Preparation and characterization of Li4Ti5O12 thin films by rapid thermal annealing

Li₄Ti₅O₁₂ thin films were prepared by solution deposition followed by rapid thermal annealing (RTA). The structural and electrochemical properties of the film were comparatively studied with the one prepared by conventional furnace annealing (CFA) through X-ray diffraction, scanning electron microscopy, cyclic voltammetry, galvanostatic lithium insertion–extraction experiments, and electrochemical impedance spectroscopy. The results show that the film prepared by RTA is homogeneous, crack-free, and pure spinel phase, and its grain size is smaller than that of the film prepared by CFA. The lithium extraction capacity of the film prepared by RTA is 59.5 μAh cm^?2 μm^?1, which is higher than 55.9 μAh cm^?2 μm^?1 of the film prepared by CFA. The capacity loss of the film prepared by RTA after being cycled 50 times is 3.1 %, which is 3.2 % lower than that of 6.3 % for the film prepared by CFA.     

Influence of annealing temperature on microstructural and electrochemical properties of rf-sputtered LiMn2O4 film cathodes

The microstructural and electrochemical properties of rf-sputtered LiMn₂O₄ films were investigated as a function of post-deposition process. The degree of crystallization in the films gradually increased with the increase of annealing temperature (T _a). The films annealed at T _a?=?973 K exhibited characteristic peaks with predominant (111) orientation representing the cubic spinel structure of Fd3m symmetry. The estimated Mn–Mn and Mn–O distances obtained from the X-ray diffraction data were observed to be increased slightly with T _a. Characteristic changes in surface morphological features were observed as a function of T _a as evidenced from scanning electron microscopy. The estimated root mean square (RMS) roughness of the films increased from 97 to 161 nm with augmentation of T _a. The electrochemical studies, viz. cyclic voltammetry (CV), specific discharge capacity and Li ion diffusion coefficient were carried out for annealed LiMn₂O₄ films in saturated aqueous electrolyte (Li₂SO₄) in the potential window of 0–1.2 V and correlated with surface morphology and grain size. The LiMn₂O₄ films annealed at T _a?=?973 K exhibited better electrochemical performance and demonstrated a discharge capacity of about 53.5 μA h cm^?2 μm^?1 with diffusion coefficient of 1.2?×?10^?13 cm² s^?1.     

Comparative study of LiMn2O4 thin film cathode grown at high, medium and low temperatures by pulsed laser deposition

LiMn₂O₄ thin films with different crystallizations were respectively grown at high, medium and low temperatures by pulsed laser deposition (PLD). Structures, morphologies and electrochemical properties of these three types of thin films were comparatively studied. Films grown at high temperature (?873 K) possessed flat and smooth surfaces and were highly crystallized with different textures and crystal sizes depending on the deposition pressure of oxygen. However, films deposited at low temperature (473 K) had rough surfaces with amorphous characteristics. At medium temperature (673 K), the film was found to consist mainly of nano-crystals less than 100 nm with relatively loose and rough surfaces, but very dense as observed from the cross-section. The film deposited at 873 K and 100 mTorr of oxygen showed an initial discharge capacity of 54.3 μAh/cm² μm and decayed at 0.28% per cycle, while the amorphous film had an initial discharge capacity of 20.2 μAh/cm² μm and a loss rate of 0.29% per cycle. Compared with the highly crystallized and the amorphous films, nano-crystalline film exhibited higher potential, more capacity and much better cycling stability. As high as 61 μAh/cm² μm of discharge capacity can be achieved with an average decaying rate of only 0.032% per cycle up to 500 cycles. The excellent performance of nano-crystalline film was correlated to its microstructures in the present study.     

Electrochemical performance of LiMn2O4 microcubes prepared by a self-templating route

LiMn₂O₄ microcubes with a size of 10–15 μm have been synthesized by a facile self-templating route starting from cubic MnCO₃. The LiMn₂O₄ microcubes exhibit a hierarchical structure, where the cubes are stacked from parallel plates with a thickness of 200 nm, where each plate is composed of interconnected nanoparticles with a size of around 200 nm. The cubic LiMn₂O₄ shows excellent rate capability and high-rate cycling stability. At 10 C, it can yield a discharge capacity of 108 mAh g^?1. A discharge capacity of 88 mAh g^?1 can be retained after 100 cycles at 10 C. The excellent electrochemical performance makes it a promising cathode for high-power Li-ion batteries.     

Preparation and characterization of nickel hexacyanoferrate films for the removal of cesium ion by electrically switched ion exchange (ESIX)

The method of electrically switched ion exchange (ESIX) involves the sequential application of reduction and oxidation potentials to an ion exchange film to induce the respective loading and unloading of Cs⁺. In this study, four films of nickel hexacyanoferrate were prepared on nickel electrodes with different preparation procedures. Films were characterized by SEM/EDX. Each film shows a different performance with regard to Cs⁺ separation. Scanning electron microscopy was used to characterize the modified film surfaces. Cyclic voltammetry was used to investigate the ion exchange capacity and stability. The four films show a better capacity for Cs⁺ separation compared to previous methods for the deposition of ESIX films. An optimal nickel hexacyanoferrate film was generated when using an applied potential of 0.2 V relative to a saturated calomel electrode (SCE) to generate the nucleation sites, followed by a 1.3 V vs. SCE potential during the growth stage of the film. This film demonstrated the highest film capacity for ion exchange initially (17.3 × 10^?3 C cm^?2) and again after 1000 cycles (11.1 × 10^?3 C cm^?2).     

Lithium intercalation in thin amorphous-silicon films

Electrochemical intercalation of lithium in thin films of amorphous hydrogenated silicon (a-Si:H), deposited at temperatures of 100 and 250°C on stainless-steel substrates, is studied. It is shown that the discharge capacity of films of identical thicknesses manufactured at a temperature of 250°C is greater than that for films produced at of 100°C. Dependence of the discharge capacity of the films manufactured at 250°C on their thickness is examined. It is established that an increase in the film thickness leads to acceleration of the decrease in the discharge capacity in the course of cycling. At a current density of 0.175 mA cm^?2, the discharge capacity of films 0.25 and 1.35 μm thick equals nearly 2 Ah g^?1 in a third cycle, whereas in a hundredth cycle it amounts to 1.10 and 0.37 Ah g^?1, respectively. The diffusion coefficient for lithium in the films is equal to ～10^-13 cm²s^?1.     

Raman spectroscopic characterization of the microstructure of V2O5 films

The vanadium pentoxide (V₂O₅) films were deposited on silicon wafer by DC magnetron sputtering. By Raman scattering measurements, the microstructure properties of the V₂O₅ films prepared with different O₂–Ar gas flow ratios and annealed at different temperatures were studied, respectively. The results revealed that the increase of O₂–Ar gas flow ratio during sputtering was of advantage to prepare the V₂O₅ film with desired layer structure. A high post-annealing temperature (below 500 °C) induced the crystallization and the formation of the integrated structure of V₂O₅ film. However, it was found that both intensities of Raman scattering peaks at 146 cm^?1 and 994 cm^?1, respectively, decreased for samples annealed at a temperature of 550 °C. The peak at 146 cm^?1 was attributed to skeleton bent vibration and that at 994 cm^?1 was due to the stretching vibration of vanadyl V=O_A bond. It showed that the high-temperature annealing was believed to have distorted the microstructure of V₂O₅ films. The oxygen vacancies were, therefore, induced, which benefited the formation of V-O_A-V bonds between layers. The result of X-ray diffraction measurements was in good agreement with that of Raman scattering spectra.     

Simple chemical route for nanorod-like cobalt oxide films for electrochemical energy storage applications

We used a simple chemical synthesis route to deposit nanorod-like cobalt oxide thin films on different substrates such as stainless steel (ss), indium tin oxide (ITO), and microscopic glass slides. The morphology of the films show that the films were uniformly spread having a nanorod-like structure with the length of the nanorods shortened on ss substrates. The electrochemical properties of the films deposited at different time intervals were studied using cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS). The film deposited after 20 cycles on ss gave the highest specific capacity of 67.6 mAh g^?1 and volumetric capacity of 123 mAh cm^?3 at a scan rate 5 mV s^?1 in comparison to 62.0 mAh g^?1 and 113 mAh cm^?3 obtained, respectively, for its counterpart on ITO. The film electrode deposited after 20 cycles on ITO gave the best rate capability and excellent cyclability with no depreciation after 2000 charge–discharge cycles.     

Morphology-controllable synthesis of LiMn2O4 particles as cathode materials of lithium batteries

We reported a new method for the preparation of morphology-controllable LiMn₂O₄ particles. In this method, dimension-different MnO₂ nanowires synthesized hydrothermally by adjusting the reaction temperature were used as the precursor. The morphology and structure of the resulting products were characterized with scanning electron microscope and X-ray diffraction, and the performances of the prepared LiMn₂O₄ samples as cathode material of lithium batteries were investigated by cyclic voltammetry and galvanostatic charge/discharge test. The results indicate that the morphology of LiMn₂O₄ transforms from tridimensional particle (TP) to unidimensional rod (UR) through quadrate lamina (QL) with increasing the diameter and length of MnO₂ nanowires. Although the cyclic stabilities of LiMn₂O₄-TP, LiMn₂O₄-QL, and LiMn₂O₄-UR are very close (the 0.1 C capacity after 50 cycles is 101, 93, and 99 mAh g^?1 at 25 °C, and 84, 78, and 82 mAh g^?1 at 50 °C, respectively), LiMn₂O₄-QL delivers much higher rate capacity (about 70 mAh g^?1 at 5 C and 30 mAh g^?1 at 10 C) than LiMn₂O₄-TP and LiMn₂O₄-UR (about 20 mAh g^?1 at 5 C, 3 mAh g^?1 at 10 C, 25 mAh g^?1 at 5 C, and 3 mAh g^?1 at 10 C).     

Structural and electrical properties of chemical solution deposited (Bi0.9Tb0.1)(Fe0.975 TM 0.025)O3±δ (TM = Ni, Mn and Ti) thin films

Effects of Tb and transition metal (TM = Ni, Mn and Ti) ions co-doping on the structural, electrical and ferroelectric properties of the BiFeO₃ thin films prepared by using a chemical solution deposition method were reported. From X-ray diffraction and Raman scattering analyses, distorted rhombohedral perovskite structures were observed for all thin films. Improved electrical and ferroelectric properties were observed for the co-doped thin films. Among the thin films, the lowest leakage current density of 2.67 × 10^?6 A/cm² (at 100 kV/cm), large remnant polarization (2P _r ) of 82.2 μC/cm² and low coercive field (2E_c) of 680 kV/cm (at 1,036 kV/cm) were measured for the (Tb, Mn) co-doped thin film.     

Synthesis of Cu2ZnSnS4 thin films by dip-coating method without sulphurization

Quaternary Cu₂ZnSnS₄ (CZTS) thin films, a promising absorber material for solar cells has been successfully deposited on glass substrates by cost effective simple dip-coating method without using either polluting chemicals or expensive vacuum facilities. X-ray diffraction pattern reveals the formation of CZTS films with tetragonal type kesterite structure. The Raman spectra of the prepared films exhibited resonance peaks corresponding to the CZTS phase. The scanning electron microscopic image shows the formation of films with smooth surface. The surface topography studied using atomic force microscope gives an rms roughness of 1.6 nm. The Hall effect studies indicate that the prepared films are p-type with a carrier concentration of 4.77 × 10²⁰ cm^?3. The energy dispersive X-ray analysis result indicate the presence of Cu, Zn, Sn and S in the film. The absorption coefficient was found to be the order of 10⁴ cm^?1 and the band gap has been found to be 1.5 eV.     

Sr,Zn co-doped TiO<Subscript>2</Subscript> xerogel film made of uniform spheres for high-performance dye-sensitized solar cells

This study comes up with the facile preparation of Sr,Zn co-doped TiO₂ xerogel film for boosting the short circuit current density of dye-sensitized solar cells (DSCs). The film contains 2.5-μm-diameter spheres assembled from 60 nm nanoparticles. X-ray photoelectron spectroscopy (XPS) shows that Sr²⁺ and Zn²⁺ ions to be well incorporated into the TiO₂ crystal lattice without forming specific strontium and zinc compositions. The crystallite size, phase composition, and band structure of the spheres depend on the dopants concentration. Isolated energy levels near valence band as a result of the foreign ions introduction improve the photocatalytic activity of the prepared TiO₂ spheres, enhancing the short circuit current density of the cells. The DSC co-doped with 0.075 at.% Sr and 0.4 at.% Zn showed the highest power conversion efficiency of 7.87 % and short circuit current density of 18.75 mA cm^?2 thanks to lower charge transfer resistance (2.16 Ω cm²), lower electron transit time (1.19 ms), and higher electron diffusion coefficient (18.1 × 10⁴ cm² S^?1) compared to the other cells, demonstrated by electrochemical impedance spectroscopy (EIS). The concept of the simultaneous introduction of alkaline earth ions and transition ions into TiO₂ xerogel films will open up a new insight into the fabrication of high performance DSCs.     

Ultra light tunable capacitor based on PZT thin film deposited onto aluminium foil

Lead zirconate titanate (PZT) thin films with a Zr/Ti ratio of 57/43, elaborated by a derived sol–gel process, have been deposited onto bare and RuO₂ coated aluminium substrate 16 μm thick. Commercial aluminium foil presents many advantages as ultra light weight (43 g m^?2), conformability, conduction, can be easily cut, and is one of the cheapest substrates used for PZT thin films deposition (<0.1$ m^-2). XRD measurements have shown a well crystallized PZT in the perovskite structure and ferroelectric behaviour has also been observed. By the use of a RuO₂ film 100 nm thick at the PZT/aluminium interface, the coercive field and tunability values have been strongly improved despite an increase of the dielectric losses. The lead excess introduced in the precursor solution has been increased up to 65 % in order to lower the crystallization temperature of the PZT around 560 °C and tunability has been studied as a function of annealing time and temperature.     

Preparation and properties of rare earth (Eu, Tb, Ho) and transition metal (Co) co-doped BiFeO3 thin films

Ferroelectric (Bi_0.9 RE _0.1)(Fe_0.975Co_0.025)O_3-δ (RE = Eu, Tb and Ho) thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates via a chemical solution deposition method. All thin films were crystallized in a distorted rhombohedral perovskite structure confirmed by using an X-ray diffraction and a Raman scattering analyses. Compared to the pure BiFeO₃ thin film, improved electrical and ferroelectric properties were observed for the co-doped thin films. Among the thin films, the lowest leakage current density of 4.28 × 10^?5 A/cm² was measured at an applied electric field of 100 kV/cm for the (Bi_0.9Ho_0.1)(Fe_0.975Co_0.025)O_3-δ thin film. This value is approximately three orders lower than that of the pure BFO thin film. Furthermore, a large remnant polarization (2P _r) of 60.2 μC/cm² and a low coercive field (2E _c ) of 561 kV/cm at 980 kV/cm were observed from the (Bi_0.9Ho_0.1)(Fe_0.975Co_0.025)O_3-δ thin film.     

Synthesis and charge-discharge performance of Li<Subscript>5</Subscript>SiN<Subscript>3</Subscript> as a cathode material of lithium secondary batteries

Li₅SiN₃ crystals are synthesized by direct reaction between Li₃N and Si₃N₄ with the molar ratio Li₃N/Si₃N₄ of 10:1. Reaction is performed at 1073 K for 1 h under a nitrogen atmosphere of 700 Torr. The lattice constant determined by the X-ray powder diffraction method is 4.718 Å. Four broad Raman peaks are observed at 196, 286, 580, and 750 cm^?1. By analogy with LiMgN, the broad peak at 580 cm^?1 with a half width of 140 cm^?1 is attributed to homogenously random distribution of Li and Si atoms. The band gap of Li₅SiN₃ is found to be a direct gap of about 2.5 eV by optical absorption and photoacoustic spectroscopy methods. Comparison with the conventional cathode materials for lithium ion batteries, this gap value is close to d-d transition energy of Mn in LiMn₂O₄ (1.63 eV or 2.00 eV) and that of Co in LiCoO₂ (2.1 eV), suggesting that Li₅SiN₃ is a possible cathode material. The 5 × 5 mm²-sized lithium secondary battery of Li₅SiN₃ cathode/propylene carbonate + LiClO₄ electrolyte/Li anode structure shows a discharge capacity of 2.4 μAh cm^?2 for a discharge current of 1.0 μA.     

Investigation on structural,morphological, and electrochemical properties of mesoporous cobalt oxide-infiltrated NaY zeolite

We report the synthesis and characterization of a new mesoporous cobalt oxide-infiltrated NaY zeolite prepared by ion-exchange route. The scanning electronic microscopy (SEM) image shows homogenous and uniform grains size distributions smaller than 1 μm, unlike to CoO_x particles, elaborated under the same conditions. The energy dispersion spectroscopy (EDS) data confirm the presence of cobalt, oxygen, silicon, and aluminum. The X-ray diffraction indicates a partial crystallization of cobalt oxide and the formation of new phases. N₂ adsorption-desorption measurement shows a high-specific surface area for the modified material (579 m² g^?1), with Barrett-Joyner-Halenda (BJH) pore diameters in the range (3–8 nm). The cyclic voltammetry indicates a typical faradic process, and the electrochemical impedance spectroscopy exhibits Warburg diffusion at low frequencies. The charge-discharge curve shows a clear improvement in the charge capacity of the modified material compared to CoO_x, due to the increased specific surface area. The galvanostatic charge-discharge tests of the modified electrode exhibit a typical battery behavior preceded by a pseudo-capacitive phenomenon.     

Facile synthesis of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> microsheets with porous micro-nanostructure as high-rate cathode materials for Li-ion batteries

Porous LiMn₂O₄ microsheets with micro-nanostructure have been successfully prepared through a simple carbon gel-combustion process with a microporous membrane as hard template. The crystal structure, morphology, chemical composition, and surface analysis of the as-obtained LiMn₂O₄ microsheets are characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscope (XPS). It can be found that the as-prepared LiMn₂O₄ sample presents the two-dimensional (2-D) sheet structure with porous structure comprised with nano-scaled particles. As cathode materials for lithium-ion batteries, the obtained LiMn₂O₄ microsheets show superior rate capacities and cycling performance at various charge/discharge rates. The LiMn₂O₄ microsheets exhibit a higher charge and discharge capacity of 137.0 and 134.7 mAh g^?1 in the first cycle at 0.5 C, and it remains 127.6 mAh g^?1 after 50 cycles, which accounts for 94.7% discharge capacity retention. Even at 10 C rate, the electrode also delivers the discharge capacity of 91.0 mAh g^?1 after 300 cycles (93.5% capacity retention). The superior electrochemical properties of the LiMn₂O₄ microsheets could be attributed to the unique microsheets with porous micro-nanostructure, more active sites of the Li-ions insertion/deinsertion for the higher contact area between the LiMn₂O₄ nano-scaled particles and the electrolyte, and better kinetic properties, suggesting the applications of the sample in high-power lithium-ion batteries.     

Protic ionic liquid-based gel polymer electrolyte: structural and ion transport studies and its application in proton battery

Proton-conducting free standing gel polymer electrolyte (GPE) films containing protic ionic liquid, 1-butyl-3-methylimidazolium hydrogen sulphate, immobilized in blend of poly(vinylidenefluoride-co-hexafluoropropylene) and poly(vinylpyrrolidone) have been prepared by solution-cast technique. Films have been characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscope (SEM), differential scanning calorimetry (DSC), complex impedance spectroscopy, and cyclic voltammetry. Ionic conductivity of the semicrystalline and porous GPE films has been obtained as ~3.9?×?10^?3 S cm^?1 at room temperature. Protonic nature of conduction in the films has been established by performing cyclic voltammetry and complex impedance spectroscopy on the cells having both blocking (stainless steel) and both reversible electrodes (Zn + ZnSO₄.7H₂O). The electrochemical stability window of the films has been found as ~3.8 V. The highest conducting film has been used as a separator and proton conductor to fabricate a proton battery of configuration Zn + ZnSO₄.7H₂O |GPE film| PbO₂ + V₂O₅. The battery shows an open circuit voltage of ~1.62 V. Energy density of the cell has been obtained as 35.2 W h kg^?1 for low current drain. Rechargeability of the cell has been tested for ten cycles. The maximum discharge capacity of the cell has been obtained as ~2.50 mA h g^?1 during the first discharge cycle.     

Structural improvement of ZnO electrodes through solution-processed routes for enhancing open-circuit voltage in dye-sensitized solar cells

We report herein one of our recent studies on nanostructured ZnO electrodes for application in dye-sensitized solar cells, focusing on achieving a higher open-circuit voltage (V_OC). ZnO films were obtained through solution-processed routes including pyrolytic conversion of layered hydroxide zinc acetate (LHZA) films deposited on a fluorine-doped tin oxide-coated conducting glass substrate by a chemical bath deposition method. The morphology of the initial LHZA and the converted ZnO films was tuned from a thick (approximately 12 μm) flower bed-/lawn-like bilayer structure to a thin (1.2 μm) lawn-like quasi-monolayer structure by decreasing the Zn source concentration in the chemical bath. V_OC was found to be enhanced with this morphological change from 0.692 (the bilayer structure) to 0.735 V (the quasi-monolayer structure). Fine tuning of the quasi-monolayer structure by introducing the grain growth effect led to V_OC of the cell as high as 0.807 V, although a short-circuit photocurrent density (J_SC) remained low. Further attempts were then made to increase J_SC while maintaining the high V_OC. When the thickness of the lawn-like monolayer film was increased up to approximately 5 μm, the resultant cell showed V_OC?=?0.750 V, J_SC?=?6.20 mA cm^?2 and a conversion efficiency (η) of 2.83%. The film with a modified flower bed-/lawn-like bilayer structure approximately 11 μm in thickness finally yielded V_OC?=?0.741 V, J_SC?=?13.6 mA cm^?2, and η?=?5.44%.     

Optical,electrical, and electrochemical behavior of p-type nanostructured SnO<Subscript>2</Subscript>:Ni (NTO) thin films

The physical and electrochemical properties of sol-gel synthesized nickel-doped tin oxide (NTO) thin films were investigated. The X-ray diffraction results showed that NTO samples exhibited a tetragonal structure. The average crystallite size and the unit cell volume of the films were reduced by Ni increment, while the stacking fault probability was increased. Furthermore, the field-emission scanning electron microscopy images clearly displayed that the worm-like surface morphology of the SnO₂ thin films was altered to the spherical feature in 3 and 10 mol% NTO samples. Moreover, by virtue of Ni incorporation, the average transparency of the SnO₂ thin films rose up from 67 to 85% in the visible region; also, the optical band gap of the SnO₂ sample (3.97 eV) increased and the thin film with 3 mol% dopant concentration showed a maximum value of 4.22 eV. The blue/green emission intensities of photoluminescence spectra of SnO₂ thin film changed via Ni doping. The Hall effect measurements revealed that by Ni addition, the electrical conductivity of tin oxide thin films altered from n- to p-type and the carrier concentration of the films decreased due to the role of Ni²⁺ ions which act as electron acceptors in NTO films. In contrast, 20 mol% Ni-doped sample had the highest mobility about 9.65 cm² (V s)^?1. In addition, the cyclic voltammogram of NTO thin films in KOH electrolyte indicated the charge storage capacity and the surface total charge density of SnO₂ thin films enhanced via Ni doping. Moreover, the diffusion constant of the samples increased from 2?×?10^?15 to 6.5?×?10^?15 cm² s^?1 for undoped and 5 mol% dopant concentration. The electrochemical impedance spectroscopy of the NTO thin films in two different potentials showed the different electrochemical behaviors of n- and p-type thin films. It revealed that the 20 mol% NTO thin film had maximum charge transfer at lower applied potential.