Li1.3Zr1.7Al0.3(PO4)3的离子交换特性

锂作为21世纪推动科学技术发展的重要元素之一,被誉为“工业味精”、“能源之星”。目前锂及其相关盐类材料已成为信息产业、核能源、航空航天技术、新型材料及军事科技等行业重点开发领域,具有极高科学价值和广阔商业前景[1￣4]。氯化锂是电解制金属锂的主要原料,它的纯度是电     

Preparation and characterization of LiMn2O4/Li1.3Al0.3Ti1.7(PO4)3/LiMn2O4 thin-film battery by spray technique

Solid-state thin-film lithium-ion battery of LiMn₂O₄/Li_1.3Al_0.3Ti_1.7(PO₄)₃/LiMn₂O₄ is prepared by spray technique using Li_1.3Al_0.3Ti_1.7(PO₄)₃ sintered pellet as both electrolyte and substrate. The thin-film battery is heat-treated by rapid thermal annealing. Phase identification, morphology and electrochemical properties of the sintered pellets and thin-film battery are investigated by X-ray diffraction, scanning electron microscopy, electrochemical impedance spectroscopy, cyclic voltammetry, and galvanostatic charge-discharge experiments, respectively. The results show that LiMn₂O₄ films with some pores are well deposited on the surface of Li_1.3Al_0.3Ti_1.7(PO₄)₃ sintered pellet. The discharge current density and temperature have considerable effect on discharge capacity of the thin-film battery. LiMn₂O₄/Li_1.3Al_0.3Ti_1.7(PO₄)₃/LiMn₂O₄ thin-film battery can be easily cycled with a capacity loss of 0.213% per cycle when 50 cycles are carried out.     

Electrical Properties of NASICON-type Structured Li1.3Al0.3Ti1.7(PO4)3 Solid Electrolyte Prepared by 1,2-Propylene glycol-assisted Sol-gel Method

Lithium-ion conductor Li_1.3Al_0.3Ti_1.7(PO₄)₃ with an ultrapure NASICON-type phase is syn-thesized by a 1,2-propylene glycol (1,2-PG)-assisted sol-gel method and characterized by differential thermal analysis-thermo gravimetric analysis, X-ray diffraction, scanning elec-tron microscopy, electrochemical impedance spectroscopy, and chronoamperometry test.Due to the use of 1,2-PG, a homogeneous and light yellow transparent precursor solu-tion is obtained without the precipitation of Ti⁴⁺ and Al³⁺ with PO₄^3-. Well crystallizedLi_1.3Al_0.3Ti_1.7(PO₄)₃ can be prepared at much lower temperatures from 850 oC to 950 oC within a shorter synthesis time compared with that prepared at a temperature above 1000 oC by a conventional solid-state reaction method. The lithium ionic conductivity of the sintered pellets is up to 0.3 mS/cm at 50 oC with an activation energy as low as 36.6 kJ/mol for the specimen pre-sintered at 700 oC and sintered at 850 oC. The high conductivity, good chemi-cal stability and easy fabrication of the Li_1.3Al_0.3Ti_1.7(PO₄)₃ provide a promising candidate as solid electrolyte for all-solid-state Li-ion rechargeable batteries.     

Effect of thermal treatment modes on ion-conducting properties of lithium-aluminum titanophosphate

Dependence of the density of the Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) ceramic on thermal treatment modes was studied. The conditions in which ceramic samples with density exceeding 90% are obtained were determined. It was found that the bulk ionic conductivity of LATP upon sintering at 1000°C for 2–6 h is (1.1–1.3) × 10^–3 S cm^–1 at 20°C, which corresponds to the maximum values for lithium-aluminum titanophosphate.     

All solid-state battery based on ceramic oxide electrolytes with perovskite and NASICON structure

The Li_0.33Lia_0.56TiO₃ and Li_1.3Ti_1.7Al_0.3(PO₄)₃ ceramics with the structures of defect-perovskite and NASICON structures with conductivity of 1–6?×?10^?6 S/cm at the room temperature are obtained. Ceramic electrolytes were developed for a solid-state battery EMF of 4.1 V and high discharge stability in time. Discharge characteristics of solid-state batteries are studied in a laboratory cell.     

Sol-gel synthesis of Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte

A modified sol-gel process was studied as applied to synthesize a lithium-conducting solid electrolyte of composition Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) using water-soluble salts Al(NO₃)₃ · 9H₂O, LiNO₃ · 3H₂O, and (NH₄)₂HPO₄ and a titanium(IV) citrate complex. As-synthesized samples were characterized using X-ray powder diffraction, DSC/TG, SEM, and impedance spectroscopy. Sintering of as-synthesized amorphous powders at 700°C was found to yield LATP with crystallite sizes of 42–48 nm. Ionic conductivity of the electrolyte measured in the frequency range 25–10⁶ Hz in disks having 86–90% density that were sintered at 1000°C was (3–4) × 10^?4 S/cm. Temperature-dependent ionic conductivity was studied in the range 25–200°C. The activation energy of conduction was determined for LATP.     

Preparation and characterization of NASICON type Li+ ionic conductors

The new scandium/aluminium co-doped NASICON phases Li_1?+?x Al _y Sc _x???y Ti_2???x (PO₄)₃ (x?=?0.3, y?=?0,0.1,0.2,0.3) were prepared by mechanical milling followed by annealing of the mixtures at 950 °C. X-ray diffraction of all samples showed the formation of NASICON structure with space group R-3c along with a minor impurity. Rietveld refinement of the X-ray data was performed to identify the structural variation. Doping with Sc³⁺ caused elongation of a- and c- axes for all the compounds when compared with undoped LiTi₂(PO₄)₃. The compound Li_1.3Sc_0.3Ti_1.7(PO₄)₃ showed a maximum of a?=?8.5504(7), c?=?20.986(3) Å at room temperature and exhibited highest coefficient of thermal expansion. The highest ionic conductivity (σ), 7.28×10^?4 S cm^?1 was observed for Li_1.3Sc_0.3Ti_1.7(PO₄)₃, two orders of magnitude higher than for the undoped phase.     

Study of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> interaction with solid lithium-containing electrolytes

Compatibility of the lithium-titanium spinel Li₄Ti₅O₁₂ in contact with precursors of lithium-conducting solid electrolytes of composition Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP), Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP), Li_0.5La_0.5TiO₃ (LLT) was studied. It was found that, in sintering of Li₄Ti₅O₁₂ brought in contact with LATP and LAGP, a solid-phase reaction occurs to give nonconducting phases (TiO₂ and Li₃PO₄). The conductivity of the stable composite Li₄Ti₅O₁₂/LLT (10%) is higher than that of the starting Li₄Ti₅O₁₂, which makes it possible to regard the composite as a promising anode material for lithium-ion batteries.     

LiVPO4F/Li3V2(PO4)3 nanostructured composite cathode materials prepared via mechanochemical way

Single-phase LiVPO₄F and LiVPO₄F/Li₃V₂(PO₄)₃ nanostructured composite cathode materials were prepared by heating of the VPO₄?+?LiF mechanochemically activated mixture to 700 °C and subsequent quick or slow cooling to room temperature, respectively. The formation of the composites was proved by a combination of different physico-chemical methods, including XRD, FTIR, ⁶Li and ³¹P NMR, SEM, TEM, and HRTEM. It has been shown that in the composites LiVPO₄F and Li₃V₂(PO₄)₃ nanocrystals well inset into each other resulting in the nanodomain composite formation. Charge–discharge curves of the composites have a sloping profile both in the high-voltage (3.0–4.5 V) and in the low-voltage (1.3–2.5 V) ranges, noticeably different from plateaus for a phase-pure LiVPO₄F, thus indicating a probable change of a two-phase regime of lithium intercalation for a single-phase one. Enhanced rate capability of the LiVPO₄F/Li₃V₂(PO₄)₃ composites is associated with their microstructure and high ionic conductivity of Li₃V₂(PO₄)₃.     

Microstructure and ionic conductivity of lithium-aluminum titanophosphate

Synthesis from aqueous peroxide solutions provides lithium-aluminum titanophosphate Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) with particles of submicron size and conductivity of (4–5) × 10^?4 S/cm at the room temperature. LATP were characterized using the methods of XRD, DTA/TG, measurement of specific surface area, ionic and electronic conductivity. According to XRD, a single-phase crystalline product with the specific surface area of 8.2 m²/g is formed as a result of precursor sintering at 700°C (the average particle size of electrolyte was 250 nm). Sizes of coherent-scattering region were calculated on the basis of the values of intrinsic broadening of diffraction maximums. Analysis of broadening of diffraction maximums indicates that the size of primary LATP crystallites after sintering at 700°C was 90 nm according to peak (113) (2θ = 24.5°) and 110 nm according to peak (104) (2θ = 20.9°). The synthesized submicron LATP powders are suitable for formation of solid electrolyte films using the method of aerosol deposition.     

Production of an electrode material modified by a lithium-conducting solid electrolyte

The process for producing the electrode material LiCoPO₄ modified by the lithium-conducting solid electrolyte Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) was studied. To create a composite consisting of an electrochemically active substance and an electrically conductive additive distributed uniformly between LiCoPO₄ particles, a peroxide solution of a LATP precursor was used. After annealing at 700°C, the two-phase composite LiCoPO₄/LATP was obtained, the conductivity of which was two orders of magnitude higher than that of binary lithium cobalt phosphate at room temperature.     

Electrochemical lithium and sodium insertion studies in 3D metal oxy-phosphate framework MoWO3(PO4)2 for battery applications

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).

     

Comparative investigations of LiVPO4F/C and Li3V2(PO4)3/C synthesized in similar soft chemical route

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.     

Wet coordination method to prepare carbon-coated Li3V2(PO4)3 cathode material for lithium ion batteries

A convenient method named wet coordination is used to prepare the sample or carbon-coated Li₃V₂(PO₄)₃ in the furnace with a flowing argon atmosphere at 600 °C for 1 h. The sample is characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM) and energy dispersive analysis of X-rays (EDAX). Galvanostatic charge–discharge between 3.3 and 4.3 V (vs. Li/Li⁺) shows that the sample exhibits a high discharge capacity of 128 mAh g^?1 with a good reversible performance under a current density of 95 mA g^?1. It suggests that carbon-coated Li₃V₂(PO₄)₃ with good electrochemical performance can be obtained via this method, which is suitable for large-scale production.     

Li3−xTi2(PO4)3 (0 ≤ x ≤ 1): A new mixed valent titanium(III/IV) phosphate with a NASICON-type structure

A new NASICON-related structure of lithium titanium phosphate Li_2.72Ti₂(PO₄)₃ has been determined. This compound crystallizes in an orthorhombic system, Pbcn, with a = 12.064 (3) Å, b = 8.663 (3) Å, c = 8.711 (4) Å, V = 910.4 (8) ų, and Z = 4. The single crystal structure of this novel mixed valent titanium(III/IV) phosphate reveals one titanium atom per asymmetric unit. Two lithium sites are characterized by a pair of distorted polyhedra, Li(1)O₄ and Li(2)O₅, which share a common edge resulting in a short Li(1) … Li(2) distance, i.e., 2.29 (5) Å. Magnetic susceptibility and microprobe analysis confirmed the structural composition. The room temperature ionic conductivity is comparable with that of the known Li_1+xTi^IV_2−xIn^III_x(PO₄)₃, which suggests possible fast ionic conductivity.     

Lithium Intercalation into ATi2(PS4)3 (A = Li,Na, Ag)

Comparison of the electrochemical insertion of lithium into ATi₂(PS₄)₃ with A = Li, Na, Ag and ATi₂(PO₄)₃ with Li, Ag is striking. Whereas only four lithium per formula unit (Li/f.u.) can be inserted reversibly into the phosphates, up to 7 and 10 Li/f.u. can be inserted reversibly in the thiophosphates with A = Li and Ag. Moreover, the Ag⁺ to Ag⁰ reduction in AgTi₂(PO₄)₃ is not reversible, but in AgTi₂(PS₄)₃ it is reversible. Strong hybridization of the Ag-5s and host antibonding bands stabilizes the formal valences Ag⁰, Ti⁺, and (PS₄)⁴⁻ in the discharged state of AgTi₂(PS₄)₃; but only the formal valence Ti²⁺ is accessible in LiTi₂(PS₄)₃. Unfortunately the large volume change associated with the lithium insertion renders the structure progressively more amorphous on cycling, which causes the capacity to fade quite dramatically on further cycling. The thiophosphates transform to the phosphates on heating in air.     

Ionothermal synthesis and rate performance studies of nanostructured Li3V2(PO4)3/C composites as cathode materials for lithium-ion batteries

Various structures and morphologies of Li₃V₂(PO₄)₃ precursors are synthesized by a novel ionothermal method using three kinds of imidazolium-based ionic liquids as both reaction mediums and structure-directing agents at ambient pressure. Nanostructured Li₃V₂(PO₄)₃/C cathode materials can be successfully prepared by a subsequent short calcination process. The structures, morphologies, and electrochemical properties are characterized by X-ray diffractometry, thermogravimetry, scanning and transmission electron microscopy, charge–discharge test, cyclic voltammetry, and electrochemical impedance spectroscopy. It shows that three kinds of materials synthesized present different morphologies and particle sizes. The result can be due to imidazolium-based ionic liquids, which combined with different anions play important role in forming the size and morphology of Li₃V₂(PO₄)₃ material. These materials present excellent performance with high rate capacity and cycle stability. Especially, the Li₃V₂(PO₄)₃/C material prepared in 1-ethyl-3-methylimadozolium trifluoromethanesulfonate ([emim][OTf]) can deliver discharge capacities of 127.4, 118.9, 105.5, and 92.8 mAh?g^?1 in the voltage range of 3.0–4.3 V at charge–discharge rate of 0.1, 1, 10, and 20 C after 50 cycles, respectively. The excellent rate performance can be attributed to the uniform nanostructure, which can make the lithium-ion diffusion and electron transfer more easily across the Li₃V₂(PO₄)₃/electrolyte interfaces.     

Les systemes binaires AlPO4−M3PO4 (M=Li,Na, K)

The liquid-solid phase diagram of the binary systems AlPO₄?M₃PO₄(M=Li, Na, K) have been established. The additional compounds Na₃Al(PO₄)₂, Na₃Al₂(PO₄)₃ and K₃Al₂(PO₄)₃ have been found again. A new compound K₃Al(PO₄)₂ is observed. The melting point of Na₃PO₄ is 1545°C and K₃PO₄ does not melt up to 1700°C.     

Effect of Al2O3 -coating on the electrochemical performances of Li3V2(PO4)3/C cathode material

The effect of Al₂O₃ -coating on Li₃V₂(PO₄)₃/C cathode material for lithium-ion batteries has been investigated. The crystalline structure and morphology of the synthesized powders have been characterized by XRD, SEM, and HRTEM, and their electrochemical performances are evaluated by CV, EIS, and galvanostatic charge/discharge tests. It is found that Al₂O₃ -coating modification stabilizes the structure of the cathode material, decreases the polarization of electrode and suppresses the rise of the surface film resistance. Electrochemical tests indicate that cycling performance and rate capability of Al₂O₃-coated Li₃V₂(PO₄)₃/C are enhanced, especially at high rates. The Al₂O₃-coated material delivers discharge capacity of 123.03 mAh g^?1 at 4 C rate, and the capacity retention of 94.15 % is obtained after 5 cycles. The results indicate that Al₂O₃ -coating should be an effective way to improve the comprehensive properties of the cathode materials for lithium-ion batteries.     

A single crystal X-ray and powder neutron diffraction study on NASICON-type Li1+xAlxTi2−x(PO4)3 (0 ≤ x ≤ 0.5) crystals: Implications on ionic conductivity

Single crystals of NASICON-type material Li_1+xTi_2−xAl_x(PO₄)₃ (LATP) with 0 ≤ x ≤ 0.5 were successfully grown using long-term sintering techniques. Sample material was studied by chemical analysis, single crystal X-ray and neutron diffraction. The Ti⁴⁺ replacement scales very well with the Al³⁺ and Li⁺ incorporation. The additional Li⁺ thereby enters the M3 cavity of the NASICON framework at x, y, z ∼ (0.07, 0.34, 0.09) and is regarded to be responsible for the enhanced Li⁺ conduction of LATP as compared to Al-free LTP. Variations in structural parameters, associated with the Ti⁴⁺ substitution with Al³⁺ + Li⁺ will be discussed in detail in this paper.