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Electrolyte management considerations in modern nickel hydrogen and nickel cadmium cell and battery designs

In the early 1980's the NASA Lewis group addressed the topic of designing nickel hydrogen cells for LEO applications. As published in 1984, the design addressed the topics of gas management, liquid management, plate expansion, and the recombination of oxygen during overcharge. This design effort followed principles set forth in an earlier Lewis paper that addressed the topic of pore size engineering. At about that same time, the beneficial effect on cycle life of lower electrolyte concentrations was verified by Hughes Aircraft as part of a Lewis funded study. A succession of life cycle tests of these concepts have been carried out that essentially verified all of this earlier work. During these past two decades, some of the mysteries involved in the active material of the nickel electrode have been resolved by careful research efforts carried out at several laboratories. At The Aerospace Corporation, Dr. Zimmerman has been developing a sophisticated model of an operating nickel hydrogen cell which will be used to model certain mechanisms that have contributed to premature failures in nickel hydrogen and nickel cadmium cells. During the course of trying to understand and model abnormal nickel hydrogen cell behaviors, we have noted that not enough attention has been paid to the potassium ion content in these cells, and more recently batteries. Several of these phenomenon have been well known in the area of alkaline fuel cells, but only recently have they been examined as they might impact alkaline cell designs. This paper will review three general areas where the potassium ion content can impact the performance and life of nickel hydrogen and nickel cadmium devices, Once these phenomenon are understood conceptually, the impact of potassium content on a potential cell design can be evaluated with the aid of an accurate model of an operating cell or battery. All three of these areas are directly related to the volume tolerance and pore size engineering aspects of the components used in the cell or battery design: (1) The gamma phase uptake of potassium ion can result in a lowering of the electrolyte concentration. This leads to a higher electrolyte resistance as well as electrolyte diffusional limitations on the discharge rate. This phenomenon will also impact the response of the cell to a reconditioning cycle. (2) The impact of low level shunt currents in multi-cell con figurations will result in the movement of potassium ion from one part of the battery to another. This will impact the electrolyte volume/vapor pressure relationships within the cell or battery. (3) The transport of water vapor from place to place under the driving force of a tempetature gradient has already impacted cells for the case where water vapor is condensed on a colder cell wall. The paper will explore the convective and diffusive movement of gases saturated with water vapor from a warmer plate pack to a cooler one - both with and without liquid communication.

Thaller, L. H.↗

Electrolyte Management Considerations in Modern Nickel Hydrogen and Nickel Cadmium Cell and Battery Designs

This paper reviews three general areas where the potassium ion content can impact the performance and life of nickel hydrogen and nickel cadmium cells. Sample calculations of the concentration or volume changes that can take place within operating cells are presented. With the aid of an accurate model of an operating cell or battery, the impact of changes of potassium ion content within a potential cell design can be estimated. All three of these areas are directly related to the volume tolerance and pore size engineering aspects of the components used in the cell or battery design.

Thaller, Lawrence H.↗

Activation parameters of flow through battery separators

Studies of the hydrodynamic flow of water and 45 percent potassium hydroxide (KOH) solution through a microporous and an ion exchange separator are described. The permeability values are interpreted in terms of a pseudoactivation process. The enthalpy of activation deltaH* and the entropy of activation deltaS* were estimated from Eyring's rate equation.

Blokhra, R. L.↗

Lifetime estimates for sterilizable silver-zinc battery separators

The lifetime of separator membranes currently employed in the electrolyte environment of silver-zinc batteries was estimated at 3 to 5 years. The separator membranes are crosslinked polyethylene film containing grafted poly (potassium acrylate)(PKA), the latter being the hydrophilic agent which promotes electrolyte ion transport. The lifetime was estimated by monitoring the rate of loss of PKA from the separators, caused by chemical attack of the electrolyte, and relating this loss rate to a known relationship between battery performance and PKA concentration in the separators.

Cuddihy, E. F.↗

Recent developments in nickel electrode analysis

Three aspects of nickel electrode analysis for Nickel-Hydrogen and Nickel-Cadmium battery cell applications are addressed: (1) the determination of active material; (2) charged state nickel (as NiOOH + CoOOH); and (3) potassium ion content in the electrode. Four deloading procedures are compared for completeness of active material removal, and deloading conditions for efficient active material analyses are established. Two methods for charged state nickel analysis are compared: the current NASA procedure and a new procedure based on the oxidation of sodium oxalate by the charged material. Finally, a method for determining potassium content in an electrode sample by flame photometry is presented along with analytical results illustrating differences in potassium levels from vendor to vendor and the effects of stress testing on potassium content in the electrode. The relevance of these analytical procedures to electrode performance is reviewed.

Whiteley, Richard V.↗

Development of potassium ion conducting hollow glass fibers

Potassium ion conducting glasses, chemically resistant to potassium, potassium sulfide and sulfur, were made and their possible utility as the membrane material for a potassium/sulfur battery was evaluated. At least one satisfactory candidate was found. It possesses an electrical resistance which makes it usable as a membrane in the form of a fine hollow fiber. It's chemical and electrochemical resistances are excellent. The other aspects of the possible potassium sulfur battery utilizing such fine hollow fibers, including the header (or tube sheet) and a cathode current collector were studied. Several cathode materials were found to be satisfactory. None of the tube sheet materials studied possessed all the desired properties. Multi-fiber cells had very limited life-time due to physical failure of fibers at the fiber/tube sheet junctions.

Tsang, F. Y.↗

Determination of the zincate diffusion coefficient and its application to alkaline battery problems

The diffusion coefficient for the zincate ion at 24 C was found to be 9.9 x 10 to the -7th power sq cm/sec + or - 30% in 45% potassium hydroxide and 1.4 x 10 to the -7th power sq cm/sec + or - 25% in 40% sodium hydroxide. Comparison of these values with literature values at different potassium hydroxide concentrations show that the Stokes-Einstein equation is obeyed. The diffusion coefficient is characteristic of the zincate ion (not the cation) and independent of its concentration. Calculations with the measured value of the diffusion coefficient show that the zinc concentration in an alkaline zincate half-cell becomes uniform throughout in tens of hours by diffusion alone. Diffusion equations are derived which are applicable to finite-size chambers. Details and discussion of the experimental method are also given.

May, C. E.↗

Determination of the zincate diffusion coefficient and its application to alkaline battery problems

The diffusion coefficient for the zincate ion at 24 C was found to be 9.9 X 10 to the minus 7th power squared cm per sec + or - 30 percent in 45 percent potassium hydroxide and 1.4 x 10 to the minus 7 squared cm per sec + or - 25 percent in 40 percent sodium hydroxide. Comparison of these values with literature values at different potassium hydroxide concentrations show that the Stokes-Einstein equation is obeyed. The diffusion coefficient is characteristic of the zincate ion (not the cation) and independent of its concentration. Calculations with the measured value of the diffusion coefficient show that the zinc concentration in an alkaline zincate half cell becomes uniform throughout in tens of hours by diffusion alone. Diffusion equations are derived which are applicable to finite size chambers. Details and discussion of the experimental method are also given.

May, C. E.↗

Polymeric membrane systems of potential use for battery separators

Two membrane systems were investigated that may have potential use as alkaline battery separators. One system comprises two miscible polymers: a support polymer (e.g., polyvinyl formal) and an ion conductor such as polyacrylic acid. The other system involves a film composed of two immiscible polymers: a conducting polymer (e.g., calcium polyacrylate) suspended in an inert polymer support matrix, polyphenylene oxide. Resistivities in 45-percent potassium hydroxide and qualitative mechanical properties are presented for films comprising various proportions of conducting and support polymers. In terms of these parameters, the results are encouraging for optimum ratios of conducting to support polymers.

Philipp, W. H.↗

Advanced sensor systems for biotelemetry

The present invention relates to telemetry-based sensing systems that continuously measures physical, chemical and biological parameters. More specifically, these sensing systems comprise a small, modular, low-power implantable biotelemetry system capable of continuously sensing physiological characteristics using implantable transmitters, a receiver, and a data acquisition system to analyze and record the transmitted signal over several months. The preferred embodiment is a preterm labor and fetal monitoring system. Key features of the invention include Pulse Interval Modulation (PIM) that is used to send temperature and pressure information out of the biological environment. The RF carrier frequency is 174-216 MHz and a pair of RF bursts (pulses) is transmitted at a frequency of about 1-2 Hz. The transmission range is 3 to 10 feet, depending on the position of the transmitter in the body and its biological environment. The entire transmitter is encapsulated in biocompatible silicone rubber. Power is supplied by on-board silver-oxide batteries. The average power consumption of the current design is less than 30 .mu.W., which yields a lifetime of approximately 6-9 months. Chip-on-Board technology (COB) drastically reduces the size of the printed circuit board from 38.times.28 mm to 22.times.8 mm. Unpackaged dies are flip-chip bonded directly onto the printed circuit board, along with surface mount resistors and capacitors. The invention can monitor additional physiological parameters including, but not limited to, ECG, blood gases, glucose, and ions such as calcium, potassium, and sodium.

Hines, John W.↗

Advanced Sensor Systems for Biotelemetry

The present invention relates to telemetry-based sensing systems that continuously measures physical, chemical and biological parameters. More specifically, these sensing systems comprise a small, modular, low-power implantable biotelemetry system capable of continuously sensing physiological characteristics using implantable transmitters, a receiver, and a data acquisition system to analyze and record the transmitted signal over several months. The preferred embodiment is a preterm labor and fetal monitoring system. Key features of the invention include Pulse Interval Modulation (PIM) that is used to send temperature and pressure information out of the biological environment. The RF carrier frequency is 174-216 MHz and a pair of RF bursts (pulses) is transmitted at a frequency of about 1-2 Hz. The transmission range is 3 to 10 feet, depending on the position of the transmitter in the body and its biological environment. The entire transmitter is encapsulated in biocompatible silicone rubber. Power is supplied by on-board silver-oxide batteries. The average power consumption of the current design is less than 30 microW, which yields a lifetime of approximately 6 - 9 months. Chip-on-Board technology (COB) drastically reduces the size of the printed circuit board from 38 x 28 mm to 22 x 8 mm. Unpackaged dies are flip-chip bonded directly onto the printed circuit board, along with surface mount resistors and capacitors. The invention can monitor additional physiological parameters including, but not limited to, ECG, blood gases, glucose, and ions such as calcium, potassium, and sodium.

Hines, John W.↗