1070-4272/03/7610-1606 $25.00 C 2003 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 76, No. 10, 2003, pp. 1606!1610. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 10, 2003,
Original Russian Text Copyright + 2003 by Arkhangel’skaya, Kas’yan, Loginova.
AND CORROSION PROTECTION OF METALS
Influence of Zinc Intercalation on Processes in Nickel Oxide
Electrode and on Service Life of Nickel!Zinc Battery
Z. P. Arkhangel’skaya, T. B. Kas’yan, and M. M. Loginova
Akkumulyatornaya Kompaniya Rigel’, Open Joint-Stock Company, St. Petersburg, Russia
Received May 28, 2003
Abstract-The dependence of capacity and service life of a nickel3zinc battery on the mechanism of zinc
transfer and the rate of zinc intercalation into nickel oxide electrodes differing in the conductivities of the ac-
tive paste and porous structures was studied.
The problem of raising the service life of nickel3
zinc (NZ) batteries, which permanently attracts atten-
tion, is mostly solved by using various methods for
making lower the solubility of zinc at the negative
electrode. It is a common practice to use for this pur-
pose electrolytes with as low KOH concentration as
possible and F
ions added to the electro-
lyte and Ca(OH)
, and other additives to
the active paste of the zinc electrode. These additives
form with zinc oxide, complex compounds sparingly
soluble in alkaline solutions . This makes it pos-
sible to slow down the processes leading to intraelec-
trode transfer of zinc in the negative electrode and to
[loss of its shape,] a factor limiting the service life
of NZ batteries.
It can be seen from  that, presently, the ser-
vice life of NZ batteries is 3003400 cycles, and
the Evercell company achieved a service life of 600
So far, all attempts to raise further the service life
of NZ batteries have failed, which is still attributed
to the necessity for improving the negative electrode.
At the same time, it was determined in  that the de-
crease in the capacity of NZ batteries after 3003400
cycles is due to impaired working capacity of the nick-
el oxide electrode (NOE) on a metal-ceramic (MC)
support. The authors failed to reveal the reason for
its degradation, since the assumption that the structure
of the active paste degrades was not confirmed.
A decrease in the capacity of a NZ battery, associ-
ated with deteriorated chargeability of an NOE on
an MC support after 250 cycles, was also noted in .
The observed dramatic rise in the potential in anodic
polarization and increase in oxygen evolution were
accounted for by nonuniform distribution of current
over the NOE surface, which results in an unbalance
in the degree of charging of different areas on the sur-
face of the positive and negative electrodes, and, as
consequence, in the loss of shape by the zinc electrode
and in its local passivation.
Data indicating that processes occurring on NOE
can strongly affect the working capacity of the zinc
electrode and limit the service life of an NZ battery
have been obtained recently using a compacted NOE
made of spherical nickel hydroxide containing cobalt
hydroxide as additive on a foamed-nickel (FN) sup-
port . In a battery with NOE on an FN support,
the intraelectrode mass transfer in the zinc electrode
is strongly decelerated, and its shape is retained af-
ter up to 2003250 cycles. This is accounted for by
the increased conductivity of active paste [spherical
], which affects the uniformity of the current
distribution both within the active paste and over
the surface of the zinc electrode.
It was also revealed that accumulation of zinc in
an FN-supported NOE as a result of interelectrode
mass transfer, occurs in the course of direct incorpo-
ration of zinc into the structure of Ni(OH)
the stages of its deposition within pores in the form
or ZnO bypassed.
The results obtained suggest that incorporation of
zinc also occurs in an MC-supported NOE, but is not
manifested clearly, being preceded by deposition of
ZnO within the porous space of the electrode.