Electrochemistry of room-temperature chloroaluminate molten salts at graphitic and nongraphitic electrodes

The electrochemistry of unbuffered and buffered neutral AlCl₃-EMIC-MC1 (EMIC =1-ethyl-3-methylimidazolium chloride and MC1= LiCl, NaCl or KCl) room-temperature molten salts was studied at graphitic and nongraphitic electrodes. In the case of the unbuffered 1 : 1 AlCl₃ : EMIC molten salt, the organic cation reductive intercalation at about –1.6 V and the AlCl₄ ^– anion oxidative intercalation at about +1.8 V were evaluated at porous graphite electrodes. It was determined that the instability of the organic cation in the graphite lattice limits the performance of a dual intercalating molten electrolyte (DIME) cell based on this electrolyte. In buffered neutral 1.1 :1.0:0.1 AIC1₃: EMIC : MCl (MC1= LiCl, NaCl and KCl) molten salts, the organic cation was intercalated into porous and nonporous graphite electrodes with similar cycling efficiencies as the unbuffered 1 : 1 melt; however, additional nonintercalating processes were also found to occur between 1 and –1.6 V in the LiCl and NaCl systems. A black electrodeposit, formed at –1.4 V in the LiCl buffered neutral melt, was analysed with X-ray photoelectron spectroscopy and X-ray diffraction and was found to be composed of LiCl, metallic phases containing lithium and aluminium, and an alumina phase formed from reaction with the atmosphere. A similar film appears to form in the NaCl buffered neutral melt, but at a much slower rate. These films are believed to form by reduction of the AlCl₄ ^– anion, a process promoted by decreasing the ionic radius of the alkali metal cation in the molten salt. The partially insulating films may limit the usefulness of the LiCl and NaCl buffered neutral melts as electrolytes for rechargeable graphite intercalation anodes and may interfere with other electrochemical processes occurring negative of –1 V.     

A new Zn|AlCl3|MnO2 galvanic cell suitable to water-activation

The Zn|3m AlCl₃ (aq)|MnO₂ galvanic cell gives an open circuit voltage (OCV) of 2.0V. When the cell is discharged at constant current (1.5 mA cm^–2 or 50 mAg^–1), its discharge curve shows a relatively flat portion in the region 2.0–1.6 V and the cell has an energy density of 550 Wh (kg of MnO₂)^–1 with a discharge capacity of 330 mA (kg of MnO₂)^–1, these values being about 2 times and 1.5 times, respectively, larger than those of the Zn|5m ZnCl₂|MnO₂ cell. The cell also shows good discharge behaviour at higher electric currents (for example 9.5 mAcm^–2 or 240 mAg^–1), and the advantages of the Zn|AlCl₃|MnO₂ cell over the Zn|ZnCl₂|MnO₂ are clear at the higher discharge currents. The high discharge voltage, energy density, and discharge capacity of the Zn|AlCl₃|MnO₂ cell are attributed to the strong buffering effect of AlCl₃ at pH3. Due to this buffering effect, the electrolytic solution causes gradual corrosion of the zinc and, consequently, the cell is suited to water-activation.     

Lithium cycling efficiency and conductivity for γ-lactone-based electrolytes

Lithium cycling efficiency on a lithium substrate as well as conductivity were examined for-lactonebased electrolytes incorporating LiClO₄ for use in nonaqueous lithium secondary batteries.-butyrolactone (BL),-valerolactone and-octanoiclactone were used. Conductivity increased with a decrease in viscosity for lactone. Lithium cycling efficiency tended to increase with a decrease in reactivity between lithium and lactone, which would be expected from the oxidation potential for lactone. In order to decrease viscosity, tetrahydrofuran (THF) was mixed with lactone. Conductivity for lactone/THF was higher than those for systems using either lactone or THF alone. For example, 1 M LiClO₄-BL/THF (mixing volume ratio =11) showed conductivity of 13.0 × 10^–3 S cm^–1, approximately 20% higher than that for BL. Lithium cycling efficiency for BL/THF, which exceeded 90%, was also higher than that for BL. Morphology of the deposited lithium in BL/THF was smoother than that in BL and similar to that in THF, as observed with a scanning electron microscope. The reason for the enhancement of the lithium cycling efficiency for BL/THF seems to be the adsorption of THF or THF-Li⁺ around the deposited Li, which has lower reactivity to Li and higher solvation power to Li⁺ than BL.     

Free lewis acid effects in electrolytes for Li/SOCl2 cells

Electrolyte solutions containing lithium tetrachloroaluminate with free aluminum chloride added, have been evaluated for use in Li/SOCl₂ cells. The optimum electrolyte composition contained 1.0 M LiAlCl₄ plus 2.0 M AlCl₃ in SOCl₂. Such a solution, when used in cells in place of the more usual 1.8 M LiAlCl₄ electrolyte, results in 45% longer reaction times. This increase can only be explained in part by a two stage discharge process. The beneficial effect of free Lewis acid in the electrolyte was found to be greater for cells containing lower surface area carbon black cathodes.     

Structure and Physicochemical Properties of Glasses in the Li2S–LiPO3 System

The temperature–concentration dependence of the electrical conductivity of glasses in the Li₂O–LiPO₃ and Li₂S–LiPO₃ systems is investigated. With the use of the Tubandt method, it is demonstrated that the electric current in glasses of these systems is provided by migration of lithium ions. The concentration dependence of the electrical conductivity is interpreted using the obtained data on the IR absorption spectra, density, microhardness, ultrasonic velocity, etc. It is found that the electrical conductivity of glasses in the Li₂S–LiPO₃ system is more than 10³ times higher than that in pure LiPO₃. The observed increase in the electrical conductivity is explained by the formation of sulfur-containing polar structural–chemical groupings of the Li⁺[S^–PO_3/2] type, whose dissociation energy is lower than that of similar oxide polar structural fragments. This results in an increase in the number of lithium ions involved in the electricity transport due to an increase in the degree of dissociation of polar structural–chemical units.     

Physicochemical properties of ZnCl2-NaCl-KCl eutectic melt

Physicochemical properties of ZnCl₂-NaCl-KCl eutectic melt were studied at 200-300 °C for the first time. Firstly, it was reconfirmed that the eutectic composition is ZnCl₂:NaCl:KCl = 0.6:0.2:0.2 in mole fraction, and that the eutectic temperature is 203 °C. Then, the density, viscosity, and ionic conductivity of the ZnCl₂-NaCl-KCl eutectic melt were measured at 200-300 °C. At 250 °C, the density was 2.43 g cm⁻³, the viscosity was 42.0 cP and the ionic conductivity was 8.53 S m⁻¹. The temperature dependencies of density and ionic conductivity were well fitted by the VTF equations with the same ideal glass transition temperature of 283 K (10 °C). It was found that the melt obeys the fractional Walden's rule which is explained by the decoupling effect. The electrochemical window of the melt was determined to be 1.7 V at 250 °C with the cathode limit being zinc metal deposition and the anode limit being chlorine gas evolution.     

Cycling behaviour of lithium-aluminium alloys formed on various aluminium substrates as negative electrodes in secondary lithium cells

The cycling efficiencies of lithium were examined on various metal substrates using different methods. The efficiency was found to be strongly dependent on the evaluating method and on the alloying process of lithium with the metal substrates. The electrochemical behaviour of the Li–Al alloys formed on several kinds of thin Al substrates were investigated in 1m propylene carbonate solution of LiClO₄ at room temperature. It was found that the cycling behaviour was dependent on the alloying rate of lithium with the Al substrate, and the electrochemically etched Al substrate, having a microstructure of a considerably preferred (100) orientation and a larger effective surface area, gave excellent cycling behaviour, showing a high cycling efficiency of 9085% at a high current density of 7 mA cm^–2.     

Effect of Li2O excess in Li6.4Ga0.2La3Zr2O12 electrolyte for all-solid-state Li-ion batteries

Li₇La₃Zr₂O₁₂ is a promising material used as solid electrolyte in all-solid-state lithium batteries. However, the lithium ionic conductivity of LLZO is limited, and the cycling stability of lithium symmetric battery based on LLZO is not good. In this research, different Ga-doped LLZO samples were prepared by adding different excess amounts of Li₂O, and the effect of excess amount of Li₂O on the structure and performance of LLZO have been researched. The results show that with the rise of the amount of Li₂O, the lithium ionic concentration increases gradually, and the lithium ionic conductivity and the ratio of grain resistance to total resistance rise first and then drop. When the excess amount of Li₂O is 10 wt.%, the sample exhibits the highest lithium ionic conductivity of 1.36 mS/cm, and the lithium symmetric battery exhibits the most stable operation.     

Emf measurements in the NaClAlCl3 system—I. Activity of AlCl3 in basic melts at temperatures close to the liquidus line

Emf measurements in the formation cell Al|AlCl₃(l), NaCl(l)|Cl₂ were carried out at different mol fractions of AlCl₃ in the range 0 < x_AlCl3 < 0.5. The activity of AlCl₃ increases strongly as the equimolar composition is approached, indicating the presence of a fairly stable AlCl^?₄ complex ion in such melts. Liquidus temperatures at various melt compositions were determined from emf-temperature curves as well as from cryoscopic measurements.     

Characterization of polypyrrole films incorporating various anions

The conductivity of polypyrrole films has been enhanced by electrochemical post-deposition doping with various anions. The change of conductivity was found to depend on the type and concentration of the anion. Results for the polypyrrole films doped with anions of H₂SO₄, (C₂H₅)₄N(O₃SC₆H₄CH₃), KI, CH₃C₆H₄SO₃H · H₂O (p-toluene sulphonic acid monohydrate), AlCl₃, KBrO₃ and HNO₃ showed that in the case of H₂SO₄, (C₂H₅)₄ N(O₃SC₆H₄CH₃) and CH₃C₆ H₄SO₃ H · H₂O the conductivity can be enhanced by up to a factor of two, from a value of 67 S cm^–1 up to 165, 102 and 95 S cm^–1, respectively. Doping with I^– had a negligible effect on the conductivity which was about 71 S cm^–1, while in the case of AlCl₃, KBrO₃ and HNO₃ the conductivity of the polypyrrole decreased significantly for certain anion concentrations.     

Glyme-based nonaqueous electrolytes for rechargeable lithium cells

Poly(ethylene glycol)dimethyl ethers [(CH₃O(CH₂CH₂O)_nCH₃, n = 1, 2, 3, and 4)] are generally known as “glymes”. This study examines the conductivity, lithium ion solvation state and charge-discharge cycling efficiency of lithium metal anodes in glyme-based electrolytes for rechargeable lithium cells. 1 M (M: mol l⁻¹) LiPF₆ was used as the solute. The properties of the glymes were investigated by using a ternary mixed solvent consisting of n-glyme, ethylene carbonate (EC) and methylethylcarbonate (MEC). This was because the solubility of LiPF₆ is far less than 1 M in an n-glyme single solvent. The glyme solutions exhibited higher conductivity and higher lithium cycling efficiency than EC/MEC. The conductivity tended to increase with decreases in ethylene oxide chain number (n) and solution viscosity. The decrease in the solution viscosity resulted from the change in the lithium ion solvation structure that occurred when a glyme was added to EC/MEC. The selective solvation of the glyme with respect to lithium ions was clearly demonstrated by -NMR measurements. The lithium cycling efficiency value depended on the charge-discharge current (I_ps). When n increased there was an increase in lithium cycling efficiency at a low I_ps and a decrease in the reduction potential of the glymes. When the conductivities including those at low temperature (below 0 °C), and charge-discharge cycling at a high current are taken into account, di- or tri-glyme is superior to the other glymes tested here.     

Fundamental study of the anodic and cathodic reactions during the electrolysis of a lithium carbonate-lithium chloride melt using a carbon anode

Cyclic voltammetry, in conjunction with the chromatographic analysis of the anode product, has been used to elucidate the reactions occurring during the electrolysis of lithium carbonate-lithium chloride melts. At a carbonate ion concentration of 0.033 mole fraction the peak anodic current densities were 3100 A m^–2 on vitreous carbon and 6900 A m^–2 on graphite with the product being carbon dioxide. The cathodic reduction of carbonate at low concentrations was found to occur at –1.0 V to –1.2 V vs a Ag/Ag(I) reference electrode which is 1.2 V less negative than the potential at which lithium ions were reduced. Voltammetric studies of the reduction of the carbonate ion indicated that the reaction mechanism involved an irreversible charge transfer.     

Electrochemical properties of Li ion polymer battery with gel polymer electrolyte based on polyurethane

Gel polymer electrolyte (GPE) was prepared using polyurethane acrylate as polymer host and its performance was evaluated. LiCoO₂/GPE/graphite cells were prepared and their electrochemical performance as a function of discharge currents and temperatures was evaluated. The precursor containing a 5 vol % curable mixture had a viscosity of 4.5 mPa s. The ionic conductivity of the GPE at 20 °C was about 4.5 × 10^–3 S cm^–1. The GPE was stable electrochemically up to a potential of 4.8 V vs Li/Li⁺. LiCoO₂/GPE/graphite cells showed a good high rate and low-temperature performance. The discharge capacity of the cell was stable with charge–discharge cycling.     

Cyclic chronopotentiometric studies of the LiAl anode in methyl acetate

The applicability of methyl acetate as a solvent for ambient temperature lithium secondary batteries was investigated using cyclic chronopotentiometry. Methyl acetate was found to be stable towards lithium-aluminium alloys and cycling up to more than 300 cycles was obtained with about 90% cycling efficiency. Water and other organic impurities have been identified in methyl acetate and a thorough purification procedure has been used to reduce these to acceptable levels. LiAsF₆, LiPF₆, LiClO₄ and LiBF₄ were investigated for use as supporting electrolytes and LiAsF₆ was found to be the best in terms of cycling efficiency, longer cycling numbers and yielding the lowest corrosion capacity loss rate. The development of the LiAl anode upon cycling was observed in parallel with the reduction in nucleation polarization potential, the increase in cycling efficiency, the lowering of concentration polarization at the electrode surface and the more ready acceptance of lithium deposition at the developed electrode. The optimum conditions for the development of the LiAl anode were found to exist at a current density of 5 mA cm^–2 and a charge density of 0.5 C cm^–2.     

Electrical conductivities of aqueous ZnSO4−H2SO4 solutions

Conductivities of aqueous ZnSO₄–H₂SO₄ solutions are reported for a wide range of ZnSO₄ and H₂SO₄ concentrations (ZnSO₄ concentrations of 01.2 M and H₂SO₄ concentrations of 02 M) at 25°C, 40°C and 60°C. The results indicate that the solution conductivity at a given ZnSO₄ concentration is controlled by the H₂SO₄ (H⁺) concentration. The variation of the specific conductivity with ZnSO₄ concentration is complex, and depends on the H₂SO₄ concentration. At H₂SO₄ concentrations lower than about 0.25 M, the addition of ZnSO₄ increases the solution conductivity, likely because the added Zn²⁺ and SO ₄ ^2– ions increase the total number of conducting ions. However, at H₂SO₄ concentrations higher than about 0.25 M, the solution conductivity decreases upon the addition of ZnSO₄. This behaviour is attributed to decreases in the amount of free water (through solvation effects) upon the addition of ZnSO₄, which in turn lowers the Grotthus-type conduction of the H⁺ ions. At H₂SO₄ concentrations of about 0.25 M, the addition of ZnSO₄ does not appreciably affect the solution conductivity, possibly because the effects of increasing concentrations of Zn²⁺ and SO ₄ ^2– ions are balanced by decreases in Grotthus conduction.Nomenclature a ion size parameter (m) - a ^* Bjerrum distance of closest approach (m) - C stoichiometric concentration (mol m^–3 or mol L^–1) - I ionic strength (mol L^–1) - k constant in Kohlrausch's law - M molar concentration (mol L^–1) - T absolute temperature (K) - z _i electrochemical valence of speciesi (equiv. mol^–1) - z (z _–|z _–|)^1/2=2 for ZnSO₄ - z ₊ valence of cation in salt (=+2 for Zn²⁺) - z _– valence of anion in salt (=–2 for SO ₄ ^2– ) Greek letters fraction of ZnSO₄ dissociated - specific conductivity (^–1 m^–1) - ^expt measured specific conductivity (^–1 m^–1) - equivalent conductivity (^–1 m² equiv.^–1) - equivalent conductivity at infinite dilution (^–1 m² equiv.^–1) - ⁰ equivalent conductivity calculated using Equation 2 (^–1 m² equiv.^–1) - _cale measured equivalent conductivity (^–1 m² equiv.^–1) - _expt equivalent conductivity of ioni at infinite dilution (^–1 m² equiv.^–1) - reciprocal of radius of ionic cloud (m^–1) - viscosity of solvent (Pa s) - dielectric constant - ± mean molar activity coefficient - density (g cm^–3)     

Aluminium electrodeposition from AlCl3-NaCl melts on glassy carbon,platinum and gold electrodes

The electrochemical deposition and dissolution of aluminium on glassy carbon, platinum and gold electrodes in chloraluminate melts have been investigated using linear sweep voltammetry and potentiostatic pulse techniques. It was shown that deposition of aluminium on the glassy carbon electrode at low overpotentials takes place by 3-D progressive nucleation and growth, with the incorporation of atoms in the crystal lattice as the rate-determining step. At overpotentials higher than –100 mV vs Al, in the melts containing more than 52 mol % of AlCl₃, diffusion of Al₂Cl ₇ ^– , takes over the control of deposition of aluminium. Alloying of platinum and gold electrodes with aluminium from the melt occurs in the underpotential region.     

Ionic conductivity and lithium electrode stability in Hydrin: LiBF4 elastomers

Three commercial elastomers, Hydrin C, Hydrin H and Hydrin T, which contain ethylene oxide and epichlorohydrin repeat units, have been investigated as polymer electrolytes in contact with lithium electrode. The influence of polyethylene glycol and fine particles of zeolite on ionic conductivity of Hydrin-LiBF₄ electrolytes and the exchange current density of the lithium electrode reaction has been studied by using impedance spectroscopy and cyclic voltammetry. The specific conductivity of the elastomeric electrolyte is about 10^–5 S cm^–1 at room temperature when polyethylene glycol is present. But the mechanical stability of the film is less. The addition of zeolite particles to the elastomers also improves the specific conductivity. When present in low concentrations, the zeolite particles show catalytic effect on the electrochemical reaction at lithium electrode at ambient temperature. The lithium electrode reaction is reversible and the electrolyte possesses good electrochemical stability.     

Overwinter greenhouse gas fluxes in two contrasting agricultural habitats

Mid-day field fluxes of nitrous oxide (N₂O), carbon dioxide (CO₂) and methane (CH₄) were measured during late winter/early spring in an arable field and an adjacent fallow in southern Germany. On the arable field, 2 dm high ridges, drawn as seed-beds for potato, were exposed to mild, partly diurnal freezing–thawing. Substantially elevated N₂O emission rates (6–750 µg N₂O-N m^–2 h^–1) were observed throughout the investigation period which coincided with freezing–thawing events in the surface soil (0–5 cm). Soil temperatures in the densely vegetated fallow were more isothermal due to an insulating snow/ice cover, resulting in much lower N₂O emission rates (0–57 µg N₂O-N m^–2 h^–1). CH₄ uptake rates were low in both habitats during soil frost (+2 to –7.5 µg CH₄-C m^–2 h^–1) but increased markedly in the fallow after spring thaw. Our data suggest that N₂O emission peaks may occur recurrently throughout the winter when soils are subjected to diurnal surface thawing. We concluded that microclimatic conditions strongly control N₂O winter loss, thus overriding ecosystem-level differences in off-season nutrient cycling. To further characterize winter-time nutrient cycling and habitat functioning in our sites, we determined NO₃ ^– and NH₄ ⁺ contents, fumigation-extractable carbon (C_mic) and nitrogen (N_mic) and enumerated protozoa and nematoda throughout the investigation period. C_mic and microbial C:N ratios in the fallow were higher in winter than during the rest of the year as indicated by a 2-year study, reflecting favorable conditions for microbial C assimilation at low temperatures in the absence of freeze–thaw perturbation. In the arable soil, C_mic contents were significantly reduced during soil freezing but recovered quickly upon warming of the soil. Dynamics of C_mic in the arable soil were paralleled by protozoan biomass and transient shifts in functional composition of the nematode community, indicating that microfaunal predation played an important role in nutrient cycling after freeze–thaw perturbation. Only minor microfaunal dynamics were observed in the climatically more stable fallow, essentially confirming the absence of perturbation at this site. Our findings provide strong evidence that overwinter N₂O formation is regulated by both the physical freeze–thaw susceptibility of the soil and the ecological functioning of the habitat.     

A new bath for the electrodeposition of aluminium. I. conductivity measurements

The conductivity of mixed hydrides of aluminium chloride and lithium-aluminium hydride in a mixed solvent of tetrahydrofuran (THF) and toluene was measured with respect to the total concentration of aluminium and also to the molar ratio of LiAlH₄ to AlCl₃. The values obtained were compared with those of the THF-benzene mixed solvent and those of the NBS (National Bureau of Standards) bath –AlCl₃ and LiAlH₄ in dithyl ether. The results showed that a solution of AlCl₃ and LiAlH₄ with a molar ratio of 3:1, respectively, in THF-toluene (80 vol% toluene) with a total concentration of aluminium of about 1.0 moll^–1, has a suitable conductivity for the electrodeposition and dissolution of aluminium. In addition to its low price, the electrolytic bath obtained has low volatility and relatively good stability with respect to the other baths studied.     

Effect of purification of 2-methyltetrahydrofuran/ethylene carbonate mixed solvent electrolytes on cyclability of lithium metal anodes for rechargeable cells

The effects of the purification of LiAsF₆–2-methyl tetrahydrofuran (2MeTHF)/ethylene carbonate (EC) mixed solvent organic electrolytes on the charge–discharge cyclability of lithium metal anodes has been investigated by using an accelerated method for evaluating lithium cycling efficiency. This method involves cycle tests on coin cells with an amorphous V₂O₅–P₂O₅ (95:5 molar ratio) cathode and an anode containing a small amount of lithium. Using this method, the cycle life of the cell was determined over a short period simply from the lithium cycling efficiency. The lithium cycling efficiency in LiAsF₆–2MeTHF/EC was improved by removing both water and organic impurities such as peroxides. An electrolyte containing less than 14ppm of water and 20ppm of organic impurities had a high lithium cycling efficiency of 97.2%.