ZINC ELECTRODE CYCLE-LIFE PERFORMANCE IN ALKALINE ELECTROLYTES HAVING REDUCED ZINC SPECIES SOLUBILITY

Electrolytes having 3.5 M hydroxide-ion concentration were tested in 1.35 Ah Zn/NiOOH cells to evaluate their ability to reduce the extent of zinc species migration and slow the rate of cell capacity decline. Alkaline-fluoride and alkaline-borate electrolytes, in which ZnO solubility is approximately 25% of that in standard 7.4 M KOH electrolyte, exhibited 0.09-0.14%/cycle zinc-electrode area loss, which may be compared to a value of 0.46%/cycle observed in standard electrolyte. In addition, no zinc penetration of the separator occurred in cells that employed alkaline-fluoride and alkaline-borate electrolytes, even when zinc-electrode overpotentials reached 290 mV at the end of charge. Less than 2% of the zinc remaining after cycling was electrochemically inactive.     

ZINC ELECTRODE CYCLE-LIFE PERFORMANCE IN ALKALINE ELECTROLYTES HAVING REDUCED ZINC SPECIES SOLUBILITY

Electrolytes having 3.5 M hydroxide-ion concentration were tested in 1.35 Ah Zn/NiOOH cells to evaluate their ability to reduce the extent of zinc species migration and slow the rate of cell capacity decline. Alkaline-fluoride and alkaline-borate electrolytes, in which ZnO solubility is approximately 25° of that in standard 7.4 M KOH electrolyte, exhibited 0.09-0.14^°/cycle zinc-electrode area loss, which may be compared to a value of 0.46^°/cycle observed in standard electrolyte, In addition, no zinc penetration of the separator occurred in cells that employed alkaline-fluoride and alkaline-borate electrolytes, even when zinc-electrode overpotcntials reached 290 mV at the end of charge. Less than 2^° of the zinc remaining after cycling was electrochemically inactive.     

Rechargeable lithium/sulfur battery with suitable mixed liquid electrolytes

The suitability of some single/binary liquid electrolytes and polymer electrolytes with a 1 M solution of LiCF₃SO₃ was evaluated for discharge capacity and cycle performance of Li/S cells at room temperature. The liquid electrolyte content in the cell was found to have a profound influence on the first discharge capacity and cycle property. The optimum, stable cycle performance at about 450 mAh g⁻¹ was obtained with a medium content (12 μl) of electrolyte. Comparison of cycle performance of cells with tetra(ethylene glycol)dimethyl ether (TEGDME), TEGDME/1,3-dioxolane (DIOX) (1:1, v/v) and 1,2-dimethoxyethane (DME)/di(ethylene glycol)dimethyl ether (DEGDME) (1:1, v/v) showed better results with the mixed electrolytes based on TEGDME. The addition of 5 vol.% of toluene in TEGDME had a remarkable effect of increasing the initial discharge capacity from 386 to 736 mAh g⁻¹ (by >90%) and stabilizing the cycle properties, attributed to the reduced lithium metal interfacial resistance obtained for the system. Polymer electrolyte based on microporous poly(vinylidene fluoride) (PVdF) membrane and TEGDME/DIOX was evaluated for ionic conductivity at room temperature, lithium metal interfacial resistance and cycle performance in room-temperature Li/S cells. A comparison of the liquid electrolyte and polymer electrolyte showed a better performance of the former.     

The coulombic efficiency of zinc electrowinning in high-purity synthetic electrolytes

Measurements of coulombic efficiency (QE) for zinc electrodeposition were carried out under mass transfer-controlled conditions using a rotating disc electrode in synthetic acidic zinc sulphate electrolytes. At 25°C in 0.8 M ZnSO₄+1.07 M H₂SO₄ prepared from reagent grade chemicals, the QE at an aluminium cathode was 95.7–97.6%. In order to study the influence of electrolyte purity on QE several preparation and purification techniques were employed. While different sources of chemicals produced different QEs, the main source of impurities seemed to be the zinc-containing reagent rather than the sulphuric acid. Improvements in purity either had a negligible effect or lowered the QE, indicating that some impurities are beneficial to electrolyte performance. In the purest solutions prepared, an effect due to residual impurities still seemed to be present. The maximum QE obtainable through variation of the three parameters, i.e. temperature, current density and electrode rotation rate, was determined for two electrolytes of different purities; the values of QE obtained were 98.4 and 98.8%, with temperature as the dominant factor. Wark's Rule (the dependence of QE on zinc/acid ratio) was obeyed approximately in the purest electrolyte prepared, over a limited range of composition.     

THE REACTIVITY AND DURABILITY OF ZINC FERRITE HIGH TEMPERATURE DESULFURIZATION SORBENTS

Cylindrical pellets of zinc ferrite high temperature desulfurization sorbent have been prepared using a number of formulation recipes and induration conditions. Physical and structural properties of the resultant sorbents were measured, and reactivity and durability screening tests were carried out using a single pellet electrobalance reactor. The formulation variables studied were ZnO to Fe₂O₃ ratio, Fe₂O₃ source, and the addition of inorganic (bentonite) and organic (methocel) binders to the sorbents. Pellet induration conditions ranged from 0.25 hours at 815^°C to 4.0 hours at 1038°C. Stronger pellets having greater attrition resistance resulted when 5% bentonite was added to the formulation recipe and when the pellets were indurated at high temperature for extended times. In contrast, bentonite content was not a significant factor in determining sorbent reactivity and durability, both of which were improved by mild induration conditions. Sorbent regeneration temperature was found to be an important factor in improving reaction durability, as was the addition of 0.5% methocel to the formulation recipe. Pellets containing catalyst-grade Fe₂O₃ were more reactive than those containing pigment-grade Fe₂O₃. This effect, however, was less important than the effect of induration conditions.     

Effect of the concentration of diphenyloctyl phosphate as a flame-retarding additive on the electrochemical performance of lithium-ion batteries

We selected diphenyloctyl phosphate (DPOF) as a flame-retardant and plasticizer, and studied the influence of different amounts of the DPOF additive on the electrochemical performance of lithium-ion batteries. The electrochemical cell performances of the additive-containing electrolytes in combination with a cell comprising an LiCoO₂ cathode and mesocarbon microbeads (MCMB) anode were tested in coin cells. The cyclic voltammetry (CV) results showed that the oxidation potential of the electrolyte containing DPOF in the concentration range from 10 to 30 wt.% is about 4.75-5.5 V versus Li/Li⁺. In the present work, a DPOF content of 10 wt.% in the 1.15 M LiPF₆/EC:EMC (4:6 by vol.%) electrolyte turned out to be the optimum condition for the improvement of the electrochemical cell performance, due to the decrease of the irreversible capacity during the first cycle and decrease of the charge-transfer resistance after 40 cycles.     

三氟甲磺酸镁电解液添加剂对高压锂离子电池的影响

以三氟甲磺酸镁(MFS)作为高电压双功能电解液添加剂，用于提高Li/LiNi_0.5Mn_1.5O₄(Li/LNMO)电池的性能。采用线性扫描伏安法(LSV)、循环伏安法(CV)、充放电和交流阻抗(EIS)进行电化学性能测试，通过SEM、XPS、FTIR对含不同电解液的Li/LNMO电池循环前后的电极表面进行了表征。结果表明，MFS在充放电过程中优先于电解液溶剂氧化分解，在两个电极上形成电解液界面膜，对电极提供保护，抑制了电解液的分解。在MFS添加量(以基础电解液质量为基准，下同)为0.3%的电解液中，Li/LNMO电池在1 C倍率下循环300次后，放电比容量从初始时的135.12 mA·h/g降至123.86 mA·h/g，容量保持率高达91.67%。与电解液中未添加MFS的电池相比，其循环后阻抗明显减小，表现出较好的循环性能。     

Symmetric electric double-layer capacitor containing imidazolium ionic liquid-based solid polymer electrolyte: Effect of TiO2 and ZnO nanoparticles on electrochemical behavior

Poly(vinylidene fluoride-co-hexafluoropropene) (PVDF–HFP)-based polymer electrolytes embedded with 1-ethyl-3-methylimidazolium tetrafluoroborate ioniliquid have been synthesized to improve the ionic conductivity. Electric double-layer capacitors (EDLC) have been prepared using the synthesized polymer electrolytes. Inorganic oxide fillers (5 wt %) such as titanium dioxide (TiO₂) and zinc oxide (ZnO) nanoparticles have been added to polymer electrolytes to compare the electrochemical behavior of the fabricated EDLC. The intrinsic dielectric constant of nanoparticles contributes in ionic dissociation which enhances ionic conductivity of electrolytes and also controls the specific capacitance of the EDLC fabricated with these electrolytes. Physicochemical properties of polymer nanocomposites have been investigated using X-ray diffraction, differential scanning calorimetry, and Fourier transform infrared analysis, which confirms decrease of crystalline phase in host polymer PVDF–HFP. The maximum voltage stability is obtained for TiO₂-based polymer electrolyte. The high specific capacitance as well as high energy density is obtained for the EDLC cell with TiO₂-based polymer electrolyte compared to EDLC with ZnO nanoparticles-based electrolyte. EDLC cells show specific capacitance of 76.4 and 44.51% of initial specific capacitance value at 2000th cycle for ZnO and TiO₂-based polymer electrolytes, respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48757.     

Effects of electrolytes on the electrochemical performance of Si/graphite/disordered carbon composite anode for lithium-ion batteries

The influences of LiBF₄, LiClO₄, lithium bis(oxalato) borate (LiBOB), LiPF₆ with VC and without VC, and the mixed electrolytes composed of different ratios of LiBOB and LiPF₆ or LiClO₄ on the electrochemical properties of Si/graphite/disordered carbon (Si/G/DC) composite electrode were systematically investigated by constant current charge-discharge and electrochemical impedance spectra (EIS) techniques. Scanning electron microscopy (SEM) was used to observe the change of electrodes in morphology after given cycle numbers. X-ray photoelectron spectroscopy (XPS) was employed to understand the influences of different mixed electrolytes on the composition of SEI layers. The results showed that Si/G/DC composite electrode in the mixed electrolytes presented better electrochemical performance than in single electrolyte. The compactness and compositions of SEI layers intensively influenced the cycle performance of Si/G/DC composite materials. LiBOB and additive VC had a good synergistic effect on the formation of the dense SEI layers. In particular, Si/G/DC in 0.5 M LiBOB + 0.38 M LiPF₆ electrolytes containing VC exhibited a high reversible capacity and excellent cycle performance.     

QUASI-SOLID-STATE DYE-SENSITIZED SOLAR CELLS BASED ON ZnO PHOTOANODE

ZnO photoanode in dye-sensitized solar cells (DSSCs) has been successfully prepared by the electro-hydrodynamic (EHD) technique. The sandwich solar cells exhibited a short-circuit photocurrent density of 7.0 mA cm^-2 and conversion efficiency of 1.65% with a quasi-solid-state electrolyte under simulated sun illumination (AM-1.5, 100 mW cm^-2). The stability and the influencing factors, such as film thickness and light intensity, on solar cell performance were discussed.     

DIRECT ELECTROCHEMICAL POWER GENERATION FROM CARBON IN FUEL CELLS WITH MOLTEN HYDROXIDE ELECTROLYTE

Historically, despite its compelling cost and performance advantages, the use of a molten metal hydroxide electrolyte has been ignored by direct carbon fuel cell (DCFC) researchers, primarily due to the potential for formation of carbonate salt in the cell. This article describes the electrochemistry of a patented medium-temperature DCFC based on a molten hydroxide electrolyte, which overcomes the historical carbonate formation.

An important technique discovered for significantly reducing carbonate formation in the DCFC is to ensure a high water content of the electrolyte. To date, four successive generations of DCFC prototypes have been built and tested to demonstrate the technology - all using graphite rods as their fuel source. These cells all used a simple design in which the cell containers served as the air cathodes and successfully demonstrated the ability to deliver more than 40 A with the current density exceeding 250 mA/cm². Conversion efficiency greater than 60% was achieved.     

TUNGSTEN TRIOXIDE HYDRATE INCORPORATED NAFION COMPOSITE MEMBRANE FOR PROTON EXCHANGE MEMBRANE FUEL CELLS OPERATED ABOVE 100°C

A new composite membrane is fabricated by incorporating tungsten trioxide hydrate into Nafion to be employed as a candidate electrolyte for proton exchange membrane fuel cells (PEMFCs) operated above 100°C. Thermal behavior and proton conductivity of the composite membrane are studied by means of thermogravimetric/differential thermal analyis (TG/DTA) and AC impedance measurements, respectively. These results demonstrate that the thermal stability of the composite membrane has no appreciable change when compared with the native Nafion membrane. The proton conductivity of the composite membrane is found to be better than that of the native Nafion membrane at high temperature and lower relative humidity. When the composite membrane is used as an electrolyte in H₂/O₂ PEMFC under the operating conditions of 110°C, 1.36 atm gas pressure, and 70% relative humidity, the observed current density value at 0.4 V is 1.5 times higher than that of the cell employing native Nafion membrane as an electrolyte.     

Identification of optimum conditions for zinc electrowinning in high-purity synthetic electrolytes

The optimum conditions for zinc electrowinning in synthetic acidic zinc sulphate electrolytes (0.8 M ZnSO₄+1.07 M H₂SO₄) were determined using response surface statistical analysis. The coulombic efficiency (QE) was optimized with respect to temperature (T), current density (J) and electrode rotation rate (n). For an electrolyte prepared from AR zinc sulphate and Aristar sulphuric acid, containing trace lead and nickel, QE reached a maximum of 98.8% on a zinc substrate under the following conditions:T=50°C,J=500 A m^–2,n=35s^–1. For a very-high-purity electrolyte, prepared by dissolution of 99.9999% zinc in Aristar sulphuric acid, a maximum QE of 98.4% was predicted and obtained at:T61°C,J890 A m^–2,n38s^–1. Using a statistical response surface model calculated during the optimization process, QE contours giving an overall view of electrolyte performance were constructed. The QE responses were determined principally byT andJ, with significant interaction betweenn andJ orT andJ, depending on the impurity composition of the electrolyte. The model was also used to predict the QE response of the above electrolytes under conditions similar to industrial practice.     

The effect of germanium on zinc electrowinning from industrial acid sulphate electrolyte

The effect ofgermanium on the electrowinning of zinc from industrial acid sulphate electrolyte was studied using X-ray diffraction, scanning electron microscopy and cyclic voltammetry techniques. Germanium concentrations > 0.1 mgl^–1 results in severe re-solution of the zinc deposit and hence decreased the zinc deposition current efficiency. Extreme fluctuations in the current efficiency occurred as a function of electrolysis time. Cyclic voltammograms obtained for Ge-containing electrolytes were characterized by a shoulder in the reverse scan prior to the cross-over potential. Vigorous hydrogen gassing occurred at the shoulder. These results are interpreted in terms of the formation of local Zn-Ge galvanic cells. Germanium concentrations to 0.2 mgl^–1 had no effect on the morphology of the 1-h zinc deposits but the preferred orientation changed from [1 1 4] [1 1 2] for Ge-free electrolyte to [1 1 2] [1 1 0] for electrolytes containing Ge.     

Hydrogen production during zinc deposition from alkaline zincate solutions

The determination of the amount of hydrogen produced during the electrodeposition of zinc from alkaline zincate solutions was carried out using the rotating ring-disc electrode (RRDE) technique. The experimental conditions for which the RRDE technique offers reliable results are discussed. Hydrogen production during zinc deposition was studied for a range of cathodic (disc) current densities (20–500 A m^–2) and electrolyte compositions (1–7 M KOH, 0.01–0.2 M zincate). It was found that an increasing amount of hydrogen was formed with increasing (disc) current density and decreasing KOH and zincate concentration. The impact of hydrogen formation during the charging process on nickel oxide/zinc secondary battery performance is expected to be small. It is concluded that in battery electrolytes (8 M KOH, 1 M zincate) hydrogen is formed chiefly by corrosion of the zinc electrode rather than by electrochemical formation during the electrochemical reduction of zinc.     

Polyterthiophene/CNT composite as a cathode material for lithium batteries employing an ionic liquid electrolyte

A polyterthiophene (PTTh)/multi-walled carbon nanotube (CNT) composite was synthesised by in situ chemical polymerisation and used as an active cathode material in lithium cells assembled with an ionic liquid (IL) or conventional liquid electrolyte, LiBF₄/EC-DMC-DEC. The IL electrolyte consisted of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF₄) containing LiBF₄ and a small amount of vinylene carbonate (VC). The lithium cells were characterised by cyclic voltammetry (CV) and galvanostatic charge/discharge cycling. The specific capacity of the cells with IL and conventional liquid electrolytes after the 1st cycle was 50 and 47 mAh g⁻¹ (based on PTTh weight), respectively at the C/5 rate. The capacity retention after the 100th cycle was 78% and 53%, respectively. The lithium cell assembled with a PTTh/CNT composite cathode and a non-flammable IL electrolyte exhibited a mean discharge voltage of 3.8 V vs Li⁺/Li and is a promising candidate for high-voltage power sources with enhanced safety.     

Impedance measurements during the cycling of a zinc electrode

Impedance spectra have been obtained during the cycling of a zinc electrode both in a Leclanché-cell-type electrolyte and in an alkaline zincate solution. Changes in impedance plots indicate an increase in the electrode area and a variation of the electrode kinetics with cycling. The kinetics of zinc deposition appear to be very sensitive to the contamination of electrolytes by dissolution products. The results confirm a correlation between the presence of an additive such as NBu₄ Br and the increase of the cycle life of the zinc electrode.     

TERNARY NaCl+LiCl+H2O MIXED ELECTROLYTE SYSTEM: DETERMINATION OF ACTIVITY COEFFICIENTS BASED ON POTENTIOMETRIC METHOD

The mean activity coefficients for NaCl in a ternary electrolyte system were determined by the potentiometric method, at 25°C, using a solvent polymeric (PVC) sodium-selective membrane electrode (Na⁺ ISE), containing N,N'-dibenzyl-N,N'-diphenyl-1,2-phenylenedioxydiacetamide as ionophore, and combined with an Ag/AgCl electrode. The potentiometric measurements were performed at the same ionic strengths in different series of mixed salt solutions, each characterized by a fixed salt molal ratio r (where r = m₁/m₂ = 1, 10, 50, 100). The nonideal behavior of the ternary NaCl(m₁) + LiCl(m₂) + H₂O electrolyte system was described based on the Pitzer ion-interaction model for mixed salts over the ionic strength ranging from 0.01 up to about 4 mol/kg. Two- and three-particle Pitzer interaction parameters for a mixed electrolyte system were determined based on potentiometric data, and the critical role of potentiometric selectivity coefficient (K₁₂) of ISE as limiting factor in the potentiometric measurements was analyzed.     

Study of the formation of a solid electrolyte interphase (SEI) in ionically crosslinked polyampholytic gel electrolytes

An ionic complex of anionic and cationic monomers was obtained by protonation of (N,N-diethylamino)ethylmethacrylate with acrylic acid. A novel ionically crosslinked polyampholytic gel electrolyte was prepared through the free radical copolymerization of the ionic complex and acrylamide in a solvent mixture of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate (1:1:1, v/v) containing 1 mol/L of LiPF₆. The impedance analysis indicated that the ionic conductivity of the polyampholytic gel electrolyte was rather close to that of solution electrolytes in the absence of a polymer at the same temperature. The temperature dependence of the conductivity was found to be well in accord with the Arrhenius behavior. The formation processes of the solid electrolyte interphase (SEI) formed in both gel and solution electrolytes during the cycles of charge-discharge were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The cyclic voltammetry curves show a strong peak at a potential of 0.68 V and an increase of the interfacial resistance from 17.2 Ω to 35.8 Ω after the first cycle of charge-discharge. The results indicate that the formation process of SEI formed in both gel and solution electrolytes was similar which could effectively prevent the organic electrolyte from further decomposition and inserting into the graphite electrode. The morphologies of SEI formed in both gel and solution electrolytes were analyzed by field emission scanning electron microscopy. The results indicate that the SEI formed in the gel electrolyte showed a rough surface consisting of smaller solid depositions. Moreover, the SEI formed in the gel electrolyte became more compact and thicker as the cycling increased.     

Optimization of EC-based multi-solvent electrolytes for low temperature applications of lithium-ion batteries

The ionic conductivities of EC-based multi-component electrolytes in various solvent compositions were measured over a wide temperature range of +40 to −40 °C, and the factors affecting the low temperature conductivities of the electrolytes were discussed. It is revealed from the experimental results that the co-solvents with high dielectric constant and low viscosity can improve the ionic conductivity at room temperature, whereas, only the co-solvents which possess low melting points can effectively expand the operating temperature range of the electrolyte. The Li-ion batteries using the optimized electrolyte of 1 M LiPF₆/EC-DMC-EMC (8.3:25:66.7) show the capacity retentions about 90.3% of their nominal capacities when discharged to 2.0 V at −40 °C at 0.1 C, demonstrating excellent low temperature performances.