Lithium cobalt oxide cathode film prepared by rf sputtering

Thin films of LiCoO₂ prepared by radio frequency magnetron sputtering on Pt-coated silicon are investigated under various deposited parameters such as working pressure, gas flow rate of Ar to O₂, and heat-treatment temperature. The as-deposited film was a nanocrystalline structure with (1 0 4) preferred orientation. After annealing at 500–700 °C, single-phase LiCoO₂ is obtained when the film is originally deposited under an oxygen partial pressure (P_O2) from 5 to 10 mTorr. When the sputtering process is performed outside these P_O2 values, a second phase of Co₃O₄ is formed in addition to the HT-LiCoO₂ phase. The degree of crystallization of the LiCoO₂ films is strongly affected by the annealing temperature; a higher temperature enhances the crystallization of the deposited LiCoO₂ film. The grain sizes of LiCoO₂ films annealed at 500, 600 and 700 °C are about 60, 95, and 125 nm, respectively. Cyclic voltammograms display well-defined redox peaks. LiCoO₂ films deposited by rf sputtering are electrochemically active. The first discharge capacity of thin LiCoO₂ films annealed at 500, 600 and 700 °C is about 41.77, 50.62 and 61.16 μAh/(cm² μm), respectively. The corresponding 50th discharge capacities are 58.1, 72.2 and 74.9% of the first discharge capacity.     

A thin film silicon anode for Li-ion batteries having a very large specific capacity and long cycle life

A thin film of Si was vacuum-deposited onto a 30 μm thick Ni foil from a source of n-type of Si, the film thickness examined being 200–1500 Å. Li insertion/extraction evaluation was performed mainly with cyclic voltammetry (CV) and constant current charge/discharge cycling in propylene carbonate (PC) containing 1 M LiClO₄ at ambient temperature. The cycleability and the Li accommodation capacity were found to depend on the film thickness. Thinner films gave larger accommodation capacity. A 500 Å thick Si film gave a charge capacity over 3500 mAh g⁻¹ being maintained during 200 cycles under 2 C charge/discharge rate, while a 1500 Å film revealed around 2200 mAh g⁻¹ during 200 cycles under 1 C rate. The initial charge loss could not be ignored but it could be reduced by controlling the deposition conditions.     

Preparation of LiCoO2 from spent lithium-ion batteries

A recycling process involving mechanical, thermal, hydrometallurgical and sol–gel steps has been applied to recover cobalt and lithium from spent lithium-ion batteries and to synthesize LiCoO₂ from leach liquor as cathodic active materials. Electrode materials containing lithium and cobalt can be concentrated with a two-step thermal and mechanical treatment. The leaching behavior of lithium and cobalt in nitric acid media is investigated in terms of reaction variables. Hydrogen peroxide in 1 M HNO₃ solution is found to be an effective reducing agent by enhancing the leaching efficiency. Of the many possible processes to produce LiCoO₂, the amorphous citrate precursor process (ACP) has been applied to synthesize powders with a large specific surface area and an exact stoichiometry. After leaching used LiCoO₂ with nitric acid, the molar ratio of Li to Co in the leach liquor is adjusted to 1.1 by adding a fresh LiNO₃ solution. Then, 1 M citric acid solution at a 100% stoichiometry is added to prepare a gelatinous precursor. When the precursor is calcined at 950 °C for 24 h, purely crystalline LiCoO₂ is successfully obtained. The particle size and specific surface-area of the resulting crystalline powders are 20 μm and 30 cm² g⁻¹, respectively. The LiCoO₂ powder is found to have good characteristics as a cathode active material in terms of charge–discharge capacity and cycling performance.     

Nanocrystalline TiO2 (anatase) for Li-ion batteries

Nanocrystalline TiO₂ (anatase) was synthesized successfully by the direct conversion of TiO₂-sol at 85 °C. The as-prepared TiO₂ at 85 °C were calcined at different temperatures and time in order to optimize the system with best electrochemical performance. The particle sizes of the synthesized materials were found to be in the range of 15–20 nm as revealed by the HR-TEM studies. Commercial TiO₂ anatase (micron size) was also studied for its Li-insertion and deinsertion properties in order to compare with the nanocrystalline TiO₂. The full cell studies were performed with LiCoO₂ cathode with the best performing nano-TiO₂ as anode. The specific capacity of the nanocrystalline TiO₂ synthesized at 500 °C/2 h in a half-cell configuration was 169 mAh g⁻¹ while for the cell with LiCoO₂ cathode, it was 95 mAh g⁻¹ in the 2 V region. The specific reversible capacity and the cycling performance of the synthesized nano-TiO₂ anode in full cell configuration across LiCoO₂ cathode are superior to that reported in the literature. Cyclic voltammetry measurements showed a larger peak separation for the micro-TiO₂ than the nano-TiO₂, clearly indicating the influence of nano-particle size on the electrochemical performance.     

Electrochemical behavior of polyamides with cyclic disulfide structure and their application to positive active material for lithium secondary battery

Polyamides (DTA-I, DTA-II, and DTA-III) containing cyclic disulfide structure were prepared by condensation between 1,2-dithiane-3,6-dicarboxylic acid (DTA) and alkyl diamine, NH₂–(CH₂)_n–NH₂ (DTA-I; n=4, DTA-II; n=6, DTA-III; n=8) and their application to positive active material for lithium secondary batteries was investigated. Cyclic voltammetry (CV) measurements under slow sweep rate (0.5 mV s⁻¹) with a carbon paste electrode containing the polyamide (DTA-I, DTA-II, or DTA-III) were performed. The results indicated that the polyamides were electroactive in the organic electrolyte solution (propylene carbonate (PC)-1,2-dimethoxyethane (DME), 1:1 by volume containing lithium salt, such as LiClO₄). The responses based on the redox of the disulfide bonds in the polyamide were observed.Test cells, Li/PC-DME (1:1. by volume) with 1 mol dm⁻³ LiClO₄/the polyamide cathode, were constructed and their performance was tested under constant current charge/discharge condition. The average capacity of the test cells with the DTA-III cathode was 64.3 Ah kg⁻¹ of cathode (135 Wh kg⁻¹ of cathode, capacity (Ah kg⁻¹) of the cathode×average cell voltage (2.10 V)). Performance of the cell with linear polyamide containing disulfide bond (–CO–(CH₂)₂–S–S–(CH₂)₂–CONH–(CH₂)₈–NH–, GTA-III) was also investigated and the average capacity was 56.8 Ah kg⁻¹ of cathode (100 Wh kg⁻¹ of cathode, capacity (Ah kg⁻¹) of the cathode×average cell voltage (1.76 V)). Cycle efficiency of the test cell with the DTA-III cathode was higher than that with the GTA-III cathode.     

Positive thin electrodes obtained from hydrothermally synthesized 4BS for lead-acid batteries

Tetrabasic lead sulfate, 4 PbO·PbSO₄ (4BS), was prepared from an aqueous suspension of leady oxide by using a simple hydrothermal method. Digesting the paste at a moderate temperature (125 °C) and heating for a short time (30 min) ensured the obtainment of particles of small, uniform size. The material was deposited on a lead alloy substrate 0.2 mm thick by spraying from aqueous suspensions. The deposits were highly uniform and homogeneous, with a coating thickness of 100 μm. A multi-step charge algorithm involving no preliminary soaking provided the best 4BS → PbO₂ conversion. The resulting electrodes delivered a capacity of 115 Ah kg⁻¹ with excellent capacity retention over more than 500 cycles at 100% depth of discharge (DOD).     

Screen-printed thin YSZ films used as electrolytes for solid oxide fuel cells

A thin yttria-stabilized zirconia (8 mol% YSZ) film was successfully fabricated on a NiO-YSZ anode substrate by a screen-printing technique. The scanning electron microscope (SEM) results suggested that the YSZ film thickness was about 31 μm after sintering at 1400 °C for 4 h in air. A 60 wt% La_0.7Sr_0.3MnO₃ + 40 wt% YSZ was screen-printed onto the YSZ film surface as cathode. A single cell was tested from 650 to 850 °C using hydrogen as fuel and ambient air as oxidant, which showed an open circuit voltage (OCV) of 1.02 V and a maximum power density of 1.30 W cm⁻² at 850 °C. The OCV was higher than 1.0 V, which suggested that the YSZ film was quite dense and that the fuel gas leakage through the YSZ film was negligible. Screen-printing can be a promising method for manufacturing YSZ films for solid oxide fuel cells (SOFCs).     

A stabilized NiO cathode prepared by sol-impregnation of LiCoO2 precursors for molten carbonate fuel cells

Layers of LiCoO₂ were formed on the internal surface of a porous NiO cathode to reduce the rate of NiO dissolution into the molten carbonate. A sol-impregnation technique assisted by acrylic acid (AA) was used to deposit gel precursors of LiCoO₂ on the pore surface of the Ni plate. Thermal treatment of the gel-coated cathode above 400 °C produced LiCoO₂ layers on the porous cathode. A number of bench-scale single cells were fabricated with LiCoO₂-coated cathodes and the cell performance was examined at atmospheric pressure for 1000 h. With the increase in the LiCoO₂ content in the cathode, the initial cell voltage decreased, but the cell performance gradually improved during the cell test. It was found from symmetric cathode cell test that the cathode was initially flooded with electrolyte, but redistribution of the electrolyte took place during the test and cell performance became comparable to that of a conventional NiO cathode. The amount of Ni precipitated in the matrix during the cell operation for 1000 h was significantly reduced by the LiCoO₂ coating. For instance, coating 5 mol% of LiCoO₂ in the cathode led to a 56% reduction of Ni precipitation in the matrix. The results obtained in this study strongly suggest that LiCoO₂ layers formed on the internal surface of the porous NiO cathode effectively suppress the rate of NiO dissolution for 1000 h.     

Improvement of 12 V overcharge behavior of LiCoO2 cathode material by LiNi0.8Co0.1Mn0.1O2 addition in a Li-ion cell

The 12 V overcharge instability of the LiCoO₂ cathode material was improved by the physical blending it with LiNi_0.8Co_0.1Mn_0.1O₂. Even though a Li-ion cell containing a LiCoO₂ cathode did not exhibit thermal runaway at 12 V at the 1 C overcharging rate, it showed thermal runaway at the 2 C overcharging rate, and the cell surface temperature reached more than 400 °C. However, the LiCoO₂ cell containing 40, 50, and 60 wt.% LiNi_0.8Co_0.1Mn_0.1O₂ did not exhibit thermal runaway at the 2 C overcharging rate. In conclusion, 60 wt.% LiNi_0.8Co_0.1Mn_0.1O₂ in the LiCoO₂ cathode showed the lowest cell surface temperature of <90 °C even at a 3 C overcharging rate.     

Li+ ion diffusion in LiMn2O4 thin film prepared by PVP sol–gel method

LiMn₂O₄ thin film (1 μm thick) was prepared on a gold substrate by the PVP sol–gel method. The electrochemical properties of the thin-film electrode were studied in an electrolyte 1 mol dm⁻³ LiClO₄/(ethylene carbonate + diethyl carbonate). The prepared LiMn₂O₄ showed a good charge–discharge performance, and the capacity fade was ca. 20% during 200 cycles. The Li⁺ ion diffusion in the LiMn₂O₄ thin film was investigated by means of potentiostatic intermittent titration technique and electrochemical impedance spectroscopy. The chemical diffusion coefficients were estimated to be 10⁻⁸ to 10⁻¹⁰ cm² s⁻¹.     

Improvement of the rate capability of LiMn2O4 by surface coating with LiCoO2

In order to use LiMn₂O₄ as a cathode material of lithium-secondary battery for an electric vehicle (EV), its rate capability should be improved. To enhance the rate capability of LiMn₂O₄ in this work, the surface of LiMn₂O₄ particle was coated with LiCoO₂ by a sol–gel method. Because LiCoO₂ has a higher electric conductivity than LiMn₂O₄, it is possible to improve the rate capability of LiMn₂O₄. After the surface coating, LiCoO₂-coated LiMn₂O₄ showed a higher discharge capacity of 120 mAh/g than as-received LiMn₂O₄ (115 mAh/g) because LiCoO₂ has a higher capacity than LiMn₂O₄. The rate capability of the coated LiMn₂O₄ improved significantly. While as-received LiMn₂O₄ maintained only 50% of its maximum capacity at a 20C rate (2400 mA/g), the LiCoO₂-coated LiMn₂O₄ maintained more than 80% of maximum capacity. LiCoO₂-coated LiMn₂O₄ with 3 wt.% conducting agent (acetylene black) showed the higher rate capability than as-received LiMn₂O₄ with 20 wt.% conducting agent. From electrochemical impedance spectroscopy (EIS) result that the first and second semicircles of coated LiMn₂O₄ were reduced, the improvement of rate capability is attributed to a decrease of passivation film that acts as an electronic insulating layer and a reduced inter-particle contact resistance. Accordingly, It is proposed that the surface coating of LiMn₂O₄ with LiCoO₂ improve the rate capability as well as the specific and volumetric energy density due to the decrease of conducting agent.     

Synthetic optimization of spherical LiCoO2 and precursor via uniform-phase precipitation

LiCoO₂ had been successfully prepared from spherical basic cobalt carbonate via a simple uniform-phase precipitation method at normal pressure, using cobalt sulfate and urea as the reactants. The preparation of spherical basic cobalt carbonate was significantly dependant on synthetic condition, such as the reactant concentration, reaction temperature and impeller speed, etc. The optimized condition resulted in spherical basic cobalt carbonate with uniform particle size distribution, as observed by scanning electron microscopy. Calcination of the uniform basic cobalt carbonate with lithium carbonate at high temperature led to a well-ordered layer-structured LiCoO₂ without shape change, as confirmed by X-ray diffraction. Due to the homogeneity of the basic cobalt carbonate, the final product, LiCoO₂, was also significantly uniform, i.e., the average particle size was of about 10 μm in diameter and the distribution was relatively narrow. As a result, the corresponding tap-density was also high approximately 2.60 g cm⁻³, of which the value is higher than that of commercialized LiCoO₂ of Hunan Ruixing, co. In the voltage range 2.8–4.2, 2.8–4.3, and 2.8–4.4 V, the discharge capacities of LiCoO₂ electrode were 153, 159, and 168 mAh g⁻¹, respectively, with better cyclability.     

NiO–YSZ cermets supported low temperature solid oxide fuel cells

Solid oxide fuel cells with thin electrolyte of two types, Sm_0.2Ce_0.8O_1.9 (SDC) (15 μm) single-layer and 8 mol% Yttria stabilized zirconia (YSZ) (5 μm) + SDC (15 μm) bi-layer on NiO–YSZ cermet substrates were fabricated by screen printing and co-firing. A Sm_0.5Sr_0.5CoO₃ cathode was printed, and in situ sintered during a cell performance test. The SDC single-layer electrolyte cell showed high electrochemical performance at low temperature, with a 1180 mW cm⁻² peak power density at 650 °C. The YSZ + SDC bi-layer electrolyte cell generated 340 mW cm⁻² peak power density at 650 °C, and showed good performance at 700–800 °C, with an open circuit voltage close to theoretical value. Many high Zr-content micro-islands were found on the SDC electrolyte surface prior to the cathode preparation. The influence of co-firing temperature and thin film preparation methods on the Zr-islands’ appearance was investigated.     

A viscous titania paste with a single coating-sintering step for 8–24 μm thick,high-haze,high-quality TiO2 films of dye-sensitized solar cells

A viscous TiO₂ paste was prepared by ball-milling commercially available P25 with ethylene glycol and citric acid. The conventional three- or four-fold deposition process was replaced by a single coating-sintering step of TiO₂ compound. That is coating the paste on Fluorine-doped SnO₂ conductive glass, followed by sintering at high temperature. TiO₂ films varying from 8 μm to 24 μm could be fabricated by this single coating-sintering step. The high viscosity of the paste, the esterification between ethylene glycol and citric acid and the subsequently polyester decomposition in the sintering process were the reasons to make high-quality thick film without cracking and delamination. 7.36% photoelectrical-conversion efficiency was achieved by using the photoelectrode with its P25 film thickness of 14.3 μm. Therefore, the paste would have promising applications for industrial production because of its low-price and simple process.     

Structural and electrical properties of LiCoO2 thin-film cathodes deposited on planar and trench structures by liquid-delivery metalorganic chemical vapour deposition

The electrochemical properties of annealed-LiCoO₂ cathodes deposited on planar and trench structures by liquid-delivery metalorganic chemical vapor deposition are investigated for various deposition temperatures and input Li:Co mole ratios. With the planar structure, the best crystallinity of the films is obtained at a deposition temperature of 450 °C and an input Li:Co mole ratio of 1.0. The deposition window for optimum initial discharge capacity and capacity retention is a deposition temperature of 450–500 °C and an input Li:Co mole ratio of 1.0, and an input Li:Co mole ratio of 1.0–1.2 at a deposition temperature of 450 °C. The initial discharge capacity and capacity retention of LiCoO₂ thin films deposited with an input Li:Co mole ratio of 1.2 at 450 °C are approximately 25 μAh/cm² μm and 77%, respectively. The initial discharge capacity of films deposited on a trench structure shows an increase of approximately 130% compared with that of films deposited on a planar structure with an input Li:Co mole ratio of 1.2. The rechargeabilities of films deposited in a trench structure are inferior to those in a planar structure because conformal growth in the trench structure is poor. Thus, a trench structure can improve the initial discharge capacity and capacity retention of lithium microbatteries.     

A high energy density lithium/sulfur–oxygen hybrid battery

In this paper we introduce a lithium/sulfur–oxygen (Li/S–O₂) hybrid cell that is able to operate either in an air or in an environment without air. In the cell, the cathode is a sulfur–carbon composite electrode containing appropriate amount of sulfur. In the air, the cathode first functions as an air electrode that catalyzes the reduction of oxygen into lithium peroxide (Li₂O₂). Upon the end of oxygen reduction, sulfur starts to discharge like a normal Li/S cell. In the absence of oxygen or air, sulfur alone serves as the active cathode material. That is, sulfur is first reduced to form a soluble polysulfide (Li₂S_x, x ≥ 4) that subsequently discharges into Li₂S through a series of disproportionations and reductions. In general, the Li/S–O₂ hybrid cell presents two distinct discharge voltage plateaus, i.e., one at ～2.7 V attributing to the reduction of oxygen and the other one at ～2.3 V attributing to the reduction of sulfur. Since the final discharge products of oxygen and sulfur are insoluble in the organic electrolyte, it is shown that the overall specific capacity of Li/S–O₂ hybrid cell is determined by the carbon composite electrode, and that the specific capacity varies with the discharge current rate and electrode composition. In this work, we show that a composite electrode composed by weight of 70% M-30 activated carbon, 22% sulfur and 8% polytetrafluoroethylene (PTFE) has a specific capacity of 857 mAh g^?1 vs. M-30 activated carbon at 0.2 mA cm^?2 in comparison with 650 mAh g^?1 of the control electrode consisting of 92% M-30 and 8% PTFE. In addition, the self-discharge of the Li/S–O₂ hybrid cell is expected to be substantially lower when compared with the Li/S cell since oxygen can easily oxidize the soluble polysulfide into insoluble sulfur.     

A novel sol–gel method to synthesize nanocrystalline LiVPO4F and its electrochemical Li intercalation performances

Lithium vanadium fluorophosphate, LiVPO₄F, a cathode material for lithium ion batteries, was synthesized by a sol–gel method followed by low temperature calcinations. V₂O₅·nH₂O hydro-gel, NH₄H₂PO₄, LiF and carbon were used as starting materials to prepare a precursor, and LiVPO₄F was finally obtained by sintering the precursor at 550 °C for 2 h. X-ray diffraction results show that the LiVPO₄F sample is triclinic structure. TEM image indicates that the LiVPO₄F particles are about 70 nm in diameter embedded in carbon network. The LiVPO₄F system showed the discharge capacity of about 130 mAh g⁻¹ in the range of 3.0–4.6 V at the first cycle, and the discharge capacity remained about 124 mAh g⁻¹ after 30 cycles. The sol–gel method is suitable for the preparation of LiVPO₄F cathode materials with good electrochemical Li intercalation performances.     

Electrochemical cycling behavior of LiCoO2 cathode prepared by mechanical alloying of hydroxides

Well-ordered high-temperature LiCoO₂ (HT-LiCoO₂) is synthesized by mechanical alloying (MA) of LiOH·H₂O and Co(OH)₂ powders and subsequent firing. Its electrochemical properties are investigated. The maximum discharge capacity of a sample mechanically alloyed and fired at 600 °C for 2 h is 152 mAh g⁻¹ at the C/40 rate, which is comparable to that obtained from a sample made by conventional solid state reactions. The cycleability is inferior, however, due to a relatively low crystallinity. When the firing temperature is increased to 850 °C, the first discharge capacity of 142 mAh g⁻¹ at the C/5 rate is increased by more than 10%, and retains 93% of its maximum value after 30 cycles. These cycling properties are about the same, or slightly higher, than those synthesized by firing a sample mixture of the same starting materials at 600 °C for 8 h and then at 850 °C for 24 h. Consequently, given the lower firing temperature and/or reduced reaction time, MA could prove a promising synthetic process for cathode materials used in rechargeable lithium batteries.     

Preparation and electrochemical/thermal properties of LiNi0.74Co0.26O2 cathode material

Electrochemical and thermal properties of LiNi_0.74Co_0.26O₂ cathode material with 5, 13 and 25 μm-sized particles have been studied by using a coin-type half-cell Li/LiNi_0.74Co_0.26O₂. The specific capacity of the material ranges from 205 to 210 mA h g⁻¹, depending on the particle size or the Brunauer, Emmett and Teller (BET) surface area. Among the particle sizes, the cathode with a particle size of 13 μm shows the highest specific capacity. Even though the material with a particle size of 5 μm exhibits the smallest capacity value of 205 mA h g⁻¹, no capacity fading was observed after 70 cycles between 4.3 and 2.75 V at the 1 C rate. Differential scanning calorimetry (DSC) studies of the charged electrode at 4.3 V show a close relationship between particle size (BET surface area) and thermal stability of the electrode, namely, a larger particle size (smaller BET surface area) leads to a better thermal stability of the LiNi_0.74Co_0.26O₂ cathode.     

Electrochemical properties of the Li-ion polymer batteries with P(VdF-co-HFP)-based gel polymer electrolyte

Gel polymer electrolytes consisting of 25 wt.% P(VdF-co-HFP), 65 wt.% ethylene carbonate + propylene carbonate and 10 wt.% LiN(CF₃SO₂)₂ are prepared using by a solvent-casting technique. The electrodes are for use in lithium-ion polymer batteries. The electrochemical characteristics of the gel polymer electrolytes are evaluated by means of ac impedance and cyclic voltammetry. The charge–discharge performance of lithium polymer and lithium-ion polymer batteries is examined. A LiCoO₂ | gel polymer electrolyte (GPE) | mesocarbon microbeads (MCMB) cell delivers a discharge capacity of 146.8 and 144.5 mAh g⁻¹ on the first and the 20th cycle, respectively. The specific discharge capacity is greater than 140 mAh g⁻¹ for up to 20 cycle at all the current densities examined.