Crystal structure studies of thermally aged LiCoO2 and LiMn2O4 cathodes

LiCoO₂ and LiMn₂O₄ cathodes were studied by X-ray diffractometry (XRD) and electron diffraction after ageing in the charged state at elevated temperature. Some cathodes were stopped at different times during ageing and XRD measurements were taken to monitor changes in the crystal structure over ageing time. The results indicate that Li-ions intercalate into the cathodes lattice during ageing thus decreasing the available discharge capacity. Analysis of electron diffraction patterns of LiCoO₂ and LiMn₂O₄ retrieved from the cathodes after ageing shows that irreversible crystallographic transformations have taken place in both electrodes. Dark field imaging illustrates that LiCoO₂ forms a layer of spinel phase on its surface. In LiMn₂O₄ a tetragonal distorted spinel is observed when the cathode has been in the 3 V regime for considerable length of time.     

Enhanced electrochemical performance and thermal stability of La2O3-coated LiCoO2

An enhanced electrochemical performance LiCoO₂ cathode was synthesized by coating with various wt.% of La₂O₃ to the LiCoO₂ particle surfaces by a polymeric method, followed by calcination at 923 K for 4 h in air. The surface-coated materials were characterized by XRD, TGA, SEM, TEM, BET and XPS/ESCA techniques. XRD patterns of La₂O₃-coated LiCoO₂ revealed that the coating did not affect the crystal structure, α-NaFeO₂, of the cathode material compared to pristine LiCoO₂. TEM images showed a compact coating layer on the surface of the core material that had an average thickness of about ∼15 nm. XPS data illustrated that the presence of two different environmental O 1s ions corresponds to the surface-coated La₂O₃ and core material. The electrochemical performance of the coated materials by galvanostatic cycling studies suggest that 2.0 wt.% coated La₂O₃ on LiCoO₂ improved cycle stability (284 cycles) by a factor of ∼7 times over the pristine LiCoO₂ cathode material and also demonstrated excellent cell cycle stability when charged at high voltages (4.4, 4.5 and 4.6 V). Impedance spectroscopy demonstrated that the enhanced performance of the coated materials is attributed to slower impedance growth during the charge-discharge processes. The DSC curve revealed that the exothermic peak corresponding to the release of oxygen at ∼464 K was significantly smaller for the La₂O₃-coated cathode material and recognized its high thermal stability.     

Control of AlPO4-nanoparticle coating on LiCoO2 by using water or ethanol

The electrochemical properties of AlPO₄-coated LiCoO₂ cathodes prepared in a water or ethanol solvent were characterized with the view of stabilizing LiCoO₂ at charge-cutoff voltages of 4.6 and 4.8 V. Under the influence of the AlPO₄ crystallinity, the coated LiCoO₂ prepared in ethanol had better capacity retention than those prepared in water. This enhancement also correlated with the improved suppression of Li-diffusivity decay in the coated cathode from the ethanol compared to that from water. In addition, the differential scanning calorimetry (DSC) results of the AlPO₄ nanoparticle-coated LiCoO₂ with ethanol showed an enhanced thermal stability.     

A study on the chemical stability and electrode performance of modified NiO cathodes for molten carbonate fuel cells

The chemical stabilities of modified NiO cathodes doped with 1.5 mol% CoO and 1.5 mol% LiCoO₂ fabricated by a conventional tape casting method were evaluated through the real MCFC single cell operation. The heat-treated samples before oxidation had proper porosities and microstructures for a MCFC cathode. At 150 mA cm⁻² in current density, the MCFC single cell using a CoO-doped NiO cathode showed stable cell voltages in the range of 0.833-0.843 V for 1000 h. In contrast, the cell using a LiCoO₂-doped NiO cathode with a maximum of 0.836 V at 500 h degraded to 0.826 V at 1000 h due to a wet seal breakdown at the cathode side. The amounts of nickel precipitated in the electrolytes of the cells using modified NiO cathodes doped with CoO and LiCoO₂ after the operation for 1000 h were 1.2 and 1.4 wt.%, respectively, which were about 60% lower than that of the standard cells using pure NiO cathodes. The enhanced chemical stability of modified NiO cathodes seems to be attributed to the fact that the presence of cobalt increases the lithium content in the cathodes by converting Ni²⁺ to Ni³⁺, resulting in stabilizing the layered crystal structure.     

Enhanced electrochemical and thermal stability of surface-modified LiCoO2 cathode by CeO2 coating

CeO₂-coated LiCoO₂ particles were successfully synthesized by a sol-gel coating of CeO₂ on the surface of the LiCoO₂ powder and subsequent heat treatment at 700 °C for 5 h. The surface-modified and pristine LiCoO₂ powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Auger electron spectroscopy (AES), slow rate cyclic voltammogram (CV), and differential scanning calorimetry (DSC). Cyclic voltammetry curves suggested that the CeO₂ coating suppressed the phase transitions. Unlike pristine LiCoO₂, the CeO₂-coated LiCoO₂ cathode exhibited better capacity retention than the pristine LiCoO₂ electrode in the higher cutoff voltage. Differential scanning calorimetric data revealed the higher thermal stability of the CeO₂-coated LiCoO₂ electrode.     

A study on electrochemical characteristics of LiCoO2/LiNi1/3Mn1/3Co1/3O2 mixed cathode for Li secondary battery

In this study, the LiCoO₂/LiNi_1/3Mn_1/3Co_1/3O₂ mixed cathode electrodes were prepared and their electrochemical performances were measured in a high cut-off voltage. As the contents of LiNi_1/3Mn_1/3Co_1/3O₂ in the mixed cathode increases, the reversible specific capacity and cycleability of the electrode enhanced, but the rate capability deteriorated. On the contrary, the rate capability of the cathode enhanced but the reversible specific capacity and cycleability deteriorated, according to increasing the contents of LiCoO₂ in the mixed cathode. The cell of LiCoO₂/LiNi_1/3Mn_1/3Co_1/3O₂ (50:50, wt.%) mixed cathode delivers a discharge capacity of ca. 168 mAh/g at a 0.2 C rate. The capacity of the cell decreased with the current rate and a useful capacity of ca. 152 mAh/g was obtained at a 2.0 C rate. However, the cell shows very stable cycleability: the discharge capacity of the cell after 20th charge/discharge cycling maintains ca. 163 mAh/g.     

Effect of Cr dopant on the cathodic behavior of LiCoO2

Compounds of the formula LiCo_1−yCr_yO₂ (0.0≤y≤0.20 and y=1.0) have been synthesized by high temperature solid-state reaction and were characterized by XRD and FT-IR. Hexagonal a and c lattice parameters increase with increasing y as expected from ionic size effects. Cyclic voltammograms reveal that the phase transformation occurring at x=0.5 in Li_1−x(Co_1−yCr_y)O₂ is suppressed for y=0.05 and 0.10. Low-current (0.01 C; 1 C=140 mA g⁻¹) galvanostatic charging curves show that the deintercalation voltage for y=0.05 and 0.10 decrease for a given x as compared to LiCoO₂. Galvanostatic charge-discharge cycling of the Li(Co_1−yCr_y)O₂ cathodes at 0.14 C and 2.7-4.3 V (vs. Li) show that increasing amount of chromium content in the LiCoO₂ lattice drastically reduces the amount of Li that can be reversibly cycled. Ex-situ XRD of the cycled cathodes show that slight cation-mixing occurs in the layered structure for y=0.05 and 0.10 and could be the reason for their poor electrochemical performance. Reversible Li intercalation/deintercalation is not possible in LiCrO₂ in the voltage range 2.7-4.3 V.     

Preparation of micro-dot electrodes of LiCoO2 and Li4Ti5O12 for lithium micro-batteries

Fabrications of micro-dot electrodes of LiCoO₂ and Li₄Ti₅O₁₂ on Au substrates were demonstrated using a sol-gel process combined with a micro-injection technology. A typical size of prepared dots was about 100 μm in diameter, and the dot population on the substrate was 2400 dots cm⁻². The prepared LiCoO₂ and Li₄Ti₅O₁₂ micro-dot electrodes were characterized with scanning electron microscopy, X-ray diffraction, micro-Raman spectroscopy, and cyclic voltammetry. The prepared LiCoO₂ and Li₄Ti₅O₁₂ micro-dot electrodes were evaluated in an organic electrolyte as cathode and anode for lithium micro-battery, respectively. The LiCoO₂ micro-dot electrode exhibited reversible electrochemical behavior in a potential range from 3.8 to 4.2 V versus Li/Li⁺, and the Li₄Ti₅O₁₂ micro-dot electrode showed sharp redox peaks at 1.5 V.     

Hydrothermal-assisted synthesis of surface aluminum-doped LiCoO2 nanobricks for high-rate lithium-ion batteries

LiCoO₂ nano-particles precursor was synthesized through a mixed-alkalis (LiOH-NaOH) hydrothermal reaction, and finally sintered into LiCoO₂ nanobricks with a sickness of ~300?nm. This LiCoO₂ nanobrick cathode delivered a specific capacity of 131.8 mAh g^?1 at 1?C between 3.0 and 4.2?V and 90% capacity retention after 100 cycles. Those synthesized LiCoO₂ nanobricks were further treated by surface Al³⁺ doping to achieve much enhanced 4.5?V lithium storage capability and cycling stability. EIS results showed the surface Al³⁺ doping operation can signification decrease the charge-transfer resistances of the LiCoO₂ cathodes for both before and after cyclings.     

High voltage stability of LiCoO2 particles with a nano-scale Lipon coating

For high-voltage cycling of rechargeable Li batteries, a nano-scale amorphous Li-ion conductor, lithium phosphorus oxynitride (Lipon), has been coated on surfaces of LiCoO₂ particles by combining a RF-magnetron sputtering technique and mechanical agitation of LiCoO₂ powders. LiCoO₂ particles coated with 0.36 wt% (∼1 nm thick) of the amorphous Lipon, retain 90% of their original capacity compared to non-coated cathode materials that retain only 65% of their original capacity after more than 40 cycles in the 3.0–4.4 V range with a standard carbonate electrolyte. The reason for the better high-voltage cycling behavior is attributed to reduction in the side reactions that cause increase of the cell resistance during cycling. Further, Lipon coated particles are not damaged, whereas uncoated particles are badly cracked after cycling. Extending the charge of Lipon-coated LiCoO₂ to higher voltage enhances the specific capacity, but more importantly the Lipon-coated material is also more stable and tolerant of high voltage excursions. A drawback of Lipon coating, particularly as thicker films are applied to cathode powders, is the increased electronic resistance that reduces the power performance.     

Correlation between AlPO4 nanoparticle coating thickness on LiCoO2 cathode and thermal stability

The thickness of an AlPO₄ coating significantly affects the thermal stability of a LiCoO₂ cathode. Increasing the coating thickness leads to not only a decrease in the exothermic reaction between the cathode and the electrolyte but also to an improvement in the cycling performance. A 1 C rate overcharge experiment up to 12 V is a good example of the thermal stability of the cathode in the Li-ion cell. Furthermore, increasing the AlPO₄ coating thickness results in the lowest cell surface temperature, which is indicative of the degree of heat generation.     

Cycling-induced degradation of LiCoO2 thin-film cathodes at elevated temperature

The cycle life of LiCoO₂-based all solid-state thin-film cells has been studied at room temperature, and at elevated temperatures of 50, 100, and 150 °C. X-ray diffraction, as well as Raman analysis, has been used to complement the electrochemical data in examining structural and chemical changes. XRD and Raman spectroscopy data indicate that elevated temperature soaks of the thin-film batteries in the quiescent state causes no discernable changes in the LiCoO₂ cathode layer. However, when the thin-film batteries are cycled at elevated temperatures, decreases in average grain size of the LiCoO₂ film occur with dramatic concomitant charge and discharge capacity loss.     

Improvement of structural and electrochemical properties of commercial LiCoO2 by coating with LaF3

Commercial LiCoO₂ has been modified with LaF₃ as a new coating material. The surface modified materials were characterized by X-ray diffraction (XRD), transmission electronic microscopy (TEM), field emission scanning electron microscopy (FE-SEM), auger electron spectroscopy (AES) and galvanostatic charge–discharge cycling. The LaF₃-coated LiCoO₂ had an initial discharge specific capacity of 177.4 mAh g⁻¹ within the potential ranges 2.75–4.5 V (vs. Li/Li⁺), and showed a good capacity retention of 90.9% after 50 cycles. It was found that the overcharge tolerance of the coated cathode was significantly better than that of the pristine LiCoO₂ under the same conditions – the capacity retention of the pristine LiCoO₂ was 62.3% after 50 cycles. The improvement could be attributed to the LaF₃ coating layer that hinders interaction between LiCoO₂ and electrolyte and stabilizes the structure of LiCoO₂. Moreover, DSC showed that the coated LiCoO₂ had a higher thermal stability than the pristine LiCoO₂.     

Performance evaluation of printed LiCoO2 cathodes with PVDF-HFP gel electrolyte for lithium ion microbatteries

In order to improve the discharge capacity in lithium ion microbatteries, a thick-film cathode was fabricated by a screen printing using LiCoO₂ pastes. The printed cathode showed a different discharge curves when the cell was tested using various (liquid, gel and solid-state) electrolytes. When a cell test was performed with organic liquid electrolyte, the maximum discharge capacity was 200 μAh cm⁻², which corresponded to approximately 133 mAh g⁻¹ when the loading weight of LiCoO₂ was calculated. An all-solid-state microbattery could be assembled using sputtered LiPON electrolyte, an evaporated Li anode, and printed LiCoO₂ cathode films without delamination or electrical problems. However, the highest discharge capacity showed a very small value (7 μAh cm⁻²). This problem could be improved using a poly(vinylidene fluoride-hexafluoro propylene) (PVDF-HFP) gel electrolyte, which enhanced the contact area and adhesion force between cathode and electrolyte. The discharge value of this cell was measured as approximately 164 μAh cm⁻² (≈110 mAh g⁻¹). As the PVDF-HFP electrolyte had a relatively soft contact property with higher ionic conductance, the cell performance was improved. In addition, the cell can be fabricated in a leakage-free process, which can resolve many safety problems. According to these results, there is a significant possibility that a film prepared using the aforementioned paste with screen printing and PVDF-HFP gel electrolyte is feasible for a microbattery.     

Lanthanum-doped LiCoO2 cathode with high rate capability

Lanthanum-doped LiCoO₂ composite cathode materials, containing 0.1-10 mol% of La were synthesized by citric acid aided combustion technique. Thermal analyses showed that the sharp decomposition reaction for pristine LiCoO₂ became sluggish upon addition of lanthanum. X-ray diffraction analyses of the composites revealed existence of minute quantities of lanthanum-rich perovskite phases—rhombohedral LaCoO₃ and tetragonal La₂Li_0.5Co_0.5O₄ (14/mmm), along with rhombohedral LiCoO₂. Electron microscopy showed a distinct grain growth with increasing La content. An increase of about two orders of magnitude in the electrical conductivity (1.09 × 10⁻³ S cm⁻¹) was observed for 1.0 mol% La-doped LiCoO₂. An excellent cycling performance with capacity retention by a factor of ∼10 in comparison to the pristine LiCoO₂ was observed for the composite cathode containing 5.0 mol% La, when 2032 type coin cells were cycled at 5C rate. This has been ascribed to the structural stability induced by La doping and presence of the ion-conducting phase La₂Li_0.5Co_0.5O₄ which acts as a solid electrolyte for Li⁺ ions. A negligible growth of impedance upon repeated cycling has been observed. Cyclic voltammetry showed a remarkable improvement in reversibility and stability of the La-doped electrodes. These composite cathodes might be very useful for high rate power applications.     

A voltammetric study concerning the structural stability of Li-overstoichiometric Mg-doped LiCoO2 powders

The effect of Mg-doping and Li overstoichiometry on the structural stability of LiCoO₂ powders has been investigated with emphasis to voltammetric properties. Microparticle cyclic voltammetry (CV) conducted in caustic NaOH to best simulate a non-aqueous electrolyte shows a marked improvement of the structure stability of doped LiCoO₂. In contrast to the unsubstituted LiCoO₂ sample which shows voltammetric peaks associated to the well-known two-phase domain and monoclinic distortion reactions, in Li_1.08Mg_0.06CoO₂, LiMg_0.06CoO₂ and Li_1.08CoO₂ samples these peaks are strongly suppressed providing direct evidence for the existence of a stable solid solution with negligible phase transitions in the reversible intercalation region (3.8-4.2 V vs. Li) as well as in the overcharged region. The effect is higher with Mg-doping, irrespective of the Li overstoichiometry. However, the concomitant presence of Mg and Li excess in the structure is important for obtaining small particle sizes. Since Mg-doping induces a quasi metallic behavior in the samples, whereas the Li excess may provide an higher initial capacity, it is suggested that the Li_1.08Mg_0.06CoO₂ composition may be of interest as positive cathode for advanced Li-ion batteries.     

LiCoO2 thin film cathode fabrication by rapid thermal annealing for micro power sources

The rapid thermal annealing (RTA) process was employed to obtain crystalline LiCoO₂ thin films. XRD analyses of the LiCoO₂ thin film show increased crystallinity with an increase in the RTA time. The Auger electron spectroscopic analysis of the LiCoO₂ film strongly suggests that the RTA process is more advantageous to obtain a stable inter layer between the substrate and the deposited film and between each deposited layer than the conventional annealing process. All-solid-state thin film cells composed of Li/lithium phosphorous oxynitride (Lipon)/LiCoO₂ systems were fabricated using the LiCoO₂ cathode treated with RTA. The optimum condition of RTA would be 900 s at 650 °C, which exhibited a good rate capability for high power applications. Two cells were connected in parallel to obtain a higher discharge current, and they showed a specific capacity of 38.4 μAh cm⁻² μm⁻¹ even at a 25C rate (current density: 7.96 mA cm⁻²).     

On the capacity fading of LiCoO2 intercalation electrodes:: the effect of cycling, storage, temperature, and surface film forming additives

The electrochemical behavior and surface chemistry of LiCoO₂ intercalation cathodes as a function of cycling and storage at 25, 45, and 60 °C was studied. The standard solutions for this work comprised ethylene carbonate (EC), ethyl-methyl carbonate (EMC), (1:2) and 1 M LiPF₆. The effect of two surface film-forming additives, vinylene carbonate (VC) and an organo-borate complex (denoted as Merck's AD25) in solutions was also explored. We analyzed temperature-dependent processes of surface film formation on the cathodes, which increase their impedance upon cycling and storage, thus making their electrochemical kinetics sluggish. We also analyzed cobalt dissolution from the cathodes at 25, 45 and 60 °C. The apparent capacity fading of the LiCoO₂ electrodes is attributed mostly to changes on their surface, rather than to bulk degradation. There are signs that the presence of HF in solutions may play a major negative role. Hence, as the electrode's surface/solution volume ratio is higher, the capacity fading of the LiCoO₂ electrodes should be lower. The main tools for this study were cyclic voltammetry, chronopotentiometry, impedance spectroscopy, electrochemical quartz crystal microbalance (EQCM), IR-spectroscopy, XRD, XPS, and SEM.     

Improved rate performance of LiCoO2-based multi-phase composite due to Pt additive

The effect of Pt additive on the microstructure and electrochemical properties of synthesized LiCoO₂-based material was investigated. Besides incorporating into LiCoO₂ lattice in small amounts, Pt additive induces dispersed Li₂PtO₃ and Pt in the LiCoO₂ matrix to form multi-phase composites. In comparison with the single phase of LiCoO₂, the multi-phase composite shows improved rate performance and cycleability at high rates. This improved rate behaviors can be attributed to the enhanced diffusion of Li⁺, which are caused by the enlarged c axis of LiCoO₂ lattice due to Pt incorporating and fast diffusion paths of Li⁺ provided by the interfaces among in LiCoO₂, Li₂PtO₃ and Pt. The dispersed Li₂PtO₃ and Pt are also beneficial to the cycleability.     

<Emphasis Type="Italic">In situ</Emphasis> microobservation of the cathode in molten carbonate fuel cells

In molten carbonate fuel cells (MCFC), the wettability of the electrode and the electrolyte distribution are very important factors influencing the active reaction area. We have observed the molten carbonate behaviour directly on the cathode (porous NiO) and the electrolyte plate (LiAlO₂) under various gas conditions and at controlled potentials using an environmental scanning electron microscope (ESEM) equipped with a hot stage. We estimated the liquid electrolyte distribution in the cathode and measured the contact angles on NiO and LiAlO₂ in the electrolyte. Moreover, the electrolyte movement in the reaction CO₂ + O₂ + 2e^– = CO₃ ^2– was observed on the surface of the porous NiO in a CO₂/O₂ atmosphere. The reaction CO₃ ^2– + 2e^– = CO + 2 O^2– of the gas generation was observed in a H₂O atmosphere. The active reaction points on the electrode are the areas where the electrolyte film is thin.