Synthesis of in situ network-like vapor-grown carbon fiber improved LiFePO4 cathode materials by microwave pyrolysis chemical vapor deposition

The low electronic conductivity of LiFePO₄ currently limits its use in lithium ion batteries. In order to solve the problem, in situ network-like vapor-grown carbon fiber (VGCF) improved LiFePO₄ cathode materials have been prepared in one step by microwave pyrolysis chemical vapor deposition. The phase, microstructure and electrochemical performances of the composites were investigated. Compared with the cathodes without in situ VGCF, the initial discharge capacity of the composite electrode increases from 84 mAh g⁻¹ to 123 mAh g⁻¹ at 3.0 C rate, and the charge transfer resistance varies from 420 Ω to 75 Ω. The possible reasons of those are proposed.     

Investigation on 3-dimensional carbon foams/LiFePO4 composites as function of the annealing time under inert atmosphere

The morphological and electrochemical investigation of 3-dimensional (3D) carbon foams coated with olivine structured lithium iron phosphate as function of the annealing time under nitrogen atmosphere is reported. The LiFePO₄ as cathode material for lithium ion batteries was prepared by a Pechini-assisted sol-gel process. The coating has been successfully performed on commercially available 3D-carbon foams by soaking in aqueous solution containing lithium, iron salts and phosphates at 70 °C for 2-4 h. After drying-out, the composites were annealed at 600 °C for different times ranging from 0.4 to 10 h under nitrogen. The formation of the olivine-like structured LiFePO₄ was confirmed by X-ray diffraction analysis performed on the powder prepared under similar conditions. The surface investigation of the prepared composites showed the formation of a homogeneous coating by LiFePO₄ on the foams. The cyclic voltammetry curves of the composites show an enhancement of electrode reaction reversibility by increasing the annealing time. The electrochemical measurements on the composites showed good performances delivering a discharge specific capacity of 85 mAh g⁻¹ at a discharging rate of C/25 at room temperature after annealing for 0.4 h and 105 mAh g⁻¹ after annealing for 5 h.     

Electrochemical performances of Co-doped LiFePO4/C obtained by hydrothermal method

LiFePO₄, C-coated LiFePO₄ (LiFePO₄/C), and Co-doped LiFePO₄/C as cathode materials for lithium ion batteries are synthesized by a hydrothermal method. The electrochemical properties of the three samples are investigated and compared by galvanostatic cycling, rate capability and cyclic voltammetry (CV) measurements. LiFePO₄, LiFePO₄/C, and Co-doped LiFePO₄/C exhibit initial discharge capacities of 88, 90 and 116 mAh g⁻¹ at 0.1 C, respectively. After annealing at 400 °C, the initial discharge capacities of the three corresponding samples increase to 115, 125 and 132 mAh g⁻¹ at 0.1 C. In both cases, Co-doped LiFePO₄/C shows the best rate performance among the three samples. CV measurements indicate that the improvement of dynamic behavior could be attributed to Co doping. All experimental observations indicate that the preparation of Co-doped LiFePO₄/C offers a way to combine the common methods to improve the performance of LiFePO₄: particle size reduction, intimate conducting phase coating and metal supervalent doping, which explain the enhanced electrochemical properties.     

Synthesis and electrochemical properties of porous LiV3O8 as cathode materials for lithium-ion batteries

In this paper, we report on the synthesis of porous LiV₃O₈ by using a tartaric acid-assisted sol-gel process and their enhanced electrochemical properties for reversible lithium storage. The crystal structure, morphology and pore texture of the as-synthesized samples are characterized by means of XRD, SEM, TEM/HRTEM and N₂ adsorption/desorption measurements. The results show that the tartaric acid plays a pore-making function and the calcination temperature is an important influential factor to the pore texture. In particular, the porous LiV₃O₈ calcined at 300 °C (LiV₃O₈-300) exhibits hierarchical porous structure with high surface area of 152.4 m² g⁻¹. The electrochemical performance of the as-prepared porous LiV₃O₈ as cathode materials for lithium ion batteries is investigated by galvanostatic charge-discharge cycling and electrochemical impedance spectroscopy. The porous LiV₃O₈-300 displays a maximum discharge capacity of 320 mAh g⁻¹ and remains 96.3% of its initial discharge capacity after 50 charge/discharge cycles at the current density of 40 mA g⁻¹ due to the enhanced charge transfer kinetics with a low apparent activity energy of 35.2 kJ mol⁻¹, suggesting its promising application as the cathode material of Li-ion batteries.     

Synthesis and characterization of in situ carbon-coated Li2FeSiO4 cathode materials for lithium ion battery

Li₂FeSiO₄/C composites with in situ carbon coating were synthesized via sol-gel method based on acid-catalyzed hydrolysis/condensation of tetraethoxysilane (TEOS) with sucrose and l-ascorbic acid as carbon additives, respectively. As-obtained Li₂FeSiO₄/C composites prepared with l-ascorbic acid as a carbon additive are composed of nanoparticulate Li₂FeSiO₄ in an intimate contact with a continuous thin layer of residual carbon and exhibit large specific surface area up to 395.7 m² g⁻¹. The results indicate that structure of the residual carbon is graphene-rich with obviously lower disordered/graphene (D/G) ratio. These as-obtained Li₂FeSiO₄/C composites exhibit first discharge capacity of 135.3 mAh g⁻¹ at C/16 and perform cycling stability, which are superior to those of Li₂FeSiO₄/C composites synthesized with sucrose as a carbon additive.     

Characterization and electrochemical properties of carbon-coated Li4Ti5O12 prepared by a citric acid sol-gel method

Since carbon coating can effectively improve electrical wiring of Li₄Ti₅O₁₂ and thus enhance its high rate performance, a novel and simple citric acid sol-gel method for in situ carbon coating is employed in this study. The effects of the amount of the carbon source in the starting xerogel on the particle size, the resistance and the electrochemical performance of the synthesized Li₄Ti₅O₁₂ samples are systematically studied. The physical and electrochemical properties of the obtained samples have been characterized by XRD, TG-DSC, SEM, TEM, BET, A.C. impedance, galvanostatically charge-discharge and cyclic voltammetry tests. The results show that the initial amount of the carbon source in the starting xerogel is a critical factor which determines the content of the coated carbon and the pore volume, therefore governs the high rate performance of the Li₄Ti₅O₁₂/C composites. The Li₄Ti₅O₁₂/C composite with in situ carbon coating of 3.5 wt% exhibits the best electrochemical performance which delivers delithiation capacities of 143.6 and 133.5 mAh g⁻¹ with fairly stable cycling performance even after 50 cycles at 0.5C and 1C rate, respectively.     

A novel method to synthesize anatase TiO2 nanowires as an anode material for lithium-ion batteries

We demonstrate a simple and novel approach for the synthesis of a kind of anatase TiO₂ nanowires. The method is based on a hydrothermal method under normal atmosphere without using the complex Teflon-lined autoclave, high concentrations NaOH solution and long react time. The as-prepared materials are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical measurements. The obtained anatase TiO₂ nanowires show excellent performance. There is a potential plateau at 1.77 and 1.88 V in the process of Li insertion and extraction, and the initial Li insertion/extraction capacities are 283 and 236 mAh g⁻¹ at the density of 20 mA g⁻¹, respectively. In the 20th cycle, the reversible capacities still remain about 216 and 159 mAh g⁻¹ at the current densities of 20 and 200 mA g⁻¹, respectively, and the coulombic efficiency is more than 98%, exhibiting excellent electrochemical performance.     

Synthesis of MnO/C composites through a solid state reaction and their transformation into MnO2 nanorods

MnO nanospheres encapsulated in carbon (MnO/C) composites were synthesized through a one-step solid state reaction between potassium permanganate and salicylic acid at 700 °C, which could be transformed into MnO₂ nanorods after being annealed in ambient atmosphere. Their formation mechanisms and electrochemical performances as anodes in Li-ion batteries (LIBs) were investigated. The first discharge capacity of MnO/C composites was 585.9 mA h g⁻¹, while that of MnO₂ was 1269 mA h g⁻¹, indicating their potential applications in LIBs.     

Porous Li4Ti5O12 anode material synthesized by one-step solid state method for electrochemical properties enhancement

A porous Li₄Ti₅O₁₂ anode material was successfully synthesized from mixture of LiCl and TiCl₄ with 70 wt% oxalic acid by a modified one-step solid state method. The anode material Li₄Ti₅O₁₂ exhibited a cubic spinel structure and only one voltage plateau occurred around 1.5 V. The initial capacity of porous Li₄Ti₅O₁₂ was 167 and 133 mAh g⁻¹ at 0.5 and 1C charge/discharge rate, respectively, and the capacity retention maintained above 98% after 200 cycles. The porous Li₄Ti₅O₁₂ structure showed promising rate performance with a capacity of 70 mAh g⁻¹ at charge/discharge 10C rate after 200 cycles. It was demonstrated that the porous structure could withstand 50C charge/discharge rate and exhibited excellent cycling stability.     

Synthesis and electrochemical properties of Li4Ti5O12

The spinel compound Li₄Ti₅O₁₂ was synthesized by a solid state method. In this synthesizing process, anatase TiO₂ and Li₂CO₃ were used as reactants. The influences of reaction temperature and calcination time on the properties of products were studied. When calcination temperature was 750 °C and calcination temperature was 24 h, the products exhibited good electrochemical properties. Its discharge capacity reached 160 mAh g⁻¹ and its capacity retention was 97% at the 50th cycle when the current rate was 1 C. When current rate increased to 10 C, its first discharge capacity could reach 136 mAh g⁻¹, and its capacity retention was 85% at the 50th cycle.     

Fabrication of highly ordered porous nickel phosphide film and its electrochemical performances toward lithium storage

Highly ordered porous Ni₃P film was successfully electrodeposited through a self-assembled monodisperse polystyrene sphere template on copper substrate after heat treatment. The spherical pores left in the film after the removal of polystyrene spheres are well-ordered and close-packed. The diameter of the pores arranged in the film is about 800 nm and the thickness of the wall connecting adjacent pores is 60 nm. As anode for lithium ion batteries, the nanostructured porous Ni₃P film exhibits improved capability and reversibility over the dense one. After 50 cycles, the reversible capacity of the porous Ni₃P film is 403 mAh g⁻¹ and 239 mAh g⁻¹ at 0.2 C and 2 C, maintaining 78.1% and 67.9% of the capacity in the 2nd cycle, respectively. The enhanced electrochemical performance of the porous film is attributed to the better contact between Ni₃P and electrolyte, which provides more sites for Li⁺ accommodation, shortens the diffusion length of Li⁺ and enhances the kinetics of electrode process. Moreover, the porous structure is stable and can sustain well even after 50 cycles.     

A precursor route to synthesize mesoporous γ-MnO2 microcrystals and their applications in lithium battery and water treatment

MnCO₃ microstructures, including 2.3 μm microplates with the thickness of 200 nm and 3.1 μm microspheres stacked with 50 nm-thick sheets, were hydrothermally prepared in the assistance of sodium dodecyl benzene sulphonate (SDBS) and dodecyl sulfonic acid sodium (SDS), respectively. With the as-synthesized MnCO₃ as precursors followed by annealing at 400 °C for 4 h, mesoporous γ-MnO₂ microplates and microspheres with the pore size of 4-50 nm, which basically preserved the initial shapes, were obtained. The Brunauer-Emmett-Teller surface areas of the as-prepared γ-MnO₂ microplates and microspheres were 52.1 m² g⁻¹ and 50.2 m² g⁻¹, respectively. The electrochemical property tests over Li⁺ batteries showed that the initial discharge capacity of γ-MnO₂ microplates and microspheres were 1997 mAh g⁻¹ and 1533 mAh g⁻¹. Noticeably, even after 100 cycles, the discharge capacity of γ-MnO₂ microplates was still as high as 626 mAh g⁻¹, indicating the decent cycle behavior. In addition, mesoporous γ-MnO₂ was also applied as adsorbents in water treatment, and γ-MnO₂ microplates and microspheres could remove about 55% and 80% of Congo red.     

Electrochemical lithium storage performance of ternary Zn-Co-Ni alloy thin film as negative electrodes by electrodeposition method

Ternary Zn-Co-Ni alloy film electrode as an anode has been investigated, for the first time, for the purpose of electrochemical lithium storage in lithium-ion batteries. In this study, the ternary Zn-Co-Ni alloy film electrode is prepared by electroplating method. The electrodes were examined using X-ray diffraction (XRD), FE-SEM with EDX, and impedance studies. The electrochemical results demonstrate that the Zn-Co-Ni alloy film electrode delivers an initial discharge capacity of 281 mAh g⁻¹ and improves to 650 mAh g⁻¹ at the end of 30th cycling with no capacity fading at 0.1 C rate. The charge-discharge properties of the Zn-Co-Ni alloy film electrode are as follows: insertion capacity of 650 mAh g⁻¹ and delithiation capacity of 512 mAh g⁻¹ in the 30th cycling, coulombic efficiency of about 80.0% and good cycling behavior. The results suggest that the ternary Zn-Co-Ni alloy thin film electrode obtained via electroplating shows a good candidate anode material for lithium-ion batteries.     

Electrochemical performance of magnetron sputter deposited LiFePO4-Ag composite thin film cathodes

LiFePO₄ thin films have been sputtered from a pure LiFePO₄ target onto Ag/SS, Ag/Si₃N₄/Si and Si₃N₄/Si substrates. All of the deposited films were annealed at 973 K for 1 hr in H₂/Ar (5 %) atmosphere. Substrate induced microstructural and crystallographic evolutions have been observed by a scanning electron microscope and X-ray diffraction. Energy dispersion spectra and X-ray photoelectron spectra revealed that Ag was mixed in the LiFePO₄ films deposited on Ag under layers. Ceramic metal composite thin films were obtained. The film conductivity (1 × 10^− 3 Scm^− 1) is therefore elevated by an order of six, compared with pure LiFePO₄ (10^− 9 Scm^− 1). The electrochemical measurements of the LiFePO₄-Ag films showed a flat plateau at 3.4 V (v.s. Li/Li⁺) and a reversible capacity of 80 mAh/g. Optimization of Ag contents may further improve the discharge capacity.     

Preparation of Fe2O3/graphene composite and its electrochemical performance as an anode material for lithium ion batteries

The micro-sized sphere Fe₂O₃ particles doped with graphene nanosheets were prepared by a facile hydrothermal method. The obtained Fe₂O₃/graphene composite as the anode material for lithium ion batteries showed a high discharge capacity of 660 mAh g⁻¹ during up to 100 cycles at the current density of 160 mA g⁻¹ and good rate capability. The excellent electrochemical performance of the composite can be attributed to that graphene served as dispersing medium to prevent Fe₂O₃ microparticles from agglomeration and provide an excellent electronic conduction pathway.     

In situ synthesis of Co3O4/graphene nanocomposite material for lithium-ion batteries and supercapacitors with high capacity and supercapacitance

Co₃O₄/graphene nanocomposite material was prepared by an in situ solution-based method under reflux conditions. In this reaction progress, Co²⁺ salts were converted to Co₃O₄ nanoparticles which were simultaneously inserted into the graphene layers, upon the reduction of graphite oxide to graphene. The prepared material consists of uniform Co₃O₄ nanoparticles (15-25 nm), which are well dispersed on the surfaces of graphene nanosheets. This has been confirmed through observations by field emission scanning electron microscopy, transmission electron microscopy and atomic force microscopy. The prepared composite material exhibits an initial reversible lithium storage capacity of 722 mAh g⁻¹ in lithium-ion cells and a specific supercapacitance of 478 F g⁻¹ in 2 M KOH electrolyte for supercapacitors, which were higher than that of the previously reported pure graphene nanosheets and Co₃O₄ nanoparticles. Co₃O₄/graphene nanocomposite material demonstrated an excellent electrochemical performance as an anode material for reversible lithium storage in lithium ion cells and as an electrode material in supercapacitors.     

Electrochemical properties of carbon-coated LiFePO<Subscript>4</Subscript> and LiFe<Subscript>0.98</Subscript>Mn<Subscript>0.02</Subscript>PO<Subscript>4</Subscript> cathode materials synthesized by solid-state reaction

Olivine structured LiFePO4/C (lithium iron phosphate) and Mn2+-doped LiFe0. 98Mn0. 024/C powders were synthesized by the solid-state reaction. The effects of manganese partial substitution and different carbon content coating on the surface of LiFePO4 were considered. The structures and electrochemical properties of the samples were measured by X-ray diffraction (XRD), cyclic voltammetry (CV), charge/discharge tests at different current densities, and electrochemical impedance spectroscopy (EIS). The electrochemical properties of LiFePO4 cathodes with x wt. ％ carbon coating (x=3, 7, 11, 15) at γ=0. 2C, 2C (1C=170 mAh·g-1) between 2. 5 and 4. 3 V were investigated. The measured results mean that the LiFePO4 with 7 wt. ％ carbon coating shows the best rate performance. The discharge capacity of LiFe0. 98Mn0. 02PO4/C composite is found to be 165 mAh·g 1 at a discharge rate, γ=0. 2C, and 105 mAh·g-1 at γ=2C, respectively. After 10cycles, the discharge capacity has rarely fallen, while that of the pristine LiFePO4/C cathode is 150 mAh·g-1 and 98 mAh·g-1 at γ=0. 2 and 2C, respectively. Compared to the discharge capacities of both electrodes above, the evident improvement of the electrochemical performance is observed, which is ascribed to the enhancement of the electronic conductivity and diffusion kinetics by carbon coating and Mn2+-substitution.     

Structural and electrochemical hydrogen storage properties of Mg2Ni-based alloys

Four different methods, i.e. hydriding combustion synthesis + mechanical milling (HCS + MM), induction melting (followed by hydriding) + mechanical milling (IM(Hyd) + MM), combustion synthesis + mechanical milling (CS + MM) and induction melting + mechanical milling (IM + MM), were used to prepare Mg₂Ni-based hydrogen storage alloys used as the negative electrode material in a nickel-metal hydride (Ni/MH) battery. The structural and electrochemical hydrogen storage properties of the Mg₂Ni-based alloys have been investigated systematically. The XRD results indicate that the as-milled products show nanocrystalline or amorphous-like structures. Electrochemical measurements show that the as-milled hydrides exhibit higher discharge capacity and better electrochemical kinetic property than the as-milled alloys. Among the four different methods, the HCS + MM product possesses the highest discharge capacity (578 mAh g⁻¹), the best high rate dischargeability (HRD) and the highest exchange current density (58.8 mA g⁻¹). It is suggested that the novel method of HCS + MM is promising to prepare Mg-based hydrogen storage electrode alloy with high discharge capacity and activity.     

Corrosion inhibition of carbon steel in tetra-n-butylammonium bromide aqueous solution by benzotriazole and Na3PO4

The corrosion inhibition behavior of benzotriazole, Na₃PO₄ and their mixture on carbon steel in 20 wt.% (0.628 mol l⁻¹) tetra-n-butylammonium bromide aerated aqueous solution was investigated by weight-loss test, potentiodynamic polarization measurement, electrochemical impedance spectroscopy and scanning electron microscope/energy dispersive X-ray techniques. The inhibition action of BTA or SP or inhibitors mixture on the corrosion of carbon steel is mainly due to the inhibition of anodic process of corrosion. The results revealed that inhibitors mixtures have shown synergistic effects at lower concentration of inhibitors. At 2 g l⁻¹ BTA and 2 g l⁻¹ SP showed optimum enhanced inhibition compared with their individual effects.     

Synthesis of LiFePO4/C cathode materials through an ultrasonic-assisted rheological phase method

LiFePO₄/C active material was synthesized using an ultrasonic-assisted rheological phase method. In addition, polyvinyl butyral (PVB) was added in various concentrations to provide carbon coating on the surface of the LiFePO₄ particles for enhanced electrical conductivity. The crystal structure, morphology, and carbon coating layer of the synthesized LiFePO₄/C was analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), respectively. The electrochemical performance of LiFePO₄/C, such as initial capacity, rate capability, cycling performance and EIS, were also evaluated. The synthesized particle had a size range of 100-150 nm and a carbon layer of about 8 nm. The LiFePO₄/C (5 wt% PVB) delivered an initial discharge capacity of 167.5 mAh/g at a 0.1 C rate. It also showed an excellent capacity retention ratio of 100% after the 50th charging/discharging. EIS results demonstrate that the charge transfer resistance of the sample decreases greatly by coating with 5 wt% PVB.