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1.
The high-temperature phase behaviour of RbH2PO4 and CsH2PO4 have been studied. RbH2PO4 undergoes a single quasi-irreversible phase transition with an enthalpy of 4.665 kJ mol?1. The transition is found to occur over the temperature range 86–111°C. CsH2PO4 undergoes two transitions at 149 and 230°C. The lower one is quasi-irreversible and has an enthalpy of 4.284 kJ mol?1. The one at 230°C is reversible and has an enthalpy of 1.071 kJ mol?1.  相似文献   

2.
Effect of the synthesis conditions of Pechini technique on crystallinity and purity of Na3Ce(PO4)2 compound was investigated. Nano-sized cerium-sodium phosphate obtained when EDTA was used as an additional chelating agent for Ln3+. The total enthalpy change of Na3Ce(PO4)2 phase transition was determined as 14.2±0.7 kJ mol−1 for sample synthesized by conventional solid-solid reaction. The phase transition process was confirmed to occur at 1060°C or in temperature range 920–1060°C depending on thermal treatment of powders.  相似文献   

3.
Triclinic LiVPO4F and monoclinic Li3V2(PO4)3 are synthesized through a soft chemical process with mechanical activation assist, followed by annealing. In this process, ascorbic acid is used as reducing agent as well as carbon source. The as-prepared samples are coated with amorphous carbon. XPS analysis results show the expected valency states of ions in LiVPO4F and Li3V2(PO4)3. The electrochemical properties of the prepared LiVPO4F/C and Li3V2(PO4)3/C cathodes are evaluated. The as-prepared LiVPO4F/C cathode shows an initial discharge specific capacity of 140?±?3 mAh?g?1 at 30 mA?g?1 in the voltage range of 3.0~4.4 V, compared with that of 138?±?3 mAh?g?1 possessed by Li3V2(PO4)3/C. Both samples exhibit good cycle performance at different current densities. The capacity delivered by LiVPO4F remains 95.5 and 91.7 % of its initial discharge capacity after 50 cycles at 150 and 750 mA?g?1, respectively, while 97.4 and 90.6 % for Li3V2(PO4)3/C. But the rate capability of LiVPO4F/C is not so good compared with as-prepared Li3V2(PO4)3/C.  相似文献   

4.
Transport properties of ionic salt CsH5(PO4)2 are studied by the impedance method. The salt’s bulk conductivity ranges from 10?8 to 10?4 S cm?1 in the temperature interval 90 to 145°C. The apparent activation energy is high (1.6–2.0 eV). The conductivity is slightly anisotropic: it is maximum in the [001] direction and minimum in the [100] direction (~5.6 and 1 times × 10?6 S cm?1, respectively, at 130°C). The conductivity of polycrystalline samples is higher by 1–2 orders of magnitude, and the activation energy drops to 1.05 eV due to the formation of a pseudoliquid layer with a high proton mobility at the intercrystallite boundary. The salt’s thermodynamic properties are examined by differential scanning calorimetry and thermogravimetry. No phase transitions are discovered in the salt up to the melting point (151.6°C), with the melting enthalpy equal to ~34 kJ mol?1. The crystallization occurs at lower temperatures (107°C) and the crystallization enthalpy (?18 kJ mol?1) is lower than the melting enthalpy. The melting is accompanied by slow decomposition of the salt. Factors affecting the proton transport in the salt are analyzed.  相似文献   

5.
Subsolidus sections in the systems Li3PO4-InPO4 (950°C) and Na3PO4-InPO4 (800, 900, and 1000°C) have been studied by X-ray powder diffraction. The compound Li3In(PO4)2 has been synthesized, and the nasicon-type solid solution Li3(1 ? x)In2 + x(PO4)3 (0.67 ≤ x ≤ 0.80). has been found to exist. In the system Na3PO4-InPO4, the solid solution Na3(1 ? x)Inx/3PO4 (0 ≤ x ≤ 0.2) and two complex phosphates exist: Na3In(PO4)2 and Na3In2(PO4)3. These complex phosphates are dimorphic, with the irreversible-transition temperature equal to 675 and 820°C, respectively. Na3In(PO4)2 degrades at 920°C. Ionic conductivity has been measured in some phases in the system.  相似文献   

6.
《Solid State Sciences》2012,14(7):864-869
A series of Li3V2(PO4)3/C cathode materials with different morphologies were successfully prepared by controlling temperatures using maleic acid as carbon source via a simple sol–gel reaction method. The Li3V2(PO4)3/C nanorods synthesized at 700 °C with diameters of about 30–50 nm and lengths of about 800 nm show the highest initial discharge capacity of 179.8 and 154.6 mA h g−1 between 3.0 and 4.8 V at 0.1 and 0.5 C, respectively. Even at a discharge rate of 0.5 C over 50 cycles, the products still can deliver a discharge capacity of 140.2 mA h g−1 in the potential region of 3.0–4.8 V. The excellent electrochemical performance can be attributed to one-dimensional nanorod structure and uniform particle size distribution. All these results indicate that the resulting Li3V2(PO4)3/C is a very strong candidate to be a cathode in a next-generation Li-ion battery for electric-vehicle applications.  相似文献   

7.
The need to improve electrodes and Li‐ion conducting materials for rechargeable all‐solid‐state batteries has drawn enhanced attention to the investigation of lithium‐rich compounds. The study of the ternary system Li‐Si‐P revealed a series of new compounds, two of which, Li8SiP4 and Li2SiP2, are presented. Both phases represent members of a new family of Li ion conductors that display Li ion conductivity in the range from 1.15(7)×10?6 Scm?1 at 0 °C to 1.2(2)×10?4 Scm?1 at 75 °C (Li8SiP4) and from 6.1(7)×10?8 Scm?1 at 0 °C to 6(1)×10?6 Scm?1 at 75 °C (Li2SiP2), as determined by impedance measurements. Temperature‐dependent solid‐state 7Li NMR spectroscopy revealed low activation energies of about 36 kJ mol?1 for Li8SiP4 and about 47 kJ mol?1 for Li2SiP2. Both compounds were structurally characterized by X‐ray diffraction analysis (single crystal and powder methods) and by 7Li, 29Si, and 31P MAS NMR spectroscopy. Both phases consist of tetrahedral SiP4 anions and Li counterions. Li8SiP4 contains isolated SiP4 units surrounded by Li atoms, while Li2SiP2 comprises a three‐dimensional network based on corner‐sharing SiP4 tetrahedra, with the Li ions located in cavities and channels.  相似文献   

8.
The phase equilibria as well as the properties and crystal structures of the compounds formed in both Li2SO4-MgSO4 and Li2SO4-Li4SiO4 systems have been studied by means of x-ray diffraction technique (at high and room temperatures) as well as by the thermal analyses (DTA, DSC, TGA, etc.). In Li2SO4-MgSO4 system there exists a compound Mg4Li2(SO4)5 formed by peritectic reaction at 840°C and decomposed at 105°C into the Li2SO4-base solid solution and MgSO4 · Mg4Li2(SO4)5 and Li2SO4-base solid solution conduct an eutectic reaction at 663°C with the composition of eutectic point lying in 22 mol% MgSO4. The solubility of MgSO4 in Li2SO4 is a little smaller than 10 mol% while at the same time the Li2SO4 phase transition temperature decreases from 574 to 560°C On the other hand, no noticeable solid solubility of Li2SO4 in MgSO4 has been observed. The reaction is an endothermal one and its heat of formation is 2.57 kJ/mol. The activation energy of the reaction calculated by thermal peak displacement method at various heating rates is 173.5 kJ/mol (1.80 ev). The crystal Mg4Li2(SO4)5 belongs to orthorhombic system with lattice parameters at 180°C: a = 8.577, b=8.741, c= 11.918 Å. The space group seems to be either P222 or P mmm. Assuming that there are two formula units in a unit cell, the density calculated is then 2.20 g/cm3 very close to that of Li2SO4 or MgSO4. Meanwhile, in Li2SO4-Li4SiO4 system a new phase Li8-2x(SiO4)8-x(SO4)x is formed by peritectic reaction at 953°C with a range of composition x=0.96 ?0.58. The crystal belongs to ortho-rhombic system with lattice parameters at x=0.8: a = 5.002, b= 6.173 and c=10.608Å. The density observed is 2.31 g/cm3 and there are 2 formula units in an unit cell. It is shown from the measurements of piezoelectric and laser SHG coefficients of the crystal that the crystal posseses a symmetrical center with the space group belonging to P mmn. The lattice parameter c has a maximum at x=0.8. In the air Li8-2x(SiO4)2-x(SO4)x can absorb 7.6 wt% water vapour and other gases which can only be desorbed by heating it at a temperature above 350°C. Neither absorption nor desorbtion can change its crystal structure, a characteristic similar to that of zeolite molecular sieve. The dewater activation energy of Li8-2x(SiO4)2-x(SO4)x is 171.5 kJ/mol. Li8-2x(SiO4)2-x(SO4)x and Li4SO4 bring about an eutectic reaction at 823°C with its eutectic composition being 12 mol% Li4SiO4. No observable solubility of Li4SiO4 in Li3SO4 has been noticed. The solubility of Li2SO4 in Li4SiO4 is approximately equal to 5 mol%. With Li2SO4 being dissolved in, the phase transition temperature of Li4SiO4 is decreased. After being fused, the specimens Li3SO4-MgSO4 and Li2SO4-Li4SiO4 are cooled at a rate of 10°C/min, their metastable eutectic systems are resulted respectively.  相似文献   

9.
Composite polymer electrolyte (CPE) films consisting of PEO, LiClO4, and Li1.3Al0.3Ti1.7(PO4)3 with fixed EO/Li = 8 but different relative compositions of the two lithium salts were prepared by the solution casting method. The CPE films were characterized using SEM, DSC, electrical impedance spectroscopy (EIS), and ion transference number measurement. It was found that the incorporation of LiClO4 and Li1.3Al0.3Ti1.7(PO4)3 into PEO by keeping EO/Li = 8 reduced the crystallinity of PEO from 50.34% to the range of 3.57–15.63% depending upon the relative composition of the two salts. The room temperature impedance spectra of the CPE films all exhibited a shape of depressed semicircle in the high frequency range and inclined line in the low frequency range, but the high temperature ones were mainly inclined lines. The Li+ ionic conductivity of the CPE films mildly increased and then decreased with increasing Li1.3Al0.3Ti1.7(PO4)3 content, and the maximum conductivities were obtained at Li1.3Al0.3Ti1.7(PO4)3 content of 15 wt % for all measuring temperatures, for example, 1.378 × 10?3 S/cm at 100 °C and 1.387 × 10?5 S/cm at 25 °C. The temperature dependence of the ionic conductivity of the CPE films follows the Vogel–Tamman–Fulcher (VTF) equation The pseudo activation energies (Ea) were rather low, 0.053–0.062 eV, indicating an easy migration of Li+ in the amorphous phase dominant PEO. The pre‐exponent constant A and ion transference number tLi+ were found to have a similar variation tendency with increasing Li1.3Al0.3Ti1.7(PO4)3 content and reached their maximums also at Li1.3Al0.3Ti1.7(PO4)3 content of 15 wt %. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 743–751, 2005  相似文献   

10.
About the Chloride Spinels Li2MgCl4, Li2MnCl4, Li2FeCl4, Li2CdCl4 FIR, Raman, and X-ray data of the spinel type chlorides Li2TCl4 (T = Mg, Mn, Fe, Cd) are presented. The vibrational spectra indicate that there is no 1:1 ordering on the octahedral sites of the lattice. Both DTA measurements and high temperature X-ray photographs show that the chloride spinels undergo a reversible phase transition to a cubic high temperature defect structure at 535°C (Li2MgCl4), 460°C (Li2MnCl4) and 385°C (Li2CdCl4), which has unit cell dimensions two times smaller than the spinel lattice. Disordering of the lithium sublattice still begins at much lower temperatures, as measurements of the electric conductivity indicate.  相似文献   

11.
The polymerization reactivity of isobutylene/SnCl4 mixtures in the absence of polar solvent, was investigated in a temperature interval from −78 to 60 °C. The mixture is nonreactive below −20 °C but slow polymerization proceeds from −20 to 20 °C with the initial rate r0 of the order 10−5 mol · l−1 · s−1. The rate of the process increases with increasing temperature up to ∼10−2 mol · l−1 · s−1 at 60 °C. Logarithmic plots of r0 and n versus 1/T exhibit a break in the range from 20 to 35 °C. Activation energy is positive with values E = 21.7 ± 4.2 kJ/mol in the temperature interval from −20 to 35 °C and E = 159.5 ± 4.2 kJ/mol in the interval from 35 to 60 °C. The values of activation enthalpy difference of molecular weights in these temperature intervals are ΔHMn = −12.7 ± 4.2 kJ/mol and −38.3 ± 4.2 kJ/mol, respectively. The polymerization proceeds quantitatively, the molecular weights of products are relatively high, n = 1500–2500 at 35 °C and about 600 at 60 °C. It is assumed that initiation proceeds via [isobutylene · SnCl4] charge transfer complex which is thermally excited and gives isobutylene radical‐cations. Oxygen inhibits the polymerization from −20 to 20 °C. Possible role of traces of water at temperatures above 20 °C is discussed. It was verified by NMR analysis that only low molecular weight polyisobutylenes are formed with high contents of exo‐ terminal unsaturated structures. In addition to standard unsaturated groups, new structures were detected in the products. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1568–1579, 2000  相似文献   

12.
Natural graphite treated by mechanical activation can be directly applied to the preparation of Li3V2(PO4)3. The carbon-coated Li3V2(PO4)3 with monoclinic structure was successfully synthesized by using natural graphite as carbon source and reducing agent. The amount of activated graphite is optimized by X-ray diffraction, scanning electron microscope, transmission electron microscope, Raman spectrum, galvanostatic charge/discharge measurements, cyclic voltammetry, and electrochemical impedance spectroscopy tests. Our results show that Li3V2(PO4)3 (LVP)-10G exhibits the highest initial discharge capacity of 189 mAh g?1 at 0.1 C and 162.9 mAh g?1 at 1 C in the voltage range of 3.0–4.8 V. Therefore, natural graphite is a promising carbon source for LVP cathode material in lithium ion batteries.  相似文献   

13.

A new type of three-dimensional (3D) oxy-phosphate materials are explored for the application of Li and Na batteries. The molybdenum tungsten oxy phosphate, MoWO3(PO4)2, was synthesized by solid-state method and evaluated for Li/Na insertion/de-insertion electrode material for the first time. The cell at charged state (vs. Li+/Li) showed a discharge capacity of 786 mAh g−1 within the voltage window of 0.3 V with amorphization of crystalline MoWO3(PO4)2 as observed from ex-situ powder XRD analysis. The structural integrity was revealed in this material, even with nearly more than 5 Li+ ions into the lattice, leading to the discharge capacity of 250 mAh g−1. The reversible charge/discharge behavior with insertion/de-insertion of 2.4 Li+ ions in the voltage range of 1.65 − 3.5 V resulted in 110 and 95 mAh g−1 at C/10 and C/5 rates, respectively. On the other hand, poor cycling performance was noticed for Na ion insertion and desertion, with a discharge capacity of 250 mAh/g within the voltage range of 0.3 − 3.5 V (vs. Na+/Na).

  相似文献   

14.
Indium Tungstate, In2(WO4)3 – an In3+ Conducting Solid Electrolyte Polycrystalline In2(WO4)3 has been electrochemically characterized and unambiguously identified as an In3+ conducting solid electrolyte. By heating, indium tungstate undergoes a phase transition between 250 °C and 260 °C transforming from a monoclinic to an orthorhombic phase for which the conduction properties have been determined. The adopted crystal structure in this high temperature region corresponds to the Sc2(WO4)3 type structure. The electrical conductivity was investigated by impedance spectroscopy in the temperature range 300–700 °C and amounts to about 3.7 · 10–5 Scm–1 at 600 °C with a corresponding activation energy of 59.5 kJ/mol. Polarization measurements indicated an exclusive current transport by ionic charge carriers with a transference number of about 0.99. In dc electrolysis experiments, the trivalent In3+ cations were undoubtedly identified as mobile species. A current transport by oxide anions was not observed.  相似文献   

15.
Anionic polymerization of N-methacryloyl-2-methylaziridine ( 1 ) proceeded with 1,1-diphenyl-3-methylpentyllithium (DMPLi) in the presence of LiCl or Et2Zn to give the polymers possessing predicted molecular weights and narrow molecular weight distributions (Mw/Mn < 1.1) at −78 ∼ −40 °C in THF. In each polymerization initiated with DMPLi/LiCl at the various temperatures ranging from −40 to −60 °C, the linear relationship between polymerization time and conversion of monomer was obtained from the GLC analysis. The rate constant and the activation energy of the anionic polymerization for 1 were determined as follows: ln k = −5.85 × 103/T + 23.3 L mol−1 s−1 and 49 ± 4 kJ mol−1, respectively. Poly( 1 ) showed the glass transition temperature at 98 °C, and gave the insoluble product at higher temperature around 150 °C through the thermal cross-linking of highly strained N-acyl-aziridine moiety.  相似文献   

16.
Crystal Structure, Phase Transition, and Potassium Ion Conductivity of Potassium Trifluoromethanesulfonate According to the results of temperature dependent powder diffractometry (Guinier‐Simon‐technique) potassium trifluoromethanesulfonate is dimorphic. The phase transition occurs between –63 °C and –45 °C. The low‐temperature modification crystallizes monoclinic with a = 10.300(3) Å, b = 6.052(1) Å, c = 14.710(4) Å, β = 111.83(2)° (–120 °C) and the room‐temperature modification with a = 10.679(5) Å, b = 5.963(2) Å, c = 14.624(5) Å, β = 111.57(3)°, Z = 6, P21. According to single crystal structure determination, potassium trifluoromethanesulfonate consists of three different potassium‐oxygen‐coordination polyhedra, linked by sulfur atoms of the trifluoromethanesulfonate groups. This results in a channel structure with all lipophilic trifluoromethane groups pointing into these channels. By means of DSC, the transition temperature and enthalpy have been determined to be –33 °C and 0.93 ± 0.03 kJ/mol, respectively. The enthalpy of melting (237 °C) for potassium trifluoromethanesulfonate is 13.59 kJ/mol, the potassium ionic conductivity is 3.68 · 10–6 Scm–1 at 205 °C.  相似文献   

17.
The rate of the fastest ene reaction between 4-phenyl-1,2,4-triazoline-3,5-dione (1) and 2,3-dimethyl-2-butene (2) is studied by means of stopped flow in solutions of benzene (k 2 = 55.6 ± 0.5 and 90.5 ± 1.3 L mol?1 s?1 at 23.3 and 40°C) and 1,2-dichloroethane (335 ± 9 L mol?1 s?1 at 23.5°C). The enthalpy of reaction (?139.2 ± 0.6 kJ/mol in toluene and ?150.2 ± 1.4 kJ/mol in 1,2-dichloroethane) and the enthalpy (20.0 ± 0.5 kJ/mol) and entropy (144 ± 2 J mol?1 K?1) of activation are determined. A clear correlation is observed between the reaction rate and ionization potential in a series of ene reactions of 4-phenyl-1,2,4-tri-azoline-3,5-dione with acyclic alkenes.  相似文献   

18.
On Na3PO4: Preparative Investigations, Crystal Structure of High Temperature Form Possibilities for preparing Na3PO4 by solid state reactions have been investigated. The existence of two modifications was proved by means of DTA and X-ray powder methods (temperature range 25–800°C). The phase transition is of first order and occurs reversibly at 325°C. The crystal structure of the high temperature form has been determined using single crystals which have been quenched to room temperature. The structure of H? Na3PO4 contains orientationally disordered PO3?4 anions and derives from the Li3Bi type of structure (Fm3m, a = 742,3 pm).  相似文献   

19.
Pan Zhou  Dawei He 《中国化学》2016,34(8):795-800
In this study, core‐shell structured Li3V2(PO4)3/C wrapped in graphene nanosheets has been successfully prepared. The reduction of graphene oxide and the synthesis of Li3V2(PO4)3/C are carried out simultaneously using a chemical route followed by a solid‐state reaction. The effects of conducting graphene are studied by X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra and electrochemical measurements. The results reveal that the graphene sheets not only form a compact and uniform coating layer throughout the Li3V2(PO4)3/C, but also stretch out and cross‐link into a conducting network around the Li3V2(PO4)3/C particles. Thus, the graphene decorated Li3V2(PO4)3/C electrode exhibits superior high‐rate capability and long‐cycle stability. It delivers a reversible discharge capacity of 178.2 mAh·g?1 after 60 cycles at a current density of 0.1 C, and the rate performances of 176, 169.3, 156.1 and 135.7 mAh·g?1 at 1, 2, 5 and 10 C, respectively. The superior electrochemical properties make the graphene decorated Li3V2(PO4)3/C composite a promising cathode material for high‐performance lithium‐ion battery.  相似文献   

20.
Lithium‐ion batteries (LIBs) are being used to power the commercial electric vehicles (EVs). However, the charge/discharge rate and life of current LIBs still cannot satisfy the further development of EVs. Furthermore, the poor low‐temperature performance of LIBs limits their application in cold climates and high altitude areas. Herein, a simple prelithiation method is developed to fabricate a new LIB. In this strategy, a Li3V2(PO4)3 cathode and a pristine hard carbon anode are used to form a primary cell, and the initial Li+ extraction from Li3V2(PO4)3 is used to prelithiate the hard carbon. Then, the self‐formed Li2V2(PO4)3 cathode and prelithiated hard carbon anode are used to form a 4 V LIB. The LIB exhibits a maximum energy density of 208.3 Wh kg−1, a maximum power density of 8291 W kg−1 and a long life of 2000 cycles. When operated at −40 °C, the LIB can keep 67 % capacity of room temperature, which is much better than conventional LIBs.  相似文献   

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