Improvement electrochemical performance of Li1.5Ni0.25Mn0.75O2.5 with Li4Ti5O12 coating

Layered cathode Li_1.5Ni_0.25Mn_0.75O_2.5 has been synthesized and coated by Li₄Ti₅O₁₂. The pristine and coated Li_1.5Ni_0.25Mn_0.75O_2.5 powders are characterized by X-ray diffraction (XRD), indicating the materials remained the layered structure before and after coating. The coated Li₄Ti₅O₁₂ has been detected by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (DEX). The electrochemical performance, especially rate performance of Li_1.5Ni_0.25Mn_0.75O_2.5 electrode, is improved effectively after Li₄Ti₅O₁₂ coating. The first discharge capacity, coulombic efficiency, and capacity retention of Li₄Ti₅O₁₂-coated Li_1.5Ni_0.25Mn_0.75O_2.5 electrode are 244 mA h g^?1, 81.5 %, and 98.3 % after 50 cycles, respectively. The Li₄Ti₅O₁₂-coated Li_1.5Ni_0.25Mn_0.75O_2.5 electrode exhibits 108 mA h g^?1 at 10 °C rate. Electrochemical impedance spectroscopy (EIS) results show that the charge transfer resistance (R _ct) of Li_1.5Ni_0.25Mn_0.75O_2.5 electrode decreases after coating, which is due to the existence of Li₄Ti₅O₁₂ with high lithium ion diffusion coefficient and suppression of the solid electrolyte interfacial (SEI) layer development and is responsible for the excellent rate capability and cyclic performance.     

Surface nitridation induced high electrochemical performance of Li4Ti5O12 using urea as a nitrogen source

Surface nitridation of the Li₄Ti₅O₁₂ particles was carried out by thermal treatment with urea as the nitrogen source in a controllable manner. The titanium nitride (TiN) was formed in the well-dispersed zones on the surface of the Li₄Ti₅O₁₂ particles, depending on the coverage of the nitride. The surface TiN formed led to a great improvement of the conductivity of the oxide. The extent of the surface nitridation exhibited a large effect on electrochemical behaviors of the Li₄Ti₅O₁₂ particles, with the Li₄Ti₅O₁₂/TiN composite (prepared using 6 % urea) providing the best initial capacity and rate capability. Thus, the electrochemical performance of the Li₄Ti₅O₁₂ particles can be achieved by optimizing surface nitridation of the oxide. The chemically inert TiN occupied the surface sites of the Li₄Ti₅O₁₂ particles which may have prevented the electrolyte from decomposition and stabilized the surface structure of the Li₄Ti₅O₁₂ particles, endowing the oxide with excellent cycleability     

Synthesis and characterization of Li4Ti5O12/graphene composite as anode material with enhanced electrochemical performance

The use of graphene as a conductive additive to enhance the rate capability and cycle stability of Li₄Ti₅O₁₂ electrode material has been demonstrated. Li₄Ti₅O₁₂ and its composite with graphene (1.86 wt%) are prepared by ball milling and simple chemical method, respectively. Among the as-synthesized composites, Li₄Ti₅O₁₂ particles uniformly clung to the graphene sheets. When used as an electrode material for lithium ion battery, the composite presents excellent rate performance and high cyclic stability. It is found that the composite displayed high-rate capacity of 118.7 mAh?g^?1 at 20 C. Furthermore, the composite exhibits good cycle stability, retaining over 96 % of its initial capacity after 50 cycles at 10 C. The excellent electrochemical performance is attributed to a decrease in the charge-transfer resistance.     

Advanced electrochemical performances of Li4Ti5O12/Ag prepared by a facile synthesis route

Spinel Li₄Ti₅O₁₂ coated by highly dispersed nanosized Ag particles was synthesized via a facile and effective ultrasonic-assisted method in this paper. X-ray diffraction (XRD) results indicated that Ag was not doped into the lattice of spinel Li₄Ti₅O₁₂. The as-synthesized Li₄Ti₅O₁₂/Ag exhibited enhanced electronic conductivity and excellent electrochemical performances. Its electronic conductivity was increased about four times compared to that of the pristine Li₄Ti₅O₁₂. Even at 10 C rate, the as-synthesized Li₄Ti₅O₁₂/Ag could keep 86.5 % of the reversible capacity at 1 C rate and its reversible capacity was higher than 140 mAhg^?1 whereas those were 75.3 % and 118 mAhg^?1 for the pristine Li₄Ti₅O₁₂.     

Synthesis and electrochemical performance of hole-rich Li4Ti5O12 anode material for lithium-ion secondary batteries

Hole-rich Li₄Ti₅O₁₂ composites are synthesized by spray drying using carbon nanotubes as additives in precursor solution, subsequently followed calcinated at high temperature in air. The structure, morphology, and texture of the as-prepared composites are characterized with XRD, Raman, BET and SEM techniques. The electrochemical properties of the as-prepared composites are investigated systematically by charge/discharge testing, cyclic voltammograms and AC impedance spectroscopy, respectively. In comparison with the pristine Li₄Ti₅O₁₂, the hole-rich Li₄Ti₅O₁₂ induced by carbon nanotubes exhibits superior electrochemical performance, especially at high rates. The obtained excellent electrochemical performances of should be attributed to the hole-rich structure of the materials, which offers more connection-area with the electrolyte, shorter diffusion-path length as well faster migration rate for both Li ions and electrons during the charge/discharge process.     

Sonochemical synthesis of LiNi0.5Mn1.5O4 and its electrochemical performance as a cathode material for 5 V Li-ion batteries

LiNi_0.5Mn_1.5O₄ was synthesized as a cathode material for Li-ion batteries by a sonochemical reaction followed by annealing, and was characterized by XRD, SEM, HRTEM and Raman spectroscopy in conjunction with electrochemical measurements. Two samples were prepared by a sonochemical process, one without using glucose (sample-S1) and another with glucose (sample-S2). An initial discharge specific capacity of 130 mA h g⁻¹ is obtained for LiNi_0.5Mn_1.5O₄ at a relatively slow rate of C/10 in galvanostatic charge–discharge cycling. The capacity retention upon 50 cycles at this rate was around 95.4% and 98.9% for sample-S1 and sample-S2, respectively, at 30 °C.     

Kinetic performance of Li4Ti5O12 anode material synthesized by the solid-state method

Li₄Ti₅O₁₂ anode was successfully synthesized by solid-state method. X-ray diffraction and scanning electron micrographs show that Li₄Ti₅O₁₂ prepared by solid-state method has a purity phase with a uniform particle size in the range of 0.5?C1???m. Cyclic voltammogram reveals that there is a big irreversible capacity for the first cycle. Li₄Ti₅O₁₂ shows a stable cycling stability at 1?C rate. After 152 cycles, the discharge capacity is 213?mAh?g^?1, which keeps 93% of it at the second cycle. Electrochemical impedance spectroscopy shows that the resistance of charge-transfer of Li₄Ti₅O₁₂ electrode decreased with increasing the storage temperatures, and the lithium diffusion coefficient is increased with increasing the storage temperatures, revealing that the kinetics of Li⁺ and electron transfer into the electrodes were much faster at high temperature than that at low temperature. The apparent activation energy of the charge transfer and lithium diffusion can be calculated to be 33.1 and 27.3?kJ?mol^?1, respectively.     

Li4Ti5O12/Ag composite as electrode materials for lithium-ion battery

The Li₄Ti₅O₁₂/Ag composites were prepared by thermal decomposition of AgNO₃ added to Li₄Ti₅O₁₂ powders. The influence of the Ag contents and the mixing media on the particle size, morphology and electrochemical performance of Li₄Ti₅O₁₂/Ag composites were investigated. The highest discharge capacity of the Li₄Ti₅O₁₂/Ag composite reached at the 5 wt.% of Ag content. Compared with alcohol medium, distilled water as mixing medium presented the Li₄Ti₅O₁₂/Ag composite with higher specific capacity and better cycling performance, leading to a reversible capacity after 50 cycles of 184.2 mAh/g with a capacity degradation of 3.31% compared to the second cycle at 2 C rate.     

Effects of Li/Ti ratios on the electrochemical properties of Li4Ti5O12 examined by time-resolved X-ray diffraction

Li₄Ti₅O₁₂ for anodic active material of lithium ion batteries is synthesized using different Li/Ti ratios of 3.5/5.0, 4.0/5.0 and 4.5/5.0 by a solid-state reaction between Li₂CO₃ and anatase TiO₂ at 850?°C. All samples contain a small amount of transformed rutile TiO₂ in the final Li₄Ti₅O₁₂, where the amount of rutile TiO₂ decreases with the increase in Li/Ti ratio. A stoichiometric Li₄Ti₅O₁₂ with Li/Ti = 4.0/5.0 shows a slightly larger particle size and higher charge capacity than those of Li-deficient and Li-excessive particles, while the discharging rate capability is shown to mainly depend on particle size regardless of Li/Ti ratio. According to the time-resolved X-ray diffraction patterns using a synchrotron source, however, no significant difference is found in spite of the difference in Li/Ti ratio, indicating the structural stability of Li₄Ti₅O₁₂ during the Li insertion and extraction process.     

High-rate Li4Ti5O12/C composites as anode for lithium-ion batteries

The Li₄Ti₅O₁₂/C composites were synthesized by a simple solid-state reaction at 800 °C for 12 h by using Super P® conductive carbon black as carbon source. X-ray diffraction analysis shows that the Li₄Ti₅O₁₂ with 0, 5, 7.5, and 10 wt% carbon shows similar patterns with cubic spinel structure. Scanning electron microscope shows that Li₄Ti₅O₁₂ aggregated seriously, but the aggregation was inhibited by the addition of Super P® carbon. The results indicate that the addition of 5 wt% carbon during sintering and a further 5 wt% carbon during slurry preparation shows the best rate capability of 110 mAh/g when the cells were charge/discharged at 10 C rate. The comparison of the charge–discharge curves shows that the higher rate improvement should further decrease the particle size of LTO or improve the conductivity of LTO itself.     

The solid solutions of Li2Mn4O8-Li1Fe5O8

A solid solution of (1 ?x)(Li₂Mn₄O₈)x(Li₁Fe₅O₈) for 0<x<1 has been investigated by Mössbauer spectroscopy at room temperature and at 80 K. The saturated magnetic moment has been measured forx>0.6. The results are explained by a change of site preference of the Li ion from the tetragonal (A) site atx=0 to the octahedral [B] site atx=1.     

Effect of heptamethyldisilazane on the electrochemical performance of LiMn2O4/Li

The effect of heptamethyldisilazane as an electrolyte stabilizer on the cycling performance of a LiMn₂O₄/Li cell at different rates at 30 °C and the storage performance at 60 °C is investigated systematically based on conductivity test, linear sweep voltage, electrochemical impedance spectroscopy, scanning electron microscopy, X-ray diffraction, and charge–discharge measurements. The results show that heptamethyldisilazane added into the LiPF₆-based electrolyte can increase the stability of the original electrolyte; coulomb efficiency, the initial discharge capacity, and cycling performance at different rates in a sense, meanwhile, improve the storage performance at elevated temperature, although the C-rate performance of the cell is a little worse than that without heptamethyldisilazane in the electrolyte. When the LiMn₂O₄/Li cell with heptamethyldisilazane in the LiPF₆-based electrolyte stored at 60 °C for a week cycles 300 times, the capacity retention is up to 91.18 %, which is much higher than that (87.18 %) without the additive in the electrolyte. This is mainly due to the lower solid electrolyte interface resistance (R _f) in the cell, followed by the better morphology and structure of the cathode after storage at 60 °C for a week compared with the LiMn₂O₄/Li cell without heptamethyldisilazane.     

Study on the electrochemical performance of LiNi0.5Mn1.5O4 with different precursor

LiNi_0.5Mn_1.5O₄ cathodes were synthesized by three different raw materials at high temperature. The samples were characterized by X-ray diffraction and scanning electron microscopy tests, respectively. The results indicate that the synthesized samples show pure spinel structure, and the samples synthesized by nickel?Cmanganese hydrate and nickel?Cmanganese oxide show regular geometrical shape. The electrochemical performance of sample synthesized by nickel?Cmanganese oxide is best. The first discharge capacity is 141 mAh/g, and the capacity retention is 98.6% after 50 cycles at 0.5?C rate. The discharge capacity at 5?C rate is still 120 mAh/g. Better crystallization, smaller specific surface area, and lower polarization may be responsible for the excellent electrochemical performance of the LiNi_0.5Mn_1.5O₄.     

Performance of solid-state hybrid supercapacitor with LiFePO4/AC composite cathode and Li4Ti5O12 as anode

We report the studies on quasi-solid battery-supercapacitor (BatCap) systems fabricated using sol–gel-prepared LiFePO₄ and its composites (LACs) with activated charcoal (AC) as hybrid cathode and Li₄Ti₅O₁₂ powder as anode separator by flexible gel polymer electrolyte (GPE) film. The GPE film comprises 1.0 M lithium trifluoromethane sulfonate (LiTf) solution in ethylene carbonate (EC)–propylene carbonate (PC) mixture, immobilized poly(vinylidene fluoride-co-hexafluoro-propylene) (PVdF-HFP), which is of high ionic conductivity (∼3.8 × 10⁻³ S cm⁻¹ at 25 °C) and electrochemical stability window (∼3 V). The effect of the addition of AC in composite electrode LACs has been analyzed using various techniques such as X-ray diffraction, porosity analysis, and electrochemical methods. The interfaces of composite LACs and GPE film not only offer high rate performance but also show high specific energy (>27.8 Wh kg⁻¹) as compared to the symmetric supercapacitors and pristine lithium iron phosphate (LiFePO₄)-based lithium ion batteries. The full BatCap systems have been characterized by cyclic voltammetry and galvanostatic charge–discharge tests. The BatCap systems with composite electrodes (LACs) offer better cyclic performance as compared to that of pristine LiFePO₄-based BatCap or LIB LiFePO₄/Li₄Ti₅O₁₂.

     

Preparation and characteristics of Li4Ti5O12 with various dopants as anode electrode for hybrid supercapacitor

Spinel-Li₄Ti₅O₁₂ is successfully synthesized by a solid phase synthesis. The Li₄Ti₅O₁₂ powders with various dopants (Al³⁺, Cr³⁺, Mg²⁺) synthesized at 800 °C are in accordance with the Li₄Ti₅O₁₂ cubic spinel phase structure. The dopants are inserted into the lattice structure of Li₄Ti₅O₁₂ without causing any changes in structural characteristics. In order to study the effect on various dopants, the hybrid supercapacitor is prepared by using un-doped Li₄Ti₅O₁₂ and doped Li₄Ti₅O₁₂ in this work. The electrochemical performance of the hybrid supercapacitor is characterized by impedance spectroscopy and cycle performance. The results show Cr³⁺ and Mg²⁺ dopants enhance the conductivity of Li₄Ti₅O₁₂. Also, Al³⁺ substitution improves the reversible capacity and cycling stability of Li₄Ti₅O₁₂. It is found that effect of dopant on the electrochemical performance of Li₄Ti₅O₁₂ as electrode material for hybrid supercapacitor where the EDLC and the Li ion secondary battery coexist in one cell system.     

Enhanced high-rate performance of sub-micro Li4Ti4.95Zn0.05O12 as anode material for lithium-ion batteries

Zn-doped Li₄Ti₅O₁₂ was prepared by a ball milling-assisted solid-state method, and the characters were determined by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, cyclic voltammetry, and galvanostatic charge–discharge testing. The results show that Li₄Ti_5?x Zn _x O₁₂ (x?=?0, 0.05) exhibits the pure phase structure, and Zn doping does not change the electrochemical reaction process and basic spinel structure of Li₄Ti₅O₁₂. The particle size of both samples is about 300–500 nm. The prepared Li₄Ti_4.95Zn_0.05O₁₂ presents an excellent rate capability and capacity retention. At the charge–discharge rate of 1C, the initial discharge capacity of Li₄Ti_4.95Zn_0.05O₁₂ is 268 mAh g^?1. After 90 cycles at 5C, the discharge capacity of Li₄Ti_4.95Zn_0.05O₁₂ is obviously higher than that of Li₄Ti₅O₁₂. The excellent electrochemical performance of the Li₄Ti_4.95Zn_0.05O₁₂ electrode could be attributed to the improvement of reversibility by doping zinc and the sub-micro particle size.     

Effects of ultrasound irradiation on Au nanoparticles deposition on carbon-coated LiNi0.5Mn1.5O4 and its performance as a cathode material for Li ion batteries

LiNi_0.5Mn_1.5O₄ (LMNO) has attracted considerable attention as a Li-ion battery cathode material, owing to its high discharge voltage of 4.7 V (vs. Li/Li⁺) and high energy density. However, the electronic conductivity of LMNO is low, resulting in a low discharge capacity at high current density. To overcome this limitation, we deposited Au nanoparticles (NPs), which have a high conductivity and chemical stability at high battery voltages, on carbon-coated LMNO (LMNO/C) using ultrasound irradiation. Consequently, Au NPs that are ∼16 nm in size were deposited on LMNO/C, and ultrasound irradiation was reported to disperse the NPs on LMNO/C more effectively than stirring. Furthermore, the deposition of Au NPs on LMNO/C using ultrasound irradiation improved its electronic conductivity, which is related to an increase in the discharge capacity due to the reduction of Ni⁴⁺ to Ni²⁺ in LMNO/C at a high current density.     

Influence of coated MnO2 content on the electrochemical performance of Li1.2Ni0.2Mn0.6O2 cathodes

Layered cathode material Li_1.2Ni_0.2Mn_0.6O₂ has been synthesized using a coprecipitation method and coated by MnO₂ with varying amounts (1, 3, 5, and 9 wt%). The physical properties and electrochemical performances of the materials are characterized by XRD, SEM, charge/discharge tests, cycle life, and rate capability tests. XRD patterns show that the pristine and coated Li_1.2Ni_0.2Mn_0.6O₂ powders exhibit layered structure. The discharge capacities and coulombic efficiencies of Li_1.2Ni_0.2Mn_0.6O₂ in the first cycle have been improved and increase with the increasing content of coated MnO₂. The 9 wt% MnO₂-coated Li_1.2Ni_0.2Mn_0.6O₂ delivers 287 mAhg^?1 for the first discharge capacity and 86.7 % for the first coulombic efficiency compared with 228 mAhg^?1 and 65.9 % for pristine Li_1.2Ni_0.2Mn_0.6O₂. However, the 5 wt% MnO₂-coated Li_1.2Ni_0.2Mn_0.6O₂ shows the best capacity retention (99.9 % for 50 cycles) and rate capability (88.6 mAhg^?1 at 10 C), while the pristine Li_1.2Ni_0.2Mn_0.6O₂ only shows 91.5 % for 50 cycles and 25.3 mAhg^?1 at 10 C. The charge/discharge curves and differential capacity vs. voltage (dQ/dV) curves show that the coated MnO₂ reacts with Li⁺ during the charge and discharge process, which is responsible for higher discharge capacity after coating. Electrochemical impedance spectroscopy results show that the R _ct of Li_1.2Ni_0.2Mn_0.6O₂ electrode decreases after coating, which is responsible for superior rate capability.     

Li4Ti2.5Cr2.5O12 as anode material for lithium battery

Chromium-substituted Li₄Ti₅O₁₂ has been investigated as a negative electrode for future lithium batteries. It has been synthesized by a solid-state method followed by quenching leading to a micron-sized material. The minimum formation temperature of Li₄Ti_2.5Cr_2.5O₁₂ was found to be around 600 °C using thermogravimetric and differential thermal analysis. X-ray diffraction, scanning electron microscopy, cyclic voltammetry (CV), impedance spectroscopy, and charge–discharge cycling were used to evaluate the synthesized Li₄Ti_2.5Cr_2.5O₁₂. The particle size of the powder was around 2–4 μm. CV studies reveal a shift in the deintercalation potential by about 40 mV, i.e., from 1.54 V for Li₄Ti₅O₁₂ to 1.5 V for Li₄Ti_2.5Cr_2.5O₁₂. High-rate cyclability was exhibited by Li₄Ti_2.5Cr_2.5O₁₂ (up to 5  C) compared to the parent compound. The conduction mechanism of the compound was examined in terms of the dielectric constant and dissipation factor. The relaxation time has been evaluated and was found to be 0.07 ms. The mobility was found to be 5.133 × 10⁻⁶ cm² V⁻¹ s⁻¹.