Improved Fabrication of Lithium Films Having Micron Features

An improved method has been devised for fabricating micron-dimension Li features. This approach is intended for application in the fabrication of lithium-based microelectrochemical devices -- particularly solid-state thin-film lithium microbatteries

Apparatus for Screening Multiple Oxygen-Reduction Catalysts

An apparatus that includes an array of multiple electrodes has been invented as a means of simultaneously testing multiple materials for their utility as oxygen-reduction catalysts in fuel cells. The apparatus ensures comparability of test results by exposing all the catalyst-material specimens to the same electrolytic test solution at the same potential. Heretofore, it has been possible to test only one specimen at a time, using a precise rotating disk electrode that provides a controlled flux of solution to the surface of the specimen

MoO3 Cathodes for High-Temperature Lithium Thin-Film Cells

MoO3 has shown promise as a cathode material that can extend the upper limit of operating temperature of rechargeable lithium thin-film electrochemical cells. Cells of this type are undergoing development for use as energy sources in cellular telephones, wireless medical sensors, and other, similarly sized portable electronic products. The LiCoO2 and LiMn2O4 cathodes heretofore used in these cells exhibit outstanding cycle lives (of the order of hundreds of thousands of cycles) at room temperature, but operation at higher temperatures reduces their cycle lives substantially: for example, at a temperature of 150 C, cells containing LiCoO2 cathodes lose half their capacities in 100 charge/discharge cycles. The superiority of MoO3 as a cathode material was demonstrated in experiments on lithium thin-film cells fabricated on glass slides. Each cell included a layer of Ti (for adhesion to the glass slide), a patterned layer of Pt that served as a cathode current collector, a cathode layer of MoO3, a solid electrolyte layer of Li3.3 PO3.8 N0.22 ("LiPON"), and an anode layer of Li. All the layers were deposited by magnetron sputtering except for the Li layer, which was deposited by thermal evaporation. These cells, along with similar ones containing LiCoO2 cathodes, were subjected to several tests, including measurements of specific capacity in charge/discharge cycling at a temperature of 150 C. The results of these measurements, plotted in the figure, showed that whereas specific capacity of the cells containing LiCoO2 cathodes faded to about half its initial value after only 100 cycles, the specific capacity of the cells containing the MoO3 cathodes faded only slightly during the first few hundred cycles and thereafter not only recovered to its initial value but continued to increase up to at least 5,500 cycles

Laser Ablation Increases PEM/Catalyst Interfacial Area

An investigational method of improving the performance of a fuel cell that contains a polymer-electrolyte membrane (PEM) is based on the concept of roughening the surface of the PEM, prior to deposition of a thin layer of catalyst, in order to increase the PEM/catalyst interfacial area and thereby increase the degree of utilization of the catalyst. The roughening is done by means of laser ablation under carefully controlled conditions. Next, the roughened membrane surface is coated with the thin layer of catalyst (which is typically platinum), then sandwiched between two electrode/catalyst structures to form a membrane/ele c t - rode assembly. The feasibility of the roughening technique was demonstrated in experiments in which proton-conducting membranes made of a perfluorosulfonic acid-based hydrophilic, protonconducting polymer were ablated by use of femtosecond laser pulses. It was found that when proper combinations of the pulse intensity, pulse-repetition rate, and number of repetitions was chosen, the initially flat, smooth membrane surfaces became roughened to such an extent as to be converted to networks of nodules interconnected by filaments (see Figure 1). In further experiments, electrochemical impedance spectroscopy (EIS) was performed on a pristine (smooth) membrane and on two laser-roughened membranes after the membranes were coated with platinum on both sides. Some preliminary EIS data were interpreted as showing that notwithstanding the potential for laser-induced damage, the bulk conductivities of the membranes were not diminished in the roughening process. Other preliminary EIS data (see Figure 2) were interpreted as signifying that the surface areas of the laser-roughened membranes were significantly greater than those of the smooth membrane. Moreover, elemental analyses showed that the sulfur-containing molecular groups necessary for proton conduction remained intact, even near the laser-roughened surfaces. These preliminary results can be taken as indications that laser-roughened PEMs should function well in fuel cells and, in particular, should exhibit current and power densities greater than those attainable by use of smooth membranes

Low-Pt-Content Anode Catalyst for Direct Methanol Fuel Cells

Combinatorial experiments have led to the discovery that a nanophase alloy of Pt, Ru, Ni, and Zr is effective as an anode catalyst material for direct methanol fuel cells. This discovery has practical significance in that the electronic current densities achievable by use of this alloy are comparable or larger than those obtained by use of prior Pt/Ru catalyst alloys containing greater amounts of Pt. Heretofore, the high cost of Pt has impeded the commercialization of direct methanol fuel cells. By making it possible to obtain a given level of performance at reduced Pt content (and, hence, lower cost), the discovery may lead to reduction of the economic impediment to commercialization

Increasing Discharge Capacities of Li-(CF)(sub n) Cells

An electrolyte additive has shown promise as a means of increasing the sustainable rates of discharge and, hence, the discharge capacities, of lithiumpoly(carbon monofluoride) electrochemical power cells. Lithium-poly(carbon monofluoride) [Li-(CF)n] cells and batteries offer very high specific energies practical values of about 600 W.h/g and a theoretical maximum value of 2,180 W.h/kg. However, because Li-(CF)n cells and batteries cannot withstand discharge at high rates, they have been relegated to niche applications that involve very low discharge currents over times of the order of hundreds to thousands of hours. Increasing the discharge capacities of Li- (CF)n batteries while maintaining high practical levels of specific energy would open new applications for these batteries. During the discharge of a Li-(CF)n cell, one of the electrochemical reactions causes LiF to precipitate at the cathode. LiF is almost completely insoluble in most non-aqueous solvents, including those used in the electrolyte solutions of Li-(CF)n cells. LiF is electrochemically inactive and can block the desired transport of ions at the cathode, and, hence, the precipitation of LiF can form an ever-thickening film on the cathode that limits the rate of discharge

Solid-State High-Temperature Power Cells

All-solid-state electrochemical power cells have been fabricated and tested in a continuing effort to develop batteries for instruments for use in environments as hot as 500 C. Batteries of this type are needed for exploration of Venus, and could be used on Earth for such applications as measuring physical and chemical conditions in geothermal and oil wells, processing furnaces, and combustion engines. In the state-of-the-art predecessors of the present solid-state power cells, fully packaged molten eutectic salts are used as electrolytes. The molten-salt-based cells can be susceptible to significant amounts of self-discharge and corrosion when used for extended times at elevated temperatures. In contrast, all-solid-state cells such as the present ones are expected to be capable of operating for many days at temperatures up to 500 C, without significant self-discharge. The solid-state cell described here includes a cathode made of FeS2, an electrolyte consisting of a crystalline solid solution of equimolar amounts of Li3PO4 and Li4SiO4, and an anode made of an alloy of Li and Si (see figure). The starting material for making the solid electrolyte is a stoichiometric mixture of Li3PO4, SiO2, and Li3CO2. This mixture is ball-milled, then calcined for two hours at a temperature of 1,100 C, then placed in a die atop the cathode material. Next, the layers in the die are squeezed together at a pressure between 60 and 120 MPa for one hour at a temperature of 600 C to form a unitary structure comprising the solid electrolyte and cathode bonded together. Finally, the lithium-alloy anode is pressure-bonded to the solid electrolyte layer, using an intermediate layer of pure lithium. In one test of a cell of this type, a discharge rate of about 1 mA per gram of cathode material was sustained for 72 hours at a temperature of about 460 C. This is about three times the discharge rate required to support some of the longer duration Venus-exploration mission scenarios

Integrated Microbatteries for Implantable Medical Devices

Integrated microbatteries have been proposed to satisfy an anticipated need for long-life, low-rate primary batteries, having volumes less than 1 mm3, to power electronic circuitry in implantable medical devices. In one contemplated application, such a battery would be incorporated into a tubular hearing-aid device to be installed against an eardrum. This device is based on existing tube structures that have already been approved by the FDA for use in human ears. As shown in the figure, the battery would comprise a single cell at one end of the implantable tube. A small volume of Li-based primary battery cathode material would be compacted and inserted in the tube near one end, followed by a thin porous separator, followed by a pressed powder of a Li-containing alloy. Current-collecting wires would be inserted, with suitably positioned insulators to prevent a short circuit. The battery would contain a liquid electrolyte consisting of a Li-based salt in an appropriate solvent. Hermetic seals would be created by plugging both ends with a waterproof polymer followed by deposition of parylene

Additive for Low-Temperature Operation of Li-(CF)n Cells

Some progress has been reported in continuing research on the use of anion-receptor compounds as electrolyte additives to increase the sustainable rates of discharge and, hence, the discharge capacities, of lithium-poly(carbon monofluoride) [Li-(CF)n, where n >1] primary electrochemical power cells. Some results of this research at a prior stage were summarized in Increasing Discharge Capacities of Li(CF)n Cells (NPO-42346), NASA Tech Briefs, Vol. 32, No. 2 (February 2008), page 37. A major difference between the present and previously reported results is that now there is some additional focus on improving performance at temperatures from ambient down to as low as 40 C. To recapitulate from the cited prior article: During the discharge of a Li-(CF)n cell, one of the electrochemical reactions causes LiF to precipitate at the cathode. LiF is almost completely insoluble in most non-aqueous solvents, including those used in the electrolyte solutions of Li- (CF)n cells. LiF is electrochemically inactive and can block the desired transport of electrons at the cathode, and, hence, the precipitation of LiF can form an ever-thickening film on the cathode that limits the rate of discharge. An anion-receptor electrolyte additive helps to increase the discharge capacity in two ways: It renders LiF somewhat soluble in the non-aqueous electrolyte solution, thereby delaying precipitation until a high concentration of LiF in solution has been reached. When precipitation occurs, it promotes the formation of large LiF grains that do not conformally coat the cathode. The net effect is to reduce the blockage caused by precipitation of LiF, thereby maintaining a greater degree of access of electrolyte to the cathode and greater electronic conductivity