Hierarchical porous cobalt oxide array films prepared by electrodeposition through polystyrene sphere template and their applications for lithium ion batteries

Hierarchical porous cobalt oxide (Co₃O₄) array films are successfully prepared by electrodeposition through polystyrene sphere monolayer template. The as-prepared Co₃O₄ array films exhibit three typical porous structures from non-close-packed bowl array to close-packed bowl array and hierarchical two layer array structures. These Co₃O₄ array films have a hierarchical porous structure, in which the skeleton is composed of ordered arrays possessing nanoporous walls. A possible growth mechanism of porous Co₃O₄ array films is proposed. As anodes for Li ion batteries, the as-prepared Co₃O₄ array films exhibit quite good cycle life and high capacity. The first discharge capacity for the three Co₃O₄ array films is 1511, 1475, 1463 mAh g⁻¹, respectively, and their initial coulombic efficiencies are as high as 72%. The specific capacity after 50 cycles for the three electrodes is 712, 665 and 640 mAh g⁻¹ at 1C rate, corresponding to 80%, 75%, 72% of the theoretical value (890 mAh g⁻¹), respectively.     

Surface modification of aluminum with tin oxide coating

Tin oxide (SnO) was coated on the surface of aluminum spherules with an average particle size of 37 μm by a chemical deposition method to improve the electrochemical properties. The samples were characterized by particle size analysis, X-ray diffraction (XRD), scanning electron microscope (SEM), ac impedance spectroscopy and galvanostatic cycling. Pure aluminum electrode delivers an initial reversible capacity of 779 mAh g⁻¹, whose capacity loss is 58% after 10 cycles. In comparison, 10 wt% SnO–Al composite delivers an initial reversible capacity of 806 mAh g⁻¹ with the capacity loss of 28% after 10 cycles. Results show that SnO coating plays an important role in the improvement of the electrochemical performances. It could not only reinforce the mechanical stability of aluminum particles, but also provide better electronic contacts to the electrode.     

Facile synthesis and electrochemical properties of Fe3O4 nanoparticles for Li ion battery anode

Nanostructured Fe₃O₄ nanoparticles were prepared by a simple sonication assisted co-precipitation method. Transmission electron microscopy, X-ray diffraction and BET surface area analysis confirmed the formation of ∼20 nm crystallites that constitute ∼200 nm nanoclusters. Galvanostatic charge-discharge cycling of the Fe₃O₄ nanoaprticles in half cell configuration with Li at 100 mA g⁻¹ current density exhibited specific reversible capacity of 1000 mAh g⁻¹. The cells showed stability at high current charge-discharge rates of 4000 mA g⁻¹ and very good capacity retention up to 200 cycles. After multiple high current cycling regimes, the cell always recovered to full reversible capacity of ∼1000 mAh g⁻¹ at 0.1 C rate.     

Cost-effective and ecologically safe electrolyte for lithium batteries

The electrochemical characteristic of solutions of lithium benzolsulfonate in dimethylsulfoxide is considered. DTA/TGA is employed to analyze the thermal stability of salt. The conductivity of solutions was determined. So, for example, conductivity lithium benzolsulfonate in dimethylsulfoxide is 3.8 mSm/cm. The area electrochemical stability of solutions is in an interval 4.5–4.6 V. Electrochemical properties of lithium manganese oxide spinel in tested solutions were investigated. The charge–discharge capacity of lithium manganese oxide spinel is 65 mAh g⁻¹ (in interval of potentials from 3.2 to 4.4 V Li/Li⁺) and 190 mAh g⁻¹ (in interval of potentials from 1.8 to 4.0 V Li/Li⁺) for vanadium oxide (V).     

Discharge properties of all-solid sodium–sulfur battery using poly (ethylene oxide) electrolyte

An all-solid sodium/sulfur battery using poly (ethylene oxide) (PEO) polymer electrolyte are prepared and tested at 90 °C. Each battery is composed of a solid sulfur electrode, a sodium metal electrode, and a solid PEO polymer electrolyte. During the first discharge, the battery shows plateau potentials at 2.27 and at 1.76 V. The first discharge capacity is 505 mAh g⁻¹ sulfur at 90 °C. The capacity drastically decreases by repeated on charge–discharge cycling but remains at 166 mAh g⁻¹ sulfur after 10 cycles. The latter value is higher than that reported for a Na/poly (vinylidene difluoride)/S battery at room temperature.     

Novel polymer electrolytes based on triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) with ionically active SiO2

A novel polymer electrolyte based on triblock copolymer of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) with ionically active SiO₂ inclusions has been designed. The electrolyte shows favorable features for ion migration such as low glass transition temperature and high concentration of amorphous phase. Combined with the effect of active SiO₂, its ionic conductivity is about 8.0 × 10⁻⁵ S cm⁻¹ at 30 °C, which exceeds that for the PEO-based systems. As applying them to cells with LiFePO₄-type cathodes, a capacity of about 147.0 mAh g⁻¹ is obtained at 60 °C, which is retained by more than 90% after 40 charge/discharge cycles. Moreover, about 100 mAh g⁻¹ could still be delivered as temperature decreases to 30 °C.     

Electrochemical performance of VOMoO4 as negative electrode material for Li ion batteries

Polycrystalline samples of VOMoO₄ are prepared by a solid-state reaction method and their electrochemical properties are examined in the voltage window 0.005–3 V versus lithium. The reaction mechanism of a VOMoO₄ electrode for Li insertion/extraction is followed by ex situ X-ray diffraction analysis. During initial discharge, a large capacity (1280 mAh g⁻¹) is observed and corresponds to the reaction of ∼10.3 Li. The ex situ XRD patterns indicate the formation of the crystalline phase Li₄MoO₅ during the initial stages of discharge, which transforms irreversibly to amorphous phases on further discharge to 0.005 V. On cycling, the reversible capacity is due to the extraction/insertion of lithium from the amorphous phases. A discharge capacity of 320 mAh g⁻¹ is obtained after 80 cycles when cycling is performed at a current density of 120 mA g⁻¹.     

Li4Ti5O12/Sn composite anodes for lithium-ion batteries: Synthesis and electrochemical performance

Li₄Ti₅O₁₂/tin phase composites are successfully prepared by cellulose-assisted combustion synthesis of Li₄Ti₅O₁₂ matrix and precipitation of the tin phase. The effect of firing temperature on the particulate morphologies, particle size, specific surface area and electrochemical performance of Li₄Ti₅O₁₂/tin oxide composites is systematically investigated by SEM, XRD, TG, BET and charge-discharge characterizations. The grain growth of tin phase is suppressed by forming composite with Li₄Ti₅O₁₂ at a calcination of 500 °C, due to the steric effect of Li₄Ti₅O₁₂ and chemical interaction between Li₄Ti₅O₁₂ and tin oxide. The experimental results indicate that Li₄Ti₅O₁₂/tin phase composite fired at 500 °C has the best electrochemical performance. A capacity of 224 mAh g⁻¹ is maintained after 50 cycles at 100 mA g⁻¹ current density, which is still higher than 195 mAh g⁻¹ for the pure Li₄Ti₅O₁₂ after the same charge/discharge cycles. It suggests Li₄Ti₅O₁₂/tin phase composite may be a potential anode of lithium-ion batteries through optimizing the synthesis process.     

Optimized performances of core-shell structured LiFePO4/C nanocomposite

A nanosized LiFePO₄/C composite with a complete and thin carbon-shell is synthesized via a ball-milling route followed by solid-state reaction using poly(vinvl alcohol) as carbon source. The LiFePO₄/C nanocomposite delivers discharge capacities of 159, 141, 124 and 112 mAh g⁻¹ at 1 C, 5 C, 15 C and 20 C, respectively. Even at a charge-discharge rate of 30 C, there is still a high discharge capacity of 107 mAh g⁻¹ and almost no capacity fading after 1000 cycles. Based on the analysis of cyclic voltammograms, the apparent diffusion coefficients of Li ions in the composite are in the region of 2.42 × 10⁻¹¹ cm² s⁻¹ and 2.80 × 10⁻¹¹ cm² s⁻¹. Electrochemical impedance spectroscopy and galvanostatic intermittent titration technique are also used to calculate the diffusion coefficients of Li ions in the LiFePO₄/C electrode, they are in the range of 10⁻¹¹-10⁻¹⁴ cm² s⁻¹. In addition, at −20 °C, it can still deliver a discharge capacity of 122 mAh g⁻¹, 90 mAh g⁻¹ and 80 mAh g⁻¹ at the charge-discharge rates of 0.1 C, 0.5 C and 1 C, respectively.     

Electrochemical performances of BiSbO4 as electrode material for lithium batteries

We present an electrochemical study of BiSbO₄, an opened layered oxide having a structure related to Aurivillius phases. Li//BiSbO₄ cells show a large specific capacity as high as 1250 mAh g⁻¹ during reduction down to 0.5 V. This reaction involves 18Li atoms per formula unit, pointing it towards a very promising cathode material for primary lithium batteries, in particular for ICD devices. The characterization of the reduction products indicates that the reduction of BiSbO₄ with lithium presumably goes along firstly with the formation of metallic Sb and Bi to follow the formation of the alloys Li₃Bi and Li₃Sb dispersed in a lithium oxide matrix. In situ X-ray diffraction experiments proved the amorphous nature of both metals and final alloys. On the other hand when Li//BiSbO₄ cells are limited to discharge down to 1.2 V, BiSbO₄ reacts with 5Li atoms. After the first discharge, that develops a specific capacity of 350 mAh g⁻¹, high cyclability has been observed.     

Effect of annealing on the electrochemical properties of ramsdellite-type lithium titanium oxide

Lithium titanium oxide (LTO) with a ramsdellite structure is an advantageous anode for lithium ion secondary batteries, because of its positive potential, which is beneficial for safety reasons. In addition, compared with other titanate anodes, it has a superior theoretical capacity of 321 mA h g⁻¹, which is close to the capacity of a practical carbonaceous anode. Our study showed that this ramsdellite-type LTO had a high discharge capacity that is stable at 250 mA h g⁻¹ at a current density of 1 mA cm⁻². However, this high capacity is only achieved by employing as-synthesized ramsdellite LTO powder. When the same powder was stored and the same evaluation was carried out, the resulting capacity was 200 mA h g⁻¹, which is lower than the capacity of as-synthesized powder. An annealing applied to the ramsdellite LTO powder appeared to restore the capacity loss after storage. Annealing at 250 °C for 5 h produced the best performance, which was even better than that obtained using the as-synthesized ramsdellite LTO powder. Moreover, we investigated the surface property of ramsdellite LTO and found that the presence of a carbon derivative is apparently responsible for blocking the Li ions insertion/extraction, and thus reducing the capacity.     

Electrochemical properties of tin phosphates with various mesopore ratios

Tin phosphates with various mesopore ratios are synthesized with surfactants as templates. The mesopore ratios of the tin phosphates are controlled by adjusting the surfactant: inorganic precursor ratios. As an anode material for Li-ion batteries, the mesoporous and non-mesoporous mixture with a high mesopore ratio exhibits enhanced cycling stability. Compared with the ∼34% (∼135 mAh g⁻¹) capacity retention after 50 cycles of the non-mesoporous tin phosphate (between 2.5 and 0.001 V), the tin-phosphate anodes with mesopore ratios of 42, 82 and 100% show capacity retentions that are enhanced by more than 50%, showing charge capacities of ∼260, ∼290, and ∼325 mAh g⁻¹, respectively (after 50 cycles). The mesoporous structures may alleviate the large volume change of the Sn nanoparticles embedded in the lithium-phosphate matrix during charge–discharge. Cycling tests of the 100% mesoporous tin phosphate between 0.8 and 0.001 V exhibit no capacity decay: ∼325 mAh g⁻¹ remains after 50 cycles. This is probably because re-oxidation of metallic tin with lithium-phosphate matrix does not occur.     

Preparation and electrochemical properties of carbon-doped TiO2 nanotubes as an anode material for lithium-ion batteries

Carbon-doped TiO₂ nanotubes were synthesized through a sol–gel and subsequent hydrothermal process. Transmission electron microscopy and X-ray diffraction showed that the products are uniformly straight tubes with the diameter around 10 nm in anatase-type. The electrochemical performances of the nanotubes were tested by constant current discharge/charge, cyclic voltammetry, and electrochemical impedance spectroscopy. The initial discharge capacity reaches 291.7 mAh g⁻¹ with a coulombic efficiency of 91.7% at a current density of 70 mA g⁻¹. There is a distinct potential plateau near 1.75 and 1.89 V (versus Li⁺/Li) in the lithium intercalation and extraction processes, respectively, and the lithium insertion capacity is about 204 mAh g⁻¹ over the plateau of 1.75 V region in the first cycle. From the 2nd to the 30th cycles, the average reversible capacity loss is less than 1.73 mAh g⁻¹ per cycle. After 30 cycles, the reversible capacity still remains 211 mAh g⁻¹ with a coulombic efficiency larger than 99.7%, implying a perfect reversibility and cycling stability.     

Electrochemical lithium storage of TiO2 hollow microspheres assembled by nanotubes

TiO₂ hollow microspheres with the shell consisting of nanotubes have been successfully synthesized via a template-free hydrothermal process and subsequent treatments. The electrochemical properties of the anatase sample have been investigated by cyclic voltammetry and galvanostatic method. The initial Li insertion/extraction capacity at a current density of 0.2 C reach 290 and 232 mAh g⁻¹ respectively. Moreover, as-prepared TiO₂ delivers a reversible capacity of ca. 150 mAh g⁻¹ after 500 cycles at 1 C, and it also shows superior high rate performance (e.g., 90 mAh g⁻¹ at 8 C) without any modification.     

A study on the electrochemical characteristics of LiFePO4 cathode for lithium polymer batteries by hydrothermal method

Phospho-olivine LiFePO₄ cathode materials were prepared by hydrothermal reaction at 150 °C. Carbon black was added to enhance the electrical conductivity of LiFePO₄. LiFePO₄-C powders (0, 3, 5 and 10 wt.%) were characterized by X-ray diffraction (XRD) and transmission electron microscope (TEM). LiFePO₄-C/solid polymer electrolyte (SPE)/Li cells were characterized electrochemically by charge/discharge experiments at a constant current density of 0.1 mA cm⁻² in a range between 2.5 and 4.3 V vs. Li/Li⁺, cyclic voltammetry (CV) and ac impedance spectroscopy. The results showed that initial discharge capacity of LiFePO₄ was 104 mAh g⁻¹. The discharge capacity of LiFePO₄-C/SPE/Li cell with 5 wt.% carbon black was 128 mAh g⁻¹ at the first cycle and 127 mAh g⁻¹ after 30 cycles, respectively. It was demonstrated that cycling performance of LiFePO₄-C/SPE/Li cells was better than that of LiFePO₄/SPE/Li cells.     

Electrochemical properties of manganese oxide coated onto carbon nanotubes for energy-storage applications

Birnessite-type manganese dioxide (MnO₂) is coated uniformly on carbon nanotubes (CNTs) by employing a spontaneous direct redox reaction between the CNTs and permanganate ions (MnO₄⁻). The initial specific capacitance of the MnO₂/CNT nanocomposite in an organic electrolyte at a large current density of 1 A g⁻¹ is 250 F g⁻¹. This is equivalent to 139 mAh g⁻¹ based on the total weight of the electrode material that includes the electroactive material, conducting agent and binder. The specific capacitance of the MnO₂ in the MnO₂/CNT nanocomposite is as high as 580 F g⁻¹ (320 mAh g⁻¹), indicating excellent electrochemical utilization of the MnO₂. The addition of CNTs as a conducting agent improves the high-rate capability of the MnO₂/CNT nanocomposite considerably. The in situ X-ray absorption near-edge structure (XANES) shows improvement in the structural and electrochemical reversibility of the MnO₂/CNT nanocomposite after heat-treatment.     

Electrochemical properties of carbon-coated Si/B composite anode for lithium ion batteries

Carbon-coated Si and Si/B composite powders prepared by hydrocarbon gas (argon + 10 mol% propylene) pyrolysis were investigated as the anodes for lithium-ion batteries. Carbon-coated silicon anode demonstrated the first discharge and charge capacity as 1568 mAh g⁻¹ and 1242 mAh g⁻¹, respectively, with good capacity retention for 10 cycles. The capacity fading rate of carbon-coated Si/B composite anode decreased as the amounts of boron increased. In addition, the cycle life of carbon-coated Si/B/graphite composite anode has been significantly improved by using sodium carboxymethyl cellulose (NaCMC) and styrene butadiene rubber (SBR)/NaCMC mixture binders compared to the poly(vinylidene fluoride, PVdF) binder. A reversible capacity of about 550 mAh g⁻¹ has been achieved at 0.05 mAm g⁻¹ rate and its capacity could be maintained up to 450 mAh g⁻¹ at high rate of 0.2 mAm g⁻¹ even after 30 cycles. The improvement of the cycling performance is attributed to the lower interfacial resistance due to good electric contact between silicon particles and copper substrate.     

The synthesis and lithium intercalation electrochemistry of VO2(B) ultra-thin nanowires

Ultra-thin (<10 nm diameter) VO₂(B) nanowires have been synthesised, characterised structurally and morphologically and their lithium intercalation electrochemistry investigated. The wires exist in bundles and exhibit significant preferred orientation. They have a capacity to intercalate lithium of 265 mAh g⁻¹ (Li_0.82VO₂(B)) at a rate of 10 mA g⁻¹ compared with thicker wires of 50–100 nm diameter which exhibit a capacity of 200 mAh g⁻¹ at the same rate. The load curves, structure and morphology remain stable on cycling.     

Influence of alkali ion doping on the electrochemical performances of tin-based composite materials

In this paper, we report an investigation of three tin-based composite materials as negative electrodes for lithium-ion batteries. Theses composites were synthesized by solid state reaction from dispersion of micrometric tin into BPO₄, Li-doped BPO₄ (LiBPO) and Na-substituted BPO₄ (NaBPO) matrix, respectively. We have investigated more particularly the influence of the two alkaline ions (Li⁺, Na⁺) introduced into the matrix on electrochemical performances. The morphology of powders was observed by SEM and the composition studied by EDX analysis. The conductivity measurements showed that the modified BPO₄ matrixes (Li or Na) exhibit improved conductivity (σ_RT = 2 × 10⁻¹¹ S cm⁻¹ for NaBPO). A focus of our interest was to relate the nature and structural composition of the composite interface between active tin and inactive matrix to the irreversible capacity in this type of composite materials. The electrochemical analysis shows a decrease of the irreversible capacity for the composite based on modified matrixes (around 150 and 190 mAh g⁻¹ for SnNaBPO and SnLiBPO, respectively) with respect to the reference composite SnBPO (245 mAh g⁻¹).     

Surface reaction of β-FeOOH film negative electrode for lithium-ion cells

Electrochemical performance of β-FeOOH thin film has been investigated for a low-cost and environmentally friendly negative electrode with a large capacity. The electrode was found out to give an initial large discharge capacity of 864 mAh g⁻¹ and good cycleability with a constant value around 700 mAh g⁻¹ at subsequent cycles. In the first charge process, one electron change reaction proceeded from the initial rest potential of 3.04-1.65 V vs. Li/Li⁺, resulting in the formation of divalent product FeOOHLi. Further charging caused the surface film formation like solid electrolyte interface (SEI) between 1.65 V and 1.18 V vs. Li/Li⁺ together with the reduction of Fe compound from divalent to partially zero-valent, followed by its film growth from 1.18 V to 0.07 V vs. Li/Li⁺.