Amorphous ATO and amorphous ATO based composite anodes for Li-ion batteries

In this study, amorphous antimony doped tin oxide (ATO) coatings on Cr coated stainless steel and multiwall carbon nanotube (MWCNT) buckypaper substrates were prepared using a radio frequency (RF) magnetron sputtering process as anode materials in lithium-ion batteries. The MWCNT anode, amorphous SnO₂:Sb anode and amorphous SnO₂:Sb-MWCNT nanocomposite anode have shown first discharge capacities of 446 mA h g⁻¹, 1064 mA h g⁻¹ and 1462 mA h g⁻¹, respectively. The best cycling performance were observed for amorphous SnO₂:Sb-MWCNT nanocomposite anode.     

Improvement of electrochemical and structural properties of LiMn2O4 spinel based electrode materials for Li-ion batteries

Spinel LiMn₂O₄ and LiM_0.02Mn_1.98O₄ (where M is Zn, Co, Ni and In) were produced via facile sol–gel method and Cu/LiMn₂O₄, Cu/LiM_0.02Mn_1.98O₄, Ag/LiMn₂O₄ and Ag/LiM_0.02Mn_1.98O₄ binary composite electrode materials were produced via electroless coating techniques as a positive electrode material for Li-ion batteries. The phase composition, morphology and electrochemical properties of the synthesized materials were investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), cyclic voltammometry (CV), galvanostatic charge–discharge tests and electrochemical impedance spectroscopy (EIS). The synthesized cathode active materials are characterized as single phase spinel LiMn₂O₄ with degree of crystallization and uniform particle size distribution. Best results were obtained with electrodes substituted with In and an initial discharge capacity of 134 mAhg⁻¹ after 50 cycles. The improvement in the cycling performance may be attributed to stabilization of spinel structure by smaller lattice constant when manganese ion was partially substituted with In³⁺ ions. EIS analysis also confirms that the obvious improvement in Ag coating is mainly attributed to the accelerated phase transformation from layered phase to spinel phase and highly stable electrolyte/electrode interface due to the suppression of electrolyte decomposition.     

Synthesis of carbon coated Fe3O4/SnO2 composite beads and their application as anodes for lithium ion batteries

Abstract

Two metal oxide materials, namely, Fe₃O₄ and SnO₂, were combined into one specially designed nanostructure for lithium ion battery application. Hollow and porous Fe₃O₄ beads with an average size of ～700 nm were first synthesised through a one-step solvothermal route, followed by the decoration of SnO₂ nanoparticles via a hydrothermal method. A thin carbon layer was coated to further enhance the overall electrochemical performances. Under the current density of 100 mA g^?1, the first reversible capacity of such composite beads reached 834·7 mA h g^?1. While being tested at a higher current density of 500 mA g^?1, carbon coated Fe₃O₄/SnO₂ delivered steady reversible capacities with 569·5 mA h g^?1 at two hundredth cycle. Such performances were attributed to the high theoretical capacities of the metal oxides, desired morphology in nanoscale, carbon coating layer and the synergistic effect between Fe₃O₄ and SnO₂.     

Electrolytic Sn/Li2O coatings for thin-film lithium ion battery anodes

Sn/Li₂O composite coatings on stainless steel substrate, as anodes of thin-film lithium battery are carried out in SnCl₂ and LiNO₃ mixed solutions by using cathodic electrochemical synthesis and subsequently annealed at 200 °C. Through cathodic polarization tests, three major regions are verified: (I) O₂ + 4H⁺ + 4e⁻ → 2H₂O (∼0.25 to −0.5 V), (II) 2H⁺ + 2e⁻ → H₂, Sn²⁺ + 2e⁻ → Sn, and NO₃⁻ + H₂O + 2e⁻ → NO₂⁻ + 2OH⁻ (−0.5 to −1.34 V), and (III) 2H₂O + 2e⁻ → H₂ + 2OH⁻ (−1.34 to −2 V vs. Ag/AgCl). The coated specimens are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and charge/discharge tests. The nano-sized Sn particles embedded in Li₂O matrix are obtained at the lower part of region II such as −1.2 V, while the micro-sized Sn with little Li₂O at the upper part, such as −0.7 V. Charge/discharge cycle tests elucidated that Sn/Li₂O composite film showed better cycle performance than Sn or SnO₂ film, due to the retarding effects of amorphous Li₂O on the further aggregation of Sn particles. On the other hand, the one tested for cut-off voltage at 0.9 V (vs. Li/Li⁺) is better than those at 1.2 and 1.5 V since the incomplete de-alloy at lower cut-off voltage may inhibit the coarsening of Sn particles, revealing capacity 587 mAh g⁻¹ after 50 cycle, and capacity retention ratio C50/C2 81.6%, higher than 63.5% and 49.1% at 1.2 and 1.5 V (vs. Li/Li⁺), respectively.     

SnO2 nanocrystals deposited on multiwalled carbon nanotubes with superior stability as anode material for Li-ion batteries

We report a novel ethylene glycol-mediated solvothermal-polyol route for synthesis of SnO₂-CNT nanocomposites, which consist of highly dispersed 3-5 nm SnO₂ nanocrystals on the surface of multiwalled carbon nanotubes (CNTs). As anode materials for Li-ion batteries, the nanocomposites showed high rate capability and superior cycling stability with specific capacity of 500 mAh g⁻¹ for up to 300 cycles. The CNTs served as electron conductors and volume buffers in the nanocomposites. This strategy could be extended to synthesize other metal oxides composites with other carbon materials.     

Improved rate capability of carbon coated Li3.9Sn0.1Ti5O12 porous electrodes for Li-ion batteries

A new sol-gel process is developed to modify the Li₄Ti₅O₁₂ anode material for improved rate capability. The new process brings about the following effects, namely (i) doping of Sn²⁺ to form Li_3.9Sn_0.1Ti₅O₁₂, (ii) carbon coating and (iii) creation of a porous structure. The doping of Sn²⁺ results in the lattice distortion without changing the phase composition. A thin layer of amorphous carbon is coated on the doped particles that contain numerous nanopores. The rate capability of the anode material made from the modified powder is significantly improved when discharged at high current rates due to the reduced charge transfer resistance.     

Microstructure and electrochemical performance of Si-SiO2-C composites as the negative material for Li-ion batteries

Si-SiO₂-C composites are synthesized by ball milling the mixture of SiO, graphite and coal pitch, and subsequent heat treatment at 900 °C in inert atmosphere. The electrochemical performance and microstructure of the composites are investigated. XRD and TEM tests indicate that the carbon-coating structure of Si-SiO₂-C composites form in pyrolysis process, which can remarkably improve the electrochemical cycling performance. The coal pitch as carbon precursor and graphite demonstrate the same important effect on the Li-alloying/de-alloying property of the Si-SiO₂-C composites. The Si-SiO₂-C composites exhibit the electrochemical reversible Li-alloying/de-alloying capacity of 700 mAh g⁻¹ and excellent cyclic stability even at about the 90th cycle.     

Hydrothermal synthesis of Co2SnO4 nanocrystals as anode materials for Li-ion batteries

Cubic spinel Co₂SnO₄ nanocrystals are successfully synthesized via a simple hydrothermal reaction in alkaline solution. The effect of alkaline concentration, hydrothermal temperature, and hydrothermal time on the structure and morphology of the resultant products were investigated based on X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It is demonstrated that pure Co₂SnO₄ nanocrystals with good crystallinity can be obtained in NaOH solution (2.0 M) at 240 °C for 48 h. The galvanostatic charge/discharge and cyclic voltammetry were conducted to measure the electrochemical performance of the Co₂SnO₄ nanocrystals. It is shown that Co₂SnO₄ nanocrystals exhibit good electrochemical activity with high reversible capacity (charge capacity) of 1088.8 mAh g⁻¹ and good capacity retention as anode materials for Li-ion batteries, much better than that of bulk Co₂SnO₄ prepared by high temperature solid-state reaction.     

Synthesis and electrochemical properties of Na-doped Li3V2(PO4)3 cathode materials for Li-ion batteries

Na-doped Li_3−xNa_xV₂(PO₄)₃/C (x = 0.00, 0.01, 0.03, and 0.05) compounds have been prepared by using sol-gel method. The Rietveld refinement results indicate that single-phase Li_3−xNa_xV₂(PO₄)₃/C with monoclinic structure can be obtained. Among three Na-doped samples and the undoped one, Li_2.97Na_0.03V₂(PO₄)₃/C sample has the highest electronic conductivity of 6.74 × 10⁻³ S cm⁻¹. Although the initial specific capacities for all Na-doped samples have no much enhancement at the current rate of 0.2 C, both cycle performance and rate capability have been improved. At the 2.0 C rate, Li_2.97Na_0.03V₂(PO₄)₃/C presents the highest initial capacity of 118.9 mAh g⁻¹ and 12% capacity loss after 80 cycles. The partial substitution of Li with Na (x = 0.03) is favorable for electrochemical rate and cyclic ability due to the enlargement of Li₃V₂(PO₄)₃ unit cells, optimizing the particle size and morphology, as well as resulting in a higher electronic conductivity.     

High stability and superior rate capability of three-dimensional hierarchical SnS2 microspheres as anode material in lithium ion batteries

3D hierarchical SnS₂ microspheres have been designed and fabricated via a one-pot biomolecule-assisted hydrothermal method. When used as anode material in rechargeable Li-ion batteries, the as-formed SnS₂ microspheres self-assembled by layered nanosheets, show high lithium storage capacity, long-term cycling stability and superior rate capability. After charge-discharge for 100 cycles, the remaining discharge capacities are kept as high as 570.3, 486.2, and 264 mAh g⁻¹ at 1C (0.65 A g⁻¹), 5C, and 10C rate, respectively. Such outstanding performance of these SnS₂ microspheres is ascribed to their unique 3D hierarchical structures. The new charge-discharge mechanism of 3D SnS₂ microsphere as anode in Li-ion battery is further revealed.     

Preparation and electrochemical characterization of single-crystalline spherical LiNi1/3Co1/3Mn1/3O2 powders cathode material for Li-ion batteries

LiNi_1/3Co_1/3Mn_1/3O₂ has aroused much interest as a new generation of cathode material for Li-ion batteries, due to its great advantages in capacity, stability, low cost and low toxicity, etc. Here we report a novel single-crystalline spherical LiNi_1/3Co_1/3Mn_1/3O₂ material that is prepared by a convenient rheological phase reaction route. The X-ray powder diffraction, scanning electron microscopy and transmission electron microscopy indicate that the particles are highly dispersed with spherical morphologies and diameters of about 1-4 μm, and more interestingly, they show a perfect single-crystalline nature, which is not usual according to the crystal growth theories and may bring extra benefits to applications. Electrochemical tests show good performance of the material in both the capacity and cycling stability as cathode material in a model cell.     

Basic molten salt process—A new route for synthesis of nanocrystalline Li4Ti5O12-TiO2 anode material for Li-ion batteries using eutectic mixture of LiNO3-LiOH-Li2O2

A nanocrystalline Li₄Ti₅O₁₂-TiO₂ duplex phase has been synthesized by a simple basic molten salt process (BMSP) using an eutectic mixture of LiNO₃-LiOH-Li₂O₂ at 400-500 °C. The microstructure and morphology of the Li₄Ti₅O₁₂-TiO₂ product are characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The sample prepared by heat-treating at 300 °C for 3 h (S-1) reveals dense agglomerates of ultra-fine nanocrystalline Li₄Ti₅O₁₂; with heat treatment at 400 °C for 3 h (S-2), there is a duplex crystallite size (fine < 10 nm, and coarse > 20 nm) of Li₄Ti₅O₁₂-TiO₂; at 500 °C for 3 h (S-3), a much coarser and less-dense distribution of lithium titanate (crystallite size ∼15-30 nm) is observed. According to the results of electrochemical testing, the S-2 sample shows initial discharge capacities of 193 mAh g⁻¹ at 0.2 C, 168 mAh g⁻¹ at 0.5 C, 146 mAh g⁻¹ at 1 C, 135 mAh g⁻¹ at 2 C, and 117 mAh g⁻¹ at 5 C. After 100 cycles, the discharge capacity is 138 mAh g⁻¹ at 1 C with a capacity retention of 95%. The S-2 sample yields the best electrochemical performance in terms of charge-discharge capacity and rate capability compared with other samples. Its superior electrochemical performance can be mainly attributed to the duplex crystallite structure, composed of fine (<10 nm) and coarse (>20) nm nanoparticles, where lithium ions can be stored within the grain boundary interfaces between the spinel Li₄Ti₅O₁₂ and the anatase TiO₂.     

High rate cycling performance of Li1.05Ni1/3Co1/3Mn1/3O2 materials prepared by sol-gel and co-precipitation methods for lithium-ion batteries

High rate performance of Li_1.05Ni_1/3Co_1/3Mn_1/3O₂ cathode materials prepared using sol-gel (SG) and co-precipitation (CP) methods were investigated. Scanning electron microscopy results showed that the particle sizes of the materials prepared by SG and CP methods were 300-400 nm and 1-2 μm, respectively. Rate capability tests were performed and compared on these cathode materials with same electrode loading (7 mg cm⁻²). Li_1.05Ni_1/3Co_1/3Mn_1/3O₂ cathode with smaller particle size (SG-nano) demonstrated higher discharge capacity than that of the cathode with larger particle size (CP-micro) at different C-rates. However, upon extended cycling at 1C and 8C, CP-micro showed better capacity retention when compared to that of SG-nano. CP-micro exhibited 95 and 91% where as SG-nano exhibited only 87 and 76%, respectively, at 1C and 8C after 50 cycles. The results showed that the use of nanosized materials was advantageous for obtaining a better rate capability where as the use of microsized materials was beneficial for better capacity retention during extended cycling at high C-rates.     

An amorphous LiCo1/3Mn1/3Ni1/3O2 thin film deposited on NASICON-type electrolyte for all-solid-state Li-ion batteries

Amorphous LiCo_1/3Mn_1/3Ni_1/3O₂ thin films were deposited on the NASICON-type Li-ion conducting glass ceramics, Li_1+x+yAl_xTi_2−xSi_yP_3−yO₁₂ (LATSP), by radio frequency (RF) magnetron sputtering below 130 °C. The amorphous films were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The Li/PEO₁₈-Li(CF₃SO₂)₂N/LATSP/LiCo_1/3Mn_1/3Ni_1/3O₂/Au all-solid-state cells were fabricated to investigate the electrochemical performance of the amorphous films. It was found that the low-temperature deposited amorphous cathode film shows a high discharge voltage and a high discharge capacity of around 130 mAh g⁻¹.     

Structural changes and thermal stability of charged LiNi1/3Co1/3Mn1/3O2 cathode material for Li-ion batteries studied by time-resolved XRD

Structural changes and their relationship with thermal stability of charged Li_0.33Ni_1/3Co_1/3Mn_1/3O₂ cathode samples have been studied using time-resolved X-ray diffraction (TR-XRD) in a wide temperature from 25 to 600 °C with and without the presence of electrolyte in comparison with Li_0.27Ni_0.8Co_0.15Al_0.05O₂ cathodes. Unique phase transition behavior during heating is found for the Li_0.33Ni_1/3Co_1/3Mn_1/3O₂ cathode samples: when no electrolyte is present, the initial layered structure changes first to a LiM₂O₄-type spinel, and then to a M₃O₄-type spinel and remains in this structure up to 600 °C. For the Li_0.33Ni_1/3Co_1/3Mn_1/3O₂ cathode sample with electrolyte, additional phase transition from the M₃O₄-type spinel to the MO-type rock salt phase takes place from about 400 to 441 °C together with the formation of metallic phase at about 460 °C. The major difference between this type of phase transitions and that for Li_0.27Ni_0.8Co_0.15Al_0.05O₂ in the presence of electrolyte is the delayed phase transition from the spinel-type to the rock salt-type phase by stretching the temperature range of spinel phases from about 20 to 140 °C. This unique behavior is considered as the key factor of the better thermal stability of the Li_1−xNi_1/3Co_1/3Mn_1/3O₂ cathode materials.