Chemical reduction of nano-scale Cu2Sb powders as anode materials for Li-ion batteries

A novel process was attempted to prepare nano-scale Cu₂Sb alloy powders as anode materials for Li-ion batteries. The preparation started with chemical reduction of Cu₂Sb in an aqueous solution with sodium citrate as a complexing agent and KBH₄ as a reducer. The analysis of scanning electron microscopy and X-ray diffraction showed that as-prepared nano-scale Cu₂Sb powders presented tetragonal structure with particle size of 50-70 nm. Cycling between 0 and 1.2 V, the nano-scale Cu₂Sb alloy showed good cyclability with a stable specific capacity of 200 mAh g⁻¹ within 25 cycles.     

Li-storage and cyclability of urea combustion derived ZnFe2O4 as anode for Li-ion batteries

The cubic ZnFe₂O₄ with the spinel structure is prepared by the urea combustion method. Powder X-ray diffraction and HR-TEM studies confirm the single-phase nature with particle size in the range, 100-300 nm. A stable and reversible capacity, 615(±10) mAh g⁻¹ (5.5 moles of Li per mole of ZnFe₂O₄) when cycled in the range, 0.005-3.0 V vs. Li at a current of 60 mA g⁻¹(0.1C) has been achieved between 15 and 50 cycles. The underlying reaction mechanism contributing to the observed capacity is the combination of ‘de-alloying-alloying’ and ‘conversion’ reactions of ‘LiZn-Fe-Li₂O composite’. Ex situ HR-TEM and SAED data on the charged-electrode confirmed the proposed reaction mechanism.     

Mixed oxides Ca2Fe2O5 and Ca2Co2O5 as anode materials for Li-ion batteries

The electrochemical performance of mixed oxides, Ca₂Fe₂O₅ and Ca₂Co₂O₅ for use in Li-ion batteries was studied with Li as the counter electrode. The compounds were prepared and characterized by X-ray diffraction and SEM. Ca₂Fe₂O₅ showed a reversible capacity of 226 mAh/g at the 14th cycle and retained 183 mAh/g at the end of 50 cycles at 60 mA/g in the voltage window 0.005-2.5 V. A reversible capacity in the range, 365-380 mAh/g, which is stable up to 50 charge-discharge cycles is exhibited by Ca₂Co₂O₅ in the voltage window, 0.005-3.0 V and at 60 mA/g. This corresponds to recycleable moles of Li of 3.9±0.1 (theoretical: 4.0). Significant improvement in the cycling performance and attainable reversible capacity were noted for Ca₂Co₂O₅ on cycling to an upper cut-off voltage of 3.0 V as compared to 2.5 V. Coulombic efficiency for both compounds is >98%. Electrochemical impedance spectroscopy (EIS) data clearly indicate the reversible formation/decomposition of polymeric surface film on the electrode surface of Ca₂Co₂O₅ in the voltage window, 0.005-3.0 V. Cyclic voltammetry results compliment the galvanostatic cycling data.     

A novel micro-spherical CoSn2/Sn alloy composite as high capacity anode materials for Li-ion rechargeable batteries

Micro-scaled spherical CoSn₂/Sn alloy powders synthesized from oxides of Sn and Co via carbothermal reduction at 800 °C were examined for use as anode materials in Li-ion battery. The phase composition and particle morphology of the CoSn₂/Sn alloy composite powders were investigated by XRD, SEM and TEM. The prepared CoSn₂/Sn alloy composite electrode exhibits a low initial irreversible capacity of ca. 140 mAh g⁻¹, a high specific capacity of ca. 600 mAh g⁻¹ at constant current density of 50 mA g⁻¹, and a good rate capability. The stable discharge capacities of 500-515 mAh g⁻¹ and the columbic efficiencies of 95.8-98.1% were obtained at current density of 500 mA g⁻¹. The relatively large particle size of CoSn₂/Sn alloy composite powder is apparently favorable for the lowering of initial capacity loss of electrode, while the loose particle structural characteristic and the Co addition in Sn matrix should be responsible for the improvement of cycling stability of CoSn₂/Sn electrode.     

Preparation of Sn2Sb alloy encapsulated carbon microsphere anode materials for Li-ion batteries by carbothermal reduction of the oxides

A novel process was proposed to prepare Sn₂Sb-encapsulated carbon microspheres (CM/Sn₂Sb) anode materials by inverse emulsion polymerization of resorcinol-formaldehyde (RF) performed in the presence of Sb₂O₃ and SnO₂ powders (1/4 molar ratio), followed by carbonization and carbothermal reduction in an inert atmosphere. The oxides powder were encapsulated within the carbon gel microspheres and the elemental Sn and Sb were reduced from their oxides by the carbonized RF gel to form crystalline Sn₂Sb alloy within carbon microspheres. The CM/Sn₂Sb presented much better cyclability than that of Sn₂Sb alloy powder. The proposed process paves an effective way to prepare high performance Sn₂Sb/C microspheres composite anode materials for lithium-ion batteries.     

Solvothermal synthesis of nanosized CoSb2 alloy anode for Li-ion batteries

The nanocrystalline CoSb₂ was prepared by a solvothermal method at various temperatures and was investigated as a potential anode material for lithium-ion batteries. It was found that the CoSb₂ is highly crystallized at 190 °C and with almost a single-phase structure. The morphology of the alloy powder plays an important role in their cycling behavior. The large reversible capacity and better capacity retention of these nanosized CoSb₂ alloys make them promising anode materials for Li-ion batteries.     

Three-dimensional porous amorphous SnO2 thin films as anodes for Li-ion batteries

Three-dimensional (3D) porous amorphous SnO₂ thin films were deposited on Ni foam substrates by Electrostatic Spray Deposition (ESD) technique as anodes for Li-ion batteries. These films display good capacity retention of 94.8% after 100 cycles at 0.5 C and rate capability of 362 mAh/g at 10 C. The improved performance originates from the fact that the 3D porous structure offers a “buffer zone” to accommodate the large volume change during cycling, and the foam-like substrate maximizes the contact area between electrode and electrolyte. The facile ESD method can be potentially extended to prepare other 3D porous functional materials.     

Electrochemical properties of SnO2/carbon composite materials as anode material for lithium-ion batteries

SnO₂/carbon composite anode materials were synthesized from SnCl₄·5H₂O and sucrose via a hydrothermal route and a post heat-treatment. The synthesized spherical SnO₂/carbon powders show a cauliflower-like micro-sized structure. High annealing temperature results in partial reduction of SnO₂. Metallic Sn starts to emerge at 500 °C. High Sn content in SnO₂/carbon composite is favorable for the increase of initial coulombic efficiency but not for the cycling stability. The SnO₂/carbon annealed at 500 °C exhibits high specific capacity (∼400 mAh g⁻¹), stable cycling performance and good rate capability. The generation of Li₂O in the first lithiation process can prevent the aggregation of active Sn, while the carbon component can buffer the big volume change caused by lithiation/delithiation of active Sn. Both of them make contribution to the better cycle stability.     

Antimonides (FeSb2, CrSb2) with orthorhombic structure and their nanocomposites for rechargeable Li-ion batteries

Intermetallic FeSb₂ and CrSb₂ and their nanocomposites (FeSb₂/C and Sb/Cr₃C₂/C) were prepared using solid-state routes, such as heat-treatment and high-energy mechanical milling, in order to enhance the electrochemical properties of Sb. These electrodes were tested as anode materials for rechargeable Li-ion batteries. The reaction mechanism of intermetallic FeSb₂ and CrSb₂ was investigated using ex situ X-ray diffraction and high resolution transmission electron microscopy. The FeSb₂/C and Sb/Cr₃C₂/C nanocomposite electrodes exhibited greatly enhanced electrochemical behaviors compared to the FeSb₂ and CrSb₂ electrodes. Additionally, the Sb/Cr₃C₂/C nanocomposite electrode showed a better electrochemical performance than the FeSb₂/C nanocomposite electrode.     

Electrodeposition and electrochemical characterisation of thick and thin coatings of Sb and Sb/Sb2O3 particles for Li-ion battery anodes

The possibilities to electrodeposit thick coatings composed of nanoparticles of Sb and Sb₂O₃ for use as high-capacity anode materials in Li-ion batteries have been investigated. It is demonstrated that the stability of the coatings depends on their Sb₂O₃ concentrations as well as microstructure. The electrodeposition reactions in electrolytes with different pH and buffer capacities were studied using chronopotentiometry and electrochemical quartz crystal microbalance measurements. The obtained deposits, which were characterised with XRD and SEM, were also tested as anode materials in Li-ion batteries. The influence of the pH and buffer capacity of the deposition solution on the composition and particle size of the deposits were studied and it is concluded that depositions from a poorly buffered solution of antimony-tartrate give rise to good anode materials due to the inclusion of precipitated Sb₂O₃ nanoparticles in the Sb coatings. Depositions under conditions yielding pure Sb coatings give rise to deposits composed of large crystalline particles with poor anode stabilities. The presence of a plateau at about 0.8 V versus Li⁺/Li due to SEI forming reactions and the origin of another plateau at about 0.4 V versus Li⁺/Li seen during the lithiation of thin Sb coatings are also discussed. It is demonstrated that the 0.4 V plateau is present for Sb coatings for which the (0 1 2) peak is the main peak in the XRD diffractogram.     

Low-temperature growth of well-crystalline Co3O4 hexagonal nanodisks as anode material for lithium-ion batteries

Uniform hexagonal-shaped cobalt oxide (Co₃O₄) nanodisks were prepared in large scale via facile aqueous solution based hydrothermal process at 110 °C. The detailed structural characterizations confirmed that the synthesized products are hexagonal cobalt oxide nanodisks, possessing very well-crystalline cubic spinel structure. A coin cell of type −2032 was assembled using the synthesized Co₃O₄ nanodisks and its charge–discharge profile was analyzed between the voltages 0.01 and to 2.5 V vs. Li/Li⁺ reference electrode. The electrochemical cell composed of Li/Co₃O₄ delivered an initial lithium insertion capacity of 2039 mAh/g. Although the cell exhibited high irreversible capacity during the first four cycles, the columbic efficiency has been improved upon cycling.     

Effect of synthesis temperature on the phase structure,morphology and electrochemical performance of Ti3C2 as an anode material for Li-ion batteries

Ti₃C₂, the most widely studied MXene, was successfully synthesised by etching Al layers from Ti₃AlC₂ in HF solution. Given its distinct 2D layered structure, Ti₃C₂ is a promising anode material in Li-ion batteries because of its efficient ion transport, available large surface areas for improved ion adsorption and fast surface redox reactions. Herein, the effects of synthesis temperature on the phase structure, morphology and electrochemical performance were investigated. The materials synthesised at different temperatures were characterised by using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Optimal etching occurred at 100?°C, and the synthesised Ti₃C₂ exhibited smooth surface and large layer space. The synthesised Ti₃C₂, as anode material for Li-ion batteries, can accommodate more Li⁺ than those of others, and it exhibits the most ideal electrochemical performance.     

High reversible capacity of SnO2/graphene nanocomposite as an anode material for lithium-ion batteries

A gas–liquid interfacial synthesis approach has been developed to prepare SnO₂/graphene nanocomposite. The as-prepared nanocomposite was characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller measurements. Field emission scanning electron microscopy and transmission electron microscopy observation revealed the homogeneous distribution of SnO₂ nanoparticles (2–6 nm in size) on graphene matrix. The electrochemical performances were evaluated by using coin-type cells versus metallic lithium. The SnO₂/graphene nanocomposite prepared by the gas–liquid interface reaction exhibits a high reversible specific capacity of 1304 mAh g⁻¹ at a current density of 100 mA g⁻¹ and excellent rate capability, even at a high current density of 1000 mA g⁻¹, the reversible capacity was still as high as 748 mAh g⁻¹. The electrochemical test results show that the SnO₂/graphene nanocomposite prepared by the gas–liquid interfacial synthesis approach is a promising anode material for lithium-ion batteries.     

High-rate characteristics of novel anode Li4Ti5O12/polyacene materials for Li-ion secondary batteries

In recent years, spinel lithium titanate (Li₄Ti₅O₁₂) as a superior anode material for energy storage battery has attracted a great deal of attention because of the excellent Li-ion insertion and extraction reversibility. However, the high-rate characteristics of this material should be improved if it is used as an active material in large batteries. One effective way to achieve this is to prepare electrode materials coated with carbon. A Li₄Ti₅O₁₂/polyacene (PAS) composite were first prepared via an in situ carbonization of phenol-formaldehyde (PF) resin route to form carbon-based composite. The SEM showed that the Li₄Ti₅O₁₂ particles in the composite were more rounded and smaller than the pristine one. The PAS was uniformly dispersed between the Li₄Ti₅O₁₂ particles, which improved the electrical contact between the corresponding Li₄Ti₅O₁₂ particles, and hence the electronic conductivity of composite material. The electronic conductivity of Li₄Ti₅O₁₂/PAS composite is 10⁻¹ S cm⁻¹, which is much higher than 10⁻⁹ S cm⁻¹ of the pristine Li₄Ti₅O₁₂. High specific capacity, especially better high-rate performance was achieved with this Li₄Ti₅O₁₂/PAS electrode material. The initial specific capacity of the sample is 144 mAh/g at 3 C, and it is still 126.2 mAh/g after 200 cycles. By increasing the current density, the sample still maintains excellent cycle performance.     

Synthesis of SnO2/Mg2SnO4 nanoparticles and their electrochemical performance for use in Li-ion battery electrodes

Uniform crystalline MgSn(OH)₆ nanocubes were synthesized by a hydrothermal method. The influences of reaction conditions were investigated and the results showed that the solvent constituents significantly affected the shape and size of MgSn(OH)₆·SnO₂/Mg₂SnO₄ has been obtained by thermal treatment at 850 °C for 8 h under a nitrogen atmosphere using MgSn(OH)₆ as the precursor. The electrochemical tests of SnO₂/Mg₂SnO₄ revealed that SnO₂/Mg₂SnO₄ has a higher capacity and better cyclability compared to pure SnO₂ or Mg₂SnO₄. The electrochemical performance of SnO₂/Mg₂SnO₄ was sensitive to the size of the nanoparticles. The lithium-driven structural and morphological changes of the electrode after cycling were also studied by the ex-situ XRD pattern and TEM tests. This work indicates that SnO₂/Mg₂SnO₄ is a promising anode material candidate for application in Li-ion batteries.     

Facile synthesis of MnO/C anode materials for lithium-ion batteries

Cubic MnO with particle sizes of ∼200 nm and ∼600 nm was synthesized by decomposition of MnCO₃. The corresponding MnO/C composite was obtained by thermal treatment of mixture of MnCO₃ and sucrose. The structure and morphology of the products were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Electrochemical experiments showed that the as-prepared MnO/C exhibited promising electrochemical properties, and could potentially be used as anode material in lithium-ion batteries. MnO/C delivered a reversible capacity of about 470 mAh/g after cycling 50 times, when testing at 75 mA/g. The reversible capacity, when tested at 150, 375, 755 mA/g, reached 440, 320, 235 mAh/g, respectively. The good electrochemical performance was ascribed to the smaller particle size and the efficient carbon coating on MnO.     

Microwave-assisted synthesis of SnS2/SnO2 composites by l-cysteine and their electrochemical performances when used as anode materials of Li-ion batteries

SnS₂/SnO₂ composites were prepared in a microwave-assisted reaction of a mixture solution of SnCl₄ and l-cysteine and were characterised by XRD, TEM, SEM and EDX. The influence of the mole ratio of SnCl₄ to l-cysteine (l-cys) on the sample was investigated. It was found that using a microwave method, SnS₂/SnO₂ composites were formed, and SnS₂/SnO₂ nanoparticles were obtained when the mole ratio of SnCl₄ to l-cysteine was 1:2. With higher contents of l-cys, when the mole ratio of SnCl₄ to l-cys was 1:4, the products were nanosheets instead of nanoparticles. Electrochemical tests demonstrated that the SnS₂/SnO₂ composites with layer structure exhibited high reversible capacities and good cycling performances when used as anode materials of Li-ion batteries. When the mole ratio of SnCl₄ to l-cys was 1:6, the initial reversible capacity of products was 593 mAh/g, and the retention capacity that was maintained was over 88%. Besides, the retention capacity of products was still excellent at high current charge/discharge.     

Ultrafine SnO2 dispersed carbon matrix composites derived by a sol-gel method as anode materials for lithium ion batteries

Ultrafine crystalline SnO₂ particles (2-3 nm) dispersed carbon matrix composites are prepared by a sol-gel method. Citric acid and hydrous SnCl₄ are used as the starting constituents. The effect of the calcination temperatures on the structure and electrochemical properties of the composites has been studied. Structure analyses show that ultrafine SnO₂ particles form and disperse in the disordered carbon matrix in the calcination temperature range of 500-800 °C, forming SnO₂/C composites, and the carbon content shows only a slight increase from 35.8 wt.% to 39.1 wt.% with the temperature. Nano-Sn particles form when the calcination temperature is increased to 900 °C, forming a SnO₂/Sn/C composite, and the carbon content is increased to 49.3 wt.%. Electrochemical testing shows that the composite anodes provide high reversible cycle stability after several initial cycles, maintaining capacities of 380-400 mAh g⁻¹ beyond 70 cycles for the calcination temperature of 600-800 °C. The effect of the structure feature of the ultrafine size of SnO₂ and the disordered carbon matrix on the lithium insertion and extraction process, especially on the reversible behavior of the lithium ion reaction during cycling, is discussed.     

Core–shell Ni0.5TiOPO4/C composites as anode materials in Li ion batteries

Pristine Ni_0.5TiOPO₄ was prepared via a traditional solid-state reaction, and then Ni_0.5TiOPO₄/C composites with core–shell nanostructures were synthesized by hydrothermally treating Ni_0.5TiOPO₄ in glucose solution. X-ray diffraction patterns indicate that Ni_0.5TiOPO₄/C crystallizes in monoclinic P2₁/c space group. Scanning electron microscopy and transmission electron microscopy show that the small particles with different sizes are coated with uniform carbon film of ∼3 nm in thickness. Raman spectroscopy also confirms the presence of carbon in the composites. Ni_0.5TiOPO₄/C composites presented a capacity of 276 mAh g⁻¹ after 30 cycles at the current density of 42.7 mA g⁻¹, much higher than that of pristine Ni_0.5TiOPO₄ (155 mAh g⁻¹). The improved electrochemical performances can be attributed to the existence of carbon shell.     

Mesoporous polyaniline or polypyrrole/anatase TiO2 nanocomposite as anode materials for lithium-ion batteries

A functional composite as anode materials for lithium-ion batteries, which contains highly dispersed TiO₂ nanocrystals in polyaniline matrix and well-defined mesopores, is fabricated by employing a novel one-step approach. The as-prepared mesoporous polyaniline/anatase TiO₂ nanocomposite has a high specific surface area of 224 m² g⁻¹ and a predominant pore size of 3.6 nm. The electrochemical performance of the as-prepared composite as anode material is investigated by cyclic voltammograms and galvanostatic method. The results demonstrate that the polyaniline/anatase nanocomposite provides larger initial discharge capacity of 233 mAh g⁻¹ and good cycle stability at the high current density of 2000 mA g⁻¹. After 70th cycles, the discharge capacity is maintained at 140 mAh g⁻¹. The excellent electrochemical performance of the polyaniline/TiO₂ nanocomposite is mainly attributed to its special structure. Furthermore, it is accessible to extend the novel strategy to other polymer/TiO₂ composites, and the mesoporous polypyrrole/anatase TiO₂ is also successfully fabricated.