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1.
ACS Appl Mater Interfaces ; 12(12): 13852-13868, 2020 Mar 25.
Artículo en Inglés | MEDLINE | ID: mdl-32167270

RESUMEN

Lithium- and manganese-rich transition-metal oxide (LMR-NMC) electrodes have been designed either as heterostructures of the primary components ("composite") or as core-shell structures with improved electrochemistry reported for both configurations when compared with their primary components. A detailed electrochemical and structural investigation of the 0.5Li2MnO3-0.5LiNi0.5Mn0.3Co0.2O2 composite and core-shell structured positive electrode materials is reported. The core-shell material shows better overall electrochemical performance compared to its corresponding composite material. While both configurations gave the same initial charge capacity of ∼300 mAh/g when cycled at a rate of 10 mA/g at 25 °C, the core-shell sample gives a discharge capacity of 232 mAh/g compared to 208 mAh/g delivered by the composite sample. Also, the core-shell sample gave better rate capability and a smaller first-cycle irreversible capacity loss than the composite sample. The improved performance of the core-shell material is attributed to its lower surface reactivity and limited structural change since the more stable Li2MnO3 shell screens the more reactive Ni-rich core material from interacting with either air or electrolyte at high potentials, thereby preventing electrode surface modification. In situ X-ray diffraction correlated with electrochemical data revealed that the composite sample shows stronger volumetric changes in the lattice parameters during charging to 4.8 V. In addition, X-ray absorption spectroscopy showed an incomplete Ni reduction process after the first discharge for the composite sample. From these results, it was shown that this leads to a more severe degradation in the composite material that affects Li+ intercalation in the subsequent discharge, thereby resulting in its poorer performance. Furthermore, to confirm these results, another LMR-NMC material with a different composition (having a Ni-poor core)-0.5Li2MnO3-0.5LiNi0.33Mn0.33Co0.33O2-was investigated. The core-shell structured positive electrode material also gave an improved electrochemical performance compared to the corresponding composite positive electrode material. These results show that the core-shell configuration could effectively be used to improve the performance of the LMR-NMC materials to enable future high-energy applications.

2.
J Am Chem Soc ; 141(6): 2305-2315, 2019 Feb 13.
Artículo en Inglés | MEDLINE | ID: mdl-30652858

RESUMEN

Orthorhombic V2O5 nanowires were successfully synthesized via a hydrothermal method. A cell-configuration system was built utilizing V2O5 as the cathode and 1 M Mg(ClO4)2 electrolyte within acetonitrile, together with Mg xMo6S8 ( x ≈ 2) as the anode to investigate the structural evolution and oxidation state and local structural changes of V2O5. The V2O5 nanowires deliver an initial discharge/charge capacity of 103 mAh g-1/110 mAh g-1 and the highest discharge capacity of 130 mAh g-1 in the sixth cycle at C/20 rate in the cell-configuration system. In operando synchrotron diffraction and in operando X-ray absorption spectroscopy together with ex situ Raman and X-ray photoelectron spectroscopy reveal the reversibility of magnesium insertion/extraction and provide information on the crystal structure evolution and changes of the oxidation states during cycling.

3.
Nat Commun ; 8: 15888, 2017 06 29.
Artículo en Inglés | MEDLINE | ID: mdl-28660877

RESUMEN

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.

4.
Adv Mater ; 26(6): 970-6, 2014 Feb 12.
Artículo en Inglés | MEDLINE | ID: mdl-24510667

RESUMEN

A flexible alkaline battery with multiwalled carbon nanotube (MWCNT) enhanced composite electrodes and polyvinyl alcohol (PVA)-poly (acrylic acid) (PAA) copolymer separator has been developed. Purified MWCNTs appear to be the most effective conductive additive, while the flexible copolymer separator not only enhances flexibility but also serves as electrolyte storage.

5.
Phys Chem Chem Phys ; 11(17): 3271-7, 2009 May 07.
Artículo en Inglés | MEDLINE | ID: mdl-19370224

RESUMEN

The electrochemical delithiation of LiCo(0.6)M(0.4)PO(4) phosphates (M = Mn, Fe, Ni) was studied by in situ synchrotron diffraction. In all three metallophosphates the oxidation-reduction of 3d-elements proceed via two-phase mechanisms leading to two-phase regions, corresponding to the Co(2+)/Co(3+) and M(2+)/M(3+) reactions. The Ni(2+)/Ni(3+) reaction was not revealed, neither by the potentiostatic intermittent titration technique (PITT) nor by diffraction. In the two-phase reaction, the olivine-like structure of the cathode remains preserved, which is characteristic of this type of materials. Pronounced solid-solution domains were observed during both lithium extraction and insertion. The thermal stability of the charged cathodes is limited by the presence of Co(3+) and its intrinsic instability in these compounds.

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