Electrochemical properties of LiFe0.9Mg0.1PO4 / carbon cathode materials prepared by ultrasonic spray pyrolysis

The LiFe_0.9Mg_0.1PO₄/C powder of pure olivine phase can be prepared with the duplex process of spray pyrolysis synthesis (at 450 ^°C) and subsequent heat treatment (at 700 ^°C for 2, 4 and 8 h). From scanning electron microscopy observation with corresponding elemental mapping images of iron, phosphorous and magnesium, it could be found that the LiFe_0.9Mg_0.1PO₄ powders are covered with fine pyrolyzed carbon. Raman spectra indicate that the phase of carbon with higher electronic conductive phase is predominant when prolonged subsequent heat treatment is carried out. The carbon coatings on the LiFe_0.9Mg_0.1PO₄ surface can improve the conductivity of the LiFe_0.9Mg_0.1PO₄ powder (3.8×10⁻⁵ S cm⁻¹) to about a factor of ∼10⁴ higher than the conductivity of LiFePO₄. The stability and cycle life of a charge/discharge cycle test of lithium ion secondary batteries are also enhanced. The results indicate that the LiFe_0.9Mg_0.1PO₄ powder, prepared at a pyrolysis temperature of 450 ^°C and with post-heat-treatment at 700 ^°C for 8 h, exhibits a specific initial discharge capacity of about 132 mA h g⁻¹ at C/10 rate, 105 mA h g⁻¹ at 1C, and 87 mA h g⁻¹ at 5C.     

First-principles studies of Mn-doped LiCoPO4

This paper investigates Mn-doped LiCoPO₄ material using first-principles calculations. Results indicate that the volume change of LiMn_xCo_1-xPO₄ to Mn_xCo_1-xPO₄ is smaller than that of undoped LiCoPO₄, which is responsible for the excellent tolerance of repeated cycling in lithium ion batteries. Combining first-principles calculations with basic thermodynamics, we calculate the average intercalation voltage of Mn-doped LiCoPO₄. It is shown that the redox couple Mn³⁺/Mn²⁺ can be observed with increasing Mn content. Therefore, the Mn ion displays some electrochemical activity during discharge/charge of LiMn_xCo_1-xPO₄ due to the coexistence of Co and Mn.     

Lithium ion conductive glass–ceramics with Li3Fe2(PO4)3 and YAG laser-induced local crystallization in lithium iron phosphate glasses

The glasses with the composition of 37.5Li₂O–(25 − x)Fe₂O₃–xNb₂O₅–37.5P₂O₅ (mol%) (x = 5,10,15) are prepared, and it is found that the addition of Nb₂O₅ is effective for the glass formation in the lithium iron phosphate system. The glass–ceramics consisting of Nasicon-type Li₃Fe₂(PO₄)₃ crystals with an orthorhombic structure are developed through conventional crystallization in an electric furnace, showing electrical conductivities of 3 × 10^− 6 Scm^− 1 at room temperature and the activation energies of 0.48 eV (x = 5) and 0.51 eV (x = 10) for Li⁺ ion conduction in the temperature range of 30–200 °C. A continuous wave Nd:YAG laser (wavelength: 1064 nm) with powers of 0.14–0.30 W and a scanning speed of 10 μm/s is irradiated onto the surface of the glasses, and the formation of Li₃Fe₂(PO₄)₃ crystals is confirmed from XRD analyses and micro-Raman scattering spectra. The crystallization of the precursor glasses is considered as new route for the fabrication of Li₃Fe₂(PO₄)₃ crystals being candidates for use as electrolyte materials in lithium ion secondary batteries.     

Carbon and transition metal containing titanium phosphates as electrodes for lithium ion batteries

We prepared transition metal containing titanium phosphates obtained from mesoporous titanium phosphate treated with cobalt and copper acetates and subsequently heated at 573 K under either air or nitrogen atmospheres. The first treatment with acetates incorporates the metal and acetate ions in the system. Moreover, it partially extracts the director agent. Total extraction of the surfactant can be reached in the copper samples after heating twice. However, the surfactant is not removed from the cobalt samples under the thermal conditions therein used. The composition of the heated materials is close to NASICON structures with a formula close to M_1.5Ti_1.5(PO₄)₃ (M = Co,Cu). A certain content in elemental carbon is observed in the samples obtained under nitrogen atmosphere, which are also more conductive than those prepared under air. The first discharge of lithium cells based in these mesoporous materials show electrochemical activity of Ti⁴⁺/Ti³⁺, Co²⁺/Co⁰ and Cu²⁺/Cu⁰ couples in the OCV–1.0 V region. Below this voltage, the discharge profiles are typical of phosphate systems where Li₃PO₄ is a product of the electrochemical reaction with lithium and, moreover, electrolyte solvent is reduced. Electrolyte is more degraded when the samples contain carbon. Capacities as high as 1600 mA h g^− 1 can be obtained at deep discharge. However, there is an irreversible capacity loss in the four systems due to the occurrence of insulating products as Li₃PO₄ and a solid electrolyte interface.     

Organic acid assisted solid-state synthesis of Li1.2Ni0.16Co0.08Mn0.56O2 nanoparticles as lithium ion battery cathodes

Lithium-rich layered oxide Li_1.2Ni_0.16Co_0.08Mn_0.56O₂ can be referred as a crystalline mixture of Li₂MnO₃ and LiNi_0.4Co_0.2Mn_0.4O₂ at equal molar ratio. In the paper, the solid state reaction of M(AC)₂·4H₂O (M = Mn, Co and Ni) and LiOH·H₂O has been performed to obtain nanocrystalline Li_1.2Ni_0.16Co_0.08Mn_0.56O₂ using a small molecular organic acid (i.e., oxalic acid (OA), citric acid (CA) or tartaric acid (TA)) as additive. The introduction of organic acids can help to improve the layered structure and inhibit the particle growth of Li_1.2Ni_0.16Co_0.08Mn_0.56O₂, and the different organic acids exert distinct influences on the structural and electrochemical properties of Li_1.2Ni_0.16Co_0.08Mn_0.56O₂. In detail, the nanoparticles obtained in the presence of OA have the smallest average size of 50–150 nm, which correspondingly exhibit the highest initial discharge capacity of 267.52 mAh g⁻¹ at 0.1C and the best high-rate capability (e.g., 152.22 mAh g⁻¹, 5C) when applied as a lithium ion battery cathode. Furthermore, the active substance obtained from TA shows the best cycling stability and a discharge capacity of 202.42 mAh g⁻¹ can be retained after 50 cycles at 0.5C.     

Diffusional mechanism of deintercalation in LiFe1 − yMnyPO4 cathode material

The paper presents the investigations on the structural, electrical and electrochemical properties of Mn substituted phospho-olivines LiFe_1 − yMn_yPO₄ and of W, Ti or Al doped LiFePO₄. The microscopic nature of the observed macroscopic, metallic-like conductivity of W, Ti, Al doped phospho-olivine samples is discussed. Some fundamental arguments against the bulk type conductivity are presented.A single phase, diffusional mechanism of deintercalation was found to appear for Mn-substituted LiFe_1 − yMn_yPO₄ samples in the whole range of lithium concentration, in contrast to the pure LiFePO₄, LiMnPO₄ and W, Ti, Al doped phospho-olivines, where a two-phase mechanism of electrochemical lithium extraction/insertion is observed.     

Effects of Li2CO3 as a secondary lithium source on the LiFePO4/C composites prepared via solid-state method

Li₂CO₃ was used as the secondary lithium source for the synthesis of LiFePO₄/C composites via a solid-state reaction method by adopting Li₃PO₄ as the main lithium source. The main purpose of using Li₂CO₃ is to compensate for the partial lithium loss during the sintering while reducing the usage of excess Li₃PO₄. In this study, the effects of Li₂CO₃ amount on the phase, structural and electrochemical properties of LiFePO₄/C material were systematically investigated. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), constant-current charge–discharge test and cyclic voltammetry (CV). The results showed that by adding an appropriate amount of Li₂CO₃, the impurities, e.g. Li₃PO₄, normally appearing in the final product, could be excluded. It was found that LiFePO₄/C with Li₂CO₃ in 6% excess (vs. stoichiometric LiFePO₄) exhibited the best electrochemical performance, which delivered initial discharge capacities of 141.7, 125.2, 119.9 and 108.9 mAh g^?1, respectively, at 0.5, 1, 2 and 5C rates. The capacity was reduced to 113.4 mAh g^?1 after 50 cycles at 2C rate, with capacity retention rate of 94.6%.     

Insertion properties of LiFe<Subscript>0.5</Subscript>Mn<Subscript>0.5</Subscript>PO<Subscript>4</Subscript> electrode materials for Li-ion batteries

This paper addresses the synthesis structural and electrochemical properties of LiFe_0.5Mn_0.5PO₄ electrode materials for Li-ion batteries. The charge–discharge reaction of Li/LiPF₆-EC–DEC/LiFe_0.5Mn_0.5PO₄ cell carried out at the 1-C rate shows a capacity retention of 128 mAh/g. The local structure of the delithiated Li _x Fe_0.5Mn_0.5PO₄ phases have been studied by Fourier transform infrared spectroscopy and magnetometry. Spectral features indicate that the structure of the delithiated phase remains in the orthorhombic system. The compositional dependence of the magnetic moment is found to be in quantitative agreement with the theoretical value predicted for oxidation of M ²⁺ ions in the high spin state. Paper presented at the 11th Euro-Conference on Science and Technology of Ionics, Batz-sur-Mer, France, 9–15 Sept. 2007     

Luminescence and energy transfer in Eu, Mn co-doped Li4SrCa(SiO4)2 for white light-emitting-diodes

Li₄(Sr_0.96Eu_0.04)(Ca_1 − xMn_x)(SiO₄)₂ phosphors were synthesized by solid-state reactions and photoluminescence (PL) properties were investigated. These phosphors have intense absorption in n-UV region, which is suitable for excitation of UV LEDs. The orange-reddish emission of Mn²⁺ can be adjusted by changing the Mn²⁺/Eu²⁺ ratio. Energy transfer from Eu²⁺ to Mn²⁺ is observed. Li₄(Sr_0.96Eu_0.04)(Ca_1 − xMn_x)(SiO₄)₂ phosphors could be used in white LEDs.     

Electrochemical characteristics of sulfur composite cathode for reversible lithium storage

The electrochemical characteristics of the sulfur composite cathode for reversible lithium storage were investigated. The sulfur composites showed novel electrochemical characteristics as well as high specific capacity and good cycleability. The sulfur composite presented the average discharge voltage of 1.9 V, which was just the half of conventional LiCoO₂ cathode materials, indicating that the double cells in series presented the same working voltage as conventional LiCoO₂ cells and meaning that the sulfur composite cells will have good interchangeability with conventional LiCoO₂ cells. The overcharge test showed that the sulfur composite cell cannot be charged over 5.0 V, indicating that the sulfur composite cell presented the intrinsic safety for overcharge. Overcharge can cause serious problems for the conventional Li ion cells. The overcharge test also showed that the sulfur composite cell was destroyed when the cell was charged over 4.0 V, resulting in that the cell cannot normally be discharged again. It is found, however, that the sulfur composite cell can be discharged again at very low current density of a 0.002-C rate after the cell was overcharged. Being much safer than lithium metal anode, the graphite anode was used to fabricate sulfur composite/graphite lithium ion cells with a prelithiated sulfur composite cathode, which was produced by electrochemical lithiation. The charge/discharge and cycling characteristics of the sulfur composite/graphite cell was investigated. The result showed that the sulfur composite/graphite cells can be normally cycled and showed the different voltages from that of the cell with the lithium metal anode. This paves the effective way to fabricate safer sulfur composite/graphite lithium ion cells.     

High-pressure Raman spectroscopic studies on orthophosphates Ba3(PO4)2 and Sr3(PO4)2

By using diamond anvil cell (DAC), high-pressure Raman spectroscopic studies of orthophosphates Ba₃(PO₄)₂ and Sr₃(PO₄)₂ were carried out up to 30.7 and 30.1 GPa, respectively. No pressure-induced phase transition was found in the studies. A methanol:ethanol:water (16:3:1) mixture was used as pressure medium in DAC, which is expected to exhibit nearly hydrostatic behavior up to about 14.4 GPa at room temperature. The behaviors of the phosphate modes in Ba₃(PO₄)₂ and Sr₃(PO₄)₂ below 14.4 GPa were quantitatively analyzed. The Raman shift of all modes increased linearly and continuously with pressure in Ba₃(PO₄)₂ and Sr₃(PO₄)₂. The pressure coefficients of the phosphate modes in Ba₃(PO₄)₂ range from 2.8179 to 3.4186 cm⁻¹ GPa⁻¹ for ν₃, 2.9609 cm⁻¹ GPa⁻¹ for ν₁, from 0.9855 to 1.8085 cm⁻¹ GPa⁻¹ for ν₄, and 1.4330 cm⁻¹ GPa⁻¹ for ν₂, and the pressure coefficients of the phosphate modes in Sr₃(PO₄)₂ range from 3.4247 to 4.3765 cm⁻¹ GPa⁻¹ for ν₃, 3.7808 cm⁻¹ GPa⁻¹ for ν₁, from 1.1005 to 1.9244 cm⁻¹ GPa⁻¹ for ν₄, and 1.5647 cm⁻¹ GPa⁻¹ for ν₂.     

Electrochemical comparison of LiFe<Subscript>0.4</Subscript>Mn<Subscript>0.595</Subscript>Cr<Subscript>0.005</Subscript>PO<Subscript>4</Subscript>/C and LiMnPO<Subscript>4</Subscript>/C cathode materials

A comparison of electrochemical performance between LiFe_0.4Mn_0.595Cr_0.005PO₄/C and LiMnPO₄/C cathode materials was conducted in this paper. The cathode samples were synthesized by a nano-milling-assisted solid-state process using caramel as carbon sources. The prepared samples were investigated by XRD, SEM, TEM, energy-dispersive X-ray spectroscopy (EDAX), powder conductivity test (PCT), carbon-sulfur analysis, electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge cycling. The results showed that LiFe_0.4Mn_0.595Cr_0.005PO₄/C exhibited high specific capacity and high energy density. The initial discharge capacity of LiFe_0.4Mn_0.595Cr_0.005PO₄/C was 163.6 mAh g^?1 at 0.1C (1C = 160 mA g^?1), compared to 112.3 mAh g^?1 for LiMnPO₄/C. Moreover, the Fe/Cr-substituted sample showed good cycle stability and rate performance. The capacity retention of LiFe_0.4Mn_0.595Cr_0.005PO₄/C was 98.84 % over 100 charge-discharge cycles, while it was only 86.64 % for the pristine LiMnPO₄/C. These results indicated that Fe/Cr substitution enhanced the electronic conductivity for the prepared sample and facilitated the Li⁺ diffusion in the structure. Furthermore, LiFe_0.4Mn_0.595Cr_0.005PO₄/C composite presented high energy density (606 Wh kg^?1) and high power density (574 W kg^?1), thus suggested great potential application in lithium ion batteries (LIBs).     

Electrochemical behavior of Li intercalation processes into a Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 cathode

Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ (X=0.17, 0.25, 0.33, 0.5) compounds are prepared by a simple combustion method. The Rietvelt analysis shows that these compounds could be classified as having the α-NaFeO₂ structure. The initial charge-discharge and irreversible capacity increases with the decrease of x in Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂. Indeed, Li[Ni_0.50Mn_0.50]O₂ compound shows relatively low initial discharge capacity of 200 mAh/g and large capacity loss during cycling, with Li[Ni_0.17Li_0.22Mn_0.61]O₂ and Li[Ni_0.25Li_0.17Mn₀.₅₈]O₂ compounds exhibit high initial discharge capacity over 245 mAh/g and stable cycle performance in the voltage range of 4.8 -2.0 V. On the other hand, XANES analysis shows that the oxidation state of Ni ion reversibly changes between Ni²⁺ and about Ni³⁺, while the oxidation state of Mn ion sustains Mn⁴⁺ during charge-discharge process. This result does not agree with the previously reported ‘electrochemistry model’ of Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂, in which Ni ion changes between Ni²⁺ and NI⁴⁺. Based on these results, we modified oxidation-state change of Mn and Ni ion during charge-discharge process.     

Electrochemical properties of Cr doped V2O5 between 3.8 V and 2.0 V

Cr_0.1V₂O_5.15 was prepared by an oxalic acid assisted sol–gel method. X-ray diffraction showed that Cr doping induced a slight expansion (ΔV/V ≈ 2.3%) in the crystal lattice of V₂O₅. The electrochemical properties of Cr_0.1V₂O_5.15 in the potential range of 3.8–2.0 V were studied by cyclic voltammetry, galvanostatic charge–discharge cycling and potentiostatic intermittent titration technique. Cyclic voltammetry showed that the irreversible phase transition of V₂O₅ during the first cycle was effectively prevented by Cr doping. This caused the good charge–discharge cycling performance of the doped material. The discharge capacities were recorded to be 200, 170 and 120 mAhg^− 1 after fifty cycles at the C/10, C/2 and 1C rates, respectively. However, ex-situ X-ray diffraction showed that the crystal structure of the material was destroyed after long-term cycling. The lithium diffusion coefficient of Cr_0.1V₂O_5.15 varied between 10^− 11 and 10^− 12 cm² s^− 1, which was larger than that of crystalline V₂O₅, and was close to those of metal doped V₂O₅ in previous reports. The improvement in lithium diffusion kinetics was regarded as an important reason for the good electrochemical performance of Cr_0.1V₂O_5.15.     

Synthesis of VO2 (B) nanorods for Li battery application

Vanadium dioxide nanorods were synthesized through a hydrothermal reaction from V₂O₅ xerogel, poly(vinyl pyrrolidone) (PVP) and lithium perchlorate (LiClO₄). The prepared samples were characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical discharge–charge cycling in lithium battery. SEM images reveal the nanorods to have dimensions on the order of 1–3 μm in length and 10–50 nm in diameter. The measured initial discharge capacity of the lithium battery with a cathode made of VO₂ (B) nanorods was 152 mA h/g.     

Superprotonic solid solutions between CsHSO4 and CsH2PO4

Solid solutions of (CsHSO₄)_1 − x(CsH₂PO₄)_x (x = 0.25-0.75) were synthesized by mechanical milling method over a wide range of compositions. Superprotonic cubic phase was confirmed for all these samples between 293 and 420 K depending on its composition. These superprotonic phases have primitive cubic structure similar to that of CsH₂PO₄. The kinetic stability of the supercooled cubic phase depends both on the composition x and the humidity of surrounding atmosphere. The most stable composition of the cubic phase was found around x = 0.67 and could be maintained for several days even under ambient atmosphere. The ionic conductivities of these superprotonic phases reached 10^− 2–10^− 3 S∙cm^− 1 at 450 K. With increasing x the ionic conductivity at the superprotonic phase decreased continuously associated with the increase of the activation energy. These findings suggest that the average number of the hydrogen bonds between XO₄ (X = S, P) units plays an important role on the stability of the cubic phase and also on the conductivity.     

Crystal field parameters and energy level structure of the MnO4 tetroxo anion in Li3PO4, Ca2PO4Cl and Sr5(PO4)3Cl crystals

A comparative study concerning the electronic structure of the Mn⁵⁺ ion in the Li₃PO₄, Ca₂PO₄Cl, Sr₅(PO₄)₃Cl host lattices has been carried out in the framework of the exchange charge model. The crystal field parameters have been evaluated using the structural data as the only input information. The 10 K absorption spectra of the investigated compounds have been measured in order to verify the correspondence between experimental and calculated energy levels. A systematic trend of the crystal field splitting of the most intense transitions has been evidenced and discussed by considering the symmetry properties of the coordination polyhedra around Mn⁵⁺.     

Pyroelectric properties in three phases coexistence Pb[(Mn0.33Nb0.67)0.5(Mn0.33Sb0.67)0.5]0.08(ZrxTi1−x)0.92O3 lead ceramics

The bulk dense Pb[(Mn_0.33Nb_0.67)_0.5(Mn_0.33Sb_0.67)_0.5]_0.08(Zr_xTi_1−x)_0.92O₃ pyroelectric ceramics have been successfully prepared by the conventional solid method. The effect of three phases coexistence in the ceramics is studied. When x = 0.95 and 0.85 in the ceramics, the maximum pyroelectric coefficient peaks appear at 23 °C and 45 °C, and the maximum values are 26.5 × 10⁻⁴ C/m² °C and 25.5 × 10⁻⁴ C/m² °C, respectively. The maximum pyroelectric coefficient appears large while the peaks widths are small. When the two kinds of ceramic powders mixed with the mol ratio of 2:1, the pyroelectric coefficient of the ceramics is above 10.0 × 10⁻⁴ C/m² °C in a broad temperature range from 20 °C to 55 °C. The possible physical mechanism of the temperature broadened phenomenon is briefly discussed.     

Electrochemical studies on mixtures of LiNi0.8Co0.17Al0.03O2 and LiCoO2 cathode materials for lithium ion batteries

Detailed electrochemical investigations have been carried out on LiNi_0.8Co_0.17Al_0.03O₂ as cathode materials for lithium ion batteries in the potential range of 2.8-4.3 V. This sample showed an initial discharge capacity of 186 mAh/g which corresponds to 67% of its theoretical capacity. The effect of addition of LiCoO₂ to LiNi_0.8Co_0.17Al_0.03O₂ in the ratio 10:90, 30:70, 50:50 has been studied. The results showed that the addition of LiCoO₂ has improved the working voltage of the cell. In addition, the percentage retention (95%) of the cell is significantly increased in the composition ratio 50:50.     

Synthesis of high performance Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C cathode material by ultrasonic-assisted sol–gel method

A novel ultrasonic-assisted sol–gel method is proposed to prepare Li₃V₂(PO₄)₃/C cathode material. X-ray diffraction analyses show that both Li₃V₂(PO₄)₃/C(A) synthesized by the ultrasonic-assisted sol–gel method and Li₃V₂(PO₄)₃/C(B) synthesized by a traditional sol–gel method have monoclinic structure. Scanning electron microscopy images indicate that the Li₃V₂(PO₄)₃/C(A) composite has a more uniform morphology than that of the Li₃V₂(PO₄)₃/C(B) composite. In the voltage range of 3.0–4.3 V (vs. Li/Li⁺), the initial specific discharge capacities of the Li₃V₂(PO₄)₃/C(A) and Li₃V₂(PO₄)₃/C(B) samples are 129.8 and 125.9 mAh g⁻¹ at 1C rate (1C = 133 mA g⁻¹), respectively. Furthermore, at 2-C charge/10-C discharge rate, the specific discharge capacity of the Li₃V₂(PO₄)₃/C(A) composite retains 113.2 mAh g⁻¹ after 50 cycles, but the Li₃V₂(PO₄)₃/C(B) composite only presents a capacity of 94.8 mAh g⁻¹.