Basic Development of Nickel - Zinc Batteries

391
safer, and/or lowercost batteries. Research on zinc/bromine, calcium/metal

sulfide, and iron/chromium (redox) cells will progress toward the technology
transfer stage, and exploratory work on such systems as solid electrolyte,
organic electrolyte, and molten-salt cells will be pursued.
Engineering Science Research will include morphological studies that
address problems hindering the timely development of near-term batteries
(lead/lead dioxide, iron/nickel oxide, and/or zinc/nickel oxide); phenomeno-
logical studies to provide basic information needed for the rational design,
operation and control of electrochemical processes; studies on physiochemi-
cal methods for electrochemical research to aid the development of advanced
tools for the detailed study of battery materials and processes; and modeling
studies aimed at quantitative prediction of the dynamic behavior of cells, cell
components and batteries.
Materials Research seeks to identify, characterize, and improve the
materials and components to be used in batteries and electrochemical pro-
cesses. Investigations of solid electrolytes, including those of ceramic (beta-
alumina, NASICON), glass, and polymeric compositions, will continue, and
advanced liquid electrolytes, such as low-temperature molten-salt mixtures
and ionizing organic liquids, will be studied.
BASIC DEVELOPMENT OF NICKEL/ZINC BATTERIES
Lockheed Palo Alto Research Laboratory, Palo Alto, CA 94304 (U.S.A.)
The goal of this program is to gain information on the modes of opera-

tion of nickel and zinc electrodes from a study of well-defined, simplified,
structural analogs and from the application of semiquantitative, theoretical
concepts. The work is designed to yield useful information for hardware
development by addressing that domain of dimensions and conditions that
exists within the confines of pores in real porous electrodes, approximately
0.1 to 20 pm.
Moving picture photographs have been taken of growing dendrites and
of the anodic reaction front as it entered the zinc pore. Coupled with optical
microscopic studies, hydrogen bubbles were found to emanate from the base
or stems of the dendritic masses. Reaction fronts penetrated at rates of
1 x 1o-5 - 1 X lop3 cm s-l, depending on superficial current densities,
corresponding to cc. 50 - 1000 mA cm-‘, respectively. In Task II, the maxi-
mum accumulated charge of Zn and NiOOH was determined for pores with
openings of 1.0 cm X 2 X 10e3 cm. For Zn the accumulated charge depended
on current density during charging, being limited by the onset of dendrite
392
formation when the rate exceeded the Zn (OH),2- diffusive flow, typically
being about 600 mC at 50 mA cmV2. For Ni, the charge was cu. 15 mC,
indicating the need for higher specific surface area than for the Zn.
Aside from the planned tasks, several other advances were made in
pursuits prompted by observations during the course of the work.
(1) The movement of isolated Zn particles in a current field was dis-
covered and determined for both the electrokinetic and electrochemical dis-
placement cases, being of the order of 5 X 10e4 cm s-l and 1 X lo-5 cm s-l,
respectively. Motion by displacement appears to be more important for
particles larger than 5 pm.
(2) Black mossy zinc was found to grow at open circuit in concentra-
tion gradients formed in zinc cells at ca. 1 X 10e5 cm s-l causing short
circuits. This correlates with other reports of shorting of commercially pur-
chased Ag/Zn cells at open circuit rather than at closed circuit, and of the
observed presence of mossy zinc at dendrites in Ag/Zn cells.
(3) The charge passed before onset of zinc dendrite growth was found
to be related to the amount of zincate ion present in the pore and to the
current density. Typically, some 100 - 800 mC could be passed across a
1 cm X 2 X 1O-3 cm pore opening at current densities corresponding to
50 - 125 mA cmP2, respectively.
(4) During the cycling of a single-pore nickel electrode (150 cycles), a
decrease in the discharge slope occurred after the 40th cycle, remaining the
same thereafter. Exfoliation of the Ni(OH),/NiOOH layer on the polished Ni
pore wall was observed during the post mortem. This preliminary informa-
tion suggests that such exfoliation is related to the deterioration in per-
formance.
During the last quarter of 1979, reaction profiles will be collected and
the influence of cycling determined on the reaction profile, capacity, and
morphology. The work for 1980 is suggested by the new findings itemized
(2) - (4) above. Thus, it is important that conditions for open-circuit shorting
by mossy zinc be determined in a series of experiments with controlled
concentrations (item (2)), that the mechanism of closed-circuit dendrite
shorting be further quantified by varying pore size and Zn(OH),2- concentra-
tion (item (3)), and that the mode of nickel electrode failure suggested by
the preliminary results (item (4)) be verified. Additionally, zinc studies
should be made in acid media just as they were in alkaline during 1979 in
preparation for Zn/C12 and Zn/Br, applications. It is anticipated that shape
change observations made during the cycling will be useful in interpreting
causes for this harmful effect.
Finally, in 1980, we propose to cycle commercially available Ni/Zn
cells to destruction and to perform post mortems to relate the research
findings with actual hardware development.
To assist in the development and production of hardware Ni/Zn cells,
technical backlogs are required for problem areas that are now anticipated
with the Ni and Zn electrodes. These are outlined as follows.
(1) More detailed information is needed on the causes of Zn dendrite
393
formation in alkaline media. In acid media, similar information is required

for the Zn/Clz and Zn/Brz systems.
(2) Shorting has also been observed at open circuit, and a detailed
study is required to outline conditions under which this deleterious phenom-
enon occurs.
(3) Shape change or slumping at the zinc electrode leads to serious
deterioration, and observations of this process during cycling are required in
the single-pore microcell.
(4) Nickel oxide exfoliation from the nickel substrate appears to be
identified as a cause for nickel electrode performance deterioration. Correla-
tions are needed for various conditions of cycling with the extent of ex-
foliation.
(5) Continued studies are needed on the effects of cycling zinc elec-
trodes (acidic and basic media) as started in this program in 1979.
Recent publications
1 T. Katan, P. T. Bergeron and S. Szpak, Evolution of reaction profiles in porous zinc
electrodes, J. Electrochem. Sot., Ext. Abstr., 79-2 (1979) (in press).
2 S. Szpak, C. J. Gabriel and T. Katan, Fragmentation of dendritic zinc clusters on elec-
trode cycling, J. Electrochem. Sot., to be submitted.
RESEARCH ON ALKALINE ZINC SECONDARY ELECTRODES WITH

EMPHASIS ON LIFE IMPROVEMENT
Linfield Research Institute, McMinnville, OR 9 7128 (U.S.A.)
The goal of the project is to provide information which will aid in the
realization of ‘a reproducibly long-lived zinc secondary battery designed and
constructed in such a manner as to retain the high energy density and power
density capabilities of the porous zinc electrode. Our approach has been to
carry out experiments based on mathematical models of the electrode devel-
oped by Professor Douglas Bennion, UCLA, and his colleagues and students.
The modelers use their best efforts to construct tractable models which
include the essential aspects of physical processes occurring in the electrodes.
The results are predictions of observable quantities related to electrode per-
formance; the predictions serve as guidelines for the experimentalist in the
laboratory, thus, hopefully, increasing the effectiveness of the laboratory
work. Agreement between model prediction and experiment serves to rein-
force one’s conviction that essential processes are understood and properly
incorporated into the model; disagreement defines limits of applicability of

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391

safer, and/or lowercost batteries. Research on zinc/bromine, calcium/metal

BASIC DEVELOPMENT OF NICKEL/ZINC BATTERIES

Lockheed Palo Alto Research Laboratory, Palo Alto, CA 94304 (U.S.A.)

The goal of this program is to gain information on the modes of opera-

formation in alkaline media. In acid media, similar information is required

RESEARCH ON ALKALINE ZINC SECONDARY ELECTRODES WITH

Linfield Research Institute, McMinnville, OR 9 7128 (U.S.A.)

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