Electrochemical intercalation of potassium into graphite in KF melt

Electrochemical intercalation of potassium into graphite in molten potassium fluoride at 1163 K was investigated by means of cyclic voltammetry, galvanostatic electrolysis and open-circuit potential measurements. It was found that potassium intercalated into graphite solely between graphite layers. In addition, the intercalation compound formed in graphite bulk in molten KF was quite unstable and decomposed very fast. X-ray diffraction measurements indicate that a very dilute potassium-graphite intercalation compound was formed in graphite matrix in the fluoride melt. Analysis with scanning electron microscope and transmission electron microscope shows that graphite was exfoliated to sheets and tubes due to lattice expansion caused by intercalation of potassium in molten KF.     

Electrochemical insertion of sodium into hard carbons

The electrochemical insertion of sodium ions into different types of hard carbons was achieved in electrolytes composed of ethylene carbonate as the solvent and NaClO₄ as the salt. For all the materials studied the sodium uptake increases when the carbon highest heat treatment temperature (HTT) decreases. PAN-based carbon fibres appear to be suitable structures to allow significant sodium insertion. Thus, T650 ex-PAN fibres lead to a reversible capacity close to 209 mAh g⁻¹. In that case, sodium insertion occurs in two main ways: one is the adsorption on the single graphene layers and the other is the concomitant insertion into the porosity that occurs below 0.1 V versus Na⁺/Na. This second mechanism, which is indicated by a low-voltage plateau on the electrochemical curves, allows significant insertion. The compared electrochemical study of two saccharose-coke samples corresponding to different regions of Dahn's classification underlines the importance of the carbon precursor and of the manufacture process. The reversible capacity is equal to 184 mAh g⁻¹ for the sample heat treated at 800 °C which presents a high hydrogen content whereas it is close to 145 mAh g⁻¹ for the one characterized by a HTT of about 1500 °C and a low hydrogen content. The best electrochemical performances are obtained for pyrolyzed cellulose carbons. Indeed, the reversible capacity is about 279 mAh g⁻¹. Outgassing these carbons at 950 °C results in such a decrease of the reversible capacity down to 145 mAh g⁻¹. That can be related either to the thermal elimination of heteroelements or to modifications of the pore size distribution. Consequently, the most suitable hard carbon material for anodic applications in rechargeable sodium-ion batteries should both present a high residual hydrogen content and a significant microporosity.     

Electrochemical insertion of lithium ions into disordered carbons derived from reduced graphite fluoride

Both covalent (obtained by direct fluorination at high temperature) and semi-ionic carbon fluorides (synthesized at room temperature) were reduced in order to obtain disordered carbons containing very small content of fluorine and different physical properties according to the reduction treatment (chemical, thermal or electrochemical). After a physical characterization (X-ray diffraction, electron spin resonance and FT-IR spectroscopies), the electrochemical behaviours of the pristine carbon fluorides and of the treated samples were investigated during the insertion of lithium using liquid carbonate-based electrolytes (LiClO₄-EC/PC, 50:50%, v/v). Both galvanostatic and voltammetric modes were performed and revealed that the voltage profiles and the capacities differed according to the starting material and the reduction treatment. Semi-ionic carbon fluoride treated in F₂ atmosphere for 2 h at 150 °C and then chemically reduced in KOH exhibits high reversible capacities (the reversible capacity is 530 mAh g⁻¹ in the second cycle); in this case, the voltage profiles show a large flat portion at potentials lower than 0.3 V which is attributed to the insertion/deinsertion of lithium ions between the small graphene sheets and/or the absorption of pseudo metallic lithium into the microporosity of the sample. Nevertheless, a part of the lithium ions are removed at potentials higher than 0.5 V versus Li⁺/Li limiting the useful capacity.     

Electrochemical intercalation of aluminium chloride in graphite in the molten sodium chloroaluminate medium

Aluminium chloride intercalation in graphite was studied by anodic oxidation of compacted graphite (rod) and graphite powder electrodes in sodium chloroaluminate melt saturated with sodium chloride at 175 °C. The studies carried out by employing both galvanostatic and cyclic voltammetric techniques had shown that the intercalation reactions take place only beyond the chlorine evolution potential of +2.2 V vs. Al on both the electrodes. The extent of intercalation reaction was directly related to the anodic potential and probably to the amount of chlorine available on the graphite anodes. In the case of graphite powder electrode, a distinctly different redox process was observed at sub-chlorine evolution potentials and this was attributed to the adsorption of chlorine on its high surface area. This finding contradicts a report in the literature that the intercalation reactions occur at potentials below chlorine evolution in the chloroaluminate melt.     

Electrochemical extraction of europium from molten fluoride media

This work concerns the extraction of europium from molten fluoride media. Two electrochemical ways have been examined: (i) the use of a reactive cathode made of copper and (ii) the co-deposition with aluminium on inert electrode, leading to the formation of europium–copper and europium–aluminium alloys, respectively, as identified by SEM-EDS analysis. Cyclic voltammetry and square wave voltammetry were used to identify the reduction pathway and to characterise the step of Cu–Eu and Al–Eu alloys formation. Then, electrochemical extractions using the two methodologies have been performed with extraction efficiency around 92% for copper electrode and 99.7% for co-reduction with aluminium ions.     

Electrochemical study on the type of immobilized acetylcholinesterase inhibition by sodium fluoride

Homogeneous cholinesterases inhibition by sodium fluoride was studied by many authors, using conventional techniques. Controversial results however were reported on the inhibition kinetics and mechanism. In this work electrochemical methods were applied to identify the type of sodium fluoride inhibition of the immobilized acetylcholinesterase taking advantage of the capabilities of the electrochemical biosensors. The acetylcholinesterase inhibition was evaluated by current measurement, at constant potential, of the mediated by K₃[Fe(CN)₆] and of the non-mediated oxidation of thiocholine iodide, produced by enzymatic acetylthiocholine iodide hydrolysis. Direct amperometric thiocholine detection was preferred for further studies, being more sensitive.The biosensor transducer response to thiocholine iodide was investigated by cyclic and hydrodynamic voltammetry. The reversibility and pH dependence (E_1/2 = 1.08-0.06 pH) of thiocholine oxidation were demonstrated.The amperometric biosensor response to acetylthiocholine iodide obtained on a modified by acetylcholinesterase adsorption carbon electrode at +0.80 V/Ag, AgCl was characterised according to IUPAC recommendations. The enzyme reaction kinetic parameters: I_max, , and K_I were evaluated under kinetically controlled conditions, for various pH and temperature values. The reversibility of the inhibition was confirmed by dilution. Based on the kinetic analysis, the inhibition of the immobilized acetylcholinesterase by sodium fluoride was found to be of a competitive type.     

Electrochemical insertion of alkaline ions into polyparaphenylene: effect of the crystalline structure of the host material

The intercalation of lithium and sodium ions into different materials derived from polyparaphenylene (PPP) (as synthesized PPP without a thermal treatment, PPP annealed for 36 h at 400 °C and PPP pyrolyzed at 700 °C for half an hour in argon atmosphere) was studied using the electrolyte composed of ethylene carbonate (EC) and propylene carbonate (PC) and MClO₄ as the alkaline salt (M=Li or Na). These materials exhibit various degrees of crystallinity: PPP is a semi-crystalline polymer with about 30% of cristallinity, whereas pyrolyzed PPP exhibits a totally disorganized structure. Spectroscopic characterization indicates that the configurations of the polymer chains are similar in these two materials. Then, we present in this work a comparative study of the intercalation of alkaline ions into these materials in order to specify the effect of the crystalline structure on the intercalation processes. The electrochemical capacities are close whatever the degree of crystallinity contrary to the potentials profiles of the galvanostatic curves. That indicates different intercalation processes into these materials. A two-step mechanism of the intercalation into PPP is proposed. First, the intercalation of the alkaline ions into the crystalline parts of the polymer occurs and secondly the insertion of Li⁺ and Na⁺ into the amorphous regions takes place at very low potentials.     

Electrochemical effect of graphite fluoride modification on Li-rich cathode material in lithium ion battery

Recently, Li-rich layered structure has been used in the cathode of lithium ion batteries because of its high specific capacity. However, this structure still has some problems including large irreversible capacity loss, significant deterioration of cycling performance and poor rate property. Therefore, in our study, graphite fluoride is used to modify the surface of Li_1.14Ni_0.133Co_0.133Mn_0.544O₂ through a facile solvent evaporating method. Due to conversion reaction of the graphite fluoride, the huge discharge capacity compensation during the first discharging can improve the coulombic efficiency significantly. As reaction products, the layer of LiF@carbon reduces the interfacial reactions and increases the reversible capacity. After modification by graphite fluoride, the discharge capacities are improved by 22% from 266 to 325?mAh?g^?1 at 0.1?C, and 13% at 2?C. After 100 cycles, the discharge capability at 1?C is increased by 13% from 180 to 203?mAh?g^?1.     

Study of lepidocrocite γ-FeOOH electrochemical reduction in neutral and slightly alkaline solutions at 25 °C

The electrochemical reduction of lepidocrocite γ-FeOOH was investigated at 25 °C in neutral or slightly alkaline solutions containing chloride, sulphate or bicarbonate anions by means of thin lepidocrocite film electrodeposited on inert gold substrate or graphite/lepidocrocite powder composite electrode. Electrochemical measurements were coupled to in situ electrochemical quartz crystal microbalance (EQCM) and ex situ SEM and FTIR analysis. The reduction of lepidocrocite occurs in all the electrolytes considered here. The initial reduction product is adsorbed ferrous ion, Feads²⁺. The desorption of Feads²⁺ is promoted as pH increases, leading to an increase of reduction depth. This promotion is related to the formation of secondary Fe^II-containing species, as revealed by SEM and FTIR. The comparison of γ-FeOOH reduction potentials and iron corrosion potentials let us state that the galvanic coupling is possible.     

在硫酸钠熔盐中合成莫来石晶须

采用Al2(SO4)3·18H2O和SiO2作为反应原料,在Na2SO4熔盐中合成了莫来石晶须,利用XRD、FESEM和SEM等手段研究了合成产物的组成和形貌,并研究了合成温度(700℃、800℃、900℃、950℃、1000℃、1100℃和1200℃)、熔盐用量(反应料与Na2SO4的质量比分别为2:1、1:1、1:2和1:4)、保温时间(2h、3h和4h)等工艺因素对合成反应的影响。结果表明:用熔盐法合成的莫来石不含其他晶相,纯度高,晶须直径在50～150nm,长度为3～8μm。研究还发现:Na2SO4熔盐的合适用量为反应料与Na2SO4的质量比是1:1,此时,混合料在900℃开始生成莫来石,950℃石英相基本消失,1000℃保温3h合成反应基本完成,超过1100℃时,合成的莫来石开始分解。因此,熔盐法合成莫来石的合理温度为1000℃保温3h。     

Direct electroreduction of oxides in molten fluoride salts

A new kind of electrolyte composed of molten fluorides has been evaluated in order to perform a feasibility study of the direct electroreduction reaction. The direct reduction of SnO₂ and Fe₃O₄ was realised in LiF–NaF at 750 °C and in LiF–CaF₂ at 850 °C for TiO₂ and TiO. The electrochemical behaviour of these oxides was studied by linear sweep voltammetry: a current corresponding to the oxide reduction was evidenced for TiO₂, SnO₂ and Fe₃O₄. After galvanostatic electrolyses, a complete conversion was obtained for all oxides, except TiO, and the structure of reduced Ti and Fe samples had a typical coral-like structure while dense drops of Sn were recovered (Sn is liquid at operating temperature). After TiO electrolysis, a thin external metallic titanium layer was detected, acting as a barrier for the oxide ion diffusion and no complete reduction can be achieved. This could be explained by a Pilling–Bedworth ratio around 1 for Ti/TiO.     

Internal cation mobility in molten CsCl-NdCl3 system at 1073 K

CsCl-NdCl₃ is the next of binary MCl-NdCl₃ systems (M: alkali metal) investigated for determination of relative internal mobilities of cations (b_Cs, b_Nd) by countercurrent electromigration method (Klemm's method). The results have been presented as isotherms of internal mobilities of Cs⁺ and Nd³⁺ ions on NdCl₃ equivalent fraction (y_Nd). It has been found that internal mobility of cesium cations is higher than neodymium ones in the entire composition range (what is typical for nonsymmetrical MCl-LnCl₃ systems (M: Li, Na, K; Ln: La, Nd, Dy)) and decreases with increase of NdCl₃ concentration in the melt. Generally, dependence of internal mobility of lanthanide cations in melts with alkali metal chlorides on lanthanide (i.e. its atomic number and concentration) seems strongly related to stability of chloride complex anions of lanthanides in the melt. Investigated systems may be divided into two classes. The first class includes MCl-NdCl₃ systems (M: Li, Na) characterized by decrease of b_Nd with increase of NdCl₃ concentration. The second includes KCl-LnCl₃ systems (Ln: La, Nd, Dy) and presented here CsCl-NdCl₃ system, and is characterized by increase of b_Ln with concentration of Ln³⁺ cation. The dependence of b_Nd on NdCl₃ concentration at 1073 K was fitted (as for other systems) by a simple equation of the form: , where is the internal mobility of Ln³⁺ cations in pure molten LnCl₃, a the difference between internal mobility of Ln³⁺ cations in pure molten LnCl₃ and infinitely diluted LnCl₃ in molten alkali metal chloride (extrapolated), and yLnCl₃ is the equivalent fraction of LnCl₃.     

Electrochemical formation of AlN in molten LiCl-KCl-Li3N systems

Electrochemical formation of aluminum nitride was investigated in molten LiCl-KCl-Li₃N systems at 723 K. When Al was anodically polarized at 1.0 V (versus Li⁺/Li), oxidation of nitride ions proceeded to form adsorbed nitrogen atoms, which reacted with the surface to form AlN film. The obtained nitrided film had a thickness of sub-micron order. The obtained nitrided layer consisted of two regions; the outer layer involving AlN and aluminum oxynitride and the inner layer involving metallic Al and AlN. When Al electrode was anodically polarized at 2.0 V, anodic dissolution of Al electrode occurred to give aluminum ions, which reacted with nitride ions in the melt to produce AlN particles (1-5 μm of diameter) of wurtzite structure.     

Mechanistic investigation into the electrolytic formation of iron from iron(III) oxide in molten sodium hydroxide

Iron(III) oxide tablets were electrolytically reduced to iron in molten sodium hydroxide at 530 °C and recovered to produce iron with 2 wt.% oxygen suitable for re-melting. The cell was operated at 1.7 V and an inert nickel anode was used. The thermodynamics and mechanism of the process was also investigated. By controlling the activity of sodium oxide in the melt, the cell could be operated below the decomposition voltage of the electrolyte with the net sequence of events being the ionization of oxygen, its subsequent transport to the anode and discharge leaving behind iron at the cathode. A reduction time of 1 h was achieved for a 1 g oxide tablet (close to the theoretical reduction time predicted by Faraday’s laws) at a current density of 520 mA cm⁻² with iron phase yields of ∼90 wt.%. The energy consumption was 2.8 kWh kg⁻¹.     

Electrodeposition of metallic molybdenum films in ZnCl2-NaCl-KCl-MoCl3 systems at 250 °C

Molybdenum metal film has been electrodeposited in ZnCl₂-NaCl-KCl (0.60:0.20:0.20, in mole fraction) melt containing MoCl₃ at 250 °C. In this melt, a dense film was obtained by potentiostatic electrolysis at 0.15 V versus Zn(II)/Zn for 3 h. However, the film had a thickness of smaller than 0.5 μm and was not adhesive. On the other hand, addition of 4 mol% of KF to the melt led to larger cathodic current in cyclic voltammogram, and gave a dense, adhesive and thicker metal film of ca. 3 μm thickness in the same electrolysis condition as above. The present process is promising as a new method for molybdenum coating at low temperatures.     

Generation of carbon nanofilaments on carbon fibers at 550 °C

Employing a relatively new method, in which carbon structures are grown from fuel rich combustion mixtures using palladium particles as catalyst, multi-scale diameter nanometer - micrometer filament structures were grown from ethylene/oxygen mixtures at 550 °C on commercial PAN micrometer carbon fibers. The filaments formed had a diameter roughly equal to the palladium particle size. At sufficiently high metal loadings (>0.05 wt.%) a bimodal catalyst size distribution formed, hence a bimodal filament size distribution was generated. Relative short, densely spaced nanofilaments (ca. 10 nm diameter), and a slightly less dense layer of larger (ca. 100 nm diameter) faster growing fibers (ca. 10 μm/h) were found to exist together to create a unique multi-scale structure. A protocol was developed such that only nano-scale fibers or a mixture of nano and sub-micron fibers could be produced. No large range order was evident in the filaments. This work demonstrates a unique ability to create a truly ’multi-scale’ carbon structure on the surface of carbon fibers. This fiber structure potentially can enhance composite material strength, ductility and energy absorption characteristics.     

Electrochemical stability of thin film LiMn2O4 cathode in organic electrolyte solutions with different compositions at 55 °C

A survey of the electrochemical stability of electrostatic spray deposited thin film of LiMn₂O₄ was performed in LiClO₄-EC-PC, LiBF₄-EC-PC, and LiPF₆-EC-PC solutions at 55 °C. The solution resistance, the surface film resistance, and the charge-transfer resistance were all found to depend on the electrolyte composition. Among the LiX-salts studied, the lowest charge transfer-resistance, and surface layer resistance were obtained in LiBF₄-EC-PC solution. There is no major influence of the electrolyte solution compositions upon lithium ion transport in the LiMn₂O₄ bulk at 55 °C. The diffusion coefficient of lithium in the solid phase varied within 10⁻¹⁰-10⁻⁸ cm² s⁻¹ in the three solutions. In general, it seems that in LiBF₄ solutions, the surface chemistry is the most stable in the three solutions examined, and hence the electrode impedance in LiBF₄ solutions was the lowest. In LiPF₆ solutions, HF seems to play an important role, and thus, the electrode impedance is relatively high due to the precipitation of surface LiF.     

Electrochemical lithium insertion in (PO2)4(WO3)2m (2 ≤ m ≤ 10): Relation among the electrochemical insertion process and structural features

In this work it is presented a review of the main results obtained during the electrochemical lithium insertion in the family of monophosphate tungsten bronzes (PO₂)₄(WO₃)_2m (2 ≤ m ≤ 10). This family of oxides is a good system in order to study the relation among the electrochemical processes observed in the course of lithium insertion and the changes of bronzes structures. By means of X-ray diffraction experiments, the nature of Li_x(PO₂)₄(WO₃)_2m phases has been elucidated and a correlation with the reversible/irreversible processes observed during the electrochemical insertion has been established. The electrical properties of the inserted Li_x(PO₂)₄(WO₃)_2m phases were measured and a relation with the amount of lithium inserted and m was also found.     

Catalyzed synthesis of rhombohedral boron nitride in sodium chloride molten salt

Although a variety of methodologies/techniques have been used to prepare h-BN powders with different sizes and purities, only a few methods are reported to synthesize r-BN. In this work, highly crystalline r-BN with a purity of 94 wt% was successfully synthesized in sodium chloride molten salt using Na₂B₄O₇ and Mg powders as starting materials at 1000 °C in nitrogen atmosphere. The sodium (Na) produced by the reaction of Mg and Na₂B₄O₇ has a positive effect on the formation r-BN in the molten salt. The effect of Na as a crystallization promoter to produce crystallized r-BN was demonstrated by heating a mixture of t-BN and Na at 800–1200 °C. The formation, dissolution and evaporation of Na in the melt was discussed. The influence of synthesis temperature on the phase composition and morphology of the final products in the melt was also investigated. The possible formation mechanism of r-BN is proposed.     

Thermochromic behavior (400 < T °C < 1200 °C) of barium carbonate/binary metal oxide mixtures

Irreversible thermochromism over a wide temperature range has been observed from the decomposition of a mixture of a barium carbonate and a metal oxide. The control of the reaction temperature can be predicted from the calculation of the Madelung energy of the barium/transition metal mixed oxide formed consecutively with the decarbonatation. Moreover, the Madelung energy of this formed mixed oxide may be predicted from bond valence considerations. This study offers a simple predictive approach to propose temperature indicators with significant optical contrast and a thermochromic temperature varying between 400 and 1200 °C.