MoO2 synthesized by reduction of MoO3 with ethanol vapor as an anode material with good rate capability for the lithium ion battery

MoO₂ synthesized through reduction of MoO₃ with ethanol vapor at 400 °C was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Its electrochemical performance as an anode material for lithium ion battery was tested by cyclic voltammetry (CV) and capacity measurements. During the reduction process, the starting material (MoO₃) collapsed into nanoparticles (∼100 nm), on the nanoparticles remains a carbon layer from ethanol decomposition. Rate capacity and cycling performance of the as-prepared product is very satisfactory. It displays 318 mAh g⁻¹ in the initial charge process with capacity retention of 100% after 20 cycles in the range of 0.01–3.00 V vs. lithium metal at a current density of 5.0 mA cm⁻², and around 85% of the retrievable capacity is in the range of 1.00–2.00 V. This suggests the application of this type of MoO₂ as anode material in lithium ion batteries.     

High power and high capacity cathode material LiNi0.5Mn0.5O2 for advanced lithium-ion batteries

Single-phase lithium nickel manganese oxide, LiNi_0.5Mn_0.5O₂, was successfully synthesized from a solid solution of Ni_1.5Mn_1.5O₄ that was prepared by means of the solid reaction between Mn(CH₃COO)₂·4H₂O and Ni(CH₃COO)₂·4H₂O. XRD pattern shows that the product is well crystallized with a high degree of Li–M (Ni, Mn) order in their respective layers, and no diffraction peak of Li₂MnO₃ can be detected. Electrochemical performance of as-prepared LiNi_0.5Mn_0.5O₂ was examined in the test battery by charge–discharge cycling with different rate, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The cycling behavior between 2.5 and 4.4 V at a current rate of 21.7 mA g⁻¹ shows a reversible capacity of about 190 mAh g⁻¹ with little capacity loss after 100 cycles. High-rate capability test shows that even at a rate of 6C, stable capacity about 120 mAh g⁻¹ is retained. Cyclic voltammetry (CV) profile shows that the cathode material has better electrochemical reversibility. EIS analysis indicates that the resistance of charge transfer (R_ct) is small in fully charged state at 4.4 V and fully discharged state at 2.5 V versus Li⁺/Li. The favorable electrochemical performance was primarily attributed to regular and stable crystal structure with little intra-layer disordering.     

Synthesis and electrochemistry of cubic rocksalt Li–Ni–Ti–O compounds in the phase diagram of LiNiO2–LiTiO2–Li[Li1/3Ti2/3]O2

On the basis of extreme similarity between the triangle phase diagrams of LiNiO₂–LiTiO₂–Li[Li_1/3Ti_2/3]O₂ and LiNiO₂–LiMnO₂–Li[Li_1/3Mn_2/3]O₂, new Li–Ni–Ti–O series with a nominal composition of Li_1+z/3Ni_1/2−z/2Ti_1/2+z/6O₂ (0 ≤ z ≤ 0.5) was designed and attempted to prepare via a spray-drying method. XRD identified that new Li–Ni–Ti–O compounds had cubic rocksalt structure, in which Li, Ni and Ti were evenly distributed on the octahedral sites in cubic closely packed lattice of oxygen ions. They can be considered as the solid solution between cubic LiNi_1/2Ti_1/2O₂ and Li[Li_1/3Ti_2/3]O₂ (high temperature form). Charge–discharge tests showed that Li–Ni–Ti–O compounds with appropriate compositions could display a considerable capacity (more than 80 mAh g⁻¹ for 0.2 ≤ z ≤ 0.27) at room temperature in the voltage range of 4.5–2.5 V and good electrochemical properties within respect to capacity (more than 150 mAh g⁻¹ for 0 ≤ z ≤ 0.27), cycleability and rate capability at an elevated temperature of 50 °C. These suggest that the disordered cubic structure in some cases may function as a good host structure for intercalation/deintercalation of Li⁺. A preliminary electrochemical comparison between Li_1+z/3Ni_1/2−z/2Ti_1/2+z/6O₂ (0 ≤ z ≤ 0.5) and Li_6/5Ni_2/5Ti_2/5O₂ indicated that charge–discharge mechanism based on Ni redox at the voltage of >3.0 V behaved somewhat differently, that is, Ni could be reduced to +2 in Li_1+z/3Ni_1/2−z/2Ti_1/2+z/6O₂ while +3 in Li_6/5Ni_2/5Ti_2/5O₂. Reduction of Ti⁴⁺ at a plateau of around 2.3 V could be clearly detected in Li_1+z/3Ni_1/2−z/2Ti_1/2+z/6O₂ with 0.27 ≤ z ≤ 0.5 at 50 °C after a deep charge associated with charge compensation from oxygen ion during initial cycle.     

Synthesis and electrochemical properties of Li1−xFe0.8Ni0.2O2–LixMnO2 (Mn/(Fe + Ni + Mn) = 0.8) material

A new type of Li_1−xFe_0.8Ni_0.2O₂–Li_xMnO₂ (Mn/(Fe + Ni + Mn) = 0.8) material was synthesized at 350 °C in air atmosphere using a solid-state reaction. The material had an XRD pattern that closely resembled that of the original Li_1−xFeO₂–Li_xMnO₂ (Mn/(Fe + Mn) = 0.8) with much reduced impurity peaks. The Li/Li_1−xFe_0.8Ni_0.2O₂–Li_xMnO₂ cell showed a high initial discharge capacity above 192 mAh g⁻¹, which was higher than that of the parent Li/Li_1−xFeO₂–Li_xMnO₂ (186 mAh g⁻¹). We expected that the increase of initial discharge capacity and the change of shape of discharge curve for the Li/Li_1−xFe_0.8Ni_0.2O₂–Li_xMnO₂ cell is the result from the redox reaction from Ni²⁺ to Ni³⁺ during charge/discharge process. This cell exhibited not only a typical voltage plateau in the 2.8 V region, but also an excellent cycle retention rate (96%) up to 45 cycles.     

Electrochemical performance of SrF2-coated LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion batteries

SrF₂-coated LiNi_1/3Co_1/3Mn_1/3O₂ cathode materials with improved cycling performance over 2.5–4.6 V were investigated. The structural and electrochemical properties of the materials were studied using X-ray diffraction (XRD), scanning electron microscope (SEM), charge–discharge tests and electrochemical impedance spectra (EIS). The results showed that the crystalline SrF₂ with about 10–50 nm particle size is uniformly coated on the surface of LiNi_1/3Co_1/3Mn_1/3O₂ particles. As the coating amount increased from 0.0 to 2.0 mol%, the initial capacity and rate capability of the coated LiNi_1/3Co_1/3Mn_1/3O₂ decreased slightly owing to the increase of the charge-transfer resistance; however, the cycling stability was improved by suppressing the increase of the resistance during cycling. 4.0 mol% SrF₂-coated LiNi_1/3Co_1/3Mn_1/3O₂ showed remarkable decrease of the initial capacity. 2.0 mol% coated sample exhibited the best electrochemical performance. It presented an initial discharge capacity of 165.7 mAh g⁻¹, and a capacity retention of 86.9% after 50 cycles at 4.6 V cut-off cycling.     

Pillared layered Li1−2xCaxCoO2 cathode materials obtained by cationic exchange under hydrothermal conditions

A simple method has been employed to prepare pillared layered Li_1−2xCa_xCoO₂ cathode materials by cationic exchange under hydrothermal conditions. The synthesized materials were characterized by means of X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), field emission scanning electron microscope (FE-SEM) and galvanostatic charge–discharge cycling. The XRD data of the products show that they are single phases and retain the layered α-NaFeO₂ type structure. The FE-SEM images of the materials prepared by hydrothermal method show uniform small particles, and the particle size of the materials is about 200 nm. The initial discharge specific capacities of layered LiCoO₂ and pillared layered Li_0.946Ca_0.027CoO₂ cathode materials calcined at 800 °C for 5 h within the potential range of 3.0–4.3 V (vs. Li⁺/Li) are 144.6 and 142.3 mAh g⁻¹, respectively, and both materials retain good charge–discharge cycling performance. However, with increasing upper cutoff voltage, the pillar effect of Ca²⁺ in Li_1−2xCa_xCoO₂ becomes more significant. The pillared layered Li_0.946Ca_0.027CoO₂ has a higher capacity with an initial discharge specific capacity of 177.9 and 215.8 mAh g⁻¹ within the potential range of 3.0–4.5 and 4.7 V (vs. Li⁺/Li), respectively, and retains good charge–discharge cycling performance.     

Hybrid supercapacitor based on MnO2 and columned FeOOH using Li2SO4 electrolyte solution

The nano-sized columned β-FeOOH was prepared by the hydrolysis process and its electrochemical capacitance performance was evaluated for the first time in Li₂SO₄ solution. A hybrid supercapacitor based on MnO₂ positive electrode and FeOOH negative electrode in Li₂SO₄ electrolyte solution was designed. The electrochemical tests demonstrated that the hybrid supercapacitor has a energy density of 12 Wh kg⁻¹ and a power density of 3700 W kg⁻¹ based on the total weight of the electrode active materials with a voltage range 0–1.85 V. This hybrid supercapacitor also exhibits a good cycling performance and keeps 85% of initial capacity over 2000 cycles.     

Preparation of the composite LaNi3.7Al1.3/Ni–S–Co alloy film and its HER activity in alkaline medium

The composite LaNi_3.7Al_1.3/Ni–S–Co alloy film was prepared by molten salt electrolysis and aquatic electrodeposition orderly. With Na₃AlF₆–La₂O₃–Al₂O₃ (91:8:1) system as molten salt electrolyte, the LaNi_3.7Al_1.3 alloy film was obtained by galvanostatic electrolysis at 100 mA cm⁻². The results showed that the La³⁺ and Al³⁺ ions could be co-reduced on the nickel cathode to form LaNi_3.7Al_1.3 film, i.e. La³⁺ + 1.3Al³⁺ + 6.9e + 3.7Ni = LaNi_3.7Al_1.3 at c.a. −0.5 V, which is much lower than that of the theoretical decomposition potential of lanthanum and aluminum. With high HER activity, the composite LaNi_3.7Al_1.3/Ni–S–Co film (η₁₅₀ = 65 mV, 353 K) could absorb large amount of H atoms, which would be oxidized and therefore effectively avoid the dissolution of the Ni–S–Co film under the state of open-circuit and consequently prolong the lifetime of the cathode.     

Hydrogen production by redox of bimetal cation-modified iron oxide

Pure hydrogen can be stored and supplied directly to polymer electrolyte fuel cell by the redox of iron oxide: Fe₃O₄ + 4H₂ → 3Fe + 4H₂O and 4H₂O + 3Fe → Fe₃O₄ + 4H₂. Four bimetal-modified samples were prepared by impregnation. The hydrogen storage properties of the samples were investigated. The result shows that the Fe₂O₃–Mo–Al sample presented the most excellent catalytic activity and cyclic stability. H₂ forming temperature and H₂ forming rate could be surprisingly decreased and enhanced, respectively. The average H₂ forming temperature at the rate of 250 μmol min⁻¹·Fe-g⁻¹ for Fe₂O₃–Mo–Al in the first 4 cycles could be decreased from 469 °C before the addition of Mo–Al to 273 °C after the addition of Mo–Al. The reason for it may be that the Mo–Al additive in the sample can prevent from the sintering of the particles and accelerate the H₂O decomposition due to Mo taking part in the redox reaction. The average storage capacity of Fe₂O₃–Mo–Al was up to 4.68 wt%.     

Charge–discharge characteristics of all-solid-state thin-filmed lithium-ion batteries using amorphous Nb2O5 negative electrodes

All-solid-state thin-filmed lithium-ion rechargeable batteries composed of amorphous Nb₂O₅ negative electrode with the thickness of 50–300 nm and amorphous Li₂Mn₂O₄ positive electrode with a constant thickness of 200 nm, and amorphous Li₃PO_4−xN_x electrolyte (100 nm thickness), have been fabricated on glass substrates with a 50 mm × 50 mm size by a sputtering method, and their electrochemical characteristics were investigated. The charge–discharge capacity based on the volume of positive electrode increased with increasing thickness of negative electrode, reaching about 600 mAh cm⁻³ for the battery with the negative electrode thickness of 200 nm. But the capacity based on the volume of both the positive and negative electrodes was the maximum value of about 310 mAh cm⁻³ for the battery with the negative electrode thickness of 100 nm. The shape of charge–discharge curve consisted of a two-step for the batteries with the negative electrode thickness more than 200 nm, but that with the thickness of 100 nm was a smooth S-shape curve during 500 cycles.     

Lithium recycling behaviour of nano-phase-CuCo2O4 as anode for lithium-ion batteries

Nano-CuCo₂O₄ is synthesized by the low-temperature (400 °C) and cost-effective urea combustion method. X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED) studies establish that the compound possesses a spinel structure and nano-particle morphology (particle size (10–20 nm)). A slight amount of CuO is found as an impurity. Galvanostatic cycling of CuCo₂O₄ at 60 mA g⁻¹ in the voltage range 0.005–3.0 V versus Li metal exhibits reversible cycling performance between 2 and 50 cycles with a small capacity fading of 2 mAh g⁻¹ per cycle. Good rate capability is also found in the range 0.04–0.94C. Typical discharge and charge capacity values at the 20th cycle are 755(±10) mAh g⁻¹ (∼6.9 mol of Li per mole of CuCo₂O₄) and 745(±10) mAh g⁻¹ (∼6.8 mol of Li), respectively at a current of 60 mA g⁻¹. The average discharge and charge potentials are ∼1.2 and ∼2.1 V, respectively. The underlying reaction mechanism is the redox reaction: Co ↔ CoO ↔ Co₃O₄ and Cu ↔ CuO aided by Li₂O, after initial reaction with Li. The galvanostatic cycling studies are complemented by cyclic voltammetry (CV), ex situ TEM and SAED. The Li-cycling behaviour of nano-CuCo₂O₄ compares well with that of iso-structural nano-Co₃O₄ as reported in the literature.     

Synthesis and electrochemical performance of doped LiCoO2 materials

Layered intercalation compounds LiM_0.02Co_0.98O₂ (M = Mo⁶⁺, V⁵⁺, Zr⁴⁺) have been prepared using a simple solid-state method. Morphological and structural characterization of the synthesized powders is reported along with their electrochemical performance when used as the active material in a lithium half-cell. Synchrotron X-ray diffraction patterns suggest a single phase HT-LiCoO₂ that is isostructural to α-NaFeO₂ cannot be formed by aliovalent doping with Mo, V, and Zr. Scanning electron images show that particles are well-crystallized with a size distribution in the range of 1–5 μm. Charge–discharge cycling of the cells indicated first cycle irreversible capacity loss in order of increasing magnitude was Zr (15 mAh g⁻¹), Mo (22 mAh g⁻¹), and V (45 mAh g⁻¹). Prolonged cycling the Mo-doped cell produced the best performance of all dopants with a stable reversible capacity of 120 mAh g⁻¹ after 30 cycles, but was inferior to that of pure LiCoO₂.     

Electrochemical studies of low-temperature processed nano-crystalline LiMn2O4 thin film cathode at 55 °C

LiMn₂O₄ thin films with nano-crystals less than 100 nm were successfully grown on polished stainless steel substrates at 400 °C and 200 m Torr of oxygen by pulsed laser deposition. A maximum discharge capacity of 62.4 μAh cm⁻² μm⁻¹ cycled between 3.0 and 4.5 V with a current density of 20 μAh cm⁻² was achieved. The effect of several overdischarge cycles was negligible, and both the effect of Jahn–Teller distortion at low potentials on capacity loss and structure instability at high potentials were effectively inhibited in this nano-crystalline film, resulting in an excellent cycling stability with a very low fading rate of capacity up to 500 cycles at 55 °C.     

Electrochemical properties of doped lithium titanate compounds and their performance in lithium rechargeable batteries

Several substituted titanates of formula Li_4−xMg_xTi_5−xV_xO₁₂ (0 ≤ x ≤ 1) were synthesized (and investigated) as anode materials in rechargeable lithium batteries. Five samples labeled as S1–S5 were calcined (fired) at 900 °C for 10 h in air, and slowly cooled to room temperature in a tube furnace. The structural properties of the synthesized products have been investigated by X-ray diffraction (XRD), scanning electron microscope (SEM) and Fourier transmission infrared (FTIR). XRD explained that the crystal structures of all samples were monoclinic while S1 and S3 were hexagonal. The morphology of the crystal of S1 was spherical while the other samples were prismatic in shape. SEM investigations explained that S4 had larger grain size diameter of 15–16 μm in comparison with the other samples. S4 sample had the highest conductivity 2.452 × 10⁻⁴ S cm⁻¹. At a voltage plateau located at about 1.55 V (vs. Li ⁺), S4 cell exhibited an initial specific discharge capacity of 198 mAh g⁻¹. The results of cyclic voltammetry for Li_4−xMg_xTi_5−xV_xO₁₂ showed that the electrochemical reaction was based on Ti⁴⁺/Ti³⁺ redox couple at potential range from 1.5 to 1.7 V. There is a pair of reversible redox peaks corresponding to the process of Li⁺ intercalation and de-intercalation in the Li–Ti–O oxides.     

All-solid-state lithium secondary batteries with oxide-coated LiCoO2 electrode and Li2S–P2S5 electrolyte

All-solid-state lithium secondary batteries using LiCoO₂ active materials coated with Li₂SiO₃ and SiO₂ oxide films and Li₂S–P₂S₅ solid electrolytes were fabricated and their electrochemical performance was investigated. The electrochemical performace of the all-solid-state cells at a high voltage region was highly improved by using oxide-coated LiCoO₂. The oxide coatings are effective in suppressing the formation of an interfacial resistance between LiCoO₂ and the solid electrolyte at a high cutoff voltage of 4.6 V (vs. Li). As a result, charge–discharge capacities and cycle performance at the cutoff voltage were improved. The cell with Li₂SiO₃-coated LiCoO₂ showed a large initial discharge capacity of 130 mAh g⁻¹ and a good capacity retention of 110 mAh g⁻¹ after 50th cycles at the cutoff voltage of 4.6 V (vs. Li).     

In situ X-ray diffraction studies on the mechanism of capacity retention improvement by coating at the surface of LiCoO2

Synchrotron based in situ X-ray diffraction technique has been used to study the mechanism of capacity fading of LiCoO₂ cycled to a higher voltage above the normal 4.2 V limit and to investigate the mechanism of capacity retention improvement by ZrO₂ surface coating on LiCoO₂. It was found that the capacity fading of LiCoO₂ cycled at higher voltage limit is closely related to the increased polarization rather than the bulk crystal structure damage. The capacity of uncoated LiCoO₂ sample dropped to less than 70 mAh g⁻¹ when charged to 4.8 V after high voltage cycling. However, when the voltage limit was further increased to 8.35 V, the capacity was partially restored and the corresponding structural changes were recovered to the similar level as seen in fresh sample. This indicates that the integrity of the bulk crystal structure of LiCoO₂ was not seriously damaged during cycling to 4.8 V. The increased polarization seems to be responsible for the fading capacity and the uncompleted phase transformation of LiCoO₂. The polarization-induced capacity fading can be significantly improved by ZrO₂ surface coating. It was proposed that the effect of ZrO₂-coating layer on the capacity retention during high voltage cycling is through the formation of protection layer on the surface of LiCoO₂ particles, which can reduce the decomposition of the electrolyte at higher voltages.     

Amorphous Si film anode coupled with LiCoO2 cathode in Li-ion cell

An amorphous silicon film with an average thickness of up to 2 μm was deposited on copper foil by direct-circuit (dc) magnetron sputtering and coupled with commercial LiCoO₂ cathode to fabricate cells. Their cycle performance and high rate capability at room temperature have been investigated. In the voltage range 2.5–3.9 V at the current density of 0.2C (0.11 mA cm⁻²), the lithiation and delithiation capacity of this cell was first increased to 0.55 mAh cm⁻² within 80 cycles and maintained stable during the following cycles. After 300 cycles its capacity still retained 0.54 mAh cm⁻². High-resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) image indicated that the sputtered film could keep an amorphous structure although the volume expansion ratio during the lithiation and delithiation was still up to 300% after 300 cycles observed from scanning electron microscopy (SEM) image. This recovered amorphous structure was believed to be beneficial for the improvement of the cycle life of the cell. Rate performance showed that the cells had a promising high rate capability. At 30C, its lithiation/delithiation capacity remained 25% of that at 0.2C.     

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.     

Preparation and electrochemical properties of composite LaNix/Ni–S–Co alloy film

The composite LaNi_x/Ni–S–Co film with considerable stability and high HER activity (η₁₅₀ = 70 mV, 353 K) was obtained by molten salt electrolysis combined with aquatic electrodeposition. LaNi_x film was prepared by galvanostatic electrolysis at 100 mA cm⁻² under 1273 K. The results showed that the La³⁺ ions could be reduced on the nickel cathode and the LaNi_x film could form, i.e. La³⁺ + 3e + xNi = LaNi_x (x = 5 or 3) at ca. −0.6 V, which is much lower than that of the decomposition potential of lanthanum, due to the strong depolarization effect of nickel. Furthermore, compared with the traditional amorphous Ni–S film, the composite LaNi_x/Ni–S–Co film could absorb large amount of H atoms, which would be oxidized and avoid the dissolution of the Ni–S–Co film under the state of open-circuit effectively and increase the HER activity.     

Intermediate-to-low temperature protonic ceramic membrane fuel cells with Ba0.5Sr0.5Co0.8Fe0.2O3-δ–BaZr0.1Ce0.7Y0.2O3-δ composite cathode

The perovskite-type Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ–BaZr_0.1Ce_0.7Y_0.2O_3-δ (BSCF–BZCY) composite oxides were synthesized by a modified Pechini method and examined as a novel composite cathode for intermediate-to-low temperature protonic ceramic membrane fuel cells (ILT-PCMFCs). Thin proton-conducting BaZr_0.1Ce_0.7Y_0.2O_3-δ (BZCY) electrolyte and NiO–BaZr_0.1Ce_0.7Y_0.2O_3-δ (NiO–BZCY) anode functional layer were prepared over porous anode substrates composed of NiO–BaZr_0.1Ce_0.7Y_0.2O_3-δ by a one-step dry-pressing/co-firing process. A laboratory-sized quad-layer cell of NiO–BZCY/NiO–BZCY(∼50 μm)/BZCY(∼20 μm)/BSCF–BZCY(∼50 μm) was operated from 550 to 700 °C with humidified hydrogen (∼3% H₂O) as fuel and the static air as oxidant. A high open-circuit potential of 1.009 V, a maximum power density of 418 mW cm⁻², and a low polarization resistance of the electrodes of 0.10 Ω cm² was achieved at 700 °C. These investigations have indicated that proton-conducting BZCY electrolyte with BSCF perovskite cathode is a promising material system for the next generation solid oxide fuel cells (SOFCs).