Vol. 99, No.

8 ANNIVERSARY ISSUE ON PRIMARY CELL SYSTEMS 197C

The Alkaline-Mercury Oxide Cell

James M. Booe ~

These alkaline-mercury oxide ceils, as commercially pro- Anodes

dueed, are dry cells, employing a depolarizer of mercuric The anodes used in the alkaline-mercuric oxide cells may
oxide, an immobilized electrolyte of potassium hydroxide be in one of the following general forms:
containing a substantial amount of zineate, and an amalgam- 1. Amalgamated zinc powder of a special grade amalga-
ated zinc anode. mated with about 10 per cent of mercury by weight is pressed
into the desired shape, such as a pellet or cylinder, under a
Historical pressure of several tons per square inch (Fig. 2). A highly
In 1884 Clarke (1) described a inereuric oxide liquid alka- porous structure is developed with considerable subsurface
line primary cell as did Bronsted (2) in 1915. During World activity during use. The maximum current-density rating is
War I attempts were made to produce mercuric oxide liquid about 18.5 ma/cm 2 (120 ma/in. 2) of apparent area.
alkaline cells.
The " R M ''2 cell, developed by Samuel Ruben 3 in the early
part of World War II, utilized a cathode-depolarizer of mer-
curie oxide and finely divided graphite compressed into a hard
pellet, an amalgamated zinc anode, and electrolyte of potas-
sium hydroxide substantially saturated with zineate, the
electrolyte being held in an absorbent spacer-barrier inter-
posed between the two electrodes, the cell elements being
housed under compression in an air-tight sealed steel ease.
The cell contained no free flowing electrolyte.
Ruben's work demonstrated the ability of his cell to with-
stand severe storage and operating conditions over extended
periods of time. The Battery Branch of the U. S. Signal
Corps recognized this and promptly sponsored the develop-
ment and establishment of production for relatively large
numbers of cells for military use. FIG. 1. Cross section of wound-anode mercuric oxide cell.
By the end of the war, peak production of the RM cell
was in excess of 1,000,000 cells per day. Production has since
continued on a large scale both for military and civilian use.
The cell as manufactured today is considerably improved
over the cells first manufactured during the last war, although
the fundamental features are retained.
A number of patents (3) were issued to Ruben covering
his developments.

Applications
Mercuric oxide cells are characterized by their high ratio
of energy to volume, long shelf life, uniform discharge poten-
tial, resistance to environmental conditions of corrosion,
temperature and pressure, and are mechanically rugged and
stable. Although these cells will operate at such elevated
temperatures as 125~ (257~ their performance at rather
low temperatures is limited except at low rates of drain.
One of the important applications of cells of this system
is in the construction of multicell military batteries. Other
uses include alarm systems, radiation detection devices, port-
able test apparatus, and scientific and clinical laboratory
instruments. The main application of mercuric oxide cells,
however, is for the "A" supply of hearing aids. The rather
uniform open circuit voltage of this system makes it applicable
as secondary standards of potential where extreme precision
is not required. Because of this characteristic the cells lend
themselves as a source of potential for the grid elements of
electron tubes.
' P. R. Mallory & Company, Inc., Indianapolis, Indiana.
2 A contraction of Ruben-Mallory used by the Signal Corps
to designate the battery.
3 Ruben Laboratories, New Rochelle, New York.
FIG. 2. Cross section of pressed-powder-anode mercuric
oxide cell.
2. Corrugated zinc foil of 99.99 per cent purity is wound
into a roll with an absorbent paper, the latter to retain elec-
trolyte at the entire interface of the anode (Fig. 1). Winding
is done in a staggered manner so that one edge of the zinc
protrudes from one end of the roll and paper from the other.
This type of anode is amalgamated, after saturation with
electrolyte, by the addition of 10 per cent of metallic mercury
to the end of the roll having the exposed edges of zinc.
3. Corrugated zinc foil or strip is wound into a roll with-
out absorbent paper and, after transferring into the negative
cell member, is amalgamated with metallic mercury.
This and other forms of wound anodes are used in cells
with gelled electrolyte. Foil type anodes have a permissible
current-density rating up to about 0.8 ma/cm 2 (5 ma/inY).

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 198C JOURNAL OF THE ELECTROCHEMICAL
Cathode
The depolarizer consists of an intimate mixture of about
92 per cent red mercuric oxide and 8 per cent micronized
graphite, the latter imparting electronic conductivity. The
mix is molded under high pressure directly into the cathode
member (Fig. 1 and 2), or is pressed as a discrete part and
assembled into the cell, depending on the type of cell pro-
duced. Permissible current-density rating of the cells based
on depolarizer area is about 15.5 ma/cm ~ (100 ma/in.2).
Electrolyte
The electrolyte-separator members used in the alkaline-
mercuric oxide cells are of two general types:
1. Liquid electrolyte of 35 to 40 per cent KOH content
containing approximately 5 per cent ZnO is absorbed in a
separator material of alpha cellulose. In wound-anode cells,
a single layer of paper is used between the zinc windings,
while in pressed-powder cells, multilayers of paper or cellulose
felt are used. In addition to this absorbent, the liquid elec-
trolyte cells require an ion-permeable "barrier" to prevent
migration of particles from the depolarizer to the anode. This
barrier, generally of parchment paper, is positioned next to
the depolarizer interface, thus leaving the cellulose absorbent
to contact the anode.
2. The other type of electrolyte-separator is a gelatinized
form of the liquid electrolyte having approximately the com-
position indicated above. Gelling is effected by the addition
of 1.5-4 per cent carboxy-methyl-ceUulose. This can produce
an electrolyte member sufficiently rigid to eliminate the need
for paper absorbent or barrier. However, for the more severe
applications a parchment barrier is used. In another arrange-
ment which also involves the anode, the electrolyte-member
is made by rigidly gelling a liquid electrolyte of approximately
the same composition with carboxy-methyl-cellulose with the
zinc powder amalgam dispersed throughout it. 4 A barrier is
required between this member and the depolarizer.
Theory of Operation
The over-all discharge reaction of this system may be
presented as:
Zn + HgO + H20 --* ZnO + Hg + H~O
with the liberation of two Faradays of electrical energy per
mole of active electrode materials. In the above over-all reac-
tion water appears on both sides of the equation; thus the
net result is that no water is abstracted from the electrolyte.
The theoretical voltage (4) of this system is in close agree-
ment with the measured value of stabilized cells, namely,
1.345 volts. The cells owe their stability, in large part, to the
presence of potassium zincate in the electrolyte in substan-
tially saturated concentration. This is produced in the prep-
aration of the electrolyte by reacting ZnO with KOH.
ZnO + 2KOH -~ K.,ZnO2 + H20
The presence of the zincate ion inhibits the chemical attack
of the KOH on the zinc anode by the mass action effect.
In newly assembled cells an initial voltage of about 1.4 volts
may be obtained. However, within a few hours the voltage
becomes stabilized at or near the 1.345 value. Uniformity and
stability is also promoted by the high degree of purity of all
cell constituents.
In addition to the rather reproducible open-circuit voltage
the system has a fairly constant discharge potential. Con-
4 Under development by The Magnavo• Company, Fort
Wayne, Indiana.
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SOCIETY August 1952
tinuous-discharge capacity is virtually equal to intermittent-
discharge performance. These characteristics are probably
due to the direct reduction of HgO to Hg without intermedi-
ate products, in combination with the fact that the electro-
lyte composition remains constant during discharge.
Cell Mechanics
The cell-discharge reactions are accompanied by definite
physical changes in the electrodes and electrolyte-tLbsorbent
member. Herein lies the necessity for a rather precise arrange-
ment of these parts if optimum performance is to be realized.
In an undischarged cell with liquid electrolyte the anode is
supported in position by a moderate compression of the elec-
trolyte-absorbent member against the cathode. In :~ome gel-
electrolyte cells, the anode is loosely anchored in the negative
terminal member as assembled; but during discharge, expan-
sion of the anode due to the formation of zinc oxide exerts
a slight but continuous compressive force on the gel-electro-
lyte member. The anode expands to about twice its original
volume during complete cell discharge..Mercury rei[eased by
the anode amalgam remains, in part, in the zinc oxide and
part accumulates on the negative terminal member. Provision
must be made to prevent this free mercury from causing a
short circuit to the positive cell member. This is acccmplished
by an extension of the sealing gasket to the absorbent or
anode sleeve (Fig. 1 and 2). Also during discharge, the de-
polarizer becomes soft due to its conversion to metallic mer-
cury. Expansion of the anode tends to force electrolyte from
the absorbent or gel; this makes it available for absorption in
the depolarizer as the latter is progressively reduced. This is
important because reduction begins substantially at the sur-
face and progresses through the depolarizer mass as the cell
is discharged.
Since the electrolyte is not consumed in the cell reactions,
a relatively small quantity is required, i.e., about 1.35 g/1000
ma hr. Furthermore the energy-volume ratio of the electrode
material is quite high. Full advantage is generally taken of
these factors in the design of cells. This high energy-volume
ratio is based on the fact that 1.00 g of HgO and 0.302 g of
zinc will produce 0.247 amp-hr of current. [Because of the
graphite in the depolarizer and mercury in the anode, 1.00 g
of depolarizer (92% HgO, 8% graphite) and 0.308 g of anode
amalgam (90% Zn, 10% Hg) will actually deliver 0.227
amp-hr.] At low rates of drain this amount of energy can
be realized, but at maximum rated drains somewhat less is
obtained, being as much as 10 to 15 per cent below the theo-
retical value, depending somewhat on the type of cell con-
struction. This performance is based on an end voltage of 0.9
volts.
The various factors of electrode reactions and their physical
manifestations must be taken into account in the design and
construction of the cell. This applies to the container as well
as to the active components. All cells are tightly sealed to
prevent loss of electrolyte, to increase rigidity, and to avoid
access of air to the active materials. All cells also have one
external member, the negative terminal, forming part of the
closure; this is generally termed the cell top (Fig. 1 and 2).
This part is of material electrochemically suitable for contact
with the anode in the presence of electrolyte. Among the ac-
ceptable metals are copper and certain of its alloys (preferably
silver plated). Steel is preferred, although it requires a plat-
ing of an amalgamable metal such as tin. It is best also for
the other external cell member and may be nickel plated to
inhibit exterior cell corrosion. Steel has the property of inert-
ness to the alkaline electrolyte and to the depolarizer with
which it must make good contact. This member serves as the
 Vol. 99, No. 8 ANNIVERSARY ISSUE ON PRIMARY CELL SYSTEMS 199C

positive ternfinal for the cell and is generally termed the cell this couple is of sufficient magnitude to electrodeposit zinc
case. Cells are tightly closed by deforming the edge of the from the electrolyte onto the terminal metal until it is com-
positive member or case around the edge of the negative from pletely covered; furthermore, this deposited zinc is amalgam-
which it is insulated by a sealing gasket (Fig. 1 and 2). Ac- ated by mercury from the anode with which it is in contact.
ceptable gasket materials are polyethylene and neoprene, the
latter being used in cells for military applications or where
abnormal temperatures are encountered.

FIG. 3. Photographs of some mercuric oxide cells showing

relative sizes and shapes. Identification (with Tables I and II)
from left to right: RM-42 ("D" size), RM-502, RM-4, RM-3,
3R, RM-I, 1R, and RM-1RX.

TABLE I. Dimensions and ratings of wound-anode

mercuric oxide cells FIG. 4. Relation between discharge current density and
Capa-
closed-circuit voltage of alkaline-mercuric oxide RM-12 cell
Dia m Ht V ol Wt city at 70~
No.
(in.) (cm) (in.) (cm) (in. a) (cma)] (oz) (g) (ma Current density of discharge
hr)
Curve [ Ma/iu3 Ma/cm 2 Average Average
cathode area cathode area ma/cm 3 ran/in)
1R 0.606 11.541 0,490 11.24/0.14 2.29 0.28 7.9, 650
2R 0.819 t2.081 0.518 11.32/0,27 14.42/0.56 115.9 1400
3R o.973 2.471 o.523 1.33 / 0.38 16.231 0.84 123.8 2000 A 122 18.9 25.4 417
4R 1.187/3,011 0. 1 !1,37/0.60 19.85[ 1.30 136,8 3200 B 61 9.45 12.7 208
C ' 30 4.65 6.3 103
D 15 2.32 3.0 50
TABLE II. Dimensions and ratings of pressed-
powder-anode mercuric oxide cells

Diam Ht Vol --.. Capa-

~A c x ty
No.
(in.) (cm) in.) (cm) (in.~) (cm~) (oz) (g) (hmr)
a

RM-1RX O. 606]1.54 .226 3.57 0.070 1.150 0.14 3.97j 250

RG-1 0.625 1.58 .660 1.67 0.200 3.28 049l 1388t 1000
RM-1 0.625/1.58 .650 t.65 0.200 3.28 0.43 12.17 1000
RG -3 1.000i2.54 .660 1.67 0.520 8.52 1.021 28.901 2000
RM-3 0.995 2.53 .650 1.65 0.5013 8.20 0.911 25.751 2000
RG-4 1.220 3.10 .6601.67 0.770 12.63 1.421 40.25 3400
RM-4 1.21013.07 .650 1.65, 0.740 12.13 1.501 42.50[ 3200
RM-502 0.53111.35 .9~t.95 0.390 6.40 1.05 29.731 2400
RM-12 0.625 1.58 .950~.95 0.60t3 9.83 1.40 39.65 3600
RM-42 1.19013. O2 .375B.03 2.6~43.60 5.85 165.5 14000

RG is General Dry Battery Co. designation.

RM is P. R. Mallory & Co. designation.
The first cells produced were exclusively for military appli-
cations and were principally used in the construction of bat-
teries for transceivers. A number of structural changes have
since been made for civilian uses and for improved military
service. The original negative-terminal zinc top was first
replaced by copper and subsequently by tin-plated steel which
is stronger, permits a more exact control of anode zinc content,
and facilitates intercell welded connections. The acceptability
of metals other than zinc for this cell part depends on a reac-
tion in which the zincate ion in the electrolyte plays an im-
portant part. Upon assembly of the cell a local couple is
established between the zinc anode and the cell top or ter-
minal metal with which it is in contact. The potential of
Fro. 5. Relation between discharge current density and out-
put per unit volume and weight of alkaline-mercuric oxide
RM-12 cell at 70~ to .9 v cutoff.
The position of the cell closure, originally at the top of the
cell with resultant close spacing between the parts, has been
somewhat changed. The radially-crimped cells (Fig. 1 and 2)
which replaced the earlier axia]ly-crimped cell, embodies a
redesign of the cell exterior which extends the edge of the
top member part way to the depolarizer and effects the seal
at this point, thus increasing the distance between the anode
and the positive member. This change, along with improved
gasketing, has virtually eliminated the possibility of cel]
failures due to internal short circuits.

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 200C JOURNAL OF THE ELECTROCHEMICAL
Another improvement in cell construction was effected for
individual cell applications where the units are not enclosed
in a battery container. When there is an electrochemical ex-
cess of anode zinc over the depolarizer, hydrogen gas is liber-
ated at the cathode member after the depolarizer is spent if
the cell is left on circuit. Under these conditions sufficient
pressure can be developed to rupture the cell. This is over-
come by a "balanced" (5) construction in which a slight ex-
cess of depolarizer is used over that stoichiometrically re-
quired for the zinc anode.
To further preclude the possibility of cell rupture from such
causes as local action at the anode, unbalanced construction,
externally applied voltage, etc., an improved venting 5arrange-
ment may be used. Essentially these ceils are made with two
cases, the outer effecting a seal with the cell top member in
such manner as to hold the latter in sealing relationship with
the top edge of the inner case. Should abnormal pressure de-
velop within the cell, the top raises slightly to permit venting
into the annular space between the two cases. Any electrolyte
vented is retained by an absorbent member in this space, and
any gas escapes through a hole in the outer case. Fig. 2 shows
a cutaway view of this construction.
Some gel-electrolyte cells are vented by scoring the cell top
to produce a weakened area. This gives way if abnormal pres-
sures are generated, allowing gas and electrolyte to pass into
a space between the top and an auxiliary terminal cap where
any electrolyte is retained by an absorbent. Double case
construction also is employed in gelled-electrolyte cells where
venting takes place through the case rather than through the
top.
Mercuric oxide cells, for the most part, differ in sizes and
shapes from those of the Leclanch6 system. Fig. 3 shows some
of the forms currently produced. (The largest cell shown is
approximately the "D" size.) At present, cells of this system
may be divided into three general groups according to their
construction and uses.
5 Subject matter for patent application.
The Silver Peroxide-Zinc Alkaline Cell
P a u l L. H o w a r d t
The alkaline-silver peroxide-zinc element has been the
subject of numerous investigations and patents. Only in
recent years, however, has interest shifted from the study of
its behavior as a secondary battery to an examination of its
applicability as a primary cell. Clarke (l) in 1883 described
battery composed of silver oxide cathodes wrapped in vege-
table parchment, bibulous paper, muslin or other suitable
material, a zinc anode, and a sodium or potassium hydroxide
electrolyte. Jirsa (2), Zimmerman (3), Kinoshita (4), and
Andre (5) have described the use of silver oxide cathodes with
anodes of iron, cadmium, or zinc. A list of the more important
patents (6) by Jungner, Hubbell, Morrison, Br6nsted, Drumm,
Andre, and others shows how extensive the investigations
have been in the secondary field.
The first practical silver peroxide-zinc alkaline reserve-type
"one shot" high-rate primary battery was developed during
World War I I through the joint efforts of the National Bureau
National Bureau of Standards, Washington, D. C.
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SOCIETY August 1952
1. Cells having a flat depolarizer element and a wound
anode. Although these ceils are generally unrented and un-
balanced, some are made with these features. This type is
primarily used for multicell battery constructions, especially
for military applications. Table I lists such cells together
with dimensions and ratings.
2. Cells having a flat depolarizer element and a flat pressed
powder anode. (Gel cells with a wound corrugated zinc anode
may be classed here.) These cells are vented and balanced
and are used primarily for single cell applications. Table I I
lists cells of this type with their dimensions and ratings.
3. Cells having a cylindrical depolarizer element and a
cylindrical pressed powder anode. These cells are vented and
balanced and are used primariIy for single cell applications
and where drain rate requirements are high. Cells of this type
are also found in Table II.
Performance of the alkaline-mercuric oxide system is repre-
sented in Fig. 4 and 5.
REFERENCES
1. C. L. CLARKE, U. S. Pat. 298,175, May 6, 1884.
2. J. N. BRONSTED, U. S. Pat. 1,219,074, March 13, 1917;
British Pat. 16,474 (1915); German Pat. 72,147 (1916).
3. SAMUEL RUBEN, U. S. Pat. 2,422,045-6, June 10, 1947;
2,473,546, June 21, 1949; 2,481,539, Sept. 13, 1949; 2,482,-
514, Sept. 20, 1949; 2,542,575-6, Feb. 20, 1951.
4. M. FRIEDMAN A N D C. E. MCCAULEY, Trans. Electrochem.
Soe., 99., 195 (1947).
5. S. RUBEN, Trans. Electrochem. Soc., 92, 183 (1947).
References not specifically referred to in the text:
GEOrtGE W. VINAL,"Primary Batteries," John Wiley & Sons,
Inc., New York, (1950).
R. W. HALLOWSAND M. A. CANTAB, "Dry Battery Develop-
m e n t s - t h e RM Mercury Cell," Wireless World, May 1948.
JohN C. LEBENS, "Portable Batteries for Built-in Power
Sources," Elec. Mfg., August 1949.
W. J. HAMER,"New Dry Cells," Product Eng., March 1950.
C. H. CLARK,"Primary Batteries," Electrochem. Engrg., June
1950.
of Standards (7), the Naval Research Laboratory (8), and
T. A. Edison, Inc., under the direction of the Bureau of
Ships.
This battery is composed of a silver peroxide cathode
consisting of a coating of silver oxide or silver chloride on a
grid material such as silver-plated copper, nickel, or silver
wire or screen, subsequently reduced to silver and electro-
lytically formed to silver peroxide (7), an anode of zinc con-
sisting of sheet zinc, zinc plated or zinc dust pasted on copper,
nickel or silver wire or screen, and an electrolyte of 25 to
35 per cent potassium hydroxide solution.
While the exact mechanisms of the electrode reactions
(8) have not been completely established, the similarity of
the changes taking place during discharge with those occurring
in other alkaline cells suggests the following as the most prob-
able mechanism (7) :
Ag20,. + 2 KOH + Zn --* K~ZnO~ + H20 + Ag~O
Ag,.O + 2 K O H + Zn-*K2ZnO2 + H 2 0 + 2 A g .