The synthesis,structure, and electrochemical properties of Li<Subscript>2</Subscript>FeSiO<Subscript>4</Subscript>-based lithium-accumulating electrode material

Different approaches to synthesis of Li₂FeSiO₄-based electrode materials for lithium intercalation, using low-cost and abundant Li-, Si-, and Fe-containing parent substances, are discussed. XRD, SEM, and a laser-diffraction analyzer of particle size were used for structure and morphology characterization of the composite electrode materials. Li₂FeSiO₄ was shown to be the main lithium-accumulating crystalline phase; minor LiFeO₂ and Li₂SiO₃ admixtures are also present. The material microparticles’ average size was shown to vary from tenths of micrometer to 1 μm. Larger objects sized ca. 2–4 μm are the microparticles’ agglomerates. The material electrochemical properties were studied by dc chronopotentiometry (galvanostatic charging–discharging) and cyclic voltammetry with potential linear sweeping. The initial reversible cycled capacity of the best samples is 170 mA h/g. The anodic and cathodic processes manifest obvious hysteresis caused by the presence of several different lithium ion energy states in the material; the transition between the states is kinetically hindered. The dependences of the specific capacity and its stability under cycling on the current load and the conductive carbon component content in the composite were elucidated.     

Impact of carbon coating thickness on the electrochemical properties of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C composites

A series of Li₃V₂(PO₄)₃/C composites with different amounts of carbon are synthesized by a combustion method. The physical and electrochemical properties of the Li₃V₂(PO₄)₃/C composites are investigated by X-ray diffraction, element analysis, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy and electrochemical measurements. The effects of carbon content of Li₃V₂(PO₄)₃/C composites on its electrochemical properties are conducted with cyclic voltammetry and electrochemical impedance. The experiment results clearly show that the optimal carbon content is 4.3 wt %, and more or less amount of carbon would be unfavorable to electrochemical properties of the Li₃V₂(PO₄)₃/C electrode materials. The results would provide some basis for further improvement on the Li₃V₂(PO₄)₃ electrode materials.     

Synthesis and characterization of macroporous Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C composites as cathode materials for Li-ion batteries

The macroporous Li₃V₂(PO₄)₃/C composite was synthesized by oxalic acid-assisted carbon thermal reaction, and the common Li₃V₂(PO₄)₃/C composite was also prepared for comparison. These samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and electrochemical performance tests. Based on XRD and SEM results, the sample has monoclinic structure and macroporous morphology when oxalic acid is introduced. Electrochemical tests show that the macroporous Li₃V₂(PO₄)₃/C sample has a high initial discharge capacity (130 mAh g⁻¹ at 0.1 C) and a reversible discharge capacity of 124.9 mAh g⁻¹ over 20 cycles. Moreover, the discharge capacity of the sample is still 91.5 mAh g⁻¹, even at a high rate of 2 C, which is better than that of the sample with common morphology. The improvement in electrochemical performance should be attributed to its improved lithium ion diffusion coefficient for the macroporous morphology, which was verfied by cyclic voltammetry and electrochemical impedance spectroscopy.     

Sol-assisted spray-drying synthesis of porous Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C microspheres as high-activity cathode materials for lithium-ion batteries

Herein, porous Li₃V₂(PO₄)₃/C microspheres made of nanoparticles are obtained by a combination of sol spray-drying and subsequent-sintering process. Beta-cyclodextrin serves as a special chelating agent and carbon source to obtain carbon-coated Li₃V₂(PO₄)₃ grains with the size of ca. 30–50?nm. The unique porous structure and continuous carbon skeleton facilitate the fast transport of lithium ion and electron. The Li₃V₂(PO₄)₃/C microspheres offer an outstanding electrochemical performance, which present a discharge capacity of 122?mAh?g^?1 at 2?C with capacity retention of 96% at the end of 1000 cycles and a high-rate capacity of 113?mAh?g^?1 at 20?C in the voltage window of 3.0–4.3?V. Moreover, the Li₃V₂(PO₄)₃/C microspheres also give considerable cycling stability and high-rate reversible capacity at a higher end-of-charge voltage of 4.8?V.

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Electrospun Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/Li<Subscript>2</Subscript>TiO<Subscript>3</Subscript> composite nanofibers for enhanced high-rate lithium ion batteries

Li₄Ti₅O₁₂/Li₂TiO₃ composite nanofibers with the mean diameter of ca. 60 nm have been synthesized via facile electrospinning. When the molar ratio of Li to Ti is 4.8:5, the Li₄Ti₅O₁₂/Li₂TiO₃ composite nanofibers exhibit initial discharge capacity of 216.07 mAh g^?1 at 0.1 C, rate capability of 151 mAh g^?1 after being cycled at 20 C, and cycling stability of 122.93 mAh g^?1 after 1000 cycles at 20 C. Compared with pure Li₄Ti₅O₁₂ nanofibers and Li₂TiO₃ nanofibers, Li₄Ti₅O₁₂/Li₂TiO₃ composite nanofibers show better performance when used as anode materials for lithium ion batteries. The enhanced electrochemical performances are explained by the incorporation of appropriate Li₂TiO₃ which could strengthen the structure stability of the hosted materials and has fast Li⁺-conductor characteristics, and the nanostructure of nanofibers which could offer high specific area between the active materials and electrolyte and shorten diffusion paths for ionic transport and electronic conduction. Our new findings provide an effective synthetic way to produce high-performance Li₄Ti₅O₁₂ anodes for lithium rechargeable batteries.     

Li<Subscript>0.99</Subscript>Ti<Subscript>0.01</Subscript>FePO<Subscript>4</Subscript>/C composite as cathode material for lithium ion battery

Three kinds of LiFePO₄ materials, mixed with carbon (as LiFePO₄/C), doped with Ti (as Li_0.99Ti_0.01FePO₄), and treated both ways (as Li_0.99Ti_0.01FePO₄/C composite), were synthesized via ball milling by solid-state reaction method. The crystal structure and electrochemical behavior of the materials were investigated using X-ray diffraction, SEM, TEM, cyclic voltammetry, and charge/discharge cycle measurements. It was found that the electrochemical behavior of LiFePO₄ could be increased by carbon coating and Ti-doping methods. Among the materials, Li_0.99Ti_0.01FePO₄/C composite presents the best electrochemical behavior, with an initial discharge capacity of 154.5 mAh/g at a discharge rate of 0.2 C, and long charge/discharge cycle life. After 120 cycles, its capacity remains at 92% of the initial capacity. The Li_0.99Ti_0.01FePO₄/C composite developed here can be used as the cathode material for lithium ion batteries.     

Preparation and electrochemical properties of Li<Subscript>0.97</Subscript>Er<Subscript>0.01</Subscript>FePO<Subscript>4</Subscript>/C composite for lithium-ion batteries

Li_0.97Er_0.01FePO₄/C composite was prepared by solid-state reaction, using particle modification with amorphous carbon from the decomposition of glucose and lattice doping with supervalent cation Er³⁺. All samples were characterized by X-ray diffraction, scanning electron microscopy, multi-point Brunauer Emmett and Teller methodes. The electrochemical tests show Li_0.97Er_0.01FePO₄/C composite obtains the highest discharge specific capacity of 154 mAh g⁻¹ at C/10 rate and the best rate capability. Its specific capacity reaches 131 mAh g⁻¹ at 2C rate. Its capacity loss is only 14.9 % when the rate varies from C/10 to 2C.     

Hot atom chemical behavior of tritium in neutron-irradiated Li<Subscript>2</Subscript>TiO<Subscript>3</Subscript> and Li<Subscript>2</Subscript>ZrO<Subscript>3</Subscript>

The annihilation behavior of irradiation defects induced in neutron-irradiated Li₂TiO₃ and Li₂ZrO₃ were investigated with the tritium release behavior. It was revealed that the common characteristics in both samples were that the annihilation process of irradiation defects consisted of two first-order processes and E’-center could act as tritium trapping site, and otherwise was the way how the E’-center annihilated. The difference was suggested to attribute to the mobility of M as M⁴⁺ (or M³⁺, etc.).     

Rapid hydrothermal synthesis of Li<Subscript>3</Subscript>VO<Subscript>4</Subscript> with different favored facets

Here, we demonstrate a new, rapid, and flexible hydrothermal method using the V₂O₅ and LiOH as the precursors to synthesize Li₃VO₄. The ratios of precursor of V₂O₅ and LiOH can be changed in a wide range to control different preferred facets and morphologies, and the reason has been discussed from the structure of Li₃VO₄. The electrical performance of the Li₃VO₄ has also been systematically investigated. The thus-synthesized Li₃VO₄ exhibits significantly improved rate capability and cycling life compared with commercial graphite, synthesized Li₄Ti₅O₁₂, and previously reported results on Li₃VO₄.     

Preparation and electrochemical performance of nano-structured Li<Subscript>2</Subscript>Mn<Subscript>4</Subscript>O<Subscript>9</Subscript> for supercapacitor

Nano-structured spinel Li₂Mn₄O₉ powder was prepared via a combustion method with hydrated lithium acetate (LiAc·2H₂O), manganese acetate (MnAc₂·4H₂O), and oxalic acid (C₂H₂O₄·2H₂O) as raw materials, followed by calcination of the precursor at 300 °C. The sample was characterized by X-ray diffraction, scanning electron microscope, and energy-dispersive X-ray spectroscopy techniques. Electrochemical performance of the nano-Li₂Mn₄O₉ material was studied using cyclic voltammetry, ac impedance, and galvanostatic charge/discharge methods in 2 mol L⁻¹ LiNO₃ aqueous electrolyte. The results indicated that the nano-Li₂Mn₄O₉ material exhibited excellent electrochemical performance in terms of specific capacity, cycle life, and charge/discharge stability, as evidenced by the charge/discharge results. For example, specific capacitance of the single Li₂Mn₄O₉ electrode reached 407 F g⁻¹ at the scan rates of 5 mV s⁻¹. The capacitor, which is composed of activated carbon negative electrode and Li₂Mn₄O₉ positive electrode, also exhibits an excellent cycling performance in potential range of 0–1.6 V and keeps over 98% of the maximum capacitance even after 4,000 cycles.     

Effects of carbon coating from sucrose and PVDF on electrochemical performance of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/C composites in different potential ranges

The carbon coated nanoflower-like Li₄Ti₅O₁₂/C composites were prepared via hydrothermal method followed by surface modification using sucrose or polyvinylidene fluoride (PVDF) as carbon sources. X-ray diffraction, SEM, TEM, Raman spectroscopy, TGA, and the electrochemical measurements were used for the materials characterization. Such modification leads to the formation of a high-conductive carbon coating. In the case of polyvinylidene fluoride use, fluorination of Li₄Ti₅O₁₂ surface takes place also. As a result, electrochemical performance of the obtained composites is improved. In the potential range of 1–3 V, Li₄Ti₅O₁₂, Li₄Ti₅O₁₂/C_PVDF, and Li₄Ti₅O₁₂/C_sucrose exhibit, respectively, the discharge capacities of 142.5, 154.3, and 170.4 mAh/g at a current of 20 mA/g and 57.2, 82.1, and 89.3mAh/g at a current of 3200 mA/g. When cycled in a potential range of 0.01–3 V, the discharge capacity of Li₄Ti₅O₁₂/C_PVDF increases up to 252 mAh/g at 20 mA/g.     

Phase equilibria in the system Li<Subscript>2</Subscript>O-MgO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The subsolidus region of the Li₂O-MgO-B₂O₃ system has been studied by X-ray powder diffraction and differential thermal analysis. Isothermal sections at 500–550 and 650–700°C have been designed. The following complex borates have been found to form: at 500–550°C, Li₂MgB₂O₅ and LiMgBO₃ are formed; at 650–700°C, a new phase Li₄MgB₂O₅ is formed along with LiMgBO₃; and at 5500–600°, Li₂MgB₂O₅ is formed.     

Glass formation in the Li<Subscript>2</Subscript>O-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript>-TeO<Subscript>2</Subscript> system

In the Li₂O-Ta₂O₅-TeO₂ system, the boundaries of the glass region have been determined. The electrical and spectral properties of glasses and crystalline materials have been investigated.     

Electochemical characteristics of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> battery with conducting polymeric binder

Lithium-ion battery based on LiMn₂O₄/Li₄Ti₅O₁₂ materials was assembled for the first time. The cathode and anode of this battery are prepared with the aqueous combined binder poly-3,4-ethylenedioxythiophene: polystyrene sulfonate/carboxymethylcellulose (without polyvinylidene fluoride). The capacity of the LiMn₂O₄/Li₄Ti₅O₁₂ battery was found to be 75 mA h g^–1 at 0.1 C and 55 mA h g^–1 at 1 C. A 95% capacity was retained after 100 charge-discharge cycles. The batteries demonstrated a high Coulombic efficiency close to 100%. Scanning electron microscopy demonstrated that using the conducting binder poly-3,4-ethylenedioxythiophene: polystyrene sulfonate/carboxymethylcellulose provides formation of dense compact layers of electrode materials with good adhesion to the substrate. The electrode structure remains maintained after 100 charge-discharge cycles.     

EPR study of the nature of the impurity centers responsible for the scintillation properties of the Li<Subscript>2</Subscript>Zn<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> crystal

The binary molybdate Li₂Zn₂(MoO₄)₃ of a new crystal type was characterized by EPR, optical spectroscopy, and X-ray diffraction methods. The crystals have the Pnma symmetry group and the lattice parameters a = 5.1139(5) Å, b = 10.4926(13) Å, c = 17.6445(22) Å; Z = 4. The crystals possess scintillation properties; emission is caused by the presence of impurity levels in the forbidden band. The EPR studies of the nature of the impurity centers responsible for the scintillation characteristics of the crystal showed that the centers were Cu²⁺ ions substituted for zinc ions in the oxygen octahedra. The directions of the main values of the g and tensors (g _zz , A _zz ) correspond to the direction of O-Cu-O of the oxygen octahedron distorted along the Z axis. The EPR spectra of the copper ions are described by the spin Hamiltonian with the parameters g _‖ = 2.38, g _⊥ = 2.06; A _‖ = 116 G, A _⊥ = 0 G.     

Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/nitrogen-doped reduced graphene oxide nanocomposite with enhanced lithium storage properties

The three-dimensional porous Li₃V₂(PO₄)₃/nitrogen-doped reduced graphene oxide (LVP/N-RGO) composite was prepared by a facile one-pot hydrothermal method and evaluated as cathode material for lithium-ion batteries. It is clearly seen that the novel porous structure of the as-prepared LVP/N-RGO significantly facilitates electron transfer and lithium-ion diffusion, as well as markedly restrains the agglomeration of Li₃V₂(PO₄)₃ (LVP) nanoparticles. The introduction of N atom also has positive influence on the conductivity of RGO, which improves the kinetics of electrochemical reaction during the charge and discharge cycles. It can be found that the resultant LVP/N-RGO composite exhibits superior rate properties (92 mA h g^?1 at 30 C) and outstanding cycle performance (122 mA h g^?1 after 300 cycles at 5 C), indicating that nitrogen-doped RGO could be used to improve the electrochemical properties of LVP cathodes for high-power lithium-ion battery application.

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Graphical abstract The three-dimensional porous Li₃V₂(PO₄)₃/nitrogen-doped reduced graphene oxide composite with significantly accelerating electron transfer and lithium-ion diffusion exhibits superior rate property and outstanding cycle performance.

     

Electrical conductivity studies in the system Li<Subscript>2</Subscript>TiO<Subscript>3</Subscript>-Li<Subscript>1.33</Subscript>Ti<Subscript>1.67</Subscript>O<Subscript>4</Subscript>

Electrical conductivity in the monoclinic Li₂TiO₃, cubic Li_1.33Ti_1.67O₄, and in their mixture has been studied by impedance spectroscopy in the temperature range 20–730 °C. Li₂TiO₃ shows low lithium ion conductivity, σ₃₀₀≈10^–6 S/cm at 300 °C, whereas Li_1.33Ti_1.67O₄ has 3×10^–8 at 20 °C and 3×10^–4 S/cm at 300 °C. Structural properties are used to discuss the observed conductivity features. The conductivity dependences on temperature in the coordinates of 1000/T versus log_e(σT) are not linear, as the conductivity mechanism changes. Extrinsic and intrinsic conductivity regions are observed. The change in the conductivity mechanism in Li₂TiO₃ at around 500–600 °C is observed and considered as an effect of the first-order phase transition, not reported before. Formation of solid solutions of Li_{2– x} Ti_{1+ x} O₃ above 900 °C significantly increases the conductivity. Irradiation by high-energy (5 MeV) electrons causes defects and the conductivity in Li₂TiO₃ increases exponentially. A dose of 144 MGy yields an increase in conductivity of about 100 times at room temperature. Electronic Publication     

Comparing the electrochemical properties of pure phase Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript> and composite Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript>/C

Compound Zn₂SnO₄ was synthesized by a hydrothermal method in which SnCl₄ · 5H₂O, ZnCl₂ and N₂H₄ · H₂O were used as reactants. Composite Zn₂SnO₄/C was then synthesized through a carbothermic reduction process using the as-prepared Zn₂SnO₄ and glucose as reactants. Comparing to the pure Zn₂SnO₄, some improved electrochemical properties were obtained for composite Zn₂SnO₄/C. When doped with 15% glucose, the composite Zn₂SnO₄/C showed the best electrochemical performance. Its first discharge capacity was about 1500 mA h g⁻¹, with a capacity retain of 500 mA h g⁻¹ in the 40th cycle at a constant current density of 100 mA/g in the voltage range of 0.05–3.0 V. There were also some differences displayed in their cyclic voltammogram.     

Structure and properties of Li<Subscript>2</Subscript>Zn<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> crystals activated with copper and chromium ions

Based on the corrected phase diagrams proper growth conditions for Li2Zn2(MoO₄)₃ crystals are selected. Large crystals (up to 100 mm), both impurity-free and activated by transition metal ions (Cu, Cr), are grown by the low-gradient Czochralski method. By the EPR method the charge state and structural position of copper and chromium ions are determined. The performed studies of luminescent properties show that for impurity-free crystals luminescence with λ = 388 nm with a two-exponential luminescence decay with τ₁ = 2 ns and τ₂ = 6 ns is observed at room temperature. At 77 K for both impurity-free crystals and those activated with transition metal ions luminescence with λ = 560 nm and the luminescence lifetime τ = 100 ns is observed, the intensity of luminescence with λ = 560 nm depending on the nature and concentration of transition metal ions. Cation vacancies responsible for the charge compensation of impurity transition metal ions are assumed to be also responsible for low-temperature luminescence.     

Phase-pure nanocrystalline Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> for a lithium-ion battery

Phase-pure nanocrystalline Li₄Ti₅O₁₂ with BET surface areas between 183 and 196 m²/g was prepared via an improved synthetic protocol from lithium ethoxide and titanium(IV) butoxide. The phase purity was proved by X-ray powder diffraction, Raman spectroscopy and cyclic voltammetry. Thin-film electrodes were prepared from two nanocrystalline samples of Li₄Ti₅O₁₂ and one microcrystalline commercial sample. Li-insertion behavior of these electrodes was related to the particle size.Presented at the 3rd International Meeting on Advanced Batteries and Accumulators, 16–20 June 2002, Brno, Czech Republic