Effects of pyridine carboxylic acid on the positive electrolyte for vanadium redox flow battery

Ionics - In this work, dipicolinic acid and quinolinic acid are employed as additives to improve the thermal stability and electrochemical performance for the positive electrolyte of vanadium redox...     

Study of the electrochemical performance of VO2+/VO2 + redox couple in sulfamic acid for vanadium redox flow battery

The present work was performed in order to evaluate sulfamic acid as the supporting electrolyte for VO²⁺/VO₂ ⁺ redox couple in vanadium redox flow battery. The oxidation process of VO²⁺ has similar electrochemical kinetics compared with the reduction process of VO₂ ⁺. The exchange current density and standard rate constant of VO²⁺/VO₂ ⁺ redox reaction on a graphite electrode in sulfamic acid are determined as 7.6?×?10^?4 A cm^?2 and 7.9?×?10^?5 cm s^?1, respectively. The energy efficiency of the cell employing sulfamic acid as supporting electrolyte in the positive side can reach 75.87 %, which is adequate for redox flow battery applied in energy storage. The addition of NH₄ ⁺ to the positive electrolyte can enhance the electrochemical performance of the cell, with larger discharge capacity and energy efficiency. The preliminary exploration shows that the vanadium sulfamate electrolyte is promising for vanadium redox flow battery and is worthy of further study.     

Effect of nickel coating on electrochemical performance of graphite anodes for lithium ion batteries

Among the different materials often studied and proposed as negative electrodes for lithium-ion batteries, graphite anodes are the most used in commercial batteries. For this study, synthetic graphite was tested. During the first discharge 0.2 Li ions were consumed for the formation of the SEI film and the capacity reaches about 387 mAh/g. But at the end of the first charge only 72% of the initial charge was recovered (the reversible capacity is about 279 mAh/g). In order to improve this performance we have deposited metallic nickel on graphite with the intention to obtain a homogeneous thin layer able to modify the nature of the SEI film, to allow the diffusion of lithium ions through the protective layer, and also to increase the performance of graphite electrodes. The results show a decrease of the irreversible capacity loss (16% instead of 28% for pure graphite electrodes) as well as better cycleability for a nickel-deposited graphite electrode with only 11% weight ratio of nickel. On the other hand, an increase of the nickel content decreases this performance.     

Effect of monocationic ionic liquids as electrolyte additives on the electrochemical and thermal properties of Li-ion batteries

The conventional electrolyte system has been compared with the ionic liquid (IL) additive containing electrolyte system at room temperature as well as elevated temperature. In this work, two types of monocationic ILs such as 1-butyl-3-methylpyrrolidinium hexafluorophosphate (Pyr IL) and 1-ethyl-3-methylimidazolium hexafluorophosphate (IMI IL) are added as an additive at two different weight ratios in 1.15 M LiPF₆ (EC/EMC = 3/7 v/v) electrolyte solution, the structural, electrochemical and thermal characteristics of LiNi_0.80Co_0.15Al_0.05O₂ (NCA)/carbon full-cell in different electrolyte formulations have been reconnoitered. X-ray diffraction (XRD) studies have proved that IL as an electrolyte additive does not alter the structural stability of cathode materials after cycling. Under room temperature, Pyr IL additives at 1 wt% and 3 wt% deliver better cycleability than others, with the retention ratios of 93.62% and 92.8%, respectively. At elevated temperature, only 1 wt% Pyr IL additive is giving stable capacity retention ratio of 80.74%. Ionic conductivity and self-extinguishing time (SET) values are increasing with respect to the amount of additive added to the electrolyte. Thermal studies reveal that 3 wt% Pyr IL is favorable regarding the safety of the battery as it shows shifting of peak to higher temperature of 272.10 °C. Among the IL additives evaluated in this study, addition of 1 wt% Pyr IL is the most desirable additive for achieving the best cycling performance as well as thermal behavior of Li-ion batteries.     

Effect of pyrolytic polyacrylonitrile on electrochemical performance of Si/graphite composite anode for lithium-ion batteries

The silicon/graphite (Si/G) composite was prepared using pyrolytic polyacrylonitrile (PAN) as carbon precursor, which is a nitrogen-doped carbon that provides efficient pathway for electron transfer. The combination of flake graphite and pyrolytic carbon layer accommodates the large volume expansion of Si during discharge-charge process. The Si/G composite was synthesized via cost-effective liquid solidification followed by carbonization process. The effect of PAN content on electrochemical performance of composites was investigated. The composite containing 40 wt% PAN exhibits a relatively better rate capability and cycle performance than others. It exhibits initial reversible specific capacity of 793.6 mAh g^?1 at a current density of 100 mA g^?1. High capacity of 661 mAh g^?1 can be reached after 50 cycles at current density of 500 mA g^?1.     

Influence of NiCl2 modification on the electrochemical performance of LiV3O8 cathode for lithium ion batteries

The 5.0, 8.0, and 10.0 wt% NiCl₂-modified LiV₃O₈ materials are successfully prepared and the effects of NiCl₂ modification on the electrochemical performance of LiV₃O₈ cathode have been investigated. The structural and surface morphologic properties of synthesized materials are characterized by X-ray diffraction and scanning electron microscopy. The electrochemical properties are investigated by charge–discharge testing and cyclic voltammetry. It is found that 8.0 wt% NiCl₂-modified LiV₃O₈ shows excellent electrochemical properties. The initial discharge capacity of 8.0 wt% NiCl₂-modified LiV₃O₈ is much higher than that of pristine LiV₃O₈, and can attain 336.7 mAh g^?1 at the current rate of 0.5 C (300 mA g^?1 is assumed to be 1 C rate). Additionally, NiCl₂ modification significantly improves the cyclability of LiV₃O₈. The NiCl₂ modification is shown to be able to suppress the capacity fade of LiV₃O₈ without specific capacity expense by suppressing the characteristic phase transitions during cycling.     

Effect of Gd3+ ions on the luminescence of opa-Gly

Published in Zhurnal Prikladnoi Spektroskopii Vol. 62, No. 5, pp. 221–224, Sepember–October, 1995.     

Effect of strain on electrochemical performance of Janus MoSSe monolayer anode material for Li-ion batteries: First-principles study

First-principles calculations are performed to investigate the effect of strain on the electrochemical performance of Janus MoSSe monolayer.The calculation focuses on the specific capacity,intercalation potential,electronic structure,and migration behavior of Li-ion under various strains by using the climbing-image nudged elastic band method.The result shows that the specific capacity is nearly unchanged under strain.But interestingly,the tensile strain can cause the intercalation potential and Li-ion migration energy barrier increase in MoSSe monolayer,whereas the compressive strain can lead to the intercalation potential and energy barrier decreasing.Thus,the rate performance of the MoSSe anode is improved.By analyzing the potential energy surface of MoSSe surface and equilibrium adsorption distance of Li-ion,we explain the physical origin of the change in the intercalation potential and migration energy barrier.The increase of MoSSe potential energy surface and the decrease of adsorption distance caused by tensile strain are the main reason that hinders Li-ion migration.     

Effect of the dose and energy of Ar+ ions on the surface properties of vanadium and its alloys

The features of processes occurring on the surface of vanadium and its alloys irradiated using the ILU ion-beam accelerator with Ar⁺ ions at an energy of 20 and 40 keV up to doses of 5.0 × 10²¹ m^?2 and 1.0 × 10²² m^?2 at T _irr ≈ 700 K are studied. The effect of the dose and energy of implanted ions on the surface hardness is obtained. The thickness of the hardened layer is more than two orders of magnitude higher than the theoretical and experimental projected range of Ar⁺ ions at an energy of 20 and 40 keV in vanadium. Structural changes in the surface layers, which are expressed in a change in the intensity of reflections from a number of planes and an increase in the crystal-lattice parameter of the irradiated materials, are also observed.     

Charge rate influence on the electrochemical performance of LiFePO<Subscript>4</Subscript> electrode with redox shuttle additive in electrolyte

Overcharge performance of LiFePO₄ cells is investigated through adding 2, 5-ditertbutyl 1, 4-dimethoxybenzene (DDB) as redox shuttle into electrolyte (RS electrolyte) at different charge rate. RS electrolytes with DDB works well as overcharge protection at low charge rate of less than 0.1 C. Novel charge/discharge characteristics are observed when charge rate increases in the cell with RS electrolyte. Especially, larger discharge capacities are obtained at the same discharge rate after charge rate gets higher than 0.1 C rate. Discharge capacity is larger in the cell with RS electrolyte than that in the cell without RS electrolyte at the same charge and discharge rate. At the same charge rate, cells with RS electrolyte have better cycling performances and larger discharge capacity than that with conventional electrolyte. These indicate that DDB accumulates in cathode with cycling and influences electrode–electrolyte interface reactions.     

Comparative calculation on Li~+ solvation in common organic electrolyte solvents for lithium ion batteries

It is important for the electrolytes to maintain and enhance the lithium ion battery electrochemical performance,and solvation of Li^+is a key parameter for the property of the electrolytes.The comparative study on Li^+ solvation structures,energy,enthalpy,Gibbs free energy,infrared and Raman spectra in common organic electrolyte solvents is completed by density functional theory(DFT)method.The solvation reaction energy results suggest that the Li^+solvation priority order is propylene carbonate(PC)>ethylene carbonate(EC)>ethyl methyl carbonate(EMC)>diethyl carbonate(DEC)>tetrahydrofuran(THF)>dimethyl carbonate(DMC)>1,3-dioxolane(DOL)>dimethoxyethane(DME)to form 5sol Li^+.It is also indicated that the most innermost solvation shell compounds formations by stepwise spontaneous solvation reaction are four cyclic solvent molecules and three linear solvent molecules combining one Li^+ forming 4sol-Li^+ and 3sol-Li^+,respectively,at room temperature.Besides,the vibration peaks for C=O and C-O bonds in carbonate ester solvents-Li^+ compounds shift to lower frequency and higher frequency,respectively,when the Li^+ concentration increases in the solvation compounds.All Li-O stretching vibration peaks shift to higher frequency until forming 2solvent-Li^+ complexes,and C-H stretching also shifts to higher frequency except for nDME-Li^+ solvation compounds.The Raman spectrum is more agile to characterize C-H vibrations and IR is agile to C=O,C-O,and Li-O vibrations for Li^+solvation compounds.     

Excellent long-term electrochemical performance of graphite oxide as cathode materials for lithium-ion batteries

A facile, scalable route has been adopted to synthesize graphite oxides with different degrees of oxidation. Subsequently, graphite oxides with rationally designed functional groups have been utilized as cathode materials for lithium-ion batteries (LIBs). The electrodes deliver the initial and second discharge capacities of 332 and 172 mAh g^?1 at a current density of 0.1 A g^?1, respectively. More importantly, a remarkable long-term cycling performance of 130 mAh g^?1 after 800 cycles has been gathered, with an ultralow capacity fading of 0.03% per cycle from the second cycle. The root cause of excellent cycling stability should be ascribed to the admirable reversibility of epoxy and carbonyl groups in graphite oxides during the Li-cycling. Meanwhile, the deep study has provided a novel way to avoid complex and expensive post-treatment process of graphite oxides, whose synthesis conditions are also optimized. Those striking features make graphite oxides as promising cathode materials for lithium-ion batteries.     

Enhancement of the electrochemical performance of silicon/carbon composite material for lithium ion batteries

The silicon/carbon (Si/C) composite material was prepared, and the electrochemical performance was investigated as a promising anode material for lithium ion batteries. The results show that the binder in the electrode acts as an important role for improving the reversible capacity of the Si/C materials during cycling. The Si/C electrode with CMC/SBR binder possesses a better cycle performance than that with PVDF binder. The Si/C composite material shows an initial reversible capacity of more than 700 mAh∙g⁻¹ and remains a reversible capacity of 597 mAh g⁻¹ after 40 cycles.     

Preparation of Si-PPy-Ag composites and their electrochemical performance as anode for lithium-ion batteries

The nanosilicon connected by polypyrrole (PPy) and silver (Ag) particles was simply synthesized by a chemical polymerization process in order to prepare Si-based anodes for Li-ion batteries. The phase structure, surface morphology, and electrochemical properties of the as-synthesized powders were analyzed by X-ray diffraction, FT-IR, scanning electron microscopy, and galvanostatic charge/discharge measurements. The cycle stability of the Si-PPy-Ag composites was greatly enhanced compared with the pure nanosilicon. A high capacity of more than 823 mA h g^?1 was maintained after 100 cycles. The improved electrochemical characteristics are attributed to the volume buffering effect as well as effective electronic conductivity of the polypyrrole and silver in the composite electrode.     

Computational screening of electroactive indolequinone derivatives as high-performance active materials for aqueous redox flow batteries

The development of an organic-based aqueous redox flow battery (RFB) using quinone as an electroactive material has attracted great attention recently. This is because this battery is inexpensive, produces high energy density, and is environment friendly in stationary electrical energy storage applications. Herein, we investigate the redox potentials and solubilities of indole-5,6-quinone and indole-4,7-quinone derivatives in terms of the substituent effects of functional groups using theoretical calculations. Our results indicate that full-site substituted derivatives of indolequinone are more useful as active materials compared to single-site substituted derivatives. In particular, our calculations reveal that the substitution of –PO₃H₂ and –SO₃H functional groups with multiple polar bonds is very effective in increasing the activity of the aqueous RFB. As a strategy to overcome the limitation that the aqueous solubility is intrinsically low because they are organic molecules, we suggest the substitution of functional groups with multiple polar bonds to the backbones of active organic materials. Among 180 indolequinone derivatives, 17 candidates that meet the redox potential standards (≦ 0.2 V or ≧ 0.9 V) and eight candidates with solubility exceeding 2 mol/L are identified. Three indolequinone derivatives that satisfy both conditions are finally presented as promising electroactive candidates for an aqueous RFB.     

Effect of Mo3+ ions on Nd3+ spin-lattice relaxation in Y3Al5O12

The content of Mo³⁺ ions in YAG:Nd garnet samples prepared by different technologies has been studied, and the spin-lattice relaxation rate of these ions at temperatures of 4–5 K measured. It is concluded is drawn that Mo³⁺ ions can play the part of rapidly relaxing centers mediating the Nd³⁺ spin-lattice relaxation at liquid-helium temperatures. This may account for a number of features in the spin-lattice relaxation of rare-earth ions in garnets, observed earlier at low temperatures. Fiz. Tverd. Tela (St. Petersburg) 40, 2026–2028 (November 1998)     

Effect of different compositions of ethylene carbonate and propylene carbonate containing iodide/triiodide redox electrolyte on the photovoltaic performance of DSSC

The effect of different compositions (in weight percent) of ethylene carbonate (EC) and propylene carbonate (PC) containing iodide/triiodide redox electrolyte on the photoelectrochemical performance of N719-sensitized nanocrystalline TiO₂ solar cell was studied. The cells consisted of 0.6 M 1-hexyl-2,3-dimethylimidazolium iodide, 0.1 M LiI, 0.05 M I₂ and 0.5 M 4-tert-butylpyridine in different compositions such as 1:1, 1:2, and 2:1 wt% of EC and PC. In 1:1 wt% of EC and PC containing redox electrolyte, short circuit photocurrent density (J _sc) increased and open circuit voltage (V _oc) decreased. But in 1:2 and 2:1 wt% of EC and PC containing redox electrolytes, V _oc increased and J _sc decreased but fill factor remained relatively constant. Dye-sensitized solar cells (DSSCs) prepared using these electrolytes give a short circuit photocurrent densities of 16.86, 12.71, and 12.09 mA/cm²; an open circuit voltages of 0.73, 0.78, and 0.79 V; fill factors of 0.63, 0.64, and 0.64; and an overall conversion efficiencies of 7.76, 6.34, and 6.13 % at an incident light of 100 mWcm^?2 for 1:1, 2:1, and 1:2 wt% of EC/PC containing redox electrolytes, respectively. The incident photon-to-current conversion efficiency was higher in the case of 1:1 wt% of EC and PC containing redox electrolyte than 1:2 and 2:1 wt% of EC and PC containing redox electrolyte. It revealed that 1:1 wt% of EC and PC containing iodide/triiodide redox electrolyte is an effective electrolyte system for the fabrication of long-term stable DSSC.     

Preparation and electrochemical performance of bramble-like ZnO array as anode materials for lithium-ion batteries

A bramble-like ZnO array with a special three-dimensional (3D) nanostructure was successfully fabricated on Zn foil through a facile two-step hydrothermal process. A possible growth mechanism of the bramble-like ZnO array was proposed. In the first step of hydrothermal process, the crystal nucleus of Zn(OH) ₄ ^2? generated by the zinc atoms and OH^? ions fold together preferentially along the positive polar (0001) to form the needle-like ZnO array. In the second step of hydrothermal process, the crystal nuclei of Zn(OH) ₄ ^2? adjust their posture to keep their c-axes vertical to the perching sites due to the sufficient environmental force and further grow preferentially along the (0001) direction so as to form bramble-like ZnO array. The electrochemical properties of the needle- and bramble-like ZnO arrays as anode materials for lithium-ion batteries were investigated and compared. The results show that the bramble-like ZnO material exhibits much better lithium storage properties than the needle-like ZnO sample. Reasons for the enhanced electrochemical performance of the bramble-like ZnO material were investigated.     

Development of a new polymer electrolyte (PMMA-CO-P4VPNO+KClO3) for solid state electrochemical cells

Polymer electrolyte films based on a co-polymer polymethyle methacrylate-co-poly 4vinyl pyridine N-oxide (PMMA-CO-P4VPNO) complexed with KClO₃ were prepared by solution cast technique. The complexation of KClO₃ salt with the polymer was confirmed by infrared studies. Measurements of the dc conductivity in the temperature range 300–410 K and transference numbers were carried out to investigate the charge transport in the polymer electrolyte system. Transference number data show that the charge transport in this polymer electrolyte system is predominantly due to ions. Using the polymer electrolyte solid state electrochemical cells were fabricated with the configuration (K)-(PMMA-CO-P4VPNO+KClO₃)-(I₂+C+electrolyte) and various parameters of the cells including open circuit voltage (OCV) and short circuit current (SCC) were evaluated. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.