Redox Activity of Sodium Vanadium Oxides towards Oxidation in Na Ion Batteries.
Ontology highlight
ABSTRACT:
SUBMITTER: Adamczyk E
PROVIDER: S-EPMC6024919 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:Na9V14O35 (η-NaxV2O5) has been synthesized via solid-state reaction in an evacuated sealed silica ampoule and tested as electroactive material for Na-ion batteries. According to powder X-ray diffraction, electron diffraction and atomic resolution scanning transmission electron microscopy, Na9V14O35 adopts a monoclinic structure consisting of layers of corner- and edge-sharing VO5 tetragonal pyramids and VO4 tetrahedra with Na cations positioned between the layers, and can be considered as sodium vanadium(IV,V) oxovanadate Na9V104.1+O19(V5+O4)4. Behavior of Na9V14O35 as a positive and negative electrode in Na half-cells was investigated by galvanostatic cycling against metallic Na, synchrotron powder X-ray diffraction and electron energy loss spectroscopy. Being charged to 4.6 V vs. Na+/Na, almost 3 Na can be extracted per Na9V14O35 formula, resulting in electrochemical capacity of ~60 mAh g-1. Upon discharge below 1 V, Na9V14O35 uptakes sodium up to Na:V = 1:1 ratio that is accompanied by drastic elongation of the separation between the layers of the VO4 tetrahedra and VO5 tetragonal pyramids and volume increase of about 31%. Below 0.25 V, the ordered layered Na9V14O35 structure transforms into a rock-salt type disordered structure and ultimately into amorphous products of a conversion reaction at 0.1 V. The discharge capacity of 490 mAh g-1 delivered at first cycle due to the conversion reaction fades with the number of charge-discharge cycles.
| S-EPMC8747075 | biostudies-literature
Project description:Polyoxometalates are key materials for energy conversion and storage due to their unique chemical tunability and electrochemical reactivity. Herein, we report that functionalization of molecular vanadium oxides, polyoxovanadates, with redox-inert Ca2+ cations leads to a significant increase in their electron storage capabilities. The electrochemical performance of the Ca2+-functionalized dodecavanadate [Ca2V12O32Cl(DMF)3]2- (={Ca 2 V 12 }) was thus compared with that of the precursor compound (H2NMe2)2[V12O32Cl]3- (={V 12 }). {Ca 2 V 12 } can store up to five electrons per cluster, while {V 12 } only shows one reversible redox transition. In initial studies, we demonstrated that {Ca 2 V 12 } can be used as an active material in lithium-ion cathodes. Our results show how redox-inert cations can be used as structural and electrostatic stabilizers, leading to major changes in the redox-chemistry of polyoxovanadates.
| S-EPMC8159454 | biostudies-literature
Project description:Vanadium-oxide-based materials exist with various vanadium oxidation states having rich chemistry and ability to form layered structures. These properties make them suitable for different applications, including energy conversion and storage. Magnesium vanadium oxide materials obtained using simple preparation route were studied as potential cathodes for rechargeable aqueous magnesium ion batteries. Structural characterization of the synthesized materials was performed using XRD and vibrational spectroscopy techniques (FTIR and Raman spectroscopy). Electrochemical behavior of the materials, observed by cyclic voltammetry, was further explained by BVS calculations. Sluggish Mg2+ ion kinetics in MgV2O6 was shown as a result of poor electronic and ionic wiring. Complex redox behavior of the studied materials is dependent on phase composition and metal ion inserted/deinserted into/from the material. Among the studied magnesium vanadium oxides, the multiphase oxide systems exhibited better Mg2+ insertion/deinsertion performances than the single-phase ones. Carbon addition was found to be an effective dual strategy for enhancing the charge storage behavior of MgV2O6.
| S-EPMC9412870 | biostudies-literature
Project description:Overcharge abuse can trigger thermal runaway when a device is left unattended. Redox shuttles, as economic and efficient electrolyte additives, have been proven to provide reliable and reversible protection for state-of-art Li-ion batteries (LIBs) against overcharge. Here, a functional organic salt, trisaminocyclopropenium perchlorate (TAC•ClO4), is developed and employed as a redox shuttle for overcharge protection in a Na-ion battery system. This type of novel redox shuttle molecule is reported for the first time. As a unique ionic compound with the smallest aromatic ring structure, TAC•ClO4 exhibits distinctive attributes of fast diffusion, high solubility, and ultrahigh chemical/electrochemical stability in both redox states. With merely 0.1 M TAC•ClO4 in electrolyte, Na3V2(PO4)3 cathode can carry overcharge current even up to 10C or 400% SOC. Na3V2(PO4)3/hard carbon cells demonstrated strong anti-overcharging ability of 176 cycles at 0.5C rate and 54 cycles at 1C rate with 100% overcharge. Moreover, TAC•ClO4 addition has little impact on the electrochemical performance of Na-ion batteries, especially on the rate performance and the initial Columbic efficiency. Interestingly, a unique and reversible electrochromic behavior of TAC•ClO4 electrolyte can promptly provide the device an overcharge alarm under a designed potential to further enhance the safety level.
| S-EPMC8186495 | biostudies-literature
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.
| S-EPMC5493763 | biostudies-literature
Project description:Layered Na-based oxides with the general composition of NaxTMO2 (TM: transition metal) have attracted significant attention for their high compositional diversity that provides tunable electrochemical performance for electrodes in sodium-ion batteries. The various compositions bring forward complex structural chemistry that is decisive for the layered stacking structure, Na-ion conductivity, and the redox activity, potentially promising new avenues in functional material properties. In this work, we have explored the maximum Na content in P2-type layered oxides and discovered that the high-content Na in the host enhances the structural stability; moreover, it promotes the oxidation of low-valent cations to their high oxidation states (in this case Ni2+). This can be rationalized by the increased hybridization of the O(2p)-TM(3d-eg*) states, affecting both the local TM environment as well as the interactions between the NaO2 and TMO2 layers. These properties are highly beneficial for the Na storage capabilities as required for cathode materials in sodium-ion batteries. It leads to excellent Na-ion mobility, a large storage capacity (>100 mAh g-1 between 2.0-4.0 V), yet preventing the detrimental sliding of the TMO2 layers (P2-O2 structural transition), as reflected by the ultralong cycle life (3000 (dis)charge cycles demonstrated). These findings expand the horizons of high Na-content P2-type materials, providing new insights of the electronic and structural chemistry for advanced cathode materials.
| S-EPMC7252945 | biostudies-literature
Project description:Manganese based layered oxides have received increasing attention as cathode materials for sodium ion batteries due to their high theoretical capacities and good sodium ion conductivities. However, the Jahn-Teller distortion arising from the manganese (III) centers destabilizes the host structure and deteriorates the cycling life. Herein, we report that zinc-doped Na0.833[Li0.25Mn0.75]O2 can not only suppress the Jahn-Teller effect but also reduce the inherent phase separations. The reduction of manganese (III) amount in the zinc-doped sample, as predicted by first-principles calculations, has been confirmed by its high binding energies and the reduced octahedral structural variations. In the viewpoint of thermodynamics, the zinc-doped sample has lower formation energy, more stable ground states, and fewer spinodal decomposition regions than those of the undoped sample, all of which make it charge or discharge without any phase transition. Hence, the zinc-doped sample shows superior cycling performance, demonstrating that zinc doping is an effective strategy for developing high-performance layered cathode materials.
| S-EPMC6323141 | biostudies-literature
Project description:Herein, we report additive- and binder-free pristine amorphous vanadium oxide (a-VOx) for Li- and Na-ion battery application. Thin films of a-VOx with a thickness of about 650 nm are grown onto stainless steel substrate from crystalline V2O5 target using pulsed laser deposition (PLD) technique. Under varying oxygen partial pressure (pO2) environment of 0, 6, 13 and 30 Pa, films bear O/V atomic ratios 0.76, 2.13, 2.25 and 2.0, respectively. The films deposited at 6‑30 Pa have a more atomic percentage of V5+ than that of V4+ with a tendency of later state increased as pO2 rises. Amorphous VOx films obtained at moderate pO2 levels are found superior to other counterparts for cathode application in Li- and Na-ion batteries with reversible capacities as high as 300 and 164 mAh g-1 at 0.1 C current rate, respectively. At the end of the 100th cycle, 90% capacity retention is noticed in both cases. The observed cycling trend suggests that more is the (V5+) stoichiometric nature of a-VOx better is the electrochemistry.
| S-EPMC6235769 | biostudies-literature
Project description:Sodium-ion batteries are commonly regarded as a promising candidate in large-scale energy storage. Layered iron/manganese oxide cathodes receive extensive attentions due to the element abundance and large theoretical capacity. However, these materials usually undergo obvious degradation of electrochemical performance due to the tendency of Mn dissolution and Fe migration during continuous sodium release and uptake. Herein, a strategy of anion-cation synergetic redox is proposed to suppress the structural deterioration originated from overusing the electrochemical activity of transition-metal ions, and decreased lattice strain as well as superior electrochemical performance are realized simultaneously. Results show that the Na0.8 Li0.2 Fe0.2 Mn0.6 O2 (NLFM) electrode is highly resistant to the erosion of moisture that is distinct from the traditional Mn/Fe-based electrodes. Moreover, the NLFM electrode demonstrates solid solution behavior without phase transition during cycles. The ultra-small volume change of 0.85% is ascribed to the negligible manganese dissolution and invisible transition-metal migration. The high-stable layered structure assures superior reversible capacity of ≈165 mA h g-1 , excellent rate capability, and splendid capacity retention of over 98.3% with 100 cycles. The findings deepen the understanding of the synergy between anion and cation redox and provide new insights to design the high-stable layered cathode for sodium-ion batteries.
| S-EPMC9165485 | biostudies-literature
Project description:Ionomer nanocomposites provide a promising solution to address ion crossover issues inherent to traditional ion-containing membranes used in batteries for grid-scale energy storage (e.g., vanadium redox flow batteries). Herein, we investigate the impact of nanoparticle surface chemistry on nanoparticle dispersion, membrane morphology, and vanadium ion permeability in a series of Nafion nanocomposites. Specifically, silica nanoparticles (SiNPs) were functionalized with various chemical moieties, seven in total, that electrostatically interact, either attractively or repulsively, with the sulfonic acid groups that coalesce to form the ionic network within Nafion. As seen from electron microscopy analysis of the nanocomposites, SiNPs with sulfonic acid end-functionality were, on average, well dispersed within the ionomer membrane, though increased vanadium ion permeability, as compared to pristine (or unmodified) Nafion, was observed and attributed to changes in the Donnan potential of the system. In contrast, SiNPs with amine end-functionality were, on average, observed to form large aggregates within the ionomer membrane. Surprisingly, nanocomposites containing a higher degree of nanoparticle aggregation demonstrated the lowest vanadium ion permeability. Fractal analysis of the low-Q small-angle neutron scattering data suggests that the interface between the ionomer and the SiNP surface transitions from rough to smooth when the nanoparticle surface is changed from sulfonic acid-functionalized to amine-functionalized.
| S-EPMC7558369 | biostudies-literature