Synthesis, crystal structure, and spectroscopic study of K0.92(2) Zn0.08(2) H1.92(2) (PO4) (Zn-KDP)

The structure of K0.92₍₂₎ Zn_0.08(2) H_1.92(2) (PO₄) was determined using single-crystal X-ray diffraction. The crystal structure of the Zn-KDP belonged to the tetragonal space group $ \mathrm{I}\overline{4}2\mathrm{d} $ , with cell parameters of a?=?b?=?7.4487(5)?Å and c?=?6.9703(5)?Å, 386.73(5) Å3, Z?=?4, and R?=?0.023. Zn²⁺ ions were used as substitutes for K⁺ ions with hydrogen vacancy. The Zn-KDP single crystals were submitted to further Raman, infrared, and ¹H NMR studies to investigate chemical group functionalisation, possible bonding between the organic and inorganic materials, and partial substitution of K⁺ by Zn²⁺. The latter partial substitution was confirmed by the deviation of IR frequencies for O–H stretching, the variation of IR and Raman frequencies for stretching and bending vibrations ν(PO₄) of H₂PO₄, and the appearance of additional Raman (147, 386 and 481 cm^?1) vibrational bands. Electrical conductivity measurements were performed on polycrystalline pellets of Zn-KDP and pure KDP at room temperatures (RT) of up to 473K. In both cases, a conductivity jump close to 453K was observed, and a stronger increase of conductivity was measured.     

Structural characteristics of olivine Li(Mg0.5Ni0.5)PO4 via TEM analysis

The structural characteristics of olivine-type lithium orthophosphate Li(Mg_0.5Ni_0.5)PO₄ synthesized via solid-state reaction have been studied using X-ray diffraction, ion beam technique, scanning electron microscopy, infrared spectroscopy, transmission electron microscopy and energy dispersive X-ray analysis. The parent LiNiPO₄ compound can be synthesized in olivine structure without any evidence of secondary phases as impurities. The structural quality of the parent LiNiPO₄ in the absence of secondary component phases resulted in the formation of hexagonal closed packed structure. The olivine analogue compound containing mixed M (M?=?Mg, Ni) cations, Li(Mg_0.5Ni_0.5)PO₄ contained Li₃PO₄ as a second phase upon synthesis, however a carbothermal reduction method produced a single-phase compound. The redox behaviour of carbon-coated Li(Mg_0.5Ni_0.5)PO₄ cathode in aqueous lithium hydroxide as the electrolyte showed reversible lithium intercalation.     

Potassium cation conduction in K3 − 2x Pb x PO4 solid solutions

New materials of the K_{3 ? 2x} Pb _x PO₄ system with high potassium-cation conductivity have been synthesized and studied. It has been found that the introduction of Pb²⁺ cations substantially increases the conductivity of K₃PO₄ due to the formation of potassium vacancies and the stabilization of the high-temperature cubic structure of the orthophosphate. At low temperatures, the maximum conductivity has been observed in the composition range x = 0.15–0.20 and varies from ～10^?2 S cm^?1 at 400°C to ～10^?1 S cm^?1 at 700°C. The factors influencing the transport properties of the materials under study have been discussed.     

Rubidium-cation conductivity of Rb<Subscript>3–2<Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript> solid solutions

New Rb₃PO₄-based ceramic materials with high rubidium-cation conductivity in the Rb_3–2x Pb _x PO₄ system have been synthesized and studied. Introduction of Pb²⁺ cations leads to a sharp increase in the conductivity of rubidium orthophosphate due to formation of cation vacancies and, at temperatures 350–550°C, also due to the stabilization of high-temperature cubic modification Rb₃PO₄. At high temperatures, the electrolytes prepared have very high ion conductivity higher than 10^–1 S cm^–1 at 700°C, which is higher than the values previously obtained in similar systems with additions of tin and cadmium ions. The factors influencing the transport properties of the materials under study are discussed.     

A neutron powder diffraction study of LiCoxFe1−xPO4 for x = 0, 0.25, 0.40, 0.60 and 0.75

X-ray and neutron powder diffraction studies have been made of the single-phase systems LiCo_xFe_1−xPO₄ (x = 0, 0.25, 0.40, 0.60 and 0.75) to establish how Co²⁺ substitutes into the LiFePO₄ olivine structure. Rietveld refinement shows that all four substituted materials have the same olivine structure (space group: Pnma) with lithium occupying octahedral (4a) sites, and Co²⁺ replacing Fe²⁺ at the octahedral (4c) sites. The a and b cell parameters decrease while the c parameter increases on the addition of Co²⁺. There are certain indications of structural instability for high Co-content compositions.     

Compatibility study of oxide and olivine cathode materials with lithium aluminum titanium phosphate

The compatibility of the solid electrolyte Li_1.5Al_0.5Ti_1.5(PO₄)₃ (LATP) with the cathode materials LiCoO₂, LiMn₂O₄, LiCoPO₄, LiFePO₄, and LiMn_0.5Fe_0.5PO₄ was investigated in a co-sintering study. Mixtures of LATP and the different cathode materials were sintered at various temperatures and subsequently analyzed by thermal analysis, X-ray diffraction, and electron microscopy. Oxide cathode materials display a rapid decomposition reaction with the electrolyte material even at temperatures as low as 500 °C, while olivine cathode materials are much more stable. The oxide cathode materials tend to decompose to lithium-free compounds, leaving lithium to form Li₃PO₄ and other metal phosphates. In contrast, the olivine cathode materials decompose to mixed phosphates, which can, in part, still be electrochemically active. Among the olivine cathode materials, LiFePO₄ demonstrated the most promising results. No secondary phases were detected by X-ray diffraction after sintering a LATP/LiFePO₄ mixture at temperatures as high as 700 °C. Electron microscopy revealed a small secondary phase probably consisting of Li₂FeTi(PO₄)₃, which is ionically conductive and should be electrochemically active as well.     

Lithium ion-poly (ethylene oxide) complexes. I. Effect of anion on conductivity

The ionic conductivities of a series of lithium salt-poly (ethylene oxide) complexes have been studied from ambient temperature to approximately 400 K. Plots of the variation of conductivity with temperature indicate a transition in behaviorr between 330–360 K. The activation energies in the high temperature regime vary from 0.16 eV (LiH₂PO₄) to 1.45 eV (LiNO₃) and in the low temperature regime from 0.86 eV (LiBF₄) to 2.47 eV (LiH₂PO₄). Conductivity values for the salts tested also exhibits wide variation. The lowest measured conductivity was 10^?9 S/cm and the highest was 10^?4 S/cm. The anion plays an important role in the total measured conductivity. Salts with oxygen-containing anions form complexes with an apparent higher conductivity when the sample is vacuum dried. This suggets hydrogen bonding with residual water in the polymer impeding anionic mobility. In one of the salt-complexes (LiBF₄) residual water and thermal history, were shown not to significantly affect conductivity.     

Electrical and mechanical properties of hot-pressed versus sintered LiTi2(PO4)3

The electrical and mechanical properties of hot-pressed versus sintered LiTi₂(PO₄)₃ were investigated. The hot-pressed LiTi₂(PO₄)₃ had a higher density and larger average grain size than the sintered material. As a result of these microstructural differences the hot-pressed material exhibited a higher total ionic conductivity and lower hardness. The electronic conductivity of both materials was the same and increased by a factor of about 10⁷ when the hot-pressed and sintered materials were heated under a reducing atmosphere.     

Electrical and electrochemical behaviour of several LiFe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript> solid solutions as cathode materials for lithium ion batteries

Several olivine phosphates were investigated in the last years as cathode materials for secondary lithium ion batteries. Among these compounds, LiFe _x Co_1 − x PO₄ solid solutions might be interesting candidates because they should combine the high potential value of Co³⁺/Co²⁺ (higher than 4.5 V vs Li⁺/Li) with the relatively high charge–discharge rate of LiFePO₄. Solid solutions were prepared by solid-state route and characterised by X-ray powder diffraction, cyclic voltammetry, impedance spectroscopy and the Hebb–Wagner method. The results show that also low amount of iron induces high electronic conductivity in the solid solutions.     

Electrical properties of Li-based NASICON compounds doped with yttrium oxide

In the present study, the electrical properties of lithium-based Li_1.3Al_0.3???x Y _x Ti_1.7(PO₄)₃ (LAYTP) system is reported. Yttrium is a rare earth element and has been found to be an excellent sintering aid in ceramic electrode materials. Earlier attempts to replace the tetravalent Ti⁴⁺ using trivalent cations like Al³⁺, Y³⁺, In³⁺, and Sc³⁺ in rhombohedral NASICON structure have resulted in enhanced electrical conductivity. The effect of trivalent cation Y³⁺ doping in an optimized system Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) is discussed. The electrical properties of this ceramic compound in temperature range of 303 to 423 K and in the microwave frequency range of 20 MHz to 1 Hz were studied for the LAYTP system using impedance spectroscopy. The role of yttrium to improve the density of the material and thereby the study of the grain and grain boundary is explored.     

Emission-tunable phosphors Ca9MgM′ (PO4)7: Eu2+,Mn2+ (M′=Li,Na, K) for white light-emitting diodes

A series of single-composition phosphors Ca₉MgM′(PO₄)₇:xEu²⁺, yMn²⁺ (CMM′ P:Eu²⁺, Mn²⁺; M′=Li, Na, K; 0.003≤x≤0.03; 0 ≤y≤0.1) were synthesized by solid state reactions. Upon excitation at 337 nm, phosphors Ca₉MgM′ (PO₄)₇: Eu²⁺ exhibit strong blue emissions centered at 417 (Ca₉MgLi(PO₄)₇:Eu²⁺), 457 (Ca₉MgNa(PO₄)₇:Eu²⁺), and 453 (Ca₉MgK(PO₄)₇:Eu²⁺) nm respectively, which correspond to the 4f⁶5d¹→4f⁷ transitions of Eu²⁺ ions, Through an effective resonance-type energy transfer, CMM′P:Eu²⁺,Mn²⁺ phosphors exhibit a series of colors by adjusting the concentration of Mn²⁺. The result indicates that CMM′P:Eu²⁺,Mn²⁺ can be potentially used as a UV excited phosphor for white light-emitting diodes (LEDs).     

Silica–zirconium phosphate–phosphoric acid composites: preparation,proton conductivity and use in gas sensors

Mesoporous composites made of silica and α-zirconium phosphate (SiO₂·xZrP) were synthesized starting from mixtures of delaminated ZrP dispersions and tetrapropylammonium oligosilicate solutions. The surface area of the composites reaches a maximum of 700 m²/g for x≈0.02, while the average pore diameter is about 40 Å for x in the range 0.05–0.35. In order to increase proton conductivity at low relative humidity (r.h.), SiO₂·xZrP·yH₃PO₄ composites were prepared and characterised by ²⁹Si and ³¹P MAS NMR and conductivity measurements. At 100 °C and 6% r.h., the conductivity of the composites, with H₃PO₄ loadings of 80% of the pore volume, rises from 5×10⁻⁴ to 2×10⁻² S/cm for x decreasing between 0.35 and 0.05, as a consequence of the concomitant increase of pore volume. For the composite with x=0.18, the dependence of conductivity on H₃PO₄ loading was also investigated at different temperatures and r.h. values. The combined increase of humidity, temperature and H₃PO₄ loading results in an increase of conductivity from 1×10⁻⁷ S/cm (y=0.09, T=25 °C, 0% r.h.) to 4×10⁻² S/cm (y=0.61, T=100 °C, 30% r.h.). SiO₂·0.18ZrP·0.61H₃PO₄ was also tested as a proton electrolyte in an oxygen sensor consisting of a disk of the composite sandwiched between a platinum sensing electrode and a reference electrode based on Ni_1−xO. The sensor is able to detect O₂ at room temperature in a dry environment with a response time of 20–30 s.     

Proton conductivity of Al(H2PO4)3–H3PO4 composites at intermediate temperature

Composites of Al(H₂PO₄)₃ and H₃PO₄ were synthesised by soft chemical methods with different Al/P ratios. The Al(H₂PO₄)₃ obtained was found to have a hexagonal symmetry with parameter a = 13.687(3)Å, c = 9.1328(1)Å. The conductivity of this material was measured by a.c. impedance spectroscopy between 100 °C and 200 °C in different atmospheres. The conductivity of pure Al(H₂PO₄)₃ in air is in the order of 10^? 6–10^? 7 S/cm between 100 and 200 °C. For samples containing small excess of H₃PO₄, much higher conductivity was observed. The impedance responses of the composites were found to be similar with AlH₂P₃O₁₀·nH₂O under different relative humidity. The conductivity of Al(H₂PO₄)₃–H₃PO₄ composite with Al/P = 1/3.5 reached 6.6 mS/cm at 200 °C in wet 5% H₂. The extra acid is found to play a key role in enhancing the conductivity of Al(H₂PO₄)₃–H₃PO₄ composite at the surface region of the Al(H₂PO₄)₃ in a core shell type behaviour. 0.7% excess of H₃PO₄ can increase the conductivity by three orders of magnitude. These composites might be alternative electrolytes for intermediate temperature fuel cells and other electrochemical devices. Conductivity (9.5 mS/cm) changed little, when the sample was held at 175 °C for over 100 h as the conductivity stabilised.     

Synthesis and characterization of LiMn1-x Fe x PO4/carbon nanotubes composites as cathodes for Li-ion batteries

Carbon nanotubes (CNT) coated with LiMn_1-x Fe _x PO₄ (0.2?≤?x?≤?0.8), as possible cathode materials, was synthesized by using a sol–gel process (Polyol method), after annealing under flowing nitrogen. X-ray diffraction (XRD) patterns of the composites confirmed the formation of the olivine structured LiMn_1-x Fe _x PO₄ phase and no secondary phases were detected. The morphological investigation revealed the formation of agglomerates with particles size ranging between 300 and 700 nm. XRD investigation of composites shows difference of the morphology by doping CNT and carbon black in the composites. Transmission electron microscopy shows the growth of nano-sized particles on CNT (20–70 nm) and the agglomeration of primary particles to form secondary particles. The X-ray photoelectron spectroscopy showed that the Fe and Mn ions are in divalent states in the LiMn_1-x Fe _x PO₄ composites. The cyclic voltamograms showed the oxidation peaks of iron and manganese ions at 3.53–3.63 and 4.05–4.33 V, respectively, while the reduction peaks were found at 3.21–3.42 V (iron reduction) and 3.85–3.93 V (manganese reduction) depending on the iron content in the composition. The LiMn_0.6Fe_0.4PO₄/CNT composite (x?=?0.4) (with 20 %?wt CNT) delivered a specific capacity of 120 mAhg^?1 (at a discharge rate of C/20 and RT).     

Ionic conductivity and crystal structure for the Li3−2xCr2−xTax(PO4)3 system

The monoclinic phase (P2₁/n) was formed for 0≤x≤0.6 and the NASICON-type rhombohedral phase (R3̄c) was obtained for the region 0.8≤x≤1.2 in the Li_3−2xCr_2−xTa_x(PO₄)₃ system. The activation energy for Li⁺ migration was ca. 0.45 eV for the monoclinic structure and ca. 0.36 eV for the rhombohedral structure. The maximum conductivity of 8.4×10⁻⁶ S cm⁻¹ at 298 K was obtained for x=0.8 of the Li_3−2xCr_2−xTa_x(PO₄)₃ system. The conductivity of LiCrTa(PO₄)₃ was enhanced about three to five times by the addition of the lithium salt due to the improvement of the sinterablity. The maximum conductivity was 2.4×10⁻⁵ S cm⁻¹ at 298 K for LiCrTa(PO₄)₃–0.2Li₃BO₃.     

XRD,impedance, and Mössbauer spectroscopy study of the Li<Subscript>3</Subscript>Fe<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> + Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> composite for Li ion batteries

The synthesis procedure of the Li₃Fe₂(PO₄)₃?+?Fe₂O₃ composite is presented. The monoclinic (A type) and hematite phases were detected by X-ray diffraction after the synthesis of the composite. The structural α–β (at a temperature of 460 K) and β–γ (at a temperature of 523 K) phase transitions in the composite were indicated by the anomalies of the electrical conductivity, dielectric permittivity, and changes of activation energies of conductivity. Two phase transitions have been detected in the Li₃Fe₂(PO₄)₃?+?Fe₂O₃ composite by ⁵⁷Fe Mössbauer spectroscopy: the phase transition in Li₃Fe₂(PO₄)₃ from the paramagnetic to antiferromagnetic phase at temperature T _N?=?29.5 K and the Morin phase transition in Fe₂O₃ at temperature T _M?=?235 K.     

Crystal structure analysis of Li<Subscript>3</Subscript>PO<Subscript>4</Subscript> powder prepared by wet chemical reaction and solid-state reaction by using X-ray diffraction (XRD)

Lithium phosphate (Li₃PO₄) is one of the promising solid electrolyte materials for lithium-ion battery because of its high ionic conductivity. A crystalline form of Li₃PO₄ had been prepared by two different methods. The first method was wet chemical reaction between LiOH and H₃PO₄, and the second method was solid-state reaction between Li₂O and P₂O₅. Crystal structure of Li₃PO₄ white powder had been investigated by using an X-ray diffraction (XRD) analysis. The results show that Li₃PO₄ prepared by wet chemical reaction belongs to orthorhombic unit cell of β-Li₃PO₄ with space group Pmn2₁. Meanwhile, Li₃PO₄ powder prepared by solid-state reaction belongs to orthorhombic unit cell of γ-Li₃PO₄ with space group Pmnb and another unknown phase of Li₄P₂O₇. The impurity of Li₄P₂O₇ was due to phase transformation in solid state reaction during quenching of molten mixture from high temperature. Ionic conductivity of Li₃PO₄ prepared by solid-state reaction was ～3.10^?7 S/cm, which was higher than Li₃PO₄ prepared by wet chemical reaction ～4.10^?8 S/cm. This increasing ionic conductivity may due to mixed crystal structures that increased Li-ion mobility in Li₃PO₄.     

Hydrothermal synthesis and properties of manganese-doped LiFePO4

A series of carbon-coated LiFe_1???x Mn _x PO₄ compounds are prepared by a hydrothermal method at 170 °C for 12 h. The structure and morphology of the prepared composites are characterized to examine the effects of Mn²⁺ substitution. All LiFe_1???x Mn _x PO₄ compositions are found to have an ordered olivine-type structure with homogeneous Fe²⁺ and Mn²⁺ distributions. The substitution leads to grain refinement from ~500 to ~150 nm, as well as to increased initial capacity and improved electronic conductivity. The amount of carbon coating varies with increased doping amount. The discharge curves of the LiFe_1???x Mn _x PO₄/C materials reveal a high discharge plateau corresponding to Fe^2+/3+ and no obvious plateau assigned to Mn^2+/3+, although a slight contribution of manganese is detected. However, the electrochemical performance, including the discharge capacity and cyclic performance, deteriorates with increased Mn content in the composite.     

Structural and electronic properties of the LiNiPO4 orthophosphate

Microcrystalline LiNiPO₄ powders have been prepared by solid-state reaction using various precursors. Characterization of the structure and morphology of powders was performed using XRD, SEM, HRTEM, Raman, and FTIR. The electronic properties of materials were investigated by SQUID and ESR. The LiNiPO₄ material adopts the olivine-like structure (Pnma S.G.). Analysis of the Raman and FTIR spectra figures out, with the aid of a molecular vibration model, the bonding between NiO₆ octahedral and (PO₄)^3? tetrahedral groups. The electronic configuration and the local cationic arrangement are confirmed by magnetic susceptibility and electron spin resonance spectroscopy.