Effect of Cobalt Content on the Electrochemical Properties and Structural Stability of NCA Type Cathode Materials

At present, the most common type of cathode materials, NCA [Li_(1-x)Ni_(0.80)Co_(0.15)Al_(0.05)O_(2), x = 0 to 1], have a very high concentration of cobalt. Since cobalt is toxic and expensive, the existing design of cathode materials is neither cost-effective nor environmentally benign. We have performed density functional theory (DFT) calculations to investigate electrochemical, electronic, and structural properties of four types of NCA cathode materials with the simultaneous decrease in Co content along with the increase in Ni content. Our results show that even if the cobalt concentration is significantly decreased from 16.70 % (NCA_I) to 4.20 % (NCA_IV), variation in intercalation potential and specific capacity is not significant. For example, in case of 50% Li concentration, the voltage drop is only ~17% while the change in specific capacity is negligible. Moreover, we have also explored the influence of sodium doping in the intercalation site on the electrochemical, electronic, and structural properties. By considering two extreme cases of NCAs (i.e., with highest and lowest Co content: NCA_I and NCA_IV respectively), we have demonstrated the importance of Na doping from the structural and electronic point of view. Our results provide insight into the design of environmentally benign, low-cost cathode materials with reduced cobalt concentration.Comment: 28 pages, 9 figures. arXiv admin note: substantial text overlap with arXiv:1704.0841

Synthesis of oxyanion-doped barium strontium cobaltferrites: stabilization of the cubic perovskite and enhancement in conductivity

In this paper we demonstrate the successful incorporation of oxyanions (borate, phosphate) into Ba1ySryCo0.8Fe0.2O3−δ (BSCF) cathode materials. For low levels of dopant, a small enhancement in the conductivity was observed; e.g. 31.6, 34.4 and 35.9 S·cm-1 for Ba0.33Sr0.67Co0.8Fe0.2O3−δ, Ba0.33Sr0.67Co0.76Fe0.19B0.05O3−δ and Ba0.33Sr0.67Co0.76Fe0.19P0.05O3−δ, respectively, at 700ºC. Most significantly, oxyanion doping was shown to improve the stability of the cubic form of BSCF at intermediate temperatures (especially for P-doping), helping to prevent the transition to a hexagonal cell, and maintaining its excellent electrical properties. The work shows the potential of oxyanion doping strategies to modify the performance of SOFC cathode materials

Life test results for an ensemble of CO2 lasers

The effects of cathode material, cathode operating temperature, anode configuration, window materials, and hydrogen additives on laser lifetime are determined. Internally oxidized copper and silber-copper alloy cathodes were tested. The cathode operating temperature was raised in some tubes through the use of thermal insulation. Lasers incorporating thermally insulated silver copper oxide cathodes clearly yielded the longest lifetimes-typically in excess of 22,000 hours. The use of platinum sheet versus platinum pin anodes had no observable effect on laser lifetime. Similarly, the choice of germanium, cadmium telluride, or zinc selenide as the optical window material appears to have no impact on lifetime

Potentialities of the sol-gel route to develop cathode and electrolyte thick layers Application to SOFC systems

In this work, we report the potential of sol–gel process to prepare cathode and electrolyte thin and thick layers on anodic NiO-YSZ supports which were also made from powders prepared by sol–gel route. YSZ and La2 − xNiO4 + δ, La4Ni3O10 were synthesized as electrolyte and cathode materials for SOFC applications. For electrolyte shaping, yttria stabilized zirconia (YSZ, 8% Y2O3) thick films were cast onto porous NiO-YSZ composite substrates by a dip-coating process using a new suspension formulation. Part of the YSZ precursor colloidal sol was added in the suspension to ensure both homogeneity and adhesion of the electrolyte on the anodic substrate after thermal treatment at 1400 °C for 2 h. By precisely controlling the synthesis parameters, dense and gas-tight layers with thicknesses in the range of 10–20 μm have been obtained. Gas-tightness was confirmed by He permeation measurements. Concerning cathode processing, a duplex microstructured cathode consisting of both La2 − xNiO4 + δ ultra-thin films (few nanometers) and La2 − xNiO4 + δ and/or La4Ni3O10 thick layers (few micrometers) was prepared on YSZ substrates by the dip-coating process, with the thickness being dependent on the nature of the dip-coated solution (polymeric sol or adequate suspension). The derived cathode microstructure, related to the number/thickness of layers and type of architecture, was correlated to the good cell electrochemical performances. Concerning cathode processing, a duplex microstructured cathode consisting of both La2 ? xNiO4 + ? ultra-thin films (few nanometers) and La2 ? xNiO4 + ? and/or La4Ni3O10 thick layers (few micrometers) was prepared on YSZ substrates by the dip-coating process, with the thickness being dependent on the nature of the dip-coated solution (polymeric sol or adequate suspension). The derived cathode microstructure, related to the number/thickness of layers and type of architecture, was correlated to the good cell electrochemical performances

Advanced rechargeable sodium batteries with novel cathodes

Various high energy density rechargeable batteries are being considered for future space applications. Of these, the sodium sulfur battery is one of the leading candidates. The primary advantage is the high energy density (760 Wh/kg theoretical). Energy densities in excess of 180 Wh/kg have been realized in practical batteries. More recently, cathodes other than sulfur are being evaluated. Researchers at JPL are evaluating various new cathode materials for use in high energy density sodium batteries for advanced space applications. The approach is to carry out basic electrochemical studies of these materials in a sodium cell configuration in order to understand their fundamental behaviors. Thus far studies have focused on alternate metal chlorides such as CuCl2 and organic cathode materials such as tetracyanoethylene (TCNE)

Effect of composition on the structure of lithium- and manganese-rich transition metal oxides

The choice of chemical composition of lithium- and manganese-rich transition metal oxides used as cathode materials in lithium-ion batteries can significantly impact their long-term viability as storage solutions for clean energy automotive applications. Their structure has been widely debated: conflicting conclusions drawn from individual studies often considering different compositions have made it challenging to reach a consensus and inform future research. Here, complementary electron microscopy techniques over a wide range of length scales reveal the effect of lithium-to-transition metal-ratio on the surface and bulk structure of these materials. We found that decreasing the lithium-to-transition metal-ratio resulted in a significant change in terms of order and atomic-level local composition in the bulk of these cathode materials. However, throughout the composition range studied, the materials consisted solely of a monoclinic phase, with lower lithium content materials showing more chemical ordering defects. In contrast, the spinel-structured surface present on specific crystallographic facets exhibited no noticeable structural change when varying the ratio of lithium to transition metal. The structural observations from this study warrant a reexamination of commonly assumed models linking poor electrochemical performance with bulk and surface structure

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Department of Energy Engineering (Energy Engineering)Solid oxide fuel cells (SOFCs) are recognized as next generation environmentally friendly energy conversion devices due to their high energy conversion efficiency, fuel flexibility, efficient reclamation of waste heat, and low pollutant emissions. Nevertheless, the commercialization of SOFCs has been impeded by reason of some issues associated with the high operating temperatures (800-1000oC) such as undesired reactions between cell components, high cost, and material compatibility challenges. Thus, reducing the operating temperatures toward an intermediate temperature range (600-800oC) is essential to overcome the aforementioned problems. In intermediate temperature SOFCs (IT-SOFCs), however, electrocatalytic activity toward oxygen reduction reaction at the cathode is significantly decreased, which in turn causes insufficient fuel cell performance. Current researches, therefore, have been focused on enhancing the performance of cathode for effective IT-SOFC operation. In this regard, the infiltration method could be an excellent cathode fabrication method, considering its outstanding advantages toward intermediate temperature operation. First, each optimized sintering temperature of cathode and electrolyte can be applied, ensuring the favorable characteristics for IT-SOFC operation. Second, due to relatively low sintering temperature, nano structured cathodes can be formed, resulting in enlarged surface area and enhancement of electrochemical performance. Finally, long term stability is improved because the thermal expansion coefficient between cathode and electrolyte is minimized. This thesis mainly focuses on the fabrication of SOFC cathode by the infiltration method to achieve high fuel cell performance in the intermediate temperature range. Herein, my research paper studying infiltrated cathode materials for IT-SOFC is presented as follows. - A Nano-structured SOFC Composite Cathode Prepared via Infiltration of La0.5Ba0.25Sr0.25Co0.8Fe0.2O3-?? into La0.9Sr0.1Ga0.8Mg0.2O3-?? for Extended Triple Phase Boundary Areaclos

Challenges and Opportunities of Layered Cathodes of LiNixMnyCo(1-x-y)O2 for High-Performance Lithium-ion Batteries

High energy density lithium-ion batteries (LIBs) are widely demanded for portable electronic devices and electrical vehicles. Layered-structure LiCoO2 oxide (LCO) has been the most commonly used cathode material in commercial LIBs. Compared to LCO, LiNi1-x-yMnxCoyO2 (NMC) cathodes are particularly attractive due to their reduced cost and higher capacity. Among the NMC cathodes, nickel-containing LiNi0.5Co0.3Mn0.2O2 (NMC532) is one of the most promising cathode materials undergoing intensive investigation, but suffers from a series of technical issues, such as structural instability, performance fading, and safety issues. In this report, material structure and synthetic methods of LiNi0.5Co0.3Mn0.2O2, as well as current issues and progresses are introduced

Ultrahigh power and energy density in partially ordered lithium-ion cathode materials

The rapid market growth of rechargeable batteries requires electrode materials that combine high power and energy and are made from earth-abundant elements. Here we show that combining a partial spinel-like cation order and substantial lithium excess enables both dense and fast energy storage. Cation overstoichiometry and the resulting partial order is used to eliminate the phase transitions typical of ordered spinels and enable a larger practical capacity, while lithium excess is synergistically used with fluorine substitution to create a high lithium mobility. With this strategy, we achieved specific energies greater than 1,100 Wh kg–1 and discharge rates up to 20 A g–1. Remarkably, the cathode materials thus obtained from inexpensive manganese present a rare case wherein an excellent rate capability coexists with a reversible oxygen redox activity. Our work shows the potential for designing cathode materials in the vast space between fully ordered and disordered compounds