Degradation thermique et etude vibrationnelle de MII(NH4)4(P3O9)2x4H2O(M II=Cu2+, Ni2+, Co2+)

We have studied the thermal behaviour under atmospheric pressure of isotypic tetrahydrate cyclotriphosphates M^II(NH₄)₄(P₃O₉)₂x4H₂O (M ^II=Cu, Ni and Co), between 25 and 1400°C, by X-ray diffraction, thermal analyses (TG and DTA) and infrared spectrometry. This study shows that the series of the compounds M^II(NH₄)₄(P₃O₉)₂x4H₂O (M ^II=Cu, Ni and Co) after elimination of water, in two different stages, and ammonia leads, at 400°C to cyclotetraphosphate M₂ ^IIP₄O₁₂ crystallized and to a thermal residue with a formula H₄P₄O₁₂ which undergoes under a thermal degradation by evolving water and pentoxide phosphorus. The kinetic characteristics of the dehydration and elimination of ammonia have been determinated. The vibrational spectra of Cu(NH₄)₄(P₃O₉)₂x4H₂O were examined and interpreted, in the domain of the valency frequencies, on the basis of the crystalline structure of its isotypic compound Co(NH₄)₄(P₃O₉)₂x4H₂O whose cycle has the site symmetry C₁, of our results of the calculation of the IR frequencies and the successive isotopic substitutions of the equivalent atoms (3P, 3Oi and 6Oe belonging to the P₃Oi₃Oe₆ ring) of the P₃O₉ ³⁻ cycle with high symmetry D_3h. This revised version was published online in August 2006 with corrections to the Cover Date.     

Etude Des Propriétés Physico-Chimiques De ZnRb 4 (P 3 O 9 ) 2 ·6H 2 O

The dehydration of ZnRb 4 (P 3 O 9 ) 2 ·;6H 2 O was investigated, between 25 and 600°;C, by TG-DTA, X-ray diffraction, IR. It leads, between 300 and 500°;C, to a mixture of long chain polyphosphates RbPO 3 and ZnRb 2 (PO 3 ) 4 which stays stable until its melting point. The IR (1400-30 cm m 1 ) and Raman spectra (1400-100 cm m 1 ) of ZnRb 4 (P 3 O 9 ) 2 ·;6H 2 O are reported and assignments of fundamental modes proposed and compared with theoretical results obtained via the MNDO method for P 3 O 9 ring with C s symmetry. (La déshydratation, sous pression atmosphérique, du cyclotriphosphate ZnRb 4 (P 3 O 9 ) 2 ·;6H 2 O, a ét´;e effectuée, entre 25 and 600°;C, par spectrométrie IR, diffraction des rayons X, ATG et ATD. Elle conduit, entre 300 and 500°;C, au mélange de polyphosphates RbPO 3 et ZnRb 2 (PO 3 ) 4 qui reste stable jusqu'à la fusion. Les spectres vibrationnels IR (1400-30 cm m 1 ) et Raman (1400-100 cm m 1 ) du sel étudié ont été interprétés dans le domaine des vibrations de valence et de déformation du cycle P 3 O 9 et comparés avec les résultats des calculs théoriques par la méthode MNDO pour un cycle isolé de symétrie C s .)     

Thermal Dehydration and Vibrational Studies of ZnK4(P3O9)2 · 6H2O

The thermal dehydration of ZnK₄(P₃O₉)₂ · 6H₂O was studied in the range 25–500°C by thermogravimetric analysis (TGA and DSC) and X‐ray diffraction. We found, based on the TGA and DSC scans, the dehydration of this salt takes place in three stages with a loss of the six water molecules. The infrared and Raman spectra of ZnK₄(P₃O₉)₂ · 6H₂O have been recorded and interpreted using a factor group analysis. The internal modes are assigned in terms of POP and PO₂ structural units using experimental and theoretical IR and Raman frequencies.     

Préparation Chimique,Caracterisation Cristallographique,Etudes Thermique et Vibrationnelle du Cyclotriphosphate Hexahydraté de Manganèse et de Tetra-Argent,MnAg 4 (P 3 O 9 ) 2 .6H 2 O

The cyclotriphosphate hexahydrate of manganese and silver, MnAg 4 (P 3 O 9 ) 2 .6H 2 O, was prepared by Boullé's process. MnAg 4 (P 3 O 9 ) 2 .6H 2 O crystallizes in the triclinic system, P-1, Z = 1 and its structure was determined by Rietveld's method. The refinement of 54 parameters by this method, using 1752 independent reflections leads to Rw p = 0.098, R p = 0.065 and R B = 0.033 on the basis of its isotype NiAg 4 (P 3 O 9 ) 2 .6H 2 O. The unit cell parameters of this salt are the following a = 8.824(1)Å, b = 8.485(1)Å, c = 6.609(1)Å, f = 90.30(1)°;, g = 92.89(1)°; and n = 107.28(1)°;. The thermal behavior of this new compound was studied, between 25 and 600°;C, under atmospheric pressure by infrared spectrometry, X-ray diffraction, thermal analyses TGA and DTA coupled. This study allows us the identification and the crystallographic characterization of a new phase, MnAg 2 (PO 3 ) 4 isotype of ZnRb 2 (PO 3 ) 4 , obtained between 350 and 450°;C, mixed with the long-chain polyphosphate of silver AgPO 3 . The kinetic characteristics of the dehydration of MnAg 4 (P 3 O 9 ) 2 .6H 2 O and the thermal phenomena accompanying this dehydration were determined and discussed on the basis of the proposed crystalline structure. The vibrational spectrum of the, MnAg 4 (P 3 O 9 ) 2 .6H 2 O, was examined and interpreted in the domain of the stretching vibrations of the P 3 O 9 rings, on the basis of the proposed crystalline structure and in the light of the calculation of the thirty fundamental IR frequencies for the idealized D 3h symmetry.     

A new class of lithium and sodium rechargeable batteries based on selenium and selenium-sulfur as a positive electrode

A new class of selenium and selenium-sulfur (Se(x)S(y))-based cathode materials for room temperature lithium and sodium batteries is reported. The structural mechanisms for Li/Na insertion in these electrodes were investigated using pair distribution function (PDF) analysis. Not only does the Se electrode show promising electrochemical performance with both Li and Na anodes, but the additional potential for mixed Se(x)S(y) systems allows for tunable electrodes, combining the high capacities of S-rich systems with the high electrical conductivity of the d-electron containing Se. Unlike the widely studied Li/S system, both Se and Se(x)S(y) can be cycled to high voltages (up to 4.6 V) without failure. Their high densities and voltage output offer greater volumetric energy densities than S-based batteries, opening possibilities for new energy storage systems that can enable electric vehicles and smart grids.     

Sulfone-based electrolytes for high-voltage Li-ion batteries

Sulfone-based electrolytes have been investigated as electrolytes for lithium-ion cells using high-voltage positive electrodes, such as LiMn₂O₄ and LiNi_0.5Mn_1.5O₄ spinels, and Li₄Ti₅O₁₂ spinel as negative electrode. In the presence of imide salt (LiTFSI) and ethyl methyl sulfone or tetramethyl sulfone (TMS) electrolytes, the Li₄Ti₅O₁₂/LiMn₂O₄ cell exhibited a specific capacity of 80 mAh g^?1 with an excellent capacity retention after 100 cycles. In a cell with high-voltage LiNi_0.5Mn_1.5O₄ positive electrode and 1 M LiPF₆ in TMS as electrolyte, the capacity reached 110 mAh g^?1 at the C/12 rate. When TMS was blended with ethyl methyl carbonate, the Li₄Ti₅O₁₂/LiNi_0.5Mn_1.5O₄ cell delivered an initial capacity of 80 mAh g^?1 and cycled fairly well for 1000 cycles under 2C rate. The exceptional electrochemical stability of the sulfone electrolytes and their compatibility with the Li₄Ti₅O₁₂ safer and stable anode were the main reason behind the outstanding electrochemical performance observed with high-potential spinel cathode materials. These electrolytes could be promising alternative electrolytes for high-energy density battery applications such as plug-in hybrid and electric vehicles that require a long cycle life.