so far due to the inefficacies of present electrode materials, particularly cathodes. Thus, from a future application perspective, this short review highlights the intrinsic challenges and corresponding strategies for the extensively researched layered transition metal oxides, polyanionic compounds, and Prussian blue analogues. In addition, the commercial feasibility of existing materials considering relevant parameters is also discussed. The insights provided in the current review may serve as an aid in designing efficient cathode materials for state-of-the-art SIBs.

19 citations

References
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Journal ArticleDOI
TL;DR: In this article, a method for generating sets of special points in the Brillouin zone which provides an efficient means of integrating periodic functions of the wave vector is given, where the integration can be over the entire zone or over specified portions thereof.
Abstract: A method is given for generating sets of special points in the Brillouin zone which provides an efficient means of integrating periodic functions of the wave vector. The integration can be over the entire Brillouin zone or over specified portions thereof. This method also has applications in spectral and density-of-state calculations. The relationships to the Chadi-Cohen and Gilat-Raubenheimer methods are indicated.

51,059 citations

Journal ArticleDOI
TL;DR: A detailed description and comparison of algorithms for performing ab-initio quantum-mechanical calculations using pseudopotentials and a plane-wave basis set is presented in this article. But this is not a comparison of our algorithm with the one presented in this paper.

47,666 citations

Journal ArticleDOI
TL;DR: Novel features are that the pseudopotential itself becomes charge-state dependent, the usual norm-conservation constraint does not apply, and a generalized eigenproblem is introduced.
Abstract: A new approach to the construction of first-principles pseudopotentials is described. The method allows transferability to be improved systematically while holding the cutoff radius fixed, even for large cutoff radii. Novel features are that the pseudopotential itself becomes charge-state dependent, the usual norm-conservation constraint does not apply, and a generalized eigenproblem is introduced. The potentials have a separable form well suited for plane-wave solid-state calculations, and show promise for application to first-row and transition-metal systems.

18,782 citations

Journal ArticleDOI
TL;DR: In this paper, the authors reviewed the challenges for further development of Li rechargeable batteries for electric vehicles and proposed a nonflammable electrolyte with either a larger window between its lowest unoccupied molecular orbital and highest occupied molecular orbital (HOMO) or a constituent that can develop rapidly a solid/ electrolyte-interface (SEI) layer to prevent plating of Li on a carbon anode during a fast charge of the battery.
Abstract: The challenges for further development of Li rechargeable batteries for electric vehicles are reviewed. Most important is safety, which requires development of a nonflammable electrolyte with either a larger window between its lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) or a constituent (or additive) that can develop rapidly a solid/ electrolyte-interface (SEI) layer to prevent plating of Li on a carbon anode during a fast charge of the battery. A high Li-ion conductivity (σ Li > 10 ―4 S/cm) in the electrolyte and across the electrode/ electrolyte interface is needed for a power battery. Important also is an increase in the density of the stored energy, which is the product of the voltage and capacity of reversible Li insertion/extraction into/from the electrodes. It will be difficult to design a better anode than carbon, but carbon requires formation of an SEI layer, which involves an irreversible capacity loss. The design of a cathode composed of environmentally benign, low-cost materials that has its electrochemical potential μ C well-matched to the HOMO of the electrolyte and allows access to two Li atoms per transition-metal cation would increase the energy density, but it is a daunting challenge. Two redox couples can be accessed where the cation redox couples are "pinned" at the top of the O 2p bands, but to take advantage of this possibility, it must be realized in a framework structure that can accept more than one Li atom per transition-metal cation. Moreover, such a situation represents an intrinsic voltage limit of the cathode, and matching this limit to the HOMO of the electrolyte requires the ability to tune the intrinsic voltage limit. Finally, the chemical compatibility in the battery must allow a long service life.

8,535 citations

Journal ArticleDOI
TL;DR: New strategies are needed for batteries that go beyond powering hand-held devices, such as using electrode hosts with two-electron redox centers; replacing the cathode hosts by materials that undergo displacement reactions; and developing a Li(+) solid electrolyte separator membrane that allows an organic and aqueous liquid electrolyte on the anode and cathode sides, respectively.
Abstract: Each cell of a battery stores electrical energy as chemical energy in two electrodes, a reductant (anode) and an oxidant (cathode), separated by an electrolyte that transfers the ionic component of the chemical reaction inside the cell and forces the electronic component outside the battery. The output on discharge is an external electronic current I at a voltage V for a time Δt. The chemical reaction of a rechargeable battery must be reversible on the application of a charging I and V. Critical parameters of a rechargeable battery are safety, density of energy that can be stored at a specific power input and retrieved at a specific power output, cycle and shelf life, storage efficiency, and cost of fabrication. Conventional ambient-temperature rechargeable batteries have solid electrodes and a liquid electrolyte. The positive electrode (cathode) consists of a host framework into which the mobile (working) cation is inserted reversibly over a finite solid–solution range. The solid–solution range, which is...

6,950 citations